Inorganic Materials Chemistry Desk Reference, Second Edition

SECOND EDITION

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE D. Sangeeta John R. LaGraff

CRC PR E S S Boca Raton London New York Washington, D.C.

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Library of Congress Cataloging-in-Publication Data Sangeeta, D. Inorganic materials chemistry desk reference.—2nd ed. / D. Sangeeta and John R. LaGraff. p. cm. Includes bibliographical references and index. ISBN 0-8493-0910-7 (alk. paper) 1. Inorganic compounds—Industrial applications—Handbooks, manuals, etc. I. LaGraff, John R. II. Title TP200.S26 2004 661—dc22 2004051930

This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage or retrieval system, without prior permission in writing from the publisher. The consent of CRC Press does not extend to copying for general distribution, for promotion, for creating new works, or for resale. Specific permission must be obtained in writing from CRC Press for such copying. Direct all inquiries to CRC Press, 2000 N.W. Corporate Blvd., Boca Raton, Florida 33431. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation, without intent to infringe.

Visit the CRC Press Web site at www.crcpress.com © 2005 by CRC Press No claim to original U.S. Government works International Standard Book Number 0-8493-0910-7 Library of Congress Card Number 2004051930 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0

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About the Authors Dr. D. Sangeeta* is a maintenance cost risk manager for GE Aircraft Engines. Prior to that she worked in GEAE’s Quality & Marketing organizations. She moved to GEAE from General Electric Global Research Center, where she worked as a materials scientist in the ceramics laboratory conducting a variety of inorganic materials chemistry-related projects on gas turbine repair technology. Prior to joining General Electric in March 1994, she was a research scientist at Battelle in Columbus, Ohio. There, she conducted research and development in the areas of sol-gel processing, metal organic chemical vapor deposition, and supercritical drying to produce ceramic films, powders, and monolithic composites. She currently holds 26 patents in the area of materials science. Dr. Sangeeta was a research associate in the materials science department at the University of Illinois, Urbana, in 1989. As a research associate she conducted research relating to sol-gel processing of ferroelectric thin films and zirconia powders. She completed her Ph.D. in chemistry with Professor W. G. Klemperer at the School of Chemical Sciences, University of Illinois, UrbanaChampaign. Her thesis work involved understanding the molecular growth pathways in silica solgel processing. She obtained her master’s degree in chemistry from the Indian Institute of Technology, Kanpur, in 1984 and her bachelor’s degree in science from Christ Church College, Kanpur, India, in 1982. John R. LaGraff is currently a lecturer in both the Physics and Chemistry Departments at Rensselaer Polytechnic Institute in Troy, New York, where he teaches general physics and chemical principles for engineers. John is also a research scientist at the New York State Department of Health’s Wadsworth Research Center in Albany, New York, where he conducts research in proteinsubstrate interactions and their application to nanobiotechnology. John LaGraff has also taught courses in physical chemistry, general chemistry, inorganic chemistry, nanoscience and materials science at Union College and Hamilton College. John LaGraff’s academic training includes a National Science Foundation Postdoctoral Fellowship in Chemistry at the University of Illinois, Urbana Champaign, where his research focused on in situ scanning probe microscopy (SPM) of nanoscale electrochemical processes on single crystal metal surfaces. This work included some of the first studies using oxide and self-assembled monolayers as nanoscale resists for SPM based electrochemical nanolithography. He received his Ph.D and M.S. degrees in ceramic science, respectively, from the University of Illinois and the New York State College of Ceramics at Alfred University, Alfred, New York. His thesis work was in the area of single crystal growth, fluorine doping and characterization of superconducting oxides. John has a B.S. degree in chemical engineering from Syracuse University. Dr. LaGraff has published approximately 30 papers, made over 60 invited or contributed presentations, and holds 8 patents.

* Formerly Sangeeta D. Ramamurthi.

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Preface to Second Edition The primary purpose of this second edition of Inorganic Materials Chemistry Desk Reference remains its value as a resource to assist in the preparation of solid state inorganic materials by chemical processing techniques. The idea for a second edition was conceived several years ago in an effort to both add new chemical precursors available to the Materials Scientists and to include existing or emerging topics where materials chemistry plays an important role, such as microelectronics, surface science, and nanotechnology. Additions to Chapter 1 include discussion of the role of materials chemistry in micro- and nano-fabrication, surface materials chemistry, self-assembly, scanning probe microscopy, and carbon fullerenes. The glossary in Chapter 2 contains over 200 new definitions related to the aforementioned topics. Chapter 3 has been greatly expanded to include 50% more new chemical precursors and their properties. The reader is referred to the preface of the first edition (following page) for more information regarding this book. JRL would like to acknowledge D. Sangeeta for inviting him to assist in the preparation of the second edition. JRL acknowledges helpful discussions with Professors Gwo-Ching Wang and Quynh Chu-LaGraff, and Dr. James N. Turner. Some of this material is based upon work supported by the National Science Foundation under Grant No. DBI-0304415. Any opinions, findings and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation (NSF). JRL would like to thank his wife, Quynh Chu-LaGraff, and their three sons, Luc, Giac, and Thai, for their patience and support. D. Sangeeta J.R. LaGraff

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Preface to First Edition This Inorganic Materials Chemistry Desk Reference is meant to be a resource to assist in the preparation of solid state inorganic materials by chemical processing techniques. Ceramic materials can be prepared by a variety of chemical routes and this handbook provides a brief introduction to inorganic materials chemistry and these processing routes, along with definitions of most commonly used terms in the field. The focus of the desk reference is a compilation of property data on inorganic precursors and on inorganic solids to assist in the selection of candidate precursors and materials for a variety of applications. The idea for such a resource for inorganic materials chemistry was conceived from my personal experience with initiating new materials chemistry-related projects, all of which began by necessity with the painstaking effort required to collect relevant information from a multitude of sources, including textbooks, handbooks, journals, proceedings, and magazines. Beginning with my thesis and postdoctoral work on sol-gel processing at the University of Illinois with Professors W. G. Klemperer and D. A. Payne, I found myself devoting a considerable fraction of my efforts to collecting relevant information in the area of materials chemistry. During my work at Battelle in Columbus, Ohio, and subsequently following my move to the General Electric Corporate Research and Development Center, it was clear to my colleagues and to me that there is a pressing need for a resource that not only explains the terms frequently used in the inorganic materials chemistry field, but also provides data on the physical properties of the precursors available for use in chemical processing techniques. Such questions as “What precursor can I select to prepare this inorganic solid?” and “Which precursor (from the processing point of view) is suitable or viable for this process?” are the types of questions that scientists and engineers need quick answers to in order to initiate a successful materials chemistry project. This resource provides a rapid reference to help answer these and other such questions. In addition, it provides physical property data on inorganic solids to answer questions such as “What kind of properties should I expect from this or similar materials?” The desk reference begins with a general introduction to the area of inorganic materials chemistry with an emphasis on chemical processing routes. Several sources of additional information are provided for newcomers to the field and for the experienced practitioners as well. The second chapter provides a quick reference to many commonly used terms in the field of inorganic materials chemistry. The primary purpose of the desk reference, that of providing data on inorganic precursors and ceramic materials, is served in Chapter 3 and Chapter 4. The third chapter is a compilation of physical property data on various organometallic, metal organic, and inorganic salt precursors used in the processes described in Chapter 1. The fourth chapter consists of seven sections detailing physical property data on inorganic solids, including oxides, carbides, nitrides, borides, selenides, tellurides, and sulfides, among others. As with any new idea, this resource is a start at compiling and organizing the information currently available. A concerted effort has been made to include all of the relevant information referenced in the multitude of published sources. However, in an emerging area such as this, new processes and products are being invented and discovered every day making it impossible to include every piece of information. With time, as more relevant information is published, this desk reference will be expanded and revised. Suggestions and input from readers are welcome and will be acknowledged gratefully. I would like to acknowledge CRC Press for inviting me to write this book and Prof. Edwin Boyer for encouraging me to take on this project. I would also like to acknowledge the contributions of the technical reviewers in their reviews of various sections of this book. Helpful discussions with Drs. William McDonald, S. Venkataramani, and James Ruud are gratefully acknowledged. I would like to thank my husband, Dr. R. Mukund, for providing key suggestions and for providing editorial and moral support throughout the project. Finally, I would like to thank my daughter, Dipali, for going to sleep on time so I could get to work at night. D. Sangeeta

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Reviewers of Second Edition Prof. Leslie A. Hull Union College Department of Chemistry Schenectady, New York

Prof. Jay J. Senkevich Rensselaer Polytechnic Institute Department of Physics, Applied Physics, and Astronomy Troy, New York

Prof. Sheo K. Dikshit Indian Institute of Technology Department of Chemistry Kanpur, India

Reviewers of First Edition Dr. Scott L. Swartz NexTech Materials, Ltd. Worthington, Ohio Prof. Sheo K. Dikshit Indian Institute of Technology Department of Chemistry Kanpur, India Prof. Leonard V. Interrante Rensselaer Polytechnic Institute Department of Chemistry Troy, New York

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Dr. Van E. Wood (Retired) Battelle Memorial Institute Columbus, Ohio Prof. Walter G. Klemperer University of Illinois School of Chemical Sciences Urbana, Illinois Dr. Barry Arkles Gelest Inc. Tullytown, Pennsylvania

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Contents Chapter 1 Introduction to Inorganic Materials Chemistry I. Introduction II. Preparation and Processing of Inorganic Materials A. Sol-Gel Process B. Hydrothermal Process C. Supercritical Drying Process D. Freeze-Drying Process E. Metal Organic Decomposition F. Metal Organic Chemical Vapor Deposition G. Aerosol Processes III. Microfabrication A. Microelectronics B. Microelectromechanical Systems (MEMS) Fabrication IV. Precursors A. Inorganic Salts B. Metal Organic Compounds C. Organometallic Compounds D. Polymeric Precursors E. Colloidal Suspension V. Additives VI. Surface Materials Chemistry VII. Nanotechnology A. Nanofabrication B. Self-Assembly C. Microcontact Printing. D. Nanotechnology Materials: Carbon Fullerenes VIII. Characterization Techniques A. Scanning Probe Microscopy B. Techniques 1. Elemental Analysis 2. Molecular and Solid State Analysis 3. Surface Characterization Techniques IX. Selected Sources of Information in Materials Chemistry A. Books B. Monographs/Proceedings C. Journals References Chapter 2 Definitions of Terms Used in Inorganic Materials Chemistry General References Selected References Chapter 3 References

Physical Properties of Inorganic Materials Precursors

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Chapter 4 Properties of Solid-State Inorganic Materials I. General Properties II. Electrical Properties References III. Magnetic Properties References IV. Optical Properties References V. Structural Properties References VI. Superconducting Compounds Sources VII. Thermal Properties References

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CHAPTER 1 Introduction to Inorganic Materials Chemistry I. INTRODUCTION Inorganic materials chemistry encompasses technologies that have traditionally existed in both inorganic chemistry and ceramics. Inorganic materials chemistry applies the expertise developed in inorganic chemistry to developing ceramic and glassy materials with improved properties and relative ease of processing. Growing acceptance in recent years of the importance of chemistry to materials preparation and processing has resulted in the recognition of materials chemistry as a distinct subdiscipline of chemistry. Materials chemistry in general can be defined as the chemical science that deals with the preparation, processing, and analysis of solid state materials. Inorganic materials chemistry, in particular, relates to the preparation, processing, and properties of inorganic materials, such as metal carbides, borides, nitrides, oxides, sulfides, selenides, tellurides, and their combinations.1 In contrast to conventional ceramic and glass processing, which require high temperatures and high pressures, inorganic materials chemistry involves preparation and processing of inorganic materials under relatively milder temperature and pressure conditions. The chemical route to ceramic materials can provide not only a milder route to ceramic and glassy materials, but also an opportunity to prepare unusual forms of existing materials such as epitaxial films, transparent films of otherwise opaque material, stable colloidal suspensions, submicron powders, and microporous membranes. Inorganic materials chemistry can also provide the opportunity to prepare novel multicomponent systems that are otherwise difficult to prepare by conventional techniques. Multicomponent systems such as Y, Ba, and Cu (1-2-3) oxide superconductors, for example, can be prepared in various forms, including films and powders prepared using novel chemical routes such as sol-gel and colloidal processing. Also, some materials, such as crystalline lead zirconate titanate [Pb(Zr,Ti)O3], which could previously be prepared only in a monolithic form or as single crystals, can now be fabricated using chemical processing techniques as polycrystalline films with properties similar to single crystals. The preparation and characterization of novel materials are currently the most popular research topics among the many areas of research in materials chemistry. Topics of interest include the development of precursors for glass, ceramic, metal, and semiconductor materials, wet chemical processing, gas phase film deposition and powder preparation, molecular, and micro- and macroscopic characterization of the resultant solid-state materials. The processing aspects of materials chemistry present the greatest opportunity for research and may deal with a variety of individual techniques, such as sol-gel processing, surface science, metal organic decomposition (MOD), metal organic chemical vapor deposition (MOCVD), colloidal processing, and nanoscale materials synthesis.

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Another important area of materials chemistry that is gaining interest is the study of the interaction between materials and their environment. These types of interactions can be characterized as corrosion, adhesion, oxidation, mechanical or chemical abrasion, thermal expansion, and chemical sensing processes. A complete understanding of such topics requires expertise in surface science, analytical chemistry, chemical kinetics, thermodynamics, and modeling of chemical processes. A common focus of such studies is the application of chemical methodologies to provide a molecular level understanding as well as improved control over the properties of the resultant materials and the interaction of these materials with the environment. Materials chemistry is also finding widespread application in areas with a strong surface science component including microelectronic processing of thin films, nanotechnology, and biotechnology. For example, new etching and cleaning solvents are being developed to assist in fabricating high aspect ratio microelectromechanical systems (MEMS), which may consist of micron-scale (and smaller) moving parts or channels to direct fluid flow across a substrate.

