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LANGE’S HANDBOOK OF CHEMISTRY James G. Speight, Ph.D. CD&W Inc., Laramie, Wyoming

Sixteenth Edition

MCGRAW-HILL New York Chicago San Francisco Lisbon London Madrid Mexico City Milan New Delhi San Juan Seoul Singapore Sydney Toronto

Library of Congress Catalog Card Number 84-643191 ISSN 0748-4585

Copyright © 2005, 1999, 1992, 1985, 1979, 1973, 1967, 1961, 1956 by The McGraw-Hill Companies, Inc. All rights reserved. Printed in the United States of America. Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a data base or retrieval system, without the prior written permission of the publisher. Copyright renewed 1972 by Norbert Adolph Lange. Copyright 1952, 1949, 1946, 1944, 1941, 1939, 1937, 1934 by McGraw-Hill, Inc. All rights reserved. 1 2 3 4 5 6 7 8 9 0

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ISBN 0-07-143220-5

The sponsoring editor for this book was Kenneth P. McCombs and the production supervisor was Sherri Souffrance. It was set in Times Roman by International Typesetting and Composition. The art director for the cover was Anthony Landi. Printed and bound by RR Donnelley.

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Information contained in this work has been obtained by The McGraw-Hill Companies, Inc. (“McGraw-Hill”) from sources believed to be reliable. However, neither McGraw-Hill nor its authors guarantee the accuracy or completeness of any information published herein and neither McGraw-Hill nor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information. This work is published with the understanding that McGraw-Hill and its authors are supplying information but are not attempting to render engineering or other professional services. If such services are required, the assistance of an appropriate professional should be sought.

ABOUT THE EDITOR James G. Speight, Ph.D., has more than 35 years’ experience in fields related to the properties and processing of conventional and synthetic fuels. He has participated in, and led, significant research in defining the uses of chemistry with heavy oil and coal. The author of well over 400 professional papers, reports, and presentations detailing his research activities, he has taught more than 50 related courses. Dr. Speight is the author, editor, or compiler of a total of 25 books and bibliographies related to fossil fuel processing and environmental issues. He lives in Laramie, Wyoming.

PREFACE TO THE SIXTEENTH EDITION

This Sixteenth Edition of Lange’s Handbook of Chemistry takes on a new format under a new editor. Nevertheless, the Handbook remains the one-volume source of factual information for chemists and chemical engineers, both professionals and students. The aim of the Handbook remains to provide sufficient data to satisfy the general needs of the user without recourse to other reference sources. The many tables of numerical data that have been compiled, as well as additional tables, will provide the user with a valuable time-saver. The new format involves division of the Handbook into four major sections, instead of the 11 sections that were part of previous editions. Section 1, Inorganic Chemistry, contains a group of tables relating to the physical properties of the elements (including recently discovered elements) and several thousand compounds. Likewise, Section 2, Organic Chemistry, contains a group of tables relating to the physical properties of the elements and several thousand compounds. Following these two sections, Section 3, Spectroscopy, presents the user with the fundamentals of the various spectroscopic techniques. This section also contains tables that are relevant to the spectroscopic properties of elements, inorganic compounds, and organic compounds. Section 4, General Information and Conversion Tables, contains all of the general information and conversion tables that were previously found in different sections of the Handbook. In Sections 1 and 2, the data for each compound include (where available) name, structural formula, formula weight, density, refractive index, melting point, boiling point, flash point, dielectric constant, dipole moment, solubility (if known) in water and relevant organic solvents, thermal conductivity, and electrical conductivity. The presentation of alternative names, as well as trivial names of long-standing use, has been retained. Section 2 also contains expanded information relating to the names and properties of condensed polynuclear aromatic compounds. Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic and Inorganic Compounds, and Heats of Melting, Vaporization, and Sublimation and Specific Heat at Various Temperatures, are also presented in Sections 1 and 2 for organic and inorganic compounds, as well as information on the critical properties (critical temperature, critical pressure, and critical volume). As in the previous edition, Section 3, Spectroscopy, retains subsections on infrared spectroscopy, Raman spectroscopy, fluorescence spectroscopy, mass spectrometry, and X-ray spectrometry. The section on Practical Laboratory Information (now Section 4), has been retained as it offers valuable information and procedures for laboratory methods. As stated in the prefaces of earlier editions, every effort has been made to select the most useful and reliable information and to record it with accuracy. It is hoped that users of this Handbook will continue to offer suggestions of material that might be included in, or even excluded from, future editions and call attention to errors. These communications should be directed to the editor through the publisher, McGraw-Hill. JAMES G. SPEIGHT, PH.D. Laramie, Wyoming

vii

PREFACE TO THE FIFTEENTH EDITION

This new edition, the fifth under the aegis of the present editor, remains the one-volume source of factual information for chemists, both professionals and students––the first place in which to “look it up” on the spot. The aim is to provide sufficient data to satisfy all one’s general needs without recourse to other reference sources. A user will find this volume of value as a time-saver because of the many tables of numerical data that have been especially compiled. Descriptive properties for a basic group of approximately 4300 organic compounds are compiled in Section 1, an increase of 300 entries. All entries are listed alphabetically according to the senior prefix of the name. The data for each organic compound include (where available) name, structural formula, formula weight, Beilstein reference (or if un- available, the entry to the Merck Index, 12th ed.), density, refractive index, melting point, boiling point, flash point, and solubility (citing numerical values if known) in water and various common organic solvents. Structural formulas either too complex or too ambiguous to be rendered as line formulas are grouped at the bottom of each facing double page on which the entries appear. Alternative names, as well as trivial names of long-standing usage, are listed in their respective alphabetical order at the bottom of each double page in the regular alphabetical sequence. Another feature that assists the user in locating a desired entry is the empirical formula index. Section 2 on General Information, Conversion Tables, and Mathematics has had the table on general conversion factors thoroughly reworked. Similarly the material on Statistics in Chemical Analysis has had its contents more than doubled. Descriptive properties for a basic group of inorganic compounds are compiled in Section 3, which has undergone a small increase in the number of entries. Many entries under the column “Solubility” supply the reader with precise quantities dissolved in a stated solvent and at a given temperature. Several portions of Section 4, Properties of Atoms, Radicals, and Bonds, have been significantly enlarged. For example, the entries under “Ionization Energy of Molecular and Radical Species” now number 740 and have an additional column with the enthalpy of formation of the ions. Likewise, the table on “Electron Affinities of the Elements, Molecules, and Radicals” now contains about 225 entries. The Table of Nuclides has material on additional radionuclides, their radiations, and the neutron capture cross sections. Revised material for Section 5 includes the material on surface tension, viscosity, dielectric constant, and dipole moment for organic compounds. In order to include more data at several temperatures, the material has been divided into two separate tables. Material on surface tension and viscosity constitute the first table with 715 entries; included is the temperature range of the liquid phase. Material on dielectric constant and dipole moment constitute another table of 1220 entries. The additional data at two or more temperatures permit interpolation for intermediate temperatures and also permit limited extrapolation of the data. The Properties of Combustible Mixtures in Air has been revised and expanded to include over 450 compounds. Flash points are to be found in Section 1. Completely revised are the tables on Thermal Conductivity for gases, liquids, and solids. Van der Waals’ constants for gases have been brought up to date and expanded to over 500 substances. Section 6, which includes Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic and Inorganic Compounds, and Heats of Melting, Vaporization, and Sublimation and Specific Heat at Various Temperatures for organic and inorganic compounds, has expanded by

ix

x

PREFACE TO THE FIFTEENTH EDITION

11 pages, but the major additions have involved data in columns where it previously was absent. More material has also been included for critical temperature, critical pressure, and critical volume. The section on Spectroscopy has been retained but with some revisions and expansion. The section includes ultraviolet-visible spectroscopy, fluorescence, infrared and Raman spectroscopy, and X-ray spectrometry. Detection limits are listed for the elements when using flame emission, flame atomic absorption, electrothermal atomic absorption, argon induction coupled plasma, and flame atomic fluorescence. Nuclear magnetic resonance embraces tables for the nuclear properties of the elements, proton chemical shifts and coupling constants, and similar material for carbon-13, boron-11, nitrogen-15, fluorine-19, silicon-29, and phosphorus-31. In Section 8, the material on solubility constants has been doubled to 550 entries. Sections on proton transfer reactions, including some at various temperatures, formation constants of metal complexes with organic and inorganic ligands, buffer solutions of all types, reference electrodes, indicators, and electrode potentials are retained with some revisions. The material on conductance has been revised and expanded, particularly in the table on limiting equivalent ionic conductance. Everything in Sections 9 and 10 on physiochemical relationships, and on polymers, rubbers, fats, oils, and waxes, respectively, has been retained. Section 11, Practical Laboratory Information, has undergone significant changes and expansion. Entries in the table on “Molecular Elevation of the Boiling Point” have been increased. McReynolds’ constants for stationary phases in gas chromatography have been reorganized and expanded. The guide to ion-exchange resins and discussion is new and embraces all types of column packing and membrane materials. Gravimetric factors have been altered to reflect the changes in atomic weights for several elements. Newly added are tables listing elements precipitated by general analytical reagents, and giving equations for the redox determination of the elements with their equivalent weights. Discussion on the topics of precipitation and complexometric titration include primary standards and indicators for each analytical technique. A new topic of masking and demasking agents includes discussion and tables of masking agents for various elements, for anions and neutral molecules, and common demasking agents. A table has been added listing the common amino acids with their pI and pKa values and their 3-letter and I-letter abbreviations. Lastly a 9-page table lists the threshold limit value (TL V) for gases and vapors. As stated in earlier prefaces, every effort has been made to select the most useful and reliable information and to record it with accuracy. However, the editor’s 50 years of involvement with textbooks and handbooks bring a realization of the opportunities for gremlins to exert their inevitable mischief. It is hoped that users of this handbook will continue to offer suggestions of material that might be included in, or even excluded from, future editions and call attention to errors. These communications should be directed to the editor. The street address will change early in 1999, as will the telephone number. JOHN A. DEAN Knoxville, Tennessee

PREFACE TO THE FIRST EDITION

This book is the result of a number of years’ experience in the compiling and editing of data useful to chemists. In it an effort has been made to select material to meet the needs of chemists who cannot command the unlimited time available to the research specialist, or who lack the facilities of a large technical library which so often is not conveniently located at many manufacturing centers. If the information contained herein serves this purpose, the compiler will feel that he has accomplished a worthy task. Even the worker with the facilities of a comprehensive library may find this volume of value as a time-saver because of the many tables of numerical data which have been especially computed for this purpose. Every effort has been made to select the most reliable information and to record it with accuracy. Many years of occupation with this type of work bring a realization of the opportunities for the occurrence of errors, and while every endeavor has been made to prevent them, yet it would be remarkable if the attempts towards this end had always been successful. In this connection it is desired to express appreciation to those who in the past have called attention to errors, and it will be appreciated if this be done again with the present compilation for the publishers have given their assurance that no expense will be spared in making the necessary changes in subsequent printings. It has been aimed to produce a compilation complete within the limits set by the economy of available space. One difficulty always at hand to the compiler of such a book is that he must decide what data are to be excluded in order to keep the volume from becoming unwieldy because of its size. He can hardly be expected to have an expert’s knowledge of all branches of the science nor the intuition necessary to decide in all cases which particular value to record, especially when many differing values are given in the literature for the same constant. If the expert in a particular field will judge the usefulness of this book by the data which it supplies to him from fields other than his specialty and not by the lack of highly specialized information in which only he and his co-workers are interested (and with which he is familiar and for which he would never have occasion to consult this compilation), then an estimate of its value to him will be apparent. However, if such specialists will call attention to missing data with which they are familiar and which they believe others less specialized will also need, then works of this type can be improved in succeeding editions. Many of the gaps in this volume are caused by the lack of such information in the literature. It is hoped that to one of the most important classes of workers in chemistry, namely the teachers, the book will be of value not only as an aid in answering the most varied questions with which they are confronted by interested students, but also as an inspiration through what it suggests by the gaps and inconsistencies, challenging as they do the incentive to engage in the creative and experimental work necessary to supply the missing information. While the principal value of the book is for the professional chemist or student of chemistry, it should also be of value to many people not especially educated as chemists. Workers in the natural sciences—physicists, mineralogists, biologists, pharmacists, engineers, patent attorneys, and librarians—are often called upon to solve problems dealing with the properties of chemical products or materials of construction. For such needs this compilation supplies helpful information and will serve not only as an economical substitute for the costly accumulation of a large library of monographs on specialized subjects, but also as a means of conserving the time required to search for

xi

xii

PREFACE TO THE FIRST EDITION

information so widely scattered throughout the literature. For this reason especial care has been taken in compiling a comprehensive index and in furnishing cross references with many of the tables. It is hoped that this book will be of the same usefulness to the worker in science as is the dictionary to the worker in literature, and that its resting place will be on the desk rather than on the bookshelf. N. A. LANGE Cleveland, Ohio May 2, 1934

CONTENTS

Preface to the Sixteenth Edition Preface to the Fifteenth Edition Preface to the First Edition xi

vii ix

Section 1. Inorganic Chemistry

1.1

Section 2. Organic Chemistry

2.1

Section 3. Spectroscopy

3.1

Section 4. General Information and Conversion Tables

4.1

Index

I.1

v

SECTION 1

INORGANIC CHEMISTRY

SECTION 1

INORGANIC CHEMISTRY 1.1 NOMENCLATURE OF INORGANIC COMPOUNDS 1.1.1 Writing Formulas 1.1.2 Naming Compounds 1.1.3 Cations 1.1.4 Anions 1.1.5 Acids Table 1.1 Trivial Names for Acids 1.1.6 Salts and Functional Derivatives of Acids 1.1.7 Coordination Compounds 1.1.8 Addition Compounds 1.1.9 Synonyms and Trade Names Table 1.2 Synonyms and Mineral Names 1.2 PHYSICAL PROPERTIES OF INORGANIC COMPOUNDS 1.2.1 Density 1.2.2 Melting Point (Freezing Temperature) 1.2.3 Boiling Point 1.2.4 Refractive Index Table 1.3 Physical Constants of Inorganic Compounds Table 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds Table 1.5 Refractive Index of Minerals Table 1.6 Properties of Molten Salts Table 1.7 Triple Points of Various Materials Table 1.8 Density of Mercury and Water Table 1.9 Specific Gravity of Air at Various Temperatures Table 1.10 Boiling Points of Water Table 1.11 Boiling Points of Water Table 1.12 Refractive Index, Viscosity, Dielectric Constant, and Surface Tension of Water at Various Temperatures Table 1.13 Compressibility of Water Table 1.14 Flammability Limits of Inorganic Compounds in Air 1.3 THE ELEMENTS Table 1.15 Subdivision of Main Energy Levels Table 1.16 Chemical Symbols, Atomic Numbers, and Electron Arrangements of the Elements Table 1.17 Atomic Numbers, Periods, and Groups of the Elements (The Periodic Table) Table 1.18 Atomic Weights of the Elements Table 1.19 Physical Properties of the Elements Table 1.20 Conductivity and Resistivity of the Elements Table 1.21 Work Functions of the Elements Table 1.22 Relative Abundances of Naturally Occurring Isotopes Table 1.23 Radioactivity of the Elements (Neptunium Series) Table 1.24 Radioactivity of the Elements (Thorium Series) Table 1.25 Radioactivity of the Elements (Actinium Series) Table 1.26 Radioactivity of the Elements (Uranium Series) 1.4 IONIZATION ENERGY Table 1.27 lonization Energy of the Elements Table 1.28 lonization Energy of Molecular and Radical Species

1.3 1.4 1.5 1.8 1.8 1.9 1.10 1.11 1.11 1.13 1.13 1.13 1.16 1.16 1.16 1.16 1.17 1.18 1.64 1.86 1.88 1.90 1.91 1.92 1.93 1.94 1.95 1.95 1.96 1.96 1.96 1.97 1.121 1.122 1.124 1.128 1.132 1.132 1.135 1.136 1.137 1.137 1.138 1.138 1.141

1.1

1.2

SECTION ONE

1.5 ELECTRONEGATIVITY Table 1.29 Electronegativity Values of the Elements 1.6 ELECTRON AFFINITY Table 1.30 Electron Affinities of Elements, Molecules, and Radicals 1.7 BOND LENGTHS AND STRENGTHS 1.7.1 Atom Radius 1.7.2 Ionic Radii 1.7.3 Covalent Radii Table 1.31 Atom Radii and Effective Ionic Radii of Elements Table 1.32 Approximate Effective Ionic Radii in Aqueous Solutions at 25°C Table 1.33 Covalent Radii for Atoms Table 1.34 Octahedral Covalent Radii for CN = 6 Table 1.35 Bond Lengths between Elements Table 1.36 Bond Dissociation Energies 1.8 DIPOLE MOMENTS Table 1.37 Bond Dipole Moments Table 1.38 Group Dipole Moments 1.8.1 Dielectric Constant Table 1.39 Dipole Moments and Dielectric Constants 1.9 MOLECULAR GEOMETRY Table 1.40 Spatial Orientation of Common Hybrid Bonds Table 1.41 Crystal Lattice Types Table 1.42 Crystal Structure 1.10 NUCLIDES Table 1.43 Table of Nuclides 1.11 VAPOR PRESSURE 1.11.1 Vapor Pressure Equations Table 1.44 Vapor Pressures of Selected Elements at Different Temperatures Table 1.45 Vapor Pressures of Inorganic Compounds up to 1 Atmosphere Table 1.46 Vapor Pressures of Various Inorganic Compounds Table 1.47 Vapor Pressure of Mercury Table 1.48 Vapor Pressure of Ice in Millimeters of Mercury Table 1.49 Vapor Pressure of Liquid Ammonia, NH3 Table 1.50 Vapor Pressure of Water Table 1.51 Vapor Pressure of Deuterium Oxide 1.12 VISCOSITY AND SURFACE TENSION Table 1.52 Viscosity and Surface Tension of Inorganic Substances 1.13 THERMAL CONDUCTIVITY Table 1.53 Thermal Conductivity of the Elements Table 1.54 Thermal Conductivity of Various Solids 1.14 CRITICAL PROPERTIES 1.14.1 Critical Temperature 1.14.2 Critical Pressure 1.14.3 Critical Volume 1.14.4 Critical Compressibility Factor Table 1.55 Critical Properties 1.15 THERMODYNAMIC FUNCTIONS (CHANGE OF STATE) Table 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds Table 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds 1.16 ACTIVITY COEFFICIENTS Table 1.58 Individual Activity Coefficients of Ions in Water at 25°C Table 1.59 Constants of the Debye-Hückel Equation from 0 to 100°C Table 1.60 Individual Ionic Activity Coefficients at Higher Ionic Strengths at 25°C

1.145 1.145 1.146 1.146 1.150 1.151 1.151 1.151 1.151 1.157 1.158 1.158 1.159 1.160 1.171 1.171 1.172 1.172 1.173 1.174 1.175 1.176 1.177 1.177 1.177 1.199 1.199 1.201 1.203 1.212 1.220 1.222 1.223 1.224 1.225 1.226 1.226 1.230 1.231 1.232 1.233 1.233 1.233 1.234 1.234 1.234 1.237 1.237

1.280 1.299 1.300 1.300 1.301

INORGANIC CHEMISTRY

1.3

1.17 BUFFER SOLUTIONS 1.17.1 Standards of pH Measurement of Blood and Biological Media Table 1.61 National Bureau of Standards (U.S.) Reference pH Buffer Solutions Table 1.62 Compositions of Standard pH Buffer Solutions [National Bureau of Standards (U.S.)] Table 1.63 Composition and pH Values of Buffer Solutions 8.107 Table 1.64 Standard Reference Values pH* for the Measurement of Acidity in 50 Weight Percent Methanol-Water Table 1.65 pH Values for Buffer Solutions in Alcohol-Water Solvents at 25°C 1.17.2 Buffer Solutions Other than Standards Table 1.66 pH Values of Biological and Other Buffers for Control Purposes 1.18 SOLUBILITY AND EQUILIBRIUM CONSTANTS Table 1.67 Solubility of Gases in Water Table 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures Table 1.69 Dissociation Constants of Inorganic Acids Table 1.70 Ionic Product Constant of Water Table 1.71 Solubility Product Constants Table 1.72 Stability Constants of Complex Ions Table 1.73 Saturated Solutions 1.19 PROTON-TRANSFER REACTIONS 1.19.1 Calculation of the Approximate Value of Solutions 1.19.2 Calculation of the Concentrations of Species Present at a Given pH Table 1.74 Proton Transfer Reactions of Inorganic Materials in Water at 25°C 1.20 FORMATION CONSTANTS OF METAL COMPLEXES Table 1.75 Cumulative Formation Constants for Metal Complexes with Inorganic Ligands Table 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands 1.21 ELECTRODE POTENTIALS Table 1.77 Potentials of the Elements and Their Compounds at 25°C Table 1.78 Potentials of Selected Half-Reactions at 25°C Table 1.79 Overpotentials for Common Electrode Reactions at 25°C Table 1.80 Half-Wave Potentials of Inorganic Materials Table 1.81 Standard Electrode Potentials for Aqueous Solutions Table 1.82 Potentials of Reference Electrodes in Volts as a Function of Temperature Table 1.83 Potentials of Reference Electrodes (in Volts) at 25°C for Water-Organic Solvent Mixtures 1.22 CONDUCTANCE Table 1.84 Properties of Liquid Semi-Conductors Table 1.85 Limiting Equivalent Ionic Conductances in Aqueous Solutions Table 1.86 Standard Solutions for Calibrating Conductivity Vessels Table 1.87 Equivalent Conductivities of Electrolytes in Aqueous Solutions at 18°C Table 1.88 Conductivity of Very Pure Water at Various Temperatures and the Equivalent Conductance’s of Hydrogen and Hydroxyl Ions 1.23 THERMAL PROPERTIES Table 1.89 Eutectic Mixtures Table 1.90 Transition Temperatures

1.301 1.301 1.303 1.304 1.304 1.306 1.307 1.307 1.308 1.310 1.311 1.316 1.330 1.331 1.331 1.343 1.343 1.350 1.350 1.351 1.352 1.357 1.358 1.363 1.380 1.380 1.393 1.396 1.397 1.401 1.404 1.405 1.405 1.407 1.408 1.411 1.412 1.417 1.418 1.418 1.418

1.1 NOMENCLATURE OF INORGANIC COMPOUNDS The following synopsis of rules for naming inorganic compounds and the examples given in explanation are not intended to cover all the possible cases.

1.4

SECTION ONE

1.1.1 Writing Formulas 1.1.1.1 Mass Number, Atomic Number, Number of Atoms, and Ionic Charge. The mass number, atomic number, number of atoms, and ionic charge of an element are indicated by means of four indices placed around the symbol: mass number atomic number

ionic charge SYMBOL number of atoms

15 3− 7N2

Ionic charge should be indicated by an Arabic superscript numeral preceding the plus or minus sign: Mg2+, PO3− 4 1.1.1.2 Placement of Atoms in a Formula. The electropositive constituent (cation) is placed first in a formula. If the compound contains more than one electropositive or more than one electronegative constituent, the sequence within each class should be in alphabetical order of their symbols. The alphabetical order may be different in formulas and names; for example, NaNH4HPO4, ammonium sodium hydrogen phosphate. Acids are treated as hydrogen salts. Hydrogen is cited last among the cations. When there are several types of ligands, anionic ligands are cited before the neutral ligands. 1.1.1.3 Binary Compounds between Nonmetals. For binary compounds between nonmetals, that constituent should be placed first which appears earlier in the sequence: Rn, Xe, Kr, Ar, Ne, He, B, Si, C, Sb, As, P, N, H, Te, Se, S, At, I, Br, Cl, O, F Examples: AsCl3, SbH3, H3Te, BrF3, OF2, and N4S4. 1.1.1.4 Chain Compounds. For chain compounds containing three or more elements, the sequence should be in accordance with the order in which the atoms are actually bound in the molecule or ion. Examples: SCN– (thiocyanate), HSCN (hydrogen thiocyanate or thiocyanic acid), HNCO (hydrogen isocyanate), HONC (hydrogen fulminate), and HPH2O2 (hydrogen phosphinate). 1.1.1.5 Use of Centered Period. A centered period is used to denote water of hydration, other solvates, and addition compounds; for example, CuSO4 · 5H2O, copper(II) sulfate 5-water (or pentahydrate). 1.1.1.6 Free Radicals. In the formula of a polyatomic radical an unpaired electron(s) is (are) indicated by a dot placed as a right superscript to the parentheses (or square bracket for coordination compounds). In radical ions the dot precedes the charge. In structural formulas, the dot may be placed to indicate the location of the unpaired electron(s). Examples:

(HO)·

(O2)2·

·

(NH+3)

1.1.1.7 Enclosing Marks. Where it is necessary in an inorganic formula, enclosing marks (parentheses, braces, and brackets) are nested within square brackets as follows: [ ( ) ],

[ { ( ) } ],

[ { [ ( ) ] } ],

[{{[()]}}]

1.1.1.8 Molecular Formula. For compounds consisting of discrete molecules, a formula in accordance with the correct molecular weight of the compound should be used. Examples: S2Cl2, S8, N2O4, and H4P2O6; not SCl, S, NO2, and H2PO3. 1.1.1.9 Structural Formula and Prefixes. In the structural formula the sequence and spatial arrangement of the atoms in a molecule are indicated. Examples: NaO(O˙ C)H (sodium formate), Cl´S´ S´Cl (disulfur dichloride).

INORGANIC CHEMISTRY

1.5

Structural prefixes should be italicized and connected with the chemical formula by a hyphen: cis-, trans-, anti-, syn-, cyclo-, catena-, o- or ortho-, m- or meta-, p- or para-, sec- (secondary), tert(tertiary), v- (vicinal), meso-, as- for asymmetrical, and s- for symmetrical. The sign of optical rotation is placed in parentheses, (+) for dextrorotary, (–) for levorotary, and (±) for racemic, and placed before the formula. The wavelength (in nanometers is indicated by a right subscript; unless indicated otherwise, it refers to the sodium D-line. The italicized symbols d- (for deuterium) and t- (for tritium) are placed after the formula and connected to it by a hyphen. The number of deuterium or tritium atoms is indicated by a subscript to the symbol. Examples:

cis-[PtCl2(NH3)2] di-tert-butyl sulfate methan-ol-d

methan-d3-ol (+)589 [Co(en)3]Cl2

1.1.2 Naming Compounds 1.1.2.1 Names and Symbols for Elements. Names and symbols for the elements are given in Table 1.3. Wolfram is preferred to tungsten but the latter is used in the United States. In forming a complete name of a compound, the name of the electropositive constituent is left unmodified except when it is necessary to indicate the valency (see oxidation number and charge number, (formerly the Stock and Ewens-Bassett systems). The order of citation follows the alphabetic listing of the names of the cations followed by the alphabetical listing of the anions and ligands. The alphabetical citation is maintained regardless of the number of each ligand. Example: K[AuS(S2)] is potassium (disulfido)thioaurate (1–). 1.1.2.2 Electronegative Constituents. The name of a monatomic electronegative constituent is obtained from the element name with its ending (-en, -ese, -ic, -ine, -ium, -ogen, -on, -orus, -um, -ur, -y, or -ygen) replaced by -ide. The elements bismuth, cobalt, nickel, zinc, and the noble gases are used unchanged with the ending -ide. Homopolyatomic ligands will carry the appropriate prefix. A few Latin names are used with affixes: cupr- (copper), aur- (gold), ferr- (iron), plumb- (lead), argent(silver), and stann- (tin). For binary compounds the name of the element standing later in the sequence in Sec. 1.1.1.3 is modified to end in -ide. Elements other than those in the sequence of Sec. 1.1.1.3 are taken in the reverse order of the following sequence, and the name of the element occurring last is modified to end in -ide; e.g., calcium stannide. ELEMENT SEQUENCE He

Li

Be

B

C

N

O

F

Ne

Na

Mg

Al

Si

P

S

Cl

Ar

K

Ca

Se

Ti

V

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ca

Ge

As

Se

B

Kr

Rb

Sr

Y

Zr

Nb

Mo

Te

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

I

Xr

Cr

Ba

La

Lu

Hr

Ta

W

Re

Os

Ir

Pr

Au

Hg

Tl

Ph

Bi

Po

Ai

Rr

Fr

Ra

Ac

Lr

1.1.2.3 Stoichiometric Proportions. The stoichiometric proportions of the constituents in a formula may be denoted by Greek numerical prefixes: mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona(Latin), deca-, undeca- (Latin), dodeca-, …, icosa- (20), henicosa- (21), …, triconta- (30), tetraconta(40), …, hecta- (100), and so on, preceding without a hyphen the names of the elements to which they refer. The prefix mono can usually be omitted; occasionally hemi- (1/2) and sesqui- (3/2) are used. No elisions are made when using numerical prefixes except in the case of icosa- when the letter “i” is elided in docosa- and tricosa-. Beyond 10, prefixes may be replaced by Arabic numerals.

1.6

SECTION ONE

When it is required to indicate the number of entire groups of atoms, the multiplicative numerals bis-, tris-, tetrakis-, pentakis-, and so on, are used (i.e., -kis is added starting from tetra-). The entity to which they refer is placed in parentheses. Examples: Ca[PF6]2, calcium bis(hexafluorophosphate); and (C10H21)3PO4, tris(decyl) phosphate instead of tridecyl which is (C13H27–). Composite numeral prefixes are built up by citing units first, then tens, then hundreds, and so on. For example, 43 is written tritetraconta- (or tritetracontakis-). In indexing it may be convenient to italicize a numerical prefix at the beginning of the name and connect it to the rest of the name with a hyphen; e.g., di-nitrogen pentaoxide (indexed under the letter “n”). 1.1.2.4 Oxidation and Charge Numbers. The oxidation number (Stock system) of an element is indicated by a Roman numeral placed in parentheses immediately following the name of the element. For zero, the cipher 0 is used. When used in conjunction with symbols, the Roman numeral may be placed above and to the right. The charge number of an ion (Ewens-Bassett system) rather than the oxidation state is indicated by an Arabic numeral followed by the sign of the charge cited and is placed in parentheses immediately following the name of the ion. Examples: P2O5, diphosphorus pentaoxide or phosphorus(V) oxide; Hg2+ 2 . mercury(I) ion or dimercury (2+) ion; K2[Fe(CN)6], potassium hexacyanoferrate(II) or potassium hexacyanoferrate(4–); PbII2PbIVO4, dilead(II) lead(IV) oxide or trilead tetraoxide. Where it is not feasible to define an oxidation state for each individual member of a group, the overall oxidation level of the group is defined by a formal ionic charge to avoid the use of fractional oxidation states; for example, O2−. 1.1.2.5 Collective Names. Collective names include: Halogens (F, Cl, Br, I, At) Chalcogens (O, S, Se, Te, Po) Alkali metals (Li, Na, K, Rb, Cs, Fr) Alkaline-earth metals (Ca, Sr, Ba, Ra) Lanthanoids or lanthanides (La to Lu) Rare-earth metals (Sc, Y, and La to Lu inclusive) Actinoids or actinides (Ac to Lr, those whose 5f shell is being filled) Noble gases (He to Rn) A transition element is an element whose atom has an incomplete d subshell, or which gives rise to a cation or cations with an incomplete d subshell. 1.1.2.6 Isotopically Labeled Compounds. The hydrogen isotopes are given special names: 1H (protium), 2H or D (deuterium), and 3H or T (tritium). The superscript designation is preferred because D and T disturb the alphabetical ordering in formulas. Other isotopes are designated by mass numbers: 10B (boron-10). Isotopically labeled compounds may be described by inserting the italic symbol of the isotope in brackets into the name of the compound; for example, H36Cl is hydrogen chloride[36Cl] or hydrogen chloride-36, and 2H38Cl is hydrogen [2H] chloride[38Cl] or hydrogen-2 chloride-38. 1.1.2.7 Allotropes. Systematic names for gaseous and liquid modifications of elements are sometimes needed. Allotropic modifications of an element bear the name of the atom together with the descriptor to specify the modification. The following are a few common examples:

INORGANIC CHEMISTRY

Symbol H O2 O3 P4 S8 Sn

Trivial name

Systematic name

Atomic hydrogen (Common oxygen) Ozone White phosphorus a-Sulfur, b-Sulfur m-Sulfur (plastic sulfur)

Monohydrogen Dioxygen Trioxygen Tetraphosphorus Octasulfur Polysulfur

1.7

Trivial (customary) names are used for the amorphous modification of an element. 1.1.2.8 Heteroatomic and Other Anions. These are ´OH, hydroxide ion (not hydroxyl) ´ CN, cyanide ion ´ NH−2 hydrogen difluoride ion ´ NH2, amide ion

A few heteroatomic anions have names ending in -ide. ´ NH´ , imide ion ´NH´ NH2, hydrazide ion ´NHOH, hydroxylamide ion ´ HS−, hydrogen sulfide ion

Added to these anions are ´ triiodide ion ´ N3, axide ion ´ O3, ozonide ion

´O´O´, peroxide ion ´ S´S´, disulfide ion

1.1.2.9 Binary Compounds of Hydrogen. Binary compounds of hydrogen with the more electropositive elements are designated hydrides (NaH, sodium hydride). Volatile hydrides, except those of Periodic Group VII and of oxygen and nitrogen, are named by citing the root name of the element (penultimate consonant and Latin affixes, Sec. 1.1.2.2) followed by the suffix -ane. Exceptions are water, ammonia, hydrazine, phosphine, arsine, stibine, and bismuthine. Examples: B2H6, diborane; B10H14, decaborane (14); B10H16, decaborane (16); P2H4, diphosphane; Sn2H6, distannane; H2Se2, diselane; H2Te2, ditellane; H2S5, pentasulfane; and pbH4, plumbane. 1.1.2.10 Neutral Radicals. Certain neutral radicals have special names ending in -yl: HO CO ClO ClO2 ClO3 CrO2 NO NO2

hydroxyl carbonyl chlorosyl* chloryl* perchloryl* chromyl nitrosyl nitryl (nitroyl)

PO SO SO2 S2O5 SeO SeO2 UO2 NpO2

phosphoryl sulfinyl (thionyl) sulfonyl (sulfuryl) disulfuryl seleninyl selenoyl uranyl neptunyl†

Radicals analogous to the above containing other chalcogens in place of oxygen are named by adding the prefixes thio-, seleno-, and so on; for example, PS, thiophosphoryl; CS, thiocarbonyl. *Similarly for the other halogens. †Similarly for the other actinide elements.

1.8

SECTION ONE

1.1.3 Cations 1.1.3.1 Monatomic Cations. Monatomic cations are named as the corresponding element; for example, Fe2+, iron(II) ion; Fe3+, iron(III) ion. This principle also applies to polyatomic cations corresponding to radicals with special names ending in -yl (Sec. 1.1.2.10); for example, PO+, phosphoryl cation; NO+, nitrosyl cation; NO2+ 2 , nitryl cation; O2+ 2 oxygenyl cation. Use of the oxidation number and charge number extends the range for radicals; for example, + UO2+ 2 uranyl(VI) or uranyl(2+) cation; UO2 , uranyl(V) or uranyl(1+) cation. 1.1.3.2 Polyatomic Cations. Polyatomic cations derived by addition of more protons than required to give a neutral unit to polyatomic anions are named by adding the ending -onium to the root of the name of the anion element; for example, PH+4phosphonium ion; H2I+, iodonium ion; H3O+, oxonium ion; CH3OH+2methyl oxonium ion. Exception: The name ammonium is retained for the NH+4 ion; similarly for substituted ammonium ions; for example, NF +4, tetrafluoroammonium ion. Substituted ammonium ions derived from nitrogen bases with names ending in -amine receive names formed by changing -amine into -ammonium. When known by a name not ending in -amine, the cation name is formed by adding the ending -ium to the name of the base (eliding the final vowel); e.g., anilinium, hydrazinium, imidazolium, acetonium, dioxanium. Exceptions are the names uronium and thiouronium derived from urea and thiourea, respectively. 1.1.3.3 Multiple Ions from One Base. Where more than one ion is derived from one base, the ionic charges are indicated in their names: N2H+5 , hydrazinium(1+) ion; N2H62+, hydrazinium(2+) ion. 1.1.4 Anions See Secs. 1.1.2.2 and 1.1.2.8 for naming monatomic and certain polyatomic anions. When an organic group occurs in an inorganic compound, organic nomenclature (q.v.) is followed to name the organic part. 1.1.4.1 Protonated Anions. Ions such as HSO4− are recommended to be named hydrogensulfate with the two words written as one following the usual practice for polyatomic anions. 1.1.4.2 Other Polyatomic Anions. Names for other polyatomic anions consist of the root name of the central atom with the ending -ate and followed by the valence of the central atom expressed by its oxidation number. Atoms and groups attached to the central atom are treated as ligands in a complex. Examples: [Sb(OH) 6− ], hexahydroxoantimonate(V); [Fe(CN 6 ] 3– , hexacyanoferrate(III); [Co(NO2)6]3–, hexanitritocobaltate(III); [TiO(C2O4)2(H2O)2]2–, oxobisoxalatodiaquatitanate(IV); [PCl6]–, hexachlorophosphate(V). Exceptions to the use of the root name of the central atom are antimonate, bismuthate, carbonate, cobaltate, nickelate (or niccolate), nitrate, phosphate, tungstate (or wolframate), and zincate. 1.1.4.3 Anions of Oxygen. Oxygen is treated in the same manner as other ligands with the number of -oxo groups indicated by a suffix; for example, SO2− 3 , trioxosulfate. The ending -ite, formerly used to denote a lower state of oxidation, may be retained in trivial names in these cases (note Sec. 1.1.5.3 also): †

Similarly for the other actinoid elements.

INORGANIC CHEMISTRY

AsO33− BrO− ClO− ClO2− IO− NO2− N2O22−

arsenite hypobromite hypochlorite chlorite hypoiodite nitrite hyponitrite

NOO2− PO3− 3 SO2− 3 S2O2− 5 S2O2− 4 S2O2− 2 SeO2− 3

1.9

peroxonitrite phosphite* sulfite disulfite dithionite thiosulfite selenite

However, compounds known to be double oxides in the solid state are named as such; for example, Cr2CuO4 (actually Cr2O3 ⋅ CuO) is chromium(III) copper(II) oxide (and not copper chromite). 1.1.4.4 Isopolyanions. Isopolyanions are named by indicating with numerical prefixes the number of atoms of the characteristic element. It is not necessary to give the number of oxygen atoms when the charge of the anion or the number of cations is indicated. Examples: Ca3Mo7O24, tricalcium 24-oxoheptamolybdate, may be shortened to tricalcium hepta2− 4− molybdate; the anion, Mo7O6− 24, is heptamolybdate(6–); S2O7 , disulfate(2–); P2O7 , diphosphate(V)(4-). When the characteristic element is partially or wholly present in a lower oxidation state than corresponds to its Periodic Group number, oxidation numbers are used; for example, [O2HP ´ O´ PO3H]2–, dihydrogendiphosphate(III, V)(2–). A bridging group should be indicated by adding the Greek letter m immediately before its name and separating this from the rest of the complex by a hyphen. The atom or atoms of the characteristic element to which the bridging atom is bonded, is indicated by numbers. Examples:

[O3P ´ S´ PO2 ´O´PO3]5–, 1, 2-m-thiotriphosphate(5–) [S3P´ O ´ PS2 ´O´PS3]5–, di-m-oxo-octathiotriphosphate(5–)

1.1.5 Acids 1.1.5.1 Acids and -ide Anions. Acids giving rise to the -ide anions (Sec. 1.1.2.2) should be named as hydrogen … -ide; for example, HCl, hydrogen chloride; HN3, hydrogen azide. Names such as hydrobromic acid refer to an aqueous solution, and percentages such as 48% HBr denote the weight/volume of hydrogen bromide in the solution. 1.1.5.2 Acids and -ate Anions. Acids giving rise to anions bearing names ending in -ate are treated as in Sec. 1.1.5.1; for example, H2GeO4, hydrogen germanate; H4[Fe(CN)6], hydrogen hexacyanoferrate(II). 1.1.5.3 Trivial Names. Acids given in Table 1.1 retain their trivial names due to long-established usage. Anions may be formed from these trivial names by changing -ous acid to -ite, and -ic acid to -ate. The prefix hypo- is used to denote a lower oxidation state and the prefix per- designates a higher oxidation state. The prefixes ortho- and meta- distinguish acids of differing water content; for example, H4SiO4 is orthosilicic acid and H2SiO3 is metasilicic acid. The anions would be named silicate (4–) and silicate(2–), respectively. 1.1.5.4 Peroxo- Group. When used in conjunction with the trivial names of acids, the prefix peroxo- indicates substitution of ´O´by ´O´O´.

*Named for esters formed from the hypothetical acid P(OH)3.

1.10

SECTION ONE

TABLE 1.1 Trivial Names for Acids

1.1.5.5 Replacement of Oxygen by Other Chalcogens. Acids derived from oxoacids by replacement of oxygen by sulfur are called thioacids, and the number of replacements are given by prefixes di-, tri-, and so on. The affixes seleno- and telluro- are used analogously. Examples: HOO´ C ˙ S, thiocarbonic acid; HSS´ C ˙ S, trithiocarbonic acid. 1.1.5.6 Ligands Other than Oxygen and Sulfur. See Sec. 1.1.7, Coordination Compounds, for acids containing ligands other than oxygen and sulfur (selenium and tellurium). 1.1.5.7 Differences between Organic and Inorganic Nomenclature. Organic nomenclature is largely built upon the scheme of substitution, that is, the replacement of hydrogen atoms by other atoms or groups. Although rare in inorganic nomenclature: NH2Cl is called chloramine and NHCl2 dichloroamine. Other substitutive names are fluorosulfonic acid and chlorosulfonic acid derived from HSO3H. These and the names aminosulfonic acid (sulfamic acid), iminodisulfonic acid, and nitrilotrisulfonic acid should be replaced by the following based on the concept that these names are formed by adding hydroxyl, amide, imide, and so on, groups together with oxygen atoms to a sulfur atom: HSO3F HSO3Cl NH2SO3H

fluorosulfuric acid chlorosulfuric acid amidosulfuric acid

NH(SO3H)2 N(SO3H)3

imidobis(sulfuric) acid nitridotris(sulfuric) acid

INORGANIC CHEMISTRY

1.11

1.1.6 Salts and Functional Derivatives of Acids 1.1.6.1 Acid Halogenides. For acid halogenides the name is formed from the corresponding acid radical if this has a special name (Sec. 1.1.2.10); for example, NOCl, nitrosyl chloride. In other cases these compounds are named as halogenide oxides with the ligands listed alphabetically; for example, BiClO, bismuth chloride oxide; VCl2O, vanadium(IV) dichloride oxide. 1.1.6.2 Anhydrides. Anhydrides of inorganic acids are named as oxides; for example, N2O5, dinitrogen pentaoxide. 1.1.6.3 Esters. Esters of inorganic acids are named as the salts; for example, (CH3)2SO4, dimethyl sulfate. However, if it is desired to specify the constitution of the compound, the nomenclature for coordination compounds should be used. 1.1.6.4 Amides. Names for amides are derived from the names of the acid radicals (or from the names of acids by replacing acid by amide); for example, SO2(NH2)2, sulfonyl diamide (or sulfuric diamide); NH2SO3H, sulfamidic acid (or amidosulfuric acid). 1.1.6.5 Salts. Salts containing acid hydrogen are named by adding the word hydrogen before the name of the anion (however, see Sec. 1.1.4.1), for example, KH2PO4, potassium dihydrogen phosphate; NaHCO3, sodium hydrogen carbonate (not bicarbonate); NaHPHO3, sodium hydrogen phosphonate (only one acid hydrogen remaining). Salts containing O2− and HO− anions are named oxide and hydroxide, respectively. Anions are cited in alphabetical order which may be different in formulas and names. Examples: FeO(OH), iron(III) hydroxide oxide; VO(SO4), vanadium(IV) oxide sulfate. 1.1.6.6 Multiplicative Prefixes. The multiplicative prefixes bis, tris, etc., are used with certain anions for indicating stoichiometric proportions when di, tri, etc., have been preempted to designate condensed anions; for example, AlK(SO4)2 · 12H2O, aluminum potassium bis(sulfate) 12-water (recall that disulfate refers to the anion S2O72−). 1.1.6.7 Crystal Structure. The structure type of crystals may be added in parentheses and in italics after the name; the latter should be in accordance with the structure. When the typename is also the mineral name of the substance itself, italics are not used. Examples: MgTiO3, magnesium titanium trioxide (ilmenite type); FeTiO3, iron(II) titanium trioxide (ilmenite).

1.1.7 Coordination Compounds 1.1.7.1 Naming a Coordination Compound. To name a coordination compound, the names of the ligands are attached directly in front of the name of the central atom. The ligands are listed in alphabetical order regardless of the number of each and with the name of a ligand treated as a unit. Thus “diammine” is listed under “a” and “dimethylamine” under “d.” The oxidation number of the central atom is stated last by either the oxidation number or charge number. 1.1.7.2 Anionic Ligands. Whether inorganic or organic, the names for anionic ligands end in -o (eliding the final -e, if present, in the anion name). Enclosing marks are required for inorganic anionic ligands containing numerical prefixes, and for thio, seleno, and telluro analogs of oxo anions containing more than one atom. If the coordination entity is negatively charged, the cations paired with the complex anion (with -ate ending) are listed first. If the entity is positively charged, the anions paired with the complex cation are listed immediately afterward.

1.12

SECTION ONE

The following anions do not follow the nomenclature rules: F− Cl− Br− I− O2− H− OH− O22−

fluoro chloro bromo iodo oxo hydrido (or hydro) hydroxo peroxo

HO2− S2− S22− HS− CN− CH3O− CH3S−

hydrogen peroxo thio (only for single sulfur) disulfido mercapto cyano methoxo or methanolato methylthio or methanethiolato

I.1.7.3 Neutral and Cationic Ligands. Neutral and cationic ligands are used without change in name and are set off with enclosing marks. Water and ammonia, as neutral ligands, are called “aqua” and “ammine,” respectively. The groups NO and CO, when linked directly to a metal atom, are called nitrosyl and carbonyl, respectively. I.1.7.4 Attachment Points of Ligands. The different points of attachment of a ligand are denoted by adding italicized symbol(s) for the atom or atoms through which the attachment occurs at the end of the name of the ligand; e.g., glycine-N or glycinato-O, N. If the same element is involved in different possible coordination sites, the position in the chain or ring to which the element is attached is indicated by numerical superscripts: e.g., tartrato(3–)-O1, O2, or tartrato(4–)-O2, O3 or tartrato(2–) O1, O4 1.1.7.5 Abbreviations for Ligand Names. Except for certain hydrocarbon radicals, for ligand (L) and metal (M), and a few with H, all abbreviations are in lowercase letters and do not involve hyphens. In formulas, the ligand abbreviation is set off with parentheses. Some common abbreviations are Ac acac Hacac Hba Bzl Hbg bpy Bu Cy D2dea dien dmf H2dmg dmg Hdmg dmso Et H4edta Hedta, edta

acetyl acetylacetonato acetylacetone benzoylacetone benzyl biguanide 2, 2′-bipyridine Butyl cyclohexyl diethanolamine diethylenetriamine dimethylformamide dimethylglyoxime dimethylglyoximato(2–) dimethylglyoximato(1–) dimethylsulfoxide ethyl ethylenediaminetetraacetic acid coordinated ions derived from H4edta

Hea

ethanolamine

en Him H2ida Me H3nta nbd ox phen Ph pip Pr pn Hpz py thf tu H3tea tren trien tn ur

ethylenediamine imidazole iminodiacetic acid methyl nitrilotriacetic acid norbornadiene oxalato(2–) from parent H2ox 1, 10-phenanthroline phenyl piperidine propyl propylenediamine pyrazole pyridine tetrahydrofuran thiourea triethanolamine 2, 2′, 2″-triaminotriethylamine triethylenetetraamine trimethylenediamine urea

INORGANIC CHEMISTRY

1.13

Examples: Li[B(NH2)4], lithium tetraamidoborate(1–) or lithium tetraamidoborate(III); [Co(NH3)5Cl]Cl3, pentaamminechlorocobalt(III) chloride or pentaamminechlorocobalt(2+) chloride; K3[Fe(CN)5CO], potassium carbonylpentacyanoferrate(II) or potassium carbonylpentacyanoferrate(3–); [Mn{C6H4(O)(COO)}2(H2O)4]–, tetraaquabis[salicylato(2–)]manganate(III) ion; [Ni(C4H7N2O2)2] or [Ni(dmg)] which can be named bis-(2, 3-butanedione dioximate)nickel(II) or bis[dimethylglyoximato(2–)]nickel(II).

1.1.8 Addition Compounds The names of addition compounds are formed by connecting the names of individual compounds by a dash (—) and indicating the numbers of molecules in the name by Arabic numerals separated by the solidus (diagonal slash). All molecules are cited in order of increasing number; those having the same number are cited in alphabetic order. However, boron compounds and water are always cited last and in that order. Examples: 3CdSO4 ⋅ 8H2O, cadmium sulfate—water (3/8); Al2(SO4)3 ⋅ K2SO4 ⋅ 24H2O, aluminum sulfate—potassium sulfate—water (1/1/24); AlCl3 · 4C2H5OH, aluminum chloride—ethanol (1/4). 1.1.9 Synonyms and Mineral Names TABLE 1.2 Synonyms and Mineral Names

(Continued)

1.14

SECTION ONE

TABLE 1.2 Synonyms and Mineral Names (Continued)

INORGANIC CHEMISTRY

TABLE 1.2 Synonyms and Mineral Names (Continued)

1.15

1.16

SECTION ONE

1.2 PHYSICAL PROPERTIES OF INORGANIC COMPOUNDS Names follow the IUPAC Nomenclature. Solvates are listed under the entry for the anhydrous salt. Acids are entered under hydrogen and acid salts are entered as a subentry under hydrogen. Formula weights are based upon the International Atomic Weights and are computed to the nearest hundredth when justified. The actual significant figures are given in the atomic weights of the individual elements. Each element that has neither a stable isotope nor a characteristic natural isotopic composition is represented in this table by one of that element’s commonly known radioisotopes identified by mass number and relative atomic mass. 1.2.1 Density Density is the mass of a substance contained in a unit volume. In the SI system of units, the ratio of the density of a substance to the density of water at 15°C is known as the specific gravity (relative density). Various units of density, such as kg/m3, lb-mass/ft3, and g/cm3, are commonly used. In addition, molar densities or the density divided by the molecular weight is often specified. Density values are given at room temperature unless otherwise indicated by the superscript figure; for example, 2.48715 indicates a density of 2.487 g/cm3 for the substance at 15°C. A superscript 20 over a subscript 4 indicates a density at 20°C relative to that of water at 4°C. For gases the values are given as grams per liter (g/L). 1.2.2 Melting Point (Freezing Temperature) The melting point of a solid is the temperature at which the vapor pressure of the solid and the liquid are the same and the pressure totals one atmosphere and the solid and liquid phases are in equilibrium. For a pure substance, the melting point is equal to the freezing point. Thus, the freezing point is the temperature at which a liquid becomes a solid at normal atmospheric pressure. The triple point of a material occurs when the vapor, liquid, and solid phases are all in equilibrium. This is the point on a phase diagram where the solid-vapor, solid-liquid, and liquid-vapor equilibrium lines all meet. A phase diagram is a diagram that shows the state of a substance at different temperatures and pressures. Melting point is recorded in a certain case as 250 d and in some other cases as d 250, the distinction being made in this manner to indicate that the former is a melting point with decomposition at 250°C while in the latter decomposition only occurs at 250°C and higher temperatures. Where a value such as –6H2O, 150 is given it indicates a loss of 6 moles of water per formula weight of the compound at a temperature of 150°C. For hydrates the temperature stated represents the compound melting in its water of hydration. 1.2.3 Boiling Point The normal boiling point (boiling temperature) of a substance is the temperature at which the vapor pressure of the substance is equal to atmospheric pressure. At the boiling point, a substance changes its state from liquid to gas. A stricter definition of boiling point is the temperature at which the liquid and vapor (gas) phases of a substance can exist in equilibrium. When heat is applied to a liquid, the temperature of the liquid rises until the vapor pressure of the liquid equals the pressure of the surrounding atmosphere (gases). At this point there is no further rise in temperature, and the additional heat energy supplied is absorbed as latent heat of vaporization to transform the liquid into gas. This transformation occurs not only at the surface of the liquid (as in the case of evaporation) but also throughout the volume of the liquid, where bubbles of gas are formed. The boiling point of a liquid is lowered if the pressure of the surrounding atmosphere (gases) is decreased. On the other hand, if the pressure of the surrounding atmosphere (gases) is increased, the boiling point is raised. For this reason, it is customary when the boiling point of a substance is given to include the pressure at which it is observed, if that pressure is other than standard, i.e., 760 mm of mercury or 1 atmosphere (STP, Standard Temperature and Pressure). The boiling

INORGANIC CHEMISTRY

1.17

point of a solution is usually higher than that of the pure solvent; this boiling-point elevation is one of the colligative properties common to all solutions. Boiling point is given at atmospheric pressure (760 mm of mercury or 101 325 Pa) unless otherwise indicated; thus 8215mm indicates that the boiling point is 82°C when the pressure is 15 mm of mercury. Also, subl 550 indicates that the compound sublimes at 550°C. Occasionally decomposition products are mentioned. 1.2.4 Refractive Index The refractive index n is the ratio of the velocity of light in a particular substance to the velocity of light in vacuum. Values reported refer to the ratio of the velocity in air to that in the substance saturated with air. Usually the yellow sodium doublet lines are used; they have a weighted mean of 589.26 nm and are symbolized by D. When only a single refractive index is available, approximate values over a small temperature range may be calculated using a mean value of 0.000 45 per degree for dn/dt, and remembering that nD decreases with an increase in temperature. If a transition point lies within the temperature range, extrapolation is not reliable. The specific refraction rD is given by the Lorentz and Lorenz equation, rD =

nD2 − 1 1 ⋅ nD2 + 2 r

where r is the density at the same temperature as the refractive index, and is independent of temperature and pressure. The molar refraction is equal to the specific refraction multiplied by the molecular weight. It is a more or less additive property of the groups or elements comprising the compound. An extensive discussion will be found in Bauer, Fajans, and Lewin, in Physical Methods of Organic Chemistry, 3d ed., A. Weissberger (ed.), vol. 1, part II, chap. 28, Wiley-Interscience, New York, 1960. The empirical Eykman equation nD2 − 1 1 ⋅ = constant nD + 0.4 ρ offers a more accurate means for checking the accuracy of experimental densities and refractive indices, and for calculating one from the other, than does the Lorentz and Lorenz equation. The refractive index of moist air can be calculated from the expression (n − 1) × 10 6 =

103.49 177.4 86.26  5748  p1 + p2 + 1+ p3 T T T  T 

where p1 is the partial pressure of dry air (in mmHg), p2 is the partial pressure of carbon dioxide (in mmHg), p3 is the partial pressure of water vapor (in mmHg), and T is the temperature (in kelvins). Example: 1-Propynyl acetate has nD = 1.4187 and density = 0.9982 at 20°C; the molecular weight is 98.102. From the Lorentz and Lorenz equation, rD =

(1.4187)2 + 1 1 ⋅ = 0.2528 2 (1.4187) + 2 0.9982

The molar refraction is MrD = (98.102)(0.2528) = 24.80 From the atomic and group refractions, the molar refraction is computed as follows: 6H 5C 1 CæC 1 O(ether) 1 O(carbonyl)

6.600 12.090 2.398 1.643 2.211 MrD = 24.942

1.18 TABLE 1.3 Physical Constants of Inorganic Compounds Abbreviations Used in the Table a, acid abs, absolute abs ale, anhydrous ethanol acet, acetone alk, alkali (aq NaOH or KOH) anhyd, anhydrous aq, aqueous aq reg, aqua regia atm, atmosphere BuOH, butanol bz, benzene c, solid state

Name

ca., approximately chl, chloroform cone, concentrated cub, cubic d, decomposes dil, dilute disprop, disproportionates EtOAc, ethyl acetate eth, diethyl ether EtOH, 95% ethanol expl, explodes fcc, face-centered cubic

Formula

Formula weight

fctetr, face-centered tetragonal FP, flash point fum, fuming fus, fusion, fuses g, gas, gram glyc, glycerol h, hot hex, hexagonal HOAc, acetic acid i, insoluble ign, ignites

Density

Melting point, °C

L, liter lq, liquid MeOH, methanol min, mineral mL, milliliter org, organic oxid, oxidizing PE, petroleum ether pyr, pyridine s, soluble satd, saturated sl, slightly Boiling point, °C

soln, solution solv, solvent (s) subl, sublimes sulf, sulfides tart, tartrate THF, tetrahydrofuran v, very vac, vacuum viol, violently volat, volatilizes <, less than >, greater than Solubility in 100 parts solvent

(Continued) 1.19

1.20 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, Boiling point, °C °C

Solubility in 100 parts solvent

(Continued)

1.21

1.22 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.23

1.24 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.25

1.26 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.27

1.28 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.29

1.30 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.31

1.32 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.33

1.34 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.35

1.36 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued) 1.37

1.38 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued) 1.39

1.40 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.41

1.42 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.43

1.44 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.45

1.46 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.47

Next Page 1.48 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

Previous Page

(Continued)

1.49

1.50 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.51

1.52 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.53

1.54 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.55

1.56 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued) 1.57

1.58

TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.59

1.60 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

(Continued)

1.61

1.62 TABLE 1.3 Physical Constants of Inorganic Compounds (Continued) Name

Formula

Formula weight

Density

Melting point, °C

Boiling point, °C

Solubility in 100 parts solvent

1.63

1.64

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds Abbreviations Used in the Table Color B BE BK CL G GN O P

Compound

brown blue black colorless gray green orange purple

Formula

R SL V W Y

red silver violet white yellow

Molecular weight

Crystal Symmetry cubic hexagonal monoclinic rhombic Rhombohedral tetragonal trigonal triclinic

C H M R RH T TG TR

Color

Crystal symmetry

Refractive index nD

Actinium Bromide Chloride Fluoride Oxide

AcBr3 AcCl3 AcF3 Ac2O3

466.7 333.4 284.0 502.0

W W W W

H H H H

Aluminum Bromide Carbide Chloride Fluoride Hydroxide Iodide Nitrate Nitride Oxide Phosphate Silicate Sulfate Sulfide

AlBr3 Al4C3 ACl3 AlF3 Al(OH)3 AlI3 Al(NO3)3 ⋅ 9H2O AlN Al2O3 AlPO4 Al2SiO5 Al2(SO4)3 Al2S3

266.7 143.9 133.3 84.0 78.0 407.7 375.1 41.0 102.0 122.0 162.0 342.2 150.2

CL Y W CL W W CL W CL W W W Y

R H H TR M

Americium Oxide IV

AmO2

275.1

B

C

Ammonium Bromide Carbonate Chlorate Chloride Chromate Fluoride Iodate Iodide Nitrate Nitrite Oxalate Perchlorate Hydrogen Phosphate Dihydrogen Phosphate Sulfate Hydrogen sulfide Thiocyanate

NH4Br (NH4)2CO3 ⋅ H2O NH4ClO3 NH4Cl (NH4)2CrO4 NH4F NH4IO3 NH4I NH4NO3 NH4NO2 (NH4)2C2O4 ⋅ H2O NH4ClO4 (NH4)2HPO4 NH4H2PO4 (NH4)2SO4 NH4HS NH4SCN

98.0 114.1 101.5 53.5 152.1 37.0 192.9 144.9 80.0 64.0 142.1 117.5 132.1 115.0 132.1 51.1 76.1

W W W W Y W W W W Y CL W W W W W CL

C C M C M H R C R

1.711

R R M T R R M

1.44–1.59 1.49 1.53 1.48–1.53 1.53 1.74 1.61–1

R H H R R R H

2.70 1.56 1.38

1.54 1.68 1.56 1.66 1.47

1.642 1.315 1.703 1.413

INORGANIC CHEMISTRY

1.65

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Antimony Bromide III Chloride III Chloride V Fluoride III Fluoride V Hydride III Iodide III Iodide V Oxide III Oxide V Oxychloride III Sulfate III Sulfide III Sulfide V

SbBr3 SbCl3 SbCl5 SbF3 SbF5 SbH3 SbI3 SbI5 Sb2O3 Sb2O5 SbOCl Sb2(SO4)3 Sb2S3 Sb2S5

361.5 228.1 299.0 178.8 216.7 124.8 502.5 756.3 291.5 323.5 173.2 531.7 339.7 403.8

CL CL W CL CL CL RD B CL Y W W BK Y

Arsenic Acid, ortho Bromide III Chloride III Chloride V Fluoride III Fluoride V Hydride III Iodide III Iodide V Oxide III Oxide V Sulfide II Sulfide III Sulfide V

H3AsO4 ⋅ 1/2H2O AsBr3 AsCl3 AsCl5 AsF3 AsF5 AsH3 AsI3 AsI5 As2O3 As2O5 As2S2 As2S3 As2S5

151.0 314.7 181.3 252.2 131.9 169.9 77.9 455.6 709.5 197.2 229.9 214.0 246.0 310.2

CL CL CL CL CL CL CL R B CL W R Y Y

Barium Bromate Bromide Carbide Carbonate Chlorate Chloride Chromate Fluoride Hydride Hydroxide Iodide Nitrate Oxalate Oxide Perchlorate Sulfate Sulfide Titanate

Ba(BrO3)2 ⋅ H2O BaBr2 BaC2 BaCO3 Ba(ClO3)2 ⋅ H2O BaCl2 BaCrO4 BaF2 BaH2 Ba(OH)2 ⋅ 8H2O BaI2 Ba(NO3)2 BaC2O4 BaO Ba(ClO4)2 BaSO4 BaS BaTiO3

411.2 297.2 161.4 197.4 322.3 208.3 253.3 175.3 139.4 315.5 391.2 261.4 225.4 153.3 336.2 233.4 169.4 233.3

CL CL G W CL CL Y CL G CL CL CL W CL CL W CL

Crystal symmetry

Refractive Index nD

R R LIQ R LIQ GAS H

1.74 1.74 1.6011

R C M

2.35

R

4.064

R LIQ

1.598

LIQ GAS GAS H M C M M M

M R T R M M R C M M C C H R C T/H

2.46–2.52 2.4–2.6

1.75 1.676 1.56–1 1.736 1.474 1.502 1.572 1.98 1.636 2.155 2.40 (Continued)

1.66

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Beryllium Bromide Carbide Chloride Fluoride Hydroxide Iodide Nitrate Nitride Oxide Sulfate Sulfate

BeBr2 Be2C BeCl2 BeF2 Be(OH)2 BeI2 Be(NO3)2 ⋅ 3H2O Be3N2 BeO BeSO4 BeSO4 ⋅ 4H2O

168.8 30.0 79.9 47.0 43.0 262.8 187.1 55.1 25.0 105.1 177.1

W Y W CL W CL W CL W CL CL

Bismuth Bromide III Chloride III Fluoride III Hydroxide III Iodide III Nitrate III Nitrate, Basic III Oxide III Oxide IV Oxide V Oxychloride III Phosphate III Sulfate III Sulfide III

BiBr3 BiCl3 BiF3 Bi(OH)3 BiI3 Bi(NO3)3 ⋅ 5H2O BiO(NO3) ⋅ H2O Bi2O3 Bi2O4 ⋅ 2H2O Bi2O5 BiOCl BiPO4 Bi2(SO4)3 Bi2S3

448.7 315.4 266.0 260.0 589.7 485.1 305.0 466.0 518.0 498.0 260.5 304.0 706.1 514.2

Y W G W RD CL W Y B B W W W B

Boron Arsenate Boric Acid Bromide Carbide Chloride Diborane Fluoride Iodide Nitride Oxide Sulfide

BAsO4 H3BO3 BBr3 B4C BCl3 B2H6 BF3 BI3 BN B2O3 B2S3

149.7 61.8 250.5 55.3 117.2 27.7 67.8 391.6 24.8 69.6 117.8

Bromine Chloride I Fluoride I Fluoride III Fluoride V Hydride I

BrCl BrF BrF3 BrF5 H Br

Cadmium Bromide Carbonate Chloride

CdBr2 CdCO3 CdCl2

Crystal symmetry

Refractive index nD

OR H OR T R RH C H T T

1.44–1.47

C

1.74

H TR H R

1.91

1.72

T M

2.15

R

1.34–1.46

W W CL BK CL CL CL W W W W

T TR LIQ RH LIQ GAS GAS

1.68

115.4 98.9 136.9 174.9 80.9

R B CL CL CL

GAS GAS LIQ LIQ GAS

272.2 172.4 228.4

W W W

H TG H

1.531216

H C

1.453625 1.352925 1.32510

INORGANIC CHEMISTRY

1.67

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Cadmium (Continued) Fluoride Hydroxide Iodide Nitrate Oxide Sulfate Sulfate Sulfide

CdF2 Cd(OH)2 CdI2 Cd(NO3)2 ⋅ 4H2O CdO CdSO4 3CdSO4 ⋅ 8H2O CdS

150.4 146.4 366.2 308.5 128.4 208.5 769.6 144.5

W W B W B W CL Y

Calcium Bromate Bromide Carbide Carbonate Chloride Chloride Chromate Fluoride Hydride Hydroxide Iodide Nitrate Nitrate Nitride Oxalate Oxide Perchlorate Peroxide Sulfate Sulfate Sulfide

CaBrO3 ⋅ H2O CaBr2 ⋅ 6H2O CaC2 CaCO3 CaCl2 CaCl2 ⋅ 6H2O CaCrO4 ⋅ 2H2O CaF2 CaH2 Ca(OH)2 CaI2 Ca(NO3)2 Ca(NO3)2 ⋅ 4H2O Ca3N2 CaC2O4 CaO Ca(ClO4)2 CaO2 CaSO4 CaSO4 ⋅ 2H2O CaS

313.9 308.0 64.1 100.1 111.0 219.1 192.1 78.1 42.1 74.1 293.9 164.1 236.2 148.3 128.1 56.1 239.0 72.1 136.1 172.2 72.1

CL CL CL CL C Y CL W CL W CL CL B CL CL CL W CL CL CL

Carbon Dioxide Disulfide Monoxide Oxybromide Oxychloride Oxysulfide

CO2 CS2 CO COBr2 COCl2 (Phosgene) COS

44.0 76.1 28.0 187.8 98.9 60.1

CL CL CL CL CL CL

Cerium Bromide III Chloride III Fluoride III Iodate IV Iodide III Molybdate III Nitrate III Oxide III Oxide IV Sulfate III Sulfide

CeBr3 CeCl3 CeF3 Ce(IO3)4 CeI3 Ce2(MoO4)3 Ce(NO3)3 ⋅ 6H2O Ce2O3 CeO2 Ce2(SO4)3 Ce2S3

380.0 246.5 197.1 839.7 520.8 760.0 434.2 328.2 172.1 568.4 376.4

CL W Y Y Y CL GN W CL Y

Crystal wymmetry C TR H C R M H

M H T R C T M C R H H C M H C C T M M C

GAS LIQ GAS LIQ GAS GAS

Refractive index nD 1.56

1.565 2.51

1.75 1.681 1.52 1.417 1.434 1.574

1.498

1.838

1.576 1.5226 2.137

1.6290

H H H R T

2.01

H C M/R C (Continued)

1.68

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Cesium Bromide Carbonate Chloride Fluoride Hydroxide Iodide Iodide III Nitrate Oxide Perchlorate Periodate Peroxide Sulfate Superoxide Trioxide

CsBr Cs2CO3 CsCl CsF CsOH CsI CsI3 CsNO3 Cs2O CsClO4 CsIO4 Cs2O2 Cs2SO4 CsO2 Cs2O3

212.8 325.8 168.4 151.9 149.9 259.8 513.7 194.9 281.8 232.4 323.8 297.8 361.9 164.9 313.8

CL CL CL CL W

Chlorine Dioxide Fluoride Trifluoride Monoxide Hydrochloric Acid Perchloric Acid

ClO2 ClF ClF3 Cl2O HCl HClO4

67.5 54.5 92.5 86.9 36.5 100.5

Y CL CL B CL CL

GAS GAS GAs GAS GAS LIQ

Chromium Bromide II Carbide III Chloride II Chloride III Fluoride II Fluoride III Iodide II Nitrate III Nitrate III Oxide II Oxide III Oxide IV Oxide VI Phosphate III Sulfate III Sulfide II Sulfide III

CrBr2 Cr3C2 CrCl2 CrCl3 CrF2 CrF3 CrI2 Cr(NO3)3 CrN CrO Cr2O3 CrO2 CrO3 CrPO4 ⋅ 6H2O Cr2(SO4) ⋅ 18H2O CrS Cr2S3

211.8 180.0 122.9 158.4 90.0 109.0 305.8 238.0 66.0 68.0 152.0 84.0 100.0 255.1 716.5 84.1 200.2

W G W V GN GN B GN

M R R R M R M

BK GN B RD V V BK B

Cobalt Bromide II Chlorate II Chloride II Fluoride II Fluoride III Hydroxide II Iodate II

CoBr2 Co(ClO3)2 ⋅ 6H2O CoCl2 CoF2 CoF3 Co(OH)2 Co(IO3)2

218.8 333.9 129.8 96.9 115.9 92.9 408.7

GN R BE R B R V

BK W R CL W Y CL Y B

Refractive index nD

C

1.642

C C

1.534 1.481

C R H

1.661; 1.669

R R R R

1.55 1.479

1.564

C

C H H R TR C M TG

H C H M H R

1.25410

2.551

1.564

1.55

INORGANIC CHEMISTRY

1.69

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Cobalt (Continued) Iodide II Nitrate II Oxide II Oxide III Oxide II–III Perchlorate II Sulfate II Sulfate II Sulfide II Sulfide III

CoI2 Co(NO3)2 ⋅ 6H2O CoO Co2O3 Co3O4 Co(ClO4)2 CoSO4 CoSO4 ⋅ 7H2O CoS Co2S3

312.7 291.0 74.9 165.9 240.8 257.8 155.0 281.1 91.0 214.1

BK R GN B BK R BE R R BK

Copper Bromide I Bromide II Carbonate, Basic II Chloride I Chloride II Chloride II Fluoride II Hydroxide I Hydroxide II Iodide I Nitrate II Oxide I Oxide II Sulfate II Sulfate II Sulfide I Sulfide II Thiocyanate I

CuBr CuBr2 2CuCO3 ⋅ Cu(OH)2 CuCl CuCl2 CuCl2 ⋅ 2H2O CuF2 ⋅ 2H2O CuOH Cu(OH)2 CuI Cu(NO3)2 ⋅ 3H2O Cu2O CuO CuSO4 CuSO4 ⋅ 5H2O Cu2S CuS CuSCN

143.5 223.4 344.7 99.0 134.5 170.5 137.6 80.6 97.6 190.5 241.6 143.1 79.5 159.6 249.7 159.1 95.6 121.6

W BK BE W Y Y W Y BE W BE R BK W BE BK BK W

Curium Bromide III Chloride III Fluoride III Fluoride IV Iodide III

CmBr3 CmCl3 CmF3 CmF4 CmI3

488 353 304 323 628

W W B W

R H H M H

Dysprosium Bromide Chloride Fluoride Iodide Nitrate Oxide Sulfate

DyBr3 DyCl3 DyF3 DyI3 Dy(NO3)3 ⋅ 5H2O Dy2O3 Dy2(SO4)3 ⋅ 8H2O

402.3 268.9 219.5 543.2 438.6 373.0 757.3

CL Y CL GN Y W Y

R M H H TR C M

Erbium Bromide Chloride Fluoride

ErBr3 ErCl3 ErF3

407.1 273.6 224.3

V V RD

R M R

Refractive index nD

H M C R C 1.50 C M H

C M M C M R M

1.48

1.731

C

2.346

C TR R TR C H

2.705 2.63 1.52

(Continued)

1.70

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color V R W R

Erbium (Continued) Iodide Oxide Sulfate Sulfide

ErI3 Er2O3 Er2(SO4)3 Er2S3

548.0 382.6 622.7 263.5

Europium Bromide II Bromide III Chloride II Chloride III Fluoride II Fluoride III Iodide II Iodide III Oxide III Sulfate III

EuBr2 EuBr3 EuCl2 EuCl3 EuF2 EuF3 EuI2 EuI3 Eu2O3 Eu2(SO4)3 ⋅ 8H2O

311.8 391.7 222.9 258.3 190.0 209.0 405.8 532.7 351.9 736.2

Fluorine Dioxide Hydride Oxide

F2O2 HF F2O

Cadolinium Bromide Chloride Fluoride Iodide Nitrate Oxide Sulfate Sulfide

Crystal symmetry

Refractive index nD

H C M

G W Y Y W GN

R R R H C R M

R R

C M

70.0 20.0 54.0

B CL CL

GAS GAS GAS

GdBr3 GdCl3 GdF3 GdI3 Gd(NO3)3 ⋅ 6H2O Gd2O3 Gd2(SO4)3 Gd2S3

397.0 263.6 214.3 538.0 451.4 362.5 602.7 410.7

W W W Y W CL Y

H H R H T C

Gallium Arsenide III Bromide III Chloride II Chloride III Fluoride III Iodide III Oxide I Oxide III Sulfide I Sulfide II

GaAs GaBr3 Ga2Cl4 GaCl3 GaF3 GaI3 Ga2O Ga2O3 Ga2S Ga2S3

144.6 309.5 281.3 176.0 126.7 450.4 155.4 187.4 171.5 235.6

G CL W CL W Y G G G Y

Germanium Bromide IV Chloride IV Fluoride IV Hydride IV Iodide IV Oxide II

GeBr4 GeCl4 GeF4 GeH4 (Germane) GeI4 GeO

392.2 214.4 148.6 76.6 580.2 88.6

G CL CL CL R G

C

C

TR RH

M (b)

1.95

H

LIQ GAS GAS C

1.627 1.464 1.00089 1.607

INORGANIC CHEMISTRY

1.71

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Germanium (Continued) Oxide IV Sulfide II Sulfide IV

GeO2 GeS GeS2

104.6 104.7 136.7

CL Y W

Gold Bromide I Bromide III Chloride I Chloride III Hydroxide III Iodide Iodide III Sulfate III Sulfide I Sulfide III

AuBr AuBr3 AuCl AuCl3 Au(OH)3 AuI AuI3 Au2(SO4)3 · H2O Au2S Au2S3

276.9 436.7 232.4 303.3 248.0 323.9 577.7 490.5 426.0 490.1

G B Y R B Y G B B B

Hafnium Bromide Carbide Chloride Fluoride Iodide Nitride Oxide Sulfide

HfBr4 HfC HfCl4 HfF4 HfI4 HfN HfO2 HfS2

498.1 190.5 320.3 254.5 686.1 192.5 210.5 242.6

W

Y W

C T H

Holmium Bromide Chloride Fluoride Iodide Oxide

HoBr3 HoCl3 HoF3 HoI3 Ho2O3

404.7 271.3 221.9 545.6 377.9

Y Y B Y

R M H

Hydrogen Bromide Chloride Fluoride Iodide Oxide Oxide-Deutero Peroxide Selenide Sulfide Telluride

HBr HCl HF HI H2O 2H2O H2O2 H2Se H2S H2Te

80.9 36.5 20.0 127.9 18.0 20.0 34.0 81.0 34.1 129.9

CL CL CL CL CL CL CL CL CL CL

GAS GAS GAS GAS LIQ LIQ LIQ GAS GAS GAS

Indium Bromide I Bromide III Chloride I Chloride III Fluoride III

InBr InBr3 InCl InCl3 InF3

194.7 354.5 150.3 221.2 171.8

B CL R CL CL

C M H

Refractive index nD

H R R

R

TR

C W CL

M

1.56

C 2.77–67

1.466 1.3333 1.3284 1.41422 1.374

(Continued)

1.72

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Indium (Continued) Iodide I Iodide III Oxide III Sulfate III Sulfide III

InI InI3 In2O3 In2(SO4)3 In2S3

241.7 495.5 277.6 517.8 325.8

B Y Y W R (b)

Iodine Bromide I Chloride I, a Chloride I, b Chloride III Fluoride V Fluoride VII Oxide IV Oxide V Iodic Acid Hydrogen Iodide

IBr ICl ICl ICl3 IF5 IF7 I2O4 I2O5 HIO3 HI

206.8 162.4 162.4 233.3 221.9 259.9 317.8 333.8 175.9 127.9

BK R R Y CL CL Y CL W CL

Iridium Bromide II Bromide IV Chloride III Chloride IV Fluoride VI Iodide III Iodide IV Oxide IV Sulfide IV

IrBr3 · 4H2O IrBr4 IrCl3 IrCl4 IrF6 IrI3 IrI4 IrO2 IrS2

504.0 511.8 298.6 334.0 306.2 572.9 699.8 224.2 256.3

GN BK GN R Y GN BK BK BK

Iron Arsenide Arsenide, di– Bromide II Bromide III Carbide Carbonate II Chloride II Chloride III Fluoride III Hydroxide II Hydroxide III Iodide II Nitrate II Nitrate III Nitride Oxide II Oxide III Oxide II-III Phosphate III Phosphide Sulfate II

FeAs FeAs2 FeBr2 FeBr3 · 6H2O Fe3C FeCO3 FeCl2 FeCl3 FeF3 Fe(OH)2 Fe(OH)3 FeI2 Fe(NO3)2 · 6H2O Fe(NO3)3 · 9H2O Fe2N FeO Fe2O3 Fe3O4 FePO4 · 2H2O Fe2P FeSO4 · 7H2O

130.8 205.7 215.7 403.7 179.6 115.9 126.8 162.2 112.9 89.9 106.9 309.7 288.0 404.0 125.7 71.9 159.7 231.6 186.9 142.7 278.0

W G GN R G G G GN W GN B BK GN CL G BK B BK W G GN

Crystal symmetry

Refractive index nD

M C M C

OR C LIQ R LIQ GAS

R GAS

1.466

H C T

R R H C H H R H H R M C TG C M H M

2.32 3.04 2.42 1.35 1.48

INORGANIC CHEMISTRY

1.73

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color Y GN BK BK Y

Iron (Continued) Sulfate III Sulfate II, Ammonium Sulfide II Sulfide III Sulfide, di

Fe2(SO4)3 (NH4)2 Fe(SO4) · 6H2O FeS Fe2S3 FeS2

399.9 392.2 87.9 207.9 120.0

Lanthanum Bromate Bromide Chloride Fluoride Iodide Molybdate Oxide Sulfate Sulfide

La(BrO3)3 · 9H2O LaBr3 LaCl3 LaF3 LaI3 La2(MoO4)3 La2O3 La2(SO4)3 La2S3

684.8 378.6 245.3 195.9 519.6 757.6 325.8 566.0 374.0

Lead Acetate II Acetate IV Arsenate II Bromide II Carbonate II Chloride II Chloride IV Chromate II Fluoride II Hydroxide II Iodate II Iodide II Molybdate II Nitrate II Oxide II Oxide IV Oxide II–IV Phosphate, III Sulfate II Sulfide II Tungstate II

Pb(C2H3O2)2 Pb(C2H3O2)4 Pb3(AsO4)2 PbBr2 PbCO3 PbCl2 PbCl4 PbCrO4 PbF2 Pb(OH)2 Pb(IO3)2 PbI2 PbMoO4 Pb(NO3)2 PbO PbO2 Pb3O4 Pb3(PO4)2 PbSO4 PbS PbWO4

325.3 443.4 899.4 367.0 267.2 278.1 349.0 323.2 245.2 241.2 557.0 461.0 367.2 331.2 223.2 239.2 685.6 811.6 303.3 239.3 455.1

W CL W W CL W Y Y CL W W Y CL CL R B R W W BK CL

Lithium Aluminum Hydride Bromide Carbonate Chloride Fluoride Hydride Hydroxide Iodide Nitrate Oxide

LiAlH4 LiBr Li2CO3 LiCl LiF LiH LiOH LiI LiNO3 Li2O

37.9 86.9 73.9 42.4 25.9 8.0 24.0 133.9 68.9 29.9

W W W W W CL W W W W

W W W G W W Y

Crystal symmetry R M H H C

Refractive index nD 1.81 1.49

H H H H R T R H

M R R R LIQ M R H H T C T T T H R C M

C M C C C T C TG C

1.80–2.08 2.22 2.33

2.30 1.782

1.95 1.85 3.911

1.784 1.43; 1.5 1.662 1.391 1.46 1.955 1.435;1.439 1.644 (Continued)

1.74

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

W CL CL W

Crystal symmetry

Lithium (Continued) Peroxide Perchlorate Phosphate Sulfate, Sulfide

Li2O2 LiClO4 Li3PO4 Li2SO4 Li2S

45.9 160.4 115.8 109.9 45.9

Lutetium Bromide Chloride Fluoride Iodide Oxide

LuBr3 LuCl3 LuF3 LuI3 Lu2O3

414.7 281.3 232.0 555.7 397.9

W W W B

TG M R H C

Magnesium Aluminate Bromide Carbonate Chloride Fluoride Hydroxide Iodide Nitrate Oxide Silicide Silicate, m Silicate, o Sulfate Sulfide

MgO · Al2O3 MgBr2 MgCO3 MgCl2 MgF2 Mg(OH)2 MgI2 Mg(NO3)2 · 6H2O MgO Mg2Si MgSiO3 Mg2SiO4 MgSO4 MgS

142.3 184.1 84.3 95.2 62.3 58.3 278.2 256.4 40.3 76.7 100.4 140.7 120.4 56.4

CL W W W CL CL W CL CL BE W W CL R

C H TG H T H H M C C M R R C

Manganese Bromide II Carbonate II Chloride II Fluoride II Iodide II Oxide II Oxide III Oxide IV Oxide II–IV Potassium Permanganate Silicide Sulfate II Sulfide II

MnBr2 MnCO3 MnCl2 MnF2 MnI2 MnO Mn2O3 MnO2 Mn3O4 KMnO4 MnSi MnSO4 MnS

214.8 114.9 125.9 92.9 308.8 70.9 157.9 86.9 228.8 158.0 83.0 151.0 87.0

W W W R W GN BK BK BK P

H R H T H C C R R R C

R GN

C

Mercury Bromide I Bromide II Chloride I Chloride II Cyanide II Fluoride I

Hg2Br2 HgBr2 Hg2Cl2 HgCl2 Hg(CN)2 Hg2F2

561.1 360.4 472.1 271.5 252.7 439.2

W CL W CL CL Y

T R T R T C

H H R M C

Refractive index nD

1.465

1.723 1.51; 1.70 1.59; 1.67 1.38 1.57

1.736 1.66 1.65 2.271

1.817

2.16

1.59

1.97; 2.66 1.72; 1.97 1.645

INORGANIC CHEMISTRY

1.75

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Mercury (Continued) Fluoride II Iodide I Iodide II Nitrate I Nitrate II Oxide I Oxide II Sulfate I Sulfate II Sulfide III

HgF2 Hg2I2 HgI2 Hg2(NO3)2 · 2H2O Hg(NO3)2 · 1/2H2O Hg2O HgO Hg2SO4 HgSO4 HgS

238.6 655.0 454.4 561.2 333.6 417.2 216.6 497.3 296.7 232.7

CL Y R/Y CL W BK Y/R CL CL R

C T T/R M

Molybdenum Carbide II Carbide IV Chloride II Chloride III Chloride V Fluoride VI Iodide II Molybdic Acid Oxide IV Oxide VI Silicide IV Sulfide IV

Mo2C MoC MoCl2 MoCl3 MoCl5 MoF6 MoI2 H2MoO4 · 4H2O MoO2 MoO3 MoSi2 MoS2

203.9 108.0 166.9 202.3 273.2 202.9 349.8 180.0 127.9 143.9 152.1 160.1

W G Y R BK Cl B Y G CL G BK

H H

Neodymium Bromide Chloride Fluoride Iodide Oxide Sulfide

NdBr3 NdCl3 NdF3 NdI3 Nd2O3 Nd2S3

384.0 250.6 201.2 524.9 336.5 384.7

V V V G BE GN

R H H R H

Neptunium Bromide II Chloride III Chloride IV Fluoride III Fluoride VI Iodide III Oxide IV

NpBr3 NpCl3 NpCl4 NpF3 NpF6 NpI3 NpO2

476.7 343.4 378.8 294.0 351.0 617.7 269.0

GN GN BN P O B GN

R H T H R R C

Nickel Arsenide Bromide II Carbonyl Chloride II Fluoride II Hydroxide II Iodide II Nitrate II Oxide II

NiAs NiBr2 Ni(CO)4 NiCl2 NiF2 Ni(OH)2 NiI2 Ni(NO3)2 · 6H2O NiO

133.6 218.5 170.7 129.6 96.7 92.7 312.5 290.8 74.7

W Y CL Y Y GN BK GN G

H

R M R H

Refractive index nD

2.45; 2.7

2.37; 2.6

2.85; 3.2

M

M T R T H

LIQ H T H M C

4.7

1.45810

2.37 (Continued)

1.76

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Nickel (Continued) Phosphide Sulfate II Sulfide II

Ni2P NiSO4 NiS

148.4 154.8 90.8

G Y BK

C TR

Niobium Bromide Carbide Chloride Fluoride Iodide Oxide

NbBr5 NbC NbCl5 NbF5 NbI5 Nb2O5

492.5 104.9 270.2 187.9 727.4 265.8

R BK W CL BRASS W

R C M M M R

Nitrogen Ammonia Hydrazine Hydrazoic Acid Hydroxylamine Nitric Acid Chloride Fluoride Iodide Oxide I (nitrous-) Oxide II (nitric-) Oxide III (tri-) Oxide IV (per-) Oxide V (penta-) Sulfide II Nitrosyl Chloride Nitrosyl Fluoride Nitryl Chloride

NH3 N2H4 NH3 NH2OH HNO3 NCl3 NF3 NI3 N2O NO N2O3 NO2 N2O5 N4S4 NOCl NOF NO2Cl

17.0 32.0 43.0 33.0 63.0 120.4 71.0 394.7 44.0 30.0 76.0 46.0 108.0 184.3 65.5 49.0 81.5

CL CL CL W CL Y CL BK CL CL B B W O O CL CL

GAS LIQ LIQ R LIQ LIQ GAS

Osmium Chloride IV Fluoride V Fluoride VI Fluoride VIII Iodide IV Oxide IV Oxide VIII Sulfide IV

OsCl4 OsF5 OsF6 OsF8 OsI4 OsO2 OsO4 OsS2

332.0 285.2 304.2 342.2 697.8 222.2 254.1 254.3

R G GN Y BK BK CL BK

T M C

Oxygen Fluoride Ozone

OF2 O3

54.0 48.0

B CL

GAS GAS

Palladium Bromide II Chloride II Fluoride II Iodide II Oxide II Sulfide II

PdBr2 PdCl2 PdF2 PdI2 PdO PdS

266.6 177.3 144.4 360.2 122.4 138.5

B R B BK G BK

GAS GAS GAS GAS R M GAS GAS GAS

M C

C T T T

Refractive index nD

1.325 1.4707 1.44023.5 1.39716

1.19316

2.046

INORGANIC CHEMISTRY

1.77

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Phosphorus Hypophosphorous Acid Phosphoric Acid Phosphorous Acid Bromide III Bromide V Chloride III Chloride V Fluoride III Fluoride V Hydride (Phosphine) Iodide III Oxide III Oxide IV Oxide V Oxybromide V Oxychloride Oxyfluoride Sulfide Sulfide V Thiobromide V Thiochloride V

H3PO2 H3PO4 H3PO3 PBr3 PBr5 PCl3 PCl5 PF3 PF5 PH3 PI3 P4O6 PO2 P2O5 POBr3 POCl3 POF3 P4S7 P2S5 PSBr3 PSCl3

66.0 98.0 82.0 270.7 430.5 137.3 208.3 88.0 126.0 34.0 411.7 219.9 63.0 142.0 286.7 153.4 104.0 348.4 222.3 302.8 169.4

CL CL CL CL Y CL W CL CL CL R W CL W CL CL CL Y Y Y CL

Platinum Bromide II Bromide IV Chloride II Chloride IV Fluoride IV Fluoride VI Hydroxide II Hydroxide IV Iodide II Oxide II Oxide IV Sulfate IV Sulfide II Sulfide III Sulfide IV

PtBr2 PtBr4 PtCl2 PtCl4 PtF4 PtF6 Pt(OH)2 Pt(OH)4 PtI2 PtO PtO2 Pt(SO4)2 · 4H2O PtS Pt2S3 PtS2

354.9 514.8 260.0 336.9 271.2 309.1 229.1 263.1 448.9 211.1 227.1 459.4 227.2 486.6 259.2

B B GN B R R BK B BK G BK Y BK G G

C

Plutonium Bromide III Carbide IV Chloride III Fluoride III Fluoride IV Fluoride VI Iodide III Nitride III Oxide IV

PuBr3 PuC PuCl3 PuF3 PuF4 PuF6 PuI3 PuN PuO2

481.7 256.0 346.4 299.0 318.0 356.0 622.7 256.0 274.0

GN SL GN P B B GN BK GN

R C H H M R R C C

Refractive index nD

R LIQ R LIQ T GAS GAS GAS H M R H

1.694519

LIQ GAS

C LIQ

1.63525

H

T

T

2.4 (Continued)

1.78

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Polonium (Continued) Bromide IV Chloride II Chloride IV Oxide IV

PoBr4 PoCl2 PoCl4 PoO2

529.7 281.0 351.9 242.0

R R Y R/Y

C R M T/C

Potassium Bromate Bromide Carbonate Chlorate Chloride Cyanide Dichromate Ferrocyanide Fluoride Hydroxide Iodate Iodide Nitrate Oxide Perchlorate Periodate Permanganate Peroxide Phosphate, o Sulfate Sulfide Superoxide Thiocyanate

KBrO3 KBr K2CO3 KClO3 KCl KCN K2Cr2O7 K4[Fe(CN)6] · 3H2O KF KOH KIO3 KI KNO3 K2O KClO4 KIO4 KMnO4 K2O2 K3PO4 K2SO4 K2S KO2 KSCN

167.0 119.0 138.2 122.6 74.6 65.1 294.2 422.4 58.1 56.1 214.0 166.0 101.1 94.2 138.6 230.0 158.0 110.2 212.3 174.3 110.3 71.1 97.2

CL CL CL CL CL CL O Y CL W CL W CL CL CL CL P Y CL CL B Y CL

TR C M M C C M/TR M/T C C/R M C R/TR C R T R R TR R/H C T R

Praseodymium Bromide Chloride Fluoride Iodide Oxide Sulfate Sulfide

PrBr3 PrCl3 PrF3 PrI3 Pr2O3 Pr2(SO4)3 · 8H2O Pr2S3

380.6 247.3 197.9 521.6 329.8 714.1 378.0

GN GN GN G Y GN B

H H H R H M

Protactinium Bromide IV Chloride IV Fluoride IV Iodide III Oxide IV

PaBr4 PaCl4 PaF4 PaI3 PaO2

470.9 372.9 307.1 611.8 263.1

R GN B BK BK

T T M R C

Radium Bromide Chloride Sulfate

RaBr2 RaCl2 RaSO4

385.8 296.1 322.1

Y Y CL

M M R

Refractive index nD

1.559 1.426; 1.431 1.409; 1.423 1.490 1.410 1.738 TR 1.577 1.35

1.677 1.335; 1.? 1.47 1.63 1.59

1.495

1.55

INORGANIC CHEMISTRY

1.79

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Rhenium Bromide III Chloride III Chloride V Fluoride IV Flouride VI Flouride VII Oxide IV Oxide VI Oxide VII Oxybromide VII Oxychloride VII Sulfide IV Sulfide VII

ReBr3 ReCl3 ReCl5 ReF4 ReF6 ReF7 ReO2 ReO3 Re2O7 ReO3Br ReO3Cl ReS2 Re2S7

425.9 292.6 363.5 262.5 300.2 319.2 218.2 234.2 484.4 314.1 269.7 250.4 596.9

B R B GN Y O BK R Y W CL BK BK

Rhodium Chloride III Fluoride III Hydroxide III Oxide III Oxide IV Sulfide III

RhCl3 RhF3 Rh(OH)3 Rh2O3 RhO2 Rh2S3

209.3 159.9 155.9 253.8 134.9 302.0

R R Y G B BK

Rubidium Bromate Bromide Carbonate Chloride Fluoride Hydroxide Iodide Nitrate Oxide Perchlorate Peroxide Sulfate Sulfide Superoxide

RbBrO3 RbBr Rb2CO3 RbCl RbF RbOH RbI RbNO3 Rb2O RbClO4 Rb2O2 Rb2SO4 Rb2S RbO2

213.4 165.4 231.0 120.9 104.5 102.5 212.4 147.5 187.0 189.4 202.9 267.0 203.0 117.5

CL CL CL CL CL W CL CL Y

Ruthenium Chloride III Fluoride V Oxide IV Oxide VIII Sulfide IV

RuCl3 RuF5 RuO2 RuO4 RuS2

207.4 196.1 133.1 165.1 165.2

R GN BE Y BK

TR/H M T R C

Samarium Bromate III Bromide II Bromide III Chloride II

Sm(BrO3)3 · 9H2O SmBr2 SmBr3 SmCl2

696.2 310.2 390.1 221.3

Y B Y B

H

Y CL Y Y

Refractive index nD

T LIQ C M C H LIQ H T

R

C C C C R C C C/R C R

1.5530 1.493 1.398 1.6474 1.52 1.4701 1.513

T

R R (Continued)

1.80

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Formula

Molecular weight

Color

Samarium (Continued) Chloride III Fluoride II Fluoride III Iodide II Iodide III Nitrate III Oxide III Sulfate III Sulfide III

SmCl3 SmF2 SmF3 SmI2 SmI3 Sm(NO3)3 · 6H2O Sm2O3 Sm2(SO4)3 · 8H2O Sm2S3

256.7 188.4 207.4 404.2 531.1 444.5 348.7 733.0 396.9

Y Y W Y Y Y Y Y Y

Scandium Bromide Chloride Fluoride Iodide Nitrate Oxide Sulfate

ScBr3 ScCl3 ScF3 ScI3 Sc(NO3)3 Sc2O3 Sc2(SO4)3

284.7 151.3 102.0 425.7 231.0 137.9 378.1

W CL

Selenium Bromide I Bromide IV Chloride I Chloride IV Fluoride IV Fluoride VI Hydride II Oxide IV Oxide VI Oxybromide Oxychloride Oxyfluoride Selenic Acid Selenous Acid

Se2Br2 SeBr4 Se2Cl2 SeCl4 SeF4 SeF6 H2Se SeO2 SeO3 SeOBr2 SeOCl2 SeOF2 H2SeO4 H2SeO3

317.7 398.6 228.8 220.8 154.9 192.9 81.0 111.0 127.0 254.8 165.9 133.0 145.0 129.0

R B B CL CL CL CL CL W O Y CL W CL

Silicon Bromide Carbide Chloride Fluoride Hydride (silane) Hydride (disilane) Hydride (trisilane) Iodide Nitride Oxide II Oxide IV (amorph) Oxychloride Sulfide

SiBr4 SiC SiCl4 SiF4 SiH4 Si2H6 Si3H8 SiI4 Si3N4 SiO SiO2 Si2OCl6 SiS2

347.7 40.1 169.9 104.1 32.1 62.2 92.3 535.7 140.3 44.1 60.1 284.9 92.2

CL BK CL CL CL CL CL CL G W CL CL W

Compound

W CL W CL

Crystal symmetry H C R M H TR M M C

Refractive index nD

1.55

RH RH H C

LIQ LIQ C LIQ GAS GAS T T LIQ LIQ LIQ R H

LIQ C/H LIQ GAS GAS GAS LIQ C H C

1.807 1.895 >1.76

1.651

1.57971 2.67

1.4588 LIQ R

INORGANIC CHEMISTRY

1.81

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Silver Bromate Bromide Carbonate Chlorate Chloride Cyanide Fluoride Iodate Iodide Nitrate Nitrite Oxide Perchlorate Phosphate, o Sulfate Sulfide Telluride Thiocyanate

AgBrO3 AgBr Ag2CO3 AgClO3 AgCl AgCN AgF AgIO3 AgI AgNO3 AgNO2 Ag2O AgCIO4 Ag3PO4 Ag3SO4 Ag2S Ag2Te AgSCN

235.8 187.8 257.8 191.3 143.3 133.9 126.9 282.8 234.8 169.9 153.9 231.8 207.4 418.6 311.8 247.8 343.4 166.0

CL Y Y W W W Y CL Y CL Y B W Y W BK G CI

Sodium Bicarbonate Bromate Bromide Carbonate Chlorate Chloride Cyanide Fluoride Hydride Hydroxide Iodate Iodide Nitrate Nitrite Oxide Perchlorate Periodate Peroxide Phosphate, o Silicate, m Sulfate Sulfide Sulfite Thiosulfate

NaHCO3 NaBrO3 NaBr Na2CO3 NaCIO3 NaCl NaCN NaF NaH NaOH NaIO3 NaI NaNO3 NaNO2 Na2O NaClO4 NaIO4 Na2O2 Na3PO4 Na2SiO3 Na2SO4 Na2S Na2SO3 Na2S2O3

84.0 150.9 102.9 106.0 106.4 58.4 49.0 42.0 24.0 40.0 197.9 149.9 85.0 69.0 62.0 122.4 213.9 78.0 163.9 122.1 142.1 78.1 126.1 158.1

W CL Cl W CL CL CL CL SL W W CL CL Y G W CL Y W CL CL W W CL

Strontium Bromide Carbonate Chloride Fluoride Hydride

SrBr2 SrCO3 SrCl2 SrF2 SrH2

247.5 147.6 158.5 125.6 89.6

W CL CL CL W

Crystal symmetry T C T C H C R H/C R R C C C R C/R M

M C C C C C C C R/C R C TR R C C/R T H

Refractive index nD 1.874,1.904 2.253

2.071 1.685,1.9

2.21 1.74

1.500 1.594 1.6412 1.535 1.513 1.544 1.452 1.336 1.470 1.358 1.775 1.34;1

1.46

M R C H M

1.52 1.48

R R C C R

1.575 1.521 1.650 1.442

1.5

(Continued)

1.82

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Strontium (Continued) Hydroxide Iodate Iodide Nitrate Oxide Peroxide Sulfate Sulfide

Sr(OH)2 Sr(IO3)2 SrI2 Sr(NO3)2 SrO SrO2 SrSO4 SrS

121.7 437.4 341.4 211.7 103.6 119.6 183.7 119.7

CL CL W CL CL CL

TR –– C C T R C

Sulfur Bromide I Chloride I Chloride II Chloride IV Fluoride I Fluoride VI Hydride Oxide IV Oxide VI Pyrosulfuric Acid Sulfuric Acid Sulfuryl Chloride Thionyl Bromide Thionyl Chloride

S2Br2 S2Cl2 SCl2 SCl4 S2F2 SF6 H2S SO2 SO3 H2S2O7 H2SO4 SO2Cl2 SOBr2 SOCl2

224.0 135.0 103.0 173.9 102.1 146.0 34.1 64.1 80.1 178.1 98.1 135.0 207.9 119.0

R Y R R CL CL CL CL CL CL CL CL Y CL

LIQ LIQ LIQ LIQ GAS GAS GAS GAS LIQ LIQ LIQ LIQ LIQ LIQ

Tantalum Bromide Carbide Chloride Fluoride Iodide Nitride Oxide Sulfide

TaBr5 TaC TaCl5 TaF5 TaI5 TaN Ta2O5 Ta2S4

580.5 193.0 358.2 275.9 815.4 194.9 441.9 490.1

Y BK Y CL BK BK CL BK

R C M M R H R H

Tellurium Bromide II Bromide V Chloride II Chloride IV Fluoride VI Hydride Iodide IV Oxide IV Oxide VI Telluric Acid, o

TeBr2 TeBr4 TeCl2 TeCl4 TeF6 H2Te TeI4 TeO2 TeO3 H2TeO6

287.4 447.3 198.5 269.4 241.6 129.6 635.2 159.6 175.6 229.7

GN Y GN W CL CL BK W Y W

Terbium Bromide Chloride

TbBr3 TbCl3

398.6 265.3

W W

Refractive index nD

W

M GAS GAS R T/R C

1.567 1.870 1.62 2.107

1.736 1.66614 1.557

1.374

1.42923 1.44412 1.52710

2.00–2.35

INORGANIC CHEMISTRY

1.83

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Terbium (Continued) Fluoride Iodide Nitrate Oxide

TBF3 TbI3 Tb(NO3)3 · 6H2O Tb2O3

215.9 539.6 453.0 365.8

W CL W

R H M C

Thalliun Bromide I Carbonate I Chloride I Chloride III Fluoride Hydroxide I Iodide I Nitrate I Oxide I Oxide III Sulfate I Sulfide I

TlBr Tl2CO3 TlCl TlCl3 TlF TlOH TlI TlNO3 Tl2O Tl2O3 Tl2SO4 Tl2S

284.3 468.8 239.8 310.8 223.4 221.4 331.3 266.4 424.7 456.7 504.8 440.8

W CL W W CL Y Y/R W BK CL CL BK

C M C H R R R/C C/TR RH C R T

Thorium Bromide Carbide Chloride Fluoride Iodide Oxide Sulfate Sulfide

ThBr4 ThC2 ThCl4 ThF4 ThI4 ThO2 Th(SO4)2 ThS2

551.7 256.1 373.9 308.0 739.7 264.0 424.2 296.2

W Y W W Y W W BK

T T T M M C M R

Thulium Bromide Chloride Fluoride Iodide Oxide

TmBr3 TmCl3 TmF3 TmI3 Tm2O3

408.7 275.2 225.9 549.6 385.9

W Y W Y Y

H M R H C

Tin Bromide II Bromide IV Chloride II Chloride IV Fluoride II Fluoride IV Hydride Iodide II Iodide IV Oxide II Oxide IV Sulfide II Sulfide IV

SnBr2 SnBr4 SnCl2 SnCl4 SnF2 SnF4 SnH4 SnI2 SnI4 SnO SnO2 SnS SnS2

278.5 438.4 189.6 260.5 156.7 194.7 122.7 372.5 626.3 143.7 150.7 150.8 182.8

Y CL W CL W W

R R R LIQ M M GAS R C T T R H

R R BK W BK Y

Refractive index nD

2.4–2.8 2.247

2.78

1.87

1.512

2.106 1.996

(Continued)

1.84

SECTION ONE

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Titanium Bromide IV Carbide IV Chloride II Chloride III Chloride IV Fluoride IV Iodide IV Nitride Oxide II Oxide IV Sulfide IV

TiBr4 TiC TiCl2 TiCl3 TiCl4 TiF4 TiI4 TiN TiO TiO2 TiS2

367.6 59.9 118.8 154.3 189.7 123.9 555.5 61.9 63.9 79.9 112.0

O G BK V Y W B Y BK BK Y

Tungsten Bromide V Carbide II Carbide IV Chloride V Chloride VI Fluoride VI Oxide IV Oxide VI Sulfide IV Tungstic Acid

WBr5 W2C WC WCl5 WCl6 WF6 WO2 WO3 WS2 H2WO4

583.4 379.7 195.9 361.1 396.6 297.8 215.9 231.9 248.0 250.0

B G G GN BE CL B Y BK Y

Uranium Bromide III Bromide IV Carbide Carbide Chloride III Chloride IV Fluoride IV Fluoride VI Nitride Oxide IV Oxide VI Oxide IV–VI Uranyl Acetate Uranyl Nitrate

UBr3 UBr4 UC UC2 UCl3 UCl4 UF4 UF6 UN UO2 UO3 U3O8 UO2(C2H3O2)2 · 6H2O UO2(NO3)2 · 6H2O

477.8 557.7 250.0 262.0 344.4 379.9 314.1 352.1 252.0 270.1 286.1 842.2 422.1 502.1

R B BK BK R GN GN Y B BK R BK Y Y

H M C T H T M R C C H R R R

Vanadium Carbide IV Chloride IV Fluoride III Fluoride V Iodide II Oxide III Oxide IV Oxide V Oxychloride V Sulfide II

VC VCl4 VF3 VF5 VI2 V2O3 VO2 V2O5 VOCl3 VS

62.9 192.7 107.9 145.9 304.7 149.9 82.9 181.9 173.3 83.0

BK R GN CL V BK BE R Y BK

C LIQ R R H RH T R LIQ H

M C H H LIQ C C C T H

Refractive index nD

1.61

2.55

H C C GAS T M H R

2.24

1.38

1.49

1

INORGANIC CHEMISTRY

1.85

TABLE 1.4 Color, Crystal Symmetry and Refractive Index of Inorganic Compounds (Continued) Compound

Formula

Molecular weight

Color

Crystal symmetry

Xenon Fluoride II Fluoride IV Fluoride VI Oxide VI

XeF2 XeF4 XeF6 XeO3

169.3 207.3 245.3 179.3

CL CL CL CL

T M M R

Yttebium Bromide III Chloride II Chloride III Fluoride III Iodide II Iodide III Oxide III Sulfate III

YbBr3 YbCl2 YbCl3 YbF3 YbI2 YbI3 Yb2O3 Yb2(SO4)3

412.8 244.0 279.3 230.0 426.9 553.8 394.1 634.3

CL GN W W BK Y CL CL

R M R H H C

Yttrium Bromide Chloride Fluoride Iodide Oxide Sulfate

YBr3 YCl3 YF3 YI3 Y2O3 Y2(SO4)3

328.6 195.3 145.9 469.6 225.8 466.0

W W W W W W

Zinc Acetate Bromide Calbonate Chloride Fluoride Hydroxide Iodide Nitrate Oxide Sulfate Sulfide

Zn(C2H3O2)2 ZnBr2 ZnCO3 ZnCl2 ZnF2 Zn(OH)2 ZnI2 Zn(NO3)2 · 6H2O ZnO ZnSO4 ZnS

183.5 225.2 125.4 136.3 103.4 99.4 319.2 297.5 81.4 161.4 97.5

CL CL CL W CL CL CL CL W CL CL

Zirconium Bromide Carbide Chloride Fluoride Iodide Nitride Oxide

ZrBr4 ZrC ZrCI4 ZrF4 ZrI4 ZrN ZrO2

410.9 103.2 233.1 167.2 598.8 105.2 123.2

W G W W W B W

Refractive index nD

1.79

M H C

M R TR H M R C T H R C/H

C C M

M

1.5452 1.168 1.687

2.01 1.669 2.36

1.59

1.86

SECTION ONE

TABLE 1.5 Refractive Index of Minerals Mineral name

Refractive index

Actinolite Adularia moonstone Adventurine feldspar Adventurine quartz Agalmatoite Agate Albite feldspar Albite moonstone Alexandrite Almandine garnet Almandite garnet Amazonite feldspar Amber Amblygonite Amethyst Anatase Andalusite Andradite garnet Anhydrite Apatite Apophyllite Aquamarine Aragonite Augelite Axinite Azurite

1.618–1.641 1.525 1.532–1.542 1.544–1.533 1.55 1.544–1.553 1.525–1.536 1.535 1.745–1.759 1.76–1.83 1.79 1.525 1.540 1.611–1.637 1.544–1.553 2.49–2.55 1.634–1.643 1.82–1.89 1.571–1.614 1.632–1.648 1.536 1.577–1.583 1.530–1.685 1.574–1.588 1.675–1.685 1.73–1.838

Barite Barytocalcite Benitoite Beryl Beryllonite Brazilianite Brownite

1.636–1.648 1.684 1.757–1.8 1.577–1.60 1.553–1.562 1.603–1.623 1.567–1.576

Calcite Cancrinite Cassiterite Celestite Cerussite Ceylanite Chalcedony Chalybite Chromite Chrysoberyl Chrysocolla Chrysoprase Citrine Clinozoisite Colemanite Coral Cordierite Corundum

1.486–1.658 1.491–1.524 1.997–2.093 1.622–1.631 1.804–2.078 1.77–1.80 1.53–1.539 1.63–1.87 2.1 1.745 1.50 1.534 1.55 1.724–1.734 1.586–1.614 1.486–1.658 1.541 1.766–1.774

Mineral name

Refractive index

Crocoite Cuprite

2.31–2.66 2.85

Danburite Demantoid garnet Diamond Diopsite Dolomite Dumortierite

1.633 1.88 2.417–2.419 1.68–1.71 1.503–1.682 1.686–1.723

Ekanite Elaeolite Emerald Enstatite Epidote Euclase

1.60 1.532–1.549 1.576–1.582 1.663–1.673 1.733–1.768 1.652–1.672

Fibrolite Fluorite

1.659–1.680 1.434

Gaylussite Glass Grossular garnet

1.517 1.44–1.90 1.738–1.745

Hambergite Hauynite Hematite Hemimorphite Hessonite garnet Hiddenite Howlite Hypersthene

1.559–1.631 1.502 2.94–3.22 1.614–1.636 1.745 1.655–1.68 1.586–1.609 1.67–1.73

Idocrase Iolite Ivory

1.713–1.72 1.548 1.54

Jadeite Jasper Jet

1.66–1.68 1.54 1.66

Kornerupine Kunzite Kyanite

1.665–1.682 1.655–1.68 1.715–1.732

Labradorite feldspar Lapis gem Lazulite Leucite

1.565 1.50 1.615–1.645 1.5085

Magnesite Malachite Meerschaum

1.515–1.717 1.655–1.909 1.53.… none

INORGANIC CHEMISTRY

1.87

TABLE 1.5 Refractive Index of Minerals (Continued) Mineral name

Refractive index

Microcline feldspar Moldavite Moss agate

1.525 1.50 1.54–1.55

Natrolite Nephrite Nephrite jade

1.48–1.493 1.60–1.63 1.600–1.627

Obsidian Oligoclase feldspar Olivine Onyx Opal Orthoclase feldspar

1.48–1.51 1.539–1.547 1.672 1.486–1.658 1.45 1.525

Painite Pearl Periclase Peridot Peristerite Petalite Phenakite Phosgenite Prase Prasiolite Prehnite Proustite Purpurite Pyrite Pyrope

1.787–1.816 1.52–1.69 1.74 1.654–1.69 1.525–1.536 1.502–1.52 1.65–1.67 2.117–2.145 1.54–1.533 1.54–1.553 1.61–1.64 2.79–3.088 1.84–1.92 1.81 1.74

Quartz

1.55

Rhodizite Rhodochrisite Rhodolite garnet Rhodonite Rock crystal Ruby Rutile

1.69 1.60–1.82 1.76 1.73–1.74 1.544–1.553 1.76–1.77 2.61–2.90

Sanidine Sapphire Scapolite Scapolite (yellow) Scheelite

1.522 1.76–1.77 1.54–1.56 1.555 1.92–1.934

Mineral name

Refractive index

Serpentine Shell Sillimanite Sinhalite Smaragdite Smithsonite Sodalite Spessartite garnet Spinel Sphalerite Sphene Spodumene Staurolite Steatite Stichtite Sulfur

1.555 1.53–1.686 1.658–1.678 1.699–1.707 1.608–1.63 1.621–1.849 1.483 1.81 1.712–1.736 2.368–2.371 1.885–2.05 1.65–1.68 1.739–1.762 1.539–1.589 1.52–1.55 1.96–2.248

Taaffeite Tantalite Tanzanite Thomsonite Tiger eye Topaz (white) Topaz (blue) Topaz (pink, yellow) Tourmaline Tremolite Tugtupite Turquoise Turquoise gem

1.72 2.24–2.41 1.691–1.70 1.531 1.544–1.553 1.638 1.611 1.621 1.616–1.652 1.60–1.62 1.496–1.50 1.61–1.65 1.61

Ulexite Uvarovite

1.49–1.52 1.87

Variscite Vivianite

1.55–1.59 1.580–1.627

Wardite Willemite Witherite Wulfenite

1.59–1.599 1.69–1.72 1.532–1.68 2.300–2.40

Zincite Zircon Zirconia (cubic) Zoisite

2.01–1.03 1.801–2.01 2.17 1.695

1.88 TABLE 1.6 Properties of Molten Salts

Material

Melting point Tm (°K)

Boiling point (°K)

Density at melting point (g ⋅ cm−3)

LiF NaF KF RbF LiCl NaCl KCl LiBr NaBr KBr NaNO2 KNO2 LiNO3 NaNO3 KNO3 RbNO3 AgNO3 TlNO3 Li2SO4 Na2SO4 K2SO4 ZnCl2 HgCl2 PbCl2 Na2WO4 Na3AlF6 KCNS

1121 1268 1131 1048 883 1073 1043 823 1020 1007 544 692 527 583 610 589 483 480 1132 1157 1347 548 550 771 969 1273 450

1954 1977 1775 1681 1655 1738 1680 1583 1665 1656 d > 593 d623 — d653 d > 613 — d > 485 706 — — — 1005 577 1227 — — —

1.83 1.96 1.91 — 1.60 1.55 1.50 2.53 2.36 2.133 1.81 — 1.78 1.90 1.87 2.48 3.97 4.90 2.00 2.07 1.88 2.39 4.37 3.77 3.85 1.84 1.60

Notes: (a) 5893 Å; (b) 5890 Å.

Critical temperature (°K) 4140 4270 3460 3280 3080 3400 3200 3020 3200 3170

Volume change on melting ∆Vf /∆Vs 100 29.4 27.4 17.2 — 26.2 25.0 17.3 24.3 22.4 16.6 — — 21.4 10.7 3.32 −0.23

Surface tension at melting point (dynes ⋅ cm−1) 252 185 141 167 137 116 99 — 100 90 120 109 116 116 110 109 148 94 225 192 144 53 — 137 202 135 101

Viscosity at melting point (centipoise)

Sound velocity at melting point (m ⋅ cm−1) 2546 2080 1827

1.73 1.43 1.38

2038 1743 1595 1470 1325 1256

5.46 2.89 2.93

1853 1808 1754

4.25

1607

Cryoscopic constant (°K/mole ⋅ kg) 2.77 16.6 21.8 38.4 13.7 20.0 25.4 27.6 34.0 55.9

5.93 15.4 30.8 89.0 25.9 58 142 66.3 68.7

1002 39.3 4.25

4952

12.7

Material LiF NaF KF RbF LiCl NaCl KCl LiBr NaBr KBr NaNO2 KNO2 LiNO3 NaNO3 KNO3 RbNO3 AgNO3 TlNO3 Li2SO4 Na2SO4 K2SO4 ZnCl2 HgCl2 PbCl2 Na2WO4 Na3AlF6 KCNS

Heat capacity, Cp (cal./°K ⋅ mole) 15.50 16.40 16.00 15.0 16.0 16.0

26.6 37.0 29.5 30.6

47.8 24.1 25.0

Heat of fusion at melting point (kcal ⋅ mole−1)

Entropy of fusion at melting point (entropy units)

6.47 8.03 6.75 6.15 4.76 6.69 6.34 4.22 6.24 6.10

5.77 6.33 5.97 5.76 5.39 6.23 6.08 5.13 6.12 6.06

5.961 3.696 2.413 1.105 2.886 2.264 1.975 5.67 9.06 2.45 4.15 4.40

11.66 6.1 4.58 1.91

27.64 3.07

Decomposition potential of melt (volts)

Measurement temperature for decomposition potential (°K)

Molar refractivity at 5461 Å (cm3 ⋅ mole−1)

Refractive index at 5461 Å

Measurement temperature for refractive index, (°K)

151 120 148

2.20 2.76 2.54

1273 1273 1273

2.89 3.41 5.43

1.32 1.25 1.28

1223 1273 1173

178.5 152.3 122.4 181 149 108 58 ~87 44 58 46 35 38 27 123 90 157 ~0.08 0.00096 52.3 46

3.30 3.25 3.37 2.95 2.83 2.97

1073 1073 1073 1073 1073 1073

1.43 0.86 1.12

973 973 973

8.32 9.65 11.75 11.81 13.19 15.40 9.63a 11.67 10.74 11.54 13.57 15.31b 16.20a 21.38 14.87 16.53 20.93 18.2 22.9 26.1 24.58 17.2 19.65

1.501 1.320 1.329 1.60 1.486 1.436 1.416a 1.356a 1.467 1.431 1.426 1.431b 1.660a 1.688b 1.452 1.395 1.388 1.588 1.661 2.024 1.542 1.290 1.537

883 1173 1173 843 1173 1173 573 873 573 573 573 573 573 573 1173 1173 1173 593 563 873 1173 1273 573

Equivalent conductance at 1.1 Tm [(ohm)−1cm2 (equiv)−1]

17.3

1.89

1.90

SECTION ONE

TABLE 1.7 Triple Points of Various Materials Substance Ammonia Argon Boron tribromide Bromine Carbon dioxide Cyclopropane Deuterium oxide 1-Hexene Hydrogen, normal Hydrogen, para Hydrogen bromide Hydrogen chloride Iodine heptafluoride Krypton Methane Methane-d1 Methane-d2 Methane-d3 Methane-d4 Molybdenum oxide tetrafluoride Molybdenum pentafluoride Neon Neptunium hexafluoride Niobium pentabromide Niobium pentachloride Nitrogen 1-Octene Oxygen Phosphorus, white Plutonium hexafluoride Propene Radon Rhenium dioxide trifluoride Rhenium heptafluoride Rhenium oxide pentafluoride Rhenium pentafluoride Succinonitrile (NIST standard) Sulfur dioxide Tantalum pentabromide Tantalum pentachloride Tungsten oxide tetrafluoride Uranium hexafluoride Water Xenon

Triplet point, oK

Pressure, mmHg

195.46 83.78 226.67 280.4 216.65 145.59 276.97 133.39 13.95 13.81 186.1 158.8 279.6 115.95 90.67 90.40 90.14 89.94 89.79 370.3 340 24.55 328.25 540.6 476.5 63.15 171.45 54.34 863 324.74 103.95 202 363 321.4 313.9 321 331.23 197.68 553 489.0 377.8 337.20 273.16 161.37

45.58 516 44.1

54 ~232

548 87.60 84.52 81.80 80.12 79.13

324 758.0

94

32 760 533.0 ~500

1.256

1 139.6 612

INORGANIC CHEMISTRY

TABLE 1.8 Density of Mercury and Water The density of mercury and pure air-free water under a pressure of 101, 325 Pa(1 atm) is given in units of grams per cubic centimeter (g ⋅ cm–3). For mercury, the values are based on the density at 20°C being 13.545 884 g ⋅ cm–.3. Water attains its maximum density of 0.999 973 g ⋅ cm–3 at 3.98°C. For water, the temperature (tm, °C) of maximum density at different pressures (p) in atmospheres is given by tm = 3.98 – 0.0225(p – 1) Density of water

Temp., °C

Density of mercury

Density of water

Temp., °C

Density of mercury

1.91

1.92

SECTION ONE

TABLE 1.9 Specific Gravity of Air at Various Temperatures The table below gives the weight in grams ⋅ 104 of 1 mL of air at 760 mm of mercury pressure and at the temperature indicated. Density in grams per milliliter is the same as the specific gravity referred to water at 4°C as unity. To convert to density referred to air at 70°F as unity, divide the values below by 12.00.

INORGANIC CHEMISTRY

1.93

TABLE 1.10 Boiling Points of Water psi 0.5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 14.69 15 16 17 18 19 20 22 24 26 28 30 32 34 36 38 40 42

Boiling point, °F 79.6 101.7 126.0 141.4 125.9 162.2 170.0 176.8 182.8 188.3 193.2 197.7 201.9 205.9 209.6 212.0 213.0 216.3 219.4 222.4 225.2 228.0 233.0 237.8 242.3 246.4 250.3 254.1 257.6 261.0 264.2 267.3 270.2

psi 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 105 110 115 120

Boiling point, °F 273.1 275.8 278.5 281.0 283.5 285.9 288.3 290.5 292.7 294.9 297.0 299.0 301.0 303.0 304.9 306.7 308.5 310.3 312.1 313.8 315.5 317.1 318.7 320.3 321.9 323.4 324.9 326.4 327.9 331.4 334.8 338.1 341.3

psi 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800 825 850 875 900 950 1000

Boiling point, °F 358.5 371.8 381.9 391.9 401.0 409.5 417.4 424.8 431.8 438.4 444.7 450.7 456.4 461.9 467.1 472.2 477.1 481.8 486.3 490.7 495.0 499.2 503.2 507.2 511.0 514.7 518.4 521.9 525.4 528.8 532.1 538.6 544.8

1.94

SECTION ONE

TABLE 1.11 Boiling Points of Water

INORGANIC CHEMISTRY

1.95

TABLE 1.12 Refractive Index, Viscosity, Dielectric Constant, and Surface Tension of Water at Various Temperatures Temp., °C

Refractive index, nD

Viscosity mN ⋅ s ⋅ m−2

Dielectric constant, e

Surface tension mN ⋅ s ⋅ m−2

TABLE 1.13 Compressibility of Water In the table below are given the relative volumes of water at various temperatures and pressures. The volume at 0°C and one normal atmosphere (760 mm of Hg) is taken as unity.

1.96

SECTION ONE

TABLE 1.14 Flammability Limits of Inorganic Compounds in Air Limits of Flammability Compound Ammonia Carbon monoxide Carbonyl sulfide Cyanogen Hydrocyanic acid Hydrogen Hydrogen sulfide

Lower volume %

Upper volume %

15.50 12.50 11.90 6.60 5.60 4.00 4.30

27.00 74.20 28.50 42.60 40.00 74.20 45.50

1.3 THE ELEMENTS The chemical elements are the fundamental materials of which all matter is composed. From the modern viewpoint a substance that cannot be broken down or reduced further is, by definition, an element. The Periodic Table presents organized information about the chemical elements. The elements are grouped into eight classes according to their properties. The electronic configuration for an element’s ground state is a shorthand representation giving the number of electrons (superscript) found in each of the allowed sublevels (s, p, d, f) above a noble gas core (indicated by brackets). In addition, values for the thermal conductivity, the electrical resistance, and the coefficient of linear thermal expansion are included. Hund’s Rule states that for a set of equal-energy orbitals, each orbital is occupied by one electron before any oribital has two. Therefore, the first electrons to occupy orbitals within a sublevel have parallel spins.

TABLE 1.15 Subdivision of Main Energy Levels Main energy level Number of sublevels(n) Number of orbitals(n2) Kind and no. of orbitals per sublevel Maximum no. of electrons per sublevel Maximum no. of electrons per main level (2n2)

1 1 1 s 1

2 2 4 s p 1 3

3 3 9 s p d 1 3 5

4 4 16 s p d f 1 3 5 7

2

2 6

2 6 10

2 6 10 14

2

8

18

32

INORGANIC CHEMISTRY

TABLE 1.16 Chemical Symbols, Atomic Numbers, and Electron Arrangements of the Elements Element name Actinium Aluminum Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Bismuth Bohrium Boron Bromine Cadmium Calcium Californium Carbon Cerium Cesium Chlorine Chromium Cobalt Copper Curium Dubnium Dysprosium Einsteinium Erbium Europium Fermium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Hassium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Lutetium Magnesium Manganese

Chemical symbol Ac Al Am Sb Ar As At Ba Bk Be Bi Bh B Br Cd Ca Cf C Ce Cs Cl Cr Co Cu Cm Db Dy Es Er Eu Fm F Fr Gd Ga Ge Au Hf Hs He Ho H In I Ir Fe Kr La Lr or Lw Pb Li Lu Mg Mn

Atomic number 89 13 95 51 18 33 85 56 97 4 83 107 5 35 48 20 98 6 58 55 17 24 27 29 96 105 66 99 68 63 100 9 87 64 31 32 79 72 108 2 67 1 49 53 77 26 36 57 103 82 3 71 12 25 (Continued)

1.97

1.98

SECTION ONE

TABLE 1.16 Chemical Symbols, Atomic Numbers, and Electron Arrangements of the Elements (Continued) Element name Meitnerium Mendelevium Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium Polonium Potassium Praseodymium Promethium Protactinium Radium Radon Rhenium Rhodium Rubidium Ruthenium Rutherfordium Samarium Scandium Seaborgium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Ununbium Ununhexium Ununnilium Ununoctium Ununquadium Unununium Uranium

Chemical symbol Mt Md Hg Mo Nd Ne Np Ni Nb N No Os O Pd P Pt Pu Po K Pr Pm Pa Ra Rn Re Rh Rb Ru Rf Sm Sc Sg Se Si Ag Na Sr S Ta Tc Te Tb Tl Th Tm Sn Ti W Uub Uuh Uun Uuo Unq Uuu U

Atomic number 109 101 80 42 60 10 93 28 41 7 102 76 8 46 15 78 94 84 19 59 61 91 88 86 75 45 37 44 104 62 21 106 34 14 47 11 38 16 73 43 52 65 81 90 69 50 22 74 112 116 110 118 114 111 92

INORGANIC CHEMISTRY

1.99

TABLE 1.16 Chemical Symbols, Atomic Numbers, and Electron Arrangements of the Elements (Continued) Element name Vanadium Xenon Ytterbium Yttrium Zinc Zirconium

Chemical symbol

Atomic number

V Xe Yb Y Zn Zr

23 54 70 39 30 40

*As of the time of writing, there were no known elements with atomic numbers 113, 115, or 117.

Hydrogen (1) Symbol, H. A colorless, odorless gas at room temperature. The most common isotope has atomic weight 1.00794. The lightest and most abundant element in the universe. • Electrons in first energy level: 1 Helium (2) Symbol, He. A colorless, odorless gas at room temperature. The most common isotope has atomic weight 4.0026. The second lightest and second most abundant element in the universe. • Electrons in first energy level: 2 Lithium (3) Symbol, Li. Classified as an alkali metal. In pure form it is silver-colored. The lightest elemental metal. The most common isotope has atomic weight 6.941. • Electrons in first energy level: 2 • Electrons in second energy level: 1 Beryllium (4) Symbol, Be. Classified as an alkaline earth. In pure form it has a grayish color similar to that of steel. Has a relatively high melting point. The most common isotope has atomic weight 9.01218. • Electrons in first energy level: 2 • Electrons in second energy level: 2 Boron (5) Symbol, B. Classified as a metalloid. The most common isotope has atomic weight 10.82. Can exist as a powder or as a black, hard metalloid. Boron is not found free in nature. • Electrons in first energy level: 2 • Electrons in second energy level: 3 Carbon (6) Symbol, C. A nonmetallic element that is a solid at room temperature. Has a characteristic hexagonal crystal structure. Known as the basis of life on Earth. The most common isotope has atomic weight 12.011. Exists in three well-known forms: graphite (a black powder) which is common, diamond (a clear solid) which is rare, and amorphous. Another form of carbon is graphite. Used in electrochemical cells, air-cleaning filters, thermocouples, and noninductive electrical resistors. Also used in medicine to absorb poisons and toxins in the stomach and intestines. Abundant in mineral rocks such as • Electrons in first energy level: 2 • Electrons in second energy level: 4 Nitrogen (7) Symbol, N. A nonmetallic element that is a colorless, odorless gas at room temperature. The most common isotope has atomic weight 14.007. The most abundant component of the

1.100

SECTION ONE

earth’s atmosphere (approximately 78 percent at the surface). Reacts to some extent with certain combinations of other elements. • Electrons in first energy level: 2 • Electrons in second energy level: 5 Oxygen (8) Symbol, O. A nonmetallic element that is a colorless, odorless gas at room temperature. The most common isotope has atomic weight 15.999. The second most abundant component of the earth’s atmosphere (approximately 21 percent at the surface). Combines readily with many other elements, particularly metals. One of the oxides of iron, for example, is known as common rust. Normally, two atoms of oxygen combine to form a molecule (O2). In this form, oxygen is essential for the sustenance of many forms of life on Earth. When three oxygen atoms form a molecule (O3), the element is called ozone. This form of the element is beneficial in the upper atmosphere because it reduces the amount of ultraviolet radiation reaching the earth’s surface. Ozone is, ironically, also known as an irritant and pollutant in the surface air over heavily populated areas. • Electrons in first energy level: 2 • Electrons in second energy level: 6 Fluorine (9) Symbol, F. The most common isotope has atomic weight 18.998. A gaseous element of the halogen family. Has a characteristic greenish or yellowish color. Reacts readily with many other elements. • Electrons in first energy level: 2 • Electrons in second energy level: 7 Neon (10) Symbol, Ne. The most common isotope has atomic weight 20.179. A noble gas present in trace amounts in the atmosphere. • Electrons in first energy level: 2 • Electrons in second energy level: 8 Sodium (11) Symbol, Na. The most common isotope has atomic weight 22.9898. An element of the alkali-metal group. A solid at room temperature. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 1 Magnesium (12) Symbol, Mg. The most common isotope has atomic weight 24.305. A member of the alkaline earth group. At room temperature it is a whitish metal. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 2 Aluminum (13) Symbol, Al. The most common isotope has atomic weight 26.98. A metallic element and a good electrical conductor. Has many of the same characteristics as magnesium, except it reacts less easily with oxygen in the atmosphere. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 3

INORGANIC CHEMISTRY

1.101

Silicon (14) Symbol, Si. The most common isotope has atomic weight 28.086. A metalloid abundant in the earth’s crust. Especially common in rocks such as granite, and in many types of sand. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 4 Phosphorus (15) Symbol, P. The most common isotope has atomic weight 30.974. A nonmetallic element of the nitrogen family. Found in certain types of rock. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 5 Sulfur (16) Symbol, S. Also spelled sulphur. The most common isotope has atomic weight 32.06. A nonmetallic element. Reacts with some other elements. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 6 Chlorine (17) Symbol, Cl. The most common isotope has atomic weight 35.453. A gas at room temperature and a member of the halogen family. Reacts readily with various other elements. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 7 Argon (18) Symbol, A or Ar. The most common isotope has atomic weight 39.94. A gas at room temperature; classified as a noble gas. Present in small amounts in the atmosphere. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 8 Potassium (19) Symbol, K. The most common isotope has atomic weight 39.098. A member of the alkali metal group. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 8 Electrons in fourth energy level: 1

Calcium (20) Symbol, Ca. The most common isotope has atomic weight 40.08. A metallic element of the alkaline-earth group. Calcium carbonate, or calcite, is abundant in the earth’s crust, especially in limestone • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 8 Electrons in fourth energy level: 2

1.102

SECTION ONE

Scandium (21) Symbol, Sc. The most common isotope has atomic weight 44.956. In the pure form it is a soft metal. Classified as a transition metal. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 9 Electrons in fourth energy level: 2

Titanium (22) Symbol, Ti. The most common isotope has atomic weight 47.88. Classified as a transition metal. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 10 Electrons in fourth energy level: 2

Vanadium (23) Symbol, V. The most common isotope has atomic weight 50.94. Classified as a transition metal. In its pure form it is whitish in color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 11 Electrons in fourth energy level: 2

Chromium (24) Symbol, Cr. The most common isotope has atomic weight 51.996. Classified as a transition metal. In its pure form it is grayish in color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 13 Electrons in fourth energy level: 1

Manganese (25) Symbol, Mn. The most common isotope has atomic weight 54.938. Classified as a transition metal. In its pure form it is grayish in color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 13 Electrons in fourth energy level: 2

Iron (26) Symbol, Fe. The most common isotope has atomic weight 55.847. In its pure form it is a dull gray metal. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 14 Electrons in fourth energy level: 2

Cobalt (27) Symbol, Co. The most common isotope has atomic weight 58.94. Classified as a transition metal. In the pure form it is silvery in color. • Electrons in first energy level: 2 • Electrons in second energy level: 8

INORGANIC CHEMISTRY

1.103

• Electrons in third energy level: 15 • Electrons in fourth energy level: 2 Nickel (28) Symbol, Ni. The most common isotope has atomic weight 58.69. Classified as a transition metal. In its pure form it is light gray to white. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 16 Electrons in fourth energy level: 2

Copper (29) Symbol, Cu. The most common isotope has atomic weight 63.546. Classified as a transition metal. In its pure form it has a characteristic red or wine color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 1

Zinc (30) Symbol, Zn. The most common isotope has atomic weight 65.39. Classified as a transition metal. In pure form, it is a dull blue-gray color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 2

Gallium (31) Symbol, Ga. The most common isotope has atomic weight 69.72. A semiconducting metal. In pure form it is light gray to white. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 3

Germanium (32) Symbol, Ge. The most common isotope has atomic weight 72.59. A semiconducting metalloid. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 4

Arsenic (33) Symbol, As. The most common isotope has atomic weight 74.91. A metalloid used as a dopant in the manufacture of semiconductors. In its pure form it is gray in color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 5

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Selenium (34) Symbol, Se. The most common isotope has atomic weight 78.96. Classified as a nonmetal. In its pure form it is gray in color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 6

Bromine (35) Symbol, Br. The most common isotope has atomic weight 79.90. A nonmetallic element of the halogen family. A reddish-brown liquid at room temperature. Has a characteristic unpleasant odor. Reacts readily with various other elements. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 7

Krypton (36) Symbol, Kr. The most common isotope has atomic weight 83.80. Classified as a noble gas. Colorless and odorless. Present in trace amounts in the earth’s atmosphere. Some common isotopes of this element are radioactive. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 8

Rubidium (37) Symbol, Rb. The most common isotope has atomic weight 85.468. Classified as an alkali metal. In its pure form it is silver-colored. Reacts easily with oxygen and chlorine. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 8 Electrons in fifth energy level: 1

Strontium (38) Symbol, Sr. The most common isotope has atomic weight 87.62. A metallic element of the alkaline-earth group. In pure form it is gold-colored. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 8 Electrons in fifth energy level: 2

Yttrium (39) Symbol, Y. The most common isotope has atomic weight 88.906. Classified as a transition metal. In its pure form it is silver-colored. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 9 Electrons in fifth energy level: 2

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Zirconium (40) Symbol, Zr. The most common isotope has atomic weight 91.22. Classified as a transition metal. In its pure form it is grayish in color. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 10 Electrons in fifth energy level: 2

Niobium (41) Symbol, Nb. The most common isotope has atomic weight 92.91. Classified as a transition metal. This element is sometimes called columbium. In pure form it is shiny, and is light gray to white in color. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 12 Electrons in fifth energy level: 1

Molybdenum (42) Symbol, Mo. The most common isotope has atomic weight 95.94. Classified as a transition metal. In its pure form, it is hard and silver-white. Used as a catalyst, as a component of hard alloys for the aeronautical and aerospace industries, and in steel-hardening processes. It is known for high thermal conductivity, low thermal-expansion coefficient, high melting point, and resistance to corrosion. Most molybdenum compounds are relatively nontoxic. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 13 Electrons in fifth energy level: 1

Technetium (43) Symbol, Tc. Formerly called masurium. The most common isotope has atomic weight 98. Classified as a transition metal. In its pure form, it is grayish in color. This element is not found in nature; it occurs when the uranium atom is split by nuclear fission. It also occurs when molybdenum is bombarded by high-speed deuterium nuclei (particles consisting of one proton and one neutron). This element is radioactive. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 14 Electrons in fifth energy level: 1

Ruthenium (44) Symbol, Ru. The most common isotope has atomic weight 101.07. A rare element, classified as a transition metal. In pure form it is silver-colored. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 15 Electrons in fifth energy level: 1

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Rhodium (45) Symbol, Rh. The most common isotope has atomic weight 102.906. Classified as a transition metal. In its pure form it is silver-colored. Occurs in nature along with platinum and nickel. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 16 Electrons in fifth energy level: 1

Palladium (46) Symbol, Pd. The most common isotope has atomic weight 106.42. Classified as a transition metal. In its pure form it is light gray to white. In nature, palladium is found with copper ore. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 0

Silver (47) Symbol, Ag. The most common isotope has atomic weight 107.87. Classified as a transition metal. In its pure form it is a bright, shiny, and silverish-white colored metal. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 1

Cadmium (48) Symbol, Cd. The most common isotope has atomic weight 112.41. Classified as a transition metal. In its pure form it is silver-colored. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 2

Indium (49) Symbol, In. The most common isotope has atomic weight 114.82. A metallic element used as a dopant in semiconductor processing. In pure form it is silver-colored. In nature, it is often found along with zinc. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 3

Tin (50) Symbol, Sn. The most common isotope has atomic weight 118.71. In pure form it is a white or grayish metal. It changes color (from white to gray) when it is cooled through a certain temperature range. It is ductile and malleable. • Electrons in first energy level: 2 • Electrons in second energy level: 8

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• Electrons in third energy level: 18 • Electrons in fourth energy level: 18 • Electrons in fifth energy level: 4 Antimony (51) Symbol, Sb. The most common isotope has atomic weight 121.76. Classified as a metalloid. In pure form, it is blue-white or blue-gray in color. Has a characteristic flakiness and brittleness. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 5

Tellurium (52) Symbol, Te. The most common isotope has atomic weight 127.60. A rare metalloid element related to selenium. In pure form, it is silverish-white and has high luster. In nature it is found along with other metals such as copper. It has a characteristic brittleness. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 6

Iodine (53) Symbol, I. The most common isotope has atomic weight 126.905. A member of the halogen family. In pure form it has a black or purple-black color. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 7

Xenon (54) Symbol, Xe. The most common isotope has atomic weight 131.29. Classified as a noble gas. Colorless and odorless; present in trace amounts in the earth’s atmosphere. • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 8

Cesium (55) Symbol, Cs. Also spelled caesium (in Britain). The most common isotope has atomic weight 132.91. Classified as an alkali metal. In pure form, it is silver-white in color, is ductile, and is malleable. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 8 Electrons in sixth energy level: 1

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SECTION ONE

Barium (56) Symbol, Ba. The most common isotope has atomic weight 137.36. Classified as an alkaline earth. In pure form it is silver-white in color, and is relatively soft; it is sometimes mistaken for lead. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Lanthanum (57) Symbol, La. The most common isotope has atomic weight 138.906. Classified as a rare earth. In pure form it is white in color, malleable, and soft. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 18 Electrons in fifth energy level: 9 Electrons in sixth energy level: 2

Cerium (58) Symbol, Ce. The most common isotope has atomic weight 140.13. Classified as a rare earth. In pure form it is light silvery-gray. It reacts readily with various other elements and is malleable and ductile. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 20 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Praseodymium (59) Symbol, Pr. The most common isotope has atomic weight 140.908. Classified as a rare earth. In pure form it is silver-gray, soft, malleable, and ductile. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 21 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Neodymium (60) Symbol, Nd. The most common isotope has atomic weight 144.24. Classified as a rare earth. In pure form it is shiny and is silvery in color. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 22

INORGANIC CHEMISTRY

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• Electrons in fifth energy level: 8 • Electrons in sixth energy level: 2 Promethium (61) Symbol, Pm. Formerly called illinium. The most common isotope has atomic weight 145. Classified as a rare earth. In pure form it is gray in color, and is highly radioactive. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 23 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Samarium (62) Symbol, Sm. The most common isotope has atomic weight 150.36. Classified as a rare earth. In pure form it is silvery-white in color with high luster. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 24 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Europium (63) Symbol, Eu. The most common isotope has atomic weight 151.96. Classified as a rare earth. In pure form it is silver-gray in color, and has ductility similar to that of lead. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 25 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Gadolinium (64) Symbol, Gd. The most common isotope has atomic weight 157.25. Classified as a rare earth. In pure form it is silver in color, is ductile, and is malleable. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 25 Electrons in fifth energy level: 9 Electrons in sixth energy level: 2

Terbium (65) Symbol, Tb. The most common isotope has atomic weight 158.93. Classified as a rare earth. In pure form it is silver-gray, soft, malleable, and ductile. • Electrons in first energy level: 2 • Electrons in second energy level: 8 • Electrons in third energy level: 18

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SECTION ONE

• Electrons in fourth energy level: 27 • Electrons in fifth energy level: 8 • Electrons in sixth energy level: 2 Dysprosium (66) Symbol, Dy. The most common isotope has atomic weight 162.5. Classified as a rare earth. In pure form it has a bright, shiny silver color. It is soft and malleable, but it has a relatively high melting point. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 28 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Holmium (67) Symbol, Ho. The most common isotope has atomic weight 164.93. Classified as a rare earth. In pure form it is silver in color. It is soft and malleable. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 29 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Erbium (68) Symbol, Er. The most common isotope has atomic weight 167.26. Classified as a rare earth. In pure form it is silverish, soft, malleable, and ductile. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 30 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Thulium (69) Symbol, Tm. The most common isotope has atomic weight 168.93. Classified as a rare earth. In pure form this element is grayish in color, soft, malleable, and ductile. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 31 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Ytterbium (70) Symbol, Yb. The most common isotope has atomic weight 173.04. Classified as a rare earth. In pure form it is silver-white in color, soft, malleable, and ductile. • Electrons in first energy level: 2 • Electrons in second energy level: 8

INORGANIC CHEMISTRY

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Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 8 Electrons in sixth energy level: 2

Lutetium (71) Symbol, Lu. The most common isotope has atomic weight 174.967. Classified as a rare earth. In its pure form, it is silver-white and radioactive, with a half-life on the order of thousands of millions of years. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 9 Electrons in sixth energy level: 2

Hafnium (72) Symbol, Hf. The most common isotope has atomic weight 178.49. Classified as a transition metal. In pure form, it is silver-colored, shiny, and ductile. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 10 Electrons in sixth energy level: 2

Tantalum (73) Symbol, Ta. The most common isotope has atomic weight 180.95. Classified as a transition metal; an element of the vanadium family. In pure form it is grayish-silver in color, ductile, and hard, with a high melting point. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 11 Electrons in sixth energy level: 2

Tungsten (74) Symbol, W. Also known as wolfram. The most common isotope has atomic weight 183.85. Classified as a transition metal. In pure form it is silver-colored. It has an extremely high melting point. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 12 Electrons in sixth energy level: 2

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SECTION ONE

Rhenium (75) Symbol, Re. The most common isotope has atomic weight 186.207. Classified as a transition metal. In pure form it is silver-white, has high density, and has a high melting point. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 13 Electrons in sixth energy level: 2

Osmium (76) Symbol, Os. The most common isotope has atomic weight 190.2. A transition metal of the platinum group. In pure form it is bluish-silver in color, dense, hard, and brittle. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 14 Electrons in sixth energy level: 2

Iridium (77) Symbol, Ir. The most common isotope has atomic weight 192.22. A transition metal of the platinum group. In pure form it is yellowish-white in color with high luster; it is hard, brittle, and has high density. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 15 Electrons in sixth energy level: 2

Platinum (78) Symbol, Pt. The most common isotope has atomic weight 195.08. Classified as a transition metal. In pure form it has a brilliant, shiny, white luster. It is malleable and ductile. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 17 Electrons in sixth energy level: 1

Gold (79) Symbol, Au. The most common isotope has atomic weight 196.967. A transition metal. In pure form it is shiny, yellowish, ductile, malleable, and comparatively soft. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32

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• Electrons in fifth energy level: 18 • Electrons in sixth energy level: 1 Mercury (80) Symbol, Hg. The most common isotope has atomic weight 200.59. Classified as a transition metal. In pure form it is silver-colored and liquid at room temperature. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 2

Thallium (81) Symbol, Tl. The most common isotope has atomic weight 204.38. A metallic element. In pure form it is bluish-gray or dull gray, soft, malleable, and ductile. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 3

Lead (82) Symbol, Pb. The most common isotope has atomic weight 207.2. A metallic element. In pure form it is dull gray or blue-gray, soft, and malleable; relatively low melting temperature. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 4

Bismuth (83) Symbol, Bi. The most common isotope has atomic weight 208.98. A metallic element. In pure form it is pinkish-white and brittle. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 5

Polonium (84) Symbol, Po. The most common isotope has atomic weight 209. Classified as a metalloid. It is produced from the decay of radium and is sometimes called radium-F. Polonium is radioactive; it emits primarily alpha particles. • Electrons in first energy level: 2 • Electrons in second energy level: 8

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SECTION ONE

• • • •

Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 6

Astatine (85) Symbol, At. The most common isotope has atomic weight 210. Formerly called alabamine. Classified as a halogen. The element is radioactive. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 7

Radon (86) Symbol, Rn. The most common isotope has atomic weight 222. Classified as a noble gas. It is radioactive, emitting primarily alpha particles, and has a short half-life. Radon is a colorless gas that results from the disintegration of radium. • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 8

Francium (87) Symbol, Fr. The most common isotope has atomic weight 223. Classified as an alkali metal. This element is radioactive, and all isotopes decay rapidly. Produced as a result of the radioactive disintegration of actinium. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 8 Electrons in seventh energy level: 1

Radium (88) Symbol, Ra. The most common isotope has atomic weight 226. Classified as an alkaline earth. In pure form it is silver-gray, but darkens quickly when exposed to air. This element is radioactive, emitting alpha particles, beta particles, and gamma rays. It has a moderately long half-life. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

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Actinium (89) Symbol, Ac. The most common isotope has atomic weight 227. Classified as a rare earth. In pure form it is silver-gray in color. This element is radioactive, emitting beta particles. The most common isotope has a half-life of 21.6 years. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 9 Electrons in seventh energy level: 2

Thorium (90) Symbol, Th. The most common isotope has atomic weight 232.038. Classified as a rare earth and a member of the actinide series. In pure form it is silver-colored, soft, ductile, and malleable. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 18 Electrons in sixth energy level: 10 Electrons in seventh energy level: 2

Protactinium (91) Symbol, Pa. Formerly called protoactinium. The most common isotope has atomic weight 231.036. Classified as a rare earth. In pure form it is silver-colored. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 20 Electrons in sixth energy level: 9 Electrons in seventh energy level: 2

Uranium (92) Symbol, U. The most common isotope has atomic weight 238.029. Classified as a rare earth. In pure form it is silver-colored, malleable, and ductile. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 21 Electrons in sixth energy level: 9 Electrons in seventh energy level: 2

Neptunium (93) Symbol, Np. The most common isotope has atomic weight 237. Classified as a rare earth. In pure form it is silver-colored, and reacts with various other elements to form compounds. • Electrons in first energy level: 2 • Electrons in second energy level: 8

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SECTION ONE

• • • • •

Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 23 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

Plutonium (94) Symbol, Pu. The most common isotope has atomic weight 244. Classified as a rare earth. In pure form it is silver-colored; when it is exposed to air, a yellow oxide layer forms. Plutonium reacts with various other elements to form compounds. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 24 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

Americium (95) Symbol, Am. The most common isotope has atomic weight 243. Classified as a rare earth. In pure form it is silver-white and malleable. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 25 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

Curium (96) Symbol, Cm. The most common isotope has atomic weight 247. Classified as a rare earth. In pure form it is silvery in color, and it reacts readily with various other elements. This element, like most transuranic elements, is dangerously radioactive. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 25 Electrons in sixth energy level: 9 Electrons in seventh energy level: 2

Berkelium (97) Symbol, Bk. The most common isotope has atomic weight 247. Classified as a rare earth. It is radioactive with a short half-life. Berkelium is a human-made element and is not known to occur in nature. • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32

INORGANIC CHEMISTRY

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• Electrons in fifth energy level: 26 • Electrons in sixth energy level: 9 • Electrons in seventh energy level: 2 Californium (98) Symbol, Cf. The most common isotope has atomic weight 251. Classified as a rare earth. It is radioactive, emitting neutrons in large quantities. It is human-made element, not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 28 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

Einsteinium (99) Symbol, E or Es. The most common isotope has atomic weight 252. Classified as a rare earth. It is radioactive with a short half-life. Einsteinium is a human-made element and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 29 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

Fermium (100) Symbol, Fm. The most common isotope has atomic weight 257. Classified as a rare earth. It has a short half-life, is human-made, and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 30 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

Mendelevium (101) Symbol, Md or Mv. The most common isotope has atomic weight 258. Classified as a rare earth. It has a short half-life, is human-made, and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 31 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

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SECTION ONE

Nobelium (102) Symbol, No. The most common isotope has atomic weight 259. Classified as a rare earth. It has a short half-life (seconds or minutes, depending on the isotope), is human-made, and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 8 Electrons in seventh energy level: 2

Lawrencium (103) Symbol, Lr or Lw. The most common isotope has atomic weight 262. Classified as a rare earth. It has a half-life less than one minute, is human-made, and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 9 Electrons in seventh energy level: 2

Rutherfordium (104) Symbol, Rf. Also called unnilquadium (Unq) and Kurchatovium (Ku). The most common isotope has atomic weight 261. Classified as a transition metal. It has a half-life on the order of a few seconds to a few tenths of a second (depending on the isotope), is human-made, and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 10 Electrons in seventh energy level: 2

Dubnium (105) Symbol, Db. Also called unnilpentium (Unp) and Hahnium (Ha). The most common isotope has atomic weight 262. Classified as a transition metal. It has a half-life on the order of a few seconds to a few tenths of a second (depending on the isotope), is human-made, and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 11 Electrons in seventh energy level: 2

INORGANIC CHEMISTRY

1.119

Seaborgium (106) Symbol, Sg. Also called unnilhexium (Unh). The most common isotope has atomic weight 263. Classified as a transition metal. It has a half-life on the order of one second or less, is human-made, and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 12 Electrons in seventh energy level: 2

Bohrium (107) Symbol, Bh. Also called unnilseptium (Uns). The most common isotope has atomic weight 262. Classified as a transition metal. It is human-made and is not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 13 Electrons in seventh energy level: 2

Hassium (108) Symbol, Hs. also called unniloctium (Uno). The most common isotope has atomic weight 265. Classified as a transition metal. It is human-made and not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 14 Electrons in seventh energy level: 2

Meitnerium (109) Symbol, Mt. Also called unnilenium (Une). The most common isotope has atomic weight 266. Classified as a transition metal. It is human-made and not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 15 Electrons in seventh energy level: 2

Ununnilium (110) Symbol, Uun. The most common isotope has atomic weight 269. Classified as a transition metal. It is human-made and not known to occur in nature. • Electrons in first energy level: 2 • Electrons in second energy level: 8

1.120

SECTION ONE

• • • • •

Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 17 Electrons in seventh energy level: 1

Unununium (111) Symbol, Uuu. The most common isotope has atomic weight 272. Classified as a transition metal. It is human-made and not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 18 Electrons in seventh energy level: 1

Ununbium (112) Symbol, Uub. The most common isotope has atomic weight 277. Classified as a transition metal. It is human-made and not known to occur in nature. • • • • • • •

Electrons in first energy level: 2 Electrons in second energy level: 8 Electrons in third energy level: 18 Electrons in fourth energy level: 32 Electrons in fifth energy level: 32 Electrons in sixth energy level: 18 Electrons in seventh energy level: 2

(113) As of this writing, no identifiable atoms of an element with atomic number 113 have been reported. The synthesis of or appearance of such an atom is believed possible because of the observation of ununqadium (Uuq, element 114) in the laboratory. Ununquadium (114) Symbol, Uuq. The most common isotope has atomic weight 285. First reported in January 1999. It is human-made and not known to occur in nature. (115) As of this writing, no identifiable atoms of an element with atomic number 115 have been reported. The synthesis or appearance of such an atom is believed possible because of the observation of ununhexium (Uuh, element 116) in the laboratory. Ununhexium (116) Symbol, Uuh. The most common isotope has atomic weight 289. First reported in January 1999. It is a decomposition product of ununoctium, and it in turn decomposes into ununquadium. It is not known to occur in nature. (117) As of this writing, no identifiable atoms of an element with atomic number 117 have been reported. The synthesis or appearance of such an atom is believed possible because of the observation of ununoctium (Uuo, element 118) in the laboratory. Ununoctium (118) Symbol, Uuo. The most common isotope has atomic weight 293. It is the result of the fusion of krypton and lead and decomposes into ununhexium. It is not known to occur in nature.

TABLE 1.17 Atomic Numbers, Periods, and Groups of the Elements (The Periodic Table) Group Period 1

1 1 H 3 Li 11 Na 19 K 37 Rb 55 Cs 87 Fr

2 3 4 5 6 7

2

4 Be 12 Mg 20 Ca 38 Sr 56 Ba 88 Ra

3

* **

*Lanthanides

*

†Actinides

**

4

5

6

7

8

9

10

11

12

13

21 Sc 39 Y 71 Lu 103 Lr

22 Ti 40 Zr 72 Hf 104 Unq

23 V 41 Nb 73 Ta 105 Unp

24 Cr 42 Mo 74 W 106 Unh

25 Mn 43 Tc 75 Re 107 Uns

26 Fe 44 Ru 76 Os 108 Uno

27 Co 45 Rh 77 Ir 109 Mt

28 Ni 46 Pd 78 Pt 110 Uun

29 Cu 47 Ag 79 Au 111 Uuu

30 Zn 48 Cd 80 Hg 112 Uub

5 B 13 Al 31 Ga 49 In 81 Tl 113 Uut

57 La 89 Ac

58 Ce 90 Th

59 Pr 91 Pa

60 Nd 92 U

61 Pm 93 Np

62 Sm 94 Pu

63 Eu 95 Am

64 Gd 96 Cm

65 Tb 97 Bk

66 Dy 98 Cf

67 Ho 99 Es

14

15

16

17

18

1 H 9 F 17 Cl 35 Br 53 I 85 At 117 Uus

2 He 10 Ne 18 Ar 36 Kr 54 Xe 86 Rn 118 Uuo

6 C 14 Si 32 Ge 50 Sn 82 Pb 114 Uuq

7 N 15 P 33 As 51 Sb 83 Bi 115 Uup

8 O 16 S 34 Se 52 Te 84 Po 116 Uuh

68 Er 100 Fm

69 Tm 101 Md

70 Yb 102 No

1.121

1.122

SECTION ONE

TABLE 1.18 Atomic Weights of the Elements Name Actinium Aluminium Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Bismuth Bohrium Boron Bromine Cadmium Caesium Calcium Californium Carbon Cerium Chlorine Chromium Cobalt Copper Curium Dubnium Dysprosium Einsteinium Erbium Europium Fermium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Hassium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Lutetium Magnesium Manganese Meitnerium Mendelevium

Atomic number

Symbol

Atomic weight

89 13 95 51 18 33 85 56 97 4 83 107 5 35 48 55 20 98 6 58 17 24 27 29 96 105 66 99 68 63 100 9 87 64 31 32 79 72 108 2 67 1 49 53 77 26 36 57 103 82 3 71 12 25 109 101

Ac Al Am Sb Ar As At Ba Bk Be Bi Bh B Br Cd Cs Ca Cf C Ce Cl Cr Co Cu Cm Db Dy Es Er Eu Fm F Fr Gd Ga Ge Au Hf Hs He Ho H In I Ir Fe Kr La Lr Pb Li Lu Mg Mn Mt Md

[227] 26.981538 [243] 121.76 39.948 74.9216 [210] 137.327 [247] 9.012182 8.98038 [264] 10.811 79.904 112.411 132.90545 40.078 [251] 12.0107 140.116 35.4527 51.9961 8.9332 63.546 [247] [262] 162.5 [252] 167.26 151.964 [257] 18.9984032 [223] 157.25 69.723 72.61 196.96655 178.49 [265] 4.002602 164.93032 1.00794 114.818 126.90447 192.217 55.845 83.8 138.9055 [262] 207.2 6.941 174.967 24.305 54.938049 [268] [258]

INORGANIC CHEMISTRY

1.123

TABLE 1.18 Atomic Weights of the Elements (Continued) Name Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium Polonium Potassium Praseodymium Promethium Protactinium Radium Radon Rhenium Rhodium Rubidium Ruthenium Rutherfordium Samarium Scandium Seaborgium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Ununbium Ununnilium Ununnunium Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium

Atomic number 80 42 60 10 93 28 41 7 102 76 8 46 15 78 94 84 19 59 61 91 88 86 75 45 37 44 104 62 21 106 34 14 47 11 38 16 73 43 52 65 81 90 69 50 22 74 112 110 111 92 23 54 70 39 30 40

Symbol Hg Mo Nd Ne Np Ni Nb N No Os O Pd P Pt Pu Po K Pr Pm Pa Ra Rn Re Rh Rb Ru Rf Sm Sc Sg Se Si Ag Na Sr S Ta Tc Te Tb Tl Th Tm Sn Ti W Uub Uun Uuu U V Xe Yb Y Zn Zr

Atomic weight 200.59 95.94 144.24 20.1797 [237] 58.6934 92.90638 14.00674 [259] 190.23 15.9994 106.42 30.973761 195.078 [244] [209] 39.0983 140.90765 [145] 231.03588 [226] [222] 186.207 102.9055 85.4678 101.07 [261] 150.36 44.95591 [263] 78.96 28.0855 107.8682 22.98977 87.62 32.066(6) 180.9479 [98] 127.6 158.92534 204.3833 232.0381 168.93421 118.71 47.867 183.84 [277] [269] [272] 238.0289 50.9415 131.29 173.04 88.90585 65.39 91.224

1.124 TABLE 1.19 Physical Properties of the Elements The relative atomic masses in the following table are based on the 12C = 12 scale; a value in brackets denotes the mass number of the most stable isotope. The data are based on the most recent values adopted by IUPAC, with a maximum of six significant figures. r denotes density, qC,m denotes melting temperature, qC, b denotes boiling temperature, and cp denotes specific heat capacity. subl. denotes sublimes

Element

Symbol

Atomic number

Relative atomic mass

Actinium Aluminium Americium Antimony Argon Arsenic (a, grey) Astatine Barium Berkelium Beryllium Bismuth Boron Bromine Cadmium Caesium Calcium Californium Carbon

Ac Al Am Sb Ar As At Ba Bk Be Bi B Br Cd Cs Ca Cf C

89 13 95 51 18 33 85 56 97 4 83 5 35 48 55 20 98 6

227.028 26.9815 (243) 121.75 39.948 74.9216 (210) 137.33 (247) 9.01218 208.980 10.81 79.904 112.41 132.905 40.08 (251) 12.011

Cerium Chlorine Chromium Cobalt Copper Curium Dysprosium Einsteinium

Ce Cl Cr Co Cu Cm Dy Es

58 17 24 27 29 96 66 99

140.12 35.453 51.996 58.9332 63.546 (247) 162.50 (252)

r/g cm−3

qC,m /°C

qC,b /°C

cp /J kg−1 K−1

10.1 2.70 11.7 6.62 1.40 (87 K) 5.72

1050 660 (1200) 630 −189

3200 2470 (2600) 1380 −186 613 subl. (380) 1640

900 140 209 519 326 (140) 192

3.51

(302) 714

1.85 9.80 2.34 3.12 8.64 1.90 1.54

1280 271 2300 −7.2 321 28.7 850

2477 1560 3930 58.8 765 690 1487

1.82 × 103 121 1.03 × 103 448 230 234 653

2.25 (graphite) 3.51 (diamond) 6.78 1.56 (238 K) 7.19 8.90 8.92

3730 subl.