II. PREPARATION AND PROCESSING OF INORGANIC MATERIALS In this section, a variety of materials preparation and processing approaches to solid-state materials in various forms are described briefly. The types of processes discussed include the solgel process, colloidal processing, hydrothermal processing, freeze-drying, supercritical drying, MOD, MOCVD or CVD, and flame hydrolysis. Of these processes, sol-gel, colloidal, and hydrothermal processing are often referred to as wet chemical processing. A. Sol-Gel Process The sol-gel process is a wet chemical route to a variety of glass and ceramic compositions. It has been mainly used for compositions and forms such as certain multicomponent systems and films of specific compositions that are not easily available or possible by conventional ceramic processing methods. In the sol-gel process, the precursors are mixed to form sols (clear to cloudy) that undergo polymerization, forming a gel. By controlling reaction conditions such as solution pH, type of precursors and solvents, reaction temperature, and additives, a variety of physical forms can be produced including films, fibers, microspheres, and monoliths. For fabricating films or fibers, the viscous liquid is used for coating films or drawing fibers. The viscosity of the liquid is carefully controlled to provide the desired physical characteristics of the film or fiber. Fine ceramic powders are produced by the sol-gel process, sometimes referred as the gel precipitation process, by varying the reaction conditions, such as the solution pH and the type of solvent media used. Monoliths are normally prepared by drying the gel in a mold. The sol-gel process has advantages and disadvantages over conventional processes. Advantages include the ability to precisely control the stoichiometry, the possibility of producing multicomponent materials not previously available, and the ability to produce high-purity materials for electronics and optics without much investment in equipment. However, drawbacks of the sol-gel process include solvent waste, large-volume shrinkage during drying, and high precursor costs. For each application, the advantages and disadvantages of the sol-gel process must be considered in comparison with other processes. The use of sol-gel techniques for producing films has, in particular, generated considerable commercial interest because of the versatility of the process in producing multicomponent homogeneous compositions with ease and cost-effectiveness. Among ceramic compositions, oxides are the most common composition prepared by the solgel process, where the precursors are hydrolyzed in water and are air dried. A general sol-gel reaction to yield oxide systems with a single component where metal alkoxides are used as precursors is given below:

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→ M x Oy/2 + yROH M x ( OR ) y + y/ 2 H2 O   ROH

where R is an alkyl or aryl. The above reaction results from two intermediate reactions called hydrolysis and condensation, which can be represented by the following equations: M x ( OR ) y + H2 O → M x ( OR ) y−1 ( OH ) + ROH

hydrolysis:

condensation: M x ( OR ) y + M x ( OR ) y−1 ( OH ) → ( OR ) y−1 M x OM x ( OR ) y−1 + ROH or M x ( OR ) y−1 ( OH ) + M x ( OR ) y−1 ( OH ) → ( OR ) y−1 M x OM x ( OR ) y−1 + H2 O The above condensed species undergo further condensation during drying and heat-treatment processes, which results in the formation of oxides. Examples of such single-component oxide systems are 3 Si ( OCH3 )4 + 2 H2 O   → SiO2 + 4 CH3 OH

CH OH

The hydrolysis and condensation reactions can be represented by Si ( OCH3 )4 + H2 O → Si ( OCH3 )3 ( OH ) + CH3 OH Si ( OCH3 )4 + Si ( OCH3 )3 ( OH ) → ( OCH3 )3 SiOSi ( OCH3 )3 + CH3 OH Si ( OCH3 )3 ( OH ) + Si ( OCH3 )3 ( OH ) → ( OCH3 )3 SiOSi ( OCH3 )3 + H2 O Other materials such as sulfides and other chalcogenides can also be prepared by the above process, with H2S or thiols normally used as sulfidating agents to form the sulfides. Carbides and nitrides can be prepared by carefully selecting appropriate alkoxide and other precursors that decompose after polymerization into carbides and nitrides with minimal oxide impurities, under reducing or nitridating (ammonia) atmospheres. The preparation process for carbides, nitrides, and borides can also be classified as an MOD process, as described later in this section. A variety of precursors have been used in the sol-gel process, and their relevant physical properties are tabulated in Chapter 3. The properties of the end products, a variety of different glass or ceramic compositions, are categorized and listed in Chapter 4. Colloidal processing is a sol-gel process in which the starting material is a colloidal suspension instead of molecular precursors. This wet chemical method is used for preparing solid-state inorganic materials from a colloidal system with the size of the dispersed phase particles ranging between 1 nm and 1 µm in at least one dimension. In order to produce a stable colloidal suspension, dispersing agents are employed or the pH of the suspension is adjusted to finely disperse the colloidal particles. A number of materials have been prepared by the above method, including UO2–PuO2 nuclear fuel spheres produced from a stable suspension of uranyl nitrate, plutonium nitrate, a modifying agent, and a gelling agent. In this example, the suspension was gelled with ammonia, washed with water, and dried prior to sintering. This route is sometimes also referred to as a gel-precipitation route.

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Other examples of colloidal processing include the preparation of monodispersed alumina and silica spheres or polydispersed titania and ceria powders from colloidal suspensions of their precursors. Fine ceramic particles can also be prepared by a sol-emulsion-gel process, in which the reactants are suspended as micelle2 in a nonmiscible solvent with the aid of a surfactant, and the droplets are then gelled to form ceramic particles. The particles are then isolated by conventional processing routes. The sol-emulsion-gel process can also be classified as a colloidal processing route. Fine zirconia particles in the range of 4 to 6 nm have been prepared by this process with ZrO(NO3)2 and NH3 reactants in xylene solvent. The zirconyl nitrate precursor was dissolved in water and dispersed in xylene using a surfactant, Tween 80. The droplets were then gelled with ammonia gas, and the resultant fine zirconia powder was separated by distillation and multiple solvent washing.3 B. Hydrothermal Process The hydrothermal process is a method of forming ceramic powders by heating and pressurizing solutions or suspensions of metal salts, oxides, hydroxides, or metal powders in water and, on occasion, in other solvents. The process is conducted in a pressure vessel called an autoclave. Normally, as the mixture is heated in this closed system, the pressure rises and these conditions result in the formation of submicron particles with controlled size and shapes.6 This route has been used to prepare a variety of monodispersed powders, materials with specific crystalline phases, and particles with controlled size and shapes, frequently at temperatures lower than those required in normal processing procedures. The hydrothermal process promotes the formation of monodispersed spheres by providing the appropriate conditions needed for homogenous nucleation. For example, monodispersed metal oxide powders are formed by homogeneous nucleation of metal hydroxide particles, which are produced by forced hydrolysis of metal alkoxides using heat and pressure in an autoclave. Forced hydrolysis is normally achieved by controlling the release of the precipitating ion. A route to yttrium-stabilized zirconia powder illustrates this concept. The reactants, yttrium chloride, zirconium oxychloride, and urea, CO(NH2)2, are mixed in an autoclave, in which the urea decomposes at temperatures between 160 and 220ºC under 5 to 7 MPa, releasing ammonia. The ammonia then reacts with the metal salts in water to form hydroxides. These hydroxides are then washed, dried, sintered, and crushed to form fine yttrium-stabilized zirconia powder.4 In other cases, the hydrothermal process can promote phase transformation. For example, tetragonal zirconia for structural applications can be prepared by such a process. Amorphous zirconia precipitated from ZrCl4 and NH4OH can be aged in an autoclave between 513 and 1093 K at 100 MPa pressure in water to form a tetragonal phase of zirconia in addition to the normal monoclinic phase.5 Metal oxides that cannot be prepared by normal oxidation of metals in an oxidizing atmosphere can also be prepared by hydrothermal processes. For example, hafnium (Hf) particles were only surface oxidized to HfO2 in water between 300 and 400ºC as a result of the formation of an oxide layer that protected the interior of the metal chips.6 However, under 50 to 150 MPa and between 300 and 700ºC in an autoclave, Hf was completely oxidized to HfO2. Complete oxidation occurs in the autoclave because the hydrides of hafnium are formed under the elevated temperature and pressure conditions, which then quickly convert to the hafnium oxide. C. Supercritical Drying Process The supercritical drying process is used for producing fine ceramic powders or monolithic materials with extremely high porosity. The supercritical drying process normally involves preparing a gel containing a large volume fraction of liquid, following which the liquid is removed above its

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critical point (hence, no surface tension) without collapsing the solid state structure in the gel. As a result, a highly porous structure called an aerogel is formed that has intricate porosity. An extensive body of information on supercritical drying exists in the area of aerogels.7 As the term indicates, aerogels are solid-state structures when the pores are filled with air and are formed by replacing the liquid in a gel with air. Much of the research in this area has focused on silicatype aerogels in both monolithic and powder forms. Some silica aerogels have been prepared with porosities up to 99.99%.8 Silica gels are normally prepared using alkoxides: Si ( OR )4 + H2 O + ROH → SiO2 + ROH where R is an alkyl (CH3, C2H5, etc.). In the above sol-gel reaction, the only by-product is a liquid, an alcohol. The gel thus formed contains alcohol trapped in the silica solid-state network. If the liquid is removed by evaporating the alcohol, the solid-state structure would collapse from the capillary pressure developed as a result of the surface tension of the liquid. However, at or above the critical point of the liquid the surface tension of the liquid disappears. Hence, under supercritical conditions the liquid can be removed without collapsing the solid-state structure, thus forming a highly porous silica material with fine particles. The solid-state network is built up of these interconnected primary particles. Certain ceramic powders have been prepared by a supercritical method called rapid expansion of supercritical solutions. In this method,9 solute nucleation and condensation occur within an expanding supercritical jet. For example, SiO2 particles with diameters less than 5 µm were prepared by rapidly expanding a solution containing 3000 ppm of SiO2 soluble species at 743 K under 60 MPa through a 60-µm diameter stainless steel nozzle with flow rates of 0.7 cm3 s−1. The experimental conditions can be varied to change the resultant particle size. D. Freeze-Drying Process The freeze-drying process is used for preparing porous monolithic materials or unagglomerated powders. This process is similar to the supercritical drying process since the process also involves liquid removal from a mixture at zero surface tension without collapsing the structure. The liquid in the gel or a slurry is first frozen, then removed by the sublimation process without collapsing the structure. In the sublimation process, the frozen liquid converts to vapor without going through the liquid stage, thus avoiding surface tension–related capillary pressure. During the freezing process, however, some liquids undergo volume change, and the freezing process can therefore potentially damage the structure. As a result, this process is limited to preparing unagglomerated powders. A variety of oxide powders with narrow particle size ranges have been prepared by this method.9a E. Metal Organic Decomposition MOD is a material synthesis method in which metal organic compounds are decomposed to form a film, fiber, or powder without the use of vacuum or gel powder techniques. The precursors, metal organic compounds, used in the MOD process are coordinated covalent molecules with a metal atom bonded to an organic ligand via bridging oxygen, sulfur, phosphorus, or nitrogen atoms. For example, carboxylates, alkoxides, and thiolates are metal organic compounds that are frequently used as precursors to oxides and sulfides. Some of these precursors can be used to produce metal coatings by decomposing or heat-treating the precursor or its solution in a reducing environment (e.g., H2, N2, Ar, etc.). Nitride coatings can also be produced from precursors where the organic ligand is bonded to the metal atom via a nitrogen atom. Nitride coatings produced by this process contain carbon impurities that can be minimized by heat-treating the material under an ammonia or nitrogen atmosphere.

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A similar process is used to prepare metal films or metal carbide films from organometallic precursors where the organic ligand is bonded to the metal directly via a carbon atom. The compounds with aryl or alkyl ligands bonded to the metal atom are suitable precursors for metal carbide–type coatings. For example, a carbosilane oligomer mixture (e.g., [–(R)2Si–CH2–Si(R)2–CH2–]n) with an Si–C backbone, dissolved in a solvent is deposited on a substrate and heat-treated from 600 to 800ºC under argon to form an SiC film. When polymers are used in this process instead of compounds or molecules, it is referred to as polymer pyrolysis. For example, polysilanes, polycarbosilanes, and polysilazanes can be pyrolyzed to form fibers or coatings of silicon carbide or silicon carbonitride.10 Metal coatings (e.g., platinum) can be prepared from organometallic precursors in reducing atmospheres by MOD. The precursors normally selected for this process should decompose without evaporating, melting, or leaving a carbon residue. To minimize volume change, precursors must also have a high metal content and a high char yield. Solid precursors require high solubility in the chosen solvent. The compounds must be stable under ambient conditions, with minimum sensitivity to air or moisture. Compatibility between the decomposition temperatures of precursors in a multicomponent system is also desirable. From a processing perspective, it is also desirable that the decomposition of the precursors not result in the formation of toxic gases. Considering the above requirements, precursors with carboxylate ligands with or without alkoxide or amide ligands are typically suitable.11 MOD should not be confused with the MOCVD method of depositing film from gases or vaporized liquid precursors under vacuum conditions.12 The techniques used for depositing and curing the films in MOD are similar to the techniques used for photoresist coating or screen printing in the electronics industry. Factors critical to achieving uniform continuous films include substrate wettability, solution or liquid viscosity, solvent type, and the curing mechanisms needed to convert an amorphous film to a crystalline film. The solutions are normally filtered to remove any particles that may cause defects in the film. The curing or pyrolysis methods used in the process can alter the crystalline phase, the grain size, and the resultant properties of the film. Nonconventional curing techniques, such as rapid thermal annealing, electron beam annealing, and lasers, have been used to alter the physical properties of the film. Compositions such as BaTiO3, SrTiO3, PbTiO3, ITO (indium-tin oxide), SnOx, YBa2Cu3O7, Pt, Au, Ag, and Pd have been deposited as films on a variety of substrates using the MOD method. Coating compositions containing dopants have also been prepared by this method. MOD has been successfully used in composite preparation. For example, SiC composites are prepared by impregnating the preforms with carbosilane polymers, which are then decomposed to yield silicon carbide. F.

Metal Organic Chemical Vapor Deposition

The MOCVD process is a type of CVD technique in which metal organic compounds, often in combination with hydrides or other reactants, are used as volatile precursors to deposit coatings on substrates. The CVD process is a method used to fabricate films or to coat particles in a fluidized bed, where the chemical constituents react near or on the heated surface. CVD utilizes volatile precursors capable of evaporating without decomposition. In contrast to the established CVD precursors, the MOCVD precursors typically vaporize at much lower temperatures. In most cases, MOCVD reactions occur in the 500 to 1000ºC temperature range and at pressures ranging from 1 torr to atmospheric pressure, whereas the conventional precursors for CVD require at least 900ºC temperatures.13 Recently, research has shown that some metal organic precursors can be decomposed at even lower temperatures.13a The precursors used in MOCVD can also be activated by plasma by using electromagnetic radiation, which is particularly useful in systems with heat-sensitive substrates or surfaces. The thermal activation process, however, is the most commonly used method of activating precursors. The chemical reactions occurring during the MOCVD process may include thermal decomposition

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(pyrolysis), reduction, hydrolysis, disproportionation, oxidation, carburization, nitridation, or their combinations. MOCVD has been most commonly used for fabricating thin films of III-V semiconductor compounds, such as gallium arsenide (GaAs), indium arsenide (InAs), indium phosphide (InP), and gallium aluminum phosphide (GaAlP), particularly in epitaxial form. To prepare the above compositions, metal alkyls or aryls [e.g., In(CH3)3, As(CH3)3] and hydrides (e.g., PH3, AsH3) are commonly used as volatile precursors. For example, fabrication of GaAs film involves a reaction between trimethyl gallium and arsine that can be represented by the following equation: Ga( CH3 )3 + AsH3 → GaAs + 3CH3 MOCVD precursors and processing equipment are relatively expensive, thus limiting the use of the technology to applications where cost is not a barrier and high quality is desired. Owing to this limitation, MOCVD is currently used extensively only in the electronics industry14 and for producing advanced lasers and infrared detector–type applications. Chemical vapor infiltration (CVI) is a type of CVD technique used for porous structures such as foam or fibrous mats or weaves. As the hot gases infiltrate through the porous media, they react and deposit on the hot surfaces, and in some cases continuous deposition eventually fills up the pores to make a composite.6 CVI is frequently used for fabricating composites at lower temperature and pressure conditions than traditional composite-forming processes such as hot pressing and hot isostatic pressing. The milder conditions help retain the mechanical and chemical integrity of the substrate. However, a major limitation of CVI is the length of time it takes to fill up the preform pores and to prepare a composite. Because of the tortuous paths in the substrate samples, films must be deposited at lower temperatures and at a slower rate compared with CVD to avoid choking the channels. However, recent developments have improved the commercial viability of CVI. Forced CVI is a technique where the gas flow is restricted to the sample, hence forcing all of the gases through the channels in the sample and filling them up at a faster rate. Temperature gradients across the sample have also been used to speed up the CVI process. CVI has been extensively used in fabricating SiC composites, where SiC preforms are filled with SiC material by chemical vapor infiltration of hydrocarbon and silane vapors. Fluidized-bed CVD is a technique where the substrate is a powder particle and the powder is suspended in a flowing gas. In order to achieve the desired coating on the particles, the density and size of the particles and the velocity, density, and viscosity of the fluidizing gas are balanced so that the particles do not settle and clog the gas inlet. The oldest application of the fluidized-bed CVD technique is for coating nuclear fuel particles (uranium–thorium carbide) with pyrolytic carbon and silicon carbide. Propane and other hydrocarbon gases are normally used as the volatile precursors for pyrolytic carbon, and methyltrichlorosilane is the preferred precursor for SiC. Similarly, a zirconium carbide coating has been deposited by fluidized-bed CVD from zirconium tetrachloride and a hydrocarbon.6,15 G. Aerosol Processes Aerosol processes can be classified as material synthesis via gas-to-particle or droplet-to-particle conversion. In a gas-to-particle conversion, gases or vapors react forming primary particles that grow further by coagulation or surface reactions. Powders produced by this process have a narrow size distribution, and the process can yield nonporous spherical particles. Materials such as carbon black, silica, and titania are produced by the gas-to-particle conversion process in flame reactors. Flame hydrolysis, which is commonly used for producing fine silica powder, can be classified as a gas-to-particle conversion process. Fine ceramic powders can be prepared by the flame hydrolysis

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method in which the precursors are oxidized in a flame to form oxides in a wide range of particle sizes. For example, SiO2 powders have been prepared by flame hydrolysis from SiCl4 oxidation in an H2/O2 stationary flame. After formation of the primary SiO2 particles in the flame, the tiny droplets of SiO2 coalesce as they move away from the flame and form larger particles from aggregates to agglomerates of SiO2. The particles can then be separated by size. In the droplet-to-particle conversion process, solution or slurry droplets are suspended in a gaseous medium by liquid atomization, where the droplets react with gases or pyrolyze at high temperatures to form powders. The particle size distribution is determined by the droplet size or processing conditions such as particle breakup during pyrolysis or drying. The particles are mostly monodispersed and porous. Spray drying and spray pyrolysis are the most common industrial methods of producing powders by the droplet-to-powder conversion process.16 Freeze-drying of droplets is another technique in which powders are produced by droplet-to-particle conversion.

III. MICROFABRICATION A. Microelectronics Microelectronic fabrication requires the ability to deposit thin films and then pattern them into functioning devices which can include transistors, capacitors, resistors, memory devices, microelectromechanical systems (MEMS), light emitting diodes (LED), etc. Understanding and control of surface chemistries of various thin-film materials and the use of lithography techniques are very important in achieving reproducible high quality devices. In order to fabricate a solid state device, for example microchips, sensors, or biological hybrid electronic devices, one or more inorganic thin films are deposited and patterned by what are commonly known as “top-down” processes. “Bottom-up” fabrication is an alternative approach that will be discussed later in the chapter. In one common top-down scheme, a film of one material is first deposited onto a starting substrate (or wafer) and then patterned by etching or removing the film in select well-defined areas. Complex three-dimensional architectures are built up by repeating the process of film deposition and patterning as often as neccessary. Often these films are made up of alternating conductive and insulating layers in order to facilitate electrical isolation of each circuit element, for example, transistors, capacitors, and resistors. Next, in the metallization step, all of the chip’s circuit elements are electrically interconnected and individual dies (or chips) are diced from the wafer and wired to the macroscopic world. Finally, the chip is enclosed or packaged in a protective material that can provide some combination of chemical, environmental, mechanical, thermal, or electrical stability. This type of top-down process is the industry standard for making memory and other microelectronic devices. It is also still commonly used and adapted for fabrication of MEMS devices and in nanofabrication, which will be discussed later in the chapter. Standard microelectronic fabrication consists of a series of techniques that allow for relatively rapid and simultaneous (or parallel) manufacture of billions of devices, with lateral feature sizes as small as 65 nm, on a single chip and many chips on a single wafer up to 300 mm in diameter. However, as demand for further decreases in feature size continues, not only do materials properties often begin to change, but new materials are identified and new fabrication and processing techniques must be developed that are more efficient and reproducible. A major initial step in the top-down fabrication of solid-state devices is the deposition and growth of a thin film. This is typically achieved by two broad classes of processing techniques: physical vapor deposition and chemical vapor deposition (CVD). Wet chemical techniques such as spin-coating of sol-gel precursors or electrodeposition are also used in some applications. In physical vapor deposition, material is transferred from a solid source or target to a substrate using techniques such as sputtering via plasma, thermal evaporation, electron beam evaporation, or laser ablation. However, as described in Section II. F, CVD involves a surface chemical reaction in a vacuum environment from sources that can be transformed to a gas. The result of the chemical

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reaction is the deposition of a thin film that is angstroms to microns thick. CVD techniques include plasma enhanced CVD, low pressure CVD, metallorganic CVD (or MOCVD), atmospheric pressure CVD, and photo-assisted CVD. The most common top-down patterning method used to make microelectronic circuits is photolithography. First, a shadow mask — essentially an optical stencil — is made as a negative of the desired chip pattern (or blueprint), with regions that either block or transmit the wavelength of the developing light. This mask is placed between the light source and a substrate, the latter which has been coated with a thin layer of photosensitive polymeric photoresist. The mask’s pattern is optically transferred to the photoresist by exposing it to light. Only light that strikes a transparent part of a mask is transmitted to the photoresist, where it either crosslinks the polymer, making it insoluble (a negative photoresist) or, conversely, photodegrades the polymer, rendering it soluble (a positive photoresist). While most resists are polymeric and used for patterning features on films, some are multilayered and consist of both metal and polymeric photoresist. Inorganic materials are also used as masks, including metals, nitrides, and oxides (e.g., Cr, Si3N4, and SiO2). The three main types of mask-substrate configurations used in photolithography are (a) contact lithography, in which the mask is placed in intimate contact with the wafer, (b) proximity lithography, in which the mask is placed very close to the substrate without touching it, and (c) projection lithography, in which a focusing lens is placed between the mask and the substrate. Contact masks are the least expensive and simplest form of optical lithography, but the mask does not have longevity owing to repeated contact with photoresist during patterning. Proximity masks alleviate mask degredation, but diffraction of light reduces the pattern resolution. Projection lithography is the workhorse of the microelectronics industry, because it has better resolution than contact lithography and the mask is not damaged by repeated contact with the substrate; however, it is expensive because of stringent light focusing requirements. After development of the photoresist, the pattern that remains in the photoresist functions as a mask by protecting regions of the substrate from being etched during subsequent patterning of the thin film. The thin film regions left bare by the patterned photoresist can be subsequently removed by a variety of chemical or physical etching techniques. These etching techniques include ion beams (dry etch), chemically assisted dry etches such as reactive ion etches (RIE), the most common technique, chemically assisted ion beam etches, and wet chemical etches. The choice of chemicals used in these techniques strongly depends on a material’s chemical stability. The remaining photoresist protects the rest of the substrate during the etching process and is subsequently removed either chemically with a solvent or with an oxygen plasma cleaner often called a photoresist asher. The patterned substrate is then cleaned, and another film (or series of films) is deposited and patterned by photolithography. This step is repeated until all the circuit elements have been patterned on the chip. One primary strength of photolithography, or the topdown approach, is that it is a batch or massively parallel process, allowing billions of circuit elements to be simultaneously patterned on individual chips across a wafer. Many selective anisotropic wet etches have been developed in the microelectronics industry. For example, hydrofluoric acid (HF) strongly etches quartz (SiO2) and is used to remove oxide from silicon without etching the silicon. Potassium hydroxide solution (KOH) is an example of an anisotropic wet etch that is often used to make MEMS and photonic devices. KOH allows the formation of high aspect ratio trenches in silicon, as it etches the (100) direction a hundred times faster than the (111) direction. Wet etching, while generally inexpensive, often suffers from feature rounding and undercutting of the resist and is used primarily for large feature-size definition. For finer feature resolution, dry etching techniques such as plasma sputtering, RIE, and chemically assisted ion beam etching are commonly used. If focusing lenses and photoresist behave perfectly, the smallest feature size that current photolithography can fabricate without significant edge blurring is limited to approximately half the wavelength of the light source. For example, older mercury lamp sources with a wavelength of 436 nm (g-line) can pattern features on the order of 0.25 µm. Currently, sources that emit at extreme