4830

795 −101 1890 1492 1083

3470 −34.7 2482 2900 2595

711 (graphite) 519 (diamond) 184 477 448 435 385

8.56

1410

2600

172

Oxidation states 3 3 3, 4, 5, 6 3, 5 3, 5 2 3, 4 2 3,5 3 1, 3, 4, 5, 6 2 1 2 3 2,4 3,4 1, 3, 4, 5, 6, 7 2,3,6 2,3 1,2 3 3 3

Erbium Europium Fermium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Lutetium Magnesium Manganese Mendelevium Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium

Er Eu Fm F Fr Gd Ga Ge Au Hf He Ho H In I Ir Fe Kr La Lr Pb Li Lu Mg Mn Md Hg Mo Nd Ne Np Ni Nb

68 63 100 9 87 64 31 32 79 72 2 67 1 49 53 77 26 36 57 103 82 3 71 12 25 101 80 42 60 10 93 28 41

167.26 151.96 (257) 18.9984 (223) 157.25 69.72 72.59 196.967 178.49 4.00260 164.930 1.0079 114.82 126.905 192.22 55.847 83.80 138.906 (260) 207.2 6.941 174.967 24.305 54.9380 (258) 200.59 95.94 144.24 20.179 237.048 58.69 92.9064

9.16 5.24

1500 826

2900 1440

167 138

1.11 (85 K) 7.95 5.91 5.35 19.3 13.3 0.147 (4 K) 8.80 0.070 (20 K) 7.30 4.93 22.5 7.86 2.16 (121 K) 6.19

−220 (27) 1310 29.8 937 1063 2220 −270 1460 −259 157 114 2440 1535 −157 920

−188 (680) 3000 2400 2830 2970 5400 −269 2600 −252 2000 184 5300 3000 −152 3470

824 (140) 234 381 322 130 146 5.19 × 103 163 1.43 × 104 238 218 134 448 247 201

11.3 0.53 9.84 1.74 7.20

327 180 1650 650 1240

1744 1330 3330 1110 2100

130 3.39 × 103 155 1.03 × 103 477

13.6 10.2 7.00 1.20 (27 K) 20.4 8.90 8.57

−38.9 2610 1020 −249 640 1453 2470

357 5560 3030 −246

138 251 188 1.03 × 103

2730 3300

439 264

3 2, 3 3 1 1 3 3 4 1, 3 4 3 1 1, 3 1, 3, 5, 7 2, 3, 4, 6 2, 3, 6 2 3 2, 4 1 3 2 2, 3, 4, 6, 7 3 1, 2 2, 3, 4, 5, 6 3 3, 4, 5, 6 2, 3 3, 5 (Continued)

1.125

1.126 TABLE 1.19 Physical Properties of the Elements (Continued) Relative atomic mass

Symbol

Atomic number

Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus

N No Os O Pd P

7 102 76 8 46 15

14.0067 (259) 190.2 15.9994 106.42 30.9738

Platinum Plutonium Polonium Potassium Praseodymium Promethium Protoactinium Radium Radon Rhenium Rhodium Rubidium Ruthenium Samarium Scandium Selenium Silicon Silver Sodium Strontium Sulphur (a, rhombic)

Pt Pu Po K Pr Pm Pa Ra Rn Re Rh Rb Ru Sm Sc Se Si Ag Na Sr S

78 94 84 19 59 61 91 88 86 75 45 37 44 62 21 34 14 47 11 38 16

195.08 (244) (209) 39.0983 140.908 (145) 231.036 226.025 (222) 186.207 102.906 85.4678 101.07 150.36 44.9559 78.96 28.0855 107.868 22.9898 87.62 32.06

Tantalum Technetium Tellurium

Ta Tc Te

73 43 52

180.948 (98) 127.60

Element

r/g cm−3 0.808 (77 K) 22.5 1.15 (90 K) 12.0 1.82 (white) 2.34 (red) 21.4 19.8 9.4 0.86 6.78 15.4 5.0 4.4 (211 K) 20.5 12.4 1.53 12.3 7.54 2.99 4.81 2.33 10.5 0.97 2.62 2.07 (a) 1.96 (b) 16.6 11.5 6.25

qC,m/°C

qC,b/°C

cp/J kg−1 K−1

Oxidation states

−210

−196

1.04 × 103

1, 2, 3, 4, 5

3000 −218 1550 44.2 (white) 590 (red) 1769 640 254 63.7 935 1030 1230 700 −71 3180 1970 38.9 2500 1070 1540 217 1410 961 97.8 768 113 (a) 119 (b) 3000 2200 450

5000 −183 3980 280 (white)

130 916 243 757 (white) 670 (red) 134

2, 3, 4, 6, 8 2 2, 4 3, 5

4530 3240 960 774 3130 2730

2, 4, 6 3, 4, 5, 6 2, 4 1 3, 4 3 4, 5 2

1140 −61.8 5630 4500 688 4900 1900 2730 685 2360 2210 890 1380 445

126 753 192 184 121 121 92 138 243 360 238 197 556 322 711 234 1.23 × 103 284 732

2, 4, 5, 6, 7 2, 3, 4 1 3, 4, 5, 6, 8 2, 3 3 2, 4, 6 4 1 1 2 2, 4, 6

5420 3500 990

138 243 201

5 7 2, 4, 6

Terbium Thallium Thorium Thulium Tin (white)

Tb Tl Th Tm Sn

65 81 90 69 50

158.925 204.383 232.038 168.934 118.71

Titanium Tungsten Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium

Ti W U V Xe Yb Y Zn Zr

22 74 92 23 54 70 39 30 40

47.88 183.85 238.029 50.9415 131.29 173.04 88.9059 65.39 91.224

8.27 11.8 11.7 9.33 7.28 (white) 5.75 (grey) 4.54 19.4 19.1 5.96 3.52 (165 K) 6.98 4.34 7.14 6.49

1360 304 1750 1540 232

2800 1460 3850 1730 2270

184 130 113 159 218

3, 4 1, 3 3, 4 2, 3 2, 4

1675 3410 1130 1900 −112 824 1500 420 1850

3260 5930 3820 3000 −108 1430 2930 907 3580

523 134 117 481 159 146 297 385 276

2, 3, 4 2, 4, 5, 6 3, 4, 5, 6 2, 3, 4, 5 2, 4, 6, 8 2, 3 3 2 2, 3, 4

1.127

1.128 TABLE 1.20 Conductivity and Resistivity of the Elements

Name

Symbol

Atomic number

Electronic configuration

Thermal conductivity, W ⋅ (m ⋅ K)−1 at 25°C

Electrical resistivity, mΩ ⋅ cm at 20°C

Coefficient of linear thermal expansion (25°C), m ⋅ m−1(× 106)

(Continued)

1.129

1.130 TABLE 1.20 Conductivity and Resistivity of the Elements (Continued)

Name

Symbol

Atomic number

Electronic configuration

Thermal conductivity, W ⋅ (m ⋅ K)−1 at 25°C

Electrical resistivity, mΩ ⋅ cm at 20°C

Coefficient of linear thermal expansion (25°C), m ⋅ m−1(× 106)

1.131

1.132

SECTION ONE

TABLE 1.21 Work Functions of the Elements The work function f is the energy necessary to just remove an electron from the metal surface in thermoelectric or photoelectric emission. Values are dependent upon the experimental technique (vacua of 10–9 or 10–10 torr, clean surfaces, and surface conditions including the crystal face identification). Element Ag Al As Au B Ba Be Bi C Ca Cd Ce Co Cr Cs Cu Eu Fe Ga Ge Gd Hf

f, eV

Element

f, eV

Element

f,eV

4.64 4.19 (3.75) 5.32 (4.75) 2.35 5.08 4.36 (5.0) 2.71 4.12 2.80 4.70 4.40 1.90 4.70 2.50 4.65 4.25 5.0 3.1 3.65

Hg In Ir K La Li Mg Mn Mo Na Nb Nd Ni Os Pb Pd Po Pr Pt Rb Re Rh

4.50 4.08 5.6 2.30 3.40 3.10 3.66 3.90 4.30 2.70 4.20 3.1 5.15 4.83 4.18 5.00 4.6 2.7 5.40 2.20 4.95 4.98

Ru Sb Sc Se Si Sm Sn Sr Ta Tb Te Th Ti Tl U V W Y Zn Zr

4.80 4.56 3.5 5.9 4.85 2.95 4.35 2.76 4.22 3.0 4.70 3.71 4.10 4.02 3.70 4.44 4.55 3.1 4.30 4.00

TABLE 1.22 Relative Abundances of Naturally Occurring Isotopes Element Aluminum Antimony Argon

Arsenic Barium

Beryllium Bismuth Boron Bromine

Mass number

Percent

Element

27 121 123 36 38 40 75 130 132 134 135 136 137 138 9 209 10 11 79 81

100 57.21(5) 42.79(5) 0.337(3) 0.063(1) 99.600(3) 100 0.106(2) 0.101(2) 2.42(3) 6.59(2) 7.85(4) 11.23(4) 71.70(7) 100 100 19.9(2) 80.1(2) 50.69(7) 49.31(7)

Cadmium

Calcium

Carbon Cerium

Mass number 106 108 110 111 112 113 114 116 40 42 43 44 46 48 12 13 136 138 140 142

Percent 1.25(4) 0.89(2) 12.49(12) 12.80(8) 24.13(14) 12.22(8) 28.7(3) 7.49(9) 96.941(18) 0.647(9) 0.135(6) 2.088(12) 0.004(3) 0.187(4) 98.89(1) 1.11(1) 0.19(1) 0.25(1) 88.43(10) 11.13(10)

INORGANIC CHEMISTRY

1.133

TABLE 1.22 Relative Abundances of Naturally Occurring Isotopes (Continued) Element Cesium Chlorine Chromium

Cobalt Copper Dysprosium

Erbium

Europium Fluorine Gadolinium

Gallium Germanium

Gold Hafnium

Helium Holmium Hydrogen Indium

Mass number

Percent

Element

133 35 37 50 52 53 54 59 63 65 156 158 160 161 162 163 164 162 164 166 167 168 170 151 153 19 152 154 155 156 157 158 160 69 71 70 72 73 74 76 197 174 176 177 178 179 180 4 165 1 2 113 115

100 75.77(7) 24.23(7) 4.345(13) 83.79(2) 9.50(2) 2.365(7) 100 69.17(3) 30.83(3) 0.06(1) 0.10(1) 2.34(6) 18.9(2) 25.5(2) 24.9(2) 28.2(2) 0.14(1) 1.61(2) 33.6(2) 22.95(15) 26.8(2) 14.9(2) 47.8(5) 52.2(5) 100 0.20(1) 2.18(3) 14.80(5) 20.47(4) 15.65(3) 24.84(12) 21.86(4) 60.108(9) 39.892(9) 21.23(4) 27.66(3) 7.73(1) 35.94(2) 7.44(2) 100 0.162(3) 5.206(5) 18.606(13) 27.297(4) 13.629(6) 35.100(7) 100 100 99.985(1) 0.015(1) 4.29(2) 95.71(2)

Iodine Iridium Iron

Krypton

Lanthanum Lead

Lithium Lutetium Magnesium

Manganese Mercury

Molybdenum

Neodymium

Neon

Nickel

Mass number

Percent

127 191 193 54 56 57 58 78 80 82 83 84 86 138 139 204 206 207 208 6 7 175 176 24 25 26 55 196 198 199 200 201 202 204 92 94 95 96 97 98 100 142 143 144 145 146 148 150 20 21 22 58 60

100 37.27(9) 62.73(9) 5.85(4) 91.75(4) 2.12(1) 0.26(1) 0.35(2) 2.25(2) 11.6(1) 11.5(1) 57.0(3) 17.3(2) 0.0902(2) 99.9098(2) 1.4(1) 24.1(1) 22.1(1) 52.4(1) 7.5(2) 92.5(2) 97.41(2) 2.59(2) 78.99(3) 10.00(1) 11.01(2) 100 0.15(1) 9.97(8) 16.87(10) 23.10(16) 13.18(8) 29.86(20) 6.87(4) 14.84(4) 9.25(3) 15.92(5) 16.68(5) 9.55(3) 24.13(7) 9.63(3) 27.13(12) 12.18(6) 23.80(12) 8.30(6) 17.19(9) 5.76(3) 5.64(3) 90.48(3) 0.27(1) 9.25(3) 68.077(9) 26.223(8) (Continued)

1.134

SECTION ONE

TABLE 1.22 Relative Abundances of Naturally Occurring Isotopes (Continued) Element

Niobium Nitrogen Osmium

Oxygen

Palladium

Phosphorus Platinum

Potassium

Praseodymium Protoactinium Rhenium Rhodium Rubidium Ruthenium

Samarium

Mass number

Percent

61 62 64 93 14 15 184 186 187 188 189 190 192 16 17 18 102 104 105 106 108 110 31 190 192 194 195 196 198 39 40 41 141 230 185 187 103 85 87 96 98 99 100 101 102 104 144 147 148 149 150 152

1.140(1) 3.634(2) 0.926(1) 100 99.634(9) 0.366(9) 0.020(3) 1.58(2) 1.6(4) 13.3(1) 16.1(1) 26.4(2) 41.0(3) 99.76(1) 0.04 0.20(1) 1.02(1) 11.14(8) 22.33(8) 27.33(3) 26.46(9) 11.72(9) 100 0.01(1) 0.79(6) 32.9(6) 33.8(6) 25.3(6) 7.2(2) 93.258(4) 0.0117(1) 6.730(3) 100 100 37.40(2) 62.60(2) 100 72.17(2) 27.83(2) 5.52(6) 1.88(6) 12.7(1) 12.6(1) 17.0(1) 31.6(2) 18.7(2) 3.1(1) 15.0(2) 11.3(1) 13.8(1) 7.4(1) 26.7(2)

Element Scandium Selenium

Silicon

Silver Sodium Strontium

Sulfur

Tantalum Tellurium

Terbium Thallium Thorium Thullium Tin

Titanium

Mass number

Percent

154 45 74 76 77 78 80 82 28 29 30 107 109 23 84 86 87 88 32 33 34 36 180 181 120 122 123 124 125 126 128 130 159 203 205 228 169 112 114 115 116 117 118 119 120 122 124 46 47 48 49 50

22.7(2) 100 0.89(2) 9.36(11) 6.63(6) 23.78(9) 49.61(10) 8.73(6) 92.23(2) 4.67(2) 3.10(1) 51.839(7) 48.161(7) 100 0.56(1) 9.86(1) 7.00(1) 82.58(1) 95.02(9) 0.75(4) 4.21(8) 0.02(1) 0.012(2) 99.988(2) 0.096(2) 2.603(4) 0.908(2) 4.816(6) 7.139(6) 18.952(11) 31.687(11) 33.799(10) 100 29.52(1) 70.48(1) 100 100 0.97(1) 0.65(1) 0.34(1) 14.53(11) 7.68(7) 24.23(11) 8.59(4) 32.59(10) 4.63(3) 5.79(5) 8.25(3) 7.44(2) 73.72(3) 5.41(2) 5.4(1)

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TABLE 1.22 Relative Abundances of Naturally Occurring Isotopes (Continued) Element Tungsten

Uranium

Vanadium Xenon

Ytterbium

Mass number

Percent

180 182 183 184 186 234 235 238 50 51 124 126 128 129 130 131 132 134 136 168

0.12(1) 26.50(3) 14.31(1) 30.64(1) 28.43(4) 0.0055(5) 0.720(1) 99.275(2) 0.250(2) 99.750(2) 0.10(1) 0.09(1) 1.91(3) 26.4(6) 4.1(1) 21.2(4) 26.9(5) 10.4(2) 8.9(1) 0.13(1)

Element

Yttrium Zinc

Zirconium

Mass number 170 171 172 173 174 176 89 64 66 67 68 70 90 91 92 94 96

Percent 3.05(6) 14.3(2) 21.9(3) 16.12(2) 31.8(4) 12.7(2) 100 48.6(3) 27.9(2) 4.1(1) 18.8(4) 0.6(1) 51.45(3) 11.22(4) 17.15(2) 17.38(4) 2.80(2)

TABLE 1.23 Radioactivity of the Elements (Neptunium Series) Element Plutonium ↓ Americium ↓ Neptunium ↓ Protactinium ↓ Uranium ↓ Thorium ↓ Radium ↓ Actinium ↓ Francium ↓ Astatine ↓

Symbol 241

Radiation

Half-life

Pu

b

13.2 years

Am

a

462 years

a

2.20 × 106 years

b

27.4 days

U

a

1.62 × 105 years

229

Th

a

7.34 × 103 years

225

Ra

b

14.8 days

Ac

a

10.0 days

Fr

a

4.8 min

At

a

1.8 × 10−2 sec

241

237

Np

233

Pa

233

225

221

217

(Continued)

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SECTION ONE

TABLE 1.23 Radioactivity of the Elements (Neptunium Series) (Continued) Element Bismuth 98% | 2% −−−−−−−−−−−−| ↓ | Polonium ↓ | Thallium | |____________| ↓ Lead ↓ Bismuth (End Product)

Symbol

Radiation

Half-life

213

Bi

b and a

213

Po

a

4.2 × 10−6 sec

Tl

b

2.2 min

Pb

b

3.32 hr

Stable

—

209

209

209

Bi

47 min

TABLE 1.24 Radioactivity of the Elements (Thorium Series) Radioelement Thorium ↓ Mesothorium I ↓ Mesothorium II ↓ Radiothorium ↓ Thorium X ↓ Th Emanation ↓ Thorium A ↓ Thorium B ↓ Thorium C 66.3% | 33.7% −−−−−−−−−−−−| ↓ | Thorium C′ ↓ | Thorium C′′ | |____________| ↓ Thorium D (End Product)

Corresponding element

Symbol

Radiation

Half-life

Thorium

232

a

1.39 × 1010 years

Radium

228

Ra

b

6.7 years

Actinium

228

Ac

b

6.13 hr

Thorium

228

a

1.91 years

Radium

224

Ra

a

3.64 days

Radon

220

Rn

a

52 sec

Polonium

216

a

0.16 sec

Lead

212

b

10.6 hr

Bismuth

212

Bi

b and a

Polonium

212

Po

a

3 × 10−7 sec

Thallium

208

Tl

b

3.1 min

Lead

208

Pb

Stable

—

Th

Th

Po Pb

60.5 min

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TABLE 1.25 Radioactivity of the Elements (Actinium Series) Radioelement Actinouranium ↓ Uranium Y ↓ Protactinium ↓ Actinium 98.8% | 1.2% −−−−−−−−−−−−| ↓ Radioactinium | ↓ | Actinium K | |____________| ↓ Actinium X ↓ Ac Emanation ↓ Actinium A ⵑ100% | ⵑ5 × 10−4% −−−−−−−−−−−−| ↓ | Actinium B ↓ | Astatine-215 | |____________| ↓ Actinium C 99.7% | 0.3% |−−−−−−−−−−−−↓ | Actinium C′ ↓ Actinium C′′ |____________| ↓ Actinium D (End Product)

Corresponding element

Symbol

Radiation

Half-life

Uranium

235

a

7.13 × 108 years

Thorium

231

b

25.6 hr

Protactinium

231

a

3.43 × 104 years

Actinium

227

b and a

21.8 years

Thorium

227

a

18.4 days

Francium

223

b

21 min

Radium

223

a

11.7 days

Radon

219

a

3.92 sec

Polonium

215

a and b

Lead

211

b

36.1 min

Astatine

215

a

ⵑ10−4 sec

Bismuth

211

a and b

2.16 min

Polonium

211

a

0.52 sec

Thallium

207

b

4.8 min

Lead

207

Stable

U Th Pa Ac

Th Fr

Ra Rn Po

Pb At

Bi

Po Tl Pb

1.83 × 10−3 s

—

TABLE 1.26 Radioactivity of the Elements (Uranium Series) Radioelement Uranium I ↓ Uranium X1 ↓ Uranium X2* ↓ Uranium II ↓ Ionium ↓ Radium ↓

Corresponding element

Symbol

Radiation

Half-life

Uranium

238

a

4.51 × 109 years

Thorium

234

b

24.1 days

Protactinium

234

b

1.18 min

Uranium

234

a

2.48 × 105 years

Thorium

230

a

8.0 × 104 years

Radium

226

a

1.62 × 103 years

U Th Pa U Th Ra

(Continued)

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TABLE 1.26 Radioactivity of the Elements (Uranium Series) (Continued) Corresponding element

Radioelement Ra Emanation ↓ Radium A 99.98% | 0.02% −−−−−−−−−−−−| ↓ | Radium B ↓ | Astatine-218 | |____________| ↓ Radium C 99.96% | 0.04% −−−−−−−−−−−−| ↓ | Radium C′ ↓ | Radium C′′ | |____________| ↓ Radium D ↓ Radium E ⵑ100% | 2 × 10−4% −−−−−−−−−−−−| ↓ | Radium F ↓ | Thallium-206 | |____________| ↓ Radium G (End Product)

Symbol

Radiation

Half-life

Radon

222

a

3.82 days

Polonium

218

a and b

3.05 min

Lead

214

b

26.8 min

Astatine

218

a

2 sec

Bismuth

214

b and a

Polonium

214

a

1.6 × 10−4 sec

Thallium

210

b

1.32 min

Lead

210

b

19.4 years

Bismuth

210

b and a

Polonium

210

a

138.4 days

Thallium

206

b

4.20 min

Lead

206

Stable

—

Rn Po

Pb At Bi

Po Tl

Pb Bi

Po Tl Pb

19.7 min

5.0 days

*Uranium X2 is an excited state of 234Pa and undergoes isomeric transition to a small extent to form uranium Z (234Pa in its ground state); the latter has a half-life of 6.7 h, emitting beta radiation and forming uranium II (234U).

1.4 IONIZATION ENERGY TABLE 1.27 Ionization Energy of the Elements The minimum amount of energy required to remove the least strongly bound electron from a gaseous atom (or ion) is called the ionization energy and is expressed in MJ ⋅ mol–1. At. no.

Spectrum (in MJ ⋅ mol−1) Element

I

II

III

IV

V

VI

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TABLE 1.27 Ionization Energy of the Elements (Continued) At. no.

Spectrum (in MJ ⋅ mol−1) Element

I

II

III

IV

V

VI

(Continued)

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TABLE 1.27 Ionization Energy of the Elements (Continued) At. no.

Spectrum (in MJ ⋅ mol−1) Element

I

II

III

IV

V

VI

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TABLE 1.28 Ionization Energy of Molecular and Radical Species Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

(Continued)

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TABLE 1.28 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

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TABLE 1.28 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In Mj ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

(Continued)

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TABLE 1.28 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In Mj ⋅ mol−1

Source: Sharon, G., et al., J. Phys. Chem. Ref. Data, 17:Suppl. No 1 (1988).

In electron volts

∆f H (ion) in kJ ⋅ mol−1

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1.5 ELECTRONEGATIVITY Electronegativity c is the relative attraction of an atom for the valence electrons in a covalent bond. It is proportional to the effective nuclear charge and inversely proportional to the covalent radius:

χ=

0.31(n + 1 ± c) + 0.50 r

where n is the number of valence electrons, c is any formal valence charge on the atom and the sign before it corresponds to the sign of this charge, and r is the covalent radius. Originally the element fluorine, whose atoms have the greatest attraction for electrons, was given an arbitrary electronegativity of 4.0. A revision of Pauling’s values based on newer data assigns −3.90 to fluorine. Values in Table 1.29 refer to the common oxidation states of the elements.

TABLE 1.29 Electronegativity Values of the Elements H 2.20 Li 0.98

Be 1.57

B C 2.04 2.55

N O F 3.04 3.44 3.90

Na 0.93

Mg 1.31

Al Si 1.61 1.90

P S Cl 2.19 2.58 3.16

K 0.82

Ca 1.00

Sc Ti V Cr Mn Fe Co Ni Cu 1.36 1.54 1.63 1.66 1.55 1.83 1.88 1.91 1.90

Zn Ga 1.65 1.81

Ge As Se Br 2.01 2.18 2.55 2.96

Rb 0.82

Sr 0.95

Y Zr 1.22 1.33

Nb 1.6

Mo Tc 2.16 2.10

Ru 2.2

Rh Pd Ag 2.28 2.20 1.93

Cd In 1.69 1.78

Sn Sb 1.96 2.05

Te 2.1

I 2.66

Cs 0.79

Ba 0.89

La 1.10

Ta 1.5

W 1.7

Os 2.2

Ir 2.2

Hg 1.9

Pb 1.8

Po 2.0

At 2.2

Fr 0.7

Ra 0.9

Ac 1.1

Hf 1.3

Lanthanides

Ce Pr Nd 1.12 1.13 1.14

Actinides

Th 1.3

Pa 1.5

U 1.7

Re 1.9

Sm 1.17 Np 1.3

Pu 1.3

Pt 2.2

Au 2.4

Gd 1.20 Am 1.3

Cm 1.3

Bk 1.3

Tl 1.8

Bi 1.9

Dy Ho 1.22 1.23

Er Tm 1.24 1.25

Cf 1.3

Fm 1.3

Es 1.3

Md 1.3

Lu 1.0 No 1.3

The greater the difference is electronegativity, the greater is the ionic character of the bond. The amount of ionic character I is given by: I = 0.46 | cA – cB | + 0.035(cA – cB)2 The bond is fully covalent when (cA – cB) < 0.5 (and I < 6%).

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1.6 ELECTRON AFFINITY TABLE 1.30 Electron Affinities of Elements, Molecules, and Radicals Electron affinity of an atom (molecule or radical) is defined as the energy difference between the lowest (ground) state of the neutral and the lowest state of the corresponding negative ion in the gas phase. A(g) + e– = A–(g) Data are limited to those negative ions which, by virtue of their positive electron affinity, are stable. Uncertainty in the final data figures is given in parentheses. Calculated values are enclosed in brackets.

Electron affinity, Atom

Next Page INORGANIC CHEMISTRY

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TABLE 1.30 Electron Affinities of Elements, Molecules, and Radicals (Continued)

Electron affinity, Atom

Electron affinity, Molecule

(Continued)

Previous Page 1.148

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TABLE 1.30 Electron Affinities of Elements, Molecules, and Radicals (Continued)

Electron affinity, Molecule

Electron affinity Radical

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TABLE 1.30 Electron Affinities of Elements, Molecules, and Radicals (Continued) C. Radical Electron affinity, Radical

(Continued)

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TABLE 1.30 Electron Affinities of Elements, Molecules, and Radicals (Continued) C. Radical Electron affinity, Radical

Source: H. Hotop and W. C. Lineberger, J. Phys. Chem. Reference Data 14:731 (1985).

1.7 BOND LENGTHS AND STRENGTHS Distances between centers of bonded atoms are called bond lengths, or bond distances. Bond lengths vary depending on many factors, but in general, they are very consistent. Of course the bond orders affect bond length, but bond lengths of the same order for the same pair of atoms in various molecules are very consistent. The bond order is the number of electron pairs shared between two atoms in the formation of the bond. Bond order for C=C and O=O is 2. The amount of energy required to break a bond is called bond dissociation energy or simply bond energy. Since bond lengths are consistent, bond energies of similar bonds are also consistent. Bonds between the same type of atom are covalent bonds, and bonds between atoms when their electronegativity differs slightly are also predominant covalent in character. Theoretically, even ionic bonds have some covalent character. Thus, the boundary between ionic and covalent bonds is not a clear line of demarcation.

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For covalent bonds, bond energies and bond lengths depend on many factors: electron affinities, sizes of atoms involved in the bond, differences in their electronegativity, and the overall structure of the molecule. There is a general trend in that the shorter the bond length, the higher the bond energy but there is no formula to show this relationship, because of the widespread variation in bond character.

1.7.1 Atom Radius The atom radius of an element is the shortest distance between like atoms. It is the distance of the centers of the atoms from one another in metallic crystals and for these materials the atom radius is often called the metal radius. Except for the lanthanides (CN = 6), CN = 12 for the elements. 1.7.2 Ionic Radii One of the major factors in determining the structures of the substances that can be thought of as made up of cations and anions packed together is ionic size. It is obvious from the nature of wave functions that no ion has a precisely defined radius. However, with the insight afforded by electron density maps and with a large base of data, new efforts to establish tables of ionic radii have been made. Effective ionic radii are based on the assumption that the ionic radius of O2– (CN 6) is 140 pm and that of F– (CN 6) is 133 pm. Also taken into consideration is the coordination number (CN) and electronic spin state (HS and LS, high spin and low spin) of first-row transition metal ions. These radii are empirical and include effects of covalence in specific metal-oxygen or metal-fluorine bonds. Older “crystal ionic radii” were based on the radius of F– (CN 6) equal to 119 pm; these radii are 14–18 percent larger than the effective ionic radii.

1.7.3 Covalent Radii Covalent radii are the distance between two kinds of atoms connected by a covalent bond of a given type (single, double, etc.).

TABLE 1.31 Atom Radii and Effective Ionic Radii of Elements Effective ionic radii, pm Coordinator number

(Continued)

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TABLE 1.31 Atom Radii and Effective Ionic Radii of Elements (Continued) Effective ionic radii, pm Coordinator number

*CN = 3

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TABLE 1.31 Atom Radii and Effective Ionic Radii of Elements (Continued) Effective ionic radii, pm Coordinator number

*CN = 10

(Continued)

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TABLE 1.31 Atom Radii and Effective Ionic Radii of Elements (Continued) Effective ionic radii, pm Coordinator number

*CN = 3 †CN = 7

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TABLE 1.31 Atom Radii and Effective Ionic Radii of Elements (Continued) Effective ionic radii, pm Coordinator number

(Continued)

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TABLE 1.31 Atom Radii and Effective Ionic Radii of Elements (Continued) Effective ionic radii, pm

Element

*CN = 11

Atom radius, pm

Coordinator number Ion Charge

4

6

8

12

TABLE 1.32 Approximate Effective Ionic Radii in Aqueous Solutions at 25°C å (in Å)

Inorganic ions −

−

− −

å (in Å)

Organic ions

1.157

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TABLE 1.33 Covalent Radii for Atoms Element Aluminum Antimony Arsenic Beryllium Boron Bromine Cadmium Carbon Chlorine Copper Fluorine Gallium Germanium Hydrogen Indium Iodine Magnesium Mercury Nitrogen Oxygen Phosphorus Silicon Selenium Silver Sulfur Tellurium Tin Zinc

Single-bond radius, pm* 126 141 121 106 88 114 148 77.2 99 135 64 126 122 30 144 133 140 148 70 66 110 117 117 152 104 137 140 131

Double-bond radius, pm 131 111

104 66.7 89

60.3

54 112

123

60 55 100 107 107 94 127 130

* Single-bond radii are for a tetrahedral (CN = 4) structure.

TABLE 1.34 Octahedral Covalent Radii for CN = 6

Triple-bond radius, pm

55 93 100

87

TABLE 1.35 Bond Lengths between Elements Elements

Bond type

Bond Length, pm

Elements

Bond type

B-B B-Br B-Cl B-F B-H B-N B-O

B2H6 BBr3 BCl3 BF3, R2BF Boranes Bridge Borazoles B(OH)3, (RO)3B

H-Al H-As H-Be H-Br H-Ca H-Cl H-F H-Ge H-I H-K H-Li H-Mg H-Na H-Sb H-Se H-Sn D-Br D-C1 D-I T-Br T-Cl

AlH AsH3 BeH HBr CaH HCl HF GeH4 HI KH LiH MgH NaH H3Sb H2Se SnH4 DBr (2HBr) DCl DI TBr (3HBr) TCl

177(1) 187(2) 172(1) 129(1) 121(2) 139(2) 142(1) 136(5)

O-H

O-O

Hydrogen 164.6 151.9 134.3 140.8 200.2 127.4 91.7 153 160.9 224.4 159.5 173.1 188.7 170.7 146.0 170.1 141.44 127.46 161.65 141.44 127.40

O-Al O-As O-Ba O-Cl O-Mg O-Os O-Pb

N-D N-N

N-O N˙O N-Si

NO2Cl NF3 NH+4 NH3, RNH2 H2NNH2 R[CO[NH2 HN˙C˙S ND (N2H) HN3 R2NNH2 N2O N+2 NO2Cl RO[NO2 NO2 N2O RNO2 NO+ SiN

179(2) 136(2) 103.4(3) 101.2 103.8 99(3) 101.3(3) 104.1 102(1) 145.1(5) 112.6(2) 111.6 124(1) 136(2) 118.8(5) 118.6(2) 122(I) 106.19 157.2

H2O ROH OH+ HOOH D2O (2H2O) OD HO[OH O+2 O−2 O2− 3 O3 AlO As2O6 bridges BaO ClO2 OCl2 MgO OsO4 PbO

95.8 97(1) 102.89 96.0(5) 95.75 96.99 148(1) 122.7 126(2) 149(2) 127.8(5) 161.8 179 190.0 148.4 168 174.9 166 193.4

Phosphorus P-Br P-Cl P-F P-H P-I P-N P-O P-S

Nitrogen N-Cl N-F N-H

Bond Length, pm

Oxygen

Boron

P-C

PBr3 PCl3 PFCl2 PH3, PH+4 PI3 Single bond Single bond p3 bonding sp3 bonding p3 bonding sp3 bonding In rings Single bond p3 bonding

223(1) 200(2) 155(3) 142.4(5) 252(1) 149.1 144.7 167 154(4) 212(5) 208(2) 220(3) 156.2 187(2)

Silicon Si-Br Si-Cl Si-F Si-H Si-I Si-O Si-Si

SiBr4, R3SiBr SiCl4, R3SiCl SiF4, R3SiF SiF6 SiH4 R3SiH Sil4 R3Sil R3SiOR H3SiSiH3

216(1) 201.9(5) 156.1(3) 158 148.0(5) 147.6(5) 234 246(2) 153.3(5) 230(2)

Sulfur S-Br S-Cl S-F S-H S-O S-S

SOBr2 S2Cl2 SOF2 H2S RSH D2S SO2 SOCl2 RSSR

227(2) 158.5(5) 158.5(5) 133.3 132.9(5) 134.5 143.21 145(2) 205(1) 1.159

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TABLE 1.36 Bond Dissociation Energies The bond dissociation energy (enthalpy change) for a bond A—B which is broken through the reaction AB → A + B is defined as the standard-state enthalpy change for the reaction at a specified temperature, here at 298 K. That is,

∆Hf298 = ∆Hf298(A) + ∆Hf298(B) – ∆Hf298(AB) All values refer to the gaseous state and are given at 298 K. Values of 0 K are obtained by subtracting $RT from the value at 298 K. To convert the tabulated values to kcal/mol, divide by 4.184.

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

(Continued)

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

(Continued)

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TABLE 1.36 Bond Dissociation Energies (Continued) Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

(Continued)

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

(Continued)

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

Bond

∆Hf298, kJ/mol

(Continued)

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TABLE 1.36 Bond Dissociation Energies (Continued)

Bond

∆Hf298, kJ/mol

INORGANIC CHEMISTRY

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TABLE 1.36 Bond Dissociation Energies (Continued)

1.8 DIPOLE MOMENTS The dipole moment is the mathematical product of the distance between the centers of charge of two atoms multiplied by the magnitude of that charge. Thus, the dipole moment (m) of a compound or molecule is: m=Q×r where Q is the magnitude of the electrical charge(s) that are separated by the distance r; the unit of measurement is the Debye (D) All bonds between equal atoms are given zero values. Because of their symmetry, methane and ethane molecules are nonpolar. The principle of bond moments thus requires that the CH3 group moment equal one H—C moment. Hence the substitution of any aliphatic H by CH3 does not alter the dipole moment, and all saturated hydrocarbons have zero moments as long as the tetrahedral angles are maintained. TABLE 1.37 Bond Dipole Moments Bond H—C Aliphatic Aromatic C—C C≡≡C C—O Ether, aliphatic Alcohol, aliphatic C==O Aliphatic Aromatic O—H C—S C==S S—H S—O S==O Aliphatic Aromatic

Moment, D* 0.3 0.0 0.0 0.0 0.74 0.7 2.4 2.65 1.51 0.9 2.0 0.65 (0.2) 2.8 3.3

Bond C—N, aliphatic C==N C≡≡N (nitrile) NC (isonitrile) N—H N—O N==O N (lone pair on sp3 N) C—P, aliphatic P—O P==O P—S P==S B—C, aliphatic B—O Se—C Si—C Si—H Si—N

*To convert debye units D into coulomb-meters, multiply by 3.33564 × 10−30.

Moment, D* 0.45 1.4 3.6 3.0 1.31 0.3 2.0 1.0 0.8 (0.3) 2.7 0.5 2.9 0.7 0.25 0.7 1.2 1.0 1.55

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TABLE 1.38 Group Dipole Moments Bond

Moment, D*

Bond

Moment, D*

*To convert debye units D into coulomb-meters, multiply by 3.33564 × 10−30.

The group moment always includes the C—X bond. When the group is attached to an aromatic system, the moment contains the contributions through resonance of those polar structures postulated as arising through charge shifts around the ring.

1.8.1 Dielectric Constant The dielectric constant (also referred to as the relative permittivity, K ) is the ratio of the permittivity of the material to the permittivity of free space and is the property of a material that determines the relative speed with which an electrical signal will travel in that material. − /C − K=C T 0

Signal speed is roughly inversely proportional to the square root of the dielectric constant. A low dielectric constant will result in a high signal propagation speed and a high dielectric constant will result in a much slower signal propagation speed. The dielectric loss factor is the tangent of the loss angle and the loss tangent (tan ∆) is defined by the relationship: tan ∆ = 2s/e u s is the electrical conductivity, e is the dielectric constant, and u is the frequency. The loss tangent is roughly wavelength independent.

1.173

INORGANIC CHEMISTRY

TABLE 1.39 Dipole Moments and Dielectric Constants Substance Air AlBr3 Ar (g) (lq) AsBr3 AsCl3 AsH3 (arsine) BBr3 BCl3 BF3 B2H6 (diborane) B4H10 B5H9 B6H10 B3H6N3 Br2 (g) (lq) BrF3 BrF5 Cl2 (g) (lq) ClF3 ClF5 ClO3F CO (g) (lq) CO2 (g) (lq) COCl2 COF2 COS COSe CS CS2 (g) (lq) CrO2Cl2 D2 (deuterium) DH D2O F2 GaCl3 GeBr4 GeBr4 GeCl4

Dielectric constant, e 1.000 536 4 3.38100 1.000 517 2 1.538−191, 1.325−132 8.8335 12.620 2.40−72, 2.0520 2.580 1.872−92.5 21.125 1.012820 3.148425 106.825 7.9124.5 2.147−65, 1.9114 4.39420, 4.2925 4.28−80 2.194−123 1.000 700 1.000 922 1.60°C, 50 atm, 1.44923 4.3422 4.47−88 3.4710 1.00290 2.63220 2.620 1.290−255, 1.277−253 1.26916.78 K 79.7520, 78.2525 1.491−220, 1.54−202

Dipole moment, D 5.2

0 1.61 1.59 0.20 0 0 0 0 0.486 2.13 2.50 0 0 1.1 1.51 0

0.554 0.023 0.112 0

1.17 0.95 0.712 0.73 1.98 0 0.47

1.87

0.85 2.95526 2.4630, 2.43025

0

Substance GeClH3 H2(g) t (lq) HBr(g) (lq) He (g) (lq) (II) (III) (IV) HCl (g) (lq)

Dielectric constant, e 1.000 253 8 1.27913.5 K, 1.22820.4 K 1.003 130 8.23−86, 3.8225 1.000 0565 0 1.0552.055 K 1.00460 14.3−114, 4.6028

HClO HCN 114.920 HCNO (isocyanate) HCNS HF 83.60 HFO HI (g) 1.002 340 (lq) 3.87−53, 2.9022 HN3 (azide) H2O (see Table 1.12) H2O2 84.20, 74.617 HNO3 H2S (g) 1.00400 (lq) 5.9310 H2Se HSO3Cl 6060 HSO3F ca. 12025 H2SO4 10025 H2Te Hg I2 IBr IF IF5 IF7 IOF5 Kr (g) (lq) Mn2O7 Ne (g) (lq) N2 (g) (lq) NH3 (g) (lq)

11.1118 37.1320 1.9723 1.7525 1.644−153.4 3.2820 1.000 063 920 1.1907−247.1 1.000 548 020 1.468−210, 1.454−203 1.00720 22.4−33.5 16.6120

Dipole moment, D 2.13 0

0.827 0

1.109

1.3 2.98 1.6 1.7 1.826 2.23 0.448 1.70 1.573 2.17 0.97 0.24

<0.2 0 0 0.726 1.95 2.18 <0.05

0 0

1.471

(Continued)

1.174

SECTION ONE

TABLE 1.39 Dipole Moments and Dielectric Constants (Continued) Substance N2H4 (hydrazine) Ni(CO)4 NO N2O (g) (lq) NO2 N2O4 N2O3 NOBr NOCl NO2Cl NOF NO2F NO3 O2 (g) (lq) O3 OF2 O2F2 (FOOF) OsO4 P (lq) PBr3 PCl3 PCl5 PCl2F3 PCl3F2 PCl4F PF3 PF5 PH3 PI3 PO3 POCl3 POF3 PSCl3 PSF3 PbCl4 ReO2Cl3 ReO3Cl S SCl2

Dielectric constant, e 52.920, 51.725 1.001 130 1.5215 2.5625, 2.4420 15

13.4 18.212

31.13−70 1.000 494 720 1.568−218.7, 1.507−193 4.75−183

4.09634 3.920 3.4325, 3.5017 2.85160, 2.7165 2.813−45 2.375−5 2.650.5 2.915 4.1265 13.725 5.822

Dipole moment, D 1.75 0.159 0.161 0.316 0.5 2.122 1.8 1.9 0.53 1.73 0.47 0

0.534 0.297 1.44 0 0.56 0.78 0.9

1.03 0 0.574 0 2.54 1.868 1.42 0.64

2.7820 3.499134 2.91525

Substance S2Cl2 dimer S2F2 FSSF isomer S = SF2 isomer SF4 SF6 S2F10 SO2 (g) (lq) SO3 SOBr2 SOCl2 SOF2 SO2Cl2 SO2F2 SbCl3 SbCl5 SbF5 SbH3 Se (lq) SeF4 SeF6 SeOCl2 SeO2 SiCl4 SiF4 SiH4 SiHCl3 SiH3Cl SnBr4 SnCl4 TeF6 TiCl4 UF6 (g) (lq) VCl4 VOBr3 VOCl3 Xe (g) (lq, II) XeF6

Dielectric constant, e

Dipole moment, D

4.7915

1.0

1.81−50

1.45 1.03 0.632 0

2.02020 1.00930 16.325 3.1118 9.0620 9.2520, 8.67525 9.1520 33.275 3.2220

0 1.63 0 9.11 1.45 1.63 1.81 1.12 3.93 0 0.12

5.44237.5 46.220 2.2480

3.16930 3.0140, 2.8920 2.84314, 2.8020 1.002 9267 2.1865 3.0525 3.625 3.425 1.001 23 1.880−111.9 4.10125

1.78 0 2.64 2.62 0 0 0 0.86 1.31 0 0 0 0 0 0 0.3 0

0.36

1.9 MOLECULAR GEOMETRY Molecular geometry is the specific three-dimensional arrangement of atoms and the positions of the atomic nuclei in a molecule. Various instrumental techniques such as x-ray crystallography and other experimental techniques can be used to derive information about the locations of atoms in a molecule. Thus, molecular geometry is associated with the specific orientation of bonding atoms. A careful analysis of electron distribution in various orbitals will usually result in correct determination of the molecular geometry.

INORGANIC CHEMISTRY

1.175

TABLE 1.40 Spatial Orientation of Common Hybrid Bonds On the assumption that the pairs of electrons in the valency shell of a bonded atom in a molecule are arranged in a definite way which depends on the number of electron pairs (coordination number), the geometrical arrangement or shape of molecules may be predicted. A multiple bond is regarded as equivalent to a single bond as far as molecular shape is concerned. Coordination number

Orbitals hybridized

Geometrical arrangement

Minimum radius ratio

1.176

SECTION ONE

TABLE 1.41 Crystal Lattice Types

INORGANIC CHEMISTRY

1.177

TABLE 1.42 Crystal Structure Unit cells of the different lattice types in each system are illustrated in Table 1.41

System

Characteristics

Essential symmetry

Axes in unit cell

Angles in unit cell

1.10 NUCLIDES The nuclide is the nucleus of a particular isotope. TABLE 1.43 Table of Nuclides Explanation of Column Headings Nuclide. Each nuclide is identified by element name and the mass number A, equal to the sum of the numbers of protons Z and neutrons N in the nucleus. The m following the mass number (for example, 69mZn) indicates a metastable isotope. An asterisk preceding the mass number indicates that the radionuclide occurs in nature. Half-life. The following abbreviations for time units are employed: y = years, d = days, h = hours, min = minutes, s = seconds, ms = milliseconds, and ns = nanoseconds. Natural abundance. The natural abundances listed are on an “atom percent” basis for the stable nuclides present in naturally occurring elements in the earth’s crust. Thermal neutron absorption cross section. Simply designated “cross section,” it represents the ease with which a given nuclide can absorb a thermal neutron (energy less than or equal to 0.025 eV) and become a different nuclide. The cross section is given here in units of barns (1 barn = 10–24 cm2). If the mode of reaction is other than (n, g), it is so indicated. Major radiations. In the last column are the principal modes of disintegration and energies of the radiations in million electronvolts (MeV). Symbols used to represent the various modes of decay are: a, alpha particle emission b–, beta particle, negatron b+, positron g, gamma radiation

K, electron capture IT, isomeric transition x, X-rays of indicated element (e.g., O-x, oxygen X-rays, and the type, K or L)

For b – and b +, values of Emax are listed. Radiation types and energies of minor importance are omitted unless useful for identification purposes. (Continued)

1.178

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.179

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.180

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.181

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.182

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.183

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.184

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.185

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.186

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.187

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.188

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.189

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.190

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.191

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.192

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.193

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

†Two different metastable states possessing the same mass number but different half-lives.

Radiation (MeV)

(Continued)

1.194

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.195

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.196

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.197

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

(Continued)

1.198

SECTION ONE

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

INORGANIC CHEMISTRY

1.199

TABLE 1.43 Table of Nuclides (Continued)

Element

A

Half-life

Natural abundance, %

Cross section, barns

Radiation (MeV)

1.11 VAPOR PRESSURE Vapor pressure is the pressure exerted by a pure component at equilibrium, at any temperature, when both liquid and vapor phases exist and thus extends from a minimum at the triple point temperature to a maximum at the critical temperature (the critical pressure), and is the most important of the basic thermodynamic properties affecting liquids and vapors. Except at very high total pressures (above about 10 MPa), there is no effect of total pressure on vapor pressure. If such an effect is present, a correction can be applied. The pressure exerted above a solid-vapor mixture may also be called vapor pressure but is normally only available as experimental data for common compounds that sublime.

1.11.1 Vapor Pressure Equations Numerous mathematical formulas relating the temperature and pressure of the gas phase in equilibrium with the condensed phase have been proposed. The Antoine equation (Eq. 1) gives good correlation with experimental values. Equation 2 is simpler and is often suitable over restricted temperature ranges. In these equations, and the derived differential coefficients for use in the Haggenmacher and Clausius-Clapeyron equations, the p term is the vapor pressure of the compound in pounds per square inch (psi), the t term is the temperature in degrees Celsius, and the T term is the absolute temperature in kelvins (t°C + 273.15).

1.200

SECTION ONE

Eq.

Vapor-pressure equation

dp/dT

1

log p = A −

B t+C

2.303 pB (t + C ) 2

2

log p = A −

B T

2.303 pB T2

3

log p = A −

B − C log T T

p

 2.303 B C  −  T2 T

−[d(ln p)/d(1/T)] 2.303 BT 2 (t + C ) 2 2.303B

2.303B – CT

Equations 1 and 2 are easily rearranged to calculate the temperature of the normal boiling point: t=

B −C A − log p

(5.1)

B A − log p

(5.2)

T=

The constants in the Antoine equation may be estimated by selecting three widely spaced data points and substituting in the following equations in sequence:  y3 − y2   t2 − t1   t3 − t1     = 1−    y2 − y1   t3 − t2   t3 + C  y −y  B =  3 1  (t1 + C )(t3 + C )  t2 + t1   B  A = y2 +    t2 + C 

In these equations, yi = log pi.

TABLE 1.44 Vapor Pressures of Selected Elements at Different Temperatures Vapor pressure temperature, °C Element

1.201

Aluminum Antimony Arsenic Barium Beryllium Bismuth Boron Cadmium Calcium Carbon Cobalt Chromium Copper Dysprosium Erbium Europium Gallium Germanium Gold Indium Iron Lanthanum Lead Lithium Magnesium Manganese Mercury Molybdenum Nickel Niobium Palladium Phosphorus

Atomic number

Atomic symbol

Boiling point, °C

E-08

E-07

E-06

E-05

E-04

E-03

E-02

E-01

1

13 52 33 56 4 83 5 48 20 6 27 24 29 66 68 63 31 32 79 77 26 57 82 49 12 25 80 42 28 41 46 15

Al Sb As Ba Be Bi B Cd Ca C Co Cr Cu Dy Er Eu Ga Ge Au In Fe La Pb Li Mg Mn Hg Mo Ni Nb Pd P

2467 1750 613 1140 2970 1560 2550 765 1484 4827 2870 2672 2567 2562 2510 1597 2403 2830 2807 2000 2750 3469 1740 1347 1107 1962 357 4612 2732 4927 2927 2804

685 279 104 272 707 347 1282 74 282 1657 922 837 722 625 649 283 619 812 807 488 892 1022 342 235 185 505 −72 1592 927 1762 842 54

742 309 127 310 762 367 1367 95 317 1757 992 902 787 682 708 319 677 877 877 539 957 1102 383 268 214 554 −59 1702 997 1867 912 69

812 345 150 354 832 409 1467 119 357 1867 1067 977 852 747 777 361 742 947 947 597 1032 1192 429 306 246 611 −44 1822 1072 1987 992 88

887 383 174 402 907 459 1582 146 405 1987 1157 1062 937 817 852 409 817 1037 1032 664 1127 1297 485 350 282 675 −27 1957 1157 2127 1082 108

972 425 204 462 997 517 1707 177 459 2137 1257 1157 1027 897 947 466 907 1137 1132 742 1227 1422 547 404 327 747 7 2117 1262 2277 1192 129

1082 475 237 527 1097 587 1867 217 522 2287 1382 1267 1132 997 1052 532 1007 1257 1252 837 1342 1562 625 467 377 837 16 2307 1382 2447 1317 157

1217 533 277 610 1227 672 2027 265 597 2457 1517 1397 1257 1117 1177 611 1132 1397 1397 947 1477 1727 715 537 439 937 46 2527 1527 2657 1462 185

1367 612 317 711 1377 777 2247 320 689 2657 1687 1552 1417 1262 1332 708 1282 1557 1567 1082 1647 1927 832 627 509 1082 80 2787 1697 2897 1647 222

1557 757 372 852 1557 897 2507 392 802 2897 1907 1737 1617 1437 1527 827 1472 1777 1767 1247 1857 2177 977 747 605 1217 125 3117 1907 3177 1877 261 (Continued)

1.202 TABLE 1.44 Vapor Pressures of Selected Elements at Different Temperatures (Continued) Vapor pressure temperature, °C Element Platinum Potassium Praseodymium Rhenium Rhodium Scandium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Tellurium Thallium Tin Titanium Tungsten Ytterbium Yttrium Zinc

Atomic number

Atomic symbol

Boiling point, °C

E-08

E-07

E-06

E-05

E-04

E-03

E-02

E-01

1

78 19 59 75 45 21 34 14 47 11 38 16 73 52 81 50 22 74 70 39 30

Pt K Pr Re Rh Sc Se Si Ag Na Sr S Ta Te TI Sn Ti W Yb Y Zn

3827 774 3127 5627 3727 2832 685 4827 2212 553 1384 45 5425 990 1457 2270 3287 5660 1466 3337 907

1292 21 797 1947 1277 772 63 992 574 74 241 −10 1957 155 283 682 1062 2117 247 957 123

1382 42 867 2077 767 837 83 1067 626 97 273 3 2097 181 319 747 1137 2247 279 1032 147

1492 65 947 2217 1472 917 107 1147 685 123 309 17 2237 209 359 807 1227 2407 317 1117 177

1612 91 1042 2387 1582 1007 133 1237 752 155 353 37 2407 242 407 897 1327 2567 365 1217 209

1747 123 1147 2587 1707 1107 164 1337 832 193 394 55 2587 280 463 997 1442 2757 417 1332 247

1907 161 1277 2807 1857 1232 199 1472 922 235 465 80 2807 323 530 1107 1577 2977 482 1467 292

2097 208 1427 3067 2037 1377 243 1632 1027 289 537 109 3057 374 609 1247 1737 3227 557 1632 344

2317 267 1617 3407 2247 1567 297 1817 1162 357 627 147 3357 433 706 1412 1937 3537 647 1832 408

2587 345 1847 3807 2507 1797 363 2057 1322 441 732 189 3707 518 827 1612 2177 3917 787 2082 487

TABLE 1.45 Vapor Pressures of Inorganic Compounds up to 1 Atmosphere Pressure, mm Hg 1 Compound name

1.203

Aluminum borohydride bromide chloride fluoride iodide oxide Ammonia heavy Ammonium bromide carbamate chloride cyanide hydrogen sulfide iodide Antimony tribromide trichloride pentachloride triiodide trioxide Argon Arsenic Arsenic tribromide trichloride trifluoride pentafluoride trioxide Arsine Barium

5

10

20

40

100

200

400

760 Melting point, °C

Temperature, °C

Formula Al Al(BH4)3 AlBr3 Al2Cl6 AlF3 AlI3 Al2O3 NH3 ND3 NH4Br N2H6CO2 NH4Cl NH4CN NH4HS NH4I Sb SbBr3 SbCl3 SbCl5 SbI3 Sb4O6 A As AsBr3 AsCl3 AsF3 AsF5 As2O3 AsH3 Ba

60

1284 81.3 100.0 1238 178.0 2148 −109.1

1421 −52.2 103.8 116.4 1298 207.7 2306 −97.5

1487 −42.9 118.0 123.8 1324 225.8 2385 −91.9

1555 −32.5 134.0 131.8 1350 244.2 2465 −85.8

1635 −20.9 150.6 139.9 1378 265.0 2549 −79.2

198.3 −26.1 160.4 −50.6 −51.1 210.9 886 93.9 49.2 22.7 163.6 574 −218.2 372 41.8 −11.4

234.5 −10.4 193.8 −35.7 −36.0 247.0 984 126.0 71.4 48.6 203.8 626 −213.9 416 70.6 +11.7

252.0 −2.9 209.8 −28.6 −28.7 263.5 1033 142.7 85.2 61.8 223.5 666 −210.9 437 85.2 +23.5

270.6 +5.3 226.1 −20.9 −20.8 282.8 1084 158.3 100.6 75.8 244.8 729 −207.9 459 101.3 36.0

−117.9 212.5 −142.6

−108.0 242.6 −130.8 984

−103.1 259.7 −124.7 1049

−98.0 279.2 −117.7 1120

290.0 14.0 245.0 −12.6 −12.3 302.8 1141 177.4 117.8 91.0 267.8 812 −204.9 483 118.7 50.0 −2.5 −92.4 299.2 −110.2 1195

1684 −13.4 161.7 145.4 1398 277.8 2599 −74.3 −74.0 303.8 19.6 256.2 −7.4 −7.0 316.0 1176 188.1 128.3 101.0 282.5 873 −202.9 498 130.0 58.7 +4.2 −88.5 310.3 −104.8 1240

1749 −3.9 176.1 152.0 1422 294.5 2665 −68.4 −67.4 320.0 26.7 271.5 −0.5 0.0 331.8 1223 203.5 143.3 114.1 303.5 957 −200.5 518 145.2 70.9 13.2 −84.3 332.5 −98.0 1301

1844 +11.2 199.8 161.8 1457 322.0 2766 −57.0 −57.0 345.3 37.2 293.2 +9.6 +10.5 355.8 1288 225.7 165.9

1947 28.1 227.0 171.6 1496 354.0 2874 −45.4 −45.4 370.8 48.0 316.5 20.5 21.8 381.0 1364 250.2 192.2

2056 45.9 256.3 180.2 1537 385.5 2977 −33.6 −33.4 396.0 58.3 337.8 31.7 33.3 404.9 1440 275.0 219.0

333.8 1085 −195.6 548 167.7 89.2 26.7 −75.5 370.0 −87.2 1403

368.5 1242 −190.6 579 193.6 109.7 41.4 −64.0 412.2 −75.2 1518

401.0 1425 −185.6 610 220.0 130.4 56.3 −52.8 457.2 −62.1 1638

660 −64 97 192.4 1040 2050 −77.7 −74.0

520 36

630.5 96.6 73.4 2.8 167 656 −189.2 814 −18 −5.9 −79.8 312.8 −116.3 850 (Continued)

1.204 TABLE 1.45 Vapor Pressures of Inorganic Compounds up to 1 Atmosphere (Continued) Pressure, mm Hg 1 Compound name Beryllium borohydride bromide chloride iodide Bismuth tribromide trichloride Diborane hydrobromide Borine carbonyl triamine Boron hydrides dihydrodecaborane dihydrodiborane dihydropentaborane tetrahydropentaborane tetrahydrotetraborane Boron tribromide trichloride trifluoride Bromine pentafluoride Cadmium chloride fluoride iodide oxide Calcium Carbon (graphite) dioxide disulfide monoxide

5

10

20

40

B10H14 B2H6 B5H9 B5H11 B4H10 BBr3 BCl3 BF3 Br2 BrF5 Cd CdCl2 CdF2 CdI2 CdO Ca C CO2 CS2 CO

100

200

400

760 Melting point, °C

Temperature, °C

Formula Be(BH4)2 BeBr2 BeCl2 BeI2 Bi BiBr3 BiCl3 B2H5Br BH3CO B3N3H6

60

+1.0 289 291 283 1021 −93.3 −139.2 −63.0 60.0 −159.7 −50.2 −90.9 −41.4 −91.5 −154.6 −48.7 −69.3 394 1112 416 1000 3586 −134.3 −73.8 −222.0

19.8 325 328 322 1099 261 242 −75.3 −127.3 −45.0

28.1 342 346 341 1136 282 264 −66.3 −121.1 −35.3

36.8 361 365 361 1177 305 287 −56.4 −114.1 −25.0

46.2 379 384 382 1217 327 311 −45.4 −106.6 −13.2

51.7 390 395 394 1240 340 324 −38.2 −101.9 −5.8

58.6 405 411 411 1271 360 343 −29.0 −95.3 +4.0

69.0 427 435 435 1319 392 372 −15.4 −85.5 18.5

79.7 451 461 461 1370 425 405 0.0 −74.8 34.3

90.0 474 487 487 1420 461 441 +16.3 −64.0 50.6

80.8 −149.5 −40.4 −29.9 −73.1 −20.4 −75.2 −145.4 −32.8 −51.0 455 618 1231 481 1100 926 3828 −124.4 −54.3 −217.2

90.2 −144.3 −30.7 −19.9 −64.3 −10.1 −66.9 −141.3 −25.0 −41.9 484 656 1286 512 1149 983 3946 −119.5 −44.7 −215.0

100.0 −138.5 −20.0 −9.2 −54.8 +1.5 −57.9 −136.4 −16.8 −32.0 516 695 1344 546 1200 1046 4069 −114.4 −34.3 −212.8

117.4 −131.6 −8.0 +2.7 −44.3 14.0 −47.8 −131.0 −8.0 −21.0 553 736 1400 584 1257 1111 4196 −108.6 −22.5 −210.0

127.8 −127.2 −0.4 10.2 −37.4 22.1 −41.2 −127.6 −0.6 −14.0 578 762 1436 608 1295 1152 4273 −104.8 −15.3 −208.1

142.3 −120.9 +9.6 20.1 −28.1 33.5 −32.4 −123.0 +9.3 −4.5 611 797 1486 640 1341 1207 4373 −100.2 −5.1 −205.7

163.8 −111.2 24.6 34.8 −14.0 50.3 −18.9 −115.9 24.3 +9.9 658 847 1561 688 1409 1288 4516 −93.0 +10.4 −201.3

−99.6 40.8 51.2 +0.8 70.0 −3.6 −108.3 41.0 25.7 711 908 1651 742 1484 1388 4660 −85.7 28.0 −196.3

−86.5 58.1 67.0 16.1 91.7 +12.7 −100.7 58.2 40.4 765 967 1751 796 1559 1487 4827 −78.2 46.5 −191.3

123 490 405 488 271 218 230 −104.2 −137.0 −58.2 99.6 −169 −47.0 −119.9 −45 −107 −126.8 −7.3 −61.4 320.9 568 520 385 851 −57.5 −110.8 −205.0

oxyselenide oxysulfide selenosulfide subsulfide tetrabromide tetrachloride tetrafluoride Cesium bromide chloride fluoride iodide Chlorine fluoride trifluoride monoxide dioxide heptoxide Chlorosulfonic acid Chromium carbonyl oxychloride Cobalt chloride nitrosyl tricarbonyl Columbium fluoride Copper Cuprous bromide chloride iodide Cyanogen bromide chloride fluoride Deuterium cyanide Fluorine oxide

COSe COS CSeS C3S2 CBr4 CCl4 CF4 Cs CsBr CsCl CsF CsI Cl2 CIF CIF3 Cl2O ClO2 Cl2O7 HSO3Cl Cr Cr(CO)6 CrO2Cl2 CoCl2 Co(CO)3NO CbF3 Cu Cu2Br2 Cu2Cl2 Cu2I2 C2N2 CNBr CNCl CNF DCN F2 F2O

−117.1 −132.4 −47.3 14.0

−102.3 −119.8 −26.5 41.2

−95.0 −113.3 −16.0 54.9

−86.3 −106.0 −4.4 69.3

−50.0 −184.6 279 748 744 712 738 −118.0 −98.5

−30.0 −174.1 341 838 837 798 828 −106.7 −143.4 −80.4 −81.6

−45.3 32.0 1616 36.0 −18.4

−23.8 53.5 1768 58.0 +3.2

−19.6 −169.3 375 887 884 844 873 −101.6 −139.0 −71.8 −73.1 −59.0 −13.2 64.0 1845 68.3 13.8

−8.2 −164.3 409 938 934 893 923 −93.3 −134.3 −62.3 −64.3 −51.2 −2.1 75.3 1928 79.5 25.7

86.3 1879 718 702 656 −76.8 −10.0 −53.8 −118.5 −46.7 −214.1 −182.3

−1.3 103.0 1970 777 766 716 −70.1 −1.0 −46.1 −112.8 −38.8 −211.0 −177.8

1628 572 546 −95.8 −35.7 −76.7 −134.4 −68.9 −223.0 −196.1

1795 666 645 610 −83.2 −18.3 −61.4 −123.8 −54.0 −216.9 −186.6

−76.4 −98.3 +8.6 85.6 96.3 +4.3 −158.8 449 993 989 947 976 −84.5 −128.8 −51.3 −54.3 −42.8 +10.2 87.6 2013 91.2 38.5 770 +11.0 121.5 2067 844 838 786 −62.7 +8.6 −37.5 −106.4 −30.1 −207.7 −173.0

−70.2 −93.0 17.0 96.0 106.3 12.3 −155.4 474 1026 1023 980 1009 −79.0 −125.3 −44.1 −48.0 −37.2 +18.3 95.2 2067 98.3 46.7 801 18.5 133.2 2127 887 886 836 −57.9 14.7 −32.1 −102.3 −24.7 −205.6 −170.0

−61.7 −85.9 28.3 109.9 119.7 23.0 −150.7 509 1072 1069 1025 1055 −71.7 −120.8 −34.7 −39.4 −29.4 29.1 105.3 2139 108.0 58.0 843 29.0 148.5 2207 951 960 907 −51.8 22.6 −24.9 −97.0 −17.5 −202.7 −165.8

−49.8 −75.0 45.7 130.8 139.7 38.3 −143.6 561 1140 1139 1092 1124 −60.2 −114.4 −20.7 −26.5 −17.8 44.6 120.0 2243 121.8 75.2 904 44.4 172.2 2325 1052 1077 1018 −42.6 33.8 −14.1 −89.2 −5.4 −198.3 −159.0

−35.6 −62.7 65.2

−21.9 −49.9 85.6

163.5 57.8 −135.5 624 1221 1217 1170 1200 −47.3 −107.0 −4.9 −12.5 −4.0 62.2 136.1 2361 137.2 95.2 974 62.0 198.0 2465 1189 1249 1158 −33.0 46.0 −2.3 −80.5 +10.0 −193.2 −151.9

189.5 76.7 −127.7 690 1300 1300 1251 1280 −33.8 −100.5 +11.5 +2.2 +11.1 78.8 151.0 2482 151.0 117.1 1050 80.0 225.0 2595 1355 1490 1336 −21.0 61.5 +13.1 −72.6 26.2 −187.9 −144.6

−138.8 −75.2 +0.4 90.1 −22.6 −183.7 28.5 636 646 683 621 −100.7 −145 −83 −116 −59 −91 −80 1615

735 −11 75.5 1083 504 422 605 −34.4 58 −6.5 −12 −223 −223.9 (Continued)

1.205

1.206 TABLE 1.45 Vapor Pressures of Inorganic Compounds up to 1 Atmosphere (Continued) Pressure, mm Hg 1 Compound name Germanium bromide chloride hydride Trichlorogermane Tetramethylgermane Digermane Trigermane Gold Helium para−Hydrogen Hydrogen bromide chloride cyanide fluoride iodide oxide(water) sulfide disulfide selenide telluride Iodine heptafluoride Iron pentacarbonyl Ferric chloride Ferrous chloride Krypton Lead bromide chloride fluoride

5

10

20

40

100

200

400

760 Melting point, °C

Temperature, °C

Formula GeBr4 GeCl4 GeH4 GeHCl3 Ge(CH3)4 Ge2H6 Ge3H6 Au He H2 HBr HCl HCN H2F2 HI H2O H2S HSSH H2Se H2Te I2 IF Fe Fe(CO)5 Fe2Cl6 FeCl2 Kr Pb PbBr2 PbCl2 PbF2

60

−45.0 −163.0 −41.3 −73.2 −88.7 −36.9 1869 −271.7 −263.3 −138.8 −150.8 −71.0 −123.3 −17.3 −134.3 −43.2 −115.3 −96.4 38.7 −87.0 1787 194.0 −199.3 973 513 547

43.3 −24.9 −151.0 −22.3 −54.6 −69.8 −12.8 2059 −271.5 −261.9 −127.4 −140.7 −55.3 −74.7 −109.6 +1.2 −122.4 −24.4 −103.4 −82.4 62.2 −70.7 1957 −6.5 221.8 −191.3 1099 578 615 861

56.8 −15.0 −145.3 −13.0 −45.2 −60.1 −0.9 2154 −271.3 −261.3 −121.8 −135.6 −47.7 −65.8 −102.3 11.2 −116.3 −15.2 −97.9 −75.4 73.2 −63.0 2039 +4.6 235.5 700 −187.2 1162 610 648 904

71.8 −4.1 −139.2 −3.0 −35.0 −49.9 +11.8 2256 −271.1 −260.4 −115.4 −130.0 −39.7 −56.0 −94.5 22.1 −109.7 −5.1 −91.8 −67.8 84.7 −54.5 2128 16.7 246.0 737 −182.9 1234 646 684 950

88.1 +8.0 −131.6 +8.8 −23.4 −38.2 26.3 2363 −270.7 −259.6 −108.3 −123.8 −30.9 −45.0 −85.6 34.0 −102.3 +6.0 −84.7 −59.1 97.5 −45.3 2224 30.3 256.8 779 −178.4 1309 686 725 1003

98.8 16.2 −126.7 16.2 −16.2 −30.7 35.5 2431 −270.6 −258.9 −103.8 −119.6 −25.1 −37.9 −79.8 41.5 −97.9 12.8 −80.2 −53.7 105.4 −39.4 2283 39.1 263.7 805 −175.7 1358 711 750 1036

113.2 27.5 −120.3 26.5 −6.3 −20.3 47.9 2521 −270.3 −257.9 −97.7 −114.0 −17.8 −28.2 −72.1 51.6 −91.6 22.0 −74.2 −45.7 116.5 −31.9 2360 50.3 272.5 842 −171.8 1421 745 784 1080

135.4 44.4 −111.2 41.6 +8.8 −4.7 67.0 2657 −269.8 −256.3 −88.1 −105.2 −5.3 −13.2 −60.3 66.5 −82.3 35.3 −65.2 −32.4 137.3 −20.7 2475 68.0 285.0 897 −165.9 1519 796 833 1144

161.6 63.8 −100.2 58.3 26.0 +3.3 88.6 2807 −269.3 −254.5 −78.0 −95.3 +10.2 +2.5 −48.3 83.0 −71.8 49.6 −53.6 −17.2 159.8 −8.3 2605 86.1 298.0 961 −159.0 1630 856 893 1219

189.0 84.0 −88.9 75.0 44.0 31.5 110.8 2966 −268.6 −252.5 −66.5 −84.8 25.9 19.7 −35.1 100.0 −60.4 64.0 −41.1 −2.0 183.0 +4.0 2735 105.0 319.0 1026 −152.0 1744 914 954 1293

26.1 −49.5 −165 −71.1 −88 −109 −105.6 1063 −259.1 −87.0 −114.3 −13.2 −83.7 −50.9 0.0 −85.5 −89.7 −64 −49.0 112.9 5.5 1535 −21 304 −156.7 327.5 373 501 855

iodide oxide sulfide Lithium bromide chloride fluoride iodide Magnesium chloride Manganese chloride Mercury Mercuric bromide chloride iodide Molybdenum hexafluoride oxide Neon Nickel carbonyl chloride Nitrogen Nitric oxide Nitrogen dioxide Nitrogen pentoxide Nitrous oxide Nitrosyl chloride fluoride Osmium tetroxide (yellow) (white) Oxygen Ozone Phosgene Phosphorus (yellow) (violet) tribromide

PbI2 PbO PbS Li LiBr LiCl LiF LiI Mg MgCl2 Mn MnCl2 Hg HgBr2 HgCl2 HgI2 Mo MoF6 MoO3 Ne Ni Ni(CO)4 NiCl2 N2 NO NO2 N2O5 N 2O NOCl NOF OsO4 OsO4 O2 O3 COCl2 P P PBr3

479 943 852 723 748 783 1047 723 621 778 1292 126.2 136.5 136.2 157.5 3102 −65.5 734 −257.3 1810

540 1039 928 838 840 880 1156 802 702 877 1434 736 164.8 165.3 166.0 189.2 3393 −49.0 785 −255.5 1979

571 1085 975 881 888 932 1211 841 743 930 1505 778 184.0 179.8 180.2 204.5 3535 −40.8 814 −254.6 2057

605 1134 1005 940 939 987 1270 883 789 968 1583 825 204.6 194.3 195.8 220.0 3690 −32.0 851 −253.7 2143

671 −226.1 −184.5 −55.6 −36.8 −143.4

731 −221.3 −180.6 −42.7 −23.0 −133.4

759 −219.1 −178.2 −36.7 −16.7 −128.7

789 −216.8 −175.3 −30.4 −10.0 −124.0

−132.0 3.2 −5.6 −219.1 −180.4 −92.9 76.6 237 7.8

−120.3 22.0 +15.6 −213.4 −168.6 −77.0 111.2 271 34.4

−114.3 31.3 26.0 −210.6 −163.2 −69.3 128.0 287 47.8

−107.8 41.0 37.4 −207.5 −157.2 −60.3 146.2 306 62.4

644 1189 1048 1003 994 1045 1333 927 838 1050 1666 879 228.8 211.5 212.5 238.2 3859 −22.1 892 −252.6 2234 −23.0 821 −214.0 −171.7 −23.9 −2.9 −118.3 −60.2 −100.3 51.7 50.5 −204.1 −150.7 −50.3 166.7 323 79.0

668 1222 1074 1042 1028 1081 1372 955 868 1088 1720 913 242.0 221.0 222.2 249.0 3964 −16.2 917 −251.9 2289 −15.9 840 −212.3 −168.9 −19.9 +1.8 −114.9 −54.2 −95.7 59.4 59.4 −201.9 −146.7 −44.0 179.8 334 89.8

701 1265 1108 1097 1076 1129 1425 993 909 1142 1792 960 261.7 237.8 237.0 261.8 4109 −8.0 955 −251.0 2364 −6.0 866 −209.7 −166.0 −14.7 7.4 −110.3 −46.3 −88.8 71.5 71.5 −198.8 −141.0 −35.6 197.3 349 103.6

750 1330 1160 1178 1147 1203 1503 1049 967 1223 1900 1028 290.7 262.7 256.5 291.0 4322 +4.1 1014 −249.7 2473 +8.8 904 −205.6 −162.3 −5.0 15.6 −103.6 −34.0 −79.2 89.5 89.5 −194.0 −132.6 −22.3 222.7 370 125.2

807 1402 1221 1273 1126 1290 1591 1110 1034 1316 2029 1108 323.0 290.0 275.5 324.2 4553 17.2 1082 −248.1 2603 25.8 945 −200.9 −156.8 +8.0 24.4 −96.2 −20.3 −68.2 109.3 109.3 −188.8 −122.5 −7.6 251.0 391 149.7

872 1472 1281 1372 1310 1382 1681 1171 1107 1418 2151 1190 357.0 319.0 304.0 354.0 4804 36.0 1151 −246.0 2732 42.5 987 −195.8 −151.7 21.0 32.4 −85.5 −6.4 −56.0 130.0 130.0 −183.1 −111.1 +8.3 280.0 417 175.3

402 890 1114 186 547 614 870 446 651 712 1260 650 −38.9 237 277 259 2622 17 795 −248.7 1452 −25 1001 −210.0 −161 −9.3 30 −90.9 −64.5 −134 56 42 −218.7 −251 −104 44.1 590 −40 (Continued)

1.207

1.208 TABLE 1.45 Vapor Pressures of Inorganic Compounds up to 1 Atmosphere (Continued) Pressure, mm Hg 1 Compound name trichloride pentachloride Phosphine Phosphonium bromide chloride iodide Phosphorus trioxide pentoxide oxychloride thiobromide thiochloride Platinum Potassium bromide chloride fluoride hydroxide iodide Radon Rhenium heptoxide Rubidium bromide chloride fluoride iodide Selenium dioxide hexafluoride oxychloride tetrachloride

5

10

20

40

100

200

400

760 Melting point, °C

Temperature, °C

Formula PCl3 PCl5 PH3 PH4Br PH4Cl PH4I P4O6 P4O10 POCl3 PSBr3 PSCl3 Pt K KBr KCl KF KOH KI Rn Re2O7 Rb RbBr RbCl RbF RbI Se SeO2 SeF6 SeOCl2 SeCl4

60

−51.6 55.5

−31.5 74.0

−21.3 83.2

−10.2 92.5

−43.7 −91.0 −25.2 384

−28.5 −79.6 −9.0 39.7 424

50.0 −18.3 2730 341 795 821 885 719 745 −144.2 212.5 297 781 792 921 748 356 157.0 −118.6 34.8 74.0

72.4 +4.6 3007 408 892 919 988 814 840 −132.4 237.5 358 876 887 982 839 413 187.7 −105.2 59.8 96.3

−21.2 −74.0 −1.1 53.0 442 2.0 83.6 16.1 3146 443 940 968 1039 863 887 −126.3 248.0 389 923 937 1016 884 442 202.5 −98.9 71.9 107.4

−13.3 −68.0 +7.3 67.8 462 13.6 95.5 29.0 3302 483 994 1020 1096 918 938 −119.2 261.0 422 975 990 1052 935 473 217.5 −92.3 84.2 118.1

+2.3 102.5 −129.4 −5.0 −61.5 16.1 84.0 481 27.3 108.0 42.7 3469 524 1050 1078 1156 976 995 −111.3 272.0 459 1031 1047 1096 991 506 234.1 −84.7 98.0 130.1

10.2 108.3 −125.0 +0.3 −57.3 21.9 94.2 493 35.8 116.0 51.8 3574 550 1087 1115 1193 1013 1030 −106.2 280.0 482 1066 1084 1123 1026 527 244.6 −80.0 106.5 137.8

21.0 117.0 −118.8 7.4 −52.0 29.3 108.3 510 47.4 126.3 63.8 3714 586 1137 1164 1245 1064 1080 −99.0 289.0 514 1114 1133 1168 1072 554 258.0 −73.9 118.0 147.5

37.6 131.3 −109.4 17.6 −44.0 39.9 129.0 532 65.0 141.8 82.0 3923 643 1212 1239 1323 1142 1152 −87.7 307.0 563 1186 1207 1239 1141 594 277.0 −64.8 134.6 161.0

56.9 147.2 −98.3 28.0 −35.4 51.6 150.3 556 84.3 157.8 102.3 4169 708 1297 1322 1411 1233 1238 −75.0 336.0 620 1267 1294 1322 1223 637 297.7 −55.2 151.7 176.4

74.2 162.0 −87.5 38.3 −27.0 62.3 173.1 591 105.1 175.0 124.0 4407 774 1383 1407 1502 1327 1324 −61.8 362.4 679 1352 1381 1408 1304 680 317.0 −45.8 168.0 191.5

−111.8 −132.5 −28.5 22.5 569 2 38 −36.2 1755 62.3 730 790 880 380 723 −71 296 38.5 682 715 760 642 217 340 −34.7 8.5

Silicon dioxide tetrachloride tetrafluoride Trichlorofluorosilane Iodosilane Diiodosilane Disiloxan Trisilane Trisilazane Tetrasilane Octachlorotrisilane Hexachlorodisiloxane Hexachlorodisilane Tribromosilane Trichlorosilane Trifluorosilane Dibromosilane Difluorosilane Monobromosilane Monochlorosilane Monofluorosilane Tribromofluorosilane Dichlorodifluorosilane Trifluorobromosilane Trifluorochlorosilane Hexafluorodisilane Dichlorofluorobromosilane Dibromochlorofluorosilane Silane Disilane Silver chloride iodide Sodium bromide chloride

Si SiO2 SiCl4 SiF4 SiFCl3 SiH3I SiH2I2 (SiH3)2O Si3H8 (SiH3)3N Si4H10 Si3Cl3 (SiCl3)2O Si2Cl6 SiHBr3 SiHCl3 SiHF3 SiH2Br2 SiH2F2 SiH3Br SiH3Cl SiH3F SiFBr3 SiF2Cl2 SiF3Br SiF3Cl Si2F6 SiFCl2Br SiFClBr2 SiH4 Si2H6 Ag AgCl AgI Na NaBr NaCl

1724

1835

−117.8 −153.0 −46.1 −124.7

−44.1 −134.8 −76.4 −53.0 3.8 −95.8 −49.7 −49.9 −6.2 74.7 17.8 27.4 −8.0 −62.6 −142.7 −40.0 −136.0 −85.7 −104.3 −145.5 −25.4 −110.5

1888 1732 −34.4 −130.4 −68.3 −47.7 18.0 −88.2 −40.0 −40.4 +4.3 89.3 29.4 38.8 +3.4 −53.4 −138.2 −29.4 −130.4 −77.3 −97.7 −141.2 −15.1 −102.9

1942 1798 −24.0 −125.9 −59.0 −33.4 34.1 −79.8 −29.0 −30.0 15.8 104.2 41.5 51.5 16.0 −43.8 −132.9 −18.0 −124.3 −68.3 −90.1 −136.3 −3.7 −94.5

2000 1867 −12.1 −120.8 −48.8 −21.8 52.6 −70.4 −16.9 −18.5 28.4 121.5 55.2 65.3 30.0 −32.9 −127.3 −5.2 −117.6 −57.8 −81.8 −130.8 +9.2 −85.0

2036 1911 −4.8 −117.5 −42.2 −14.3 64.0 −64.2 −9.0 −11.0 36.6 132.0 63.8 73.9 39.2 −25.8 −123.7 +3.2 −113.3 −51.1 −76.0 −127.2 17.4 −78.6

2083 1969 +5.4 −113.3 −33.2 −4.4 79.4 −55.9 +1.6 −1.1 47.4 146.0 75.4 85.4 51.6 −16.4 −118.7 14.1 −107.3 −42.3 −68.5 −122.4 28.6 −70.3

−63.4 −144.0 −92.6

−144.0 −81.0 −86.5 −65.2 −179.3 −114.8 1357 912 820 439 806 865

−133.0 −68.8 −68.4 −45.5 −168.6 −99.3 1500 1019 927 511 903 967

−127.0 −63.1 −59.0 −35.6 −163.0 −91.4 1575 1074 983 549 952 1017

−120.5 −57.0 −48.8 −24.5 −156.9 −82.7 1658 1134 1045 589 1005 1072

−112.8 −50.6 −37.0 −12.0 −150.3 −72.8 1743 1200 1111 633 1063 1131

−108.2 −46.7 −29.0 −4.7 −146.3 −66.4 1795 1242 1152 662 1099 1169

−101.7 −41.7 −19.5 +6.3 −140.5 −57.5 1865 1297 1210 701 1148 1220

−112.5 −68.9 −68.7 −27.7 46.3 −5.0 +4.0 −30.5 −80.7 −152.0 −60.9 −146.7

2151 2053 21.0 −170.2 −19.3 +10.7 101.8 −43.5 17.8 +14.0 63.6 166.2 92.5 102.2 70.2 −1.8 −111.3 31.6 −98.3 −28.6 −57.0 −115.2 45.7 −58.0 −69.8 −91.7 −34.2 −3.2 23.0 −131.6 −44.6 1971 1379 1297 758 1220 1296

2220 2141 38.4 −100.7 −4.0 27.9 125.5 −29.3 35.5 31.0 81.7 189.5 113.6 120.6 90.2 +14.5 −102.8 50.7 −87.6 −13.3 −44.5 −106.8 64.6 −45.0 −55.9 −81.0 −26.4 +15.4 43.0 −122.0 −29.0 2090 1467 1400 823 1304 1379

2287 2227 56.8 −94.8 +12.2 45.4 149.5 −15.4 53.1 48.7 100.0 211.4 135.6 139.0 111.8 31.8 −95.0 70.5 −77.8 +2.4 −30.4 −98.0 83.8 −31.8 −41.7 −70.0 −18.9 35.4 59.5 −111.5 −14.3 2212 1564 1506 892 1392 1465

1420 1710 −68.8 −90 −120.8 −57.0 −1.0 −144.2 −117.2 −105.7 −93.6 −33.2 −1.2 −73.5 −126.6 −131.4 −70.2 −93.9 −82.5 −139.7 −70.5 −142 −18.6 −112.3 −99.3 −185 −132.6 960.5 455 552 97.5 755 800 (Continued)

1.209

1.210 TABLE 1.45 Vapor Pressures of Inorganic Compounds up to 1 Atmosphere (Continued) Pressure, mm Hg 1 Compound name cyanide fluoride hydroxide iodide Strontium Strontium oxide Sulfur monochloride hexafluoride Sulfuryl chloride Sulfur dioxide trioxide (a) trioxide (b) trioxide (g ) Tellurium chloride fluoride Thallium Thallous bromide chloride iodide Thionyl bromide Thionyl chloride Tin Stannic bromide Stannous chloride Stannic chloride iodide hydride

5

10

20

40

100

200

400

760 Melting point, °C

Temperature, °C

Formula NaCN NaF NaOH NaI Sr SrO S S2Cl2 SF5 SO2Cl2 SO2 SO3 SO3 SO3 Te TeCl4 TeF5 Tl TlBr TlCl TlI SOBr2 SOCl2 Sn SnBr4 SnCl2 SnCl4 SnI4 SnH4

60

817 1077 739 767 2068 183.8 −7.4 −132.7 −95.5 −39.0 −34.0 −15.3 520 −111.3 825

440 −6.7 −52.9 1492 316 −22.7 −140.0

928 1186 843 857 847 2198 223.0 +15.7 −120.6 −35.1 −83.0 −23.7 −19.2 −2.0 605 −98.8 931 490 487 502 +18.4 −32.4 1634 58.3 366 −1.0 156.0 −125.8

983 1240 897 903 898 2262 243.8 27.5 −114.7 −24.8 −76.8 −16.5 −12.3 +4.3 650 233 −92.4 983 522 517 531 31.0 −21.9 1703 72.7 391 +10.0 175.8 −118.5

1046 1300 953 952 953 2333 264.7 40.0 −108.4 −13.4 −69.7 −9.1 −4.9 11.1 697 253 −83.0 1040 559 550 567 44.1 −10.5 1777 88.1 420 22.0 196.2 −111.2

1115 1363 1017 1005 1018 2410 288.3 54.1 −101.5 −1.0 −60.5 −1.0 +3.2 17.9 753 273 −78.4 1103 598 589 607 58.8 +2.2 1855 105.5 450 35.2 218.8 −102.3

1156 1403 1057 1039 1057

1214 1455 1111 1083 1111

1302 1531 1192 1150 1192

1401 1617 1286 1225 1285

1497 1704 1378 1304 1384

305.5 63.2 −96.8 +7.2 −54.6 +4.0 8.0 21.4 789 287 −73.8 1143 621 612 631 68.3 10.4 1903 116.2 467 43.5 234.2 −96.6

327.2 75.3 −90.9 17.8 −46.9 10.5 14.3 28.0 838 304 −67.9 1196 653 645 663 80.6 21.4 1968 131.0 493 54.7 254.2 −89.2

359.7 93.5 −82.3 33.7 −35.4 20.5 23.7 35.8 910 330 −57.3 1274 703 694 712 99.0 37.9 2063 152.8 533 72.0 283.5 −78.0

399.6 115.4 −72.6 51.3 −23.0 32.6 32.6 44.0 997 360 −48.2 1364 759 748 763 119.2 56.5 2169 177.7 577 92.1 315.5 −65.2

444.6 138.0 −63.5 69.2 −10.0 44.8 44.8 51.6 1087 392 −38.6 1457 819 807 823 139.5 75.4 2270 204.7 623 113.0 348.0 −52.3

564 992 318 651 800 2430 112.8 −80 −50.2 −54.1 −73.2 16.8 32.3 62.1 452 224 −37.8 3035 460 430 440 −52.2 −104.5 231.9 31.0 246.8 −30.2 144.5 −149.9

Tin tetramethyl trimethyl-ethyl trimethyl-propyl Titanium chloride Tungsten Tungsten hexafluoride Uranium hexafluoride Vanadyl trichloride Xenon Zinc chloride fluoride diethyl Ziroconium bromide chloride iodide

Sn(CH3)4 −51.3 Sn(CH3)3 ⋅ C2H5 −30.0 Sn(CH3)3 ⋅ C3H7 −12.0 −13.9 TiCl4 W 3990 −71.4 WF6 −38.8 UF6 −23.2 VOCl3 Xe −168.5 Zn 487 428 ZnCl2 970 ZnF2 −22.4 Zn(C2H5)2 207 ZrBr4 190 ZrCl4 ZrI4 264

−31.0 −7.6 +10.7 +9.4 4337 −56.5 −22.0 +0.2 −158.2 558 481 1055 0.0 237 217 297

−20.6 +3.8 21.8 21.3 4507 −49.2 −13.8 12.2 −152.8 593 508 1086 +11.7 250 230 311

−9.3 16.1 34.0 34.2 4690 −41.5 −5.2 26.6 −147.1 632 536 1129 24.2 266 243 329

+3.5 30.0 48.5 48.4 4886 −33.0 +4.4 40.0 −141.2 673 566 1175 38.0 281 259 344

11.7 38.4 57.5 58.0 5007 −27.5 10.4 49.8 −137.7 700 584 1207 47.2 289 268 355

22.8 50.0 69.8 71.0 5168 −20.3 18.2 62.5 −132.8 736 610 1254 59.1 301 279 369

39.8 67.3 88.0 90.5 5403 −10.0 30.0 82.0 −125.4 788 648 1329 77.0 318 295 389

58.5 87.6 109.6 112.7 5666 +1.2 42.7 103.5 −117.1 844 689 1417 97.3 337 312 409

78.0 108.8 131.7 136.0 5927 17.3 55.7 127.2 −108.0 907 732 1497 118.0 357 331 431

−30 3370 −0.5 69.2 −111.6 419.4 365 872 −28 450 437 499

1.211

1.212

SECTION ONE

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds Substance

*Crystalline solid.

State

Eq.

Range,°C

A

B

C

1.213

INORGANIC CHEMISTRY

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds (Continued) Substance

State

Eq.

Range,°C

A

B

C

(Continued)

1.214

SECTION ONE

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds (Continued) Substance

State

Eq.

Range,°C

A

B

C

INORGANIC CHEMISTRY

1.215

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds (Continued) Substance

State

Eq.

Range,°C

A

B

C

(Continued)

1.216

SECTION ONE

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds (Continued) Substance

State

Eq.

Range,°C

A

B

C

1.217

INORGANIC CHEMISTRY

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds (Continued) Substance

State

Eq.

Range,°C

A

B

C

(Continued)

1.218

SECTION ONE

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds (Continued) Substance (Continued)

State

Eq.

Range,°C

A

B

C

1.219

INORGANIC CHEMISTRY

TABLE 1.46 Vapor Pressures of Various Inorganic Compounds (Continued) Substance (Continued)

State

Eq.

Range,°C

A

B

C

1.220

SECTION ONE

TABLE 1.47 Vapor Pressure of Mercury Temp. °C

mm of Hg

Temp. °C

mm of Hg

Temp. °C

mm of Hg

INORGANIC CHEMISTRY

1.221

TABLE 1.47 Vapor Pressure of Mercury (Continued) Temp. °C

*

Critical point.

mm of Hg

Temp. °C

mm of Hg

Temp. °C

mm of Hg

1.222

SECTION ONE

TABLE 1.48 Vapor Pressure of Ice in Millimeters of Mercury For temperatures from –99 to 0°C. The values in the table are for ice in contact with its own vapor. Where the ice is in contact with air at a temperature t°C, this correction must be added: Correction = 20p/(100)(t + 273). t, °C

p, mm Hg

t, °C

p, mm Hg

t, °C

p, mm Hg

INORGANIC CHEMISTRY

1.223

TABLE 1.48 Vapor Pressure of Ice in Millimeters of Mercury (Continued) t, °C

p, mm Hg

t, °C

p, mm Hg

t, °C

p, mm Hg

t°C.

p in atm

66 68 70 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100 102 104 106 108 110 112 114 116 118 120 122 124 126 128 130 132 132.3

29.784 31.211 32.687 34.227 35.813 37.453 39.149 40.902 42.712 44.582 46.511 48.503 50.558 52.677 54.860 57.111 59.429 61.816 64.274 66.804 69.406 72.084 74.837 77.668 80.578 83.570 86.644 89.802 93.045 96.376 99.796 103.309 106.913 110.613 111.3(c.p.)

TABLE 1.49 Vapor Pressure of Liquid Ammonia, NH3 t°C.

p in atm

t°C.

−78 −76 −74 −72 −70 −68 −66 −64 −62 −60 −58 −56 −54 −52 −50 −48 −46 −44 −42 −40 −38 −36 −34 −32 −30 −28 −26 −24 −22 −20 −18 −16 −14 −12 −10 −8

0.0582 0.0683 0.0797 0.0929 0.1078 0.1246 0.1437 0.1651 0.1891 0.2161 0.2461 0.2796 0.3167 0.3578 0.4034 0.4536 0.5087 0.5693 0.6357 0.7083 0.7875 0.8738 0.9676 1.0695 1.1799 1.2992 1.4281 1.5671 1.7166 1.8774 2.0499 2.2349 2.4328 2.6443 2.8703 3.1112

−6 −4 −2 0 +2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64

p in atm 3.3677 3.6405 3.9303 4.2380 4.5640 4.9090 5.2750 5.6610 6.0685 6.4985 6.9520 7.4290 7.9310 8.4585 9.0125 9.5940 10.2040 10.8430 11.512 12.212 12.943 13.708 14.507 15.339 16.209 17.113 18.056 19.038 20.059 21.121 22.224 23.372 24.562 25.797 27.079 28.407

1.224

SECTION ONE

TABLE 1.50 Vapor Pressure of Water For temperatures from –10 to 120°C. The values in the table are for water in contact with its own vapor. Where the water is in contact with air at a temperature t in degrees. Celsius, the following correction must be added: Correction (when t ≤ 40°C) = p(0.775 – 0.000 313t)/100; correction (when t > 50°C) = p(0.0652 – 0.000 087 5t)/100. t, °C

p, mm Hg

t, °C

p, mm Hg

t, °C

p, mm Hg

t, °C

p, mm Hg

INORGANIC CHEMISTRY

1.225

TABLE 1.50 Vapor Pressure of Water (Continued) t, °C

p, mm Hg

t, °C

p, mm Hg

t, °C

t, °C

p, mm Hg

p, mm Hg

TABLE 1.51 Vapor Pressure of Deuterium Oxide t, °C

p, mm Hg

t, °C

p, mm Hg

t, °C

p, mm Hg

0 1 2 3 3.8 10

3.65 3.93 4.29 4.65 5.05 7.79

20 30 40 50 60 70

15.2 28.0 49.3 83.6 136.6 216.1

80 90 100 101.43

331.6 495.5 722.2 760.0

1.226

SECTION ONE

1.12 VISCOSITY AND SURFACE TENSION Viscosity is the shear stress per unit area at any point in a confined fluid divided by the velocity gradient in the direction perpendicular to the direction of flow. If this ratio is constant with time at a given temperature and pressure for any species, the fluid is called a Newtonian fluid. The absolute viscosity (m) is the sheer stress at a point divided by the velocity gradient at that point. The most common unit is the poise (1 kg/m sec) and the SI unit is the Pa.sec (1 kg/m sec). As many common fluids have viscosities in the hundredths of a poise the centipoise (cp) is often used. One centipoise is then equal to one mPa sec. The kinematic viscosity (v) is ratio of the absolute viscosity to density at the same temperature and pressure. The most common unit corresponding to the poise is the stoke (1 cm2/sec) and the SI unit is m2/sec. The molecules in a gas-liquid interface are in tension and tend to contract to a minimum surface area. This tension may be quantified by the surface tension (s), which is the force in the plane of the surface per unit length. TABLE 1.52 Viscosity and Surface Tension of Inorganic Substances For the majority of compounds the dependence of the surface tension g on the temperature can be given as: g = a – bt where a and b are constants and t is the temperature in degrees Celsius. The values of the dipole moment are for the gas phase. Surface tension mN ⋅ m−1 Substance

Viscosity, mN ⋅ s ⋅ m−2

a

b

INORGANIC CHEMISTRY

TABLE 1.52 Viscosity and Surface Tension of Inorganic Substances (Continued)

Substance

Viscosity, mN ⋅ s ⋅ m−2

Surface tension mN ⋅ m−1 a

b

(Continued)

1.227

1.228

SECTION ONE

TABLE 1.52 Viscosity and Surface Tension of Inorganic Substances (Continued) Surface tension mN ⋅ m−1 Substance

Viscosity, mN ⋅ s ⋅ m−2

a

b

INORGANIC CHEMISTRY

TABLE 1.52 Viscosity and Surface Tension of Inorganic Substances (Continued) Surface tension mN ⋅ m−1 Substance

Viscosity, mN ⋅ s ⋅ m−2

a

b

(Continued)

1.229

1.230

SECTION ONE

TABLE 1.52 Viscosity and Surface Tension of Inorganic Substances (Continued) Surface tension mN ⋅ m−1 Substance

Viscosity, mN ⋅ s ⋅ m−2

a

b

1.13 THERMAL CONDUCTIVITY The thermal conductivity is a measure of the effectiveness of a material as a thermal insulator. The energy transfer rate through a body is proportional to the temperature gradient across the body and the cross sectional area of the body. In the limit of infinitesimal thickness and temperature difference, the fundamental law of heat conduction is: Q = lAdT/dx

INORGANIC CHEMISTRY

1.231

where Q is the heat flow, A is the cross-sectional area, dT/dx is the temperature/thickness gradient, and l is the thermal conductivity. A substance with a large thermal conductivity value is a good conductor of heat; one with a small thermal conductivity value is a poor heat conductor i.e. a good insulator.

TABLE 1.53 Thermal Conductivity of the Elements

Element number

Element symbol

Thermal conductivity (W/m)/K 27°C, 81°F

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61 63 65 67

H Li B N F Na Al P Cl K Sc V Mn Co Cu Ga As Br Rb Y Nb Tc Rh Ag In Sb I Cs La Pr Pm Eu Tb Ho

0.1815 84.7 27 0.02598 0.0279 141 237 0.235 0.0089 102.5 15.8 30.7 7.82 100 401 40.6 50 0.122 58.2 17.2 53.7 50.6 150 429 81.6 24.3 0.449 35.9 13.5 12.5 17.9 13.9 11.1 16.2

Element number

Element symbol

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68

He Be C O Ne Mg Si S Ar Ca Ti Cr Fe Ni Zn Ge Se Kr Sr Zr Mo Ru Pd Cd Sn Te Xe Ba Ce Nd Sm Gd Dy Er

Thermal conductivity (W/m)/K 27°C, 81°F 0.152 200 155 0.02674 0.0493 156 148 0.269 0.0177 200 21.9 93.7 80.2 90.7 116 59.9 2.04 0.00949 35.3 22.7 138 117 71.8 96.8 66.6 2.35 0.00569 18.4 11.4 16.5 13.3 10.6 10.7 14.3

1.232

SECTION ONE

TABLE 1.54 Thermal Conductivity of Various Solids All values of thermal conductivity, k, are in millijoules cm–1 ⋅ s–1 ⋅ K–1. To convert to mW ⋅ m–1 ⋅ K–1m, divide

values by 10. For values in millicalories, divide by 4.184. Substance

t, °C

k

Next Page INORGANIC CHEMISTRY

1.233

TABLE 1.54 Thermal Conductivity of Various Solids (Continued) t, °C

Substance

1.14

k

CRITICAL PROPERTIES Critical temperature (Tc), critical pressure (Pc), and critical volume (Vc) represent three widely used pure component constants. These critical constants are very important properties in chemical engineering field because almost all other thermo chemical properties are predictable from boiling point and critical constants with using corresponding state theory. Therefore, precise prediction of critical constants is very necessary.

1.14.1

Critical Temperature The critical temperature of a compound is the temperature above which a liquid phase cannot be formed, no matter what the pressure on the system. The critical temperature is important in determining the phase boundaries of any compound and is a required input parameter for most phase equilibrium thermal property or volumetric property calculations using analytic equations of state or the theorem of corresponding states. Critical temperatures are predicted by various empirical methods according to the type of compound or mixture being considered. Another somewhat simpler method for estimating the critical temperature of pure compounds requires the normal boiling point, the relative density, and the compound family. log Tc = A + B log10 (relative density) + C log Tb where Tc and Tb are the critical and normal boiling temperatures, respectively, expressed in degrees Kelvin. The relative density of the liquid at 15°C is 0.1 MPa. The regression constants A, B, and C are available by family (Table 2-384). For pure inorganic compounds, the method only requires the normal boiling point as input. Tc = 1.64Tb

1.14.2

Critical Pressure The critical pressure of a compound is the vapor pressure of that compound at the critical temperature. Below the critical temperature, any compound above its vapor pressure will be a liquid.

Previous Page 1.234

SECTION ONE

1.14.3

Critical Volume The critical volume of a compound is the volume occupied by a specified mass of a compound at its critical temperature and critical pressure.

1.14.4

Critical Compressibility Factor The critical compressibility factor of a compound is calculated from the experimental or predicted values of the critical properties. Zc = (PcVc)/(RTc) Critical compressibility factors are used as characterization parameters in corresponding states methods to predict volumetric and thermal properties. The factor varies from approximately 0.23 for water to 0.26-0.28 for most hydrocarbons to above 0.30 for light gases. TABLE 1.55 Critical Properties Substance

Tc, °C

Air Aluminum tribromide Aluminum trichloride Ammonia Antimony tribromide Antimony trichloride Argon Arsenic Arsenic trichloride Arsine Arsine-d3

−140.6 490 356 132.4 631.4 521 −122.3 1400 318 99.9 98.9

Bismuth tribromide Bismuth trichloride Boron pentafluoride Boron tribromide Boron trichloride Boron trifluoride Bromine Antimony tribromide Antimony trichloride Argon Arsenic Arsenic trichloride Arsine Arsine-d3

946 906 205 308 178.8 −12.3 315 631.4 521 −122.3 1400 318 99.9 98.9

Benzaldehyde Benzene Benzoic acid Benzonitrile Benzyl alcohol Biphenyl Bismuth tribromide Bismuth trichloride Boron pentafluoride Boron tribromide Boron trichloride

422 288.90 479 426.3 422 516 946 906 205 308 178.8

Pc, atm

Pc, MPa

37.2 28.5 26 111.3 56

3.77 2.89 2.63 11.28 5.67

48.1 58.4 63.3

Vc, cm3 ⋅ mol−1

pc, g ⋅ cm−3

92.7 310 261 72.5

0.313 0.860 0.510 0.235

4.87

270 74.6

0.84 0.536

5.91 6.41

252 133

0.720 0.588

118

11.96

301 261

1.49 1.21

48.1 38.2 49.2 102 56

4.87 3.87 4.98 10.3 5.67

272 266 124 135

0.921 0.441 0.549 1.184

48.1

4.87

270 74.6

0.84 0.536

58.4 63.3

5.91 6.41

252 133

0.720 0.588

45.9 48.31 41.55 41.55 42.4 38.0

4.65 4.895 4.21 4.21 4.3 3.85 11.96

324 255 341 339 334 502 301 261

0.327 0.306 0.358 0.304 0.324 0.307 1.49 1.21

4.87 3.87

272 266

0.921 0.441

118 48.1 38.2

INORGANIC CHEMISTRY

1.235

TABLE 1.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Carbon dioxide Carbon disulfide Carbon monoxide Carbonyl chloride Carbonyl sulfide Cesium Chlorine Chlorine pentafluroide Chlorine trifluoride

31.1 279 −140.2 182 102 1806 143.8 142.6 153.5

72.8 78.0 34.5 56 58

7.38 7.90 3.50 5.67 5.88

76.1 51.9

Deuterium (equilibrium) Deuterium (normal) Deuterium bromide Deuterium chloride Deuterium hydride (DH) Deuterium iodide Deuterium oxide Diborane Dihydrogen disulfide Dihydrogen heptasulfide Dihydrogen hexasulfide Dihydrogen octasulfide Dihydrogen pentasulfide Dihydrogen tetrasulfide Dihydrogen trisulfide

−234.8 −234.7 88.8 50.3 −237.3 148.6 370.9 166 299 742 707 767 657 582 465

Flurorine

−129.0

Germanium tetrachloride

276.9

Hafnium tetrabromide Hafnium tetrachloride Hafnium tetraiodide Helium (equilibrium) Helium-3 Helium-4 Hydrazine Hydrogen (equilibrium) Hydrogen (normal) Hydrogen bromide Hydrogen chloride Hydrogen cyanide Hydrogen deuteride Hydrogen fluoride Hydrogen iodide Hydrogen selenide Hydrogen sulfide Iodine Krypton Mercury Mercury(II) bromide Mercury(II)chloride Mercury(II) iodide

473 450 643 −267.96 −269.85 −267.96 380 −240.17 −239.91 89.8 51.40 183.5 −237.25 188 150.7 137 100.4 546 −63.75 1477 789 700 799

Neon Niobium pentabromide Niobium pentachloride Niobium pentafluoride

−228.71 737 534 464

Vc,cm3 ⋅ mol-1

pc, g ⋅ cm-3

7.71 5.26

94.0 173 93.1 190 140 300 124 230.9

0.468 0.41 0.301 0.52 0.44 0.44 0.573 0.565

16.28 16.43

1.650 1.665

60.4 60.3

0.0668 0.0669

14.64

1.483

62.8

0.0481

55.6

0.360

66.2

0.574

213.8 39.5 58.3 33 36 32 38.4 43.1 50.6

21.66 4.00 5.91 3.34 3.65 3.24 3.89 4.37 5.13

51.47

5.215

38

3.85

330

0.650

57.0

5.86

415 304 528

2.261 1.13 2.24 14.5 12.77 12.8 84.4 82.0 53.2 14.64 64 82.0 88 88.2 115 54.3 1587

0.2289 0.1182 0.227 1.47 1.294 1.297 8.55 8.31 5.39 1.483 6.5 8.31 8.9 8.94 11.7 5.50 160.8

72.5 57.3 96.1 65.4 65.0 100.0 81.0 139 62.8 69 131

1.20 1.05 1.30 0.06930 0.0414 0.0698 0.333 0.0308 0.0310 0.809 0.45 0.195 0.048 0.29 0.976

98.5 155 91.2

0.31 0.164 0.9085

27.2

2.77

62

6.28

41.7 469 400 155

0.4835 1.05 0.68 1.21 (Continued)

1.236

SECTION ONE

TABLE 1.55 Critical Properties (Continued) Substance Nitric oxide Nitrogen-14 Nitrogen-15 Nitrogen chloride difluoride Nitrogen dioxide (equilibrium) Nitrogen trideuteride (ND3) Nitrogen trifluoride Nitrous oxide Nitrosyl chloride Nitryl fluoride Osmium tetroxide Oxygen Oxygen difluoride Ozone Phosgene Phosphine Phosphine-d3 Phosphonium chloride Phosphorus Phosphorus bromide difluoride Phosphorus chloride difluoride Phosphorus dibromide fluoride Phosphorus dichloride fluoride Phosphorus pentachloride Phosphorus trichloride Phosphorus trifluoride Phosphoryl chloride difluoride Phosphoryl trichloride Phosphoryl trifluoride

Tc, °C

Pc, atm

−92.9 146.94 146.8 64.3 158.2 132.4 −39.3 36.434 167 76.3

64.6 33.5 33.5 50.8 100

6.55 3.39 3.39 5.15 10.1 4.53 7.2545 9.12

132 −118.56 −58.0 −12.10

170 49.77 48.9 53.8

17.2 5.043 4.95 5.45

182 51.3 50.4 49.1 721 113 89.2 254 189.9 372 290 −1.9 150.7 329 73.4

56 64.5

5.67 6.54

72.7

7.37

44.6

4.52

49.3

5.00

42.7 43.4

4.33 4.40

Radon Rhenium(VII) oxide Rhenium(VI) oxide tetrachloride Rubidium

104 669 508 1832

Selenium Silane Silicon chloride trifluoride Silicon tetrabromide Silicon tetrachloride Silicon tetrafluoride Silicon trichloride fluoride Sulfur Sulfur dioxide Sulfur hexafluoride Sulfur tetrafluoride Sulfur trioxide

1493 −3.5 34.5 390 234 −14.0 165.4 1041 157.7 45.6 91.7 217.9

Tantalum pentabromide Tantalum pentachloride Tin(IV) chloride Titanium tetrachloride Tungsten (VI) oxide tetrachloride

44.7 71.596 90

Pc, MPa

701 494 318.7 365 509

41.8

4.24

62

6.28

47.8 34.2

4.84 3.47

37 36.7 35.3 116 77.8 37.1

3.75 3.72 3.57 11.7 7.88 3.76

81

8.2

37.0 46

3.75 4.66

Uranium hexafluoride

232.7

45.5

4.61

Water

374.2

217.6

22.04

Vc,cm3 ⋅ mol−1 58 89.5 90.4

pc, g ⋅ cm−3 0.52 0.313 0.332

170

0.557

97.4 139

0.4525 0.471

73.4 97.7 88.9

0.436 0.553 0.540

190

0.52

260

0.528

139 334 161 250

1.6

326

0.521

122 198

0.5240 0.734

0.95 0.34

130

0.633

461 400 351 340 338

1.26 0.89 0.742 0.558 1.01

250 56.0

1.41 0.325

INORGANIC CHEMISTRY

1.237

TABLE 1.55 Critical Properties (Continued) Tc, °C

Substance Xenon

16.583

Zirconium tetrabromide Zirconium tetrachloride Zirconium tetraiodide

532 505 687

Vc,cm3 ⋅ mol−1

pc, g ⋅ cm−3

5.84

118

1.105

5.77

415 319 528

0.99 0.730 1.13

Pc, atm

Pc, MPa

57.64 56.9

1.15 THERMODYNAMIC FUNCTIONS (CHANGE OF STATE) All substances can exist in one of three forms (also called states or phases) that basically depend on the temperature of the substance. These states or phases are (1) solid, (2) liquid, and (3) gas. The solid-to-liquid transition is a melting process, and the heat required is the heat of melting. The liquid-to-solid transition is the reverse process, and the heat liberated is the heat of freezing. The solid-to-gas transition is a sublimation process, and the heat required is the heat of sublimation. The liquid-to-gas transition is a vaporization process, and the heat required is the heat of vaporization (heat of boiling). Both the gas-to-solid and the gas-to-liquid processes are condensation processes and have an associated heat of condensation. Each change of state is accompanied by a change in the energy of the system. Wherever the change involves the disruption of intermolecular forces, energy must be supplied. The disruption of intermolecular forces accompanies the state going toward a less ordered state. As the strengths of the intermolecular forces increase, greater amounts of energy are required to overcome them during a change in state. The melting process for a solid is also referred to as fusion, and the enthalpy-change associated with melting a solid is often called the heat of fusion (AHfus). The heat needed for the vaporization of a liquid is called the heat of vaporization (AHvap). The specific heat is the amount of heat per unit mass required to raise the temperature by one degree Celsius. The relationship between heat and temperature change is usually expressed in the form shown below where c is the specific heat. The relationship does not apply if a phase change is encountered, because the heat added or removed during a phase change does not change the temperature. Q = cm∆T i.e., heat added is equal to the specific heat multiplied by the mass (weight) multiplied by the temperature difference (∆T = tfinal – tinitial) TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds Substance Ac Actinium Al Aluminum Al3+ std. state Al6BeO10 Al(BH4)3 AlBr3 std. state Al4C3 Al(CH3)3 Al(OAc)3 AlCl3 std. state AlCl3 ⋅ 6H2O AlF3 std. state

Physical state

∆iH° kJ ⋅ mol−1

c c g aq c lq c aq c lq c c aq c c aq

0 0 330.0(40) −538.4(15) −5624 −16.3 −527.2 −895 −216 136.4 −1892.4 −704.2 −1033 −2692 −1510.4(13) −1531.0

∆iG° kJ ⋅ mol−1

S° J ⋅ deg−1 ⋅ mol−1

0 0 289.4 −485.3 −5317 145.0 −488.5 −799 −203 −10.0

56.5 28.30(10) 164.554(4) −325.(10) 175.6 289.1 180.2 −74.5 89 209.4

−628.8 −878 −2269 −1431.1 −1322

109.29 −152.3 377 66.5(5) −363.2

C°p J ⋅ deg−1 ⋅ mol−1 27.2 24.4 21.4 265.19 194.6 100.58

155.6 91.13

75.13 (Continued)

1.238

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° C°p J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.239

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° C°p J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.240

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

C°p J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.241

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° C°p J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.242

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

C°p J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.243

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° C°p J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.244

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.245

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.246

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.247

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.248

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.249

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.250

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.251

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.252

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.253

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.254

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.255

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.256

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.257

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.258

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.259

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.260

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.261

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.262

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.263

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.264

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.265

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.266

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.267

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.268

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.269

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.270

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.271

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.272

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.273

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.274

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.275

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.276

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.277

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

1.278

SECTION ONE

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

INORGANIC CHEMISTRY

1.279

TABLE 1.56 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of the Elements and Inorganic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° S° C°p kJ ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1 J ⋅ deg−1 ⋅ mol−1

1.280

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds Abbreviation Used in the Table Hm, enthalpy of melting (at the melting point) in kJ ⋅ mol–1 Hv, enthalpy of vaporization (at the boiling point) in kJ ⋅ mol–1 Hs, enthalpy of sublimation (or vaporization at 298 K) in kJ ⋅ mol–1 Cp, specific heat (at temperature specified on the Kelvin scale) for the physical state in existence (or specified: c, lq, g) at that temperature in J ⋅ K–1 ( mol–1 Ht, enthalpy of transition (at temperature specified, superscript, measured in degrees Celsius) in kJ ⋅ mol–1 Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.281

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.282

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.283

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.284

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.285

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.286

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.287

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.288

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.289

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.290

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.291

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.292

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.293

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.294

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.295

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.296

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.297

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

(Continued)

1.298

SECTION ONE

TABLE 1.57 Heats of Fusion, Vaporization, and Sublimation and Specific Heat at Various Temperatures of the Elements and Inorganic Compounds (Continued) Cp Substance

∆Hm

∆Hv

∆Hs

400 K

600 K

800 K

1000 K

INORGANIC CHEMISTRY

1.299

1.16 ACTIVITY COEFFICIENTS The activity coefficient is the ratio of the chemical activity of any substance to its molar concentration. The measured concentration of a substance may not be an accurate indicator of its chemical effectiveness, as represented by the equation for a particular reaction, in which case an activity coefficient is arbitrarily established and used instead of the concentration… Although it is not possible to measure an individual ionic activity coefficient, fi, it may be estimated from the following equation of the Debye-Hückel theory: − log fi =

Azi2 I I + Bao I

where I is the ionic strength of the medium, and å is the ion-size parameter—the effective ionic radius (Table 1.32). The values of A and B vary with the temperature and dielectric constant of the solvent; values from 0 to 100C for aqueous medium (å in angstrom units) are listed in Table 1.59. Corresponding values of A and B for unit weight of solvent (when employing molality) can be obtained by multiplying the corresponding values for unit volume (molarity units) by the square root of the density of water at the appropriate temperature. The ionic strength can be estimated from the summation of the product molarity times ionic charge squared for all the ionic species present in the solution, i.e., I = 0.5 (c1z12 + c2z22 + … + ci z2i ). Values for the activity coefficients of ions in water at 25°C are given in Table 8.1 in terms of their effective ionic radii. At moderate ionic strengths a considerable improvement is effected by subtracting a term bI from the Debye-Hückel expression; b is an adjustable parameter which is 0.2 for water at 25°C. Table 1.58 gives the values of the ionic activity coefficients (for zi from 1 to 6) with å taken to be 4.6Å. In general, the mean ionic activity coefficient is given by f± = ( x + y ) f+x f−y where f+, f– are the individual ionic activity coefficients, and x,y are the charge numbers (z+, z–) of the respective ions. In binary electrolyte solution. f± =

f+ f−

In ternary electrolytes, e.g., BaCl2 or K2SO4, f± = 3 f+ f−2 or f± = 3 f+2 f− In quaternary electrolytes, e.g., LaCl3 or K3[Fe(CN)6], f± = 4 f+ f−3 or f± = 4 f+3 f−

1.300

SECTION ONE

TABLE 1.58 Individual Activity Coefficients of Ions in Water at 25°C fi at Ionic Strength of Effective Ionic Radii å (in Å)

0.001

0.01

0.005

0.05

0.1

TABLE 1.59 Constants of the Debye-Hückel Equation from 0 to 100°C − log fi =

Azi2 I I + Bao I Unit Volume of Solvent

Unit Volume of Solvent Temp., °C

Temp., °C

The values for unit weight of solvent (molality scale) can be obtained by multiplying the corresponding values for unit volume by the square root of the density of water at the appropriate temperature.

INORGANIC CHEMISTRY

1.301

TABLE 1.60 Individual Ionic Activity Coefficients at Higher Ionic Strengths at 25°C The values were calculated from the modified Debye-Hückel equation utilizing the modifications proposed by Robinson and by Guggenheim and Bates: −

0.511I log fi = − 0.2 I 1 + 1.5 I zi2

where I is the ionic strength and å is assumed to be 4.6 Å.

I

−

log10 fi zi2

1.17 BUFFER SOLUTIONS A buffer solution is a solution that resists changes in pH when small quantities of an acid or an alkali are added. An acidic buffer solution is a solution that has a pH less than 7. Acidic buffer solutions are commonly made from a weak acid and one of its salts. A common example is a mixture of ethanoic acid and sodium ethanoate in solution. In this case, if the solution contained equal molar concentrations of both the acid and the salt, the pH would be 4.76. The pH of the buffer solution can be changed by changing the ratio of acid to salt, or by choosing a different acid and one of its salts. An alkaline buffer solution has a pH greater than 7. Alkaline buffer solutions are commonly made from a weak base and one of its salts. An example is a mixture of ammonia solution and ammonium chloride solution. If these were mixed in equal molar proportions, the solution would have a pH of 9.25. To prepare the standard pH buffer solutions recommended by the National Bureau of Standards (U.S.), the indicated weights of the pure materials should be dissolved in water of specific conductivity not greater than 5 micromhos. The tartrate, phthalate, and phosphates can be dried for 2 h at 100°C before use. Potassium tetroxalate and calcium hydroxide need not be dried. Fresh-looking crystals of borax should be used. Before use, excess solid potassium hydrogen tartrate and calcium hydroxide must be removed. Buffer solutions pH 6 or above should be stored in plastic containers and should be protected from carbon doxide with soda-lime traps. The solutions should be replaced within 2 to 3 weeks, or sooner if formation of mold is noticed. A crystal of thymol may be added as a preservative.

1.17.1 Standards for pH Measurement of Blood and Biological Media Blood is a well-buffered medium. In addition to the NBS phosphate standard of 0.025 M (pHs = 6.480 at 38°C), another reference solution containing the same salts, but in the molal ratio 1:4, has an ionic

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SECTION ONE

strength of 0.13. It is prepared by dissolving 1.360 g of KH2PO4 and 5.677 g of Na2HPO4 (air weights) in carbon dioxide-free water to make 1 liter of solution. The pHs is 7.416 ± 0.004 at 37.5 and 38°C. The compositions and pHs values of tris(hydroxymethyl)aminomethane, covering the pH range 7.0 to 8.9, are listed in Table 1.63. When there are two or more acid groups per molecule, or a mixture is composed of several overlapping acids, the useful range is larger. Universal buffer solutions consist of a mixture of acid groups which overlap such that successive pKa values differ by 2 pH units or less. The PrideauxWard mixture comprises phosphate, phenyl acetate, and borate plus HCl and covers the range from 2 to 12 pH units. The McIlvaine buffer is a mixture of citric acid and Na2HPO4 that covers the range from pH 2.2 to 8.0. The Britton-Robinson system consists of acetic acid, phosphoric acid, and boric acid plus NaOH and covers the range from pH 4.0 to 11.5. A mixture composed of Na2CO3, NaH2PO4, citric acid, and 2-amino-2-methyl-1,3-propanediol covers the range from pH 2.2 to 11.0. General directions for the preparation of buffer solutions of varying pH but fixed ionic strength are given by Bates.* Preparation of McIlvaine buffered solutions at ionic strengths of 0.5 and 1.0 and Britton-Robinson solutions of constant ionic strength have been described by Elving et al.† and Frugoni,‡ respectively.

*

Bates, Determination of pH, Theory and Practice, Wiley, New York, 1964, pp. 121–122. Elving, Markowitz, and Rosenthal, Anal. Chem., 28:1179 (1956). ‡ Frugoni, Gazz. Chim. Ital., 87:L403 (1957). †

TABLE 1.61 National Bureau of Standards (U.S.) Reference pH Buffer Solutions

Source: R. G. Bates, J. Res. Natl. Bur. Stand. (U.S.), 66A:179(1962) and B. R. Staples and R. G. Bates, J. Res. Natl. Bur. Stand. (U.S.), 73A:37 (1969). Note: The uncertainty is ±0.003 in pH in the range 0–50°C, rising to ±0.02 above 70°C.

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TABLE 1.62 Compositions of Standard pH Buffer Solutions [National Bureau of Standards (U.S.)]

TABLE 1.63 Composition and pH Values of Buffer Solutions 8.107 Values based on the conventional activity pH scale as defined by the National Bureau of Standards (U.S.) and pertain to a temperature of 25°C [Ref: Bower and Bates, J. Research Natl. Bur. Standards (U.S.), 55:197 (1955) and Bates and Bower, Anal. Chem., 28:1322 (1956)]. Buffer value is denoted by column headed b.

INORGANIC CHEMISTRY

1.305

TABLE 1.63 Composition and pH Values of Buffer Solutions 8.107 (Continued)

pH

pH

pH

(Continued)

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TABLE 1.63 Composition and pH Values of Buffer Solutions 8.107 (Continued)

The phosphate-succinate system gives the values of pHs Molality Molality KH2PO4 = Na2HC6H5O7

pHs

∆(pHs/∆t)

0.005 0.010 0.015 0.020 0.025

6.251 6.197 6.162 6.131 6.109

−0.000 86 deg−1 −0.000 71 −0.004

TABLE 1.64 Standard Reference Values pH for the Measurement of Acidity in 50 Weight Percent Methanol-Water

OAc = acetate Suc = succinate Reference: R. G. Bates, Anal Chem., 40(6):35A (1968).

INORGANIC CHEMISTRY

1.307

TABLE 1.65 pH Values for Buffer Solutions in Alcohol-Water Solvents at 25°C Liquid-junction potential not included. Solvent composition (weight per cent alcohol)

0.01M H2C2O4, 0.01M NH4HC2O4

0.01M H2Suc, 0.01M LiHSuc

Methanol-Water Solvents 2.15 2.19 2.25 2.30 2.38 2.47 2.58 2.76 3.13 3.73 3.90 4.10 4.39 4.84 5.20 5.79 Ethanol-Water Solvents 2.15 2.32 2.51 2.98

0 10 20 30 40 50 60 70 80 90 92 94 96 98 99 100 0 30 50 71.9 100

4.12 4.30 4.48 4.67 4.87 5.07 5.30 5.57 6.01 6.73 6.92 7.13 7.43 7.89 8.23 8.75

0.01M HSal, 0.01M NaSal

7.53

4.12 4.70 5.07 5.71 8.32

Suc = succinate

Sal = salicylate

1.17.2 Buffer Solutions Other Than Standards The range of the buffering effect of a single weak acid group is approximately one pH unit on either side of the pKa. The ranges of some useful buffer systems are collected in Table 1.66. After all the components have been brought together, the pH of the resulting solution should be determined at the temperature to be employed with reference to standard reference solutions. Buffer components should be compatible with other components in the system under study; this is particularly significant for buffers employed in biological studies. Check tables of formation constants to ascertain whether metal-binding character exists.

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TABLE 1.66 pH Values of Biological and Other Buffers for Control Purposes

INORGANIC CHEMISTRY

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TABLE 1.66 pH Values of Biological and Other Buffers for Control Purposes (Continued)

(Continued)

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TABLE 1.66 pH Values of Biological and Other Buffers for Control Purposes (Continued)

1.18 SOLUBILITY AND EQUILIBRIUM CONSTANT The equilibrium constant is the value of the reaction quotient for a system at equilibrium. The reaction quotient is the ratio of molar concentrations of the reactants to those of the products, each concentration being raised to the power equal to the coefficient in the equation. For the hypothetical chemical reaction A+B↔C+D the equilibrium constant, K, is: K = [C][D]/[A][B] The notation [A] signifies the molar concentration of species A. An alternative expression for the equilibrium constant can involve the use of partial pressures. The equilibrium constant can be determined by allowing a reaction to reach equilibrium, measuring the concentrations of the various solution-phase or gas-phase reactants and products, and substituting these values into the relevant equation.

INORGANIC CHEMISTRY

1.311

TABLE 1.67 Solubility of Gases in Water The column (or line entry) headed “a” gives the volume of gas (in milliliters) measured at standard conditions (0°C and 760 mm or 101.325 kN ⋅ m–2) dissolved in 1 mL of water at the temperature stated (in degrees Celsius) and when the pressure of the gas without that of the water vapor is 760 mm. The line entry “A” indicates the same quantity except that the gas itself is at the uniform pressure of 760 mm when in equilibrium with water. The column headed “l” gives the volume of the gas (in milliliters) dissolved in 1 mL of water when the pressure of the gas plus that of the water vapor is 760 mm. The column headed “q” gives the weight of gas (in grams) dissolved in 100 g of water when the pressure of the gas plus that of the water vapor is 760 mm. Air*

Acetylene Temp., °C

a

q

a(×103)

Ammonia % oxygen in air

*Free from NH3 and CO2; total pressure of air + water vapor is 760 mm.

a

q

Bromine a

q

Next Page 1.312 TABLE 1.67 Solubility of Gases in Water

Previous Page

(Continued)

1.313

1.314 TABLE 1.67 Solubility of Gases in Water (Continued)

*Atmospheric nitrogen containing 98.815% N2 by volume + 1.185% inert gases.

TABLE 1.67 Solubility of Gases in Water

1.315

1.316 TABLE 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures Solubilities are expressed as the number of grams of substance of stated molecular formula which when dissolved in 100 g of water make a saturated solution at the temperature stated (°C).

(Continued)

1.317

1.318 TABLE 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures (Continued)

(Continued)

1.319

1.320 TABLE 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures (Continued)

(Continued)

1.321

1.322 TABLE 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures (Continued)

(Continued)

1.323

1.324 TABLE 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures (Continued) Substance

(Continued)

1.325

1.326 TABLE 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures (Continued) Substance

(Continued)

1.327

1.328 TABLE 1.68 Solubility of Inorganic Compounds and Metal Salts of Organic Acids in Water at Various Temperatures (Continued) Substance

*Properly called dihydrogen ethylenediaminetetraacetate (Na2H2 EDTA ⋅ 2H2O).

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TABLE 1.69 Dissociation Constants of Inorganic Acids The dissociation constant of an acid Ka may conveniently be expressed in terms of the pKa value where pKa = −log10 (Ka/mol dm−3). The values given in the following table are for aqueous solutions at 298 K: the pK1, pK2, and pK3 values refer to the first, second, and third ionizations respectively. Name

Formula

Aluminium ion (hydrated) Ammonium ion Arsenic(III) acid Arsenic(V) acid Boric acid Bromic(1) acid Carbonic acid

[Al(H2O)6]3+ NH4+ H3AsO3 H3AsO4 H3BO3 HOBr H2CO3

Chloric(I) acid Chloric(III) acid Chromium(III) ion (hydrated) Hydrazinium ion Hydrocyanic acid Hydrofluoric acid Hydrogen peroxide Hydrogen sulphide

HOCl HClO2 [Cr(H2O)6]3+ N2H5+ HCN HF H2O2 H2S +

Hydroxyammonium ion Iodic(I) acid Iodic(V) acid Iron(III) ion (hydrated) Lead(II) ion (hydrated) Nitrous acid Phosphinic acid Phosphoric(V) acid

NH3OH HOI HIO3 [Fe(H2O)6]3+ [Pb(H2O)n]2+ HNO2 H3PO2 H3PO4

Phosphonic acid

H3PO3

Silicic acid

H2SiO3

Sulphuric acid Sulphurous acid

H2SO4 H2SO3

pKa 4.9 (pK1) 9.25 9.22 (pK1) 2.30 (pK1) 9.24 (pK1) 8.70 6.38a (pK1) 10.32 (pK2) 7.43 2.0 3.9 (pK1) 7.93 9.40 3.25 11.62 (pK1) 7.05 (pK1) 12.92 (pK2) 5.82 10.52 0.8 2.22 (pK1) 7.8 (pK1) 3.34 2.0 2.15 (pK1) 7.21 (pK2) 12.36 (pK3) 2.00 (pK1) 6.58 (pK2) 9.9 (pK1) 11.9 (pK2) 1.92 (pK2) 1.92 (pK1) 7.21 (pK2)

{

{

{

{ { {

a Some of the unionized acid exists as dissolved CO2 molecules rather than H2CO3: pK1 for the molecular species H2CO3 is approximately 3.7.

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INORGANIC CHEMISTRY

TABLE 1.70 Ionic Product Constant of Water This table gives values of pKw on a modal scale, where Kw is the ionic activity product constant of water. Values are from W. L. Marshall and E. U. Franck, J. Phys. Chem. Ref. Data, 10:295 (1981).

TABLE 1.71 Solubility Product Constants The data refer to various temperatures between 18 and 25°C, and were complied from values cited by Bjerrum, Schwarzenbach, and Sillen, Stability Constants of Metal Complexes, Part II, Chemical Society, London, 1958, and values taken from publications of the IUPAC Solubility Data Project: Solubility Data Series, international Union of Pure and Applied Chemistry, Pergamon Press, Oxford, 1979–1992; H. L. Clever, and F. J. Johnston, J. Phys Chem. Ref. Data, 9:751 (1980); Y. Marcus, Ibid. 9:1307 (1980); H. L. Clever, S. A. Johnson, and M. E. Derrick, Ibid. 14:631 (1985), and 21:941 (1992). In the table, “L” is the abbreviation of the organic ligand. Compound

Formula

pKsp

Ksp

(Continued)

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

INORGANIC CHEMISTRY

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

(Continued)

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

INORGANIC CHEMISTRY

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

(Continued)

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

INORGANIC CHEMISTRY

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

(Continued)

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

INORGANIC CHEMISTRY

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

(Continued)

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TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

INORGANIC CHEMISTRY

1.341

TABLE 1.71 Solubility Product Constants (Continued) Compound

Formula

pKsp

Ksp

(Continued)

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TABLE 1.71 Solubility Product Constants (Continued) Compound

pKsp

Formula

Ksp

TABLE 1.72 Stability Constants of Complex Ions The stability constant of a complex ion is a measure of its stability with respect to dissociation into its constituent species at a given temperature, e.g. the formation of the tetra-amminecopper(II) ion may be represented by the equation Cu2+ + 4NH3 = [Cu(NH3)4]2+ and the stability constant is given by Kstab =

[Cu( NH 3 )24+ ] [Cu 2 + ][NH 3 ]4

The higher the stability constant the more stable the complex ion. v denotes the stoichiometric number of a molecule, atom or ion, and is positive for a product and negative for a reactant.

Equilibrium Ag+ + 2CN- = [Ag(CH)2]− Ag+ + NH3 = [Ag(NH3)]+ [Ag(NH3)]+ + NH3 = [Ag(NH3)2]+ Ag+ + 2NH3 = [Ag(NH3)2]+ Ag+ + 2S2O32− = [Ag(S2O3)2]3− Al3+ + 6F − = [AlF6]3− Al(OH)3 + OH− = [Al(OH)4]− Cd2+ + 4CN− = [Cd(CN)4]2− Cd2+ + 4I− = [CdI4]2− Cd2+ + 4NH3 = [Cd(NH3)4]2+ Co2+ + 6NH3 = [Co(NH3)6]2+ Co3+ + 6NH3 = [Co(NH3)6]3+ Cr(OH)3 + OH− = [Cr(OH)4]− Cu+ + 4CN− = [Cu(CN)4]3− Cu2+ + 4Cl− = [CuCl4]2− Cu+ + 2NH3 = [Cu(NH3)2]+

Kstab (mol ⋅ dm −3 ) Σv 1⋅0 × 1021 2⋅5 × 103 6⋅3 × 103 1⋅7 × 107 1⋅0 × 1013 6 × 1019 40 7⋅1 × 1016 2 × 106 4⋅0 × 106 7⋅7 × 104 4⋅5 × 1033 1 × 10−2 2⋅0 × 1027 4⋅0 × 105 1 × 1011

  Kstab log10  −3 Σv  (mol ⋅ dm )   21⋅0 3⋅4 3⋅8 7⋅2 13⋅0 19⋅8 1⋅6 16⋅9 6⋅3 6⋅6 4⋅9 33⋅7 −2 27⋅3 5⋅6 11

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INORGANIC CHEMISTRY

TABLE 1.72 Stability Constants of Complex Ions (Continued)   Kstab log10  −3 Σv   (mol ⋅ dm ) 

Kstab (mol ⋅ dm −3 ) Σv

Equilibrium

2⋅0 × 104 (K1) 4⋅2 × 103 (K2) 1⋅0 × 103 (K3) 1⋅7 × 102 (K4) 1⋅4 × 1013 (K = K1K2K3K4) ca. 1024 ca. 1031 8 × 10−2 1⋅4 × 102 16 1 2⋅5 × 1041 1⋅7 × 1016 2⋅0 × 1030 7⋅1 × 102 4⋅8 × 107 50 5 × 103 5 × 1016 3⋅8 × 109 10

Cu2+ + NH3 = [Cu(NH3)]2+ [Cu(NH3)]2+ + NH3 = [Cu(NH3)2]2+ [Cu(NH3)2]2+ + NH3 = [Cu(NH3)3]2+ [Cu(NH3)3]2+ + NH3 = [Cu(NH3)4]2+ Cu2+ + 4NH3 = [Cu(NH3)4]2+ Fe2+ + 6CN− = [Fe(CN)6]4− Fe3+ + 6CN− = [Fe(CN)6]3− Fe3+ + 4Cl− = [FeCl4]− Fe3+ + SCN− = [Fe(SCN)]2+ [Fe(SCN)]2+ + SCN− = [Fe(SCN)2]+ [Fe(SCN)2]+ + SCN− = Fe(SCN)3 Hg2+ + 4CN− = [Hg(CN)4]2− Hg2+ + 4Cl− = [HgCl4]2− Hg2+ + 4I− = [HgI4]2− I− + I2 = I3− Ni2+ + 6NH3 = [Ni(NH3)6]2+ Pb(OH)2 + OH− = [Pb(OH)3]− Sn(OH)4 + 2OH− = [Sn(OH)6]2− Zn2+ + 4CN− = [Zn(CN)4]2− Zn2+ + 4NH3 = [Zn(NH3)4]2+ Zn(OH)2 + 2OH− = [Zn(OH)4]2−

4⋅3 3⋅6 3⋅0 2⋅2 13⋅1 ca. 24 ca. 31 −1⋅1 2⋅1 1⋅2 0 41⋅4 16⋅2 30⋅3 2⋅9 7⋅7 1⋅7 3⋅7 16⋅7 9⋅6 1⋅0

TABLE 1.73 Saturated Solutions The following table provides the data for making saturated solutions of the substances listed at the temperature designated. Data are provided for making saturated solutions by weight (g of substance per 100 g of saturated solution) and by volume (g of substance per 100 ml of saturated solution and the ml of water required to make such a solution). To make one fluid ounce of a saturated solution: multiply the grams of substance per 100 ml of saturated solution by 4.55 to obtain the number of grains required, by 0.01039 to obtain the number of avoirdupois ounces, by 0.00947 to obtain the number of apothecaries (Troy) ounces; also multiply the ml of water by 16.23 to obtain the number of minims, or divide by 100 to obtain the number of fluid ounces. To make one fluid dram: multiply the grams of substance per 100 ml of saturated solution by 0.5682 to obtain the number of grains required; also multiply the ml of water by 0.60 to obtain the number of minims required.

Substance acetanilide p-acetophenetidin p-acetotoluide alanine aluminum ammonium sulfate aluminum chloride hydrated aluminum fluoride aluminum potassium sulfate aluminum sulfate

Formula C6H5NHCOCH3 C6H4(OC2H5)NHCH3CO CH3CONHC6H4CH3 CH3CH(NH2)COOH Al2(SO4)3(NH4)2SO4 ⋅ 24H2O AlCl3 ⋅ 6H2O Al2F6 ⋅ 5H2O AlK(SO4)2 Al2(SO4)3 ⋅ 18H2O

Temp, °C 25 25 25 25 25 25 20 25 25

g/100 g satd soln 0.54 0.0766 0.12 14.1 12.4 55.5 0.499 6.62 48.8

g/100 ml satd soln 0.54 0.0766 0.12 14.7 13 75 0.5015 7.02 63

ml water/ 100 ml satd soln 99.2 99.92 99.7 89.5 92 60 100.0 99.1 66

Specific gravity 0.997 1.00 0.9979 1.042 1.05 1.35 1.0051 1.061 1.29 (Continued)

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TABLE 1.73 Saturated Solutions (Continued)

Substance o-aminobenzoic acid DL-a-amino-n-butyric acid DL-a-aminoisobutyric acid ammonium arsenate ammonium benzoate ammonium bromide ammonium carbnonate ammonium chloride ammonium citrate, dibasic ammonium dichromate ammonium iodide ammonium molybdate ammonium nitrate ammonium oxalate ammonium perchlorate ammonium periodate ammonium persulfate ammonium phosphate, dibasic ammonium phosphate, monobasic ammonium salicylate ammonium silicofluoride ammonium sulfate ammonium sulfite ammonium thiocyanate amyl alcohol aniline aniline hydrochloride aniline sulfate L-asparagine barium bromide barium chlorate barium chloride barium iodide barium nitrate barium nitrite barium perchlorate benzamide benzoic acid beryllium sulfate boric acid n-butyl alcohol cadmium bromide cadmium chlorate cadmium chloride cadmium iodide cadmium sulfate calcium bromide

g/100 g satd soln

g/100 ml satd soln

ml water/ 100 ml satd soln

NH4Cl (NH4)2HC6H5O7 (NH4)2Cr2O7 NH4I (NH4)6Mo7O24 ⋅ 4H2O NH4NO3 (NH4)2C2O4 ⋅ H2O NH4ClO4 NH4IO4 (NH4)2S2O8 (NH4)2 ⋅ HPO4

25 25 25 20 25 15 25 15 25 25 25 25 25 25 25 16 25 14.5

0.52 17.8 13.3 32.7 18.6 41.7 20 26.3 48.7 27.9 64.5 30.6 68.3 4.95 21.1 2.63 42.7 56.2

0.519 18.6 13.7 40.2 19.4 53.8 22 28.3 60.5 33 106.2 39 90.2 5.06 23.7 2.68 53 75.5

99.4 86.2 89.5 83.0 84.7 75.2 88 79.3 61.5 85 58.3 88 41.8 97.0 88.7 99.2 71 58.8

0.999 1.046 1.031 1.228 1.040 1.290 1.10 1.075 1.22 1.18 1.646 1.27 1.320 1.019 1.123 1.018 1.24 1.343

NH4H2PO4

25

28.4

83

1.16

NH4C7H5O3 (NH4)2SiF6 (NH4)2SO4 (NH4)2SO3.H2O NH4CNS C5H11OH C6H5NH2 C6H5NH2 ⋅ HCl (C6H5NH2)2 ⋅ H2SO4 NH2COCH2CH(NH2)COOH BaBr2 Ba(ClO3)2 BaCl2 BaI2 ⋅ 712 H2O Ba(NO3)2 Ba(NO2)2 Ba(ClO4)2 C6H5CONH2 C7H6O2 BeSO4 ⋅ 4H2O H3BO3 CH3(CH2)2CH2OH CdBr2 ⋅ 4H2O Cd(ClO3)2 ⋅ 12H2O CdCl2 ⋅ 212 H2O CdI2 3(CdSO4) ⋅ 8H2O CaBr2

25 17.5 20 25 25 25 22 25 25 25 20 25 20 25 25 17 25 25 25 25 25 25 25 18 25 20 25 20

50.8 15.7 42.6 39.3 62.2 2.61 3.61 49 5.88 2.44 51 28.5 26.3 68.8 9.4 40 75.3 1.33 0.367 28.7 4.99 79.7 52.9 76.4 54.7 45.9 43.4 58.8

56.4 92.3 71.7 73.2 43 96.9 96.2 56 96 98.2 83.8 92.6 93.8 71.1 97.9 89.4 47.8 98.6 99.63 93.0 97 17.1 83.9 54.0 80.8 86.3 91.8 75.0

1.145 1.095 1.248 1.204 1.14 0.995 0.998 1.10 1.02 1.007 1.710 1.294 1.27 2.277 1.080 1.490 1.936 0.999 1.00 1.301 1.02 0.845 1.775 2.284 1.778 1.590 1.619 1.82

Formula C6H4NH2COOH CH3CH2CH(NH2)COOH (CH3)2C(NH2)COOH NH4H2AsO4 NH4C7H5O2 NH4Br

Temp, °C

33 58.2 17.2 53.1 47.3 71 2.60 3.61 54 6 2.46 87.2 36.8 33.4 157.0 10.2 59.6 145.8 1.33 0.367 37.3 5.1 67.3 94.0 174.5 97.2 73.0 70.3 107.2

Specific gravity

INORGANIC CHEMISTRY

1.345

TABLE 1.73 Saturated Solutions (Continued)

Substance calcium chlorate calcium chloride calcium chromate calcium ferrocyanide calcium iodide calcium lactate calcium nitrite calcium sulfate camphoric acid carbon disulfide cerium nitrate cesium bromide cesium chloride cesium iodide cesium nitrate cesium perchlorate cesium periodate cesium sulfate chloral hydrate chloroform chromic oxide chromium potassium sulfate citric acid cobalt chlorate cobalt nitrate cobalt perchlorate cupric ammonium chloride cupric ammonium sulfate cupric bromide cupric chlorate cupric chloride cupric nitrate cupric selenate cupric sulfate dextrose ether ethyl acetate ferric ammonium citrate ferric ammonium oxalate ferric ammonium sulfate ferric chloride ferric nitrate ferric perchlorate ferrous sulfate gallic acid D-glutamic acid glycine hydroquinone m-hydroxybenzoic acid

Formula Ca(ClO3)2 ⋅ 2H2O CaCl2 ⋅ 6H2O CaCrO4 ⋅ 2H2O Ca2Fe(CN)6 CaI2 Ca(C3H5O3)2 ⋅ 5H2O Ca(NO2)2 ⋅ 4H2O CaSO4 ⋅ 2H2O C8H14(COOH)2 CS2 Ce(NO3)3 ⋅ 6H2O CsBr CsCl CsI CsNO3 CsClO4 CsIO4 Cs2SO4 CCl3CHO ⋅ H2O CHCl3 CrO3 Cr2K2(SO4)4 ⋅ 24H2O (CH2)2COH(COOH)3 ⋅ H2O Co(ClO3)2 Co(NO3)2 Co(ClO4)2 CuCl2 ⋅ 2NH4Cl ⋅ 2H2O CuSO4 ⋅ (NH4)2SO4 CuBr2 Cu(ClO3)2 CuCl2 ⋅ 2H2O Cu(NO3)2 ⋅ 6H2O CuSeO4 CuSO4 ⋅ 5H2O C6H12O6 ⋅ H2O (C2H5)2O CH3COOC2H5 Fe(NH4)3(C2O4)3 ⋅ 3H2O FeSO4 ⋅ (NH4)2SO4 FeCl3 Fe(NO3)3 Fe(ClO4)3 ⋅ 10H2O FeSO4 ⋅ 7H2O C6H2(OH)3COOH ⋅ H2O C5H9O4N NH2CH2COOH C6H4(OH)2 C6H4OHCOOH

Temp, °C

g/100 g satd soln

g/100 ml satd soln

18 25 18 25 20 25 18 25 25 22 25 21.4 25 22.8 25 25 15 25 25 29.4 18 25 25 18 18 26 25 19 25 18 25 20 21.2 25 25 22 25 25 25 16.5 25 25 25 25 25 25 25 20 25

64.0 46.1 14.3 36.5 67.6 4.95 45.8 0.208 0.754 0.173 63.7 53.1 65.7 48.0 21.9 2.01 2.10 64.5 79.4 0.703 62.5 19.6 67.5 64.2 49.7 71.8 30.3 15.3 55.8 62.2 53.3 56.0 14.7 18.5 49.5 5.45 7.47 67.7 51.5 19.1 73.1 46.8 79.9 42.1 1.15 0.86 20.0 6.7 0.975

110.7 67.8 16.4 49.6 143.8 5 65.7 0.208 0.754 0.173 119.9 89.8 126.3 74.1 26.1 2.03 2.13 129.8 120 0.705 106.3 22 88.6 119.3 78.2 113.5 35.5 17.3 102.5 105.2 80 94.5 17.2 22.3 59 5.34 7.44 97 65 22.4 131.1 70.2 132.1 52.8 1.15 0.86 21.7 6.78 0.975

ml water/ 100 ml satd soln 62.3 79.2 98.7 86.2 69.0 96 77.8 99.70 99.246 99.63 68.2 79.5 65.9 80.5 92.9 99.0 99.5 71.7 31 99.57 64.0 90 42.7 66.5 79.1 44.7 82 96.0 81.2 64.1 70 74.3 99.4 98.7 60 93.0 92.1 46 61 94.3 48.3 79.8 33.2 72.7 99.05 99.15 86.8 94.4 99.03

Specific gravity 1.729 1.47 1.149 1.357 2.125 1.01 1.427 0.999 1.00 0.998 1.880 1.693 1.923 1.545 1.187 1.010 1.017 2.013 1.51 1.0028 1.703 1.12 1.311 1.857 1.572 1.581 1.17 1.131 1.84 1.692 1.50 1.688 1.165 1.211 1.19 0.985 0.996 1.43 1.26 1.165 1.793 1.50 1.656 1.255 1.002 1.0002 1.083 1.012 1.000 (Continued)

1.346

SECTION ONE

TABLE 1.73 Saturated Solutions (Continued)

Substance lactose lead acetate lead bromide lead chlorate lead chloride lead iodide lead nitrate DL-leucine L-leucine lithium benzoate lithium bromate lithium carbonate lithium chloride lithium citrate lithium dichromate lithium fluoride lithium formate lithium iodate lithium nitrate lithium perchlorate lithium salicylate lithium sulfate magnesium bromide magnesium chlorate magnesium chloride magnesium chromate magnesium dichromate magnesium iodate magnesium iodide magnesium molybdate magnesium nitrate magnesium perchlorate magnesium selenate magnesium sulfate manganese chloride manganese nitrate manganese silicofluoride manganese sulfate mercuric acetate mercuric bromide mercury bichloride methylene blue methyl salicylate monochloracetic acid b-naphthalenesulfonic acid nickel ammonium sulfate nickel chlorate nickel chlorate nickel nitrate

Formula C12H22O11 ⋅ H2O Pb(C2H3O2)2 PbBr2 Pb(ClO3)2 PbCl2 PbI2 Pb(NO3)2 C6H13O2N C6H13O2N LiC7H5O2 LiBrO3 Li2CO3 LiCl ⋅ H2O Li3C6H5O7 Li2Cr2O7 ⋅ H2O LiF LiCHO2 LiIO3 LiNO3 LiClO4 ⋅ 3H2O LiC7H5O3 Li2SO4 ⋅ H2O MgBr2 ⋅ 6H2O Mg(ClO3)2 MgCl2 ⋅ 6H2O MgCr2O4 ⋅ 7H2O MgCrO7 ⋅ 5H2O Mg(IO3)2 ⋅ 4H2O MgI2.8H2O MgMoO4 Mg(NO3)2 ⋅ 6H2O Mg(ClO4)2 ⋅ 6H2O MgSeO4 MgSO4 ⋅ 7H2O MnCl2 Mn(NO3)2 ⋅ 6H2O MnSiF6 MnSO4 Hg(C2H3O2)2 HgBr2 HgCl2 C16H18N3ClS ⋅ 3H2O C6H4OHCOOCH3 CH2ClCOOH C10H7SO3H NiSO4(NH4)2SO4 ⋅ 6H2O Ni(ClO3)2 Ni(ClO3)2 ⋅ 6H2O Ni(NO3)2 ⋅ 6H2O

Temp, °C

g/100 g satd soln

g/100 ml satd soln

25 25 25 18 25 25 25 25 25 25 18 15 25 25 18 18 18 18 19 25 25 25 18 18 25 18 25 18 18 25 25 25 20 25 25 18 17.5 25 25 25 25 25 25 25 30 25 18 18 25

15.9 36.5 0.97 60.2 1.07 0.08 37.1 0.976 2.24 27.7 60.4 1.36 45.9 31.8 52.6 0.27 27.9 44.6 48.9 37.5 52.7 27.2 50.1 56.3 62.5 42.0 81.0 6.44 59.7 15.9 42.1 49.9 35.3 55.3 43.6 57.3 37.7 39.4 30.2 0.609 6.6 4.25 0.12 78.8 56.9 9.0 56.7 64.5 77

17 49.0 0.98 117.0 1.08 0.08 53.6 0.975 2.24 30.4 110.5 1.38 59.5 38.6 82.9 0.27 31.8 69.9 64.5 47.6 63.6 33 83.1 90.0 79 59.7 138.8 6.95 114.0 18.4 58.6 73.6 50.8 72 63.2 93.2 54.5 59.1 38 0.610 6.96 4.3 0.12 105 67.9 9.5 94.2 107.2 122

ml water/ 100 ml satd soln 90 85.1 99.6 77.3 99.6 99.7 91.0 98.9 97.85 79.6 72.5 100.0 70.2 82.8 74.8 99.9 80.4 86.8 67.5 79.5 57.1 88.5 82.8 69.7 47.5 82.5 32.6 100.8 77.1 97.4 80.5 73.9 93.0 58.5 82.0 69.2 90.1 90.8 88 99.6 98.5 97 99.88 28 51.4 96 72.0 59.1 36

Specific gravity 1.07 1.340 1.006 1.944 1.007 0.998 1.445 0.999 1.0012 1.100 1.830 1.014 1.296 1.213 1.574 1.002 1.140 1.566 1.318 1.269 1.206 1.21 1.655 1.594 1.26 1.422 1.712 1.078 1.909 1.159 1.388 1.472 1.440 1.30 1.449 1.624 1.446 1.499 1.26 1.0023 1.054 1.01 1.00 1.33 1.193 1.05 1.658 1.661 1.58

INORGANIC CHEMISTRY

1.347

TABLE 1.73 Saturated Solutions (Continued)

Substance nickel perchlorate nickel perchlorate nickel sulfate DL-norleucine oxalic acid phenol b-phenylalanine m-phenylenediamine p-phenylenediamine phenyl salicylate phenyl thiourea phosphomolybdic acid phosphotungstic acid potassium acetate potassium antimony tartrate potassium bicarbonate potassium bitartrate potassium bromate potassium bromide potassium carbonate potassium chlorate potassium chloride potassium chromate potassium citrate potassium dichromate potassium ferricyanide potassium ferrocyanide potassium fluoride potassium formate potassium hydroxide potassium iodate potassium iodide potassium meta-antimonate potassium nitrate potassium nitrite potassium oxalate potassium perchlorate potassium periodate potassium permanganate potassium sodium tartrate potassium stannate potassium sulfate quinine salicylate resorcinol rubidium bromate rubidium bromide rubidium chloride rubidium iodate rubidium iodide rubidium nitrate

Formula

Temp, °C

Ni(ClO4)2 26 Ni(ClO4)2 ⋅ 9H2O 18 25 NiSO4 ⋅ 6H2O C6H13NO2 25 H2C2O4 ⋅ 2H2O 25 20 C6H5OH C6H5CH2CH(NH2)COOH 25 C6H8N2 20 20 C6H8N2 C6H4OHCOOC6H5 25 CS(NH2)NHC6H5 25 20MoO3 ⋅ 2H3PO4 ⋅ 48H2O 25 Approx. 20WO3 ⋅ 2H3PO4 ⋅ 25H2O 25 KC2H3O2 25 KSbOC4H4O6 25 KHCO3 25 KC4H5O6 25 KBrO3 25 KBr 25 K2CO3 ⋅ 112H2O 25 KClO3 25 KCl 25 K2CrO4 25 K3C6H5O7 25 K2Cr2O7 25 K3Fe(CN)6 22 K4Fe(CN)6 25 KF ⋅ 2H2O 18 KCHO2 18 KOH 15 KIO3 25 KI 25 KSbO3 18 KNO3 25 KNO2 20 K2C2O4 ⋅ H2O 25 KClO4 25 KIO4 13 KMnO4 25 KNaC4H4O6 ⋅ 4H2O 25 K2SnO3 15.5 K2SO4 25 C20H24N2O2 ⋅ C6H4(OH)COOH.2H2O 25 C6H4(OH)2 25 RbBrO3 16 RbBr 25 RbCl 25 RbIO3 15.6 RbI 24.3 RbNO3 25

g/100 g satd soln

g/100 ml satd soln

ml water/ 100 ml satd soln

70.8 52.4 47.3 1.13 9.81 6.1 2.88 23.1 3.69 0.015 0.24 74.3 71.4 68.7 7.64 26.6 0.65 7.53 40.6 52.9 8.0 26.5 39.4 60.91 13.0 32.1 24.0 48.0 76.8 51.7 8.40 59.8 2.73 28.0 74.3 28.3 2.68 0.658 7.10 39.71 42.7 10.83 0.065 58.8 2.15 52.7 48.6 2.72 63.6 40.1

112.2 82.7 64 1.13 10.3 6.14 2.89 23.8 3.70 0.015 0.24 135 160 97.1 8.02 31.6 0.65 7.89 56.0 82.2 8.41 31.2 54.1 92.1 14.2 38.1 28.2 72.0 120.6 79.2 8.99 103.2 2.81 33.4 121.5 34 2.72 0.661 7.43 51.9 69.2 11.8 0.065 67.2 2.18 85.6 72.8 2.78 117.7 55.0

46.4 75.1 71 98.97 94.2 94.5 97.5 79.3 96.67 99.84 99.6 46 64 44.3 96.9 87.5 99.3 97.5 82.0 73.5 96.6 86.8 83.7 59.2 95.0 80.8 89.2 78.0 36.4 74.2 98.0 69.1 99.7 86.0 42.3 86 99.0 99.83 97.3 78.8 92.9 96.9 99.84 47.2 99.4 76.9 77.1 99.5 67.3 82.4

Specific gravity 1.584 1.576 1.35 0.999 1.044 1.0057 1.0035 1.032 1.0038 0.999 0.998 1.81 2.24 1.413 1.049 1.188 0.999 1.054 1.380 1.559 1.051 1.178 1.381 1.514 1.092 1.187 1.173 1.500 1.571 1.536 1.071 1.721 1.025 1.193 1.649 1.20 1.014 1.005 1.046 1.308 1.620 1.086 0.999 1.142 1.016 1.625 1.050 1.022 1.850 1.375 (Continued)

1.348

SECTION ONE

TABLE 1.73 Saturated Solutions (Continued)

Substance rubidium perchlorate rubidium periodate rubidium sulfate silicotungstic acid silver acetate silver bromate silver fluoride silver nitrate silver perchlorate sodium acetate sodium ammonium sulfate sodium arsenate sodium benzenesulfonate sodium benzoate sodium bicarbonate sodium bisulfate sodium bromide sodium carbonate sodium chlorate sodium chloride sodium chromate sodium citrate sodium dichromate sodium ferrocyanide sodium fluoride sodium formate sodium hydroxide sodium hypophosphite sodium iodate sodium iodide sodium molybdate sodium nitrate sodium nitrite sodium oxalate sodium paratungstate sodium perchlorate sodium periodate sodium phenolsulfonate sodium phosphate dibasic sodium phosphate tribasic sodium pyrophosphate sodium salicylate sodium selenate sodium silicofluoride sodium sulfate sodium sulfate sodium sulfide sodium sulfite, anhydrous sodium thiocyanate

Formula RbClO4 RbIO4 Rb2SO4 H4SiW12O40 Ag(C2H3O2) AgBrO3 AgF ⋅ 2H2O AgNO3 AgClO4 ⋅ H2O NaC2H3O2 NaNH4SO4 Na3AsO4 ⋅ 12H2O NaC6H5SO3 NaC7H5O2 NaHCO3 NaHSO4 ⋅ H2O NaBr ⋅ 2H2O Na2CO3 ⋅ 10H2O NaClO3 NaCl Na2CrO4 Na3C6H5O7 ⋅ 5H2O Na2Cr2O7 Na4Fe(CN)6 NaF NaCHO2 NaOH NaH2PO2 NaIO3 ⋅ H2O NaI Na2MoO4 NaNO3 NaNO2 Na2(CO2)2 (Na2O)3(WO3)7 ⋅ 16H2O NaClO4 NaIO4 ⋅ 3H2O C6H4(OH)SO3Na Na2HPO4 Na3PO4 Na2H2P2O7 ⋅ 6H2O NaC7H5O3 Na2SeO4 NaSiF6 Na2SO4 Na2SO4 ⋅ 10H2O Na2S ⋅ 9H2O Na2SO3 NaCNS

Temp, °C

g/100 g satd soln

25 16 25 18 25 25 15.8 25 25 25 15 17 25 25 15 25 25 25 25 25 18 25 18 25 25 18 25 16 25 25 18 25 20 25 0 25 25 25 17 14 25 25 18 20 25 25 25 25 25

1.88 0.645 33.8 90.6 1.10 0.204 64.5 71.5 84.5 33.6 25.2 21.1 16.4 36.0 8.28 59 48.6 22.6 51.7 26.5 40.1 48.1 63.9 17.1 3.98 44.7 50.8 52.1 8.57 64.8 39.4 47.9 45.8 3.48 26.7 67.8 12.6 16.1 4.2 9.5 13.0 53.6 29.0 0.773 21.8 27.7 52.3 23 62.9

g/100 ml satd soln 1.90 0.648 45.6 258 1.11 0.2037 168.4 164 237.1 40.5 29.6 23.5 17.6 41.5 8.80 87 75.0 28.1 74.3 31.7 57.4 61.2 111.4 19.4 4.14 58.9 77 72.4 9.21 124.3 56.6 66.7 62.3 3.58 35.2 114.1 13.9 17.4 4.4 10.5 14.4 67.0 38.1 0.737 26.4 33.3 63 28.5 87

ml water/ 100 ml satd soln 99.3 99.85 89.7 26.8 99.40 99.65 92.7 65.5 43.5 80.0 87.9 88.0 90.1 73.9 97.6 60 79.4 96.5 69.6 88.1 85.7 66.0 63.0 93.9 99.7 73.0 74 66.6 98.5 67.7 87.0 72.5 73.8 99.1 96.5 54.1 96.2 90.5 99.9 99.8 95.8 58.0 93.4 99.76 94.5 87.0 57 95.5 51

Specific gravity 1.012 1.0052 1.354 2.843 1.0047 0.9985 2.61 2.29 2.806 1.205 1.174 1.119 1.076 1.152 1.061 1.47 1.542 1.242 1.440 1.198 1.430 1.272 1.743 1.131 1.038 1.316 1.51 1.386 1.075 1.919 1.435 1.391 1.359 1.025 1.316 1.683 1.103 1.079 1.043 1.103 1.104 1.248 1.313 1.0054 1.208 1.207 1.20 1.24 1.38

INORGANIC CHEMISTRY

1.349

TABLE 1.73 Saturated Solutions (Continued)

Substance sodium thiosulfate sodium tungstate stannous chloride strontium chlorate strontium chloride strontium iodide strontium nitrate strontium nitrite strontium perchlorate strontium salicylate succinic acid succinimide sucrose tartaric acid tetraethyl ammonium iodide tetramethyl ammonium iodide thallium chloride thallium nitrate thallium nitrite thallium perchlorate thallium sulfate trichloroacetic acid uranyl chloride uranyl nitrate urea urea phosphate urethan D-valine DL-valine zinc acetate zinc benzenesulfonate zinc chlorate zinc chloride zinc iodide zinc phenolsulfonate zinc selenate zinc silicofluoride zinc sulfate zinc valerate

ml water/ 100 ml satd soln

Temp, °C

g/100 g satd soln

g/100 ml satd soln

Na2S2O3 ⋅ 5H2O Na2WO4 ⋅ 10H2O SnCl2 Sr(ClO3)2 SrCl2 ⋅ 6H2O SrI2 ⋅ 6H2O Sr(NO3)2 Sr(NO2)2 Sr(ClO4)2 Sr(C7H5O3)2 (CH2)2(COOH)2 (CH2CO)2NH ⋅ H2O C12H22O11 C2H2(OH)2(COOH)2 N(C2H5)4I N(CH3)4I

25 18 15 18 15 20 25 19 25 25 25 25 25 15 25 25

66.8 42.0 72.9 63.6 33.4 64.0 44.2 39.3 75.6 4.58 7.67 30.6 67.89 58.5 32.9 5.51

93 66.1 133.1 117.0 45.5 137.8 65.3 56.8 158.5 4.68 7.82 32.7 90.9 76.9 36.2 5.60

46 91.3 49.5 67.0 90.7 77.5 82.5 87.8 50.8 97.5 94.5 74.2 43.0 54.7 74.0 96.1

1.39 1.573 1.827 1.839 1.36 2.15 1.477 1.445 2.084 1.019 1.021 1.067 1.340 1.31 1.102 1.016

TlCl TlNO3 TlNO2 TlClO4 Tl2SO4 CCl3COOH UO2Cl2 UO2(NO3)2 ⋅ 6H2O (NH2)2CO CO(NH2)2 ⋅ H3PO4 NH2CO2C2H5 (CH3)2CHCH(NH2)COOH (CH3)2CHCH(NH2)COOH Zn(C2H3O2)2 Zn(C6H5SO3)2 Zn(ClO3)2 ZnCl2 Znl2 (C6H5OSO3)2Zn ⋅ 8H2O ZnSeO4 ZnSiF6 ⋅ 6H2O ZnSO4 ⋅ 7H2O Zn(C5H9O2)2

25 25 25 25 25 25 18 25 25 24.5 25 25 25 25 25 18 25 18 25 22 20 25 25

0.40 10.4 32.1 13.5 5.48 92.3 76.2 68.9 53.8 52.4 82.8 8.14 6.61 25.7 29.5 65.0 67.5 81.2 39.8 37.8 32.9 36.7 1.27

0.40 11.4 43.7 15.2 5.74 149.6 208.5 120 62 66.1 88.8 8.26 6.68 30.0 34.9 124.4 128 221.3 47.3 58.9 47.2 54.6 1.27

99.6 98.0 92.5 97.1 99.0 12.41 65.2 54.5 53.5 60.1 18.5 93.3 94.5 86.5 83.4 67.0 61 51.2 71.5 97.0 96.3 94.7 98.8

1.0005 1.093 1.360 1.122 1.047 1.615 2.736 1.74 1.15 1.26 1.073 1.015 1.012 1.165 1.182 1.914 1.89 2.725 1.185 1.559 1.434 1.492 1.001

Formula

Specific gravity

1.350

SECTION ONE

1.19 PROTON TRANSFER REACTIONS A proton transfer reaction is a reaction in which the main feature is the intermolecular or intramolecular transfer of a proton from one binding site to another. In the detailed description of proton transfer reactions, especially of rapid proton transfers between electronegative atoms, it should always be specified whether the term is used to refer to the overall process, including the more-or-less encounter-controlled formation of a hydrogen bonded complex and the separation of the products or, alternatively, the proton transfer event (including solvent rearrangement) by itself. For the general proton transfer reaction: HB = H+ + B the acidic dissociation constant is formulated as follows: Ka =

[H + ][B] [HB]

The most common charge types for the acid HB and its conjugate base B are CH3COOH = H+ + CH3COO–(acetic acid, acetate ion) HSO4− = H+ + SO42− (hydrogen sulfate ion, sulfate ion) NH4+ = H+ + NH3 (ammonium ion, ammonia) Acids which have more than one acidic hydrogen ionize in steps, as shown for phosphoric acid: H3PO4 = H+ + H2PO4− H2PO4− = H+ + HPO42− HPO42− = H+ + PO43−

pK1 = 2.148 pK2 = 7.198 pK3 = 11.90

K1 = 7.11 × 10–3 K2 = 6.34 × 10–8 K3 = 1.26 × 10–12

If the basic dissociation constant Kb for the equilibrium such as NH3 + H2O = NH4 + OH is required, pKb may be calculated from the relationship pKb = pKw – pKa Ia general, for an organic acid, a useful estimate of its pKa value can sometimes be obtained by making a comparison with recognizably similar compounds for which pKa values are known: (1) alkyl chains, alicyclic rings, or saturated carbocyclic rings fused to aromatic or heterocyclic rings can be replaced by methyl or ethyl groups; (2) acid-strengthening inductive and mesomeric effects of a nitro group attached to an aromatic ring are very similar to those of a nitrogen atom located at the same position in a heteroaromatic ring (e.g., 3-hydroxypyridine and 3-nitrophenol).