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ultraviolet energies or use x-rays with wavelengths of ~10 to 250 nm can define much smaller features. However, at these high energies, additional care must go into the design of the photoresist and lenses. Finally, electron beam technology can pattern elements with feature sizes on the order of 10 nm. Another benefit of electron beam patterning is that masks and resists can be eliminated. However, electron beam lithography has two primary limitations: (a) It has slow throughput owing to serial patterning, where the beam must be rastered across the surface to pattern each device, and (b) the instrumentation is expensive. Parallel electron beam systems have recently become available, but they are still slower and less reliable than traditional optical lithography. Etch-stopping is also an important aspect of patterning a film. If the etch is stopped too soon, the film is considered underetched, which results in electrical shorts. However, if underlying films are overetched, then the previously patterned elements can be damaged. Hence, suitable etch-stop techniques are an extremely important consideration when developing etching techniques for a new thinfilm material. Ideally, the etch technique used will automatically stop when it perforates the thin film and reaches the underlying material. Such selective wet or dry chemical etches make use of the different chemical reactivities of materials or etch anisotropies for a given material. Other common etch-stop techniques include thermal oxidation to form chemically resistant layers, ion implantation to make a material either more or less reactive to a given etch, electrochemical monitoring, mass spectroscopy to detect chemically distinct species from underlying films, and simply timing the etch. Aside from growth conditions such as temperature and stoichiometry, a number of factors are important for growing thin films with minimal lattice defects, including surface cleanliness and roughness at the atomic scale, surface flatness across the entire wafer, lattice-matching of the thin film with the underlying substrate, and coefficient of thermal expansion matching. If these factors are not carefully controlled, the thin film can develop excessive interface strain and other defects that impair the film’s mechanical and electrical quality. Surface cleanliness and atomic-scale smoothness are often simultaneously obtained by the application of one or more techniques including wet chemical etches, mechanical polishing, plasma etches, sputtering, and thermal annealing. The process by which macroscopic smoothness or flatness across a wafer or chip is achieved is often called planarization. Planar films are obtained by two primary methods: ion implantation and chemical mechanical polishing. Etching, which involves the removal of film material, can lead to macroscopically uneven deposition of subsequent films including nonplanar crossovers. To avoid this complication, researchers often replace etch patterning techniques with ion implantation. Ion implantation involves taking a high energy plasma of charged ions and accelerating them at a masked substrate. Unprotected regions of a substrate are ballistically bombarded with high-energy charged ions (tens to hundreds of keV) that embed themselves in the film, resulting in a Gaussian depth profile normal to the surface. The higher the ion energy is, the deeper the average penetration. Ion implantation is often used to dope semiconductors, thus changing their electrical properties. At low implant doses, a material can be given a range of electrical properties from conducting to semiconducting; thus, ion implantation can be used to make components of devices such as resistors, transistors, and tunnel junctions. At higher doping doses, implanted regions of a film can be made highly resistive, to make integrated resistors or even insulating for device isolation and patterning. Since no film material is removed during ion implantation, the implanted film can remain planar. Subsequent films are deposited over a flat surface, reducing defects that occur when the film is deposited over etched features. Ion implantation requires understanding how a material behaves as it is implanted by high energy ions, how the implanted ions rearrange upon subsequent annealing procedures, and how to design photoresists that block energetic ions without degrading or hardening. For example, the atomic masses of constituent ions in the thin film and the material’s density determine the average depth of penetration of implanted ions. It is more difficult to penetrate a dense close-packed metal film than many oxide films, which have more open and hence less dense structures. Ion implantation can cause standard polymeric photoresists to swell, distort, and bond to the substrate. These issues can result in patterned features that do not meet design specifications and difficultly in removing resist without damaging the substrate.

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Another much more common method for planarizing a film, commonly used after metallization of a wafer, is chemical mechanical polishing. This technique makes use of a polishing pad and a chemically reactive abrasive slurry where a surface composed of two or more chemically and physically different materials (e.g., copper interconnects on silicon devices) is planarized. Features that stick out from the film tend to polish faster than low uniform features, resulting in nearly atomically flat planar surfaces. Other materials considerations required during microelectronic fabrication include lattice matching between the substrate material’s crystal structure and the film to be deposited, matching of the coefficients of themal expansion over all temperatures encountered during fabrication and subsequent device usage, and how a material’s properties respond to various dopants and doping methods. Lattice matching requires that both the substrate and the film to be deposited have some interplanar distances that are nearly identical, or else the thin film may develop excessive dislocations or eventually become excessively granular and rough. The relative coefficients of thermal expansion of the substrate and the film should also be as similar as possible, or film cracking or delamination may occur during the repeated temperature cycling that happens during thin-film deposition and other thermal processes during microfabrication. Doping of thin films is often required to change their electrical characteristics to make circuit elements such as resistors, diodes, and transistors or to help enhance (or impede) selective etching. For example, Group V elements such as phosphorous and arsenic are used as donor dopants in silicon to create n-type material, where electrons are the dominant charge carrier. Group III elements such as boron are used as acceptor dopants to make silicon a p-type material where conduction is dominated by holes. The three most common thinfilm doping techniques are diffusion from a gaseous source, diffusion from a solid source, and ion implantation. Masks are used to control the lateral position on a substrate where the dopant will penetrate. A subsequent backend anneal is often required to finish distributing the dopants within the film and to electrically activate dopant ions. Unfortunately, most of the top-down techniques discussed here are reaching their limitations with respect to even smaller device fabrication. In order to effectively reduce feature sizes much below 100 nm, investigators are not only pursuing some novel top-down approaches, but developing so-called bottom-up strategies, as discussed in Section VII. B. Microelectromechanical Systems (MEMS) Fabrication MEMS are devices that integrate electrical and mechanical elements on a chip along with the technologies associated with fabricating and packaging them. MEMS are already finding applications as pressure sensors, accelerometers in automobile airbags, optical switches, and inkjet printer heads and in biotechnology and chemical analysis. MEMS components can include moving parts, microfluidic channels, positionally controlled mirrors, and microreactors. MEMS fabrication techniques differ from standard solid-state microelectronic processing because the films to be patterned are usually orders of magnitude greater in thickness, and many of the patterned parts must be able to freely move past each other or, in the case of microfluidic channels, remain open for fluid flow. For example, using sacrificial layers and deep RIE (DRIE), one can make moving parts such as gears out of patterned thin films. Sacrificial layers such as SiO2 are often used to release silicon MEMS components patterned on top of the SiO2. DRIE forms high aspect ratio structures on silicon and makes use of sidewall passivation to avoid lateral etching. For example, alternating the RIE gases SF6 and C4F8 will, respectively, etch and passivate the trench repeatedly until the required etch depth is obtained, which is often defined by an underlying SiO2 layer. This SiO2 layer acts as a release in that a selective chemical etch such as HF will remove it and undercut the patterned Si structure. If the Si structure is not anchored to the substrate below the SiO2 layer, then it is free to move. This general etching strategy may also be applied to other materials systems once their surface and bulk interactions with various etching solutions are better understood.

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MEMS devices are also being constructed from nonsilicon materials such as plastics, elastomers, amorphous diamond, and piezoelectrics, which require the development of new etch chemistries for fabrication. MEMS also has potential uses in biotechnology, especially in microfluidics, and has uses in drug delivery, in-vivo monitoring, cell manipulation, biosensors, gene or protein chips, neural probes, microsurgery, and retinal or cochlear implants. A problem called stiction is sometimes encountered during both MEMS fabrication and subsequent device operation. Stiction is the attractive electrostatic or van der Waal’s interactions between two initially free surfaces in extremely close proximity that keeps the pieces from moving past one another. To avoid stiction, the surface chemistries must be carefully controlled by either cleaning or coating with a molecular-level lubricant. For example, supercritical CO2 is often used to clean MEMS devices, while free surfaces can be chemically modifed with self-assembled monolayers or other molecular-level coatings. In recent years, supercritical CO2 has been more widely applied in MEMS fabrication, microfabrication, and nanofabrication as a wafer cleaner, a resist developer and stripper, and as a polishing solvent. Using water and other solvents for cleaning small or delicate features commonly found in MEMS fabrication or nanotechnology is often impractical because of high surface energy effects and limitations in the solubility of the solvent. Even if water, for example, is forced with pressure to penetrate nanoscale features, the high surface tension and resultant large capillary forces can cause features to collapse. Above 31°C and 75 atm, CO2 becomes supercritical, which means its liquid and gaseous states are indistinguishable. Supercritical CO2 has an extremely low viscosity and zero surface tension and thus easily wets most surfaces while penetrating small trenches in photoresist and etched substrate features. Nanoscale interconnects of copper have also recently been fabricated by using supercritical CO2 as a carrier fluid for incorporating copper into holes and trenches smaller than 100 nm. Supercritical CO2 may be an enabling technology in achieving the smaller feature sizes encountered in MEMS devices and nanotechnology. IV. PRECURSORS In this section, the precursors used for the processes described in preceding sections are classified by groups. The precursors can be molecular or polymeric or a colloidal suspension of particles. Information on the properties of individual precursor properties is provided in Chapter 3. A. Inorganic Salts Inorganic salts are often used as molecular precursors in wet chemical processes such as solgel, colloidal, and hydrothermal processes. Inorganic salts are ionic compounds; examples are listed in Table 1.1. B. Metal Organic Compounds Metal organic compounds are covalent or inorganic coordinate compounds in which the metal center is bonded to the ligand via a noncarbon atom such as oxygen, sulfur, phosphorus, or nitrogen. Table 1.1 Inorganic Salt Precursors Inorganic Salts

Examples

Metal halides Metal carbonates Metal sulfates Metal nitrates Metal hydroxides Salts with mixed ligands

MgCl2, LiF, KCl, SiCl4, TiCl4, CuCl2, KBr, ZrOCl2 MgCO3, CaCO3, Na2CO3, SrCO3 MgSO4, BaSO4, K2SO4, PbSO4 LiNO3, KNO3, Fe(NO3)2 Ca(OH)2, Mg(OH)2, Al(OH)3, Fe(OH)3, Zr(OH)4 (CH3)3SnNO3, (C2H5)3SiCl, (CH3)2Si(OH)2

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Table 1.2 Metal Organic Compounds Metal Organic Compounds

General Formula

Selected Examples

Metal alkoxides Metal carboxylates

–M(–OR), where R is an alkyl –M(–OC(O)R)x, where R is an alkyl

Metal ketonates

–M(–OC(R)CH(R′)CO–)x, where R is an alkyl or aryl —

Al(OC3H7)3, Si(OCH3)4, Ti(OC3H7)4, Zr(OC4H9)4 Al(OC(O)CH3)3, Pb(OC(O)(CH3)2, – acetates Pb(OC(O)CH2CH3)4, – propionate Al(OC(O)C6H5)3, – benzoate Ca(OC(CH3)CH(CH3)CO)2, – pentanedionate Al(OC(C(CH3)3)CH(C(CH3)3)CO)2 – heptanedionate (CH3)2AlNH2, (C2H5)2AlN(CH3)2, (CH3)BeN(CH3)2, (iC3H7)3GeNH2, (C3H7)3PbN(C2H5)2

Metal amides (sometimes also referred to as amines) Metal thiolates Metal azides Metal thiocyanides Metal organic compounds with mixed functional group

–M(–SR)x, where R is an alkyl or an aryl –MN3 –M(–NCS)x —

(CH3)2Ge(SC2H5), Hg(C4H3S)2, (SCH3)Ti(C5H5)2, (CH3)Zn(SC6H5) (CH3)3SnN3, CH3HgN3 (C2H5)3Sn(NCS) (C4H9)Sn(OC(O)CH3)3, (C5H5)2TiCl2, (C5H5)Ti(OC(O)CH3)3

Table 1.3 Organometallic Presursors Organometallic Compounds

Selected Examples

Metal alkyls Metal aryls Metal alkenyls Metal alkynyls Metal carbonyls Mixed organometallic ligands

As(CH3)3, Ca(CH3)2, Sn(CH3)4, – methyl Ca(C6H5)2, – phenyl Al(CH=CH2)3, Ca(CH=CHCH3)2, – vinyl, propenyl Al(CCH)3, Ca(CCH)2, – acetylnyl Co2(CO)8, Mn2(CO)12, W(CO)6, – carbonyl Ca(CCC6H5)2 – phenylacetylnyl (C5H5)3U(CCH) – cyclopentadienyl/ethynyl

In the literature, the organometallic compounds described in the next section are also referred to as metal organic compounds. Metal organic compounds are used as precursors for both wet chemical– and dry vapor–related processes. Examples of metal organic compounds are provided in Table 1.2. C. Organometallic Compounds Organometallic compounds are covalent or coordinate compounds in which the ligand is bonded to the metal center via a carbon atom. Like metal organic compounds, organometallic compounds are used as precursors for both wet chemical– and dry vapor–related processes. Commonly used organometallic precursors are listed in Table 1.3. D. Polymeric Precursors In some processes, such as MOD and sol-gel processing, polymeric precursors can be used as starting materials for producing glassy or ceramic compositions. These polymers are sometimes referred to as preceramic polymers. Selected examples of such polymers are given in Table 1.4. E. Colloidal Suspension Suspensions of molecular precursors or a suspension of oxide, hydroxide, sulfide, and other such powders in a given solvent can also be used as a starting material for preparing ceramic or

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Table 1.4 Polymeric Precursors Polymer

Formula

Miscellaneous

Polycarbosilane

–[(RR′)Si–CH2–]x

Polysilazane

Borazines

–[(RR′)Si–NR–]x, where R is an organic unit or H 1. –[Si(RR′)O–]x: linear, where R is an alkyl or aryl 2. Sesquisiloxane: ladder 3. –[Si(CH3)2OSi(CH3)2(C6H4)m–] siloxanesilarylene 4. Random and block copolymers of the above –[Si(RR′)–]n, where R is an alkyl or aryl –[Si(CH)(CH)–] – Silalkylene –[BRNR′–]n: cyclic or chain repeat units

Precursor to SiC in MOD and sol-gel–type processes where R is an active functional group such as an olefin, acetylene, H Precursor to Si3N4 or silicon carbonitride in a manner similar to polycarbosilanes Used in sol-gel processing and in situ multiphase systems used as precursors to SiO2 or silicon oxycarbide

Carboranes

Cage compounds of B and C

Phophasphazenes

–[N = P(R2)–]n, where R is an organic, organometallic, or inorganic unit

Polystannoxanes

–[Sn(R)2–O–R′–O–Sn(R)2–O–]n: chain, where R is an organic unit. Drum- or ladder-type structures also possible –[Ge(RR′)–]n

Polysiloxanes

Polysilane

Polygermanes

Precursors to SiC, as photoresist and photoinitiators Precursors to BN in CVD/MOCVD-type process or sol-gel-type process Precursors to B4C in MOCVD- or MOD-type processes Most common types of functional groups include alkoxy, aryloxy, arylamide, carboxylate, and halide —

Can be used in microlithographic applications such as polysilanes

glassy materials. A widely used silica colloidal suspension, Stober spheres, with monodispersed particles can produce a variety of glassy products.17

V. ADDITIVES Additives are chemicals normally employed in wet chemical processes to change physical or chemical properties of the system. Additives used in wet chemical processing of inorganic materials can be classified as catalysts, dispersants (detergents and other surfactants), and binders. Catalysts are materials that increase the efficiency of the reaction or the rate of reaction and are regenerated at the end of the reaction. The most commonly used catalytic additives in systems are organic and inorganic acids and bases. For example, silicone polymers with functional groups such as alkoxy can be polymerized to form cross-linked silicones or silicates using a tin octaoate catalyst. Similarly, inorganic acids and bases are employed to catalyze the hydrolysis and condensation reactions in the sol-gel process involving metal alkoxides. Dispersants (detergents and other surfactants) are composed of varying proportions of polar and nonpolar groups used in two-phase systems to provide a homogeneous dispersion or emulsion. Although dispersants are present in small quantities, they exert a marked effect on the surface behavior of the system. Surfactants form interfaces between solid–solid, solid–liquid, solid–gas, liquid–liquid, and liquid–gas phases, whereas dispersants form interfaces between solid and liquid only. Dispersants are applicable to slurry systems (solid–liquid) in ceramic processing, whereas emulsion-type processing requires surfactants suitable for liquid–liquid systems. In many systems containing oil and water (water-in-oil or oil-in-water) or systems containing insoluble solids in a liquid medium, surfactants are used to form homogeneous emulsions. Depending upon the system under consideration, the type of surfactant used in producing a homogeneous emulsion can change drastically. There are two types of surfactants: ionic and nonionic. Nonionic surfactants are characterized by their HLB (hydrophobic-lipophilic balance) number to indicate the polarity in the © 2005 by CRC Press

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compound. A higher HLB number indicates a higher polarity of the surfactant, whereas a lower HLB number indicates the lipophilic (nonpolar) nature of the surfactant. For example, an ethylene glycol fatty acid ester has an HLB number of 2.6, suitable for a water-in-oil-type emulsion, whereas polyoxoethylene fatty alcohol has an HLB number of 15.4, suitable for an oil-in-water-type emulsion. However, ionic surfactants such as sodium oleate (NaOOCC15H31) ionize in an aqueous medium to provide low-energy interfaces, forming a solution or an emulsion. Detergents can be classified into three groups: anionic, cationic, and nonionic surfactants. Anionic detergents such as sodium toluene sulfonate have a large anion, which can be used to stabilize suspensions containing negatively charged particles or particles that adsorb the anionic surfactants via charge repulsion. Similarly, cationic detergents such as quaternary ammonium acetate have large cations that can be used for stabilizing suspensions containing positively charged particles via charge repulsion. Nonionic detergents such as alkyl polyethoxy benzene, with long steric groups, are used for stabilizing suspensions by steric hinderance. In practice, both the charge repulsion and the steric hindrance play an important role for all surfactants. Inorganic surfactants or detergents such as nitric acid, silicic acid, ammonium hydroxide, and sulfuric acid are also used to stabilize suspensions in aqueous media.18 Binders are polymers and colloidal particles that are adsorbed on particle surfaces to bridge between ceramic particles for interparticle flocculation. In ceramic processing, binders improve the wetting and change the viscosity and sedimentation characteristics of the slurry for ease of processing. Binders are used in slurries or tapes during ceramic processing to glue the ceramic particles in the green state and to obtain higher densities after sintering. Soluble silicates and polyalkyl glycols are common binders used in ceramic processing. Polyvinyl alcohol is one of the most common binders used in an aqueous medium. Polyvinyl pyrrolidone is another binder frequently used in both aqueous and organic media. Sodium silicate, an inorganic binder, is also frequently employed for binding purposes in ceramic processing.

VI. SURFACE MATERIALS CHEMISTRY Atoms at surfaces often deform or structurally rearrange in order to reduce their free energy. Consequently, surface properties often vary significantly from bulk materials properties. This may not have a significant impact when the surface area to volume ratio is quite small, as is seen in micron-scale particles; however, as particle size drops into submicron dimensions, the properties of the surface atoms may dominate the measured properties. Surface science is mostly concerned with the understanding and control of the physical and chemical properties of surface and near surface atoms. This requires not only developing models for surface thermodynamics, kinetics, and quantum size effects, but also the development of techniques that are capable of characterizing surfaces at or near the atomic level. The understanding developed in surface science can also have practical benefits such as improving fabrication methods for thin-film devices, including atomic layer deposition, designing corrosion-resistant surfaces, and developing better catalysts. In this section the discussion is limited to solid-liquid interfaces that not only benefit from an understanding of inorganic materials chemistry but are important in the subsequent discussion of nanotechnology fabrication methods. In addition to the need to control the chemistry of surfaces in standard ultra-high vacuum–based microelectronic processing techniques, it is important to control solid–liquid interfaces encountered in wet etching, flocculation-deflocculation of powders, colloidal suspensions, electrochemistry, and emerging areas in nanotechnology including self-assembly, some forms of soft lithography, and microfluidics. Rendering a materials surface hydrophobic or hydrophilic (i.e., nonpolar vs. polar) is one way to precisely control interaction forces between the surface and other materials, organic molecules, or biomolecules. Until the past 10 to 15 years, modern surface science experiments have been carried out primarily in ultra-high vacuum environments (~10−9 torr). Such a high vacuum

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was required for two main reasons: (a) Many surface characterization techniques require a vacuum for the analysis beam to operate in, and (b) a high vacuum maintains a pristine and uncontaminated surface, which is important in microelectronic fabrication, including thin film deposition. However, with the advent of scanning probe microscopy techniques and certain surface spectroscopies that can both detect monolayer adsorbates and operate in liquids, the nanoscale structural and chemical properties of the solid–liquid interface have become accessible. Surface forces, electrochemical phenomena, molecular self-assembly, and biomolecule patterning can now be explored with the resolution previously only afforded to vacuum-based surface science.

VII. NANOTECHNOLOGY The prefix nano often refers to 10−9, or 1/1,000,000,000, of a unit of measurement. One nanometer (1 nm) is 10−9 meters, or one billionth of a meter. Atoms have diameters on the order of 0.1 nm; DNA strands have widths of a few nanometers, a white blood cell 10,000 nm, a human hair about 100,000 nm, and a grain of sand 1,000,000 nm. The ability to make and fabricate structures in which at least one dimension of the material is between 1 and 100 nm and then assemble them into larger arrays has led to the term nanotechnology.19 While molecular biologists, chemists, physicists, and materials scientists have been working at the nanoscale in one form of another for decades, only recently have the tools become available to truly observe and fabricate structures at the nanoscale. The discovery of the scanning tunneling microscope (STM) in the early 1980s, and soon thereafter, the scanning force microscope (SFM), for the first time clearly revealed the nanoscale world of individual atoms and molecules on surfaces. These scanning probe microscopy (SPM) techniques are considered the primary enabling technologies in the development of the nanotechnology field and will be discussed in detail in Section IX. Nanotechnology has also benefited tremendously from the discovery of two new nanoscale forms (or allotropes) of carbon called buckyballs and nanotubes. In addition, advances in the rational design of materials, including biomimetics, the science of molecular self-assembly, especially as it occurs on solid substrates, and developments of new soft lithographic techniques such as microcontact printing, have further spurred the development of nanotechnology. As device and feature sizes on chips are reduced significantly below micron dimensions, the surface area to volume ratio can exceed 10%. Consequently, surface effects can dominate material bulk physical and chemical properties. Also, at the nanoscale, materials properties no longer strictly obey bulk continuum laws (e.g., fermi-dirac statistics, etc.) but can instead enter the realm between atomic and molecular quantum mechanics and bulk material, where a small cluster of atoms may exhibit size-dependent quantum effects. This promise of improved or even unique electrical, mechanical, magnetic, and optical properties at the nanoscale is generating excitement in the scientific community. Real nanotechnology examples already exist in everyday life. For example, some sunscreens make use of nanosized zinc oxide particles suspended in a clear lotion to block the sun’s damaging ultraviolet (UV) rays. These zinc oxide particles have sizes that effectively block UV wavelengths (100 to 400 nm) yet are too small to block longer wavelength visible light (~400 to 700 nm); hence the lotion remains transparent. Another example is found in the data storage industry, where data density has increased significantly with the development of magnetoresistive devices formed by alternating layers of magnetic and electrically conducting materials only a few nanometers thick. The electron conductivity in one layer is coupled to the magnetic dipoles in neighboring layers. As these dipoles are ordered and their orientations switched, stepwise changes in conductivity up to several orders of magnitude can occur. Giant magnetoresistive devices are made from alternating nanoscale films of Ni-Fe or Au-Co alloys with nanoscale films of a metallic conductor such as Cu. While this book focuses on inorganic materials, it is worth briefly mentioning that microfabrication and nanofabrication techniques are increasingly being integrated with biomolecules such as

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DNA to form hybrid biological devices such as prosthetics, implants, sensors, and “lab-on-a-chip” type diagnostics and microarrays. For example, DNA microarrays are fabricated using ink-jet technology that applies thousands of micron-scale regions to an inorganic substrate, each with different short segments of DNA. Microfluidics requires fabrication of micro- and nano-scale channels on a chip that can be used to transport fluids around a surface. This technology has been used to make devices that can integrate various functions on a chip such as miniature chemical reactors, sorting cells and DNA by size, and the analysis of biofluids. Quantum dots are beginning to be used in labeling biomolecules and cells. Quantum dots are nanoparticles (2 to 10 nm in diameter) that may be supported on a solid substrate or freely suspended in a liquid. Their optical and electrical properties are often a function of their size. For example, CdSe and CdS particles fluoresce at different colors depending on the particle size. Of course, nature has been working at the nanoscale for millions of years in the areas of self-assembly (e.g., cell membranes) and molecular-scale data storage within strands of DNA. A. Nanofabrication In addition to some of the top-down fabrication methods discussed previously, nanotechnologists are pursuing bottom-up fabrication strategies using a variety of methods including SPM manipulation and self-assembly. A bottom-up approach to device fabrication places circuit elements and wiring only where needed. For example, if one needs a wire on a substrate, then only a wire is fabricated on the surface. There is no need for masking, patterning, and removal of excess material found in most microelectronic fabrication techniques. There are now many examples of successful demonstrations of the bottom-up approach, including nanoscale wires and transistors fabricated from individual carbon nanotubes, self-assembly of gold particles using single stranded DNA, and inorganic-biological hybrid devices fabricated by a number of techniques including microcontact printing. SPMs were probably the first instruments used for rudimentary bottom-up nanolithography by manipulating matter at the nano- and atomic-scales. For example, individual xenon atoms were rearranged on a Ni surface with a low-temperature STM to spell out “IBM,”20 nanoscale copper clusters have been grown electrochemically with an SFM tip on both oxide-passivated copper surfaces,21 and gold surfaces have been passivated with nanoresists made from self-assembled alkanethiol monolayers,22 and more recently, the SFM tip has been used as a nano-pen to write alkanethiol features on gold surfaces with line widths on the order of 10 nm.23 Nanolithography with a scanning tip is an extremely slow serial process compared with standard top-down photolithographic methods. However, the ability to create nanoscale structures or devices and the ability to characterize them quickly makes SPM an extremely powerful tool in developing a fundamental understanding of nanoscale devices and in preparing practical devices that require only a small number of devices, such as sensor components. B. Self-Assembly Self-assembly commonly occurs in nature during the formation of seashells, cell walls, membranes, and myelin, and in nanotechnology it is used mostly as a bottom-up technique. Biological membranes are composed of lipid and bilipid layers. These elongated lipid biomolecules have hydrophilic head groups, hydrophobic tail groups, and strong attractive van der Waals intermolecular interactions between the long chain groups. In bilipid membranes, the hydrophilic head groups point out into the aqueous environment, while the hydrophobic tail groups bury themselves in the interior of the membrane away from water. Self-assembly on an inorganic substrate occurs in a similar fashion but often involves a chemical bond or strong intermolecular interaction of the head group with the substrate and a corresponding ordering in two dimensions of the molecules across the surface. Alkanethiols are one primary example of molecules that self-assemble on noble metal