1.19.1 Calculation of the Approximate pH Value of Solutions Strong acid: Strong base: Weak acid: Weak base:

pH = −log [acid] pH = 14.00 + log [base] pH = 1/2pKa – 1/2 log [acid] pH = 14.00 – 1/2pKb + 1/2 log [base]

INORGANIC CHEMISTRY

Salt formed by a weak acid and a strong base: pH = 7.00 + 1/2pKa + 1/2 log[salt] Acid salts of a dibasic acid: pH = 1/2pK1 + 1/2pK2 – 1/2 log [salt] + 1/2 log(K1 + [salt]) Buffer solution consisting of a mixture of a weak acid and its salt:  [salt ] + [H 3O + ] − [OH − ]  pH = pKa + log    [acid ] + [H 3O + ] − [OH − ] 

1.19.2 Calculation of Concentrations of Species Present at a Given pH

α0 =

[H + ]n [H A] = n + n + n −1 + n−2 Cacid [H ] + K1[H ] + K1K2 [H ] + L + K1K2 L Kn

α1 =

K1[H + ]n−1 [H n−1A − ] = Cacid [H + ]n + K1[H + ]n−1 + K1K2 [H + ]n−2 + L + K1K2 L Kn

α2 =

+ n

+ n −1

[H ] + K1[H ]

[H A 2− ] K1K2 [H + ]n−2 = n−2 + n−2 + K1K2 [H ] + L + K1K2 L Kn Cacid M

αn =

+ n

+ n −1

[H ] + K1[H ]

[A n− ] K1K2 L Kn = + n−2 + K1K2 [H ] + L + K1K2 L Kn Cacid

1.351

1.352 TABLE 1.74 Proton Transfer Reactions of Inorganic Materials in Water at 25°C Substance

Formula or remarks

pK1

pK2

(Continued)

1.353

1.354 TABLE 1.74 Proton Transfer Reactions of Inorganic Materials in Water at 25°C (Continued) Substance

Formula or remarks

pK1

pK2

(Continued)

1.355

1.356 TABLE 1.74 Proton Transfer Reactions of Inorganic Materials in Water at 25°C (Continued) Substance

Formula or remarks

pK1

pK2

Source: J. J. Christensen, L. D. Hansen, and R. M. Izatt, Handbook of Proton Ionization Heats and Related Thermodynamic Quantities, Wiley-Interscience, New York, 1976; D. D. Perrin, Ionisation Constants of Inorganic Acids and Bases in Aqueous Solution, 2d ed., Pergamon Press, 1982.

INORGANIC CHEMISTRY

1.357

1.20 FORMATION CONSTANTS The formation constant of a metal complex is the equilibrium constant for the formation of a complex ion from its components in solution. Each value listed is the logarithm of the overall formation constant for the cumulative binding of a ligand L to the central metal cation M, viz.: Comulative formation constant M + L = ML M + 2L = ML2 ...................... M + nL = MLn

Stepwise stability constants

K1 K2

k1 k1k2

Kn

k1k2 … kn

As an example, the entries in Table 1.75 for the zinc ammine complexes represent these equilibria: Zn2+ + NH3 = Zn(NH3)2+

K1 =

[ Zn( NH 3 )2 + ] [ Zn 2 + ][ NH 3 ]

Zn2+ + 2NH3 = Zn(NH3)22+

K2 =

[ Zn( NH 3 )22 + ] [ Zn 2 + ][ NH 3 ]2

Zn2+ + 3NH3 = Zn(NH3)32+

K3 =

[ Zn( NH 3 )32 + ] [ Zn 2 + ][ NH 3 ]3

Zn2+ + 4NH3 = Zn(NH3)42+

K4 =

[ Zn( NH 3 )24+ ] [ Zn 2 + ][ NH 3 ]4

If the stepwise stability or formation constants of the reactions are desired, for the first step log K1 = log k1 = 2.37. For the second and succeeding steps the equilibria and corresponding constants are as follows: Zn(NH3)2+ + NH3 = Zn(NH3)22+

log k2 = log k2 − log k1 = 2.44

Zn(NH3)22+

+ NH3 =

Zn(NH3)32+

log k3 = log k2 − log k1 = 3.50

Zn(NH3)32+

+ NH3 =

Zn(NH3)42+

log k4 = log k4 − log k3 = 2.15

The reverse of the association or formation reactions would represent the dissociation or instability constant for the systems, i.e., –log Kf = log Kinstab. The data in the tables generally refer to temperatures of about 20 to 25°C. Most of the values in Table 1.75 refer to zero ionic strength, but those in Table 1.76 often refer to a finite ionic strength.

1.358

SECTION ONE

TABLE 1.75 Cumulative Formation Constants for Metal Complexes with Inorganic Ligands log K1

log K2

log K3

log K4

log K5

log K6

INORGANIC CHEMISTRY

1.359

TABLE 1.75 Cumulative Formation Constants for Metal Complexes with Inorganic Ligands (Continued) log K1

log K2

log K3

log K4

log K5

log K6

(Continued)

1.360

SECTION ONE

TABLE 1.75 Cumulative Formation Constants for Metal Complexes with Inorganic Ligands (Continued) log K1

log K2

log K3

log K4

log K5

log K6

INORGANIC CHEMISTRY

1.361

TABLE 1.75 Cumulative Formation Constants for Metal Complexes with Inorganic Ligands (Continued) log K1

log K2

log K3

log K4

log K5

log K6

(Continued)

1.362

SECTION ONE

TABLE 1.75 Cumulative Formation Constants for Metal Complexes with Inorganic Ligands (Continued) log K1

log K2

log K3

log K4

log K5

log K6

INORGANIC CHEMISTRY

1.363

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands Temperature is 25°C and ionic strengths are approaching zero unless indicated otherwise: (a) At 20°C, (b) at 30°C, (c) 0.1 M uni-univalent salt, (d) 1.0 M uni-univalent salt, (e) 2.0 M uni-univalent salt present. log K1

log K2

log K3

log K4

(Continued)

1.364

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued) log K1

log K2

log K3

log K4

INORGANIC CHEMISTRY

1.365

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

(Continued)

1.366

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

INORGANIC CHEMISTRY

1.367

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

(Continued)

1.368

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

Next Page INORGANIC CHEMISTRY

1.369

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

(Continued)

Previous Page 1.370

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

INORGANIC CHEMISTRY

1.371

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

(Continued)

1.372

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

INORGANIC CHEMISTRY

1.373

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

(Continued)

1.374

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

INORGANIC CHEMISTRY

1.375

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued)

(Continued)

1.376

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued) log K1

log K2

log K3

log K4

INORGANIC CHEMISTRY

1.377

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued) log K1

log K2

log K3

log K4

(Continued)

1.378

SECTION ONE

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued) log K1

log K2

log K3

log K4

INORGANIC CHEMISTRY

TABLE 1.76 Cumulative Formation Constants for Metal Complexes with Organic Ligands (Continued) log K1

log K2

log K3

log K4

1.379

1.380

SECTION ONE

1.21 ELECTRODE POTENTIALS The electrode potential is the difference between the charge on an electrode and the charge in the solution. The electrode potential is denoted as the electromotive force (EMF) and the electromotive force of any electrolytic cell is the sum of the potentials produced at two electrodes. TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C Standard potentials are tabulated except when a solution composition is stated; the latter are formal potentials and the concentrations are in mol/liter.

Half-reaction

Standard or formal potential

Solution composition

INORGANIC CHEMISTRY

1.381

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

(Continued)

1.382

SECTION ONE

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

INORGANIC CHEMISTRY

1.383

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

(Continued)

1.384

SECTION ONE

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

INORGANIC CHEMISTRY

1.385

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

(Continued)

1.386

SECTION ONE

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

INORGANIC CHEMISTRY

1.387

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

(Continued)

1.388

SECTION ONE

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

INORGANIC CHEMISTRY

1.389

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

(Continued)

1.390

SECTION ONE

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

INORGANIC CHEMISTRY

1.391

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

(Continued)

1.392

SECTION ONE

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued)

Half-reaction

Standard or formal potential

Solution composition

INORGANIC CHEMISTRY

1.393

TABLE 1.77 Potentials of the Elements and Their Compounds at 25°C (Continued) Standard or formal potential

Half-reaction

Solution composition

Source: A. J. Bard, R. Parsons, and J. Jordan (eds.), Standard Potentials in Aqueous Solution (prepared under the auspices of the International Union of Pure and Applied Chemistry), Marcel Dekker, New York, 1985; G. Charlot et al., Selected Constants: Oxidation-Reduction Potentials of Inorganic Substances in Aqueous Solution, Butterworths, London, 1971.

TABLE 1.78 Potentials of Selected Half-Reactions at 25°C A summary of oxidation-reduction half-reactions arranged in order of decreasing oxidation strength and useful for selecting reagent systems. Half-reaction +

−

F2(g) + 2H + 2e = 2HF O3 + H2O + 2e− = O2 + 2OH− O3 + 2H+ + 2 e− = O2 + H2O Ag2+ + e− = Ag+ 2− − S2O2− 8 + 2e = 2SO4 + − HN3 + 3H + 2e = NH+4 + N2 H2O2 + 2H+ + 2 e− = 2H2O Ce4+ + e− = Ce3+ MnO4− + 4H+ + 3e− = MnO2(c) + 2H2O 2HClO + 2H+ + 2e− = Cl2 + H2O 2HBrO + 2H+ + 2e− = Br2 + H2O H5IO6 + H+ + 2e− = IO3 + 3H2O NiO2 + 4H+ + 2e− = Ni2+ + 2H2O Bi2O4(bismuthate) + 4H+ + 2e− = 2BiO+ + 2H2O MnO4− + 8H+ + 5e− = Mn2+ + 4H2O 2BrO3− + 12H+ + 10e− = Br2 + 6H2O PbO2 + 4H+ +2e− = Pb2+ + 2H2O Cr2O72− + 14H+ + 6e− = 2Cr3+ + 7H2O Cl2 + 2e− = 2Cl− 2HNO2 + 4H+ + 4e− = N2O + 3H2O N2H+5 + 3H+ + 2e− = 2NH+4 MnO2 + 4H+ + 2e− = Mn2+ + 2H2O O2 + 4H+ + 4e− = 2H2O ClO4− + 2H+ + 2e− = ClO3− + H2O

E°, volts 3.053 1.246 2.075 1.980 1.96 1.96 1.763 1.72 1.70 1.630 1.604 1.603 1.593 1.59 1.51 1.478 1.468 1.36 1.3583 1.297 1.275 1.23 1.229 1.201 (Continued)

1.394

SECTION ONE

TABLE 1.78 Potentials of Selected Half-Reactions at 25°C (Continued)

INORGANIC CHEMISTRY

TABLE 1.78 Potentials of Selected Half-Reactions at 25°C (Continued)

1.395

1.396

SECTION ONE

TABLE 1.79 Overpotentials for Common Electrode Reactions at 25°C The overpotential is defined as the difference between the actual potential of an electrode at a given current density and the reversible electrode potential for the reaction.

Electrode

* At 0.23 A/cm2.† At 0.72 A/cm2. The overpotential required for the evolution of O2 from dilute solutions of HClO4, HNO3, H3PO4 or H2SO4 onto smooth platinum electrodes is approximately 0.5 V.

INORGANIC CHEMISTRY

1.397

TABLE 1.80 Half-Wave Potentials of Inorganic Materials All values are in volts vs. the saturated calomel electrode. Element

E1/2, volts

Solvent system

(Continued)

1.398

SECTION ONE

TABLE 1.80 Half-Wave Potentials of Inorganic Materials (Continued) Element

E1/2, volts

Solvent system

INORGANIC CHEMISTRY

1.399

TABLE 1.80 Half-Wave Potentials of Inorganic Materials (Continued) Element

E1/2, volts

Solvent system

(Continued)

1.400

SECTION ONE

TABLE 1.80 Half-Wave Potentials of Inorganic Materials (Continued) Element

E1/2, volts

Solvent system

INORGANIC CHEMISTRY

1.401

TABLE 1.80 Half-Wave Potentials of Inorganic Materials (Continued) Element

E1/2, volts

Solvent system

TABLE 1.81 Standard Electrode Potentials for Aqueous Solutions Acidic solutions ([H+] = 1.0 mol kg−1) Half-reaction Li+ + e− Í Li K+ + e− Í K Na+ + e- Í Na La3+ + 3e− Í La Mg2+ + 2e− Í Mg 1 − − 2H2 + e Í H Be2+ + 2e− Í Be Zr4+ + 4e− Í Zr Al3+ + 3e− Í Al Ti3+ + 3e− Í Ti Mn2+ + 2e− Í Mn V2+ + 2e− Í V SiO2(glass) + 4H+ + 4e− Í Si + 2H2O Zn2+ + 2e− Í Zn U4+ + e− Í U3+ Fe2+ + 2e− Í Fe Cr3+ + e− Í Cr2+ Cd2+ + 2e− Í Cd PbSO4 + 2e− Í Pb + SO42− Eu3+ + e− Í Eu2+

E°(V) −3.045 −2.925 −2.714 −2.37 −2.356 −2.25 −1.97 −1.70 −1.67 −1.21 −1.18 −1.13 −0.888 −0.763 −0.52 −0.44 −0.424 −0.403 −0.351 −0.35 (Continued)

1.402

SECTION ONE

TABLE 1.81 Standard Electrode Potentials for Aqueous Solutions (Continued) Acidic solutions ([H+] = 1.0 mol kg−1) Half-reaction Co2+ + 2e− H3PO4 + 2H+ +2e− Ni2+ + 2e− V3+ + e− 2− 2SO4 + 4H+ + 2e− N2 + 5H+ + 4e− CO2 + 2H+ + 2e− AgI + e− Sn2+ + 2e− Pb2+ + 2e− 2H+ + 2e− HCOOH + 2H+ + 2e− AgBr + e− TiO2+ + 2H+ S + 2H+ + 2e− Sn4+ + 2e− SO42− + 4H+ +2e− Cu2+ + e− AgCl + e− HCHO + 2H+ +2e− UO22+ + 4H+ + 2e− VO2+ + 2H+ + e− Cu2+ + 2e− Fe(CN)63− + e− 2H2SO3 + 2H+ + 4e− H2SO3 + 4H+ + 4e− 4H2SO3 + 4H+ + 6e− Cu+ + e− I2 + 2e− I3− + 2e− MnO4− + e− S2O62− + 4H+ + 2e− CH3OH + 2H+ + 2e− HN3 + 11H+ + 8e− O2 + 2H+ + 2e− Rh3+ + 3e− (NCS)2 + 2e− Fe3+ + e− Hg22+ + 2e− Ag+ + e− 2NO3− + 4H+ + 2e− Hg2+ + 2e− NO3− + 3H+ + 2e− NO3− + 4H+ + 3e− NHO2 + H+ + e− N2O4 + 4H+ + 4e− Br2 + 2e− N2O4 + 2H+ + 2e− H2O2 + H+ + e− ClO4− + 2H+ + 2e− O2 + 4H+ + 4e− MnO2 + 4H+ + 2e−

Í Co Í H3PO3 + H2O Í Ni Í V2+ Í S2O62− + 2H2O Í N2H5+ Í HCOOH Í Ag + I− Í Sn Í Pb Í H2 Í HCHO + H2O Í Ag + Br− Í + e− Ti3+ + H2O Í H2S Í Sn2+ Í H2SO3 + H2O Í Cu+ Í Ag + Cl− Í CH3OH Í U4+ + 2H2O Í V3+ + H2O Í Cu Í Fe(CN)64− Í S2O32− + 3H2O Í S + 3H2O Í S4O62− + 6H2O Í Cu Í 2I− Í 3I− Í MnO42− Í 2H2SO3 Í CH4 + H2O Í 3NH4+ Í H2O2 Í Rh Í 2NCS− Í Fe2+ Í 2Hg Í Ag Í N2O4 + 2H2O Í Hg Í HNO2 + H2O Í NO + 2H2O Í NO + H2O Í 2NO + 2H2O Í 2Br− Í 2HNO2 Í ⋅OH + H2O Í ClO3− + H2O Í 2H2O Í Mn2+ + 2H2O

E°(V) −0.277 −0.276 −0.257 −0.255 −0.253 −0.23 −0.16 −0.152 −0.136 −0.125 0.000 +0.056 +0.071 +0.100 +0.144 +0.15 +0.158 +0.159 +0.222 +0.232 +0.27 +0.337 +0.340 +0.361 +0.400 +0.500 +0.507 +0.520 +0.5355 +0.536 +0.56 +0.569 +0.59 +0.695 +0.695 +0.76 +0.77 +0.771 +0.796 +0.799 +0.803 +0.911 +0.94 +0.957 +0.996 +1.039 +1.065 +1.07 +1.14 +1.201 +1.229 +1.23

INORGANIC CHEMISTRY

1.403

TABLE 1.81 Standard Electrode Potentials for Aqueous Solutions (Continued) Acidic Solutions ([H+] = 1.0 mol kg−1) Half-reaction

E°(V)

N2H5+ + 3H+ + 2e− Í 2NH4+ Cl2 + 2e− Í 2Cl− Cr2O72− + 14H+ + 6e− Í 2Cr3+ + 7H2O PbO2 + 4H+ + 2e− Í Pb2+ + 2H2O 2BrO3− + 12H+ + 10e− Í Br2 + 6H2O Mn3+ + e− Í Mn2+ Au3+ + 3e− Í Au NiO2 + 4H+ + 2e− Í Ni2+ + 2H2O 2HBrO + 2H+ + 2e− Í Br2 + 2H2O 2HClO + 2H+ + 2e− Í Cl2 + 2H2O PbO2 + SO42− + 4H+ + 2e− Í PbSO4 + 2H2O MNO4− + 4H+ + 3e− Í MnO2 + 2H2O Ce4+ + e− Í Ce3+ H2O2 + 2H+ + 2e− Í 2H2O Au+ + e− Í Au Co3+ + e− Í Co2+ HN3 + 3H+ + 2e− Í NH4+ + N2 S2O82− + 2e− Í 2SO42− O3 + 2H+ + 2e− Í O2 + H2O (OH + H+ + e− Í H2O F2 + 2H+ +2e− Í 2HF

+1.275 +1.358 +1.36 +1.468 +1.478 +1.51 +1.52 +1.593 +1.604 +1.630 +1.698 +1.70 +1.72 +1.763 +1.83 +1.92 +1.96 +1.96 +2.075 +2.38 +3.053

Basic Solutions ([OH−] = 1.0 mol kg−1) Half-reaction −

E°(V) −

Ca(OH)2 + 2e Í Ca + 2OH Mg(OH)2 + 2e− Í Mg + 2OH− Al(OH)4- + 3e− Í Al + 4OH− SiO32- + 3H2O + 4e− Í Si + 6OH− Mn(OH)2 + 2e− Í Mn + 2OH− 2TiO2 + H2O + 2e− Í Ti2 O3 + 2OH− Cr(OH)3 + 3e− Í Cr + 3OH− Zn(OH)42− + 2e− Í Zn + 4OH− Zn(NH3)42+ + 2e− Í Zn + 4NH3 MnO2 + 2H2O + 4e− Í Mn + 4OH− Cd(CN)42− + 2e− Í Cd + 4CN− SO42− + H2O + 2e− Í SO32− + 2OH− 2H2O + 2e− Í H2 + 2OH− − HFeO2 + H2O + 2e− Í Fe + 3OH− Co(OH)2 + 2e− Í Co + 2OH− CrO42− + 4H2O + 3e− Í Cr(OH)4− + 4OH− Ni(OH)2 + 2e− Í Ni + 2OH− FeO2− + H2O + e− Í HFeO2− + OH− 2SO32− + 3H2O + 4e− Í S2O32− + 6OH− Ni(NH3)62+ + 2e− Í Ni + 6NH3 S + 2e− Í S2− O2 + e− Í O2− CuO + H2O + 2e− Í Cu + 2OH− Mn2O3 + 3H2O + 2e− Í 2Mn(OH)2 + 2OH− 2CuO + H2O + 2e− Í Cu2O + 2OH− O2 + H2O + 2e- Í HO2− + OH− MnO2 + 2H2O + 2e− Í Mn(OH)2 + 2OH−

−3.026 −2.687 −2.310 −1.7 −1.56 −1.38 −1.33 −1.285 −1.04 −0.980 −0.943 −0.94 −0.828 −0.8 −0.733 −0.72 −0.72 −0.69 −0.58 −0.476 −0.45 −0.33 −0.29 −0.25 −0.22 −0.065 −0.05 (Continued)

1.404

SECTION ONE

TABLE 1.81 Standard Electrode Potentials for Aqueous Solutions (Continued) Basic solutions ([OH−] = 1.0 mol kg−1) Half-reaction NO3− + H2O + 2e− Í NO2− + 2OH− Co(NH3)63+ + e− Í Co(NH3)62+ HgO (red form) + H2O + 2e− Í Hg + 2OH− N2H4 + 2H2O + 2e− Í 2NH3 + 2OH− Co(OH)3 + e− Í Co(OH)2 + OH− HO2− + H2O + e− Í −OH + 2OH− O2− + H2O + e− Í HO−2 + OH− ClO3− + H2O + 2e− Í ClO2− + 2OH− Ag2O + H2O + 2e− Í 2Ag + 2OH− Ag(NH3)2+ + e− Í Ag + 2NH3 ClO4− + H2O + 2e− Í ClO3− + 2OH− O2 + 2H2O + e− Í 4OH− NiO2 + 2H2O + 2e− Í Ni(OH)2 + 2OH− FeO42− + 2H2O + 3e− Í FeO2− + 4OH− BrO3− + 3H2O + 6e− Í Br− + 6OH− MnO42− + 2H2O + 2e− Í MnO2 + 4OH− ClO2− + H2O + 2e− Í ClO− + 2OH− BrO− + H2O + 2e− Í Br− + 2OH− HO2− + H2O + 2e− Í 3OH− ClO− + H2O + 2e− Í Cl− + 2OH− ClO2 + e− Í ClO2− O3 + H2O + 2e− Í O2 + 2OH− OH + e− Í OH−

E°(V) +0.01 +0.058 +0.098 +0.1 +0.17 +0.184 +0.20 +0.295 +0.342 +0.373 +0.374 +0.401 +0.490 +0.55 +0.584 +0.62 +0.681 +0.766 +0.867 +0.890 +1.041 +1.246 +1.985

TABLE 1.82 Potentials of Reference Electrodes in Volts as a Function of Temperature Liquid-junction potential included.

* Bates et al., J. Research Natl. Bur. Standards, 45, 418 (1950). † Bates and Bower, J. Research Natl. Bur. Standards, 53, 283 (1954). ‡ Hetzer, Robinson and Bates, J. Phys. Chem., 66, 1423 (1962). § Hetzer, Robinson and Bates, J. Phys. Chem., 68, 1929 (1964).

INORGANIC CHEMISTRY

1.405

TABLE 1.83 Potentials of Reference Electrodes (in Volts) at 25°C for Water-Organic Solvent Mixtures

1.22 CONDUCTANCE Conductivity. The standard unit of conductance is electrolytic conductivity (formerly called specific conductance) k, which is defined as the reciprocal of the resistance [Ω−1] of a 1-m cube of liquid at a specified temperature [Ω–1 ⋅ m–1]. See Table 1.86 and the definition of the cell constant. In accurate work at low concentrations it is necessary to subtract the conductivity of the pure solvent (Table 2.69) from that of the solution to obtain the conductivity due to the electrolyte. Resistivity (Specific Resistance) 1 k

[Ω ⋅ m ]

S 1 =k R d

[Ω −1 ]

r= Conductance of an Electrolyte Solution

where S is the surface area of the electrode, or the mean cross-sectional area of the solution [m2], and d is the mean distance between the electrodes [m].

1.406

SECTION ONE

Equivalent Conductivity Λ=

k C

[Ω −1 ⋅ m 2 ⋅ equiv −1 ]

In the older literature, C is the concentration in equivalents per liter. The volume of the solution in cubic centimeters per equivalent is equal to 1000/C, and Λ = 1000 k/C, the units employed in Table 8.32 [Ω–1 ⋅ cm2 ⋅ equiv–1]. The formula unit used in expressing the concentration must be specified; for example, NaCl, 1/2K2SO4, 1/3LaCl3. The equivalent conductivity of an electrolyte is the sum of contributions of the individual ions. At infinite dilution: Λ° = l°c + l°a, where l°c and l°a are the ionic conductances of cations and anions, respectively, at infinite dilution (Table 1.87). Ionic Mobility and Ionic Equivalent Conductivity lc = Fuc

la = Fua

and

[Ω−1 ⋅ m2 ⋅ equiv−1]

where F is the Faraday constant, and uc, ua are the ionic mobilities [m2 ⋅ s–1 ⋅ V–1]. Λ = aF(uc + ua) = a(lc + la) where a is the degree of electrolytic dissociation, Λ/Λ°. The electric mobility u of a species is the magnitude of the velocity in an electric field [m ⋅ s–1] divided by the magnitude of the strength of the electric field E[V ⋅ m–1]. Ostwald Dilution Law Kd =

α 2C 1−α

where Kd is the dissociation constant of the weak electrolyte. In general for an electrolyte which yields n ions: Kd =

C ( n−1) Λn ( Λo − Λ ) Λ o ( n −1)

Transference Numbers or Hittorf Transport Numbers Tc =

lc lc + la

Ta =

Tc uc l c = = Ta ua l a l c = Tc Λ

l a = Ta Λ

la lc + la

Tc + Ta = 1

TABLE 1.84 Properties of liquid Semi-conductors Density at °K* (g cm−3) Material Si Ge AlSb GaSb InSb GaAs InAs ZnTe CdTe Cul Ga2Te3 In2Te3 Mg2Si Mg2Ge Mg2Sn Mg2Pb GeTe SnTe PbTe PbSe PbS Bi2Se3 Bi2Te3 Sb2Te3 Se (hex) Te

Melting point (°K) 1693 1210 1353 985 809 1511 1215 1512 1365 875 1063 940 1375 1388 1051 823 998 1063 1190 1361 1392 979 858 895 493 725

1.407

*At melting point.

Electrical conductivity at °K* Ω−1 ⋅ cm−1

Solid

Liquid

Solid

Liquid

2.30 5.26 4.18 5.60 5.76 5.16 5.5

2.53 5.51 4.72 6.06 6.48 5.71 5.89

580 1250 160 280 2900 300 3600

12000 14000 9900 10600 10000 7900 6800

5.36 5.35 5.77 1.84

4.84 5.086 5.54 2.27 3.20 3.52 5.20 5.57 5.85 7.45 7.10 6.45 6.97 7.26 6.09 3.975 5.775

3.45 5.00 5.97 6.15 7.69 7.57 7.07 7.27 7.5 6.29 4.69 6.1

Atomization Heat of Entropy energy fusion of fusion (kcal/mole) (kcal/mole) (e.u.) 204 178 160 134 121 146 130 109 99

12.1 8.35 14.2 12.0 11.6 23.2 12.6

7.1 6.9 5.2 6.1 7.2 7.7 5.2

2.6

1120 1140 2040 3530 2400 1440 420 300 250 450 1250 900

9800 8400 10600 8600 2600 1800 1520 450 220 900 2580 1850

20.4

5.0

11.4 9.3 11.3 8.0 7.5 8.5 8.7

3.6 3.8 5.7 3.7 3.1 3.1 3.1

28.35 23.65 1.5 4.17

6.6 5.3 3 5.7

Thermoelectric power (mV per °K) Solid Liquid −90 −160 −60 −120 — —

0 −60 0 −20 — —

550 −290 −50

490 −85 30

130 21 140 28 −60 −10 −120 −60 −220 −220 −90 −35 −45 −3 90 11

Activation energy for viscous flow (kcal per mole)

Entropy of Viscosity of viscous flow liquid at °K* (e.u.) (centipoises)

8.63 2.74 10 2.7 2.0 6.5 6.2 9.0 5.75

2.1 2.85 2.2 5.0 9.4 7.8 3 6.5 7.7

11 13 13.9 9.5 9.5 9.6 4.70 4.90 6.85 6.85 9.80 9.7 2.7 6.1 3.94 1.18

7 7.5 2.3 3.8 5.8 6.2 5.8 6.1 6.0 7.5 7.5 5.05 7.80 7.35 6.7 6.7

0.348 0.135 0.250 0.368 0.363 0.320 0.174 0.868 0.435 0.432 0.546 0.323 0.299 0.311 0.520 0.560 0.375 0.348 0.243 0.240 0.319 0.540 0.198 0.513 6.63 0.357

1.408

SECTION ONE

TABLE 1.85 Limiting Equivalent Ionic Conductances in Aqueous Solutions In 10–4 m2 ⋅ S ⋅ equiv–1 or mho ⋅ cm2 ⋅ equiv–1.

INORGANIC CHEMISTRY

1.409

TABLE 1.85 Limiting Equivalent Ionic Conductances in Aqueous Solutions (Continued)

(Continued)

1.410

SECTION ONE

TABLE 1.85 Limiting Equivalent Ionic Conductances in Aqueous Solutions (Continued)

INORGANIC CHEMISTRY

1.411

TABLE 1.86 Standard Solutions for Calibrating Conductivity Vessels The values of conductivity k are corrected for the conductivity of the water used. The cell constant q of a conductivity cell can be obtained from the equation

θ=

KRRsolv Rsolv − R

where R is the resistance measured when the cell is filled with a solution of the composition stated in the table below, and Rsolv is the resistance when the cell is filled with solvent at the same temperature.

Grams KCI per kilogram solution (in vacuo)

*Virtually 0.0100 M. From the data of Jones and Bradshaw, J. Am. Chem. Soc., 55, 1780 (1933). The original data have been converted from (int. ohm)–1cm–1.

1.412 TABLE 1.87

Equivalent Conductivities of Electrolytes in Aqueous Solutions at 18°C

The unit of Λ in the table is Ω–1 ⋅ cm–2 ⋅ equiv–1. The entities to which the equivalent relates are given in the first column.

(Continued)

1.413

1.414 TABLE 1.87

Equivalent Conductivities of Electrolytes in Aqueous Solutions at 18°C (Continued)

The unit of Λ in the table is Ω–1 ⋅ cm–2 ⋅ equiv–1. The entities to which the equivalent relates are given in the first column.

(Continued)

1.415

1.416

TABLE 1.87

Equivalent Conductivities of Electrolytes in Aqueous Solutions at 18°C (Continued)

The unit of Λ in the table is Ω–1 ⋅ cm–2 ⋅ equiv–1. The entities to which the equivalent relates are given in the first column.

INORGANIC CHEMISTRY

1.417

TABLE 1.88 Conductivity of Very Pure Water at Various Temperatures and the Equivalent Conductances of Hydrogen and Hydroxyl Ions

Source: Data from T. S Light and S.L. Licht. Anal Chem., 59: 2327–2330(1987).

1.417

1.418

SECTION ONE

1.23 THERMAL PROPERTIES TABLE 1.89 Eutectic Mixtures The eutectic temperature qC,E is the lowest temperature at which both the solid components of a mixture are in equilibrium with the liquid phase. qC,m denotes melting temperature.

Component 1

qc,m /°C

Component 2

qC,m/°C

qC,E/°C

Sn Sn Sn Sn Sn Sb Bi Bi Cd

232 232 232 232 232 630 271 271 321

Pb Zn Ag Cu Bi Pb Pb Cd Zn

327 420 961 1083 271 327 327 321 420

183 198 221 227 140 246 124 146 270

Composition of eutectic mixture (per cent by mass) Sn, Sn, Sn, Sn, Sn, Sb, Bi, Bi, Cd,

63⋅0 91⋅0 96⋅5 99⋅2 42⋅0 12⋅0 55⋅5 60⋅0 83⋅0

Pb, Zn, Ag, Cu, Bi, Pb, Pb, Cd, Zn,

TABLE 1.90 Transition Temperatures

θC,t denotes transition temperature Substance sulphur Tin Iron Sodium sulphate Mercury(II) iodide Ammonium chloride Caesium chloride Copper(I) mercury(II) Iodide

System Rhombic (a) Í Monoclinic (b) Grey (a) White (b) a (body-centered cubic) Í g (face-centered cubic) g (body-centered cubic) Í d (face-centered cubic) Na2So4 10H2O Í Na2SO4 + 10H2O Tetragonal (red) Í Orthorhombic (yellow) a (CsCl structure) Í b (NaCl structure) CsCl structure Í NaCl structure Tetragonal (red) Í Cubic (dark brown)

qC,t/°C 95.6 906 1401 32.4 126 184 445 69

37⋅0 9⋅0 3⋅5 0⋅8 58⋅0 88⋅0 44⋅5 40⋅0 17⋅0

SECTION 2

ORGANIC CHEMISTRY

SECTION 2

ORGANIC CHEMISTRY 2.1 NOMENCLATURE OF ORGANIC COMPOUNDS 2.1.1 Nonfunctional Compounds Table 2.1 Straight-Chain Alkanes Table 2.2 Fused Polycyclic Hydrocarbons Table 2.3 Heterocyclic Systems Table 2.4 Suffixes for Heterocyclic Systems Table 2.5 Trivial Names of Heterocyclic Systems Suitable for Use in Fusion Names Table 2.6 Trivial Names for Heterocyclic Systems that are Not Recommended for Use in Fusion Names 2.1.2 Functional Compounds Table 2.7 Characteristic Groups for Substitutive Nomenclature Table 2.8 Characteristic Groups Cited Only as Prefixes in Substitutive Nomenclature Table 2.9 Radicofunctional Nomenclature 2.1.3 Specific Functional Groups Table 2.10 Alcohols and Phenols Table 2.11 Names of Some Carboxylic Acids Table 2.12 Phosphorus-Containing Compounds 2.1.4 Stereochemistry 2.1.5 Amino Acids Table 2.13 Formula and Nomenclature of Amino Acids Table 2.14 Acid-Base Properties of Amino Acids Table 2.15 Acid-Base Properties of Amino Acids with Ionizable Side Chains 2.1.6 Carbohydrates 2.1.7 Miscellaneous Compounds Table 2.16 Representative Terpenes Table 2.17 Representative Fatty Acids Table 2.18 Pyrimidines and Purines that Occur in DNA and RNA Table 2.19 Organic Radicals 2.2 PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS Table 2.20 Physical Constants of Organic Compounds Table 2.21 Melting Points of Derivatives of Organic Compounds Table 2.22 Melting Points of n-Paraffins Table 2.23 Boiling Point and Density of Alkyl Halides Table 2.24 Properties of Carboxylic Acids Table 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons Table 2.26 Properties of Naturally Occurring Amino Acids Table 2.27 Hildebrand Solubility Parameters of Organic Liquids Table 2.28 Hansen Solubility Parameters of Organic Liquids Table 2.29 Group Contributions to the Solubility Parameter 2.3 VISCOSITY AND SURFACE TENSION Table 2.30 Viscosity and Surface Tension of Organic Compounds Table 2.31 Viscosity of Aqueous Glycerol Solutions Table 2.32 Viscosity of Aqueous Sucrose Solutions 2.4 REFRACTION AND REFRACTIVE INDEX Table 2.33 Atomic and Group Refractions

2.4 2.4 2.4 2.10 2.13 2.13 2.14 2.17 2.18 2.19 2.20 2.23 2.23 2.24 2.30 2.35 2.38 2.47 2.47 2.48 2.48 2.48 2.54 2.54 2.55 2.56 2.57 2.64 2.65 2.254 2.255 2.255 2.256 2.257 2.267 2.268 2.269 2.270 2.270 2.272 2.287 2.287 2.287 2.288

2.1

2.2

SECTION TWO

Table 2.34 Refractive Indices of Organic Compounds 2.289 Table 2.35 Solvents Having the Same Refractive Index and the Same Density at 25°C 2.294 2.5 VAPOR PRESSURE AND BOILING POINTS 2.296 Table 2.36 Vapor Pressures of Various Organic Compounds 2.297 Table 2.37 Boiling Points of Common Organic Compounds at Selected Pressures 2.315 Table 2.38 Organic Solvents Arranged by Boiling Points 2.348 Table 2.39 Boiling Points of n-Paraffins 2.350 2.6 FLAMMABILITY PROPERTIES 2.351 Table 2.40 Boiling Points, Flash points, and Ignition Temperatures of Organic Compounds 2.352 Table 2.41 Properties of Combustible Mixtures in Air 2.426 2.7 AZEOTROPIC MIXTURES 2.434 Table 2.42 Binary Azeotropic (Constant-Boiling) Mixtures 2.435 Table 2.43 Ternary Azeotropic Mixtures 2.454 2.8 FREEZING MIXTURES 2.460 Table 2.44 Compositions of Aqueous Antifreeze Solutions 2.460 2.9 BOND LENGTHS AND STRENGTHS 2.464 Table 2.45 Bond Lengths between Carbon and Other Elements 2.464 Table 2.46 Bond Dissociation Energies 2.467 2.10 DIPOLE MOMENTS AND DIELECTRIC CONSTANTS 2.468 Table 2.47 Bond Dipole Moments 2.468 Table 2.48 Group Dipole Moments 2.469 Table 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds 2.470 2.11 IONIZATION ENERGY 2.494 Table 2.50 Ionization Energy of Molecular and Radical Species 2.495 2.12 THERMAL CONDUCTIVITY 2.506 Table 2.51 Thermal Conductivities of Gases as a Function of Temperature 2.506 Table 2.52 Thermal Conductivity of Various Substances 2.509 2.13 ENTHALPIES AND GIBBS ENERGIES OF FORMATION, ENTROPIES, AND HEAT CAPACITIES (CHANGE OF STATE) 2.512 2.13.1 Thermodynamic Relations 2.512 Table 2.53 Enthalpies and Gibbs energies of Formation, Entropies, and Heat Capacities of Organic Compounds 2.515 Table 2.54 Heats of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds 2.561 2.14 CRITICAL PROPERTIES 2.591 Table 2.55 Critical Properties 2.592 Table 2.56 Lydersen’s Critical Property Increments 2.607 Table 2.57 Vetere Group Contribution to Estimate Critical Volume 2.608 Table 2.58 Van der Waals’ Constants for Gases 2.609 2.15 EQUILIBRIUM CONSTANTS 2.620 Table 2.59 pK, Values of Organic Materials in Water at 25°C 2.620 Table 2.60 Selected Equilibrium Constants in Aqueous Solution at Various Temperatures 2.670 Table 2.61 pK, Values for Proton-Transfer Reactions in Non-aqueous Solvents 2.676 2.16 INDICATORS 2.677 Table 2.62 Acid-Base Indicators 2.677 Table 2.63 Mixed Indicators 2.680 Table 2.64 Fluorescent Indicators 2.682

ORGANIC CHEMISTRY

2.17

2.18

2.19

2.20

2.21

2.22

Table 2.65 Selected List of Oxidation-Reduction Indicators Table 2.66 Indicators for Approximate pH Determination Table 2.67 Oxidation-Reduction Indicators ELECTRODE POTENTIALS Table 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C ELECTRICAL CONDUCTIVITY Table 2.69 Electrical Conductivity of Various Pure Liquids Table 2.70 Limiting Equivalent Ionic Conductance in Aqueous Solutions Table 2.71 Properties of Organic Semi-Conductors LINEAR FREE ENERGY RELATIONSHIPS Table 2.72 Hammett and Taft Substituent Constants Table 2.73 pK °a and Rho Values for Hammett Equation Table 2.74 pK °a and Rho Values for Taft Equation Table 2.75 Special Hammett Sigma Constants POLYMERS Table 2.76 Names and Structures of Polymers Table 2.77 Plastics Table 2.78 Properties of Commercial Plastics Table 2.79 Properties of Natural and Synthetic Rubbers Table 2.80 Density of Polymers Listed by Trade Name Table 2.81 Density of Polymers Listed by Chemical Name Table 2.82 Density of Polymers at Various Temperatures Table 2.83 Surface Tension (Liquid Phase) of Polymers Table 2.84 Interfacial Tension (Liquid Phase) of Polymers Table 2.85 Thermal Expansion Coefficients of Polymers Table 2.86 Heat Capacities of Polymers Table 2.87 Thermal Conductivity of Polymers Table 2.88 Thermal Conductivity of Foamed Polymers Table 2.89 Thermal Conductivity of Polymers with Fillers Table 2.90 Resistance of Selected Polymers and Rubber to Various Chemicals at 20°C Table 2.91 Gas Permeability Constants (1010 P) at 25°C for Polymers and Rubber Table 2.92 Vapor Permeability Constants (1010 P) at 35°C for Polymers Table 2.93 Hildebrand Solubility Parameters of Polymers Table 2.94 Hansen Solubility Parameters of Polymers Table 2.95 Refractive Indices of Polymers FATS, OILS, AND WAXES Table 2.96 Physical Properties of Fats and Oils Table 2.97 Physical Properties of of Waxes PETROLEUM PRODUCTS Table 2.98 Physical Properties of Petroleum Products

2.3 2.684 2.686 2.686 2.687 2.687 2.698 2.698 2.699 2.700 2.702 2.703 2.707 2.708 2.709 2.709 2.730 2.739 2.740 2.776 2.777 2.778 2.780 2.782 2.783 2.784 2.786 2.798 2.798 2.799 2.800 2.801 2.803 2.804 2.805 2.807 2.807 2.808 2.810 2.811 2.811

2.4

SECTION TWO

2.1 NOMENCLATURE OF ORGANIC COMPOUNDS The following synopsis of rules for naming organic compounds and the examples given in explanation are not intended to cover all the possible cases.

2.1.1 Nonfunctional Compounds 2.1.1.1 Alkanes. The saturated open-chain (acyclic) hydrocarbons (CnH2n+2) have names ending in -ane. The first four members have the trivial names methane (CH4), ethane (CH3CH3 or C2H6), propane (C3H8), and butane (C4H10). For the remainder of the alkanes, the first portion of the name is derived from the Greek prefix that cites the number of carbons in the alkane followed by -ane with elision of the terminal -a from the prefix.

TABLE 2.1 Straight-Chain Alkanes n*

Name

n*

Name

n*

Name

n*

Name

* n = total number of carbon atoms. † Formerly called enneane. ‡ Formerly called hendecane. § Formerly called eicosane.

For branching compounds, the parent structure is the longest continuous chain present in the compound. Consider the compound to have been derived from this structure by replacement of hydrogen by various alkyl groups. Arabic number prefixes indicate the carbon to which the alkyl group is attached. Start numbering at whichever end of the parent structure that results in the lowestnumbered locants. The arabic prefixes are listed in numerical sequence, separated from each other by commas and from the remainder of the name by a hyphen. If the same alkyl group occurs more than once as a side chain, this is indicated by the prefixes di-, tri-, tetra-, etc. Side chains are cited in alphabetical order (before insertion of any multiplying prefix). The name of a complex radical (side chain) is considered to begin with the first letter of its complete name. Where names of complex radicals are composed of identical words, priority for citation is given to that radical which contains the lowest-numbered locant at the first cited point of difference in the radical. If two or more side chains are in equivalent positions, the one to be assigned the lowest-numbered locant is that cited first in the name. The complete expression for the side chain may be enclosed in parentheses for clarity or the carbon atoms in side chains may be indicated by primed locants. If hydrocarbon chains of equal length are competing for selection as the parent, the choice goes in descending order to (1) the chain that has the greatest number of side chains, (2) the chain whose side chains have the lowest-numbered locants, (3) the chain having the greatest number of carbon atoms in the smaller side chains, or (4) the chain having the least-branched side chains.

ORGANIC CHEMISTRY

2.5

These trivial names may be used for the unsubstituted hydrocarbon only: Isobutane Isopentane

(CH3)2CHCH3 (CH3)2CHCH2CH3

Neopentane Isohexane

(CH3)4C (CH3)2CHCH2CH2CH3

Univalent radicals derived from saturated unbranched alkanes by removal of hydrogen from a terminal carbon atom are named by adding -yl in place of -ane to the stem name. Thus the alkane ethane becomes the radical ethyl. These exceptions are permitted for unsubstituted radicals only: Isopropyl Isobutyl sec-Butyl tert-Butyl

(CH3)2CH— (CH3)2CHCH2—CH3CH2CH(CH3)— (CH3)3C—

Isopentyl Neopentyl tert-Pentyl Isohexyl

(CH3)2CHCH2CH2— (CH3)3CCH2— CH3CH2C(CH3)2— (CH3)2CHCH2CH2CH2—

Note the usage of the prefixes iso-, neo-, sec-, and tert-, and note when italics are employed. Italicized prefixes are never involved in alphabetization, except among themselves; thus sec-butyl would precede isobutyl, isohexyl would precede isopropyl, and sec-butyl would precede tert-butyl. Examples of alkane nomenclature are

2.6

SECTION TWO

Bivalent radicals derived from saturated unbranched alkanes by removal of two hydrogen atoms are named as follows: (1) If both free bonds are on the same carbon atom, the ending -ane of the hydrocarbon is replaced with -ylidene. However, for the first member of the alkanes it is methylene rather than methylidene. Isopropylidene, sec-Butylidene, and neopentylidene may be used for the unsubstituted group only. (2) If the two free bonds are on different carbon atoms, the straight-chain group terminating in these two carbon atoms is named by citing the number of methylene groups comprising the chain. Other carbon groups are named as substituents. Ethylene is used rather than dimethylene for the first member of the series, and propylene is retained for CH3[CH[CH2[ ∂ (but trimethylene is [CH2[CH2[CH2[). Trivalent groups derived by the removal of three hydrogen atoms from the same carbon are named by replacing the ending -ane of the parent hydrocarbon with -ylidyne. 2.1.1.2 Alkenes and Alkynes. Each name of the corresponding saturated hydrocarbon is converted to the corresponding alkene by changing the ending -ane to -ene. For alkynes the ending is -yne. With more than one double (or triple) bond, the endings are -adiene, -atriene, etc. (or -adiyne, -atriyne, etc.). The position of the double (or triple) bond in the parent chain is indicated by a locant obtained by numbering from the end of the chain nearest the double (or triple) bond; thus CH3CH2CH˙CH2 is 1-butene and CH3CæCCH3 is 2-butyne. For multiple unsaturated bonds, the chain is so numbered as to give the lowest possible locants to the unsaturated bonds. When there is a choice in numbering, the double bonds are given the lowest locants, and the alkene is cited before the alkyne where both occur in the name. Examples: CH3CH2CH2CH2CH˙CH[CH˙ CH2 1,3-Octadiene CH2˙CHCæCCH˙CH2 1,5-Hexadiene-3-yne CH3CH˙CHCH2CæCH 4-Hexen-1-yne CHæCCH2CH˙CH2 1-Penten-4-yne Unsaturated branched acyclic hydrocarbons are named as derivatives of the chain that contains the maximum number of double and/or triple bonds. When a choice exists, priority goes in sequence to (1) the chain with the greatest number of carbon atoms and (2) the chain containing the maximum number of double bonds. These nonsystematic names are retained. Ethylene CH2˙CH2 Allene CH2˙C˙CH2 Acetylene HCæCH An example of nomenclature for alkenes and alkynes is

Univalent radicals have the endings -enyl, -ynyl, -dienyl, -diynyl, etc. When necessary, the positions of the double and triple bonds are indicated by locants, with the carbon atom with the free valence numbered as 1. Examples: 2-Propenyl CH2˙CH[CH2[ CH3[CæC[ 1-Propynyl CH3[CæC[CH2CH˙CH2[ 1-Hexen-4-ynyl

ORGANIC CHEMISTRY

2.7

These names are retained: Vinyl (for ethenyl) CH2˙CH[ Allyl (for 2-propenyl) CH2˙CH[CH2[ Isopropenyl (for 1-methylvinyl but for unsubstituted radical only)

CH2˙C(CH3)[

Should there be a choice for the fundamental straight chain of a radical, that chain is selected which contains (1) the maximum number of double and triple bonds, (2) the largest number of carbon atoms, and (3) the largest number of double bonds. These are in descending priority. Bivalent radicals derived from unbranched alkenes, alkadienes, and alkynes by removing a hydrogen atom from each of the terminal carbon atoms are named by replacing the endings -ene, -diene, and -yne by -enylene, -dienylene, and -ynylene, respectively. Positions of double and triple bonds are indicated by numbers when necessary. The name vinylene instead of ethenylene is retained for [CH˙CH[. 2.1.1.3 Monocyclic Aliphatic Hydrocarbons. Monocyclic aliphatic hydrocarbons (with no side chains) are named by prefixing cyclo- to the name of the corresponding open-chain hydrocarbon having the same number of carbon atoms as the ring. Radicals are formed as with the alkanes, alkenes, and alkynes. Examples:

For convenience, aliphatic rings are often represented by simple geometric figures: a triangle for cyclopropane, a square for cyclobutane, a pentagon for cyclopentane, a hexagon (as illustrated) for cyclohexane, etc. It is understood that two hydrogen atoms are located at each corner of the figure unless some other group is indicated for one or both. 2.1.1.3 Monocyclic Aromatic Compounds. Except for six retained names, all monocyclic substituted aromatic hydrocarbons are named systematically as derivatives of benzene. Moreover, if the substituent introduced into a compound with a retained trivial name is identical with one already present in that compound, the compound is named as a derivative of benzene. These names are retained:

2.8

SECTION TWO

The position of substituents is indicated by numbers, with the lowest locant possible given to substituents. When a name is based on a recognized trivial name, priority for lowest-numbered locants is given to substituents implied by the trivial name. When only two substituents are present on a benzene ring, their position may be indicated by o- (ortho-), m- (meta-), and p- (para-) (and alphabetized in the order given) used in place of 1,2-, 1,3-, and 1,4-, respectively. Radicals derived from monocyclic substituted aromatic hydrocarbons and having the free valence at a ring atom (numbered 1) are named phenyl (for benzene as parent, since benzyl is used for the radical C6H5CH2[), cumenyl, mesityl, tolyl, and xylyl. All other radicals are named as substituted phenyl radicals. For radicals having a single free valence in the side chain, these trivial names are retained: Benzyl C6H5CH2[ Benzhydryl (alternative to diphenylmethyl) (C6H5)2CH[ Cinnamyl C6H5CH˙CH[CH2[

Phenethyl C6H5CH2CH2[ Styryl C6H5CH˙CH[ Trityl (C6H5)3C[

Otherwise, radicals having the free valence(s) in the side chain are named in accordance with the rules for alkanes, alkenes, or alkynes. The name phenylene (o-, m-, or p-) is retained for the radical [C6H4[. Bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals, with the carbon atoms having the free valences being numbered 1,2-, 1,3-, or 1,4-, as appropriate. Radicals having three or more free valences are named by adding the suffixes -triyl, -tetrayl, etc. to the systematic name of the corresponding hydrocarbon. 2.1.1.4 Fused Polycyclic Hydrocarbons. The names of polycyclic hydrocarbons containing the maximum number of conjugated double bonds end in -ene. Here the ending does not denote one double bond. Names of hydrocarbons containing five or more fixed benzene rings in a linear arrangement are formed from a numerical prefix followed by -acene. Numbering of each ring system is fixed but it follows a systematic pattern. The individual rings of each system is oriented so that the greatest number of rings are (1) in a horizontal row and (2) the maximum number of rings is above and to the right (upper-right quadrant) of the horizontal row. When two orientations meet these requirements, the one is chosen that has the fewest rings in the lower-left quadrant. Numbering proceeds in a clockwise direction, commencing with the carbon atom not engaged in ring fusion that lies in the most counterclockwise position of the uppermost ring (upper-right quadrant); omit atoms common to two or more rings. Atoms common to two or more rings are designated by adding lowercase roman letters to the number of the position immediately preceding. Interior atoms follow the highest number, taking a clockwise sequence wherever there is a choice. Anthracene and phenanthrene are two exceptions to the rule on numbering. Two examples of numbering follow:

ORGANIC CHEMISTRY

2.9

When a ring system with the maximum number of conjugated double bonds can exist in two or more forms differing only in the position of an “extra’’ hydrogen atom, the name can be made specific by indicating the position of the extra hydrogen(s). The compound name is modified with a locant followed by an italic capital H for each of these hydrogen atoms. Carbon atoms that carry an indicated hydrogen atom are numbered as low as possible. For example, 1H-indene is illustrated in Table 2.2; 2H-indene would be

Names of polycyclic hydrocarbons with less than the maximum number of noncumulative double bonds are formed from a prefix dihydro-, tetrahydro-, etc., followed by the name of the corresponding unreduced hydrocarbon. The prefix perhydro- signifies full hydrogenation. For example, 1,2dihydronaphthalene is

Examples of retained names and their structures are as follows:

Polycyclic compounds in which two rings have two atoms in common or in which one ring contains two atoms in common with each of two or more rings of a contiguous series of rings and which contain at least two rings of five or more members with the maximum number of noncumulative double bonds and which have no accepted trivial name are named by prefixing to the name of the parent ring or ring system designations of the other components. The parent name should contain as many rings as possible (provided it has a trivial name). Furthermore, the attached component(s) should be as simple as possible. For example, one writes dibenzophenanthrene and not naphthophenanthrene because the attached component benzo- is simpler than napththo-. Prefixes designating attached components are formed by changing the ending -ene into -eno-; for example, indeno- from indene. Multiple prefixes are arranged in alphabetical order. Several abbreviated prefixes are recognized; the parent is given in parentheses: Acenaphtho(acenaphthylene) Anthra(anthracene) Benzo(benzene)

Naphtho(naphthalene) Perylo(perylene) Phenanthro(phenanthrene)

2.10

SECTION TWO

TABLE 2.2 Fused Polycyclic Hydrocarbons Listed in order of increasing priority for selection as parent compound.

*Asterisk after a compound denotes exception to systematic numbering.

ORGANIC CHEMISTRY

2.11

TABLE 2.2 Fused Polycyclic Hydrocarbons (Continued)

For monocyclic prefixes other than benzo-, the following names are recognized, each to represent the form with the maximum number of noncumulative double bonds: cyclopenta-, cyclohepta-, cycloocta-, etc. Isomers are distinguished by lettering the peripheral sides of the parent beginning with a for the side 1,2, and so on, lettering every side around the periphery. If necessary for clarity, the numbers of the attached position (1,2, for example) of the substituent ring are also denoted. The prefixes are cited in alphabetical order. The numbers and letters are enclosed in square brackets and placed immediately after the designation of the attached component. Examples are

2.1.1.5 Bridged Hydrocarbons. Saturated alicyclic hydrocarbon systems consisting of two rings that have two or more atoms in common take the name of the open-chain hydrocarbon containing the same total number of carbon atoms and are preceded by the prefix bicyclo-. The system is numbered commencing with one of the bridgeheads, numbering proceeding by the longest possible path to the second bridgehead. Numbering is then continued from this atom by the longer remaining unnumbered path back to the first bridgehead and is completed by the shortest path from the atom next to the first bridgehead. When a choice in numbering exists, unsaturation is given the lowest numbers. The number of carbon atoms in each of the bridges connecting the bridgeheads is indicated in brackets in descending order. Examples are

2.12

SECTION TWO

2.1.1.6 Hydrocarbon Ring Assemblies. Assemblies are two or more cyclic systems, either single rings or fused systems, that are joined directly to each other by double or single bonds. For identical systems naming may proceed (1) by placing the prefix bi- before the name of the corresponding radical or (2), for systems joined through a single bond, by placing the prefix bi- before the name of the corresponding hydrocarbon. In each case, the numbering of the assembly is that of the corresponding radical or hydrocarbon, one system being assigned unprimed numbers and the other primed numbers. The points of attachment are indicated by placing the appropriate locants before the name; an unprimed number is considered lower than the same number primed. The name biphenyl is used for the assembly consisting of two benzene rings. Examples are

For nonidentical ring systems, one ring system is selected as the parent and the other systems are considered as substituents and are arranged in alphabetical order. The parent ring system is assigned unprimed numbers. The parent is chosen by considering the following characteristics in turn until a decision is reached: (1) the system containing the larger number of rings, (2) the system containing the larger ring, (3) the system in the lowest state hydrogenation, and (4) the highest-order number of ring systems. Examples are given, with the deciding priority given in parentheses preceding the name: (1) 2-Phenylnaphthalene (2) and (4) 2-(2′-Naphthyl)azulene (3) Cyclohexylbenzene 2.1.1.7 Radicals from Ring Systems. Univalent substituent groups derived from polycyclic hydrocarbons are named by changing the final e of the hydrocarbon name to -yl. The carbon atoms having free valences are given locants as low as possible consistent with the fixed numbering of the hydrocarbon. Exceptions are naphthyl (instead of naphthalenyl), anthryl (for anthracenyl), and phenanthryl (for phenanthrenyl). However, these abbreviated forms are used only for the simple ring systems. Substituting groups derived from fused derivatives of these ring systems are named systematically. 2.1.1.8 Cyclic Hydrocarbons with Side Chains. Hydrocarbons composed of cyclic and aliphatic chains are named in a manner that is the simplest permissible or the most appropriate for the chemical intent. Hydrocarbons containing several chains attached to one cyclic nucleus are generally named as derivatives of the cyclic compound, and compounds containing several side chains and/or cyclic radicals attached to one chain are named as derivatives of the acyclic compound. Examples are 2-Ethyl-l-methylnaphthalene 1,5-Diphenylpentane

Diphenylmethane 2,3-Dimethyl-l-phenyl-l-hexene

Recognized trivial names for composite radicals are used if they lead to simplifications in naming. Examples are 1-Benzylnaphthalene

1,2,4-Tris(3-p-tolylpropyl)benzene

Fulvene, for methylenecyclopentadiene, and stilbene, for 1,2-diphenylethylene, are trivial names that are retained. 2.1.1.9 Heterocyclic Systems. Heterocyclic compounds can be named by relating them to the corresponding carbocyclic ring systems by using replacement nomenclature. Heteroatoms are denoted by prefixes ending in a. If two or more replacement prefixes are required in a single name, they are cited in the order of their listing in the table. The lowest possible numbers consistent with the numbering of

ORGANIC CHEMISTRY

2.13

TABLE 2.3 Heterocyclic Systems Heterocyclic atoms are listed in decreasing order of priority.

*When immediately followed by -in or -ine, phospha- should be replaced by phosphor-, arsa- by arsen-, and stiba- by antimon-. The saturated six-membered rings corresponding to phosphorin and arsenin are named phosphorinane and arsenane. A further exception is the replacement of borin by borinane.

the corresponding carbocyclic system are assigned to the heteroatoms and then to carbon atoms bearing double or triple bonds. Locants are cited immediately preceding the prefixes or suffixes to which they refer. Multiplicity of the same heteroatom is indicated by the appropriate prefix in the series: di-, tri-, tetra-, penta-, hexa-, etc. If the corresponding carbocyclic system is partially or completely hydrogenated, the additional hydrogen is cited using the appropriate H- or hydro- prefixes. A trivial name along with the state of hydrogenation may be used. In the specialist nomenclature for heterocyclic systems, the prefix or prefixes (Table 2.3) are combined with the appropriate stem from Table 2.4, ending in an a where necessary. Examples of acceptable usage, including (1) replacement and (2) specialist nomenclature, are

TABLE 2.4 Suffixes for Heterocyclic Systems

*Unsaturation corresponding to the maximum number of noncumulative double bonds. Heteroatoms have the normal valences. † For phosphorus, arsenic, antimony, and boron, there are special provisions (Table 2.3). ‡ Expressed by prefixing perhydro- to the name of the corresponding unsaturated compound. § Not applicable to silicon, germanium, tin, and lead; perhydro- is prefixed to the name of the corresponding unsaturated compound.

2.14

SECTION TWO

TABLE 2.5 Trivial Names of Heterocyclic Systems Suitable for Use in Fusion Names Listed in order of increasing priority as senior ring system.

* Asterisk after a compound denotes exception to systematic numbering.

ORGANIC CHEMISTRY

TABLE 2.5 Trivial Names of Heterocyclic Systems Suitable for Use in Fusion Names (Continued)

* Asterisk after a compound denotes exception to systematic numbering.

2.15

2.16

SECTION TWO

Radicals derived from heterocyclic compounds by removal of hydrogen from a ring are named by adding -yl to the names of the parent compounds (with elision of the final e, if present). These exceptions are retained: Furyl (from furan) Pyridyl (from pyridine) Piperidyl (from piperidine) Quinolyl (from quinoline) Isoquinolyl Thenylidene (for thienylmethylene)

Furfuryl (for 2-furylmethyl) Furfurylidene (for 2-furylmethylene) Thienyl (from thiophene) Thenylidyne (for thienylmethylidyne) Furfurylidyne (for 2-furylmethylidyne) Thenyl (for thienylmethyl)

Also, piperidino- and morpholino- are preferred to 1-piperidyl- and 4-morpholinyl-, respectively. TABLE 2.5 Trivial Names of Heterocyclic Systems Suitable for Use in Fusion Names (Continued)

* Asterisk after a compound denotes exception to systematic numbering.

ORGANIC CHEMISTRY

2.17

TABLE 2.6 Trivial Names for Heterocyclic Systems That Are Not Recommended for Use in Fusion Names Listed in order of increasing priority.

* Denotes position of double bond. † For 1-piperidyl, use piperidino. ‡ For 4-morpholinyl, use morpholino.

If there is a choice among heterocyclic systems, the parent compound is decided in the following order of preference: 1. A nitrogen-containing component 2. A component containing a heteroatom, in the absence of nitrogen, as high as possible (Table 2.3). 3. A component containing the greater number of rings

2.18

SECTION TWO

4. 5. 6. 7.

A component containing the largest possible individual ring A component containing the greatest number of heteroatoms of any kind A component containing the greatest variety of heteroatoms A component containing the greatest number of heteroatoms first listed in Table 2.3

If there is a choice between components of the same size containing the same number and kind of heteroatoms, choose as the base component that one with the lower numbers for the heteroatoms before fusion. When a fusion position is occupied by a heteroatom, the names of the component rings to be fused are selected to contain the heteroatom.

2.1.2 Functional Compounds There are several types of nomenclature systems that are recognized. Which type to use is sometimes obvious from the nature of the compound. Substitutive nomenclature, in general, is preferred because of its broad applicability, but radicofunctional, additive, and replacement nomenclature systems are convenient in certain situations. 2.1.2.1 Substitutive Nomenclature. The first step is to determine the kind of characteristic (functional) group for use as the principal group of the parent compound. A characteristic group is a recognized combination of atoms that confers characteristic chemical properties on the molecule in which it occurs. Carbon-to-carbon unsaturation and heteroatoms in rings are considered nonfunctional for nomenclature purposes. Substitution means the replacement of one or more hydrogen atoms in a given compound by some other kind of atom or group of atoms, functional or nonfunctional. In substitutive nomenclature, each substituent is cited as either a prefix or a suffix to the name of the parent (or substituting radical) to which it is attached; the latter is denoted the parent compound (or parent group if a radical). When oxygen is replaced by sulfur, selenium, or tellurium, the priority for these elements is in the descending order listed. The higher valence states of each element are listed before considering the successive lower valence states. Derivative groups have priority for citation as principal group after the respective parents of their general class. Systematic names formed by applying the principles of substitutive nomenclature are single words except for compounds named as acids. First, select the parent compound, and thus the suffix, from the characteristic group (Table 2.7). All remaining functional groups are handled as prefixes that precede, in alphabetical order, the parent name. Two examples are:

Structure I contains an ester group and an ether group. Since the ester group has higher priority, the name is ethyl 2-methoxy-6-methyl-3-cyclohexene-1-carboxylate. Structure II contains a carbonyl group, a hydroxy group, and a bromo group. The latter is never a suffix. Between the other two, the carbonyl group has higher priority, the parent has -one as suffix, and the name is 4-bromo-l-hydroxy2-butanone. Selection of the principal alicyclic chain or ring system is governed by these selection rules: 1. For purely alicyclic compounds, the selection process proceeds successively until a decision is reached: (a) the maximum number of substituents corresponding to the characteristic group

ORGANIC CHEMISTRY

2.

3.

4. 5.

6.

2.19

(Table 2.7) (b) the maximum number of double and triple bonds considered together, (c) the maximum length of the chain, and (d) the maximum number of double bonds. If the characteristic group occurs only in a chain that carries a cyclic substituent, the compound is named as an aliphatic compound into which the cyclic component is substituted; a radical prefix is used to denote the cyclic component. This chain need not be the longest chain. If the characteristic group occurs in more than one carbon chain and the chains are not directly attached to one another, then the chain chosen as parent should carry the largest number of the characteristic group. If necessary, the selection is continued as in rule 1. If the characteristic group occurs only in one cyclic system, that system is chosen as the parent. If the characteristic group occurs in more than one cyclic system, that system is chosen as parent which (a) carries the largest number of the principal group or, failing to reach a decision, (b) is the senior ring system. If the characteristic group occurs both in a chain and in a cyclic system, the parent is that portion in which the principal group occurs in largest number. If the numbers are the same, that portion is chosen which is considered to be the most important or is the senior ring system. TABLE 2.7 Characteristic Groups for Substitutive Nomenclature Listed in order of decreasing priority for citation as principal group or parent name.

(Continued)

2.20

SECTION TWO

TABLE 2.7 Characteristic Groups for Substitutive Nomenclature (Continued)

*Carbon atoms enclosed in parentheses are included in the name of the parent compound and not in the suffix or prefix.

TABLE 2.8 Characteristic Groups Cited Only as Prefixes in Substitutive Nomenclature

*Formerly iodoxy.

ORGANIC CHEMISTRY

2.21

7. When a substituent is itself substituted, all the subsidiary substituents are named as prefixes and the entire assembly is regarded as a parent radical. 8. The seniority of ring systems is ascertained by applying the following rules successively until a decision is reached: (a) all heterocycles are senior to all carbocycles, (b) for heterocycles, the preference follows the decision process described under Heterocyclic Systems (p. 1.11) (c) the largest number of rings, (d) the largest individual ring at the first point of difference, (e) the largest number of atoms in common among rings, (f) the lowest letters in the expression for ring functions, (g) the lowest numbers at the first point of difference in the expression for ring junctions, (h) the lowest state of hydrogenation, (i) the lowest-numbered locant for indicated hydrogen, (j) the lowestnumbered locant for point of attachment (if a radical), (k) the lowest-numbered locant for an attached group expressed as a suffix, (l) the maximum number of substituents cited as prefixes, (m) the lowest-numbered locant for substituents named as prefixes, hydro prefixes, -ene, and -yne, all considered together in one series in ascending numerical order independent of their nature, and (n) the lowest-numbered locant for the substituent named as prefix which is cited first in the name. 2.1.2.2 Numbering of Compounds. If the rules for aliphatic chains and ring systems leave a choice, the starting point and direction of numbering of a compound are chosen so as to give lowestnumbered locants to these structural factors, if present, considered successively in the order listed below until a decision is reached. Characteristic groups take precedence over multiple bonds. 1. Indicated hydrogen, whether cited in the name or omitted as being conventional 2. Characteristic groups named as suffix following ranking order (Table 2.7) 3. Multiple bonds in acyclic compounds; in bicycloalkanes, tricycloalkanes, and polycycloalkanes, double bonds having priority over triple bonds; and in heterocyclic systems whose names end in -etine, -oline, or -olene 4. The lowest-numbered locant for substituents named as prefixes, hydro prefixes, -ene, and -yne, all considered together in one series in ascending numerical order 5. The lowest locant for that substituent named as prefix which is cited first in the name For cyclic radicals, indicated hydrogen and thereafter the point of attachment (free valency) have priority for the lowest available number. 2.1.2.3 Prefixes and Affixes. Prefixes are arranged alphabetically and placed before the parent name; multiplying affixes, if necessary, are inserted and do not alter the alphabetical order already attained. The parent name includes any syllables denoting a change of ring number or relating to the structure of a carbon chain. Nondetachable parts of parent names include 1. 2. 3. 4. 5. 6. 7.

Forming rings; cyclo-, bicyclo-, spiroFusing two or more rings: benzo-, naphtho-, imidazoSubstituting one ring or chain member atom for another: oxa-, aza-, thiaChanging positions of ring or chain members: iso-, sec-, tert-, neoShowing indicated hydrogen Forming bridges: ethano-, epoxyHydro-

Prefixes that represent complete terminal characteristic groups are preferred to those representing only a portion of a given group. For example, for the prefix [C(˙O)CH3, the name (formylmethyl) is preferred to (oxoethyl). The multiplying affixes di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, and so on are used to indicate a set of identical unsubstituted radicals or parent compounds. The forms bis-, tris-, tetrakis-, pentakis-, and so on are used to indicate a set of identical radicals or parent compounds each

2.22

SECTION TWO

substituted in the same way. The affixes bi-, ter-, quater-, quinque-, sexi-, septi-, octi-, novi-, deci-, and so on are used to indicate the number of identical rings joined together by a single or double bond. Although multiplying affixes may be omitted for very common compounds when no ambiguity is caused thereby, such affixes are generally included throughout this handbook in alphabetical listings. An example would be ethyl ether for diethyl ether. 2.1.2.4 Conjunctive Nomenclature. Conjunctive nomenclature may be applied when a principal group is attached to an acyclic component that is directly attached by a carbon-carbon bond to a cyclic component. The name of the cyclic component is attached directly in front of the name of the acyclic component carrying the principal group. This nomenclature is not used when an unsaturated side chain is named systematically. When necessary, the position of the side chain is indicated by a locant placed before the name of the cyclic component. For substituents on the acyclic chain, carbon atoms of the side chain are indicated by Greek letters proceeding from the principal group to the cyclic component. The terminal carbon atom of acids, aldehydes, and nitriles is omitted when allocating Greek positional letters. Conjunctive nomenclature is not used when the side chain carries more than one of the principal group, except in the case of malonic and succinic acids. The side chain is considered to extend only from the principal group to the cyclic component. Any other chain members are named as substituents, with appropriate prefixes placed before the name of the cyclic component. When a cyclic component carries more than one identical side chain, the name of the cyclic component is followed by di-, tri-, etc., and then by the name of the acyclic component, and it is preceded by the locants for the side chains. Examples are

When side chains of two or more different kinds are attached to a cyclic component, only the senior side chain is named by the conjunctive method. The remaining side chains are named as prefixes. Likewise, when there is a choice of cyclic component, the senior is chosen. Benzene derivatives may be named by the conjunctive method only when two or more identical side chains are present. Trivial names for oxo carboxylic acids may be used for the acyclic component. If the cyclic and acyclic components are joined by a double bond, the locants of this bond are placed as superscripts to a Greek capital delta that is inserted between the two names. The locant for the cyclic component precedes that for the acyclic component, e.g., indene-∆1,α-acetic acid. 2.1.2.5 Radicofunctional Nomenclature. The procedures of radicofunctional nomenclature are identical with those of substitutive nomenclature except that suffixes are never used. Instead, the functional class name (Table 2.9) of the compound is expressed as one word and the remainder of the molecule as another that precedes the class name. When the functional class name refers to a characteristic group that is bivalent, the two radicals attached to it are each named, and when different, they are written as separate words arranged in alphabetical order. When a compound contains more than one kind of group, that kind is cited as the functional group or class name that occurs higher in the table, all others being expressed as prefixes. Radicofunctional nomenclature finds some use in naming ethers, sulfides, sulfoxides, sulfones, selenium analogs of the preceding three sulfur compounds, and azides.

ORGANIC CHEMISTRY

2.23

TABLE 2.9 Radicofunctional Nomenclature Groups are listed in order of decreasing priority.

2.1.2.5 Replacement Nomenclature. Replacement nomenclature is intended for use only when other nomenclature systems are difficult to apply in the naming of chains containing heteroatoms. When no group is present that can be named as a principal group, the longest chain of carbon and heteroatoms terminating with carbon is chosen and named as though the entire chain were that of an acyclic hydrocarbon. The heteroatoms within this chain are identified by means of prefixes aza-, oxa-, thia-, etc. Locants indicate the positions of the heteroatoms in the chain. Lowest-numbered locants are assigned to the principal group when such is present. Otherwise, lowest-numbered locants are assigned to the heteroatoms considered together and, if there is a choice, to the heteroatoms cited earliest in Table 2.3. An example is 13

12

11

10

9

8

7

6

5

4

3

2

1

HO[CH2[O[CH2[CH2[O[CH2[CH2[ N[CH2[CH2[ N[CH2[ COOH H H 13-Hydroxy-9,12-dioxa-3,6-diazatridecanoic acid

2.1.3 Specific Functional Groups 2.1.3.1 Acetals and Acylals. Acetals, which contain the group >C(OR)2, where R may be different, are named (1) as dialkoxy compounds or (2) by the name of the corresponding aldehyde or ketone followed by the name of the hydrocarbon radical(s) followed by the word acetal. For example, CH3[CH(OCH3)2 is named either (1) 1,1-dimethoxyethane or (2) acetaldehyde dimethyl acetal. A cyclic acetal in which the two acetal oxygen atoms form part of a ring may be named (1) as a heterocyclic compound or (2) by use of the prefix methylenedioxy for the group [O[CH2[O[ as a substituent in the remainder of the molecule. For example,

Acylals, R1R2C(OCOR3)2, are named as acid esters;

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SECTION TWO

α-Hydroxy ketones, formerly called acyloins, had been named by changing the ending -ic acid or -oic acid of the corresponding acid to -oin. They are preferably named by substitutive nomenclature; thus CH3[CH(OH) [CO[CH3

3-Hydroxy-2-butanone (formerly acetoin)

2.1.3.2 Acid Anhydrides. Symmetrical anhydrides of monocarboxylic acids, when unsubstituted, are named by replacing the word acid by anhydride. Anhydrides of substituted monocarboxylic acids, if symmetrically substituted, are named by prefixing bis- to the name of the acid and replacing the word acid by anhydride. Mixed anhydrides are named by giving in alphabetical order the first part of the names of the two acids followed by the word anhydride, e.g., acetic propionic anhydride or acetic propanoic anhydride. Cyclic anhydrides of polycarboxylic acids, although possessing a heterocyclic structure, are preferably named as acid anhydrides. For example,

2.1.3.3 Acyl Halides. Acyl halides, in which the hydroxyl portion of a carboxyl group is replaced by a halogen, are named by placing the name of the corresponding halide after that of the acyl radical. When another group is present that has priority for citation as principal group or when the acyl halide is attached to a side chain, the prefix haloformyl- is used as, for example, in fluoroformyl-. 2.1.3.4 Alcohols and Phenols. The hydroxyl group is indicated by a suffix -ol when it is the principal group attached to the parent compound and by the prefix hydroxy- when another group with higher priority for citation is present or when the hydroxy group is present in a side chain. When confusion may arise in employing the suffix -ol, the hydroxy group is indicated as a prefix; this terminology is also used when the hydroxyl group is attached to a heterocycle, as, for example, in the name 3-hydroxythiophene to avoid confusion with thiophenol (C6H5SH). Designations such as isopropanol, sec-butanol, and tert-butanol are incorrect because no hydrocarbon exists to which the suffix can be added. Many trivial names are retained. (Table 2.10). TABLE 2.10 Alcohols and Phenols

ORGANIC CHEMISTRY

TABLE 2.10 Alcohols and Phenols (Continued)

2.25

2.26

SECTION TWO

The radicals (RO[) are named by adding -oxy as a suffix to the name of the R radical, e.g., pentyloxy for CH3CH2CH2CH2CH2O[. These contractions are exceptions: methoxy (CH3O[), ethoxy (C2H5O[), propoxy (C3H7O[), butoxy (C4H9O[), and phenoxy (C6H5O[). For unsubstituted radicals only, one may use isopropoxy [(CH3)2CH[O[], isobutoxy [(CH3)2CH2CH[O[], sec-butoxy [CH3CH2CH(CH3)[O[], and tert-botoxy [(CH3)3C[O[]. Bivalent radicals of the form O[Y[O are named by adding -dioxy to the name of the bivalent radicals except when forming part of a ring system. Examples are [O[CH2[O[ (methylenedioxy), [O[CO[O[ (carbonyldioxy), and [O[SO2[O[ (sulfonyldioxy). Anions derived from alcohols or phenols are named by changing the final -ol to -olae. Salts composed of an anion, RO[, and a cation, usually a metal, can be named by citing first the cation and then the RO anion (with its ending changed to -yl oxide), e.g., sodium benzyl oxide for C6H5CH2ONa. However, when the radical has an abbreviated name, such as methoxy, the ending -oxy is changed to -oxide. For example, CH3ONa is named sodium methoxide (not sodium methylate). 2.1.3.5 Aldehydes. When the group [C(˙O)H, usually written [CHO, is attached to carbon at one (or both) end(s) of a linear acyclic chain the name is formed by adding the suffix -al (or -dial) to the name of the hydrocarbon containing the same number of carbon atoms. Examples are butanal for CH3CH2CH2CHO and propanedial for, OHCCH2CHO. Naming an acyclic polyaldehyde can be handled in two ways. First, when more than two aldehyde groups are attached to an unbranched chain, the proper affix is added to -carbaldehyde, which becomes the suffix to the name of the longest chain carrying the maximum number of aldehyde groups. The name and numbering of the main chain do not include the carbon atoms of the aldehyde groups. Second, the name is formed by adding the prefix formyl- to the name of the -dial that incorporates the principal chain. Any other chains carrying aldehyde groups are named by the use of formylalkyl- prefixes. Examples are

When the aldehyde group is directly attached to a carbon atom of a ring system, the suffixcarbaldehyde is added to the name of the ring system, e.g., 2-naphthalenecarbaldehyde. When the aldehyde group is separated from the ring by a chain of carbon atoms, the compound is named (1) as a derivative of the acyclic system or (2) by conjunctive nomenclature, for example, (1) (2-naphthyl)propionaldehyde or (2) 2-naphthalenepropionaldehyde. An aldehyde group is denoted by the prefix formyl- when it is attached to a nitrogen atom in a ring system or when a group having priority for citation as principal group is present and part of a cyclic system. When the corresponding monobasic acid has a trivial name, the name of the aldehyde may be formed by changing the ending -ic acid or -oic acid to -aldehyde. Examples are Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde

Acrylaldehyde (not acrolein) Benzaldehyde Cinnamaldehyde 2-Furaldehyde (not furfural)

ORGANIC CHEMISTRY

2.27

The same is true for polybasic acids, with the proviso that all the carboxyl groups must be changed to aldehyde; then it is not necessary to introduce affixes. Examples are Glyceraldehyde Glycolaldehyde Malonaldehyde

Succinaldehyde Phthalaldehyde (o-, m-, p-)

These trivial names may be retained: citral (3,7-dimethyl-2,6-octadienal), vanillin (4-hydroxy-3methoxybenzaldehyde), and piperonal (3,4-methylenedioxybenzaldehyde). 2.1.3.6 Amides. For primary amides the suffix -amide is added to the systematic name of the parent acid. For example, CH3[CO[NH2 is acetamide. Oxamide is retained for H2N[CO[CO[NH2. The name -carboxylic acid is replaced by -carboxamide. For amino acids having trivial names ending in -ine, the suffix -amide is added after the name of the acid (with elision of e for monomides). For example, H2N[CH2[CO[NH2 is glycinamide. In naming the radical R[CO[NH[, either (1) the -yl ending of RCO[ is changed to -amido or (2) the radicals are named as acylamino radicals. For example,

The latter nomenclature is always used for amino acids with trivial names. N-substituted primary amides are named either (1) by citing the substitutents as N prefixes or (2) by naming the acyl group as an N substituent of the parent compound. For example,

2.1.3.7 Amines. Amines are preferably named by adding the suffix -amine (and any multiplying affix) to the name of the parent radical. Examples are CH3CH2CH2CH2CH2NH2 Pentylamine H2NCH2CH2CH2CH2CH2NH2 1,5-Pentyldiamine or pentamethylenediamine Locants of substituents of symmetrically substituted derivatives of symmetrical amines are distinguished by primes or else the names of the complete substituted radicals are enclosed in parentheses. Unsymmetrically substituted derivatives are named similarly or as N-substituted products of a primary amine (after choosing the most senior of the radicals to be the parent amine). For example,

Complex cyclic compounds may be named by adding the suffix -amine or the prefix amino- (or aminoalkyl-) to the name of the parent compound. Thus three names are permissible for

Complex linear polyamines are best designated by replacement nomenclature. These trivial names are retained: aniline, benzidene, phenetidine, toluidine, and xylidine. The bivalent radical [NH[linked to two identical radicals can be denoted by the prefix imino-, as well as when it forms a bridge between two carbon ring atoms. A trivalent nitrogen atom linked to

2.28

SECTION TWO

three identical radicals is denoted by the prefix nitrilo-. Thus ethylenediaminetetraacetic acid (an allowed exception) should be named ethylenedinitrilotetraacetic acid. 2.1.3.8 Ammonium Compounds. Salts and hydroxides containing quadricovalent nitrogen are named as a substituted ammonium salt or hydroxide. The names of the substituting radicals precede the word ammonium, and then the name of the anion is added as a separate word. For example, (CH3)4N+I− is tetramethylammonium iodide. When the compound can be considered as derived from a base whose name does not end in -amine, its quaternary nature is denoted by adding ium to the name of that base (with elision of e), substituent groups are cited as prefixes, and the name of the anion is added separately at the end. Examples are C6H5NH+3HSO−4 Anilinium hydrogen sulfate + 2− [(C6H5NH3) ]2PtCl 6 Dianilinium hexachloroplatinate The names choline and betaine are retained for unsubstituted compounds. In complex cases, the prefixes amino- and imino- may be changed to ammonio- and iminio- and are followed by the name of the molecule representing the most complex group attached to this nitrogen atom and are preceded by the names of the other radicals attached to this nitrogen. Finally the name of the anion is added separately. For example, the name might be 1-trimethylammonio-acridine chloride or 1-acridinyltrimethylammonium chloride. When the preceding rules lead to inconvenient names, then (1) the unaltered name of the base may be used followed by the name of the anion or (2) for salts of hydrohalogen acids only the unaltered name of the base is used followed by the name of the hydrohalide. An example of the latter would be 2-ethyl-p-phenylenediamine monohydrochloride. 2.1.3.9 Azo Compounds. When the azo group ([N˙N[) connects radicals derived from identical unsubstituted molecules, the name is formed by adding the prefix azo- to the name of the parent unsubstituted molecules. Substituents are denoted by prefixes and suffixes. The azo group has priority for lowest-numbered locant. Examples are azobenzene for C6H5[N˙N[C6H5, azobenzene4-sulfonic acid for C6H5[N˙N[C6H5SO3H, and 2′,4-dichloroazobenzene-4′-sulfonic acid for ClC6H4[N˙N[C6H3ClSO3H. When the parent molecules connected by the azo group are different, azo is placed between the complete names of the parent molecules, substituted or unsubstituted. Locants are placed between the affix azo and the names of the molecules to which each refers. Preference is given to the more complex parent molecule for citation as the first component, e.g., 2-aminonaphthalene-l-azo-(4′chloro-2′-methylbenzene). In an alternative method, the senior component is regarded as substituted by RN˙N-, this group R being named as a radical. Thus 2-(7-phenylazo-2-naphthylazo)anthracene is the name by this alternative method for the compound named anthracene-2-azo-2′-naphthalene-7′-azobenzene. 2.1.3.10 Azoxy Compounds. Where the position of the azoxy oxygen atom is unknown or immaterial, the compound is named in accordance with azo rules, with the affix azo replaced by azoxy. When the position of the azoxy oxygen atom in an unsymmetrical compound is designated, a prefix NNO- or ONN- is used. When both the groups attached to the azoxy radical are cited in the name of the compound, the prefix NNO- specifies that the second of these two groups is attached directly to [N(O)[; the prefix ONN- specifies that the first of these two groups is attached directly to [N(O)[. When only one parent compound is cited in the name, the prefixed ONN- and NNO- specify that the group carrying the primed and unprimed substituents is connected, respectively, to the [N(O)[ group. The prefix NON- signifies that the position of the oxygen atom is unknown; the azoxy group is then written as [N2O[. For example,

ORGANIC CHEMISTRY

2.29

2.1.3.11 Boron Compounds. Molecular hydrides of boron are called boranes. They are named by using a multiplying affix to designate the number of boron atoms and adding an Arabic numeral within parentheses as a suffix to denote the number of hydrogen atoms present. Examples are pentaborane(9) for B5H9 and pentaborane(11) for B5H11. Organic ring systems are named by replacement nomenclature. Three- to ten-membered monocyclic ring systems containing uncharged boron atoms may be named by the specialist nomenclature for heterocyclic systems. Organic derivatives are named as outlined for substitutive nomenclature. 2.1.3.12 Carboxylic Acids. Carboxylic acids may be named in several ways. First, [COOH groups replacing CH3[ at the end of the main chain of an acyclic hydrocarbon are denoted by adding -oic acid to the name of the hydrocarbon. Second, when the [COOH group is the principal group, the suffix -carboxylic acid can be added to the name of the parent chain whose name and chain numbering does not include the carbon atom of the [COOH group. The former nomenclature is preferred unless use of the ending -carboxylic acid leads to citation of a larger number of carboxyl groups as suffix. Third, carboxyl groups are designated by the prefix carboxy- when attached to a group named as a substituent or when another group is present that has higher priority for citation as principal group. In all cases, the principal chain should be linked to as many carboxyl groups as possible even though it might not be the longest chain present. Examples are

Removal of the OH from the [COOH group to form the acyl radical results in changing the ending -oic acid to -oyl or the ending -carboxylic acid to -carbonyl. Thus the radical CH3CH2CH2CH2CO[ is named either pentanoyl or butanecarbonyl. When the hydroxyl has not been removed from all carboxyl groups present in an acid, the remaining carboxyl groups are denoted by the prefix carboxy-. For example, HOOCCH2CH2CH2CH2CH2CO[ is named 6-carboxyhexanoyl. Many trivial names exist for acids (Table 2.11). Generally, radicals are formed by replacing -ic acid by -oyl.* When a trivial name is given to an acyclic monoacid or diacid, the numeral 1 is always given as locant to the carbon atom of a carboxyl group in the acid or to the carbon atom with a free valence in the radical RCO[. 2.1.3.13 Ethers (R1[O[R2). In substitutive nomenclature, one of the possible radicals, R[O[, is stated as the prefix to the parent compound that is senior from among R1 or R2. Examples are methoxyethane for CH3OCH2CH3 and butoxyethanol for C4H9OCH2CH2OH. When another principal group has precedence and oxygen is linking two identical parent compounds, the prefix oxy- may be used, as with 2,2′-oxydiethanol for HOCH2CH2OCH2CH2OH. Compounds of the type RO[Y[OR, where the two parent compounds are identical and contain a group having priority over ethers for citation as suffix, are named as assemblies of identical units. For example, HOOC[CH2[O[CH2CH2[O[CH2[COOH is named 2,2′-(ethylenedioxy) diacetic acid.

*Exceptions: formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, malonyl, succinyl, glutaryl, furoyl, and thenoyl.

2.30

SECTION TWO

TABLE 2.11 Names of Some Carboxylic Acids

* Systematic names should be used in derivatives formed by substitution on a carbon atom. Note: The names in parentheses have been discontinued.

Linear polyethers derived from three or more molecules of aliphatic dihydroxy compounds, particularly when the chain length exceeds ten units, are most conveniently named by open-chain replacement nomenclature. For example, CH3CH2[O[CH2CH2[O[CH2CH3 could be 3,6dioxaoctane or (2-ethoxy)ethoxyethane. An oxygen atom directly attached to two carbon atoms already forming part of a ring system or to two carbon atoms of a chain may be indicated by the prefix epoxy-. For example, CH2[CH[CH2Cl is named 1-chloro-2,3-epoxypropane. 8O7 Symmetrical linear polyethers may be named (1) in terms of the central oxygen atom when there is an odd number of ether oxygen atoms or (2) in terms of the central hydrocarbon group when there is an even number of ether oxygen atoms. For example, C2H5[O[C4H8[O[C4H8[O[C2H5 is bis-(4-ethoxybutyl)ether, and 3,6-dioxaoctane (earlier example) could be named 1,2-bis(ethoxy)ethane.

ORGANIC CHEMISTRY

2.31

Partial ethers of polyhydroxy compounds may be named (1) by substitutive nomenclature or (2) by stating the name of the polyhydroxy compound followed by the name of the etherifying radical(s) followed by the word ether. For example,

Cyclic ethers are named either as heterocyclic compounds or by specialist rules of heterocyclic nomenclature. Radicofunctional names are formed by citing the names of the radicals R1 and R2 followed by the word ether. Thus methoxyethane becomes ethyl methyl ether and ethoxyethane becomes diethyl ether. 2.1.3.14 Halogen Derivatives. Using substitutive nomenclature, names are formed by adding prefixes listed in Table 2.8 to the name of the parent compound. The prefix perhalo- implies the replacement of all hydrogen atoms by the particular halogen atoms. Cations of the type R1R2X+ are given names derived from the halonium ion, H2X+, by substitution, e.g., diethyliodonium chloride for (C2H5)2I+Cl−. Retained are these trivial names; bromoform (CHBr3), chloroform (CHCl3), fluoroform (CHF3), iodoform (CHI3), phosgene (COCl2), thiophosgene (CSCl2), and dichlorocarbene radical ( CCl2). Inorganic nomenclature leads to such names as carbonyl and thiocarbonyl halides (COX2 and CSX2) and carbon tetrahalides (CX4). 2.1.3.15 Hydroxylamines and Oximes. For RNH[OH compounds, prefix the name of the radical R to hydroxylamine. If another substituent has priority as principal group, attach the prefix hydroxyamino- to the parent name. For example, C6H5NHOH would be named N-phenylhydroxylamine, but HOC6H4NHOH would be (hydroxyamino)phenol, with the point of attachment indicated by a locant preceding the parentheses. Compounds of the type R1NH[OR2 are named (1) as alkoxyamino derivatives of compound R1H, (2) as N,O-substituted hydroxylamines. (3) as alkoxyamines (even if R1 is hydrogen), or (4) by the prefix aminooxy- when another substituent has priority for parent name. Examples of each type are 1. 2. 3. 4.

2-(Methoxyamino)-8-naphthalenecarboxylic acid for CH3ONH[C10H6COOH O-Phenylhydroxylamine for H2N[O[C6H5 or N-phenylhydroxylamine for C6H5NH[OH Phenoxyamine for H2N[O[C6H5 (not preferred to O-phenylhydroxylamine) Ethyl (aminooxy)acetate for H2N[O[CH2CO[OC2H5

Acyl derivatives, RCO[NH[OH and H2N[O[CO[R, are named as N-hydroxy derivatives of amides and as O-acylhydroxylamines, respectively. The former may also be named as hydroxamic acids. Examples are N-hydroxyacetamide for CH3CO[NH[OH and O-acetylhydroxylamine for H2N[O[CO[CH3. Further substituents are denoted by prefixes with O- and/or N-locants. For example, C6H5NH[O[C2H5 would be O-ethyl-N-phenylhydroxylamine or N-ethoxylaniline. For oximes, the word oxime is placed after the name of the aldehyde or ketone. If the carbonyl group is not the principal group, use the prefix hydroxyimino-. Compounds with the group N[OR are named by a prefix alkyloxyimino- oxime O-ethers or as O-substituted oximes. Compounds with the group C˙N(O)R are named by adding N-oxide after the name of the alkylideneaminc compound. For amine oxides, add the word oxide after the name of the base, with locants. For example, C5H5N[O is named pyridine N-oxide or pyridine 1-oxide. 2.1.3.16 Imines. The group C˙NH is named either by the suffix -imine or by citing the name of the bivalent radical R1R2C as a prefix to amine. For example, CH3CH2CH2CH˙NH could be named 1-butanimine or butylideneamine. When the nitrogen is substituted, as in CH2˙N[CH2CH3, the name is N-(methylidene)ethylamine.

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SECTION TWO

Quinones are exceptions. When one or more atoms of quinonoid oxygen have been replaced by NH or NR, they are named by using the name of the quinone followed by the word imine (and preceded by proper affixes). Substituents on the nitrogen atom are named as prefixes. Examples are

2.1.3.17 Ketenes. Derivatives of the compound ketene, CH2˙C˙O, are named by substitutive nomenclature. For example, C4H9CH˙C˙O is butyl ketene. An acyl derivative, such as CH3CH2[CO[CH2CH˙C˙O, may be named as a polyketone, 1-hexene-1,4-dione. Bisketene is used for two to avoid ambiguity with diketene (dimeric ketene). 2.1.3.18 Ketones. Acyclic ketones are named (1) by adding the suffix -one to the name of the hydrocarbon forming the principal chain or (2) by citing the names of the radicals R1 and R2 followed by the word ketone. In addition to the preceding nomenclature, acyclic monoacyl derivatives of cyclic compounds may be named (3) by prefixing the name of the acyl group to the name of the cyclic compound. For example, the three possible names of

When the cyclic component is benzene or naphthalene, the -ic acid or -oic acid of the acid corresponding to the acyl group is changed to -ophenone or -onaphthone, respectively. For example, C6H5[CO[CH2CH2CH3 can be named either butyrophenone (or butanophenone) or phenyl propyl ketone. Radicofunctional nomenclature can be used when a carbonyl group is attached directly to carbon atoms in two ring systems and no other substituent is present having priority for citation. When the methylene group in polycarbocyclic and heterocyclic ketones is replaced by a keto group, the change may be denoted by attaching the suffix -one to the name of the ring system. However, when ≥CH in an unsaturated or aromatic system is replaced by a keto group, two alternative names become possible. First, the maximum number of noncumulative double bonds is added after introduction of the carbonyl group(s), and any hydrogen that remains to be added is denoted as indicated hydrogen with the carbonyl group having priority over the indicated hydrogen for lowernumbered locant. Second, the prefix oxo- is used, with the hydrogenation indicated by hydro prefixes; hydrogenation is considered to have occurred before the introduction of the carbonyl group. For example,

When another group having higher priority for citation as principal group is also present, the ketonic oxygen may be expressed by the prefix oxo-, or one can use the name of the carbonylcontaining radical, as, for example, acyl radicals and oxo-substituted radicals. Examples are

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2.33

Diketones and tetraketones derived from aromatic compounds by conversion of two or four CH groups into keto groups, with any necessary rearrangement of double bonds to a quinonoid structure, are named by adding the suffix -quinone and any necessary affixes. Polyketones in which two or more contiguous carbonyl groups have rings attached at each end may be named (1) by the radicofunctional method or (2) by substitutive nomenclature. For example,

Some trivial names are retained: acetone (2-propanone), biacetyl (2,3-butanedione), propiophenone (C6H5[CO[CH2CH3), chalcone (C6H5[CH˙CH[CO[C6H5), and deoxybenzoin (C6H5[CH2[CO[C6H5). These contracted names of heterocyclic nitrogen compounds are retained as alternatives for systematic names, sometimes with indicated hydrogen. In addition, names of oxo derivatives of fully saturated nitrogen heterocycles that systematically end in -idinone are often contracted to end in -idone when no ambiguity might result. For example,

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SECTION TWO

2.1.3.19 Lactones, Lactides, Lactams, and Lactims. When the hydroxy acid from which water may be considered to have been eliminated has a trivial name, the lactone is designated by substituting -olactone for -ic acid. Locants for a carbonyl group are numbered as low as possible, even before that of a hydroxyl group. Lactones formed from aliphatic acids are named by adding -olide to the name of the nonhydroxylated hydrocarbon with the same number of carbon atoms. The suffix -olide signifies the change of CH…CH3 into C…C˙O. O Structures in which one or more (but not all) rings of an aggregate are lactone rings are named by placing -carbolactone (denoting the[O[CO[bridge) after the names of the structures that remain when each bridge is replaced by two hydrogen atoms. The locant for [CO[ is cited before that for the ester oxygen atom. An additional carbon atom is incorporated into this structure as compared to the -olide. These trivial names are permitted: g-butyrolactone, g-valerolactone, and d-valerolactone. Names based on heterocycles may be used for all lactones. Thus, g-butyrolactone is also tetrahydro-2-furanone or dihydro-2(3H)-furanone. Lactides, intermolecular cyclic esters, are named as heterocycles. Lactams and lactims, containing a[CO[NH[and[C(OH) ˙N[group, respectively, are named as heterocycles, but they may also be named with -lactam or -lactim in place of -olide. For example,

2.1.3.20 Nitriles and Related Compounds. For acids whose systematic names end in -carboxylic acid, nitriles are named by adding the suffix -carbonitrile when the [CN group replaces the [COOH group. The carbon atom of the [CN group is excluded from the numbering of a chain to which it is attached. However, when the triple-bonded nitrogen atom is considered to replace three hydrogen atoms at the end of the main chain of an acyclic hydrocarbon, the suffix -nitrile is added to the name of the hydrocarbon. Numbering begins with the carbon attached to the nitrogen. For example, CH3CH2CH2CH2CH2CN is named (1) pentanecarbonitrile or (2) hexanenitrile. Trivial acid names are formed by changing the endings -oic acid or -ic acid to -onitrile. For example, CH3CN is acetonitrile. When the [CN group is not the highest priority group, the [CN group is denoted by the prefix cyano-. In order of decreasing priority for citation of a functional class name, and the prefix for substitutive nomenclature, are the following related compounds:

2.1.3.21 Peroxides. Compounds of the type R[O[OH are named (1) by placing the name of the radical R before the word hydroperoxide or (2) by use of the prefix hydroperoxy- when another parent name has higher priority. For example, C2H5OOH is ethyl hydroperoxide.

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2.35

Compounds of the type R1O[OR2 are named (1) by placing the names of the radicals in alphabetical order before the word peroxide when the group [O[O[ links two chains, two rings, or a ring and a chain, (2) by use of the affix dioxy to denote the bivalent group [O[O[ for naming assemblies of identical units or to form part of a prefix, or (3) by use of the prefix epidioxy- when the peroxide group forms a bridge between two carbon atoms, a ring, or a ring system. Examples are methyl propyl peroxide for CH3[O[O[C3H7 and 2,2′-dioxydiacetic acid for HOOC[CH2[O[O[CH2[COOH. 2.1.3.21 Phosphorus Compounds. Acyclic phosphorus compounds containing only one phosphorus atom, as well as compounds in which only a single phosphorus atom is in each of several functional groups, are named as derivatives of the parent structures (Table 2.12). Often these are purely hypothetical parent structures. When hydrogen attached to phosphorus is replaced by a hydrocarbon group, the derivative is named by substitution nomenclature. When hydrogen of an [OH group is replaced, the derivative is named by radicofunctional nomenclature. For example, C2H5PH2 is ethylphosphine; (C2H5)2PH, diethylphosphine; CH3P(OH)2, dihydroxy-methyl-phosphine or methylphosphonous acid; C2H5[PO(Cl)(OH), ethylchlorophosphonic acid or ethylphosphonochloridic acid or hydrogen chlorodioxoethylphosphate(V); CH3CH(PH2)COOH, 2-phosphinopropionic acid; HP(CH2COOH)2, phosphinediyldiacetic acid; (CH3)HP(O)OH, methylphosphinic acid or hydrogen hydridomethyldioxophosphate(V); (CH3O)3PO, trimethyl phosphate; and (CH3O)3P, trimethyl phosphite. 2.1.3.22 Salts and Esters of Acids. Neutral salts of acids are named by citing the cation(s) and then the anion, whose ending is changed from -oic to -oate or from -ic to -ate. When different acidic residues are present in one structure, prefixes are formed by changing the anion ending -ate to -atoor -ide to -ido-. The prefix carboxylato- denotes the ionic group [COO−. The phrase (metal) salt of (the acid) is permissible when the carboxyl groups are not all named as affixes. Acid salts include the word hydrogen (with affixes, if appropriate) inserted between the name of the cation and the name of the anion (or word salt). Esters are named similarly, with the name of the alkyl or aryl radical replacing the name of the cation. Acid esters of acids and their salts are named as neutral esters, but the components are cited TABLE 2.12 Phosphorus-Containing Compounds

2.36

SECTION TWO

in the order: cation, alkyl or aryl radical, hydrogen, and anion. Locants are added if necessary. For example,

Ester groups in R1[CO[OR2 compounds are named (1) by the prefix alkoxycarbonyl- or aryloxycarbonyl- for [CO[OR2 when the radical R1 contains a substituent with priority for citation as principal group or (2) by the prefix acyloxy- for R1[CO[O[ when the radical R2 contains a substituent with priority for citation as principal group. Examples are

The trivial name acetoxy is retained for the CH3[CO[O[ group. Compounds of the type R2C(OR2)3 are named as R2 esters of the hypothetical ortho acids. For example, CH3C(OCH3)3 is trimethyl orthoacetate. 2.1.3.22 Silicon Compounds. SiH4 is called silane; its acyclic homologs are called disilane, trisilane, and so on, according to the number of silicon atoms present. The chain is numbered from one end to the other so as to give the lowest-numbered locant in radicals to the free valence or to substitutents on a chain. The abbreviated form silyl is used for the radical SiH3[. Numbering and citation of side chains proceed according to the principles set forth for hydrocarbon chains. Cyclic nonaromatic structures are designated by the prefix cyclo-. When a chain or ring system is composed entirely of alternating silicon and oxygen atoms, the parent name siloxane is used with a multiplying affix to denote the number of silicon atoms present. The parent name silazane implies alternating silicon and nitrogen atoms; multiplying affixes denote the number of silicon atoms present. The prefix sila- designates replacement of carbon by silicon in replacement nomenclature. Prefix names for radicals are formed analogously to those for the corresponding carbon-containing compounds. Thus silyl is used for SiH3[, silyene for [SiH2[, silylidyne for [SiH<, as well as trily, tetrayl, and so on for free valences(s) on ring structures. 2.1.3.23 Sulfur Compounds Bivalent Sulfur. The prefix thio, placed before an affix that denotes the oxygen-containing group or an oxygen atom, implies the replacement of that oxygen by sulfur. Thus the suffix -thiol denotes [SH, -thione denotes [(C)˙S and implies the presence of an ˙S at a nonterminal carbon atom, -thioic acid denotes [(C)˙S]OH Í [(C)˙O]SH (that is, the O-substituted acid and the S-substituted acid, respectively), -dithioc acid denotes [[C(S)SH, and -thial denotes [(C)HS (or -carbothialdehyde denotes [CHS). When -carboxylic acid has been used for acids, the sulfur analog is named -carbothioic acid or -carbodithioic acid. Prefixes for the groups HS[ and RS[ are mercapto- and alkylthio-, respectively; this latter name may require parentheses for distinction from the use of thio- for replacement of oxygen in a trivially named acid. Examples of this problem are 4-C2H5[C6H4[CSOH named p-ethyl(thio)benzoic acid and 4-C2H5[S[C6H4[COOH named p-(ethylthio)benzoic acid. When [SH is not the principal group, the prefix mercapto- is placed before the name of the parent compound to denote an unsubstituted [SH group.

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2.37

The prefix thioxo- is used for naming ˙S in a thioketone. Sulfur analogs of acetals are named as alkylthio- or arylthio-. For example, CH3CH(SCH3)OCH3 is 1-methoxy-1-(methylthio)ethane. Prefix forms for -carbothioic acids are hydroxy(thiocarbonyl)- when referring to the O-substituted acid and mercapto(carbonyl)- for the S-substituted acid. Salts are formed as with oxygen-containing compounds. For example, C2H5[S[Na is named either sodium ethanethiolate or sodium ethyl sulfide. If mercapto- has been used as a prefix, the salt is named by use of the prefix sulfido- for [S−. Compounds of the type R1[S[R2 are named alkylthio- (or arylthio-) as a prefix to the name of R1 or R2, whichever is the senior. 2.1.3.24 Sulfonium Compounds. Sulfonium compounds of the type R1R2R3S+X− are named by citing in alphabetical order the radical names followed by -sulfonium and the name of the anion. For heterocyclic compounds, -ium is added to the name of the ring system. Replacement of CH by sulfonium sulfur is denoted by the prefix thionia-, and the name of the anion is added at the end. 2.1.3.25 Organosulfur Halides. When sulfur is directly linked only to an organic radical and to a halogen atom, the radical name is attached to the word sulfur and the name(s) and number of the halide(s) are stated as a separate word. Alternatively, the name can be formed from R[SOH, a sulfenic acid whose radical prefix is sulfenyl-. For example, CH3CH2[S[Br would be named either ethylsulfur monobromide or ethanesulfenyl bromide. When another principal group is present, a composite prefix is formed from the number and substitutive name(s) of the halogen atoms in front of the syllable thio. For example, BrS[COOH is (bromothio)formic acid. 2.1.3.26 Sulfoxides. Sulfoxides, R1[SO[R2, are named by placing the names of the radicals in alphabetical order before the word sulfoxide. Alternatively, the less senior radical is named followed by sulfinyl- and concluded by the name of the senior group. For example, CH3CH2[SO[CH2CH2CH3 is named either ethyl propyl sulfoxide or 1-(ethylsulfinyl)propane. When an SO group is incorporated in a ring, the compound is named an oxide. 2.1.3.27 Sulfones. Sulfones, R1[SO2[R2, are named in an analogous manner to sulfoxides, using the word sulfone in place of sulfoxide. In prefixes, the less senior radical is followed by -sulfonyl-. When the SO2 group is incorporated in a ring, the compound is named as a dioxide. 2.1.3.28 Sulfur Acids. Organic oxy acids of sulfur, that is, [SO3H, [SO2H, and [SOH, are named sulfonic acid, sulfinic acid, and sulfenic acid, respectively. In subordinate use, the respective prefixes are sulfo-, sulfino, and sulfeno-. The grouping [SO2[O[SO2[ or [SO[O[SO is named sulfonic or sulfinic anhydride, respectively. Inorganic nomenclature is employed in naming sulfur acids and their derivatives in which sulfur is linked only through oxygen to the organic radical. For example, (C2H5O)2SO2 is diethyl sulfate and C2H5O[SO2[OH is ethyl hydrogen sulfate. Prefixes O- and S- are used where necessary to denote attachment to oxygen and to sulfur, respectively, in sulfur replacement compounds. For example, CH3[S[SO2[ONa is sodium S-methyl thiosulfate. When sulfur is linked only through nitrogen, or through nitrogen and oxygen, to the organic radical, naming is as follows: (1) N-substituted amides are designated as N-substituted derivatives of the sulfur amides and (2) compounds of the type R[NH[SO3H may be named as N-substituted sulfamic acids or by the prefix sulfoamino- to denote the group HO3S[NH[. The groups [N˙SO and [N˙SO2 are named sulfinylamines and sulfonylamines, respectively. 2.1.3.29 Sultones and Sultams. Compounds containing the group [SO2[O[ as part of the ring are called -sultone. The [SO2[ group has priority over the [O[ group for lowest-numbered locant. Similarly, the [SO2[N˙ group as part of a ring is named by adding -sultam to the name of the hydrocarbon with the same number of carbon atoms. The [SO2[ has priority over [N˙ for lowest-numbered locant.

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SECTION TWO

2.1.4 Stereochemistry Concepts in stereochemistry, that is, chemistry in three-dimensional space, are in the process of rapid expansion. This section will deal with only the main principles. The compounds discussed will be those that have identical molecular formulas but differ in the arrangement of their atoms in space. Stereoisomers is the name applied to these compounds. Stereoisomers can be grouped into three categories: (1) Conformational isomers differ from each other only in the way their atoms are oriented in space, but can be converted into one another by rotation about sigma bonds. (2) Geometric isomers are compounds in which rotation about a double bond is restricted. (3) Configurational isomers differ from one another only in configuration about a chiral center, axis, or plane. In subsequent structural representations, a broken line denotes a bond projecting behind the plane of the paper and a wedge denotes a bond projecting in front of the plane of the paper. A line of normal thickness denotes a bond lying essentially in the plane of the paper. 2.1.4.1 Conformational Isomers. A molecule in a conformation into which its atoms return spontaneously after small displacements is termed a conformer. Different arrangements of atoms that can be converted into one another by rotation about single bonds are called conformational isomers (see Fig. 2.1). A pair of conformational isomers can be but do not have to be mirror images of each other. When they are not mirror images, they are called diastereomers.

FIGURE 2.1 (b) staggered.

Conformations of ethane. (a) Eclipsed;

2.1.4.2 Acyclic Compounds. Different conformations of acyclic compounds are best viewed by construction of ball-and-stick molecules or by use of Newman projections (see Fig. 2.2). Both types of representations are shown for ethane. Atoms or groups that are attached at opposite ends of a single bond should be viewed along the bond axis. If two atoms or groups attached at opposite ends of the bond appear one directly behind the other, these atoms or groups are described as eclipsed. That portion of the molecule is described as being in the eclipsed conformation. If not eclipsed, the atoms or groups and the conformation may be described as staggered. Newman projections show these conformations clearly. Certain physical properties show that rotation about the single bond is not quite free. For ethane there is an energy barrier of about 3 kcal ⋅ mol−1 (12 kJ ⋅ mol−1 ). The potential energy of the molecule is at a minimum for the staggered conformation, increases with rotation, and reaches a maximum at the eclipsed conformation. The energy required to rotate the atoms or groups about the carbon-carbon bond is called torsional energy. Torsional strain is the cause of the rela- FIGURE 2.2 Newman projections for ethane. (a) Staggered; (b) eclipsed. tive instability of the eclipsed conformation or any intermediate skew conformations. In butane, with a methyl group replacing one hydrogen on each carbon of ethane, there are several different staggered conformations (see Fig. 2.3). There is the anti-conformation in which the methyl groups are as far apart as they can be (dihedral angle of 180°). There are two gauche conformations in which the methyl groups are only 60° apart; these are two nonsuperimposable mirror images of each other. The anti-conformation is more stable than the gauche by about 0.9 kcal ⋅ mol−1 (4 kJ ⋅ mol−1). Both are free of torsional strain. However, in a gauche conformation the methyl groups are closer together than the sum of their van der Waals’ radii. Under these conditions van der Waals’ forces are repulsive and raise the energy of conformation. This strain can affect not only the relative stabilities of

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2.39

FIGURE 2.3 Conformations of butane. (a) Anti-staggered; (b) eclipsed; (c) gauche-staggered; (d) eclipsed; (e) gauche-staggered; (f) eclipsed. (Eclipsed conformations are slightly staggered for convenience in drawing; actually they are superimposed.)

various staggered conformations but also the heights of the energy barriers between them. The energy maximum (estimated at 4.8 to 6.1 kcal ⋅ mol−1 or 20 to 25 kJ ⋅ mol−1) is reached when two methyl groups swing past each other (the eclipsed conformation) rather than past hydrogen atoms. 2.1.4.3 Cyclic Compounds. Although cyclic aliphatic compounds are often drawn as if they were planar geometric figures (a triangle for cyclopropane, a square for cyclobutane, and so on), their structures are not that simple. Cyclopropane does possess the maximum angle strain if one considers the difference between a tetrahedral angle (109.5°) and the 60° angle of the cyclopropane structure. Nevertheless the cyclopropane structure is thermally quite stable. The highest electron density of the carbon-carbon bonds does not lie along the lines connecting the carbon-carbon bonds does not lie along the lines connecting the carbon atoms. Bonding electrons lie principally outside the triangular internuclear lines and result in what is known as bent bonds (see Fig. 2.4). FIGURE 2.4 The bent bonds (“tear drops”) of Cyclobutane has less angle strain than cyclo- cyclopropane. propane (only 19.5°). It is also believed to have some bent-bond character associated with the carbon-carbon bonds. The molecule exists in a nonplanar conformation in order to minimize hydrogen-hydrogen eclipsing strain. Cyclopentane is nonplanar, with a structure that resembles an envelope (see Fig. 2.5). Four of the carbon atoms are in one plane, and the fifth is out of that plane. The molecule is in continual motion so that the out-of-plane carbon moves rapidly around the ring.

FIGURE 2.5 The conformations of cyclopentane.

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SECTION TWO

FIGURE 2.6 The two chair conformations of cyclohexane; a = axial hydrogen atom and e = equatorial hydrogen atom.

The 12 hydrogen atoms of cyclohexane do not occupy equivalent positions. In the chair conformation six hydrogen atoms are perpendicular to the average plane of the molecule and six are directed outward from the ring, slightly above or below the molecular plane (see Fig. 2.6). Bonds which are perpendicular to the molecular plane are known as axial bonds, and those which extend outward from the ring are known as equatorial bonds. The three axial bonds directed upward originate from alternate carbon atoms and are parallel with each other; a similar situation exists for the three axial bonds directed downward. Each equatorial bond is drawn so as to be parallel with the ring carbon-carbon bond once removed from the point of attachment to that equatorial bond. At room temperature, cyclohexane is interconverting rapidly between two chair conformations. As one chair form converts to the other, all the equatorial hydrogen atoms become axial and all the axial hydrogens become equatorial. The interconversion is so rapid that all hydrogen atoms on cyclohexane can be considered equivalent. Interconversion is believed to take place by movement of one side of the chair structure to produce the twist boat, and then movement of the other side of the twist boat to give the other chair form. The chair conformation is the most favored structure for cyclohexane. No angle strain is encountered since all bond angles remain tetrahedral. Torsional strain is minimal because all groups are staggered. In the boat conformation of cyclohexane (see Fig 2.7) eclipsing torsional strain is significant, although no angle strain is encountered. Nonbonded interaction between the two hydrogen atoms across the ring from each other (the “flagpole” hydrogens) is unfavorable. The boat conformation is about 6.5 kcal ⋅ mol−1 (27 kJ ⋅ mol−1) higher in energy than the chair form at 25°C. FIGURE 2.7 The boat conformation of cyclohexane. a = A modified boat conformation of cyclo- axial hydrogen atom and e = equatorial hydrogen atom. hexane, known as the twist boat (see Fig. 2.8), or skew boat, has been suggested to minimize torsional and nonbounded interactions. This particular conformation is estimated to be about 1.5 kcal ⋅ mol−1 ⋅ (6 kJ ⋅ mol−1) lower in energy than the boat form at room temperature. The medium-size rings (7 to 12 ring atoms) are relatively free of angle strain and can easily take a variety of spatial arrangements. They are not large enough to avoid all nonbonded interactions between atoms. Disubstituted cyclohexanes can exist as cis- FIGURE 2.8 Twist-boat conformation of cyclohexane. trans isomers as well as axial-equatorial conformers. Two isomers are predicted for 1,4-dimethylcyclohexane (see Fig. 2.9). For the trans isomer the diequatorial conformer is the energetically favorable form. Only one cis isomer is observed, since the two conformers of the cis compound are identical. Interconversion takes place between the conformational (equatorial-axial isomers) but not configurational (cis-trans) isomers. The bicyclic compound decahydronaphthalene, or bicyclo[4.4.0]decane, has two fused six-membered rings. It exists in cis and trans forms (see Fig. 2.10), as determined by the configurations at the

ORGANIC CHEMISTRY

2.41

FIGURE 2.9 Two isomers of 1,4-dimethylcyclohexane. (a) Trans isomer; (b) cis isomer.

bridgehead carbon atoms. Both cis- and trans-decahydronaphthalene can be constructed with two chair conformations. 2.1.4.4 Geometrical Isomerism. Rotation about a carbon-carbon double bond is restricted because of interaction between the p orbitals which make up to pi bond. Isomerism due to such restricted rotation about a bond is known as geometric isomerism. Parallel overlap of the p orbitals of each carbon atom of the double bond forms the molecular orbital of the pi bond. The relatively large barrier to rotation about the pi bond is estimated to be nearly 63 kcal ⋅ mol−1 (263 kJ ⋅ mol−1). When two different substituents are attached to each carbon atom of the double bond, cis-trans isomers can exist. In the case of cis-2-butene (see Fig. 2.11a), both methyl groups are on the same side of the double bond. The other isomer has the methyl groups on opposite sides and is designated as trans-2-butene (see Fig. 2.11b). Their physical properties are quite different. Geometric isomerism can also exist in ring systems; examples were cited in the previous discussion on conformational isomers. For compounds containing only double-bonded atoms, the reference plane contains the double bonded atoms and is perpendicular to the plane containing these atoms and those directly attached to them. It is customary to draw the formulas so that the reference plane is perpendicular to that of the paper. For cyclic compounds the reference plane is that in which the ring skeleton lies or to which it approximates. Cyclic structures are commonly drawn with the ring atoms in the plane of the paper.

FIGURE 2.10 Two isomers of decahydronaphthalene, or bicyclo[4.4.0]decane. (a) Trans isomer; (b) cis isomer.

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SECTION TWO

FIGURE 2.11 Two isomers of 2-butene. (a) Cis isomer, bp 3.8°C, mp −138.9°C, dipole moment 0.33 D; (b) trans isomer, bp 0.88°C, mp −105.6°C, dipole moment 0 D.

2.1.4.5 Sequence Rules for Geometric Isomers and Chiral Compounds. Although cis and trans designations have been used for many years, this approach becomes useless in complex systems. To eliminate confusion when each carbon of a double bond or a chiral center is connected to different groups, the Cahn, Ingold, and Prelog system for designating configuration about a double bond or a chiral center has been adopted by IUPAC. Groups on each carbon atom of the double bond are assigned a first (1) or second (2) priority. Priority is then compared at one carbon relative to the other. When both first priority groups are on the same side of the double bond, the configuration is designated as Z (from the German zusammen, “together”), which was formerly cis. If the first priority groups are on opposite sides of the double bond, the designation is E (from the German entgegen, “in opposition to”), which was formerly trans. (See Fig. 2.12). When a molecule contains more than one double bond, each E or Z prefix has associated with it the lower-numbered locant of the double bond concerned. Thus (see also the rules that follow)

When the sequence rules permit alternatives, preference for lower-numbered locants and for inclusion in the principal chain is allotted as follows in the order stated: Z over E groups and cis over trans cyclic groups. If a choice is still not attained, then the lower-numbered locant for such a preferred group at the first point of difference is the determining factor. For example,

Rule 1. Priority is assigned to atoms on the basis of atomic number. Higher priority is assigned to atoms of higher atomic number. If two atoms are isotopes of the same element, the atom of higher mass number has the higher priority. For example, in 2-butene, the carbon atom of each methyl group receives first priority over the hydrogen atom connected to the same carbon atom. Around the asymmetric carbon atom in chloroiodomethanesulfonic acid, the priority sequence is I, Cl, S, H. In 1bromo-1-deuteroethane, the priority sequence is Cl, C, D, H.

FIGURE 2.12 Configurations designated by priority groups. (a) Z (cis); (b) E (trans).

ORGANIC CHEMISTRY

2.43

Rule 2. When atoms attached directly to a double-bonded carbon have the same priority, the second atoms are considered and so on, if necessary, working outward once again from the double bond or chiral center. For example, in 1-chloro-2-methylbutene, in CH3 the second atoms are H, H, H and in CH2CH3 they are C, H, H. Since carbon has a higher atomic number than hydrogen, the ethyl group has the next highest priority after the chlorine atom.

Rule 3. When groups under consideration have double or triple bonds, the multiple-bonded atom is replaced conceptually by two or three single bonds to that same kind of atom. A 7A . However, a Thus, ˙ A is considered to be equivalent to two A’s, 7 8A or and æ A equals [A 8A A 7A has priority over æ A. Actually, real 7 has priority over ˙ A; likewise a real both atoms of [A 8A 8A C[O C[O a multiple bond are duplicated, or triplicated, so that C ˙ O is treated as ∂ ∂ , that is ∂ and C[O O C (O) 7CH C[ [ [ [ [ [N ∂ , and C æ N is treated as 7 8 7 8 . A phenyl carbon becomes [C[C . (N) (N) (C) (C) 8CH (C) Only the double-bonded atoms themselves are duplicated, not the atoms or groups attached to them. The duplicated atoms (or phantom atoms) may be considered as carrying atomic number zero. For example, among the groups OH, CHO, CH2OH, and H, the OH group has the highest priority, and the C(O, O, H) of CHO takes priority over the C(O, H, H) of CH2OH. 2.1.4.6 Chirality and Optical Activity. A compound is chiral (the term dissymmetric was formerly used) if it is not superimposable on its mirror image. A chiral compound does not have a plane of symmetry. Each chiral compound possesses one (or more) of three types of chiral element, namely, a chiral center, a chiral axis, or a chiral plane. 2.1.4.7 Chiral Center. The chiral center, which is the chiral element most commonly met, is exemplified by an asymmetric carbon with a tetrahedral arrangement of ligands about the carbon. The ligands comprise four different atoms or groups. One “ligand” may be a lone pair of electrons; another, a phantom atom of atomic number zero. This situation is encountered in sulfoxides or with a nitrogen atom. FIGURE 2.13 Asymmetric (chiral) carbon in the lactic Lactic acid is an example of a molecule with an acid molecule. asymmetric (chiral) carbon. (See Fig. 2.13.) A simpler representation of molecules containing asymmetric carbon atoms is the Fischer projection, which is shown here for the same lactic acid configurations. A Fischer projection involves

drawing a cross and attaching to the four ends the four groups that are attached to the asymmetric carbon atom. The asymmetric carbon atom is understood to be located where the lines cross. The horizontal lines are understood to represent bonds coming toward the viewer out of the plane of the paper. The vertical lines represent bonds going away from the viewer behind the plane of the paper as if the vertical line were the side of a circle. The principal chain is depicted in the vertical direction;

2.44

SECTION TWO

the lowest-numbered (locant) chain member is placed at the top position. These formulas may be moved sideways or rotated through 180° in the plane of the paper, but they may not be removed from the plane of the paper (i.e., rotated through 90°). In the latter orientation it is essential to use thickened lines (for bonds coming toward the viewer) and dashed lines (for bonds receding from the viewer) to avoid confusion. 2.1.4.8 Enantiomers. Two nonsuperimposable structures that are mirror images of each other are known as enantiomers. Enantiomers are related to each other in the same way that a right hand is related to a left hand. Except for the direction in which they rotate the plane of polarized light, enantiomers are identical in all physical properties. Enantiomers have identical chemical properties except in their reactivity toward optically active reagents. Enantiomers rotate the plane of polarized light in opposite directions but with equal magnitude. If the light is rotated in a clockwise direction, the sample is said to be dextrorotatory and is designed as (+). When a sample rotates the plane of polarized light in a counterclockwise direction, it is said to be levorotatory and is designed as (−). Use of the designations d and l is discouraged. 2.1.4.9 Specific Rotation. Optical rotation is caused by individual molecules of the optically active compound. The amount of rotation depends upon how many molecules the light beam encounters in passing through the tube. When allowances are made for the length of the tube that contains the sample and the sample concentration, it is found that the amount of rotation, as well as its direction, is a characteristic of each individual optically active compound. Specific rotation is the number of degrees of rotation observed if a 1-dm tube is used and the compound being examined is present to the extent of 1 g per 100 mL. The density for a pure liquid replaces the solution concentration. Specific rotation = [α ] =

observed rotation (degrees) length (dm) × (g/100 ml)

The temperature of the measurement is indicated by a superscript and the wavelength of the light employed by a subscript written after the bracket; for example, [a]20 590 implies that the measurement was made at 20°C using 590-nm radiation. 2.1.4.10 Optically Inactive Chiral Compounds. Although chirality is a necessary prerequisite for optical activity, chiral compounds are not necessarily optically active. With an equal mixture of two enantiomers, no net optical rotation is observed. Such a mixture of enantiomers is said to be racemic and is designated as (±) and not as dl. Racemic mixtures usually have melting points higher than the melting point of either pure enantiomer. A second type of optically inactive chiral compounds, meso compounds, will be discussed in the next section. 2.1.4.11 Multiple Chiral Centers. The number of stereoisomers increases rapidly with an increase in the number of chiral centers in a molecule. A molecule possessing two chiral atoms should have four optical isomers, that is, four structures consisting of two pairs of enantiomers. However, if a compound has two chiral centers but both centers have the same four substituents attached, the total number of isomers is three rather than four. One isomer of such a compound is not chiral because it is identical with its mirror image; it has an internal mirror plane. This is an example of a diastereomer. The achiral structure is denoted as a meso compound. Diastereomers have different physical and chemical properties from the optically active enantiomers. Recognition of a plane of symmetry is usually the easiest way to detect a meso compound. The stereoisomers of tartaric acid are examples of compounds with multiple chiral centers (see Fig. 2.14), and one of its isomers is a meso compound. When the asymmetric carbon atoms in a chiral compound are part of a ring, the isomerism is more complex than in acyclic compounds. A cyclic compound which has two different asymmetric carbons with different sets of substituent groups attached has a total of 22 = 4 optical isomers: an enantiometric pair of cis isomers and an enantiometric pair of trans isomers. However, when the two

ORGANIC CHEMISTRY

2.45

FIGURE 2.14 Isomers of tartaric acid.

asymmetric centers have the same set of substituent groups attached, the cis isomer is a meso compound and only the trans isomer is chiral. (See Fig. 2.15). 2.1.4.12 Torsional Asymmetry. Rotation about single bonds of most acyclic compounds is relatively free at ordinary temperatures. There are, however, some examples of compounds in which nonbonded interactions between large substitutent groups inhibit free rotation about a sigma bond. In some cases these compounds can be separated into pairs of enantiomers. A chiral axis is present in chiral biaryl derivatives. When bulky groups are located at the ortho positions of each aromatic ring in biphenyl, free rotation about the single bond connecting the two rings is inhibited because of torsional strain associated with twisting rotation about the central single bond. Interconversion of enantiomers is prevented (see Fig. 2.16). For compounds possessing a chiral axis, the structure can be regarded as an elongated tetrahedron to be viewed along the axis. In deciding upon the absolute configuration it does not matter from which end it is viewed; the nearer pair of ligands receives the first two positions in the order of precedence (see Fig. 2.17). A chiral plane is exemplified by the plane containing the benzene ring and the bromine and oxygen atoms in the chiral compound (see Fig. 2.18). Rotation of the benzene ring around the oxygen-to-ring single bonds is inhibited when x is small (although no critical size can be reasonably established). 2.1.4.13 Absolute Configuration. The terms absolute stereochemistry and absolute configuration are used to describe the three-dimensional arrangement of substituents around a chiral element. A general system for designating absolute configuration is based upon the priority system and sequence rules. Each group attached to a chiral center is assigned a number, with number one the highest-priority group. For example, the groups attached to the chiral center of 2-butanol (see Fig. 2.19) are assigned

FIGURE 2.15 Isomers of cyclopropane-1,2-dicarboxylic acid. (a) Trans isomer; (b) meso isomer.

2.46

SECTION TWO

FIGURE 2.16 Isomers of biphenyl compounds with bulky groups attached at the ortho positions.

FIGURE 2.17 Example of a chiral axis.

FIGURE 2.18 Example of a chiral plane.

FIGURE 2.19 Viewing angle as a means of designating the absolute configuration of compounds with a chiral axis. (a) (R)-2-Butanol (sequence clockwise); (b) (S)-2-butanol (sequence counterclockwise).

ORGANIC CHEMISTRY

2.47

these priorities: 1 for OH, 2 for CH2CH3, 3 for CH3, and 4 for H. The molecule is then viewed from the side opposite the group of lowest priority (the hydrogen atom), and the arrangement of the remaining groups is noted. If, in proceeding from the group of highest priority to the group of second priority and thence to the third, the eye travels in a clockwise direction, the configuration is specified R (from the Latin rectus, “right”); if the eye travels in a counterclockwise direction, the configuration is specified S (from the Latin sinister, “left”). The complete name includes both configuration and direction of optical rotation, as for example, (S)-(+)-2-butanol. The relative configurations around the chiral centers of many compounds have been established. One optically active compound is converted to another by a sequence of chemical reactions which are stereospecific; that is, each reaction is known to proceed spatially in a specific way. The configuration of one chiral compound can then be related to the configuration of the next in sequence. In order to establish absolute configuration, one must carry out sufficient stereospecific reactions to relate a new compound to another of known absolute configuration. Historically the configuration of D-(+)-2,3-dihydroxypropanal has served as the standard to which all configuration has been compared. The absolute configuration assigned to this compound has been confirmed by an X-ray crystallographic technique.

2.1.5 Amino Acids An amino acid is an organic compound containing an amine group (-NH2) and a carboxylic acid group (-CO2H) in the same molecule. While there are many forms of amino acids, all of the important amino acids found in living organisms are alpha-amino acids. Alpha amino acids have the carboxylic acid group and the amino group attached to the same carbon atom. The simplest amino acid is glycine (H2NCH2COOH) and contains no asymmetric carbon atoms (tetrahedral carbon atoms with four different groups attached). All of the other amino acids contain an asymmetric carbon atom and are therefore optically active. Under physiological aqueous conditions a proton transfer from the acid to the base occurs, forming a dipolar ion or zwitterion, because TABLE 2.13 Formula and Nomenclature of Amino Acids Name

Abbr.

Alanine Arginine Asparagine Aspartic acid Cysteine Glutamine Glutamic acid Glycine Histidine

ala arg asn asp cys gln glu gly his

Isoleucine Leucine Lysine Methionine Phenylalanine Proline

ile leu lys met phe pro

Serine Threonine Tryptophan

ser thr trp

Tyrosine Valine

tyr val

Linear structural formula CH3[CH(NH2)[COOH HN˙C(NH2)[NH[(CH2)3-CH(NH2)-COOH H2N[CO[CH2[CH(NH2)[COOH HOOC[CH2[CH(NH2)[COOH HS[CH2[CH(NH2)[COOH H2N[CO[(CH2)2[CH(NH2)[COOH HOOC[(CH2)2[CH(NH2)[COOH NH2[CH2[COOH NH-CH˙N[CH˙C[CH2CH(NH2)[COOH ∂ ∂ [[[ [ [ [ [ [[[ CH3-CH2-CH(CH3)[CH(NH2)[COOH (CH3)2[CH[CH2[CH(NH2)[COOH H2N[(CH2)4[CH(NH2)[COOH CH3[S[(CH2)2[CH(NH2)[COOH C6H5[CH2[CH(NH2)[COOH NH[(CH2)3[CH-COOH ∂ ∂ [[ [ [ [ [ [ [ HO[CH2[CH(NH2)[COOH CH3[CH(OH)[CH(NH2)[COOH C6H4[NH[CH˙C[CH2[CH(NH2)[COOH ∂ ∂ [[[[ [ [ [ [ [ [ HO[p[C6H4[CH2[CH(NH2)[COOH (CH3)2[CH[CH(NH2)[COOH

2.48

SECTION TWO

TABLE 2.14 Acid-Base Properties of Amino Acids Amino acid

pKa1*

Glycine Alanine Valine Leucine Isoleucine Methionine Proline Phenylalanine Tryptophan Asparagine Glutamine Serine Threonine Tyrosine

2.34 2.34 2.32 2.36 2.36 2.28 1.99 1.83 2.83 2.02 2.17 2.21 2.09 2.20

pKa2*

pl

9.60 9.69 9.62 9.60 9.60 9.21 10.60 9.13 9.39 8.80 9.13 9.15 9.10 9.11

5.97 6.00 5.96 5.98 6.02 5.74 6.30 5.48 5.89 5.41 5.65 5.68 5.60 5.66

*In all cases pKa1 corresponds to ionization of the carboxyl group; pKa2 corresponds to deprotonation of the ammonium ion.

the carboxylic acid is a much stronger acid than is the ammonium ion. The actual structure of glycine in solution, for example, is +H3NCH2COO− at pH 7 rather than H2NCH2COOH. At very low pH the acid group can be protonated and at very high pH the ammonium group can be deprotonated, but the forms of amino acids relevant to living organisms are the zwitterions.

TABLE 2.15 Acid-Base Properties of Amino Acids with Ionizable Side Chains Amino acid

pKa1*

pKa2

pKa of side chain

pl

Aspartic acid Glutamic acid

1.88 2.19

9.60 9.67

3.65 4.25

2.77 3.22

Lysine Arginine Histidine

2.18 2.17 1.82

8.95 9.04 9.17

10.53 12.48 6.00

9.74 10.76 7.59

*In all cases pKa1 corresponds to ionization of the carboxyl group of RCHCO2H, and pKa2 ∂ to ionization of the ammonium ion. NH3 +

2.1.6 Carbohydrates Carbohydrates consist of the elements carbon, hydrogen, and oxygen. In their basic form, carbohydrates are simple sugars or monosaccharides. These simple sugars can combine with each other to form more complex carbohydrates. The combination of two simple sugars is a disaccharide. Carbohydrates consisting of two to ten simple sugars are called oligosaccharides, and those with a larger number are called polysaccharides. 2.1.6.1 Sugars. Sugars are white crystalline carbohydrates that are soluble in water and generally have a sweet taste. Monosaccharides are simple sugars

2.49

ORGANIC CHEMISTRY

The classification system of monosaccharides is based on the number of carbons in the sugar: Number of carbon atoms

Category name

4 5

Tetrose Pentose

6

Hexose

7

Heptose

Examples Erythrose, Threose Arabinose, Ribose, Ribulose, Xylose, Xylulose, Lyxose Allose, Altrose, Fructose, Galactose, Glucose, Gulose, Idose, Mannose, Sorbose, Talose Sedoheptulose

Many saccharide structures differ only in the orientation of the hydroxyl groups (-OH). This slight structural difference makes a big difference in the biochemical properties, organoleptic properties (e.g., taste), and in the physical properties such as melting point and Specific Rotation (how polarized light is distorted). A chain-form monosaccharide that has a carbonyl group (C˙O) on an end carbon forming an aldehyde group (-CHO) is classified as an aldose. When the carbonyl group is on an inner atom forming a ketone, it is classified as a ketose. 2.1.6.1.1 Tetroses H

C

O

H

C OH

H

C OH

H

HO C H C OH

H

CH2OH D-Erythrose

O

C

CH2OH D-Threose

2.1.6.1.2 Pentoses The ribose structure is a component of deoxyribonucleic acid (DNA) and ribonucleic acids (RNA). O

H

H C

OH

H C

OH

H C

H C

OH

H C

OH

HO C

H C

OH

H C

OH

H C

H

C

CH2OH D-Ribose

2.1.6.1.3 C6H12O6. H

C

O

Hexoses. H

C

O

H

O

C

CH2OH D-Arabinose

C

H

O

C

O

OH

HO C

H

H

HO C

H

OH

H C

CH2OH

OH

CH2OH

D-Xylose

D-Lyxose

Hexoses, such as the ones illustrated here, have the molecular formula H 1 O C 2

H

C

O

H

C

O

H

C

O

H

H C

C

O

H

C

O

H C

OH HO C

H

H C

OH HO C

H

H C

OH HO C

H

OH

HO C

H

H C

OH

H C

OH HO 3 C

HO C

H

H C

OH

OH HO C

H

HO C

H

H C

OH

H C

OH

H C

H

H

HO C

H

H C

OH

H C

OH

5

CH2OH D-Allose

CH2OH D-Altrose

4

H C 6

H OH

H C

OH HO C

H

OH

H C

OH

OH

CH2OH

D-Glucose

CH2OH D-Mannose

H C

CH2OH D-Gulose

H C HO C H C

OH

CH2OH D-Idose

HO C H C

OH

CH2OH D-Galactose

H C

OH

CH2OH D-Talose

2.50

SECTION TWO

Structures that have opposite configurations of a hydroxyl group at only one position, such as glucose and mannose, are called epimers. Glucose, also called dextrose, is the most widely distributed sugar in the plant and animal kingdoms and it is the sugar present in blood as “blood sugar”. The chain form of glucose is a polyhydric aldehyde, meaning that it has multiple hydroxyl groups and an aldehyde group. Fructose, also called levulose, is shown here in the chain and ring forms. CH2OH C HO C

O

HOCH2

H

H C

OH

H C

OH

H

O

CH2OH O H H OH H H OH

H HO HO

CH2OH HO

H

H

CH2OH D-Fructose (a ketose)

CH2OH O H H OH HO HO OH

HO

H

OH

H

Galactose

Fructose

H

Mannose

2.1.6.1.4 Heptoses Sedoheptulose has the same structure as fructose, but it has one extra carbon. CH2OH C O HO C H H

C OH

H

C OH

H

C OH CH2OH

D-Sedoheptulose

2.1.6.1.5 Chain and Ring Structure. Many simple sugars can exist in a chain form or a ring form, as illustrated by the hexoses above. The ring form is favored in aqueous solutions, and the mechanism of ring formation is similar for most sugars. The glucose ring form is created when the oxygen on carbon number 5 links with the carbon comprising the carbonyl group (carbon number 1) and transfers its hydrogen to the carbonyl oxygen to create a hydroxyl group. The rearrangement produces alpha-glucose when the hydroxyl group is on the opposite side of the -CH2OH group, or betaglucose when the hydroxyl group is on the same side as the -CH2OH group. Isomers that differ only in their configuration about their carbonyl carbon atom are called anomers. The symbol ‘d’ (or ‘D’) is used to indicate that the shows that a sugar is dextrorotary, i.e., it rotates polarized light to the right, but can also denote a specific configuration. On the other hand, the symbol ‘1’ (or ‘L’) indicates that the sugar is laevorotatory, i.e., it rotates polarized light to the left. Again the symbol may be used to indicate a specific configuration. H

1

C 2

H C 3

HO C 4

H C 5

H C 6

O

6

H OH OH

CH2OH d-Glucose (an aldose)

CH2OH

CH2OH

5

OH

O

H

H

H OH H

4

HO H

OH

H OH H

1

OH 3

O

H HO

H

2

OH

α-d-Glucose

H

OH

β-d-Glucose

ORGANIC CHEMISTRY

2.51

2.1.6.2 Stereochemistry. Saccharides with identical functional groups but with different spatial configurations have different chemical and biological properties. Stereochemistry is the study of the arrangement of atoms in three-dimensional space. Stereoisomers are compounds in which the atoms are linked in the same order but differ in their spatial arrangement. Compounds that are mirror images of each other but are not identical are called enantiomers. The following structures illustrate the difference between b-D-glucose and b-L-glucose. Identical molecules can be made to correspond to each other by flipping and rotating. However, enantiomers cannot be made to correspond to their mirror images by flipping and rotating. Glucose is sometimes illustrated as a “chair form” because it is a more accurate representation of the bond angles of the molecule. CH2OH

CH2OH O

H

OH

HO

O

H OH H HO

H

H H HO H

CH2OH O H H

H

H

HO HO

OH

H

OH

HO

β-d-Glucose H HO

HO

H

H

O

β-d-Glucose (chair form)

OH H

OH

H

H

OH H OH HO

H

H

β-l-Glucose

OH

OH

OH H

HO H H

O

CH2OH

CH2OH β-d-Glucose

β-l-Glucose

2.1.6.3 Sugar Alcohols, Amino Sugars, and Uronic Acids. Sugars may be modified by natural or laboratory processes into compounds that retain the basic configuration of saccharides, but have different functional groups. Sugar alcohols, also known as polyols, polyhydric alcohols, or polyalcohols, are the hydrogenated forms of the aldoses or ketoses. For example, glucitol, also known as sorbitol, has the same linear structure as the chain form of glucose, but the aldehyde (-CHO) group is replaced with a -CH2OH group. Other common sugar alcohols include the monosaccharides erythritol and xylitol and the disaccharides lactitol and maltitol. Sugar alcohols have about half the calories of sugars and are frequently used in low-calorie or “sugar-free” products. Amino sugars or aminosaccharides replace a hydroxyl group with an amino (-NH2) group. Glucosamine is an amino sugar used to treat cartilage damage and reduce the pain and progression of arthritis. Uronic acids have a carboxyl group (-COOH) on carbon number six.

H

CH2OH

CH2OH

C OH

O

HO C H H

C OH

H

C OH CH2OH

Glucitol Sorbitol (a sugar alcohol)

H

COOH OH

HO

OH

H OH H H

H

O

H

H OH H NH2

or Glucosamine (an amino sugar)

HO

H H

OH

Glucuronic acid (a uronic acid)

2.52

SECTION TWO

2.1.6.3 Disaccharides. Disaccharides consist of two simple sugars and the common disaccharides are sucrose, lactose, and maltose. Component monosaccharides

Disaccharide

Description

Sucrose Lactose Maltose

common table sugar main sugar in milk product of starch hydrolysis

Glucose + fructose galactose + glucose glucose + glucose

CH2OH CH2OH O

H

H

CH2OH

H

HOCH2 O

H OH H

HO

OH

O

H

H

CH2OH

OH

H OH H H

CH2OH H O

H

H

H OH H

HO

OH

O

H

H OH H

H H

O

H H

H OH H

CH2OH

O

O

HO

H HO

HO H

O

H

OH H

OH

OH

OH

Sucrose

Maltose

Lactose

Lactose has a molecular structure consisting of galactose and glucose. It is of interest because it is associated with lactose intolerance, which is the intestinal distress caused by a deficiency of lactase, an intestinal enzyme needed to absorb and digest lactose in milk. Undigested lactose ferments in the colon and causes abdominal pain, bloating, gas, and diarrhea. Yogurt does not cause these problems because lactose is consumed by the bacteria that transform milk into yogurt. Maltose consists of two a-D-glucose molecules with the alpha bond at carbon 1 of one molecule attached to the oxygen at carbon 4 of the second molecule. This is called a 1al4 linkage. Cellobiose is a disaccharide consisting of two b-D-glucose molecules that have a 1b l4 linkage. Cellobiose has no taste, whereas maltose is about one-third as sweet as sucrose. 2.1.6.4 Polysaccharides. Polysaccharides are polymers of simple sugars but, unlike sugars, polysaccharides are insoluble in water. 2.1.6.4.1 Starch. Starch is the major form of stored carbohydrate in plants. Starch is composed of a mixture of two substances: amylose, an essentially linear polysaccharide, and amylopectin, a highly branched polysaccharide. Both forms of starch are polymers of a-d-glucose. Natural starch contains 10–20% amylose and 80–90% amylopectin. Amylose molecules consist typically of 200 to 20,000 glucose units that form a helix as a result of the bond angles between the glucose units. CH2OH

CH2OH

CH2OH

CH2OH

O

O

O

O

H

H

H

H OH H

H

O H

OH

H

H OH H

H

O H

OH

H

H OH H

CH2OH H

O H

OH

Amylose

O

H

H OH H

H

H OH H O

H

OH

O H

OH

ORGANIC CHEMISTRY

2.53

Amylopectin differs from amylose in being highly branched. Short side chain of about 30 glucose units are attached approximately every twenty to thirty glucose units along the chain. Amylopectin molecules may contain up to two million glucose units. CH2OH

CH2OH

O

H

H

O

H

H OH H O

O

O H

OH

H

CH2OH

CH2OH

O

O

H

H

H

H OH H

OH CH2

H

H

H

O

H

H

H

H

H

H OH H O

O

OH

O

H

H OH H

H OH H O

OH

CH2OH

CH2OH O

H OH H O

H

H

H OH H

OH

H

O

OH

H

OH

Amylopectin

Starches are transformed into many commercial products by hydrolysis with acids or enzymes. The resulting products are assigned a Dextrose Equivalent (DE) value that is related to the degree of hydrolysis. A DE value of 100 corresponds to completely hydrolyzed starch, which is pure glucose (dextrose). Maltodextrins are not sweet and have DE values less than 20. Syrups, such as corn syrup, have DE values from 20 to 95. “High fructose corn syrup,” commonly used to sweeten soft drinks, is made by enzymatically isomerizing a portion of the glucose into fructose, which is about twice as sweet as glucose. 2.1.6.4.2 Glycogen. Glucose is stored as glycogen in animal tissues by the process of glycogenesis. When glucose cannot be stored as glycogen or used immediately for energy, it is converted to fat. Glycogen is a polymer of a-d-glucose identical to amylopectin, but the branches in glycogen tend to be shorter (about 13 glucose units) and more frequent. The glucose chains are organized globularly, like the branches of a tree, surrounding a pair of molecules of glycogenin, a protein with a molecular weight of 38,000 that acts as a primer at the core of the structure. Glycogen is easily converted back to glucose to provide energy. 2.1.6.4.2 Cellulose. Cellulose is a polymer of b-d-glucose, which in contrast to starch, is oriented with -CH2OH groups alternating above and below the plane of the cellulose molecule thus producing long, unbranched chains. The absence of side chains allows cellulose molecules to lie close together and form rigid structures. Cellulose is the major structural material of plants. Wood is largely cellulose, and cotton is almost pure cellulose. Cellulose can be hydrolyzed to its constituent glucose units by microorganisms that inhabit the digestive tract of termites and ruminants. Cellulose may be modified in the laboratory by treating it with nitric acid (HNO3) to replace all the hydroxyl groups with nitrate groups (-ONO2) to produce cellulose nitrate that is an explosive component of smokeless powder. CH2OH

H

O

H

O OH H H

OH

CH2OH

H

CH2OH

O H Cellulose

H

OH

OH H

H

O

H

H OH H

H O

O

H

H

H OH H H

OH

H OH

H

O CH2OH

O

2.54

SECTION TWO

2.1.7 Miscellaneous Compounds TABLE 2.16 Representative Terpenes Monoterpenes OH

O CH

α-Phellandrene (eucalyptus)

Menthol (peppermint)

Citral (lemon grass)

Sesquiterpenes

OH

OH H

O

α-Selinene (celery)

Farnesol (ambrette)

Abscisic acid (a plant hormone)

Diterpenes

OH

Cembrene (pine)

Vitamin A (present in mammalian tissue and fish oil; important substance in the chemistry of vision)

Triterpenes

Squalene (shark liver oil) Tetraterpenes

β-Carotene (present in carrots and other vegetables; enzymes in the body cleave β-carotene to vitamin A)

CO2H

2.55

ORGANIC CHEMISTRY

TABLE 2.17 Representative Fatty Acids Number of Carbons Common name

Systematic name

Structural formula

Melting point °C

CH3(CH2)10CO2H CH3(CH2)12CO2H CH3(CH2)14CO2H CH3(CH2)16CO2H CH3(CH2)18CO2H

44 58 63 69 75

Saturated fatty acids 12 14 16 18 20

Lauric acid Myristic acid Palmitic acid Stearic acid Arachidic acid

Dodecanoic acid Tetradecanoic acid Hexadecanoic acid Octadecanoic acid Icosanoic acid

Unsaturated fatty acids 18

Oleic acid

cis-9-Octadecenoic acid

H

H C

CH3(CH2)7

18

Linoleic acid

cis,cis-9, 12Octadecadienoic acid

(CH2)7COH

H

HH C

C

CH3(CH2)4

18

Linoleimic acid

cis,cis,cis-9, 12, 15Octadecatrienoic acid

Arachidonic acid cis,cis,cis,cis-5, 8, 11, 14Icosatetraenoic acid

H C

H

(CH2)7COH

HH C

C

H C CH3(CH2)4

−12

O

C

CH2

CH3CH2

20

4 O

C

HH C

C

H C

—

O

C

CH2

CH2

(CH2)7COH

HH

HH

HH

C

C CH2

C

C CH2

C

C CH2

−49

H C

O (CH2)3COH

2.56

SECTION TWO

TABLE 2.18 Pyrimidines and Purines That Occur in DNA and RNA Name

Structure

Occurrence

Pyrimidines NH2 4

Cytosine

N3

5

DNA and RNA

6 1N H

2

O O 4

H3C

3

NH

5

Thymine

DNA

6 2

1N H

O

O 4

Uracil

3

NH

5

RNA

6 1N H

2

Purines

O NH2

7

Adenine

6

N

5

9N

4

N1

8

H

DNA and RNA

2 3N

O 7

Guanine

6

N

5

9N

4

H

1

NH

8

DNA and RNA

2

N3

NH2

ORGANIC CHEMISTRY

2.57

TABLE 2.19 Organic Radicals For more comprehensive lists, see the various lists of radicals given in the subject indexes of the annual and decennial indexes of Chemical Abstracts. Name

Formula

Name

Formula

(Continued)

2.58

SECTION TWO

TABLE 2.19 Names and Formulas of Organic Radicals (Continued ) Name

Formula

Name

Formula

ORGANIC CHEMISTRY

2.59

TABLE 2.19 Names and Formulas of Organic Radicals (Continued) Name

Formula

Name

Formula

(Continued)

2.60

SECTION TWO

TABLE 2.19 Names and Formulas of Organic Radicals (Continued) Name

Formula

Name

Formula

ORGANIC CHEMISTRY

2.61

TABLE 2.19 Names and Formulas of Organic Radicals (Continued) Name

Formula

Name

Formula

(Continued)

2.62

SECTION TWO

TABLE 2.19 Names and Formulas of Organic Radicals (Continued) Name

Formula

Name

Formula

ORGANIC CHEMISTRY

2.63

TABLE 2.19 Names and Formulas of Organic Radicals (Continued) Name

Formula

Name

Formula

(Continued)

2.64

SECTION TWO

TABLE 2.19 Names and Formulas of Organic Radicals (Continued) Name

Formula

Name

Formula

2.2 PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS Names of the compounds (Table 2.20) are arranged alphabetically. Usually substitutive nomenclature is employed; exceptions generally involve ethers, sulfides, sulfones, and sulfoxides. Each compound is given a number within its letter classification; thus compound c209 is 3-chlorophenol. Formula Weights are based on the International Atomic Weights of 1993 and are computed to the nearest hundredth when justified. The actual significant figures are given in the atomic weights of the individual elements; see Table 3.2. Density values are given at room temperature unless otherwise indicated by the superscript figure; thus 0.9711112 indicates a density of 0.9711 for the substance at 112°C. A density of 0.89916 14 indicates a density of 0.899 for the substance at 16°C relative to water at 4°C. Refractive Index, unless otherwise specified, is given for the sodium line at 589.6 nm. The temperature at which the measurement was made is indicated by the superscript figure; otherwise it is assumed to be room temperature. Melting Point is recorded in certain cases as 250 d and in some other cases as d 250, the distinction being made in this manner to indicate that the former is a melting point with decomposition at 250°C, while the latter decomposition occurs only at 250°C and higher temperatures. Where a value such as [2H2O, 120 is given, it indicates a loss of 2 moles of water per formula weight of the compound at a temperature of 120°C. Boiling Point is given at atmospheric pressure (760 mmHg) unless otherwise indicated; thus 8215mm indicates that the boiling point is 82°C when the pressure is 15 mm Hg. Also, subl 550 indicates that the compound sublimes at 550°C. Flash Point is given in degrees Celsius, usually using a closed cup. When the method is known, the acronym appears in parentheses after the value: closed cup (CC), Cleveland closed cup (CCC), open cup (OC), Tag closed cup (TCC), and Tag open cup (TOC). Because values will vary with the specific procedure employed, and many times the method was not stated, the values listed for the flash point should be considered only as indicative. Solubility is given in parts by weight (of the formula weight) per 100 parts by weight of the solvent and at room temperature. Other temperatures are indicated by the superscript. Another way in which solubility is explicitly stated is in weight (in grams) per 100 mL of the solvent. In the case of gases, the solubility is often expressed as 5 mL10, which indicates that at 10°C, 5 mL of the gas is soluble in 100 g (or 100 mL, if explicitly stated) of the solvent.