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surfaces such as gold, silver, and copper to form self-assembled monolayers. The thiol head group forms a chemical bond with the substrate, and the long chain hydrocarbon tails order owing to van der Waal’s attractive interactions. These self-assembled monolayers are used as nanoscale resists, building blocks for nanoscale devices, and templates for biomolecule adhesion. Controlling the chemistry of the inorganic substrate, in addition to the chemistry of the molecule to be adsorbed, is critical in the formation of self-assembled monolayers. Self-assembled monolayers of alkanethiols are considered nanoscale structures, as the film thickness normal to the substrate is only the length of a single molecule (~1 to 3 nm). C. Microcontact Printing Microcontact printing is a soft lithography technique that makes use of the surface chemistry of inorganic substrates to control the transfer of a molecular species such as organic solutions of thiols or biomolecules from an elastomeric stamp, usually polydimethylsiloxane (PDMS), to the substrate. The stamps are first fabricated with features ranging from the nanoscale to microns in size. Next, an ink containing the molecule to be patterned is applied to the PDMS stamp and the inked stamp brought in contact with the substrate. For effective transfer to occur to the substrate, the molecule must have a higher chemical affinity for the substrate than the stamp. Features with lateral dimensions as low as 40 nm have been fabricated with microcontact printing. Microcontact printing still suffers from distortion and registration, particulary in multilevel patterning requiring two or more stamping or lithography steps. D. Nanotechnology Materials: Carbon Fullerenes Two forms of carbon are often used as building blocks for bottom-up nanofabrication: buckyballs and carbon nanotubes. These two new forms of carbon bring the number of carbon allotropes to four, each with crystal structures of different dimensionality, including three-, two-, one-, and zero-dimensional, with markedly different properties. Diamond has a three-dimensional facecentered cubic structure, with four of the eight tetrahedral sites occupied. This highly symmetric cubic structure and sp3 coordinated covalent bonding makes diamond the hardest substance known. Diamond’s extremely high thermal conductivity has also generated considerable interest in using it as a substrate to manage the heat generated by microelectronic devices. The two-dimensional form of carbon is graphite, which consists of sheets with three-fold sp2 coordinated atoms arranged in hexagonal benzene-like rings. The weak van der Waal’s intermolecular attractions between sheets of graphite make it cleave easily along these planes and gives it its slippery feeling. Since it is easily cleavable with the well-known carbon–carbon bond length of 1.41 Å, it is a commonly used as a calibration standard for SPMs. The third, zero-dimensional, allotrope of carbon was discovered by accident in 1985 and consists of 60 atoms arranged in pentagons and hexagons to form a soccer ball–like sphere called a buckminster fullerene, or more commonly, a buckyball. Since buckyballs are essentially carbon sheets wrapped around points, they are considered zero-dimensional materials. The fourth form of carbon is the one-dimensional nanotube, which is essentially a hollow cylinder formed by rolling up a sheet of graphite and capping it at one or both ends with a buckyball hemisphere. Nanotubes come in single- and multiwalled varieties respectively called single-walled nanotubes, which are typically conductive, and multiwalled nanotubes, whose electrical properties can range from insulating to semiconducting. Nanotubes are only a few nanometers in diameter but can be many microns in length and can have electrical properties ranging from insulating to semiconducting to conducting, depending on doping levels. C60 is the most common type of buckyball and can be formed into monomolecular layers on surfaces with potential applications as electronic or sensor components. It can also be doped (e.g., CHBr3) and made to to exhibit superconductivity. Compared to buckyballs, carbon nanotubes have © 2005 by CRC Press

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seen a wider array of potential practical applications. They have been arranged on substrates using bottom-up methods to form nanoscale wires and functioning transistors. When mounted on larger SFM tips, nanotube tips’ low radii of curvature and high strength have made for superior imaging. Carbon nanotubes have also been incorporated into polymer matrices to form nanocomposites that electrostatically interact with automobile paints or for thermal management of electronic devices on satellites. High surface area, dense grass-like arrays of nanotubes have also been grown out of substrates and have potential application as sensors or supports for catalysts, biomolecules, and cells.

VIII. CHARACTERIZATION TECHNIQUES A. Scanning Probe Microscopy The STM and SFM are the two primary types of a class of characterization instruments called SPMs, whose common feature is a small tip, or probe, that is rastered across a surface while measuring a specific tip–sample interaction parameter, for example, tunneling current or tip–substrate intermolecular forces. Depending on SPM design and choice of tip materials, these SPMs can create nanoscale topological surface maps by using other tip–sample interaction parameters such as magnetic, electrostatic, chemical, thermal, electrochemical, frictional, and superconducting properties. The STM operates by applying a voltage bias between an atomically sharp tip and an electrically conducting surface. Electrons flow from the occupied electronic states near the Fermi level of one electrode to the unoccupied states in the other electrode, yielding a small tunneling current. This tunneling current depends exponentially on the tip–sample separation. In order to measure the surface topography of a conductive material, the tip must be moved or rastered incrementally across the surface. This is accomplished by mounting the tip on a piezoelectric actuator that controls the tip’s position across the surface along the x and y coordinates and the height normal to the surface in the z-direction. The STM is operated in two common imaging modes: constant height and constant current. In the constant height mode (z constant), the tip is scanned across the surface at constant height while monitoring the tunneling current. As tip–sample separation varies, the tunneling current will vary, yielding a real space topographic image of the surface that has enough resolution to resolve individual atoms and vacancies. In constant current mode, a feedback mechanism is used so that as the tip is rastered across the surface, the tip–sample separation is varied to maintain a constant tunneling current. Mapping out this tip–sample separation in x and y coordinates generates a topographical surface map. The SFM, also called the atomic force microscope, behaves like an old fashioned phonograph stylus except that the SFM stylus, or tip, is much smaller, with radii of curvature between 1 and 100 nm. Instead of the tunneling current of an STM, the SFM tip–sample interaction parameters are surface forces such as van der Waal’s and electrostatic intermolecular interactions. SFM tips are mounted to the end of cantilevers that have different effective spring constants depending on the material and geometry. One can vary the applied force on the surface by controlling the position of the tip normal to the surface. As the force exerted between the tip and surface varies, the cantilever will deflect a small amount. There are also two primary imaging modes for SFM, contact mode, which includes constant height and constant force methods, and tapping mode. In constant height mode, the SFM tip is rastered across the surface with a piezoelectric actuator, while the cantilever deflection, or tip–sample interaction force, is monitored with a laser system. Any variations in force correspond to variations in surface topography, which creates a three-dimensional topographic image of the surface. In constant force mode, the tip–sample force is maintained constant by using a feedback loop as the tip is rastered across the surface. This feedback loop maintains a constant deflection (or force) on the tip by raising and lowering the tip as it traces surface features. In tapping mode

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SFM, an oscillating tip is kept near its resonance frequency while the tip is either in contact or extremely close to the surface. This oscillating tip is extremely sensitive to small tip–sample interaction forces, including long-range van der Waal’s interactions and medium to short range polar interactions. The primary benefit of tapping mode SFM is that it significantly reduces tip–sample interaction forces that can destroy delicate surfaces. Tapping mode’s major drawback is that if desired, it is difficult, if not impossible, to achieve lattice-scale resolution. The resolution of the SFM is often limited by the radius of curvature of the tip. A smaller radius of curvature results in better resolution of nanoscale features and fewer imaging artifacts. Carbon nanotubes with radii of curvature on the order of 10 nm or less are currently being adhered to SFM cantilevers and offer the best resolution to date. While the resolution of an SFM is typically not as good as the STM, it has the advantages of being able to image insulating materials and biomolecules and is generally simpler to use than the STM. B. Techniques Many other techniques can be used to characterize the inorganic precursors, process intermediates, solid state products, and surfaces described in this book. The discussions of the various characterization techniques available are given in Chapter 2 along with their applicability. The characterization techniques can be classified under elemental, molecular and surface analyses. Some techniques listed below can provide both elemental and molecular analyses of materials. 1. Elemental Analysis Atomic absorption spectroscopy Auger electron spectroscopy Electron probe microanalysis (EPMA) Electron spectroscopy for chemical analysis (ESCA) Energy dispersive spectroscopy (EDS) Flame photometry Wavelength dispersive spectroscopy (WDS) X-ray fluorescence

2. Molecular and Solid State Analysis Chromatography [gas chromatography (GC), size exclusion chromatography (SEC)] Electron diffraction Electron microscopy [scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning TEM (STEM)] Electron spin resonance (ESR) Infrared spectroscopy (IR) Mass spectrometry Mercury porosimetry Mossbauer spectroscopy Nuclear magnetic resonance (NMR) Neutron diffraction Optical microscopy Optical rotatory dispersion (ORD) Raman spectroscopy Rutherford back scattering (RBS) Small angle x-ray scattering (SAXS) Thermal analysis [differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), differential thermal analysis (DTA) temperature desorption spectroscopy (TDS), thermomechanical analysis (TMA)]

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UV spectroscopy X-ray techniques [x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), x-ray emission, x-ray absorption]

3. Surface Characterization Techniques Electron energy loss spectroscopy (EELS) Ellipsometry Extended x-ray adsorption fine structure (EXAFS) Helium (or atom) diffraction Lateral (or frictional) force microscopy (LFM) Low-energy electron diffraction (LEED) Magnetic force microscopy (MFM) Near-edge x-ray adsorption fine structure (NEXAFS) Near field scanning Reflection high-energy electron diffraction (RHEED) Scanning tunneling microscopy (STM) Scanning force microscopy (SFM) Secondary ion mass spectroscopy (SIMS) Surface enhanced raman spectroscopy (SERS) Surface extended x-ray adsorption fine structure (SEXAFS) Surface force apparatus

IX. SELECTED SOURCES OF INFORMATION IN MATERIALS CHEMISTRY A. Books Ball, P., Made to Measure, Princeton University Press, Princeton, NJ, 1997. Brinker, C.J. and Scherer, G.W., Sol-Gel Science: The Physics and Chemistry of Sol-Gel Science, Academic Press, San Diego, CA, 1990. Campbell, S.A., The Science and Engineering of Microelectronic Fabrication, Oxford University Press, New York, 1996. Hubbard, A.T., Ed., Surface Imaging and Visualization, CRC Press, Boca Raton, FL, 1995. Interrante, L.V., Casper, L.A., and Ellis, A.B., Eds., Materials Chemistry: An Emerging Discipline, American Chemical Society, Washington, DC, 1995. Israelachvili, J., Intermolecular and Surface Forces, Academic Press, New York, 1992. Jones, R.W., Fundamentals of Sol-Gel Technology, Institute of Metals, North American Publication Center, Brookfield, VT, 1989. Klein, L.C., Ed., Sol-Gel Technology for Thin Films, Fibers, Preforms, Electronics, and Specialty Shapes, Noyes, Park Ridge, NJ, 1988. Lee, B.L. and Pope, E.J.A., Eds., Chemical Processing of Ceramics, Marcel Dekker, New York, 1994. Madou, M., Fundamentals of Microfabrication, CRC Press, Boca Raton, FL, 1997. Mark, J.E., Allcock, H.R., and West, R., Inorganic Polymers, Prentice Hall Polymer Science and Engineering Series, Englewood Cliffs, NJ, 1992. Narula, C.K., Ceramic Precursor Technology and Its Applications, Marcel Dekker, New York, 1995. Poole, C.P. and Owens, F.J., Introduction to Nanotechnology, John Wiley and Sons, New York, 2003. Rao, C.N.R., Ed., Chemistry of Advanced Materials, Blackwell Scientific, Oxford, 1993. Ring, T.A., Fundamentals of Ceramic Powder Processing and Synthesis, Academic Press, New York, 1996. Segal, D., Chemical Synthesis of Advanced Ceramic Materials, Cambridge University Press, London, 1989. Shanefield, D.J., Organic Additives and Ceramic Processing, Kluwer Academic, Boston, 1995. Somorjai, G.A. Introduction to Surface Chemistry and Catalysis, John Wiley & Sons, New York, 1994.

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B. Monographs/Proceedings Better Ceramics through Chemistry, several volumes (symposium proceedings), published by Materials Research Society, Pittsburgh, PA. Critical Reviews in Solid State and Materials Science, CRC Press, Boca Raton, FL. Innovations in Materials Processing, edited by F.M. Doyle et al., TMS Publication, Warrendale, PA, 1989. Inorganic Synthesis, John Wiley & Sons, New York. Nanofabrication and Biosystems: Integrating Materials Science, Engineering, and Biology, edited by H.C. Hoch, L.W. Jelinski, H.G. Craighead, Cambridge University Press, New York, 1996. Sol-Gel Optics, edited by J.D. Mackenzie, SPIE, Bellingham, PA, 1990. Sol-Gel Science and Technology, edited by M.A. Aegerter et al., World Scientific, Teaneck, NJ, 1989. Ultrastructure Processing (or Chemical Processing or Advanced Materials), several volumes, published by John Wiley & Sons, New York.

C. Journals Advanced Materials, published by VCH, Cambridge, U.K. Chemistry of Materials, published by American Chemical Society, Washington, DC. Journal of Materials Chemistry, published by The Royal Society of Chemistry, Cambridge, U.K. Journal of Sol-Gel Science and Technology, published by Kluwer Academic Publishers, Norwell, MA.

Additional articles also appear in: Journal of Materials Research, published by Materials Research Society, Pittsburgh, PA. Journal of Nanoscience and Nanotechnology, published by American Scientific Publishers, Stevenson Ranch, CA. Journal of Non-Crystalline Solids, published by Elsevier Scientific Publishers, Amsterdam, The Netherlands. Journal of the American Ceramic Society, published by American Ceramic Society, Westerville, OH. Journal of the American Chemical Society, published by American Chemical Society, Washington, DC. Langmuir, published by American Chemical Society, Washington, DC. Materials Letters, published by Elsevier Scientific Publishers, Amsterdam, The Netherlands. Nanoletters, published by American Chemical Society, Washington, D.C.

REFERENCES 1. Interrante, L.V., Chemistry of materials: The newest ACS Journal, Chem. Mater., 1(1), 1, 1989. 2. Shinoda, K. and Friberg, S., Emulsion and Solubilization, John Wiley & Sons, New York, 1986. 3. Ramamurthi, S.D. et al., Nanometer-sized particles prepared by a sol-emulsion-gel method, J. Am. Ceram. Soc., 73(9), 2760, 1990. 4. Matijevic, E., Monodispersed metal (hydrous) oxides: a fascinating field of colloid science, Acc. Mater. Res., 14, 22, 1981. 5. Tani, E. et al., Formation of ultrafine zirconia under hydrothermal conditions, J. Am. Ceram. Soc., 66(1), 11, 1983. 6. Toroya, H. et al., Hydrothermal oxidation of Hf metal chips in the preparation of monoclinic HfO powders, J. Am. Ceram. Soc., 66, 148, 1983. 7. Aerogels: Proceedings of the First International Symposium, Wurzburg, Germany, Springer-Verlag, New York, 1985. 8. LeMay, J.D. et al., Low density microcellular materials, MRS Bull., 15, 19, 1990. 9. Matson, D.W. et al., Formation of silica powder from the rapid expansion of supercritical solutions, Mater. Lett., 4, 429, 1986. 9a. Real, M.W., Freeze drying alumina powders, Proc. Br. Ceram. Soc., 38, 59, 1986. 10. Fischer, H.E. et al., Fiber coatings derived from molecular precursors, MRS Bull., 59, April 1991.