TABLE 2.20 Physical Constants of Organic Compounds Abbreviations Used in the Table abs, absolute acet, acetone alc, alcohol (ethanol usually) alk, alkali (aqueous NaOH or KOH) anhyd, anhydrous aq, aqueous, water as, asymmetrical atm, atmosphere BuOH, 1-butanol bz, benzene c, cold chl, chloroform conc, concentrated d, decomposes or decomposed D, dextrorotatory deliq, deliquescent dil, dilute diox, 1,4-dioxane DL, inactive (50% D and 50% L)

DMF, dimethylformamide E, trans (German “entgegen”) EtOAc, ethyl acetate eth, diethyl ether EtOH, ethanol, 95% expl, explodes glyc, glycerol h, hot HOAc, acetic acid hyd, hydrolysis hygr, hygroscopic i, insoluble ign, ignites i-PrOH, isopropyl alcohol, 2-propanol L, levorotatory m, meta configuration Me, methyl MeOH methanol

misc, miscible; soluble in all proportions NaOH, aqueous sodium hydroxide o, ortho configuration org, organic p, para configuration PE, petroleum ether pyr, pyridine s, soluble sec, secondary sl, slight, slightly soln, solution solv, solvent subl, sublimes s, symmetrical sym, symmetrical tert, tertiary v, very v sl s, very slightly soluble v, s very soluble

vac, vacuo or vacuum vols, volumes Z, cis (German “zusamman”) >, greater than <, less than ~, approximately ±, inactive [50% (+) and 50% (−)] a, alpha (first) position b, beta (second) position g, gamma (third) position d, delta (fourth) position w, omega position (farthest from parent functional group)

2.65

(Continued)

2.66 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.67

2.68 TABLE 2.20 Physical Constants of Organic Compounds (Continued)

No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.69

2.70 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.71

2.72

TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.73

2.74

TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.75

2.76 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.77

2.78 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.79

2.80 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.81

2.82

TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.83

2.84

TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.85

2.86 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.87

2.88 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.89

2.90 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.91

2.92 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.93

2.94 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.95

Next Page 2.96 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

Previous Page

(Continued)

2.97

2.98 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.99

2.100 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.101

2.102 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.103

2.104 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.105

2.106 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

2.107

(Continued)

2.108 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula Beilstein weight reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.109

2.110 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.111

2.112 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.113

2.114 TABLE 2.20 Physical Constants of Organic Compounds (Continued)

No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.115

2.116 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

c177 c178

4-Chloro-3-methylphenol 1-Chloro-2-methyl-2phenylpropane

CH3(Cl)C6H3OH

142.59

6, 381

C6H5(CH3)2CH2Cl

168.67

52, 320

65–68 1.047

1.524020

235 9610mm

i aq; s alc, bz, chl, eth, acet 92

(Continued) 2.117

2.118 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.119

2.120 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.121

2.122 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.123

2.124 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.125

2.126 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.127

2.128 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.129

2.130 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.131

2.132 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.133

2.134 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.135

2.136 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.137

2.138 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.139

2.140 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.141

2.142 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.143

2.144 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

2.145

(Continued)

2.146 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.147

2.148 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.149

2.150 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.151

Next Page 2.152 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

Previous Page

(Continued)

2.153

2.154 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.155

2.156 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.157

2.158 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.159

2.160 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.161

2.162 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.163

2.164 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.165

2.166 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.167

2.168 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.169

2.170 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.171

2.172 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.173

2.174 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.175

2.176 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.177

2.178 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.179

2.180 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.181

2.182 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.183

2.184 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.185

2.186 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.187

2.188 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.189

2.190 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.191

2.192 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.193

2.194 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.195

2.196 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.197

2.198 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.199

2.200 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

Next Page

(Continued)

2.201

Previous Page 2.202 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.203

2.204 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.205

2.206 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.207

2.208 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.209

2.210 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.211

2.212 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.213

2.214 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.215

2.216 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.217

2.218

TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.219

2.220 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.221

2.222

TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.223

2.224 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.225

2.226 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.227

2.228 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.229

2.230 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.231

2.232 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.233

2.234 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.235

2.236 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.237

2.238 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.239

2.240 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.241

2.242 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.243

2.244 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.245

2.246 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued)

2.247

2.248 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

(Continued) 2.249

2.250 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

2.251

(Continued)

2.252 TABLE 2.20 Physical Constants of Organic Compounds (Continued) No.

Name

Formula

Formula weight

Beilstein reference

Density, g/mL

Refractive index

Melting point, °C

Boiling point, °C

Flash point, °C

Solubility in 100 parts solvent

2.253

TABLE 2.21 Melting Points of Derivatives of Organic Compounds (a) Derivatives of Alcohols 3,5-Dinitro-benzoate qC,m/°C Methanol Ethanol Propan-1-ol Propan-2-ol Butan-1-ol 2-Methylpropan-1-ol Butan-2-ol

109 94 75 122 64 88 76

3,5-Dinitro-benzoate qC,m/°C 2-Methylpropan-2-ol Pentan-1-ol Hexan-1-ol Phenylmethanol Cyclohexanol Ethane-1,2-diol (glycol)

142 46 61 113 113 169*

(b) Derivatives of Phenols 4-Methylbenzenesulphonate qC,m/°C

3,5-Dinitro benzoate qC,m/°C Phenol 2-Methylphenol 3-Methylphenol 4-Methylphenol Naphthalen-1-ol Naphthalen-2-ol

146 138 165 189 217 210

96 55 51 70 88 125

4-Methylbenzene sulphonate qC,m/°C

3,5-Dinitrobenzoate qC,m/°C Benzene-1,2-diol Benzene-1,3-diol Benzene-1,4-diol 2-Nitrophenol 3-Nitrophenol 4-Nitrophenol

152* 201* 317* 155 159 188

— 81* 159* 83 113 97

(c) Derivatives of Aldehydes and Ketones 2,4-Dinitro-Phenylhydrazone qC,m/°C Methanal Ethanal Propanal Butanal Benzaldehyde 2-Hydroxybenzaldehyde Ethanedial Trichloroethanal

166 168 155 126 237 252 dec. 327 131

2,4-Dinitro-Phenylhydrazone qC,m/°C Propanone Butanone Pentan-3-one Pentan-2-one Heptan-4-one Phenylethanone Diphenylmethanone Cyclohexanone

126 116 156 144 75 250 239 162

(d) Derivatives of Amines

Methylamine Ethylamine Propylamine Butylamine (Phenylmethyl) amine Phenylamine Cyclohexylamine 2-Methylphenylamine 3-Methylphenylamine 4-Methylphenylamine Dimethylamine Diethylamine Diphenylamine * Disubstituted derivative. ‡ Boiling temperature.

2.254

Ethanoyl derivative θC,m /°C

Benzoyl derivative θC,m /°C

4-Methyl-benzene sulphonyl derivative θC,m /°C

28 205* 47 229‡ 60 114 104 112 66 152 116‡ 186‡ 103

80 69 85 70 105 163 147 143 125 158 42 42 180

75 62 52 65 116 103 87 110 114 118 87 60 142

ORGANIC CHEMISTRY

2.255

TABLE 2.22 Melting Points of n-Paraffins Melting point °C

°F

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 30 40

–182 –183 –188 –138 –130 –95 –91 –57 –54 –30 –26 –10 –5 6 10 18 22 28 32 36 66 82

–296 –297 –306 –216 –202 –139 –132 –71 –65 –22 –15 14 23 43 50 64 72 82 90 97 151 180

50 60

92 99

198 210

Number of carbon atoms

TABLE 2.23 Boiling Point and Density of Alkyl Halides Chloride Name

B.p., °C

Methyl Ethyl n-Propyl n-Butyl n-Pentyl n-Hexyl n-Heptyl n-Octyl Isopropyl Isobutyl see-Butyl tert-Butyl

Bromide

Density at 20°C

B.p., °C

–24 12.5 47 78.5 108 134 160 185

.890 .884 .883 .882 .880 .879

5 38 71 102 130 156 180 202

36.5 69 68 51

.859 .875 .871 .840

60 91 91 73

Cyclohexyl

142.5

1.000

165

Vinyl(Haloethene) Allyl (3-Halopropene) Crotyl (1-Halo-2-butene)

–14 45 84

.938

16 71

Density at. 20°C

Iodide B.p., °C

Density at 20°C

43 72 102 130 157 180 204 225.5

2.279 1.933 1.747 1.617 1.517 1.441 1.401

1.310 1.261 1.258 1.222

89.5 120 119 100d

1.705 1.605 1.595

1.398

56 103 132

1.440 1.335 1.276 1.223 1.173

(Continued)

2.256

SECTION TWO

TABLE 2.23 Boiling Point and Density of Alkyl Halides (Continued) Chloride Name Methylvinylcarbinyl (3-Halo-1-butene) Propargyl (3-Halopropyne)

B.p., °C

Bromide

Iodide

Density at 20°C

B.p., °C

Density at 20°C

B.p., °C

90

1.520

115

201 8510 9211 18420 23015

Density at 20°C

64 65

Benzyl a-Phenylethyl b-Phenylethyl Diphenylmethyl Triphenylmethyl

179 9215 9220 17319 310

1.102

Dihalomethane Trihalomethane Tetrahalomethane 1,1-Dihaloethane 1,2-Dihaloethane Trihaloethylene Tetrahaloethylene Benzal halide Benzotrihalide

40 61 77 57 84 87 121 205 221

1.336 1.489 1.595 1.174 1.257

99 151 189.5 110 132 164

9310 12719

2.49 2.89 3.42 2.056 2.180 2.708

180d subl. subl. 179 d

3.325 4.008 4.32 2.84 2.13

subl. 14020 1.38

TABLE 2.24 Properties of Carboxylic Acids

Name Formic Acetic Propionic Butyric Valeric Caproic Caprylic Capric Lauric Myristic Palmitic Stearic Oleic Linoleic Linolenic Cyclohexanecarboxylic Phenylacetic Benzoic o-Toluic m-Toluic p-Toluic o-Chlorobenzoic m-Chlorobenzoic p-Chlorobenzoic o-Bromobenzoic m-Bromobenzoic

Formula HCOOH CH3COOH CH3CH2COOH CH3(CH2)2COOH CH3(CH2)3COOH CH3(CH2)4COOH CH3(CH2)6COOH CH3(CH2)8COOH CH3(CH2)10COOH CH3(CH2)12COOH CH3(CH2)14COOH CH3(CH2)16COOH cis-9-Octadecenoic cis,cis-9,12-Octadecadienoic cis,cis,cis-9,12,15-Octadecatrienoic cyclo-C6H11COOH C6H5CH2COOH C6H5COOH o-CH3C6H4COOH m-CH3C6H4COOH p-CH3C6H4COOH o-ClC6H4COOH m-ClC6H4COOH p-ClC6H4COOH o-BrC6H4COOH m-BrC6H4COOH

M.p., °C 8 16.6 –22 –6 –34 –3 16 31 44 54 63 70 16 –5 –11 31 77 122 106 112 180 141 154 242 148 156

B.p., °C 100.5 118 141 164 187 205 239 269 225100 251100 269100 287100 22310 23016 23217 233 266 250 359 263 275

Solub., g/100 g H2O ∞ ∞ ∞ ∞ 3.7 1.0 0.7 0.2 i. i. i. i. i. i. i. 0.20 1.66 0.34 0.12 0.10 0.03 0.22 0.04 0.009 0.18 0.04

ORGANIC CHEMISTRY

2.257

TABLE 2.24 Properties of Carboxylic Acids (Continued)

Name p-Bromobenzoic o-Nitrobenzoic m-Nitrobenzoic p-Nitrobenzoic Phthalic Isophthalic Terephthalic Salicylic p-Hydroxybenzoic Anthranilic m-Aminobenzoic p-Aminobenzoic o-Methoxybenzoic m-Methoxybenzoic p-Methoxybenzoic (Anisic)

Formula p-BrC6H4COOH o-O2NC6H4COOH m-O2NC6H4COOH p-O2NC6H4COOH o-C6H4(COOH)2 m-C6H4(COOH)2 p-C6H4(COOH)2 o-HOC6H4COOH p-HOC6H4COOH o-H2NC6H4COOH m-H2NC6H4COOH p-H2NC6H4COOH o-CH3OC6H4COOH m-CH3OC6H4COOH p-CH3OC6H4COOH

M.p., °C

Solub., g/100 g H2O

B.p., °C

254 147 141 242 231 348 300 subl. 159 213 146 179 187 101 110 184

0.006 0.75 0.34 0.03 0.70 0.01 0.002 0.22 0.65 0.52 0.77 0.3 0.5 0.04

TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Boiling point (°C)760

Indan Hydrindene 2,3-Dihydroindene

118.18

–51

178

Indene Indonaphthene

116.16

–2

183

Naphthalene Tar Camphor White Tar Moth Flakes

128.19

81

218

2-Methylnaphthalene b-Methylnaphthalene

142.20

35

241

1-Methylnaphthalene a-Methylnaphthalene

142.20

–22

245

Biphenyl Diphenyl Phenylbenzene Bibenzene

154.21

71

255

2-Ethylnaphthalene b-Ethylnaphthalene

156.23

–7

258

2.258

SECTION TWO

TABLE 2.25 (Continued )

Structure

The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Boiling point (°C)760

1-Ethylnaphthalene

156.23

–14

259

2,6-Dimethylnaphthalene

156.23

110

262

2,7-Dimethylnaphthalene

156.23

97

262

1,7-Dimethylnaphthalene

156.23

263

1,3-Dimethylnaphthalene

156.23

265

1,6-Dimethylnaphthalene

156.23

266

2,3-Dimethylnaphthalene Guaiene

156.23

105

268

1,4-Dimethylnaphthalene a-Dimethylnaphthalene

156.23

8

268

4-Methylbiphenyl

168.24

50

268

1,5-Dimethylnaphthalene

156.23

80

269

ORGANIC CHEMISTRY

2.259

TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Boiling point (°C)760

Azulene

128.19

100

270 d

1,2-Dimethylnaphthalene

156.23

–4

271

Acenaphthylene

152.21

93

–270 d

3-Methylbiphenyl

168.24

5

273

3,5-Dimethylbiphenyl

182.27

Acenaphthene Naphthyleneethylene

154.21

96

279

1,3,7-Trimethylnaphthalene

170.25

14

280

2,3,5-Trimethylnaphthalene

170.25

25

285

2,3,6-Trimethylnaphthalene

170.25

101

286

Fluorene 2,3-Benzindene Diphenylenemethane

166.23

117

294

9-Methylfluorene

180.25

275

47

(Continued)

2.260

SECTION TWO

TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Boiling point (°C)760

4-Methylfluorene

180.25

3-Methylfluorene

180.25

85

316

2-Methylfluorene

180.25

104

318

1-Methylfluorene

180.25

1-Phenylnaphthalene a-Phenylnaphthalene

204.28

–45

334

Phenanthrene o-Diphenyleneethylene

178.24

101

338

Anthracene

178.24

216

340

3-Methylphenanthrene

192.26

65

352

2-Methylphenanthrene

192.26

–318

355

ORGANIC CHEMISTRY

2.261

TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Boiling point (°C)760

9-Methylphenanthrene

192.26

92

355

2-Methylanthracene

192.26

209

359 sub

4,5-Methylenephenanthrene 4H-Cyclopenteno[def]phenanthrene 4H-Cyclopenta[def]phenanthrene 4,5-Phenanthrylenemethane

190.24

116

359

4-Methylphenanthrene

192.26

1-Methylphenanthrene

192.26

123

359

2-Phenylnaphthalene b-Phenylnaphthalene

204.28

104

360

1-Methylanthracene

192.26

86

363

3,6-Dimethylphenanthrene

206.29

2,7-Dimethylanthracene

206.29

363

241

–370 (Continued)

2.262

SECTION TWO

TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

2,6-Dimethylanthracene

206.29

250

2,3-Dimethylanthracene

206.29

252

Fluoranthene Idryl 1,2-Benzacenaphthene Benzo[jk]fluorine Benz[a]acenaphthylene

202.26

111

9,10-Dimethylanthracene

206.29

183

Pyrene Benzo[def]phenanthrene

202.26

156

2,7-Dimethylpyrene

230.32

Benzo[b]fluorene 11 H-Benzo[b]fluorene 2,3-Benzofluorene Isonaphthofluorene

216.29

Benzo[c]fluorene 7H-Benzo[c]fluorene 3,4-Benzofluorene

216.29

Benzo[a]fluorene 11 H-Benzo[a]fluorene 1,2-Benzofluorene Chrysofluorene

216.29

2-Methylpyrene 4-Methylpyren

216.29

Boiling point (°C)760

–370

383

393

396

209

402

406

190

407

410

2.263

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TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Boiling point (°C)760

1-Methylpyrene 3-Methylpyren

216.29

410

4-Methylpyrene 1-Methylpyren

216.29

410

Benzo[ghi]fluoranthene

226.28

432

Benzo[c]phenanthrene 3,4-Benzophenanthrene

238.30

68

Benz[a]anthracene 1,2-Benzanthracene Tetraphene 2,3-Benzophenanthrene Naphthanthracene

228.30

162

435 sub

Triphenylene 9,10-Benzophenanthrene lsochrysene

228.30

199

439

Chrysene 1,2-Benzophenanthrene Benzo[a]phenanthrene

228.30

256

441

6-Methylchrysene

242.32

(Continued)

2.264

SECTION TWO

TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Boiling point (°C)760

1-Methylchrysene

242.32

257

Naphthacene Benz[b]anthracene 2,3-Benzanthracene Tetracene

228.30

257

450 sub

2,2′-Dinaphthyl 2,2′-Binaphthyl b,b′-Binaphthyl b,b′-Dinaphthyl

254.34

188

452753 sub

Benzo[b]fluoranthene 2,3-Benzofluoranthene 3,4-Benzofluoranthene Benz[e]acephenanthrylene

252.32

168

481

Benzo[j]fluoranthene 7,8-Benzofluoranthene 10,11-Benzofluoranthene

252.32

166

∼480

Benzo[k]fluoranthene 8,9-benzofluoranthene 11,12-Benzofluoranthene

252.32

217

481

Benzo[e]pyrene 4,5-Benzpyrene 1,2-Benzopyrene

252.32

179

493

Benzo[a]pyrene 1,2-Benzpyrene 3,4-Benzopyrene Benzo[def]chrysene

252.32

177

496

2.265

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TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Perylene peri-Dinaphthalene

252.32

278

3-Methylcholanthrene 20-Methylcholanthrene

268.38

180

Indeno[1,2,3-cd]pyrene o-Phenylenepyrene

276.34

Dibenz[a,c]anthracene 278.36 1,2:3,4-Dibenzanthracene Naphtho-2′,3′,:9,10-phenanthrene

205

Dibenz[a,h]anthracene 1,2:5,6-Dibenzanthracene

278.36

270

Dibenz[a,i]anthracene 1,2:6,7-Dibenzanthracene 1,2-Benzonaphthacene Isopentaphene

278.36

264

Dibenz[a,j]anthracene 1,2:7,8-Dibenzanthracene a,a′-Dibenzanthracene Dinaphthanthracene

278.36

198

Boiling point (°C)760

(Continued)

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SECTION TWO

TABLE 2.25 The Structure, Melting Point, and Boiling Points of Polycyclic Aromatic Hydrocarbons (Continued)

Structure

*Key: d = decomposes;

IUPAC nomeclature (synonyms)

Molecular weight

Melting point (°C)

Benzo[b]chrysene 1,2:6,7-Dibenzophenanthrene 3,4-Benzotetraphene Naphtho-2′,1′:1,2-anthracene

278.36

294

Picene Dibenzo[a;i]phenanthrene 3,4-Benzochrysene 1,2:7,8-Dibenzophenanthrene

278.36

368

Benzo[ghi]perylene 1,12-Benzoperylene

276.34

278

Anthanthrene Dibenzo[def, mno]chrysene

276.34

Coronene Hexabenzobenzene

300.36

439 cor

Dibenzo[a,e]pyrene

302.38

234

sub = sublimes.

Boiling point (°C)760

519

525?

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TABLE 2.26 Properties of Naturally Occurring Amino Acids

Name

Three- Oneletter letter code code

Alanine Arginine Asparagine Aspartic acid Cystein Glutamine Glutamic acid Glycine

Ala Arg Asn Asp Cys Gln Glu Gly

A R N D C Q E G

Histidine

His

H

Isoleucine Leucine Lysine Methionine

Ile Leu Lys Met

I L K M

Phenylalanine Phe

F

Proline Serine Threonine

Pro Ser Thr

P S T

Tryptophane

Trp

W

Side chains (–R) R-CH(NH2)COOH -CH3 -(CH2)3-CNH(˙NH)NH3 -CH2-CONH2 -CH2-COOH -CH2-SH -(CH2)2-CONH2 -(CH2)2-COOH -H N CH2

Volume ∆Hion kJ ⋅ mol–1 Å3

ASAmc Å2

ASAnpl sc Å2

ASApol sc Å2

88.6 173.4 117.7 111.1 108.5 143.9 138.4 60.1

46 45 45 45 36 45 45 85

67 89 44 48 35 53 61

107 69 58 69 91 77

153.2

43

102

49

166.7 166.7 168.6 162.9

42 43 44 44

140 137 119 117

48 43

147.18

189.9

43

175

97.12 87.08 101.11

122.7 89.0 116.1

38 42 44

105 44 74

36 28

186.21

277.8

42

190

27

193.6

42

144

43

140

43

117

Mol weight

pKa

71.08 156.20 114.11 115.09 103.14 128.14 129.12 57.06

12

44.9

4.5 9.1–9.5

4.6 36.0

4.6

1.6

137.15

6.2

43.6

N -CH(CH3)-C2H5 -CH(CH3)2-CH2 -(CH2)4-NH2 -(CH2)2-S-CH3

113.17 113.17 128.18 131.21

CH2 * -CH2-OH -CH2-(CH3)-OH CH2

10.4

53.6

N Tyrosine

Tyr

Y

Valine

Val

V

CH2 -CH-(CH3)2 α-amino α-carboxyl

OH

163.18

9.7

99.14

25.1

6.8–7.9 3.5–4.3

Enthalpies of ionization of side chains at 25°C, ∆Hion, are from [20]; van der Waals volume from [21]; ASAmc, surface area of the backbone,

a

pol ASAnpl sc , nonpolar surface area of the side chains, and ASAsc , polar surface area of the side chains are taken [17].

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SECTION TWO

TABLE 2.27 Hildebrand Solubility Parameters of Organic Liquids Solvent

d (Mpa1/2)

Acetaldehyde Acetic acid Acetone Acetonitrile Acetyl chloride N-Acetylpiperidine Acrylic acid Allyl acetate Allyl alcohol Ammonia Benzene Bromobenzene 1,3-Butadiene Butane 1,3-Butanediol 1-Butanol 2-Butanol tert-Butanol Butyl acetate Butyl amine Butyl ether Butyl lactate Carbon disulfide Chloroacetonitrile Chlorobenzene Chloroethane Chloromethane Cyclohexane Cyclohexanol Cyclopentane Decalin Decane Diamyl ether Dibenzyl ether Dibutyl amine Dibutyl fumarate Dibutyl phenyl phosphate Dibutyl phthalate Diethylamine Diethlene glycol Diethyl ether Diisopropyl ether Diisopropyl ketone N,N-Dimethylformamide Dimethyl sulfone Dimethylsulfoxide 1,4-Dioxane Ethane Ethanol Ethyl acetate Ethylamine Ethylbenzene b

H-bonding tendencyb 21.1 20.7 20.2 24.3 19.4 22.9 24.5 18.8 24.1 33.3 18.8 20.2 14.5 13.9 23.7 23.3 22.1 21.7 17.4 17.8 16.0 19.2 20.4 25.8 19.4 18.8 19.8 16.8 23.3 17.8 18.0 13.5 14.9 19.2 16.6 18.4 17.8 19.0 16.4 24.8 15.1 14.1 16.4 24.8 29.7 24.5 20.5 12.3 26.0 18.6 20.5 18.0

p denotes poor; m, moderate; s, strong.

m s m p m s s m s s p p p p s s s s m s m m p p p m m p s p p p m m s m m m s s m m m m m m m p s m s p

Solvent

d (Mpa1/2)

Ethyl chloride Ethylenediamine Ethylene dichloride Ethylene glycol Ethylene glycol dimethylether Ethylene oxide Ethyl formate Ethyl methacrylate Formic acid Furan Heptane Hexane 1-Hexene Hydrazine Hydrogen Isobutanol Isobutyl acetate Isobutylene Isoprene Isopropanol Isopropyl acetate Methane Methanol Methyl acetate Methyl acrylate Methyl butyl ketone Methyl ethyl ketone Methyl formate Methyl isopropyl ketone Methyl methacrylate Nitrobenzene Nitroethane Octane Pentane Propane 1-Propanol 2-Propanol Pyridine Quinoline Silicon tetrachloride Styrene Succinic anhydride Tetra chloromethane Tetrahydrofuran Toluene 1,1,2-Trichloroethane Trichloromethane Water Xylene

H-bonding tendencyb 18.8 25.2 20.0 29.9 17.6

m s p s m

22.7 19.2 17.0 24.7 19.2 15.1 14.9 15.1 37.0 6.1 21.5 17.0 13.7 15.1 23.5 17.2 11.0 29.6 19.6 18.2 17.0 19.0 20.9 17.4 18.0 20.5 22.7 15.6 14.3 13.1 24.3 23.5 21.9 22.1 15.1 19.0 31.5 17.6 18.6 18.2 19.6 19.0 47.9 18.0

m m m s m p p p s p s m p p s m p s m m m m m m m p p p p p s s s s p p s p m p p p s p

ORGANIC CHEMISTRY

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TABLE 2.28 Hansen Solubility Parameters of Organic Liquids

Solvent Acetic acid Acetone Acetonitrile Acetyl chloride Benzene Benzaldehyde Benzyl chloride Bromoform N-Butane Butyronitrile Carbon tetrachloride Carbon disulfide Chlorobenzene Chloroform Cyclohexanol Cyclohexylamine N-Decane Diacetone alcohol o-Dichlorobenzene Diethyl carbonate Diethyl ketone Dimethyl phthalate Dimethyl sulfoxide Ethanol Ethyl acetate Ethyl bromide Ethyl formate Ethylene carbonate Ethylene dichloride Formic acid Furan Methanol Methyl acetate Methyl chloride Methylene dichloride Nitrobenzene Nitroethane Nitromethane 1-Octanol 2-Octanol Phenol 1-Propanol 2-Propanol Quinoline Styrene Tetrahydrofuran Toluene Trimethyl phosphate Water

V (cm3/mol) 57.1 74.0 52.6 71.0 29.4 101.5 115.0 87.5 101.4 27.0 97.1 60.0 102.1 80.7 106.0 115.2 195.9 124.2 112.8 121.0 106.4 163.0 71.3 58.5 98.5 76.9 80.2 66.0 79.4 37.8 72.5 40.7 79.7 55.4 63.9 102.7 71.5 54.3 157.7 159.1 87.5 75.2 76.8 118.0 115.6 81.7 106.8 99.9 18.0

Solubility parameter (MPa1/2) dd

dp

dh

dt

14.5 15.5 15.3 15.8 18.4 19.4 18.8 21.5 14.1 15.3 17.8 20.5 19.0 17.8 17.4 17.4 15.8 15.8 19.2 16.6 15.8 18.6 18.4 15.8 15.8 16.6 15.5 19.4 19.0 14.3 17.8 15.1 15.5 15.3 18.2 20.1 16.0 15.8 17.0 16.2 18.0 16.0 15.8 19.4 18.6 16.8 18.0 16.8 15.5

8.0 10.4 18.0 10.6 0.0 7.4 7.2 4.1 0.0 12.5 0.0 0.0 4.3 3.1 4.1 3.1 0.0 8.2 6.3 3.1 7.6 4.8 16.4 8.8 5.3 8.0 8.4 21.7 7.4 11.9 1.8 12.3 7.2 6.1 6.3 8.6 15.5 18.8 3.3 4.9 5.9 6.8 6.1 7.0 1.0 5.7 1.4 16.0 16.0

13.5 7.0 6.1 3.9 2.0 5.3 2.7 6.1 0.0 5.1 0.6 0.6 2.0 5.7 13.5 6.5 0.0 4.8 3.3 6.1 4.7 4.9 10.2 19.4 7.2 5.1 8.4 5.1 4.1 16.6 5.3 22.3 7.6 3.9 6.1 4.1 4.5 5.1 11.9 11.0 14.9 17.4 16.4 7.6 4.1 8.0 2.0 10.2 42.4

21.3 20.1 24.6 19.4 18.6 21.5 20.3 22.7 14.1 20.5 17.8 20.5 19.6 19.0 22.5 18.8 15.8 20.9 20.5 18.0 18.2 22.1 26.6 26.6 18.2 19.0 19.6 29.5 20.9 25.0 18.6 29.7 18.8 17.0 20.3 22.1 22.7 25.0 20.9 20.3 24.1 24.6 23.5 22.1 19.0 19.4 18.2 25.4 47.9

2.270

SECTION TWO

TABLE 2.29 Group Contributions to the Solubility Parameter Fi

Fi

Group

(1)

(2)

(3)

[Br [Cl

340 250–270

258 205

300 230

[F

…

41

80

[H [I [NO2 [ONO2 [O[ [OH [PO4 [S— [SH

80–100 425 440 440 70 … 500 225 315

… … … … 115 226 … 209 …

… … … … 125 369 … 225 …

C

–93

32

0

[CH˙

19

84

40

[CF2[

150

115

…

[CF3

274

156

…

CH

28

86

68

[CH˙ [CH2—

111 133

122 131

109 137

7 CH28

190

127

…

[CH3

214

148

205

Group

(1)

(2)

(3)

410

355

480

…

…

600

… 275 310 … … 222 285

… 263 327 … … … …

725 335 250 319 375 … …

…

567

375

23

…

105–115

21

…

[C6H4

658

705

673

[C6H5

735

683

741

95–105

–23

…

1146

…

…

[CæN O ; [C[NH2 O ; NH2[C[O[ —CO— —COO— —COOH —CO3— —CæC— CHæC— O O ; ; [C[O[C[

[C˙C[C˙C[20–30

[C10H7

a

Adapted from D. W. Van Krevelen, Properties of Polymers, 2nd ed. (Elsevier, Amsterdam, 1976), p. 134. The references referred to for the Fi values are (1) P.A. Small, J. Appl. Chem. 3, 71 (1953); (2) K. L. Hoy, J. Paint Technol. 42, 76 (1970); (3) D. W. Van Krevelen, Properties of Polymers, 2nd ed. (Elsevier, Amsterdam, 1976), p. 134.

2.3 VISCOSITY AND SURFACE TENSION The dynamic viscosity, or coefficient of viscosity, h of a Newtonian fluid is defined as the force per unit area necessary to maintain a unit velocity gradient at right angles to the direction of flow between two parallel planes a unit distance apart. The SI unit is pascal-second or netwon-second per meter squared [N ⋅ s ⋅ m−2]. The c.g.s. unit of viscosity is the poise [P]; 1 cPæ1 mN ⋅ s ⋅ m−2. Kinematic viscosity v is the ratio of the dynamic viscosity to the density of a fluid. The SI unit is meter squared per second [m2 ⋅ s−1]. The c.g.s. units are called stokes [cm2 ⋅ s−1]; poises = stokes × density.

ORGANIC CHEMISTRY

2.271

Fluidity f is the reciprocal of the dynamic viscosity. The primary reference liquid for viscosity measurements is water. The absolute viscosity of water at 20°C is 1.0019 (±0.0003) mN ⋅ s ⋅ m−2 (or centipoise), as determined by Swindells, Coe, and Godfrey, J. Research Natl. Bur. Standards 48:1 (1952). The relative viscosity of water, h/h20°, is 0.8885 at 25°C, 0.7960 at 30°C, and 0.6518 at 40°C. Values at temperatures between 15 and 60°C are best represented by Cragoe’s equation: log

η 1.2348(20 − t ) − 0.001 467(t − 20)2 = η20o t + 96

− The Reynolds number for flow in a tube is defined by dnr/h, where d is the diameter of the tube, n− is the average velocity of the fluid along the tube, r is the density of the fluid, and h is its dynamic viscosity. At flow velocities corresponding with values of the Reynolds number of greater than 2000, turbulence is encountered. The surface tension of a liquid, g, is the force per unit length on the surface that opposes the expansion of the surface area. In the literature the surface tensions are expressed in dyn ⋅ cm−1; 1 dyn ⋅ cm−1 = 1 mN ⋅ m−1 in the SI system. For the large majority of compounds the dependence of the surface tension on the temperature can be given as g = a − bt where a and b are constants and t is the temperature in degrees Celsius. The values of a and b given in Tables 2.30 can be used to calculate the values of surface tension for the particular compound within its liquid range. For example, the least-squares constants for acetic anhydride (liquid from −73 to 140°C) are 35.52 and 0.1436, respectively. At 20°C, g = 35.52 − 0.1436(20) = 32.64 dyn ⋅ cm−1.

2.272

SECTION TWO

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds For the majority of substances the dependence of the surface tension g on the temperature can be given as: g = a − bt where a and b are constants and t is the temperature in degrees Celsius. In the SI system the surface tensions are expressed in mN ⋅ m−1 (= dyn ⋅ cm−1). A compilation of some 2200 liquid compounds has been prepared by J. J. Jasper, J. Phys. Chem. Reference Data 1:841 (1972). The SI unit of viscosity is pascal-second (Pa ⋅ s) or Newton-second per meter squared (N ⋅ s ⋅ m−2). Values tabulated are mN ⋅ s ⋅ m−2 (= centipoise, cP). The temperature in degrees Celsius at which the viscosity of a substance was measured is shown in parentheses after the value.

ORGANIC CHEMISTRY

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TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

(Continued)

2.274

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TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

Next Page ORGANIC CHEMISTRY

2.275

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

(Continued)

Previous Page 2.276

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TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

ORGANIC CHEMISTRY

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TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

(Continued)

2.278

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TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.279

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

(Continued)

2.280

SECTION TWO

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.281

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

(Continued)

2.282

SECTION TWO

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.283

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

(Continued)

2.284

SECTION TWO

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.285

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

(Continued)

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SECTION TWO

TABLE 2.30 Viscosity and Surface Tension of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.287

TABLE 2.31 Viscosity of Aqueous Glycerol Solutions % Weight glycerol 100 99 98 97 96 95 80 50 25 10

Grams per liter

Relative density 25°/25°C

20°C

25°C

30°C

1261 1246 1231 1216 1201 1186 966.8 563.2 265.0 102.2

1.262 01 1.259 45 1.256 85 1.254 25 1.251 65 1.249 10 1.209 25 1.127 20 1.061 15 1.023 70

1 495 1 194 971 802 659 543.5 61.8 6.032 2.089 1.307

942 772 627 521 434 365 45.72 5.024 1.805 1.149

622 509 423 353 296 248 34.81 4.233 1.586 1.021

Viscosity, mN ⋅ s ⋅ m–2

TABLE 2.32 Viscosity of Aqueous Sucrose Solutions % Weight sucrose

Grams per liter

75 70 65 60 50 40 30

1034 943.0 855.6 771.9 614.8 470.6 338.1

Relative density 20°/4°C 1.379 0 1.347 2 1.316 3 1.286 5 1.299 6 1.176 4 1.127 0

Viscosity, mN ⋅ s ⋅ m–2 15°C 4 039 746.9 211.3 79.49 19.53 7.463 3.757

20°C 2 328 481.6 147.2 58.49 15.43 6.617 3.187

25°C 1 405 321.6 105.4 40.03 12.40 5.164 2.735

2.4 REFRACTION AND REFRACTIVE INDEX The refractive index n is the ratio of the velocity of light in a particular substance to the velocity of light in vacuum. Values reported refer to the ratio of the velocity in air to that in the substance saturated with air. Usually the yellow sodium doublet lines are used; they have a weighted mean of 589.26 nm and are symbolized by D. When only a single refractive index is available, approximate values over a small temperature range may be calculated using a mean value of 0.000 45 per degree for dn/dt, and remembering that nD decreases with an increase in temperature. If a transition point lies within the temperature range, extrapolation is not reliable. The specific refraction rD is given by the Lorentz and Lorenz equation, RD =

nD2 − 1 1 ⋅ nD2 + 2 r

where r is the density at the same temperature as the refractive index, and is independent of temperature and pressure. The molar refraction is equal to the specific refraction multiplied by the molecular weight. It is a more or less additive property of the groups or elements comprising the compound. A set of atomic refractions is given in Table 1.12; an extensive discussion will be found in Bauer, Fajans, and Lewin, in Physical Methods of Organic Chemistry, 3d ed., A. Weissberger (ed.), vol. 1, part II, chap. 28, Wiley-Interscience, New York, 1960. The empirical Eykman equation nD2 − 1 1 ⋅ = constant nD + 0.4 r

2.288

SECTION TWO

offers a more accurate means for checking the accuracy of experimental densities and refractive indices, and for calculating one from the other, than does the Lorentz and Lorenz equation. The refractive index of moist air can be calculated from the expression 103.49 177.4 86.26  5748  p1 + p2 + 1+ p3  T T T T 

(n − 1) × 10 6 =

where p1 is the partial pressure of dry air (in mmHg), p2 is the partial pressure of carbon dioxide (in mmHg), p3 is the partial pressure of water vapor (in mmHg), and T is the temperature (in kelvins). Example: 1-Propynyl acetate has nD = 1.4187 and density = 0.9982 at 20°C; the molecular weight is 98.102. From the Lorentz and Lorenz equation, rD =

(1.4187)2 + 1 1 ⋅ = 0.2528 (1.4187)2 + 2 0.9982

The molar refraction is MrD = (98.102)(0.2528) = 24.80 From the atomic and group refractions in Table 5.19, the molar refraction is computed as follows: 6H 5C 1 CæC 1 O(ether) 1 O(carbonyl)

6.600 12.090 2.398 1.643 2.211 MrD = 24.942

TABLE 2.33 Atomic and Group Refractions Group H C Double bond (C˙C) Triple bond (CæC) Phenyl (C6H5) Naphthyl (C10H7) O (carbonyl) (C˙O) O (hydroxyl) (O—H) O (ether, ester) (C—O—) F (one fluoride) (polyfluorides) Cl Br I S (thiocarbonyl) (C˙S) S (thiol) (S—H) S (dithia) (—S—S—) Se (alkyl selenides) 3-membered ring 4-membered ring

MrD

Group

MrD

1.100 2.418 1.733 2.398 25.463 43.00 2.211 1.525 1.643 0.95 1.1 5.967 8.865 13.900 7.97 7.69 8.11 11.17 0.71 0.48

N (primary aliphatic amine) N (sec-aliphatic amine) N (tert-aliphatic amine) N (primary aromatic amine) N (sec-aromatic amine) N (tert-aromatic amine) N (primary amide) N (sec amide) N (tert amide) N (imidine) N (oximido) N (carbimido) N (hydrazone) N (hydroxylamine) N (hydrazine) N (aliphatic cyanide) (CæN) N (aromatic cyanide) N (aliphatic oxime) NO (nitroso) NO (nitrosoamine) NO2 (alkyl nitrate) (alkyl nitrite) (aliphatic nitro) (aromatic nitro) (nitramine)

2.322 2.499 2.840 3.21 3.59 4.36 2.65 2.27 2.71 3.776 3.901 4.10 3.46 2.48 2.47 3.05 3.79 3.93 5.91 5.37 7.59 7.44 6.72 7.30 7.51

ORGANIC CHEMISTRY

2.289

TABLE 2.34 Refractive Indices of Organic Compounds Substance Acenaphthene Acetaldehyde Acetamide Acetanilide Acetic acid Acetic anhydride Acetone Acetonitrile Acetophenone Acetyl chloride Acetylene Adipic acid Alloxan + 4H2O Allyl alcohol p-Aminobenzoic acid 2-Aminopyridine n-Amyl alcohol act-Amyl alcohol sec-Amyl alcohol tert-Amyl alcohol Aniline Aniline hydrochloride Anisole Anthracene Anthraquinone Azobenzene Benzaldehyde Benzene Benzoic acid Benzoic anhydride Benzoin Benzonitrile Benzophenone (a) Benzoquinone Benzoyl chloride Benzoyl peroxide Benzyl alcohol Benzyl benzoate Benzyl chloride Benzyl cinnamate Borneol (DL) a-Bromonaphthalene Bromobenzene Bromoform n-Butane n-Butyl alcohol iso-Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol n-Butyl chloride n-Butyric acid iso-Butyric acid

Formula C12H10 C2H4O C2H5ON C8H9ON C2H4O2 C4H6O3 C3H6O C2H3N C8H8O C2H3OCl C2H2 C6H10O4 C4H10O8N2 C3H6O C7H7O2N C5H6N2 C5H12O C5H12O C5H12O C5H12O C6H7N C6H8NCl C7H8O C14H10 C14H8O C12H10N2 C7H6O C6H6 C7H6O2 C14H10O3 C14H12O2 C7H5N C13H10O C6H4O2 C7H5OCl C14H10O4 C7H8O C14H12O2 C7H7Cl C16H14O2 C10H18O C10H7Br C6H5Br CHBr3 C4H10 C4H10O C4H10O C4H10O C4H10O C4H9Cl C4H8O2 C4H8O2

Density, g/ml 1.220 0.788/16° 1.159 1.21/4° 1.0492 1.0850/15° 0.787/25° 0.7828 1.0329/15° 1.1051 0.61/–80° 1.366

Refractive index 1.6048/98.8° 1.3316 1.4274/78° 1.3718 1.3904 1.3620/15° 1.3460 1.5342/19° 1.3898

0.8573/15°

1.4135

0.8154 0.816 0.8103 0.809 1.026/15° 1.222/4° 0.9925/25° 1.243 1.419/4°

1.414/13° 1.4053 1.4045 1.5863 1.5150/22°

1.0504/15° 0.8790 1.2656/15° 1.1989/15°

1.5463/17.6° 1.5011 1.5397/15° 1.5767/15°

1.0093/15° 1.085/50°

1.5289

1.212

1.5537

1.049/15° 1.114/18° 1.0983

1.5396 1.5681/21° 1.5415/15°

1.01 1.4888/16.5° 1.4978/15° 2.900/15° 0.5788 (at sat. pressure) 0.8098 0.8169 0.808 0.7887 0.9074/0 0.9587 0.950

1.6601/16.5° 1.5625/15° 1.6005/15° 1.3993 1.3968/17.5° 1.3949/25° 1.3878 1.4015 1.3991 (Continued)

2.290

SECTION TWO

TABLE 2.34 Refractive Indices of Organic Compounds (Continued) Substance Camphene (DL) Camphor(D) Carbitol (Diethyleneglycolmonomethylether) Carbon disulphide Carbon tetrabromide Carbon tetrachloride Cellosolve (Glycolmonoethylether) Chloral hydrate Chloroacetic acid Chlorobenzene Chloroform Cholesterol Cineol (Eucalyptol) Cinnamic acid (trans) Cinnamyl alcohol Citric acid o-Cresol m-Cresol p-Cresol Cumene Cyclohexane Cyclohexanol Cyclohexanone Cyclohexene p-Cymene cis-Decalin trans-Decalin Dibenzyl n-Dibutyl phthalate Diethylamine Difluorodichloromethane (Freon 12) Difluoromonochloromethane (Freon 22) Dimethylamine Dimethylaniline Dioxane Diphenyl Diphenylamine Epichlorhydrin Ethane Ethanolamine di-Ethanolamine tri-Ethanolamine Ether (diethyl) Ethyl acetate Ethyl acetoacetate Ethyl alcohol Ethylamine

Refractive index

Formula

Density, g/ml

C10H16 C10H16O C6H14O3

0.879 0.992/10° 0.9902

1.4402/80°

CS2 CBr4 CCl4 C4H10O2

1.2927/0° 2.9109/99.5° 1.6320/0° 0.9311

1.6276

C2H3O2Cl3 C2H3O2Cl C6H5Cl CHCl3 C27H46O C10H18O C9H8O2 C9H10O C6H8O7 C7H8O C7H8O C7H8O C9H12 C6H12 C6H12O C6H10O C6H10 C10H14 C10H18 C10H18 C14H14 C16H22O4 C4H11N CCl2F2

1.9081 1.39/75° 1.066 1.4985/15° 1.067 0.9267 1.247 1.0440 1.542/18° 1.051 1.035 1.035 0.8615 0.7786 0.9624 0.9478 0.8108 0.8766 0.8963 0.8703/18° 0.995 1.0465 0.7108/18°

1.4607

1.4297/65° 1.5248 1.4467 1.4584/18° 1.5819 1.5372/40° 1.5406 1.5316 1.4909 1.4262 1.4656/22° 1.4507 1.4467 1.5006 1.4811 1.4697/18°

1.3873/18°

CHClF2 C2H7N C8H11N C4H8O2 C12H10 C12H11N C3H5OCl C2H6 C2H7ON C4H11O2N C6H15O3N C4H10O C4H8O2 C6H10O3 C2H6O C2H7N

0.6804/0° 0.9557 1.0338 1.180/0° 1.159 1.180

1.350/17° 1.5582 1.4224 1.5852/79°

1.022 1.0966 1.1242 0.714/20° 0.9245 1.0282 0.7893 0.7057/0°

1.4539 1.4776 1.4852 1.3538 1.3701/25° 1.4209/16° 1.3610/20.5°

1.4420/11.6°

ORGANIC CHEMISTRY

2.291

TABLE 2.34 Refractive Indices of Organic Compounds (Continued) Substance Ethylbenzene Ethyl benzoate Ethyl bromide Ethyl chloride Ethylene Ethylenediamine Ethylene dibromide Ethylene dichloride Ethylene glycol Ethylene oxide Ethyl formate Ethyl iodide Ethyl mercaptan Ethyl nitrate Ethyl nitrite Ethyl oxalate Ethyl salicylate Ethyl sulphate Eugenol Fluorescein Fluorobenzene Formaldehyde Formamide Formic acid Fructose Fumaric acid Furfural Furfuryl alcohol Furan Glucose Glycerol Glyceryl trioleate Glyceryl tripalmitate Glyceryl tristearate Glycine Guaiacol n-Heptane Hexachlorotethane Hexamine n-Hexane Hippuric acid Hydroquinone Indene Iodoform Isobutane Isopentane isoprene Isooctane Isoquinoline Lactic acid Lactose + H2O Maleic acid

Formula C8H10 C9H10O2 C2H5Br C2H5Cl C2H4 C2H8N2 C2H4Br2 C2H4Cl2 C2H6O2 C2H4O C3H6O2 C2H5I C2H6S C2H5O3N C2H5O2N C6H10O4 C9H10O3 C4H10O4S C10H12O2 C20H12O5 C6H5F CH2O CH3ON CH2O2 C6H12O6 C4H4O4 C5H4O2 C5H6O2 C4H4O C6H12O6 C3H8O3 C57H104O6 C51H98O6 C57H110O6 C2H5O2N C7H8O2 C7H16 C2Cl6 C6H12N4 C6H14 C9H9O3N C6H6O2 C9H8 CHI3 C4H10 C5H12 C5H8 C8H18 C9H7N C3H6O3 C12H24O1 C4H4O4

Density, g/ml

Refractive index

0.8669 1.0509/15° 1.4555 0.9214/0°

1.4959 1.5068/17.3° 1.4239

0.902/15° 2.1785 1.2521 1.1155 0.877/7° 0.9168 1.9133/30° 0.8315/25° 1.109 0.900/15° 1.0785 1.131 1.180/18° 1.0620/25°

1.4540/26.1° 1.5379 1.4443 1.4274 1.3597/7° 1.3598 1.5168/15° 1.4351 1.3853

1.0236 0.815/–20° 1.1334 1.220 1.598 1.635 1.1594 1.1282/23° 0.9644/0° 1.544/25° 1.2604/17.5° 0.8992/50° 0.8752/70° 0.8559/90°

1.4677

1.1287/21.4° 0.6838 2.091 0.6594 1.371 1.358 0.996 4.008 0.5572 (at sat. press.) 0.6192 0.6806 0.6919 1.099 1.2485 1.525 1.5920

1.4101 1.5226 1.4010/18° 1.5439/19°

1.4472 1.3714

1.5261 1.4852 1.4216 1.4730 1.4561/60° 1.4381/80° 1.4385/80°

1.3877

1.3749

1.5766

1.3538 1.4194 1.3915 1.6223/25° 1.4414

(Continued)

2.292

SECTION TWO

TABLE 2.34 Refractive Indices of Organic Compounds (Continued) Substance Maleic anhydride Malonic acid Maltose + H2O Menthol (L) Mesitylene Metaldehyde Methane Methyl acetate Methyl alcohol Methylamine Methylaniline Methyl anthranilate Methyl benzoate Methyl bromide Methyl carbonate Methyl chloride Methylene bromide Methylene chloride Methyl ethyl ketone Methyl formate Methyl iodide Methyl methacrylate Methyl sulphate Methyl salicylate Monofluorotrichloromethane (Freon 11) Morpholine Naphthalene a-Naphthol b-Naphthol a-Naphthylamine b-Naphthylamine Nicotine (L) Nitrobenzene Nitroethane Nitromethane 1-Nitropropane 2-Nitropropane n-Octane n-Octyl alcohol Oleic acid Oxalic acid Palmitic acid Paraformaldehyde Paraldehyde n-Pentane Phosgene Phenanthrene Phenol Phthalic acid Phthalic anhydride Phthalimide

Refractive index

Formula

Density, g/ml

C4H2O3 C3H4O4 C12H24O1 C10H20O C9H12 (C2H4O)n CH4 C3H6O2 CH4O CH5N C7H9N C8H9O2N C8H8O2 CH3Br C3H6O3 CH3Cl CH2Br2 CH2Cl2 C4H8O C2H4O2 CH3I C5H8O2 C2H6O4S C8H8O3 CCl3F

0.934 1.631/15° 1.540 0.903/15° 0.8652

C4H9ON C10H8 C10H8O C10H8O C10H9N C10H9N C10H14N2 C6H5O2N C2H5O2N CH3O2N C3H7O2N C3H7O2N C8H18 C8H18O C18H34O2 C2H2O4 C16H32O2 (CH2O)n C6H12O3 C5H12 COCl2 C14H10 C6H6O C8H6O4 C8H4O3 C8H5O2N

0.9994 1.14 1.099/99° 1.272 1.1196/25° 1.0614/98° 1.0097 1.1732/25° 1.050 1.137 1.001 0.990 0.7025 0.8270 0.898

1.6703/51° 1.6493/98° 1.5280 1.5530 1.3916 1.3818 1.4015 1.3941 1.3974 1.4292 1.4582

0.8527/62°

1.4339/60°

0.9943 0.6262

1.4049 1.3575

1.17 1.073 1.593 1.527/4°

1.6567/129° 1.5245/40.6°

0.9280 0.7910 0.699/–10.8° 0.9891 1.1682/18.6° 1.0937/15° 1.732/0° 1.0694 0.991/–25° 2.8098/15° 1.3348/15° 0.8054 0.9867/15° 2.251/30° 0.936 1.3348/15° 1.1787/25° 1.494/17°

1.4994

1.3593/20° 1.3276/25° 1.5702/21.2° 1.5205/15° 1.3687

1.4237 1.3814/15° 1.344 1.5293/21° 1.413 1.3874 1.538/18.1°

1.4545 1.5822/100° 1.6206/98.7°

ORGANIC CHEMISTRY

2.293

TABLE 2.34 Refractive Indices of Organic Compounds (Continued) Substance a-Picoline b-Picoline g-Picoline Picric acid Picryl chloride Pinene (Turpentine) Piperidine Propane n-Propyl acetate n-Propyl alcohol iso-Propyl alcohol Propylene Pyridine Pyrocatechol Pyrogallol Quinhydrone Quinoline Resorcinol Salicylic acid Stearic acid Styrene Succinic acid Succinic anhydride Sucrose Sylvan (2-Methylfuran) Tartaric acid (meso-) Tartaric acid (racemic) + H2O Tartaric acid (D) Tartaric acid (L) Tetralin Thiophen Thiourea Thymol Toluene o-Toluidine m-Toluidine p-Toluidine Trichloroethylene Tri-o-cresyl phosphate Tri-p-cresyl phosphate Triethylamine Trimethylamine Trinitrotoluene Triphenylmethane Urea Uric acid n-Valeric acid iso-Valeric acid Vanillin o-Xylene m-Xylene p-Xylene

Formula

Density, g/ml

C6H7N C6H7N C6H7N C6H3O7N3 C6H2O6N3Cl C10H16 C5H11N C3H8 C5H10O2 C3H8O C3H8O C3H6 C5H5N C6H6O2 C6H6O3 C12H10O4 C9H7N C6H6O2 C7H6O3 C18H36O2 C8H8 C4H6O4 C4H4O3 C12H22O11 C5H6O C4H6O6 C4H8O7

0.9443 0.9566 0.9548 1.763 1.797 0.861 0.8606

C4H6O6 C4H6O6 C10H12 C4H4S CH4N2S C10H14O C7H8 C7H9N C7H9N C7H9N C2HCl3 C21H21O4P C21H21O4P C6H15N C3H9N C7H5O6N3 C19H16 CH4ON2 C5H4O3N4 C5H10O2 C5H10O2 C8H8O3 C8H10 C8H10 C8H10

1.7598 1.7598

0.887 0.8035 0.7855 0.5139 (at sat. press.) 0.9831 1.344 1.401 1.095 1.285/15° 1.443 0.9408 0.9060 1.564/15° 1.234 1.588/15° 0.916 1.666 1.697

1.0644 1.405 0.969 0.8670 1.0035 0.987/25° 0.961/50° 1.4597/15°

0.7495/0° 0.6709/0° 1.654

Refractive index 1.5010 1.5068 1.5058

1.4685/15° 1.4530 1.3844 1.3850 1.3776 1.5102

1.6269

1.4335/70° 1.5469

1.5453/17° 1.5287

1.4969 1.5688 1.5686 1.5532/59.1° 1.4782

1.4003

1.335 1.893 0.942 0.937/15°

1.4086 1.4018/22.4°

0.8802 0.8642 0.8611

1.5054 1.4972 1.4958 (Continued)

2.294

SECTION TWO

TABLE 2.35 Solvents Having the Same Refractive Index and the Same Density at 25°C

ORGANIC CHEMISTRY

2.295

TABLE 2.35 Solvents Having the Same Refractive Index and the Same Density at 25°C (Continued)

(Continued)

2.296

SECTION TWO

TABLE 2.35 Solvents Having the Same Refractive Index and the Same Density at 25°C (Continued)

2.5 VAPOR PRESSURE AND BOILING POINT The vapor pressure is the pressure exerted by a pure component at equilibrium at any temperature when both liquid and vapor phases exist and thus extends from a minimum at the triple point temperature to a maximum at the critical temperature, the critical pressure the and is the most important of the basic thermodynamic properties affecting liquids and vapors. Except at very high total pressures (above about 10 MPa), there is no effect of total pressure on vapor pressure. If such an effect is present, a correction can be applied. The pressure exerted above a solid-vapor mixture may also be called vapor pressure but is normally only available as experimental data for common compounds that sublime. Numerous mathematical formulas relating the temperature and pressure of the gas phase in equilibrium with the condensed phase have been proposed. The Antoine equation (Eq. 1) gives good correlation with experimental values. Equation 2 is simpler and is often suitable over restricted temperature ranges. In these equations, and the derived differential coefficients for use in the Haggenmacher and Clausius-Clapeyron equations, the p term is the vapor pressure of the compound in pounds per square inch (psi), the t term is the temperature in degrees Celsius, and the T term is the absolute temperature in kelvins (t°C + 273.15).

Eq.

1 2 3

dp/dT

−[d(ln p)/d(1/T)]

B t+C

2.303 pB (t + C ) 2

2.303 BT 2 (t + C ) 2

B T

2.303 pB T2

2.303B

 2.303 B C  p −  T2 T

2.303B − CT

Vapor-pressure equation log p = A −

log p = A −

B log p = A − − C log T T

Equations 1 and 2 are easily rearranged to calculate the temperature of the normal boiling point: t=

B −C A − log p

T=

B A − log P

ORGANIC CHEMISTRY

2.297

The constants in the Antoine equation may be estimated by selecting three widely spaced data points and substituting in the following equations in sequence:  y3 − y2   t2 − t1   t3 − t1     =1−    y2 − y1   t3 − t2   t3 + C   y − y1  B= 3  (t1 + C )(t3 + C )  t3 − t1   B  A = y2 +    t2 + C 

In these equations, yi = log pi.

TABLE 2.36 Vapor Pressures of Various Organic Compounds Substance Acenaphthene Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetophenone Acetyl bromide Acetyl chloride Acetylene Acetyl iodide Acrylic acid Acrylonitrile Allyl isothiocyanate m-Aminobenzotrifluoride p-Aminophenol Aniline Anthracene 9,10-Anthracenedione Benzene Benzenethiol Benzoic acid Benzonitrile Benzophenone Benzotrifluoride Benzoyl chloride Benzyl acetate Benzyl alcohol

Eq.

Range, °C

1 2 1 1 1 1 1 2 1 1 1 1 1 1 1 1 1

147–187 147–288 liq liq liq liq liq 30–100 liq liq –130 to –83 –82 to –72 liq 20–70 –20 to 140 10–50 0–96 96–300 130–185 102–185 100–160 176–380 224–286 285–370 –12 to 3 8–103 52–198 60–110 liq 48–202 200–306 –20 to 180 140–200 46–156 122–205

1 1 2 1 2 2 1 1 1 2 1 1 1 1 2 1 1

A 7.728 19 8.033 8.005 52 7.387 82 7.149 48 7.117 14 7.119 88 9.135 2 5.197 02 6.948 87 9.140 2 7.099 9 4.181 44 8.538 67 7.038 55 5.126 58 7.651 86 7.170 30 –3.357 50 7.320 10 8.91 7.674 01 12.305 8.002 9.106 4 6.905 65 6.990 19 9.033 6.746 31 7.349 66 7.162 94 7.007 08 7.924 5 8.457 05 7.198 17

B

C

2 534.234 2834.99 1 600.017 1 533.313 1 444.718 1 210.595 1 314.4 2 878.8 545.784 1 115.954 1 232.6 711.0 355.452 2305.843 1 232.53 791.434 1 940.6 1 650.21 699.157 1 731.515 3 761 2 819.63 5 747.9 3 341.94 1 885.9 1 211.033 1 529.454 3 333.3 1 436.72 2 331.4 2 051.855 1 331.30 2 372.1 2 623.206 1 632.593

245.576 291.809 222.309 199.817 229.664 230 150.396 223.554 280.9 253.4 108.160 266.547 222.47 154.019 218.0 193.58 –331.343 206.049 247.02

244.2 220.790 203.048 181.0 195.0 173.074 220.58 259.067 172.790 (Continued)

2.298

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.299

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.300

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.301

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.302

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.303

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.304

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.305

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.306

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.307

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.308

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.309

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.310

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.311

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.312

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

ORGANIC CHEMISTRY

2.313

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

(Continued)

2.314

SECTION TWO

TABLE 2.36 Vapor Pressures of Various Organic Compounds (Continued) Substance

Eq.

Range, °C

A

B

C

TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures Pressure, mm Hg Compound

1

Name

Formula

Acenaphthalene Acetal Acetaldehyde Acetamide Acetanilide Acetic acid anhydride Acetone Acetonitrile Acetophenone Acetyl chloride Acetylene Acridine Acrolein (2-propenal) Acrylic acid Adipic acid Allene (propadiene) Allyl alcohol (propen-1-ol-3) chloride (3-chloropropene) isopropyl ether isothiocyanate n-propyl ether 4-Allylveratrole iso-Amyl acetate n-Amyl alcohol iso-Amyl alcohol sec-Amyl alcohol (2-pentanol) tert-Amyl alcohol sec-Amylbenzene iso-Amyl benzoate bromide (1-bromo-3-methylbutane)

C12H10 C6H14O2 C2H4O C2H5NO C8H9NO C2H4O2 C4H6O3 C3H6O C2H3N C8H8O C2H3OCl C2H2 C13H9N C3H4O C3H4O2 C6H10O4 C3H4 C3H6O C3H5Cl C6H12O C4H5NS C6H12O C11H14O2 C7H14O2 C5H12O C5H12O C5H12O C5H12O C11H16 C12H16O2 C5H11Br

5

10

20

40

60

100

200

400

760

197.5 50.1 −22.6 158.0 227.2 63.0 82.2 +7.7 27.0 133.6 +3.2 −107.9 256.0 +2.5 86.1 265.0 −72.5 50.0 −4.5 29.0 89.5 35.8 183.7 83.2 85.8 80.7 70.7 55.3 124.1 186.8 60.4

222.1 66.3 −10.0 178.3 250.5 80.0 100.0 22.7 43.7 154.2 16.1 −100.3 284.0 17.5 103.3 287.8 −61.3 64.5 10.4 44.3 108.0 52.6 204.0 101.3 102.0 95.8 85.7 69.7 145.2 210.2 78.7

250.0 84.0 +4.9 200.0 227.0 99.0 119.8 39.5 62.5 178.0 32.0 −92.0 314.3 34.5 122.0 312.5 −48.5 80.2 27.5 61.7 129.8 71.4 226.2 121.5 119.8 113.7 102.3 85.7 168.0 235.8 99.4

277.5 102.2 20.2 222.0 303.8 118.1 139.6 56.5 81.8 202.4 50.8 −84.0 346.0 52.5 141.0 337.5 −35.0 96.6 44.6 79.5 150.7 90.5 248.0 142.0 137.8 130.6 119.7 101.7 193.0 262.0 120.4

Temperature, °C −23.0 −81.5 65.0 114.0 −17.2 1.7 −59.4 −47.0 37.1 −50.0 −142.9 129.4 −64.5 +3.5 159.5 −120.6 −20.0 −70.0 −43.7 −2.0 −39.0 85.0 0.0 +13.6 +10.0 +1.5 −12.9 29.0 72.0 −20.4

114.8 −2.3 −65.1 92.0 146.6 +6.3 24.8 −40.5 −26.6 64.0 −35.0 −133.0 165.8 −46.0 27.3 191.0 −108.0 +0.2 −52.0 −23.1 +25.3 −18.2 113.9 +23.7 34.7 30.9 22.1 +7.2 55.8 104.5 +2.1

131.2 +8.0 −56.8 105.0 162.0 17.5 36.0 −31.1 −16.3 78.0 −27.6 −128.2 184.0 −36.7 39.0 205.5 −101.0 10.5 −42.9 −12.9 38.3 −7.9 127.0 35.2 44.9 40.8 32.2 17.2 69.2 121.6 13.6

148.7 19.6 −47.8 120.0 180.0 29.9 48.3 −20.8 −5.0 92.4 −19.6 −122.8 203.5 −26.3 52.0 222.0 −93.4 21.7 −32.8 −1.8 52.1 +3.7 142.8 47.8 55.8 51.7 42.6 27.9 83.8 139.7 26.1

168.2 31.9 −37.8 135.8 199.6 43.0 62.1 −9.4 +7.7 109.4 −10.4 −116.7 224.2 −15.0 66.2 240.5 −85.2 33.4 −21.2 +10.9 67.4 16.4 158.3 62.1 68.0 63.4 54.1 38.8 100.0 158.3 39.8

181.2 39.8 −31.4 145.8 211.8 51.7 70.8 −2.0 15.9 119.8 −4.5 −112.8 238.7 −7.5 75.0 251.0 −78.8 40.3 −14.1 18.7 76.2 25.0 169.6 71.0 75.5 71.0 61.5 46.0 110.4 171.4 48.7

Melting Point, °C 95 −123.5 81 113.5 16.7 −73 −94.6 −41 20.5 −112.0 −81.5 110.5 −87.7 14 152 −136 −129 −136.4 −80

−117.2 −11.9

(Continued)

2.315

2.316 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name n-butyrate formate iodide (1-iodo-3-methylbutane) isobutyrate Amyl isopropionate iso-Amyl isovalerate n-Amyl levulinate iso-Amyl levulinate nitrate 4-tert-Amylphenol Anethole Angelonitrile Aniline 2-Anilinoethanol Anisaldehyde o-Anisidine (2-methoxyaniline) Anthracene Anthraquinone Azelaic acid Azelaldehyde Azobenzene Benzal chloride (a,a-Dichlorotoluene) Benzaldehyde Benzanthrone Benzene Benzenesulfonylchloride Benzil Benzoic acid anhydride Benzoin Benzonitrile

1

5

10

20

60

100

200

400

760

113.1 65.4 84.4 104.4 97.6 125.1 180.5 177.0 88.6 189.0 164.2 77.5 119.9 209.5 176.7 155.2 250.0 285.0 286.5 123.0 216.0 138.3 112.5 390.0 26.1 174.5 255.8 186.2 270.4 258.0 123.5

133.2 83.2 103.8 124.2 117.3 146.1 203.1 198.1 106.7 213.0 186.1 96.3 140.1 230.6 199.0 175.3 279.0 314.6 309.6 142.1 240.0 160.7 131.7 426.5 42.2 198.0 283.5 205.8 299.1 284.4 144.1

155.3 102.7 125.8 146.0 138.4 169.5 227.4 222.7 126.5 239.5 210.5 117.7 161.9 254.5 223.0 197.3 310.2 346.2 332.8 163.4 266.1 187.0 154.1

178.6 123.3 148.2 168.8 160.2 194.0 253.2 247.9 147.5 266.0 235.3 140.0 184.4 279.6 248.0 218.5 342.0 379.9 356.5 185.0 293.0 214.0 179.0

60.6 224.0 314.3 227.0 328.8 313.5 166.7

80.1 251.5 347.0 249.2 360.0 343.0 190.6

Temperature, °C

Formula C9H18O2 C6H12O2 C5H11I C9H18O2 C8H16O2 C10H20O2 C10H18O3 C10H18O3 C5H11NO3 C11H16O C10H12O C5H7N C6H7N C8H11NO C8H8O2 C7H9NO C14H10 C14H8O2 C9H16O4 C9H18O C12H10N2 C7H6Cl2 C7H6O C17H10O C6H6 C6H5ClO2S C14H10O2 C7H6O2 C14H10O3 C14H12O2 C7H5N

40

21.2 −17.5 −2.5 14.8 +8.5 27.0 81.3 75.6 +5.2 62.6 −8.0 34.8 104.0 73.2 61.0 145.0 190.0 178.3 33.3 103.5 35.5 26.2 225.0 −36.7 65.9 128.4 96.0 143.8 135.6 28.2

47.1 +5.4 +21.9 40.1 33.7 54.4 110.0 104.0 28.8 109.8 91.6 +15.0 57.9 134.3 102.6 88.0 173.5 219.4 210.4 58.4 135.7 64.0 50.1 274.5 −19.6 96.5 165.2 119.5 180.0 170.2 55.3

59.9 17.1 34.1 52.8 46.3 68.6 124.0 118.8 40.3 125.5 106.0 28.0 69.4 149.6 117.8 101.7 187.2 234.2 225.5 71.6 151.5 78.7 62.0 297.2 −11.5 112.0 183.0 132.1 198.0 188.1 69.2

74.0 30.0 47.6 66.6 60.0 83.8 139.7 134.4 53.5 142.3 121.8 41.0 82.0 165.7 133.5 116.1 201.9 248.3 242.4 85.0 168.3 94.3 75.0 322.5 −2.6 129.0 202.8 146.7 218.0 207.0 83.4

90.0 44.0 62.3 81.8 75.5 100.6 155.8 151.7 67.6 160.3 139.3 55.8 96.7 183.7 150.5 132.0 217.5 264.3 260.0 100.2 187.9 112.1 90.1 350.0 +7.6 147.7 224.5 162.6 239.8 227.9 99.6

99.8 53.3 71.9 91.7 85.2 110.3 165.2 162.6 76.3 172.6 149.8 65.2 106.0 194.0 161.7 142.1 231.8 273.3 271.8 110.0 199.8 123.4 99.6 368.8 15.4 158.2 238.2 172.8 252.7 241.7 109.8

Melting Point, °C

93 22.5 −6.2 2.5 5.2 217.5 286 106.5 68 −16.1 −26 174 +5.5 14.5 95 121.7 42 132 −12.9

Benzophenone Benzotrichloride (a,a,a-Trichlorotoluene) Benzotrifluoride (a,a,a-Trifluorotoluene) Benzoyl bromide chloride nitrile Benzyl acetate alcohol Benzylamine Benzyl bromide (a-bromotoluene) chloride (a-chlorotoluene) cinnamate Benzyldichlorosilane Benzyl ethyl ether phenyl ether isothiocyanate Biphenyl 1-Biphenyloxy-2,3-epoxypropane d-Bornyl acetate Bornyl n-butyrate formate isobutyrate propionate Brassidic acid Bromoacetic acid 4-Bromoanisole Bromobenzene 4-Bromobiphenyl 1-Bromo-2-butanol 1-Bromo-2-butanone cis-1-Bromo-1-butene trans-1-Bromo-butene 2-Bromo-1-butene cis-2-Bromo-2-butene trans-2-Bromo-2-butene 1,4-Bromochlorobenzene 1-Bromo-1-chloroethane

C13H10O C7H5Cl3 C7H5F3 C7H5BrO C7H5ClO C8H5NO C9H10O2 C7H8O C7H9N C7H7Br C7H7Cl C16H14O2 C7H8Cl2Si C9H12O C13H12O C8H7NS C12H10 C15H14O2 C12H20O2 C14H24O2 C11H18O2 C14H24O2 C13H22O2 C22H42O2 C2H3BrO2 C7H7BrO C6H5Br C12H9Br C4H9BrO C4H7BrO C4H7Br C4H7Br C4H7Br C4H7Br C4H7Br C6H4BrCl C2H4BrCl

108.2 45.8 −32.0 47.0 32.1 44.5 45.0 58.0 29.0 32.2 22.0 173.8 45.3 26.0 95.4 79.5 70.6 135.5 46.9 74.0 47.0 70.0 64.6 209.6 54.7 48.8 +2.9 98.0 23.7 +6.2 −44.0 −38.4 −47.3 −39.0 −45.0 32.0 −36.0

141.7 73.7 −10.3 75.4 59.1 71.7 73.4 80.8 54.8 59.6 47.8 206.3 70.2 52.0 127.7 107.8 101.8 169.9 75.7 103.4 74.8 99.8 93.7 241.7 81.6 77.8 27.8 133.7 45.4 30.0 −23.2 −17.0 −27.0 −17.9 −24.1 59.5 −18.0

157.6 87.6 −0.4 89.8 73.0 85.5 87.6 92.6 67.7 73.4 60.8 221.5 83.2 65.0 144.0 121.8 117.0 187.2 90.2 118.0 89.3 114.0 108.0 256.0 94.1 91.9 40.0 150.6 55.8 41.8 −12.8 −6.4 −16.8 −7.2 −13.8 72.7 −9.4

175.8 102.7 12.2 105.4 87.6 100.2 102.3 105.8 81.8 88.3 75.0 239.3 96.7 79.6 160.7 137.0 134.2 205.8 106.0 133.8 104.0 130.0 123.7 272.9 108.2 107.8 53.8 169.8 67.2 54.2 −1.4 +5.4 −5.3 +4.6 −2.4 87.8 0.0

195.7 119.8 25.7 122.6 103.8 116.6 119.6 119.8 97.3 104.8 90.7 255.8 111.8 95.4 180.1 153.0 152.5 226.3 123.7 150.7 121.2 147.2 140.4 290.0 124.0 125.0 68.6 190.8 79.5 68.2 +11.5 18.4 +7.2 17.7 +10.5 103.8 +10.4

208.2 130.0 34.0 133.4 114.7 127.0 129.8 129.3 107.3 115.6 100.5 267.0 121.3 105.5 192.6 163.8 165.2 239.7 135.7 161.8 131.7 157.6 151.2 301.5 133.8 136.0 78.1 204.5 87.0 77.3 19.8 27.2 15.4 26.2 18.7 114.8 17.0

224.4 144.3 45.3 147.7 128.0 141.0 144.0 141.7 120.0 129.8 114.2 281.5 133.5 118.9 209.2 177.7 180.7 255.0 149.8 176.4 145.8 172.2 165.7 316.2 146.3 150.1 90.8 221.8 97.6 89.2 30.8 38.1 26.3 37.5 29.9 128.0 28.0

249.8 165.6 62.5 169.2 149.5 161.3 165.5 160.0 140.0 150.8 134.0 303.8 152.0 139.6 233.2 198.0 204.2 280.4 172.0 198.0 166.4 194.2 187.5 336.8 165.8 172.7 110.1 248.2 112.1 107.0 47.8 55.7 42.8 54.5 46.5 149.5 44.7

276.8 189.2 82.0 193.7 172.8 185.0 189.0 183.0 161.3 175.2 155.8 326.7 173.0 161.5 259.8 220.4 229.4 309.8 197.5 222.2 190.2 218.2 211.2 359.6 186.7 197.5 132.3 277.7 128.3 126.3 66.8 75.0 61.9 74.0 66.0 172.6 63.4

305.4 213.5 102.2 218.5 197.2 208.0 213.5 204.7 184.5 198.5 179.4 350.0 194.3 185.0 287.0 243.0 254.9 340.0 223.0 247.0 214.0 243.0 235.0 382.5 208.0 223.0 156.2 310.0 145.0 147.0 86.2 94.7 81.0 93.9 85.5 196.9 82.7

48.5 −21.2 −29.3 0 −0.5 33.5 −51.5 −15.3 −4 −39 39

69.5 29

61.5 49.5 12.5 −30.7 90.5

−100.3 −133.4 −111.2 −114.6 16.6

(Continued)

2.317

2.318 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name 1-Bromo-2-chloroethane 2-Bromo-4,6-dichlorophenol 1-Bromo-4-ethyl benzene (2-Bromoethyl)-benzene 2-Bromoethyl 2-chloroethyl ether (2-Bromoethyl)-cyclohexane 1-Bromoethylene Bromoform (tribromomethane) 1-Bromonaphthalene 2-Bromo-4-phenylphenol 3-Bromopyridine 2-Bromotoluene 3-Bromotuluene 4-Bromotoluene 3-Bromo-2,4,6-trichlorophenol 2-Bromo-1,4-xylene 1,2-Butadiene (methyl allene) 1,3-Butadiene n-Butane iso-Butane (2-methylpropane) 1,3-Butanediol 1,2,3-Butanetriol 1-Butene cis-2-Butene trans-2-Butene 3-Butenenitrile iso-Butyl acetate n-Butyl acrylate alcohol iso-Butyl alcohol sec-Butyl alcohol

1

5

10

20

60

100

200

400

760

49.5 193.2 135.5 148.2 129.8 138.0 −31.9 85.9 198.8 224.5 107.8 112.0 117.8 116.4 229.3 135.7 −28.3 −46.8 −44.2 −54.1 141.2 202.5 −48.9 −39.8 −42.7 60.2 59.7 85.1 70.1 61.5 54.1

66.8 216.5 156.5 169.8 150.0 160.0 −17.2 106.1 224.2 251.0 127.7 133.6 138.0 137.4 253.0 156.4 −14.2 −33.9 −31.2 −41.5 161.0 222.0 −36.2 −26.8 −29.7 78.0 77.6 104.0 84.3 75.9 67.9

86.0 242.0 182.0 194.0 172.3 186.2 −1.1 127.9 252.0 280.2 150.0 157.3 160.0 160.2 278.0 181.0 +1.8 −19.3 −16.3 −27.1 183.8 243.5 −21.7 −12.0 −14.8 98.0 97.5 125.2 100.8 91.4 83.9

106.7 268.0 206.0 219.0 195.8 213.0 +15.8 150.5 281.1 311.0 173.4 181.8 183.7 184.5 305.8 206.7 18.5 −4.5 −0.5 −11.7 206.5 264.0 −6.3 +3.7 +0.9 119.0 118.0 147.2 117.5 108.0 99.5

Temperature, °C

Formula C2H4BrCl C6H3BrCl2O C8H9Br C8H9Br C4H8BrClO C8H15Br C2H3Br CHBr3 C10H7Br C12H9BrO C5H4BrN C7H7Br C7H7Br C7H7Br C6H2BrCl3O C8H9Br C4H6 C4H6 C4H10 C4H10 C4H10O2 C4H10O3 C4H8 C4H8 C4H8 C4H5N C6H12O2 C7H12O2 C4H10O C4H10O C4H10O

40

−28.8 84.0 30.4 48.0 36.5 38.7 −95.4 84.2 100.0 16.8 24.4 14.8 10.3 112.4 37.5 −89.5 −102.8 −101.5 −109.2 22.2 102.0 −104.8 −96.4 −99.4 −19.6 −21.2 −0.5 −1.2 −9.0 −12.2

−7.0 115.6 42.5 76.2 63.2 66.6 −77.8 22.0 117.5 135.4 42.0 49.7 50.8 47.5 146.2 65.0 −72.7 −87.6 −85.7 −94.1 67.5 132.0 −89.4 −81.1 −84.0 +2.9 +1.4 +23.5 +20.0 +11.6 +7.2

+4.1 130.8 74.0 90.5 76.3 80.5 −68.8 34.0 133.6 152.3 55.2 62.3 64.0 61.1 163.2 78.8 −64.2 −79.7 −77.8 −86.4 85.3 146.0 −81.6 −73.4 −76.3 14.1 12.8 35.5 30.2 21.7 16.9

16.0 147.7 90.2 105.8 90.8 95.8 −58.8 48.0 150.2 171.8 69.1 76.0 78.1 75.2 181.8 94.0 −54.9 −71.0 −68.9 −77.9 100.0 161.0 −73.0 −64.6 −67.5 26.6 25.5 48.6 41.5 32.4 27.3

29.7 165.8 108.5 123.2 106.6 113.0 −48.1 63.6 170.2 193.8 84.1 91.0 93.9 91.8 200.5 110.6 −44.3 −61.3 −59.1 −68.4 117.4 178.0 −63.4 −54.7 −57.6 40.0 39.2 63.4 53.4 44.1 38.1

38.0 177.6 121.0 133.8 116.4 123.7 −41.2 73.4 183.5 207.0 94.1 100.0 104.1 102.3 213.0 121.6 −37.5 −55.1 −52.8 −62.4 127.5 188.0 −57.2 −48.4 −51.3 48.8 48.0 72.6 60.3 51.7 45.2

Melting Point, °C −16.6 68 −45.0

−138 8.5 5.5 95 −28 39.8 28.5 +9.5 −108.9 −135 −145 77 −130 −138.9 −105.4 −98.9 −64.6 −79.9 −108 −114.7

tert-Butyl alcohol iso-Butyl amine n-Butylbenzene iso-Butylbenzene sec-Butylbenzene tert-Butylbenzene iso-Butyl benzoate n-Butyl bromide (1-bromobutane) iso-Butyl n-butyrate carbamate Butyl carbitol (diethylene glycol butyl ether) n-Butyl chloride (1-chlorobutane) iso-Butyl chloride sec-Butyl chloride (2-Chlorobutane) tert-Butyl chloride sec-Butyl chloroacetate 2-tert-Butyl-4-cresol 4-tert-Butyl-2-cresol iso-Butyl dichloroacetate 2,3-Butylene glycol (2,3-butanediol) 2-Butyl-2-ethylbutane-1,3-diol 2-tert-Butyl-4-ethylphenol n-Butyl formate iso-Butyl formate sec-Butyl formate sec-Butyl glycolate iso-Butyl iodide (1-iodo-2methylpropane) isobutyrate isovalerate levulinate naphthylketone (1-isovaleronaphthone) 2-sec-Butylphenol 2-tert-Butylphenol 4-iso-Butylphenol 4-sec-Butylphenol

C4H10O C4H11N C10H14 C10H14 C10H14 C10H14 C11H14O2 C4H9Br C8H16O2 C5H11NO2 C8H18O3

−20.4 −50.0 22.7 14.1 18.6 13.0 64.0 −33.0 +4.6 70.0

−3.0 −31.0 48.8 40.5 44.2 39.0 93.6 −11.2 30.0 83.7 95.7

+5.5 −21.0 62.0 53.7 57.0 51.7 108.6 −0.3 42.2 96.4 107.8

14.3 −10.3 76.3 67.8 70.6 65.6 124.2 +11.6 56.1 110.1 120.5

24.5 +1.3 92.4 83.3 86.2 80.8 141.8 24.8 71.7 125.3 135.5

31.0 8.8 102.6 93.3 96.0 90.6 152.0 33.4 81.3 134.6 146.0

39.8 18.8 116.2 107.0 109.5 103.8 166.4 44.7 94.0 147.2 159.8

52.7 32.0 136.9 127.2 128.8 123.7 188.2 62.0 113.9 165.7 181.2

68.0 50.7 159.2 149.6 150.3 145.8 212.8 81.7 135.7 186.0 205.0

82.9 68.6 183.1 172.8 173.5 168.5 237.0 101.6 156.9 206.5 231.2

C4H9Cl C4H9Cl C4H9Cl C4H9Cl C6H11ClO2 C11H16O C11H16O C6H10Cl2O2 C4H10O2 C10H12O2 C12H15O C5H10O2 C5H10O2 C5H10O2 C6H12O3 C4H9I

−49.0 −53.8 −60.2

−28.9 −34.3 −39.8

−18.6 −24.5 −29.2

−7.4 −13.8 −17.7

41.8 98.0 103.7 54.3 68.4 122.6 106.2 −4.7 −11.4 −13.3 53.6 +5.0

54.6 112.0 118.0 67.5 80.3 136.8 121.0 +6.1 −0.8 −3.1 66.0 17.0

68.2 127.2 134.0 81.4 93.4 151.2 137.0 18.0 +11.0 +8.4 79.8 29.8

13.0 +5.9 +3.4 −11.4 93.0 153.7 161.7 106.6 116.3 178.0 165.4 39.8 32.4 29.6 104.0 51.8

24.0 16.0 14.2 −1.0 105.5 167.0 176.2 119.8 127.8 191.9 179.0 51.0 43.4 40.2 116.4 63.5

40.0 32.0 31.5 +14.6 124.1 187.8 197.8 139.2 145.6 212.0 200.3 67.9 60.0 56.8 135.5 81.0

58.8 50.0 50.0 32.6 146.0 210.0 221.8 160.0 164.0 233.5 223.8 86.2 79.0 75.2 155.6 100.3

77.8 68.9 68.0 51.0 167.8 232.6 247.0 183.0 182.0 255.0 247.8 106.0 98.2 93.6 177.5 120.4

−123.1 −131.2 −131.3 −26.5

17.0 70.0 74.3 28.6 44.0 94.1 76.3 −26.4 −32.7 −34.4 28.3 −17.0

+5.0 −1.9 −5.0 −19.0 83.6 143.9 150.8 96.7 107.8 167.8 154.0 31.6 24.1 21.3 94.2 42.8

C8H16O2 C9H18O2 C9H16O3 C15H16O C10H14O C10H14O C10H14O C10H14O

+4.1 16.0 65.0 136.0 57.4 56.6 72.1 71.4

28.0 41.2 92.1 167.9 86.0 84.2 100.9 100.5

39.9 53.8 105.9 184.0 100.8 98.1 115.5 114.8

52.4 67.7 120.2 201.6 116.1 113.0 130.3 130.3

67.2 82.7 136.2 219.7 133.4 129.2 147.2 147.8

75.9 92.4 147.0 231.5 143.9 140.0 157.0 157.9

88.0 105.2 160.2 246.7 157.3 153.5 171.2 172.4

106.3 124.8 181.8 269.7 179.7 173.8 192.1 194.3

126.3 146.4 205.5 294.0 203.8 196.3 214.7 217.6

147.5 168.7 229.9 320.0 228.0 219.5 237.0 242.1

−80.7

25.3 −85.0 −88.0 −51.5 −75.5 −58 −112.4 65

22.5

−95.3 −90.7

(Continued)

2.319

2.320 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name 4-tert-Butylphenol 2-(4-tert-Butylphenoxy)ethyl acetate 4-tert-Butylphenyl dichlorophosphate tert-Butyl phenyl ketone (pivalophenone) iso-Butyl propionate 4-tert-Butyl-2,5-xylenol 4-tert-Butyl-2,6-xylenol 6-tert-Butyl-2,4-xylenol 6-tert-Butyl-3,4-xylenol Butyric acid iso-Butyric acid Butyronitrile iso-Valerophenone Camphene Campholenic acid d-Camphor Camphylamine Capraldehyde Capric acid n-Caproic acid iso-Caproic acid iso-Caprolactone Capronitrile Capryl alcohol (2-octanol) Caprylaldehyde Caprylic acid (octanoic acid) Caprylonitrile Carbazole Carbon dioxide disulfide monoxide

1

5

10

20

60

100

200

400

760

Temperature, °C

Formula C10H14O C14H20O3 C10H13Cl2 O2P C11H14O C7H14O2 C12H18O C12H18O C12H18O C12H18O C4H8O2 C4H8O2 C4H7N C11H14O C10H16 C10H16O2 C10H16O C10H19N C10H20O C10H20O2 C6H12O2 C6H12O2 C6H10O2 C6H11N C8H18O C8H16O C8H16O2 C8H15N C12H9N CO2 CS2 CO

40

70.0 118.0 96.0

99.2 150.0 129.6

114.0 165.8 146.0

129.5 183.3 164.0

146.0 201.5 184.3

156.0 212.8 197.2

170.2 228.0 214.3

191.5 250.3 240.0

214.0 277.6 268.2

238.0 304.4 299.0

57.8 −2.3 88.2 74.0 70.3 83.9 25.5 14.7 −20.0 58.3

85.7 +20.9 119.8 103.9 100.2 113.6 49.8 39.3 +2.1 87.0

97.6 41.5 45.3 51.9 125.0 71.4 66.2 38.3 9.2 32.8 73.4 92.3 43.0

125.7 68.6 74.0 78.8 142.0 89.5 83.0 66.4 34.6 57.6 92.0 114.1 67.6

99.0 32.3 135.0 119.0 115.0 127.0 61.5 51.2 13.4 101.4 47.2 139.8 82.3 83.7 92.0 152.2 99.5 94.0 80.3 47.5 70.0 101.2 124.0 80.4

114.3 44.8 151.0 135.0 131.0 143.0 74.0 64.0 25.7 116.8 60.4 153.9 97.5 97.6 106.3 165.0 111.8 107.0 95.7 61.7 83.3 110.2 136.4 94.6

130.4 58.5 169.8 152.2 148.5 159.7 88.0 77.8 38.4 133.8 75.7 170.0 114.0 112.5 122.2 179.9 125.0 120.4 112.3 76.9 98.0 120.0 150.6 110.6

−134.3 −124.4 −73.8 −54.3 −222.0 −217.2

−119.5 −44.7 −215.0

−114.4 −34.3 −212.8

−108.6 −22.5 −210.0

140.8 67.6 180.3 163.6 158.2 170.0 96.5 86.3 47.3 144.6 85.0 180.0 124.0 122.0 132.0 189.8 133.3 129.6 123.2 86.8 107.4 126.0 160.0 121.2 248.2 −104.8 −15.3 −208.1

154.0 79.5 195.0 176.0 172.0 184.0 108.0 98.0 59.0 158.0 97.9 193.7 138.0 134.6 145.3 200.0 144.0 141.4 137.2 99.8 119.8 133.9 172.2 134.8 265.0 −100.2 −5.1 −205.7

175.0 97.0 217.5 196.0 192.3 204.5 125.5 115.8 76.7 180.1 117.5 212.7 157.9 153.0 164.8 217.1 160.8 158.3 157.8 119.7 138.0 145.4 190.3 155.2 292.5 −93.0 +10.4 −201.3

197.7 116.4 241.3 217.8 214.2 226.7 144.5 134.5 96.8 204.2 138.7 234.0 182.0 173.8 186.3 240.3 181.0 181.0 182.1 141.0 157.5 156.5 213.9 179.5 323.0 −85.7 28.0 −196.3

220.0 136.8 265.3 239.8 236.5 249.5 163.5 154.5 117.5 228.0 160.5 256.0 209.2 195.0 208.5 268.4 202.0 207.7 207.0 163.7 178.5 168.5 237.5 204.5 354.8 −78.2 46.5 −191.3

Melting Point, °C 99

−71

−74 −47

50 178.5

31.5 −1.5 −35 −38.6 16 244.8 −57.5 −110.8 −205.0

oxyselenide (carbonyl selenide) oxysulfide (carbonyl sulfide) tetrabromide tetrachloride tetrafluoride Carvacrol Carvone Chavibetol Chloral (trichloroacetaldehyde) hydrate (trichloroacetaldehyde hydrate) Chloranil Chloroacetic acid anhydride 2-Chloroaniline 3-Chloroaniline 4-Chloroaniline Chlorobenzene 2-Chlorobenzotrichloride (2-a,a,a-tetrachlorotoluene) 2-Chlorobenzotrifluoride (2-chloro-a,a,a-trifluorotoluene) 2-Chlorobiphenyl 4-Chlorobiphenyl a-Chlorocrotonic acid Chlorodifluoromethane Chlorodimethylphenylsilane 1-Chloro-2-ethoxybenzene 2-(2-Chloroethoxy) ethanol bis-2-Chloroethyl acetacetal 1-Chloro-2-ethylbenzene 1-Chloro-3-ethylbenzene 1-Chloro-4-ethylbenzene 2-Chloroethyl chloroacetate 2-Chloroethyl 2-chloroisopropyl ether 2-Chloroethyl 2-chloropropyl ether 2-Chloroethyl a-methylbenzyl ether Chloroform (trichloromethane)

COSe COS CBr4 CCl4 CF4 C10H14O C10H14O C10H12O2 C2HCl3O C2H3Cl3O2 C6Cl4O2 C2H3ClO2 C4H4Cl2O3 C6H6ClN C6H6ClN C6H5Cl C6H5Cl C7H4Cl4 C7H4ClF3 C12H9Cl C12H9Cl C4H5ClO2 CHClF2 C8H11ClSi C8H9ClO C4H9ClO2 C6H12Cl2O2 C8H9Cl C8H9Cl C8H9Cl C4H6Cl2O2 C5H10Cl2O C5H10Cl2O C10H13ClO CHCl3

−117.1 −102.3 −132.4 −119.8

−95.0 −113.3

−86.3 −106.0

−50.0 −30.0 −184.6 −174.1 70.0 98.4 57.4 86.1 83.6 113.3 −37.8 −16.0 −9.8 +10.0 70.7 89.3 43.0 68.3 67.2 94.1 46.3 72.3 63.5 89.8 59.3 87.9 −13.0 +10.6

−19.6 −169.3 113.2 100.4 127.0 −5.0 19.5 97.8 81.0 108.0 84.8 102.0 102.1 22.2

101.8

0.0 24.7 89.3 109.8 96.4 129.8 70.0 95.6 −122.8 −110.2 29.8 56.7 45.8 72.8 53.0 78.3 56.2 83.7 17.2 43.0 18.6 45.2 19.2 46.4 46.0 72.1 24.7 50.1 29.8 56.5 62.3 91.4 −58.0 −39.1

69.0

−8.2 −164.3 127.9 116.1 143.2 +7.2 29.2 106.4 94.2 122.4 99.2 116.7 117.8 35.3

−76.4 −98.3 96.3 +4.3 −158.8 145.2 133.0 159.8 20.2 39.7 116.1 109.2 138.2 115.6 133.6 135.0 49.7

−70.2 −93.0 106.3 12.3 −155.4 155.3 143.8 170.7 29.1 46.2 122.0 118.3 148.0 125.7 144.1 145.8 58.3

−61.7 −85.9 119.7 23.0 −150.7 169.7 157.3 185.5 40.2 55.0 129.5 130.7 159.8 139.5 158.0 159.9 70.7

−49.8 −75.0 139.7 38.3 −143.6 191.2 179.6 206.8 57.8 68.0 140.3 149.0 177.8 160.0 179.5 182.3 89.4

−35.6 −62.7 163.5 57.8 −135.5 213.8 203.5 229.8 77.5 82.1 151.3 169.0 197.0 183.7 203.5 206.6 10.0

−21.9 −49.9 189.5 76.7 −127.7 237.0 227.5 254.0 97.7 96.2 162.6 189.5 217.0 208.8 228.5 230.5 132.2

117.9

135.8

155.0

167.8

185.0

208.0

233.0

262.1

28.7

37.1 134.7 146.0 108.0 −103.7 70.0 86.5 90.7 97.6 56.1 58.1 60.0 86.0 63.0 70.0 106.0 −29.7

50.6 151.2 164.0 121.2 −96.5 84.7 101.5 104.1 112.2 70.3 73.0 75.5 100.0 77.2 84.8 121.8 −19.0

65.9 169.9 183.8 135.6 −88.6 101.2 117.8 118.4 127.8 86.2 89.2 91.8 116.0 92.4 101.5 139.6 −7.1

75.4 182.1 196.0 144.4 −83.4 111.5 127.8 127.5 138.0 96.4 99.6 102.0 126.2 102.2 111.8 150.0 +0.5

88.3 197.0 212.5 155.9 −76.4 124.7 141.8 139.5 150.7 110.0 113.6 116.0 140.0 115.8 125.6 164.8 10.4

108.3 219.6 237.8 173.8 −65.8 145.5 162.0 157.2 169.8 130.2 133.8 137.0 159.8 135.7 146.3 186.3 25.9

130.0 243.8 264.5 193.2 −53.6 168.6 185.0 176.5 190.5 152.2 156.7 159.8 182.2 156.5 169.8 210.8 42.7

152.2 267.5 292.9 212.0 −40.8 193.5 208.0 196.0 212.6 177.6 181.1 184.3 205 180.0 194.1 235.0 61.3

−6.0 34 75.5

−138.8 90.1 −22.6 −183.7 +0.5 −57 51.7 290 61.2 46 0 −10.4 70.5 −45.2

−160

−80.2 −53.3 −62.6

−63.5

(Continued)

2.321

2.322 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name 1-Chloronaphthalene 4-Chlorophenethyl alcohol 2-Chlorophenol 3-Chlorophenol 4-Chlorophenol 2-Chloro-3-phenylphenol 2-Chloro-6-phenylphenol Chloropicrin (trichloronitromethane) 1-Chloropropene 2-Chloropyridine 3-Chlorostyrene 4-Chlorostyrene 1-Chlorotetradecane 2-Chlorotoluene 3-Chlorotoluene 4-Chlorotoluene Chlorotriethylsilane 1-Chloro-1,2,2-trifluoroethylene Chlorotrifluoromethane Chlorotrimethylsilane trans-Cinnamic acid Cinnamyl alcohol Cinnamylaldehyde Citraconic anhydride cis-a-Citral d-Citronellal Citronellic acid Citronellol Citronellyl acetate Coumarin o-Cresol (2-cresol; 3-methylphenol)

1

5

10

20

60

100

200

400

760

204.2 210.0 126.4 164.8 172.0 261.3 261.6 71.8 +1.3 125.0 142.2 143.5 240.3 115.0 116.6 117.1 101.6 −55.0 −102.5 21.9 253.3 199.8 199.3 165.8 181.8 160.0 214.5 179.8 178.8 240.0 146.7

230.8 234.5 149.8 188.7 196.0 289.4 289.5 91.8 18.0 147.7 165.7 166.0 267.5 137.1 139.7 139.8 123.6 −41.7 −92.7 39.4 276.7 224.6 222.4 189.8 205.0 183.8 236.6 201.0 197.8 264.7 168.4

259.3 259.3 174.5 214.0 220.0 317.5 317.0 111.9 37.0 170.2 190.0 191.0 296.0 159.3 162.3 162.3 146.3 −27.9 −81.2 57.9 300.0 250.0 246.0 213.5 228.0 206.5 257.0 221.5 217.0 291.0 190.8

Temperature, °C

Formula C10H7Cl C8H9ClO C6H5ClO C6H5ClO C6H5ClO C12H9ClO C12H9ClO CCl3NO2 C3H5Cl C5H4ClN C8H7Cl C8H7Cl C14H29Cl C7H7Cl C7H7Cl C7H7Cl C6H15ClSi C2ClF3 CClF3 C3H9ClSi C9H8O2 C9H10O C9H8O C5H4O3 C10H16O C10H18O C10H18O2 C10H20O C12H22O2 C9H6O2 C7H8O

40

80.6 84.0 12.1 44.2 49.8 118.0 119.8 −25.5 −81.3 13.3 25.3 28.0 98.5 +5.4 +4.8 +5.5 −4.9 −116.0 −149.5 −62.8 127.5 72.6 76.1 47.1 61.7 44.0 99.5 66.4 74.7 106.0 38.2

104.8 114.3 38.2 72.0 78.2 152.2 153.7 −3.3 −63.4 38.8 51.3 54.5 131.8 30.6 30.3 31.0 +19.8 −102.5 −139.2 −43.6 157.8 102.5 105.8 74.8 90.0 71.4 127.3 93.6 100.2 137.8 64.0

118.6 129.0 51.2 86.1 92.2 169.7 170.7 +7.8 −54.1 51.7 65.2 67.5 148.2 43.2 43.2 43.8 32.0 −95.9 −134.1 −34.0 173.0 117.8 120.0 88.9 103.9 84.8 141.4 107.0 113.0 153.4 76.7

134.4 145.0 65.9 101.7 108.1 186.7 189.8 20.0 −44.0 65.8 80.0 82.0 166.2 56.9 57.4 57.8 45.5 −88.2 −128.5 −23.2 189.5 133.7 135.7 103.8 119.4 99.8 155.6 121.5 126.0 170.0 90.5

153.2 162.0 82.0 118.0 125.0 207.4 208.2 33.8 −32.7 81.7 96.5 98.0 187.0 72.0 73.0 73.5 60.2 −79.7 −121.9 −11.4 207.1 151.0 152.2 120.3 135.9 116.1 171.9 137.2 140.5 189.0 105.8

165.6 173.5 92.0 129.4 136.1 219.6 220.0 42.3 −25.1 91.6 107.2 108.5 199.8 81.8 83.2 83.3 69.5 −74.1 −117.3 −4.0 217.8 162.0 163.7 131.3 146.3 126.2 182.1 147.2 149.7 200.5 115.5

180.4 188.1 106.0 143.0 150.0 237.0 237.1 53.8 −15.1 104.6 121.2 122.0 215.5 94.7 96.3 96.6 82.3 −66.7 −111.7 +6.0 232.4 177.8 177.7 145.4 160.0 140.1 195.4 159.8 161.0 216.5 127.4

Melting Point, °C −20 7 32.5 42 +6 −64 −99.0 −15.0 +0.9 +7.3 −157.5

133 33 −7.5

70 30.8

m-Cresol (3-cresol; 3-methylphenol) p-Cresol (4-cresol; 4-methylphenol) cis-Crotonic acid trans-Crotonic acid cis-Crotononitrile trans-Crotononitrile Cumene 4-Cumidene Cuminal Cuminyl alcohol 2-Cyano-2-n-butyl acetate Cyanogen bromide chloride iodide Cyclobutane Cyclobutene Cyclohexane Cyclohexaneethanol Cyclohexanol Cyclohexanone 2-Cyclohexyl-4,6-dinitrophenol Cyclopentane Cyclopropane Cymene cis-Decalin trans-Decalin Decane Decan-2-one 1-Decene Decyl alcohol Decyltrimethylsilane Dehydroacetic acid Desoxybenzoin Diacetamide Diacetylene (1,3-butadiyne) Diallyldichlorosilane

C7H8O C7H8O C4H6O2 C4H6O2 C4H5N C4H5N C9H12 C9H13N C10H12O C10H14O C7H11NO2 C2N2 CBrN CClN CIN C4H8 C4H6 C6H12 C8H16O C6H12O C6H10O C12H14N2O5 C5H10 C3H6 C10H14 C10H18 C10H18 C10H22 C10H20O C10H20 C10H22O C13H30Si C8H8O4 C14H12O C4H7NO2 C4H2 C6H10Cl2Si

52.0 53.0 33.5

76.0 76.5 57.4

−29.0 −19.5 +2.9 60.0 58.0 74.2 42.0 −95.8 −35.7 −76.7 25.2 −92.0 −99.1 −45.3 50.4 21.0 +1.4 132.8 −68.0 −116.8 17.3 22.5 −0.8 16.5 44.2 14.7 69.5 67.4 91.7 123.3 70.0 −82.5 +9.5

−7.1 +3.5 26.8 88.2 87.3 103.7 68.7 −83.2 −13.3 −61.4 47.2 −76.0 −83.4 −25.4 77.2 44.0 26.4 161.8 −49.6 −104.2 43.9 50.1 +30.6 42.3 71.9 40.3 97.3 96.4 122.0 156.2 95.0 −68.0 34.8

87.8 88.6 69.0 80.0 +4.0 15.0 38.3 102.2 102.0 118.0 82.0 −76.8 −10.0 −53.8 57.7 −67.9 −75.4 −15.9 90.0 56.0 38.7 175.9 −40.4 −97.5 57.0 64.2 47.2 55.7 85.8 53.7 111.3 111.0 137.3 173.5 108.0 −61.2 47.4

101.4 102.3 82.0 93.0 16.4 27.8 51.5 117.8 117.9 133.8 96.2 −70.1 −1.0 −46.1 68.6 −58.7 −66.6 −5.0 104.0 68.8 52.5 191.2 −30.1 −90.3 71.1 79.8 65.3 69.8 100.7 67.8 125.8 126.5 153.0 192.0 122.6 −53.8 61.3

116.0 117.7 96.0 107.8 30.0 41.8 66.1 134.2 135.2 150.3 111.8 −62.7 +8.6 −37.5 80.3 −48.4 −56.4 +6.7 119.8 83.0 67.8 206.7 −18.6 −82.3 87.0 97.2 85.7 85.5 117.1 83.3 142.1 144.0 171.0 212.0 138.2 −45.9 76.4

125.8 127.0 104.5 116.7 38.5 50.9 75.4 145.0 146.0 161.7 121.5 −57.9 14.7 −32.1 88.0 −41.8 −50.0 14.7 129.8 91.8 77.5 216.0 −11.3 −77.0 97.2 108.0 98.4 95.5 127.8 93.5 152.0 154.3 181.5 224.5 148.0 −41.0 86.3

138.0 140.0 116.3 128.0 50.1 62.8 88.1 158.0 160.0 176.2 133.8 −51.8 22.6 −24.9 97.6 −32.8 −41.2 25.5 142.7 103.7 90.4 229.0 −1.3 −70.0 110.8 123.2 114.6 108.6 142.0 106.5 165.8 169.5 197.5 241.3 160.6 −34.0 99.7

157.3 157.3 133.9 146.0 68.0 81.1 107.3 180.0 182.8 197.9 152.2 −42.6 33.8 −14.1 111.5 −18.9 −27.8 42.0 161.7 121.7 110.3 248.7 +13.8 −59.1 131.4 145.4 136.2 128.4 163.2 126.7 186.2 191.0 219.5 265.2 180.8 −20.9 119.4

179.0 179.4 152.2 165.5 88.0 101.5 129.2 203.2 206.7 221.7 173.4 −33.0 46.0 −2.3 126.1 −3.4 −12.2 60.8 183.5 141.4 132.5 269.8 31.0 −46.9 153.5 169.9 160.1 150.6 186.7 149.2 208.8 215.5 244.5 293.0 202.0 −6.1 142.0

202.8 201.8 171.9 185.0 108.0 122.8 152.4 227.0 232.0 246.6 195.2 −21.0 61.5 +13.1 141.1 +12.9 +2.4 80.7 205.4 161.0 155.6 291.5 49.3 −33.5 177.2 194.6 186.7 174.1 211.0 172.0 231.0 240.0 269.0 321.0 223.0 +9.7 165.3

10.9 35.5 15.5 72 −96.0

−34.4 58 −6.5 −50 +6.6 23.9 −45.0 −93.7 −126.6 −68.2 −43.3 −30.7 −29.7 +3.5 +7

60 78.5 −34.9

(Continued)

2.323

2.324 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name Dialyl sulfide Diisoamyl ether oxalate sulfide Dibenzylamine Dibenzyl ketone (1,3-diphenyl2-propanone) 1,4-Dibromobenzene 1,2-Dibromobutane dl-2,3-Dibromobutane meso-2,3-Dibromobutane 1,2-Dibromodecane Di(2-bromoethyl) ether a,b-Dibromomaleie Anhydride 1,2-Dibromo-2-methylpropane 1,3-Dibromo-2-methylpropane 1,2-Dibromopentane 1,2-Dibromopropane 1,3-Dibromopropane 2,3-Dibromopropene 2,3-Dibromo-1-propanol Diisobutylamine 2,6-Ditert-butyl-4-cresol 4,6-Ditert-butyl-2-cresol 4,6-Ditert-butyl-3-cresol 2,6-Ditert-butyl-4-ethylphenol 4,6-Ditert-butyl-3-ethylphenol Diisobutyl oxalate 2,4-Ditert-butylphenol Dibutyl phthalate sulfide

1

5

10

20

40

60

100

200

400

760

Temperature, °C

Formula

Melting Point, °C

C6H10S C10H22O C12H22O4 C10H22S C14H15N C15H14O

−9.5 18.6 85.4 43.0 118.3 125.5

14.4 44.3 116.0 73.0 149.8 159.8

26.6 57.0 131.4 87.6 165.6 177.6

39.7 70.7 147.7 102.7 182.2 195.7

54.2 86.3 165.7 120.0 200.2 216.6

63.7 96.0 177.0 130.6 212.2 229.4

75.8 109.6 192.2 145.3 227.3 246.6

94.8 129.0 215.0 166.4 249.8 272.3

116.1 150.3 240.0 191.0 274.3 301.7

138.6 173.4 265.0 216.0 300.0 330.5

−83

C6H4Br2 C4H8Br2 C4H8Br2 C4H8Br2 C10H20Br2 C4H8Br2O C4H2Br2O3 C4H8Br2 C4H8Br2 C5H10Br2 C3H6Br2 C3H6Br2 C3H4Br2 C3H6Br2O C8H19N C15H24O C15H24O C15H24O C16H26O C16H26O C10H18O4 C14H22O C16H22O4 C8H18S

61.0 7.5 +5.0 +1.5 95.7 47.7 50.0 −28.8 14.0 19.8 −7.0 +9.7 −6.0 57.0 −5.1 85.8 86.2 103.7 89.1 111.5 63.2 84.5 148.2 +21.7

79.3 33.2 30.0 26.6 123.6 75.3 78.0 −3.0 40.0 45.4 +17.3 35.4 +17.9 84.5 +18.4 116.2 117.3 135.2 121.4 142.6 91.2 115.4 182.1 51.8

87.7 46.1 41.6 39.3 137.3 88.5 92.0 +10.5 53.0 58.0 29.4 48.0 30.0 98.2 30.6 131.0 132.4 150.0 137.0 157.4 105.3 130.0 198.2 66.4

103.6 60.0 56.4 53.2 151.0 103.6 106.7 25.7 67.5 72.0 42.3 62.1 43.2 113.5 43.7 147.0 149.0 167.0 154.0 174.0 120.3 146.0 216.2 80.5

120.8 76.0 72.0 68.0 167.4 119.8 123.5 42.3 83.5 87.4 57.2 77.8 57.8 129.8 57.8 164.1 167.4 185.3 172.1 192.3 137.5 164.3 235.8 96.0

131.6 86.0 82.0 78.0 177.5 130.0 133.8 53.7 93.7 97.4 66.4 87.8 67.0 140.0 67.0 175.2 179.0 196.1 183.9 204.4 147.8 175.8 247.8 105.8

146.5 99.8 95.3 91.7 190.2 144.0 147.7 68.8 107.4 110.1 78.7 101.3 79.5 153.0 79.2 190.0 194.0 211.0 198.0 218.0 161.8 190.0 263.7 118.6

168.5 120.2 115.7 111.8 209.6 165.0 168.0 92.1 117.8 130.2 97.8 121.7 98.0 173.8 97.6 212.8 217.5 233.0 220.0 241.7 183.5 212.5 287.0 138.0

192.5 143.5 138.0 134.2 229.8 188.0 192.0 119.8 150.6 151.8 118.5 144.1 119.5 196.0 118.0 237.6 243.4 257.1 244.0 264.6 205.8 237.0 313.5 159.0

218.6 166.3 160.5 157.3 250.4 212.5 215.0 149.0 174.6 175.0 141.6 167.5 141.2 219.0 139.5 262.5 269.3 282.0 268.6 290.0 229.5 260.8 340.0 182.0

87.5 −64.5

−26 34.5

−34.5

−70.3 −5.5 −34.4 −70

−79.7

Diisobutyl d-tartrate Dicarvaryl-mono-(6-chloro-2-xenyl) phosphate Dicarvacryl-2-tolyl phosphate Dichloroacetic acid 1,2-Dichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobutane 2,3-Dichlorobutane 1,2-Dichloro-1,2-difluoroethylene Dichlorodifluoromethane Dichlorodiphenyl silane Dichlorodiisopropyl ether Di(2-chloroethoxy) methane Dichloroethoxymethylsilane 1,2-Dichloro-3-ethylbenzene 1,2-Dichloro-4-ethylbenzene 1,4-Dichloro-2-ethylbenzene cis-1,2-Dichloroethylene trans-1,2-Dichloro ethylene Di(2-chloroethyl) ether Dichlorofluoromethane 1,5-Dichlorohexamethyltrisiloxane Dichloromethylphenylsilane 1,1-Dichloro-2-methylpropane 1,2-Dichloro-2-methylpropane 1,3-Dichloro-2-methylpropane 2,4-Dichlorophenol 2,6-Dichlorophenol a,a-Dichlorophenylacetonitrile Dichlorophenylarsine 1,2-Dichloropropane 2,3-Dichlorostyrene 2,4-Dichlorostyrene 2,5-Dichlorostyrene 2,6-Dichlorostyrene

C12H22O6 C32H34ClO4P

117.8 204.2

151.8 234.5

169.0 249.3

188.0 264.5

208.5 280.5

221.6 290.7

239.5 304.9

264.7 323.8

294.0 342.0

324.0 361.0

180.2 C27H33O4P 44.0 C2H2Cl2O2 20.0 C6H4Cl2 12.1 C6H4Cl2 C6H4Cl2 −23.6 C4H8Cl2 −25.2 C4H8Cl2 −82.0 C2Cl2F2 −118.5 CCl2F2 109.6 C12H10Cl2Si 29.6 C6H12Cl2O 53.0 C5H10Cl2O2 −33.8 C8H8Cl2OSi 46.0 C8H8Cl2 47.0 C8H8Cl2 38.5 C8H8Cl2 −58.4 C2H2Cl2 −65.4 C2H2Cl2 23.5 C4H8Cl2O −91.3 CHCl2F 26.0 C6H18Cl2O2Si3 35.7 C7H8Cl2Si −31.0 C4H8Cl2 −25.8 C4H8Cl2 −3.0 C4H8Cl2 53.0 C6H4Cl2O 59.5 C6H4Cl2O 56.0 C8H5Cl2N 61.8 C6H5AsCl2 −38.5 C3H6Cl2 61.0 C8H6Cl2 53.5 C8H6Cl2 55.5 C8H6Cl2 C8H6Cl2 47.8

209.3 69.8 46.0 39.0

221.8 82.6 59.1 52.0 54.8 +11.5 +8.5 −57.3 −97.8 158.0 68.2 94.0 −1.3 90.0 92.3 83.2 −29.9 −38.0 62.0 −67.5 65.1 77.4 +2.6 +6.7 32.0 92.8 101.0 98.1 116.0 −6.1 104.6 97.4 98.2 90.0

237.0 96.3 73.4 66.2 69.2 24.5 21.2 −48.3 −90.1 176.0 82.2 109.5 +11.3 105.9 109.6 99.8 −19.4 −28.0 76.0 −58.6 79.0 92.4 14.6 18.7 44.8 107.7 115.5 113.8 133.1 +6.0 120.5 111.8 114.0 105.5

251.5 111.8 89.4 82.0 84.8 37.7 35.0 −38.2 −81.6 195.5 97.3 125.5 24.4 123.8 127.5 118.0 −7.9 −17.0 91.5 −48.8 94.8 109.5 28.2 32.0 58.6 123.4 131.6 130.0 151.0 19.4 137.8 129.2 131.0 122.4

260.3 121.5 99.5 92.2 95.2 47.8 43.9 −31.8 −76.1 207.5 106.9 135.8 32.6 135.0 139.0 129.0 −0.5 −10.0 101.5 −42.6 105.0 120.0 37.0 40.2 67.5 133.5 141.8 141.0 163.2 28.0 149.0 140.0 142.0 133.3

272.5 134.0 112.9 105.0 108.4 60.2 56.0 −23.0 −68.6 223.8 119.7 149.6 44.1 149.8 153.3 144.0 +9.5 −0.2 114.5 −33.9 118.2 134.2 48.2 51.7 78.8 146.0 154.6 154.5 178.9 39.4 163.5 153.8 155.8 147.6

290.0 152.3 133.4 125.9 128.3 79.7 74.0 −10.0 −57.0 248.0 139.0 170.0 61.0 172.0 176.0 166.2 24.6 +14.3 134.0 −20.9 138.3 155.5 65.8 68.9 96.1 165.2 175.5 176.2 202.8 57.0 185.7 176.0 178.0 169.0

309.8 173.7 155.8 149.0 150.2 100.8 94.2 +5.0 −43.9 275.5 159.8 192.0 80.3 197.0 201.7 191.5 41.0 30.8 155.4 −6.2 160.2 180.2 85.4 87.8 115.4 187.5 197.7 199.5 228.8 76.0 210.0 200.0 202.5 193.5

330.0 194.4 179.0 173.0 173.9 123.5 116.0 20.9 −29.8 304.0 182.7 215.0 100.6 222.1 226.6 216.3 59.0 47.8 178.5 +8.9 184.0 205.5 106.0 108.0 135.0 210.0 220.0 223.5 256.5 96.8 235.0 225.0 227.0 217.0

−0.3 −3.0 −65.6 −104.6 142.4 55.2 80.4 −12.1 75.0 77.2 68.0 −39.2 −47.2 49.3 −75.5 52.0 63.5 −8.4 −4.2 +20.6 80.0 87.6 84.0 100.0 −17.0 90.1 82.2 83.9 75.7

73.5

9.7 −17.6 −24.2 53.0 −80.4 −112

−40.8 −76.4 −61.2 −80.5 −50.0 −135 −53.0

45.0

(Continued)

2.325

2.326 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name 3,4-Dichlorostyrene 3,5-Dichlorostyrene 1,2-Dichlorotetraethylbenzene 1,4-Dichlorotetraethylbenzene 1,2-Dichloro-1,1,2,2-tetrafluoroethane Dichloro-4-tolysilane 3,4-Dichloro-a,a,a-trifluorotoluene Dicyclopentadiene Diethoxydimethylsilane Diethoxydiphenylsilane Diethyl adipate Diethylamine N-Diethylaniline Diethyl arsanilate 1,2-Diethylbenzene 1,3-Diethylbenzene 1,4-Diethylbenzene Diethyl carbonate cis-Diethyl citraconate Diethyl dioxosuccinate Diethylene glycol Diethyleneglycol-bis-chloroacetate Diethylene glycol dimethyl ether Di(2-methoxyethyl) ether glycol ethyl ether Diethyl ether ethylmalonate fumarate glutarate Diethylhexadecylamine

1

5

10

20

40

60

100

200

400

760

Temperature, °C

Formula C8H6Cl2 C8H6Cl2 C14H20Cl2 C14H20Cl2 C2Cl2F4 C7H8Cl2Si C7H3Cl2F3 C10H8 C6H16O2Si C16H20O2Si C10H18O4 C4H11N C10H15N C10H16AsNO3 C10H14 C10H14 C10H14 C5H10O3 C9H14O4 C8H10O5 C4H10O3 C8H12Cl2O5

57.2 53.5 105.6 91.7 −95.4 46.2 11.0 −19.1 111.5 74.0

86.0 82.2 138.7 126.1 −80.0 71.7 38.3 34.1 +2.4 142.8 106.6

49.7 38.0 22.3 20.7 20.7 −10.1 59.8 70.0 91.8 148.3

78.0 62.6 48.7 46.8 47.1 +12.3 88.3 98.0 120.0 180.0

100.4 97.4 155.0 143.8 −72.3 84.2 52.2 47.6 13.3 157.6 123.0 −33.0 91.9 74.8 62.0 59.9 60.3 23.8 103.0 112.0 133.8 195.8

C6H14O3 C6H14O3 C4H10O C9H16O4 C8H12O4 C9H16O4 C20H43N

13.0 45.3 −74.3 50.8 53.2 65.6 139.8

37.6 72.0 −56.9 77.8 81.2 94.7 175.8

50.0 85.8 −48.1 91.6 95.3 109.7 194.0

116.2 111.8 172.5 162.0 −63.5 97.8 67.3 62.0 25.3 174.3 138.3 −22.6 107.2 88.0 76.4 74.5 74.7 36.0 118.2 126.8 148.0 212.0

133.7 129.2 192.2 183.2 −53.7 113.2 84.0 77.9 38.0 193.2 154.6 −11.3 123.6 102.6 92.5 90.4 91.1 49.5 135.7 143.8 164.3 229.0

144.6 140.0 204.8 195.8 −47.5 122.6 95.0 88.0 46.3 205.0 165.8 −40. 133.8 111.8 102.6 100.7 101.3 57.9 146.2 153.7 174.0 239.5

158.2 153.8 220.7 212.0 −39.1 135.5 109.2 101.7 57.6 220.0 179.0 +6.0 147.3 123.8 116.2 114.4 115.3 69.7 160.0 167.7 187.5 252.0

181.5 176.0 245.6 238.5 −26.3 153.5 129.0 121.8 74.2 243.8 198.2 21.0 168.2 141.9 136.7 134.8 136.1 86.5 182.3 188.0 207.0 271.5

205.7 200.0 272.8 265.8 −12.0 175.2 150.5 144.2 93.2 259.7 219.1 38.0 192.4 161.0 159.0 156.9 159.0 105.8 206.5 210.8 226.5 291.8

230.0 225.0 302.0 296.5 +3.5 196.3 172.8 166.6 113.5 296.0 240.0 55.5 215.5 181.0 183.5 181.1 183.8 125.8 230.3 233.5 244.8 313.0

63.0 100.3 −38.5 106.0 110.2 125.4 213.5

77.5 116.7 27.7 122.4 126.7 142.8 235.0

86.8 126.8 −21.8 132.4 137.7 153.2 248.5

99.5 140.3 −11.5 146.0 151.1 167.8 265.5

118.0 159.0 +2.2 166.0 172.2 189.5 292.8

138.5 180.3 17.9 188.7 195.8 212.8 324.6

159.8 201.9 34.6 211.5 218.5 237.0 355.0

Melting Point, °C

−94 −12.1 32.9 −21 38.9 −34.4 −31.4 −83.9 −43.2 −43

−116.3 +0.6

Diethyl itaconate ketone (3-pentanone) malate maleate malonate mesaconate oxalate phthalate sebacate 2,5-Diethylstyrene Diethyl succinate isosuccinate sulfate sulfide sulfite d-Diethyl tartrate dl-Diethyl tartrate 3,5-Diethyltoluene Diethylzinc 1-Dihydrocarvone Dihydrocitronellol 1,4-Dihydroxyanthraquinone Dimethylacetylene (2-butyne) Dimethylamine N,N-Dimethylaniline Dimethyl arsanilate Di(a-methylbenzyl) ether 2,2-Dimethylbutane 2,3-Dimethylbutane Dimethyl citraconate 1,1-Dimethylcyclohexane cis-1,2-Dimethylcyclohexane trans-1,2-Dimethylcyclohexane trans-1,3-Dimethylcyclohexane cis-1,3-Dimethylcyclohexane cis-1,4-Dimethylcyclohexane trans-1,4-Dimethylcyclohexane Dimethyl ether

C9H14O4 C5H10O C8H14O5 C8H12O4 C7H12O4 C9H14O4 C6H10O4 C12H14O4 C14H26O4 C12H16 C8H14O4 C8H14O4 C4H10O4S C4H10S C4H10O3S C8H14O6 C8H14O6 C11H16 C4H10Zn C10H16O C10H22O C14H8O4 C4H6 C2H7N C8H11N C8H12AsNO3 C16H18O C6H14 C6H14 C7H10O4 C8H16 C8H16 C8H16 C8H16 C8H16 C8H16 C8H16 C2H6O

51.3 −12.7 80.7 57.3 40.0 62.8 47.4 108.8 125.3 49.7 54.6 39.8 47.0 −39.6 10.0 102.0 100.0 34.0 −22.4 46.6 68.0 196.7 −73.0 −87.7 29.5 15.0 96.7 −69.3 −63.6 50.8 −24.4 −15.9 −21.1 −19.4 −22.7 −20.0 −24.3 −115.7

80.2 +7.5 110.4 85.6 67.5 91.0 71.8 140.7 156.2 78.4 83.0 66.7 74.0 −18.6 34.2 133.0 131.7 61.5 0.0 75.5 91.7 239.8 −57.9 −72.2 56.3 39.6 128.3 −50.7 −44.5 78.2 −1.4 +7.3 +1.7 +3.4 0.0 +3.2 −1.7 −101.1

95.2 17.2 125.3 100.0 81.3 105.3 83.8 156.0 172.1 92.6 96.6 80.0 87.7 −8.0 46.4 148.0 147.2 75.3 +11.7 90.0 103.0 259.8 −50.5 −64.6 70.0 51.8 144.0 −41.5 −34.9 91.8 +10.3 18.4 13.0 14.9 +11.2 14.5 +10.1 −93.3

111.0 27.9 141.2 115.3 95.9 120.3 96.8 173.6 189.8 108.5 111.7 94.7 102.1 +3.5 59.7 164.2 163.8 90.2 24.2 106.0 115.0 282.0 −42.5 −56.0 84.8 65.0 160.3 −31.1 −24.1 106.5 23.0 31.1 25.6 27.4 23.6 27.1 22.6 −85.2

128.2 39.4 157.8 131.8 113.3 137.3 110.6 192.1 207.5 125.8 127.8 111.0 118.0 16.1 74.2 182.3 181.7 107.0 38.0 123.7 127.6 307.4 −33.9 −46.7 101.6 79.7 179.6 −19.5 −12.4 122.6 37.3 45.3 39.7 41.4 37.5 41.1 36.5 −76.2

139.3 46.7 169.0 142.4 123.0 147.9 119.7 204.1 218.4 136.8 138.2 121.4 128.6 24.2 83.8 194.0 193.2 117.7 47.2 134.7 136.7 323.3 −27.8 −40.7 111.9 88.6 191.5 −12.1 −4.9 132.7 45.7 54.4 48.7 50.4 46.4 50.1 45.4 −70.4

154.3 56.2 183.9 156.0 136.2 161.6 130.8 219.5 234.4 151.0 151.1 134.8 142.5 35.0 96.3 208.5 208.0 131.7 59.1 149.7 145.9 344.5 −18.8 −32.6 125.8 101.0 206.8 −2.0 +5.4 145.8 57.9 66.8 61.0 62.5 58.5 62.3 57.6 −62.7

177.5 70.6 205.3 177.8 155.5 183.2 147.9 243.0 255.8 173.2 171.7 155.1 162.5 51.3 115.8 230.4 230.0 152.4 77.0 171.8 160.2 377.8 −5.0 −20.4 146.5 119.8 229.7 +13.4 21.1 165.8 76.2 85.6 79.6 81.0 76.9 80.8 76.0 −50.9

203.1 86.3 229.5 201.7 176.8 205.8 166.2 267.5 280.3 198.0 193.8 177.7 185.5 69.7 137.0 254.8 254.3 176.5 97.3 197.0 176.8 413.0 +10.6 −7.1 169.2 140.3 254.8 31.0 39.0 188.0 97.2 107.0 100.9 102.1 97.8 101.9 97.0 −37.8

227.9 102.7 253.4 225.0 198.9 229.0 185.7 294.0 305.5 223.0 216.5 201.3 209.5 88.0 159.0 280.0 280.0 200.7 118.0 223.0 193.5 450.0 27.2 +7.4 193.1 160.5 281.9 49.7 58.0 210.5 119.5 129.7 123.4 124.4 120.1 124.3 119.3 −23.7

−42 −49.8 −40.6 1.3 −20.8 −25.0 −99.5 17 −28

194 −32.5 −96 +2.5 −99.8 −128.2 −34 −50.0 −80.0 −92.0 −76.2 −87.4 −36.9 −138.5

(Continued)

2.327

2.328 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name 2,2-Dimethylhexane 2,3-Dimethylhexane 2,4-Dimethylhexane 2,5-Dimethylhexane 3,3-Dimethylhexane 3,4-Dimethylhexane Dimethyl itaconate 1-Dimethyl malate Dimethyl maleate malonate trans-Dimethyl mesaconate 2,7-Dimethyloctane Dimethyl oxalate 2,2-Dimethylpentane 2,3-Dimethylpentane 2,4-Dimethylpentane 3,3-Dimethylpentane 2,3-Dimethylphenol (2,3-xylenol) 2,4-Dimethylphenol (2,4-xylenol) 2,5-Dimethylphenol (2,5-xylenol) 3,4-Dimethylphenol (3,4-xylenol) 3,5-Dimethylphenol (3,5-xylenol) Dimethylphenylsilane Dimethyl phthalate 3,5-Dimethyl-1,2-pyrone 4,6-Dimethylresorcinol Dimethyl sebacate 2,4-Dimethylstyrene 2,5-Dimethylstyrene a,a-Dimethylsuccinic anhydride Dimethyl sulfide

1

5

10

20

60

100

200

400

760

65.7 73.8 68.1 68.0 70.0 75.6 171.0 196.3 160.0 140.0 161.0 114.0 123.3 40.3 50.1 41.8 46.2 173.0 161.5 161.5 181.5 176.2 114.2 232.7 198.0 167.8 245.0 153.2 145.6 175.8 +2.6

85.6 94.1 88.2 87.9 90.4 96.0 189.8 219.5 182.2 159.8 183.5 136.0 143.3 59.2 69.4 60.6 65.5 196.0 184.2 184.2 203.6 197.8 136.4 257.8 221.0 192.0 269.6 177.5 168.7 197.5 18.7

106.8 115.6 109.4 109.1 112.0 117.7 208.0 242.6 205.0 180.7 206.0 159.7 163.3 79.2 89.8 80.5 86.1 218.0 211.5 211.5 225.2 219.5 159.3 283.7 245.0 215.0 293.5 202.0 193.0 219.5 36.0

Temperature, °C

Formula C8H18 C8H18 C8H18 C8H18 C8H18 C8H18 C7H10O4 C6H10O5 C6H8O4 C5H8O4 C7H10O4 C10H22 C4H6O4 C7H16 C7H16 C7H16 C7H16 C8H10O C8H10O C8H10O C8H10O C8H10O C8H12Si C10H10O4 C7H8O2 C8H10O2 C12H22O4 C10H12 C10H12 C6H8O3 C2H6S

40

−29.7 −23.0 −26.9 −26.7 −25.8 −22.1 69.3 75.4 45.7 35.0 46.8 +6.3 20.0 −49.0 −42.0 −48.0 −45.9 56.0 51.8 51.8 66.2 62.0 +5.3 100.3 78.6 49.0 104.0 34.2 29.0 61.4 −75.6

−7.9 −1.1 −5.3 −5.5 −4.4 +0.2 94.0 104.0 73.0 59.8 74.0 30.5 44.0 −28.7 −20.8 −27.4 −25.0 83.8 78.0 78.0 93.8 89.2 30.3 131.8 107.6 76.8 139.8 61.9 55.9 88.1 −58.0

+3.1 +9.9 +5.2 +5.3 +6.1 11.3 106.6 118.3 86.4 72.0 87.8 42.3 56.0 −18.7 −10.3 −17.1 −14.4 97.6 91.3 91.3 107.7 102.4 42.6 147.6 122.0 90.7 156.2 75.8 69.0 102.0 −49.2

15.0 22.1 17.2 17.2 18.2 23.5 119.7 133.8 101.3 85.0 102.1 55.8 69.4 −7.5 +1.1 −5.9 −2.9 112.0 105.0 105.0 122.0 117.0 56.2 164.0 136.4 105.8 175.8 90.8 84.0 116.3 −39.4

28.2 35.6 30.5 30.4 31.7 37.1 133.7 150.1 117.2 100.0 118.0 71.2 83.6 +5.0 13.9 +6.5 +9.9 129.2 121.5 121.5 138.0 133.3 71.4 182.8 152.7 122.5 196.0 107.7 100.2 132.6 −28.4

36.7 44.2 39.0 38.9 40.4 45.8 142.6 160.4 127.1 109.7 127.8 80.8 92.8 13.0 22.1 14.5 18.1 139.5 131.0 131.0 148.0 143.5 81.3 194.0 163.8 133.2 208.0 118.0 110.7 142.4 −21.9

48.2 56.0 50.6 50.5 52.5 57.7 153.7 175.1 140.4 121.9 141.5 93.9 104.8 23.9 33.3 25.4 29.3 152.2 143.0 143.0 161.0 156.0 94.2 210.0 177.5 147.3 222.6 132.3 124.7 155.3 −12.0

Melting Point, °C

−90.7

38 −62 −52.8 −123.7 −135 −119.5 −135.0 75 25.5 74.5 62.5 68

51.5 38

−83.2

d-Dimethyl tartrate dl-Dimethyl tartrate N,N-Dimethyl-2-toluidine N,N-Dimethyl-4-toluidine Di(nitrosomethyl) amine Diosphenol 1,4-Dioxane Dipentene Diphenylamine Diphenyl carbinol (benzhydrol) chlorophosphate disulfide 1,2-Diphenylethane (dibenzyl) Diphenyl ether 1,1-Diphenylethylene trans-Diphenylethylene 1,1-Diphenylhydrazine Diphenylmethane Diphenyl sulfide Diphenyl-2-tolyl thiophosphate 1,2-Dipropoxyethane 1,2-Diisopropylbenzene 1,3-Diisopropylbenzene Dipropylene glycol Dipropyleneglycol monobutyl ether isopropyl ether Di-n-propyl ether Diisopropyl ether Di-n-propyl ketone (4-heptanone) Di-n-propyl oxalate Diisopropyl oxalate Di-n-propyl succinate Di-n-propyl d-tartrate Diisopropyl d-tartrate Divinyl acetylene (1,5-hexadiene-3-yne) 1,3-Divinylbenzene Docosanae

C6H10O6 C6H10O6 C9H13N C9H13N C2H5N3O2 C10H16O2 C4H8O2 C10H16 C12H11N C13H12O C12H10ClPO3 C12H10S2 C14H14 C12H10O C14H12 C14H12 C12H12N2 C13H12 C12H10S C18H17O3PS C8H18O2 C12H18 C12H18 C6H14O3 C10H22O3 C9H20O3 C6H14O C6H14O C7H14O C8H14O4 C8H14O4 C10H18O4 C10H18O6 C10H18O6 C6H6 C10H10 C22H46

102.1 100.4 28.8 50.1 +3.2 66.7 −35.8 14.0 108.3 110.0 121.5 131.6 86.8 66.1 87.4 113.2 126.0 76.0 96.1 159.7 −38.8 40.0 34.7 73.8 64.7 46.0 −43.3 −57.0 23.0 53.4 43.2 77.5 115.6 103.7 −45.1 32.7 157.8

133.2 131.8 54.1 74.3 27.8 95.4 −12.8 40.4 141.7 145.0 160.5 164.0 119.8 97.8 119.6 145.8 159.3 107.4 129.0 179.6 −10.3 67.8 62.3 102.1 92.0 72.8 −22.3 −37.4 44.4 80.2 69.0 107.6 147.7 133.7 −24.4 60.0 195.4

148.2 147.5 66.2 86.7 40.0 109.0 −1.2 53.8 157.0 162.0 182.0 180.0 136.0 114.0 135.0 161.0 176.1 122.8 145.0 201.6 +5.0 81.8 76.0 116.2 106.0 86.2 −11.8 −27.4 55.0 93.9 81.9 122.2 163.5 148.2 −14.0 73.8 213.0

164.3 164.0 80.2 100.0 53.7 124.0 +12.0 68.2 175.2 180.9 203.8 197.0 153.7 130.8 151.8 179.8 194.0 139.8 162.0 215.5 22.3 96.8 91.2 131.3 120.4 100.8 0.0 −16.7 66.2 108.6 95.6 138.0 180.4 164.0 −2.8 88.7 233.5

182.4 182.4 95.0 116.3 68.2 141.2 25.2 84.3 194.3 200.0 227.9 214.8 173.7 150.0 170.8 199.0 213.5 157.8 182.8 230.6 42.3 114.0 107.9 147.4 136.3 117.0 +13.2 −4.5 78.1 124.6 110.5 154.8 199.7 181.8 +10.0 105.5 254.5

193.8 193.8 105.2 126.4 77.7 151.3 33.8 94.6 206.9 212.0 244.2 226.2 186.0 162.0 183.4 211.5 225.9 170.2 194.8 240.4 55.8 124.3 118.2 156.5 146.3 126.8 21.6 +3.4 85.8 134.8 120.0 166.0 211.7 192.6 18.1 116.0 268.3

208.8 209.5 118.1 140.3 90.3 165.6 45.1 108.3 222.8 227.5 265.0 241.3 202.8 178.8 198.6 227.4 242.5 186.3 211.8 252.5 74.2 138.7 132.3 169.9 159.8 140.3 33.0 13.7 96.0 148.1 132.6 180.3 227.0 207.3 29.5 130.0 286.0

230.5 232.3 138.3 161.6 110.0 186.2 62.3 128.2 247.5 250.0 299.5 262.6 227.8 203.3 222.8 251.7 267.2 210.7 236.8 270.3 103.8 159.8 153.7 189.9 180.0 160.0 50.3 30.0 111.2 168.0 151.2 202.5 250.1 228.2 46.0 151.4 314.2

255.0 257.4 161.5 185.4 131.3 209.5 81.8 150.5 274.1 275.6 337.2 285.8 255.0 230.7 249.8 278.3 294.0 237.5 263.9 290.0 140.0 184.3 177.6 210.5 203.8 183.1 69.5 48.2 127.3 190.3 171.8 226.5 275.6 251.8 64.4 175.2 343.5

280.0 282.0 184.8 209.5 153.0 232.0 101.1 174.6 302.0 301.0 378.0 310.0 284.0 258.5 277.0 306.5 322.2 264.5 292.5 310.0 180.0 209.0 202.0 231.8 227.0 205.6 89.5 67.5 143.7 213.5 193.5 250.8 303.0 275.0 84.0 199.5 376.0

61.5 89 −61

10 52.9 68.5 61 51.5 27 124 44 26.5

−105

−122 −60 −32.6

−66.9 44.5

(Continued)

2.329

2.330 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name n-Dodeccane 1-Dodecene n-Dodecyl alcohol Dodecylamine Dodecyltrimethylsilane Elaidic acid Epichlorohydrin 1,2-Epoxy-2-methylpropane Erucic acid Estragole (p-methoxy allyl benzene) Ethane Ethoxydimethylphenylsilane Ethoxytrimethylsilane Ethoxytriphenylsilane Ethyl acetate acetoacetate Ethylacetylene (1-butyne) Ethyl acrylate a-Ethylacrylic acid a-Ethylacrylonitrile Ethyl alcohol (ethanol) Ethylamine 4-Ethylaniline N-Ethylaniline 2-Ethylanisole 3-Ethylanisole 4-Ethylanisole Ethylbenzene Ethyl benzoate benzoylacetate bromide

1

5

10

20

90.0 87.8 134.7 127.8 137.7 223.5 16.6 −40.3 254.5 93.7 −142.9 76.2 −20.7 213.5 −13.5 67.3 −68.7 +2.0 82.0 +5.0 −2.3 −58.3 93.8 80.6 69.0 73.9 73.9 25.9 86.0 150.3 −47.5

104.6 102.4 150.0 141.6 153.8 242.3 29.0 −29.5 270.6 108.4 −136.7 91.0 −9.8 230.0 −3.0 81.1 −59.9 13.0 94.4 17.7 +8.0 −48.6 109.0 96.0 83.1 88.5 88.5 38.6 101.4 166.8 −37.8

60

100

200

400

760

167.2 162.2 213.0 203.0 222.0 312.4 79.3 17.5 336.5 168.7 −110.2 151.5 38.1 295.0 42.0 138.0 −21.6 61.5 144.0 71.6 48.4 −12.3 170.6 156.9 142.1 149.7 149.2 92.7 164.8 223.8 +4.5

191.0 185.5 235.7 225.0 248.0 337.0 98.0 36.0 358.8 192.0 −99.7 175.0 56.3 319.5 59.3 158.2 −6.9 80.0 160.7 92.2 63.5 +2.0 194.2 180.8 164.2 172.8 172.3 113.8 188.4 244.7 21.0

216.2 208.0 259.0 248.0 273.0 362.0 117.9 55.5 381.5 215.0 −88.6 199.5 75.7 344.0 77.1 180.8 +8.7 99.5 179.2 114.0 78.4 16.6 217.4 204.0 187.1 196.5 196.5 136.2 213.4 265.0 38.4

Temperature, °C

Formula C12H26 C12H24 C12H26O C12H27N C15H34Si C18H34O2 C3H5ClO C4H8O C22H42O2 C10H12O C2H6 C10H16OSi C5H14OSi C20H20OSi C4H8O2 C6H10O3 C4H6 C5H8O2 C5H8O2 C5H7N C2H6O C2H7N C8H11N C8H11N C9H12O C9H12O C9H12O C8H10 C9H10O2 C11H12O3 C2H5Br

40

47.8 47.2 91.0 82.8 91.2 171.3 −16.5 −69.0 206.7 52.6 −159.5 36.3 −50.9 167.0 −43.4 28.5 −92.5 −29.5 47.0 −29.0 −31.3 −82.3 52.0 38.5 29.7 33.7 33.5 −9.8 44.0 107.6 −74.3

75.8 74.0 120.2 111.8 122.1 206.7 +5.6 −50.0 239.7 80.0 −148.5 63.1 −31.0 198.2 −23.5 54.0 −76.7 −8.7 70.7 −6.4 −12.0 −66.4 80.0 66.4 55.9 60.3 60.2 +13.9 72.0 136.4 −56.4

121.7 118.6 167.2 157.4 172.1 260.8 42.0 −17.3 289.1 124.6 −129.8 107.2 +3.7 247.0 +9.1 96.2 −50.5 26.0 108.1 31.8 19.0 −39.8 125.7 113.2 98.9 104.8 104.7 52.8 118.2 181.8 −26.7

132.1 128.5 177.8 168.0 184.2 273.0 50.6 −9.7 300.2 135.2 −125.4 127.5 11.5 258.3 16.6 106.0 −43.4 33.5 116.7 40.6 26.0 −33.4 136.0 123.6 109.0 115.5 115.4 61.8 129.0 191.9 −19.5

146.2 142.3 192.0 182.1 199.5 288.0 62.0 +1.2 314.4 148.5 −119.3 131.4 22.1 273.5 27.0 118.5 −34.9 44.5 127.5 53.0 34.9 −25.1 149.8 137.3 122.3 129.2 128.4 74.1 143.2 205.0 −10.0

Melting Point, °C −9.6 −31.5 24

51.5 −25.6 33.5 −183.2

−82.4 −45 −130 −71.2 −112 −80.6 −4 −63.5

−94.9 −34.6 −117.8

a-bromoisobutyrate n-butyrate isobutyrate Ethylcamphoronic anhydride Ethyl isocaproate carbamate carbanilate Ethylcetylamine Ethyl chloride chloroacetate chloroglyoxylate a-chloropropionate trans-cinnamate 3-Ethylcumene 4-Ethylcumene Ethyl cyanoacetate Ethylcyclohexane Ethylcyclopentane Ethyl dichloroacetate N,N-diethyloxamate N-Ethyldiphenylamine Ethylene Ethylene-bis-(chloroacetate) Ethylene chlorohydrin (2-chloroethanol) diamine (1,2-ethanediamine) dibromide (1,2-dibromethane) dichloride (1,2-dichloroethane) glycol (1,2-ethanediol) glycol diethyl ether (1,2-diethoxyethane) glycol dimethyl ether (1,2-dimethoxyethane) glycol monomethyl ether (2-methoxyethanol) oxide Ethyl a-ethylacetoacetate fluoride formate

C6H11BrO2 C6H12O2 C6H12O2 C11H16O5 C8H16O2 C3H7NO2 C9H11NO2 C18H39N C2H5Cl C4H7ClO2 C4H5ClO3 C5H9ClO2 C11H12O2 C11H16 C11H16 C5H7NO2 C8H16 C7H14 C4H6Cl2O2 C8H15NO3 C14H15N C2H4 C6H8Cl2O4 C2H5ClO C2H8N2 C2H4Br2 C2H4Cl2 C2H6O2 C6H14O2

10.6 −18.4 −24.3 118.2 11.0 107.8 133.2 −89.8 +1.0 −5.1 +6.6 87.6 28.3 31.5 67.8 −14.5 −32.2 9.6 76.0 98.3 −168.3 112.0 −4.0 −11.0 −27.0 −44.5 53.0 −33.5

35.8 +4.0 −2.4 149.8 35.8 65.8 131.8 168.2 −73.9 25.4 +18.0 30.2 108.5 55.5 58.4 93.5 +9.2 −10.8 34.0 106.3 130.2 −158.3 142.4 +19.0 +10.5 +4.7 −24.0 79.7 −10.2

48.0 15.3 +8.4 165.0 48.0 77.8 143.7 186.0 −65.8 37.5 29.9 41.9 134.0 68.8 72.0 106.0 20.6 −0.1 46.3 121.7 146.0 −153.2 158.0 30.3 21.5 18.6 −13.6 92.1 +1.6

61.8 27.8 20.6 181.8 61.7 91.0 155.5 205.5 −56.8 50.4 42.0 54.3 150.3 83.6 86.7 119.8 33.4 +11.7 59.5 137.7 162.8 −147.6 173.5 42.5 33.0 32.7 −2.4 105.8 14.7

77.0 41.5 33.8 199.8 76.3 105.6 168.8 226.5 −47.0 65.2 56.0 68.2 169.2 99.9 103.3 133.8 47.6 25.0 74.0 154.4 182.0 −141.3 191.0 56.0 45.8 48.0 +10.0 120.0 29.7

86.7 50.1 42.3 211.5 85.8 114.8 177.3 239.8 −40.6 74.0 65.2 77.3 181.2 110.2 113.8 142.1 56.7 33.4 83.6 166.0 193.7 −137.3 201.8 64.1 53.8 57.9 18.1 129.5 39.0

99.8 62.0 53.5 226.6 98.4 126.2 187.9 256.8 −32.0 86.0 76.6 89.3 196.0 124.3 127.2 152.8 69.0 45.0 96.1 180.3 209.8 −131.8 215.0 75.0 62.5 70.4 29.4 141.8 51.8

119.7 79.8 71.0 248.5 117.8 144.2 203.8 283.3 −18.6 103.8 94.5 107.2 219.3 145.4 148.3 169.8 87.8 62.4 115.2 202.8 233.0 −123.4 237.3 91.8 81.0 89.8 45.7 158.5 71.8

141.2 100.0 90.0 272.8 139.2 164.0 220.0 313.0 −3.9 123.8 114.7 126.2 245.0 168.2 171.8 187.8 109.1 82.3 135.9 226.5 258.8 −113.9 259.5 110.0 99.0 110.1 64.0 178.5 94.1

163.6 121.0 110.0 298.0 160.4 184.0 237.0 342.0 +12.3 144.2 135.0 146.5 271.0 193.0 195.8 206.0 131.8 103.4 156.5 252.0 286.0 −103.7 283.5 128.8 117.2 131.5 82.4 197.3 119.5

C4H10O2

−48.0

−26.2

−15.3

−3.0

+10.7

19.7

31.8

50.0

70.8

93.0

C3H8O2

−13.5

+10.2

22.0

34.3

47.8

56.4

68.0

85.3

104.3

124.4

C2H4O C8H14O3 C2H5F C3H6O2

−89.7 40.5 −117.0 −60.5

−73.8 67.3 −103.8 −42.2

−65.7 80.2 −97.7 −33.0

−56.6 94.6 −90.0 −22.7

−46.9 110.3 −81.8 −11.5

−40.7 120.6 −76.4 −4.3

−32.1 133.8 −69.3 −5.4

−19.5 153.2 −58.0 20.2

−4.9 175.6 −45.5 37.1

+10.7 198.0 −32.0 54.3

−93.3 −88.2

49 52.5 −139 −26

12

−111.3 −138.6

−169 −69 8.5 10 −35.3 −15.6

−111.3 −79

(Continued)

2.331

2.332 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name 2-furoate glycolate 3-Ethylhexane 2-Ethylhexyl acrylate Ethylidene chloride (1,1-dichloroethane) fluoride (1,1-difluoroethane) Ethyl iodide Ethyl l-leucinate Ethyl levulinate Ethyl mercaptan (ethanethiol) Ethyl methylcarbamate Ethyl methyl ether 1-Ethylnaphthalene Ethyl a-naphthyl ketone (1-propionaphthone) Ethyl 3-nitrobenzoate 3-Ethylpentane 4-Ethylphenetole 2-Ethylphenol 3-Ethylphenol 4-Ethylphenol Ethyl phenyl ether (phenetole) Ethyl propionate Ethyl propyl ether Ethyl salicylate 3-Ethylstyrene 4-Ethylstyrene Ethylisothiocyanate 2-Ethyltoluene 3-Ethyltoluene 4-Ethyltoluene

1

5

10

20

40

60

100

200

400

760

Temperature, °C

Formula C7H8O3 C4H8O3 C8H18 C11H20O2 C2H4Cl2 C2H4F2 C2H5I C8H17NO2 C7H12O3 C2H6S C4H9NO2 C3H8O C12H12

37.6 14.3 −20.0 50.0 −60.7 −112.5 −54.4 27.8 47.3 −76.7 26.5 −91.0 70.0

63.8 38.8 +2.1 77.7 −41.9 −98.4 −34.3 57.3 74.0 −59.1 51.0 −75.6 101.4

77.1 50.5 12.8 91.8 −32.3 −91.7 −24.3 72.1 87.3 −50.2 63.2 −67.8 116.8

91.5 63.9 25.0 106.3 −21.9 −84.1 −13.1 88.0 101.8 −40.7 76.1 −59.1 133.8

107.5 78.1 38.5 123.7 −10.2 −75.8 −0.9 106.0 117.7 −29.8 91.0 −49.4 152.0

117.5 87.6 47.1 134.0 −2.9 −70.4 +7.2 117.8 127.6 −22.4 100.0 −43.3 164.1

130.4 99.8 58.9 147.9 +7.2 −63.2 18.0 131.8 141.3 −13.0 112.0 −34.8 180.0

150.1 117.8 76.7 168.2 22.4 −52.0 34.1 149.8 160.2 +1.5 130.0 −22.0 204.6

172.5 138.0 97.0 192.2 39.8 −39.5 52.3 167.3 183.0 17.7 149.8 −7.8 230.8

195.0 158.2 118.5 216.0 57.4 −26.5 72.4 184.0 206.2 35.0 170.0 +7.5 258.1

C13H12O C9H9NO4 C7H16 C10H14O C8H10O C8H10O C8H10O C8H10O C5H10O2 C5H12O C9H10O3 C10H12 C10H12 C3H5NS C9H12 C9H12 C9H12

124.0 108.1 −37.8 48.5 46.2 60.0 59.3 18.1 −28.0 −64.3 61.2 28.3 26.0 13.2 9.4 7.2 7.6

155.5 140.2 −17.0 75.7 73.4 86.8 86.5 43.7 −7.2 −45.0 90.0 55.0 52.7 +10.6 34.8 32.3 32.7

171.0 155.0 −6.8 89.5 87.0 100.2 100.2 56.4 +3.4 −35.0 104.2 68.3 66.3 22.8 47.6 44.7 44.9

188.1 173.6 +4.7 103.8 101.5 114.5 115.0 70.3 14.3 −24.0 119.3 82.8 80.8 36.1 61.2 58.2 58.5

206.9 192.6 17.5 119.8 117.9 130.0 131.3 86.6 27.2 −12.0 136.7 99.2 97.3 50.8 76.4 73.3 73.6

218.2 205.0 25.7 129.8 127.9 139.8 141.7 95.4 35.1 −4.0 147.6 109.6 107.6 59.8 86.0 82.9 83.2

233.5 220.3 36.9 143.5 141.8 152.0 154.2 108.4 45.2 +6.8 161.5 123.2 121.5 71.9 99.0 95.9 96.3

255.5 244.6 53.8 163.2 161.6 171.8 175.0 127.9 61.7 23.3 183.7 144.0 142.0 90.0 119.0 115.5 116.1

280.2 270.6 73.0 185.7 184.5 193.3 197.4 149.8 79.8 41.6 207.0 167.2 165.0 110.1 141.4 137.8 136.4

306.0 298.0 93.5 208.0 207.5 214.0 219.0 172.0 99.1 61.7 231.5 191.5 189.0 131.0 165.1 161.3 162.0

Melting Point, °C 34

−96.7 −117 −105 −121 −27

47 −118.6 −45 −4 46.5 −30.2 −72.6 1.3 −5.9 −95.5

Ethyl trichloroacetate Ethyltrimethylsilane Ethyltrimethyltin Ethyl isovalerate 2-Ethyl-1,4-xylene 4-Ethyl-1,3-xylene 5-Ethyl-1,3-xylene Eugenol iso-Eugenol Eugenyl acetate Fencholic acid d-Fenchone dl-Fenchyl alcohol Fluorene Fluorobenzene 2-Fluorotoluene 3-Fluorotoluene 4-Fluorotoluene Formaldehyde Formamide Formic acid trans-Fumaryl chloride Furfural (2-furaldehyde) Furfuryl alcohol Geraniol Geranyl acetate Geranyl n-butyrate Geranyl isobutyrate Geranyl formate Glutaric acid Glutaric anhydride Glutaronitrile Glutaryl chloride Glycerol Glycerol dichlorohydrin (1,3-dichloro-2-propanol) Glycol diacetate

C4H5Cl3O2 C5H14Si C5H14Sn C7H14O2 C10H14 C10H14 C10H14 C10H12O2 C10H12O2 C12H14O3 C10H16O2 C10H16O C10H18O C13H10 C6H5F C7H7F C7H7F C7H7F CH2O CH3NO CH2O2 C4H2Cl2O2 C5H4O2 C5H6O2 C10H18O C12H20O2 C14H24O2 C14H24O2 C11H18O2 C5H8O4 C5H6O3 C5H6N2 C5H6Cl2O2 C3H8O3 C3H6Cl2O C6H10O4

20.7 −60.6 −30.0 −6.1 25.7 26.3 22.1 78.4 86.3 101.6 101.7 28.0 45.8 −43.4 −24.2 −22.4 −21.8

45.5 −41.4 −7.6 +17.0 52.0 53.0 48.8 108.1 117.0 132.3 128.7 54.7 70.3 129.3 −22.8 −2.2 −0.3 +0.3

70.5 −20.0 +15.0 18.5 31.8 69.2 73.5 96.8 90.9 61.8 155.5 100.8 91.3 56.1 125.5 28.0

96.3 −5.0 38.5 42.6 56.0 96.8 102.7 125.2 119.6 90.3 183.8 133.3 123.7 84.0 153.8 52.2

57.7 −31.8 +3.8 28.7 65.6 66.4 62.1 123.0 132.4 148.0 142.3 68.3 82.1 146.0 −12.4 +8.9 +11.0 11.8 −88.0 109.5 +2.1 51.8 54.8 68.0 110.0 117.9 139.0 133.0 104.3 196.0 149.5 140.0 97.8 167.2 64.7

38.3

64.1

77.1

70.6 −21.0 16.1 41.3 79.8 80.6 76.5 138.7 149.0 164.2 155.8 83.0 95.6 164.2 −1.2 21.4 23.4 24.0 −79.6 122.5 10.3 65.0 67.8 81.0 125.6 133.0 153.8 147.9 119.8 210.5 166.0 156.5 112.3 182.2 78.0

85.5 −9.0 30.0 55.2 96.0 97.2 92.6 155.8 167.0 183.0 171.8 99.5 110.8 185.2 +11.5 34.7 37.0 37.8 −70.6 137.5 24.0 79.5 82.1 95.7 141.8 150.0 170.1 164.0 136.2 226.3 185.5 174.6 128.3 198.0 93.0

94.4 −1.2 38.4 64.0 106.2 107.4 103.0 167.3 178.2 194.0 181.5 109.8 120.2 197.8 19.6 43.7 45.8 46.5 −65.0 147.0 32.4 89.0 91.5 104.0 151.5 160.3 180.2 174.0 147.2 235.5 196.2 189.5 139.1 208.0 102.0

107.4 +9.2 50.0 75.9 120.0 121.2 116.5 182.2 194.0 209.7 194.0 123.6 132.3 214.7 30.4 55.3 57.5 58.1 −57.3 157.5 43.8 101.0 103.4 115.9 165.3 175.2 193.8 187.7 160.7 247.0 212.5 205.5 151.8 220.1 114.8

125.8 25.0 67.3 93.8 140.2 141.8 137.4 204.7 217.2 232.5 215.0 144.0 150.0 240.3 47.2 73.0 75.4 76.0 −46.0 175.5 61.4 120.0 121.8 133.1 185.6 196.3 214.0 207.6 182.6 265.0 236.5 230.0 172.4 240.0 133.3

146.0 42.8 87.6 114.0 163.1 164.4 159.6 228.3 242.3 257.4 237.8 166.8 173.2 268.6 65.7 92.8 95.4 96.1 −33.0 193.5 80.3 140.0 141.8 151.8 207.8 219.8 235.0 228.5 205.8 283.5 261.0 257.3 195.3 263.0 153.5

167.0 62.0 108.8 134.3 186.9 188.4 183.7 253.5 267.5 282.0 264.1 191.0 201.0 295.0 84.7 114.0 116.0 117.0 −19.5 210.5 100.6 160.0 161.8 170.0 230.0 243.3 257.4 251.0 230.0 303.0 287.0 286.2 217.0 290.0 174.3

90.8

106.1

115.8

128.0

147.8

168.3

190.5

−99.3

−10 295 19 5 35 113 −42.1 −80 −110.8 −92 8.2

97.5

17.9 −31

(Continued)

2.333

2.334 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name Glycolide (1,4-dioxane-2,6-dione) Guaicol (2-methoxyphenol) Heneicosane Heptacosane Heptadecane Heptaldehyde (enanthaldehyde) n-Heptane Heptanoic acid (enanthic acid) 1-Heptanol Heptanoyl chloride (enanthyl chloride) 2-Heptene Heptylbenzene Heptyl cyanide (enanthonitrile) Hexachlorobenzene Hexachloroethane Hexacosane Hexadecane 1-Hexadecene n-Hexadecyl alcohol (cetyl alcohol) n-Hexadecylamine (cetylamine) Hexaethylbenzene n-Hexane 1-Hexanol 2-Hexanol 3-Hexanol 1-Hexene n-Hexyl levulinate n-Hexyl phenyl ketone (enanthophenone) Hydrocinnamic acid Hydrogen cyanide (hydrocyanic acid)

1

5

10

20

C9H10O2 CHN

60

100

200

400

760

Temperature, °C

Formula C4H4O4 C7H8O2 C21H44 C27H56 C17H36 C7H14O C7H16 C7H14O2 C7H16O C7H13ClO C7H14 C13H20 C7H13N C6Cl6 C2Cl6 C26H54 C16H34 C16H32 C16H34O C16H35N C18H30 C6H14 C6H14O C6H14O C6H14O C6H12 C11H20O3 C13H18O

40

−53.9 24.4 14.6 +2.5 −57.5 90.0 100.0

103.0 79.1 188.0 248.6 145.2 32.7 −12.7 101.3 64.3 54.6 −14.1 94.6 47.8 149.3 49.8 240.0 135.2 131.7 158.3 157.8 134.3 −34.5 47.2 34.8 25.7 −38.0 120.0 130.3

116.6 92.0 205.4 266.8 160.0 43.0 −2.1 113.2 74.7 64.6 −3.5 110.0 61.6 166.4 73.5 257.4 149.8 146.2 177.8 176.0 150.3 −25.0 58.2 45.0 36.7 −28.1 134.7 145.5

132.0 106.0 223.2 284.6 177.7 54.0 +9.5 125.6 85.8 75.0 +8.3 126.0 76.3 185.7 87.6 275.8 164.7 162.0 197.8 195.7 168.0 −14.1 70.3 55.9 49.0 −17.2 150.2 161.0

148.6 121.6 243.4 305.7 195.8 66.3 22.3 139.5 99.8 86.4 21.5 144.0 92.6 206.0 102.3 295.2 181.3 178.8 219.8 215.7 187.7 −2.3 83.7 67.9 62.2 −5.0 167.8 178.9

158.2 131.0 255.3 318.3 207.3 74.0 30.6 148.5 108.0 93.5 30.0 154.8 103.0 219.0 112.0 307.8 193.2 190.8 234.3 228.8 199.7 +5.4 92.0 76.0 70.7 +2.8 179.0 189.8

173.2 144.0 272.0 333.5 223.0 84.0 41.8 160.0 119.5 102.7 41.3 170.2 116.8 235.5 124.2 323.2 208.5 205.3 251.7 245.8 216.0 15.8 102.8 87.3 81.8 13.0 193.6 204.2

194.0 162.7 296.5 359.4 247.8 102.0 58.7 179.5 136.6 116.3 58.6 193.3 137.7 258.5 143.1 348.4 231.7 226.8 280.2 272.2 241.7 31.6 119.6 103.7 98.3 29.0 215.7 225.0

217.0 184.1 323.8 385.0 274.5 125.5 78.0 199.6 155.6 130.7 78.1 217.8 160.0 283.5 163.8 374.6 258.3 250.0 312.7 300.4 268.5 49.6 138.0 121.8 117.0 46.8 241.0 248.3

240.0 205.0 350.5 410.6 303.0 155.0 98.4 221.5 175.8 145.0 98.5 244.0 184.6 309.4 185.6 399.8 287.5 274.0 344.0 330.0 298.3 68.7 157.0 139.9 135.5 66.0 266.8 271.3

102.2 −71.0

133.5 −55.3

148.7 −47.7

165.0 −39.7

183.3 −30.9

194.0 −25.1

209.0 −17.8

230.8 −5.3

255.0 +10.2

279.8 25.9

52.4 152.6 211.7 115.0 12.0 −34.0 78.0 42.4 34.2 −35.8 64.0 21.0 114.4 32.7 204.0 105.3 101.6 122.7 123.6

Melting Point, °C 97 28.3 40.4 59.5 22.5 −42 −90.6 −10 34.6

230 186.6 56.6 18.5 4 49.3 130 −95.3 −51.6 −98.5

48.5 −13.2

Hydroquinone 4-Hydroxybenzaldehyde α-Hydroxyisobutyric acid α-Hydroxybutyronitrile 4-Hydroxy-3-methyl-2-butanone 4-Hydroxy-4-methyl-2-pentanone 3-Hydroxypropionitrile Indene Iodobenzene Iodononane 2-Iodotoluene α-Ionone Isoprene Lauraldehyde Lauric acid Levulinaldehyde Levulinic acid d-Limonene Linalyl acetate Maleic anhydride Menthane 1-Menthol Menthyl acetate benzoate formate Mesityl oxide Methacrylic acid Methacrylonitrile Methane Methanethiol Methoxyacetic acid N-Methylacetanilide Methyl acetate acetylene (propyne) acrylate alcohol (methanol) Methylamine

C6H6O2 C7H6O2 C4H8O3 C5H9NO C5H10O2 C6H12O2 C3H5NO C9H8 C6H5I C9H19I C7H7I C13H20O C5H8 C12H24O C12H24O2 C5H8O2 C5H8O3 C10H16 C12H20O2 C4H2O3 C10H20 C10H20O C12H22O2 C17H24O2 C11H20O2 C6H10O C4H6O2 C4H5N CH4 CH4S C3H6O3 C9H11NO C3H6O2 C3H4 C4H6O2 CH4O CH5N

132.4 121.2 73.5 41.0 44.6 22.0 58.7 16.4 24.1 70.0 37.2 79.5 −79.8 77.7 121.0 28.1 102.0 14.0 55.4 44.0 +9.7 56.0 57.4 123.2 47.3 −8.7 25.5 −44.5 −205.9 −90.7 52.5 −57.2 −111.0 −43.7 −44.0 −95.8

153.3 153.2 98.5 65.8 69.3 46.7 87.8 44.3 50.6 96.2 65.9 108.8 −62.3 108.4 150.6 54.9 128.1 40.4 82.5 63.4 35.7 83.2 85.8 154.2 75.8 +14.1 48.5 −23.3 −119.0 −75.3 79.3 103.8 −38.6 −97.5 −23.6 −25.3 −81.3

163.5 169.7 110.5 77.8 81.0 58.8 102.0 58.5 64.0 109.0 79.8 123.0 −53.3 123.7 166.0 68.0 141.8 53.8 96.0 78.7 48.3 96.0 100.0 170.0 90.0 26.0 60.0 −12.5 −195.5 −67.5 92.0 118.6 −29.3 −90.5 −13.5 −16.2 −73.8

174.6 186.8 123.8 90.7 94.0 72.0 117.9 73.9 78.3 123.0 95.6 139.0 −43.5 140.2 183.6 82.7 154.1 68.2 111.4 95.0 62.7 110.3 115.4 186.3 105.8 37.9 72.7 −0.6 −191.8 −58.8 106.5 135.1 −19.1 −82.9 −2.7 −6.0 −65.9

192.0 206.0 138.0 104.8 108.2 86.7 134.1 90.7 94.4 138.1 112.4 155.6 −32.6 157.8 201.4 98.3 169.5 84.3 127.7 111.8 78.3 126.1 132.1 204.3 123.0 51.7 86.4 +12.8 −187.7 −49.2 122.0 152.2 −7.9 −74.3 +9.2 +5.0 −56.9

203.0 217.5 146.4 113.9 117.4 96.0 144.7 100.8 105.0 147.7 123.8 166.3 −25.4 168.7 212.7 108.4 178.0 94.6 138.1 122.0 88.6 136.1 143.2 215.8 133.8 60.4 95.3 21.5 −185.1 −43.1 131.8 164.2 −0.5 −68.8 17.3 12.1 −51.3

216.5 233.5 157.7 125.0 129.0 108.2 157.7 114.7 118.3 159.8 138.1 181.2 −16.0 184.5 227.5 121.8 190.2 108.3 151.8 135.8 102.1 149.4 156.7 230.4 148.0 72.1 106.6 32.8 −181.4 −34.8 144.5 179.8 +9.4 −61.3 28.0 21.2 −43.7

238.0 256.8 175.2 142.0 146.5 126.8 178.0 135.6 139.8 179.0 160.0 202.5 −1.2 207.8 249.8 142.0 208.3 128.5 173.3 155.9 122.7 168.3 178.8 253.2 169.8 90.0 123.9 50.0 −175.5 −22.1 163.5 202.3 24.0 −49.8 43.9 34.8 −32.4

262.5 282.6 193.8 159.8 165.5 147.5 200.0 157.8 163.9 199.3 185.7 225.2 +15.4 231.8 273.8 164.0 227.4 151.4 196.2 179.5 146.0 190.2 202.8 277.1 194.2 109.8 142.5 70.3 −168.8 −7.9 184.2 227.4 40.0 −37.2 61.8 49.9 −19.7

286.2 310.0 212.0 178.8 185.0 167.9 221.0 181.6 188.6 219.5 211.0 250.0 32.6 257.0 299.2 187.0 245.8 175.0 220.0 202.0 169.5 212.0 227.0 301.0 219.0 130.0 161.0 90.3 −161.5 +6.8 204.0 253.0 57.8 −23.3 80.2 64.7 −6.3

170.3 115.5 79 −47 −2 −28.5

−146.7 44.5 48 33.5 −96.9 58 42.5 54.5 −59 15 −182.5 −121 102 −98.7 −102.7 −97.8 −93.5

(Continued)

2.335

2.336 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name N-Methylaniline Methyl anthranilate benzoate 2-Methylbenzothiazole α-Methylbenzyl alcohol Methyl bromide 2-Methyl-l-butene 2-Methyl-2-butene Methyl isobutyl carbinol (2-methyl4-pentanol) n-butyl ketone (2-hexanone) isobutyl ketone (4-methyl-2-pentanone) n-butyrate isobutyrate caprate caproate caprylate chloride chloroacetate cinnamate α-Methylcinnamic acid Methylcyclohexane Methylcyclopentane Methylcyclopropane Methyl n-decyl ketone (n-dodecan-2-one) dichloroacetate N-Methyldiphenylamine Methyl n-dodecyl ketone (2-tetradecanone) Methylene bromide (dibromomethane) chloride (dichloromethane)

1

5

10

20

40

60

100

200

400

760

Temperature, °C

Formula C7H9N C8H9NO2 C8H8O2 C8H7NS C8H10O CH3Br C5H10 C5H10

36.0 77.6 39.0 70.0 49.0 −96.3 −89.1 −75.4

62.8 109.0 64.4 97.5 75.2 −80.6 −72.8 −57.0

76.2 124.2 77.3 111.2 88.0 −72.8 −64.3 −47.9

90.5 141.5 91.8 125.5 102.1 −64.0 −54.8 −37.9

106.0 159.7 107.8 141.2 117.8 −54.2 −44.1 −26.7

115.8 172.0 117.4 150.4 127.4 −48.0 −37.3 −19.4

129.8 187.8 130.8 163.9 140.3 −39.4 −28.0 −9.9

149.3 212.4 151.4 183.2 159.0 −26.5 −13.8 +4.9

172.0 238.5 174.7 204.5 180.7 −11.9 +2.5 21.6

195.5 266.5 199.5 225.5 204.0 +3.6 20.2 38.5

C6H14O C6H12O C6H12O C5H10O2 C5H10O2 C11H22O2 C7H14O2 C9H18O2 CH3Cl C3H5ClO2 C10H10O2 C10H10O2 C7H14 C8H12 C4H8 C12H24O C3H4Cl2O2 C13H13N C14H28O CH2Br2 CH2Cl2

−0.3 +7.7 −1.4 −26.8 −34.1 63.7 +5.0 34.2

+22.1 28.8 +19.7 −5.5 −13.0 93.5 30.0 61.7 −99.5 19.0 108.1 155.0 −14.0 −33.8 −80.6 106.0 26.7 134.0 130.0 −13.2 −52.1

33.3 38.8 30.0 +5.0 −2.9 108.0 42.0 74.9 −92.4 30.0 123.0 169.8 −3.2 −23.7 −72.8 120.4 38.1 149.7 145.5 −2.4 −43.3

45.4 50.0 40.8 16.7 +8.4 123.0 55.4 89.0 −84.8 41.5 140.0 185.2 +8.7 −12.8 −64.0 136.0 50.7 165.8 161.3 +9.7 −33.4

58.2 62.0 52.8 29.6 21.0 139.0 70.0 105.3 −76.0 54.5 157.9 201.8 22.0 −0.6 −54.2 152.4 64.7 184.0 179.8 23.3 −22.3

67.0 69.8 60.4 37.4 28.9 148.6 79.7 115.3 −70.4 63.0 170.0 212.0 30.5 +7.2 −48.0 163.8 73.6 195.4 191.4 31.6 −15.7

78.0 79.8 70.4 48.0 39.6 161.5 91.4 128.0 −63.0 73.5 185.8 224.8 42.1 17.9 −39.3 177.5 85.4 210.1 206.0 42.3 −6.3

94.9 94.3 85.6 64.3 55.7 181.6 109.8 148.1 −51.2 90.5 209.6 245.0 59.6 34.0 −26.0 199.0 103.2 232.8 228.2 58.5 +8.0

113.5 111.0 102.0 83.1 73.6 202.9 129.8 170.0 −38.0 109.5 235.0 266.8 79.6 52.3 −11.3 222.5 122.6 257.0 253.3 79.0 24.1

131.7 127.5 119.0 102.3 92.6 224.0 150 193.0 −24.0 130.3 263.0 288.0 100.9 71.8 +4.5 246.5 143.0 282.0 278.0 98.6 40.7

−2.9 77.4 125.7 −35.9 −53.7 −96.0 77.1 3.2 103.5 99.3 −35.1 −70.0

Melting Point, °C −57 24 −12.5 15.4 −93 −135 −133 −56.9 −84.7 −84.7 −18 −40 −97.7 −31.9 33.4 −126.4 −142.4

−7.6 −52.8 −96.7

Methyl ethyl ketone (2-butanone) 2-Methyl-3-ethylpentane 3-Methyl-3-ethylpentane Methyl fluoride formate a-Methylglutaric anhydride Methyl glycolate 2-Methylheptadecane 2-Methylheptane 3-Methylheptane 4-Methylheptane 2-Methyl-2-heptene 6-Methyl-3-hepten-2-ol 6-Methyl-5-hepten-2-ol 2-Methylhexane 3-Methylhexane Methyl iodide laurate levulinate methacrylate myristate a-naphthyl ketone (1-acetonaphthone) b-naphthyl ketone (2-acetonaphthone) n-nonyl ketone (undecan-2-one) palmitate n-pentadecyl ketone (2-heptdecanone) 2-Methylpentane 3-Methylpentane 2-Methyl-1-pentanol 2-Methyl-2-pentanol Methyl n-pentyl ketone (2-heptanone) phenyl ether (anisole) 2-Methylpropene Methyl propionate 4-Methylpropiophenone 2-Methylpropionyl bromide Methyl propyl ether

C4H8O C8H18 C8H18 CH3F C2H4O2 C6H8O3 C3H6O3 C18H38 C8H18 C8H18 C8H18 C8H16 C8H16O C8H16O C7H16 C7H16 CH3I C13H26O2 C6H10O3 C5H8O2 C15H30O2 C12H10O C12H10O C11H22O C17H34O2 C17H34O C6H14 C6H14 C6H14O C6H14O C7H14O C7H8O C4H8 C4H8O2 C10H12O C4H7BrO C4H10O

−48.3 −24.0 −23.9 −147.3 −74.2 93.8 +9.6 119.8 −21.0 −19.8 −20.4 −16.1 41.6 41.9 −40.4 −39.0 87.8 39.8 −30.5 115.0 115.6 120.2 68.2 134.3 129.6 −60.9 −59.0 15.4 −4.5 19.3 +5.4 −105.1 −42.0 59.6 13.5 −72.2

−28.0 −1.8 −1.4 −137.0 −57.0 125.4 33.7 152.0 +1.3 +2.6 +1.5 +6.7 65.0 66.0 −19.5 −18.1 −55.0 117.9 66.4 −10.0 145.7 146.3 152.3 95.5 166.8 161.6 −41.7 −39.8 38.0 +16.8 43.6 30.0 −96.5 −21.5 89.3 38.4 −54.3

−17.7 +9.5 +9.9 −131.6 −48.6 141.8 45.3 168.7 12.3 13.3 12.4 17.8 76.7 77.8 −9.1 −7.8 −45.8 133.2 79.7 +1.0 160.8 161.5 168.5 108.9 184.3 178.0 −32.1 −30.1 49.6 27.6 55.5 42.2 −81.9 −11.8 103.8 50.6 −45.4

−6.5 +6.0 21.7 35.2 22.3 36.2 −125.9 −119.1 −39.2 −28.7 157.7 177.5 58.1 72.3 186.0 204.8 24.4 37.9 25.4 38.9 24.5 38.0 30.4 44.0 89.3 102.7 90.4 104.0 +2.3 14.9 +3.6 16.4 −35.6 −24.2 149.0 166.0 93.7 109.5 11.0 25.5 177.8 195.8 178.4 196.8 185.7 203.8 123.1 139.0 202.0 196.4 214.3 −21.4 −9.7 −19.4 −7.3 61.6 74.7 38.8 51.3 67.7 81.2 55.8 70.7 −73.4 −63.8 −1.0 +11.0 120.2 138.0 64.1 79.4 −35.4 −24.3

14.0 43.9 45.0 −115.0 −21.9 189.9 81.8 216.3 46.6 47.6 46.6 52.8 111.5 112.8 23.0 24.5 −16.9 176.8 119.3 34.5 207.5 208.6 214.7 148.6

25.0 55.7 57.1 −109.0 −12.9 205.0 93.7 231.5 58.3 59.4 58.3 64.6 122.6 123.8 34.1 35.6 −7.0 190.8 133.0 47.0 222.6 223.8 229.8 161.0

41.6 73.6 75.3 −99.9 +0.8 229.1 111.8 254.5 76.0 77.1 76.1 82.3 139.5 140.0 50.8 52.4 +8.0

60.0 94.0 96.2 −89.5 16.0 255.5 131.7 279.8 96.2 97.4 96.3 102.2 156.6 156.6 69.8 71.6 25.3

79.6 115.6 118.3 −78.2 32.0 282.5 151.5 306.5 117.6 118.9 117.7 122.5 175.5 174.3 90.0 91.9 42.4

153.4 63.0 245.3 246.7 251.6 181.2

175.8 82.0 269.8 270.5 275.8 202.3

197.7 101.0 295.8 295.5 301.0 224.0

226.7 −1.9 +0.1 83.4 58.8 89.8 80.1 −57.7 18.7 149.3 88.8 −17.4

242.0 +8.1 10.5 94.2 69.2 100.0 93.0 −49.3 29.0 164.2 101.6 −8.1

265.8 24.1 26.5 111.3 85.0 116.1 112.3 −36.7 44.2 187.4 120.5 +6.0

291.7 41.6 44.2 129.8 102.6 133.2 133.8 −22.2 61.8 212.7 141.7 22.5

319.5 60.3 63.3 147.9 121.2 150.2 155.5 −6.9 79.8 238.5 163.0 39.1

−85.9 −114.5 −90 −99.8

−109.5 −120.8 −121.1

−118.2 −64.4 5

18.5 55.5 15 30 −154 −118 −103 −37.3 −140.3 −87.5

(Continued)

2.337

2.338 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name n-propyl ketone (2-pentanone) isopropyl ketone (3-methyl-2-butanone) 2-Methylquinoline Methyl salicylate a-Methyl styrene 4-Methyl styrene Methyl n-tetradecyl ketone (2-hexadecanone) thiocyanate isothiocyanate undecyl ketone (2-tridecanone) isovalerate Monovinylacetylene (butenyne) Myrcene Myristaldehyde Myristic acid (tetradecanoic acid) Napthalene 1-Naphthoic acid 2-Naphthoic acid 1-Naphthol 2-Naphthol 1-Naphthylamine 2-Naphthylamine Nicotine 2-Nitroaniline 3-Nitroaniline 4-Nitroaniline 2-Nitrobenzaldehyde 3-Nitrobenzaldehyde Nitrobenzene Nitroethane

1

5

10

20

40

60

100

200

400

760

Temperature, °C

Formula C5H10O C5H10O C10H9N C8H8O3 C9H10 C9H10

−12.0 −19.9 75.3 54.0 7.4 16.0

+8.0 −1.0 104.0 81.6 34.0 42.0

17.9 +8.3 119.0 95.3 47.1 55.1

28.5 18.3 134.0 110.0 61.8 69.2

39.8 29.6 150.8 126.2 77.8 85.0

47.3 36.2 161.7 136.7 88.3 95.0

56.8 45.5 176.2 150.0 102.2 108.6

71.0 59.0 197.8 172.6 121.8 128.7

86.8 73.8 211.7 197.5 143.0 151.2

103.3 88.9 246.5 223.2 165.4 175.0

C16H32O C2H3NS C2H3NS C13H26O C6H12O2 C4H4 C10H16 C14H28O C14H28O2 C10H8 C11H8O2 C11H8O2 C10H8O C10H8O C10H9N C10H9N C10H14N2 C6H6N2O2 C6H6N2O2 C6H6N2O2 C7H5NO3 C7H5NO3 C6H5NO2 C2H5NO2

109.8 −14.0 −34.7 86.8 −19.2 −93.2 14.5 99.0 142.0 52.6 156.0 160.8 94.0

151.5 +9.8 −8.3 117.0 +2.9 −77.7 40.0 132.0 174.1 74.2 184.0 189.7 125.5 128.6 137.7 141.6 91.8 135.7 151.5 177.6 117.7 127.4 71.6 +1.5

167.3 21.6 +5.4 131.8 14.0 −70.0 53.2 148.3 190.8 85.8 196.8 202.8 142.0 145.5 153.8 157.6 107.2 150.4 167.8 194.4 133.4 142.8 84.9 12.5

184.6 34.5 20.4 147.8 26.4 −61.3 67.0 166.2 207.6 101.7 211.2 216.9 158.0 161.8 171.6 175.8 123.7 167.7 185.5 213.2 150.0 159.0 99.3 24.8

203.7 49.0 38.2 165.7 39.8 −51.7 82.6 186.0 223.5 119.3 225.0 231.5 177.8 181.7 191.5 195.7 142.1 186.0 204.2 234.2 168.8 177.7 115.4 38.0

215.0 58.1 47.5 176.6 48.2 −45.3 92.6 198.3 237.2 130.2 234.5 241.3 190.0 193.7 203.8 208.1 154.7 197.8 216.5 245.9 180.7 189.5 125.8 46.5

230.5 70.4 59.3 191.5 59.8 −37.1 106.0 214.5 250.5 145.5 245.8 252.7 206.0 209.8 220.0 224.3 169.5 213.0 232.1 261.8 196.2 204.3 139.9 57.8

254.4 89.8 77.5 214.0 77.3 −24.1 126.0 240.4 272.3 167.7 263.5 270.3 229.6 234.0 244.9 249.7 193.8 236.3 255.3 284.5 220.0 227.4 161.2 74.8

279.8 110.8 97.8 238.3 96.7 −10.1 148.3 267.9 294.6 193.2 281.4 289.5 255.8 260.6 272.2 277.4 219.8 260.0 280.2 310.2 246.8 252.1 185.8 94.0

307.0 132.9 119.0 262.5 116.7 +5.3 171.5 297.8 318.0 217.9 300.0 308.5 282.5 288.0 300.8 306.1 247.3 284.5 305.7 336.0 273.5 278.3 210.6 114.0

104.3 108.0 61.8 104.0 119.3 142.4 85.8 96.2 44.4 −21.0

Melting Point, °C −77.8 −92 −1 −8.3 −23.2

−51 35.5 28.5

23.5 57.5 80.2 160.5 184 96 122.5 50 111.5 71.5 114 146.5 40.9 58 +5.7 −90

Nitroglycerin Nitromethane 2-Nitrophenol 2-Nitrophenyl acetate 1-Nitropropane 2-Nitropropane 2-Nitrotoluene 3-Nitrotoluene 4-Nitrotoluene 4-Nitro-1,3-xylene (4-nitro-m-xylene) Nonacosane Nona lecane n-Nonane 1-Nonanol 2-Nonanone Octacosane Octadecane n-Octane n-Octanol (1-octanol) 2-Octanone n-Octyl acrylate iodide (1-Iodooctane) Oleic acid Palmitaldehyde Palmitic acid Palmitonitrile Pelargonic acid Pentachlorobenzene Pentachloroethane Pentachloroethylbenzene Pentachlorophenol Pentacosane Pentadecane 1,3-Pentadiene 1,4-Pentadiene Pentaethylbenzene Pentaethylchlorobenzene

C3H5N3O9 CH3NO2 C6H5NO3 C8H7NO4 C3H7NO2 C3H7NO2 C7H7NO2 C7H7NO2 C7H7NO2 C8H9NO2 C29H60 C19H40 C9H20 C9H20O C9H18O C28H58 C18H38 C8H18 C8H18O C8H18O C11H20O2 C8H17I C18H34O2 C16H32O C16H32O2 C16H31N C9H18O2 C6HCl5 C2HCl5 C6H5Cl5 C6HCl5O C25H52 C15H32 C5H8 C5H8 C16H26 C16H25Cl

127 −29.0 49.3 100.0 −9.6 −18.8 50.0 50.2 53.7 65.6 234.2 133.3 +1.4 59.5 32.1 226.5 119.6 −14.0 54.0 23.6 58.5 45.8 176.5 121.6 153.6 134.3 108.2 98.6 +1.0 96.2

167 −7.9 76.8 128.0 +13.5 4.1 79.1 1.0 85.0 95.0 260.8 166.3 25.8 86.1 59.0 260.3 152.1 +8.3 76.5 48.4 87.7 74.8 208.5 154.6 188.1 168.3 126.0 129.7 27.2 130.0

188 +2.8 90.4 142.0 25.3 15.8 93.8 96.0 100.5 109.8 286.4 183.5 38.0 99.7 72.3 277.4 169.6 19.2 88.3 60.9 102.0 90.0 223.0 171.8 205.8 185.8 137.4 144.3 39.8 148.0

194.2 91.6 −71.8 −83.5 86.0 90.0

230.0 121.0 −53.8 −66.2 120.0 183.8

248.2 135.4 −45.0 −57.1 135.8 140.7

210 14.1 105.8 155.8 37.9 28.2 109.6 112.8 117.7 125.8 303.6 200.8 51.2 113.8 87.2 295.4 187.5 31.5 101.0 74.3 117.8 105.9 240.0 190.0 223.8 204.2 149.8 160.0 53.9 166.0 192.2 266.1 150.2 −34.8 −47.7 152.4 158.1

235 27.5 122.1 172.8 51.8 41.8 126.3 130.7 136.0 143.3 323.2 220.0 66.0 129.0 103.4 314.2 207.4 45.1 115.2 89.8 135.6 123.8 257.2 210.0 244.4 223.8 163.7 178.5 69.9 186.2 211.2 285.6 167.7 −23.4 −37.0 171.9 178.2

251 35.5 132.6 181.7 60.5 50.3 137.6 142.5 147.9 153.8 334.8 232.8 75.5 139.0 113.8 326.8 219.7 53.8 123.8 90.0 145.6 135.4 269.8 222.6 256.0 236.6 172.3 190.1 80.0 199.0 223.4 298.4 178.4 −16.5 −30.0 184.2 191.0

46.6 146.4 194.1 72.3 62.0 151.5 156.9 163.0 168.5 350.0 248.0 88.1 151.3 127.4 341.8 236.0 65.7 135.2 111.7 159.1 150.0 286.0 239.5 271.5 251.5 184.4 205.5 93.5 216.0 239.6 314.0 194.0 −6.7 −20.6 200.0 208.0

63.5 167.6 213.0 90.2 80.0 173.7 180.3 186.7 191.7 373.2 271.8 107.5 170.5 148.2 364.8 260.6 83.6 152.0 130.4 180.2 173.3 309.8 264.1 298.7 277.1 203.1 227.0 114.0 241.8 261.8 339.0 216.1 +8.0 −6.7 224.1 230.3

82.0 191.0 233.5 110.6 99.8 197.7 206.8 212.5 217.5 397.2 299.8 128.2 192.1 171.2 388.9 288.0 104.0 173.8 151.0 204.0 199.3 334.7 292.3 326.0 304.5 227.5 251.6 137.2 269.3 285.0 365.4 242.8 24.7 +8.3 250.2 257.2

101.2 214.5 253.0 131.6 120.3 222.3 231.9 238.3 244.0 421.8 330.0 150.8 213.5 195.0 412.5 317.0 125.6 195.2 172.9 227.0 225.5 360.0 321.0 353.8 332.0 253.5 276.0 160.5 299.0 309.3 390.3 270.5 42.1 26.1 277.0 285.0

11 −29 45 −108 −93 −4.1 15.5 51.9 +2 63.8 32 −53.7 −5 −19 61.6 28 −56.8 −15.4 −16 −45.9 14 34 64.0 31 12.5 85.5 −22 188.5 53.3 10

(Continued)

2.339

2.340 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name n-Pentane iso-Pentane (2-methylbutane) neo-Pentane (2,2-dimethylpropane) 2,3,4-Pentanetriol 1-Pentene a-Phellandrene Phenanthrene Phenethyl alcohol (phenyl cellosolve) 2-Phenetidine Phenol 2-Phenoxyethanol 2-Phenoxyethyl acetate Phenyl acetate Phenylacetic acid Phenylacetonitrile Phenylacetyl chloride Phenyl benzoate 4-Phenyl-3-buten-2-one Phenyl isocyanate isocyanide Phenylcyclohexane Phenyl dichlorophosphate m-Phenylene diamine (1,3-phenylenediamine) Phenylglyoxal Phenylhydrazine N-Phenyliminodiethanol 1-Phenyl-1,3-pentanedione 2-Phenylphenol 4-Phenylphenol 3-Phenyl-1-propanol

1

5

10

20

C6H8N2 C8H6O2 C6H8N2 C10H15NO2 C11H12O2 C12H10O C12H10O C9H12O

60

100

200

400

760

Temperature, °C

Formula C5H12 C5H12 C5H12 C5H12O3 C5H10 C10H16 C14H10 C8H10O2 C8H11NO C6H6O C8H10O2 C10H12O3 C8H8O2 C8H8O2 C8H7N C8H7ClO C13H10O2 C10H10O C7H5NO C7H5N C12H16 C6H5Cl2O2P

40

Melting Point, °C

−76.6 −82.9 −102.0 155.0 −80.4 20.0 118.2 58.2 67.0 40.1 78.0 82.6 38.2 97.0 60.0 48.0 106.8 81.7 10.6 12.0 67.5 66.7

−62.5 −65.8 −85.4 159.3 −63.3 45.7 154.3 85.9 94.7 62.5 196.6 143.5 64.8 127.0 89.0 75.3 141.5 112.2 36.0 37.0 96.5 95.9

−50.1 −57.0 −76.7 204.5 −54.5 58.0 173.0 100.0 108.6 73.8 121.2 128.0 78.0 141.3 103.5 89.0 157.8 127.4 48.5 49.7 111.3 110.0

−40.2 −47.3 −67.2 220.5 −46.0 72.1 193.7 114.8 123.7 86.0 136.0 144.5 92.3 156.0 119.4 103.6 177.0 143.8 62.5 63.4 126.4 125.9

−29.2 −36.5 −56.1 239.6 −34.1 87.8 215.8 130.5 139.9 100.1 152.2 162.3 108.1 173.6 136.3 119.8 197.6 161.3 77.7 78.3 144.0 143.4

−22.2 −29.6 −49.0 249.8 −27.1 97.6 229.9 141.2 149.8 108.4 163.2 174.0 118.1 184.5 147.7 129.8 210.8 172.6 87.7 88.0 154.2 153.6

−12.6 −20.2 −39.1 263.5 −17.7 110.6 249.0 154.0 163.5 121.4 176.5 189.2 131.6 198.2 161.8 143.5 277.8 187.8 100.6 101.0 169.3 168.0

+1.9 −5.9 −23.7 284.5 −3.4 130.6 277.1 175.0 184.0 139.0 197.6 211.3 151.2 219.5 184.2 163.8 254.0 211.0 120.8 120.8 191.3 189.8

18.5 +10.5 −7.1 307.0 +12.8 152.0 308.0 197.5 207.0 160.0 221.0 235.0 173.5 243.0 208.5 186.0 283.5 235.4 142.7 142.3 214.6 213.0

36.1 27.8 +9.5 327.2 30.1 175.0 340.2 219.5 228.0 181.9 245.3 259.7 195.9 265.5 233.5 210.0 314.0 261.0 165.6 165.0 240.0 239.5

−129.7 −159.7 −16.6

99.8 75.8 145.0 98.0 100.0

131.2 75.0 101.6 170.2 128.5 131.6 102.4

163.8 100.7 131.5 213.4 159.9 163.3 193.8 131.2

182.5 115.5 148.2 233.0 178.0 180.3 213.0 147.4

194.0 124.2 158.7 245.3 189.8 192.2 225.3 156.8

209.9 136.2 173.5 260.6 204.5 205.9 240.9 170.3

233.0 153.8 195.4 284.5 226.7 227.9 263.2 191.2

259.0 173.5 218.2 311.3 251.2 251.8 285.5 212.8

285.5 193.5 243.5 337.8 276.5 275.0 308.0 235.0

62.8 73 19.5

74.7

147.0 87.8 115.8 195.8 144.0 146.2 176.2 116.0

99.5

40.6 11.6 −6.7 76.5 −23.8 70.5 41.5 +75

56.5 164.5

Phenyl isothiocyanate Phorone iso-Phorone Phosgene (carbonyl chloride) Phthalic anhydride Phthalide Phthaloyl chloride 2-Picoline Pimelic acid a-Pinene b-Pinene Piperidine Piperonal Propane Propenylbenzene Propionamide Propionic acid anhydride Propionitrile Propiophenone n-Propyl acetate iso-Propyl acetate n-Propyl alcohol (1-propanol) iso-Propyl alcohol (2-propanol) n-Propylamine Propylbenzene Propyl benzoate n-Propyl bromide (1-bromopropane) iso-Propyl bromide (2-bromopropane) n-Propyl n-butyrate isobutyrate iso-Propyl isobutyrate Propyl carbamate n-Propyl chloride (1-chloropropane) iso-Propyl chloride (2-chloropropane) iso-Propyl chloroacetate Propyl chloroglyoxylate

C7H5NS C9H14O C9H14O CCl2O C8H4O3 C8H6O2 C8H4Cl2O2 C6H7N C7H12O4 C10H16 C10H16 C5H11N C8H6O3 C3H8 C9H10 C3H7NO C3H6O2 C6H10O3 C3H5N C9H10O C5H10O2 C5H10O2 C3H8O C3H8O C3H9N C9H12 C10H12O2 C3H7Br C3H7Br C7H14O2 C7H14O2 C7H14O2 C4H9NO2 C3H7Cl C3H7Cl C5H9ClO2 C5H7ClO3

47.2 42.0 38.0 −92.9 96.5 95.5 86.3 −11.1 163.4 −1.0 +4.2 87.0 −128.9 17.5 65.0 4.6 20.6 −35.0 50.0 −26.7 −38.3 −15.0 −26.1 −64.4 6.3 54.6 −53.0 −61.8 −1.6 −6.2 −16.3 52.4 −68.3 −78.8 +3.8 9.7

75.6 63.3 66.7 −77.0 124.3 127.7 118.3 +12.6 196.2 +24.6 30.0 −7.0 117.4 −115.4 43.8 91.0 28.0 45.3 −13.6 77.9 −5.4 −17.4 +5.0 −7.0 −46.3 31.3 83.8 −33.4 −42.5 +22.1 +16.8 +5.8 77.6 −50.0 −61.1 28.1 32.3

89.8 81.5 81.2 −69.3 134.0 144.0 134.2 24.4 212.0 37.3 42.3 +3.9 132.0 −108.5 57.0 105.0 39.7 57.7 −3.0 92.2 +5.0 −7.2 14.7 +2.4 −37.2 43.4 98.0 −23.3 −32.8 34.0 28.3 17.0 90.0 −41.0 −52.0 40.2 43.5

115.5 95.6 96.8 −60.3 151.7 161.3 151.0 37.4 229.3 51.4 58.1 15.8 148.0 −100.9 71.5 119.0 52.0 70.4 +8.8 107.6 16.0 +4.2 25.3 12.7 −27.1 56.8 114.3 −12.4 −22.0 47.0 40.6 29.0 103.2 −31.0 −42.0 53.9 55.6

122.5 111.3 114.5 −50.3 172.0 181.0 170.0 51.2 247.0 66.8 71.5 29.2 165.7 −92.4 87.7 134.8 65.8 85.6 22.0 124.3 28.8 17.0 36.4 23.8 −16.0 71.6 131.8 −0.3 −10.1 61.5 54.3 42.4 117.7 −19.5 −31.0 68.7 68.8

133.3 121.4 125.6 −44.0 185.3 193.5 182.2 59.9 258.2 76.8 81.2 37.7 177.0 −87.0 97.8 144.3 74.1 94.5 30.1 135.0 37.0 25.1 43.5 30.5 −9.0 81.1 143.3 +7.5 −2.5 70.3 63.0 51.4 126.5 −12.1 −23.5 78.0 77.2

147.7 134.0 140.6 −35.6 202.3 210.0 197.8 71.4 272.0 90.1 94.0 49.0 191.7 −79.6 111.7 156.0 85.8 107.2 41.4 149.3 47.8 35.7 52.8 39.5 +0.5 94.0 157.4 18.0 +8.0 82.6 73.9 62.3 138.3 −2.5 −13.7 90.3 88.0

169.6 153.5 163.3 −22.3 228.0 234.5 222.0 89.0 294.5 110.2 114.1 66.2 214.3 −68.4 132.0 174.2 102.5 127.8 58.2 170.2 64.0 51.7 66.8 53.0 15.0 113.5 180.1 34.0 23.8 101.0 91.8 80.2 155.8 +12.2 +1.3 108.8 104.7

194.0 175.3 188.7 −7.6 256.8 261.8 248.3 108.4 318.5 132.3 136.1 85.7 238.5 −55.6 154.7 194.0 122.0 146.0 77.7 194.2 82.0 69.8 82.0 67.8 31.5 135.7 205.2 52.0 41.5 121.7 112.0 100.0 175.8 29.4 18.1 128.0 123.0

218.5 197.2 215.2 +8.3 284.5 290.0 275.8 128.8 342.1 155.0 158.3 106.0 263.0 −42.1 179.0 213.0 141.1 167.0 97.1 218.0 101.8 89.0 97.8 82.5 48.5 159.2 231.0 71.0 60.0 142.7 133.9 120.5 195.0 46.4 36.5 148.6 150.0

−21.0 28 −104 130.8 73 88.5 −70 103 −55 −9 37 −187.1 −30.1 79 −22 −45 −91.9 21 −92.5 −127 −85.8 −83 −99.5 −51.6 −109.9 −89.0 −95.2

−112.8 −117

(Continued)

2.341

2.342 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound

1

5

10

20

40

60

100

200

400

760

Temperature, °C

Melting Point, °C

Name

Formula

Propylene Propylene glycol (1,2-Propanediol) Propylene oxide n-Propyl formate iso-Propyl formate 4,4′-iso-Propylidenebisphenol n-Propyl iodide (1-iodopropane) iso-Propyl iodide (2-iodopropane) n-Propyl levulinate iso-Propyl levulinate Propyl mercaptan (1-propanethiol) 2-iso-Propylnaphthalene iso-Propyl b-naphthyl ketone (2-isobutyronaphthone) 2-iso-Propylphenol 3-iso-Propylphenol 4-iso-Propylphenol Propyl propionate 4-iso-Propylstyrene Propyl isovalerate Pulegone Pyridine Pyrocatechol Pyrocaltechol diacetate (1,2-phenylene diacetate) Pyrogallol Pyrotartaric anhydride Pyruvic acid Quinoline iso-Quinoline Resorcinol

C3H6 C3H8O2 C3H6O C4H8O2 C4H8O2 C15H16O2 C3H7I C3H7I C8H14O3 C8H14O3 C3H8S C13H14 C14H14O

−131.9 45.5 −75.0 −43.0 −52.0 193.0 −36.0 −43.3 59.7 48.0 −56.0 76.0 133.2

−120.7 70.8 −57.8 −22.7 −32.7 224.2 −13.5 −22.1 86.3 74.5 −36.3 107.9 165.4

−112.1 83.2 −49.0 −12.6 −22.7 240.8 −2.4 −11.7 99.9 88.0 −26.3 123.4 181.0

−104.7 96.4 −39.3 −1.7 −12.1 255.5 +10.0 0.0 114.0 102.4 −15.4 140.3 197.7

−96.5 111.2 −28.4 +10.8 −0.2 273.0 23.6 +13.2 130.1 118.1 −3.2 159.0 215.6

−91.3 119.9 −21.3 18.8 +7.5 282.9 32.1 21.6 140.6 127.8 +4.6 171.4 227.0

−84.1 132.0 −12.0 29.5 17.8 297.0 43.8 32.8 154.0 141.8 15.3 187.6 242.3

−73.3 149.7 +2.1 45.3 33.6 317.5 61.8 50.0 175.6 161.6 31.5 211.8 264.0

−60.9 168.1 17.8 62.6 50.5 339.0 81.8 69.5 198.0 185.2 49.2 238.5 288.2

−47.7 188.2 34.5 81.3 68.3 360.5 102.5 89.5 221.2 208.2 67.4 266.0 313.0

C9H12O C9H12O C9H12O C6H12O2 C11H14 C8H16O2 C10H16O C5H5N C6H6O2 C10H10O4

56.6 62.0 67.0 −14.2 34.7 +8.0 58.3 −18.9

97.0 104.1 108.0 19.4 76.0 45.1 94.0 13.2 118.3 145.7

111.7 119.8 123.4 31.6 91.2 58.0 106.8 24.8 134.0 161.8

127.5 136.2 139.8 45.0 108.0 72.8 121.7 38.0 150.6 179.8

137.7 146.6 149.7 53.8 118.4 82.3 130.2 46.8 161.7 191.6

150.3 160.2 163.3 65.2 132.8 95.0 143.1 57.8 176.0 206.5

170.1 182.0 184.0 82.7 153.9 113.9 162.5 75.0 197.7 228.7

192.6 205.0 206.1 102.0 178.0 135.0 189.8 95.6 221.5 253.3

214.5 228.0 228.2 122.4 202.5 155.9 221.0 115.4 245.5 278.0

15.5 26 61 −76

98.0

83.8 90.3 94.7 +8.0 62.3 32.8 82.5 +2.5 104.0 129.8 151.7 99.7 45.8 89.6 92.7 138.0

167.7 114.2 57.9 103.8 107.8 152.1

185.3 130.0 70.8 119.8 123.7 168.0

204.2 147.8 85.3 136.7 141.6 185.3

216.3 158.6 94.1 148.1 152.0 195.8

232.0 173.8 106.5 163.2 167.6 209.8

255.3 196.1 124.7 186.2 190.0 230.8

281.5 221.0 144.7 212.3 214.5 253.4

309.0 247.4 165.0 237.7 240.5 276.5

133

69.7 21.4 59.7 63.5 108.4

C6H6O3 C5H6O3 C3H4O3 C9H7N C9H7N C6H6O2

−185 −112.1 −92.9 −98.8 −90 −112

−42 105

13. −15. 24. 110.

Safrole Salicylaldehyde Salicylic acid Sebacic acid Selenophene Skatole Stearaldehyde Stearic acid Stearyl alcohol (1-octadecanol) Styrene Styrene dibromide [(1,2-dibromoethyl) benzene] Suberic acid Succinic anhydride Succinimide Succinyl chloride a-Terpineol Terpenoline 1,1,1,2-Tetrabromoethane 1,1,2,2-Tetrabromoethane Tetraisobutylene Tetracosane 1,2,3,4-Tetrachlorobenzene 1,2,3,5-Tetrachlorobenzene 1,2,4,5-Tetrachlorobenzene 1,1,2,2-Tetrachloro-1,2-difluoroethane 1,1,1,2-Tetrachloroethane 1,1,2,2-Tetrachloroethane 1,2,3,5-Tetrachloro-4-ethylbenzene Tetrachloroethylene 2,3,4,6-Tetrachlorophenol 3,4,5,6-Tetrachloro-1,2-xylene Tetradecane Tetradecylamine Tetradecyltrimethylsilane Tetraethoxysilane 1,2,3,4-Tetraethylbenzene

C10H10O2 C7H6O2 C7H6O3 C10H18O4 C4H4Se C9H9N C18H36O C18H36O2 C18H36O C8H8 C8H8Br2

63.8 33.0 113.7 183.0 −39.0 95.0 140.0 173.7 150.3 −7.0 86.0

93.0 60.1 136.0 215.7 −16.0 124.2 174.6 209.0 185.6 +18.0 115.6

107.6 73.8 146.2 232.0 −4.0 139.6 192.1 225.0 202.0 30.8 129.8

123.0 88.7 156.8 250.0 +9.1 154.3 210.6 243.4 220.0 44.6 145.2

140.1 105.2 172.2 268.2 24.1 171.9 230.8 263.3 240.4 59.8 161.8

150.3 115.7 182.0 279.8 33.8 183.6 244.2 275.5 252.7 69.5 172.2

165.1 129.4 193.4 294.5 47.0 197.4 260.0 291.0 269.4 82.0 186.3

186.2 150.0 210.0 313.2 66.7 218.8 285.0 316.5 293.5 101.3 207.8

210.0 173.7 230.5 332.8 89.8 242.5 313.8 343.0 320.3 122.5 230.0

233.0 196.5 256.0 352.3 114.3 266.2 342.5 370.0 349.5 145.2 245.0

C8H14O4 C4H4O3 C4H5NO2 C4H4Cl2O2 C10H18O C10H16 C2H2Br4 C2H2Br4 C16H32 C24H50 C6H2Cl4 C6H2Cl4 C6H2Cl4 C2Cl4F2 C2H2Cl4 C2H2Cl4 C8H6Cl4 C2Cl4 C6H2Cl4O C8H6Cl4 C14H30 C14H31N C17H38Si C8H20O4Si C14H22

172.8 92.0 115.0 39.0 52.8 32.3 58.0 65.0 63.8 183.8 68.5 58.2

205.5 115.0 143.2 65.0 80.4 58.0 83.3 95.5 93.7 219.6 99.6 89.0

219.5 128.2 157.0 78.0 94.3 70.6 95.7 110.0 108.5 237.6 114.7 104.1

238.2 145.3 174.0 91.8 109.8 84.8 108.5 126.0 124.5 255.3 131.2 121.6

−37.5 −16.3 −3.8 77.0 −20.6 100.0 94.4 76.4 102.6 120.0 16.0 65.7

−16.0 +7.4 +20.7 110.0 +2.4 130.3 125.0 106.0 135.8 150.7 40.3 96.2

−5.0 19.3 33.0 126.0 13.8 145.5 140.3 120.7 152.0 166.2 52.6 111.6

+6.7 32.1 46.2 143.7 26.3 161.0 156.0 135.6 170.0 183.5 65.8 127.7

254.6 163.0 192.0 107.5 126.0 100.0 123.2 144.0 142.2 276.3 149.2 140.0 146.0 19.8 46.7 60.8 162.1 40.1 179.1 174.2 152.7 189.0 201.5 81.1 145.8

265.4 174.0 203.0 117.2 136.3 109.8 132.0 155.1 152.6 288.4 160.0 152.0 157.7 28.1 56.0 70.0 175.0 49.2 190.0 185.8 164.0 200.2 213.3 90.7 156.7

279.8 189.0 217.4 130.0 150.1 122.7 144.0 170.0 167.5 305.2 175.7 168.0 173.5 33.6 68.0 83.2 191.6 61.3 205.2 200.5 178.5 215.7 227.8 103.6 172.4

300.5 212.0 240.0 149.3 171.2 142.0 161.5 192.5 190.0 330.5 198.0 193.7 196.0 55.0 87.2 102.2 215.3 79.8 227.2 223.0 201.8 239.8 250.0 123.5 196.0

322.8 237.0 263.5 170.0 194.3 163.5 181.0 217.5 214.6 358.0 225.5 220.0 220.5 73.1 108.2 124.0 243.0 100.0 250.4 248.3 226.8 264.6 275.0 146.2 221.4

345.5 261.0 287.5 192.5 217.5 185.0 200.0 243.5 240.0 386.4 254.0 246.0 245.0 92.0 130.5 145.9 270.0 120.8 275.0 273.5 252.5 291.2 300.0 168.5 248.0

11 −7 159 134. 95 63.5 69.3 58.5 −30.6

142 119.6 125.5 17 35

51.1 46.5 54.5 139 2 −6 −3 −1 69 5

11

(Continued)

2.343

2.344 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound Name Tetraethylene glycol Tetraethylene glycol chlorohydrin Tetraethyllead Tetraethylsilane Tetralin 1,2,3,4-Tetramethylbenzene 1,2,3,5-Tetramethylbenzene 1,2,4,5-Tetramethylbenzene 2,2,3,3-Tetramethylbutane Tetramethylene dibromide (1,4-dibromobutane) Tetramethyllead Tetramethyltin Tetrapropylene glycol monoisopropyl ether Thioacetic acid (mercaptoacetic acid) Thiodiglycol (2,2′-thiodiethanol) Thiophene Thiophenol (benzenethiol) a-Thujone Thymol Tiglaldehyde Tiglic acid Tiglonitrile Toluene Toluene-2,4-diamine 2-Toluic nitrile (2-tolunitrile) 4-Toluic nitrile (4-tolunitrile) 2-Toluidine 3-Toluidine 4-Toluidine 2-Tolyl isocyanide

1

5

10

20

40

60

100

200

400

760

Temperature, °C

Formula C8H18O5 C8H17ClO4 C8H20Pb C8H20Si C10H12 C10H14 C10H14 C10H14 C8H18 C4H8Br2

153.9 110.1 38.4 −1.0 38.0 42.6 40.6 45.0 −17.4 32.0

183.7 141.8 63.6 +23.9 65.3 68.7 65.8 65.0 +3.2 58.8

197.1 156.1 74.8 36.3 79.0 81.8 77.8 74.6 13.5 72.4

212.3 172.6 88.0 50.0 93.8 95.8 91.0 88.0 24.6 87.6

228.0 190.0 102.4 65.3 110.4 111.5 105.8 104.2 36.8 104.0

237.8 200.5 111.7 74.8 121.3 121.8 115.4 114.8 44.5 115.1

250.0 214.7 123.8 88.0 135.3 135.7 128.3 128.1 54.8 128.7

268.4 236.5 142.0 108.0 157.2 155.7 149.9 149.5 70.2 149.8

288.0 258.2 161.8 130.2 181.8 180.0 173.7 172.1 87.4 173.8

307.8 281.5 183.0 153.0 207.2 204.4 197.9 195.9 106.3 197.5

C4H12Pb C4H12Sn C15H32O15 C2H4O2S C4H10O2S C4H4S C6H6S C10H16O C10H14O C5H8O C5H8O2 C5H7N C7H8 C7H10N2 C8H7N C8H7N C7H9N C7H9N C7H9N C8H7N

−29.0 −51.3 116.6 60.0 42.0 −40.7 18.6 38.3 64.3 −25.0 52.0 −25.5 −26.7 106.5 36.7 42.5 44.0 41.0 42.0 25.2

−6.8 −31.0 147.8 87.7 96.0 −20.8 43.7 65.7 92.8 −1.6 77.8 −2.4 −4.4 137.2 64.0 71.3 69.3 68.0 68.2 51.0

+4.4 −20.6 163.0 101.5 128.0 −10.9 56.0 79.3 107.4 +10.0 90.2 +9.2 +6.4 151.7 77.9 85.8 81.4 82.0 81.8 64.0

16.6 −9.3 179.8 115.8 165.0 0.0 69.7 93.7 122.6 23.2 103.8 22.1 18.4 167.9 93.0 101.7 95.1 96.7 95.8 78.2

30.3 +3.5 197.7 131.8 210.0 +12.5 84.2 110.0 139.8 37.0 119.0 36.7 31.8 185.7 110.0 109.5 110.0 113.5 111.5 94.0

39.2 11.7 209.0 142.0 240.5 20.1 93.9 120.2 149.8 45.8 127.8 46.0 40.3 196.2 120.8 130.0 119.8 123.8 121.5 104.0

50.8 22.8 223.3 154.0 285 30.5 106.6 134.0 164.1 57.7 140.5 58.2 51.9 211.5 135.0 145.2 133.0 136.7 133.7 117.7

68.8 39.8 245.0

89.0 58.5 268.3

110.0 78.0 292.7

Melting Point, °C

−136 −31 −6 −24 79 −102 −20 −27 −16.5

46.5 125.8 154.2 185.5 75.4 158.0 77.8 69.5 232.8 156.0 167.3 153.0 157.6 154.0 137.8

64.7 146.7 177.8 209.6 95.5 179.2 99.7 89.5 256.0 180.0 193.0 176.2 180.6 176.9 159.9

84.4 168.0 201.0 231.8 116.8 198.5 122.0 110.6 280.0 205.2 217.6 199.7 203.3 200.4 183.5

−38.3

51 64 −95 99 −13 29 −16 −31 44

4-Tolylhydrazine Tribromoacetaldehyde 1,1,2-Tribromobutane 1,2,2-Tribromobutane 2,2,3-Tribromobutane 1,1,2-Tribromoethane 1,2,3-Tribromopropane Triisobutylamine Triisobutylene 2,4,6-Tritertbutylphenol Trichloroacetic acid Trichloroacetic anhydride Trichloroacetyl bromide 2,4,6-Trichloroaniline 1,2,3-Trichlorobenzene 1,2,4-Trichlorobenzene 1,3,5-Trichlorobenzene 1,2,3-Trichlorobutane 1,1,1-Trichloroethane 1,1,2-Trichloroethane Trichloroethylene Trichlorofluoromethane 2,4,5-Trichlorophenol 2,4,6-Trichlorophenol Tri-2-chlorophenylthiophosphate 1,1,1-Trichloropropane 1,2,3-Trichloropropane 1,1,2-Trichloro-1,2,2-trifluoroethane Tricosane Tridecane Tridecanoic acid Triethoxymethylsilane Triethoxyphenylsilane 1,2,4-Triethylbenzene 1,3,4-Triethylbenzene

C7H10N2 C2HBr3O C4H7Br3 C4H7Br3 C4H7Br3 C2H3Br3 C3H5Br3 C12H27N C12H24 C18H30O C2HCl3O2 C4Cl6O3 C2BrCl3O C6H4Cl3N C6H3Cl3 C6H3Cl3 C6H3Cl3 C4H7Cl3 C2H3Cl3 C2H3Cl3 C2HCl3 CCl3F C6H3Cl3O C6H3Cl3O C18H12Cl3O3 PS C3H5Cl3 C3H5Cl3 C2Cl3F3 C23H48 C13H28 C13H26O2 C7H18O3Si C12H20O3Si C12H18 C12H18

82.4 18.5 45.0 41.0 38.2 32.6 47.5 32.3 18.0 95.2 51.0 56.2 −7.4 134.0 40.0 38.4 +0.5 −52.0 −24.0 −43.8 −84.3 72.0 76.5 188.2

110.0 45.0 73.5 69.0 66.0 58.0 75.8 57.4 44.0 126.1 76.0 85.3 +16.7 157.8 70.0 67.3 63.8 27.2 −32.0 −2.0 −22.8 −67.6 102.1 105.9 217.2

123.8 58.0 87.8 83.2 79.8 70.6 90.0 69.8 56.5 142.0 88.2 99.6 29.3 170.0 85.6 81.7 78.0 40.0 −21.9 +8.3 −12.4 −59.0 117.3 120.2 231.2

138.6 72.1 103.2 98.6 94.6 84.2 105.8 83.0 70.0 158.0 101.8 114.3 42.1 182.6 101.8 97.2 93.7 55.0 −10.8 21.6 −1.0 −49.7 134.0 135.8 246.7

154.1 87.8 120.2 116.0 111.8 100.0 122.8 97.8 86.7 177.4 116.3 131.2 57.2 195.8 119.8 114.8 110.8 71.5 +1.6 35.2 +11.9 −39.0 151.5 152.2 261.7

165.0 97.5 131.6 127.0 122.2 110.0 134.0 107.3 96.7 188.0 125.9 141.8 66.7 204.5 131.5 125.7 121.8 82.0 9.5 44.0 20.0 −32.3 162.5 163.5 271.5

178.0 110.2 146.0 141.8 136.3 123.5 148.0 119.7 110.0 203.0 137.8 155.2 79.5 214.6 146.0 140.0 136.0 96.2 20.0 55.7 31.4 −23.0 178.0 177.8 283.8

198.0 130.0 167.8 163.5 157.8 143.5 170.0 138.0 130.2 226.2 155.4 176.2 98.4 229.8 168.2 162.0 157.7 118.0 36.2 73.3 48.0 −9.1 201.5 199.0 302.8

219.5 151.6 192.0 188.0 182.2 165.4 195.0 157.8 153.0 250.6 175.2 199.8 120.2 246.4 193.5 187.7 183.0 143.0 54.6 93.0 67.0 +6.8 226.5 222.5 322.0

242.0 174.0 216.2 213.8 206.5 188.4 220.0 179.0 179.0 276.3 195.6 223.0 143.0 262.0 218.5 213.0 208.4 169.0 74.1 113.9 86.7 23.7 251.8 246.0 341.3

−28.8 +9.0 −68.0 170.0 59.4 137.8 −1.5 71.0 46.0 47.9

−7.0 33.7 −49.4 206.3 98.3 166.3 +22.8 98.8 74.2 76.0

+4.2 46.0 −40.3 223.0 104.0 181.0 34.6 112.6 88.5 90.2

16.2 59.3 −30.0 242.0 120.2 195.8 47.2 127.2 104.0 105.8

29.9 74.0 −18.5 261.3 137.7 212.4 61.7 143.5 121.7 122.6

38.3 83.6 −11.2 273.8 148.2 222.0 70.4 153.2 132.2 133.4

50.0 96.1 −1.7 289.8 162.5 236.0 82.7 167.5 146.8 147.7

67.7 115.6 +13.5 313.5 185.0 255.2 101.0 188.0 168.3 168.3

87.5 137.0 30.2 339.8 209.4 276.5 121.8 210.5 193.7 193.2

108.2 158.0 47.6 366.5 234.0 299.0 143.5 233.5 218.0 217.5

65.5

−26 16.5 −22

57

78 52.5 17 63.5 −30.6 −36.7 −73 62 68. −77. −14. −35 47. −6.2 41

(Continued)

2.345

2.346 TABLE 2.37 Boiling Points of Common Organic Compounds at Selected Pressures (Continued) Pressure, mm Hg Compound

1

Name

Formula

Triethylborine Triethyl camphoronate citrate Triethyleneglycol Triethylheptylsilane Triethyloctylsilane Triethyl orthoformate phosphate Triethylthallium Trifluorophenylsilane Trimethallyl phosphate 2,3,5-Trimethylacetophenone Trimethylamine 2,4,5-Trimethylaniline 1,2,3-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3,5-Trimethylbenzene 2,2,3-Trimethylbutane Trimethyl citrate Trimethyleneglycol (1,3-propandiol) 1,2,4-Trimethyl-5-ethylbenzene 1,3,5-Trimethyl-2-ethylbenzene 2,2,3-Trimethylpentane 2,2,4-Trimethylpentane 2,3,3-Trimethylpentane 2,3,4-Trimethylpentane 2,2,4-Trimethyl-3-pentanone Trimethyl phosphate 2,4,5-Trimethylstryene 2,4,6-Trimethylsytrene Trimethylsuccinic anhydride

C6H15B C15H26O6 C12H20O7 C6H14O4 C13H30Si C14H32Si C7H16O3 C6H15O4P C6H15Tl C6H5F3Si C12H21PO4 C11H14O C3H9N C9H13N C9H12 C9H12 C9H12 C7H16 C9H14O7 C3H8O2 C11H16 C11H16 C8H18 C8H18 C8H18 C8H18 C8H16O C3H9O4P C11H14 C11H14 C7H10O3

5

10

20

40

60

100

200

400

760

−101.0 250.8 242.2 235.2 196.0 208.0 106.0 163.7 136.0 60.1 255.0 201.3 −27.0 182.3 129.0 122.7 118.6 41.2 241.3 172.8 160.3 158.4 67.8 58.1 72.0 71.3 102.2 145.0 171.8 157.8 179.8

−81.0 276.0 267.5 256.6 221.0 235.0 125.7 187.0 163.5 78.7 288.5 224.3 −12.5 203.7 152.0 145.4 141.0 60.4 264.2 193.8 184.5 183.5 88.2 78.0 92.7 91.8 118.4 167.8 196.1 182.3 205.5

−56.2 301.0 294.0 278.3 247.0 262.0 146.0 211.0 192.1 98.3 324.0 247.5 +2.9 234.5 176.1 169.2 164.7 80.9 287.0 214.2 208.1 208.0 109.8 99.2 114.8 113.5 135.0 192.7 221.2 207.0 231.0

Temperature, °C

107.0 114.0 70.0 73.7 +5.5 39.6 +9.3 −31.0 93.7 79.0 −97.1 68.4 16.8 13.6 9.6

150.2 138.7 144.0 99.8 104.8 29.2 67.8 37.6 −9.7 131.0 108.0 −81.7 95.9 42.9 38.3 34.7

106.2 59.4 43.7 38.8 −29.0 −36.5 −25.8 −26.3 14.7 26.0 48.1 37.5 53.5

146.2 87.2 71.2 67.0 −7.1 −15.0 −3.9 −4.1 36.0 53.7 77.0 65.7 82.6

−148.0 166.0 144.0 158.1 114.6 120.6 40.5 82.1 51.7 +0.8 149.8 122.3 −73.8 109.0 55.9 50.7 47.4 −18.8 160.4 100.6 84.6 80.5 +3.9 −4.3 +6.9 +7.1 46.4 67.8 91.6 79.7 97.4

−140.6 183.6 171.1 174.0 130.3 137.7 53.4 97.8 67.7 12.3 169.8 137.5 −65.0 123.7 69.9 64.5 61.0 −7.5 177.2 115.5 99.7 96.0 16.0 +7.5 19.2 19.3 57.6 83.0 107.1 94.8 113.8

−131.4 201.8 190.4 191.3 148.0 155.7 67.5 115.7 85.4 25.4 192.0 154.2 −55.2 139.8 85.4 79.8 76.1 +5.2 194.2 131.0 106.0 113.2 29.5 20.7 33.0 32.9 69.8 100.0 124.2 111.8 131.0

−125.2 213.5 202.5 201.5 158.2 168.0 76.0 126.3 95.7 33.2 207.0 165.7 −48.8 149.5 95.3 89.5 85.8 13.3 205.5 141.1 126.3 123.8 38.1 29.1 41.8 41.6 77.3 110.0 135.5 122.3 142.2

−116.0 228.6 217.8 214.6 174.0 184.3 88.0 141.6 112.1 44.2 225.7 179.7 −40.3 162.0 108.8 102.8 98.9 24.4 219.6 153.4 140.3 137.9 49.9 40.7 53.8 53.4 87.6 124.0 149.8 136.8 156.5

Melting Point, °C 135

−63.0

−117 67 −25 −44 −44 −25. 78.

−112. −107. −101. −109.

Triphenylmethane Triphenylphosphate Tripropyleneglycol Tripropyleneglycol monobutyl ether Tripropyleneglycol monoisopropyl ether Tritolyl phosphate Undecane Undecanoic acid 10-Undecenoic acid Undecan-2-ol n-Valeric acid iso-Valeric acid g-Valerolactone Valeronitrile Vanillin Vinyl acetate 2-Vinylanisole 3-Vinylanisole 4-Vinylanisole Vinyl chloride (1-chloroethylene) cyanide (acrylonitrile) fluoride (1-fluoroethylene) Vinylidene chloride (1,1-dichloroethene) 4-Vinylphenetole 2-Xenyl dichlorophosphate 2,4-Xyaldehyde 2-Xylene (2-xylene) 3-Xylene (3-xylene) 4-Xylene (4-xylene) 2,4-Xylidine 2,6-Xylidine

C19H16 C18H15O4P C9H20O4 C13H28O4 C12H26O4 C21H21O4P C11H24 C11H22O2 C11H20O2 C11H24O C5H10O2 C5H10O2 C5H8O2 C5H9N C8H8O3 C4H6O2 C9H10O C9H10O C9H10O C2H3Cl C3H3N C2H3F C2H2Cl2 C10H12O C12H9Cl2PO C9H10O C8H10 C8H10 C8H10 C8H11N C8H11N

169.7 193.5 96.0 101.5 82.4 154.6 32.7 101.4 114.0 71.1 42.2 34.5 37.5 −6.0 107.0 −48.0 41.9 43.4 45.2 −105.6 −51.0 −149.3 −77.2 64.0 138.2 59.0 −3.8 −6.9 −8.1 52.6 44.0

188.4 230.4 125.7 131.6 112.4 184.2 59.7 133.1 142.8 99.0 67.7 59.6 65.8 +18.1 138.4 −28.0 68.0 69.9 72.0 −90.8 −30.7 −138.0 −60.0 91.7 171.1 85.9 +20.2 +16.8 +15.5 79.8 72.6

197.0 249.8 140.5 147.0 127.3 198.0 73.9 149.0 156.3 112.8 79.8 71.3 79.8 30.0 154.0 −18.0 81.0 83.0 85.7 −83.7 −20.3 −132.2 −51.2 105.6 187.0 99.0 32.1 28.3 27.3 93.0 87.0

206.8 269.7 155.8 161.8 143.7 213.2 85.6 166.0 172.0 127.5 93.1 84.0 95.2 43.3 170.5 −7.0 94.7 97.2 100.0 −75.7 −9.0 −125.4 −41.7 120.3 205.0 114.0 45.1 41.1 40.1 107.6 102.7

215.5 290.3 173.7 179.8 161.4 229.7 104.4 185.6 188.7 143.7 107.8 98.0 101.9 57.8 188.7 +5.3 110.0 112.5 116.0 −66.8 +3.8 −118.0 −31.1 136.3 223.8 129.7 59.5 55.3 54.4 123.8 120.2

221.2 305.2 184.6 190.2 173.2 239.8 115.2 197.2 199.5 153.7 116.6 107.3 122.4 66.9 199.8 13.0 119.8 122.3 126.1 −61.1 11.8 −113.0 −24.0 146.4 236.0 139.8 68.8 64.4 63.5 133.7 131.5

228.4 322.5 199.0 204.4 187.8 252.2 128.1 212.5 213.5 167.2 128.3 118.9 136.5 78.6 214.5 23.3 132.3 135.3 139.7 −53.2 22.8 −106.2 −15.0 159.8 251.5 152.2 81.3 76.8 75.9 146.8 146.0

239.7 349.8 220.2 224.4 209.7 271.8 149.3 237.8 232.8 187.7 146.0 136.2 157.7 97.7 237.3 38.4 151.0 154.0 159.0 −41.3 38.7 −95.4 −1.0 180.0 275.3 172.3 100.2 95.5 94.6 166.4 168.0

249.8 379.2 244.3 247.0 232.8 292.7 171.9 262.8 254.0 209.8 165.0 155.2 182.3 118.7 260.0 55.5 172.1 175.8 182.0 −28.0 58.3 −84.0 +14.8 202.8 301.5 194.1 121.7 116.7 115.9 188.3 193.7

259.2 413.5 267.2 269.5 256.6 313.0 195.8 290.0 275.0 232.0 184.4 175.1 207.5 140.8 285.0 72.5 194.0 197.5 204.5 −13.8 78.5 −72.2 31.7 225.0 328.5 215.5 144.4 139.1 138.3 211.5 217.9

93.4 49.4

−25.6 29.5 24.5 −34.5 −37.6

81.5

−153.7 −82 −160.5 −122.5

75 −25.2 −47.9 +13.3

2.347

2.348

SECTION TWO

TABLE 2.38 Organic Solvents Arranged by Boiling Points

ORGANIC CHEMISTRY

2.349

TABLE 2.38 Organic Solvents Arranged by Boiling Points (Continued)

(Continued)

2.350

SECTION TWO

TABLE 2.38 Organic Solvents Arranged by Boiling Points (Continued)

TABLE 2.39 Boiling Points of n-Paraffins Carbon number 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

Boiling point, °C 36 69 98 126 151 174 196 216 235 253 271 287 302 317 331 344 356 369 380 391 402 412 422 432 441 450 459 468 476 483 491 498 505 512 518 525 531 537 543 548

Boiling point, °F 97 156 209 258 303 345 385 421 456 488 519 548 576 602 627 651 674 696 716 736 755 774 792 809 825 841 858 874 889 901 916 928 941 958 964 977 988 999 1009 1018

ORGANIC CHEMISTRY

2.351

2.6 FLAMMABILITY PROPERTIES The flash point of a substance is the lowest temperature at which the substance gives off sufficient vapor to form an ignitable mixture with air near its surface or within a vessel. The fire point is the temperature at which the flame becomes self-sustained and the burning continues. At the flash point, the flame does not need to be sustained. The fire point is usually a few degrees above the flash point. ASTM test methods include procedures using a closed cup (ASTM D-56, ASTM D-93, and ASTM D-3828), which is preferred, and an open cup (ASTM D-92, ASTM D-I310). When several values are available, the lowest temperature is usually taken in order to assure safe operation of the process. The ignition temperature (or ignition point) is the minimum temperature required to initiate selfsustained combustion of a substance (solid, liquid, or gaseous) and independent of external ignition sources or heat. Flash points, lower and upper flammability limits, and auto-ignition temperatures are the three properties that are used to indicate safe operating limits of temperature when processing organic materials. Prediction methods are somewhat erratic, but, together with comparisons with reliable experimental values for families or similar compounds, they are valuable in setting a conservative value for each of the properties. The upper and lower flammability limits are the boundary-line mixtures of vapor or gas with air, which, if ignited, will just propagate flame and are given in terms of percent by volume of gas or vapor in the air. Each of these limits also has a temperature at which the flammability limits are reached. The temperature corresponding to the lower-limit partial vapor pressure should equal the flash point. The temperature corresponding to the upper-limit partial vapor pressure is somewhat above the lower limit and is usually considerably below the auto-ignition temperature. Flammability limits are calculated at one atmosphere total pressure and are normally considered synonymous with explosive limits. Limits in oxygen rather than air are sometimes measured and available. Limits are generally reported at 298°K and 1 atmosphere. If the temperature or the pressure is increased, the lower limit will decrease while the upper limit will increase, giving a wider range of compositions over which flame will propagate. The auto-ignition temperature is the minimum temperature for a substance to initiate selfcombustion in air in the absence of a spark or flame. The temperature is no lower than and is generally considerably higher than the temperature corresponding to the upper flammability limit. Large differences can occur in reported values determined by different procedures. The lowest reasonable value should be accepted in order to assure safety. Values are also sometimes given in oxygen rather than in air. One simple method of estimating auto-ignition temperatures is to compare values for a compound with other members of its homologous series on a plot vs. carbon number as the temperature decreases and carbon number increases.

2.352

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

Acetal CH3CH(OC2H5)2 (Acetaldehydediethylacetal) Acetaldehyde CH3CHO (Acetic aldehyde) (Ethanal) Acetaldehydediethylacetal Acetaldel Acetanilide CH3CONHC6H5

215 (102)

−5 (−21)

446 (230)

70 (21)

−38 (−39)

347 (175)

Acetic Acid, Glacial CH3COOH Acetic Acid, Isopropyl Ester Acetic Acid, Methyl Ester Acetic Acid, n-Propyl Ester Acetic Aldehyde Acetic Anhydride (CH3CO)2O (Ethanoic anhydride) Acetic Ester Acetic Ether Acetoacetanilide CH3COCH2CONHC6H5 o-Acetoacet Anisidide CH3COCH2CONHC6H4OCH3 Acetoacetic Acid, Ethyl Ester Acetoethylamide Acetone CH3COCH3 (Dimethyl Ketone) (2-Propanone) Acetone Cyanohydrin (CH3)2C(OH)CN (2-Hydroxy2-Methyl Propionitrile) Acetonitrile CH3CN (Methyl Cyanide) Acetonyl Acetone (CH2COCH3)2 (2,5-Hexanedione) Acetophenone C6H5COCH3 (Phenyl Methyl Ketone) p-Acetotoluidide CH3CONHC6H4CH3 Acetyl Acetone Acetyl Chloride CH3COCl (Ethanoyl Chloride)

245 (118)

Compound

See Acetal. See Aldol. 582 (306)

985 ± 10 (530)

337 (169) (oc) 103 (39)

867 (463) See Isopropyl Acetate. See Methyl Acetate. See Propyl Acetate. See Acetaldehyde

284 (140)

120 (49)

600 (316) See Ethyl Acetate. See Ethyl Acetate.

133 (56)

365 (185) 325 (168) See Ethyl acetoacetate. See N-Ethylacetamide. −4 869 (−20) (465)

248 (120) Decomposes

165 (74)

1270 (688)

179 (82)

42 (6)

975 (524)

378 (192)

174 (79)

920 (499)

396 (202)

170 (77)

1058 (570)

583 (306)

334 (168)

124 (51)

40 (4)

See 2,4-Pentanedione. 734 (390)

ORGANIC CHEMISTRY

2.353

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Acetylene CH:CH (Ethine) (Ethyne) N-Acetyl Ethanolamine CH3C:ONHCH2CH2OH (N-(2-Hydroxyethyl) acetamide) N-Acetyl Morpholine CH3CONCH2CH2OCH2CH: Acetyl Oxide Acetylphenol Acrolein CH2:CHCHO (Acrylic Aldehyde) Acrylic Acid (Glacial) CH2CHCOOH Acrylic Aldehyde Acrylonitrile CH2:CHCN (Vinyl Cyanide) (Propenenitrile) Adipic Acid HOOC(CH2)4COOH Adipic Ketone Adiponitrile NC(CH2)4CN Alcohol Aldol CH3CH(OH)CH2CHO (3-Hydroxybutanal) (b-Hydroxybuteraldehyde)

Allyl Acetate CH3COCH2CH:CH2 Allyl Alcohol CH2:CHCH2OH Allylamine CH2:CHCH2NH2 (2-Propenylamine) Allyl Bromide CH2:CHCH2Br (3-Bromopropene) Allyl Caproate CH3(CH2)4COOCH2CH:Cl (Allyl Hexanoate) (2-Propenyl Hexanoate)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

−118 (−83)

Gas

581 (305)

304–308 (151–153) @10 mm Decomposes Decomposes

355 (179) (oc)

860 (460)

235 (113) See Acetic Anhydride. See Phenyl Acetate.

125 (52)

−15 (−26)

287 (142)

122 (50)

171 (77)

32 (0)

898 (481)

509 (265) @100 mm

385 (196)

788 (420)

563 (295)

200 (93)

428 (220) Unstable 820 (438) See Acrolein.

See Cyclopentanone.

See Ethyl Alcohol, Methyl Alcohol. 174–176 (79–80) @12 mm Decomposes @176 (80) 219 (104) 206 (97) 128 (53)

150 (66)

482 (250)

72 (22) 70 (21) −20 (−29)

705 (374) 713 (378) 705 (374)

160 (71)

30 (−1)

563 (295)

367–370 (186–188)

150 (66)

(Continued)

2.354

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Allyl Chloride CH2:CHCH2Cl (3-Chloropropene) Allyl Chlorocarbonate Allyl Chloroformate CH2:CHCH2OCOCl (Allyl Chlorocarbonate) Allylene Allyl Ether (CH2:CHCH2)2O (Diallyl Ether) Allylidene Diacetate CH2:CHCH(OCOCH3)2 Allyl Isothiocyanate Allylpropenyl Allyl Trichloride Allyl Vinyl Ether Alpha Methyl Pyridine Aminobenzene 2-Aminobiphenyl 1-Aminobutane 2-Amino-1-Butanol CH3CH2CHNH2CH2OH 1-Amino-4-Ethoxybenzene β-Aminoethyl Alcohol Amyl Acetate CH3COOC5H11 (1-Pentanol Acetate) Comm. sec-Amyl Acetate CH3COOCH(CH3)(CH2)2CH3 (2-Pentanol Acetate) Amyl Alcohol CH3(CH2)3CH2OH (1-Pentanol) sec-Amyl Alcohol CH3CH2CH2CH(OH)CH3 (Diethyl Carbinol) Amylamine C5H11NH2 (Pentylamine) sec-Amylamine CH3(CH2)2CH(CH3)NH2 (2-Aminopentane) (Methylpropylcarbinylamine) p-tert-Amylaniline (C2H5)(CH2)2CC6H4NH2 Amylbenzene C6H5C5H11 (Phenylpentane)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

113 (45)

−25 (−32)

737 (485)

223–237 (106–114)

See Allyl Chloroformate. 88 (31) See Propyne.

203 (95)

20 (−7)

225 (107) @50 mm

180 (82)

249 (121)

See Mustard Oil. See 1,4-Hexadiene. See 1,2,3-Trichloropropane. See Vinyl Allyl Ether. 2-Picoline. See Aniline. See 2-Biphenylamine. See Butylamine. 165 (74) See p-Phenetidine. See Ethanolamine. 60 680 (16) (360) 70 (21) 89 (32)

280 (138)

91 (33)

572 (300)

245 (118)

94 (34)

650 (343)

210 (99)

30 (−1)

198 (92)

20 (−7)

498–504 (259–262) 365 (185)

215 (102) 150 (66) (oc)

352 (178)

300 (149)

2.2

22

ORGANIC CHEMISTRY

2.355

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Amyl Bromide CH3CH2CH2CH2CH2Br (1-Bromopentane) Amyl Butyrate C5H11OOCC3H7 Amyl Carbinol Amyl Chloride CH3(CH2)3CH2Cl (1-Chloropentane) tert-Amyl Chloride CH3CH2CCl(CH3)CH3 Amyl Chlorides (Mixed) C5H11Cl Amylcyclohexane C5H11C6H11 Amylene β-Amylene-cis C2H5CH:CHCH3 (2-Pentene-cis) β-Amylene-trans C2H5CH:CHCH3 (2-Pentene-trans) Amylene Chloride Amyl Ether C5H11OC5H11 (Diamyl Ether) (Pentyloxypentane) Amyl Formate HCOCC5H11 Amyl Lactate C2H5OCOOCH2CH(CH3)C2H5 Amyl Laurate C11H23COOC5H11 Amyl Maleate (CHCOOC5H11)2 Amyl Mercaptan C5H11SH (1-Pentanethiol) Amyl Mercaptans (Mixed) CH3(CH2)4SH Amyl Naphthalene C10H7C5H11 Amyl Nitrate CH3(CH2)4NO2 Amyl Nitrite CH3(CH2)4NO2 Amyl Oleate C17H33COOC5H11 Amyl Oxalate (COOC5H11)2 (Diamyl Oxalate)

Boiling point °F (°C)

Flash point, °F (°C)

128–9 (53–54) @746 mm 365 (185)

90 (32) 135 (57)

223 (106)

55 (13)

Ignition point, °F (°C)

See Hexyl Alcohol.

187 (86) 185–228 (85–109) 395 (202)

38 (3)

99 (37)

<–4 (<–20)

97 (36)

<–4 (<–20)

500 (260) 653 (345)

462 (239) See 1-Pentene.

374 (190)

267 (131) 237–239 (114–115) @36 mm 554–626 (290–330) 518–599 (270–315) 260 (127) 176–257 (80–125) 550 (288) 306–315 (153–157) 220 (104) 392–464 (200–240) @20 mm 464–523 (240–273)

See 1,5-Dichloropentane. 135 338 (57) (170)

79 (26) 175 (79) 300 (149) 270 (132) 65 (18) 65 (18) 255 (124) 118 (48) 410 (210) 366 (186) 245 (118) (Continued)

2.356

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound o-Amyl Phenol C5H11C6H4OH p-tert-Amyl Phenol p-sec-Amylphenol C5H11C6H4OH 2-(p-tert-Amylphenoxy) Ethanol C5H11C6H4OCH2CH2OH 2-(p-tert-Amylphenoxy) Ethyl Laurate C11H23COO(CH2)2OC6H4C5H11 p-tert-Amylphenyl Acetate CH3COOC6H4C5H11 p-tert-Amylphenyl Butyl Ether C5H11C6H4OC4H9 Amyl Phenyl Ether CH3(CH2)4OC6H5 (Amoxybenzene) p-tert-Amylphenyl Methyl Ether C5H11C6H4OCH3 Amyl Phthalate Amyl Propionate C2H5COO(CH2)4CH3 (Pentyl Propionate) Amyl Salicylate HOC6H4COOC5H11 Amyl Stearate CH3(CH2)16COOC5H11 Amyl Sulfides, (Mixed) C5H11S Amyl Tolene C5H11C6H4CH3 Amyl Xylyl Ether C5H11OC6H3(CH3)2 Aniline C6H5NH2 (Aminobenzene) (Phenylamine) Aniline Hydrochloride C6H5NH2HCl 2-Anilinoethanol C6H5NHCH2CH2OH (b-Anilinoethanol Ethoxyaniline) (b-Hydroxyethylaniline) β-Anilinoethanol Ethoxyaniline o-Anisaldehyde o-Anisidine H2NC6H4OCH3 (2-Methoxyaniline)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

455–482 (235–250)

219 (104)

482–516 (250–269) 567–590 (297–310) 464–500 (240–260) @6 mm 507–511 (264–266)

270 (132) 280 (138) 410 (210)

540–550 (282–288)

275 (135)

421–444 (216–229)

185 (85)

462–469 (239–243)

210 (99)

275–347 (135–175)

106 (41)

712 (378)

512 (267) 680 (360) 338–356 (170–180) 400–415 (204–213) 480–500 (249–260) 364 (184)

270 (132) 365 (185) 185 (85) 180 (82) 205 (96) 158 (70)

1139 (615)

473 (245) 547 (286)

380 (193) 305 (152)

See Pentaphen.

240 (116)

See Diamyl Phthalate.

See 2-Anilinoethanol.

435 (224)

See o-Methoxy Benzaldehyde. 244 (118)

ORGANIC CHEMISTRY

2.357

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Anisole C6H5OCH3 (Methoxybenzene) (Methyl Phenyl Ether) Anol Anthracene (C6H4CH)2 Anthraquinone C6H4(CO)2C6H4 Asphalt (Petroleum Pitch) Aziridine Azobisisobutyronitrile N:CC(CH3)2N:NC(CH3)2C:N Benzaldehyde C6H5CHO (Benzenecarbonal) Benzedrine C6H5CH2CH(CH3)NH2 (1-Phenyl Isopropyl Amine) Benzene C6H6 (Benzol) Benzine Benzocyclobutene Benzoic Acid C6H5COOH Benzol p-Benzoquinone C6H4O2 (Quinone) Benzotrichloride C6H5CCl3 (Toluene, a,a,a-Trichloro) (Phenyl Chloroform) Benzotrifluoride C6H5CF3 Benzoyl Chloride C6H5COCl (Benzene Carbonyl Chloride) Benzyl Acetate CH3COOCH2C6H5 Benzyl Alcohol C6H5CH2OH (Phenyl Carbinol) Benzyl Benzoate C6H5COOCH2C6H5 Benzyl Butyl Phthalate C4H9COOC6H4COOCH2C6H5 (Butyl Benzyl Phthalate)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

309 (154)

125 (52)

887 (475)

644 (340) 716 (380) >700 (>371)

250 (121) 365 (185) 400+ (204+)

Decomposes 355 (179)

147 (64) 145 (63)

392 (200)

<212 (<100)

176 (80)

12 (−11)

306 (152) 482 (250)

95 (35) 250 (121)

Sublimes

100–200 (38–93)

1040 (560)

429 (221)

260 (127)

412 (211)

216 (102) 387 (197)

54 (12) 162 (72)

417 (214) 403 (206)

195 (90) 200 (93)

860 (460) 817 (436)

614 (323) 698 (370)

298 (148) 390 (199)

896 (480)

See Cyclohexanol. 1004 (540)

905 (485) See Ethyleneimine.

377 (192)

928 (498) See Petroleum Ether. 477 (247) 1058 (570) See Benzene.

(Continued)

2.358

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Benzyl Carbinol Benzyl Chloride C6H5CH2Cl (a-Chlorotoluene) Benzyl Cyanide C6H5CH2CN (Phenyl Acetonitrile) (a-Tolunitrile) N-Benzyldiethylamine C6H5CH2N(C2H5)2 Benzyl Ether Benzyl Mercaptan C6H5CH2SH (a-Toluenethiol) Benzyl Sallcilate OHC6H4COOCH2C6H5 (Salycilic Acid Benzyl Ester) Bicyclohexyl [CH2(CH2)4CH]2 (Dicyclohexyl) Biphenyl C6H5C6H5 (Diphenyl) (Phenylbenzene) 2-Biphenylamine NH2C6H4C6H5 (2-Aminobiphenyl) Bromobenzene C6H5Br (Phenyl Bromide) 1-Bromo Butane 4-Bromodiphenyl C6H5C6H4Br Bromoethane Bromomethane 1-Bromopentane 3-Bromopropene o-Bromotoluene BrC6H4CH3 p-Bromotoluene BrC6H4CH3 1,3-Butadiene CH2:CHCH:CH2 Butadiene Monoxide CH2:CHCHOCH2 (Vinylethylene Oxide) Butanal Butanal Oxime Butane CH3CH2CH2CH3 1,3-Butanediamine NH2CH2CH2CHNH2CH3

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

354 (179)

153 (67)

452 (233.5)

235 (113)

405–420 (207–216)

170 (77)

383 (195)

158 (70)

406 (208)

>212 (>100)

462 (239)

165 (74)

473 (245)

489 (254)

235 (113)

1004 (540)

570 (299)

842 (450)

313 (156)

124 (51)

592 (311)

291 (144)

See Phenethyl Alcohol. 1085 (585)

See Dibenzyl Ether.

1049 (565) See Butyl Bromide.

See Ethyl Bromide. See Methyl Bromide. See Amyl Bromide. See Allyl Bromide. 359 (182) 363 (184) 24 (−4) 151 (66)

174 (79) 185 (85) 788 (420)

Gas <–58 (<–50) See Butyraldehyde. See Butyraldoxime.

31 (−1) 289–302 (143–150)

−76 (−60) 125 (52)

550 (287)

ORGANIC CHEMISTRY

2.359

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 1,2-Butanediol CH3CH2CHOHCH2OH (1,2-Dihydroxybutane) (Ethylethylene Glycol) 1,3-Butanediol 1,4-Butanediol HOCH2CH2CH2CH2OH 2,3-Butanediol CH3CHOHCHOHCH3 2,3-Butanedione CH3COCOCH3 (Diocetyl) 1-Butanethiol CH3CH2CH2CH2SH (Butyl Mercaptan) 2-Butanethiol C4H9SH (sec-Butyl Mercaptan) 1-Butanol 2-Butanol 2-Butanone 2-Butenal 1-Butene CH3CH2CH:CH2 (a-Butylene) 2-Butene-cis CH3CH:CHCH3 2-Butene-trans CH3CH:CHCH3 (b-Butylene) Butenediol HOCH2CH:CHCH2OH (2-Butene-1,4-Diol)

Boiling point °F (°C)

Flash point, °F (°C)

381 (194)

104 (40)

442 (228) 363 (184) 190 (88)

See b-Butylene Glycol. 250 (121) 756 (402) 80 (27)

208 (98)

35 (2)

185 (85)

−10 (−23)

Ignition point, °F (°C)

21 (−6)

See Butyl Alcohol. See sec-Butyl Alcohol. See Methyl Ethyl Ketone. See Crotonaldehyde. 725 (385)

38.7 (4) −34 (1)

617 (325) 615 (324)

286–300 (141–149)

263 (128)

@20 mm 2-Butene-1,4-Diol 2-Butene Nitrile Butoxybenzene 1-Butoxybutane 2,β-Butoxyethoxyethyl Chloride C4H9CH2CH2OCH2CH2Cl 1-(Butoxyethoxy)2Propanol CH3CH(OH)CH2OC2H4OC2H4C2H5 b-Butoxyethyl Salicylate OCH6H4COOCH2CH2OC4 N-Butyl Acetamide CH3CONHC4H9 N-Butylacetanilide CH3(CH2)3N(C6H5)COCH3 Butyl Acetate CH3COOC4H9 (Butylethanoate)

See Butenediol. See Crotononitrile. See Butyl Phenyl Ether. See Dibutyl Ether. 392–437 (200–225) 445 (229)

190 (88) 250 (121)

509 (265)

367–378 (186–192) 455–464 (235–240) 531–538 (277–281) 260 (127)

315 (157) 240 (116) 286 (141) 72 (22)

797 (425) (Continued)

2.360

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound sec-Butyl Acetate CH3COOCH(CH3)C2H5 Butyl Acetoacetate CH3COCH2COO(CH2)3CH3 Butyl Acetyl Ricinoleate C17H32(OCOCH3)(COOC4H9) Butyl Acrylate CH2:CHCOOC4H9 Butyl Alcohol CH3(CH2)2CH2OH (1-Butanol) (Propylcarbinol) (Propyl Methanol) sec-Butyl Alcohol CH3CH2CHOHCH3 (2-Butanol) (Methyl Ethyl Carbinol) tert-Butyl Alcohol (CH3)2COHCH3 (2-Methyl-2-Propanol) (Trimethyl Carbinol) Butylamine C4H9NH2 (1-Amino Butane) sec-Butylamine CH3CH2CH(NH2)CH3 tert-Butylamine (CH3)3C:NH2 Butylamine Oleate C17H33COONH3C4H9 tert-Butylaminoethyl Methacrylate (CH3)3CNHC2H4OOCC(CH3):CH2 N-Butylaniline C6H5NHC4H9 Butylbenzene C6H5C4H9 sec-Butylbenzene C6H5CH(CH3)C2H5 tert-Butylbenzene C6H5C(CH3)3 Butyl Benzoate C6H5COOC4H9 2-Butylbiphenyl C6H5C6H4C4H9 Butyl Bromide CH3(CH2)2CH2Br (1-Bromo Butane) Butyl Butyrate CH3(CH2)2COOC4H9

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

234 (112) 417 (214) 428 (220)

88 (31) 185 (85) 230 (110)

725 (385)

260 (127) Polymerizes 243 (117)

84 (29)

559 (292)

98 (37)

650 (343)

201 (94)

75 (24)

761 (405)

181 (83)

52 (11)

892 (478)

172 (78)

10 (−12)

594 (312)

145 (63) 113 (45)

16 (−9) 716 (380)

200–221 (93–105)

150 (66) 205 (96)

465 (241) 356 (180) 344 (173) 336 (169) 482 (250) −554 (−290) 215 (102)

225 (107) 160 (71) 126 (52) 140 (60) 225 (107) >212 (>100) 65 (18)

305 (152)

128 (53)

770 (410) 784 (418) 842 (450)

806 (430) 509 (265)

ORGANIC CHEMISTRY

2.361

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Butylcarbamic Acid, Ethyl Ester tert-Butyl Carbinol (CH3)3CCH2OH (2,2-Dimethyl-1-Propanol) Butyl Carbitol 4-tert-Butyl Catechol (OH)2C6H3C(CH3)3 Butyl Chloride C4H9Cl (1-Chlorobutane) sec-Butyl Chloride CH3CHClC2H5 (2-Chlorobutane) tert-Butyl Chloride (CH3)3CCl (2-Chloro-2-Methyl-Propane) 4-tert-Butyl-2Chlorophenol ClC6H3(OH)C(CH3)3 tert-Butyl-m-Cresol C6H3(C4H9)(CH3)OH p-tert-Butyl-o-Cresol (OH)C6H3CH3C(CH3)3 Butylcyclohexane C4H9C6H11 (1-Cyclohexylbutane) sec-Butylcyclohexane CH3CH2CH(CH3)C6H11 (2-Cyclohexylbutane) tert-Butylcyclohexane (CH3)3CC6H11 N-Butylcyclohexylamine C6H11NH(C4H9) Butylcyclopentane C4H9C5H9 Butyl Ether Butylethylacetaldehyde Butyl Ethylene Butyl Ethyl Ether Butyl Formate HCOOC4H9 (Butyl Methanoate) (Formic Acid, Butyl Ester) Butyl Glycolate CH2OHCOOC4H9 tert-Butyl Hydroperoxide (CH3)3COOH n-Butyl Isocyanate CH3(CH2)3NCO (Butyl Isocyanate) Butyl Isovalerate C4H9OOCCH2CH(CH3)2

Boiling point °F (°C)

Flash point, °F (°C)

237 (114)

98 (37)

Ignition point, °F (°C)

See N-Butylurethane.

See Diethylene Glycol Monobutyl Ether. 545 (285) 170 (77)

266 (130) 15 (−9)

155 (68)

<32 (<0)

124 (51)

<32 (<0)

453–484 (234–251)

225 (107)

451–469 (233–243) 278–280 (137–138) 352–356 (178–180)

116 (47) 244 (118)

464 (240)

475 (246)

351 (177)

531 (277)

333–336 (167–169) 409 (209) 314 (157)

648 (342) 200 (93) 480 (250) See Dibutyl Ether. See 2-Ethylhexanal. See 1-Hexene. See Ethyl Butyl Ether.

225 (107)

64 (18)

∼356 (∼180)

235 (113)

142 (61) <80 (<27) 66 (19)

302 (150)

127 (53)

612 (322)

(Continued)

2.362

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Butyl Lactate CH3CH(OH)COOC4H9 Butyl Mercaptan tert-Butyl Mercaptan Butyl Methacrylate CH2:C(CH3)COO(CH2)3CH3 Butyl Methanoate N-Butyl Monoethanolamine C4H9NHC2H4OH Butyl Naphthalene C4H9C10H7 Butyl Nitrate CH3(CH2)3ONO2 2-Butyloctanol C6H13CH(C4H9)CH2OH Butyl Oleate C17H33COOC4H9

Butyl Oxalate (COOC4H9)2 (Butyl Ethanedioate) tert-Butyl Peracetate diluted with 25% of benzene CH3CO(O2)C(CH3)3 tert-Butyl Perbenzoate C6H5COOOC(CH3)3 tert-Butyl Peroxypivalate diluted with 25% of mineral spirits (CH3)3COOCOC(CH3)3 β-(p-tert-Butyl Phenoxy) Ethanol (CH3)3CC6H4OCH2CH2OH β-(p-tert-Butylphenoxy) Ethyl Acetate (CH3)3CC6H6OCH2CH2OCOCH3 Butyl Phenyl Ether CH3(CH2)3OC6H5 (Butoxybenzene) 4-tert-Butyl-2-Phenylphenol C6H5C6H3OHC(CH3)3 Butyl Propionate C2H5COOC4H9 Butyl Ricinoleate C18H33O3C4H9 Butyl Sebacate [(CH2)4COOC4H9]2 Butyl Stearate C17H35COOC4H9 tert-Butylstyrene

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

320 (160)

160 (71)

720 (382)

325 (163) 378 (192)

277 (136) 486 (252) 440.6–442.4 (227–228) @15 mm 472 (244)

See 1-Butanethiol. See 2-Methyl-2-Propanethiol. 126 (52) See Butyl Formate. 170 (77) 680 (360) 97 (36) 230 (110) 356 (180)

Explodes on heating.

265 (129) (oc) <80 (<27)

Explodes on heating. Explodes on heating.

>190 (>88) >155 (>68)

293-313 (145-156)

248 (120)

579–585 (304–307)

324 (162)

410 (210)

180 (82)

385–388 (196–198) 295 (146) 790 (421) 653 (345) 650 (343) 426 (219)

320 (160) 90 (32) 230 (110) 353 (178) 320 (160) 177 (81)

799 (426)

671 (355)

ORGANIC CHEMISTRY

2.363

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound tert-Butyl Tetralin C4H9C10H11 Butyl Trichlorosilane CH3(CH2)3SiCl3 N-Butylurethane CH3(CH2)3NHCOOC2H5 (Butylcarbamic Acid, Ethyl Ester) (Ethyl Butylcarbamate) Butyl Vinyl Ether 2-Butyne CH3C$CCH3 (Crotonylene) Butyraldehyde CH3(CH2)2CHO (Butanal) (Butyric Aldehyde) Butyraldol C8H16O2 Butyraldoxime C4H8NOH (Butanal Oxime) Butyric Acid CH3(CH2)2COOH Butyric Acid, Ethyl Ester Butyric Aldehyde Butyric Anhydride [CH3(CH2)2CO]2O Butyric Ester Butyrolactone CH2CH2CH2COO | [ [[ [ [ [ [ [| Butyrone Butyronitrile CH3CH2CH2CN Caproic Acid (CH3)(CH2)4COOH (Hexanoic Acid) Carbolic Acid Carbon Bisulfide Carbon Disulfide CS2 (Carbon Bisulfide) Cetane Chloroacetic Acid CH2ClCOOH Chloroacetophenone C6H5COCH2Cl (Phenacyl Chloride) 2-Chloro-4,6-di-tert-Amylphenol (C5H11)2C6H2ClOH Chloro-4-tert-Amylphenol C5H11C6H3ClOH

Boiling point °F (°C)

Flash point, °F (°C)

300 (149) 396–397 (202–203)

680 (360) 130 (54) 197 (92)

81 (27) 169 (76)

Ignition point, °F (°C)

See Vinyl Butyl Ether. −4 (<–20) −8 425 (−22) (218)

280 (138) @ 50 mm 306 (152)

165 (74)

327 (164)

161 (72)

136 (58) 830 (443) See Ethyl Butyrate. See Butyraldehyde.

388 (196)

180 (54)

535 (279)

399 (204)

209 (98)

243 (117) 400 (204)

See 4-Heptanone. 76 (24) 215 (102)

See Ethyl Butyrate.

935 (501) 716 (380)

See Phenol. See Carbon Disulfide. 115 (46)

−22 (−30)

372 (189) 477 (247)

259 (126) 244 (118)

320–354 (160–179) @ 22 mm 487–509 (253–265)

250 (121)

194 (90) See Hexadecane. >932 (>500)

225 (107) (Continued)

2.364

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2-Chloro-4-tert-Amyl-Phenyl Methyl Ether C5H11C6H3ClOCH3 p-Chlorobenzaldehyde ClC6H4CHO Chlorobenzene C6H5Cl (Chlorobenzol) (Monochlorobenzene) (Phenyl Chloride) Chlorobenzol o-Chlorobenzotrifluoride ClC6H4CF3 (o-Chloro-a,a,a-trifluorotoluene) Chlorobutadiene 2-Chloro-1,3-Butadiene CH2:CCl:CH:CH2 (Chlorobutadiene) (Chloroprene) 1-Chlorobutane 2-Chlorobutene-2 CH3CCl:CHCH3 Chlorodinitrobenzene Chloroethane 2-Chloroethanol CH2ClCH2OH (2-Chloroethyl Alcohol) (Ethylene Chlorohydrin) 2-Chloroethyl Acetate CH3COOCH2CH2Cl 2-Chloroethyl Alcohol Chloro-4-Ethylbenzene C2H5C6H4Cl Chloroethylene 2-Chloroethyl Vinyl Ether 2-Chloroethyl-2-Xenyl Ether C6H5C6H4OCH2CH2Cl 1-Chlorohexane CH3(CH2)4CH2Cl (Hexyl Chloride) Chloroisopropyl Alcohol Chloromethane 1-Chloro-2-Methyl Propane 1-Chloronaphthalene C10H7Cl 2-Chloro-5Nitrobenzotrifluoride C6H3CF3(2-Cl, 5-NO2) (2-Chloro-a,a,a-Trifluoro-5Nitrotoluene) 1-Chloro-1-Nitroethane C2H4NO2Cl

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

518–529 (270–276)

230 (110)

417 (214) 270 (132)

190 (88) 82 (28)

306 (152)

138 (59)

138 (59)

See 2-Chloro-1,3-Butadiene. −4 (−20)

1099 (593)

See Chlorobenzene.

143–159 (62–71)

264–266 (129–130)

See Butyl Chloride. −3 (−19) See Dinitrochlorobenzene. See Ethyl Chloride. 140 797 (60) (425)

291 (144)

151 (66)

364 (184)

147 (64)

613 (323) 270 (132)

See Vinyl Chloride. See Vinyl 2-Chloroethyl Ether. 320 (160) 95 (35)

505 (263) 446 (230)

See 1-Chloro-2-Propanol. See Methyl Chloride. See Isobutyl Chloride. 250 >1036 (121) (>558) 275 (135)

344 (173)

133 (56)

See 2-Chloroethanol.

2.365

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 1-Chloro-1-Nitropropane CHNO2ClC2H5 2-Chloro-2-Nitropropane CH3CNO2ClCH3 1-Chloropentane b-Chlorophenetole C6H5OCH2CH2Cl (b-Phenoxyethyl Chloride) o-Chlorophenol ClC6H4OH p-Chlorophenol C6H4OHCl 2-Chloro-4-Phenylphenol C6H5C6H3ClOH Chloroprene 1-Chloropropane 2-Chloropropane 2-Chloro-1-Propanol CH3CHClCH2OH (b-Chloropropyl Alcohol) (Propylene Chlorohydrin 1-Chloro-2-Propanol CH2ClCHOHCH3 (Chloroisopropyl Alcohol) (sec-Propylene Chlorohydrin) 1-Chloro-1-Propene 3-Chloropropene α-Chloropropionic Acid CH3CHClCOOH 3-Chloropropionitrile ClCH2CH2CN 2-Chloropropionyl Chloride

β-Chloropropyl Alcohol 1-Chloropropylene CH3CH:CHCl (1-Chloro-1-Propene) 2-Chloropropylene CH3CCl:CH2 (b-Chloropropylene) (2-Chloropropene) 2-Chloropropylene Oxide γ-Chloropropylene Oxide Chlorotoluene C6H4ClCH3 (Tolyl Chloride) α-Chlorotoluene Chlorotrifluoroethylene 2-Chloro-α,α,α-Trifluoro-5Nitrotoluene

Boiling point °F (°C)

Flash point, °F (°C)

285 (141) 273 (134)

144 (62) 135 (57)

306–311 (152–155)

225 (107)

Ignition point, °F (°C)

See Amyl Chloride.

347 (175) 428 (220) 613 (323)

271–273 (133–134)

261 (127)

147 (64) 250 (121) 345 (174) See 2-Chloro-1,3-Butadiene. See Propyl Chloride. See Isopropyl Chloride. 125 (52)

125 (52)

See 1-Chloropropylene. See Allyl Chloride. 352–374 (178–190) 348.8 (176) Decomposes 230 (110) 95–97 (35–36) 73 (23)

225 (107) 168 (76)

932 (500)

88 (31) See 2-Chloro-1-Propanol. <21 (<–6) <–4 (<–20)

See Epichlorohydrin. See Epichlorohydrin. 320 (160)

126 (52) See Benzyl Chloride. See Trifluorochloroethylene. See 2-Chloro-5-Nitrobenzotrifluoride. (Continued)

2.366

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound

Boiling point °F (°C)

o-Chloro-a,a,a-Trifluorotoluene Coal Oil Coal Tar Light Oil Coal Tar Pitch Creosote Oil o-Cresol CH3C6H4OH (Cresylic Acid) (o-Hydroxytoluene) (o-Methyl Phenol) p-Cresyl Acetate CH3C6H4OCOCH3 (P-Tolyl Acetate) Cresyl Diphenyl Phosphate (C6H5O)2[(CH3)2C6H4O]-PO4 Cresylic Acid Crotonaldehyde CH3CH:CHCHO (2-Butenal) (Crotonic Aldehyde) (Propylene Aldehyde) Crotonic Acid CH3CH:CHCOOH Crotononitrile CH3CH:CHCN (2-Butenenitrile) Crotonyl Alcohol CH3CH:CHCH2OH (2-Buten-1-ol) (Crotyl Alcohol) 1-Crotyl Bromide CH3CH:CHCH2Br (1-Bromo-2-Butene) 1-Crotyl Chloride CH3CH:CHCH2Cl (1-Chloro-2-Butene) Cumene C6H5CH(CH3)2 (Cumol) (2-Phenyl Propane) (Isopropyl Benzene) Cumene Hydroperoxide C6H5C(CH3)2OOH Cyanamide NH2CN 2-Cyanoethyl Acrylate CH2CHCOOCH2CH2CN N-(2-Cyanoethyl) Cyclohexylamine C6H11NHC2H4CN

382–752 (194–400) 376 (191)

Flash point, °F (°C)

Ignition point, °F (°C)

See o-Chlorobenzotrifluoride. See Fuel Oil No. 1. <80 (<27) 405 (207) 165 637 (74) (336) 178 1110 (81) (599)

195 (91) 734 450 (390) (232) See o-Cresol. 216 55 (102) (13)

450 (232)

372 (189) 230–240.8 (110–116)

190 (88) <212 (<100)

745 (396)

250 (121)

81 (27)

660 (349)

306 (152)

96 (36)

795 (424)

Explodes on heating. 500 (260) Decomposes Polymerizes

175 (79) 286 (141) 255 (124) 255 (124)

2.367

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Cyclamen Aldehyde (CH3)2CHC6H4CH(CH3)CH2CHO (Methyl Para-Isopropyl Phenyl Propyl Aldehyde) Cyclobutane C4H8 (Tetramethylene) 1,5,9-Cyclododecatriene C12H18 Cycloheptane CH2(CH2)5CH2 | [ [[ [ [ [| Cyclohexane C6H12 (Hexahydrobenzene) (Hexamethylene) 1,4-Cyclohexane Dimethanol C8H16O2 Cyclohexanethiol C6H11SH (Cyclohexylmercaptan) Cyclohexanol C6H11OH (Anol) (Hexolin) (Hydralin) Cyclohexanone C6H10O (Pimelic Ketone) Cyclohexene CH2CH2CH2CH2CH:CH | [ [[ [ [ [ [ [ [[ [| 3-Cyclohexene-1Carboxaldehyde Cyclohexenone C6H8O Cyclohexyl Acetate CH3CO2C6H11 (Hexolin Acetate) Cyclohexylamine C6H11NH2 (Aminocyclohexane) (Hexahydroaniline) Cyclohexylbenzene C6H5C6H11 (Phenylcyclohexone) Cyclohexyl Chloride CH2(CH2)4CHCl | [ [[ [ [ [| (Chlorocyclohexane) Cyclohexylcyclohexanol C6H11C6H10OH Cyclohexyl Formate CH2(CH2)4HCOOCH | [ [[[[[|

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

190 (88)

55 (13) 448 (231) 246 (119)

160 (71) <70 (<21)

179 (82)

−4 (−20)

473 (245)

525 (274)

332 (167)

600 (316)

315–319 (157–159)

110 (43)

322 (161)

154 (68)

572 (300)

313 (156)

111 (44)

788 (420)

181 (83)

<20 (<–7)

471 (244)

See 1,2,3,6Tetrahydrobenzaldehyde. 313 (156) 350 (177)

93 (34) 136 (58)

635 (335)

274 (134)

88 (31)

560 (293)

459 (237)

210 (99)

288 (142)

90 (32)

304–313 (151–156) 324 (162)

270 (132) 124 (51) (Continued)

2.368

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Cyclohexylmethane o-Cyclohexylphenol C6H11C6H4OH Cyclohexyltrichlorosilane C6H11SiCl3 1,5-Cyclooctadiene C8H10 Cyclopentane C5H10 Cyclopentene CH:CHCH2CH2CH2 | [ [[ [ [ [ [ [| Cyclopentanol CH2(CH2)3CHOH | [ [[ [ [ [ [ [| Cyclopentanone OCCH2CH2CH2CH2 | [ [[ [ [ [ [ [| (Adipic Ketone) Cyclopropane (CH2)3 (Trimethylene) p-Cymene CH3C6H4CH(CH3)2 Tech. (4-Isopropyl-1-Methyl Benzene) Decahydronaphthalene C10H18 (Decalin) Decahydronaphthalene-trans C10H18 Decalin Decane CH3(CH2)8CH3 Decanol CH3(CH2)8CH2OH (Decyl Alcohol) 1-Decene CH3(CH2)7CH:CH2 Decyl Acrylate CH3(CN2)9OCOCH:CH2 Decyl Alcohol Decylamine CH3(CH2)9NH2 (1-Aminodecane) Decylbenzene C10H21C6H5 tert-Decylmercaptan C10H21SH Decylnaphthalene C10H21C10H7 Decyl Nitrate CH3(CH2)9ONO2

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

See Methylcyclohexane. 273 (134)

298 (148) @10 mm 406 (208) 304 (151) 121 (49) 111 (44)

196 (91) 95 (35) <20 (<–7) −20 (−29)

286 (141)

124 (51)

267 (131)

79 (26)

682 (361) 743 (395)

−29 (−34) 349 (176)

382 (194) 369 (187) 345 (174) 444.2 (229)

928 (498) 117 (47) 127 (53) 136 (58)

817 (436) 833 (445) 482 (250)

129 491 (54) (255) See Decahydronaphthalene. 115 410 (46) (210) 180 550 (82) (288)

342 (172) 316 (158) @50 mm

<131 (<55) 441 (227)

429 (221)

210 (99)

491–536 (255–280) 410–424 (210–218) 635–680 (335–360) 261 (127) @11 mm

225 (107) 190 (88) 350 (177) 235 (113)

455 (235)

See Decanol.

ORGANIC CHEMISTRY

2.369

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Diacetone Alcohol CH3COCH2C(CH3)2OH Diacetyl Diallyl Ether Diallyl Phthalate C6H4(CO2C3H5)2 1,3-Diaminobutane 1,3-Diamino-2-Propanol NH2CH2CHOHCH2NH2 1,3-Diaminopropane Diamylamine (C5H11)2NH Diamylbenzene (C5H11)2C6H4 Diamylbiphenyl C5H11(C6H4)2C5H11 (Diaminodiphenyl) Di-tert-Amylcyclohexanol (C5H11)2C6H9OH Diamyidlphenyl Diamylene C10H20 Diamyl Ether Diamyl Maleate (CHCOOC5H11)2 Diamyl Naphthalene C10H6(C5H11)2 2,4-Diamylphenol (C5H11)2C6H3OH Di-tert-Amylphenoxy Ethanol C6H3(C5H11)2OC2H4OH Diamyl Phthalate C6H4(COOC5H11)2 (Amyl Phthalate) Diamyl Sulfide (C5H11)2S o-Dianisldine [NH2(OCH3)C6H3)2 (o-Dimethoxybenzidine Dibenzyl Ether (C6H5CH2)2O (Benzyl Ether) Dibutoxy Ethyl Phthalate C6H4(COOC2H4OC4H9)2 Dibutoxymethane CH2(OC4H9)2 Dibutoxy Tetraglycol (C4H9OC2H4OC2H4)2O (Tetraethylene Glycol Dibutyl Ether) N,N-Dibutylacetamide CH3CON(C4H9)2

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

328 (164)

148

1118

554 (290) 266 (130) 356 (180) 491–536 (255–280) 687–759 (364–404) 554–572 (290–300) 302 (150) 505–572 (263–300) 624 (329) 527 (275) 615 (324) 475–490 (246–254) @ 50 mm 338–356 (170–180)

See 2,3-Butanedione. See Allyl Ether. 330 (166) See 1,3-Butanediamine. 270 (132) See 1,3-Propanediamine. 124 (51) 225 (107) 340 (171) 270 (132) See Diamylbiphenyl. 118 (48) See Amyl Ether. 270 (132) 315 (159) 260 (127) 300 (149) 245 (118) 185 (85) 403 (206)

568 (298)

275 (135)

437 (225) 330–370 (166–188) 635 (335)

407 (208) (oc) 140 (60) 305 (152)

469–482 (243–250)

225 (107) (Continued)

2.370

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Dibutylamine (C4H9)2NH Di-sec-Butylamine [C2H5(CH3)CH]2NH Dibutylaminoethanol (C4H9)2NC2H4OH 1-Dibutylamino-2-Propanol N,N-Dibutylanlline C6H5N(CH2CH2CH2CH3)2 Di-tert-Butyl-p-Cresol C6H2(C4H9)2(CH3)OH Dibutyl Ether (C4H9)2O (1-Butoxybutane) (Butyl Ether) 2,5-Di-tert-Butylhydroquinone [C(CH3)3]2C6H2(OH)2 (DTBHQ) Dibutyl Isophthalate C6H4(CO2C4H9)2 N,N1-Di-sec-Butyl-pPhenylenediamine C6H4[-NHCH(CH3)CH2CH3]2 Dibutylisopropanolamine CH3CHOHCH2N(C4H9)2 Dibutyl Maleate (-CHCO2C4H9)2 Dibutyl Oxalate C4H9OOCCOOC4H9 Di-tert-Butyl Peroxide (CH3)3COOC(CH3)3 Dibutyl Phthalate C6H4(CO2C4H9)2 (Dibutyl-o-Phthatate) n-Dibutyl Tartrate (COOC4H9)2(CHOH)2 (Dibutyl-d-2,3Dihydroxybutanedioate) N,N-Dibutyltoluenesulfonamide CH3C6H4SO3N(C4H9)2 Dicaproate Dicapryl Phthalate C6H4[COOCH(CH3)C6H13]2 Dichloroacetyl Chloride CHCl2COCl (Dichloroethanoyl Chloride) 3,4-Dichloroaniline NH2C6H3Cl2 o-Dichlorobenzene C6H4Cl2 (o-Dichlorobenzol)

Boiling point °F (°C) 322 (161) 270–275 (132–135) 432 (222) 505–527 (263–275) 495–511 (257–266) 286 (141)

Flash point, °F (°C)

Ignition point, °F (°C)

117 (47) 75 (24) 200 (93) See Dibutylisopropanolamine. 230 (110) 261 (127) 77 382 (25) (194)

420 (216)

790 (421)

322 (161) 270 (132)

625 (329)

472 (244) 231 (111) 644 (340)

205 (96) 285 (141) 220 (104) 65 (18) 315 (157)

757 (402)

650 (343)

195 (91)

544 (284)

392 (200) @10 mm

330 (166)

444 (229) Decomposes

441–453 (227–234) @4.5 mm 225–226 (107–108) 522 (272) 356 (180)

See Triethylene Glycol. 395 (202) 151 (66) 331 (166) 151 (66)

1198 (648)

ORGANIC CHEMISTRY

2.371

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound p-Dichlorobenzene C6H4Cl2 2,3-Dichlorobutadiene-1,3 CH2:C(Cl)C(Cl):CH2 1,2-Dichlorobutane CH3CH2CHClCH2Cl 1,4-Dichlorobutane CH2ClCH2CH2CH2Cl 2,3-Dichlorobutane CH3CHClCHClCH3 1,3-Dichloro-2-Butene CH2ClCH:CClCH3 3,4-Dichlorobutene-1 CH2ClCHClCHCH2 1,3-Dichlorobutene-2 CH2ClCH:CClCH3 Dichlorodimethylsilane 1,1-Dichloroethane 1,2-Dichloroethane Dichloroethanoyl Chloride 1,1-Dichloroethylene Dichloroisopropyl Ether ClCH2CH(CH3)OCH(CH3)CH2Cl [Bis (b-Chloroisopropyl) Ether] 2,2-Dichloro Isopropyl Ether [ClCH2CH(CH3)]2O [Bis(2-Chloro-1-Mothylethyl) Ether] Dichloromethane 1,1-Dichloro-1-Nitro Ethane CH3CCl2NO2 1,1-Dichloro-1-Nitro Propane C2H5CCl2NO2 1,5-Dichloropentane CH2Cl(CH2)3CH2Cl (Amylene Chloride) (Pentamethylene Dichloride) 2,4-Dichlorophenol Cl2C6H3OH 1,2-Dichloropropane 1,3-Dichloro-2-Propanol CH2ClCHOHCH2Cl 1,3-Dichloropropene CHCl:CHCH2Cl 2,3-Dichloropropene CH2CClCH2Cl a, b-Dichlorostyrene C6H5CCl:CHCl Dicyclohexyl Dicyclohexylamine (C6H11)2NH

Boiling point °F (°C) 345 (174) 212 (100)

Flash point, °F (°C)

Ignition point, °F (°C)

369 (187)

150 (66) 50 694 (10) (368) 527 (275) 126 (52) 194 (90) 80 (27) 113 (45) 80 (27) See Dimethyldichlorosilane. See Ethylidene Dichloride. See Ethylene Dichloride. See Dichloroacetyl Chloride. See Vinylidene Chloride. 185 (85)

369 (187)

185 (85)

311 (155) 241–253 (116–123) 262 (128) 316 (158) 258 (126)

255 (124) 289 (143) 352–358 (178–181)

410 (210) 346 (174) 219 (104) 201 (94)

496 (258)

See Methylene Chloride. 168 (76) 151 (66) >80 (>27)

237 (114) See Propylene Dichloride. 165 (74) 95 (35) 59 (15) 225 (107) See Bicyclohexyl. >210 (>99) (Continued)

2.372

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Dicyclopentadiene C10H12 Didecyl Ether (C10H21)2O (Decyl Ether) Diesel Fuel Oil No. 1-D

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

342 (172)

90 (32) 419 (215)

937 (503)

Diesel Fuel Oil No. 2-D Diesel Fuel Oil No. 4-D Diethanolomine (HOCH2CH2)2NH 1,2-Diethoxyethane Diethylacetaldehyde Diethylacetic Acid N,N-Diethyl-acetoacetamide CH3COCH2CON(C2H5)2 Diethyl Acetoacetate CH3COC(C2H5)2COOC2H5 Diethylamine (C2H5)2NH 2-Diethyl (Amino) Ethanol 2-(Diethylamino) Ethyl Acrylate CH2:CHCOOCH2CH2HN(CH3CH2)2 3-(Diethylamino)-Propylamine (C2H5)2NCH2CH2CH2NH2 (N,N-Diethyl-1,3-Propanediamine) N,N-Diethylaniline C6H5N(C2H5)2 (Phenyldiethylamine) o-Diethyl Benzene C6H4(C2H5)2 m-Diethyl Benzene C6H4(C2H5)2 p-Diethyl Benzene C6H4(C2H5)2 N,N-Diethyl-1,3-Butanediamine C2H5NHCH2CH2CHN(C2H5)CH3 [1,3-Bis(ethylamino) Buiane] D1-2-Ethylbutyl Phthalate C6H4[COOCH2CH(C2H5)2]2 Diethyl Carbamyl Chloride (C2H5)2NCOCl Diethyl Carbinol Diethyl Carbonate (C2H5)2CO3 (Ethyl Carbonate)

514 (268)

Decomposes 412–424 (211–218) Decomposes 134 (57) Decomposes

100 Min. (38) 125 Min. (52) 130 Min. (54) 342 (172)

1224 (662)

See Diethyl Glycol. See 2-Ethylbutyraldehyde. See 2-Ethylbutyric Acid. 250 (121) 170 (77) −9 594 (−23) (312) See N,N-Diethylethanolamine. 195 (91)

337 (169)

138 (59)

421 (216)

185 (85)

1166 (630)

362 (183) 358 (181) 358 (181) 354–365 (179–185)

135 (57) 133 (56) 132 (55) 115 (46)

743 (395) 842 (450) 806 (430)

662 350 369–374 (187–190) 259 (126)

381 (194) 325–342 (163–172) See sec-Amyl Alcohol. 77 (25)

ORGANIC CHEMISTRY

2.373

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Diethylcyclohexane C10H20 1,3-Diethyl-1,3-Diphenyl Urea [(C2H5)(C6H5)N]2CO Diethylene Diamine Diethylene Dioxide Diethylene Glycol O(CH2CH2OH)2 (2,2-Dihydroxyethyl Ether) Diethylene Glycol Methyl Ether CH3OC2H4OC2H4OH (2-(2-Methoxyethoxy) Ethanol) Diethylene Glycol Methyl Ether Acetate CH3COOC2H4OC2H4OCH3 Diethylene Glycol Monobutyl Ether C4H9OCH2CH2OCH2CH2OH Diethylene Glycol Monoethyl Ether Acetate C4H9O(CH2)2O(CH2)2OOCCH3 Diethylene Glycol Monoethyl Ether CH2OHCH2OCH2-CH2OC2H5 Diethylene Glycol Monoethyl Ether Acetate C2H5O(CH2)2O(CH2)2OOCCH3 Diethylene Glycol Monoisobutyl Ether (CH3)2CHCH2O(CH2)2O(CH2)2OH Diethylene Glycol Monomethyl Ether CH3O(CH2)O(CH2)2OH Diethylene Glycol MonoMethyl Ether Formal CH2(CH3OCH2CH2OCH2CH2O)2 Diethylene Glycol Phthalate C6H4[COO(CH2)2OC2H5]2 Diethylene Oxide Diethylene Triamine NH2CH2CH2NHCH2CH2NH2 N,N-Diethylethanolamine (C2H5)2NC2H4OH (2-(Diethylamino) Ethanol) Diethyl Ether N,N-Diethylethylene-diamine (C2H5)2NC2H4NH2 Diethyl Fumarate C2H5OCOCH:CHCOOC2H5 Diethyl Glycol (C2H5OCH2)2 (1,2-Diethoxyethane)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

344 (173) 620 (327) 299 (150)

120 (49) 302 (150) 144 (62)

464 (240)

472 (244)

255 (124)

435 (224)

379 (193)

205 (96)

465 (240)

410 (210)

180 (82)

448 (231)

172 (78)

400 (204)

476 (247)

240 (116)

570 (298.9)

396 (202)

201 (94)

400 (204)

424 (218)

225 (107)

680 (360)

422–437 (217–225)

222 (106)

452–485 (233–252)

381 (194)

205 (96)

581 (305)

310 (154)

See p-Dioxane.

343 (173) See Tetrahydrofuran. 404 (207) 324 (162)

208 (98) 140 (60)

293 (145) 442 (217) 252 (122)

115 (46) 220 (104) 95 (35)

676 (358) 608 (320) See Ethyl Ether.

401 (205) (Continued)

2.374

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Diethyl Ketone C2H5COC2H5 (3-Pentanone) N,N-Diethyllauramide C11H23CON(C2H5)2 Diethyl Maleate (–CHCO2C2H3)2 Diethyl Malonate CH2(COOC2H3)2 (Ethyl Malonate) Diethyl Oxide 3,3-Diethylpentane CH3CH2C(C2H5)2CH2CH3 Diethyl Phthalate C6H4(COOC2H5)2 p-Diethyl Phthalate N,N-Diethylstearamide C17H35CON(C2H5)2 Diethyl Succinate (CH2COOCH2CH3)2 Diethyl Sulfate (C2H5)2SO4 (Ethyl Sulfate) Diethyl Tartrate CHOHCOO(C2H5)2 Diethyl Terephthalate C6H4(COOC2H5)2 (p-Diethyl Phthalate) 3,9-Diethyl-6-tridecanol Diglycol Chlortormate O:(CH2CH2OCOCl)2 Diglycol Chlorohydrin HOCH2CH2OCH2CH2Cl Diglycol Diacetate (CH3COOCH2CH2)2O Diglycol Dilevulleate (CH2CH2OOC(CH2)2COCH3)2:O Diglycol Laurate C16H32O4 Dihexyl Dihexylamine [CH3(CH2)5]2NH Dihexyl Ether Dihydropyran CH2CH2CH2:CHCHO | [ [[[[[[[[ [| o-Dihydroxybenione C6H4(OH)2 (Pyrocalechol)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

217 (103)

55 (13)

842 (450)

331–351 (166–177) @2 mm 438 (226) 390 (199)

>150 (>66)

295 (146) 565 (296) 246–401 (119–205) @1 mm 421 (216) Decomposes, giving Ethyl Ether 536 (280) 576 (302)

256–261 (124–127) @5 mm 387 (197) 482 (250)

559–617 (293–325)

250 (121) 200 (93)

See Ethyl Ether. 554 (290) 322 855 (161) (457) See Diethyl Terephthalate. 375 (191) 195 (90) 220 (104) 200 (93) 243 (117) See Heptadecanol. 295 (146) 225 (107) 255 (124) 340 (171)

186 (86)

290 (143) See Dodecane. 220 (104) See Hexyl Ether. 0 (−18)

473 (245)

260 (127)

451–469 (233–243)

662 (350)

817 (436)

2.375

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound p-Dihydroxybenione C6H4(OH)2 (Hydroquinone) 1,2-Dihydroxybenione 2,2-Dihydroxyethyl Ether 2,5-Dihydroxyhexane Diisobutylamine [(CH3)2CHCH2]2NH [Bis(b-Methylpropyl) Amine] Diisobutyl Carbinol [(CH3)2CHCH2]2CHOH (Nonyl Alcohol) Diisobutylene Diisobutylene (CH3)3CCH2C(CH3):CH2 (2,4,4-Trimethy-H2-Pentane) Diisobutyl Ketone [(CH3)2CHCH2]2CO (2,6-Dimethyl-4 Heptanone) (Isovalerone) Diisobutyl Phthalate C6H4[COOCH2OH(CH3)2]2 Diisodecyl Adipoia C10H21O2C(CH2)2CO2-C10H21 Diisodecyl Phthalate C6H4(COOC10H21)2 Diisooctyl Phthalate (C8H17COO)2C2H4 Diisopropanolamine [CH3CH(OH)-CH2]2NH Diisopropyl Diisopropylamine [(CH3)2CH]2NH Diisopropyl Benzene [(CH3)2CH]2C6H4 N,N-Diisopropyl-ethanolamine [(CH3)2CH]2NC2H4OH Diisopropyl Ether Diisopropyl Maleate (CH3)2CHOCOCH: CHCOOCH(CH3)2 Diisopropylmethanol Diisopropyl Peroxydicarbonate (CH3)2CHOCOOCOOCH(CH3)2 Diketene CH2:CCH2C(O)O | [ [[[ [ [| (Vinylaceto-b-Lactone) 2,5-Dimethoxyaniline NH2C6H3(OCH3)2 2,5-Dimethoxy Chlorobenzene C8H9ClO2 1,2-Dimethoxyethane

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

547 (286)

329 (165)

959 (515)

See 1,2-Butanediol. See Diethylene Glycol. See 2,5-Hexanediol. 273–286 (134–141)

85 (29)

353 (178)

165 (74)

214 (101)

See 2,4,4-Trimethyl-1-Pentene. 23 736 (−5) (391)

335 (168)

120 (49)

321 (327) 660 (349) 182 (250) 398 (370) 480 (249)

365 810 (185) (432) 225 (107) 450 755 (232) (402) 450 (232) 260 705 (127) (374) See 2,3-Dimethylbutane. 30 600 (−1) (316) 170 840 (77) (449) 175 (79) See Isopropyl Ether. 220 (104)

183 (84) 401 (205) 376 (191) 444 (229)

745 (396)

See 2,4-Dimethyl-3-Pentanol. Explodes on heating. 261 (127)

93 (34)

518 (270) 460–467 (238–242)

302 (150) 243 (117)

735 (391)

See Ethylene Glycol Dimethyl Ether. (Continued)

2.376

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Dimethoxyethyl Phthalate C6H4(COOCH2CH2OCH3)2 (Bis(2-methoxyethyl) Phthalate) Dimethoxymethane Dimethoxy Tetraglycol CH3OCH2(CH2OCH2)3CH2OCH3 (Tetraethylene Glycol Dimethyl Ether) Dimethylacetamide (CH3)2NC:OCH3 (DMAC) Dimethylamine (CH3)2NH 1,2-Dimethylbenzene 1,3-Dimethylbenzene 1,4-Dimethylbenzene Dimethylbenzylcarbinyl Acetate C6H5CH2C(CH3)2OOCCH3 (alpha, alpha-Dimethylphenethyl Acelate) 2,2-Dimethylbutane (CH3)3CCH2CH3 (Neohexane) 2,3-Dimethylbutane (CH3)2CHCH(CH3)2 (Diisopropyl) 1,3-Dimethylbutanol 2,3-Dimethyl-1-Butene CH3CH(CH3)C(CH3):CH2 2,3-Dimethyl-2-Butene CH3C(CH3):C(CH3)2 1,3-Dimethylbutyl Acetate CH3COOCH(CH3)CH2CH(CH3)2 1,3-Dimethylbutylamine CH3CHNH2(CH2)CH(CH3)2 (2-Amino-4-Methylpeniane) Dimethyl Carbinol Dimethyl Carbonate Dimethyl Chloracetal ClCH2CH(OCH3)2 Dimethylcyanamide (CH3)2NCN 1,2-Dimethylcyclohexane (CH3)2C6H10 1,3-Dimethylcyclohexane (CH3)2C6H10 (Hexahydroxylene) 1,4-Dimethylcyclohexane (CH3)2C6H10 (Hexahydroxylol) 1,4-Dimethylcyclohexane-cis C6H10(CH3)2

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

644 (340)

410 (210)

750 (399)

528 (276)

285 (141)

330 (165)

158 (70)

914 (490)

45 (7)

Gos

752 (400)

See Methylal.

See o–Xylene. See m-Xylene. See p-Xylene. 205 (96)

122 (50)

−54 (–48)

761 (405)

136 (58)

−20 (–29)

761 (405)

133 (56) 163 (73) 284–297 (140–147) 223–228 (106–109)

See Methyl Isobutyl Carbinol. <–4 680 (<–20) (360) <–4 753 (<–20) (401) 113 (45) 55 (13) See Isopropyl Alcohol. See Methyl Carbonate.

259–270 (126–132) 320 (160) 260 (127) ~256 (124)

111 (44) 160 (71)

450 (232)

~50 (10)

579 (304) 583 (306)

248 (120)

52 (11)

579 (304)

255 (124)

61 (16)

2.377

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 1,4-Dimethylcyclohexane-trans C6H10(CH3)2 Dimethyl Decalin C10H16(CH2)2 Dimethyldichlorosilane (CH3)2SiCl2 (Dichlorodimethylsilane) Dimethyldioxane CH3CHCH2OCH2(CH3)CHO | [ [[[[[[[[[ [ [[| 1,3-Dimethyl-1-3Diphenylcyclobutane (C6H5CCH3)2(CH2)2 Dimethylene Oxide Dimethyl Ether Dimethyl Ethyl Carbinol 2,4-Dimethyl-3-Ethylpentane CH3CH(CH3)CH(CH2H5) CH(CH3)2 (3-Ethyl-2,4Dimethylpentane) N,N-Dimethylformamide HCON(CH3)2 2,5-Dimethylfuran OC(CH3):CHCH:C(CH3) | [ [[[[[ [ [[| Dimethyl Glycol Phthalate C6H4[COO(CH2)2OCH3]2 3,3-Dimethylheptane CH3(CH2)3C(CH3)2CH2CH3 2,6-Dimethyl-4-Heptanone 2,3-Dimethylhexane CH3CH(CH3)CH(CH3)C2H5CH3 2,4-Dimethylhexane CH3CH(CH3)CH(CH3)C2H5CH3 Dimethyl Hexynol C4H9CCH3(OH)C$CH (3,5-Dimethyl-1-Hexyn-3-ol) 1,1-Dimethylhydrazine (CH3)2NNH2 (Dimethylhydrazine, Unsymmetrical) Dimethylisophthalate CH3OOCC6H4COOCH3 N,N-Dimethylisopropanolamine (CH3)2NCH2CH(OH)CH3 Dimethyl Ketone Dimethyl Maleate (−CHCOOCH3)2 2,6-Dimethylmorpholine CH(CH3)CH2OCH2CH(CH3)NH | [ [[[[[ [ [[ [[ [[ [[ [| 2,3-Dimethyloctane CH3(CH2)4CH(CH3)CH(CH3)CH3 3,4-Dimethyloctane C3H7CH(CH3)CH(CH3)C3H7

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

246 (119) 455 (235) 158 (70)

51 (11) 184 (84) <70 (<21)

455 (235)

243 (117)

75 (24)

585–588 (307–309)

289 (143)

279 (137)

See Ethylene Oxide. See Methyl Ether. See 2-Methyl-2-Butanol. 734 (390)

307 (153) 200 (93)

136 (58) 45 (7)

446 (230) 279 (137) 237 (114) 229 (109) 302 (150)

369 (187) 617 (325) See Diisobutyl Ketone. 45 820 (7) (438) 50 (10) 135 (57)

145 (63)

5 (−15)

257 (125)

280 (138) 95 (35)

393 (201) 296 (147)

235 (113) 112 (44)

327 (164) 324 (162)

<131 (<55) <131 (<55)

833 (445)

480 (249)

See Acetone.

437 (225)

(Continued)

2.378

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Boiling point °F (°C)

Flash point, °F (°C)

2,3-Dimethylpentaldehyde CH3CH2CH(CH3)CH(CH3)CHO 2,3-Dimethylpentane CH3CH(CH3)CH(CH3)CH2CH3 2,4-Dimethylpentane (CH3)2CHCH2CH(CH3)2 2,4-Dimethyl-3-Pentanol (CH3)2CHCHOHCH(CH3)2 (Diisopropylmethanol) Dimethyl Phthalate C6H4(COOCH3)2 Dimethylpiperazine-cis C6H14N2 2,2-Dimethylpropane (CH3)4C (Neopentane) 2,2-Dimethyl-1-Propanol 2,5-Dimethylpyrazine CH3C:CHN:C(CH3)CH:N | [ [[[[[[ [ [[| Dimethyl Sebacate [−(CH2)4COOCH3]2 (Methyl Sebacate) Dimethyl Sulfate (CH3)2SO4 (Methyl Sulfate) Dimethyl Sulfide (CH3)2S Dimethyl Sulfoxide (CH3)2SO

293 (145) 194 (90) 177 (81) 284 (140)

94 (34) <20 (<−7) 10 (−12) 120 (49)

540 (282) 329 (165) 49 (9)

295 (146) 155 (68)

Dimethyl Terephthalate C6H4(COOCH3)2 (Dimethyl-1,4-Benzene Dicarboxylate) (DMT) 2,4-Dinitroaniline (NO2)2C6H3NH2 1,2-Dinitro Benzol C6H4(NO2)2 (o-Dinitrobenzene) Dinitrochlorobenzene C6H3Cl(NO2)2 (Chlorodinitrobenzene) 2,4-Dinitrotoluene (NO2)2C6H3CH3 Dioctyl Adipate [−(CH2)2COOCH2CH(C2H5)C4-H9]2 [Bis(2-Ethylhexyl) Adipate] [Di(2-Ethylhexyl) Adipate] Dioctyl Azelate (CH2)7[COOCH2CH(C2H5)C4H9]2 (Bis(2-Ethylhexyl) Azelate) (Di(2-Ethylhexyl) Azelate)

Compound

Ignition point, °F (°C)

635 (335)

915 (490)

842 (450)

311 (155)

See tert-Butyl Carbinol. 147 (64)

565 (296)

293 (145)

370 (188)

182 (83)

370 (188)

99 (37) 372 (189)

403 (206) 419 (215)

543 (284)

<0 (<−18) 203 (95) (oc) 308 (153)

604 (318)

435 (224) 302 (150)

599 (315)

382 (194)

572 (300) 680 (360)

404 (207) 402 (206)

710 (377)

709 (376)

440 (227)

705 (374)

965 (518)

ORGANIC CHEMISTRY

2.379

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Dioctyl Ether (C8H17)2O (Octyl Ether) Dioctyl Phthalate C6H4[CO2CH2CH(C2H5)C4H9]2 [Di(2-Ethylhexyl) Phthalate] [Bis(2-Ethylhexyl) Phthalate] p-Dioxane OCH2CH2OCH2CH2 | [ [[[ [ [[| (Diethylene Dioxide) Dioxolane OCH2CH2OCH2 | [ [[ [ [ [[| Dipe ntene C10H16 (Cinene) (Limonene) Diphenyl Diphenylamine (C6H5)2NH (Phenylaniline) 1,1-Diphenylbutane (C6H5)2CHC3H7 1,3-Diphenyl-2-buten-1-one Diphenyldichlorosllane (C6H5)2SiCl2 Diphenyldodecyl Phosphite (C6H5O)2POC10H21 1,1-Diphenylethane (uns) (C6H5)2CHCH3 1,2-Diphenylethane (sym) C6H5CH2CH2C6H5 Diphenyl Ether Diphenylmethane (C6H5)2CH2 (Ditane) Diphenyl Oxide (C6H5)2O (Diphenyl Ether) 1,1-Diphenylpentane (C6H5)2CHC4H9 1,1-Diphenylpropane CH3CH2CH(C6H5)2 Diphenyl Phthalate C6H4(COOC6H5)2 Dipropylamine (C3H7)2NH Dipropylene Glycol (CH3CHOHCH2)2O Dipropylene Glycol Methyl Ether CH3OC3H6OC3H6OH

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

558 (292)

>212 (>100)

401 (205)

420 (215)

735 (390)

214 (101)

54 (12)

356 (180)

165 (74)

35 (2)

339 (170)

113 (45)

575 (302)

307 (153)

1173 (634)

561 (294)

>212 (>100)

851 (455)

581 (305)

546 (286) 544 (284)

288 (142) 425 (218) >212 (>100) 264 (129)

508 (264)

266 (130)

905 (485)

496 (258)

239 (115)

1144 (618)

586 (308) 541 (283) 761 (405) 229 (109) 449 (232) 408 (209)

>212 (>100) >212 (>100) 435 (224) 63 (17) 250 (121) 186 (86)

824 (440) 860 (460)

458 (237)

See Biphenyl.

See Dypnone.

824 (440) 896 (480) See Diphenyl Oxide.

570 (299)

(Continued)

2.380

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Dipropyl Ether Dipropyl Ketone Ditane Ditridecyl Phthalate C6H4(COOC13H27)2 Divinyl Acetylene ($CCH:CH2)2 (1,5-Hexadien-3-yne) Divinylbenzene C6H4(CH:CH2)2 Divinyl Ether (CH2:CH)2O (Ethenylaxyethene) (Vinyl Ether) Dodecane CH3(CH2)10CH3 (Dihexyl) 1-Dodecanethiol CH3(CH2)11SH (Dodecyl Mercaptan) (Lauryl Mercaptan) 1-Dodecanol CH3(CH2)11OH (Louryl Alcohol) Dodecyl Bromide Dodecylene (a) C16H21CH:CH2 (1-Dodecane) Dodecyl Mercaptan tert-Dodecyl Mercaptan C12H25SH 4-Dodecyloxy-2-HydroxyBenzophenone C25H34O3 Dodecyl Phenol C12H25C6H4OH Dypnone C6H5COCH:C(CH3)C6H5 (1,3-Diphenyl-2-Buten-1-one) Eicosane C20H42 Epichlorohydrin CH2CHOCH2Cl | [ [ [[| (2-Chloropropylene Oxide) (g-Chloropropylene Oxide) 1,2-Epoxyethane Erythrene Ethanal Ethane CH3CH3

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

See n-Propyl Ether. See 4-Heptanone. See Diphenylmethane. 547 @5 mm (286) 183 (84)

470 (243) <−4 (<−20)

392 (200) 83 (28)

169 (76) <−22 (<−30)

680 (360)

421 (216)

165 (74)

397 (203)

289 (143) @15 mm

262 (128)

491 (255)

260 (127)

406 (208)

<212 (<100)

428–451 (220–233)

205 (96) 498 (254)

527 (275) See Lauryl Bromide. 491 (255)

See 1-Dodecanethiol.

597–633 (314–334) 475 (246) @50 mm 651 (344) 239 (115)

715 (379)

325 (163) (oc) 350 (177) >212 (>100) 88 (31)

450 (232) 772 (411)

See Ethylene Oxide. See 1,3-Butadiene. See Acetaldehyde. −128 (−89)

882 (472)

ORGANIC CHEMISTRY

2.381

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 1,2-Ethanediol 1,2-Ethanediol Diformate HCOOCH2CH2OOCH (Ethylene Formate) (Ethylene Glycol Diformate) (Glycol Diformate) Ethanethiol Ethanoic Acid Ethanoic Anhydride Ethanol Ethanolamine NH2CH2CH2OH (2-Amino Ethanol) (b-Aminoethyl Alcohol) Ethanoyl Chloride Ethene Ethenyl Ethanoate Ethenyloxyethene Ether Ethine Ethoxyacetylene C2H5OC:CH Ethoxybenzene C6H5OC2H5 (Ethyl Phenyl Ether) (Phenetole) 2-Ethoxy-3,4-Dihydro-2-Pyran C7H12O2 2-Ethoxy Ethanol 2-Ethoxyethyl Acetate CH3COOCH2CH2OC2H5 (Ethyl Glycol Acetate) 3-Ethoxypropanal C2H5OC2H4CHO (3-Ethoxypropionaldehyde) 1-Ethoxypropane 3-Ethoxypropionaldehyde C2H5OCH2CH2CHO 3-Ethoxypropionic Acid C2H5OCH2CH2COOH Ethoxytriglycol C2H5O(C2H4O)3H (Triethylene Glycol, Ethyl Ether) Ethyl Abietale C19H29COOC2H5 N-Ethylacetamide CH3CONHC2H5 (Acetoethylamide) N-Ethyl Acetanilide CH3CON(C2H5)(C6H5) Ethyl Acetate CH3COOC2H5 (Acetic Ester) (Acetic Ether) (Ethyl Ethanoate)

Boiling point °F (°C)

Flash point, °F (°C)

345 (174)

200 (93)

Ignition point, °F (°C)

See Ethylene Glycol.

See Ethyl Mercaptan. See Acetic Acid. See Acetic Anhydride. See Ethyl Alcohol. 342 (172)

186 (86)

770 (410)

See Acetyl Chloride. See Ethylene. See Vinyl Acetate. See Divinyl Ether. See Ethyl Ether. See Acetylene. 124 (51) 342 (172) 289 (143) 313 (156)

<20 (<−7) 145 (63) 111 (44) See Ethylene Glycol Monoethyl Ether. 117 716 (47) (380)

275 (135)

100 (38)

275 (135) 426 (219) 492 (256)

See Ethyl Propyl Ether. 100 (38) 225 (107) 275 (135)

662 (350) 401 (205)

352 (178) 230 (110)

400 (204) 171 (77)

126 (52) 24 (−4)

800 (426)

(Continued)

2.382

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Ethyl Acetoacetate C2H5CO2CH2COCH3 (Acetoacetic Acid, Ethyl Ester) (Ethyl 3-Oxobutanoate) Ethyl Acetyl Glycolate CH3COOCH2COOC2H5 (Ethyl Glycolate Acetate) Ethyl Acrylate CH2:CHCOOC2H5 Ethyl Alcohol C2H5OH (Grain Alcohol, Ethanol) Ethylamine C2H5NH2 70% aqueous solution (Aminoethane) Ethyl Amino Ethanol C2H5NHC2H4OH [2-(Ethylamino)ethanol] Ethylaniline C2H5NH(C6H5) Ethylbenzene C2H5C6H5 (Ethylbenzol) (Phenylethane) Ethyl Benzoate C6H5COOC2H5 Ethylbenzol Ethyl Bromide C2H5Br (Bromoethane) Ethyl Bromoacetate BrCH2COOC2H5 2-Ethylbutanol Ethyl Butanoate 2-Ethyl-1-Butanol 2-Ethyl-1-Butene (C2H5)2C:CH2 3-(2-Ethylbutoxy) Propionic Acid CH3CH2CH(C2H5)CH2[OCH2CH2COOH 2-Ethylbutyl Acetate CH3COOCH2CH(C2H5)2 2-Ethylbutyl Acrylate CH2:CHCOOCH2CH[ (C2H5)C2H5 2-Ethylbutyl Alcohol (C2H5)2CHCH2OH (2-Ethyl-1-Butanol) Ethylbutylamine CH3CH2CH2CH2[NHCH3CH2 Ethyl Butylcarbamate Ethyl Butyl Carbonate (C2H5)(C4H9)CO3

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

356 (180)

135 (57)

563 (295)

−365 (−185)

180 (82)

211 (99) 173 (78)

50 (10) 55 (13)

702 (372) 685 (363)

62 (17)

<0 (<−18)

725 (385)

322 (161)

160 (71)

401 (205) 277 (136)

185 (85) 70 (21)

810 (432)

414 (212)

190 (88)

914 (490)

100 (38)

None

See Ethylbenzene.

318 (159)

144 (62) 392 (200) @100 mm 324 (162) 180 (82) @10 mm 301 (149) 232 (111) 275 (135)

952 (511)

118 (48) See 2-Ethylbutyraldehyde. See Ethyl Butyrate. See 2-Ethylbutyl Alcohol. <−4 599 (<−20) (315) 280 (138) 130 (54) 125 (52) 135 (57) (oc) 64 (18) See N-Butylurethane. 122 (50)

ORGANIC CHEMISTRY

2.383

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Ethyl Butyl Ether C2H5OC4H9 (Butyl Ethyl Ether) 2-Ethyl Butyl Glycol (C2H5)2CHCH2OC2H4OH [2-(2-Ethylbutoxy)ethanol] Ethyl Butyl Ketone C2H5CO(CH2)3CH3 (3-Heptanone) 2-Ethyl-2-Butyl-1,3-Propanediol HOCH2C(C2H5)(C4H9)CH2OH 2-Ethylbutyraldehyde (C2H5)2CHCHO (Diethyl Acetaldehyde) (2-Ethylbutanal) Ethyl Butyrate CH3CH2CH2COOC2H5 (Butyric Acid, Ethyl Ester) (Butyric Ester) (Ethyl Butanoate) 2-Ethylbutyric Acid (C2H5)2CHCOOH (Diethyl Acetic Acid) 2-Ethylcaproaldehyde Ethyl Caproate C5H11COOC2H5 (Ethyl Hexoate) (Ethyl Hexanoate) Ethyl Caprylate CH3(CH2)6COOC2H5 (Ethyl Octoate) Ethyl Octanoate Ethyl Chloride C2H5Cl (Chloroethane) (Hydrochloric Ether) (Muriatic Ether) Ethyl Chloroacetate ClCH2COOC2H5 Ethyl Chlorocarbonate Ethyl Chloroformate ClCOOC2H5 (Ethyl Chlorocarbonate) (Ethyl Chloromethanoate) Ethyl Chloromethanoate Ethyl Crotonate CH3CH:CHCOOC2H5 Ethyl Cyanoacetate CH2CNCOOC2H5 Ethylcyclobutane C2H5C4H7

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

198 (92)

40 (4)

386 (197)

180 (82)

299 (148)

115 (46)

352 (178) @50 mm 242 (117)

280 (138)

248 (120)

75 (24)

865 (463)

380 (193)

210 (99)

752 (400)

333 (167)

120 (49)

405–408 (207–209)

175 (79)

70 (21)

See 2-Ethylhexanal.

54 (12)

295 (146)

See Diethyl Carbonate. −58 966 (−50) (519)

201 (94)

147 (64) See Ethyl Chloroformate. 61 932 (16) (500)

282 (139) 401–408 (205–209) 160 (71)

See Ethyl Chloroformate. 36 (2) 230 (110) <4 410 (<−16) (210) (Continued)

2.384

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Ethylcyclohexane C2H5C6H11 N-Ethylcyclohexylamine C6H11NHC2H5 Ethylcyclopentane C2H5C5H9 Ethyl Decanoate C9H19COOC2H5 (Ethyl Caprate) N-Ethyldiethanolamine C2H5N(C2H4OH)2 Ethyl Dimethyl Methane Ethylene H2C:CH2 (Ethene) Ethylene Acetate Ethylene Carbonate OCH2CH2OCO | [ [[ [ [ [[| Ethylene Chlorohydrin Ethylene Cyanohydrin CH2(OH)CH2CN (Hydracrylonitrile) Ethylenediamine H2NCH2CH2NH2 Anydrous 76% Ethylene Dichloride CH2ClCH2Cl (1,2-Dichloroethone) 2,2-Ethylenedioxydiethanol Ethylene Formate Ethylene Glycol HOC2H4OH (1,2-Ethanediol) (Glycol) Ethylene Glycol n-Butyl Ether HOCH2CH2OC4H9 Ethylene Glycol Diacetate Ethylene Glycol Dibutyl Ether C4H9OC2H4OC4H9 Ethylene Glycol Diethyl Ether C2H5OCH2CH2OC2H5 Ethylene Glycol Diformate Ethylene Glycol Dimethyl Ether CH3O(CH2)2OCH3 (1,2-Dimethoxyethane) Ethylene Glycol Ethylbutyl Ether (C2H5)2CHCH2OCH2CH2OH

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

269 (132)

95 (35) 86 (30) <70 (<21) >212 (>100)

460 (238)

218 (103) 469 (243) 487 (253)

280 (138) See Isopentane.

−155 (−104)

351 (177) @100 mm 445 (229) Decomposes 241 (116) 239–252 (115–122) 183 (84)

387 (197)

340 (171) 399 (204) 251 (122) 174 (79) @630 mm 386 (197)

500 (260)

842 (450) See Glycol Diacetate. 290 (143) See 2-Chloroethanol. 265 (129) 104 (40) 150 56 (13)

725 (385) (66) 775 (413)

See Triethylene Glycol. See 1,2-Ethanediol Diformate. 232 748 (111) (398)

150 (66) See Glycol Diacetate. 185 (85) 95 406 (35) See 1,2-Ethanediol Diformate. 29 395 (−2) (202)

180 (85)

ORGANIC CHEMISTRY

2.385

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Ethylene Glycol Ethylhexyl Ether C4H9CH(C2H5)CH2OCH2CH2OH Ethylene Glycol Isopropyl Ether (CH3)2CHOCH2CH2OH Ethylene Glycol Monoacetate CH2OHCH2OOCCH3 (Glycol Monoacetate) Ethylene Glycol Monoacrylate CH2:CHCOOC2H4CH (2-Hydroxyethylacrylate) Ethylene Glycol Monobenzyl Ether C6H5CH2OCH2CH2OH Ethylene Glycol Monobutyl Ether C4H9O(CH2)2(OH) (2-Butoxyethanol) Ethylene Glycol Monobutyl Ether Acetate C4H9O(CH2)2OOCCH3 Ethylene Glycol Monoethyl Ether HOCH2CH2OC2H5 (2-Ethoxyethanol) Ethylene Glycol Monoethyl Ether Acetate CH3COOCH2CH2OC2H5 (Cellosolve Acetate) Ethylene Glycol Monoisobutyl Ether (CH3)2CHCH2OCH2CH2OH Ethylene Glycol Monomethyl Ether CH3OCH2CH2OH (2-Methoxyethanol) Ethylene Glycol Monomethyl Ether Acetal CH3CH(OCH2CH2OCH3)2 Ethylene Glycol Monomethyl Ether Acetate CH3O(CH2)2OOCCH3 Ethylene Glycol Monomethyl Ether Formal CH2(OCH2CH2OCH3)2 Ethylene Glycol Phenyl Ether C6H5OC2H4OH (2-Phenoxyethanol)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

442 (228)

230 (110)

289 (143)

92 (33)

357 (181)

215 (102)

410 (210) 493 (256)

220 (104) (oc) 265 (129)

665 (352)

340 (171)

143 (62)

460 (238)

377 (192)

160 (71)

645 (340)

275 (135)

110 (43)

455 (235)

313 (156)

124 (52)

715 (379)

316–323 (158–162)

136 (58)

540 (282)

255 (124)

102 (39)

545 (285)

405 (207)

200 (93)

293 (145)

120 (49)

394 (201)

155 (68)

473 (245)

260 (127)

740 (392)

(Continued)

2.386

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Ethylene Oxide CH2OCH2 | [ [[| (Dimethylene Oxide) (1,2-Epoxyethane) (Oxirane) Ethylenimine NHCH2CH2 | [ [ [[| (Aziridine) Ethyl Ethanoate N-Ethylethanolomine C2H5NHC2H4OH Ethyl Ether C2H5OC2H5 (Diethyl Ether) (Diethyl Oxide) (Ether) (Ethyl Oxide) Ethylethylene Glycol Ethyl Fluoride C2H5F (1-Fluoroethane) Ethyl Formate HCO2C2H5 (Ethyl Methanoate) (Formic Acid, Ethyl Ester) Ethyl Formate (ortho) (C2H5O)3CH (Triethyl Orthoformate) Ethyl Glycol Acetate 2-Ethylhexaldehyde 2-Ethylhexanal C4H9CH(C2H5)CHO (Butylethylacelaldehyde) (2-Ethylcaproaldehyde) (2-Ethylhexaldehyde) 2-Ethyl-1,3-Hexanediol C3H7CH(OH)CH(C2H5)CH2OH 2-Ethylhexanoic Acid C4H9CH(C2H5)COOH (2-Ethyl Hexoic Acid) 2-Ethylhexanol C4H9CH(C2H5)CH2OH (2-Ethylhexyl Alcohol) (Octyl Alcohol) 2-Ethylhexenyl 2-Ethylhexoic Acid 2-Ethylhexyl Acetate CH3COOCH2CH(C2H5)C4H9 (Octyl Acetate) 2-Ethylhexyl Acrylate CH:CHCOOCH2CH[ (C2H5)C4H9

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

51 (11)

−20

1058 with No Air

132 (56)

12 (−11)

608 (320)

322 (161) 95 (35)

See Ethyl Acetate. 160 (71) −49 (−45)

356 (180)

See 1,2-Butanediol. −36 (−38) 130 (54)

−4 (–20)

291 (144)

86 (30)

325 (163)

See 2-Ethoxyethyl Acetate. See 2-Ethylhexanal. 112 375 (44) (190)

472 (244) 440 (227)

260 (127) 245 (118)

680 (360) 700 (371)

359 (182)

164 (73)

448 (231)

390 (199)

See 2-Ethyl-3-Propylacrolein. See 2-Ethylhexanoic Acid. 160 515 (71) (268)

266 (130) @50 mm

180 (82)

851 (455)

485 (252)

ORGANIC CHEMISTRY

2.387

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2-Ethylhexylamine C4H9CH(C2H5)CH2NH2 N-2-(Ethylhexyl) Anlline C6H5NHCH2CH(C2H5)C4H9 2-Ethylhexyl Chloride C4H9CH(C2H5)CH2Cl N-(2-Ethylhexyl)cyclohexylamine C6H11NH[CH2CH[ (C2H5)C4H9] 2-Ethylhexyl Ether [C4H9CH(C2H5)CH2]2O 1,1-Ethylidene Dichloride CH3CHCl2 (1,1-Dichloroethane) 1,2-Ethylidene Dichloride ClCH2CH2Cl Ethyl Isobutyrate (CH3)2CHCOOC2H5 2-Ethylisohexanol (CH3)2CHCH2CH(C2H5)CH2OH (2-Ethyl Isohexyl Alcohol) (2-Ethyl-4-Methyl Pentanol) Ethyl Lactate CH3CHOHCOOC2H5 Tech. Ethyl Malonate Ethyl Mercaptan C2H5SH (Ethanethiol) (Ethyl Sulfhydrate) Ethyl Methacrylate CH2:C(CH3)COOC2H5 (Ethyl Methyl Acrylate) Ethyl Methanoate Ethyl Methyl Acrylate Ethyl Methyl Ether 7-Ethyl-2-Methyl-4Hendecanol C4H9CH(C2H5)C2H4CHOHCH2CH(CH3)2 Ethyl Methyl Ketone 4-Ethylmorpholine CH2CH2OC2H4NCH2CH3 | [ [ [ [ [ [[| 1-Ethylnaphthalene C10H7C2H5 Ethyl Nitrate CH3CH2ONO2 (Nitric Ether) Ethyl Nitrite C2H5ONO (Nitrous Ether)

Boiling point °F (°C)

Flash point, °F (°C)

337 (169) 379 (193) @50 mm 343 (173) 342 (172) @50 mm 517 (269) 135–138 (57–59)

140 (60) 325 (163)

235 (113) 2 (−17)

183 (84) 230 (110) 343–358 (173–181)

55 (13) <70 (<21) 158 (70)

824 (440)

115 (46) 131 (55) See Diethyl Malonate. <0 (<−18)

752 (400)

309 (154)

9 (35)

239–248 (115–120)

Ignition point, °F (°C)

140 (60) 265 (129)

600 (316)

572 (300)

68 (20)

507 (264)

See Ethyl Formate. See Ethyl Methacrylate. See Methyl Ethyl Ether. 285 (141)

280 (138)

See Methyl Ethyl Ketone 90 (32)

496 (258) 190 (88)

896 (480) 50 (10)

63 (17)

−31 (−35)

194 (90) (Continued)

2.388

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 3-Ethyloctane C5H11CH(C2H5)C2H5 4-Ethyloctane C4H9CH(C2H5)C3H7 Ethyl Oxalate (COOC2H5)2 (Oxalic Ether) (Diethyl Oxalate) Ethyl Oxide p-Ethylphenol HOC6H4C2H5 Ethyl Phenylacetate C6H5CH2COOC2H5 Ethyl Phenyl Ether Ethyl Phenyl Ketone C2H5COC6H5 (Propiophenone) Ethyl Phthalyl Ethyl Glycolate C2H5OCOC6H4OCOCH2OCOC2H5 Ethyl Propenyl Ether CH3CH:CHOCH2CH3 Ethyl Proplonate C2H5COOC2H5 2-Ethyl-3-Propylacrolein C3H7CH:C(C2H5)CHO (2-Ethylhexenal) 2-Ethyl-3-Propylacrylic Acid C3H7CH:C(C2H5)COOH Ethyl Propyl Ether C2H5OC3H7 (1-Ethoxypropane) m-Ethyltoluene CH3C6H4C2H5 (1-Methyl-3-Ethylbenzene) o-Ethyltoluene CH3C6H4C2H5 (1-Methyl-2-Ethylbenzene) p-Ethyltoluene CH3C6H4C2H5 (1-Methyl-4-Ethylbenzene) Ethyl p-Toluene Sulfonamide C7H7SO2NHC2H5 Ethyl p-Toluene Sulfonate C7H7SO3C2H5 Ethyl Vinyl Ether Ethyne Fluorobenzene C6H5F Formal Formalin

Boiling point °F (°C) 333 (167) 328 (164) 367 (186)

Flash point, °F (°C)

446 (230) 445 (229) 168 (76)

425 (218)

See Ethyl Ether. 219 (104) 210 (99) See Ethoxybenzene. 210 (99)

608 (320)

365 (185)

158 (70) 210 (99) 347 (175)

>19 (>−7) 54 (12) 155 (68)

450 (232) 147 (64)

330 (166) <−4 (<−20)

426 (219) 529 (276)

Ignition point, °F (°C)

824 (440)

322 (161)

896 (480)

329 (165)

824 (440)

324 (162)

887 (475)

208 (98) @745 mm 345 (174)

185 (85)

260 (127) 316 (158) See Vinyl Ethyl Ether. See Acetylene. 5 (−15) See Methylal. See Formaldehyde.