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11. Mantese, J.V. et al., Metal organic decomposition (MOD): A nonvacuum spin-on liquid-based, thin film method, MRS Bull., October, 48, 1989 (and references therein). 12. Vest, R.W. and Vest, G.M., Metallo-Organic Decomposition for Dielectric Films, Report to the Office of Naval Research, November 30, 1990. 13. Pierson, H.D., Handbook of Chemical Vapor Deposition: Principles, Technology, and Applications, Noyes, Park Ridge, NJ, 1992. 13a. Ferroelectric Thin Films Symposium Proceedings, Published by the Materials Research Society, Pittsburgh, PA, 1990–1996. 14. Proceedings of the 3rd International Conference on Metallo-Organic Vapor Phase Epitaxy, American Association of Crystal Growth, Universal City, CA, 1986. 15. Kaae, J.L., Codeposition of compounds by chemical vapor deposition in fluidized bed of particles, Ceram. Eng. Sci. Proc., 9(9–10), 1159, 1988. 16. Willeke, K. et al., Eds., Aerosol Measurements, Principles, Techniques, and Applications, Van Nostrand Reinhold, New York, 1993, chap. 33. 17. Iler, R.K., The Chemistry of Silica, A Wiley-Interscience Publication, John Wiley & Sons, New York, 1979. 18. Shinoda, K. and Friberg, S., Emulsion and Solubilization, John Wiley & Sons, New York, 1986, pp. 70–80. 19. See for example, Scientific American, 285, 32, 2001 and articles within. 20. Eigler, D.M. and Schweizer, E.K., Positioning single atoms with a scanning tunnelling microscope, Nature, 344, 524, 1990. 21. LaGraff, J.R. and Gewirth, A., Enhanced electrochemical deposition with an atomic force microscope, J. Phys. Chem., 98, 11246, 1994. 22. LaGraff, J.R. and Gewirth, A., Nanometer-scale mechanism for the constructive modification of Cu single crystals and alkanethiol passivated Au(111) with an atomic force microscope, J. Phys. Chem., 99, 10009, 1995. 23. Piner, D., Zhu, J., Xu, F., Hong, S., and Mirkin, C.A., “Dip-pen” nanolithography, Science, 283, 661, 1999.

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CHAPTER 2 Definitions of Terms Used in Inorganic Materials Chemistry

A Abrasives Materials with high hardness values of 2 to 25 GPa used for grinding, cutting, and polishing metals and other ceramic or glass materials. Aluminum oxide, silicon carbide, silicon nitride, and titanium nitride are common abrasive materials. Absorption Edge Fine Structure (AEFS) An absorption technique that uses a synchrotron radiation source to study the local structure of a compound. The local structure is associated with inner shell transitions in the atomic structure of a compound where the x-rays are absorbed in the absorption edge (8.95 to 9.03 KeV in the CuCl spectrum). The absorption edges in the spectrum represent abrupt changes in x-ray absorption peak intensities. In many cases, this spectroscopy technique helps determine the oxidation state of the element in a compound. For example, the AEFS spectra of CuCl and CuCl2 · H2O exhibit peaks corresponding to transitions from 1s orbital to higher orbitals, and the entire spectrum in CuCl2 · H2O is displaced to higher energies, reflecting the higher oxidation state of copper (+2). Also, an additional peak owing to a 1s q three-dimensional transition is observed in the CuCl2 · H2O spectrum. Acceptor A dopant (e.g., an impurity species such as boron added to a silicon crystal) that accepts electrons from the valence band of the host crystal forming electron holes in the valence band yielding a p-type material. See also, donor, dope, n-type, p-type. Acetate An organic ligand [CH3C(=O)O] normally bonded to a metal center via an oxygen atom in a metal organic compound. Other common acetate-type ligands include amylacetate [CH3(CH2)2CH2-OC(O)O], crotyl acetate [CH3CH=CHC(O)O], and benzoate [C6H5C(O)O].

O O C CH3 Acetate ligand

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Acetylacetonate A chelating ligand [OC(CH3)CH(CH3)CO] bonded with two oxygens to the metal center in a metal organic compound. See also chelates. CH3 O C CH O C CH3 Acetylacetonate ligand (acac)

Acoustooptic Material Materials that change their refractive indexes as a result of induced strain. A plane elastic wave in such a material produces a periodic strain pattern with spacing equal to the acoustic wavelength; this strain in turn produces an acoustooptic variation in the refractive index. Examples of acoustooptic material include LiNbO3, LiTaTiO3, PbMoO4, and PbMoO5. Actinide Fourteen elements from thorium to lawrencium following actinium in the periodic table. These elements are uniquely characterized by partially or fully filled 5f orbitals. Actinoid See actinide. Actinon See actinide. Activated Carbon A highly reactive form of carbon with surface area in the range of 300 to 2000 m2/g produced by chemical or gas activation of sawdust, peat, and other raw organic forms. Applications of activated carbon include decolorization and purification of materials in addition to its use as an adsorption media and as a support in oxidation catalysis. Adatom An atom that has been chemisorbed or physisorbed onto a materials surface. A surface point defect that, along with surface vacancies, participates in atom transport across a surface. Adhesion The joining of two surfaces at an interface. The work of adhesion to separate two phases, A and B, is given by Wad = LA + LB  LAB, where LA and LB are the interfacial energies (surface tensions or surface energies in ergs per square centimeter) of the freshly separated surfaces, and LAB is the interfacial energy of the joined A–B phases. Adlayer The monolayer (or molecular monolayer) formed by the adsorption of atoms (or molecules) onto a materials surface (or substrate). Adsorbate An adsorbed atomic or molecular monolayer on a materials surface. For a strongly bonded monolayer to form, substrate-adsorbate bonds must typically be stronger than adsorbateadsorbate bonds, or the adsorbate atoms or molecules will coarsen into either islands or multilayers. Adsorption The trapping or attractive interaction of molecules or atoms onto a surface or substrate. See also chemisorption and physisorption. Adsorption Site Sites on a surface where adsorption is favorable, including monatomic step edges, multiple atomic height step edges, and kink sites along step edges. AEFS See absorption edge fine structure. AEM See analytical electron microscopy. Aerogel Solid-state material characterized by high porosity (>90%), small pore size (2 to 100 nm), small particle size (2 to 10 nm), and low density (0.004 to 0.2 g/cm3). The term aerogel was coined by the inventor, Kistler, who prepared inorganic (oxides of Si, Al, W, Sn, Fe, etc.) and organic (cellulose, gelatin, agar, etc.) hydrogels and replaced the liquid in the gel with air. When the liquid is merely evaporated from the gel, the surface tension of the liquid usually causes dramatic volume shrinkage. However, in aerogels, when the liquid is removed at or above the critical point (at zero surface tension) of the liquid, the structure does not collapse, resulting in a highly porous aerogel material.1 © 2005 by CRC Press

Aerosil Tradename (Degussa) of fumed silica produced by the flame-oxidation process. Aerosil is a silica powder with a high surface area (150 to 200 m2/g), small particle sizes (10 to 15 nm), and a high affinity to absorb moisture. See also fumed silica. Aerosol A colloidal suspension of liquid (also called hydrosol) or solid particles in gas. Fog is a suspension of liquid droplets in air, whereas smoke is a suspension of solid particles in air. AES See auger electron spectroscopy. Agglomeration A process in which two or more particles or clusters are held together by weak cohesive forces. In many samples, cohesive forces result from electrostatic surface charges generated during handling or processing of ceramic powders. Aggregate A particle or an assembly of particles held together by strong inter- or intramolecular or atomic cohesive forces. Aggregates are normally stable to handling and ordinary dispersive techniques such as high-speed mixing and ultrasonics. Aggregates can be arranged in coacervate (spherical), tactoid (elliptical), crystalloid (cylindrical), or flock (haphazard) forms, with rod-, plate-, or spherical-shaped particles. Aging Process of restructuring and change in materials properties with time. Examples include condensation reactions, dissolution, reprecipitation, and phase transformation after gelation in the sol-gel process. See also syneresis. Physical aging (or structural relaxation) refers to changes in the properties of an amorphous material during annealing, as its structure relaxes toward that of the equilibrium liquid. The term aging is also used in electronic, magnetic, or structural materials that are hysteretic in nature. Aging results when the properties of the material deteriorate as a consequence of repeated cycling through the hysteresis loop. See also hysteresis. Albite A clay mineral, soda feldspar, NaAlSi3O8, used in producing refractory materials. Alcoholysis A reaction between an alcohol and a metal oxide oligomer resulting in metal–alkoxy bond formation. This reaction can be represented by  M  O  M  + ROH q  M  OR + HO  M 

where M is the metal and R is the alkyl group. Alcoxolation A condensation reaction between metalhydroxy and metalalkoxy bonds on two different reactants/compounds in the sol-gel process in which an alcohol is released as a byproduct. The alcoxolation reaction can be represented by  M  OH + RO  M  q  M  O  M  + ROH

where M is the metal and R is the alkyl group. Alite Tricalcium silicate (with the acronym C3S), a polymorph of calcium silicate. Alite is a stable phase of calcium silicate between its melting temperature of 2070°C down to 1250°C. Alite is a component in the clinker composition. Alkali Metals Elements from lithium to francium in group IA of the periodic table, with one electron in the outer s shell. Alkaline Earth Metals Elements from beryllium to radium in group IIA of the periodic table, with two electrons in the outer s shell. Alkanethiol Long chain hydrocarbons with a thiol head group that can chemisorb onto noble metals such as gold and silver and tend to order via attractive van der Waal’s interactions between the carbon chains. Chain length and tail group chemistry can be tailored to precisely control surface chemical and physical properties. Alkanethiols are often used as model surfaces, nanoscale resists, and templates for biomolecule adhesion. See also self-assembled monolayer. Alkene Ligands Organic ligands characterized by double bonds, with the general formula RHC = CHR, where R = H or an alkyl group. Alkene acts as a ligand to a variety of metals in © 2005 by CRC Press

organometallic compounds by bonding through the U-bonds. Butadienyl (CH2 = CH  CH = CH) is an example. Alkoxide A class of metal organic compounds with the general formula M(OR)x, where M is the metal and R is the alkyl group, and the alkoxy ligand is attached to the metal via the oxygen atom. Silicon alkoxides commonly used in the sol-gel process include Si(OCH3)4, Si(OC2H5)4, and Si(OiC3H4). Metal Alkoxides M OR Examples H CH3 C O CH3 CH3 H C O Ti O C H CH3 CH3 O C CH3 CH3 H CH3

OCH3 OCH3

Al OCH3

Aluminum (III) methoxide

Titanium (IV) isopropoxide

Alkyl Organic ligands with the general formula CnH2n+1. Alkyl ligands are formed as a result of removing one hydrogen atom from the carbon atom in an alkane and are commonly bonded to metal centers in an organometallic compound via carbon. Alkyl ligands are frequently used in organometallic precursors. For example, methane (CH4) produces a methyl ligand/group, CH3. Other such ligands include ethyl (C2H5), propyl (C3H7), and butyl (C4H9). Compound containing alkyl ligands H 5C 2 Al C2H5 H5C2 Triethyl aluminum

Alkyne Ligands Organic ligands characterized by a triple bond with the general formula RC } CR , where R = H or an alkyl group. Like alkene, alkynes act as ligands to a variety of metals in organometallic compounds by bonding through the U-bonds. Compound containing alkyne ligand H5C2 Al C CCH3 H5C2 Diethyl(methylacetylenyl) aluminum