ORGANIC CHEMISTRY

2.389

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Formaldehyde HCHO 37% Methanol-free 37%, 15% Methanol (Formalin) (Methylene Oxide) Formamide HCONH2 Formic Acid HCOOH 90% Solution Formic Acid, Butyl Ester Formic Acid, Ethyl Ester Formic Acid, Methyl Ester Fuel Oil No. 1 (Kerosene) (Range Oil) Fuel Oil No. 2

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

−3 (−19) 214 (101)

Gas 185 (85)

795 (424)

122 (50) 410 (210) Decomposes 213 (101)

304–574 (151–301)

Fuel Oil No. 4 Fuel Oil No. 5 Light Heavy

Fuel Oil No. 6 2-Furaldehyde Furan CH:CHCH:CHO | [ [[[ [ [ [[| (Furfuran) Furfural OCH:CHCH:CHCHO | [ [[[ [ [ [| (2-Furaldehyde) (Furfuraldehyde) (Furol) Furfuraldehyde Furfuran Furfuryl Acetate OCH:CHCH:CCH2OOCCH3 | [ [[[ [ [[| Furfuryl Alcohol OCH:CHCH:CCH2OH | [ [[[ [ [ [ [| Furfurylamine C4H3OCH2NH2 Furol Fusel Oil Gas Oil

310 (154) 156 (69) 122 (50)

1004 (539) 813 (434)

See Butyl Formate. See Ethyl Formate. See Methyl Formate. 100–162 410 (38–72) (210) 126–204 (52–96) 142–240 (61–116)

494 (257) 505 (263)

156–336 (69–169) 160–250 (71–121) 150–270 (66–132)

765 (407) See Furfural.

88 (31)

<32 (<0)

322 (161)

140 (60)

600 (316)

See Furfural. See Furan. 356–367 (180–186)

185 (85)

340 (171)

167 (75) (oc) 99 (37)

295 (146)

915 (491)

See Furfural. See Isoamyl Alcohol. 500–700 (260–371)

150+ (66+)

640 (338) (Continued)

2.390

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Gasoline C5H12 to C9H20 56–60 Octane 73 Octane 92 Octane 100 Octane Gasoline 100–130 (Aviation Grade)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

100–400 (38–204)

−45 (−43) −45 (−43) −36 (−38)

536 (280) 853 (456)

−50 (−46)

824 (440) 880 (471)

340 (171)

−50 (−46) 0 (−18) 390 (199)

360 (182)

200 (93)

496 (258)

280 (138)

812 (433)

597 (314)

356 (180)

765 (407)

540 (282)

332 (167)

790 (421)

135 (57) @2 mm

141 (61)

779 (415)

375 (191)

191 (88)

Gasoline 115–145 (Aviation Grade) Gasoline (Casinghead) Glycerine HOCH2CHOHCH2OH (Glycerol) α,β-Glycerine Dichiorohydrin CH2ClCHClCH2OH Glycerol Glyceryl Triacetate (C3H5)(OOCCH3)3 (Triacelin) Glyceryl Tributyrate C3H5(OOCC3H7)3 (Tributyrin) (Butyrin) (Glycerol Tributyrate) Glyceryl Trinitrate Glyceryl Tripropionate (C2H5COO)3C3H5 (Tripropionin) Glycidyl Acrylate CH2:CHCOOCH2CHCH2O | [ [ [[| Glycol Glycol Diacetate (CH2OOCCH3)2 (Ethylene Acetate) (Ethylene Glycol Diaceate) Glycol Dichloride Glycol Diformate Glycol Dimercaptoacetate (HSCH2C:OOCH2[)2 (GDMA) Glycol Monoacetate Grain Alcohol Hendecane CH3(CH2)9CH3 (Undecane) Heptadecanol C4H9CH(C2H5)C2H4– CH(OH)C2H4CH(C2H5)2 (3,9-Diethyl-6-Tridecanol)

698 (370)

See Glycerine.

See Nitroglycerine.

280 (138) 1.2 mm

See Ethylene Glycol. 900 (482)

See Ethylene Dichloride. See 1,2-Ethanediol Diformate. 396 (202) See Ethylene Glycol Monoacetate. See Ethyl Alcohol.

384 (196)

149 (65)

588 (309)

310 (154)

ORGANIC CHEMISTRY

2.391

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Heptane CH3(CH2)5CH3 2-Heptanol CH3(CH2)4CH(OH)CH3 3-Heptanol CH3CH2CH(OH)C4H9 3-Heptanone 4-Heptanone (C3H7)2CO (Butyrone) (Dipropyl Ketone) 1-Heptene 3-Heptene (mixed cis and trans) C3H7CH:CHC2C5 (3-Heptylene) Heptylamine CH3(CH2)6NH2 (1-Aminoheptane) Heptylene C5H11CH:CH2 (1-Heptene) Heptylene-2-trans C4H9CH:CHCH3 (2-Heptene-trans) Hexachlorobutadiene CCl2:CClCCl:CCl2 Hexachloro Diphenyl Oxide (C6H2Cl3)2O [Bis(Trichlorophenyl) Ether] Hexadecane CH3(CH2)14CH3 (Cetane) tert-Hexadecanethiol C16H33SH (Hexadecyl-tert-Mercaptan) Hexadecylene-1 CH3(CH2)13CH:CH2 (1-Hexadecene) Hexadecyltrichiorosilane C16H33SiCl3 2,4-Hexadienal CH3CH:CHCH:CHC(O)H 1,4-Hexadiene CH3CH:CHCH2CH:CH2 (Allylpropenyl) Hexanal CH3(CH2)4CHO (Caproaldehyde) (Hexaldehyde) Hexane CH3(CH2)4CH3 (Hexyl Hydride)

Boiling point °F (°C) 209 (98) 320 (160) 313 (156)

Flash point, °F (°C)

Ignition point, °F (°C)

290 (143)

25 (−4) 160 (71) 140 (60) See Ethyl Butyl Ketone. 120 (49)

203 (95)

21 (−6)

311 (155)

130 (54)

201 (94)

<32 (<0)

208 (98)

<32 (<0)

399 (204)

See Heptylene.

500 (260)

1130 (610) 1148 (620) 549 (287)

>212 (>100)

298–307 (148–153) @11 mm 525 (274)

(265) (129) >212 (>100)

516 (269) 339 (171) 151 (66)

295 (146) 154 (68) −6 (−21)

268 (131)

90 (32)

156 (69)

−7 (−22)

396 (202)

464 (240)

437 (225) (Continued)

2.392

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 1,2-Hexanediol 2,5-Hexanediol CH3CH(OH)CH2[CH2CH(OH)CH3 (2,5-Dihydroxyhexane) 2,5-Hexanedione 1,2,6-Hexanetriol HOCH2CH(OH)[(CH2)3CH2OH Hexanoic Acid 1-Hexanol 2-Hexanone 3-Hexanone C2H5COC3H7 (Ethyl n-Propyl Ketone) 1-Hexene CH2:CH(CH2)3CH3 (Butyl Ethylene) 2-Hexene-cis C3H7CH:CHCH3 3-Hexenol-cis CH3CH2CH:CHCH2CH2OH (3-Hexen-l-ol) (Leaf Alcohol) Hexyl Acetate (CH3)2CH(CH2)3OOCCH3 (Methylamyl Acetate) Hexyl Alcohol CH3(CH2)4CH2OH (Amyl Carbinol) (1-Hexanol) sec-Hexyl Alcohol C4H9CH(OH)CH3 (2-Hexanol) Hexylamine CH3(CH2)5NH2 Hexyl Chloride Hexyl Cinnamic Aldehyde C6H13C(CHO):CHC6H5 (Hexyl Cinnamaldehyde) Hexylene Glycol CH2OHCHOH(CH2)3CH3 (1,2-Hexanediol) Hexyl Ether C6H13OC6H13 (Dihexyl Ether) Hexyl Methacrylate C6H13OOCC(CH3):CH2 Hydracrylonitrile Hydralin Hydroquinone C6H4(OH)2 (Quinol) (Hydroquinol)

Boiling point °F (°C) 429 (221)

352 (178) @5 mm

253 (123)

Flash point, °F (°C)

See Hexylene Glycol. 230 (110) See Acetonyl Acetone. 375 (191) See Caproic Acid. See Hexyl Alcohol. See Methyl Butyl Ketone. 95 (35)

146 (63)

<20 (<−7)

156 (69) 313 (156)

<−4 (<−20) 130 (54)

285 (141)

113 (45)

311 (155)

145 (63)

284 (140)

136 (58)

269 (132) 486 (252)

85 (29) See 1-Chlorohexane. >212 (>100)

385 (196)

215 (102)

440 (227)

170 (77)

388–464 (198–240)

547 (286)

Ignition point, °F (°C)

487 (253)

365 (185)

180 (82) See Ethylene Cyanohydrin. See Cyclohexanol. 329 960 (165) (516)

ORGANIC CHEMISTRY

2.393

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Boiling point Compound°F (°C) °F (°C) Hydroquinone Di-(β-Hydroxyethyl) Ether C6H4([OCH2CH2OH)2 Hydroquinone Monomethyl Ether CH3OC6H4OH (4-Methoxy Phenol) (Para-Hydroxyanisole) o-Hydroxybenzaldehyde 3-Hydroxybutanal b-Hydroxybutyraldehyde Hydroxycitronellal (CH3)2C(OH)(CH2)3— CH(CH3)CH2CHO (Citronellal Hydrate) (3,7-Dimethyl-7-Hydroxyoctanal) N-(2-Hydroxyethyl)-acetamide 2-Hydroxyethyl Acrylate (HEA) b-Hydroxyethylaniline N-(2-Hydroxyethyl) Cyclohexylamine C6H11NH2 CH2OHCH2NHCH2CH2NH2 4-(2-Hydroxyethyl) Morpholine C2H4OC2H4NC2H4OH | [ [ [[[[| 1-(2-Hydroxyethyl) Piperazine HOCH2CH2[NCH2CH2NHCH2CH2 | [ [ [[[[ [[[| n-(2-Hydroxyethyl) Propylenediamine CH3CH(NHC2H4OH)CH2NH2 4-Hydroxy-4-Methyl-2-Pentanone 2-Hydroxy-2-methylpropionitrile Hydroxypropyl Acrylate o-Hydroxytoluene Ionone Alpha (α-Ionone) C(CH3)2CH2CH2CH:C(CH3)— | [ [ [[[[ [ [ [ [ [[ [[| CHCH:CHC(CH3):O (a-Cyclocitrylideneacetone) [4-(2,6,6-Trimethyl2-Cyclohexen-1-yl)-3-Buten-2-one] Ionone Beta (b-Ionone) C(CH3)2CH2CH2CH2– C(CH3):CCHCHC(CH3):O (b-Cyclocitrylidene-acetone) [4-(2,6,6-Trimethyl-1Cyclohexen-1-yl)-3-Buten-2-one]

Flash point, °F (°C) 365–392 @ 0.3 mm (185–200) 475 (246)

Ignition point, 435 (224)

875 (468)

270 (132)

790 (421)

See Salicylaldehyde. See Aldol. See Aldol. 201–205 (94–96) @1 mm

410 (210)

>212 (>100)

See N-Acetyl Ethanolamine. 214 1.8 (101) @100°C See 2-Anilinoethanol. 249 (121)

437 (225)

210 (99)

475 (246)

255 (124)

465 (241)

259–262 (126–128) @12 mm

284 (140) @18 mm

260 (127) See Diacetone Alcohol. See Acetone Cyanohydrin. See Propylene Glycol Monoacrylate. See o-Cresol. >212 (>100)

>212 (>100)

(Continued)

2.394

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Isoamyl Acetate CH3COOCH2CH2CH(CH3)2 (Banana Oil) (3-Methyl-1-Butanol Acetate) (2-Methyl Butyl Ethanoate) Isoamyl Alcohol (CH3)2CHCH2CH2OH (Isobutyl Carbinol) (Fusel Oil) (3-Methyl-1-Butanol) tert-Isoamyl Alcohol Isoamyl Butyrate C3H7CO2(CH2)2CH(CH3)2 (Isopentyl Butyrate) Isoamyl Chloride (CH3)2CHCH2CH2Cl (1-Chloro-3-Methylbutane) Isobornyl Acetate C10H17OOCCH3 Isobutane (CH3)3CH (2-Methylpropane) Isobutyl Acetate CH3COOCH2CH(CH3)2 (b-Methyl Propyl Ethanoate) Isobutyl Acrylate (CH3)2CHCH2OOCCH:CH2 Isobutyl Alcohol (CH3)2CHCH2OH (Isopropyl Carbinol) (2-Methyl-1-Propanol) Isobutylamine (CH3)2CHCH2NH2 Isobutylbenzene (CH3)2CHCH2C6H5 Isobutyl Butyrate C3H7CO2CH2(CH3)2 Isobutyl Carbinol Isobutyl Chloride (CH3)2CHCH2Cl (1-Chloro-3-Methyl-propane) Isobutylcyclohexane (CH3)2CHCH2C6H11 Isobutylene Isobutyl Formate HCOOCH2CH(CH3)2 Isobutyl Heptyl Ketone (CH3)2CHCH2COCH2[ CH(CH3)CH2CH(CH3)2 (2,6,8-Trimethyl-4-Non-anone) Isobutyl Isobutyrate (CH3)2CHCOOCH2[CH(CH3)2

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

290 (143)

77 (25)

680 (360)

270 (132)

109 (43)

662 (350)

352 (178)

See 2-Methyl-2-Butanol. 138 (59)

212 (100)

<70 (<21)

428–435 (220–224) 11 (−12)

190 (88)

244 (118)

64 (18)

790 (421)

142–145 (61–63) @15 mm 225 (107)

86 (30)

800 (427)

82 (28)

780 (415)

15 (−9) 131 (55) 122 (50) See Isoamyl Alcohol. <70 (<21)

712 (378) 802 (427)

150 (66) 343 (173) 315 (157) 156 (69)

860 (460)

336 (169)

525 (274)

208 (98) 412–426 (211–219)

See 2-Methylpropene. <70 (<21) 195 (91)

608 (320) 770 (410)

291–304 (144–151)

101 (38)

810 (432)

ORGANIC CHEMISTRY

2.395

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Isobutyl Phenylacetate (CH3)2CHCH2OOCCH2C6H5 Isobutyl Phosphate PO4(CH2CH(CH3)2)3 (Triisobutyl Phosphate) Isobutyl Vinyl Ether Isobutyraldehyde (CH3)2CHCHO (2-Methylpropanal) Isobutyric Acid (CH3)2CHCOOH Isobutyric Anhydride [(CH3)2CHCO]2O Isobutyronitrile (CH3)2CHCN (2-Methylpropanenitrile) (Isopropylcyanide) Isodecaldehyde C9H19CO Isodecane C7H15CH(CH3)2 (2-Methylnonane) Isodecanoic Acid C9H19COOH Isoevgenol (CH3CHCH)C6H3OHOCH3 (1-Hydroxy-2 Methoxy4-Propenylbanzene) Isoheptane (CH3)2CHC4H9 (2-Methylhexane) (Ethylisobutylmelhane) tert-Isohexyl Alcohol C2H5(CH3)C(OH)C2H5 (3-Methyl-3-Pentanol) Isooctane (CH3)2CHCH4C(CH3)3 (2,2,4-Trimethylpentane) Isooctyl Alcohol C7H15CH2OH (Isooctanol) Isooctyl Nitrate C8H17NO3 Isooctyl Vinyl Ether Isopentaldehyde (CH3)2CHCH2CHO Isopentane (CH3)2CHCH2CH3 (2-Methylbutane) (Ethyl Dimethyl Methane)

Boiling point °F (°C)

Flash point, °F (°C)

477 (247) 302 (150) @20 mm

>212 (>100) 275 (135)

Ignition point, °F (°C)

See Vinyl Isobutyl Ether. −1 (−18)

385 (196)

306 (152) 360 (182) 214–216 (101–102)

132 (56) 139 (59) 47 (8)

900 (481) 625 (329) 900 (482)

387 (197) 333 (167)

185 (85)

489 (254) 514 (268)

300 (149) >212 (>100)

194 (90)

<0 (−18)

252 (122)

115 (46)

210 (99)

40 (4.5)

83–91 (182–195)

180 (82)

106–109 (41–43) @1 mm

205 (96)

142 (61)

250 (121) 82 (28)

410 (210)

784 (418)

See Vinyl Isooctyl Ether. 48 (9) <–60 788 (<–51) (420)

(Continued)

2.396

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Isopentanoic Acid (CH3)2CHCH2COOH (Isovaleric Acid) Isophorone COCHC(CH3)CH2C(CH3)2CH2 | [ [ [[ [ [ [ [ [ [ [ [ [[| Isophthaloyl Chloride C6H4(COCl)2 (m-Phthalyl Dichloride) Isoprene CH2:C(CH3)CH:CH2 (2-Methyl-1,3-Butadiene) Isopropanol Isopropenyl Acetate CH3COOC(CH3):CH2 (1-Methylvinyl Acetate) Isopropenyl Acetylene CH2:C(CH3)C:CH 2-Isopropoxypropane 3-Isopropoxyproplonitrile (CH3)2CHOCH2CH2CN Isopropyl Acetate (CH3)2CHOOCCH3 Isopropyl Alcohol (CH3)2CHOH (Isopropanol) (Dimethyl Carbinol) (2-Propanol) 87.9% iso Isopropylamine (CH3)2CHNH2 Isopropylbenzene Isopropyl Benzoate C6H5COOCH(CH3)2 Isopropyl Bicyclohexyl C15H28 2-Isopropylbiphenyl C15H16 Isopropyl Carbinol Isopropyl Chloride (CH3)2CHCl (2-Chloropropane) Isopropylcyclohexane (CH3)2CHC6H11 (Hexahydrocumene) (Normanthane) Isopropylcyclohexylamine C6H11NHCHC2H6 Isopropyl Ether (CH3)2CHOCH(CH3)2 (2-Isopropoxypropane) (Diisopropyl Ether)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

361 (183)

781 (416)

419 (215)

184 (84)

529 (276)

356 (180)

93 (34)

−65 (−54)

743 (395)

207 (97)

See Isopropyl Alcohol. 60 (16)

808 (431)

92 (33) 149 (65) @10 mm 194 (90) 181 (83)

860 (460)

<19 (<–7) See Isopropyl Ether. 155 (68) 35 (2) 53 (12)

860 (460) 750 (399)

57

89 (32) 426 (219) 530–541 (277–283) 518 (270) 95 (35)

(14) −35 (−37) See Cumene. 210 (99) 255 (124) 285 (141) See Isobutyl Alcohol. −26 (−32)

310 (154.5)

156 (69)

756 (402)

446 (230) 815 (435) 1100 (593) 541 (283)

93 (34) −18 (−28)

830 (443)

ORGANIC CHEMISTRY

2.397

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Isopropylethylene Isopropyl Formate HCOOCH(CH3)2 (Isopropyl Methanoate) 4-Isopropylheptane C3H7CH(C3H7)C3H7 (m-Dihydroxybenzene) Isopropyl-2-Hydroxypropanoate Isopropyl Lactate CH3CHOHCCOCH(CH3)2 (Isopropyl-2-Hydroxypropionate) Isopropyl Methanoate 4-Isopropyl-1-Methyl Benzene Isopropyl Vinyl Ether Isovalerone Jet Fuel Jet A and Jet A-1 Jet Fuel Jet B Jet Fuel JP-4 Jet Fuel JP-5 Jet Fuel JP-6 Kerosene Lactonitrile CH3CH(OH)CN Lanolin (Wool Grease) Lard Oil (Commercial or Animal) No. 1

Boiling point °F (°C)

Ignition point, °F (°C)

153 (67)

See 3-Methyl-1-Butene. 22 905 (−6) (485)

155 (68)

491 (255) See Isopropyl Lactate.

331–334 (166–168)

400–550 (204–288)

250 (121) 361 (183)

Lard Oil (Pure) No. 2 Mineral Lauryl Alcohol Lauryl Bromide CH3(CH2)10CH2Br (Dodecyl Bromide) Lauryl Mercaptan Linalool (CH3)2C:CHCH2CH2C(CH3)— OHCA:CH2 (3,7-Dimethyl-1,6-Octadiene-3-01) Linseed Oil

Flash point, °F (°C)

356 (180) @45 mm 383–390 (195-199)

600+ (316+)

130 (54) See Isopropyl Formate. See p-Cymene. See Vinyl Isopropyl Ether. See Diisobutyl Ketone. 110–150 (43–66) −10 to +30 (−23 to –1) −10 to +30 (−23 to –1) 95–145 (35–63) 100 (38) See Fuel Oil No. 1. 171 (77) 460 (238) 395 (202) 440 (227) 500 (260) 419 (215) 404 (207) See 1-Dodecanol. 291 (144)

464 (240) 475 (246) 446 (230)

833 (445) 833 (445)

See 1-Dodecanethiol. 160 (71)

432 (222)

650 (343) (Continued)

2.398

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Lubricating Oil (Paraffin Oil, includes Motor Oil) Lubricating Oil, Spindle (Spindle Oil) Lubricating Oil, Turbine (Turbine Oil) Lynalyl Acetate (CH3)2C:CHCH2CH2— C([OOCCH3)CH:CH2 (Bergamol) Maleic Anhydride (COCH)2O Marsh Gas 2-Mercaptoethanol HSCH2CH2OH Mesitylene Mesityl Oxide (CH3)2CCHCOCH3 Metaldehyde (C2H4O)4 a-Methacrolein Methacrylic Acid CH2:C(CH3)COOH Methacrylonitrile C4H5N Methallyl Alcohol CH2C(CH3)CH2OH Methallyl Chloride CH2C(CH3)CH2Cl Methane CH4 (Marsh Gas) Methanol Methanethiol o-Methoxybenzaldehyde CH3OC6H4CHO (o-Anisaldehyde) Methoxybenzene 3-Methoxybutanol CH3CH(OCH3)CH2CH2OH 3-Methoxybutyl Acetate CH3OCH(CH3)CH2CH2OOCCH3 (Butoxyl) 3-Methoxybutyraldehyde CH3CH(OCH3)CH2CHO (Aldol Ether) 2-Methoxyethanol

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

680 (360)

300–450 (149–232)

500–700 (260–371) 478 (248) 700 (371)

226–230 (108–110)

169 (76) 400 (204) 185 (85)

396 (202) 315 (157) 266 (130) subl. 233–240 (112–116) 316 (158) 194 (90) 237 (114) 162 (72) −259 (−162)

275 (135)

322 (161) 275-343 (135–173) 262 (128)

215 890 (102) (477) See Methane. 165 (74) See 1,3,5-Trimethylbenzene. 87 652 (31) (344) 97 (36) See 2-Methylpropenal. 171 (77) 34 (1.1) 92 (33) 11 (−12)

154 (68)

999 (537) See Methyl Alcohol. See Methyl Mercaptan. 104 (40) See Anisole. 165 (74) 170 (77) 140 (60) See Ethylene Glycol Monomethyl Ether.

ORGANIC CHEMISTRY

2.399

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2-Methoxyethyl Acrylate C2H3COOC2H4OCH3 Methoxy Ethyl Phthalate (Methox) 3-Methoxypropionitrile CH3OC2H4CN 3-Methoxypropylamine CH3OC3H6NH2 Methoxy Triglycol CH3O(C2H4O)3H (Triethylene Glycol, Methyl Ether) Methoxytriglycol Acetate CH3COO(C2H4O)3CH3 Methyl Abietate C19H29COOCH3 (Abalyn) Methyl Acetate CH3COOCH3 (Acetic Acid Methyl Ester) (Methyl Acetic Ester) Methyl Acetic Ester Methyl Acetoacetate CH3CO2CH2COCH3 P-Methyl Acetophenone CH3C6H4COCH3 (Methyl-p-Tolyl Ketone) (p-Acetotoluene) Methylacetylene Methyl Acrylate CH2:CHCOOCH3 Methylal CH3OCH2OCH3 (Dimethoxymethane) (Formal) Methyl Alcohol CH3OH (Methanol) (Wood Alcohol) Methylamine CH3NH2 2-(Methylamino) Ethanol Methylamyl Acetate Methylamyl Alcohol Methyl Amyl Ketone CH3CO(CH2)4CH3 2-Heptanone 2-Methylaniline 4-Methylaniline Methyl Anthranilate H2NC6H4CO2CH3 (Methyl-ortho-Amino Benzoate) (Nevoli Oil, Artificial)

Boiling point °F (°C)

Flash point, °F (°C)

142 (61) @17 mm 376–412 (191–211) 320 (160) 241 (116) 480 (249)

180 (82)

266 (130) 680–689 (360–365) Decomposes 140 (60)

Ignition point, °F (°C)

275 (135) 149 (65) 90 (32) 245 (118) 260 (127) 356 (180) 14 (−10) (454)

850 3.1 16

338 (170) 439 (226)

See Methyl Acetate. 170 (77) 205 (96)

176 (80) 111 (44)

See Propyne. 27 (−3) −26 (−32)

875 (468) 459 (237)

147 (64)

52 (11)

867 (464)

21 (−6)

806 4 (430) See N-Methylethanolamine. See Hexyl Acetate. See Methyl Isobutyl Carbinol. 102 740 (39) (393)

302 (150)

536 (280)

See o-Toluidine. See p-Toluidine. 275 @15 mm (135)

>212 (>100)

(Continued)

2.400

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Methylbenzene Methyl Benzoate C6H5COOCH3 (Niobe Oil) a-Methylbenzyl Alcohol a-Methylbenzylamine C6H5CH(CH3)NH2 a-Methylbenzyl Dimethyl Amine C6H5CH(CH3)N(CH3)2 a-Methylbenzyl Ether C6H5CH(CH3)OCH(CH3)C6H5 2-Methylbiphenyl C6H5C6H4CH3 Methyl Borate B(OCH3)3 (Trimethyl Borate) Methyl Bromide CH3Br (Bromomethane) 2-Methyl-1,3-Butadiene 2-Methylbutane 3-Methyl-2-Butanethiol C5H11SH (Sec-Isoamyl Mercaptan) 2-Methyl-1-Butanol CH3CH2CH(CH3)CH2OH 2-Methyl-2-Butanol CH3CH2(CH3)2COH (tert-Isoamyl Alcohol) (Dimethyl Ethyl Carbinol) 3-Methyl-1-Butanol 3-Methyl-1-Butanol Acetate 2-Methyl-1-Butene CH2:C(CH3)CH2CH3 2-Methyl-2-Butene (CH3)2C:CCHCH3 (Trimethylethylene) 3-Methyl-1-Butene (CH3)2CHCH:CH2 (Isopropylethylene) N-Methylbutylamine CH3CH2CH2CH2NHCH3 2-Methyl Butyl Ethanoate Methyl Butyl Ketone CH3CO(CH2)3CH3 (2-Hexanone) 3-Methyl Butynol (CH3)2C(OH)C:CH 2-Methylbutyraldehyde CH3CH2CH(CH3)CHO Methyl Butyrate CH3OOCCH2CH2CH3

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

302 (150)

181 (83)

371 (188) 384 (196)

See Phenyl Methyl Carbinol. 175 (79) 175 (79)

548 (287) 492 (255) 156 (69)

275 (135) 280 (137) <80 (<27)

38.4 (4)

999 (537)

See Toluene

936 (502)

See Isoprene. See Isopentane. 230 (110)

37 (3)

262 (128) 215 (102)

122 (50) 67 (19)

725 (385) 819 (437)

See Isoamyl Alcohol. See Isoamyl Acetate. 88 (31) 101 (38)

<20 (<–7) <20 (<–7)

68 (20)

<20 (<–7)

196 (91)

55 (13)

262 (128)

77 (25)

218 (103) 198–199 (92–93) 215 (102)

77 (25) 49 (9) 57 (14)

689 (365)

See Isoamyl Acetate. 795 (423)

2.401

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Methyl Carbonate CO(OCH3)2 (Dimethyl Carbonate) Methyl Cellosolve Acetate CH3COOC2H4OCH3 (2-Methoxyethyl Acetate) Methyl Chloride CH3Cl (Chloromethane) Methyl Chloroacetate CH2ClCOOCH3 (Methyl Chloroethanoate) Methyl Chloroethanoate Methyl-p-Cresol CH3C6H4OCH3 (p-Methylanisole) Methyl Cyanide Methylcyclohexane CH2(CH2)4CHCH3 | [ [ [ [[[| (Cyclohexylmethane) (Hexahydrotoluene) 2-Methylcyclohexanol C7H13OH 3-Methylcyclohexonol CH3C6H10OH 4-Methylcyclohexanol C7H13OH Methylcyclohexanone C7H12O 4-Methylcyclohexene CH:CHCH2CH(CH3)CH2CH2 | [ [ [ [[[[[[[[[ [| Methylcyclohexyl Acetate C9H16O2 Methyl Cyclopentadiene C6H8 Methylcyclopentane C6H12 2-Methyldecane CH3(CH2)7CH(CH3)2 Methyldichlorosilane CH3HsiCl2 N-Methyldiethanolamine CH3N(C2H4OH)2 1-Methyl-3,5-Diethyl-benzene (CH3)C6H3(C2H5)2 (3,5-Diethyltoluene) Methyl Dihydroabietate C19H31COOCH3 Methylene Chloride CH2Cl2 (Dichloromethane)

Boiling point °F (°C)

Flash point, °F (°C)

192 (89)

66 (19) (oc) ~111 (~44)

292 (144) −11 (−24)

−50

266 (130)

135 (57)

Ignition point, °F (°C)

1170 (632)

See Methyl Chloroacetate. 140 (60) See Acetonitrile. 214 (101)

25 (−4)

482 (250)

329 (165)

149 (65) 158 (70) 158 (70) 118 (48) 30 (−1)

565 (296) 563 (295) 563 (295)

343 (173) 325 (163) 217 (103) 351–381 (177–194) 163 (73) 161 (72) 374 (190) 106 (41) 464 (240) 394 (201)

147 (64) 120 (49) <20 (<–7)

689–698 (365–370) 104 (40)

361 (183)

15 (−9) 260 (127)

833 (445) 496 (258) 437 (225) >600 (316)

851 (455)

None

1033 (556) (Continued)

2.402

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Methylenedianiline H2NC6H4CH2C6H4NH2 (MDA) (p,p′-DiaminodiPhenylmethane) Methylene Dlisocyanate CH2(NCO)2 Methylene Oxide N-Methylethanolamine CH3NHCH2CH2OH (2-(Methylamino) Ethanol) Methyl Ether (CH3)2O (Dimethyl Ether) (Methyl Oxide) Methyl Ethyl Carbinol 2-Methyl-2-Ethyl1,3-Dioxolane (CH3)(C2H5)COCH2CH2O | [ [ [[[ [| Methyl Ethylene Glycol Methyl Ethyl Ether CH3OC2H5 (Ethyl Methyl Ether) 2-Methyl-4-Ethylhexane (CH3)2CHCH2CH(C2H5)2 (4-Ethyl-2-Methylhexane) 3-Methyl-4-Ethylhexane C2H5CH(CH3)CH(C2H5)2 (3-Ethyl-4-Methylhexane) Methyl Ethyl Ketone C2H5COCH3 (2-Butanone) (Ethyl Methyl Ketone) Methyl Ethyl Ketoxime CH3C(C2H5):HOH 2-Methyl-3-Ethylpentane (CH3)2CHCH(C2H5)2 (3-Ethyl-2-Methylpentane) 2-Methyl-5-Ethyl-piperidine NHCH(CH3)CH2CH2CH(C2H5)CH2 | [ [ [ [[[[[[[[[ [ [ [ [ [| 2-Methyl-5-Ethylpyridine N:C(CH3)CH:CHC(C2H5):CH | [ [ [ [[[[[[[ [ [[ [ [| Methyl Formate CH3OOCH (Formic Acid, Methyl Ether) 2-Methylfuran C4H3OCH3 (Sylvan) Methyl Glycol Acetate CH2OHCHOHCH2CO1CH3 (Propylene Glycol Acetate)

Boiling point °F (°C)

Flash point, °F (°C)

748–750 (398–399) @78 mm

428

Ignition point, °F (°C)

(220) 185 (85) See Formaldehyde. 319 (159) −11 (−24)

165 (74) Gas

662 (350)

244 (118)

See sec-Butyl Alcohol. 74 (23)

51 (11)

See Propylene Glycol. −35 (−37)

374 (190)

273 (134)

<70 (<21)

536 (280)

284 (140)

75 (24)

176 (80)

16 (−9)

759 (404)

306–307 (152–153) 241 (116)

156–170 (69–77) <70 (<21)

860 (460)

326 (163)

126 (52)

353 (178)

155 (68)

90 (32)

−2 (−19)

144–147 (62–64)

−22 (−30) 111 (44)

840 (449)

ORGANIC CHEMISTRY

2.403

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Methyl Heptolocyl Ketone C17H35COCH3 Methylheptenone (CH3)2C:CH(CH2)2COCH3 (6-Methyl-5-Hepten-2-one) Methyl Heptine Carbonate CH3(CH2)4C:CCOOCH3 (Methyl 2-Octynoate) Methyl Heptyl Ketone C7H15COCH4 (5-Methyl-2-Octanone) 2-Methylhexane (CH3)2CH(CH2)3CH3 3-Methylhexane CH3CH2CH(CH3)CH2CH2CH3 Methyl Hexyl Ketone CH3COC6H13 (2-Octanone) (Octanone) Methyl-3-Hydroxybutyrate CH3CHOHCH2COOCH3 Methyl Ionone C14H22O (Irone) Methyl Isoamyl Ketone CH3COCH2CH2CH(CH3)2 Methyl Isobutyl Carbinol CH3CHOHCH2CHCH3CH3 (1,3-Dimethylbutanol) (4-Methyl-2-Pentanol) (Methylamyl Alcohol) Methylisobutylcarbinol Acetate Methyl Isobutyl Ketone CH3COCH2CH(CH3)2 (Hexone) (4-Methyl-2-Pentanone) Methyl Isopropenyl Ketone CH2COC:CH2(CH3) Methyl Isocyanate CH3NCO (Methyl Carbonimide) Methyl Iso Eugenol CH3CH:CHC6H3(OCH3)2 (Propenyl Guaiacol) Methyl Lactate CH3CHOHCOOCH3

Methyl Mercaptan CH3SH (Methanethiol)

Boiling point °F (°C)

Flash point, °F (°C)

329 (165) @3 mm 343–345 (173–174)

255 (124)

Ignition point, °F (°C)

135 (57) 190 (88)

361–383 (183–195)

140 (60)

680 (360)

194 (90) 198 (92) 344 (173.5)

<0 (<–18) 25 (−4) 125 (52)

536 (280) 536 (280)

347 (175) 291 (144) @16 mm 294 (146) 266–271 (130–133)

180 (82) >212 (>100) 96 (36) 106 (41)

375 (191)

See 4-Methyl-2Pentanol Acetate. 244 (118)

64 (18)

840 (448)

208 (98) 102 (39)

19 (−7)

994 (534)

504–507 (262–264)

>212 (>100)

293 (145) @2.2 mm

121 725 (49) (385)

@2.2 mm 212 (100)

42.4 (6) (Continued)

2.404

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound b-Methyl Mercaptopropionaldehyde CH3SC2H4CHO (3-(Methylthio) Propionalde-hyde) Methyl Methacrylate CH2:C(CH3)COOCH3 Methyl Methanoate 4-Methylmorpholine C2H4OC2H4NCH3 | [ [ [ [ [ [ [ [ [| 1-Methylnaphthalene C10H7CH3 Methyl Nonyl Ketone C9H19COCH3 Methyl Oxide Methyl Pentadecyl Ketone C15H31COCH3 2-Methyl-1,3-Pentadiene CH2:C(CH3)CH:CHCH3 4-Methyl-1,3-Pentadiene CH2:CHCH2:C(CH3)2 Methylpentaldehyde CH3CH2CH2C(CH3)HCHO | [ [ [ [[[[[[[ [ [ [ [| (Methyl Pentanal) Methyl Pentanal 2-Methylpentane (CH3)2CH(CH2)2CH3 (Isohexane) 3-Methylpentane CH3CH2CH(CH3)CH2CH3 2-Methyl-1,3-Pentanediol CH3CH2CH(OH)CH(CH3)CH2OH 2-Methyl-2,4-Pentanediol (CH3)2C(OH)CH2CH(OH)CH3 2-Methylpentanoic Acid C3H7CH(CH3)COOH 2-Methyl-1-Pentanol CH3(CH2)2CH(CH3)CH2OH 4-Methyl-2-Pentanol 4-Methyl-2-Pentanol Acetate CH3COOCH(CH3)CH2CH(CH3)2 (Methylisobutylcarbinol Acetate) 4-Methyl-2-Pentanone 2-Methyl-1-Pentene CH2:C(CH3)CH2CH2CH3 4-Methyl-1-Pentene CH2:CHCH2CH(CH3)2

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

~329 (~165)

142 (61)

491 (255)

212 (100)

50 (10) See Methyl Formate. 75 (24)

239 (115) 472 (244) 433 (223) 313 (156) @3 mm 169 (76) 168 (76) 243 (117)

140 (60) 146 (63) 419 (215) 385 (196) 381 (194) 298 (148)

984 (529) 192 (89) See Methyl Ether. 248 (120) <–4 (<–20) −30 (−34) 68 (20) See Methylpentaldehyde. <20 583 (<–7) (306)

295 (146)

<20 532 (<–7) (278) 230 (110) 205 (96) 225 712 (107) (378) 129 590 (54) (310) See Methyl Isobutyl Carbinol. 110 660 (43) (349)

143 (62) 129 (54)

See Methyl Isobutyl Ketone. <20 572 (<−7) (300) <20 572 (<–7) (300)

ORGANIC CHEMISTRY

2.405

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2-Methyl-2-Pentene (CH3)2C:CHCH2CH3 4-Methyl-2-Pentene CH3CH:CHCH(CH3)2 3-Methyl-1-Pentynol (C2H5)(CH3)C(OH)C:CH o-Methyl Phenol Methyl Phenylacetate C6H5CH2COOCH3 Methylphenyl Carbinol C6H5CH(CH3)OH (a-Methylbenzyl Alcohol) (Styralyl Alcohol) (sec-Phenethyl Alcohol) Methyl Phenyl Carbinyl Acetate C6H5CH(CH3)OOCH3 (a-Methyl-Benzyl Acetate) (Styrolyl Acetate) (sec-Phenylethyl Acetate) (Phenyl Methylcarbinyl Acetate) Methyl Phenyl Ether Methyl Phthalyl Ethyl Glycolate CH3COOC6H4COO– CH2COOC2H5 1-Methyl Piperazine CH3NCH2CH2NHCH2CH2 | [ [ [ [[[[ [ [ [ [| 2-Methylpropanal 2-Methylpropane 2-Methyl-2-Propanethiol (CH3)3CSH (tert-Butyl Mercaptan) 2-Methyl Propanol-1 2-Methyl-2-Propanol 2-Methylpropenal CH2:C(CH3)CHO (Methacrolein) (a-Methyl Acrolein) 2-Methylpropene CH2:C(CH3)CH3 (g-Butylene) (Isobutylene) Methyl Propionate CH3COOCH2CH3 Methyl Propyl Acetylene CH3C2H4ClCCH3 (2-Hexyne) Methyl Propyl Carbinol CH3CHOHC3H7 (2-Pentanol)

Boiling point °F (°C)

Flash point, °F (°C)

153 (67) 133–137 (56–58) 250 (121)

<20 (<–7) <20 (<–7) 101 (38)

424 (218) 399 (204)

195 (91) 200 (93)

Ignition point, °F (°C)

See o-Cresol.

195 (91)

See Anisole. 590 (310)

380 (193)

280 (138)

108 (42)

149–153 (65–67)

See Isobutyraldehyde. See Isobutane. <–20 (<–29) See Isobutyl Alcohol. See tert-Butyl Alcohol.

154 (68)

35 (2)

20 (−7)

869 (465)

176 (80) 185 (85)

28 (−2) <14 (<–10)

247 (119)

105 (41)

876 (469)

(Continued)

2.406

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Methylpropylcarbinylumine Methyl n-Propyl Ether CH3OC3H7 Methyl Propyl Ketone CH3COC3H7 (2-Pentanone) 2-Methylpyrazine N:C(CH3)CH:NCH:CH | [ [ [ [[[[ [ [ [ [| 2-Methyl Pyridine Methylpyrrole N(CH3)CH:CHCH:CH | [ [ [ [[[[ [ [ [ [| Methylpyrrolidine CH3NC4H5 1-Methyl-2-Pyrrolidone CH3NCOCH2CH2CH2 | [ [ [ [[[[ [| (N-Methyl-2-Pyrrolidone) Methyl Salicylate HOC6H4COOCH3 (Oil of Wintergreen) (Gaultheria Oil) (Betula Oil) (Sweet-Birch Oil) Methyl Stearate C17H35COOCH3 a-Methylstyrene 1-Methylethenyl Benzene 1-Methyl-1-phenylethene Methyl Sulfate 2-Methyltetrahydrofuran C4H7OCH3 Methyl Toluene Sulfonate CH3C6H4SO3CH3 Methyltrichlorosilane CH3SiCl3 (Methyl Silico Chloroform) (Trichloromethylsilane) Methyl Undecyl Ketone C11H23COCH3 (2-Tridecanone) 1-Methylvinyl Acetate Methyl Vinyl Ether Methyl Vinyl Ketone CH3COCH:CH2 Mineral Wax Morpholine OC2H4NHCH2CH2 | [ [ [ [[[ [ [ [| Mustard Oil C3H5N:C:S (Allyl Isothiocyanate)

Boiling point °F (°C) 102 (39) 216 (102)

Flash point, °F (°C)

Ignition point, °F (°C)

See sec-Amylamine. <–4 (<–20) 45 (7)

846 (452)

122 (50) See 2-Picoline. 234 (112)

61 (16)

180 (82) 396 (202)

7 (−14) 204 (96)

655 (346)

432 (222)

205 (96)

850 (454)

421 (216) 329–331 (165–166)

307 (153) 129 (54)

1066 (574)

176 (80) 315 (157) @8 mm 151 (66)

248 (120)

See Dimethyl Sulfate. 12 (−11) 306 (152) 15 (−9)

225 (107)

262 (128)

See Isopropenyl Acetate. See Vinyl Methyl Ether. 20 (−7) See Wax, Ozocerite. 98 (37)

304 (151)

115 (46)

177 (81)

>760 (>404)

915 (491) 555 (290)

ORGANIC CHEMISTRY

2.407

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound

Boiling point °F (°C)

Naphtha, Coal Naphtha, Petroleum Naphtha V.M. & P., 50° Flash (10) Naphtha V.M. & P., High Flash Naphtha V.M. & P., Regular Naphthalene C10H8 b-Naphthol C10H7OH (b-Hydroxy Naphthalene) (2-Naphthol) 1-Naphthylamine C10H7NH2 Nechexane Neopentone Neopentyl Glycol HOCH2C(CH3)2CH2OH (2,2-Dimethyl 1,3 Propanediol) Nicoline C10H14N2 Niobe Oil Nitric Ether p-Nitroaniline NO2C6H4NH2 Nitrobenzene C6H5NO2 (Nitrobenzol) (Oil of Mirbane) 1,3-Nitrobenzotrifluoride C6H4NO2CF3 a,m,a-Trifluoronitrotoluene Nitrobenzol Nitrobiphenyl C6H5C6H4NO2 p-Nitrochlorobenzene C6H4ClNO2 (1-Chloro-4-Nitrobenzene) Nitrocyclohexane CH2(CH2)4CHNO2 Nitroethane C2H5NO2 Nitroglycerine C3H5(NO3)3 (Glyceryl Trinitrate) Nitromethane CH3NO2 1-Nitronaphthalene C10H7NO2

240–290 (116–143) 280–350 (138–177) 212–320 (100–160) 424 (218) 545 (285)

572 (300)

Flash point, °F (°C)

Ignition point, °F (°C)

107 (42) See Petroleum Ether. 50 (10) 85 (29) 28 (−2) 174 (79) 307 (153)

531 (277) 450 (232) 450 (232) 450 (232) 979 (526)

410 (210)

315 (157) See 2,2-Dimethylbutane. See 2,2-Dimethylpropane. 265 750 (129) (399)

475 (246)

471 (244)

637 (336) 412 (211)

See Methyl Benzoate. See Ethyl Nitrate. 390 (199) 190 (88)

397 (203)

217 (103)

626 (330) 468 (242)

See Nitrobenzene. 290 (143) 261 (127)

403 (206) Decomposes 237 (114) 502 (261) Explodes 214 (101) 579 (304)

900 (482)

190 (88) 82 (28) Explodes

778 (414) 518 (270)

95 (35) 327 (164)

785 (418)

(Continued)

2.408

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 1-Nitropropane CH3CH2CH2NO2 2-Nitropropane CH3CH(NO2)CH3 (sec-Nitropropane) sec-Nitropropane m-Nitrotoluene C6H4CH3NO2 o-Nitrotoluene C6H4CH3NO2 p-Nitrotoluene HO2C6H4CH3 2-Nitro-p-toludine CH3C6H3(NH2)NO2 Nitrous Ether Nonadecane CH3(CH2)17CH3 Nonane C9H20 Nonane (iso) C6H13CH(CH3)2 (2-Methyloctane) Nonane C5H11CH(CH3)C2H5 (3-Methyloctane) Nonane C4H9CH(CH3)C3H7 (4-Methyloctane) Nonene C9H18 (Nonylene) Nonyl Acetate CH2COOC9H19 Nonyl Alcohol Nonylbenzene C9H19C6H5 tert-Nonyl Mercaptan C9H19SH Nonylnaphthalene C9H19C10H7 Nonylphenol C6H4(C9H19)OH 2,5-Norbornadiene C7H8 (NBD) Octadecane C18H38 Octadecylene a CH3(CH2)15CH:CH2 (1-Octadecene) Octadecyltrichlorosilane C18H37SiCl3 (Trichlorooctadecylsilane)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

268 (131) 248 (120)

96 (36) 75 (24)

789 (421) 802 (428)

450 (232) 432 (222) 461 (238)

628 (331) 303 (151) 290 (143)

See 2-Nitropropane. 223 (106) 223 (106) 223 (106) 315 (157) See Ethyl Nitrite. >212 (>100) 88 (31)

446 (230) 401 (205) 428 (220)

291 (144)

428 (220)

288 (142)

437 (225)

270–290 (132–143) 378 (192) 468–486 (242–252) 370–385 (188–196) 626–653 (330–345) 559–567 (293–297) 193 (89)

78 (26) 155 (68) See Diisobutyl Carbinol. 210 (99) 154 (68) <200 (<93) 285 (141) −6 (−21)

603 (317) 599 (315)

>212 (>100) >212 (>100)

716 (380)

193 (89)

441 (227) 482 (250)

ORGANIC CHEMISTRY

2.409

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Octadecyl Vinyl Ether Octane CH3(CH2)6CH3 1-Octanethiol C8H17SH (n-Octyl Mercapian) 1-Octanol 2-Octanol CH3CHOH(CH2)5CH3 1-Octene CH2:C7H14 Octyl Acetate Octyl Alcohol CH3(CH2)6CH2OH (1-Octanol) Octylamine CH3(CH2)6CH2NH2 (1-Aminooctane) tert-Octylamine (CH3)3CCH2C(CH3)2NH2 (1,1,3,3-Tetramethylbutylamine) Octyl Chloride CH3(CH2)7Cl Octylene Glycol (CH3(CH2)2CHOH)2 tert-Octyl Mercaptan C8H17SH

Boiling point °F (°C) 258 (126) 390 (199)

Oxalic Ether Oxirane Paraffin Oil (See also Lubricating Oil) Paraformaldehyde HO(CH2O)nH Paraldehyde (CH3CHO)3 1,2,3,4,5-Pentamethyl Benzene C6H(CH3)5 (Pentamethylbenzene)

Ignition point, °F (°C)

See Vinyl Octodecyl Ether. 56 403 (13) (206) 156 (69)

381 (194)

See Octyl Alcohol. 190 (88) 70 446 (21) (230) See 2-Ethylhexyl Acetate. 178 (81)

338 (170)

140 (60)

284 (140)

91 (33)

363 (184) 250 (121)

359 (182) 475 (246) 318–329 (159–165)

p-Octylphenyl Salicylate C21H26O3 Oil of Mirbane Oil of Wintergreen Oleic Acid C8H17CH:CH(CH2)7COOH (Red Oil) Distilled

Flash point, °F (°C)

158 (70) 230 (110) 115 (46) (oc) 420 (216) See Nitrobenzene. See Methyl Salicylate.

547 (286)

372 (189)

255 (124) 449 (232)

364 (184) See Ethyl Oxalate. See Ethylene Oxide. 444 (229) 158 (70) 96 (36) 200 (93)

635 (335)

780 (416)

685 (363)

572 (300) 460 (238) 800 est (427)

(Continued)

2.410

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Pentamethylene Dichloride Pentamethylene Glycol Pentamethylene Oxide O(CH2)4CH2 | [ [ [ [ [ [| (Tetrahydropyran) Pentanal Pentane CH3(CH2)3CH3 1,5-Pentanediol HO(CH2)5OH (Pentamethylene Glycol) 2,4-Pentanedione CH3COCH2COCH3 (Acetyl Acetone) Pentanoic Acid C4H9COOH (Valeric Acid) 1-Pentanol 2-Pentanol 3-Pentanol CH3CH2CH(OH)CH2CH3 (tert-n-Amyl Alcohol) 1-Pentanol Acetate 2-Pentanol Acetate 2-Pentanone 3-Pentanone Pentaphen C5H11C6H4OH (p-tert-Amyl Phenol) 1-Pentene CH3(CH2)2CH:CH2 (Amylene) 1-Pentene-cis 2-Pentene-trans Pentylamine Pentyloxypentane Pentyl Propionate 1-Pentyne HC1CC3H7 (n-Propyl Acetylene) Perchloroethylene Cl2C˙CCl2 (Tetrachloroethylene) Perhydrophenanthrene C14H24 (Tetradecahydro Phenanthrene) Petroleum, Crude Oil

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

See 1,5-Dichloropentane. See 1,5-Pentanediol. 178 (81)

−4 (−20)

97 (36) 468 (242)

See Valeraldehyde. <–40 (<–40) 265 (129)

500 (260) 635 (335)

284 (140)

93 (34)

644 (340)

366 (186)

205 (96)

752 (400)

241 (116)

See Amyl Alcohol. See Methyl Propyl Carbinol. 105 815 (41) (435)

482 (250)

See Amyl Acetate. See sec-Amyl Acetate. See Methyl Propyl Ketone. See Diethyl Ketone. 232 (111)

86 (30)

0 (−18)

527 (275) See b-Amylene-cis. See b-Amylene-trans. See Amylamine. See Amyl Ether. See Amyl Propionate.

104 (40)

<–4 (<–20)

250 (121)

None

187–192 (86–89)

None

475 (246)

20–90 (−7 to 32)

2.411

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Petroleum Ether (Benzine) (Petroleum Naphtha) Petroleum Pitch b-Pheliandrene CH2:CCH:CHCH[CH(CH3)2]CH2CH2 | [ [ [ [[[[ [ [ [ [ [ [ [ [ [ [| (p-Mentha-1(7), 2-Diene) Phenanthrene (C6H4CH)2 (Phenanthrin) Phenethyl Alcohol C6H5CH2CH2OH (Benzyl Carbinol) (Phenylethyl Alcohol) o-Phenetidine H2NC6H4OC2H5 (2-Ethoxyaniline) (o-Amino-Phenetole) p-Phenetidine C2H5OC0H4NH2 (1-Amino-4-Ethoxy-benzene) (p-Aminophenetole) Phenetole Phenol C6H5OH (Carbolic Acid) 2-Phenoxyethanol Phenoxy Ethyl Alcohol C6H5O(CH2)2OH (2-Phenoxyethanol) (Phenyl Cellosolve) N-(2-Phenoxyethyl) Anlline C6H5O(CH2)3NHC6H5 b-Phenoxyethyl Chloride Phenylacetaldehyde C6H5CH2CHO (a-Toluic Aldehyde) Phenyl Acetate CH3COOC6H5 (Acetylphenol) Phenylocetic Acid C6H5CH2COOH (a-Toluic Acid) Phenylamine N-Phenylaniline Phenylbenzene Phenyl Bromide Phenyl Carbinol Phenyl Chloride Phenyicyclohexane Phenyl Didecyl Phosphite (C6H5O)P(OC10H21)2

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

95–140 (35–60)

<0 (<–18)

550 (288)

340 (171)

120 (49)

644 (340)

340 (171)

430 (221)

205 (96)

442–446 (228–230)

239 (115)

378–484 (192–251)

241 (116)

358 (181)

175 (79)

See Asphalt.

See Ethoxybenzene. 1319 (715) See Ethylene Glycol, Phenyl Ether. 468 (242)

250 (121)

396 (202) 383 (195)

338 (170) See b-Chlorophenetole. 160 (71)

384 (196)

176 (80)

504 (262)

>212 (>100) See Aniline. See Diphenylamine. See Biphenyl. See Bromobenzene. See Benzyl Alcohol. See Chlorobenzene. See Cyclohexylbenzene. 425 (218) (Continued)

2.412

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound N-Phenyldiethanolamine C6H5N(C2H4OH)2 Phenyidiethylamine o-Phenylenediamine NH2C6H4NH2 (1,2-Diaminobenzene) Phenylethane N-Phenylethanolamine C6H5NHC2H4OH Phenylethyl Acetate (b) C6H5CH2CH2OOCCH3 Phenylethyl Alcohol Phenylethylene N-Phenyl-N-Ethylethanolamine C6H5N(C2H5)C2H4OH Phenylhydrazine C6H5NHNH2 Phenylmethane Phenylmethyl Ethanol Amine C6H5N(CH3)C2H4OH (2-(N-Methylaniline)Ethanol) Phenyl Methyl Ketone 4-Phenylmorpheline C6H5NC2H4OCH2CH2 | [ [ [ [ [ [ [ [ [| Phenylpentane o-Phenylphenol C6H5C6H4OH Phenylpropane 2-Phenylpropane Phenylpropyl Alcohol C6H5(CH2)3OH (Hydrocinnamic Alcohol) (3-Phenyl-l-propanol) (Phenylethyl Carbinol) Phenyl Propyl Aldehyde C6H5CH2CH2CHO (3-Phenylpropionaldehyde) (Hydrocinnamic Aldehyde) Phenyl Toluene o C6H5C6H4CH3 (2-Methylbiphenyl) Phorone (CH3)2CCHCOCHC(CH3)2 Phosphine PH3 Phthalic Acid C6H4(COOH)2 Phthalic Anhydride C6H4(CO)2O

Boiling point °F (°C) 376 (191) 513 (267)

545 (285) 435 (224)

514 (268) @740 mm

Flash point, °F (°C)

Ignition point, °F (°C)

385 (196) See N,N-Diethylaniline. 313 (156) See Ethylbenzene. 305 (152) 230 (110) See Phenethyl Alcohol. See Styrene. 270 (132) (oc)

Decomposes

190 (88)

378 (192) @100 mm

280 (138)

730 (387)

685 (362)

See Toluene.

518 (270)

547 (286)

426 (219)

See Acetophenone. 220 (104) (oc) See Amylbenzene. 255 (124) See Propylbenzene. See Cumene. 212 (100)

986 (530)

205 (96)

500 (260)

>212 (>100)

388 (198) −126 (−88) 552 (289) 543 (284)

185 (85)

923 (495)

212 (100) 334 (168) 305 (152)

1058 (570)

2.413

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound m-Phthalyl Dichloride 2-Picoline CH3C5H4N (2-Methylpyridine) 4-Picoline CH3C5H4N (4-Methylpyridine) Pinane C10H18 a-Pinene C10H16 Pine Oil Steam Distilled

Pine Pitch Pine Tar Pine Tar Oil (Wood Tar Oil) Piperazine HNCH2CH2NHCH2CH2 | [ [ [ [ [ [ [ [ [ [ [ [ [ [| Piperidine (CH2)5NH (Hexahydropyridine) Polyamyl Naphthalene Mixture of Polymers Polyethylene Glycols OH(C2H5O)nC2H4OH Polyoxyethylene Lauryl Ether C12H25O(OCH2CH2)nOH Polypropylene Glycols OH(C3H6O)nC3H4OH Polyvinyl Alcohol Mixture of Polymers Potasslum Xanthate KS2C-OC2H5 Propanal CH3CH2CHO (Propionaldehyde) Propane CH3CH2CH3 1,3-Propanediamine NH2CH2CH2CH2NH2 (1,3-Diaminopropane) (Trimethylenediamine) 1,2-Propanediol 1,3-Propanediol 1-Propanol

Boiling point °F (°C) 262 (128) 292 (144) 336 (151) 312 (156) 367–439 (186–226)

490 (254) 208 (98)

294 (146) 223 (106) 667–747 (353–397)

Decomposes

392 (200) Decomposes 120 (49) −44 (−42) 276 (136)

Flash point, °F (°C)

Ignition point, °F (°C)

See Isophthaloyl Chloride. 102 1000 (39) (538) (oc) 134 (57)

91 (33) 172 (78) 138 (59) 285 (141) 130 (54) 144 (62) 178 (81) (oc) 61 (16)

523 (273) 491 (255)

671 (355)

360 (182) 360–550 (182–287) >200 (>93) 365 (185) 175 (79) 205 (96) −22 (−30)

405 (207) 842 (450)

75 (24)

See Propylene Glycol. See Trimethylene Glycol. See Propyl Alcohol. (Continued)

2.414

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2-Propanol 2-Propanone Propanoyl Chloride Propargyl Alcohol HC1CCH2OH (2-Propyn-1-ol) Propargyl Bromide HC1CCH2Br (3-Bromopropyne) Propene 2-Propenylamine Propenyl Ethyl Ether CH3CH:CHOCH2CH3 b-Propiolactone C3H4O2 Propionaldehyde Propionic Acid CH3CH2COOH Propionic Anhydride (CH3CH2CO)2O Propionic Nitrile CH3CH2CN (Propionitrile) Propionic Chloride CH3CH2COCl (Propanoyl Chloride) Propyl Acetate C3H7OOCCH3 (Acetic Acid, n-Propyl Ester) Propyl Alcohol CH3CH2CH2OH (1-Propanol) Propylamine CH3(CH2)2NH2 Propylbenzene C3H7C6H5 (Phenylpropane) 2-Propylbiphenyl C6H5C6H4C3H7 n-Propyl Bromide C3H7Br (1-Bromopropane) n-Propyl Butyrate C3H7COOC3H7 Propyl Carbinol Propyl Chloride C3H7Cl Propyl Chlorothiolformate C3H7SCOCl Propylcyclohexane H7C3C6H11 Propylcyclopentane C3H7C5H9 (1-Cyclopentylpropane)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

See Isopropyl Alcohol. See Acetone. See Propionyl Chloride. 239 (115)

97 (36)

192 (89)

50 (10)

615 (324) See Propylene. See Allylamine.

158 (70) 311 (155)

<20 (<–7) 165 (74)

297 (147) 336 (169) 207 (97)

126 (52) 145 (63) 36 (2)

176 (80)

54 (12)

215 (102)

55 (13)

842 (450)

207 (97)

74 (23)

775 (412)

120 (49) 319 (159)

−35 (−37) 86 (30)

604 (318) 842 (450)

∼536 (∼280) 160 (71)

>212 (>100)

833 (445) 914 (490)

290 (143)

99 (37) See Butyl Alcohol. <0 (<–18) 145 (63)

See Propanal.

115 (46) 311 (155) 313–315 (156–157) 269 (131)

870 (465) 545 (285)

968 (520)

478 (248) 516 (269)

2.415

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

Propylene CH2:CHCH3 (Propene) Propylene Aldehyde Propylene Carbonate OCH2CH2CH2OCO | [ [ [ [ [ [ [ [ [ [ [ [| Propylene Chlorohydrin sec-Propylene Chlorohydrin Propylenedlamine CH3CH(NH2)CH2NH2

−53 (−47)

Gas

851 (455)

Propylene Dichloride CH3CHCICH2Cl (1,2-Dichloropropane) Propylene Glycol CH3CHOHCH2OH (Methyl Ethylene Glycol) (1,2-Propanediol) Propylene Glycol Acetate Propylene Glycol Isopropyl Ether Propylene Glycol Methyl Ether CH3OCH2CHOHCH3 (1-Methoxy-2-propanol) Propylene Glycol Methyl Ether Acetate (99% Pure) Propylene Glycol Monoacylate CH2:CHCOO(C3H6)OH (Hydroxypropyl Acrylate) Propylene Oxide OCH2CHCH3 | [ [ [ [| n-Propyl Ether (C3H7)2O (Dipropyl Ether) Propyl Formate HCOOC3H7 Propyl Methanol Propyl Nitrate CH3CH2CH2NO3 Propyl Proplonate CH3CH2COOCH2CH2CH3 Propyltrichlorosilane (C3H7)SiCl3 Propyne CH3C1CH (Allylene) (Methylacetylene) Pseudocumene Pyridine CH < (CHCH)2 >N

205 (96)

See 2-Chloro-1-Propanol. See 1-Chloro-2-Propanol. 92 780 (33) (416) (oc) 60 1035 (16) (557)

370 (188)

210 (99)

283 (140) 248 (120)

See Methyl Glycol Acetate. 110 (43) 90 (32)

295 (146)

108 (42)

410 (210)

207 (97)

94 (35)

−35 (−37)

840 (449)

194 (90)

70 (21)

370 (188)

178 (81)

27 (−3)

851 (455)

231 (111) 245 (118) 254 (123.5) −10 (−23)

68 (20) 175 (79) 98 (37)

Compound

468 (242)

246 (119)

See Crotonaldehyde. 275 (135)

700 (371)

See Butyl Alcohol.

239 (115)

347 (175)

See 1,2,4-Trimethylbenzene. 68 900 (20) (482) (Continued)

2.416

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Pyrrole (CHCH)2NH (Azole) Pyrrolidine NHCH2CH2CH2CH2 | [ [ [ [ [ [ [ [ [ [ [| (Tetrahydropyrrole) 2-Pyrrolidine NHCOCH2CH2CH2 | [ [ [ [ [ [ [ [ [ [| Quinoline C6H4N:CHCH:CH | [ [ [ [ [ [ [ [ [ [| Range Oil Rape Seed Oil (Colza Oil) Resorcinol C6H4(OH)2 (Dihydroxybenzol) Rhodinol CH2:C(CH3)(CH2)3CH— (CH3)(CH2)2OH Rosin Oil Salicylaldehyde HOC6H4CHO (o-Hydroxybenzaldehyde) Salicylic Acid HOC6H4COOH Safrole C3H5C6H3O2CH2 (4-allyl-1,2-Mathylenedioxybenzene) Santatol C15H24O (Arheol) Sesame Oil

Boiling point °F (°C)

Flash point, °F (°C)

268 (131)

102 (39)

186–189 (86–87)

37 (3)

473 (245)

265 (129)

460 (238)

896 (480)

See Fuel Oil No. 1.

531 (277)

325 (163) 261 (127)

836 (447) 1126 (608)

237–239 (114–115) @12 mm >680 (>360) 384 (196)

>212 (>100) 266 (130) 172 (78)

648 (342)

Sublimes @169 (76) 451 (233)

315 (157)

1004 (540)

∼575 (∼300)

>212 (>100)

Soy Bean Oil Sperm Oil No. 1 No. 2

Stearic Acid CH3(CH2)16COOH Steryl Alcohol CH3(CH2)17OH (1-Ocladecanol) Styrene C6H5CH:CH2 (Cinnamene) (Phenylethylene) (Vinyl Benzene)

Ignition point, °F (°C)

726 (386) 410 (210) @15 mm 295 (146)

212 (100)

491 (255) 540 (282) 428 (220) 460 (238) 385 (196)

88 (31)

833 (445) 586 (308)

743 (395) 842 (450) 914 (490)

ORGANIC CHEMISTRY

2.417

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Styrene Oxide C6H5CHOCH2 Succinonitrile NCCH2CH2CN (Ethylene Dicyanide) Sulfolane CH2(CH2)3SO2 (Tetrahydrothiophene-1,1-Dioxide) (Tetramethylune Sulfone) Tartaric Acid (d, 1) (CHOHCO2H)2 Terephthalle Acid C6H4(COOH)2 (para-Phthalic Acid) (Benzene-para-Dicarboxylic Acid) Terephthaloyl Chloride C6H4(COCI)2 (Terephthalyl Dichloride) (p-Phthalyl Dichloride) (1,4-Benzenedicarbonyl Chloride) o-Terphenyl (C6H5)2C6H4 m-Terphenyl (C6H5)2C6H4 Terpineol C10H17OH (Terpilenol) Terpinyl Acetate C10H17OOCCH3 Tetraamylbenzene (C5H11)4C6H2 1,1,2,2-Tetrabromoethane CHBr2CHBr2 (Acetylene Tetrabromide) 1,2,4,5-Tetrachlorobenzene C6H12Cl4 Tetradecane CH3(CH2)12CH3 Tetradecanol C14H29OH 1-Tetradecene CH2:CH(CH2)11CH3 tert-Tetradecyl Mercaptan C14H29SH Tetraethoxypropane (C2H5O)4C3H4 Tetra (2-Ethylbutyl) Silicate [C2H5CH(C2H5)CH2O]4Si Tetraethylene Glycol HOCH2(CH2OCH2)3CH2OH

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C) 929 (498)

509–513 (265–267)

165 (74) 270 (132)

545 (285)

350 (177)

Sublimes above 572 (300) 498 (259)

410 (210) (oc) 500 (260)

925 (496)

356 (180)

630 (332) 685 (363) 417–435 (214–224)

325 (163) 375 (191) 195 (91)

428 (220) 608–662 (320–350) 275 (135)

200 (93) 295 (146)

472 (245) 487 (253) 507 (264)

311 (155) 212 (100) 285 (141) (oc) 230 (110) 250 (121) 190 (88) 335 (168)

493 (256) 496–532 (258–278) 621 (327) 460 (238) @50 mm Decomposes

797 (425)

635 (335)

392 (200)

455 (235)

360 (182) (Continued)

2.418

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Tetraethylene Glycol, Dimethyl Ether Tetraethylene Pentamine H2N(C2H4NH)3C2H4NH2 Tetra (2-Ethylhexyl) Silicate [C4H9CH(C2H5)CH2O]4Si Tetrafluoroethylene F2C:CF2 (TFE) (Perfluoroethylene) 1,2,3,6-Tetrahydrobenzaldehyde CH2CH:CHCH2CH2CHCHO | [ [ [ [ [ [ [ [ [ [ [ [ [ [ [| (3-Cyclohexene-1-Carboxaldehyde) endo-Tetrahydrodicyclopentadiene C10H16 (Tricyclodecane) Tetrahydrofuran OCH2CH2CH2CH2 | [ [ [ [ [ [ [| (Diethylene Oxide) (Tetramethylene Oxide) Tetrahydrofurfuryl Alcohol C4H7OCH2OH Tetrahydrofurfuryl Oleale C4H7OCH2OOCC17H33 Tetrahydronaphthalene C6H2(CH3)2C2H4 (Tetralin) Tetrahydropyran Tetrahydropyran-2-Methanol OCH2CH2CH2CH2CHCH2OH | [ [ [ [ [ [ [ [ [ [ [ [| Tetrahydropyrrole Tetralin 1,1,3,3-Tetramethoxy-propane [(CH3O)2CH]2CH2 1,2,3,4-Tetramethylbenzene 95% C6H2(CH3)4 (Prohnitene) 1,2,3,5-Tetramethylbenzene 85.5% C6H2(CH3)4 (Isodurene) 1,2,4,5-Tetramethylbenzene 95% C6H2(CH3)4 (Durene) Tetramethylene Tetramethyleneglycol CH2OH(CH2)2CH2OH Tetramethylene Oxide Tetramethyl Lead, Compounds Pb(CH3)4

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

See Dimethoxy Tetraglycol. 631 (333)

325 (163) 390 (199)

−105 (−76)

328 (164)

610 (321)

392 (200)

135 (57)

379 (193)

523 (273)

151 (66)

6 (−14)

610 (321)

352 (178) @743 mm 392–545 (200–285) @16 mm 405 (207)

167 (75)

540 (282)

368 (187)

361 (183) 399–401 (204–205) 387–389 (197–198) 385 (196)

230 (110)

390 (199) 160 (71)

725 (385)

See Pentamethylene Oxide. 200 (93) See Pyrrolidine. See Tetrahydronophthalene. 170 (77) 166 800 (74) est. (427) 160 800 (71) est. (427) 130 (54) See Cyclobutane 734 (390) See Tetrahydrofuran. 100 (38)

2.419

ORGANIC CHEMISTRY

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2,2,3,3-Tetramethyl Pentane (CH3)3CC(CH3)2CH2CH3 2,2,3,4-Tetramethyl-pentane (CH3)3CCH(CH3)CH(CH3)2 Thialdine SCH(CH3)SCH(CH3)NHCHCH3 | [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [| 2,2-Thiodiethanol (HOCH2CH2)2S (Thiodiethylene Glycol) Thiodiethylene Glycol Thiodiglycol (CH2CH2OH)2S (Thiodiethylene Glycol) (Beta-bis-Hydroxyethyl Sulfide) (Dihydroxyethyl Sulfide) Thiophene SCH:CHCH:CH | [ [ [ [ [ [ [ [ [| 1,4-Thioxane O(CH2CH2)2S (1,4-Oxathiane) Toluene C6H5CH3 (Methylbenzene) (Phenylmethane) (Toluol) Toluene-2,4-Diisocyanate CH3C6H3(NCO)2 p-Toluenesulfonic Acid C6H4(SO3H)(CH3) Toluhydroquinone C6H3(OH)2CH3 (Methylhydroquinone) o-Toluidine CH3C6H4NH2 (2-Methylaniline) p-Toluidine CH3C6H4NH2 (4-Mothylaniline) Toluol m-Tolydiethanolamine (HOC2H4)2NC6H4CH3 (MTDEA) 2,4-Tolylene Diisocyanate o-Tolyl Phosphate o-Tolyl p-Toluene Sulfonate C14H14O3S Transformer Oil (Tronsil Oil) Triacetin

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

273 (134) 270 (132) 172 Decomposes

<70 (<21) <70 (<21) <70 200 (93)

806 (430)

540 (282)

320 (160)

541 (283)

See 2,2-Thiodiethanol. 320 (160)

184 (84)

30 (−1)

300 (149)

108 (42)

231 (111)

40 (4)

484 (251) 295 (140) @ 20 mm 545 (285)

260 (127) 363 (184) 342 (172)

875 (468)

392 (200)

185 (85)

900 (482)

392 (200)

188 (87)

900 (482)

400 (204)

740 (393)

568 (298)

896 (480)

See Toluene. 0.6

See Toluene-2,4-Diisocyanate. See Tri-o-Cresyl Phosphate. 363 (184) 295 (146) See Glyceryl Triacetate. (Continued)

2.420

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Triamylamine (C5H11)3N Triamylbenzene (C5H11)3C6H3 Tributylamine (C4H9)3N Tri-n-Butyl Borate B(OC4H9)3 Tributyl Citrate C3H4(OH)(COOC4H9)3 Tributyl Phosphate (C4H9)3PO4 Tributylphosphine (C4H9)3P Tributyl Phosphite (C4H9)3PO3 1,2,4-Trichlorobenzene C6H3CI3 1,1,1-Trichloroethane CH3CCI3 (Methyl Chloroform) Trichloroethylene CIHC:CCI2 1,2,3-Trichloropropane CH2CICHCICH2CI (Allyl Trichloride) (Glyceryl Trichlorohydrin) Trichlorosllane HSiCI3 Tri-o-Cresyl Phosphate (CH3C6H4)3PO4 (o-Tolyl Phosphate) Tridecanol CH3(CH2)12OH 2-Tridecanone Tridecyl Acrylate CH2:CHCOOC13H27 Tridecyl Alcohol C12H25CH2OH (Tridecanol) Tridecyl Phosphite (C10H21O)3P Triethanolamine (CH2OHCH2)3N (2,2′,2′′-Nitrilotriethanol) 1,1,3-Triethoxyhexane CH(OC2H5)2CH2CH(OC2H5)C8H7

Triethylamine (C2H5)3N

Boiling point °F (°C)

Flash point, °F (°C)

453 (234) 575 (302) 417 (214) 446 (230) 450 (232) 560 (293) 473 (245) 244–250 (118–121) @7 mm 415 (213) 165 (74)

215 (102) 270 (132) 187 (86) 200 (93) 315 (157) 295 (146)

188 (87) 313 (156)

89 (32) 770 (410) Decomposes 525 (274) 302 (150) @10 mm 485–503 (252–262) 356 (180) @0.1 mm 650 (343) 271 (133) @50 mm Decomposes @760 mm 193 (89)

Ignition point, °F (°C)

695 (368)

392 (200) 248 (120) 222 (105)

1060 (571)

788 (420) 160 (71)

7 (−14) 437 (225)

725 (385)

250 (121) See Methyl Undecyl Ketone. 270 (132) 180 (82) 455 (235) 354 (179) 210 (99)

16 (−7)

480 (249)

ORGANIC CHEMISTRY

2.421

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 1,2,4-Triethylbenzene (C2H5)3C6H3 Triethyl Cltrate HOC(CH2CO2C2H5)CO2H2H5 Triethylene Glycol HOCH2(CH2OCH2)2CH2OH (Dicaproate) Triethylene Glycol Diacetate CH3COO(CH2CH2O)3COCH3 (TDAC) Triethylene Glycol, Dimethyl Ether CH3(OCH2)3OCH3 Triethylene Glycol, Ethyl Ether Triethylene Glycol, Methyl Ether Triethyleneglycol Monobutyl Ether C4H9O(C2H4O)3H Triethylenetetramine N2NCH2(CH2NHCH2)2CH2NH2 Triethyl Phosphate (C2H5)3PO4 (Ethyl Phosphate) Trifluorochloroethylene CF2:CFCI (R-1113) (Chlorotrifluoroethylene) Triglycol Dichloride ClCH2(CH3OCH2)2CH2Cl Trihexyl Phosphite (C6H13)3PO3 Triisopropanolamine [(CH3)2COH]3N (1,1′,1′′-Nitrolotri-2-propanol) Triisopropylbenzene C6H3(CH3CHCH3)3 Triisopropyl Borate (C3H7O)3B Triiauryl Trithiophosphite [CH3(CH2)11S]3P Trimethylamine (CH3)3N 1,2,3-Trimethylbenzene C6H3(CH3)3 (Hemellitol) 1,2,4-Trimethylbenzene C6H3(CH3)3 (Pseudocumene) 1,3,5-Trimethylbenzene C6H3(CH3)3 (Mesitylene) Trimethyl Borate 2,2,3-Trimethylbutane (CH3)3C(CH3)CHCH3 (Triptane––an isomer of Heptane)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

423 (217) 561 (294) 546 (286)

181 (83) 303 (151) 350 (177)

700 (371)

572 (300)

345 (174)

421 (216)

232 (111) See Ethoxytriglycol. See Methoxy Triglycol. 290 (143) 275 (135) 240 (115)

270 (132) 532 (278) 408–424 (209–218)

640 (338) 850 (454)

−18 (−28) 466 (241) 275–286 (135–141) @2 mm 584 (307) 495 (237) 288 (142)

250 (121) 320 (160) 320 (160)

608 (320)

207 (97) 82 (28) 398 (203)

38 (3) 349 (176)

111 (44)

374 (190) 878 (470)

329 (165)

112 (44)

932 (500)

328 (164)

122 (50)

1039 (559)

178 (81)

See Methyl Borate. <32 (<0)

774 (412) (Continued)

2.422

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2,3,3-Trimethyl-1-Butene (CH3)3CC(CH3):CH2 (Heplylene) Trimethyl Carbinol Trimethylchlorosiiane (CH3)3SiCI 1,3,5-Trimethylcyclohexane (CH3)3C6H9 (Hexahydromesitylene) Trimethylcyclohexanol CH(OH)CH2C(CH3)2CH2CH(CH3)CH2 | [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [[ [ [ [| 3,3,5-Trimethyl-1-Cyclohexanol CH2CH(CH3)CH2C(CH3)2CH2CHOH | [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [| Trimethylene Trimethylenediamine Trimethylene Glycol HO(CH2)3OH (1,3-Propanediol) Trimethylethylene 2,5,5-Trimethylheptane C2H5C(CH3)2(CH2)2CH(CH3)2 2,2,5-Trimethylhexane (CH3)3C(CH2)2CH(CH3)2 3,5,5-Trimethylhexanol CH3C(CH3)2CH2CH(CH3)CH2CH2OH 2,4,8-Trimethyl-6-Nonanol C4H9CH(OH)C7H15 (2,6,8-Trimethyl-4-nonanol) 2,6,8-Trimethyl-4-Nonanol (CH3)2CHCH2CH(OH)CH2CH(CH3)CH2CH(CH3)2 2,6,8-Trimethyl-4-Nonanone (CH3)2CHCH2CH(CH3)CH2COCH2CH(CH3)2 2,2,4-Trimethylpentane (CH3)3CCH2CH(CH3)2 2,3,3-Trimethylpentane CH3CH2C(CH3)2CH(CH3)2 2,2,4-Trimethyl-1,3-Pentanediol (CH3)2CHCH(OH)C(CH3)2CH2OH 2,2,4-Trimethyl pentanediol Diisobutyrate C16H30O4 2,2,4-Trimethyl 1,3-Pentanediol Isobutyrate (CH3)2CHCH(OH)C(CH3)2CH2OOCCH(CH3)2 2,2,4-Trimethylpentanediol Isobutyrate Benzoate C19H28O4

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

172 (78)

<32 (<0)

707 (375)

135 (57) 283 (139)

See tert-Butyl Alcohol. −18 (−28) 597 (314)

388 (198)

165 (74)

388 (198)

190 (88) See Cyclopropane. See 1,3-Propanediamine.

417 (214)

752 (400)

381 (194)

See 2-methyl-2-Butene. <131 (<55) 55 (13) (oc) 200 (93)

491 (255)

199 (93)

438 (226)

200 (93)

425 (218)

195 (91)

211 (99) 239 (115) 419–455 (215–235)

10 (−12) <70 (<21) 235 (113)

779 (415) 797 (425) 655 (346)

536 (280)

250 (121)

795 (424)

356–360 125 mm (180–182)

248 (120)

740 (393)

167 (75) @10 mm

325 (163)

304 (151) 255 (124)

527 (275)

ORGANIC CHEMISTRY

2.423

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound 2,3,4-Trimethyl-1-Pentene H2C:C(CH3)CH(CH3)CH(CH3)2 2,4,4-Trimethyl-1-Pentene CH2:C(CH3)CH2C(CH3)3 (Diisobutylene) 2,4,4-Trimethyl-2-Pentene CH3CH:C(CH3)C(CH3)3 3,4,4-Trimethyl-2-Pentene (CH3)3CC(CH3):CHCH3 Trimethyl Phosphite (CH3O)3P Trioctyl Phosphite (C8H17O)3P [Tris (2-Ethylhexyl) Phosphite] Trioxane OCH2OCH2OCH2 | [ [ [ [ [ [ [ [ [| Triphenylmethane (C6H5)3CH Triphenyl Phosphate (C6H5)3PO4 Triphenylphosphine Triphenyl Phosphite (C6H5O)3PO3 Triphenylphosphorus (C6H5)3P (Triphenylphosphine) Tripropylamine (CH3CH2CH2)3N Tripropylene C9H18 (Propylene Trimer) Tripropylene Glycol H(OC3H6)3OH Tripropylene Glycol Methyl Ether HO(C3H6O)2C3H6OCH3 Tris (2-Ethylhexyl) Phosphite Tung Oil (China Wood Oil) Turkey Red Oil Turpentine Undecane 2-Undecanol C4H9CH(C2H5)C2H4CH(OH)CH3 Valeraldehyde CH3(CH2)3CHO (Pentanal)

Boiling point °F (°C)

Flash point, °F (°C)

Ignition point, °F (°C)

214 (101) 214 (101)

<70 (<21) 23 (−5)

495 (257) 736 (391)

221 (105)

35 (2) (oc) <70 (<21) 130 (54) 340 (171)

581 (305)

113 (45)

777 (414)

234 (112) 232–234 (111–112) 212 (100) @0.01 mm 239 (115) Sublimes 678 (359) 750 (399) 311–320 (155–160) @0.1 mm 711 (377)

617 (325)

>212 (>100) 428 (220) See Triphenylphosphorus. 425 (218) 356 (180)

313 (156) 271–288 (133–142)

105 (41) 75 (24)

514 (268) 470 (243)

285 (141) 250 (121)

437 (225)

See Trioctyl Phosphite. 552 855 (289) (457) 476 833 (247) (445) 95 488 (35) (253) See Hendecane. 235 (113)

217 (103)

54 (12)

300 (149)

432 (222) (Continued)

2.424

SECTION TWO

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Valeric Acid Vinyl Acetate CH2:CHOOCCH3 (Ethenyl Ethanoate) Vinylaceto-b-Lactone Vinyl Acetylene CH2:CHC:CH (1-Buten-3-yne) Vinyl Allyl Ether CH2:CHOCH2CH2O(CH2)3CH3 (Allyl Vinyl Ether) Vinylbenzene Vinylbenzylchloride CICH2H6H4CH:CH2 Vinyl Bromide Vinyl Butyl Ether CH2:CHOCH4H9 (Butyl Vinyl Ether) Vinyl Butyrate CH2:CHOCOC3H7 Vinyl 2-Chloroethyl Ether CH2:CHOCH2CH2CI (2-Chloroethyl Vinyl Ether) Vinyl Chloride CH2CHCI (Chloroethylene) Vinyl Crotonate CH2:CHOCOCH:CHCH3 Vinyl Cyanide 4-Vinyl Cyclohexene C8H12 Vinyl Ether Vinyl Ethyl Alcohol CH2:CH(CH2)2OH (3-Buten-1-ol) Vinyl Ethyl Ether CH2:CHOC2H5 (Ethyl Vinyl Ether) Vinyl 2-Ethylhexoate CH2:CHOCOCH(C2H5)C4H9 Vinyl 2-Ethylhexyl Ether C10H20O (2-Ethylhexyl Vinyl Ether) 2-Vinyl-5-Ethylpyridine N:C(CH:CH2)CH:CHC(C2H5):CH | [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [| Vinyl Fluoride CH2:CHF Vinylidene Chloride CH2:CCI2 (1,1-Dichloroethylene) Vinylidene Fluoride CH2:CF2

Boiling point °F (°C) 161 (72)

Flash point, °F (°C) See Pentanoic Acid. 18 (−8)

Ignition point, °F (°C) 756 (402)

See Diketene. 41 (5) 153 (67)

444 (229) 60 (15.8) 202 (94)

<68 (<20) See Styrene. 220 (104) None 15 (−9)

242 (117) 228 (109)

68 (20) 80 (27)

7 (−14)

−108.4 (−78)

273 (134) 266 (130) 233 (112)

78 (26) See Acrylonitrile. 61 (16) See Divinyl Ether. 100 (38)

986 (530) 437 (255)

882 (472)

517 (269)

96 (36)

<–50 (<–46)

395 (202)

365 (185) 352 (178)

165 (74) 135 (57)

395 (202)

248 (120)

200 (93)

@50 mm −97.5 (−72) 89 (32)

−19 (−28)

−122.3 (−86)

1058 (570)

ORGANIC CHEMISTRY

2.425

TABLE 2.40 Boiling Points, Flash Points, and Ignition Temperatures of Organic Compounds (Continued) Compound Vinyl Isobutyl Ether CH2:CHOCH2CH(CH3)CH3 (Isobutyl Vinyl Ether) Vinyl Isooctyl Ether CH2:CHO(CH2)5CH(CH3)2 (Isooctyl Vinyl Ether) Vinyl Isopropyl Ether CH2:CHOCH(CH3)2 (Isopropyl Vinyl Ether) Vinyl 2-Methoxyethyl Ether CH2:CHOC2H4OCH3 (1-Methoxy-2-Vinyloxyethane) Vinyl Methyl Ether CH2:CHOCH3 (Methyl Vinyl Ether) Vinyl Octadecyl Ether CH2:CHO(CH2)17CH3 (Octadecyl Vinyl Ether) Vinyl Propionate CH2:CHOCOC2H5 1-Vinylpyrrolidone CH2:CHNCOCH2CH2CH2 | [ [ [ [ [ [ [ [ [ [| (Vinyl-2-Pyrrolidone) Vinyl-2-Pyrrolidone Vinyl Trichlorosilane CH2:CHSiCI3 Wax, Microcrystalline

Boiling point °F (°C)

Flash point, °F (°C)

182 (83)

15 (−9)

347 (175)

140 (60)

133 (56)

−26 (−32)

228 (109)

64 (18)

White Tar Wood Alcohol Wood Tar Oil Wool Grease m-Xylene C6H4(CH3)2 (1,3-Dimethylbenzene) o-Xylene C6H4(CH3)2 (1,2-Dimethylbenzene) (o-Xylol) p-Xylene C6H4(CH3)2 (1,4-Dimethylbenzene) o-Xylidine C6H3(CH3)2NH2 (o-Dimethylaniline) o-Xylol

522 (272)

43 (6) 297–369 (147–187) @5 mm 203 (95) 205 (96)

549 (287) 350 (177) 34 (1) 209 (98)

@14 mm 195 (91)

Wax, Ozocerite (Mineral Wax) Wax, Paraffin

Ignition point, °F (°C)

>700 (>371)

282 (139)

See 1-Vinylpyrrolidone. 70 (21) >400 (>204) 236 (113) 390 (199) See Naphthalene. See Methyl Alcohol. See Pine Tar Oil. See Lanolin. 81 (27)

473 (245)

982 (527)

292 (144)

90 (32)

867 (463)

281 (138)

81 (27)

984 (528)

435 (224)

206 (97) See o-Xylene.

2.426

SECTION TWO

TABLE 2.41 Properties of Combustible Mixtures in Air The autoignition temperature is the minimum temperature required for self-sustained combustion in the absence of an external ignition source. The value depends on specified test conditions. The flammable (explosive) limits specify the range of concentration of the vapor in air (in percent by volume) for which a flame can propagate. Below the lower flammable limit, the gas mixture is too lean to burn; above the flammable limit, the mixture is too rich.

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

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2.427

TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

(Continued)

2.428

SECTION TWO

TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

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TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

(Continued)

Next Page 2.430

SECTION TWO

TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

Previous Page ORGANIC CHEMISTRY

2.431

TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

(Continued)

2.432

SECTION TWO

TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

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TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

(Continued)

2.434

SECTION TWO

TABLE 2.41 Properties of Combustible Mixtures in Air (Continued)

Substance

Autoignition temperature, °C

Flammable (explosive) limits, percent by volume of fuel (25°C, 760 mm) Lower

Upper

2.7 AZEOTROPIC MIXTURES An azeotrope is liquid mixture of two or more components that boils at a temperature either higher or lower than the boiling point of any of the individual components. In industrial situation, if the components of a solution are very close in boiling point and cannot be separated by conventional distillation, a substance can be added that forms an azeotrope with one component, modifying its boiling point and making it separable by distillation.

ORGANIC CHEMISTRY

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures

2.435

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SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

ORGANIC CHEMISTRY

2.437

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Esters (continued)

(Continued)

2.438

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

ORGANIC CHEMISTRY

2.439

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Ketones (continued)

(Continued)

2.440

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Formic acid (continued)

ORGANIC CHEMISTRY

2.441

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Acetic acid (continued)

(Continued)

2.442

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Butyric acid (continued)

ORGANIC CHEMISTRY

2.443

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued) C. Binary azeotropes containing alchohols

(Continued)

2.444

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Ethanol (continued)

ORGANIC CHEMISTRY

2.445

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

1-Propanol (continued)

(Continued)

2.446

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

ORGANIC CHEMISTRY

2.447

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

2-Methyl-2-propanol (continued)

(Continued)

2.448

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

ORGANIC CHEMISTRY

2.449

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Benzyl alcohol (continued)

(Continued)

2.450

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

1,2-Ethanediol (continued)

ORGANIC CHEMISTRY

2.451

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

(Continued)

2.452

SECTION TWO

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

Solvent: acetamide (continued)

ORGANIC CHEMISTRY

2.453

TABLE 2.42 Binary Azeotropic (Constant-Boiling) Mixtures (Continued)

(Continued)

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SECTION TWO

TABLE 2.43 Ternary Azeotropic Mixtures A. Ternary azeotropes containing water and alcohols Composition, wt % System

BP of azeotrope, °C

Water

Alcohol

Other component

ORGANIC CHEMISTRY

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TABLE 2.43 Ternary Azeotropic Mixtures (Continued) A. Ternary azeotropes containing water and alcohols Composition, wt % System

BP of azeotrope, °C

Water

Alcohol

Other component

2.456

TABLE 2.43 Ternary Azeotropic Mixtures (Continued)

B. Other ternary azeotropes System

BP of azeotrope, °C

Composition, wt%

System

BP of azeotrope, °C

Composition, wt%

2.457

2.458 TABLE 2.43 Ternary Azeotropic Mixtures (Continued)

B. Other ternary azeotropes System

BP of azeotrope, °C

Composition, wt%

System

BP of azeotrope, °C

Composition, wt%

2.459

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SECTION TWO

2.8 FREEZING MIXTURES A freezing mixture a mixture of substances (such as salt and ice) to obtain a temperature below the freezing point of the solvent (such as water).

TABLE 2.44 Compositions of Aqueous Antifreeze Solutions

*Values are for pure alcohol. Since some commercial antifreezes contain small amounts of water, slightly higher volume concentrations than those given in the table may be required. Antifreezes also contain corrosion inhibitors and other additives to make them function properly as cooling liquids. These affect freezing point slightly and specific gravity to a greater degree.

ORGANIC CHEMISTRY

2.461

TABLE 2.44 Compositions of Aqueous Antifreeze Solutions (Continued)

†Eveready Prestone marketed for antifreeze purposes, is 97% ethylene glycol containing fractional percentages of soluble and insoluble ingredients to prevent foaming, creepage and water corrosion in automobile cooling systems.

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SECTION TWO

TABLE 2.44 Compositions of Aqueous Antifreeze Solutions (Continued)

*Values are for pure alcohol. Since some commercial antifreezes contain small amounts of water, slightly higher volume concentrations than those given in the table may be required. Antifreezes also contain corrosion inhibitors and other additives to make them function properly as cooling liquids. These affect freezing point slightly and specific gravity to a greater degree. †The values are those reported by Bosart and Snoddy (Jour. Ind. Eng. Chem., 19, 506 (1927), and Lane (Jour. Ind. Eng. Chem., 17, 924 (1925)) but modified by adding 2°F to all temperatures below 0°F.

ORGANIC CHEMISTRY

2.463

TABLE 2.44 Compositions of Aqueous Antifreeze Solutions (Continued)

*Saturation temperatures of sodium chloride dihydrate; at these temperatures NaCl ⋅ 2H2O separates leaving the brine of the eutectic composition (E).

Propylene glycol, a satisfactory antifreeze with the advantage of being nontoxic, can be combined with glycerol, also an efficient nontoxic antifreeze, to give a mixture that can be tested for freezing point with an ethylene glycol (Prestone) hydrometer. A mixture of 70% propylene glycol and 30% glycerol (% by weight of water-free materials), when diluted, can be tested on the standard instrument used for ethylene glycol solutions.

2.464

SECTION TWO

2.9 BOND LENGTHS AND STRENGTHS Distances between centers of bonded atoms are called bond lengths, or bond distances. Bond lengths vary depending on many factors, but in general, they are very consistent. Of course the bond orders affect bond length, but bond lengths of the same order for the same pair of atoms in various molecules are very consistent. The bond order is the number of electron pairs shared between two atoms in the formation of the bond. Bond order for C˙C and O˙O is 2. The amount of energy required to break a bond is called bond dissociation energy or simply bond energy. Since bond lengths are consistent, bond energies of similar bonds are also consistent. Bonds between the same type of atom are covalent bonds, and bonds between atoms when their electronegativity differs slightly are also predominant covalent in character. Theoretically, even ionic bonds have some covalent character. Thus, the boundary between ionic and covalent bonds is not a clear line of demarcation. For covalent bonds, bond energies and bond lengths depend on many factors: electron afinities, sizes of atoms involved in the bond, differences in their electronegativity, and the overall structure of the molecule. There is a general trend in that the shorter the bond length, the higher the bond energy but there is no formula to show this relationship, because of the widespread variation in bond character. TABLE 2.45 Bond Lengths between Carbon and Other Elements Bond Length, µm

Bond type Carbon-carbon Single bond Paraffinic: —C—C— In presence of —C˙C— or of aromatic ring In presence of —C˙O bond In presence of two carbon-oxygen bonds In presence of two carbon-carbon double bonds Aryl-C˙O In presence of one carbon-carbon triple bond: —C—CæC— In presence of one carbon-nitrogen triple bond: —C—CæN In compounds with tendency to dipole formation, e.g., C˙C—C˙O In aromatic compounds In presence of carbon-carbon double and triple bounds: —C˙C—CæC— In presence of two carbon-carbon triple bounds: —CæC—C˙C— Double bond Single: —C˙C— Conjugated with a carbon-carbon double bond: —C˙C—C˙C— Conjugated with a carbon-oxygen double bond: —C˙C—C˙O Cumulative: —C˙C˙C—or —C˙C˙O Triple bond Simple: —CæC— Conjugated: —CæC—C˙C—, —CæC—C˙O, or —CæC—ary1 Bond type

154.1(3) 153(1) 151.6(5) 149(1) 142.6(5) 147(2) 146.0(3) 146.6(5) 144(1) 139.5(5) 142.6(5) 137.3(4) 133.7(6) 133.6(5) 136(1) 130.9(5) 120.4(2) 120.6(4)

Bond length, pm Carbon-halogen

Paraffinic: R—X Olenfinic: —C˙C—X Aromatic: Ar-X Acetylenic: —CæC—X

Fluorine

Chlorine

137.9(5) 133.3(5) 132.8(5) (127)

176.7(2) 171.9(5) 170(1) 163.5(5)

Bromine 193.8(5) 189(1) 185(1) 179.5(10)

Iodine 213.9(1) 209.2(5) 205(1) 199(2)

ORGANIC CHEMISTRY

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TABLE 2.45 Bond Lengths between Carbon and Other Elements (Continued) Bond type Carbon-carbon

Bond Length, µm

2.466

SECTION TWO

TABLE 2.45 Bond Lengths between Carbon and Other Elements (Continued) Bond type Carbon-oxygen

Bond Length, µm

ORGANIC CHEMISTRY

TABLE 2.46 Bond Dissociation Energies

2.467

2.468

SECTION TWO

2.10 DIPOLE MOMENTS AND DIELECTRIC CONSTANTS The permanent dipole moment of an isolated molecule depends on the magnitude of the charge and on the distance separating the positive and negative charges. It is defined as   µ =  ∑ qi ri  i  where the summation extends over all charges (electrons and nuclei) in the molecule. The numerical values of the dipole moment, expressed in the c.g.s. system of units, are in debye units, D, where 1 D = 10−18 esu of charge × centimeters. The conversion factor to SI units is 1 D = 3.335 64 × 10−30 C ⋅ m [coulomb-meter] Tables 2.49 contain a selected group of compounds for which the dipole moment is given. An extensive collection of dipole moments (approximately 7000 entries) is contained in A. L. McClellan, Tables of Experimental Dipole Moments, W. H. Freeman, San Francisco, 1963. A critical survey of 500 compounds in the gas phase is given by Nelson, Lide, and Maryott, NSRDS-NBS 10, Washington, D.C., 1967. If two oppositely charged plates exist in a vacuum, there is a certain force of attraction between them, as stated by Coulomb’s law: F=

1 q1q2 ⋅ 4πε 0 εr 2

where F is the force, in newtons, acting on each of the charges q1 and q2, r is the distance between the charges, e is the dielectric constant of the medium between the plates, and e0 is the permittivity of free space. q1, q2 are expressed in coulombs and r in meters. If another substance, such as a solvent, is in the space separating these charges (or ions in a solution), their attraction for each other is less. The dielectric constant is a measure of the relative effect a solvent has on the force with which two oppositely charged plates attract each other. The dielectric constant is a unitless number. Dielectric constants for a selected group of inorganic and organic compounds are included in Tables 2.49 and 1.52. An extensive list has been compiled by Maryott and Smith, National Bureau Standards Circular 514, Washington, D.C., 1951. For gases the values of the dielectric constant can be adjusted to somewhat different conditions of temperature and pressure by means of the equation (ε − 1)t , p p = (ε − 1)20o ,1 atm 760 [1 + 0.003 411(t − 20)] where p is the pressure (in mmHg) and t is the temperature (in °C). The errors associated with this equation probably do not exceed 0.02% for gases between 10 and 30°C and for pressures between 700 and 800 mm. The dielectric constants of selected gases will be found in Table 1.52. TABLE 2.47 Bond Dipole Moments Moment, D* Group C—CH3 C—C2H5 C—C(CH3)3 C—CH˙CH2 C—CæCH C—F

Aromatic C—X 0.37 0.37 0.5 <0.4 0.7 1.47

Aliphatic C—X 0.0 0.0 0.0 0.6 0.9 1.79

ORGANIC CHEMISTRY

TABLE 2.48 Group Dipole Moments

*To convert debye units D into coulomb-meters, multiply by 3.33564 × 10−30.

2.469

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SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds The temperature in degrees Celsius at which the dielectric constant and dipole moment were measured is shown in this table in parentheses after the value. In some cases, the dipole moment was determined with the substance dissolved in a solvent, and the solvent used is also shown in parentheses after the temperature. The dielectric constant (permittivity) tabulated is the relative dielectric constant, which is the ratio of the actual electric displacement to the electric field strength when an external field is applied to the substance, which is the ratio of the actual dielectric constant to the dielectric constant of a vacuum. The table gives the static dielectric constant ⑀, measured in static fields or at relatively low frequencies where no relaxation effects occur. The dipole moment is given in debye units D. The conversion factor to SI units is I D = 3.33564 × 10−30C ⋅ m. Alternative names for entries are listed in Table 2.20 at the bottom of each double page. List of Abbreviations B, benzene C, CCl4 cHex, cyclohexane D, 1,4-dioxane

g, gas Hx, hexane lq, liquid

ORGANIC CHEMISTRY

2.471

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.472

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.473

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.474

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.475

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.476

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.477

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.478

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.479

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.480

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.481

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.482

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.483

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.484

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.485

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.486

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.487

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.488

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.489

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.490

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.491

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.492

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.493

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

(Continued)

2.494

SECTION TWO

TABLE 2.49 Dielectric Constant (Permittivity) and Dipole Moment of Organic Compounds (Continued)

2.11 IONIZATION ENERGY The ionization energy or ionization potential is the energy necessary to remove an electron from the neutral atom. It is a minimum for the alkali metals that have a single electron outside a closed shell. It generally increases across a row on the periodic maximum for the noble gases that have closed shells. For example, sodium requires only 496 kJ/mol or 5.14 eV/atom to ionize it while neon, the noble gas immediately preceding it in the periodic table, requires 2081 kJ/mol or 21.56 eV/atom. The ionization energy is one of the primary energy considerations used in quantifying chemical bonds. The electron affinity is a measure of the energy change when an electron is added to a neutral atom to form a negative ion. For example, when a neutral chlorine atom in the gaseous form picks up an electron to form a Cl− ion, it releases energy of 349 kJ/mol or 3.6 eV/atom. It is said to have an electron affinity of -349 kJ/mol and this large number indicates that it forms a stable negative ion. Small numbers indicate that a less stable negative ion is formed. Group VIA and VIIA in the periodic table have the largest electron affinities. Note: 1 kJ/mol = .010364 eV/atom

ORGANIC CHEMISTRY

2.495

TABLE 2.50 Ionization Energy of Molecular and Radical Species This table gives the first ionization potential in MJ ⋅ mol−1 and in electron volts. Also listed is the enthalpy of formation of the ion at 25°C (298 K). Ionization energy Species Acenaphthene Acenaphthylene Acetaldehyde Acetamide Acetic acid Acetic anhydride Acetone Acetonitrile Acetophenone Acetyl chloride Acetyl fluoride Acetylene Allene Allyl alcohol Allylamine 3-Amino-I-propanol Aniline Anthracene Azoxybenzene Azulene Benzaldehyde Benzamide Benzene Benzenethiol Benzoic acid Benzonitrile Benzophenone p-Benzoquinone Benzoyl chloride Benzyl alcohol Benzylamine Biphenyl Bromoacetylene Beomobenzene Bromochlorodifluoromethane Bromochloromethane Bromodichloromethane Bromethane Bromethylene Bromomethane 1-Bromonaphthalene Bromopentafluorobenzene 1-Bromopropane 2-Bromopropane 3-Bromopropene p-Bromotoluene Bromotrichloromethane Bromotrifluoromethane 1,2-Butadiene

In MJ ⋅ mol−1

In electron volts

0.741 0.793 0.98696(7) 0.931(3) 1.029(2) 0.965 0.9364 1.1766(5) 0.896(3) 1.047(5) 1.111(2) 1.1000(2) 0.935(1) 0.933(5) 0.845 0.87 0.7449(2) 0.719(3) 0.78 0.715(2) 0.916(2) 0.912 0.89212(2) 0.801(2) 0.914 0.928 0.873(5) 0.969(2) 0.920 0.82 0.834(5) 0.767(2) 0.995(2) 0.866(2) 1.141 1.039(1) 1.02 0.992 0.946(2) 1.0171(3) 0.781 0.923(2) 0.982(1) 0.972(1) 0.972(1) 0.837(1) 1.02 1.10 0.871

7.68 8.22(4) 10.2290(7) 9.65(3) 10.66(2) 10.0 9.705 12.194(5) 9.29(3) 10.85(5) 11.51(2) 11.400(2) 9.69(1) 9.67(5) 8.76 9.0 7.720(2) 7.45(3) 8.1 7.41(2) 9.49(2) 9.45 9.2459(2) 8.30(2) 9.47 9.62 9.05(5) 10.04(18) 9.54 8.5 8.64(5) 7.95(2) 10.31(2) 8.98(2) 11.83 10.77(1) 10.6 10.28 9.80(2) 10.541(3) 8.09 9.57(2) 10.18(1) 10.07(1) 10.07(1) 8.67(1) 10.6 11.4 9.03

∆f H (ion) in kJ ⋅ mol−1 896 1053 821 693 596 398 719 1252 810 804 667 1328 1126 808 891 651 832 949 1123 1004 878 811 975 913 620 1146 923 847 816 720 917 950 1242 971 702 1085 973 930 1025 979 956 212 898 874 1018 908 980 451 1034

2.496

SECTION TWO

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

Next Page ORGANIC CHEMISTRY

2.497

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

(Continued)

Previous Page 2.498

SECTION TWO

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

ORGANIC CHEMISTRY

2.499

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

(Continued)

2.500

SECTION TWO

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

ORGANIC CHEMISTRY

2.501

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

(Continued)

2.502

SECTION TWO

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

ORGANIC CHEMISTRY

2.503

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

(Continued)

2.504

SECTION TWO

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

ORGANIC CHEMISTRY

2.505

TABLE 2.50 Ionization Energy of Molecular and Radical Species (Continued) Ionization energy Species

In MJ ⋅ mol−1

In electron volts

∆f H (ion) in kJ ⋅ mol−1

2.506

2.12 THERMAL CONDUCTIVITY

TABLE 2.51 Thermal Conductivities of Gases as a Function of Temperature The coefficient k, expressed in J ⋅ sec−1 ⋅ cm−1 ⋅ K−1, is the quantity of heat in joules, transmitted per second through a sample one centimeter in thickness and one square centimeter in area when the temperature difference between the two sides is one degree kelvin (or Celsius). The tabulated values are in microjoules. Temperature, °C Substance Acetone Acetaldehyde Acetonitrile Acetylene Air Ammonia Argon Benzene Boron trifluoride Bromine Bromomethane 1-Butanamine Butane Carbon dioxide Carbon disulfide Carbon monoxide Carbon tetrachloride Chlorine Chlorodifluorimethane Chloroethane Chloroform Chloromethane Cyclohexane Cyclopropane 2-Methyl-2-propanol Neon Nitric oxide Nitrogen Nitromethane

−40

−20 80

118−75 164−60

64

410 205 211

72 103

433 221 226

0

20

40

60

80

100

120

140

95

107 109

124 126

166

224 270 259 186

173 176 137 290 311 321 211 165

207

205 256 238 176

156 159 124 269 299 301 206 146

190 195 151

184 242 218 166

140 142 112 248 284 280 196 126

324

336

342149

184

205 241

266

42

186 45

50 82

54 94

59 104

193 192

213 207

117 176110 233 215

278 75 100

80

86

134 84 130 141

151 91 142 163

167 99 155

518 285 282

537 301 295

1356.5 135 144 67 228 59 79 110 90

154 160 76 245 64 85 116 105

84 77

105 99

174 176 85 262 70 93 122 120 75 117 120

454 238 241

476 254 256

497 269 270

225 556 317 307

160

109184

186 107

204 116

320 139

333 155

385227

Nitrous oxide Octafluorocyclobutane Oxygen Pentane Propane 2-Propanol Sulfur dioxide Sulfur hexafluoride Tetrafluoromethane Thiophene 1,1,2-Trichlorotrifluoroethane Triethylamine Water Xenon Deuterium Deuterium oxide Dibromomethane Dichlorodifluoromethane 1,1-Dichloroethane 1,2-Dichloroethane Dichlorofluoromethane Dichloromethane 1,2-Dichlorotetrafluoroethane Diethylamine Diethyl ether 1,4-Dioxane Ethane Ethanol Ethene Ethyl acetate Ethylamine Ethylene Ethylene oxide Ethyl formate Ethyl nitrate Fluorine Helium Heptane

121

137

152

211

228

116

132

245 130 151

168 120 261 171 15131

83

184 190 278

294

311

192

215

238

163

328 218 262

330

353 250127

379

201 235

275227

338327

106

126 235 152110 87 36−73 1150

142

159

1222

1297

175 54 1372

191

207

1448

1523

224

195 241

133 216 257 72

239 89227

358220

263 74110 81

91

84 69

92 81

100 93

94 93

97

100

105

117

138 129 127

137

212 1276

159

158

230 1343

194200 144 140

161 99

137

104327

118 113

179 178

199 200

135

157

182 126

204 141

257

288

133 206 262

151

153 220

228 155 23049 115 169 241

136 178

282

79

100

121

142

164

247 1423 100

264 1481 115

278 1540 130

294 1598

309 1661

211227

153 243 244 187 344

268 269 207

351213

170

191

211

234

193 186 159 325 1720 174

256 206 178

279 226 197

218 222 167 316 209

1778 (Continued)

2.507

2.508

TABLE 2.51 Thermal Conductivities of Gases as a Function of Temperature (Continued) Temperature, °C Substance Hexane Hydrogen Hydrogen bromide Hydrogen chloride Hydrogen cyanide Hydrogen sulfide Iodomethane Krypton Methane Methanol Methyl acetate 2-Methylbutane 2-Methylpropane

−40

−20

1494 64 107

1607 70 117 99 116

257

79 280

0 109 1724 77 128 110 129 46 85 307 67 122 141

20

40

60

1828 84 138 121 143 53

1925 90 148 132 156 60 95 361

2025 97

334

156

176

80

100

120

140

178

201

224

247

160 271

104 240227

191 143 169 68

75

387 174 15070 196

416 197

82 110 445 221 177 215 23393

89

241 195 271

263 215

284 237 421

ORGANIC CHEMISTRY

2.509

TABLE 2.52 Thermal Conductivity of Various Substances All values of thermal conductivity, k, are in millijoules cm−1 ⋅ s−1 ⋅ K−1.

(Continued)

2.510

SECTION TWO

TABLE 2.52 Liquid Thermal Conductivity of Various Substances (Continued)

ORGANIC CHEMISTRY

TABLE 2.52 Liquid Thermal Conductivity of Various Substances (Continued)

2.511

2.512

SECTION TWO

2.13 ENTHALPIES AND GIBBS ENERGIES OF FORMATION, ENTROPIES, AND HEAT CAPACITIES (CHANGE OF STATE) The tables in this section contain values of the enthalpy and Gibbs energy of formation, entropy, and heat capacity at 298.15 K (25°C). No values are given in these tables for metal alloys or other solid solutions, for fused salts, or for substances of undefined chemical composition. The physical state of each substance is indicated in the column headed “State” as crystalline solid (c), liquid (lq), or gaseous (g). Solutions in water are listed as aqueous (aq). The values of the thermodynamic properties of the pure substances given in these tables are, for the substances in their standard states, defined as follows: For a pure solid or liquid, the standard state is the substance in the condensed phase under a pressure of 1 atm (101, 325 Pa). For a gas, the standard state is the hypothetical ideal gas at unit fugacity, in which state the enthalpy is that of the real gas at the same temperature and at zero pressure. The values of ∆f H° and ∆f G° that are given in the tables represent the change in the appropriate thermodynamic quantity when one mole of the substance in its standard state is formed, isothermally at the indicated temperature, from the elements, each in its appropriate standard reference state. The standard reference state at 25°C for each element has been chosen to be the standard state that is thermodynamically stable at 25°C and 1 atm pressure. The standard reference states are indicated in the tables by the fact that the values of ∆f H° and ∆f G° are exactly zero. The values of S° represent the virtual or “thermal” entropy of the substance in the standard state at 298.15 K (25°C), omitting contributions from nuclear spins. Isotope mixing effects are also excluded except in the case of the 1H[2H system. Solutions in water are designated as aqueous, and the concentration of the solution is expressed in terms of the number of moles of solvent associated with 1 mol of the solute. If no concentration is indicated, the solution is assumed to be dilute. The standard state for a solute in aqueous solution is taken as the hypothetical ideal solution of unit molality (indicated as std. state or ss). In this state the partial molal enthalpy and the heat capacity of the solute are the same as in the infinitely dilute real solution. For some tables the uncertainty of entries is indicated within parentheses immediately following the value; viz., an entry 34.5(4) implies 34.5 ± 0.4 and an entry 34.5(12) implies 34.5 ± 1.2. References: D. D. Wagman, et al., The NBS Tables of Chemical Thermodynamic Properties, in J. Phys. Chem. Ref. Data, 11: 2, 1982; M. W. Chase, et al., JANAF Thermochemical Tables, 3rd ed., American Chemical Society and the American Institute of Physics, 1986 (supplements to JANAF appear in J. Phys. Chem. Ref. Data); Thermodynamic Research Center, TRC Thermodynamic Tables, Texas A&M University, College Station, Texas; I. Barin and O. Knacke, Thermochemical Properties of Inorganic Substances, Springer-Verlag, Berlin, 1973; J. B. Pedley, R. D. Naylor, and S. P. Kirby, Thermochemical Data of Organic Compounds, 2nd ed., Chapman and Hall, London, 1986; V. Majer and V. Svoboda, Enthalpies of Vaporization of Organic Compounds, International Union of Pure and Applied Chemistry, Chemical Data Series No. 32, Blackwell, Oxford, 1985.

2.13.1 THERMODYNAMIC RELATIONS Enthalpy of Formation. Once standard enthalpies are assigned to the elements, it is possible to determine standard enthalpies for compounds. For the reaction: C(graphite) + O2(g) → CO2(g)

∆H° = −393.51 kJ

(6.1)

Since the elements are in their standard states, the enthalpy change for the reaction is equal to the standard enthalpy of CO2 less the standard enthalpies of C and O2, which are zero in each instance. Thus, ∆f H° = −393.51 − 0 − 0 = −393.51 kJ

(6.2)

Tables of enthalpies, such as Tables 2.53 and 1.56, can be used to determine the enthalpy for any reaction at 1 atm and 298.15 K involving the elements and any of the compounds appearing in the tables. The solution of 1 mole of HCl gas in a large amount of water (infinitely dilute real solution) is represented by: HCl(g) + inf H2O → H+(aq) + Cl−(aq)

(6.3)

ORGANIC CHEMISTRY

2.513

The heat evolved in the reaction is ∆H° = −74.84 kJ. With the value of ∆f H° from Table 2.53, one has for the reaction: ∆f H° = ∆f H°[H+ (aq)] + ∆f H°[Cl−(aq)] − ∆f H°[HCl(g)] for the standard enthalpy of formation of the pair of ions H+ and Cl− in aqueous solution (standard state, m = 1). To obtain the ∆f H° values for individual ions, the enthalpy of formation of H+(aq) is arbitrarily assigned the value zero at 298.15 K. Thus, from Eq. (6.4): ∆f H°[Cl−(aq)] = −74.84 + (−92.31) = −167.15 kJ With similar data from Tables 2.53 and 1.56, the enthalpies of formation of other ions can be determined. Thus, from the ∆f H°[KCl(aq, std. state, m = 1 or aq, ss)] of −419.53 kJ and the foregoing value for ∆f H°[Cl−(aq, ss)]: ∆ f H o[K + (aq, ss)] = ∆ f H o[KCl(aq, ss)] − ∆ f H o[Cl − (aq, ss)] = − 419.53 − ( −167.15) = −252.38 kJ Enthalpy of Vaporization (or Sublimation) When the pressure of the vapor in equilibrium with a liquid reaches 1 atm, the liquid boils and is completely converted to vapor on absorption of the enthalpy of vaporization ∆Hv at the normal boiling point Tb. A rough empirical relationship between the normal boiling point and the enthalpy of vaporization (Trouton’s rule) is: ∆Hv = 88 J ⋅ mol −1 ⋅ K −1 Tb It is best applied to nonpolar liquids which form unassociated vapors. To a first approximation, the enthalpy of sublimation ∆Hs at constant temperature is: ∆Hs = ∆Hm + ∆Hv where ∆Hm is the enthalpy of melting. The Clapeyron equation expresses the dynamic equilibrium existing between the vapor and the condensed phase of a pure substance: dP ∆Hv = dT T∆V where ∆V is the volume increment between the vapor phase and the condensed phase. If the condensed phase is solid, the enthalpy increment is that of sublimation. Substitution of V = RT/P into the foregoing equation and rearranging gives the ClausiusClapeyron equation, dP ∆Hv = p dT RT 2 or ∆Hv = − R

d (ln P) 1/T

which may be used for calculating the enthalpy of vaporization of any compound provided its boiling point at any pressure is known. If an Antoine equation is available, differentiation and insertion into the foregoing equation gives: ∆Hv =

4.5757T 2 B (T + C − 273.15)2

2.514

SECTION TWO

Inclusion of a compressibility factor into the foregoing equation, as suggested by the Haggenmacher equation improves the estimate of ∆Hv: ∆Hv =

RT 2  dP  P  dT 

 Tc3 P  1 − 3   T Pc 

1/ 2

where Tc and Pc are critical constants (Table 2.55). Although critical constants may be unknown, the compressibility factor is very nearly constant for all compounds belonging to the same family, and an estimate can be deduced from a related compound whose critical constants are available. Heat Capacity (or Specific Heat) The temperature dependence of the heat capacity is complex. If the temperature range is restricted, the heat capacity of any phase may be represented adequately by an expression such as: Cp = a + bT + cT 2 in which a, b, and c are empirical constants. These constants may be evaluated by taking three pieces of data: (T1, Cp,1), (T2, Cp,2), and (T3, Cp,1), and substituting in the following expressions: C p,1 C p ,2 C p,3 + + =c (T1 − T2 )(T1 − T3 ) (T2 − T1 )(T2 − T3 ) (T3 − T2 )(T3 − T1 ) C p,1 − C p,2 − [(T1 + T2 )c] = b T1 − T2 (C p,1 − bT1 ) − cT12 = a Smoothed data presented at rounded temperatures, such as are available in Tables 2.54 and 1.57, plus the C°p values at 298 K listed in Table 2.53, are especially suitable for substitution in the foregoing parabolic equations. The use of such a parabolic fit is appropriate for interpolation, but data extrapolated outside the original temperature range should not be sought. Enthalpy of a System The enthalpy increment of a system over the interval of temperature from T1 to T2, under the constraint of constant pressure, is given by the expression: H2 − H1 =

∫

T2

C p dT

T1

The enthalpy over a temperature range that includes phase transitions, melting, and vaporization, is represented by: H2 − H1 =

∫

T2

C p (c, II ) dT + ∆Ht +

T1

+

∫

Tm

C p (c, I )dT + ∆Hm

T1

∫

Tb

C p ( lq) dT + ∆Hv +

Tm

∫

T2

C p ( g) dT

Tb

Integration of heat capacities, as expressed by Eq. (6.13), leads to: ∆H = a(T2 − T1 ) +

(

b T22 − T12 2

) + c(T23 − T13 ) 3

2.515

ORGANIC CHEMISTRY

Entropy In the physical change of state, ∆Sm =

∆Hm Tm

∆Sv =

∆Hv Tb

∆Ss =

∆Hs Ts

is the entropy of melting (or fusion),

is the entropy of vaporization, and

is the entropy of sublimation A general expression for the entropy of a system, involving any phase transitions, is S2 − S1 =

∫

C p (c, II) dT ∆Ht + + T T

Tt

T1

+

∫

C p (1q) dT ∆Hv + + T T Tm

∫

Tb

C p (c, I) dT ∆Hm + T T

Tm

Tb

∫

Tm

Tb

C p (g) dT T

If Cp is independent of temperature, ∆S = C p (ln T2 − ln T1 ) = 2.303 C p log

T2 T1

If the heat capacities change with temperature, an empirical equation may be inserted in before integration. Usually the integration is performed graphically from a plot of either Cp /T versus T or Cp versus ln T.

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds Substance Acenaphthene Acenaphthylene Acetaldehyde Acetaldoxime Acetamide Acetamidoguanidine nitrate 1-Acetamido-2-nitroguanidine 5-Acetamidotetrazole Acetanilide Acetic acid ionized; std. state, m = 1 Acetic anhydride

Physical state c c lq g c lq c c c c c lq g aq lq

∆f H° kJ ⋅ mol−1 70.34 186.7 −192.2 −166.1 −77.9 −81.6 −317.0 −494.0 −193.6 −5.0 −210.6 −484.4 −432.2 −486.34 −624.4

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1 188.9

−127.6 −133.0

−390.2 −374.2 −369.65 −489.14

160.4 263.8

190.4 166.4 89.0 55.3

115.0

91.3

159.9 283.5 86.7 268.8

123.6 63.4 −6.3 168.230 (Continued)

2.516

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance Acetone Acetonitrile Acetophenone Acetyl bromide Acetyl chloride Acetylene Acetylene-d2 Acetylenedicarboxylic acid Acetyl fluoride 1-Acetylimidazole Acetyl iodide Acridine Adamantane

Physical state

∆f H° kJ ⋅ mol−1

lq g lq g lq lq lq g g g c g c lq c c

−248.4 −217.1 31.4 74.0 −142.5 −223.5 −272.9 −242.8 227.4 221.5 −578.2 −442.1 −574.0 −163.5 179.4 −194.1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

−152.7 −152.7 86.5 91.9 −17.0

198.8 295.3 149.7 243.4 249.6

126.3 74.5 91.5 52.2 204.6

−208.2 −205.8 209.0 205.9

201.0 295.1 201.0 208.9

117.0 67.8 44.1 49.3

ORGANIC CHEMISTRY

2.517

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.518

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.519

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.520

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.521

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.522

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.523

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.524

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.525

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.526

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.527

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.528

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.529

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.530

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.531

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical State

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.532

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical State

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.533

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical State

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.534

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical State

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.535

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical State

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.536

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.537

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.538

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

ORGANIC CHEMISTRY

2.539

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.540

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

Next Page ORGANIC CHEMISTRY

2.541

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

Previous Page 2.542

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.543

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.544

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.545

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.546

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.547

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.548

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.549

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.550

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.551

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.552

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.553

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.554

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.555

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.556

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.557

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.558

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.559

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

(Continued)

2.560

SECTION TWO

TABLE 2.53 Enthalpies and Gibbs Energies of Formation, Entropies, and Heat Capacities of Organic Compounds (Continued) Substance

Physical state

∆f H° kJ ⋅ mol−1

∆f G° kJ ⋅ mol−1

S° Cp° J ⋅ deg−1⋅mol−1 J ⋅ deg−1 ⋅ mol−1

ORGANIC CHEMISTRY

2.561

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds Abbreviations Used in the Table ∆Hm, enthalpy of melting (at the melting point) in kJ ⋅ mol −1 ∆Hv, enthalpy of vaporization (at the boiling point) in kJ ⋅ mol −1 ∆Hs, enthalpy of sublimation (or vaporization at 298 K) in kJ ⋅ mol −1 Cp, specific heat (at temperature specified on the Kelvin scale) for the physical state in existence (or specified: c, lq, g) at that temperature in J ⋅ K−1 ⋅ mol −1 ∆Ht, enthalpy of transition (at temperature specified, superscript, measured in degrees Celsius) in kJ ⋅ mol−1

(Continued)

2.562

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.563

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.564

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.565

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.566

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.567

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.568

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.569

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.570

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.571

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.572

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.573

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.574

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.575

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.576

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.577

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.578

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.579

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.580

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.581

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.582

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.583

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.584

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.585

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.586

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.587

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.588

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.589

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

(Continued)

2.590

SECTION TWO

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

ORGANIC CHEMISTRY

2.591

TABLE 2.54 Heat of Fusion, Vaporization, Sublimation, and Specific Heat at Various Temperatures of Organic Compounds (Continued)

2.14 CRITICAL PROPERTIES Critical temperature (Tc), critical pressure(Pc), and critical volume (Vc) represent three widely used pure component constants. These critical constants are very important properties in chemical engineering field because almost all other thermo chemical properties are predictable from boiling point and critical constants with using corresponding state theory. Therefore, precise prediction of critical constants is very necessary. 2.14.1 Critical Temperature The critical temperature of a compound is the temperature above which a liquid phase cannot be formed no matter what the pressure on the system. The critical temperature is important in determining the phase boundaries of any compound and is a required input parameter for most phase equilibrium thermal property or volumetric property calculations using analytic equations of state or the theorem of corresponding states. Critical temperatures are predicted by various empirical methods according to the type of compound or mixture being considered. 2.14.2 Critical Pressure The critical pressure of a compound is the vapor pressure of that compound at the critical temperature. Below the critical temperature, any compound above its vapor pressure will be a liquid. 2.14.3 Critical Volume The critical volume of a compound is the volume occupied by a specified mass of a compound at its critical temperature and critical pressure.

Next Page 2.592

SECTION TWO

2.14.4

Critical Compressibility Factor The critical compressibility factor of a compound is used as a characterization parameter in corresponding states methods to predict volumetric and thermal properties. The factor varies from approximately 0.23 for water to 0.26–0.28 for most hydrocarbons to above 0.30 for light gases. TABLE 2.55 Critical Properties Substance Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetophenone Acetyl chloride Acetylene Acrylic acid Acrylonitrile Allene Allyl alcohol 2-Aminoethanol Aniline Anthracene Benzaldehyde Benzene Benzoic acid Benzonitrile Benzyl alcohol Biphenyl Bromobenzene Bromochlorodifluoromethane Bromoethane Bromomethane Bromopentafluorobenzene 1-Bromopropane 2-Bromopropane Bromotrifluoromethane 1,2-Butadiene 1,3-Butadiene Butanal Butane Butanenitrile Butanoic acid 1-Butanol 2-Butanol 2-Butanone 1-Butene cis-2-Butene trans-2-Butene 3-Butenenitrile 1-Buten-3-yne Butyl acetate 1-Butylamine sec-Butylamine tert-Butylamine

Tc, °C 193 319.56 333 235.0 272.4 436.4 235 35.2 342 263 120 272.0 341 426 610 422 288.90 479 426.3 422 516 397 158.8 230.8 173.4 397 –1.8 –14.2 67.1 170.6 152 264.1 151.97 312.3 351 289.9 263.1 263.63 146.5 147.5 147.5 312.3 182 306.7 258.8 241.2 210.8

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

55 57.1 39.5 46.4 47.7 38 58 60.6 56 45 54.0 56.4 44 49.5 28.6 45.9 48.31 41.55 41.55 42.4 38.0 44.6 41.98 61.5 85 44.6

5.57 5.786 4.0 4.700 4.85 3.85 5.88 6.14 5.67 4.56 5.47 5.71 4.46 4.89 2.90 4.65 4.895 4.21 4.21 4.3 3.85 4.52 4.254 6.23 8.61 4.52

154 171.3 290 209 173 386 204 113 210 210 162 203 196 287 554 324 255 341 339 334 502 324 246 215 156

0.286 0.351 0.352 0.278 0.237 0.311 0.325 0.231 0.343 0.253 0.247 0.286 0.312 0.324 0.333 0.327 0.306 0.358 0.304 0.324 0.307 0.485 0.672 0.507 0.609

200 219 221 258 255 285 290 275 269 267 240 238 238 265 202 400 277 278 292

0.462 0.462 0.76 0.247 0.245 0.279 0.228 0.242 0.304 0.270 0.276 0.270 0.234 0.240 0.236 0.253 0.258 0.290 0.264 0.263 0.250

39.2 44.4 42.7 42.6 37.34 38.3 39.8 43.56 41.47 41.52 39.7 40.5 40.5 38.3 49 31 41.9 41.4 37.9

3.97 4.50 4.33 4.32 3.784 3.88 4.03 4.414 4.202 4.207 4.02 4.10 4.10 3.88 4.96 3.14 4.25 4.20 3.84

Previous Page ORGANIC CHEMISTRY

2.593

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

(Continued)

2.594

SECTION TWO

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

ORGANIC CHEMISTRY

2.595

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

(Continued)

2.596

SECTION TWO

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

ORGANIC CHEMISTRY

2.597

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

(Continued)

2.598

SECTION TWO

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

ORGANIC CHEMISTRY

2.599

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

(Continued)

2.600

SECTION TWO

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

ORGANIC CHEMISTRY

2.601

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

(Continued)

2.602

SECTION TWO

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

ORGANIC CHEMISTRY

2.603

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

(Continued)

2.604

SECTION TWO

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

ORGANIC CHEMISTRY

2.605

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

(Continued)

2.606

SECTION TWO

TABLE 2.55 Critical Properties (Continued) Substance

Tc, °C

Pc, atm

Pc, MPa

Vc, cm3 ⋅ mol−1

rc, g ⋅ cm−3

ORGANIC CHEMISTRY

2.607

TABLE 2.56 Lydersen’s Critical Property Increments ∆T

∆p

∆n

0.020

0.227

55

0.020

0.227

55

0.012

0.210

51

0.00

0.210

41

0.018

0.198

45

0.018

0.198

45

0.0

0.198

36

0.0 0.005 0.005

0.198 0.153 0.153

36 (36) (36)

0.013

0.184

44.5

0.012

0.192

46

(−0.007)

(0.154)

(31)

0.011

0.154

37

0.011 0.011

0.154 0.154

36 36

0.018 0.017 0.010 0.012

0.224 0.320 (0.50) (0.83)

18 49 (70) (95)

0.082 0.031 0.021 (0.014)

0.06 (−0.02) 0.16 (0.12)

(18) (3) 20 (8)

0.040

0.29

60

(0.033)

(0.2)

(50)

0.048 0.085 0.047 (0.02)

0.33 (0.4) 0.47 (0.12)

73 80 80 (11)

0.031

0.095

28

0.031

0.135

(37)

Nonring Increments —CH3 | [CH2 | [CH | | [C[ | ˙CH2 | ˙ CH | ˙ CH[ ˙C˙ æCH æC— Ring Increments —CH2— | [CH | | [C[ | | ˙ CH | ˙ CH[ ˙C˙ Halogen Increments —F —Cl —Br —I Oxygen Increments —OH (alcohols) —OH (phenols) —O— (nonring) —O— (ring) | [C˙O (nonring) | [C˙O (ring) | H C˙O (aldehyde) —COOH (acid) —COO— (ester) ˙O (except for combinations above) Nitrogen Increments —NH2 | [NH (nonring)

2.608

SECTION TWO

TABLE 2.56 Lydersen’s Critical Property Increments (Continued)

Nitrogen Increments (continued) | [NH (ring) | [NH[ (nonring) | [N[(ring) —CN —NO2 Sulfur Increments —SH —S— (nonring) —S— (ring) ˙S Miscellaneous | [Si— | [B— | Nonring:

∆T

∆p

∆n

(0.024)

(0.09)

(27)

0.014

0.17

(42)

(0.007) (0.060) (0.055)

(0.13) (0.36) (0.42)

(32) (80) (78)

0.015 0.015 (0.008) (0.003)

0.27 0.27 (0.24) (0.24)

55 55 (45) (47)

0.03

(0.54)

(0.03)

†There are no increments for hydrogen. All bonds shown as free are connected with atoms other than hydrogen. Values in parentheses are based upon too few experimental values to be reliable. From vapor-pressure measurements and a calculational technique 87 similar to Fishtine [6], it has been suggested that the C—H ring increment common to two condensed saturated rings be given the | value of ∆T = 0.064.

TABLE 2.57 Vetere Group Contribution to Estimate Critical Volume Group Nonring: In linear chain: CH3, CH2, CH, C In side chain CH3, CH2, CH, C | | ˙CH2, ˙ CH, ˙ C[ ˙C˙ æCH, æC— Ring: CH2, CH, C | | ˙ CH, ˙ C[

F Cl Br I —OH (alcohols) —OH (phenols) —O— (nonring) —O— (ring) —O— (epoxy)

∆Vi

3.360 2.888 2.940 2.908 2.648 2.813 2.538

0.770 1.237 0.899 0.702 0.704 1.553 1.075 0.790 —0.252

Group | [C˙O (nonring) | [C˙O (ring) | [HC˙O (aldehyde)

∆Vi 1.765 1.500 2.333

—COOH —COO— | [NH2 | [NH (nonring) | [NH (ring) | [N— (nonring) | [N— (ring) —CN —NO2

1.652 1.607

—SH —S— (nonring) —S— (ring)

1.537 0.591 0.911

2.184 2.333 1.736 1.793 1.883 2.784 1.559

ORGANIC CHEMISTRY

TABLE 2.58 Van der Waalls’ Constants for Gases

The van der Waals’ equation of state for a real gas is:  n2 a   P + 2  (V − nb) = nRT V  

for n moles

where P is the pressure. V the volume (in liters per mole = 0.001 m3 per mole in the SI system), T the temperature (in degrees Kelvin), n the amount of substance (in moles), and R the gas constant. To use the values of a and b in the table, P must be expressed in the same units as in the gas constant. Thus, the pressure of a standard atmosphere may be expressed in the SI system as follows: 1 atm = 101,325 N ⋅ m−2 = 101,325 Pa = 1.01325 bar The appropriate value for the gas constant is: 0.083 144 1 L ⋅ bar ⋅ K−1 ⋅ mol−1

or

0.082 056 L ⋅ atm ⋅ K−1 ⋅ mol−1

The van der Waals’ constants are related to the critical temperature and pressure, Tc and Pc, in Table 2.55 by: a= Substance Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetyl chloride Acetylene Acrylic acid Acrylonitrile Allene Allyl alcohol Aluminum trichloride 2-Aminoethanol Ammonia Ammonium chloride Aniline Antimony tribromide Argon Arsenic trichloride Arsine Benzaldehyde Benzene Benzonitrile Benzyl alcohol Biphenyl Bismuth trichloride Boron trichloride Boron trifluoride Bromine (Br2) Bromobenzene Bromochlorodifluoromethane Bromoethane Bromomethane Bromotrifluoromethane

27 R2 Tc2 64 Pc

and b =

RTc 8 Pc

a, L2 ⋅ bar ⋅ mol−2 11.37 17.71 26.8 16.02 17.89 12.80 4.516 19.45 18.37 8.235 15.17 42.63 7.616 4.225 2.380 29.14 42.08 1.355 17.23 6.327 30.30 18.82 33.89 34.7 47.16 33.89 15.60 3.98 9.75 28.96 12.79 11.89 6.753 8.502

b, L ⋅ mol−1 0.08695 0.1065 0.157 0.1124 0.1169 0.08979 0.05218 0.1127 0.1222 0.07467 0.1036 0.2450 0.0431 0.03713 0.00734 0.1486 0.1658 0.03201 0.1039 0.06048 0.1553 0.1193 0.1727 0.173 0.2130 0.1025 0.1222 0.05443 0.0591 0.1541 0.1055 0.08406 0.05390 0.0891 (Continued)

2.609

2.610

SECTION TWO

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

ORGANIC CHEMISTRY

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

(Continued)

2.611

2.612

SECTION TWO

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

ORGANIC CHEMISTRY

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

(Continued)

2.613

2.614

SECTION TWO

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

ORGANIC CHEMISTRY

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

(Continued)

2.615

2.616

SECTION TWO

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

ORGANIC CHEMISTRY

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

(Continued)

2.617

2.618

SECTION TWO

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

ORGANIC CHEMISTRY

TABLE 2.58 Van der Walls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

(Continued)

2.619

2.620

SECTION TWO

TABLE 2.58 Van der Waalls’ Constants for Gases (Continued) Substance

a, L2 ⋅ bar ⋅ mol−2

b, L ⋅ mol−1

2.15 EQUILIBRIUM CONSTANTS The equilibrium constant, K, relates to a chemical reaction at equilibrium. It can be calculated if the equilibrium concentration of each reactant and product in a reaction at equilibrium is known. There are several types of equilibrium constants. Each is constant at a constant temperature.

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C

Ionic strength m is zero unless otherwise indicated. Protonated cations are designated by (+ 1), (+ 2), etc., after the pKa value; neutral species by (0), if not obvious; and negatively charged acids by (−1), (−2), etc.

ORGANIC CHEMISTRY

TABLE 2.59

2.621

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.622

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.623

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.624

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.625

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.626

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.627

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.628

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.629

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.630

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.631

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.632

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.633

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.634

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.635

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.636

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.637

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.638

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.639

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.640

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.641

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.642

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.643

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.644

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.645

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.646

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.647

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.648

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.649

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.650

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.651

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.652

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.653

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.654

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.655

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.656

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.657

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.658

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.659

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.660

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

Next Page ORGANIC CHEMISTRY

TABLE 2.59

2.661

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

Previous Page 2.662

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.663

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.664

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.665

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.666

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

2.667

pK, Values of Organic Materials in Water at 25°C (Continued)

(Continued)

2.668

SECTION TWO

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

ORGANIC CHEMISTRY

TABLE 2.59

pK, Values of Organic Materials in Water at 25°C (Continued)

2.669

2.670

TABLE 2.60 Selected Equilibrium Constants in Aqueous Solution at Various Temperatures Abbreviations Used in the Table (+ 1), protonated cation (0), neutral molecule (−1), singly ionized anion

(−2), doubly ionized anion pKauto, negative logarithm (base 10) of autoprotolysis constant pKsp, negative logarithm (base 10) of solubility product

(Continued)

2.671

2.672

TABLE 2.60 Selected Equilibrium Constants in Aqueous Solution at Various Temperatures (Continued)

(Continued) 2.673

2.674

TABLE 2.60 Selected Equilibrium Constants in Aqueous Solution at Various Temperatures (Continued)

2.675

2.676

SECTION TWO

TABLE 2.61 pK, Values for Proton-Transfer Reactions in Non-aqueous Solvents

a

Dimethylsulfoxide. b Glacial acetic acid. c Acetonitrile. d Acetone + 10% water.

ORGANIC CHEMISTRY

2.677

2.16 INDICATORS An acid-base indicator is a conjugate acid-base pair of which the acid form and the base form are of different colors. These indicators are used to show the relative acidity or alkalinity of the test material. Acid-base indicators are dyes that are themselves weak acids and bases. The conjugate acid-base forms of the dye are of different colors. An indicator does not change color from pure acid to pure alkaline at specific hydrogen ion concentration, but, rather, color change occurs over a range of hydrogen ion concentrations. This range is termed the color change interval and is expressed as a pH range. The chemical structures of the dyes are often complex but can be represented chemically by the symbol HIn. The acid-base indicator reaction is represented as: HIn + H2O H3O+ + In

(1)

TABLE 2.62 Acid-Base Indicators pH range Indicator Brilliant cresyl blue Methyl violet Crystal violet Ethyl violet Methyl Violet 6B Cresyl red 2-(p-Dimethylaminophenylazo) pyridine Malachite green Methyl green Cresol red (o-Cresolsulfonephthalein) Quinaldine red p-Methyl red Metanil yellow Pentamethoxy red Metanil yellow p-Phenylazodiphenylamine Thymol blue (Thymolsulfonephthalein) m-Cresol purple p-Xylenol blue Benzopurpurin 4B Tropeolin OO Orange IV 4-o-Tolylazo-o-toluidine Methyl violet 6B Phloxine B Erythrosine, disodium salt Benzopupurine 4B N,N-dimethyl-p-(m-tolylazo) aniline 2,4-Dinitrophenol N,N-Dimethyl-p-phenylazoaniline Methyl yellow Bromophenol blue Tetrabromophenol blue Direct purple

Minimum

Color

Maximum

Acid

Alkaline

0.0 0.0 0.0 0.0 0.1 0.2 0.2

1.0 1.6 1.8 2.4 1.5 1.8 1.8

red-orange yellow yellow yellow yellow red yellow

blue blue blue blue blue yellow blue

0.2 0.2 1.0 1.0 1.0 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.3 1.4 1.4 1.5 2.1 2.2 2.2 2.6 2.8 2.8 2.9 3.0 3.0 3.0

1.8 1.8 2.0 2.2 3.0 2.3 2.3 2.4 2.6 2.8 2.8 2.8 3.8 3.2 2.8 2.8 3.2 4.1 3.6 4.2 4.8 4.0 4.4 4.0 4.6 4.6 4.6

yellow yellow red colorless red red red-violet red red red red red violet red red orange blue colorless orange violet red colorless red red yellow yellow blue-purple

blue-green blue yellow red yellow yellow colorless yellow yellow yellow yellow yellow red yellow yellow yellow violet pink red red yellow yellow yellow yellow blue-violet blue red (Continued)

2.678

SECTION TWO

TABLE 2.62 Acid-Base Indicators (Continued) pH range Indicator Congo red Methyl orange Bromochlorophenol blue Ethyl orange p-Ethoxychrysoidine Alizarin sodium sulfonate a-Naphthyl red Bromocresol green Resazurin Bromophenol green 2,5-Dinitrophenol Methyl red 2-(p-Dimethylaminophenylazo) pyridine Lacmoid Azolitmin Litmus Alizarin red S Chlorophenol red Cochineal Propyl red Hematoxylin Bromocresol purple Bromophenol red Chlorophenol red p-Nitrophenol Alizarin Bromothymol blue Indo-oxine Bromophenol blue m-Dinitrobenzoylene urea Phenol red (Phenolsulfonephthalein) Rosolic acid Brilliant yellow Quinoline blue Neutral red Phenol red m-Nitrophenol Cresol red (o-Cresolsulfonephthalein) a-Naphtholphthalein Curcumin m-Cresol purple (m-Cresolsulfonephthalein) Tropeolin OOO 2,6-Divanillydenecyclohexanone Thymol blue (Thymolsulfonephthalein) p-Xylenol blue Turmeric Phenolphthalein o-Cresolphthalein p-Naphtholphthalein Ethyl bis(2,4-dimethylphenyl acetate)

Minimum

Color Acid

Alkaline

3.1 3.1 3.2 3.4 3.5 3.7 3.7 3.8 3.8 4.0 4.0 4.2 4.4

Maximum 4.9 4.4 4.8 4.8 5.5 5.2 5.7 5.4 6.4 5.6 5.8 6.2 5.6

blue red yellow red red yellow red yellow orange yellow colorless red red

red yellow blue yellow yellow violet yellow blue violet blue yellow yellow yellow

4.4 4.5 4.5 4.6 4.8 4.8 4.8 5.0 5.2 5.2 5.4 5.6 5.6 6.0 6.0 6.2 6.4 6.4 6.4 6.6 6.6 6.8 6.8 6.8 7.0 7.3 7.4 7.4 7.6 7.8 8.0 8.0 8.0 8.0 8.2 8.2 8.4

6.2 8.3 8.3 6.0 6.4 6.2 6.6 6.0 6.8 7.0 6.8 6.6 7.2 7.6 8.0 7.6 8.0 8.0 8.0 7.9 8.6 8.0 8.4 8.6 8.8 8.8 8.6 9.0 8.9 9.4 9.6 9.6 10.0 10.0 9.8 10.0 9.6

red red red yellow yellow red red red yellow yellow yellow colorless yellow yellow red yellow colorless yellow yellow yellow colorless red yellow colorless yellow yellow yellow yellow yellow yellow yellow yellow yellow colorless colorless colorless colorless

blue blue blue red red violet yellow blue violet red red yellow red blue blue blue yellow red red orange blue orange yellow yellow red blue red violet rose-red red purple blue orange red red pink blue

ORGANIC CHEMISTRY

2.679

TABLE 2.62 Acid-Base Indicators (Continued) pH range Indicator

Minimum

Maximum

Color Acid

Ethyl bis(2,4-dinitrophenyl acetate) α-Naphtholbenzein Thymolphthalein Nile blue A Alizarin yllow CG Alizarin yellow R Salicyl yellow

8.4 8.5 9.4 10.0 10.0 10.2 10.0

9.6 9.8 10.6 11.0 12.0 12.0 12.0

colorless yellow colorless blue yellow yellow yellow

Diazo violet Nile blue Curcumin Malachite green hydrochloride Methyl blue Brilliant cresyl blue Alizarin Nitramine

10.1 10.1 10.2 10.2 10.6 10.8 11.0 11.0

12.0 11.1 11.8 12.5 13.4 12.0 12.4 13.0

yellow blue yellow green-blue blue blue red colorless

Poirier’s blue Tropeolin O Indigo carmine Sodium indigosulfonate Orange G 2,4,6-Trinitrotoluene 1,3,5-Trinitrobenzene 2,4,6-Trinitrobenzoic acid Clayton yellow

11.0 11.0 11.4 11.4 11.5 11.7 12.0 12.0 12.2

13.0 13.0 13.0 13.0 14.0 12.8 14.0 13.4 13.2

blue yellow blue blue yellow colorless colorless blue yellow

Alkaline blue green blue purple lilac orange red orangebrown violet red red colorless pale violet yellow purple orange brown violet-pink orange yellow yellow pink orange orange violet-pink amber

2.680 TABLE 2.63 Mixed Indicators Mixed indicators give sharp color changes and are especially useful in titrating to a given titration exponent (pI). The information given in this table is from the two-volume work Volumetric Analysis by Kolthoff and Stenger, published by Interscience Publishers, Inc., New York, 1942 and 1947, and reproduced with their permission.

* Store in a dark bottle. † Excellent indicator.

2.681

2.682

SECTION TWO

TABLE 2.64 Fluorescent Indicators

ORGANIC CHEMISTRY

2.683

TABLE 2.64 Fluorescent Indicators (Continued)

Indicator solutions: 1, 1% solution in ethanol; 2, 0.1% solution in ethanol; 3, 0.05% solution in 90% ethanol; 4, sodium or potassium salt in distilled water, 5; 0.2% solution in 70% ethanol; 6, distilled water.

2.684

TABLE 2.65 Selected List of Oxidation-Reduction Indicators

* Transition point is at higher potential than the tabulated formal potential because the molar absorptivity of the reduced form is very much greater than that of the oxidized form. † Trans = first noticeable color transition; often 60 mV less than E° ‡ Values of E° are obtained by extrapolation from measurements in weakly acid or weakly alkaline systems.

2.685

2.686

SECTION TWO

TABLE 2.66 Indicators for Approximate pH Determination No. 1.

Dissolve 60 mg methyl yellow, 40 mg methyl red, 80 mg bromthymol blue, 100 mg thymol blue and 20 mg phenolphthalein in 100 ml of ethanol and add enough 0.1N NaOH to produce a yellow color. No. 2. Dissolve 18.5 mg methyl red, 60 mg bromthymol blue and 64 mg phenolphthalein in 100 ml of 50% ethanol and add enough 0.1N NaOH to produce a green color. Color pH 1 2 3 4 5 6

No. 1 cherry-red rose red-orange orange-red orange yellow

Color No. 2 red red red deeper red orange-red orange-yellow

pH 7 8 9 10 11

No. 1

No. 2

yellowish-green green bluish-green blue —

greenish-yellow green greenish-blue violet reddish-violet

TABLE 2.67 Oxidation-Reduction Indicators

Common name

Transition potential, Reference volts (N hydrogen electrode = 0.000)

p-ethoxychrysoidine diphenylamine diphenylbenzidine diphenylamine-sulfonic acid or barium salt naphthidine dimethylferroin eriogreen B erioglaucin A xylene cyanole FF 2,2′-dipyridyl ferrous ion N-phenylanthranilic acid methylferroin ferroin (o-phenanthrolineferrous ion) chloroferroin nitroferroin α-naphtolflavone

1 2 3 4 5 6 7 7 11 6 8 6 9 6 6 10

0.76 0.776 0.776 0.84 — 0.97 0.99 1.0 1.0 1.03 1.08 1.08 1.12 1.17 1.31 —

Color Reduced form

Oxidized form

red colorless colorless colorless colorless red yellow yellowish-green

yellow purple purple purple red yellowish-green orange red

red colorless red red red red pale straw

colorless pink pale-blue pale-blue pale-blue pale greenish-blue brownish-orange

ORGANIC CHEMISTRY

2.687

2.17 ELECTRODE POTENTIALS The potential of a polarographic or voltammetric indicator electrode at the point, on the rising part of a polarographic or voltammetric wave, where the difference between the total current and the residual current is equal to one-half of the limiting current. The quarter-wave potential, the three-quarterwave potential, etc., may be similarly defined.

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C. The solvent system in this table are listed below: A, acetonitrile and a perchlorate salt such as LiClO4 or a tetraalkyl ammonium salt B, acetic acid and an alkali acetate, often plus a tetraalkyl ammonium iodide C, 0.05 to 0.175M tetraalkyl ammonium halide and 75% 1,4-dioxane D, buffer plus 50% ethanol (EtOH) Abbreviations Used in the Table Bu, butyl Et, ethyl EtOH, ethanol M, molar Compound

Me, methyl MeOH, methanol PrOh, propanol Solvent system

E1/2

(Continued)

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SECTION TWO

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

(Continued)

ORGANIC CHEMISTRY

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TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

(Continued)

2.690

SECTION TWO

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

ORGANIC CHEMISTRY

2.691

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

(Continued)

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SECTION TWO

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

ORGANIC CHEMISTRY

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TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

(Continued)

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SECTION TWO

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

ORGANIC CHEMISTRY

2.695

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

(Continued)

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SECTION TWO

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued) Compound

Solvent system

E1/2

ORGANIC CHEMISTRY

TABLE 2.68 Half-Wave Potentials (vs. Saturated Calomel Electrode) of Organic Compounds at 25°C (Continued)

2.697

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SECTION TWO

2.18 ELECTRICAL CONDUCTIVITY

TABLE 2.69 Electrical Conductivity of Various Pure Liquids

ORGANIC CHEMISTRY

TABLE 2.69 Electrical Conductivity of Various Pure Liquids (Continued)

TABLE 2.70 Limiting Equivalent Ionic Conductances in Aqueous Solutions

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SECTION TWO

TABLE 2.71 Properties of Organic Semiconductors Band Gap

Substance

Formula

Resistivity, ohm-cm

Conduc- Photo tivity, Conduct, eV eV

POLYACENES Anthracene

300

0.83

––

Tetracene

10

0.85

3.6

Pyrene

300

1.01

3.2

Perylene

10

0.98

––

Chrysene

100

1.10

3.2

Coronene

0.2

1.15

––

Pyranthrene

107

0.54

0.85

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TABLE 2.71 Properties of Organic Semiconductors (Continued) Band Gap

Substance

Resistivity, ohm-cm

Formula

Conduc- Photo tivity, Conduct, eV eV

POLYACENES WITH QUINONOID ATTACHEMENTS O

Violanthrone

O

1000

0.39

0.84

106

0.54

1.14

300

0.28

—

O

Pyranthrone

O AZO-AROMATIC COMPOUNDS

O

Indanthrone black

O N

N

N

N

1,9,4,10-Anthradipyrimidine

1000 N

1.61

—

N (Continued)

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SECTION TWO

TABLE 2.71 Properties of Organic Semiconductors (Continued) Band Gap

Substance

Resistivity, ohm-cm

Formula

Conduc- Photo tivity, Conduct, eV eV

N NH PHTHALOCYANINES

N

N

N N

104

1.2

1.56

106

0.74

-

HN N

FREE RADICALS α,α-Diphenyl β-pieryl hydrazyl

NO 2 N N

NO2

NO2

2.19 LINEAR FREE ENERGY RELATIONSHIPS Many equilibrium and rate processes can be systematized when the influence of each substituent on the reactivity of substrates is assigned a characteristic constant s and the reaction parameter r is known or can be calculated. The Hammett equation log

K = σρ Ko

describes the behavior of many meta- and para-substituted aromatic species. In this equation K° is the acid dissociation constant of the reference in aqueous solution at 25°C and K is the corresponding constant for the substituted acid. Separate sigma values are defined by this reaction for meta and para substituents and provide a measure of the total electronic influence (polar, inductive, and resonance effects) in the absence of conjugation effects. Sigma constants are not valid of substituents ortho to the reaction center because of anomalous (mainly steric) effects. The inductive effect is transmitted about equally to the meta and para positions. Consequently, sm is an approximate measure of the size of the inductive effect of a given substituent and sp − sm is an approximate measure of a substituent’s resonance effect. Values of Hammett sigma constants are listed in Table 2.72. Taft sigma values s* perform a similar function with respect to aliphatic and alicyclic systems. Values of s* are listed in Table 2.72. The reaction parameter r depends upon the reaction series but not upon the substituents employed. Values of the reaction parameter for some aromatic and aliphatic system are given in Tables 2.73 and 2.74. Since substituent effects in aliphatic systems and in meta positions in aromatic systems are essentially inductive in character, s* and sm values are often related by the expression. sm = 0.217 s* − 0.106. Substituent effects fall off with increasing distance from the reaction center; generally a factor of 0.36 corresponds to the interposition of a [CH2[ group, which enables s * values to be estimated for R[CH2[groups not otherwise available.

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Two modified sigma constants have been formulated for situations in which the substituent enters into resonance with the reaction center in an electron-demanding transition state (s+) or for an electronrich transition state (s −).s − constants give better correlations in reactions involving phenols, anilines, and pyridines and in nucleophilic substitutions. Values of some modified sigma constants are given in Table 2.75.

TABLE 2.72 Hammett and Taft Substituent Constants

(Continued)

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SECTION TWO

TABLE 2.72 Hammett and Taft Substituent Constants (Continued)

ORGANIC CHEMISTRY

TABLE 2.72 Hammett and Taft Substituent Constants (Continued)

(Continued)

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SECTION TWO

TABLE 2.72 Hammett and Taft Substituent Constants (Continued)

ORGANIC CHEMISTRY

2.707

TABLE 2.73 pK°a and Rho Values for Hammett Equation Acid Arenearsonic acids pK1 pK2 Areneboronic acids (in aqueous 25% ethanol) Arenephosphonic acids pK1 pK2 α-Aryladoximes Benzeneseleninic acids Benzenesulfonamides (20°C) Benzenesulfonanilides (20°C) X—C6H4—SO2—NH—C6H5 C6H5—SO2—NH—C6H4—X Benzoic acids Cinnamic acids Phenols Phenylacetic acids Phenylpropiolic acids (in aqueous 35% dioxane) Phenylpropionic acids Phenyltrifluoromethylcarbinols Pyridine-1-oxides 2-Pyridones 4-Pyridones Pyrroles 5-Substituted pyrrole-2carboxylic acids Thiobenzoic acids Thiophenols Trifluoroacetophenone hydrates 5-Substituted topolones Protonated cations of Acetophenones Anilines C-Aryl-N-dibutylamidines (in aqueous 50% ethanol) N,N-Dimethylanilines Isoquinolines 1-Naphthylamines 2-Naphthylamines Pyridines Quinolines

pK°a

r

3.54 8.49 9.70

1.05 0.87 2.15

1.84 6.97 10.70 4.78 10.00

0.76 0.95 0.86 1.03 1.06

8.31 8.31 4.21 4.45 9.92 4.30 3.24 4.45 11.90 0.94 11.65 11.12 17.00 2.82 2.61 6.50 10.00 6.42

1.16 1.74 1.00 0.47 2.23 0.49 0.81 0.21 1.01 2.09 4.28 4.28 4.28 1.40 1.0 2.2 1.11 3.10

−6.0 4.60 11.14 5.07 5.32 3.85 4.29 5.18 4.88

2.6 2.90 1.41 3.46 5.90 2.81 2.81 5.90 5.90

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SECTION TWO

TABLE 2.74 pK°a and Rho Values for Taft Equation Acid

pK°a

r

RCOOH RCH2COOH RCæC—COOH H2C˙C(R)—COOH (CH3)2C˙C(R)—COOH cis-C6H5—CH˙C(R)—COOH trans-C6H5—CH˙C(R)—COOH R—CO—CH2—COOH HON˙C(R)—COOH RCH2OH RCH(OH)2 R1CO—NHR2 CH3CO—C(R)˙C(OH)CH3 CH3CO—CH(R)—CO—OC2H5 R—CO—NHOH R1R2C˙NOH (R1, R2 not acyl groups) (R)(CH3CO)C˙NOH RC(NO2)2H RSH RCH2SH R—CO—SH

4.66 4.76 2.39 4.39 4.65 3.77 4.61 4.12 4.84 15.9 14.4 22.0 9.25 12.59 9.48 12.35 9.00 5.24 10.22 10.54 3.52

1.62 0.67 1.89 0.64 0.47 0.63 0.47 0.43 0.34 1.42 1.42 3.1* 1.78 3.44 0.98 1.18 0.94 3.60 3.50 1.47 1.62

Protonated cations of RNH2 R1R2NH R1R2R3N R1R2PH R1R2R3P

10.15 10.59 9.61 3.59 7.85

3.14 3.23 3.30 2.61 2.67

*s* for R1CO and R2.

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TABLE 2.75 Special Hammett Sigma Constants Substituent —CH3 —C(CH3)3 —C6H5 —CF3 —F —Cl —Br —I —CN —CHO —CONH2 —COCH3 —COOH —CO—OCH3 —CO—OCH2CH3 —N2+ —NH2 —N(CH3)2 —N(CH3)3+ —NH—CO—CH3 —NO2 —OH —O− —OCH3 —SF5 —SCF3 —SO2CH3 —SO2CF3

s +m

s +p

−0.07 −0.06 0.11 0.52 0.35 0.40 0.41 0.36 0.56

−0.31 −0.26 −0.18 0.61 −0.07 0.11 0.15 0.14 0.66

0.32 0.37 0.37

0.42 0.49 0.48

0.16

−1.3 −1.7 0.41 −0.60 0.79 −0.92

0.36 0.67

0.05

−0.78

s −p −0.17

0.74 0.02 0.23 0.26 0.88 1.13 0.63 0.85 0.73 0.66 0.68 3.2 −0.66

1.25 −0.81 −0.27 0.70 0.57 1.05 1.36

2.20 POLYMERS Polymers are mixtures of macromolecules with similar structures and molecular weights that exhibit some average characteristic properties. In some polymers long segments of linear polymer chains are oriented in a regular manner with respect to one another. Such polymers have many of the physical characteristics of crystals and are said to be crystalline. Polymers that have polar functional groups show a considerable tendency to be crystalline. Orientation is aided by alignment of dipoles on different chains. Van der Waals’ interactions between long hydrocarbon chains may provide sufficient total attractive energy to account for a high degree of regularity within the polymers. Irregularities such as branch points, comonomer units, and cross-links lead to amorphous polymers. They do not have true melting points but instead have glass transition temperatures at which the rigid and glasslike material becomes a viscous liquid as the temperature is raised. Elastomers. Elastomers is a generic name for polymers that exhibit rubberlike elasticity. Elastomers are soft yet sufficiently elastic that they can be stretched several hundred percent under tension. When the stretching force is removed, they retract rapidly and recover their original dimensions. Polymers that soften or melt and then solidify and regain their original properties on cooling are called thermoplastic. A thermoplastic polymer is usually a single strand of linear polymer with few if any cross-links. Thermosetting Polymers. Polymers that soften or melt on warming and then become infusible solids are called thermosetting. The term implies that thermal decomposition has not taken place.

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SECTION TWO

Thermosetting plastics contain a cross-linked polymer network that extends through the finished article, making it stable to heat and insoluble in organic solvents. Many molded plastics are shaped while molten and are then heated further to become rigid solids of desired shapes. Synthetic Rubbers. Synthetic rubbers are polymers with rubberlike characteristics that are prepared from dienes or olefins. Rubbers with special properties can also be prepared from other polymers, such as polyacrylates, fluorinated hydrocarbons, and polyurethanes. Structural Differences. Polymers exhibit structural differences. A linear polymer consists of long segments of single strands that are oriented in a regular manner with respect to one another. Branched polymers have substituents attached to the repeating units that extend the polymer laterally. When these units participate in chain propagation and link together chains, a cross-linked polymer is formed. A ladder polymer results when repeating units have a tetravalent structure such that a polymer consists of two backbone chains regularly cross-linked at short intervals. Generally polymers involve bonding of the most substituted carbon of one monomeric unit to the least substituted carbon atom of the adjacent unit in a head-to-tail arrangement. Substituents appear on alternate carbon atoms. Tacticity refers to the configuration of substituents relative to the backbone axis. In an isotactic arrangement, substituents are on the same plane of the backbone axis; that is, the configuration at each chiral center is identical.

In a syndiotactic arrangement, the substituents are in an ordered alternating sequence, appearing alternately on one side and then on the other side of the chain, thus

In an atactic arrangement, substituents are in an unordered sequence along the polymer chains. Copolymerization. Copolymerization occurs when a mixture of two or more monomer types polymerizes so that each kind of monomer enters the polymer chain. The fundamental structure resulting from copolymerization depends on the nature of the monomers and the relative rates of monomer reactions with the growing polymer chain. A tendency toward alternation of monomer units is common.

Random copolymerization is rather unusual. Sometimes a monomer which does not easily form a homopolymer will readily add to a reactive group at the end of a growing polymer chain. In turn, that monomer tends to make the other monomer much more reactive. In graft copolymers the chain backbone is composed of one kind of monomer and the branches are made up of another kind of monomer.

The structure of a block copolymer consists of a homopolymer attached to chains of another homopolymer. [XXXX[YYY[XXXX[YYY[ Configurations around any double bond give rise to cis and trans stereoisomerism.

ORGANIC CHEMISTRY

2.711

2.20.1 Additives Antioxidants Antioxidants markedly retard the rate of autoxidation throughout the useful life of the polymer. Chain-terminating antioxidants have a reactive [NH or [OH functional group and include compounds such as secondary aryl amines or hindered phenols. They function by transfer of hydrogen to free radicals, principally to peroxy radicals. Butylated hydroxytoluene is a widely used example. Peroxide-decomposing antioxidants destroy hydroperoxides, the sources of free radicals in polymers. Phosphites and thioesters such as tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, and dialkyl thiodipropionates are examples of peroxide-decomposing antioxidants.

Antistatic Agents External antistatic agents are usually quaternary ammonium salts of fatty acids and ethoxylated glycerol esters of fatty acids that are applied to the plastic surface. Internal antistatic agents are compounded into plastics during processing. Carbon blacks provide a conductive path through the bulk of the plastic. Other types of internal agents must bloom to the surface after compounding in order to be active. These latter materials are ethoxylated fatty amines and ethoxylated glycerol esters of fatty acids, which often must be individually selected to match chemically each plastic type. Antistatic agents require ambient moisture to function. Consequently their effectiveness is dependent on the relative humidity. They provide a broad range of protection at 50% relative humidity. Much below 20% relative humidity, only materials which provide a conductive path through the bulk of the plastic to ground (such as carbon black) will reduce electrostatic charging.

Chain-Transfer Agents Chain-transfer agents are used to regulate the molecular weight of polymers. These agents react with the developing polymer and interrupt the growth of a particular chain. The products, however, are free radicals that are capable of adding to monomers and initiating the formation of new chains. The overall effect is to reduce the average molecular weight of the polymer without reducing the rate of polymerization. Branching may occur as a result of chain transfer between a growing but rather short chain with another and longer polymer chain. Branching may also occur if the radical end of a growing chain abstracts a hydrogen from a carbon atom four or five carbons removed from the end. Thiols are commonly used as chain-transfer agents.

Coupling Agents Coupling agents are molecular bridges between the interface of an inorganic surface (or filler) and an organic polymer matrix. Titanium-derived coupling agents interact with the free protons at the inorganic interface to form organic monomolecular layers on the inorganic surface. The titanatecoupling-agent molecule has six functions:

2.712

SECTION TWO

where Type

m

n

Monoalkoxy Coordinate Chelate

1 4 1

3 2 2

Function 1 is the attachment of the hydrolyzable portion of the molecule to the surface of the inorganic (or proton-bearing) species. Function 2 is the ability of the titanate molecule to transesterify. Function 3 affects performance as determined by the chemistry of alkylate, carboxyl, sulfonyl, phenolic, phosphate, pyrophosphate, and phosphite groups. Function 4 provides van der Waals’ entanglement via long carbon chains. Function 5 provides thermoset reactivity via functional groups such as methacrylates and amines. Function 6 permits the presence of two or three pendent organic groups. This allows all functionality to be controlled to the first-, second-, or third-degree levels. Silane coupling agents are represented by the formula Z[R[SiY3 where Y represents a hydrolyzable group (typically alkoxy); Z is a functional organic group, such as amino, methacryloxy, epoxy; and R typically is a small aliphatic linkage that serves to attach the functional organic group to silicon in a stable fashion. Bonding to surface hydroxy groups of inorganic compounds is accomplished by the [SiY3 portion, either by direct bonding of this group or more commonly via its hydrolysis product [Si(OH)3. Subsequent reaction of the functional organic group with the organic matrix completes the coupling reaction and establishes a covalent chemical bond from the organic phase through the silane coupling agent to the inorganic phase.

Flame Retardants Flame retardants are thought to function via several mechanisms, dependent upon the class of flame retardant used. Halogenated flame retardants are thought to function principally in the vapor phase either as a diluent and heat sink or as a free-radical trap that stops or slows flame propagation. Phosphorus compounds are thought to function in the solid phase by forming a glaze or coating over the substrate that prevents the heat and mass transfer necessary for sustained combustion. With some additives, as the temperature is increased, the flame retardant acts as a solvent for the polymer, causing it to melt at lower temperatures and flow away from the ignition source. Mineral hydrates, such as alumina trihydrate and magnesium sulfate heptahydrate, are used in highly filled thermoset resins.

Foaming Agents (Chemical Blowing Agents) Foaming agents are added to polymers during processing to form minute gas cells throughout the product. Physical foaming agents include liquids and gases. Compressed nitrogen is often used in injection molding. Common liquid foaming agents are short-chain aliphatic hydrocarbons in the C5 to C7 range and their chlorinated or fluorinated analogs. The chemical foaming agent used varies with the temperature employed during processing. At relatively low temperatures (15 to 200°C), the foaming agent is often 4,4′-oxybis-(benzenesulfonylhydrazide) or p-toluenesulfonylhydrazide. In the midrange (160 to 232°C), either sodium hydrogen carbonate or 1,1′ azobisformamide is used. For the high range (200 to 285°C), there are p-toluenesulfonyl semicarbazide, 5-phenyltetrazole and analogs, and trihydrazinotriazine.

ORGANIC CHEMISTRY

2.713

Inhibitors Inhibitors slow or stop polymerization by reacting with the initiator or the growing polymer chain. The free radical formed from an inhibitor must be sufficiently unreactive that it does not function as a chain-transfer agent and begin another growing chain. Benzoquinone is a typical free-radical chain inhibitor. The resonance-stabilized free radical usually dimerizes or disproportionates to produce inert products and end the chain process. Lubricants Materials such as fatty acids are added to reduce the surface tension and improve the handling qualities of plastic films. Plasticizers Plasticizers are relatively nonvolatile liquids which are blended with polymers to alter their properties by intrusion between polymer chains. Diisooctyl phthalate is a common plasticizer. A plasticizer must be compatible with the polymer to avoid bleeding out over long periods of time. Products containing plasticizers tend to be more flexible and workable. Ultraviolet Stabilizers 2-Hydroxybenzophenones represent the largest and most versatile class of ultraviolet stabilizers that are used to protect materials from the degradative effects of ultraviolet radiation. They function by absorbing ultraviolet radiation and by quenching electronically excited states. Hindered amines, such as 4-(2,2,6,6-tetramethylpiperidinyl) decanedioate, serve as radical scavengers and will protect thin films under conditions in which ultraviolet absorbers are ineffective. Metal salts of nickel, such as dibutyldithiocarbamate, are used in polyolefins to quench singlet oxygen or electronically excited states of other species in the polymer. Zinc salts function as peroxide decomposers. Vulcanization and Curing Originally, vulcanization implied heating natural rubber with sulfur, but the term is now also employed for curing polymers. When sulfur is employed, sulfide and disulfide cross-links form between polymer chains. This provides sufficient rigidity to prevent plastic flow. Plastic flow is a process in which coiled polymers slip past each other under an external deforming force; when the force is released, the polymer chains do not completely return to their original positions. Organic peroxides are used extensively for the curing of unsaturated polyester resins and the polymerization of monomers having vinyl unsaturation. The [O[O[ bond is split into free radicals which can initiate polymerization or cross-linking of various monomers or polymers. Plastics Homopolymer. Acetal homopolymers are prepared from formaldehyde and consist of highmolecular-weight linear polymers of formaldehyde.

2.714

SECTION TWO

The good mechanical properties of this homopolymer result from the ability of the oxymethylene chains to pack together into a highly ordered crystalline configuration as the polymers change from the molten to the solid state. Key properties include high melt point, strength and rigidity, good frictional properties, and resistance to fatigue. Higher molecular weight increases toughness but reduces melt flow. Copolymer. Acetal copolymers are prepared by copolymerization of 1,3,5-trioxane with small amounts of a comonomer. Carbon-carbon bonds are distributed randomly in the polymer chain. These carbon-carbon bonds help to stabilize the polymer against thermal, oxidative, and acidic attack.

Acrylics Poly(methyl Methacrylate). The monomer used for poly(methyl methacrylate), 2-hydroxy-2methylpropanenitrile, is prepared by the following reaction:

2-Hydroxy-2-methylpropanenitrile is then reacted with methanol (or other alcohol) to yield methacrylate ester. Free-radical polymerization is initiated by peroxide or azo catalysts and produce poly(methyl methacrylate) resins having the following formula:

Key properties are improved resistance to heat, light, and weathering. This polymer is unaffected by most detergents, cleaning agents, and solutions of inorganic acids, alkalies, and aliphatic hydrocarbons. Poly(methyl methacrylate) has light transmittance of 92% with a haze of 1 to 3% and its clarity is equal to glass. Poly(methyl Acrylate). The monomer used for preparing poly(methyl acrylate) is produced by the oxidation of propylene. The resin is made by free-radical polymerization initiated by peroxide or azo catalysts and has the following formula:

Resins vary from soft, elastic, film-forming materials to hard plastics. Poly(acrylic Acid) and Poly(methacrylic Acid). Glacial acrylic acid and glacial methacrylic acid can be polymerized to produce water-soluble polymers having the following structures:

ORGANIC CHEMISTRY

2.715

These monomers provide a means for introducing carboxyl groups into copolymers. In copolymers these acids can improve adhesion properties, improve freeze-thaw and mechanical stability of polymer dispersions, provide stability in alkalies (including ammonia), increase resistance to attack by oils, and provide reactive centers for cross-linking by divalent metal ions, diamines, or epoxides. Functional Group Methacrylate Monomers. Hydroxyethyl methacrylate and dimethylaminoethyl methacrylate produce polymers having the following formulas:

The use of hydroxyethyl (also hydroxypropyl) methacrylate as a monomer permits the introduction of reactive hydroxyl groups into the copolymers. This offers the possibility for subsequent crosslinking with an HO-reactive difunctional agent (diisocyanate, diepoxide, or melamine-formaldehyde resin). Hydroxyl groups promote adhesion to polar substrates. Use of dimethylaminoethyl (also tert-butylaminoethyl) methacrylate as a monomer permits the introduction of pendent amino groups which can serve as sites for secondary cross-linking, provide a way to make the copolymer acid-soluble, and provide anchoring sites for dyes and pigments. Poly(acrylonitrile).

Poly(acrylonitrile) polymers have the following formula:

Alkyds Alkyds are formulated from polyester resins, cross-linking monomers, and fillers of mineral or glass. The unsaturated polyester resins used for thermosetting alkyds are the reaction products of polyfunctional organic alcohols (glycols) and dibasic organic acids. Key properties of alkyds are dimensional stability, colorability, and arc track resistance. Chemical resistance is generally poor. Alloys Polymer alloys are physical mixtures of structurally different homopolymers or copolymers. The mixture is held together by secondary intermolecular forces such as dipole interaction, hydrogen bonding, or van der Waals’ forces. Homogeneous alloys have a single glass transition temperature which is determined by the ratio of the components. The physical properties of these alloys are averages based on the composition of the alloy. Heterogeneous alloys can be formed when graft or block copolymers are combined with a compatible polymer. Alloys of incompatible polymers can be formed if an interfacial agent can be found. Allyls Diallyl Phthalate (and Diallyl 1,3-Phthalate). These allyl polymers are prepared from

2.716

SECTION TWO

These resulting polymers are solid, linear, internally cyclized, thermoplastic structures containing unreacted allylic groups spaced at regular intervals along the polymer chain. Molding compounds with mineral, glass, or synthetic fiber filling exhibit good electrical properties under high humidity and high temperature conditions, stable low-loss factors, high surface and volume resistivity, and high arc and track resistance. Cellulosics 10.3.6.1 Cellulose Triacetate. Cellulose triacetate is prepared according to the following reaction:

Because cellulose triacetate has a high softening temperature, it must be processed in solution. A mixture of dichloromethane and methanol is a common solvent. Cellulose triacetate sheeting and film have good gauge uniformity and good optical clarity. Cellulose triacetate products have good dimensional stability and resistance to water and have good folding endurance and burst strength. It is highly resistant to solvents such as acetone. Cellulose triacetate products have good heat resistance and a high dielectric constant. Cellulose Acetate, Propionate, and Butyrate. Cellulose acetate is prepared by hydrolyzing the triester to remove some of the acetyl groups; the plastic-grade resin contains 38 to 40% acetyl. The propionate and butyrate esters are made by substituting propionic acid and its anhydride (or butyric acid and its anhydride) for some of the acetic acid and acetic anhydride. Plastic grades of celluloseacetate-propionate resin contain 39 to 47% propionyl and 2 to 9% acetyl; cellulose-acetate-butyrate resins contain 26 to 39% butyryl and 12 to 15% acetyl. These cellulose esters form tough, strong, stiff, hard plastics with almost unlimited color possibilities. Articles made from these plastics have a high gloss and are suitable for use in contact with food. Cellulose Nitrate. Cellulose nitrate is prepared according to the following reaction:

The nitrogen content for plastics is usually about 11%, for lacquers and cement base it is 12%, and for explosives it is 13%. The standard plasticizer added is camphor. Key properties of cellulose nitrate are good dimensional stability, low water absorption, and toughness. Its disadvantages are its flammability and lack of stability to heat and sunlight. Ethyl Cellulose. Ethyl cellulose is prepared by reacting cellulose with caustic to form caustic cellulose, which is then reacted with chloroethane to form ethyl cellulose. Plastic-grade material contains 44 to 48% ethoxyl. Although not as resistant as cellulose esters to acids, it is much more resistant to bases. An outstanding feature is its toughness at low temperatures. Rayon. Viscose rayon is obtained by reacting the hydroxy groups of cellulose with carbon disulfide in the presence of alkali to give xanthates. When this solution is poured (spun) into an acid medium, the reaction is reserved and the cellulose is regenerated (coagulated).

ORGANIC CHEMISTRY

2.717

Epoxy Epoxy resin is prepared by the following condensation reaction:

The condensation leaves epoxy end groups that are then reacted in a separate step with nucleophilic compounds (alcohols, acids, or amines). For use as an adhesive, the epoxy resin and the curing resin (usually an aliphatic polyamine) are packaged separately and mixed together immediately before use. Epoxy novolac resins are produced by glycidation of the low-molecular-weight reaction products of phenol (or cresol) with formaldehyde. Highly cross-linked systems are formed that have superior performance at elevated temperatures. Fluorocarbon 10.3.8.1 Poly(tetrafluoroethylene). Poly(tetrafluoroethylene) is prepared from tetrafluoroethylene and consists of repeating units in a predominantly linear chain:

Tetrafluoroethylene polymer has the lowest coefficient of friction of any solid. It has remarkable chemical resistance and a very low brittleness temperature (−100°C). Its dielectric constant and loss factor are low and stable across a broad temperature and frequency range. Its impact strength is high. Fluorinated Ethylene-Propylene Resin. Polymer molecules of fluorinated ethylene-propylene consist of predominantly linear chains with this structure:

Key properties are its flexibility, translucency, and resistance to all known chemicals except molten alkali metals, elemental fluorine and fluorine precursors at elevated temperatures, and concentrated perchloric acid. It withstands temperatures from −270° to 250°C and may be sterilized repeatedly by all known chemical and thermal methods. Perfluoroalkoxy Resin. Perfluoroalkoxy resin has the following formula:

It resembles polytetrafluoroethylene and fluorinated ethylene propylene in its chemical resistance, electrical properties, and coefficient of friction. Its strength, hardness, and wear resistance are about equal to the former plastic and superior to that of the latter at temperatures above 150°C.

2.718

SECTION TWO

Poly(vinylidene Fluoride). Poly(vinylidene fluoride) consists of linear chains in which the predominant repeating unit is

It has good weathering resistance and does not support combustion. It is resistant to most chemicals and solvents and has greater strength, wear resistance, and creep resistance than the preceding three fluorocarbon resins. Poly(1-Chloro-1,2,2-Trifluoroethylene). Poly(1-chloro-1,2,2-trifluoroethylene consists of linear chains in which the predominant repeating unit is

It possesses outstanding barrier properties to gases, especially water vapor. It is surpassed only by the fully fluorinated polymers in chemical resistance. A few solvents dissolve it at temperatures above 100°C, and it is swollen by a number of solvents, especially chlorinated solvents. It is harder and stronger than perfluorinated polymers, and its impact strength is lower. Ethylene-Chlorotrifluoroethylene Copolymer. Ethylene-chlorotrifluoroethylene copolymer consists of linear chains in which the predominant 1:1 alternating copolymer is

This copolymer has useful properties from cryogenic temperatures to 180°C. Its dielectric constant is low and stable over a broad temperature and frequency range . Ethylene-Tetrafluoroethylene Copolymer. linear chains in which the repeating unit is

Ethylene-tetrafluoroethylene copolymer consists of

[[CH2[CH2[CF2[CF2[]n Its properties resemble those of ethylene-chlorotrifluoroethylene copolymer. Poly(vinyl Fluoride).

Poly(vinyl fluoride) consists of linear chains in which the repeating unit is [[CH2[CHF[]n

It is used only as a film, and it has good resistance to abrasion and resists staining. It also has outstanding weathering resistance and maintains useful properties from −100 to 150°C.

Nitrile Resins The principal monomer of nitrile resins is acrylonitrile (see “Polyacrylonitrile”), which constitutes about 70% by weight of the polymer and provides the polymer with good gas barrier and chemical resistance properties. The remainder of the polymer is 20 to 30% methylacrylate (or styrene), with 0 to 10% butadiene to serve as an impact-modifying termonomer.

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Melamine Formaldehyde The monomer used for preparing melamine formaldehyde is formed as follows:

Hexamethylolmelamine can further condense in the presence of an acid catalyst; ether linkages can also form (see “Urea Formaldehyde”). A wide variety of resins can be obtained by careful selection of pH, reaction temperature, reactant ratio, amino monomer, and extent of condensation. Liquid coating resins are prepared by reacting methanol or butanol with the initial methylolated products. These can be used to produce hard, solvent-resistant coatings by heating with a variety of hydroxy, carboxyl, and amide functional polymers to produce a cross-linked film. Phenolics Phenol-Formaldehyde Resin. Phenol-formaldehyde resin is prepared as follows: C6H5OH + H2C˙O → [[C6H2(OH)CH2[]n One-Stage Resins. The ratio of formaldehyde to phenol is high enough to allow the thermosetting process to take place without the addition of other sources of cross-links. Two-Stage Resins. The ratio of formaldehyde to phenol is low enough to prevent the thermosetting reaction from occurring during manufacture of the resin. At this point the resin is termed novolac resin. Subsequently, hexamethylenetetramine is incorporated into the material to act as a source of chemical cross-links during the molding operation (and conversion to the thermoset or cured state). Polyamides Nylon 6, 11, and 12. This class of polymers is polymerized by addition reactions of ring compounds that contain both acid and amine groups on the monomer.

Nylon 6 is polymerized from 2-oxohexamethyleneimine (6 carbons); nylon 11 and 12 are made this way from 11- and 12-carbon rings, respectively. 10.3.12.2 Nylon 6/6, 6/9, and 6/12. As illustrated below, nylon 6/6 is polymerized from 1,6hexanedioic acid (six carbons) and 1,6-hexanediamine (six carbons).

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SECTION TWO

Other nylons are made this way from direct combinations of monomers to produce types 6/9, 6/10, and 6/12. Nylon 6 and 6/6 possess the maximum stiffness, strength, and heat resistance of all the types of nylon. Type 6/6 has a higher melt temperature, whereas type 6 has a higher impact resistance and better processibility. At a sacrifice in stiffness and heat resistance, the higher analogs of nylon are useful primarily for improved chemical resistance in certain environments (acids, bases, and zinc chloride solutions) and for lower moisture absorption. Aromatic nylons, [[NH[C6H4[CO[]n (also called aramids), have specialty uses because of their improved clarity.

Poly(amide-imide) Poly(amide-imide) is the condensation polymer of 1,2,4-benzenetricarboxylic anhydride and various aromatic diamines and has the general structure:

It is characterized by high strength and good impact resistance, and retains its physical properties at temperatures up to 260°C. Its radiation (gamma) resistance is good.

Polycarbonate Polycarbonate is a polyester in which dihydric (or polyhydric) phenols are joined through carbonate linkages. The general-purpose type of polycarbonate is based on 2,2-bis(4′-hydroxybenzene)propane (bisphenol A) and has the general structure:

Polycarbonates are the toughest of all thermoplastics. They are window-clear, amazingly strong and rigid, autoclavable, and nontoxic. They have a brittleness temperature of −135°C. Polyester Poly(butylene Terephthalate). Poly(butylene terephthalate) is prepared in a condensation reaction between dimethyl terephthalate and 1,4-butanediol and its repeating unit has the general structure

This thermoplastic shows good tensile strength, toughness, low water absorption, and good frictional properties, plus good chemical resistance and electrical properties.

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Poly(ethylene Terephthalate). Poly(ethylene terephthalate) is prepared by the reaction of either terephthalic acid or dimethyl terephthalate with ethylene glycol, and its repeating unit has the general structure.

The resin has the ability to be oriented by a drawing process and crystallized to yield a highstrength product. Unsaturated Polyesters. Unsaturated polyesters are produced by reaction between two types of dibasic acids, one of which is unsaturated, and an alcohol to produce an ester. Double bonds in the body of the unsaturated dibasic acid are obtained by using maleic anhydride or fumaric acid. PCTA Copolyester. Poly(1,4-cyclohexanedimethylene terephthalic acid) (PCTA) copolyester is a polymer of cyclohexanedimethanol and terephthalic acid, with another acid substituted for a portion of the terephthalic acid otherwise required. It has the following formula:

Polyimides. Polyimides have the following formula:

They are used as high-temperature structural adhesives since they become rubbery rather than melt at about 300°C.

Poly(methylpentene) Poly(methylpentene) is obtained by a Ziegler-type catalytic polymerization of 4-methyl-1-pentene. Its key properties are its excellent transparency, rigidity, and chemical resistance, plus its resistance to impact and to high temperatures. It withstands repeated autoclaving, even at 150°C.

Polyolefins 10.3.17.1 Polyethylene. Polymerization of ethylene results in an essentially straight-chain highmolecular-weight hydrocarbon. CH2˙CH2 → [[CH2[CH2[]n Branching occurs to some extent and can be controlled. Minimum branching results in a “highdensity” polyethylene because of its closely packed molecular chains. More branching gives a less compact solid known as “low-density” polyethylene.

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SECTION TWO

A key property is its chemical inertness. Strong oxidizing agents eventually cause some oxidation, and some solvents cause softening or swelling, but there is no known solvent for polyethylene at room temperature. The brittleness temperature is −100°C for both types. Polyethylene has good low-temperature toughness, low water absorption, and good flexibility at subzero temperatures. Polypropylene. The polymerization of propylene results in a polymer with the following structure:

The desired form in homopolymers is the isotactic arrangement (at least 93% is required to give the desired properties). Copolymers have a random arrangement. In block copolymers a secondary reactor is used where active polymer chains can further polymerize to produce segments that use ethylene monomer. Polypropylene is translucent and autoclavable and has no known solvent at room temperature. It is slightly more susceptible to strong oxidizing agents than polyethylene. Polybutylene. Polybutylene is composed of linear chains having an isotactic arrangement of ethyl side groups along the chain backbone.

It has a helical conformation in the stable crystalline form. Polybutylene exhibits high tear, impact, and puncture resistance. It also has low creep, excellent chemical resistance, and abrasion resistance with coilability. Ionomer. Ionomer is the generic name for polymers based on sodium or zinc salts of ethylenemethacrylic acid copolymers in which interchain ionic bonding, occurring randomly between the long-chain polymer molecules, produces solid-state properties. The abrasion resistance of ionomers is outstanding, and ionomer films exhibit optical clarity. In composite structures ionomers serve as a heat-seal layer.

Poly(phenylene Sulfide) Poly(phenylene sulfide) has the following formula:

The recurring para-substituted benzene rings and sulfur atoms form a symmetrical rigid backbone. The high degree of crystallization and the thermal stability of the bond between the benzene ring and sulfur are the two properties responsible for the polymer’s high melting point, thermal stability, inherent flame retardance, and good chemical resistance. There are no known solvents of poly (phenylene sulfide) that can function below 205°C.

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Polyurethane 10.3.19.1 Foams. Polyurethane foams are prepared by the polymerization of polyols with isocyanates.

Commonly used isocyanates are toluene diisocyanate, methylene diphenyl isocyanate, and polymeric isocyanates. Polyols used are macroglycols based on either polyester or polyether. The former [poly(ethylene phthalate) or poly(ethylene 1,6-hexanedioate)] have hydroxyl groups that are free to react with the isocyanate. Most flexible foam is made form 80/20 toluene diisocyanate (which refers to the ratio of 2,4-toluene diisocyanate to 2,6-toluene diisocyanate). High-resilience foam contains about 80% 80/20 toluene diisocyanate and 20% poly(methylene diphenyl isocyanate), while semiflexible foam is almost always 100% poly(methylene diphenyl isocyanate). Much of the latter reacts by trimerization to form isocyanurate rings. Flexible foams are used in mattresses, cushions, and safety applications. Rigid and semiflexible foams are used in structural applications and to encapsulate sensitive components to protect them against shock, vibration, and moisture. Foam coatings are tough, hard, flexible, and chemically resistant. Elastomeric Fiber. with diisocyanates.

Elastomeric fibers are prepared by the polymerization of polymeric polyols

The structure of elastomeric fibers is similar to that illustrated for polyurethane foams.

Silicones Silicones are formed in the following multistage reaction :

The silanols formed above are unstable and under dehydration. On polycondensation, they give polysiloxanes (or silicones) which are characterized by their three-dimensional branched-chain structure. Various organic groups introduced within the polysiloxane chain impart certain characteristics and properties to these resins. Methyl groups impart water repellency, surface hardness, and noncombustibility. Phenyl groups impart resistance to temperature variations, flexibility under heat, resistance to abrasion, and compatibility with organic products.

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SECTION TWO

Vinyl groups strengthen the rigidity of the molecular structure by creating easier cross-linkage of molecules. Methoxy and alkoxy groups facilitate cross-linking at low temperatures. Oils and gums are nonhighly branched- or straight-chain polymers whose viscosity increases with the degree of polycondensation. Styrenics Polystyrene Polystyrene has the following formula:

Polystyrene is rigid with excellent dimensional stability, has good chemical resistance to aqueous solutions, and is an extremely clear material. Impact polystyrene contains polybutadiene added to reduce brittleness. The polybutadiene is usually dispersed as a discrete phase in a continuous polystyrene matrix. Polystyrene can be grafted onto rubber particles, which assures good adhesion between the phases. Acrylonitrile-Butadiene-Styrene (ABS) Copolymers. This basic three-monomer system can be tailored to yield resins with a variety of properties. Acrylonitrile contributes heat resistance, high strength, and chemical resistance. Butadiene contributes impact strength, toughness, and retention of low-temperature properties. Styrene contributes gloss, processibility, and rigidity. ABS polymers are composed of discrete polybutadiene particles grafted with the styrene-acrylonitrile copolymer; these are dispersed in the continuous matrix of the copolymer. Styrene-Acrylonitrile (SAN) Copolymers. SAN resins are random, amorphous copolymers whose properties vary with molecular weight and copolymer composition. An increase in molecular weight or in acrylonitrile content generally enhances the physical properties of the copolymer but at some loss in case of processing and with a slight increase in polymer color. SAN resins are rigid, hard, transparent thermoplastics which process easily and have good dimensional stability—a combination of properties unique in transparent polymers. Sulfones Below are the formulas for three polysulfones.

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The isopropylidene linkage imparts chemical resistance, the ether linkage imparts temperature resistance, and the sulfone linkage imparts impact strength. The brittleness temperature of polysulfones is −100°C. Polysulfones are clear, strong, nontoxic, and virtually unbreakable. They do not hydrolyze during autoclaving and are resistant to acids, bases, aqueous solutions, aliphatic hydrocarbons, and alcohols.

Thermoplastic Elastomers Polyolefins. In these thermoplastic elastomers the hard component is a crystalline polyolefin, such as polyethylene or polypropylene, and the soft portion is composed of ethylene-propylene rubber. Attractive forces between the rubber and resin phases serve as labile cross-links. Some contain a chemically cross-linked rubber phase that imparts a higher degree of elasticity. Styrene-Butadiene-Styrene Block Copolymers. Styrene blocks associate into domains that form hard regions. The midblock, which is normally butadiene, ethylene-butene, or isoprene blocks, forms the soft domains. Polystyrene domains serve as cross-links. Polyurethanes. The hard portion of polyurethane consists of a chain extender and polyisocyanate. The soft component is composed of polyol segments. Polyesters. The hard portion consists of copolyester, and the soft portion is composed of polyol segments.

Vinyl Poly(vinyl Chloride) (PVC). Polymerization of vinyl chloride results in the formation of a polymer with the following formula:

When blended with phthalate ester plasticizers, PVC becomes soft and pliable. Its key properties are good resistance to oils and a very low permeability to most gases. Poly(vinyl Acetate) Poly(vinyl acetate) has the following formula:

Poly(vinyl acetate) is used in latex water paints because of its weathering, quick-drying, recoatability, and self-priming properties. It is also used in hot-melt and solution adhesives. Poly(vinyl Alcohol) Poly(vinyl alcohol) has the following formula:

It is used in adhesives, paper coating and sizing, and textile warp size and finishing applications. Poly(vinyl Butyral) Poly(vinyl butyral) is prepared according to the following reaction:

2.726

SECTION TWO

Its key characteristics are its excellent optical and adhesive properties. It is used as the interlayer film for safety glass. Poly(vinylidene Chloride) reaction:

Poly(vinylidene chloride) is prepared according to the following

CH2˙CCl2 + CH2˙CHCl → [[CH2[CCl2[CH2[CHCl[]n Random copolymer Urea Formaldehyde The reaction of urea with formaldehyde yields the following products, which are used as monomers in the preparation of urea formaldehyde resin. H2N[CO[NH2 + H2CO → H2N[CO[NH[CH2OH + HOCH2[NH[CO[NH[CH2OH The reaction conditions can be varied so that only one of those monomers is formed. 1-Hydroxymethylurea and 1,3-bis(hydroxymethyl)urea condense in the presence of an acid catalyst to produce urea formaldehyde resins. A wide variety of resins can be obtained by careful selection of the pH, reaction temperature, reactant ratio, amino monomer, and degree of polymerization. If the reaction is carried far enough, an infusible polymer network is produced. Liquid coating resins are prepared by reacting methanol or butanol with the initial hydroxymethylureas. Ether exchange reactions between the amino resin and the reactive sites on the polymer produce a cross-linked film.

2.20.3 Rubber Gutta Percha Gutta percha is a natural polymer of isoprene (3-methyl-1,3-butadiene) in which the configuration around each double bond is trans. It is hard and horny and has the following formula:

Natural Rubber Natural rubber is a polymer of isoprene in which the configuration around each double bond is cis (or Z ):

Its principal advantages are high resilience and good abrasion resistance.

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2.727

Chlorosulfonated Polyethylene Chlorosulfonated polyethylene is prepared as follows:

Cross-linking, which can occur as a result of side reactions, causes an appreciable gel content in the final product. The polymer can be vulcanized to give a rubber with very good chemical (solvent) resistance, excellent resistance to aging and weathering, and good color retention in sunlight.

Epichlorohydrin Epichlorohydrin is a product of covulcanization of epichlorohydrin (epoxy) polymers with rubbers, especially cis-polybutadiene. Its advantages include impermeability to air, excellent adhesion to metal, and good resistance to oils, weathering, and low temperature.

Nitrile Rubber (NBR, GRN, Buna N) Nitrile rubber can be prepared as follows:

Nitrile rubber is also known as nitrile-butadiene rubber (NBR), government rubber nitrile (GRN), and Buna N. It possesses resistance to oils up to 120°C and excellent abrasion resistance and adhesion to metal.

Polyacrylate Polyacrylate has the following formula:

It possesses oil and heat resistance to 175°C and excellent resistance to ozone. cis-Polybutadiene Rubber (BR) cis-Polybutadiene is prepared by polymerization of butadiene by mostly, 1,4-addition. CH2˙CH[CH˙CH2 → [[CH2[CH˙CH[CH2[]n The polybutadiene produced is in the Z (or cis) configuration.

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SECTION TWO

cis-Polybutadiene has good abrasion resistance, is useful at low temperature, and has excellent adhesion to metal. Polychloroprene (Neoprene) Polychloroprene is prepared as follows:

It has very good weathering characteristics, is resistant to ozne and to oil, and is heat-resistant to 100°C. Ethylene-Propylene-Diene Rubber (EPDM) Ethylene-propylene-diene rubber is polymerized from 60 parts ethylene, 40 parts propylene, and a small amount of nonconjugated diene. The nonconjugated diene permits sulfur vulcanization of the polymer instead of using peroxide. It is a very lightweight rubber and has very good weathering and electrical properties, excellent adhesion, and excellent ozone resistance. Polyisobutylene (Butyl Rubber) Polyisobutylene is prepared as follows:

It possesses excellent ozone resistance, very good weathering and electrical properties, and good heat resistance. (Z)-Polyisoprene (Synthetic Natural Rubber) Polymerization of isoprene by 1,4-addition produces polyisoprene that has a cis (or Z) configuration.

Polysulfide Rubbers Polysulfide rubbers are prepared as follows: Cl[R[Cl + Na[S[S[S[S[Na → HS[[R[S[S[S[S[]nR[SH

ORGANIC CHEMISTRY

2.729

where R can be [CH2CH2[,[CH2CH2[O[CH2CH2[, or [CH2CH2[O[CH2[O[CH2CH2[. Polysulfide rubbers posses excellent resistance to weathering and oils and have very good electrical properties. Poly(vinyl Chloride) (PVC) Poly(vinyl chloride) has the following structures:

PVC polymer plus special plasticizers are used to produce flexible tubing which has good chemical resistance. Silicone Rubbers Silicone rubbers are prepared as follows:

Other groups may replace the methyl groups. Silicone rubbers have excellent ozone and weathering resistance, good electrical properties, and good adhesion to metal. Styrene-Butadiene Rubber (GRS, SBR, Buna S) Styrene-butadiene rubber is prepared from the free-radical copolymerization of one part by weight of styrene and three parts by weight of 1,3-butadiene. The butadiene is incorporated by both 1,4-addition (80%) and 1,2-addition (20%). The configuration around the double bond of the 1,4-adduct is about 80% trans. The product is a random copolymer with these general features:

Styrene-butadiene rubber (SBR) is also known as government rubber styrene (GRS) and Buna S. Urethane See Table 2.79

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SECTION TWO

TABLE 2.76 Names and Structures of Polymers Common name

Acronym, alternate name

Amylose

Class

Structure of repeat unit

Polysaccharide CH2OH O HO

Cellulose

Cellulose acetate

Rayon Cellophane Regenerated cellulose

Polysaccharide

CA

Cellulose ester

OH

HO

CH2OH O

O HO

n

OH

OH

CH2OH O

O HO

CH2 O

n

OR

CH2OR O

O RO

CH 2 O

O

OH

OH

RO

O

O n

OR

OR O R= Cellulose nitrate

CN

Cellulose ester

C

RO

CH3

OR

CH2OR O

O RO

CH2 O

n

OR

OR R= Hydroxypropylcellulose

HPC

Cellulose ester

NO2

RO

OR

CH2OR O

O RO

CH2 O

R=

(CH2)3

O n

OR

OR

Ladder polymer

O

OH

Double-strand polymer n

Phenol-formaldehyde

Bakelite

Phenolic polymer

OH CH2

n

2.731

ORGANIC CHEMISTRY

TABLE 2.76 Names and Structures of Polymers (Continued) Common name

Acronym, alternate name

Polyacetal

Class

Structure of repeat unit

Polyacetal

H C

O n

R Polyacetylene

Polyalkyne

Polyacrylamide

Vinyl polymer

CH

CH

CH

CH2

n

n

C NH2 O

Poly(acrylic acid)

CH

Vinyl polymer

CH2 n

C O H O

Polyacrylonitrile

PAN

Poly(L-alanine)

Vinyl polymer

CH

CH2 n

CN O

Polypeptide NH

CH

C

n

CH3 Polyamide

Nylon

O

Polyamide NH

Polyaniline

R NH

Polyamine

O

C R′ C

n

NH n

Polybenzimidazole

Polybenzobisoxazole

Polybenzobisthiazole

PBI

PBO

PBT

Polyheteroaromatic

Polyheteroaromatic

Polyheteroaromatic

N

N

N H

N H

N

N

O

O

N

N

S

S

n

n

n

(Continued)

2.732

SECTION TWO

TABLE 2.76 Names and Structures of Polymers (Continued) Common name Poly(g-benzyl-Lglutamate)

Acronym, alternate name PBLG

Class

Structure of repeat unit O

Polypeptide NH

CH

C

n

(CH2)2 O

1,2-Polybutadiene

cis-1,4-Polybutadiene

PBD

PBD

Diene polymer

C

CH2

O

CH

CH2

CH

CH2

n

Diene polymer n

H trans-1,4-Polybutadiene

PBD

H

Diene polymer

H H

Poly(butene-1)

PB-1

Poly(a-olefin)

n

CH CH2 n

CH2CH3 Polybutyleneterephthalate

PBT

Polyester (CH2)4 O

O

O

C

C n

Poly(⑀-caprolactam)

Nylon-6

Polyamide

O NH

Poly(⑀-caprolactone)

Polyester

PC

(CH2)5

n

(CH2)5

n

O NH

Polycarbonate

C

C

Polyester O

CH3

O

C

C n

CH3 cis, trans1,4-Polychloroprene

Neoprene

Diene polymer H

n

Cl

Cl

H

n

cis Polychlorotrifluoro ethylene

PCTFE

Vinyl polymer

trans Cl F C

C

F

F

n

2.733

ORGANIC CHEMISTRY

TABLE 2.76 Names and Structures of Polymers (Continued) Common name

Acronym, alternate name

Polydiethylsiloxane

PDES

Class

Structure of repeat unit CH2CH3

Polysiloxane

Si

O n

CH2CH3 Polydimethylsiloxane

PDMS

CH3

Polysiloxane

Si

O n

CH3 Polydiphenylsiloxane

PDPS

Polysiloxane

Si

O n

Polyester

O

Polyester O

Polyetheretherketone

PEEK

R O

O

C

Polyketone

R′

C

n

O O

C n

Polyethylene

PE

Poly(ethylene imine)

Polyolefin

CH2

Polyamine

Poly(ethylene oxide) [Poly(ethylene glycol)]

PEO (PEG)

Polyether

Polyethyleneterephthalate

PET

Polyester

CH2

CH2

CH2

CH2

(CH2)2 O

n

NH

CH2

n

O

n

O

O

C

C n

Polyglycine

O

Polypeptide NH

Poly(hexamethylene adipamide)

Nylon-66

C

n

Polyamide O

O NH

Polyhydroxybutyrate

CH2

PHB

(CH2)6

Polyester

NH

C

CH3 O

CH

(CH2)4

C

n

O CH2

C

n

(Continued)

2.734

SECTION TWO

TABLE 2.76 Names and Structures of Polymers (Continued) Common name

Acronym, alternate name

Polyimide

PI

Class

Structure of repeat unit

Polyimide

O

O C

C

C

C

N

N

Poly(imino-1,3-phenylene iminoisophthaloyl) (Nomex)

n

O

O Polyaramide HN

O

O

NH C

C n

Poly(imino-1,4-phenylene iminoterephthaloyl) (Kevlar)

Polyisobutylene

Polyaramide HN

NH

O

O

C

C n

Butyl rubber

CH3

Vinylidene polymer

C

CH2 n

CH3 Polyisocyanate

PIC

O

Polyamide N

C n

R Polyisocyanide

N

Polyisocyanide

R

C n

cis-1,4-Polyisoprene

tran-1,4-Polyisoprene

Polylactam

cis-PIP, Natural rubber

Diene polymer

trans-PIP, Gutta percha

Diene polymer

CH3 H

n

H

CH3 O

Polyamide NH

Polylactone

n

Polyester

(CH2)m

C

n

O O

C

(CH2)m n

Poly(p-methyl styrene)

Vinyl polymer

CH

CH2 n

CH3

ORGANIC CHEMISTRY

2.735

TABLE 2.76 Names and Structures of Polymers (Continued) Common name Poly(methyl acrylate)

Acronym, alternate name PMA

Class Vinyl polymer

Structure of repeat unit CH

CH2

C O

n

CH3

O Poly(methyl methacrylate)

PMMA

Vinylidene polymer

CH3 C

CH2

C O

n

CH3

O CH3 Poly(a-methyl styrene)

Poly(methylene oxide)

Polymethylphenylsiloxane

PMO

PMPS

Vinylidene polymer

C

Polyether

CH2 O

Polysiloxane

CH2 n

n

CH3 Si

O n

Polynitrile

Polyimine

C N

n

R Polynucleotide

base

Polynucleotide phosphate

Poly(n-pentene-2)

Poly(a-olefin)

Poly(n-pentene-1)

Poly(a-olefin)

Polypeptides [Poly(a-amino acid)]

Polypeptide

sugar

CH

CH

CH3

CH2CH3

n

n

CH CH2

n

CH2CH2CH3 O NH

CH C n

R Poly(p-phenylene oxide)

PPO

Polyether O n

(Continued)

2.736

SECTION TWO

TABLE 2.76 Names and Structures of Polymers (Continued) Common name

Acronym, alternate name

Poly(p-phenylene sulfide)

PPS

Class

Structure of repeat unit

Polysulfide S n

Poly(p-phenylene vinylene)

Polyaromatic CH2

CH2 n

Poly(p-phenylene)

PP

Polyaromatic n

Polyphosphate

O

Inorganic polymer

P

O

R O n

OR′ Polyphosphazene

R

Inorganic polymer

P

N n

R′ Polyphosphonate

O

Inorganic polymer

P

O

R O n

R′ Polypropylene

PP

Poly(a-olefin)

CH

CH2 n

CH3 Poly(propylene oxide)

PPO

C

Polyether

CH2 O n

CH3 Poly(pyromellitimide-1,4diphenyl ether) (Kapton)

Polyimide

C

C

C

C

N

N O

Polypyrrole

O

O

O n

O

Polyheterocyclic N

Polysilane

Inorganic polymer

n

R Si R′

n

2.737

ORGANIC CHEMISTRY

TABLE 2.76 Names and Structures of Polymers (Continued) Common name

Acronym, alternate name

Polyailazane

Polysiloxane

Class

Structure of repeat unit R

Inorganic polymer

Silicones

Si

N

R′

R′′

n

R

Inorganic polymer

Si

O n

R′ Polystyrene

PS Styrofoam

CH CH2

Vinyl polymer

n

Polysulfide

Thiokol

Polysulfide R

Polysulfur

Polytetrafluoroethylene (Teflon)

Poly(tetramethylene oxide)

Polysulfur

PTFE

PTMO

Polythiophene

S

Poly(a-olefin)

Polyether

F

C

C

F

F

R NH

Polyurethane O

R O

n

n

S

NH

Poly(L-valine)

n

CH2 CH2 CH2 CH2 O

Polyurea

Adiprene

n

8n

F

Polyheterocyclic

Polyurea

Polyurethane

Sm

O

O

C NH R′ NH

C

O

O

C NH R′ NH

C

n

n

O

Polypeptide NH

CH C

n

CH(CH3)2 Poly(vinyl acetate)

PVAc

Vinyl polymer

CH O

CH2 C

CH3

n

O (Continued)

2.738

SECTION TWO

TABLE 2.76 Names and Structures of Polymers (Continued) Common name

Acronym, alternate name

Poly(vinyl alcohol)

PVA

Class Vinyl polymer

Structure of repeat unit CH

CH2

n

OH Poly(vinyl chloride)

Poly(vinyl fluoride)

Poly(2-vinyl pyridine)

PVC

PVF

PVP

Vinyl polymer

CH

Vinyl polymer

CH

Vinyl polymer

CH

CH2 n

Cl CH2

n

F CH2

n

N

Poly(N-vinyl pyrrolidone)

Poly(vinylidene chloride)

Vinyl polymer

PVDC Saran

Vinylidene polymer

CH

CH2

N

O

Cl C

CH2 n

Cl Poly(vinylidiene fluoride)

PVDF

Vinylidiene polymer

F C

CH2 n

F Vinyl polymer

Vinyl polymer

n

R

R′′

C

C

R′ R′′′

n

ORGANIC CHEMISTRY

2.739

TABLE 2.77 Plastics Acetals Acrylics Poly(methyl methacrylate) (PMMA) Poly(acrylonitrile) Alkyds Alloys Acrylic-poly(vinyl chloride) alloy Acrylonitrile-butadiene-styrene-poly(vinyl chloride) alloy (ABS-PVC) Acrylonitrile-butadiene-styrene-polycarbonate alloy (ABS-PC) Allyls Allyl-diglycol-carbonate polymer Diallyl phthalate (DAP) polymer Cellulosics Cellulose acetate resin Cellulose-acetate-propionate resin Cellulose-acetate-butyrate resin Cellulose nitrate resin Ethyl cellulose resin Rayon Chlorinated polyether Epoxy Fluorocarbons Poly(tetrafluoroethylene) (PTFE) Poly(chlorotrifluoroethylene) (PCTFE) Perfluoroalkoxy (PFA) resin Fluorinated ethylene-propylene (FEP) resin Poly(methylpentene) Polyolefins (PO) Low-density polyethylene (LDPE) High-density polyethylene (HDPE) Ultrahigh-molecular-weight polyethylene (UHMWPE) Polypropylene (PP) Polybutylene (PB) Polyallomers Poly(phenylene oxide) Poly(phenylene sulfide) (PPS) Polyurethanes Silicones Styrenics Polystyrene (PS) Acrylonitrile-butadiene-styrene (ABS) copolymer Styrene-acrylonitrile (SAN) copolymer Styrene-butadiene copolymer Sulfones Polysulfone (PSF)

Fluorocarbons (continued) Poly(vinylidene fluoride) (PVDF) Ethylene-chlorotrifluoroethylene copolymer Ethylene-tetrafluoroethylene copolymer Poly(vinyl fluoride) (PVF) Melamine formaldehyde Melamine phenolic Nitrile resins Phenolics Polyamides Nylon 6 Nylon 6/6 Nylon 6/9 Nylon 6/12 Nylon 11 Nylon 12 Aromatic nylons Poly(amide-imide) Poly(aryl ether) Polycarbonate (PC) Polyesters Poly(butylenes terephthalate) (PBT) [also called polytetramethylene terephthalate (PTMT)] Poly(ethylene terephthalate) (PET) Unsaturated polyesters (SMC, BMC) Butadiene-maleic acid copolymer (BMC) Styrene-maleic acid copolymer (SMC) Polyimide Sulfones (continued) Poly(ether sulfone) Poly(phenyl sulfone) Thermoplastic elastomers Polyolefin Polyester Block copolymers Styrene-butadiene block copolymer Styrene-isoprene block copolymer Styrene-ethylene block copolymer Styrene-butylene block copolymer Urea formaldehyde Vinyls Poly(vinyl chloride) (PVC) Poly(vinyl acetate) (PVAC) Poly(vinylidene chloride) Poly(vinyl butyrate) (PVB) Poly(vinyl formal) Poly(vinyl alcohol) (PVAL)

2.740

TABLE 2.78 Properties of Commercial Plastics

(Continued)

2.741

2.742

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.743

2.744

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.745

2.746

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.747

2.748

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.749

2.750

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.751

2.752

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.753

2.754

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.755

2.756

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.757

2.758

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.759

2.760

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.761

2.762

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.763

2.764

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.765

2.766

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.767

2.768

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.769

Next Page

2.770

TABLE 2.78 Properties of Commercial Plastics (Continued)

Previous Page

(Continued)

2.771

2.772

TABLE 2.78 Properties of Commercial Plastics (Continued)

(Continued)

2.773

2.774

TABLE 2.78 Properties of Commercial Plastics (Continued)

( Continued)

2.775

2.776

TABLE 2.79 Properties of Natural and Synthetic Rubbers

ORGANIC CHEMISTRY

TABLE 2.80 Density of Polymers Listed by Trade Name Common or trade name Acetate Rayon Acrylic Acrylonitrile-styrene copolymer Acrylonitrile-styrene-butadiene copolymer (ABS) Aniline-formaldehyde Benzylcellulose Bisphenol-A polycarbonate (BPAPC) Butyl rubber Cellulose I Cellulose II Cellulose III Cellulose IV Cellulose acetate Cellulose acetate-butyrate Cellulose formate fiber Cellulose nitrate Cellulose propionate Cellulose triacetate Cellulose tributyrate Chlorinated polyether Cotton Cotton, acetylated Ethylcellulose Ethylene-propylene copolymer (EPM) Glass Glass and asbestos Kevlar Lignocellulose Maleic anhydride-styrene copolymer Melamine-formaldehyde Methyl polyvinyl ketone Methylcellulose Nomex Nylon 6 Nylon 66 Nylon-610 Nylon-12 Rubber, butyl Rubber (unvulcanized) Rubber (hard) (Ebonite) Rubber, chlorinated (Neoprene) (CR), unvulcanized Rubber, chlorinated (Neoprene) (CR), vulcanized Rubber, fluorinated silicone Rubber, silicone Rubber, silicone (vulcanized) Rubber, styrene-butadiene (SBR), (unvulcanized) Rubber, styrene-butadiene (SBR), (vulcanized) Silk Toluene-sulfonamide-formaldehyde Urea-formaldehyde Urea-thiourea-formaldehyde Viscose Rayon Wool

r(g/cm3) 1.32 1.16 1.075–1.10 1.04–1.07 1.22–1.25 1.22 1.20 0.92 1.582–1.630 1.583–1.62 1.61 1.61 1.28–1.32 1.14–1.22 1.45 1.35–1.40 1.18–1.24 1.28–1.33 1.16 1.40 1.50–1.54 1.43 1.09–1.17 0.86 3.54 2.5 1.44 1.45 1.286 1.16 1.12 1.362 1.38 1.12–1.24 1.13–1.15, 1.22–1.25 1.156 1.02–1.034 0.92 0.91 1.11–1.17 1.23 1.32–1.42 1.0 0.80 1.3–2.3 0.93–0.94 0.961 1.25–1.35 1.21–1.35 1.16 1.477 1.5 1.28–1.33

2.777

TABLE 2.81 Density of Polymers Listed by Chemical Name Chemical name Polyacetylaldehyde acrolein acrylic acid acrylonitrile (PAN) acrylonitrile-vinyl acetate amide-6 (PA-6) amide-66 (PA-66) amide-610 (PA-610) amide-12 (PA-12) aryl ether ether ketone (PEEK) arylate bisphenol carbonate (BPAPC) butadiene-1,2, isotactic butadiene-1,2, syndiotactic butadiene-1,4-cis butadiene-1,4-trans 1-butene butene butyl acrylate sec.-butyl acrylate butylene tert.-butyl methacrylate -n-butyl methacrylate sec.-butyl methacrylate tert.-butylstyrene caprolactam, nylon carbonate (PC) chlorobutadiene chloroprene (Neoprene rubber) (CR), unvulcanized chloroprene (Neoprene rubber) (CR), vulcanized chlorotrifluoroethylene dichlorostyrene 2,2-dimethylpropyl acrylate dimethylsiloxane dodecyl methacrylate 1-ethylpropyl acrylate etheretherketone (PEEK) ethyl acrylate ethyl methacrylate ethylbutadiene ethylene ethylene (amorphous) ethylene (crystalline) ethylene (high density: HDPE) ethylene (linear low density: LLDPE) ethylene (low density: LDPE) ethylene (medium density: MDPE) ethylene glycol ethylene glycol fumarate ethylene glycol isophthalate, cryst. 2.778

r(g/cm3) 1.07 1.322 1.22 1.01–1.17, 1.20 1.14 1.12–1.24 1.13–1.15, 1.22–1.25 1.156 1.02–1.034 1.20 1.21 1.20 0.96 0.96 1.01 0.93–0.97, 1.01 0.85 0.91–0.92 1.08 1.05 0.60 1.03 1.055 1.04 0.957 0.985 1.14–1.2 1.25 1.23 1.32–1.42 2.03 1.38 1.04 0.970 0.93 1.04 1.27 1.095, 1.12 1.11, 1.12 0.891 0.870, 0.910–0.965 0.85 0.99 0.941–0.965 0.918–0.935 0.910–0.925 0.926–0.940 1.0951 1.385 1.358

TABLE 2.81 Density of Polymers Listed by Chemical Name (Continued) Chemical name ethylene glycol phthalate ethylene glycol waxes ethylene isophthalate ethylene phthalate ethylene terephthalate (PETP) formaldehyde –n-hexyl methacrylate imide isobutene isobutyl methacrylate isobutylene isoprene (1,4–) –N-isopropylacrylamide isopropyl acrylate isopropyl methacrylate methacrylonitrile methyl acrylate methyl methacrylate (PMMA) 4-methyl-1-pentene myrcene oxymethylene (POM) phenylene oxide polysulfide (Thiokol A) polysulfide (Thiokol B) propyl methacrylate propylene (PP) propylene, amorphous propylene, head-to-head propylene, isotactic propylene, isotactic (crystalline) propylene, syndiotactic (crystalline) propylene oxide styrene (PS) styrene, crystalline styrene-butadiene thermoplastic elastomer sulfone tetrafluoroethylene (PTFE) trifluorochloroethylene vinyl acetate (PVAC) vinyl alcohol (PVA) vinyl butyral vinyl chloride vinyl chloride-co-methyl acrylate vinyl chloride, flexible vinyl chloride, rigid vinyl chloride acrylonitrile (60/40) vinylethylene vinyl formal vinyl pyrrolidone (PVP) vinyl-vinylidene chloride vinylcarbazole vinylidene chloride (PVDC) vinylidene fluoride (PVDF) vinylisobutyl ether –m-xylene adipamide

r(g/cm3) 1.352 1.15–1.20 1.34 1.34 1.33–1.42 1.425 1.01 1.43 0.917 1.02–1.04 0.87–0.93 0.900–0.913 1.070–1.118 1.08 1.04 1.10 1.07–1.223 1.16–1.20 0.84 0.895 1.41–1.435 1.00–1.06 1.60 1.65 1.06–1.08 0.85–0.92 0.87 0.878 0.90–0.92 0.92–0.939 0.93 1.00 1.04–1.09 1.08–1.111 0.93–1.10 1.24 2.28–2.344 2.11–2.13 1.08–1.25 1.21–1.31 1.07–1.20 1.37–1.44 1.34 1.25–1.35 1.35–1.55 1.28 0.889 1.2–1.4 1.25 1.70 1.20 1.65–1.875 1.75–1.78 0.91–0.92 1.22 2.779

2.780

TABLE 2.82 Density of Polymers at Various Temperatures Temperature (deg C) Natural rubber, unvulcanized Natural rubber, cured Polyamide, Nylon 6 Polyamide, Nylon 6,6

0

20

0.9283 0.9211

0.9162 0.9093

Poly(butene-1), isotactic Poly(n-butyl methacrylate) g1.063a Poly(e-caprolactone) Polycarbonate, (with Bisphenol A) Poly(cyclohexyl methacrylate) Poly (2,6-dimethylphenylene ether) Poly(dimethyl siloxane)

40

1.045 1.043

60

1.032 1.030

80

1.004 0.990 1.057 1.005 0.993 1.037 1.023 g1.192 g1.186 g1.180 g1.174 g1.167 g1.101 g1.095 g1.090 g1.084 1.066 g1.061 g1.057 g1.052 g1.048 g1.043 0.9742 0.9566 0.9393 0.9222 0.9053 0.8887 0.9566 0.9389

140

160

180

200

220

240

1.176

260

280

300

320

340

0.797 0.975

0.786 0.961

0.776 0.947

0.765 0.933

0.755

1.165 1.154 1.143 0.963 1.100 1.086 1.071 0.745

1.010 g1.161

1.150

1.136

1.123

1.109

1.095 1.081 1.067 1.053 1.039 1.025

1.054 1.041 1.028 1.015 g1.039 g1.035 g1.030 g1.026

1.012

0.997 0.983 0.968 0.953 0.939

360

380

0.8722 0.8560 0.8400 0.8242 1.113 1.098 1.084

0.801 0.785 0.774 0.7847 0.7735 0.789 0.778

Polyethylene, linear

0.790 0.763 0.7624 0.766

0.780 0.769 0.752 0.7514 0.753

0.759

0.749

1.172 1.156 1.140 1.125 g1.131 g1.125 g1.119 0.9297 0.9195 0.9093 g1.181 g1.184 g1.179 g1.175

Poly(methyl methacrylate), isotactic Poly(o-methyl styrene) Polyoxyethylene Polyoxymethylene Polypropylene, atactic

120

1.018 1.017

Polyetheretherketone Polyethylene, branched

Poly(ethylene terephthalate) Poly(ethyl methacrylate) Polyisobutylene Poly(methyl methacrylate)

100

g1.113 1.103 0.8992 0.8891 0.8791 0.8691 g1.177 g1.171 g1.166 1.153 g1.174 g1.168 1.148 1.153 g1.170 g1.165 g1.160 g1.155 g1.150 1.140 g1.220 1.204 1.189 1.174 1.160 g1.016

1.011 g1.006 1.063 1.048

1.033

1.018

0.827

0.816

0.802

0.8592 1.139 1.136 1.141 1.128 1.146

1.126 1.123 1.129

1.112

1.097

1.082

1.117

1.106

1.094

1.132

1.119

0.9881 0.9777 0.9674 0.9571 1.004 0.990 0.976 1.167 1.151

1.067 1.052

Polypropylene, isotactic Polystyrene

Polysulfone, (with Bisphenol A) Polytetrafluoroethylene Polytetrahydrofuran Poly(vinyl acetate) Poly(vinyl chloride) Poly(vinyl methyl ether) g = glass.

a

1.0260 1.0142 1.0025 0.9909 0.9795 0.9681 g1.044 g1.040 g1.035 1.0125 1.0021 0.9919 g1.040 g1.034 1.026 1.016 1.005 0.994 0.984 g1.232 g1.226 g1.221 g1.216 g1.211 g1.206 g1.201

g1.196

0.944 0.931 1.1783 1.1615 1.352 1.0580 1.0436 1.0294

g1.189

0.919 1.1449 1.338 1.0152

0.907 0.895 1.1285 1.322 1.0011 0.9871

0.764 0.763 0.9569 0.9818 0.973 g1.195

0.754 0.753

0.744 0.743

0.9717 0.961 0.950 1.183 1.170

0.734 0.724 0.714 0.705

0.939 0.928 0.916 0.905 0.893 1.157 1.144 1.130 1.117 1.104 1.091 1.078 1.548 1.504

2.781

2.782

SECTION TWO

TABLE 2.83 Surface Tension (Liquid Phase) of Polymers Polymer Poly(oxyhexafluoropropylene) Poly[heptadecafluorodecyl)methylsiloxane] Poly(dimethylsiloxane) Poly[methyl(trifluoropropyl)siloxane] Poly(tetrafluoroethylene) Poly(oxyisobutylene) Poly(vinyl octanoate) Polypropylene, atactic Paraffin wax Poly(1,2-butadiene) Poly(t-butyl methacrylate) Poly(oxypropylene) Poly(i-butyl methacrylate) Poly(chlorotrifluoroethylene) Poly(vinyl hexadecanoate) Poly(n-butyl methacrylate) Poly(oxytetramethylene) Poly(methoxyethylene) Poly(n-butyl acrylate) Polyethylene, branched Poly(isobutylene) Polyethylene, linear Poly(oxydecamethylene) Poly(vinyl acetate) Poly(2-methylstyrene) Poly(oxydodecamethyleneoxyisophthaloyl) Polystyrene Poly(methyl acrylate) Poly(methyl methacrylate) Poly(epichlorohydrin) Polychloroprene Poly(oxyethyleneoxyterephthaloyl) Poly(oxyethylene) Poly(hexamethylene adipamide) Poly(oxyisophthaloyloxypropylene)

MW ∞ Mn ∼ 19600 ∞ ∞ ∞ M ∼ 30000 … Melt index ~ 1000 … Mn ~ 1000 Mv ~ 6000 Mn ~ 4100 Mv ~ 35000 Mn ~ 1280 … Mv ~ 37000 Mn ~ 32000 Mn ~ 46500 M ~ 32000 Mn ~ 7000 ∞ Mw ~ 67000 … Mw ~ 120000 Mn ~ 3000 … Mv ~ 44000 Mn ~ 25000 Mv ~ 3000 Mn ~ 1500 Mv ~ 30000 Mn ~ 16000 ∞ Mn ~ 17000 …

gLV at 20°C (mN/m) 18.4 (25°C) 18.5 (25°C) 21.3 (20°C) 24.4 (25°C) 25.6 27.5 28.7 29.4 30.0 (20°C) 30.4 (25°C) 30.5 30.7 (25°C) 30.9 30.9 30.9 31.2 31.8 31.8 33.7 34.3 35.6 (24°C) 35.7 36.1 36.5 38.7 40.0 40.7 41.0 41.1 43.2 (25°C) 43.6 44.5 45.0 (24°C) 46.4 49.3

−dg /dT [mN/(mK)] 0.059 (Mn ~ 7000) … 0.048 (106 cS) … 0.053 (Mn = 1038) 0.066 0.061 0.056 ~0.06 … 0.059 0.073 0.060 0.067 0.066 0.059 0.060 0.075 0.070 0.060 0.064 (Mn ~ 2700) 0.057 0.068 0.066 0.058 0.070 0.072 0.070 0.076 … 0.086 0.064 0.076 (Mn ~ 6000) 0.064 0.083

ORGANIC CHEMISTRY

2.783

TABLE 2.84 Interfacial Tension (Liquid Phase) of Polymers Polymer pair Polychloroprene/polystyrene Polychloroprene/poly(n-butyl methacrylate) Poly(methyl methacrylate)/poly (t-butyl methacrylate) Poly(methyl methacrylate)/polystyrene Poly(dimethylsiloxane)/polypropylene Poly(methyl methacrylate)/poly(n-butyl methacrylate) Poly(dimethylsiloxane)/poly(t-butyl methacrylate) Polybutadiene/poly(dimethylsiloxane) Poly(methyl acrylate)/poly(n-butyl acrylate) Poly(dimethylsiloxane)/poly(isobutylene) Poly(n-butyl methacrylate)/poly(vinyl acetate) Poly(dimethylsiloxane)/poly(n-butyl methacrylate) Polystyrene/poly(vinyl acetate) Polyethylene/polystyrene Poly(oxyethylene)/poly(oxtetramethylene) Polychloroprene/Polyethylene, branched Polyethylene, linear/poly(n-butyl acrylate) Polyethylene, branched/poly(oxytetramethylene) Poly(dimethylsiloxane)/polyethylene, branched Poly(oxytetramethylene)/poly(vinyl acetate) Polyethylene, branched/poly(i-butyl methacrylate) Polyethylene, branched/poly(oxydodecamethyleneoxyisophthaloyl) Polyethylene, branched/poly(t-butyl methacrylate) Poly(dimenthylsiloxane)/polystyrene Poly(dimethylsiloxane)/poly(oxytetramethylene) Poly(dimethylsiloxane)/polychloroprene Polyethylene, linear/poly(n-butyl methacrylate) Polyethylene, linear/polystyrene Poly(dimentylsiloxane)/poly(vinyl acetate) Poly(isobutylene)/poly(vinyl acetate) Polyethylene, linear/poly(methyl acrylate) Polyethylene/poly(caprolactam) Poly(dimethylsiloxane)/poly(oxyethylene) Polyethylene, branched/poly(oxyethylene) Polyethylene, linear/poly(methyl methacrylate) Polyethylene, linear/poly(vinyl acetate) Polyethylene, linear/poly(hexamethylene adipamide) Polyethylene, branched/poly(oxyisophthaloyloxpropylene)

g12 at 20°C (mN/m) 0.5 (140°C) 1.6 (140°C) 3.0 3.2 3.2 3.4 3.6 4.0 4.0 4.0 4.2 4.2 4.2 4.4 (200°C) 4.5 4.6 5.0 5.0 5.3 5.5 5.5 5.9 5.9 6.1 6.4 7.1 7.1 8.3 8.4 9.9 10.6 10.7 (250°C) 10.9 11.6 11.9 14.5 14.9 15.4

−dg /dT [mN/(mK)] … … 0.005 0.013 0.002 0.012 0.003 0.009 0.008 0.016 0.011 0.004 0.004 … 0.005 0.008 0.014 0.007 0.002 0.008 0.010 0.011 0.016 ~0 0.001 0.005 0.015 0.020 0.008 0.020 0.018 … 0.008 0.016 0.018 0.027 0.018 0.030

2.784

TABLE 2.85 Thermal Expansion Coefficients of Polymers Temperature (deg C) Natural Rubber, unvulcanized Natural Rubber, cured

0

20

6.6

6.6

6.5

6.4 6.7

40

60

80

100

120

140

160

180

200

220

Polyamide, Nylon 6 Polyamide, Nylon 6,6 Poly(butene-1), isotactic Poly(n-butyl methacrylate) g3.8a Poly(e-caprolactone) Polycarbonate, (with Bisphenol A) Poly(cyclohexyl methacrylate) Poly(2,6-dimethylphenylene ether) Poly(dimethyl siloxane)

6.4

g2.4

9.06 9.0

260

280

4.7

4.7 6.6

4.7 6.6 6.8

300

320

340

6.9

6.8

7.0

7.2

6.7 7.4

6.7 7.4

6.7 7.4

6.7

6.5

6.7 7.3

6.7

6.2 6.4

6.3

6.2

6.1

g2.6

g2.6

g2.6

g2.6

6.1 6.4 g2.6

6.3 g2.6

5.8

5.9

6.1

6.2

6.3

6.4

6.6

6.7

6.8

g2.5

g2.5

g2.5

5.9

6.0

6.2

6.3

6.4

g2.1

g2.1

g2.1

g2.1

g2.1

g2.1

g2.1

g2.1

7.1

7.3

7.4

7.6

7.7

7.8

9.11

9.17

9.4

9.2

9.23

g2.1 9.29

9.35

9.41

9.47

9.53

9.59

6.7

6.7 7.5 7.14

6.7 7.2 7.18

6.7 6.9 7.24 7.0 7.9

6.7

6.7

Polyetheretherketone Polyethylene, branched Polyethylene, linear

7.6 Poly(ethylene terephthalate) Poly(ethyl methacrylate) Polyisobutylene Poly(methyl methacrylate)

240

6.7

7.32 7.0 6.8

g2.7 5.51

g2.1

g2.7 5.54

g2.7 5.61 g2.1 g2.5

6.0 5.65 g2.4 g2.9

5.68 g2.7

g1.8

g2.7 5.58 g1.8 g2.2

g2.1

g2.1

g2.1

g2.1

g2.1

5.72 5.5 5.4 5.2 5.2

5.75 5.8 5.7 5.2 5.2

6.1 6.0 5.2

6.4

6.7

7.0

5.2

5.2

5.2

7.2

7.5

6.8

6.8

6.8

360

380

6.7

6.7

Poly(methyl methacrylate), isotactic Poly(o-methyl styrene) Polyoxyethylene Polyoxymethylene

g2.2 g2.6

6.4

6.3

g2.6

g2.6

Polypropylene, atactic Polypropylene, isotactic

6.1

g2.0

g = glass

a

6.1

5.9

5.8

5.7

7.1

7.1

5.3 7.1

5.3 7.1

5.3 7.1 7.9

7.7

9.3

5.78

Polystyrene

Polysulfone, (with Bisphenol A) Polytetrafluoroethylene Polytetrahydrofuran Poly(vinyl acetate) Poly(vinyl chloride) Poly(vinyl methyl ether)

6.2

g2.8

g2.8

g2.3 g2.9 g2.1

g2.5 g2.9 g2.1

5.0 g2.1

7.13

7.17

6.7 7.20

6.87

6.92

6.96

5.2 g2.1

6.7 7.23 4.7 7.01

5.79 5.1 5.3 g2.1

5.81 5.1 5.4 g2.1

5.82 5.1 5.6 g2.2

6.7

6.7

6.7

5.5 7.06

6.2

6.6 6.7 6.7 5.84 5.1 5.7 g2.2

7.1

7.1

6.8

6.8

6.6 6.7 6.7 5.85 5.1 5.8 5.5

6.6 6.7

6.7

6.7

6.7

6.7

6.0 5.7

6.2 5.8

6.3 5.8

6.4 5.9

5.87 5.9 5.6

6.5 6.0

6.1

6.1

14.4

14.7

2.785

2.786

SECTION TWO

TABLE 2.86 Heat Capacities of Polymers

Polymer

Abbreviations

Molecular a weight g/mol

Cpb Tg (K)

Temp. (K)

kJ/kg·K

J/mol·K

∆Cpc J/mol·K

1. Main-chain carbon polymers Poly(acrylics) Poly(iso-butyl acrylate)

PiBA

128.17

249

Poly(n-butyl acrylate)

PnBA

128.17

218

Poly(ethyl acrylate)

PEA

100.12

249

Poly(methyl acrylate)

PMA

86.09

279

220 240 300 500 80 180 300 440 90 200 300 500 100 200 300 500

1.2156 1.3365 1.8108 2.3388 0.5598 1.0632 1.8201 2.1803 0.5792 1.0301 1.7867 2.2189 0.6154 0.9816 1.765 2.143

155.80 171.30 232.09 299.77 71.75 136.27 233.28 279.45 57.99 103.13 178.88 222.16 52.98 84.51 151.99 184.49

36.60

50 150 300 350 50 150 300 500 100 200 300 600

0.3694 0.8967 1.960 2.214 0.3465 0.9057 NA 2.616 0.6733 1.2190 2.086 3.071

19.98 48.50 106.00 114.90 18.74 48.99 NA 141.50 37.78 68.40 117.02 172.31

29.10

30 130 300 450 30 130 300 450

0.2140 0.7775 1.924 2.409 0.1761 0.7898 1.924 2.409

11.79 42.838 106.03 132.73 9.704 43.516 106.03 132.73

28.91

100 200 300

0.674 1.110 1.555 2.202 3.127 0.7020 1.3319 1.903 2.079

9.45 15.57 21.81 30.89 43.87 59.08 112.09 160.18 174.98

45.40

45.60

42.30

Poly(dienes) 1,4-Poly(butadiene) cis-

PBD

54.09 171

trans-

Poly(1-butene)

Poly(1-butenylene) cis-

180

PB

56.11

PBUT

55.10

249

171

trans-

190

28.20

23.06

26.48

Poly(alkenes) Poly(ethylene)

Poly(1-hexene)

PE

PHE

14.03

84.16

252

223

600 100 200 250 290

(c)

10.1

(s) (m) (a) (a) (a)

25.1

2.787

ORGANIC CHEMISTRY

TABLE 2.86 Heat Capacities of Polymers (Continued) Abbreviations

Molecular a weight g/mol

Tg (K)

Temp. (K)

kJ/kg·K

J/mol·K

PiB

56.11

200

50 150 300 380

0.2440 0.8660 1.962 2.311

13.69 (a) 48.59 110.09 (a) 129.66

22.29

Poly(2-methylbutadiene) cis-

PMBD

68.12 200

P4MPE

84.16

303

Poly(1-pentene)

PPE

70.14

233

Poly(propylene)

PP

42.08

260

0.3573 0.9025 1.911 2.216 0.5610 1.090 1.4449 1.728 1.253 1.338 2.058 2.770 0.6238 1.132 1.622 2.099 3.178

24.34 61.48 130.20 144.80 47.21 91.75 121.60 145.40 87.90 93.82 144.34 194.32 26.25 47.63 68.24 88.34 133.73

30.87 (a)

Poly(4-methyl-1-pentene)

50 150 300 360 80 180 250 300 200 220 300 470 100 200 300

0.5472 1.1557 1.8524 2.3673 1.2229 1.5710 2.0190 2.1127 0.5155 1.4666 1.9489 2.0462 1.8264 1.9091 2.2396 0.5248 0.9456 1.307 0.5904 1.032 1.395 0.5742 1.3755 2.0766 2.4323

77.81 164.34 263.41 336.63 173.90 223.40 287.10 300.43 58.84 167.42 222.47 233.57 310.77 324.83 381.06 45.18 81.41 112.50 50.25 87.81 118.70 57.49 137.72 207.91 243.52

Polymer Poly(isobutene)

Cpb

600 Poly(methacrylics) Poly(n-butyl methacrylate) PnBMA

142.20

293

Poly(i-butyl methacrylate)

PiBMA

142.20

326

Poly(ethyl methacrylate)

PEMA

114.15

338

Poly(hexyl methacrylate)

PHMA

170.25

268

Poly(methacrylic acid)

PMAA

86.09

—

Poly(methacrylamide)

PMAM

85.11

—

Poly(methyl methacrylate)

PMMA

100.12

378

80 200 300 450 230 300 350 400 80 300 350 380 270 300 420 100 200 300 100 200 300 100 300 400 550

∆Cpc J/mol·K

33.7 (a)

27.03 (a)

(c) 17.37 (c) (s) (m) (a) 29.70

39.00

31.70

—

—

—

33.5

(Continued)

2.788

SECTION TWO

TABLE 2.86 Heat Capacities of Polymers (Continued)

Polymer

Abbreviations

Moleculara weight g/mol

Cpb Tg (K)

Temp. (K)

kJ/kg·K

J/mol·K

∆Cpc J/mol·K

Poly(styrenes) Poly(styrene)

—,a-methyl

—, p-bromo-

—, p-chloro-

—, p-fluoro-

—, p-iodo-

—, p-methyl-

Poly(acrylonitrile)

PS

0.4548 1.2230 1.2730 400 1.9322 600 2.4417 PaMS 118.18 441 100 0.4712 300 1.2752 460 2.1868 490 2.3331 PBS 183.05 410 300 0.79650 350 0.92349 420 1.2651 550 1.4641 PCS 138.60 406 300 1.0229 350 1.19848 410 1.6331 550 1.9134 PFS 122.14 384 130 0.47611 200 0.62048 300 0.93079 380 1.2672 PIS 230.05 424 300 0.67607 400 0.89102 430 1.1145 550 1.2570 PMS 118.18 380 300 1.2743 350 1.4917 390 1.9449 500 2.2766 Poly(vinyl halides) and Poly(vinyl nitriles) PAN

Poly(chlorotrifluoroethylene) PC3FE

Poly(tetrafluoroethylene)

PTFE

104.15

373

53.06

378

116.47

325

50.01

240

Poly(trifluoroethylene)

P3FE

82.02

304

Poly(vinyl chloride)

PVC

62.50

354

100 300

100 200 300 370 80 200 300 320 100 200 300 700 100 200 300 100 300 360 380

0.5695 0.9286 1.297 1.624 0.2787 0.6257 0.85945 0.90667 0.3873 0.6893 0.9016 1.028 1.454 0.4049 0.7128 1.078 0.4291 0.9496 1.457 1.569

47.37 (g) 127.38 132.58 201.24 254.30 55.69 150.70 (g) 258.44 275.72 145.800 169.045 231.582 267.995 141.780 166.110 226.345 265.195 58.152 75.786 113.687 154.773 155.53 204.980 256.41 289.17 150.600 176.290 229.846 269.05 30.22 49.27 68.83 86.16 32.46 72.87 100.10 105.60 19.37 34.47 45.09 51.42 72.69 33.21 58.46 88.40 26.82 59.35 91.08 98.05

30.7 (a)

25.3

31.9

31.1

33.3

37.9

34.6

—

—

7.82 (s) (m) 21.00

(g) (g)

19.37(a)

ORGANIC CHEMISTRY

2.789

TABLE 2.86 Heat Capacities of Polymers (Continued) Cpb

Abbreviations

Moleculara weight g/mol

Tg (K)

Temp. (K)

kJ/kg·K

Poly(vinylidene chloride)

PVC2

96.95

255

Poly(vinylidene fluoride)

PVF2

64.03

233

Poly(vinyl fluoride)

PVF

46.04

314

100 200 250 300 100 150 230 250 300 100 200 300 310

0.3745 0.5932 0.7115 NA 0.4435 0.6185 0.8918 0.7856 NA 0.5204 0.8692 1.301 1.353

Polymer

J/mol·K 36.31 57.51 68.98 NA 28.40 39.60 57.10 50.30 NA 23.96 40.02 59.91 62.29

∆Cpc J/mol·K 70.26

22.80

17.80(a)

Others Poly(p-phenylene)

76.10

—

Poly(iminoadipoyNylon 612 liminododecamethylene)

310.48

319

Poly(imioadipoyliminohexamethylene)

Nylon 66

226.32

323

Poly(iminohexamethylene- Nylon 69 iminoazelaoyl)

268.40

331

Poly(iminohexamethylene- Nylon 610 iminosebacoyl)

282.43

323

Poly(vinyl acetate)

Poly(vinyl alcohol)

Poly(vinyl benzoate)

Poly(p-xylylene)

PPP

80 0.3708 150 0.58135 250 0.92926 300 1.117 PVAc 86.09 304 80 0.3230 300 1.183 320 1.8409 370 1.898 PVA 44.05 358 60 0.2674 150 0.7187 250 1.185 300 1.546 PVBZ 148.16 347 190 0.71808 300 1.1025 400 1.8390 500 2.0333 PPX 104.15 286 220 0.91445 250 1.0576 300 1.3022 410 1.8686 2. Main-chain heteroatom polymers Poly(amides) 230 300 400 600 230 300 400 600 230 300 400 600 230 300 400 600

1.2296 1.5926 2.4842 3.1596 1.1139 1.4638 2.3794 2.793 1.1980 1.5204 2.3840 3.0720 1.2069 1.5644 2.3975 3.1041

28.22 (sc) — 44.241 (sc) 70.717 (sc) 85.040 (sc) 27.81 53.7 101.86 158.48 163.37 11.78 — 31.66 52.21 68.11 106.39 69.5 163.35 272.47 301.25 95.241 (sc) 37.6(a) 110.149 (sc) 135.622 (sc) 194.619 (sc)

381.78 494.48 771.30 980.986 252.10 331.30 538.50 632.1 321.53 408.080 639.874 824.534 340.870 441.820 677.125 876.685

214.8(a)

145.0(a)

—

—

(Continued)

2.790

SECTION TWO

TABLE 2.86 Heat Capacities of Polymers (Continued) Cpb

Abbreviations

Moleculara weight g/mol

Tg (K)

Poly(imino(1-oxohexamethylene))

Nylon 6

113.16

313

Poly(imino1-oxododecamethylene)

Nylon 12

Poly(imino1-oxoundecamethylene)

Nylon 11

Polymer

Temp. (K)

kJ/kg·K

J/mol·K

0.4400 1.5023 2.5186 2.7881 1.2874 1.6952 2.4709 3.2786 1.2996 1.7507 2.4567 3.2449 0.5904 1.032 1.214 1.395

49.78 170.00 285.00 315.50 254.020 334.49 487.565 646.945 238.21 320.91 450.314 594.794 50.25 87.81 103.30 118.70

230 300 350 390 230 300 350 390 230 300 350 390 220 300 350 390 220 300 350 390 220 300 350 390 230 300 350 390

1.102 1.315 1.498 1.622 0.958 1.218 1.397 1.537 0.929 1.170 1.356 1.516 0.936 1.347 1.595 1.768 0.830 1.153 1.382 1.548 0.959 1.297 1.541 1.747 1.213 1.455 1.647 1.802

78.33 93.47 106.5 115.3 109.3 139.0 159.4 175.4 53.00 66.75 77.36 86.49 122.8 176.7 209.3 232.0 122.1 169.7 203.4 227.8 83.50 112.9 134.2 152.1 120.2 144.2 163.3 178.6

80 150 300 450

0.54302 0.87449 1.9706 2.2147

108.734 175.107 394.595 443.470

70 300 400 600 197.32 314 230 300 400 600 183.30 316 230 300 400 600 85.11 — 100 200 250 300 Poly(amino acids)

Poly(methacrylamide)

PMAM

Poly(L-alanine)

PALA

71.08

—

Poly(L-asparagine)

PASN

114.10

—

Polyglycine

PGLY

57.05

—

Poly(L-methionine)

PMET

131.19

—

Poly(L-phenylalanine)

PPHE

147.18

—

Poly(L-serine)

PSER

87.08

—

Poly(L-valine)

PVAL

99.13

—

∆Cpc J/mol·K 93.6(a)

—

—

—

—

—

—

—

—

—

—

Poly(esters) Poly(butylene adipate)

PBAD

200.24

199

140.046

ORGANIC CHEMISTRY

2.791

TABLE 2.86 Heat Capacities of Polymers (Continued) Abbreviations

Moleculara weight g/mol

Poly(butylene terephthalate)

PBT

Poly(ethylene terephthalate)

Cpb Tg (K)

Temp. (K)

220.23

248 320

PET

192.16

342

Poly(tridecanolactone)

PTDL

212.34

237

Poly(trimethylene adipate)

PTMA

186.21

—

Poly(trimethylene succinate) PTMS

158.15

—

150 200 300 400 570 100 300 400 600 185 260 300 395 300 310 330 360 300 310 330 360 100 210 300 350 100 200 300

Polymer

Poly(g-butyrolactone)

PBL

86.09

214

Poly(⑀-caprolactone)

PCL

114.15

209

Poly(glycolide)

PGL

58.04

318

Poly(b-propiolactone)

PPL

72.07

249

Poly(ethylene oxalate)

PEOL

116.07

306

Poly(ethylene sebacate)

PES

228.29

245

Poly(oxy-2,6-dimethyl1,4-phenylene)

PPO

120.15

kJ/kg·K

350 100 300 400 550 100 240 300 400 100 300 320 360 120 200 300 410

0.61075 0.82262 1.6134 1.8187 2.1678 0.4393 1.172 1.8203 2.1136 0.95 1.45 1.79 2.15 NA 1.8710 1.9137 1.9776 NA 1.8401 1.8721 1.9201 0.6012 1.024 1.810 1.870 0.62322 1.0243 1.4229 1.8138 1.9415 0.5250 1.127 1.999 2.098 0.5568 1.044 1.878 2.081 0.49910 1.1175 1.6395 1.7012 0.66292 0.95269 1.9245 2.1923

80 300 500 570

0.4418 1.2459 2.1232 2.2555

J/mol·K

∆Cpc J/mol·K

134.505(sc) 106.77 181.166 77.812 355.311 400.532 477.407 84.42 77.8 (a) 225.2 349.80 406.15 202 — 308 380 457 NA — 348.401 356.341 368.252 NA — 291.014 296.074 303.664 51.760 57.4 88.170 155.858(m) 161.031(m) 71.140 59.5 116.923 162.42 207.04 (s) 221.62 (m) 30.470 44.4 65.42 116.039 (m) 121.75 (m) 40.130 50.4 75.220 135.354 (m) 149.994 (m) 57.930 56.23 129.705 190.295 (m) 197.456 (m) 151.338 (s) 154.059 217.490 (sc) 439.34 (m) 500.500 (m)

Poly(oxides) 482

53.08 149.70 255.10 271.00

31.9 (a)

(Continued)

2.792

SECTION TWO

TABLE 2.86 Heat Capacities of Polymers (Continued)

Polymer

Abbreviations

Cpb

Moleculara weight g/mol

Tg (K)

Temp. (K) 100 200 300

Poly(oxyethylene)

POE

44.05

206

Polyoxymethylene

POM

30.03

190

Poly(oxy-1,4-phenylene)

POPh

92.10

358

Poly(oxypropylene)

POPP

58.08

198

Poly(oxytetramethylene)

PO4M

72.11

189

Poly(oxytrimethylene)

PO3M

58.08

195

kJ/kg·K

J/mol·K

330

0.6114 0.9507 1.257 1.995 2.223 0.5554 0.7266 1.283 1.920 2.292 1.185 1.367 1.694 2.003 0.537 1.014 1.915 2.105 0.5465 1.033 1.985 2.081 0.5095 0.9464 1.373 2.055 2.107

26.93 41.88 55.36 87.89 97.91 16.68 21.82 38.52 57.67 68.83 109.10 125.90 156.00 184.50 31.21 58.89 111.23 122.27 39.41 74.52 143.15 150.04 29.59 54.97 79.73 119.34 122.37

50 100 300 360 110 300 400 450 50 100 300 340 170 300 400 434 100 300 450 560

0.38820 0.73995 1.6184 1.7525 0.59700 1.3183 1.9282 2.0009 0.3672 0.7131 1.591 1.657 0.58914 1.0207 1.3662 1.4686 0.43143 1.207 1.9570 2.207

39.678 (sc) 75.630 (sc) 165.417 (m) 179.125 (m) 94.419 (a) 208.507 (a) 304.968 (m) 316.463 (m) 27.23 52.88 118.0 122.9 70.762 122.60 164.091 176.399 109.70 (s) 306.8 (s) 497.60 (m) 561.3 (m)

450 100 150 300 600 300 350 400 600 80 180 300 370 80 180 300 340 80 180 300

∆Cpc J/mol·K

(s) 38.96 (s) (s) (m) (s) 27.47 (s) (s) (m) (s) (s) (m) (m) (s) (s) (m) (m) (s) (s) (m) (m) (s) (s) (s) (m)

21.4 (a)

32.15

46.49

50.73

Others Poly(diethyl siloxane)

PDES

102.21

135

Poly(dimethyl itaconate)

PDMI

158.16

377

Poly(dimethyl siloxane)

PDMS

74.15

146

Poly(4-hydroxybenzoic acid) PHBA

120.11

434

Poly(4,4′-isopropylidene diphenylenecarbonate)

254.27

418

PC

30.189

54.23

27.7 (a)

34

48.5

ORGANIC CHEMISTRY

2.793

TABLE 2.86 Heat Capacities of Polymers (Continued) Cpb

Abbreviations

Moleculara weight g/mol

Tg (K)

Temp. (K)

PEEK

288.30

419

Poly(oxy-1,4-phenylenePBISP sulphonyl-1,4-phenylene-oxy1,4-phenylene-(1-methylidene)1,4-phenylene) Poly(1,4-phenylene sulphonyl) PAS

442.54

458.5

140.16

492.6

Poly(1-propene sulphone)

P1PS

106.14

SEt

78.96

300 419 500 750 200 300 500 540 150 300 500 620 10 30 100 300 400

Polymer Poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene)

Trigonal selenium

303.4

600 a

kJ/kg·K NA 1.789 1.928 2.358 0.75870 1.1161 1.9436 2.0251 0.597 1.009 1.571 1.642 0.01580 1.165 0.2304 0.318 0.3338 0.4777 0.4343

J/mol·K

∆Cpc J/mol·K

NA 78.1 515.8 555.9 679.8 335.754 102.482 493.934 860.132 896.19 83.7 — 141.4 220.2 230.1 1.677 — 123.7 18.19 (s) 13.29 25.11 26.36 (s) 37.72 (m) 34.29

This is the molecular weight of the repeat unit of the polymer. Except the data for PTDL and P1PS, Cp data reported in the unit of kJ/kg·K were converted from the Cp data which were directly cited from the literature, using the molecular weight of the repeat unit. c Specific heat increment at Tg. b

2.794

SECTION TWO

TABLE 2.87 Thermal Conductivity of Polymers Polymer

Temperature (K)

k (W/m K)

Polyamides Polylauryllactam (nylon-12)

0.25 0.19

Polycaprolactam (nylon-6) Moldings Crystalline Amorphous Melt Poly(hexamethylene adipamide) (nylon-6,6) Moldings Crystalline Amorphous Melt Poly(hexamethylene dodecanediamide) (nylon-6, 12) Poly(hexamethylene sebacamide) (nylon-6, 10) Polyundecanolactam (nylon-11)

293 303 303 523

0.24 0.43 0.36 0.210

293 303 303 523

0.24 0.43 0.36 0.15 0.22 0.22 0.23

Polycarbonates, polyesters, polyethers, and polyketones Polyacetal Polyaryletherketone Poly(butylene terephthalate) (PBT)

293 293

Polycarbonate (Biphenol A) Temperature dependence

293 300–573 150–400

Poly(dially carbonate) Poly(2,6-dimethyl-1,4-phenylene ether) Polyester Cast, rigid Chlorinated Polyetheresteramide

0.23 0.3 0.30 0.29 0.16 0.20

0.21 0.12

303 353

Polyetheretherketone (PEEK) Poly(ethylene terephthalate) (PET) Temperature dependence Poly(oxymethylene)

293 200–350 293 293 100–400

Temperature dependence Poly(phenylene oxide) Molding grade

0.17 0.33 0.24–0.34 0.20–0.26 0.25 0.15 0.292 0.44

0.23 Epoxides

Epoxy resin Casting grade Temperature dependence

293 300–500

0.19 0.19–0.34

293 311–460

0.29 0.146–0.248 0.238 0.25 0.25 0.34

Halogenated olefin polymers Polychlorotrifluoroethylene Poly(ethylene-tetrafluoroethylene) copolymer Polytetrafluoroethylene

Low-temperature dependence

293 298 345 5–20.8

ORGANIC CHEMISTRY

2.795

TABLE 2.87 Thermal Conductivity of Polymers (Continued) Polymer

Temperature (K)

Poly(tetrafluoroethylene-hexafluoropropylene) copolymer (Teflon EEP) Poly(vinyl chloride) Rigid Flexible Chlorinated Temperature dependence

k (W/m K) 0.202

293 293 293 103 273 373 293 293 298–433

Poly(vinylidene chloride) Poly(vinylidene fluoride)

0.21 0.17 0.14 0.129 0.158 0.165 0.13 0.13 0.17–0.19

Hydrocarbon polymers Polybutene Polybutadiene Extrusion grade Poly(butadiene-styrene) copolymer (SBR) 23.5% styrene content Pure gum vulcanizate Carbon black vulcanizate Polychloroprene (neoprene) Unvulcanized Pure gum vulcanizate Carbon black vulcanizate Poly(1,3-cyclopentylenevinylene) [poly(2-norbornene)] Polyethylene Low density Medium density High density Temperature dependence Molecular-weight dependence Poly(ethylene-propylene) copolymer Polyisobutylene Polyisoprene (natural rubber) Unvulcanized Pure gum vulcanizate Carbon black vulcanizate Poly(4-methyl-1-pentene) Polypropylene Temperature dependence Polystyrene

0.22 293

0.22

0.190–0.250 0.300 293

0.19 0.192 0.210 0.29 0.33 0.42 0.52

20–573 0.355 0.13

293

273 373 473 573 673

Poly(p-xylylene) (PPX)

0.13 0.15 0.28 0.167 0.12 0.2 0.105 0.128 0.13 0.14 0.160 12

Polyimides Polyetherimide Polyimide Thermoplastic Thermoset Temperature dependence

0.07 293

0.11 0.23–0.50

300–500 (Continued)

2.796

SECTION TWO

TABLE 2.87 Thermal Conductivity of Polymers (Continued) Polymer

Temperature (K)

k (W/m K)

Phenolic resins Poly(phenol-formaldehyde) resin Casting grade Molding grade Poly(phenol-furfural) resin Molding grade

0.15 0.25 293

0.25

Polysaccharides Cellulose Cotton Rayon Sulfite pulp, wet Sulfite pulp, dry Laminated Kraft paper Alkali cellulose Different papers Cellulose acetate Cellulose acetate butyrate Cellulose nitriate Cellulose propionate Ethylcellulose

303–333 293 293

0.071 0.054–0.07 0.8 0.067 0.13 0.046–0.067 0.029–0.17 0.20 0.33 0.23 0.20 0.21

Polysiloxanes Poly(dimethylsiloxane)

Poly(methylphenylsiloxane) 9.5% phenyl, d = 1110 kg/m3 48% phenyl, d = 1070 kg/m3 62% phenyl, d = 1110 kg/m3

230 290 340 410

0.25 0.22 0.20 0.17

273 323 373 273 323 373 273 323 373

0.158 0.150 0.144 0.143 0.136 0.127 0.141 0.137 0.132

293 240–310

0.18 0.18 0.29 0.288 0.18 0.26

293 293

0.21 0.31

293

0.26

333 413

0.251 0.184

Polysulfide and polysulfones Polyarylsulfone Polyethersulfone Poly(phenylene sulfide) Poly(phenylene sulfone) Udel polysulfone Polyurethanes Polyurethane Casting resin Elastomer Vinyl Polymers Polyacrylonitrile Poly(acrylonitrile-butadiene)copolymer (NBR) 35% acrylonitrile

ORGANIC CHEMISTRY

2.797

TABLE 2.87 Thermal Conductivity of Polymers (Continued) Polymer Poly(acrylonitrile-butadiene-styrene) copolymer (ABS) Injection molding grade Poly(acrylonitrile-styrene) copolymer Poly(i-butyl methacrylate) At 0.82 atm Poly(n-butyl methacrylate) At 0.82 atm Poly(butyl methacrylate-triethylene glycol dimethacrylate) copolymer Poly(chloroethylene-vinyl acetate) copolymer

Poly(dially phthalate) Poly(ethyl acrylate)

Poly(ethyl methacrylate) At 0.82 atm Poly(ethylene vinyl acetate) Poly(methyl methacrylate) Poly(methyl methacrylate-acrylonitrile) copolymer Poly(methyl methacrylate-styrene) copolymer Poly(vinyl acetate) Poly(vinyl acetate-vinyl chloride) copolymer Poly(vinyl alcohol) Poly(N-vinyl carbozole) Poly(vinyl fluoride) Poly(vinyl formal) Molding grade

Temperature (K)

293

k (W/m K) 0.33 0.18 0.13 0.45

293 325 375 310.9 422.1 533.2 273 293

293 443 243 333 293

0.15 0.134 0.146 0.218 0.21 0.213 0.230 0.213 0.175 0.34 0.21 0.18 0.21–0.21 0.159 0.167 0.2 0.126 0.168 0.14 0.17 0.27

2.798

SECTION TWO

TABLE 2.88 Thermal Conductivity of Foamed Polymers Name Poly(acrylonitrile-butadiene) copolymer d = 160–400 kg/m3 Cellulose acetate d = 96–128 kg/m3 Polychloroprene (Neoprene) d = 112 kg/m3 d = 192 kg/m3 Poly(dimethylsiloxane) Sheet, d = 160 kg/m3 Epoxy d = 32–48 kg/m3 d = 80–128 kg/m3 Polythylene Extruded plank d = 35 kg/m3 d = 64 kg/m3 d = 96 kg/m3 d = 144 kg/m3 Sheet, extruded, d = 43 kg/m3 Sheet, crosslinked, d = 26–38 kg/m3 Polyisocyanurate d = 24–56 kg/m3 Polyisoprene (natural rubber) d = 56 kg/m3 d = 320 kg/m3 Phenolic resin d = 32–64 kg/m3 d = 112–160 kg/m3 Polypropylene d = 64–96 kg/m3 Polystyrene d = 16 kg/m3 d = 32 kg/m3 d = 64 kg/m3 d = 96 kg/m3 d = 160 kg/m3 Poly(styrene-butadiene) copolymer (SBR) d = 72 kg/m3 Poly(urea-formaldehyde) resin d = 13–19 kg/m3 Polyurethane Air blown, d = 20–70 kg/m3 At 0°C At 20°C At 70°C CO2 blown, d = 64 kg/m3, at 20°C 20% closed cells, at 20°C 90% closed cells, at 20°C 500 mm cell size, at 20°C 100 mm cell size, at 20°C Poly(vinyl chloride) d = 56 kg/m3 d = 112 kg/m3

k (W/m K) 0.036–0.043 0.045–0.46 0.040 0.065 0.086 0.016–0.022 0.035–0.040

0.053 0.058 0.058 0.058 0.040–0.049 0.036–0.040 0.012–0.02 0.036 0.043 0.029–0.032 0.035–0.040 0.039 0.040 0.036 0.033 0.036 0.039 0.030 0.026–0.030

0.033 0.036 0.040 0.016 0.033 0.016 0.024 0.016 0.035 0.040

ORGANIC CHEMISTRY

2.799

TABLE 2.89 Thermal Conductivity of Polymers with Fillers Name

k (W/m K)

Polyacetal 5–20% polytetrafluoroethylene (PTFE) Poly(acrylonitrile-butadiene-styrene) copolymer (ABS) 20% glass fiber Polyaryletherketone 40% glass fiber Poly(butylene terephthalate) (PBT) 30% glass fiber 40–45% glass fiber Polycarbonate 10% glass fiber 30% glass fiber Polychloroprene (Neoprene) 33% carbon black Poly(dially phthalate) Glass fiber Epoxy resin 50% aluminum 25% Al2O3 50% Al2O3 75% Al2O3 30% mica 50% mica Silica Polyetheretherketone (PEEK) 30% glass fiber 30% carbon fiber Polyethylene 30% glass fiber Poly(ethylene terephthalate) (PET) 30% glass fiber 45% glass fiber 30% graphite fiber 40% polyacrylonitrile (PAN) carbon fiber Polyimide Thermoplastic, 15% graphite Thermoplastic, 40% graphite Thermoset, 50% glass fiber

0.20 0.20 0.44 0.29 0.21 0.42 0.22 0.32 0.210

0.21–0.62 1.7–3.4 0.35–0.52 0.52–0.69 1.4–1.7 0.24 0.39 0.42–0.84 0.21 0.21 0.36–0.46 0.29 0.31 0.71 0.72 0.87 1.73 0.41

Name

k (W/m K)

Polyisoprene (natural rubber) 33% carbon black 0.28 Poly(melamine-formaldehyde) resin Asbestor 0.544–0.73 Cellulose fiber 0.27–0.42 Glass fiber 0.42–0.48 Macerated fabric 0.443 Wood flour/cellulose 0.17–0.48 Poly(melamine-phenolic) resin Cellulose fiber 0.17–0.29 Wood flour 0.17–0.29 Nylon-6 (polycaprolactam) 30–35% glass fiber 0.24–0.28 Nylon-6,6 [poly(hexamethylene adipamide)] 30–33% glass fiber 0.21–0.49 40% glass fiber and mineral 0.46 30% graphite or polyacrylonitrile (PAN) carbon fiber 1.0 Nylon-6,12 [poly(hexamethylenedodecanediamide)] 30–35% glass fiber 0.427 Poly(phenylene oxide) 30% glass fiber 0.16 Poly(phenylene sulfide) 40% glass fiber 0.288 30% carbon fiber 0.28–0.75 Polypropylene 40% talc 0.32 40% CaCO3 0.29 40% glass fiber 0.37 Polystyrene 20% glass fiber 0.25 Poly(styrene-acrylonitrile) copolymer 20% glass fiber 0.28 Poly(styrene-butadiene) copolymer (SBR) 33% carbon black 0.300 Polytetrafluoroethylene 25% glass fiber 0.33–0.41 Poly(urea-formaldehyde) resin 33% a-cellulose 0.423

2.800

TABLE 2.90 Resistance of Selected Polymers and Rubber to Various Chemicals at 20°C The information in this table is intended to be used only as a general guide. The chemical resistance classifications are E = excellent (30 days of exposure causes no damage), G = good (some damage after 30 days), F = fair (exposure may cause crazing, softening, swelling, or loss of strength), N = not recommended (immediate damage may occur).

TABLE 2.91 Gas Permeability Constants (1010 P) at 25°C for Polymers and Rubber The gas permeability constant P is P=

amount of permeant (area) × (time) × (driving forced across the film)

The gas permeability constant is the amount of gas expressed in cubic centimeters passed in 1 s through a 1−cm2 area of film when the pressure across a film thickness of 1 cm is 1 cmHg and the temperature is 25°C. All tabulated values are multiplied by 1010 and are in units of seconds−1 (centimeters of Hg)−1. Other temperatures are indicated by exponents and are expressed in degrees Celsius.

2.801

(Continued)

2.802

TABLE 2.91 Gas Permeability Constants (1010 P) at 25°C for Polymers and Rubber (Continued)

TABLE 2.92 Vapor Permeability Constants (1010 P) at 35°C for Polymers

2.803

2.804

SECTION TWO

TABLE 2.93 Hildebrand Solubility Parameters of Polymers Polymer Cellulose Cellulose diacetate Cellulose nitrate (11.83% N) Epoxy resin Natural rubber Poly(4-acetoxystyrene) Poly(acrylic acid) —, butyl ester —, methyl ester Poly(acrylonitrile) Poly(butadiene) Poly(butadiene-co-acrylonitrile) BUNA N (72/55) (61/39) Poly(butadiene-co-styrene) BUNA S (85/15) Poly(butadiene-co-vinylpyridine) (75/25) Poly(chloroprene)

Poly(dimethyl siloxane) Poly(ethylene) Poly(ethylene) Poly(ethylene-co-vinyl-acetate) Poly(tetra-fluoroethylene) Poly(heptamethylene p,p′-bibenzoate) Poly(4-hydroxystyrene) Poly(isobutene)

Poly(isobutene-co-isoprene) butyl rubber Poly(isoprene) 1,4-cis

Poly(methacrylic acid) —, isobutyl ester —, ethyl ester —, methyl ester Poly(methacrylonitrile) Poly(methylene) poly(a-methyl styrene)

d (MPa1/2) 32.02 23.22 21.44 22.3 16.2 17.09 22.7

T (°C)

Calc. Calc.

25

18.0 18.52 20.77 20.7 26.09 16.2 17.15

35

18.93 20.5

25 75

25 75

17.41 17.39 19.13 18.42 19.19 17.6 14.9 16.6 16.4 16.2 18.6 17.0 12.7 19.50 23.9 16.06 16.47 16.06 16.47

Method

Visc.

Swelling Swelling Swelling Calc. IPGC Calc. Calc. IPGC Calc. Obs.

25

30

25 75 25 25 35

Calc. Swelling Calc. Calc. Calc. Obs. IPGC IPGC Calc. Visc. Visc. Av. Swelling

25

15.18 16.68 16.57 20.46 16.6 16.68

25 25 35 35

14.7 18.31 18.58 21.9 14.3 18.75

140

25

Calc.

Swelling Swelling Calc. IPGC Swelling

25 20 30

Calc. Extrap. Visc.

ORGANIC CHEMISTRY

2.805

TABLE 2.93 Hildebrand Solubility Parameters of Polymers (Continued) Polymer Poly(s-methylstyrene-co-acrylonitrile) Poly(oxyethylene) Poly(propylene) Poly(styrene) Poly(styrene-co-n-butyl-methacrylate) Poly(thioethylene) Poly(vinyl acetate) Poly(vinyl alcohol) Poly(vinyl chloride) Poly(vinyl chloride), chlorinated Poly(vinyl propionate)

d (MPa1/2) 16.4 20.2 18.8 18.72 15.1 19.19 19.62 25.78 19.28 19.8 19.0 18.01

T (°C)

Method

180 25 25 35 140

IPGC IPGC

IPGC Swelling Calc.

25

Calc. Obs. Visc.

25 35

TABLE 2.94 Hansen Solubility Parameters of Polymers Polymer (trade name, supplier) Acrylonitrile-butadiene elastomer (Hycar 1052, BF Goodrich) Alcohol soluble resin (Pentalyn 255, Hercules) Alcohol soluble resin (Pentalyn 830, Hercules) Alkyd, long oil (66% oil length, Plexal P65, Polyplex) Alkyd, short oil (Coconut oil 34% phthalic anhydride; Plexal C34) Blocked isocyanate (Phenol, Suprasec F5100, ICI) Cellulose acetate (Cellidore A, Bayer) Cellulose nitrate (1/2 s; H-23, Hagedon) Epoxy (Epikote 1001, Shell) Ester gum (Ester gum BL, Hercules) Furfuryl alcohol resin (Durez 14383, Hooker Chemical) Hexamethoxymethyl melamine (Cymel 300 American Cyanimid) Isoprene elastomer (Cariflex IR 305, Shell) Methacrylonitrile/methacrylic acid copolymer Nylon 66 Nylon 66 (Zytel, DuPont) Petroleum hydrocarbon resin (Piceopale 110, Penn. Ind. Chem.)

Solubility parameter (MPa1/2) dd

dp

dh

dt

18.6

8.8

4.2

21.0

17.5

9.3

14.3

24.4

20.5

5.8

10.9

23.5

20.42

3.44

4.56

21.20

18.50

9.21

4.91

21.24

20.19

13.16

13.07

27.42

18.60

12.73

11.01

25.08

15.41

14.73

8.84

23.08

20.36

12.03

11.48

26.29

19.64

4.73

7.77

21.65

21.16

13.56

12.81

28.21

20.36

8.53

10.64

24.51

16.57 17.39 18.62

1.41 14.32 5.11

−0.82 12.28 12.28

16.65 25.78 22.87

18.62

0.00

14.12

23.37

17.55

11.19

3.60

17.96 (Continued)

2.806

SECTION TWO

TABLE 2.94 Hansen Solubility Parameters of Polymers (Continued) Polymer (trade name, supplier) Phenolic resin (Resole, Phenodur 373 U Chemische Werke Albert) Phenolic resin, pure (Super Beckacite 1001, Reichhold) Poly(4-acetoxy,a-acetoxy styrene) Poly(4-acetoxystyrene) Poly (acrylonitrile) Polyamid, thermoplastic (Versamid 930, General Mills) Poly(p-benzamide) cis-Poly(butadiene)elastomer (Bunahuls CB10, Chemische Werke Huels) Poly(isobutylene) (Lutonal IC/123, BASF) Poly(ethyl methacrylate) (Lucite 2042, DuPont) Poly(ethylene terephthalate) Poly(4-hydroxystyrene) Poly(methacrylic acid) Poly(methacrylonitrile) Poly(methyl methacrylate) Poly(sulfone), Bisphenol A (Polystyrene LG, BASF) Poly(sulfone), Bisphenol A (Udel) Poly(vinyl acetate) (Mowilith 50, Hoechst) Poly(vinyl butyral) (Butvar B76, Shawinigan) Poly(vinyl chloride) (Vipla KR K = 50, Montecatini) Poly(vinyl chloride) Poly(vinyl chloride) Saturated polyester (Desmophen 850, Bayer) Styrene-butadiene (SBR) raw elastomer (Polysar 5630, Polymer Corp.) Terpene resin (Piccolyte S-1000, Penn. Ind. Chem.) Urea-formaldehyde resin (Plastopal H, BASF) Vinylidene cyanide/4-acetoxy,a-acetoxy styrene copolymer Vinylidene cyanide/4-chloro-styrene copolymer (Rohm and Haas) Poly(styrene)

Solubility parameter (MPa1/2) dd

dp

dh

dt

19.74

11.62

14.59

27.15

23.26 17.80 17.80 18.21

6.55 10.23 9.00 16.16

8.35 7.37 8.39 6.75

25.57 21.89 21.69 25.27

17.43 18.0

−1.92 11.9

14.89 7.9

23.02 23.0

17.53

2.25

3.42

18.00

14.53

2.52

4.66

15.47

17.60 19.44 17.60 17.39 18.00

9.66 3.48 10.03 12.48 15.96

3.97 8.59 13.71 15.96 7.98

20.46 21.54 24.55 26.80 25.37

21.28

5.75

4.30

22.47

19.03

0.00

6.96

20.26

20.93

11.27

9.66

25.66

18.60

4.36

13.03

23.12

18.23 18.72 18.82

7.53 10.03 10.03

8.35 3.07 3.07

21.42 21.46 21.54

21.54

14.94

12.28

28.95

17.55

3.36

2.70

18.07

16.47

0.37

2.84

16.72

20.81 21.48 16.98 18.64

8.29 11.25 12.07 10.52

12.71 7.16 8.18 7.51

25.74 21.89 22.38 22.69

ORGANIC CHEMISTRY

2.807

TABLE 2.95 Refractive Indices of Polymers

Polymer name Acetal homopolymer Acrylics Ally diglycol carbonate Cellulose acetate Cellulose acetate butyrate Cellulose ester Cellulose nitrate Cellulose propionate Chlorotrifluoroethylene (CTFE) Diallyl isophthalate Epoxies Ethyl cellulose Fluorinated ethylene-propylene Methylpentene polymer Nylon Phenol formaldehyde Phenoxy polymer Polyacetal Polyallomer Polyallyl methacrylate Polyamide nylon 6/6 Polyamide nylon 11 Polybutylene Polycarbornate Poly(cyclohexyl methacrylate) Poly(diallyl phthalate) Polyester Poly(ester-styrene) Polyethylene (low density)

Refractive index (20°C, 68°F) 1.48 1.49–1.52 1.50 1.46–1.50 1.46–1.49 1.47–1.50 1.49–1.51 1.46–1.49 1.42 1.57 1.55–1.65 1.47 1.34 1.485 1.52–1.53 1.50–1.70 1.60 1.48 1.49 1.52 1.53 1.52 1.50 1.57–1.59 1.51 1.57 1.53–1.58 1.54–1.57 1.51

Polymer name Polyethylene (medium Density) Polyethylene (high density) Polyethylene dimethacrylate Poly(ethylene terephthalate) Poly(methyl-α−chloroacrylate) Poly(methyl methacrylate) Polypropylene Poly(propyl methacrylate) Polystyrene Polysulfone Poly(tetrafluoroethylene) (PTFE) Poly(trifluorochloroethylene) Poly(trifluoroethylene) Poly(vinyl alcohol) Poly(vinyl acetal) Poly(vinyl acetate) Poly(vinyl butyral) Poly(vinyl chloride) Poly(vinyl cyclohexene dioxide) Poly(vinyl formal) Poly(vinyl naphthalene) Poly(vinylidene chloride) Poly(vinylidene fluoride) Silicone polymer Styrene acrylonitrile copolymer Styrene butadiene thermoplastic Styrene methacrylate copolymer Urea formaldehyde Urethane

Refractive index (20°C, 68°F) 1.52 1.54 1.51 1.57–1.58 1.52 1.49 1.49 1.48 1.57–1.60 1.63 1.35 1.43 1.35–1.37 1.49–1.53 1.48 1.46–1.47 1.49 1.52–1.55 1.53 1.60 1.68 1.60–1.63 1.42 1.43 1.56–1.57 1.52–1.55 1.53 1.54–1.58 1.50–1.60

2.21 FATS, OILS, AND WAXES Fats, oils, and waxes belong to the group of naturally occurring organic materials called lipids. Lipids are those constituents of plants or animals that are insoluble in water but soluble in other organic solvents. The fats and oils of vegetable and animal origin belong to the class of triglycerides, i.e., fatty acid tri-esters of glycerol. The component fatty acid (acyl) radicals can be saturated or unsaturated. Their chain lengths, degrees of unsaturation, and relative positions in the molecule determine the character of the fat or fatty oil. Thus a triglyceride of the (saturated) plamitic or stearic acids (i.e., solid fatty acids with sixteen and eighteen carbon atoms respectively) will be a solid. Oleic acid is liquid at room temperature; it is an unsaturated fatty acid with eighteen carbon atoms and one double bond. It occurs in olive oil, also in peanut and sesame oils. Linseed oil contains linoleic and linolenic acids (in addition to oleic, plamitic, and stearic acids). These acids are still more unsaturated in character; there are two double bonds in the molecule of linoleic acid, and three in that of linolenic acid. Waxes are usually the plastic substances deposited by insects or obtained from plants. Waxes are esters of various fatty acids with higher, usually monohydric alcohols. The wax of pharmacy is principally yellow wax (beeswax), the material of which honeycomb is made. It consists chiefly of cerotic acid and myricin and is used in making ointments, cerates, etc. Other waxes include petroleum wax that is a mixture of paraffin hydrocarbons that melts above room temperature.

2.808

TABLE 2.96 Physical Properties of Fats and Oils

2.809

2.810 TABLE 2.97 Physical Properties of Waxes

ORGANIC CHEMISTRY

2.811

2.22 PETROLEUM PRODUCTS Petroleum is an extremely complex naturally occurring mixture of hydrocarbon compounds, usually with minor amounts of nitrogen-, oxygen-, and sulfur-containing compounds as well as trace amounts of metal-containing compounds. Petroleum products are, for example, fuels and lubricants that are manufactured from petroleum as well as other products of industrial interest. Petrochemicals are also manufactured from petroleum.

TABLE 2.98

Physical Properties of Petroleum Products Molecular weight

Specific gravity

Benzene n-Butane iso-Butane n-Butene iso-Butene Diesel fuel Ethane Ethylene Fuel oil No. 1 Fuel oil No. 2 Fuel oil No.4 Fuel oil No.5 Fuel oil No. 6 Gasoline n-Hexane n-Heptane

78.1 58.1 58.1 56.1 56.1 170–198 30.1 28.0

0.879 0.601

Kerosene Methane Naphthalene Neohexane Neopentane n-Octane iso-Octane n-Pentane iso-Pentane n-pentene Propane Propylene Toluene Xylene

154.0 16.0 128.2 86.2 72.1 114.2 114.2 72.1 72.1 70.1 44.1 42.2 92.1 106.2

198.0

113.0 86.2 100.2

0.595 0.875 0.572 0.875 0.920 0.959 0.960 0.960 0.720 0.659 0.668 0.800 0.553 0.649 0.707 0.702 0.626 0.621 0.641

0.867 0.861

Boiling point, °F

Ignition temperature, °F

Flash point, °F

Flammability limits in air, % v/v

176.2 31.1 10.9 21.2 19.6

1040 761 864 829 869

1.35–6.65 1.86–8.41 1.80–8.44 1.98–9.65 1.8–9.0

−127.5 −154.7 304–574

959 914 410 494 505

100–400 155.7 419.0

536 437 419

12 −76 −117 Gas Gas 100–130 Gas Gas 100–162 126–204 142–240 156–336 150 −45 −7 25

304–574 −258.7 424.4 121.5 49.1 258.3 243.9 97.0 82.2 86.0 −43.8 −53.9 321.1 281.1

410 900–1170 959 797 841 428 837 500 788 569 842 856 992 867

100–162 Gas 174 −54 Gas 56 10 −40 −60 –– Gas Gas 40 63

3.0–12.5 2.8–28.6 0.7–5.0

1.4–7.6 1.25–7.0 1.00–6.00 0.7–5.00 5.0–15.0 0.90–5.90 1.19–7.58 1.38–7.11 0.95–32 0.79–5.94 1.40–7.80 1.31–9.16 1.65–7.70 2.1–10.1 2.00–11.1 1.27–6.75 1.00–6.00

SECTION 3

SPECTROSCOPY

SECTION 3

SPECTROSCOPY 3.1 INFRARED ABSORPTION SPECTROSCOPY Table 3.1 Absorption Frequencies of Single Bonds to Hydrogen Table 3.2 Absorption Frequencies of Triple Bonds Table 3.3 Absorption Frequencies of Cumulated Double Bonds 3.1.1 Intensities of Carbonyl Bands 3.1.2 Position of Carbonyl Absorption Table 3.4 Absorption Frequencies of Carbonyl Bands Table 3.5 Absorption Frequencies of Other Double Bonds Table 3.6 Absorption Frequencies of Aromatic Bands Table 3.7 Absorption Frequencies of Miscellaneous Bands Table 3.8 Absorption Frequencies in the Near Infrared Table 3.9 Infrared Transmitting Materials Table 3.10 Infrared Transmission Characteristics of Selected Solvents Table 3.11 Values of Absorbance for Percent Absorption Table 3.12 Transmittance-Absorbance Conversion Table Table 3.13 Wave number/Wavelength Conversion Table 3.2 RAMAN SPECTROSCOPY Table 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon Table 3.15 Raman Frequencies of Triple Bonds Table 3.16 Raman Frequencies of Cumulated Double Bonds Table 3.17 Raman Frequencies of Carbonyl Bands Table 3.18 Raman Frequencies of Other Double Bonds Table 3.19 Raman Frequencies of Aromatic Compounds Table 3.20 Raman Frequencies of Sulfur Compounds Table 3.21 Raman Frequencies of Ethers Table 3.22 Raman Frequencies of Halogen Compounds Table 3.23 Raman Frequencies of Miscellaneous Compounds Table 3.24 Principal Argon-Ion Laser Plasma Lines 3.3 ULTRAVIOLET-VISIBLE SPECTROSCOPY Table 3.25 Electronic Absorption Bands for Representative Chromophores Table 3.26 Ultraviolet Cutoffs of Spectrograde Solvents Table 3.27 Absorption Wavelength of Dienes Table 3.28 Absorption Wavelength of Enones and Dienones Table 3.29 Solvent Correction for Ultraviolet-Visible Spectroscopy Table 3.30 Primary Bands of Substituted Benzene and Heteroaromatics Table 3.31 Wavelength Calculation of the Principal Band of Substituted Benzene Derivatives 3.4 FLUORESCENCE SPECTROSCOPY Table 3.32 Fluorescence Spectroscopy of Some Organic Compounds Table 3.33 Fluorescence Quantum Yield Values 3.5 FLAME ATOMIC EMISSION, FLAME ATOMIC ABSORPTION, ELECTROTHERMAL (FURNACE) ATOMIC ABSORPTION, ARGON INDUCTION COUPLED PLASMA, AND PLASMA ATOMIC FLUORESCENCE 3.51 Common Spectroscopic Relationships Table 3.34 Detection Limits in ng/mL Table 3.35 Sensitive Lines of the Elements

3.3 3.3 3.9 3.10 3.11 3.12 3.12 3.16 3.19 3.20 3.26 3.28 3.29 3.31 3.33 3.36 3.37 3.38 3.42 3.43 3.44 3.46 3.48 3.50 3.51 3.52 3.53 3.53 3.54 3.55 3.56 3.57 3.58 3.58 3.59 3.59 3.60 3.61 3.63

3.64 3.64 3.67 3.72

3.1

3.2

SECTION THREE

3.6 NUCLEAR MAGNETIC RESONANCE Table 3.36 Nuclear Properties of the Elements Table 3.37 Proton Chemical Shifts Table 3.38 Estimation of Chemical Shift for Protons of CH2 and Methine Groups Table 3.39 Estimation of Chemical Shift of Proton Attached to a Double Bond Table 3.40 Chemical Shifts in Mono-substituted Benzene Table 3.41 Proton Spin Coupling Constants Table 3.42 Proton Chemical Shifts of Reference Compounds Table 3.43 Solvent Positions of Residual Protons in Incompletely Deuterated Solvents Table 3.44 Carbon-13 Chemical Shifts Table 3.45 Estimation of Chemical Shifts of Alkane Carbons Table 3.46 Effect of Substituent Groups on Alkyl Chemical Shifts Table 3.47 Estimation of Chemical Shifts of Carbon Attached to a Double Bond Table 3.48 Carbon-13 Chemical Shifts in Substituted Benzenes Table 3.49 Carbon-13 Chemical Shifts in Substituted Pyridines Table 3.50 Carbon-13 Chemical Shifts of Carbonyl Group Table 3.51 One-Bond Carbon-Hydrogen Spin Coupling Constants Table 3.52 Two-Bond Carbon-Hydrogen Spin Coupling Constants Table 3.53 Carbon-Carbon Spin Coupling Constants Table 3.54 Carbon-Fluorine Spin Coupling Constants Table 3.55 Carbon-13 Chemical Shifts of Deuterated Solvents Table 3.56 Carbon-13 Coupling Constants with Various Nuclei Table 3.57 Boron-11 Chemical Shifts Table 3.58 Nitrogen-15 (or Nitrogen-14) Chemical Shifts Table 3.59 Nitrogen-15 Chemical Shifts in Mono-substituted Pyridine Table 3.60 Nitrogen-15 Chemical Shifts for Standards Table 3:61 Nitrogen-15 to Hydrogen-1 Spin Coupling Constants Table 3.62 Nitrogen-15 to Carbon-13 Spin Coupling Constants Table 3.63 Nitrogen-15 to Fluorine-19 Spin Coupling Constants Table 3.64 Fluorine-19 Chemical Shifts Table 3.65 Fluorine-19 Chemical Shifts for Standards Table 3.66 Fluorine-19 to Fluorine-19 Spin Coupling Constants Table 3.67 Silicon-29 Chemical Shifts Table 3.68 Phosphorus-31 Chemical Shifts Table 3.69 Phosphorus-31 Spin Coupling Constants 3.7 MASS SPECTROMETRY 3.7.1 Correlation of Mass Spectra with Molecular Structure 3.7.2 Mass Spectra and Structure Table 3.70 Isotopic Abundances and Masses of Selected Elements Table 3.71 Table of Mass Spectra 3.8 X-RAY METHODS Table 3.72 Wavelengths of X-Ray Emission Spectra in Angstroms Table 3.73 Wavelengths of Absorption Edges in Angstroms Table 3.74 Critical X-Ray Absorption Energies in keV Table 3.75 X-Ray Emission Energies in keV Table 3.76 b Filters for Common Target Elements Table 3.77 Interplanar Spacing for Ka, Radiation, d versus 20 Table 3.78 Analyzing Crystals for X-Ray Spectroscopy Table 3.79 Mass Absorption Coefficients for K1 Lines and W La, Line

3.76 3.77 3.80 3.83

3.83 3.84 3.85 3.86 3.86 3.87 3.90 3.90 3.91 3.92 3.93 3.94 3.95 3.96 3.96 3.97 3.98 3.98 3.99 3.100 3.103 3.103 3.104 3.104 3.104 3.105 3.106 3.106 3.106 3.107 3.110 3.111 3.111 3.113 3.115 3.115 3.126 3.128 3.130 3.133 3.135 3.138 3.138 3.139 3.140

SPECTROSCOPY

3.3

3.1 INFRARED ABSORPTION SPECTROSCOPY Infrared (IR) absorption spectroscopy is a common technique that is used to identify the major functional groups in a compound. The identification of these groups depends upon the amount of infrared radiation absorbed and the particular frequency (measured in cm−1, wave-numbers) at which these groups absorb. Thus, infrared absorption spectroscopy is the measurement of the wavelength and intensity of the absorption of mid-infrared light by a sample. Mid-infrared light (2.5 – 50 mm, 4000 – 200 cm−1) is energetic enough to excite molecular vibrations to higher energy levels. The wavelength of many infrared absorption bands are characteristic of specific types of chemical bonds, and infrared spectroscopy finds its greatest utility for qualitative analysis of organic and organometallic molecules. Infrared spectroscopy is used to confirm the identity of a particular compound and as a tool to help determine the structure of a molecule. Significant for the identification of the source of an absorption band are intensity (weak, medium or strong), shape (broad or sharp), and position (cm−1) in the spectrum. Characteristic examples are provided in the table below to assist the user in becoming familiar with the intensity and shape absorption bands for representative absorptions.

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, strong

var, of variable strength w, weak w–m, weak to moderately strong

(Continued)

3.4

SECTION THREE

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued) Group

Band, cm−1 Alkane residues attached to carbon (continued)

Remarks

SPECTROSCOPY

3.5

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued) Group

Band, cm−1

Remarks

Alkane residues attached to miscellaneous atoms (continued)

(Continued)

3.6

SECTION THREE

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued) Group

Band, cm−1

Remarks

Alkane residues attached to miscellaneous atoms (continued)

SPECTROSCOPY

3.7

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued) Group

Band, cm−1

Remarks

(Hydroxyl group O[H compounds) (Continued)

(Continued)

3.8

SECTION THREE

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued) Group

Band, cm−1 Amine, imine, ammonium, and amide N[H

Remarks

SPECTROSCOPY

3.9

TABLE 3.1 Absorption Frequencies of Single Bonds to Hydrogen (Continued) Group

Band, cm−1

Remarks

Amine, imine, ammonium, and Miscellaneous R[H

TABLE 3.2 Absorption Frequencies of Triple Bonds Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, strong

var, of variable strength w–m, weak to moderately strong

(Continued)

3.10

SECTION THREE

TABLE 3.2 Absorption Frequencies of Triple Bonds (Continued) Group

Band, cm−1

Remarks

*Conjugation with olefinic or acetylenic groups lowers the frequency and raises the intensity. Conjugation with carbonyl groups usually has little effect on the position of absorption.

TABLE 3.3 Absorption Frequencies of Cumulated Double Bonds Abbreviations Used in the Table m–s, moderate to strong vs, very strong s, strong w, weak

SPECTROSCOPY

3.11

TABLE 3.3 Absorption Frequencies of Cumulated Double Bonds (Continued) Group

Band, cm−1

Remarks

3.1.1 Intensities of Carbonyl Bands Acids generally absorb more strongly than esters, and esters more strongly than ketones or aldehydes. Amide absorption is usually similar in intensity to that of ketones but is subject to much greaer variations.

3.12

SECTION THREE

3.1.2 Position of Carbonyl Absorption The general trends of structural variation on the position of C˙O stretching frequencies may be summarized as follows: 1. The more electronegative the group X in the system R[CO[X[, the higher is the frequency. 2. a, b Unsaturation causes a lowering of frequency of 15 to 40 cm−1, except in amides, where little shift is observed and that usually to higher frequency. 3. Further conjugation has relatively little effect. 4. Ring strain in cyclic compounds causes a relatively large shift to higher frequency. This phenomenon provides a remarkably reliable test of ring size, distinguishing clearly between four-, five-, and larger-membered-ring ketones, lactones, and lactams. Six-ring and larger ketones, lactones, and lactams show the normal frequency found for the open-chain compounds. 5. Hydrogen bonding to a carbonyl group causes a shift to lower frequency of 40 to 60 cm−1. Acids, amides, enolized b-keto carbonyl systems, and o-hydroxyphenol and o-aminophenyl carbonyl compounds show this effect. All carbonyl compounds tend to give slightly lower values for the carbonyl stretching frequency in the solid state compared with the value for dilute solutions. 6. Where more than one of the structural influences on a particular carbonyl group is operating, the net effect is usually close to additive.

TABLE 3.4 Absorption Frequencies of Carbonyl Bands All bands quoted are strong.

SPECTROSCOPY

3.13

TABLE 3.4 Absorption Frequencies of Carbonyl Bands (Continued) Groups

Band, cm−1

Remarks

(Continued)

3.14

SECTION THREE

TABLE 3.4 Absorption Frequencies of Carbonyl Bands (Continued) Groups

Band, cm−1

Remarks

SPECTROSCOPY

TABLE 3.4 Absorption Frequencies of Carbonyl Bands (Continued) Groups

Band, cm−1

Remarks

3.15

3.16

SECTION THREE

TABLE 3.5 Absorption Frequencies of Other Double Bonds Abbreviations Used in the Table m, moderately strong m–s, moderate to strong var, of variable strength

vs, very strong w, weak

SPECTROSCOPY

3.17

TABLE 3.5 Absorption Frequencies of Other Double Bonds (Continued) Group

Band, cm−1 Imines, oximes, and amidines

Remarks C˙N[ (Continued)

(Continued)

3.18

SECTION THREE

TABLE 3.5 Absorption Frequencies of Other Double Bonds (Continued) Group

Band, cm−1 Nitro compounds N˙O (Continued)

Remarks

SPECTROSCOPY

TABLE 3.6 Absorption Frequencies of Aromatic Bands Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, srong

var, of variable strength w–m, weak to moderately strong

3.19

3.20

SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, strong var, of variable strength

vs, very strong w, weak w–m, weak to moderately strong

SPECTROSCOPY

3.21

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued) Group

Band, cm−1

Remarks

Sulfur compounds

(Continued)

3.22

SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued) Group

Band, cm−1 Sulfur compounds (Continued)

Remarks

SPECTROSCOPY

3.23

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued) Group

Band, cm−1

Remarks

Phosphorus compounds (Continued)

(Continued)

3.24

SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued) Group

Band, cm−1 Boron compounds (Continued)

Remarks

SPECTROSCOPY

3.25

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued) Group

Band, cm−1

Remarks

Halogen compounds (Continued)

(Continued)

3.26

SECTION THREE

TABLE 3.7 Absorption Frequencies of Miscellaneous Bands (Continued) Band, cm−1

Group

Inorganic ions (Continued)

TABLE 3.8 Absorption Frequencies in the Near Infrared Values in parentheses are molar absorptivity.

Remarks

SPECTROSCOPY

3.27

TABLE 3.8 Absorption Frequencies of the Near Infrared (Continued) Class

Band, cm−1

Remarks

(Continued)

3.28

SECTION THREE

TABLE 3.8 Absorption Frequencies of the Near Infrared (Continued) Class

TABLE 3.9 Infrared Transmitting Materials

Band, cm−1

Remarks

SPECTROSCOPY

3.29

TABLE 3.9 Infrared Transmitting Materials (Continued)

* Usual for internal reflection work.

TABLE 3.10 Infrared Transmission Characteristics of Selected Solvents Transmission below 80%, obtained with a 0.10-mm cell path, is shown as shaded area.

(Continued)

3.30

SECTION THREE

TABLE 3.10 Infrared Transmission Characteristics of Selected Solvents (Continued)

SPECTROSCOPY

3.31

TABLE 3.10 Infrared Transmission Characteristics of Selected Solvents (Continued)

TABLE 3.11 Values of Absorbance for Percent Absorption To convert percent absorption (% A) to absorbance, find the present absorption to the nearest whole digit in the left-hand column; read across to the column located under the tenth of a percent desired, and read the value of absorbance. The value of absorbance corresponding to 26.8% absorption is thus 0.1355.

3.32

SECTION THREE

TABLE 3.11 Values of Absorbance for Percent Absorption (Continued) %A

.0

.1

.2

.3

.4

.5

.6

.7

.8

.9

SPECTROSCOPY

3.33

TABLE 3.11 Values of Absorbance for Percent Absorption (Continued) %A

.0

.1

.2

.3

.4

.5

.6

.7

.8

.9

TABLE 3.12 Transmittance-Absorbance Conversion Table This table gives absorbance values to four significant figures corresponding to % transmittance values, which are given to three significant figures. The values of % transmittance are given in the left-hand column and in the top row. For example, 8.4% transmittance corresponds to an absorbance of 1.076. Interpolation is facilitated and accuracy is maximized if the % transmittance is between 1 and 10, by multiplying its value by 10, finding the absorbance corresponding to the result, and adding 1. For example, to find the absorbance corresponding to 8.45% transmittance, note that 84.5% transmittance corresponds to an absorbance of 0.0731, so that 8.45% transmittance corresponds to an absorbance of 1.0731. For % transmittance values between 0.1 and 1, multiply by 100, find the absorbance corresponding to the result, and add 2. Conversely, to find the % transmittance corresponding to an absorbance between 1 and 2, subtract 1 from the absorbance, find the % transmittance corresponding to the result, and divide by 10. For example, an absorbance of 1.219 can best be converted to % transmittance by noting that an absorbance of 0.219 would correspond to 60.4% transmittance; dividing this by 10 gives the desired value, 6.04% transmittance. For absorbance values between 2 and 3, subtract 2 from the absorbance, find the % transmittance corresponding to the result, and divide by 100.

(Continued)

3.34

SECTION THREE

TABLE 3.12 Transmittance-Absorbance Conversion Table (Continued) % Transmittance

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

SPECTROSCOPY

3.35

TABLE 3.12 Transmittance-Absorbance Conversion Table (Continued) % Transmittance

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

3.36

SECTION THREE

TABLE 3.13 Wavenumber/Wavelength Conversion Table This table is based on the conversion: wavenumber (in cm−1) = 10,000/wavelength (in mm). For example, 15.4 mm is equal to 649 cm−1.

SPECTROSCOPY

3.37

3.2 RAMAN SPECTROSCOPY Raman spectroscopy is the measurement of the wavelength and intensity of inelastically scattered light from molecules. The Raman scattered light occurs at wavelengths that are shifted from the incident light by the energies of molecular vibrations. The mechanism of Raman scattering is different from that of infrared absorption but Raman and IR spectra provide complementary information for the identification of organic functionalities. Raman spectra arise from the absorption of monochromatic light by a sample before it is emitted as scattered light. As in infrared spectra, Raman spectra are recorded in wavenumbers. Frequently a Raman spectrum will reveal something that was missed in the infrared spectrum. This is because a bond that has no dipole moment (i.e., it is electrically symmetrical) will appear in the Raman spectrum but will not appear in the infrared spectrum. Typical applications for Raman spectroscopy are in structure determination, multicomponent qualitative analysis, and quantitative analysis. The Raman scattering transition moment is: R = < Xi ∂ a ∂ Xj > where Xi and Xj are the initial and final states, respectively, and a is the polarizability of the molecule: a = ao + (r−re)(da/dr) + ... higher terms where r is the distance between atoms and ao is the polarizability at the equilibrium bond length, re. Polarizability can be defined as the ease of which an electron cloud can be distorted by an external electric field. Since ao is a constant and < Xi ∂ Xj > = 0, R simplifies to: R = < Xi ∂ (r − re)(da/dr) ∂ Xj > The result is that there must be a change in polarizability during the vibration for that vibration to inelastically scatter radiation. The polarizability depends on how tightly the electrons are bound to the nuclei. In the symmetric stretch the strength of electron binding is different between the minimum and maximum internuclear distances. Therefore the polarizability changes during the vibration and this vibrational mode scatters Raman light (the vibration is Raman active). In the asymmetric stretch the electrons are more easily polarized in the bond that expands but are less easily polarized in the bond that compresses. There is no overall change in polarizability and the asymmetric stretch is Raman inactive. Raman line intensities are proportional to: ν⋅ s(ν) ⋅I⋅ exp(−Ei /kT) ⋅ C where ν is the frequency of the incident radiation, s (ν) is the Raman cross section (typically 10−29 cm2), I is the radiation intensity, exp(−Ei /kT) is the Boltzmann factor for state i, and C is the analyte concentration.

3.38

SECTION THREE

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon Abbreviations Used in the Table m, moderately strong m–s, moderate to strong m–vs, moderate to very strong s, strong vs, very strong

vw, very weak w, weak w–m, weak to moderately strong w–vs, weak to very strong

SPECTROSCOPY

3.39

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued) Group

Band, cm−1

Remarks

Saturated C[H and C[C (Continued)

(Continued)

3.40

SECTION THREE

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued) Group

Band, cm−1 Saturated C[H and C[C (Continued)

Remarks

SPECTROSCOPY

3.41

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued) Group

Band, cm−1

Remarks

Saturated C[H (Continued)

(Continued)

3.42

SECTION THREE

TABLE 3.14 Raman Frequencies of Single Bonds to Hydrogen and Carbon (Continued) Group

Band, cm−1 N[H and C[N Bonds (Continued)

TABLE 3.15 Raman Frequencies of Triple Bonds Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, strong

s–vs, strong to very strong vs, very strong

Remarks

SPECTROSCOPY

3.43

TABLE 3.15 Raman Frequencies of Triple Bonds (Continued) Group

Band, cm−1

Remarks

TABLE 3.16 Raman Frequencies of Cumulated Double Bonds Abbreviations Used in the Table s, strong vs, very strong

vw, very weak w, weak

(Continued)

3.44

SECTION THREE

TABLE 3.16 Raman Frequencies of Cumulated Double Bonds (Continued) Group

Band, cm−1

Remarks

TABLE 3.17 Raman Frequencies of Carbonyl Bands Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, strong

s–vs, strong to very strong vs, very strong w, weak

SPECTROSCOPY

TABLE 3.17 Raman Frequencies of Carbonyl Bands (Continued) Group

Band, cm−1

Remarks

3.45

3.46

SECTION THREE

TABLE 3.18 Raman Frequencies of Other Double Bonds Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, strong w–m, weak to moderately strong

vs, very strong w, weak s–vs, strong to very strong

SPECTROSCOPY

3.47

TABLE 3.18 Raman Frequencies of Other Double Bonds (Continued) Group

Band, cm−1

Remarks

(Continued)

3.48

SECTION THREE

TABLE 3.18 Raman Frequencies of Other Double Bonds (Continued) Band, cm−1

Group Nitroalkanes Primary

Secondary

Remarks

1560–1548 (m–s) 1395–1370 (s) 915–898 (m–s) 894–873 (m–s) 618–609 (w) 640–615 (w) 494–472 (w–m) 1553–1547 (m) 1375–1360 (s) 908–868 (m) 863–847 (s) 625–613 (m) 560–516 (s)

Tertiary

Sensitive to substitutes attached to CNO2 group

Shoulder Broad; useful to distinguish from secondary nitroalkanes

Sharp band

1543–1533 (m) 1355–1345 (s)

Nitrogen oxides +

−

N→O

1612–1602 (s) 1252 (m) 1049–1017 (s) 835 (s) 541 (w) 469 (w)

TABLE 3.19 Raman Frequencies of Aromatic Compounds Abbreviations Used in the Table m, moderately strong m–s, moderate to strong m–vs, moderate to very strong s, strong s–vs, strong to very strong

var, of variable strength vs, very strong w, weak w–m, weak to moderately strong

SPECTROSCOPY

TABLE 3.19 Raman Frequencies of Aromatic Compounds (Continued) Group

Band, cm−1

Remarks

Substitution patterns of the benzene ring (Continued)

3.49

3.50

SECTION THREE

TABLE 3.20 Raman Frequencies of Sulfur Compounds Abbreviations Used in the Table m, moderately strong m–s, moderate to strong s, strong

s–vs, strong to very strong vs, very strong w–m, weak to moderately srong

SPECTROSCOPY

TABLE 3.20 Raman Frequencies of Sulfur Compounds (Continued) Group

Band, cm−1

Remarks

TABLE 3.21 Raman Frequencies of Ethers Abbreviations Used in the Table m, moderately strong s, strong

[O[O[

800–770 (var)

var, of variable strength vs, very strong

3.51

3.52

SECTION THREE

TABLE 3.22 Raman Frequencies of Halogen Compounds Abbreviations Used in the Table m–s, moderate strong s, strong

var, of variable strength vs, very strong

SPECTROSCOPY

3.53

TABLE 3.23 Raman Frequencies of Miscellaneous Compounds Abbreviations Used in the Table m–s, moderately strong s, strong

vs, very strong vvs, very very strong

TABLE 3.24 Principal Argon-Ion Laser Plasma Lines

(Continued)

3.54

SECTION THREE

TABLE 3.24 Principal Argon-Ion Laser Plasma Lines (Continued)

3.3 ULTRAVIOLET SPECTROSCOPY Ultraviolet spectroscopy involves the excitation of an electron in its ground state level to a higher energy level. This is accomplished by irradiating a sample with ultraviolet light (electromagnetic radiation with wavelengths in the range of 200 nanometers (nm) to 400 nm). The wavelength of maximum absorption (lmax) can be calculated by using Woodward’s Rules. lmax has a specific degree of absorbance associated with it. The absorbance at a particular wavelength is dependent upon the intensity or molar absorbtivity, e, of the incident light. The molar absorbtivity is related to the absorbance: e = log (I0 /I)/c.l where I0 is the initial light intensity, I is the final light intensity, c is the concentration of sample in moles per liter, l is the path length of sample tube in centimeters. Beer’s Law relates the absorbance A to I0 and I (A = log [I0/I]). Hence the equation for molar absorbtivity is: e = A/c.l where A is the absorbance at lmax. Molecules with two or more isolated chromophores (absorbing groups) absorb light of nearly the same wavelength as does a molecule containing only a single chromophore of a particular type. The

SPECTROSCOPY

3.55

intensity of the absorption is proportional to the number of that type of chromophore present in the molecule. The solvent chosen must dissolve the sample, yet be relatively transparent in the spectral region of interest. In order to avoid poor resolution and difficulties in spectrum interpretation, a solvent should not be employed for measurements that are near the wavelength of or are shorter than the wavelength of its ultraviolet cutoff, that is, the wavelength at which absorbance for the solvent alone approaches one absorbance unit. Appreciable interaction between chromophores does not occur unless they are linked directly to each other, or forced into close proximity as a result of molecular stereochemical configuration. Interposition of a single methylene group, or meta orientation about an aromatic ring, is sufficient to insulate chromophores almost completely from each other. Certain combinations of functional groups afford chromophoric systems that give rise to characteristic absorption bands. Sets of empirical rules, often referred to as Woodward’s Rules or the Woodward-Fieser Rules, enable the absorption maxima of dienes and enones and dienones to be predicted. To the respective base values (absorption wavelength of parent compound) are added the increments for the structural features or substituent groups present. When necessary, a solvent correction is also applied. Ring substitution on the benzene ring affords shifts to longer wavelengths and intensification of the spectrum. With electron-withdrawing substituents, practically no change in the maximum position is observed. The spectra of heteroaromatics are related to their isocyclic analogs, but only in the crudest way. As with benzene, the magnitude of substituent shifts can be estimated, but tautomeric possibilities may invalidate the empirical method. When electronically complementary groups are situated para to each other in disubstituted benzenes, there is a more pronounced shift to a longer wavelength than would be expected from the additive effect due to the extension of the chromophore from the electron-donating group through the ring to the electron-withdrawing group. When the para groups are not complementary, or when the groups are situated ortho or meta to each other, disubstituted benzenes show a more or less additive effect of the two substituents on the wavelength maximum. TABLE 3.25 Electronic Absorption Bands for Representative Chromophores Chromophore

System

λmax

⑀max

(Continued)

3.56

SECTION THREE

TABLE 3.25 Electronic Absorption Bands for Representative Chromophores (Continued) Chromophore

System

λmax

⑀max

SPECTROSCOPY

3.57

TABLE 3.26 Ultraviolet Cutoffs of Spectrograde Solvents

TABLE 3.27 Absorption Wavelength of Dienes Heteroannular and acyclic dienes usually display molar absorptivities in the 8000 to 20,000 range, whereas homoannular dienes are in the 5000 to 8000 range. Poor correlations are obtained for cross-conjugated polyene systems such as

The correlations presented here are sometimes referred to as Woodward’s rules or the Woodward-Fieser rules.

3.58

SECTION THREE

TABLE 3.28 Absorption Wavelength of Enones and Dienones

TABLE 3.29 Solvent Correction for Ultraviolet-Visible Spectroscopy Solvent Chloroform Cyclohexane Diethyl ether 1,4-Dioxane Ethanol Hexane Methanol Water

Correction, nm +1 +11 +5 0 +11 0 −8

SPECTROSCOPY

3.59

TABLE 3.30 Primary Bands of Substituted Benzene and Heteroaromatics In methanol. Base value: 203.5 nm

TABLE 3.31 Wavelength Calculation of the Principal Band of Substituted Benzene Derivatives In ethanol.

(Continued)

3.60

SECTION THREE

TABLE 3.31 Wavelength Calculation of the Principal Band of Substituted Benzene Derivatives (Continued)

*Value may be decreased markedly by steric hindrance to coplanarity.

3.4 FLUORESCENCE SPECTROSCOPY Fluorescence spectroscopy is a measure of the optical emission from atoms that have been excited to higher energy levels by absorption of electromagnetic radiation. The main advantage of fluorescence detection compared to absorption measurements is the greater sensitivity achievable because the fluorescence signal has a very low background. The resonant excitation provides selective excitation of the analyte to avoid interferences. Fluorescence spectroscopy is useful to study the electronic structure of atoms and to make quantitative measurements. Analytical applications include flames and plasmas diagnostics, and enhanced sensitivity in atomic analysis. Because of the differences in the nature of the energy-level structure between atoms and molecules, discussion of laser-induced fluorescence from molecules is found in a separate document. Analysis of solutions or solids requires that the analyte atoms be desolvated, vaporized, and atomized at a relatively low temperature in a heat pipe, flame, or graphite furnace. A hollow-cathode lamp or laser provides the resonant excitation to promote the atoms to higher energy levels. The atomic fluorescence is dispersed and detected by monochromators and photomultiplier tubes, similar to atomic-emission spectroscopy instrumentation. TABLE 3.32 Fluorescene Spectroscopy of Some Organic Compounds

SPECTROSCOPY

3.61

TABLE 3.32 Fluorescene Spectroscopy of Some Organic Compounds (Continued)

(Continued)

3.62

SECTION THREE

TABLE 3.32 Fluorescene Spectroscopy of Some Organic Compounds (Continued)

SPECTROSCOPY

TABLE 3.32 Fluorescene Spectroscopy of Some Organic Compounds (Continued)

TABLE 3.33 Fluorescene Quantum Yield Values

* POPOP, p-bis[2-(5-phenyloxazoyl)]benzene. † ANS, anilino-8-naphthalene sulfonic acid. ‡ TNS, 2-p-toluidinylnaphthalene-6-sulfonate.

3.63

3.64

SECTION THREE

3.5 FLAME ATOMIC EMISSION, FLAME ATOMIC ABSORPTION, ELECTROTHERMAL (FURNACE) ATOMIC ABSORPTION, ARGON INDUCTION COUPLED PLASMA, AND PLASMA ATOMIC FLUORESCENCE The tables of atomic emission and atomic absorption lines are presented in two parts. In Table 3.34 the data are arranged in alphabetic order by name of the element, whereas in Table 3.35 the sensitive lines of the elements are arranged in order of decreasing wavelengths. The detection limits in the table correspond generally to the concentration of an element required to give a net signal equal to three times the standard deviation of the noise (background) in accordance with IUPAC recommendations. Detection limits can be confusing when steady-state techniques such as flame atomic emission or absorption, and plasma atomic emission or fluorescence, are compared with the electrothermal or furnace technique which uses the entire sample and detects an absolute amount of the analyte element. To compare the several methods on the basis of concentration, the furnace detection limits assume a 20-mL sample. Data for the several flame methods assume an acetylene–nitrous oxide flame residing on a 5- or 10-cm slot burner. The sample is nebulized into a spray chamber placed immediately ahead of the burner. Detection limits are quite dependent on instrument and operating variables, particularly the detector, the fuel and oxidant gases, the slit width, and the method used for background correction and data smoothing. 3.5.1

Common Spectroscopic Relationships Electromagnetic Radiation. Electromagnetic radiation travels in straight lines in a uniform medium, has a velocity of 299,792,500 m ⋅ s−1 in a vacuum, and possesses properties of both a wave motion and a particle (photon). Wavelength l is the distance from crest to crest; frequency v is the number of waves passing a fixed point in a unit length of time. Wavelength and frequency are related by the relation c = lv where c is the velocity of light (in a vacuum). In any material medium the speed of propagation is smaller than this and is given by the product nc, where n is the refractive index of the medium. Radiation is absorbed or emitted only is discrete packets called photons and quanta: E = hv where E is the energy of the quantum and h is Planck’s constant. The relation between energy and mass is given by the Einstein equation: ∆E = ∆mc2 where ∆E is the energy release and ∆m is the loss of mass. Strictly, the mass of a particle depends on its velocity, but here the masses are equated to their rest masses (at zero velocity). The Wien displacement law states that the wavelength of maximum emission lm of a blackbody varies inversely with absolute temperature; the product lmT remains constant. When lm is expressed in micrometers, the law becomes lmT = 2898 In terms of sm, the wavenumber of maximum emission: sm = 3.48T Another useful version is hvm = 5kT, where k is the Boltzmann constant. Stefan’s law states that the total energy J radiated by a blackbody per unit time and area (power per unit area) varies as the fourth power of the absolute temperature: J = aT −4 where a is a constant whose value is 5.67 × 10−8 W ⋅ m−2 ⋅ K−4.

SPECTROSCOPY

3.65

The relationship between the voltage of an X-ray tube (or other energy source), in volts, and the wavelength is given by the Duane-Hunt equation: l=

hc 12, 398 = V eV

where the wavelength is expressed in angstrom units. Laws of Photometry. The time rate at which energy is transported in a beam of radiant energy is denoted by the symbol P0 for the incident beam, and by P for the quantity remaining unabsorbed after passage through a sample or container. The ratio of radiant power transmitted by the sample to the radiant power incident on the sample is the transmittance T: T=

P P0

The logarithm (base 10) of the reciprocal of the transmittance is the absorbance A: 1 A = − log T = log   T When a beam of monochromatic light, previously rendered plane parallel, enters an absorbing medium at right angles to the plane-parallel surfaces of the medium, the rate of decrease in radiant power with the length of light path (cuvette interior) b, or with the concentration of absorbing material C (in grams per liter) will follow the exponential progression, often referred to as Beer’s law: T = 10−abC

or

A = abC

where a is the absorptivity of the component of interest in the solution. When C is expressed in moles per liter, T = 10−⑀bC

or

A = ⑀bC

where e is the molar absorptivity. The total fluorescence (or phosphorescence) intensity is proportional to the quanta of light absorbed, P0 – P, and to the efficiency f, which is the ratio of quanta absorbed to quanta emitted: F = (P0 – P)f = P0f (1 – e-⑀bC) When the terms ebC is not greater than 0.05 (or 0.01 in phosphorescence), F = kfP0⑀bC where the term k has been introduced to handle instrumental artifacts and the geometry factor because fluorescence (and phosphorescence) is emitted in all directions but is viewed only through a limited aperture. The thickness of a transparent film or the path length of infrared absorption cells b, in centimeters, is given by b=

1  n    2 nD  ν1 − ν 2 

where n is the number of fringes (peaks or troughs) between two wavenumbers n–1 and n–2, and nD is the refractive index of the sample material (unity for the air path of an empty cuvette). If measurements are made in wavelength, as micrometers, the expression is b=

1 2 nD

 n l 1l 2   −   l 2 l1

3.66

SECTION THREE

Grating Equation. The light incident on each groove is diffracted or spread out over a range of angles, and in certain directions reinforcement or constructive interference occurs, as stated in the grating formula: ml = b(sin i ± sinr) where b is the distance between adjacent grooves, i is the angle of incidence, r is the angle of reflection (both angles relative to the grating normal), and m is the order number. A positive sign applies where incoming and emergent beams are on the same side of the grating normal. The blaze wavelength is that wavelength for which the angle of reflectance from the groove face and the angle of reflection (usually the angle of incidence) from the grating are identical. The Bragg equation ml = 2d sinq states the condition for reinforcement of reflection from a crystal lattice, where d is the distance between each set of atomic planes and q is the angle of reflection. Ionization of Metals in a Plasma. A loss in spectrochemical sensitivity results when a free metal atom is split into a positive ion and an electron: M = M+ + e− The degree of ionization ai is defined as l=

hc 12, 398 = eV V

At equilibrium, when the ionization and recombination rates are balanced, the ionization constant Ki (in atm) is given by Ki =

[M + ][e − ]  α i2  =  PΣM [M]  1 − α i2 

where PΣM (in atm) is the total atom concentration of metal in all forms in the plasma. The ionization constant can be calculated from the Saha equation: log Ki = −5040

g +g − Ei 5 + log T − 6.49 + log Μ e T 2 gΜ

where Ei is the ionization potential of the metal in eV (Table 4.2), T is the absolute temperature of the plasma (in kelvins), and the g terms are the statistical weights of the ionized atom, the electron, and the neutral atom. For the alkali metals the final term is zero; for the alkaline earth metals, it is 0.6. To suppress the ionization of a metal, another easily ionized metal (denoted a deionizer or radiation buffer) is added to the sample. To ensure that ionization is suppressed for the test element, the product (Ki)MPM of the deionizer must exceed the similar product for the test element one hundredfold (for 1 percent residual ionization of the test element).

SPECTROSCOPY

3.67

TABLE 3.34 Detection Limits in ng/mL The detection limits in the table correspond generally to the concentration of analyte required to give a net signal equal to three times the standard deviation of the background in accordance with IUPAC recommendations.

(Continued)

3.68

SECTION THREE

TABLE 3.34 Detection Limits in ng/mL (Continued)

SPECTROSCOPY

3.69

TABLE 3.34 Detection Limits in ng/mL (Continued)

(Continued)

3.70

SECTION THREE

TABLE 3.34 Detection Limits in ng/mL (Continued)

SPECTROSCOPY

TABLE 3.34 Detection Limits in ng/mL (Continued)

3.71

3.72

SECTION THREE

TABLE 3.35 Sensitive Lines of the Elements In this table the sensitive lines of the elements are arranged in order of decreasing wavelengths. A Roman numeral II following an element designation indicates a line classified as being emitted by the singly ionized atom. In the column headed Sensitivity, the most sensitive line of the nonionized atom is indicated by U1, and other lines by U2, U3, and so on, in order of decreasing sensitivity. For the singly ionized atom the corresponding designations are V1, V2, V3, and so on.

SPECTROSCOPY

3.73

TABLE 3.35 Sensitive Lines of the Elements (Continued)

(Continued)

3.74

SECTION THREE

TABLE 3.35 Sensitive Lines of the Elements (Continued)

SPECTROSCOPY

3.75

TABLE 3.35 Sensitive Lines of the Elements (Continued)

(Continued)

3.76

SECTION THREE

TABLE 3.35 Sensitive Lines of the Elements (Continued)

3.6 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY Nuclear magnetic resonance (NMR) spectroscopy is based on the principle that nuclei absorb radiation of slightly different frequency depending upon their local magnetic environments. Certain atoms have a nuclear spin similar to the spin of an electron. The spinning of charged particles (the proton or protons in the nucleus bears a positive charge) generates a magnetic field. When an atom is placed in an external magnetic field, the magnetic field generated by the nucleus will be aligned with or against the external magnetic field. At some frequency of electromagnetic radiation, the nucleus will absorb energy and “flip” over so that it reverses its alignment with respect to the external magnetic field. This is known as the nuclear magnetic resonance (NMR) phenomenon. It is generally concerned with the nuclear magnetic resonance of hydrogen atoms and is therefore sometimes called proton magnetic resonance (PMR). It is also standard practice for the frequency of radiation to be kept constant while the strength of the external magnetic field is varied. At some value of the magnetic field strength, the energy required to flip the proton matches the energy of the radiation. Absorption will occur and a signal will be observed. The spectrum that results from all these absorptions is called an NMR spectrum. Absorptions that occur at relatively low field strengths are downfield relative to those that occur at higher field strengths. The field strength at which a proton will absorb energy is called the chemical shift (measured in parts per million, ppm or 6, relative to the absorbance of tetramethylsilane). The chemical shift of a proton depends upon the proton’s electronic environment. Electron withdrawing atoms (or groups) that are nearby a proton will decrease the electron density about that proton; this is known as a deshielding effect. The proton’s absorption will occur downfield from what is expected. Specifically, the proton will absorb at a smaller field strength than a proton experiencing no deshielding effects. Electron releasing atoms (or groups) that are nearby a proton will increase the proton’s electron density; the proton is experiencing a shielding effect. The proton’s absorbance will occur upfield (higher magnetic field strength) from what is expected. The signal that arises from a proton’s absorption may occur as a singlet, a doublet, a triplet, etc. The number of peaks in the signal depends upon the neighboring protons. Protons that are in identical electronic environments are equivalent protons; those that are in nonidentical electronic environments are nonequivalent protons. A proton that has n nonequivalent adjacent protons will have a signal with n + 1 peaks, called an n + 1 multiplet. This is the result of spin-spin splitting of the protons. The differences in resonance frequencies are very small. For instance, the difference in resonance frequency for the protons in chloromethane and fluoromethane is 72 Hz. Since the incident radiation had a frequency of 60 MHz, this difference is about 1 part per million. This cannot be measured accurately; therefore, differences are measured as the difference between the resonant frequency of a reference compound and the substance to be analyzed. The most common reference is tetramethylsilane (CH3)4Si, TMS. Thus, when a compound is analyzed, the resonance of each individual proton is reported in terms of how far (in Hz) the proton is shifted from the protons of tetramethylsilane. The shift from tetramethylsilane for a given proton depends upon the strength of the applied magnetic field. The protons in tetramethylsilane resonate at 0 ppm. Most protons in organic compounds

SPECTROSCOPY

3.77

will resonate at higher frequencies and the position of the absorbance gives valuable information about the molecular environment of a particular proton, leading to structural information about the compound under investigation. The nucleus of carbon-13 is magnetic. This property enables detection of the nuclei of carbon-13 atoms by nuclear magnetic resonance. By detecting the location of carbon-13 atoms in carbon-based molecules, structural information about the molecules can also be produced. Other nuclei of different atoms can also be detected and structural information deduced.

TABLE 3.36 Nuclear Properties of the Elements In the following table the magnetic moment m is in multiples of the nuclear magneton mN (eh/4pMc) with diamagnetic correction. The spin I is in multiples of h/2p, and the electric quadrupole moment Q is in multiples of 10−28 square meters. Nuclei with spin 1/2 have no quadrupole moment. Sensitivity is for equal numbers of nuclei at constant field. NMR frequency at any magnetic field is the entry for column 5 multiplied by the value of the magnetic field in kilogauss. For example, in a magnetic field of 23.490 kG, protons will process at 4.2576 × 23.490 kG = 100.0 MHz. Radionuclides are denoted with an asterisk. The data were extracted from M. Lederer and V. S. Shirley, Table of Isotopes, 7th ed., Wiley-Interscience, New York, 1978; A. H. Wapstra and G. Audi, “The 1983 Atomic Mass Evaluation,” Nucl. Phys. A432:1–54 (1985); V. S. Shirley, ed., Table of Radioactive Isotopes, 8th ed., Wiley-Interscience, New York, 1986; and P. Raghavan, “Table of Nuclear Moments,” At. Data Nucl. Data Tables, 42:189 (1989).

(Continued)

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TABLE 3.36 Nuclear Properties of the Elements (Continued)

SPECTROSCOPY

3.79

TABLE 3.36 Nuclear Properties of the Elements (Continued)

(Continued)

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TABLE 3.36 Nuclear Properties of the Elements (Continued)

TABLE 3.37 Proton Chemical Shifts Values are given on the officially approved d scale; t = 10.00 – d Abbreviations Used in the Table R, alkyl group

Ar, aryl group

SPECTROSCOPY

3.81

TABLE 3.37 Proton Chemical Shifts (Continued)

(Continued)

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SECTION THREE

TABLE 3.37 Proton Chemical Shifts (Continued)

Unsaturated cyclic systems

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3.83

TABLE 3.38 Estimation of Chemical Shift for Protons of CH2 and Methine Groups dCH2 = 0.23 + C1 + C2

dCH = 0.23 + C1 + C2 + C3

*R, alkyl group; Ar, aryl group; Ph, phenyl group.

TABLE 3.39 Estimation of Chemical Shift of Proton Attached to a Double Bond Positive Z values indicate a downfield shift, and an arrow indicates the point of attachment of the substituent group to the double bond.

(Continued)

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TABLE 3.39 Estimation of Chemical Shift of Proton Attached to a Double Bond (Continued)

TABLE 3.40 Chemical Shifts in Monosubstituted Benzene d = 7.27 + ∆i

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3.85

TABLE 3.40 Chemical Shifts in Monosubstituted Benzene (Continued)

*X = Cl, alkyl, OH, or NH2.

TABLE 3.41 Proton Spin Coupling Constants

(Continued)

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TABLE 3.41 Proton Spin Coupling Constants (Continued)

TABLE 3.42 Proton Chemical Shifts of Reference Compounds Relative to tetramethylsilane.

*DMSO, dimethyl sulfoxide.

TABLE 3.43 Solvent Positions of Residual Protons in Incompletely Deuterated Solvents Relative to tetramethylsilane.

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TABLE 3.43 Solvent Positions of Residual Protons in Incompletely Deuterated Solvents (Continued) Solvent

Group

d, ppm

tert-Butanol-d1 (CH3)3COD Chloroform-d1 Cyclohexane-d12 Deuterium oxide Dimethyl-d6-formamide-d1

Methyl Methine Methylene Hydroxyl Methyl Formyl Methyl Absorbed water Methylene Methyl Methyl Hydroxyl Methylene C-2 Methine C-3 Methine C-4 Methine Methyl Methine Hydroxyl

1.28 7.25 1.40 4.7* 2.75; 2.95 8.05 2.51 3.3* 3.55 2.60 3.35 4.8* 5.35 8.5 7.0 7.35 2.3 7.2 11.3*

Dimethyl-d6 sulfoxide 1,4-Dioxane-d8 Hexamethyl-d18-phosphoramide Methanol-d4 Dichloromethane-d2 Pyridine-d5

Toluene-d8 Trifluoroacetic acid-d1

*These values may vary greatly, depending upon the solute and its concentration.

TABLE 3.44 Carbon-13 Chemical Shifts Values given in ppm on the d scale, relative to tetramethylsilane.

(Continued)

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TABLE 3.44 Carbon-13 Chemical Shifts (Continued)

Next Page SPECTROSCOPY

TABLE 3.44 Carbon-13 Chemical Shifts (Continued) Unsaturated cyclic systems (Continued)

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TABLE 3.45 Estimation of Chemical Shifts of Alkane Carbons Relative to tetramethylsilane. Positive terms indicate a downfield shift. dc = −2.6 + 9.1na + 9.4nb − 2.5ng + 0.3nd + 0.1n⑀

(plus any correction factors)

where na is the number of carbons bonded directly to the ith carbon atom and nb, ng , nd , and n⑀ are the number of carbon atoms two, three, four, and five bonds removed. The constant is the chemical shift for methane.

TABLE 3.46 Effect of Substituent Groups on Alkyl Chemical Shifts These increments are added to the shift value of the appropriate carbon atom as calculated from Table 3.45.

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TABLE 3.46 Effect of Substituent Groups on Alkyl Chemical Shifts (Continued)

[I [NH2 [NH3+ [NHR [NR2 [NR3+ [NO2 [CN [SH [SR [CH˙CH2 [C6H5 [CæCH

−8 29.3 26 36.9 42 31 63 4 11 20 20 23 4.5

4 24 24 31

11.3 11.3 8 8.3 6 5 4 3 12 7 6 9 5.5

57 1 11

17

12 10 6 6

4 3 11

7

−1.0 −4.6 −5 −3.5 −3 −7 −3 −6 −3 −0.5 −2 −3.5

*R, alkyl group; Ar, aryl group.

TABLE 3.47 Estimation of Chemical Shifts of Carbon Attached to a Double Bond The olefinic carbon chemical shift is calculated from the equation dc = 123.3 + 10.6na + 7.2nb − 7.9na − 1.8nb

(plus any steric correction terms)

where n is the number of carbon atoms at the particular position, namely, b

a

a¢

b¢

C[C˙C[C Substituents on both sides of the double bond are considered separately. Additional vinyl carbons are treated as if they were alkyl carbons. The method is applicable to alicyclic alkenes; in small rings carbons are counted twice, i.e., from both sides of the double bond where applicable. The constant in the equation is the chemical shift for ethylene. The effect of other substituent groups is tabulated below.

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TABLE 3.47 Estimation of Chemical Shifts of Carbon Attached to a Double Bond (Continued)

TABLE 3.48 Carbon-13 Chemical Shifts in Substituted Benzenes dc = 128.5 + ∆

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TABLE 3.49 Carbon-13 Chemical Shifts in Substituted Pyridines* dC(k) = Ck + ∆i

* May be used for disubstituted, polyheterocyclic, and polynuclear systems if deviations due to steric and mesomeric effects are allowed for.

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TABLE 3.50 Carbon-13 Chemical Shifts Carbonyl Group O X C

Y

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TABLE 3.51 One-Bond Carbon-Hydrogen Spin Coupling Constants

(Continued)

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TABLE 3.51 One-Bond Carbon-Hydrogen Spin Coupling Constants (Continued) Structure

JCH, Hz

Structure

TABLE 3.52 Two-Bond Carbon-Hydrogen Spin Coupling Constants

TABLE 3.53 Carbon-Carbon Spin Coupling Constants

*R, alkyl group; Ar, aryl group.

JCH, Hz

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TABLE 3.53 Carbon-Carbon Spin Coupling Constants (Continued) Structure

JCC, Hz

Structure

JCC, Hz

*R, alkyl group; Ar, aryl group.

TABLE 3.54 Carbon-Fluorine Spin Coupling Constants

(Continued)

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TABLE 3.54 Carbon-Fluorine Spine Coupling Constants (Continued )

*Ar, aryl group; R, alkyl group.

TABLE 3.55 Carbon-13 Chemical Shifts of Deuterated Solvents Relative to tetramethylsilane.

TABLE 3.56 Carbon-13 Coupling Constants with Various Nuclei

3.99

SPECTROSCOPY

TABLE 3.56 Carbon-13 Coupling Constants with Various Nuclei (Continued) Nuclei

Structure

1

J, Hz

2

J, Hz

3

J, Hz

4

J, Hz

TABLE 3.57 Boron-11 Chemical Shifts Values given in ppm on the d scale, relative to B(OCH3)3.

(Continued)

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TABLE 3.57 Boron-11 Chemical Shifts (Continued) Values given in ppm on the d scale, relative to B(OCH3)3.

TABLE 3.58 Nitrogen-15 (or Nitrogen-14) Chemical Shifts Values given in ppm on the d scale, relative to NH3 liquid.

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TABLE 3.58 Nitrogen-15 (or Nitrogen-14) Chemical Shifts (Continued)

(Continued)

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TABLE 3.58 Nitrogen-15 (or Nitrogen-14) Chemical Shifts (Continued) Unsaturated cyclic systems (contined)

SPECTROSCOPY

TABLE 3.59 Nitrogen-15 Chemical Shifts in Mono-substituted Pyridine

d = 317.3 + ∆i

TABLE 3.60 Nitrogen-15 Chemical Shifts for Standards Values given in ppm, relative to NH3 liquid at 23°C.

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TABLE 3.61 Nitrogen-15 to Hydrogen-1 Spin Coupling Constants

TABLE 3.62 Nitrogen-15 to Carbon-13 Spin Coupling Constants

TABLE 3.63 Nitrogen-15 to Fluorine-19 Spin Coupling Constants

SPECTROSCOPY

TABLE 3.64 Fluorine-19 Chemical Shifts Values given in ppm on the d scale, relative to CCl3F.

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TABLE 3.65 Fluorine-19 Chemical Shifts for Standards

TABLE 3.66 Fluorine-19 to Fluorine-19 Spin Coupling Constants

TABLE 3.67 Silicon-29 Chemical Shifts Values given in ppm on the d scale relative to tetramethylsilane.

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TABLE 3.67 Silicon-29 Chemical Shifts (Continued)

TABLE 3.68 Phosphorus-31 Chemical Shifts Values given in ppm on the d scale, relative to 85% H3PO4.

(Continued)

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TABLE 3.68 Phosphorus-31 Chemical Shifts (Continued)

SPECTROSCOPY

TABLE 3.68 Phosphorus-31 Chemical Shifts (Continued)

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TABLE 3.69 Phosphorus-31 Spin Coupling Constants

SPECTROSCOPY

3.111

TABLE 3.69 Phosphorus-31 Spin Coupling Constants (Continued)

3.7 MASS SPECTROMETRY 3.7.1 Correlation of Mass Spectra with Molecular Structure Molecular Identification. In the identification of a compound, the most important information is the molecular weight. The mass spectrometer is able to provide this information, often to four decimal places. One assumes that no ions heavier than the molecular ion form when using electronimpact ionization. The chemical ionization spectrum will often show a cluster around the nominal molecular weight. Several relationships aid in deducing the empirical formula of the parent ion (and also molecular fragments). From the empirical formula hypothetical molecular structures can be proposed, using the entries in the formula indices of Beilstein and Chemical Abstracts. Natural Isotopic Abundances. The relative abundances of natural isotopes produce peaks one or more mass units larger than the parent ion (Table 3.70(a)). For a compound CwHxOzNy, a formula allows one to calculate the percent of the heavy isotope contributions from a monoisotopic peak, PM, to the PM+1 peak: 100

PM +1 = 0.015 x + 1.11w + 0.37 y + 0.37z PM

Tables of abundance factors have been calculated for all combinations of C, H, N, and O up to mass 500 (J. H. Beynon and A. E. Williams, Mass and Abundance Tables for Use in Mass Spectrometry, Elsevier, Amsterdam, 1963). Compounds that contain chlorine, bromine, sulfur, or silicon are usually apparent from prominent peaks at masses 2, 4, 6, and so on, units larger than the nominal mass of the parent of fragment ion. For example, when one chlorine atom is present, the P + 2 mass peak will be about one-third the intensity of the parent peak. When one bromine atom is present, the P + 2 mass peak will be about the same intensity as the parent peak. The abundance of heavy isotopes is treated in terms of the binominal expansion (a + b)m, where a is the relative abundance of the light isotope, b is the relative abundance of the heavy isotope, and m is the number of atoms of the particular element present in the molecule. If two bromine atoms are present, the binominal expansion is (a + b)2 = a2 + 2ab + b2 Now substituting the percent abundance of each isotope (79Br and 81Br) into the expansion, (0.505)2 + 2(0.505)(0.495) + (0.495)2 gives

0.255 + 0.500 + 0.250

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which are the proportions of P:(P + 2) : (P + 4), a triplet that is slightly distorted from a 1 : 2 : 1 pattern. When two elements with heavy isotopes are present, the binomial expansion (a + b)m(c + d)n is used. Sulfur-34 enhances the P + 2 peak by 4.2%; silicon-29 enhances the P + 1 peak by 4.7% and the P + 2 peak by 3.1%. Exact Mass Differences. If the exact mass of the parent or fragment ions are ascertained with a high-resolution mass spectrometer, this relationship is often useful for combinations of C, H, N, and O (Table 3.70(b): Exact mass difference from nearest integral mass+ 0.0051z − 0.0031y = number of hydrogens 0.0078 One substitutes integral numbers (guesses) for z (oxygen) and y (nitrogen) until the divisor becomes an integral multiple of the numerator within 0.0002 mass unit. For example, if the exact mass is 177.0426 for a compound containing only C, H, O, and N (Note the odd mass which indicates an odd number of nitrogen atoms), then 0.0426 + 0.0051z − 0.0031y = 7 hydrigen atoms 0.0078 when z = 3 and y = 1. The empirical formula is C9H7NO3 since 177 − 7(1) − 1(14) − 3(16) = 9 carbon atoms 12 Number of Rings and Double Bonds. The total number of rings and double bonds can be determined from the empirical formula (CwHxOzNy) by the relationship 1 2( 2 w − x + y + z ) when covalent bonds comprise the molecular structure. Remember the total number for a benzene ring is four (one ring and three double bonds); a triple bond has two. General Rules 1. If the nominal molecular weight of a compound containing only C, H, O, and N is even, so is the number of hydrogen atoms it contains. 2. If the nominal molecular weight is divisible by four, the number of hydrogen atoms is also divisible by four. 3. When the nominal molecular weight of a compound containing only C, H, O, and N is odd, the number of nitrogen atoms must be odd. Metastable Peaks. If the mass spectrometer has a field-free region between the exit of the ion source and the entrance to the mass analyzer, metastable peaks m* may appear as a weak, diffuse (often humped-shape) peak, usually at a nonintegral mass. The one-step decomposition process takes the general form: Original ion → daughter ion + neutral fragment

SPECTROSCOPY

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The relationship between the original ion and daughter ion is given by m* =

(mass of daughter ion)2 mass of original ion

For example, a metastable peak appeared at 147.9 mass units in a mass spectrum with prominent peaks at 65, 91, 92, 107, 108, 155, 172, and 200 mass units. Try all possible combinations in the above expression. The fit is given by 147.9 =

(172)2 200

which provides this information: 2001 → 172+ + 28 The probable neutral fragment lost is either CH2 ˙ CH2 or CO. 3.7.2 Mass Spectra and Structure The mass spectrum is a fingerprint for each compound because no two molecules are fragmented and ionized in exactly the same manner on electron-impact ionization. In reporting mass spectra the data are normalized by assigning the most intense peak (denoted as base peak) a value of 100. Other peaks are reported as percentages of the base peak. A very good general survey for interpreting mass spectral data is given by R. M. Silverstein, G. C. Bassler, and T. C. Morrill, Spectrometric Identification of Organic Compounds, 4th ed., Wiley, New York, 1981. Initial Steps in Elucidation of a Mass Spectrum 1. Tabulate the prominent ion peaks, starting with the highest mass. 2. Usually only one bond is cleaved. In succeeding fragmentations a new bond is formed for each additional bond that is broken. 3. When fragmentation is accompanied by the formation of a new bond as well as by the breaking of an existing bond, a rearrangement process is involved. These will be even mass peaks when only C, H, and O are involved. The migrating atom is almost exclusively hydrogen; six-membered cyclic transition states are most important. 4. Tabulate the probable groups that (a) give rise to the prominent charged ion peaks and (b) list the neutral fragments. General Rules for Fragmentation Patterns 1. Bond cleavage is more probable at branched carbon atoms: tertiary > secondary > primary. The positive charge tends to remain with the branched carbon. 2. Double bonds favor cleavage beta to the carbon (but see rule 6). 3. A strong parent peak often indicates a ring. 4. Saturated ring systems lose side chains at the alpha carbon. Upon fragmentation, two ring atoms are usually lost. 5. A heteroatom induces cleavage at the bond beta to it. 6. Compounds that contain a carbonyl group tend to break at this group; the positive charge remains with the carbonyl portion.

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7. For linear alkanes, the initial fragment lost is an ethyl group (never a methyl group), followed by propyl, butyl, and so on. An intense peak at mass 43 suggests a chain longer than butane. 8. The presence of Cl, Br, S, and Si can be deduced from the unusual isotopic abundance patterns of these elements. These elements can be traced through the positively charged fragments until the pattern disappears or changes due to the loss of one of these atoms to a neutral fragment. 9. When unusual mass differences occur between some fragments ions, the pressure of F (mass difference 19), I (mass difference 127), or P (mass difference 31) should be suspected. Characteristic Low-Mass Fragment Ions Mass 30 = Primary amines Masses 31, 45, 59 = Alcohol or ether Masses 19 and 31 = Alcohol Mass 66 = Monobasic carboxylic acid Masses 77 and 91 = Benzene ring Characteristic Low-Mass Neutral Fragments from the Molecular Ion = From alcohols, aldehydes, ketones = Fluorides = Aromatic nitriles or nitrogen heterocycles = Indicates either CHO or C2H5 = Indicates either CH2O or NO = Thiols = CH2CO via rearrangement from a methyl ketone or an aromatic acetate or an aryl-NHCOCH3 group Mass 43 = C3H7 or CH3CO Mass 45 = COOH or OC2H5

Mass 18 (H2O) Mass 19 (F) and 20 (HF) Mass 27 (HCN) Mass 29 Mass 30 Mass 33 (HS) and 34 (H2S) Mass 42

Table 3.71 is condensed, with permission, from the Catalog of Mass Spectral Data of the American Petroleum Institute Research Project 44. These, and other tables, should be consulted for further and more detailed information. Included in the table are all compounds for which information was available through the C7 compounds. The mass number for the five most important peaks for each compound are listed, followed in each case by the relative intensity in parentheses. The intensities in all cases are normalized to the n-butane 43 peak taken as 100. Another method for expressing relative intensities is to assign the base peak a value of 100 and express the relative intensities of the other peaks as a ratio to the base peak. Taking ethyl nitrate as an example, the tabulated values would be Ethyl nitrate

91(0.01)(P)

46(100)

29(44.2)

30(30.5)

76(24.2)

The compounds are arranged in the table according to their molecular formulas. Each formula is arranged alphabetically, except that C is first if carbon occurs in the molecules, followed by H if it occurs. The formulas are then arranged alphabetically and according to increasing number of atoms of each kind, all C4 compounds being listed before any C5 compounds, and so on. Nearly all these spectra have been recorded using 70-V electrons to bombard the sample molecules.

SPECTROSCOPY

TABLE 3.70 Isotopic Abundances and Masses of Selecteded Elements

TABLE 3.71 Table of Mass Spectra

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TABLE 3.71 Table of Mass Spectra (Continued)

SPECTROSCOPY

3.117

TABLE 3.71 Table of Mass Spectra (Continued)

(Continued)

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TABLE 3.71 Table of Mass Spectra (Continued)

SPECTROSCOPY

3.119

TABLE 3.71 Table of Mass Spectra (Continued)

(Continued)

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TABLE 3.71 Table of Mass Spectra (Continued)

SPECTROSCOPY

3.121

TABLE 3.71 Table of Mass Spectra (Continued)

(Continued)

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TABLE 3.71 Table of Mass Spectra (Continued)

SPECTROSCOPY

3.123

TABLE 3.71 Table of Mass Spectra (Continued)

(Continued)

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TABLE 3.71 Table of Mass Spectra (Continued)

SPECTROSCOPY

3.125

TABLE 3.71 Table of Mass Spectra (Continued)

(Continued)

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TABLE 3.71 Table of Mass Spectra (Continued)

Source: L. Meites, ed., Handbook of Analytical Chemistry, McGraw-Hill, New York, 1963. J. A. Dean, ed., Analytical Chemistry Handbook, McGraw-Hill, New York, 1995.

3.8 X-RAY METHODS An X-ray tube operating at a voltage V (in keV) emits a continuous X-ray spectrum, the minimum wavelength of which is given by l min = 12.398/V with the wavelength expressed in angstroms. For expressing the wavelength in kX units, divide by the factor 1.00202. Tables 3.72 and 3.73 are based on the K and L wavelength values as published by Y. Cauchois and H. Hulubei (Tables de Constantes et Données Numériques, I. Longueurs d’Onde des Émissions X et des Discontinuités d’Absorption X, Hermann, Paris, 1947) and by the International Union of Crystallography (International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, England, 1962). Wavelength accuracy is only to about 1 in 25 000 except for the lines employed in X-ray diffraction work. Use of energy-proportional detectors for X-rays creates a need for energy values of K and L absorption edges (Table 3.74) and emission series (Table 3.75). These values were obtained by a conversion to keV of tabulated experimental wavelength values and smoothed by a fit to Moseley’s law. Although values are listed to 1 eV, chemical form may shift absorption edges and emission lines as much as 10 to 20 eV. S. Fine and C. F. Hendee [Nucelonics, 13(3):36 (1955)] also give values for Kb2, Lg1, and Lb2 lines. The relative intensities of X-ray emission lines from targets varies for different elements. However, one can assume a ratio of Ka1/Ka2 = 2 for the commonly used targets. The ratio of Ka2/Ka1 from these targets varies from 6 to 3.5. The intensities of Kb2 radiations amount to about 1 percent of that of the corresponding Ka1 radiation. In practical applications these ratios have to be corrected for differential absorption in the window of the tube and air path, the ratio of scattering factors for and differential absorption in the crystal, and for sensitivity characteristics of the detector. Generalizing, the intensities of radiations from the K and L series are as follows:

SPECTROSCOPY

3.127

Emission line

Ka1

Ka2

Kb1

Kb2

La1

La2

Lb1

Lb2

Lg1

Relative intensity

500

250

80–150

5

100

10

30

60

40

For angles at which the Ka1, Ka2 doublet is not resolved, a mean wavelength [K α = (2Ka1 + Ka2)/3] can be used. Filters. The K spectra of the light metals, often used as target material in the production of X-rays for diffraction studies, contain three strong lines, α1, α2 and b1, of which the a lines form a doublet with a narrow wavelength separation. The Kb radiation can be eliminated by using a thin foil filter, usually of the element of next lower atomic number to that of the target element: the Ka lines are transmitted with a relatively small loss of intensity. Table 3.76, restricted to the K wavelengths of target elements in common use, lists the calculated thicknesses of b filters required to reduce the Kb1/Ka1 integrated intensity ratio to 1/100. Interplanar Spacings. Diffractometer alignment procedures require the use of a well-prepared polycrystalline specimen. Two standard samples found to be suitable are silicon amd α-quartz (including Novaculite). The 2q values of several of the most intense reflections for these materials are listed in Table 3.77 (Tables of Interplanar Spacings d vs. Diffraction Angle 2q for Selected Targets, Picker Nuclear, White Plains, N.Y., 1966). To convert to d for Ka or to d for Ka2, multiply the tabulated d value (Table 3.77) for Ka1 by the factor given below: Element

Kα

Ka2

W Ag Mo Cu Ni Co Fe Cr

1.007 69 1.002 63 1.002 02 1.000 82 1.000 77 1.000 72 1.000 67 1.000 57

1.023 07 1.007 89 1.006 04 1.002 48 1.002 32 1.002 16 1.002 04 1.001 70

Analyzing Crystals. The range of wavelengths usable with various analyzing crystals are governed by the d spacings of the crystal planes and by the geometric limits to which the goniometer can be rotated. The d value should be small enough to make the angle 2q greater than approximately 10 or 15 deg, even at the shortest wavelength used: otherwise excessively long analyzing crystals would be needed to prevent the direct fluorescent beam from entering the detector. A small d value is also favorable for producing a large dispersion of the spectrum to give good separation of adjacent lines. On the other hand, a small d value imposes an upper limit to the range of wavelengths that can be analyzed. Actually the goniometer is limited mechanically to about 150 deg for a 2q value. A final requirement is the reflection efficiency and minimization of higher-order reflections. Table 3.78 gives a list of crystals commonly used for X-ray spectroscopy. The long-wavelength analyzers are prepared by dipping an optical flat into the film of the metal fatty acid about 50 times to produce a layer 180 molecules in thickness. Lithium fluoride is the optimum crystal for all wavelengths less than 3 Å. Pentaerythritol (PET) and potassium hydrogen phthalate (KAP) are usually the crystals of choice for wavelengths from 3 to 20 Å. Two crystals suppress even-ordered reflections: silicon (111) and calcium fluoride (111). Mass Absorption Coefficients. Radiation traversing a layer of substance is diminished in intensity by a constant fraction per centimeter thickness x of material. The emergent radiant power P, in terms of incident radiant power P0, is given by P = P0 exp (−mx) which defines the total linear absorption coefficient m. Since the reduction of intensity is determined by the quantity of matter traversed by the primary beam, the absorber thickness is best expressed on

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a mass basis, in g/cm2. The mass absorption coefficient m/r, expressed in units cm2/g, where r is the density of the material, is approximately independent of the physical state of the material and, to a good approximation, is additive with respect to the elements composing a substance. Table 3.79 contains values of m/r for the common target elements employed in X-ray work. A more extensive set of mass absorption coefficients for K, L, and M emission lines within the wavelength range from 0.7 to 12 Å is contained in K. F. J. Heinrich’s paper in T. D. McKinley, K. F. J. Heinrich, and D. B. Wittry (eds.), The Electron Microprobe, Wiley, New York, 1966, pp. 351-377. This article should be consulted to ascertain the probable accuracy of the values and for a compilation of coefficients and exponents employed in the computations.

TABLE 3.72 Wavelengths of X-Ray Emission Spectra in Angstroms Atomic No.

Element

Ka2

Ka1

Kb1

La1

Lb1

SPECTROSCOPY

3.129

TABLE 3.72 Wavelengths of X-Ray Emission Spectra in Angstroms (Continued) Atomic No.

Element

Ka2

Ka1

Kb1

La1

Lb1

(Continued)

3.130

SECTION THREE

TABLE 3.72 Wavelengths of X-Ray Emission Spectra in Angstroms (Continued) Atomic No.

Element

Ka2

Ka1

Kb1

La1

Lb1

TABLE 3.73 Wavelengths of Absorption Edges in Angstroms Atomic No.

Element

K

LI

LII

LIII

SPECTROSCOPY

3.131

TABLE 3.73 Wavelengths of Absorption Edges in Angstroms (Continued) Atomic No.

Element

K

LI

LII

LIII

(Continued)

3.132

SECTION THREE

TABLE 3.73 Wavelengths of Absorption Edges in Angstroms (Continued) Atomic No.

Element

K

L1

L11

L111

SPECTROSCOPY

3.133

TABLE 3.74 Critical X-Ray Absorption Energies in KeV Atomic No.

Element

K

L1

L11

L111

(Continued)

3.134

SECTION THREE

TABLE 3.74 Critical X-Ray Absorption Energies in KeV (Continued) Atomic No.

Element

K

L1

L11

L111

SPECTROSCOPY

3.135

TABLE 3.74 Critical X-Ray Absorption Energies in KeV (Continued) Atomic No.

Element

K

L1

L11

L111

TABLE 3.75 X-Ray Emission Energies in KeV

(Continued)

3.136

SECTION THREE

TABLE 3.75 X-Ray Emission Energies in KeV (Continued) Atomic No.

Element

Kb1

Ka1

Lb1

La1

SPECTROSCOPY

3.137

TABLE 3.75 X-Ray Emission Energies in KeV (Continued) Atomic No.

Element

Kb1

Ka1

Lb1

La1

3.138

SECTION THREE

TABLE 3.76 b Filters for Common Target Elements

TABLE 3.77 Interplanar Spacing for Ka, Radiation, d versus 20

SPECTROSCOPY

TABLE 3.78 Analyzing Crystals for X-Ray Spectroscopy

3.139

3.140

SECTION THREE

TABLE 3.79 Mass Absorption Coefficients for Ka1 Lines and W La, Line

SPECTROSCOPY

3.141

TABLE 3.79 Mass Absorption Coefficients for K1 Lines and W La1, Line (Continued)

(Continued)

3.142

SECTION THREE

TABLE 3.79 Mass Absorption Coefficients for K1 Lines and W La1, Line (Continued)

SECTION 4

GENERAL INFORMATION AND CONVERSION TABLES

SECTION 4

GENERAL INFORMATION AND CONVERSION TABLES 4.1 GENERAL INFORMATION Table 4.1 SI Prefixes Table 4.2 Greek Alphabet 4.2 PHYSICAL CONSTANTS AND CONVERSION FACTORS Table 4.3 Physical Constants Table 4.4 Conversion Factors 4.3 CONVERSION OF THERMOMETER SCALES Table 4.5 Temperature Conversion 4.4 DENSITY AND SPECIFIC GRAVITY Table 4.6 Hydrometer Conversion 4.5 BAROMETRY AND BAROMETRIC CORRECTIONS Table 4.7 Barometer Temperature Correction––Metric Units Table 4.8 Barometric Latitude-Gravity––Metric Units Table 4.9 Barometric Correction for Gravity––Metric Units Table 4.10 Reduction of the Barometer to Sea Level-Metric Units Table 4.11 Pressure Conversion Table 4.12 Conversion of Weighings in Air to Weighings in Vacuo Table 4.13 Factors for Reducing Gas Volumes to Normal (Standard) Temperature and Pressure (760 mmHg) 4.6 VISCOSITY Table 4.14 Viscosity Conversion 4.7 PHYSICAL CHEMISTRY EQUATIONS EQUATIONS FOR GASES 4.7.1 Equations of State (PVT Relations for Real Cases) 4.7.2 Properties of Gas Molecules Table 4.15 Molar Equivalent of One Liter of Gas at Various Temperatures and Pressures Table 4.16 Corrections to Be Added to Molar Values to Convert to Molal 4.8 COOLING Table 4.17 Cooling Mixtures Table 4.18 Molecular Lowering of the Melting or Freezing Point 4.9 DRYING AND HUMIDIFICATION Table 4.19 Drying Agents Table 4.20 Solutions for Maintaining Constant Humidity Table 4.21 Concentration of Solutions of H2SO4, NaOH, and CaCl2 Giving Specified Vapor Pressures and Percent Humidity at 25°C Table 4.22 Relative Humidity from Wet and Dry Bulb Thermometer Readings Table 4.23 Relative Humidity from Dew Point Readings Table 4.24 Mass of Water Vapor in Saturated Air 4.10 MOLECULAR WEIGHT Table 4.25 Molecular Elevation of the Boiling Point 4.11 Heating Baths Table 4.26 Substances that Can Be Used for Heating Baths 4.12 SEPARATION METHODS Table 4.27 Solvents of Chromatographic Interest Table 4.28 McReynolds’ Constants for Stationary Phases in Gas Chromatography 4.12.1 McReynolds’ Constants Table 4.29 Characteristics of Selected Supercritical Fluids

4.3 4.3 4.4 4.4 4.4 4.8 4.28 4.29 4.41 4.45 4.47 4.48 4.51 4.53 4.54 4.58 4.59 4.61 4.66 4.66 4.67 4.68 4.69 4.70 4.73 4.73 4.73 4.74 4.75 4.75 4.76 4.77 4.77 4.79 4.80 4.81 4.81 4.83 4.83 4.83 4.84 4.86 4.83 4.94 4.1

4.2

SECTION FOUR

4.12.2 Chromatographic Behavior of Solutes Table 4.30 Typical Performances in HPLC for Various Conditions 4.12.3 Ion-Exchange (Normal Pressure, Columnar) Table 4.31 Ion-Exchange Resins Table 4.32 Relative Selectivity of Various Counter Cations Table 4.33 Relative Selectivity of Various Counter Anions 4.13 GRAVIMETRIC ANALYSIS Table 4.34 Gravimetric Factors Table 4.35 Elements Precipitated by General Analytical Reagents Table 4.36 Cleaning Solutions for Fritted Glassware Table 4.37 Common Fluxes Table 4.38 Membrane Filters Table 4.39 Porosities of Fritted Glassware Table 4.40 Tolerances for Analytical Weights Table 4.41 Heating Temperatures, Composition of Weighing Forms, and Gravimetric Factors 4.14 VOLUMETRIC ANALYSIS Table 4.42 Primary Standards for Aqueous Acid-Base Titrations Table 4.43 Titrimetric (Volumetric) Factors Table 4.44 Equations for the Redox Determinations of the Elements with Equivalent Weights Table 4.45 Standard Solutions for Precipitation Titrations Table 4.46 Indicators for Precipitation Titrations Table 4.47 Properties and Applications of Selected Metal Ion Indicators Table 4.48 Variation of a4 with pH Table 4.49 Formation Constants of EDTA Complexes at 25°C, Ionic Strength Approaching Zero Table 4.50 Cumulative Formation Constants of Ammine Complexes at 20°C, Ionic Strength 0.1 Table 4.51 Masking Agents for Various Elements Table 4.52 Masking Agents for Anions and Neutral Molecules Table 4.53 Common Demasking Agents Table 4.54 Amino Acids pI and pKQ Values Table 4.55 Tolerances of Volumetric Flasks Table 4.56 Pipette Capacity Tolerances Table 4.57 Tolerances of Micropipets (Eppendorf) Table 4.58 Buret Accuracy Tolerances Table 4.59 Factors for Simplified Computation of Volume Table 4.60 Cubical Coefficients of Thermal Expansion Table 4.61 General Solubility Rules for Inorganic Compounds Table 4.62 Concentration of Commonly Used Acids and Bases Table 4.63 Standard Stock Solutions Table 4.64 TLV Concentration Limits for Gases and Vapors Table 4.65 Some Common Reactive and Incompatible Chemicals Table 4.66 Chemicals Recommended for Refrigerated Storage Table 4.67 Chemicals Which Polymerize or Decompose on Extended Refrigeration 4.15 SIEVES AND SCREENS Table 4.68 U.S. Standard Sieves 4.16 THERMOMETRY 4.16.1 Temperature Measurement Table 4.69 Fixed Points in the ITS-90 Table 4.70 Values of K for Stem Correction of Thermometers 4.17 THERMOCOUPLES Table 4.71 Thermoelectric Values in Millivolts at Fixed Points for Various Thermocouples

4.90 4.95 4.95 4.97 4.101 4.102 4.104 4.104 4.130 4.132 4.133 4.133 4.134 4.134 4.135 4.137 4.137 4.138 4.145 4.149 4.150 4.151 4.152 4.152 4.152 4.153 4.155 4.156 4.157 4.158 4.158 4.158 4.159 4.159 4.160 4.161 4.161 4.162 4.165 4.173 4.179 4.179 4.180 4.180 4.180 4.180 4.180 4.182 4.182 4.184

GENERAL INFORMATION AND CONVERSION TABLES

Table 4.72 Type B Thermocouples: Platinum-30% Rhodium Alloy vs. Platinum-6% Rhodium Alloy Table 4.73 Type E Thermocouples: Nickel-Chromium Alloy vs. Copper-Nickel Alloy Table 4.74 Type J Thermocouples: Iron vs. Copper-Nickel Alloy Table 4.75 Type K Thermocouples: Nickel-Chromium Alloy vs. Nickel-Aluminum Alloy Table 4.76 Type N Thermocouples: Nickel-14.2% Chromium-1.4% Silicon Alloy vs. Nickel-4.4% Silicon-0.1% Magnesium Alloy Table 4.77 Type R Thermocouples: Platinum-13% Rhodium Alloy vs. Platinum Table 4.78 Type S Thermocouples: Platinum-10% Rhodium Alloy vs. Platinum Table 4.79 Type T Thermocouples: Copper vs. Copper-Nickel Alloy

4.3

4.185 4.186 4.187 4.188 4.188 4.190 4.191 4.192

4.1 GENERAL INFORMATION TABLE 4.1 SI Prefixes

*In the case of complex entities such as organic ligands (particularly if they are substituted) the multiplying prefixes bis-, tris-, tetrakis-, pentakis-, . . . are used, i.e., -kis is added starting from tetra-. The modified entity is often placed within parentheses to avoid ambiguity.

4.4

SECTION FOUR

TABLE 4.2 Greek Alphabet

4.2 PHYSICAL CONSTANTS AND CONVERSION FACTORS TABLE 4.3 Physical Constants

GENERAL INFORMATION AND CONVERSION TABLES

4.5

TABLE 4.3 Physical Constants (Continued)

(Continued)

4.6

SECTION FOUR

TABLE 4.3 Physical Constants (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.7

TABLE 4.3 Physical Constants (Continued)

*The digits in parentheses following a numerical value represent the standard deviation of that value in terms of the final listed digits. 1 The term million electronvolts is frequently used in place of megaelectronvolts. 2 The ångström and bar are approved for temporary use with SI units; however, they should not be introduced if not used at present.

4.8

SECTION FOUR

TABLE 4.4 Conversion Factors Relations which are exact are indicated by an asterisk (*). Factors in parentheses are also exact. Other factors are within ±5 in the last significant figure.

GENERAL INFORMATION AND CONVERSION TABLES

4.9

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.10

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.11

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.12

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.13

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.14

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

1 2

EMU, the electromagnetic system of electrical units based on dynamics. ESU, the electrostatic system of electrical units based on static data.

GENERAL INFORMATION AND CONVERSION TABLES

4.15

TABLE 4.4 Conversion Factors (Continued)

1 2

EMU, the electromagnetic system of electrical units based on dynamics. ESU, the electrostatic system of electrical units based on static data.

(Continued)

4.16

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.17

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.18

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.19

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.20

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.21

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.22

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.23

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.24

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.25

TABLE 4.4 Conversion Factors (Continued)

(Continued)

4.26

SECTION FOUR

TABLE 4.4 Conversion Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.4 Conversion Factors (Continued)

4.27

4.28

SECTION FOUR

4.3 CONVERSION OF THERMOMETER SCALES The following abbreviations are used: °F, degrees Fahrenheit; °C, degrees Celsius; K, degrees Kelvin; °Ré, degrees Reaumur; °R, degrees Rankine; °Z, degrees on any scale; (fp) “Z”, the freezing point of water on the Z scale; and (bp) “Z”, the boiling point of water on the Z scale. Reference: Dodds, Chemical and Metallurigical Engineering 38:476 (1931). o F − 32 180

=

oC 100

=

o Ré 80

o Z − ( fp)“Z” K − 273 o R − 492 = = 100 180 ( bp)“Z” − ( fp)“Z”

=

Examples (1) To find the Fahrenheit temperature corresponding to −20°C: o F − 32 180

=

oC 100

or

o F − 32 180

=

−20 100

o F − 32 = ( −20)(180) = −36 100 °F = − 4 (2) To find the Reaumur temperature corresponding to 20°F: o F − 32 180

=

o Ré 80

=

20 − 32 o Ré = 180 80

20°F = − 5.33°Ré

i.e.,

(3) To find the correct tempeature on a thermometer reading 80°C and that shows a reading of −0.30°C in a melting ice/water mixture and 99.0°C in steam at 760 mm pressure of mercury: oC 100 i.e.,

=

Z − ( fp)“Z” 80 − ( − 0.30) = ( bp)“Z” − ( fp)“Z” 99.0 − ( − 0.30) °C = 80.87 (corrected)

GENERAL INFORMATION AND CONVERSION TABLES

4.29

TABLE 4.5 Temperature Conversion The column of figures in bold and which is headed “Reading in °F. or °C. to be converted” refers to the temperature either in degrees Fahrenheit or Celsius which it is desired to convert into the other scale. If converting from Fahrenheit degrees to Celsius degrees, the equivalent temperature will be found in the column headed “°C.”; while if converting from degrees Celsius to degrees Fahrenheit, the equivalent temperature will be found in the column headed “°F.” This arrangement is very similar to that of Sauveur and Boylston, copyrighted 1920, and is published with their permission.

(Continued)

4.30

SECTION FOUR

TABLE 4.5 Temperature Conversion (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.31

TABLE 4.5 Temperature Conversion (Continued)

(Continued)

4.32

SECTION FOUR

TABLE 4.5 Temperature Conversion (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.33

TABLE 4.5 Temperature Conversion (Continued)

(Continued)

4.34

SECTION FOUR

TABLE 4.5 Temperature Conversion (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.35

TABLE 4.5 Temperature Conversion (Continued)

(Continued)

4.36

SECTION FOUR

TABLE 4.5 Temperature Conversion (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.37

TABLE 4.5 Temperature Conversion (Continued)

(Continued)

4.38

SECTION FOUR

TABLE 4.5 Temperature Conversion (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.39

TABLE 4.5 Temperature Conversion (Continued)

(Continued)

4.40

SECTION FOUR

TABLE 4.5 Temperature Conversion (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.41

4.4 DENSITY AND SPECIFIC GRAVITY

Alcoholometer. This hydrometer is used in determining the density of aqueous ethyl alcohol solutions; the reading in degrees is numerically the same as the percentage of alcohol by volume. The scale known as Tralle gives the percentage by volume. Wine and Must hydrometer relations are given below. Ammoniameter. This hydrometer, employed in finding the density of aqueous ammonia solutions, has a scale graduated in equal divisions from 0° to 40°. To convert the reading to specific gravity multiply by 3 and subtract the resulting number from 1000. Balling Hydrometer. See under Saccharometers. Barkometer or Barktrometer. This hydrometer, which is used in determining the density of tanning liquors, has a scale from 0° to 80° Bk; the number to the right of the decimal point of a specific gravity reading is the corresponding Bk degree; thus, a specific gravity of 1.015 is 15° Bk. Baumé Hydrometers. For liquids heavier than water: This hydrometer was originally based on the density of a 10% sodium chloride solution, which was given the value of 10°, and the density of pure water, which was given the value of 0°; the interval between these two values was divided into ten equal parts. Other reference points have been taken with the result that so much confusion exists that there are about 36 different scales in use, many of which are incorrect. In general a Baumé hydrometer should have inscribed on it the temperature at which it was calibrated and also the temperature of the water used in relating the density to a specific gravity. The following expression gives the relation between the specific gravity and several of the Baumé scales: Specific gravity = m = 145 at 60°/60°F (15.56°C) = 144

m m − Baumé

for the American Scale

for the old scale used in Holland

= 146.3 at 15°C

for the Gerlach Scale

= 144.3 at 15°C

for the Rational Scale generally used in Germany

For liquids lighter than water: Originally the density of a solution of 1 gram of sodium chloride in 9 grams of water at 12.5°C was given a value of 10°Bé. The scale between these points was divided into ten equal parts and these divisions were repeated throughout the scale giving a relation which could be expressed by the formula: Specific gravity = 145.88/(135.88 + Bé), which is approximately equal to 146/(136 + Bé). Other scales have since come into more general use such as that of the Bureau of Standards in which the specific gravity at 60°/60°F = 140/(130 + Bé) and that of the American Petroleum Institute (A.P.I. Scale) in which the specific gravity at 60°/60°F = 141.5/(131.5 + API°). See also special table for conversion to density and Twaddell scale. Beck’s Hydrometer. This hydrometer is graduated to show a reading of 0° in pure water and a reading of 30° in a solution with a specific gravity of 0.850, with equal scale divisions above and below these two points. Brix Hydrometer. See under Saccharometers.

4.42

SECTION FOUR

Cartier’s Hydrometer. This hydrometer shows a reading of 22° when immersed in a solution having a density of 22° Baumé but the scale divisions are smaller than on the Baumé hydrometer in the ratio of 16 Cartier to 15 Baumé. Fatty Oil Hydrometer. The graduations on this hydrometer are in specific gravity within the range 0.908 to 0.938. The letters on the scale correspond to the specific gravity of the various common oils as follows: R, rape; O, olive; A, almond; S, sesame; HL, hoof oil; HP, hemp; C, cotton seed; L, linseed. See also Oleometer below. Lactometers. These hydrometers are used in determining the density of milk. The various scales in common use are the following: New York Board of Health has a scale graduated into 120 equal parts, 0° being equal to the specific gravity of water and 100° being equal to a specific gravity of 1.029. Quevenne lactometer is graduated from 15° to 40° corresponding to specific gravities from 1.015 to 1.040. Soxhlet lactometer has a scale from 25° to 35° corresponding to specific gravities from 1.025 to 1.035 respectively. Oleometer. A hydrometer for determining the density of vegetable and sperm oils with a scale from 50° to 0° corresponding to specific gravities from 0.870 to 0.970. See also Fatty Oil Hydrometer above. Saccharometers. These hydrometers are used in determining the density of sugar solutions. Solutions of the same concentration but of different carbohydrates have very nearly the same specific gravity and in general a concentration of 10 grams of carbohydrate per 100 mL of solution shows a specific gravity of 1.0386. Thus, the wt. of sugar in 1000 mL soln. is (a) for conc. <12g/100 mL: (wt. of 1000 mL soln. − 1000) ⫼ 0.386; (b) for conc. >12g/100mL: (wt of 1000 mL soln. − 1000) ⫼ 0.385. Brix hydrometer is graduated so that the number of degrees is identical with the percentage by weight of cane sugar and is used at the temperature indicated on the hydrometer. Balling’s saccharometer is used in Europe and is practically identical with the Brix hydrometer. Bates brewers’ saccharometer which is used in determining the density of malt worts is graduated so that the divisions express pounds per barrel (32 gallons). The relation between degrees Bates (= b) and degrees Balling (= B) is shown by the following formula: B = 260b/(360 + b). See also below under Wine and Must Hydrometer. Salinometer. This hydrometer, which is used in the pickling and meat packing plants, is graduated to show percentage of saturation of a sodium chloride solution. An aqueous solution is completely saturated when it contains 26.4% pure sodium chloride. The range from 0% to 26.4% is divided into 100 parts, each division therefore representing 1% of saturation. In another type of salinometer, the degrees correspond to percentages of sodium chloride expressed in grams of sodium chloride per 100 mL of water. Sprayometer (Parrot and Stewart). This hydrometer which is used in determining the density of lime sulfur solutions has two scales; one scale is graduated from 0° to 38° Baumé and the other scale is from 1.000 to 1.350 specific gravity. Tralle Hydrometer. See Alcoholometer above. Twaddell Hydrometer. This hydrometer, which is used only for liquids heavier than water, has a scale such that when the reading is multiplied by 5 and added to 1000 the resulting number is the specific gravity with reference to water as 1000. To convert specific gravity at 60°/60°F to Twaddell degrees, take the decimal portion of the specific gravity value and multiply it by 200; thus a specific gravity of 1.032 = 0.032 ⫻ 200 = 6.4° Tw. See also special table for conversion to density and Baumé scale.

GENERAL INFORMATION AND CONVERSION TABLES

4.43

Wine and Must Hydrometer. This instrument has three scales. One scale shows readings of 0° to 15° Brix for sugar (see Brix Hydrometer above); another scale from 0° to 15° Tralle is used for sweet wines to indicate the percentage of alcohol by volume; and a third scale from 0° to 20° Tralle is used for tart wines to indicate the percentage of alcohol by volume. Conversion of Specific Gravity at 25°/25°C to Density at any Temperature from 0° to 40°C.∗ Liquids change volume with change in temperature, but the amount of this change, b (coefficient of cubical expansion), varies widely with different liquids, and to some extent for the same liquid at different temperatures. The table below, which is calculated from the relationship:

Fβ t =

density of water at 25o C ( = 0.99705) 1 − β (25 − t )

may be used to find d t, the density (weight of 1 mL) of a liquid at any temperature (t) between 0° and 40°C if the specific gravity at 25°/25°C (S) and the coefficient of cubical expansion (b) are known. Substitutions are made in the equations: d t = SFbt

(4.2)

dt Fb t

(4.3)

S=

Factors (Fbt) Density t°C = sp. gr. 25°/25° ⫻ Fbt

∗b = coefficient of cubical expansion. ∗Cf. Dreisbach, Ind., Eng. Chem., Anal. Ed. 12:160 (1940).

4.44

SECTION FOUR

Examples. All examples are based upon an assumed coefficient of cubical expansion, b, of 1.3 ⫻ 10−3. Example 1. To find the density of a liquid at 20°C, d 20, which has a specific gravity (S) of 1.250025 −: 25 From the table above Fbt at 20°C = 1.0036. d 20 = d t = SFbt = 1.2500 ⫻ 1.0036 = 1.2545 −4 : Example 2. To find the density at 20°C (d 20) of a liquid which has a specific gravity of 1.250017 Since the density of water at 4°C is equal to 1, specific gravity at 17°/4° = d 17 = 1.2500. Substitution in Equation 3 with Fbt at 17°C, by interpolation from the table, equal to 1.00756, gives Sp. gr. 25°/25° = S = 1.2500 ⫼ 1.00756 Substitution of this value for S in Equation 2 with Fbt at 20°C, from the table, equal to 1.0036, gives d 20 = d t = (1.2500 ⫼ 1.00756) ⫻ 1.0036 = 1.2451 Example 3. To find the specific gravity at 20°/4°C of a liquid which has a specific gravity of 1.250025 4: Since the density of water at 4°C is equal to 1, specific gravity 25°/4° = d 25 = 1.2500; and, specific gravity 20°/4° = d 20. Substitution in Equation 3, with d t = 1.2500; and, with Fbt at 25°C, from the table, equal to 0.99705, gives Sp. gr. 25°/25° = S = 1.2500 ⫼ 0.99705 Substitution of this value for S in Equation 2, with Fb t at 20°C, from the table, equal to 1.0036, gives Sp. gr. 20°/4° = d 20 = (1.2500 ⫼ 0.99705) ⫻ 1.0036 = 1.2582 −: Example 4. To find the density at 25°C of a liquid which has a specific gravity of 1.250015 15 Since the density of water at 15°C = 0.99910, d 15 = sp. gr. 15°/15° ⫻ 0.99910 = 1.2500 ⫻ 0.99910 Substitution in Equation 3, with Fbt at 15°C, from the table, equal to 1.0102, gives Sp. gr. 25°/25° = S = (1.2500 ⫻ 0.99910) ⫼ 1.0102 Substitution of this value for S in Equation 2, with Fbt at 25°, from the table, equal to 0.99705, gives d26 = d t = (1.2500 ⫻ 0.99910 ⫼ 1.0102) ⫻ 0.99705 = 1.2326

GENERAL INFORMATION AND CONVERSION TABLES

4.45

TABLE 4.6 Hydrometer Conversion This table gives the relation between density (c.g.s.) and degrees on the Baumé and Twaddell scales. The Twaddell scale is never used for densities less than unity. See also Sec. 2.1.2.1, Hydrometers.

* NIST, National Institute for Science and Technology (formerly the National Bureau of Standards, U.S.). † A.P.I is the American Petroleum Institute.

4.46

SECTION FOUR

TABLE 4.6 Hydrometer Conversion (Continued)

Density

Degrees Baumé (NIST* scale)

Degrees Baumé (A.P.I. †scale)

Density

Degrees Baumé (NIST* scale)

Degrees Baumé (A.P.I. †scale)

* NIST, National Institute for Science and Technology (formerly the National Bureau of Standards, U.S.).

GENERAL INFORMATION AND CONVERSION TABLES

4.47

4.5 BAROMETRY AND BAROMETRIC CORRECTIONS In principle, the mercurial barometer balances a column of pure mercury against the weight of the atmosphere. The height of the column above the level of the mercury in the reservoir can be measured and serves as a direct index of atmospheric pressure. The space above the mercury in a barometer tube should be a Torricellian vacuum, perfect except for the practically negligible vapor pressure of mercury. The perfection of the vacuum is indicated by the sharpness of the click noted when the barometer tube is inclined. A barometer should be in a vertical position, suspended rather than fastened to a wall, and in a good light but not exposed to direct sunlight or too near a source of heat. The standard conditions for barometric measurements are 0°C and gravity as at 45° latitude and sea level. There are numerous sources of error, but corrections for most of these are readily applied. Some of the corrections are very small, and their application may be questionable in view of the probably larger errors. The degree of consistency to be expected in careful measurements is about 0.13 mm with a 6.4-mm tube, increasing to 0.04 mm with a tube 12.7 mm in diameter. In reading a barometer of the Fortin type (the usual laboratory instrument for precision measurements), the procedure should be as follows: (1) Observe and record the temperature as indicated by the thermometer attached to the barometer. The temperature correction is very important and may be affected by heat from the observer’s body. (2) Set the mercury in the reservoir at zero level, so that the point of the pin above the mercury just touches the surface, making a barely noticeable dimple therein. Tap the tube at the top and verify the zero setting. (3) Bring the vernier down until the view at the light background is cut off at the highest point of the meniscus. Record the reading. The corrections to be made on the reading are as follows: (1) Temperature, to correct for the difference in thermal expansion of the mercury and the brass (or glass) to which the scale is attached. This correction converts the reading into the value of 0°C. The brass scale table is applicable to the Fortin barometer. See Tables 4.8 (latitude-gravity correction), and Tables 4.9 (altitude-gravity correction), to compensate for differences in gravity, which would affect the height of the mercury column by variation in mass. If local gravity is unknown, an approximate correction may be made from the tables. Local values of gravity are often subject to irregularities which lead to errors even when the corrections here provided are made. It is, therefore, advisable to determine the local value of gravity, from which the correction can be effected in the following manner: g −g  Bt = Br +  1 0  × Br  g0  in which Bt and Br are the true and the observed heights of the barometer, respectively. g0 is standard gravity (980 665 cm ⋅ s−2), and g1 is the local gravity. It may be noted that for most localities, g1 is smaller than g0, which makes the correction negative. These corrections compensate the reading to gravity at 45° latitude and sea level. (3) Correction for capillary depression of the level of the meniscus. This varies with the tube diameter and actual height of the meniscus in a particular case. Some barometers are calibrated to allow for an average value of the latter and approximating the correction. See table. (4) Correction for vapor pressure of mercury. This correction is usually negligible, being only 0.001 mm at 20°C and 0.006 mm at 40°C. This correction is added. See table of vapor pressure of mercury. The corrections above do not apply to aneroid barometers. These instruments should be calibrated at regular intervals by checking them against a corrected mercurial barometer. For records on weather maps, meteorologists customarily correct barometer readings to sea level, and some barometers may be calibrated accordingly. Such instruments are not suitable for laboratory use where true pressure under standard conditions is required. Scale corrections should be specified in the maker’s instructions with the instrument, and are also indicated by the lack of correspondence between a gauge mark usually placed exactly 76.2 cm from the zero point and the 76.2-cm scale graduation.

4.48

SECTION FOUR

TABLE 4.7 Barometer Temperature Correction—Metric Units The values in the table below are to be subtracted from the observed readings to correct for the difference in the expansion of the mercury and the glass scale at different temperatures.

GENERAL INFORMATION AND CONVERSION TABLES

4.49

TABLE 4.7 Barometer Temperature Correction—Metric Units (Continued) The values in the table below are to be subtracted from the observed readings to correct for the difference in the expansion of the mercury and the glass scale at different temperatures.

4.50

SECTION FOUR

TABLE 4.7 Barometer Temperature Correction—Metric Units (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.51

TABLE 4.7 Barometer Temperature Correction—Metric Units (Continued)

TABLE 4.8 Barometric Latitude-Gravity—Metric Units The values in the table below are to be subtracted from the barometric reading for latitudes from 0 to 45° inclusive, and are to be added from 46 to 90°.

(Continued)

4.52

SECTION FOUR

TABLE 4.8 Barometric Latitude-Graviy—Metric Units (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.53

TABLE 4.9 Barometric Correction for Gravity—Metric Units The values in Table 4.9 are to be subtracted from the readings taken on a mercurial barometer to correct for the decrease in gravity with increase in altitude.

4.54

SECTION FOUR

TABLE 4.10 Reduction of the Barometer to Sea Level-Metric Units A barometer located at an elevation above sea level will show a reading lower than a barometer at sea level by an amount approximately 2.5 mm (0.1 in) for each 30.5 m (100 ft) of elevation. A closer approximation can be made by reference to the following tables, which take into account (1) the effect of altitude of the station at which the barometer is read, (2) the mean temperature of the air column extending from the station down to sea level, (3) the latitude of the station at which the barometer is read, and (4) the reading of the barometer corrected for its temperature, a correction which is applied only to mercurial barometers since the aneroid barometers are compensated for temperature effects. Example. A barometer which has been corrected for its temperature reads 650 mm at a station whose altitude is 1350 m above sea level and at a latitude of 30°. The mean temperature (outdoor temperature) at the station is 20°C. Table A (metric units) gives for these conditions a temperature-altitude factor of . . . . . . . . . . . . . The Latitude Factor Table gives for 135.2 at 30° lat. a correction of . . . . . . . . . . . . . . . . . . . . . . . Therefore, the corrected value of the temperature-altitude factor is . . . . . . . . . . . . . . . . . . . . . . . . Entering Table B (metric units), with a temperature-altitude factor of 135.37 and a barometric reading of 650 mm (corrected for temperature), the correction is found to be . . . . . . . . . . . . . . . . . . . . Accordingly the barometric reading reduced to sea level is 650 + 109.6 = 759.6 mm.

135.2 +0.17 135.37 109.6

Latitude Factor–English or Metric Units. For latitudes 0°−45° add the latitude factor, for 45°–90° subtract the latitude factor, from the values obtained in Table A.

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.10 Reduction of the Barometer to Sea Level—Metric Units (Continued)

* From Smithsonian Meteorological Tables, 3d ed., 1907.

4.55

4.56

SECTION FOUR

TABLE 4.10 Reduction of the Barometer to Sea Level—Metric Units (Continued) B. Values in millimeters to be added.*

*From Smithsonian Meteorological Tables, 3d ed., 1907.

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.10 Reduction of the Barometer to Sea Level—Metric Units (Continued) B. Values in millimeters to be added.*

*From Smithsonian Meteorological Tables, 3d ed., 1907.

4.57

4.58

SECTION FOUR

TABLE 4.11 Pressure Conversion

1 bar = 105 pascal.

GENERAL INFORMATION AND CONVERSION TABLES

4.59

TABLE 4.12 Conversion of Weighings in Air to Weighings in Vacuo If the mass of a substance in air is mf, its density rm, the density of weights used in making the weighing rw, and the density of air ra, the true mass of the substance in vacuo, mvac, is  1 1  mvac = m f + ρ a m f  −   ρm ρw  For most purposes it is sufficient to assume a density of 8.4 for brass weights, and a density of 0.0012 for air under ordinary conditions. The equation then becomes  1 1  mvac = m f + 0.0012 m f  −   ρ m 8.4  The table which follows gives the values of k (buoyancy reduction factor), which is the correction necessary because of the buoyant effect of the air upon the object weighed; the table is computed for air with the density of 0.0012; m is the weight in grams of the object when weighted in air; weight of object reduced to “in vacuo” = m + km/1000.

(Continued)

4.60

SECTION FOUR

TABLE 4.12 Conversion of Weighings in Air to Weighings in Vacuo (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.61

TABLE 4.13 Factors for Reducing Gas Volumes to Normal (Standard) Temperature and Pressure (760 mmHg) Examples: (a) 20 mL of dry gas at 22°C and 730 mm = 20 × 0.8888 = 17.78 mL at 0°C and 760 mm. (b) 20 mL of a gas over water at 22° and 730 mm = 20 × (factor corrected for aqueous tension; i.e., 730 – 19.8 or 710.2 mm) = 20 mL of dry gas at 22° and 710.2 mm = 20 × 0.86475 = 17.30 mL at 0°C and 760 mm. Mass in milligrams of 1 mL of gas at S.T.P.: acetylene, 1.173; carbon dioxide, 1.9769; hydrogen, 0.0899; nitric oxide (NO), 1.3402; nitrogen, 1.25057; oxygen, 1.42904.

(Continued)

4.62

SECTION FOUR

TABLE 4.13 Factors for Reducing Gas Volumes to Normal (Standard) Temperature and Pressure (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.63

TABLE 4.13 Factors for Reducing Gas Volumes to Normal (Standard) Temperature and Pressure (Continued)

(Continued)

4.64

SECTION FOUR

TABLE 4.13 Factors for Reducing Gas Volumes to Normal (Standard) Temperature and Pressure (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.65

TABLE 4.13 Factors for Reducing Gas Volumes to Normal (Standard) Temperature and Pressure (Continued)

4.66

SECTION FOUR

4.6 VISCOSITY Viscosity is the shear stress per unit area at any point in a confined fluid divided by the velocity gradient in the direction perpendicular to the direction of flow. If this ratio is constant with time at a given temperature and pressure for any species, the fluid is called a Newtonian fluid. The absolute viscosity (m) is the shear stress at a point divided by the velocity gradient at that point. The most common unit is the poise (1 kg/m sec) and the SI unit is the Pa.sec (1 kg/m sec). As many common fluids have viscosities in the hundredths of a poise the centipoise (cp) is often used. One centipoise is then equal to one mPa sec. The kinematic viscosity (v) is ratio of the absolute viscosity to density at the same temperature and pressure. The most common unit corresponding to the poise is the stoke (1 cm2/sec) and the SI unit is m2/sec.

TABLE 4.14 Viscosity Conversion Centistokes to Saybolt, Redwood, and Engler units. Poise = cgs unit of absolute viscosity Centipoise = 0.01 poise Stoke = cgs unit of kinematic viscosity Centistoke = 0.01 stoke Centipoises = centistokes × density (at temperature under consideration) Reyn (1 lb ⋅ s per sq in) = 69 × 105 centipoises Cf. Jour. Inst. Pet. Tech., Vol. 22, p. 21 (1936); Reports of A. S. T. M. Committee D-2, 1936 and 1937. The values of Saybolt Universal Viscosity at 100°F and at 210°F are taken directly from the comprehensive ASTM Viscosity Table, Special Technical Publication No. 43A (1953) by permission of the publishers, American Society for Testing Materials, West Conshohocken, PA.

GENERAL INFORMATION AND CONVERSION TABLES

4.67

TABLE 4.14 Viscosity Conversion (Continued)

*At higher values use the same ratio as above for 100 centistokes; e.g., 102 centistokes = 102 × 4.635 Saybolt seconds at 100°F. To obtain the Saybolt Universal viscosity equivalent to a kinematic viscosity determined at t°F., multiply the equivalent Saybolt Universal viscosity at 100°F. by 1 + (t – 100) 0.000064; e.g., 10 centistokes at 210°F are equivalent to 58.91 × 1.0070, or 59.32 Saybolt Universal Viscosity at 210°F.

4.7 PHYSICAL CHEMISTRY EQUATIONS FOR GASES A number of physical chemistry relationships, not enumerated in other sections (see Index), will be discussed in this section. Boyle’s law states that the volume of a given quantity of a gas varies inversely as the pressure, the temperature remaining constant. That is, V=

constant P

or

PV = constant

A convenient form of the law, true strictly for ideal gases, is PV 1 1 = P2 V2 Charles’ law, also known as Gay-Lussac’s law, states that the volume of a given mass of gas varies directly as the absolute temperature if the pressure remains constant, that is, V = constant T Combining the laws of Boyle and Charles into one expression gives PV PV 1 1 = 2 2 T1 T2

4.68

SECTION FOUR

In terms of moles, Avogadro’s hypothesis can be stated: The same volume is occupied by one mole of any gas at a given temperature and pressure. The number of molecules in one mole is known as the Avogadro number constant NA. The behavior of all gases that obey the laws of Boyle and Charles, and Avogadro’s hypothesis, can be expressed by the ideal gas equation: PV = nRT where R is called the gas constant and n is the number of moles of gas. If pressure is written as force per unit area and the volume as area times length, then R has the dimensions of energy per degree per mole—8.314 J ⋅ K−1⋅ mol−1 or 1.987 cal ⋅ K−1 ⋅ mol−1. Dalton’s law of partial pressures states that the total pressure exerted by a mixture of gases is equal to the sum of the pressures which each component would exert if placed separately into the container: Ptotal = p1 + p2 + p3 + L There are two ways to express the fraction which one gaseous component contributes to the total mixture: (1) the pressure fraction, pi/Ptotal, and (2) the mole fraction, ni/ntotal. 4.7.1 Equations of State (PVT Relations for Real Gases) 1. Virial equation represents the experimental compressibility of a gas by an empirical equation of state: PV = Ap + Bp P + C p P 2 + L or PV = Av + BvV +

Cv +L V2

where A, B, C, . . . are called the virial coefficients and are a function of the nature of the gas and the temperature. 2. Van der Waals’ equation:  an 2   P + 2  (V − nb) = nRT V   where the term an2/V 2 is the correction for intermolecular attraction among the gas molecules and the nb term is the correction for the volume occupied by the gas molecules. The constants a and b must be fitted for each gas from experimental data; consequently the equation is semiempirical. The constants are related to the critical-point constants as follows: a = 3PcV 2 V b= c 3 8 PcVc R= 3Tc Substitution into van der Waals’ equation and rearrangement leads to only the terms P/Pc, V/Vc, and T/Tc, which are called the reduced variables PR, VR, and TR. For 1 mole of gas,  3  1 8  PR + 2   VR −  = TR VR  3 3 

GENERAL INFORMATION AND CONVERSION TABLES

4.69

3. Berthelot’s equation of state, used by many thermodynamicists, is  9 PTc  Tc2   PV = nRT 1 + 1 − 6 2   T   128 PT  This equation requires only knowledge of the critical temperature and pressure for its use and gives accurate results in the vicinity of room temperature for unassociated substances at moderate pressures.

4.7.2 Properties of Gas Molecules Vapor Density. Substitution of the Antoine vapor-pressure equation for its equivalent log P in the ideal gas equation gives log ρ vap = log M − log R − log(t + 273.15) + A −

B t+C

where rvap is the vapor density in g ⋅ mL−1 at t°C, M is the molecular weight, R is the gas constant, and A, B, and C are the constants of the Antoine equation for vapor pressure. Since this equation is based on the ideal gas law, it is accurate only at temperatures at which the vapor of any specific compound follows this law. This condition prevails at reduced temperatures (TR) of about 0.5 K. Velocities of Molecules. The mean square velocity of gas molecules is given by u2 =

3kT 3 RT = m M

where k is Boltzmann’s constant and m is the mass of the molecule. The mean velocity is given by  8u 2  u =   3π 

1/ 2

Viscosity. On the assumption that molecules interact like hard spheres, the viscosity of a gas is 5   mkT  η=  16σ 2   π 

1/ 2

where s is the molecular diameter. Mean Free Path. The mean free path of a gas molecule l and the mean time between collisions t are given by m l= πρσ 2 2

τ=

1 4η = u 5P

Graham’s Law of Diffusion. The rates at which gases diffuse under the same conditions of temperature and pressure are inversely proportional to the square roots of their densities: r1  ρ2  =  r2  ρ1 

1/ 2

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SECTION FOUR

Since r = MP/RT for an ideal gas, it follows that r1  M2  =  r2  M1 

1/ 2

Henry’s Law. The solubility of a gas is directly proportional to the partial pressure exerted by the gas: pi = kxi Joule-Thompson Coefficient for Real Gases. This expresses the change in temperature with respect to change in pressure at constant enthalpy:  ∂T  µπ =    ∂P  H

TABLE 4.15 Molar Equivalent of One Liter of Gas at Various Temperatures and Pressures The values in this table, which give the number of moles in 1 liter of gas, are based on the properties of an “ideal” gas and were calculated by use of the formula: Moles/liter =

P 273 1 × × 760 T 22.40

where P is the pressure in millimeters of mercury and T is the temperature in kelvins (= t°C + 273). To convert to moles per cubic foot multiply the values in the table by 28.316.

GENERAL INFORMATION AND CONVERSION TABLES

4.71

TABLE 4.15 Molar Equivalent of One Liter of Gas at Various Temperatures and Pressures (Continued)

(Continued)

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SECTION FOUR

TABLE 4.15 Molar Equivalent of One Liter of Gas at Various Temperatures and Pressures (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.73

TABLE 4.16 Corrections to Be Added to Molar Values to Convert to Molal

4.8 COOLING

TABLE 4.17 Cooling Mixtures The table below gives the lowest temperature that can be obtained from a mixture of the inorganic salt with finely shaved dry ice. With the organic substances, dry ice (−78°C) in small lumps can be added to the solvent until a slight excess of dry ice remains or liquid nitrogen (−196°C) can be poured into the solvent until a slush is formed that consists of the solid-liquid mixture at its melting point.

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SECTION FOUR

TABLE 4.18 Molecular Lowering of the Melting or Freezing Point Cryoscopic constants. The cryoscopic constant Kf gives the depression of the melting point ∆T (in degrees Celsius) produced when 1 mol of solute is dissolved in 1000 g of a solvent. It is applicable only to dilute solutions for which the number of moles of solute is negligible in comparison with the number of moles of solvent. It is often used for molecular weight determinations. M2 =

1000 w2 K f w1∆T

where w1 is the weight of the solvent and w2 is the weight of the solute whose molecular weight is M2.

Next Page

4.9 DRYING HUMIDIFICATION TABLE 4.19 Drying Agents

a

b

d

f

May form explosive mixtures when contacting organic material. e H2 formed. Used as column drying of organic liquids.

Explosive C2H2 formed. Strong reductant.

c

Slow in drying action.

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Previous Page 4.76

SECTION FOUR

A saturated aqueous solution in contact with an excess of a definite solid phase at a given temperature will maintain constant humidity in an enclosed space. Table 4.20 gives a number of salts suitable for this purpose. The aqueous tension (vapor pressure, in millimeters of Hg) of a solution at a given temperature is found by multiplying the decimal fraction of the humidity by the aqueous tension at 100 percent humidity for the specific temperature. For example, the aqueous tension of a saturated solution of NaCl at 20°C is 0.757 ⫻ 17.54 = 13.28 mmHg and at 80°C it is 0.764 ⫻ 355.1 = 271.3 mmHg.

TABLE 4.20 Solutions for Maintaining Constant Humidity

GENERAL INFORMATION AND CONVERSION TABLES

4.77

TABLE 4.21 Concentration of Solutions of H2SO4, NaOH, and CaCl2 Giving Specified Vapor Pressures and Percent Humidity at 25°C

Concentrations are expressed in percentage of anhydrous solute by weight.

TABLE 4.22 Relative Humidity from Wet and Dry Bulb Thermometer Readings

(Continued)

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SECTION FOUR

TABLE 4.22 Relative Humidity from Wet and Dry Bulb Thermometer Readings (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.23 Relative Humidity from Dew Point Readings

4.79

4.80

SECTION FOUR

TABLE 4.24 Mass of Water Vapor in Saturated Air The values in the table are grams of water contained in a cubic meter (m3) of saturated air at a total pressure 101 325 Pa (1 atm).

GENERAL INFORMATION AND CONVERSION TABLES

4.81

4.10 MOLECULAR WEIGHT TABLE 4.25 Molecular Elevation of the Boiling Point Ebullioscopic constants. Molecular weights can be determined with the relation: M = Eb

1000 w2 w1 ∆Tb

where ∆Tb is the elevation of the boiling point brought about by the addition of w2 grams of solute to w1 grams of solvent and Eb is the ebullioscopic constant. In the column headed “Barometric correction” is the number of degrees for each millimeter of difference between the barometric reading and 760 mmHg to be subtracted from Eb if the pressure is lower, or added if higher, than 760 mm. In general, the effect is within experimental error if the pressure is within 10 mm of 760 mm. The ebullioscopic constant, a characteristic property of the solvent, may be calculated from the relation: Eb =

RTb2 M ∆ vap H

where R is the molar gas constant, M is the molar mass of the solvent, and ∆vapH the molar enthalpy (heat) of vaporization of the solvent.

4.82

SECTION FOUR

TABLE 4.25 Molecular Elevation of the Boiling Point (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.83

TABLE 4.25 Molecular Elevation of the Boiling Point (Continued)

4.11 HEATING BATHS TABLE 4.26 Substances That Can Be Used for Heating Baths

4.12 SEPARATION METHODS 4.12.1 McReynolds’ Constants The Kovats Retention indices (R.I.) indicate where compounds will appear on a chromatogram with respect to unbranched alkanes injected with the sample. By definition, the R.I. for pentane is 500, for hexane is 600, for heptane is 700, and so on, regardless of the column used or the operating conditions, although the exact conditions and column must be specified, such as liquid loading, particular support used, and any pretreatment. For example, suppose that on a 20% squalane column at 100°C, the retention times for hexane, benzene, and octane are found to be 15, 16, and 25 min, respectively. On a graph of ln tR⬘ (naperian logarithm of the adjusted retention time) of the alkanes versus their retention indices, a R.I. of 653 for benzene is read off the graph. The number 653 for benzene means that it elutes halfway between hexane and heptane on a logarithmic time scale. If the experiment is repeated with a dinonyl phthalate column, the R.I for benzene is found to be 736 (lying between heptane and octane), which implies that dinonyl phthalate will retard benzene slightly more than squalane will; that is, dinonyl phthalate is slightly more polar than squalane by ∆I = 83 units. The difference gives a measure of solute-solvent interaction due to all intermolecular forces other than London dispersion forces. The latter are the principal solute-solvent effects with squalane.

4.84 TABLE 4.27 Solvents of Chromatographic Interest

4.85

4.86 TABLE 4.28 McReynolds’ Constants for Stationary Phases in Gas Chromatography

(Continued)

4.87

4.88 TABLE 4.28 McReynolds’ Constants for Stationary Phases in Gas Chromatography (Continued )

Note: USP code is the United States Pharmacopeia designation.

4.89

4.90

SECTION FOUR

Now the overall effects due to hydrogen bonding, dipole moment, acid-base properties, and molecular configuration can be expressed as

∑ ∆ I = ax ′ + by′ + cz′ + du′ + es′ where x⬘ = ∆I for benzene, y⬘ = ∆I for 1-butanol, z⬘ = ∆I for 2-pentanone, u⬘ = ∆I for 1-nitropropane, and s⬘ = ∆I for pyridine (or dioxane). 4.12.2 Chromatographic Behavior of Solutes Retention Behavior. On a chromatogram the distance on the time axis from the point of sample injection to the peak of an eluted component is called the uncorrected retention time tR. The corresponding retention volume is the product of retention time and flow rate, expressed as volume of mobile phase per unit time: VR = t R Fc The average linear velocity u of the mobile phase in terms of the column length L and the average linear velocity of eluent tM (which is measured by the transit time of a nonretained solute) is u=

L tM

The adjusted retention time t⬘R is given by t R′ = t R − t M When the mobile phase is a gas, a compressibility factor j must be applied to the adjusted retention volume to give the net retention volume: VN = jVR′ The compressibility factor is expressed by j=

3 [( Pi / Po )2 − 1] 2 [( Pi / Po )3 − 1]

where Pi is the carrier gas pressure at the column inlet and Po that at the outlet. Partition Ratio. The partition ratio is the additional time a solute band takes to elute, as compared with an unretained solute (for which k⬘ = 0), divided by the elution time of an unretained band: k′ =

t R − t M VR − VM = tM VM

Retention time may be expressed as t R = t M (1 + k ′ ) =

L (1 + k ′ ) u

GENERAL INFORMATION AND CONVERSION TABLES

4.91

Relative Retention. The relative retention a of two solutes, where solute 1 elutes before solute 2, is given variously by

α=

k2′ VR′,2 t R′ ,2 = = k1′ VR′,1 t R′ ,1

The relative retention is dependent on (1) the nature of the stationary and mobile phases and (2) the column operating temperature. Column Efficiency. Under ideal conditions the profile of a solute band resembles that given by a Gaussian distribution curve (Fig. 4.1). The efficiency of a chromatographic system is expressed by the effective plate number Neff, defined from the chromatogram of a single band, 2

Neff

 t′   t′  L = = 16  R  = 5.54  R  H  Wb   W1/ 2 

2

where L is the column length, H is the plate height, t⬘R is the adjusted time for elution of the band center, Wb is the width at the base of the peak (Wb = 4s) as determined from the intersections of tangents to the inflection points with the baseline, and W1/2 is the width at half the peak height. Column efficiency, when expressed as the number of theoretical plates Ntheor uses the uncorrected retention time in the foregoing expression. The two column efficiencies are related by  k′  Neff = Ntheor    k ′ + 1

2

Band Asymmetry. The peak asymmetry factor AF is often defined as the ratio of peak half-widths at 10% of peak height, that is, the ratio b/a, as shown in Fig. 4.2. When the asymmetry ratio lies outside the range 0.95–1.15 for a peak of k⬘ = 2, the effective plate number should be calculated from the expression N=

41.7(t R′ /W0.1 ) ( a/b) + 1.25

Resolution. The degree of separation or resolution, Rs, of two adjacent peaks is defined as the distance between band peaks (or centers) divided by the average bandwidth using Wb, as shown in Fig. 4.3. Rs =

t R,2 − t R,1 0.5(W2 + W1 )

For reasonable quantitative accuracy, peak maxima must be at least 4s apart. If so, then Rs = 1.0, which corresponds approximately to a 3% overlap of peak areas. A value of Rs = 1.5 (for 6s) represents essentially complete resolution with only 0.2% overlap of peak areas. These criteria pertain to roughly equal solute concentrations.

4.92 Profile of a solute band. FIGURE 4.1

GENERAL INFORMATION AND CONVERSION TABLES

4.93

Band asymmetry FIGURE 4.2

The fundamental resolution equation incorporates the terms involving the thermodynamics and kinetics of the chromatographic system: Rs =

1  α − 1  k ′   L    4  α   1 + k′   H 

1/ 2

Three separate factors affect resolution: (1) a column selectivity factor that varies with a, (2) a capacity factor that varies with k⬘ (taken usually as k2), and (3) an efficiency factor that depends on the theoretical plate number.

Definition of resolution FIGURE 4.3

4.94

SECTION FOUR

TABLE 4.29 Characteristics of Selected Supercritical Fluids

Time of Analysis. The retention time required to perform a separation is given by 2

α   (1 + k ′ )3   H  t R = 16 Rs2   α − 1   ( k ′ )2   u  Now tR is a minimum when k⬘ = 2, that is, when tR = 3tM. There is little increase in analysis time when k⬘ lies between 1 and 10. A twofold increase in the mobile-phase velocity roughly halves the analysis time (actually it is the ratio H/u which influences the analysis time). The ratio H/u can be obtained from the experimental plate height/velocity graph. High-Performance Liquid Chromatography. Typical performances for various experimental conditions are given in Table 4.30. The data assume these reduced parameters: h = 3, v = 4.5. The reduced plate height is h=

H L = d p Nd p

The reduced velocity of the eluent is v=

udp Ldp = DM t M DM

GENERAL INFORMATION AND CONVERSION TABLES

4.95

TABLE 4.30 Typical Performances in HPLC for Various Conditions

Assumed reduced parameters: h = 3, v = 4.5. These are optimum values from a graph of reduced plate height versus reduced linear velocity of the mobile phase.

In these expressions, dp is the particle diameter of the stationary phase that constitutes one plate height. DM is the diffusion coefficient of the solute in the mobile phase.

4.12.3 Ion-Exchange (Normal Pressure, Columnar) Ion-exchange methods are based essentially on a reversible exchange of ions between an external liquid phase and an ionic solid phase. the solid phase consists of a polymeric matrix, insoluble, but permeable, which contains fixed charge groups and mobile counter ions of opposite charge. These counter ions can be exchanged for other ions in the external liquid phase. Enrichment of one or several of the components is obtained if selective exchange forces are operative. The method is limited to substances at least partially in ionized form. Chemical Structure of Ion-Exchange Resins. An ion-exchange resin usually consists of polystyrene copolymerized with divinylbenzene to build up an inert three-dimensional, cross-linked matrix of hydrocarbon chains. Protruding from the polymer chains are the ion-exchange sites distributed statistically throughout the entire resin particle. The ionic sites are balanced by an equivalent number of mobile counter ions. The type and strength of the exchanger is determined by these active groups. Ion-exchangers are designated anionic or cationic, according to whether they have an affinity for negative or positive counter ions. Each main group is further subdivided into strongly or weakly ionized groups. A selection of commercially available ion-exchange resins is given in Table 4.31.

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The cross-linking of a polystyrene resin is expressed as the proportion by weight percent of divinylbenzene in the reaction mixture; for example, “⫻ 8” for 8 percent cross-linking. As the percentage is increased, the ionic groups come into effectively closer proximity, resulting in increased selectivity. Intermediate cross-linking, in the range of 4 to 8 percent, is usually used. An increase in cross-linking decreases the diffusion rate in the resin particles; the diffusion rate is the rate-controlling step in column operations. Decreasing the particle size reduces the time required for attaining equilibrium, but at the same time decreases the flow rate until it is prohibitively slow unless pressure is applied. In most inorganic chromatography, resins of 100 to 200 mesh size are suitable; difficult separations may require 200 to 400 mesh resins. A flow rate of 1 mL ⭈ cm−2 ⭈ min−1 is often satisfactory. With HPLC columns, the flow rate in long columns of fine adsorbent can be increased by applying pressure. Macroreticular Resins. Macroreticular resins are an agglomerate of randomly packed microspheres which extend through the agglomerate in a continuous non-gel pore structure. The channels throughout the rigid pore structure render the bead centers accessible even in nonaqueous solvents, in which microreticular resins do not swell sufficiently. Because of their high porosity and large pore diameters, these resins can handle large organic molecules. Microreticular Resins. Microreticular resins, by contrast, are elastic gels that, in the dry state, avidly absorb water and other polar solvents in which they are immersed. While taking up solvent, the gel structure expands until the retractile stresses of the distended polymer network balance the osmotic effect. In nonpolar solvents, little or no swelling occurs and diffusion is impaired. Ion-Exchange Membranes. Ion-exchange membranes are extremely flexible, strong membranes, composed of analytical grade ion-exchange resin beads (90%) permanently enmeshed in a poly(tetrafluoroethylene) membrane (10%). The membranes offer an alternative to column and batch methods, and can be used in many of the same applications as traditional ion exchange resins. Three ion-exchange resin types have been incorporated into membranes: AG 1-X8, AG 50W-X8, and Chelex 100. Functional Groups. Sulfonate exchangers contain the group SO3−, which is strongly acidic and completely dissociated whether in the H form or the cation form. These exchangers are used for cation exchange. Carboxylate exchangers contain [COOH groups which have weak acidic properties and will only function as cation exchangers when the pH is sufficiently high (pH > 6) to permit complete dissociation of the [COOH site. Outside this range the ion exchanger can be used only at the cost of reduced capacity.

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TABLE 4.31 Ion-Exchange Resins Dowex is the trade name of Dow resins; X (followed by a numeral) is percent cross-linked. Mesh size (dry) are available in the range 50 to 100, 100 to 200, 200 to 400, and sometimes minus 400. S-DVB is the acronym for styrene-divinylbenzene. MP is the acronym for macroporous resin. Mesh size (dry) is available in the range 20 to 50, 100 to 200, and 200 to 400. Bio-Rex is the trade name for certain resins sold by Bio-Rad Laboratories. Amberlite and Duolite are trade names of Rohm & Haas resins.

(Continued)

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TABLE 4.31 Ion-Exchange Resins (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.31 Ion-Exchange Resins (Continued)

(Continued)

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TABLE 4.31 Ion-Exchange Resins (Continued)

Source: J.A. Dean, ed., Analytical Chemistry Handbook, McGraw-Hill, New York, 1995.

Quaternary ammonium exchangers contain [R4N+ groups which are strongly basic and completely dissociated in the OH form and the anion form. Tertiary amine exchangers possess [R3NH2 groups which have exchanging properties only in an acidic medium when a proton is bound to the nitrogen atom. Aminodiacetate exchangers have the [N(CH2COOH)2 group which has an unusually high preference for copper, iron, and other heavy metal cations and, to a lesser extent, for alkaline earth cations. The resin selectivity for divalent over monovalent ions is approximately 5000 to 1. The resin functions as a chelating resin at pH 4 and above. At very low pH, the resin acts as an anion exchanger. This exchanger is the column packing often used for ligand exchange.

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4.101

Ion-Exchange Equilibrium. Retention differences among cations with an anion exchanger, or among anions with a cation exchanger, are governed by the physical properties of the solvated ions. The stationary phase will show these preferences: 1. The ion of higher charge. 2. The ion with the smaller solvated radius. Energy is needed to strip away the solvation shell surrounding ions with large hydrated radii, even though their crystallographic ionic radii may be less than the average pore opening in the resin matrix. 3. The ion that has the greater polarizability (which determines the Van der Waals’ attraction). To accomplish any separation of two cations (or two anions) of the same net charge, the stationary phase must show a preference for one more than the other. No variation in the eluant concentration will improve the separation. However, if the exchange involves ions of different net charges, the separation factor does depend on the eluant concentration. The more dilute the counterion concentration in the eluant, the more selective the exchange becomes for polyvalent ions. In the case of an ionized resin, initially in the H-form and in contact with a solution containing K+ ions, an equilibrium exists: resin, H+ + K+ K resin, K+ + H+ which is characterized by the selectivity coefficient, kK/H: kK/H =

[K + ]r [H + ] [H + ]r [K + ]

where the subscript r refers to the resin phase. Table 4.32 contains selectivity coefficients for cations and Table 4.33 for anions. Relative selectivities are of limited use for the prediction of the columnar exchange behavior of a cation because they do not take account of the influence of the aqueous phase. More specific information about the behavior to be expected from a cation in a column elution experiment is given by the equilibrium distribution coefficient Kd.

TABLE 4.32 Relative Selectivity of Various Counter Cations

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TABLE 4.33 Relative Selectivity of Various Counter Anions

The partitioning of the potassium ion between the resin and solution phases is described by the concentration distribution ratio, Dc: ( Dc )K =

[K + ]r [K + ]

Combining the equations for the selectivity coefficient and for Dc: ( Dc )K = kK/H

[H + ]r [H + ]

The foregoing equation reveals that essentially the concentration distribution ratio for trace concentrations of an exchanging ion is independent of the respective solution of that ion and that the uptake of each trace ion by the resin is directly proportional to its solution concentration. However, the concentration distribution ratios are inversely proportional to the solution concentration of the resin counterion. To accomplish any separation of two cations (or two anions), one of these ions must be taken up by the resin in distinct preference to the other. This preference is expressed by the separation factor (or relative retention), aK/Na, using K+ and Na+ as the example: a K/Na =

k ( Dc )K = K/H = KK/Na ( Dc )Na kNa/H

GENERAL INFORMATION AND CONVERSION TABLES

4.103

The more a deviates from unity for a given pair of ions, the easier it will be to separate them. If the selectivity coefficient is unfavorable for the separation of two ions of the same charge, no variation in the concentration of H+ (the eluant) will improve the separation. The situation is entirely different if the exchange involves ions of different net charges. Now the separation factor does depend on the eluant concentration. For example, the more dilute the counterion concentration in the eluant, the more selective the exchange becomes for the ion of higher charge. In practice, it is more convenient to predict the behavior of an ion, for any chosen set of conditions, by employing a much simpler distribution coefficient, Dg, which is defined as the concentration of a solute in the resin phase divided by its concentration in the liquid phase, or: Dg = Dg =

concentration of solute, resin phase concentration of solute, liquid phase

% solute within exchanger volume of solution × % solute within solution mass of exchanger

Dg remains constant over a wide range of resin to liquid ratios. In a relatively short time, by simple equilibration of small known amounts of resin and solution followed by analysis of the phases, the distribution of solutes may be followed under many different sets of experimental conditions. Variables requiring investigation include the capacity and percent cross-linkage of resin, the type of resin itself, the temperature, and the concentration and pH of electrolyte in the equilibrating solution. By comparing the ratio of the distribution coefficients for a pair of ions, a separation factor (or relative retention) is obtained for a specific experimental condition. Instead of using Dg, separation data may be expressed in terms of a volume distribution coefficient Dv, which is defined as the amount of solution in the exchanger per cubic centimeter of resin bed divided by the amount per cubic centimeter in the liquid phase. The relation between Dg and Dv is given by: Dv = Dg r where r is the bed density of a column expressed in the units of mass of dry resin per cubic centimeter of column. The bed density can be determined by adding a known weight of dry resin to a graduated cylinder containing the eluting solution. After the resin has swelled to its maximum, a direct reading of the settled volume of resin is recorded. Intelligent inspection of the relevant distribution coefficients will show whether a separation is feasible and what the most favorable eluant concentration is likely to be. In the columnar mode, an ion, even if not eluted, may move down the column a considerable distance and with the next eluant may appear in the eluate much earlier than indicated by the coefficient in the first eluant alone. A distribution coefficient value of 12 or lower is required to elute an ion completely from a column containing about 10 g of dry resin using 250 to 300 mL of eluant. A larger volume of eluant is required only when exceptionally strong tailing occurs. Ions may be eluted completely by 300 to 400 mL of eluant from a column of 10 g of dry resin at Dg values of around 20. The first traces of an element will appear in the eluate at around 300 mL when its Dg value is about 50 to 60. Example Shaking 50 mL of 0.001 M cesium salt solution with 1.0 g of a strong cation exchanger in the H-form (with a capacity of 3.0 mequiv ⋅ g−1) removes the following amount of cesium. The selectivity coefficient, kCs/H, is 2.56, thus: [Cs + ]r [H + ] = 2.56 [Cs + ][H + ]r The maximum amount of cesium which can enter the resin is 50 mL ⫻ 0.001 M = 0.050 equiv. The minimum value of [H+]r = 3.00 – 0.05 = 2.95 mequiv, and the maximum value, assuming

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complete exchange of cesium ion for hydrogen ion, is 0.001 M. The minimum value of the distribution ratio is: [Cs + ]r (2.56)(2.95) = = 7550 [Cs + ] 0.001 ( 7550)(1.0 g) Amount of Cs, resin phase = = 151 Amount of Cs, solution phase 50 mL ( Dc )Cs =

Thus, at equilibrium the 1.0 g of resin removed is: 100% − x = 151 x with all but 0.66% of cesium ions from solution. If the amount of resin were increased to 2.0 g, the amount of cesium remaining in solution would decrease to 0.33%, half the former value. However, if the depleted solution were decanted and placed in contact with 1 g of fresh resin, the amount of cesium remaining in solution would decrease to 0.004%. Two batch equilibrations would effectively remove the cesium from the solution.

4.13 GRAVIMETRIC ANALYSIS

TABLE 4.34 Gravimetric Factors In the following table the elements are arranged in alphabetical order. Example: To convert a given weight of Al2O3 to its equivalent of Al, multiply by the factor at the right, 0.52926; similarly to convert Al to Al2O3, multiply by the factor at the left, 1.8894.

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

4.127

TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.34 Gravimetric Factors (Continued)

(Continued)

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TABLE 4.34 Gravimetric Factors (Continued)

TABLE 4.35 Elements Precipitated by General Analytical Reagents This table includes the more common reagents used in gravimetric determinations. The lists of elements precipitated are not in all cases exhaustive. The usual solvent for a precipitating agent is indicated in parentheses after its name or formula. When the symbol of an element or radical is italicized, the element may be quantitatively determined by the use of the reagent in question.

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.35 Elements Precipitated by General Analytical Reagents (Continued)

(Continued)

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TABLE 4.35 Elements Precipitated by General Analytical Reagents (Continued)

TABLE 4.36 Cleaning Solutions for Fritted Glassware

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.37 Common Fluxes

TABLE 4.38 Membrane Filters

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TABLE 4.39 Porosities of Fritted Glassware

TABLE 4.40 Tolerances for Analytical Weights This table gives the individual and group tolerances established by the National Bureau of Standards (Washington, D.C.) for classes M, S, S-1, and P weights. Individual tolerances are “acceptance tolerances” for new weights. Group tolerances are defined by the National Bureau of Standards as follows: “The corrections of individual weights shall be such that no combination of weights that is intended to be used in a weighing shall differ from the sum of the nominal values by more than the amount listed under the group tolerances.” For class S-1 weights, two-thirds of the weights in a set must be within one-half of the individual tolerances given below. No group tolerances have been specified for class P weights. See Natl. Bur. Standards Circ. 547, sec. 1 (1954).

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.41 Heating Temperatures, Composition of Weighing Forms, and Gravimetric Factors The minimum temperature required for heating a pure precipitate to constant weight is frequently lower than that commonly recommended in gravimetric procedures. However, the higher temperature is very often still to be preferred in order to ensure that contaminating substances are expelled. The thermal stability ranges of various precipitates as deduced from thermograms are also tabulated. Where a stronger ignition is advisable, the safe upper limit can be ascertained. Gravimetric factors are based on the 1993 International Atomic Weights. The factor Ag: 0.7526 given in the first line of the table indicates that the weight of precipitate obtained (AgCl) is to be multiplied by 0.7526 to calculate the corresponding weight of silver.

(Continued)

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TABLE 4.41 Heating Temperatures, Composition of Weighing Forms, and Gravimetric Factors (Continued)

4.14 VOLUMETRIC ANALYSIS TABLE 4.42 Primary Standards for Aqueous Acid-Base Titrations

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TABLE 4.43 Titrimetric (Volumetric) Factors Acids The following factors are the equivalent of 1 mL of normal acid. Where the normality of the solution being used is other than normal, multiply the factors given in the table below by the normality of the solution employed. The equivalents of the esters are based on the results of saponification. The indicators methyl orange and phenolphthalein are indicated by the abbreviations MO and pH, respectively.

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.43 Titrimetric (Volumetric) Factors (Continued) Acids (Continued)

(Continued)

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TABLE 4.43 Titrimetric (Volumetric) Factors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.43 Titrimetric (Volumetric) Factors (Continued) Iodine (Continued)

(Continued)

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TABLE 4.43 Titrimetric (Volumetric) Factors (Continued) Potassium permanganate The following factors are the equivalent of 1 mL of normal potassium permanganate. Where the normality of the solution being used is other than normal, multiply the factors given in the table below by the normality of the solution employed.

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.43 Titrimetric (Volumetric) Factors (Continued) Silver nitrate The following factors are the equivalent of normal silver nitrate. Where the normality of the solution being used is other than normal, multiply the factors given in the table below by the normality of the solution employed.

(Continued)

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TABLE 4.43 Titrimetric (Volumetric) Factors (Continued) Sodium thiosulfate The following factors are the equivalent of ImL of normal sodium thiosulfate. Where the normality of the solution being used is other than normal, multiply the factors given in the table below by the normality of the solution employed.

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.44 Equations for the Redox Determinations of the Elements with Equivalent Weights

(Continued)

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TABLE 4.44 Equations for the Redox Determinations of the Elements with Equivalent Weights (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.44 Equations for the Redox Determinations of the Elements with Equivalent Weights (Continued)

(Continued)

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TABLE 4.44 Equations for the Redox Determinations of the Elements with Equivalent Weights (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.44 Equations for the Redox Determinations of the Elements with Equivalent Weights (Continued)

Note: Additional procedural information plus interferences and general remarks will be found in J. A. Dean, ed., Analytical Chemistry Handbook, McGraw-Hill, New York, Second Edition, 2004.

TABLE 4.45 Standard Solutions for Precipitation Titrations The list given below includes the substances that are most used and most useful for the standardization of solutions for precipitation titrations. Primary standard solutions are denoted by the letter (P) in Column 1.

*Meets standards of purity (and impurity) set by the American Chemical Society.

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TABLE 4.46 Indicators for Precipitation Titrations

*Meets standards of purity (and impurity) set by the American Chemical Society.

Next Page

TABLE 4.47 Properties and Applications of Selected Metal Ion Indicators

4.151

Source: J. A. Dean, ed., Analytical Chemistry Handbook, McGraw-Hill, New York, Second Edition, 2004.

Previous Page 4.152

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TABLE 4.48 Variation of a4 with pH

TABLE 4.49 Formation Constants of EDTA Complexes at 25°C, Ionic Strength Approaching Zero

TABLE 4.50 Cumulative Formation Constants of Ammine Complexes at 20°C, Ionic Strength 0.1

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.51 Masking Agents for Various Elements

(Continued)

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TABLE 4.51 Masking Agents for Various Elements (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.52 Masking Agents for Anions and Neutral Molecules

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TABLE 4.53 Common Demasking Agents Abbreviations: DPC, diphenylcarbazide; HDMG, dimethylglyoxime; PAN, 1-(2-pyridylazo)-2-naphthol.

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TABLE 4.53 Common Demasking Agents (Continued)

TABLE 4.54 Amino Acids pI and pKQ Values This table lists the pKa and pI (pH at the isoelectric point) values of α-amino acids commonly found in proteins along with their abbreviations. The dissociation constants refer to aqueous solutions at 25°C.

Source: E. L. Smith, et al., Principles of Biochemistry, 7th ed., McGraw-Hill, New York, 1983; H. J. Hinz, ed., Thermodynamic Data for Biochemistry and Biotechnology, Springer-Verlag, Heidelberg, 1986.

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TABLE 4.55 Tolerances of Volumetric Flasks

*Accuracy tolerances for volumetric flasks at 20°C are given by ASTM standard E288.

TABLE 4.56 Pipette Capacity Tolerances

*Accuracy tolerances for volumetric transfer pipets are given by ASTM standard E969 and Federal Specification NNNP-395. †Accuracy tolerances for measuring pipets are given by Federal Specification NNN-P-350 and for serological pipets by Federal Specification NNN-P-375.

TABLE 4.57 Tolerances of Micropipets (Eppendorf)

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.58 Burette Accuracy Tolerances

*Class A conforms to specifications in ASTM E694 for standard taper stopcocks and to ASTM E287 for Teflon or polytetrafluoroethylene stopcock plugs. The 10-mL size meets the requirements for ASTM D664.

TABLE 4.59 Factors for Simplified Computation of Volume The volume is determined by weighing the water, having a temperature of t°C, contained or delivered by the apparatus at the same temperature. The weight of water, w grams, is obtained with brass weights in air having a density of 1.20 mg/mL. For apparatus made of soft glass, the volume contained or delivered at 20°C is given by v20 = wf20 mL where v20 is the volume at 20° and f20 is the factor (apparent specific volume) obtained from the table below for the temperature t at which the calibration is performed. The volume at any other temperature t⬘ may then be obtained from v⬘ = v20[1 + 0.00002(t⬘ – 20)] mL For apparatus made of any other material, the volume contained or delivered at the temperature t is vt = wft mL where w is again the weight in air obtained with brass weights (in grams), and ft is the factor given in the third column of the table for the temperature t. The volume at any temperature t⬘ may then be obtained from v⬘t = vt[1 + b(t⬘ – t)]mL where b is the cubical coefficient of thermal expansion of the material from which the apparatus is made. Approximate values of b for some frequently encountered materials are given in Table 4.60.

(Continued)

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TABLE 4.59 Factors for Simplified Computation of Volume (Continued)

TABLE 4.60 Cubical Coefficients of Thermal Expansion This table lists values of b, the cubical coefficient of thermal expansion, taken from “Essentials of Quantitative Analysis,” by Benedetti-Pichler, and from various other sources. The values of b represents the relative increases in volume for a change in temperature of 1°C at temperatures in the vicinity of 25°C, and is equal to 3a, where a is the linear coefficient of thermal expansion. Data are given for the types of glass from which volumetic apparatus is most commonly made, and also for some other materials which have been or may be used in the fabrication of apparatus employed in analytical work.

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TABLE 4.61 General Solubility Rules for Inorganic Compounds

TABLE 4.62 Concentration of Commonly Used Acids and Bases Freshly opened bottles of these reagents are generally of the concentrations indicated in the table. This may not be true of bottles long opened and this is especially true of ammonium hydroxide, which rapidly loses its strength. In preparing volumetric solutions, it is well to be on the safe side and take a little more than the calculated volume of the concentrated reagent, since it is much easier to dilute a concentrated solution than to strengthen one that is too weak. A concentrated C.P. reagent usually comes to the laboratory in a bottle having a label which states its molecular weight w, its density (or its specific gravity) d, and its percentage assay p. When such a reagent is used to prepare an aqueous solution of desired molarity M, a convenient formula to employ is V=

100 wM pd

where V is the number of milliliters of concentrated reagent required for 1 liter of the dilute solution. Example: Sulfuric acid has the molecular weight 98.08. If the concentrated acid assays 95.5% and has the specific gravity 1.84, the volume required for 1 liter of a 0.1 molar solution is V=

100 × 95.08 × 0.1 = 5.58 mL 95.5 × 1.84

(Continued)

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TABLE 4.62 Concentration of Commonly Used Acids and Bases (Continued)

*V, mL = volume in milliliters needed to prepare 1 liter of 1 molar solution.

TABLE 4.63 Standard Stock Solutions

*1000 mg/mL as the element in a final volume of 1 liter unless stated otherwise.

GENERAL INFORMATION AND CONVERSION TABLES

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TABLE 4.63 Standard Stock Solutions (Continued)

(Continued)

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TABLE 4.63 Standard Stock Solutions (Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors Exposure limits (threshold limit value or TLV) are those set by the Occupational Safety and Health Administration and represent conditions to which most workers can be exposed without adverse effects. The TLV value is expressed as a time weighted average airborne concentration over a normal 8-hour workday and 40-hour workweek.

(Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors (Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors (Continued)

(Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors (Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors (Continued)

(Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors (Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors (Continued)

(Continued)

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TABLE 4.64 TLV Concentration Limits for Gases and Vapors (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.65 Some Common Reactive and Incompatible Chemicals

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TABLE 4.65 Some Common Reactive and Incompatible Chemicals (Continued)

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TABLE 4.65 Some Common Reactive and Incompatible Chemicals (Continued)

(Continued)

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TABLE 4.65 Some Common Reactive and Incompatible Chemicals (Continued)

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TABLE 4.65 Some Common Reactive and Incompatible Chemicals (Continued)

(Continued)

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TABLE 4.65 Some Common Reactive and Incompatible Chemicals (Continued)

GENERAL INFORMATION AND CONVERSION TABLES

TABLE 4.66 Chemicals Recommended for Refrigerated Storage

TABLE 4.67 Chemicals Which Polymerize or Decompose on Extended Refrigeration

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4.15 SIEVES AND SCREENS TABLE 4.68 U.S. Standard Sieves

Specifications are from ASTM E.11-81/ISO 565. The sieve numbers are the approximate number of openings per linear inch.

4.16 THERMOMETRY 4.16.1 Temperature Measurement The new international temperature scale, known as ITS-90, was adopted in September 1989. However, neither the definition of thermodynamic temperature nor the definition of the kelvin or the Celsius temperature scales has changed; it is the way in which we are to realize these definitions that has changed. The changes concern the recommended thermometers to be used in different regions of the temperature scale and the list of secondary standard fixed points. The changes in temperature determined using ITS-90 from the previous IPTS-68 are always less than 0.4 K, and almost always less than 0.2 K, over the range 0–300 K. The ultimate definition of thermodynamic temperature is in terms of pV (pressure × volume) in a gas thermometer extrapolated to low pressure. The kelvin (K), the unit of thermodynamic temperature, is defined by specifying the temperature of one fixed point on the scale––the triple point of water which is defined to be 273.16 K. The Celsius temperature scale (°C) is defined by the equation °C = K − 273.15 where the freezing point of water at 1 atm is 273.15 K.

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4.181

TABLE 4.69 Fixed Points in the ITS-90

The fixed points in the ITS-90 are given in Table 4.54. Platinum resistance thermometers are recommended for use between 14 K and 1235 K (the freezing point of silver), calibrated against the fixed points. Below 14 K either the vapor pressure of helium or a constant-volume gas thermometer is to be used. Above 1235 K radiometry is to be used in conjunction with the Planck radiation law, Ll = c1l−5 (ec2/lT – 1)−1 where Ll is the spectral radiance at wavelength l. The first radiation constant, c1, is 3.741 83 ⫻ 10−16 W ⭈ m2 and the second radiation constant, c2, has a value of 0.014 388 m ⭈ K. When a thermometer which has been standardized for total immersion is used with a part of the liquid column at a temperature below that of the bulb, the reading is low and a correction must be applied. The stem correction, in degrees Celsius, is given by KL(to – tm) = degrees Celsius where K = constant, characteristic of the particular kind of glass and temperature (see Table 4.65) L = length of exposed thermometer, °C (that is, the length not in contact with vapor or liquid being measured) to = observed temperature on thermometer tm = mean temperature of exposed column (obtained by placing an auxiliary thermometer alongside with its bulb midpoint) For thermometers containing organic liquids, it is sufficient to use the approximate value, K = 0.001. In such thermometers the value of K is practically independent of the kind of glass.

4.182

SECTION FOUR

TABLE 4.70 Values of K for Stem Correction of Thermometers

4.17 THERMOCOUPLES The thermocouple reference data in Tables 4.71 to 4.79 give the thermoelectric voltage in millivolts with the reference junction at 0°C. Note that the temperature for a given entry is obtained by adding the corresponding temperature in the top row to that in the left-hand column, regardless of whether the latter is positive or negative. The noble metal thermocouples, Types B, R, and S, are all platinum or platinum-rhodium thermocouples and hence share many of the same characteristics. Metallic vapor diffusion at high temperatures can readily change the platinum wire calibration, hence platinum wires should only be used inside a nonmetallic sheath such as high-purity alumina. Type B thermocouples (Table 4.72) offer distinct advantages of improved stability, increased mechanical strength, and higher possible operating temperatures. They have the unique advantage that the reference junction potential is almost immaterial, as long as it is between 0°C and 40°C. Type B is virtually useless below 50°C because it exhibits a double-value ambiguity from 0°C to 42°C. Type E thermoelements (Table 4.73) are very useful down to about liquid hydrogen temperatures and may even be used down to liquid helium temperatures. They are the most useful of the commercially standardized thermocouple combinations for subzero temperature measurements because of their high Seebeck coefficient (58 mV/°C), low thermal conductivity, and corrosion resistance. They also have the largest Seebeck coefficient (voltage response per degree Celsius) above 0°C of any of the standardized thermocouples which makes them useful for detecting small temperature changes. They are recommended for use in the temperature range from −250 to 871°C in oxidizing or inert atmospheres. They should not be used in sulfurous, reducing, or alternately reducing and oxidizing atmospheres unless suitably protected with tubes. They should not be used in vacuum at high temperatures for extended periods of time. Type J thermocouples (Table 4.74) are one of the most common types of industrial thermocouples because of the relatively high Seebeck coefficient and low cost. They are recommended for use in the temperature range from 0 to 760°C (but never above 760°C due to an abrupt magnetic transformation that can cause decalibration even when returned to lower temperatures). Use is permitted in vacuum and in oxidizing, reducing, or inert atmospheres, with the exception of sulfurous atmospheres above 500°C. For extended use above 500°C, heavy-gauge wires are recommended. They are not recommended for subzero temperatures. These thermocouples are subject to poor conformance characteristics because of impurities in the iron. The Type K thermocouple (Table 4.75) is more resistant to oxidation at elevated temperatures than the Type E, J, or T thermocouple, and consequently finds wide application at temperatures above 500°C. It is recommended for continuous use at temperatures within the range −250 to 1260°C in inert or oxidizing atmospheres. It should not be used in sulfurous or reducing atmospheres, or in vacuum at high temperatures for extended times.

GENERAL INFORMATION AND CONVERSION TABLES

4.183

The Type N thermocouple (Table 4.76) is similar to Type K but it has been designed to minimize some of the instabilities in the conventional Chromel-Alumel combination. Changes in the alloy content have improved the order/disorder transformations occurring at 500°C and a higher silicon content of the positive element improves the oxidation resistance at elevated temperatures. The Type R thermocouple (Table 4.77) was developed primarily to match a previous platinum10% rhodium British wire which was later found to have 0.34% iron impurity in the rhodium. Comments on Type S also apply to Type R. The Type S thermocouple (Table 4.78) is so stable that it remains the standard for determining temperatures between the antimony point (630.74°C) and the gold point (1064.43°C). The other fixed point used is that of silver. The Type S thermocouple can be used from −50°C continuously up to about 1400°C, and intermittently at temperatures up to the freezing point of platinum (1769°C). The thermocouple is most reliable when used in a clean oxidizing atmosphere, but may also be used in inert gaseous atmospheres or in a vacuum for short periods of time. It should not be used in reducing atmospheres, nor in those containing metallic vapor (such as lead or zinc), nonmetallic vapors (such as arsenic, phosphorus, or sulfur), or easily reduced oxides, unless suitably protected with nonmetallic protecting tubes. The Type T thermocouple (Table 4.79) is popular for the temperature region below 0°C (but see under Type E). It can be used in vacuum, or in oxidizing, reducing, or inert atmospheres.hydrometer is graduated so that the number of degrees is identical with the percentage by weight of cane sugar and is used at the temperature indicated on the hydrometer.

4.184

TABLE 4.71 Thermoelectric Values in Millivolts at Fixed Points for Various Thermocouples Abbreviations Used in the Table FP, freezing point NBP, normal boiling point

BP, boiling point TP, triple point

*Defining fixed points of the International Temperature Scale of 1990 (ITS-90). Except for the triple points, the assigned values of temperature are for equilibrium states at a pressure of one standard atmosphere (101 325 Pa).

TABLE 4.72 Type B Thermocouples: Platinum-30% Rhodium Alloy vs. Platinum-6% Rhodium Alloy Thermoelectric voltage in millivolts; reference junction at 0°C.

4.185

4.186 TABLE 4.73 Type E Thermocouples: Nickel-Chromium Alloy vs. Copper-Nickel Alloy Thermoelectric voltage in millivolts; reference junction at 0°C.

TABLE 4.74 Type J Thermocouples: Iron vs. Copper-Nickel Alloy Thermoelectric voltage in millivolts; reference junction at 0°C.

4.187

4.188 TABLE 4.75 Type K Thermocouples: Nickel-Chromium Alloy vs. Nickel-Aluminum Alloy Thermoelectric voltage in millivolts; reference junction at 0°C.

TABLE 4.76 Type N Thermocouples: Nickel-14.2% Chromium-1.4% Silicon Alloy vs. Nickel-4.4% Silicon-0.1% Magnesium Alloy Thermoelectric voltage in millivolts; reference junction at 0°C.

4.189

4.190 TABLE 4.77 Type R Thermocouples: Platinum-13% Rhodium Alloy vs. Platinum Thermoelectric voltage in millivolts; reference junction at 0°C.

TABLE 4.78 Type S Thermocouples: Platinum-10% Rhodium Alloy vs. Platinum Thermoelectric voltage in millivolts; reference junction at 0°C.

4.191

4.192 TABLE 4.79 Type T Thermocouples: Copper vs. Copper-Nickel Alloy Thermoelectric voltage in millivolts; reference junction at 0°C.

INDEX

Index Terms

Links

A Absolute viscosity, definition

1.226

Absorbance, conversion to percent absorption

3.31

Absorption bands, ultraviolet spectroscopy

2.55

Absorption edges

3.130

Absorption energies, X-ray

3.133

Absorption frequencies: infrared

3.3

near infrared

3.26

Absorption spectroscopy, infrared (See Infrared absorption spectroscopy) Acetals, infrared absorption Acid anhydrides, infrared absorption

3.20 3.3

Acid-base indicators

2.677

Acid-base titration, standards

4.137

Acidity, measurement of

1.306

Acids: concentrations for general use inorganic, naming inorganic, salts and functional derivatives

4.161 1.9 1.11

Acid value: fats and oils

2.808

waxes

2.810

Actinium series of the elements, radioactivity

1.137

Activity coefficients: definition

1.299 This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Activity coefficients: (Cont.) ions in water at 25°C

1.300

ternary electrolytes

1.299

quaternary electrolytes

1.299

Addition compounds, inorganic compounds

1.301

1.13

Air, specific gravity at various temperatures

1.92

Alcohols: melting points of derivatives nomenclature

2.254 2.24

Alcohol-water freezing mixtures Aldehydes, infrared absorption

2.460

2.461

3.13

Alkanes, straight chain: infrared absorption

2.4

nomenclature

2.4

Alkenes, infrared absorption

3.16

Alkyl halides: density

2.255

aldehydes

3.13

Amides, infrared absorption Amidines, infrared absorption

3.8

3.14

3.16

Amines: infrared absorption melting points of derivatives

3.8 2.254

Amino acids: acid-base properties

2.48

definition

2.47

formula

2.47

molecular weight nomenclature pKa

2.267

2.267 2.47 2.267

4.157

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Amino acids: (Cont.) structure

2.267

Amino sugars

2.51

Ammine complexes, formation constants

4.152

Ammonia, liquid, vapor pressure

1.223

Ammonium ions, infrared absorption

3.8

Amylopectin

2.53

Amylose

2.52

Analytical weights, tolerance Anions, nomenclature Antifreeze solutions, composition

4.134 1.8 2.461

Approximate effective ionic radii in aqueous solution 1.151 Approximate pH value of solutions, calculation Argon-ion laser plasma lines

1.350 3.53

Aromatic compounds: infrared absorption

3.19

Raman spectroscopy

3.48

Asphalt, thermal conductivity

1.128

Atomic absorption spectroscopy

3.64

Atomic and group refractions

2.288

Atomic emission spectroscopy

3.64

Atomic fluorescence spectroscopy

3.64

Atomic numbers of the elements

1.232

1.4

1.97

1.121

1.124

Atomic radii: elements

1.151

inorganic compounds

1.151

Atomic weights of the elements

1.121

Atoms, covalent radii

1.158

Auto-ignition temperature

2.351

Azeotropic mixtures

2.434

alcohols

2.426

2.435

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Azeotropic mixtures (Cont.) aldehydes

2.436

amines

2.436

binary

2.439

binary azeotropes containing organic acids

2.439

binary azeotropes containing water

2.435

esters

2.436

ethers

2.438

halogenated hydrocarbons

2.436

hydrocarbons

2.438

inorganic acids

2.435

ketones

2.438

nitriles

2.439

organic acids

2.435

ternary azeotropic mixtures

2.454

Azo compounds, infrared absorption

3.17

B Barometer-temperature correction

4.48

Barometric conversion

4.47

Barometric correction for gravity

4.53

Barometric correction to sea level

4.54

Barometric latitude-gravity

4.51

Barometry

4.47

Bases, concentrations for general use

4.161

Benzene and heteroaromatics, ultraviolet absorption

3.59

Benzene derivatives, ultraviolet absorption

3.59

Binary azeotropes containing: acetamido

2.451

acetic acid

2.440

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Binary azeotropes containing: (Cont.) acetone

2.451

allyl alcohol

2.448

aniline

2.452

benzene

2.453

benzyl alcohol

2.448

bis(2-hydroxyethyl) ether

2.453

1-butanol

2.446

2-butanone

2.451

2-butoxyethanol

2.449

butyric acid

2.441

iso-butyric acid

2.442

cyclohexanol

2.447

1,2-ethanediol

2.449

1,2-ethanediol monoacetate

2.450

ethanol

2.443

2-ethoxyethanol

2.449

formic acid

2.439

methanol

2.443

3-methyl-1-butanol

2.447

2-methyl-2-propanol

2.446

phenol

2.448

1-propanol

2.444

2-propanol

2.445

propionic acid

2.441

pyridine

2.452

thiophene

2.453

Boiling point

2.296

alkyl halides

2.255

carboxylic acids

2.256

elements

1.18

1.124

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Boiling point (Cont.) inorganic compounds

1.16

1.18

organic compounds

2.65

2.297

organic compounds at selected pressures

2.315

organic solvents

2.348

petroleum products

2.811

water at various pressures Bond dipole moments inorganic compounds

1.93

1.94

1.171

2.468

2.352

1.173

Bond dissociation energies: elements and inorganic compounds

1.160

organic compounds

2.467

Bond lengths: between elements

1.159

carbon and other elements

2.466

carbon-carbon

2.464

carbon halogen

2.464

carbon-nitrogen

2.465

carbon-oxygen

2.465

carbon selenium

2.466

carbon-silicon

2.466

carbon sulfur

2.466

inorganic compounds

1.150

organic compounds

2.464

Bond strengths, inorganic compounds

1.150

Bonds, spatial orientation of common hybrid

1.175

Boron-11 chemical shifts

3.99

Boron compounds, infrared absorption

3.23

Brines, freezing point

2.463

Buffer solutions

1.301

composition of standard solutions

2.465

1.304

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Buffer solutions (Cont.) National Bureau of Standards reference pH solutions

1.303

non-standard

1.307

values of biological and other buffers for control purposes

1.308

Burettes, tolerances for

4.159

C Calculation of concentrations of species present at a given pH

1.351

Carbohydrates

2.48

stereochemistry

2.51

structures

2.49

Carbon-13 chemical shifts

3.87

Carbon-13 chemical shifts of deuterated solvents

3.98

Carbon-carbon bond lengths

2.464

Carbon-carbon spin coupling constants

3.96

Carbon-fluorine spin coupling constants

3.97

Carbon halogen bond lengths Carbon-hydrogen spin coupling constants

2.465

2.464 3.95

Carbon-nitrogen bond lengths

2.465

Carbon-oxygen bond lengths

2.465

Carbon selenium bond lengths

2.466

Carbon-silicon bond lengths

2.466

Carbon spin coupling constants with various nuclei

3.95

Carbon sulfur bond lengths Carboxylate ions, infrared absorption

2.466 3.14

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Carbonyl compounds: infrared absorption

3.12

raman spectroscopy

3.44

Carboxylic acids (See also Fatty acids): boiling point

2.256

formula

2.55

infrared absorption

3.14

melting point

2.256

nomenclature

2.30

solubility in water

2.256

Cations, nomenclature

1.8

Cellulose

2.256

2.53

Change of state (See Thermodynamic functions) Chemicals: reactive and incompatible

4.173

refrigerated storage

4.179

Chemical symbols of the elements

1.97

Chirality

2.43

1.124

Chromatography: behavior of solutes

4.90

ion exchange

4.95

ion exchange resins

4.97

solvents

4.84

supercritical fluids

4.94

Cleaning solutions for fritted glassware

4.132

Coal, thermal conductivity

1.232

Color, inorganic compounds

1.64

Common hybrid bonds, spatial orientation

1.175

Complex inorganic ions, stability constants

1.343

Compressibility, water at various temperatures

1.95

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Index Terms

Links

Compressibility factor, critical: elements

1.233

inorganic compounds

1.233

organic compounds

2.592

Computation of volume

4.159

Conductance: conductivity of very pure water

1.417

equivalent conductance of hydrogen and hydroxyl ions

1.418

equivalent conductivity of electrolytes in aqueous solution

1.412

limiting equivalent ionic conductance in aqueous solutions

1.408

limiting equivalent ionic conductance in aqueous solutions properties of liquids

2.699 1.407

standard solutions for calibrating conductivity vessels

1.411

Conductivity: elements

1.128

organic compounds

2.698

water, very pure

1.417

Conductivity vessels, standard solutions for calibrating Constant humidity, solutions for Constants, Debye-Hückel equation Conversion factors

1.411 4.76 1.300 4.8

Cooling mixtures

4.73

Coordination compounds, naming

1.11

Copper vs. copper nickel alloy thermocouple

4.192

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Covalent radii

1.151

atoms

1.158

inorganic compounds

1.151

octahedral covalent radii for CN = 6

1.158

Critical compressibility factor, elements

1.233

inorganic compounds

1.233

organic compounds

2.593

Critical density, organic compounds

2.593

Critical pressure: elements

1.233

inorganic compounds

1.233

organic compounds

2.593

Critical properties: elements

1.233

inorganic compounds

1.233

lydersen's increments

2.607

organic compounds

2.593

Critical temperature: elements

1.233

inorganic compounds

1.233

organic compounds

2.593

Critical volume: elements

1.233

inorganic compounds

1.233

organic compounds

2.593

vetere group contributions

2.608

Cryoscopic constants

4.74

Crystal lattice, types

1.176

Crystal structure

1.177

Crystals, X-ray spectroscopy

3.138

Crystal symmetry, inorganic compounds

1.64

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Cubical coefficients of thermal expansion Cyclopropane, triple point

4.160 1.90

D Dative (coordination) bonds

1.172

Debye-Hückel equation, constants

1.300

Demasking agents

4.156

Density

4.41

alkyl halides

2.255

elements

1.124

fats

2.808

inorganic compounds

1.16

mercury

1.91

natural and synthetic rubber

2.776

oils

2.808

organic compounds

2.65

petroleum products

2.811

polymers

2.740

water

1.91

waxes

2.810

Deuterium oxide, vapor pressure

1.225

Dielectric constant

1.173

inorganic compounds

1.173

organic compounds

2.470

water at various temperatures Dielectric loss factor

2.289

2.777

2.780

1.95 1.172

Dienes, ultraviolet absorption

3.57

Dienones, ultraviolet absorption

3.58

3.57

bonds

1.171

2.468

groups

1.172

2.468

Dipole moments:

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Dipole moments: (Cont.) molecules

1.173

Disaccharides

2.48

components

2.470

2.52

Dissociation constants, inorganic acids

1.330

Dissociation energies, bonds

1.160

DNA

2.56

Double bonds, cumulated: infrared absorption

3.10

Raman spectroscopy

3.43

Double bonds, miscellaneous: infrared absorption

3.16

Raman spectroscopy

3.46

Drying agents

4.75

Dynamic viscosity

2.270

E Ebullioscopic constants

4.81

EDTA complexes, formation constants

4.152

Effective ionic radii, elements

1.151

Electrode potentials: elements and their compounds

1.380

half-wave potentials of inorganic materials

1.397

half-wave potentials of organic materials

2.687

organic compounds

2.687

overpotentials for common electrode reactions

1.396

reference electrodes as a function of temperature 1.404 water-organic solvent mixtures

1.404

selected half-reactions at 25°C

1.383

standard electrode potentials for aqueous solutions

1.401

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Electrode reactions, overpotentials

1.396

Electron affinity: elements

1.146

molecules

1.146

radicals

1.148

Electron arrangements of the elements Electronegativity values, elements

1.97 1.145

Electrolytes, equivalent conductivity in aqueous solution

1.412

Elements

1.96

approximate effective ionic radii in aqueous solution

1.151

atomic numbers

1.97

atomic weight

1.122

atomic radii

1.151

boiling point

1.18

bond lengths between chemical symbols conductivity

1.121

1.124

1.159 1.97

1.124

1.128

definition

1.96

effective atomic radii

1.151

electrode potentials

1.380

electron affinity

1.146

electron arrangements electronegativity energy levels

1.97 1.145 1.96

enthalpy of formation

1.237

entropy

1.237

formula

1.18

formula weight

1.18

Gibbs energy of formation

1.237

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Index Terms

Links

Elements (Cont.) groups

1.121

heat capacity

1.237

heat of fusion

1.280

heat of sublimation

1.280

heat of vaporization

1.280

ionization energy

1.138

main energy levels

1.96

masking agents

4.153

melting point

1.18

nuclear properties

3.77

oxidation states

1.124

periodic table

1.121

periods

1.121

physical properties

1.18

precipitation of

4.130

radioactivity

1.135

resistivity

1.128

solubility

1.18

specific heat

1.280

specific heat capacity

1.124

sublimation points

1.124

thermal conductivity

1.128

vapor pressure

1.201

work functions

1.132

Element sequence, naming inorganic compounds Emission energies, X-ray Energy levels, elements

1.99

1.124

1.124

1.136

1.137

1.231

1.5 3.135 1.96

Energy of formation: elements

1.237

inorganic compounds

1.237

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Enones, ultraviolet absorption

3.58

Enthalpy of formation (See Heat of formation) Enthalpy of fusion (See Heat of fusion) Enthalpy of sublimation (See Heat of sublimation) Enthalpy of vaporization (See Heat of vaporization) Entropies: elements

1.237

inorganic compounds

1.237

Epoxides, infrared absorption

3.20

Equilibrium constant: definition

1.310

pK values for proton transfer reactions

2.676

pKa values of organic materials in water

2.620

2.620

organic material is aqueous solution at various temperatures

2.670

Equivalent conductance of hydrogen and hydroxyl ions

1.418

Equivalent conductivity of electrolytes in aqueous solution

1.412

Esters: infrared absorption

3.12

Raman spectroscopy

3.45

Ethers: infrared spectroscopy

3.20

Raman spectroscopy

3.51

Eutectic mixtures

1.418

Explosive limits, (See Flammability and flammability limits)

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

F Fats, oils and waxes

2.807

properties

2.808

Fatty acids, (See also Carboxylic acids): formula

2.55

nomenclature

2.30

Filters, membrane

4.133

Fixed points, thermocouples

4.182

Fixed points, thermometry

4.182

Flammability: auto-ignition temperature

2.351

flash point

2.351

ignition temperature

2.351

limits of inorganic compounds in air

1.96

limits of petroleum products in air

2.811

lower flammability limits

2.351

organic compounds

2.351

upper flammability limits

2.351

Flammability limits organic compounds

2.426

2.426

2.426

2.351 2.426

Flash point: organic compounds

2.65

petroleum products

2.811

Fluidity, definition Fluorescence spectroscopy quantum yield values

2.352

2.271 3.60 3.63

Fluorescent indicators

2.682

Fluorine-19 chemical shifts

3.105

3.106

Fluorine-19 to fluorine-19 spin coupling constants

3.106

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Fluxes

4.133

Formation constants: ammine complexes

4.152

EDTA complexes, formation constants

4.152

inorganic ligands

1.358

metal complexes

1.357

organic ligands

1.363

Formula weight: elements

1.18

inorganic compounds

1.18

organic compounds

2.65

Freezing point: lowering

4.74

magnesium chloride brines

2.463

sodium chloride brines

2.463

Freezing mixtures

2.460

2.461

2.463

Freezing temperature (See Melting point) Fritted glassware: cleaning solutions

4.132

porosity

4.134

Functional compounds, organic, nomenclature

2.18

Fused polycyclic aromatic hydrocarbons: boiling point

2.257

formula

2.257

molecular weight

2.257

melting point

2.257

nomenclature

2.10

structure

2.257

2.257

Fusion, heat of (See Heat of fusion)

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

G Gases: conversion of volume to STP

4.61

molar equivalent of various temperatures and pressures

4.70

physical chemistry equations solubility in water

4.67 1.311

thermal conductivity as a function of temperature

2.506

TLV concentration limits

4.165

Van der Waal's constants

2.609

Gas permeability constants for polymers and rubber

2.801

Gibbs energy of formation: elements

1.237

inorganic compounds

1.237

Glycerol: aqueous solutions, relative density

2.287

aqueous solutions, surface tension

2.287

Glycerol-water freezing mixtures

2.462

Glycol-water freezing mixtures

2.462

Gravimetric factors

4.104

Group dipole moments

1.172

4.135

Groups, organic: nomenclature

2.19

2.20

2.23

H Halogen compounds, infrared absorption

3.24

Hammett and Taft substituent constants

2.703

Hammett equation, values for

2.707

Hammett sigma constants

2.709

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Hansen solubility parameters: organic liquids

2.269

polymers

2.805

Heat capacity: elements

1.237

inorganic compounds

1.237

organic compounds

2.515

polymers

2.785

Heating baths, substances for

4.83

Heating temperatures for precipitates

4.135

Heat of formation, organic compounds

2.495

2.515

Heat of fusion: elements

1.280

inorganic compounds

1.280

organic compounds

2.561

Heat of sublimation: elements

1.280

inorganic compounds

1.280

organic compounds

2.561

Heat of vaporization: elements

1.280

inorganic compounds

1.280

organic compounds

2.561

Heteroaromatics, ultraviolet absorption

3.59

Heterocyclic systems: nomenclature

2.13

suffixes

2.13

trivial names

2.14

1-Hexene, triple point

1.90

2.17

Hildebrand solubility parameters: organic liquids

2.268

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Index Terms

Links

Hildebrand solubility parameters: (Cont.) polymers

2.804

Humidity: constant, solutions for

4.76

relative

4.77

Hybrid bonds, spatial orientation

4.79

1.175

Hydrocarbons, fused polycyclic aromatic: boiling point

2.257

formula

2.257

molecular weight

2.257

melting point

2.257

nomenclature

2.10

structure

2.257

2.257

Hydrocarbons, saturated: infrared absorption Raman spectroscopy Hydrogen, equivalent conductance Hydrometers

3.3 3.38 1.418 4.41

conversion between

4.45

Hydroxyl compounds: infrared absorption Raman spectroscopy

3.6 3.41

Hydroxyl ions: equivalent conductance

1.418

I Ice, vapor pressure

1.222

ICP spectroscopy, (See Induction coupled plasma spectroscopy) Ignition temperature (ignition point): definition

2.351

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Ignition temperature (ignition point): (Cont.) organic compounds

2.352

petroleum products

2.811

Imides, infrared absorption

3.15

Imines, infrared absorption

3.8

Incompatible chemicals

3.16

4.173

Indicators: acid-base

2.677

fluorescent

2.682

metal ion

4.151

mixed

2.680

oxidation-reduction

2.684

pH determination

2.686

Induction coupled plasma spectroscopy Infrared absorption spectroscopy

3.64 3.3

acetals

3.20

acid anhydrides

3.12

aldehydes

3.13

alkane residues attached to miscellaneous atoms

3.4

alkenes

3.16

amides

3.14

aromatic compounds

3.19

atoms bonded to hydrogen by a single bond

3.3

azo compounds

3.17

boron compounds

3.23

carboxylate ions

3.14

carbonyl bonds

3.12

carboxylic acids

3.14

double bonds, cumulated

3.10

double bonds, miscellaneous

3.16

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Infrared absorption spectroscopy (Cont.) epoxies

3.20

esters and lactones

3.12

halogen compounds

3.24

inorganic ions

3.26

ketals

3.20

ketones

3.13

hydroxyl compounds

3.6

imides

3.15

inorganic ions

3.26

near infrared

3.26

N-H bonds (amines, imines, ammonium ions, amides)

3.8

nitro compounds, absorption

3.17

phosphorus compounds

3.21

phthalanes

3.20

sulfates

3.21

sulfonamides

3.21

sulfones

3.21

sulfoxides

3.21

sulfur compounds

3.21

thiocarbonyls

3.21

thioesters and acids

3.15

thiols

3.21

thiosulfonates

3.21

transmission characteristics of selected solvents

3.29

transmitting materials

3.28

transmittance-absorbance conversion

3.33

triple bonds

3.9

urea and derivatives

3.15

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Index Terms

Links

Infrared absorption spectroscopy (Cont.) urethanes

3.15

values of absorbance for percent absorption

3.31

wave number—wavelength conversion

3.36

Inorganic acids

1.9

dissociation constants

1.330

naming

1.9

trivial names

1.9

1.10

1.10

1.11

salts and functional derivatives Inorganic addition compounds

1.13

Inorganic anions: limiting equivalent ionic conductance in aqueous solutions inorganic cations Inorganic cations

1.409 1.408 1.8

limiting equivalent ionic conductance in aqueous solutions

1.408

Inorganic compounds: boiling point

1.18

color, crystal symmetry, and refractive index

1.64

electrode potentials

1.380

enthalpy of formation

1.237

entropy

1.237

flammability limits formula

1.96 1.4

formula weight

1.18

1.18

Gibbs energy of formation

1.237

half wave potentials

1.397

heat capacity

1.237

heat of fusion

1.280

heat of sublimation

1.280

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Inorganic compounds: (Cont.) heat of vaporization melting point

1.280 1.18

naming

1.5

nomenclature

1.3

physical constants

1.18

physical properties

1.16

proton-transfer reactions

1.350

saturated solutions

1.343

solubility

1.18

solubility of inorganic compounds in water

1.5

1.310

1.311

solubility of metal salts of organic acids in water 1.311 solubility product constants

1.331

solubility rules

4.161

specific heat

1.280

surface tension

1.226

synonyms and mineral names

1.13

thermodynamic functions

1.237

vapor pressures

1.203

viscosity

1.226

writing formulas

1.212

1.4

Inorganic coordination compounds

1.11

Inorganic ions, infrared absorption

3.23

Inorganic ligands, formation constants with metal complexes

1.358

Inorganic materials in water: half-wave potentials of inorganic materials

1.397

proton transfer reactions of at 25°C

1.352

Interplanar spacing, X-ray spectroscopy

3.138

Iodine value: fats and oils

2.808

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Index Terms

Links

Iodine value: (Cont.) waxes

2.810

Ion exchange chromatography

4.95

Ion exchange resins

4.97

Ionic charge

1.4

Ionic conductance, limiting equivalent in aqueous solutions

1.408

Ionic radii: approximate effective, in aqueous solution at 25°C

1.157

inorganic compounds

1.151

Ionization energy: elements

1.138

molecular species

1.141

2.495

radical species

1.141

2.495

Ions, activity coefficients in water at 25°C

1.300

1.301

Interfacial tension of polymers in the liquid phase

2.783

Iron vs. copper-nickel alloy thermocouple

4.187

Isotopic abundances of the elements: mass spectrometry

3.115

natural

1.132

K Ketals, infrared absorption

3.20

Ketones: infrared absorption melting points of derivatives Kinematic viscosity, definition

3.13 2.254 1.226

2.271

L Lactones, infrared absorption Lattice, crystal types

3.12 1.176

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Index Terms

Links

Lengths between elements, bond

1.159

Limiting equivalent ionic conductance in aqueous solutions: inorganic anions

1.409

inorganic cations

1.408

organic anions

1.410

organic cations

1.410

Linear free energy relationships

2.702

Liquid ammonia, vapor pressure

1.223

Liquid semi-conductors: conductance and conductivity

1.407

properties

1.407

Loss tangent

1.172

Lydersen's critical property increments

2.607

M Magnesium chloride brines, freezing point Main energy levels of the elements

2.463 1.96

1.99

Masking agents for: anions

4.155

elements

4.153

neutral molecules

4.155

Mass absorption coefficients, X-ray spectroscopy

3.140

Mass number

1.4

elements

1.132

Mass spectrometry

3.111

isotopic abundances of the elements McReynolds' constants

3.115 4.83

4.86

Mechanical properties: natural and synthetic rubber

2.776

polymers

2.740

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Index Terms

Links

Metal ion indicators

4.151

Melting point: carboxylic acids

2.256

derivatives of organic compounds

2.54

elements

1.18

inorganic compounds

1.16

lowering

4.74

organic compounds

2.65

paraffins

2.255

polymers

2.740

waxes

2.810

1.124

Melting points of derivatives of organic compounds: alcohols

2.254

aldehydes

2.254

amines

2.254

ketones

2.254

phenols

2.254

Membrane filters

4.133

Mercury: density

1.91

vapor pressure

1.220

Metal complexes, formation constants

1.357

Metal salts of organic acids, solubility in water

1.311

Methane, triple point Micropipets, tolerances for

1.358

1.363

1.90 4.158

Minerals: names

1.13

refractive index

1.86

Mixed indicators

2.680

Molar refraction

2.288

Molecular geometry, definition

1.174

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Index Terms

Links

Molecular weight, elevation of the boiling point

4.81

Molecular weight of petroleum products

2.811

Molecules, inorganic: dielectric constant

1.173

dipole moments

1.173

electron affinity

1.146

ionization energy

1.141

Molten salts: properties

1.88

Monosaccharides

2.48

classification

2.49

Monosubstitued benzenes, nuclear magnetic resonance spectroscopy

3.84

N Naming, (See Nomenclature) Naphthalene: thermal conductivity

1.232

National Bureau of Standards reference pH buffer solutions

1.303

Naturally occurring isotopes: Mass spectrometry

3.115

Relative abundances

1.132

Neptunium series of the elements, radioactivity

1.135

Nickel-chromium alloy vs. nickel aluminum alloy thermocouple

4.188

Nickel-chromium silicon alloy vs. nickel silicon magnesium alloy thermocouple Nitro compounds, infrared absorption

4.189 3.17

Nitrogen-15 and nitrogen-14 chemical shifts

3.100

Nitrogen-15 to proton spin coupling constants

3.104

3.103

This page has been reformatted by Knovel to provide easier navigation.

Index Terms

Links

Nitrogen-15 to carbon-13 spin coupling constants

3.104

Nitrogen-15 to fluorine-19 spin coupling constants

3.104

Nitrogen ring systems: nomenclature

2.14

Nitrogen-oxygen ring systems, nomenclature

2.14

Nomenclature: anions

1.8

cations

1.8

coordination compounds

1.11

element sequence

1.5

inorganic compounds

1.4

organic compounds

2.4

organic radicals

2.57

synonyms and mineral names

1.13

Non-standard buffer solutions Nuclear magnetic resonance spectroscopy

1.307 3.76

boron-11 chemical shifts

3.99

carbon-13 chemical shifts

3.87

carbon-13 chemical shifts of deuterated solvents

3.98

carbon-carbon spin coupling constants

3.96

carbon-fluorine spin coupling constants

3.97

carbon-hydrogen spin coupling constants

3.95

carbon spin coupling constants with various nuclei

3.95

fluorine-19 chemical shifts

3.105

3.106

fluorine-19 to fluorine-19 spin coupling constants

3.106

nitrogen-15 and nitrogen-14 chemical shifts

3.100

3.103

nitrogen-15 to carbon-13 spin coupling constants

3.104

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Index Terms

Links

Nuclear magnetic resonance spectroscopy (Cont.) nitrogen-15 to fluorine-19 spin coupling constants

3.104

nitrogen-15 to proton spin coupling constants

3.104

nuclear properties of the elements

3.77

monosubstituted benzenes

3.84

phosphorus-31 chemical shifts

3.107

phosphorus-31 spin coupling constants

3.110

proton chemical shifts

3.80

protons attached to double bonds

3.83

proto in deuterated solvents

3.86

proton spin coupling constants

3.85

reference compounds

3.86

silicon-29 chemical shifts

3.106

Nuclear properties of the elements

3.77

Nuclides, natural abundance, cross-section, radiation 1.177 Number of atoms

1.4

Numerical, prefixes

4.3

O 1-Octene, triple point Oils

1.90 2.807

properties

2.808

Oligosaccharides

2.48

Optical activity

2.43

Organic acids, solubility of metal salts in water

1.311

Organic anions, limiting equivalent ionic conductance in aqueous solutions

1.410

Organic cations, limiting equivalent ionic conductance in aqueous solutions

1.410

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Index Terms

Links

Organic compounds: auto-ignition temperature boiling point

2.426 2.19

boiling points at selected pressures

2.315

bond dissociation energies

2.467

bond lengths

2.464

characteristic groups

2.19

chirality

2.43

conductivity

2.297

2.352

2.20

2.698

density

2.19

dielectric constants

2.470

dipole moments

2.468

electrode potentials

2.687

energy of formation

2.515

enthalpies

2.515

entropies

2.515

equilibrium constants

2.620

flammability properties

2.351

flash point

2.19

formula weight

2.19

half-wave potentials of organic materials

2.687

Hansen solubility parameters

2.269

heat capacity

2.515

heat of formation

2.495

heat of fusion

2.561

heat of sublimation

2.561

heat of vaporization

2.561

hildebrand solubility parameters

2.268

ignition temperature (ignition point)

2.352

ionization energy

2.495

lower flammability limits

2.426

2.289

2.294

2.470

2.670

2.676

2.352

2.805

2.515

2.804

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Index Terms

Links

Organic compounds: (Cont.) melting point

2.19

nomenclature

2.4

optical activity

2.43

physical properties

2.64

proton transfer reactions

2.676

radicofunctional

2.23

refractive index

2.19

saturated solutions

2.294

2.20

2.23

2.807

1.343

solubility

2.19

stereochemistry

2.38

surface tension

2.272

thermal conductivity

2.509

upper flammability limits

2.426

vapor pressure

2.297

viscosity

2.272

Organic groups, nomenclature

2.289

2.19

Organic ions, limiting equivalent ionic conductance in aqueous solutions

2.699

Organic ligands, formation constants with metal complexes

1.363

Organic liquids: hansen solubility parameters

2.268

hildebrand solubility parameters

2.268

Organic radicals, nomenclature Organic semi-conductors

2.57 2.700

Organic solvents, (See also Solvents): boiling points

2.348

chromatographic use

4.84

infrared transmission

3.29

refractive index and density

2.294

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Index Terms

Links

Organic solvents, (See also Solvents): (Cont.) supercritical fluids

4.94

ultraviolet absorption

3.57

Overpotentials for common electrode reactions

1.396

Oxidation-reduction indicators

2.684

Oxidation states of the elements

1.124

Oximes, infrared absorption

3.16

Oxygen ring systems, nomenclature

2.14

3.58

P Paraffin wax, thermal conductivity

1.232

Paraffins: boiling points

2.350

melting points

2.255

Periodic table

1.121

Periods of the elements

1.121

Permittivity (See Dielectric constant) Petroleum products, physical properties

2.811

pH: Approximate pH value of solutions, calculation

1.350

calculation of concentrations of species present at a given pH

1.351

measurement, blood and biological media

1.301

reference values of acidity measurement

1.306

values for buffer solutions

1.307

pH determination indicators

2.686

Pipet capacity, tolerances for

4.158

pKa values of organic materials in water

2.620

pK values for proton transfer reactions

2.676

Phenols: melting points of derivatives

2.254

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Index Terms

Links

Phenols: (Cont.) nomenclature

2.24

Phosphorous acids, formula

2.35

Phosphorus-31 chemical shifts

3.107

Phosphorus-31 spin coupling constants

3.110

Phosphorus-containing compounds: infrared absorption

3.21

nomenclature

2.35

Phthalanes, infrared absorption

3.20

Physical constants

4.4

elements

1.18

inorganic compounds

1.18

Physical properties: elements

1.18

1.124

inorganic compounds

1.16

1.18

natural and synthetic rubber organic compounds

2.776 2.64

polymers

2.740

waxes

2.810

Plastics

2.739

Properties

2.740

Platinum rhodium alloy vs. platinum thermocouple

4.190

4.191

Polycyclic aromatic hydrocarbons: boiling point

2.257

formula

2.257

melting point

2.257

molecular weight

2.257

nomenclature

2.10

structure

2.257

2.257

Polymers

2.709

chemical name

2.778

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Index Terms

Links

Polymers (Cont.) density

2.740

density at various temperatures

2.780

electrical properties

2.740

gas permeability constants

2.801

heat capacities

2.786

hildebrand solubility parameters

2.804

interfacial tension, liquid phase

2.783

mechanical properties

2.740

names and structures

2.730

physical properties

2.740

refractive indices

2.807

resistance to chemicals

2.800

surface tension

2.782

thermal conductivity

2.794

thermal expansion coefficients

2.784

trade names

2.777

Polysaccharides

2.48

Porosity of fritted glassware

4.134

Precipitates, heating temperatures

4.135

Precipitation of the elements, reagents for

4.130

Precipitation, standard solutions

4.149

2.777

2.798

2.799

2.52

Prefixes: numerical

4.3

SI

4.3

Pressure conversion

4.58

Pressure, critical: elements

1.233

inorganic compounds

1.233

Propene, triple point

1.90

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Index Terms

Links

Properties, critical: elements

1.233

inorganic compounds

1.233

Proton chemical shifts

3.80

Protons attached to double bonds

3.83

Protons in deuterated solvents

3.86

Proton spin coupling constants

3.85

Proton-transfer reactions inorganic materials in water at 25°C

1.350 1.352

Purines, in DNA

2.56

Pyrimidines, in DNA

2.56

Q Quaternary electrolytes, activity coefficient

1.299

Quantum yield values, Fluorescence spectroscopy

3.60

R Radicals: electron affinity

1.146

ionization energy

1.141

Radioactivity: actinium series

1.137

neptunium series

1.135

thorium series

1.136

uranium series

1.137

Raman spectroscopy

3.37

aromatic compounds

3.48

carbonyl compounds

3.44

double bonds, cumulated

3.43

double bonds, miscellaneous

3.46

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Index Terms

Links

Raman spectroscopy (Cont.) ethers

3.51

halogen compounds

3.52

heterocyclic rings

3.53

N-H bonds

3.41

saturated compounds

3.38

single bonds

3.38

sulfur compounds

3.50

triple bonds

3.42

Reactive chemicals

4.173

Redox equations

4.145

Reference electrodes as a function of temperature

1.404

Reference buffer solutions

1.301

Reference compounds, nuclear magnetic resonance spectroscopy

3.86

Refractive index: atomic and group refractions definition

2.288 1.17

fats and oils

2.287

2.808

inorganic compounds

1.17

minerals

1.86

organic compounds

2.65

polymers

1.64

2.287

2.294

2.807

water at various temperatures waxes

1.95 2.810

Refrigerated storage chemicals

4.179

Relative abundances: naturally occurring isotopes

1.132

Relative density, glycerol, aqueous solutions, relative density

2.287

sucrose, aqueous solutions

2.287

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Index Terms

Links

Relative humidity

4.77

4.79

Relative permittivity (See Dielectric constant) Resistivity, elements

1.128

Reynolds number, definition

2.271

RNA

2.56

Rubber, natural and synthetic: gas permeability constants

2.801

mechanical properties

2.776

physical properties

2.776

resistance to chemicals

2.800

S Salts and functional derivatives of inorganic acids, naming

1.11

Saponification value: fats and oils

2.808

waxes

2.810

Saturated solutions, inorganic and organic compounds

1.343

Screens, (See Sieves and screens) Selected half-reactions at 25°C, electrode potentials

1.383

Semi-conductors, organic

2.700

Separation methods

4.83

Sieves and screens

4.180

Silicon-29 chemical shifts

3.106

Single bonds, infrared absorption

3.3

SI prefixes

4.3

Sodium chloride brines, freezing point

2.463

Solidification point, fats and oils

2.808

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Index Terms

Links

Solubility: carboxylic acids in water

2.256

elements

1.18

inorganic compounds

1.18

Solubility and equilibrium contacts

1.310

Solubility of gases in water

1.311

Solubility of inorganic compounds in water

1.311

Solubility of metal salts of organic acids in water

1.311

Solubility parameters: group contributions

2.270

hansen

2.269

2.805

hildebrand

2.268

2.804

Solubility product constants: complex inorganic ions

1.342

inorganic compounds

1.331

Solubility rules for inorganic compounds Solutes, behavior in chromatography

4.161 4.90

Solutions, standard stock

4.163

Solvents, refractive index and density

2.294

Spatial orientation of common hybrid bonds

1.175

Specific gravity, (See Density): air at various temperatures

1.92

Specific heat: elements

1.280

inorganic compounds

1.280

organic compounds

2.561

Specific refraction: definition

2.287

Spectroscopy, infrared absorption, (See Infrared absorption spectroscopy) Stability constants, complex inorganic ions

1.343

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Index Terms

Links

Standard buffer solutions

1.303

Standard electrode potentials for aqueous solutions

1.401

Standard reference values of pH for the measurement of acidity

1.306

Standards, for acid-base titration

4.137

Standard solutions for calibrating conductivity vessels

1.411

Standard solutions for precipitation

4.149

Standard stock solutions

4.163

Starch

2.52

Steam correction for thermometers Stereochemistry

4.182 2.38

Structure: crystal

177

Sublimation, heat of (See Heat of sublimation) Sublimation points, elements Succinonitrile, triple point

1.124 1.90

Sucrose: aqueous solutions, relative density

2.287

aqueous solutions, surface tension

2.287

Suffixes for heterocyclic systems

2.13

Sulfates, infrared absorption

3.21

Sulfonamides, infrared absorption

3.21

Sulfonates, infrared absorption

3.21

Sulfones, infrared absorption

3.21

Sulfoxides, infrared absorption

3.21

Sulfur compounds, infrared absorption

3.21

Sulfur ring systems, nomenclature

2.14

Supercritical fluids

4.94

Surface tension: definition

2.271

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Index Terms

Links

Surface tension: (Cont.) inorganic compounds

1.226

organic compounds

2.272

polymers, liquid phase

2.782

water at various temperatures

1.95

Synonyms, inorganic compounds

1.13

T Target elements, X-ray spectroscopy Temperature conversion

3.138 4.28

Temperature, critical: elements

1.233

inorganic compounds

1.233

Ternary electrolytes, activity coefficient

1.299

Ternary azeotropes containing: allyl alcohol

2.455

1-butanol

2.455

2-butanol

2.455

ethanol

2.454

methanol

2.454

3-methyl-1-butanol

2.455

2-methyl-1-propanol

2.455

2-methyl-2-propanol

2.455

1-propanol

2.454

2-propanol

2.454

Ternary azeotropes containing water Terpenes, formula

2.456 2.54

Thermal conductivity: asphalt

1.232

coal

1.232

elements

1.231

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Index Terms

Links

Thermal conductivity: (Cont.) gases, as a function of temperature

2.506

naphthalene

1.232

organic compounds

2.509

paraffin (wax)

1.232

polymers

2.794

various solids

1.232

Thermal expansion coefficients of polymers

2.784

Thermal expansion, cubical coefficients

4.160

Thermal properties

1.418

Thermocouples

4.182

copper vs. copper nickel alloy

4.192

iron vs. copper-nickel alloy

4.187

2.798

2.799

nickel-chromium alloy vs. nickel aluminum alloy

4.188

nickel-chromium silicon alloy vs. nickel silicon magnesium alloy platinum rhodium alloy vs. platinum Thermocouples, fixed points

4.189 4.190

4.191

4.184

Thermodynamic functions: inorganic compounds

1.237

organic compounds

2.512

Thermometers, stem correction

4.182

Thermometry

4.180

Thiocarbonyl compounds, infrared absorption

3.21

Thioesters and acids, infrared absorption

3.15

Thiols, infrared absorption

3.21

Thiosulfonates, infrared absorption

3.21

Thorium series of the elements: radioactivity

1.136

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Index Terms

Links

Titrimetric factors

4.138

TLV concentration limits for gases and vapors

4.165

Tolerances for: analytical weights

4.134

burettes

4.159

micropipets

4.158

pipet capacity

4.158

volumetric flasks

4.158

Transition temperatures

1.418

Transmission characteristics of selected solvents

3.29

Transmittance-absorbance conversion, infrared spectroscopy

3.33

Transmitting materials, infrared absorption

3.28

Triple bonds: infrared absorption

3.9

raman spectroscopy

3.42

Triple points: cyclopropane

1.90

1-hexene

1.90

inorganic compounds

1.90

methane

1.90

1-octene

1.90

propene

1.10

U Ultraviolet spectroscopy

3.54

absorption bands for representative chromophores 3.55 benzene and heteroaromatics

3.59

benzene derivatives

3.59

cutoffs for spectrograde solvents

3.57

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Index Terms

Links

Ultraviolet spectroscopy (Cont.) dienes

3.57

enones and dienones

3.58

solvent correction

3.58

Woodward-Fieser rules

3.57

Ununbium

1.120

Ununhexium

1.120

Ununoctium

1.120

Ununnilium

1.119

Ununquadium

1.120

Unununium

1.120

Uranium series of the elements, radioactivity

1.137

Urea and derivatives, infrared absorption

3.15

Urethanes, infrared absorption

3.15

Uronic acids

2.51

V Values of absorbance for percent absorption Van der Waal's constants for gases

3.31 2.609

Vaporization, heat of (See Heat of vaporization) Vapor pressure

1.199

ammonia, liquid

1.223

definition

1.199

deuterium oxide

1.225

equations

1.199

ice

1.222

inorganic compounds

1.212

inorganic compounds up to 1 atmosphere

1.203

liquid ammonia

1.223

mercury

1.220

organic compounds

2.297

2.296

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Index Terms

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Vapor pressure (Cont.) selected elements at different temperatures

1.201

various inorganic compounds

1.212

water

1.224

Vapor pressure equations

1.199

Vapors, TLV concentration limits

4.165

Viscosity

4.66

absolute, definition

1.226

conversion of scales

4.66

dynamic

2.270

glycerol solutions, aqueous

2.287

inorganic compounds

1.226

kinematic, definition

1.226

organic compounds

2.272

sucrose solutions, aqueous solutions

2.287

water

2.271

1.95

Volume: computation

4.159

conversion to STP

4.61

Volume, critical: elements

1.233

inorganic compounds

1.233

Volumetric factors

4.138

Volumetric flasks, tolerances for

4.158

W Water: boiling point at various pressures

1.93

compressibility at various temperatures

195

critical properties density

1.94

1.236 1.91

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Water: (Cont.) dielectric constant

1.95

refractive index at various temperatures

1.95

solubility of gases in

1.311

surface tension

1.95

vapor pressure

1.224

viscosity at various temperatures

1.95

Water-alcohol freezing mixtures

2.460

Water-glycerol freezing mixtures

2.462

Water-glycol freezing mixtures

2.462

2.461

Water-organic solvent mixtures, electrode potentials

404

Water vapor in saturated air Wavelengths of absorption edges Wave number, conversion to wavelength

4.80 3.130 3.36

Wax, thermal conductivity

1.232

Waxes

2.807

physical properties Weight, conversion from air to vacuum Work functions of the elements

2.810 4.59 1.132

Writing formulas: element sequence

1.5

inorganic compounds

1.4

placement of atoms in a formula

1.4

X X-ray absorption energies

3.133

X-ray emission energies, X-ray

3.135

X-ray emission spectra

3.128

X-ray spectroscopy

3.126

crystals

3.138

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Index Terms

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X-ray spectroscopy (Cont.) filters for target elements

3.138

interplanar spacing

3.138

mass absorption coefficients

3.140

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