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Allotelluric Acid A chemical compound with the formula H6TeO6. Allotelluric acids are weak acids with the successive dissociation constants K1 ~ 2 × 10–8, K2 ~ 10–11, and K3 ~ 3 × 10–15. Allotropes Different structural arrangements of a crystalline element. Allotropes may differ in the coordination environment (short-range) of the element or the long-range order (layers and stacking) of the crystal. For example, diamond and graphite are allotropes of carbon differing in the long-range order. Alloys Intermetallic phases or solid solutions of two or more metals. Copper and gold form a variety of alloys. Allyl Group An organic ligand with the molecular formula CH2 = CH  CH2, normally bonded to metal centers via the carbon on the CH2 group or through U-bonds. See alkene ligands for a general description. Alumina Crystalline forms of Al2O3: ␣-Alumina One of the two forms of anhydrous alumina in which the oxide ions form a hexagonal closed-packed (hcp) array and the aluminum ions are distributed symmetrically among the octahedral sites. This form of alumina is hard and resistant to hydration and attack by acids and is stable at high temperatures. ␤-Alumina Family of compounds with the general formula M2O · nAl2O3, where n is 5 to 11, M is monovalent cation, Alkali+, Cu+, Ag+, Ga+, In+, Tl+, H3O+. The most common member of this family is sodium G-alumina, which is a by-product of the glassmaking process. ␦-Alumina Anhydrous alumina produced at 850°C from L-alumina. ␥-Alumina One of the two forms of anhydrous alumina in which the crystal structure is regarded as a defect spinel structure with a cation deficiency. L-Alumina is readily hydrated and dissolves in acids. ␩-Alumina Anhydrous alumina produced from Al(OH)3 at 400°C. ␪-Alumina A form of alumina produced from I-alumina at 1100 to 1150°C. Aluminous Cement Cement consisting of lime (CaCO3) and alumina in equal parts with small amounts of iron oxide, silica, magnesia, alkali oxides, and titania. Alunite An iron mineral with the formula Fe3(SO4)2(OH)5 · 2H2O. Amethyst An impure form of quartz silica that is violet or purple in color. The uneven color in the crystals can be uniformly distributed by heating the crystals to elevated temperatures. Heating changes the color to yellow or green and further heating removes all color, leaving the crystals transparent. Aminoboranes Boron compounds with one or more amino group substituents on boron represented by the formula (R2N)xBRy, where R is alkyl, aryl, or H. (CH3)2N–B(CH3)2 is one such example. Some studies indicate U interactions between B and N in aminoboranes. Ammonolysis The process in which a metal nitrogen bond is formed as a result of a reaction between amines (ammonia, organic amines) and compounds containing a metal oxygen bond. Amorphous Compounds or materials with only a short-range order and no long-range order in their structures. Amorphous materials include glassy (e.g., fused silica) and noncrystalline (e.g., gel) materials. Amorphous materials can be prepared by quenching the melt, neutron bombardment, sol-gel, interdiffusion, and other methods. Amorphous Semiconductors Unlike crystalline Si and Ge semiconductors, amorphous semiconductors are noncrystalline/amorphous glass-type materials. Various chalcogenides are examples of amorphous semiconductors, and amorphous silicon can be semiconducting. See also chalcogenide glasses. Amosite A rock-forming gray-brown mineral that belongs to the class of amphibole minerals. The chemical formula of amosite is [(Mg,Fe)7Si8O22(OH)2]. Asbestos is derived from this mineral. Amphiboles A type of rock-forming mineral used for producing asbestos, which contains double6 stranded, cross-linked chains or bands with the composition (Si 4O11 )n. Amphiboles include a © 2005 by CRC Press

blue asbestos mineral (crocidolite) and a gray-brown asbestos mineral (amosite). Other examples include actinolite [Ca2(Mg,Fe)5Si8O22(OH,F)2], anthophyllite [(Mg,Fe)2Si8O22(OH,F)2], and tremolite [Ca2Mg3Si8O22(OH)]. Amphiphilic Amphiphilic molecules such as lipids, copolymers, and surfactants generally consist of a hydrophilic head group and a hydrophobic tail group (often a long chain hydrocarbon), for example, alkanethiols. See also self-assembly. Amphoteric Behavior The behavior pertaining to self-ionization, in which a chemical species consists of both an acidic and a basic site and hence can act as an acid and a base, respectively, toward other reactants. Examples of compounds exhibiting amphoteric behavior include water (H+, OH–), aluminum hydroxide, and zinc hydroxide. Amphoteric Cations Cations that are neither strong basic cations nor cations in complex anions. The amphoteric cationic radius for a given oxidation state falls between the two types of cations. Examples of amphoteric cations include Be, Ga, Cr, Mn, Fe, Al, Th, U, Pb, Hf, Sn,Ti, and Bi. Examples of strong basic cations include Ba, Sr, Na, Mg, Mn, and examples of cations in complex anions include B, C, Si, V, W, Mo, Se. Analytical Electron Microscopy (AEM) Technique used for elemental analysis of samples during scanning or transmission electron microscopy (SEM and TEM). Analytical electron microscopy includes energy dispersive spectroscopy (EDS) and wavelength dispersive spectroscopy (WDS) techniques for determining the elemental composition of a sample. See electron microscopy with microanalysis and wavelength dispersive spectroscopy. Anatase One of the forms of crystalline titania in which titanium is octahedrally coordinated to oxygen atoms. Andradite Specific types of ferrimagnetic (garnets) complex oxides with the general formula A3B2X3O12, where A = Ca, NaCa; B = Fe, Te, CaZr, Ti, Zn; X = Si, Ge, Zn, Ge, V. Anelasticity The departure from linear (Hookean) elasticity in viscoelastic or plastic materials. Unlike elastic materials, in anelastic materials, as the stress is removed, the deformation is recovered slowly, not instantaneously. Examples of materials exhibiting anelasticity include glass materials at their transition temperature and polycrystalline materials at high temperatures. See also viscoelasticity. Anisotropic Noncentrosymmetric materials with net directionality in physical properties. Directionally solidified crystals, ferroelectrics, graphite, and one- or two-dimensional fiber-reinforced composites are examples of anisotropic materials. See also isotropic. Anisotropic Magnetoresistance (AMR) A change in a materials resistance when a current flowing through a sample changes from being parallel to internal magnetic moments to perpendicular. Examples include Ni-Fe alloys and iron filings. See also magnetoresistance, giant magnetoresistance, and colossal magnetoresistance. Annealing A process in which the material is thermally treated to release stresses produced during the ceramic-forming process. In glasses, annealing stabilizes the glass structure to produce homogenous material and to avoid property variation from region to region. Anode An electrode at which oxidation occurs in an electrochemical cell (e.g., copper dissolution: Cu(s) q Cu2+(aq) + 2e–). See also cathode. Anodic Oxidation An electrolyte method used for growing oxide films on metals (Al, Ta, Nb, Ti, Zr). The metal anode is dipped into the salt or acid solution (electrolyte), and during the electrolysis process the oxide ions are attracted to the anode, resulting in film growth at the anode. Anorthite A clay mineral, lime feldspar, Ca(Al2Si2)O8, used in producing refractory materials. Antiferroelectric Dielectric materials that spontaneously polarize as a result of an applied external field. However, the individual dipoles in the material are arranged such that the adjacent © 2005 by CRC Press

dipoles are antiparallel, which results in a net polarization of zero. Examples of antiferroelectric materials include PbZrO3, NaNbO3, and NH4H2PO4. Antiferromagnetism A condition in which the magnetic moments in a material are strongly coupled in an antiparallel fashion, resulting in zero net magnetization. Several transition metal monoxides (such as MnO, FeO, NiO, and CoO) are antiferromagnetic. Antifluorite Structures A cubic close-packed structure in which the tetrahedral sites are occupied completely and octahedral sites are vacant such as in the K2O structure. Antiknock Additives Organolead compounds used as additives in gasoline for antiknock properties during fuel combustion. Antiphase Boundaries Subgrain boundaries that involve relative lateral displacement of two parts within the same crystal. Antireflective (AR) Films Films that provide reduced reflectance and increased transmittance. The antireflective properties are provided by multiple layers or by graded-refractive index (GRIN) coatings in which the refractive index changes gradually through the thickness of the film or by a sequence of quarter-wave layers. Silica and titania coatings have been developed for AR applications. Antistatic Films A type of coating that reduces the charge buildup on a material substrate. Antistatic coatings are normally composed of electrically conductive materials. Indium-tin oxide (ITO) films are frequently used for their antistatic properties. Apatite A crystalline phosphorus mineral with an idealized general formula of 3Ca3(PO4)2; CaX2 [i.e., Ca10(PO4)3X2]. Common members of the apatite group include fluoroapatite [Ca5(PO4)3F], chloroapatite [Ca5(PO4)3Cl], and hydroxyapatite [Ca5(PO4)3OH]. Aprotic Solvent A solvent consisting of no labile protons, such as dioxane, tetrahydrofuran, and dimethylformamide. Aprotic Solvents

O

O

CH3 H C N CH3 O

Tetrahydrofuran (THF)

Dimethylformamide

O Dioxane

Aqua Regia A mixture of 25 vol% HCl (37 wt%) and 75 vol% HNO3 (70 wt%) used for dissolving metal ceramic surface layers during chemical etching or surface cleaning processes. Aragonite A mineral found in temperate seas that is used for producing CaCO3. Arene or Aryl Ligands Cyclic unsaturated organic ligands consisting of alternate double bonds. Benzyl and phenyl are examples of two such ligands. Compound containing aryl ligands

Al

Triphenyl aluminum

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AR Films See antireflective films. Argentite A silver sulfide (Ag2S, silver glance) mineral used for producing silver. Aryl Ligands See arene or aryl ligands. Asbestos A fibrous silicate mineral collectively known as asbestos derived from rock-forming minerals such as hydrous magnesium silicate chrysotile, Mg3Si2O5(OH)4, with a fibrous structure. Athermal Phase Transition A transformation between crystalline phases that is independent of temperature. However, the transition may be affected by applied stress and strain. Atomic Absorption Analysis A spectrometric method used for quantitative measurements of metals in a sample by comparing the optical absorbance of the elements in the sample with a reference containing known amounts of elements. Atomic Emission Analysis See inductively coupled plasma (ICP) spectroscopy. Atomic Force Microscope (AFM) See scanning force microscope (SFM). Auger Electrons Electrons emitted as a result of the decay of an excited state of an atom to a lower energy level. See also auger electron spectroscopy. Auger Electron Spectroscopy (AES) An electron spectroscopy technique in which the kinetic energy of an emitted electron (secondary) is measured to identify the elemental composition of the sample. The electrons are emitted as a result of the decay of an excited species during a secondary process. First, the atom is excited or ionized by the bombarding radiation, and then the excited species decays to the lower energy level, emitting an electron. The elemental species is characterized by the kinetic energy of the emitted electron. A+* q A++  e 

This technique is useful in identifying the presence or absence of elements on the surface of the sample. Auger Spectroscopy See auger electron spectroscopy and auger electrons. Austenite A solid solution of carbon (less than 1 wt%) in L-Fe that forms as the iron melt is cooled down to temperatures in the range of 800 to 1400°C. Autoclave A pressure vessel used for performing reactions at elevated pressures and temperatures. The vessels are tubular in structure to withstand high pressures (a few to several thousand psi) at high temperatures (as high as 500°C). The autoclaves are used for hydrothermal processing to crystallize a variety of materials at high pressures without going to high temperatures and for supercritical drying of gels and precipitates. Autoclaves are also used for leaching and separation of materials. See also hydrothermal processing and supercritical drying. Azeotrope Solutions of multiple-liquid components that produce vapors of the same composition as the liquid when these solutions are boiled, for example, a solution of 4.5 wt% water in ethanol with evaporate with no change in composition (i.e., the compositions of the liquid and vapor are the same). See also zeotrope. Azides Nitride compounds with the formula M(N3)x, where M is a metal.

B Baddeleyite A zirconium oxide (ZrO2), which is the main mineral of zirconium metal. In the baddeleyite structure Zr4+ is seven-coordinated with three oxygen atoms in the upper plane and four oxygen atoms in the lower plane. Baking Powder A mixture of Ca(H2PO4)2 · H2O and NaHCO3 with 40% starch coating. The mixture tends to produce CO2 very quickly when it is mixed with water. For this reason, a slowacting acid, NaAl(SO4)2, is incorporated in the mixture to reduce the excessive effervescence of CO2. © 2005 by CRC Press

Ballistic Aggregation In cluster growth or formation of aggregates, the process in which a monomer or a particle travels in a straight line to its point of attachment on the aggregate. Ballistic aggregation is more appropriate to particle growth in the vapor phase, whereas Brownian diffusion (where aggregating species follow a random path) is more applicable to gelation. Ball Milling A ceramic process for mixing and comminution of precursor oxides in dry or slurry forms. In ball milling, powders are mixed and the agglomerates are broken into smaller particles in a rotating mill with ceramic pieces such as balls or cylinders (usually composed of a hard oxide, such as zirconia) of various sizes. The fine powder or particles thus produced compact and sinter efficiently with increased sintering rates to fabricate dense ceramic parts. Band Gap The energy difference between the highest occupied band (the valence band) and the lowest vacant band in the electronic structure of metals, semiconductors, and insulators. Band gaps in ceramic oxides normally range from 2 to 10 eV. Band Theory The theory that describes electronic structures of metals, semiconductors, insulators, and other solids. The difference between these solids can be explained by occupancy of the valence bands and the band gap in their electronic structure. For example, lead (Pb) is a metal since it has a partially filled valence band (4f145d106s26p2; completely delocalized outer shell electrons) with a band gap of 0 eV. Silicon (Si), however, is a semiconductor with (3s23p2; partially delocalized sp3 orbitals) a band gap of only 1.1 eV; hence, the electrons in the valence band can be thermally excited to the conduction band. Diamond (C) is an insulator (2s22p2; localized sp3 orbitals) with a completely forbidden band gap of 6 eV. The band gap increases from metals to insulators. Barium Magnetoplumbite (BaM) A hard oxide composed of barium, iron, and lead oxides, used widely as a permanent magnet in a variety of applications. In addition to the abrasive properties, BaM is also lightweight and inexpensive. For magnetic properties of BaM refer to Chapter 4. Bastnaesite A lanthanide mineral with the formula MIIICO3F. Battery Electrochemical cells that convert chemical energy into electrical energy. One of the most important types of batteries is a sodium–sulfur cell, which consists of a molten sodium anode and a molten sulfur cathode separated by a G-alumina solid electrolyte. This is a highdensity cell (i.e., with high energy/power-to-mass ratio) normally used for applications such as in electric cars and power station load leveling. The other types of batteries are miniature cells used for longer life rather than high power output. These are the lithium-iodine or silveriodine type of batteries normally used for pacemakers and watches. Bauxite An alumina ore (aluminum hydroxides and aluminum oxohydroxides) used as a source for aluminum. Bauxite is most commonly used for manufacturing refractory bricks. Bayerite An aluminum mineral composed of aluminum hydroxide, F-Al(OH)3, with a hexagonal close packing of OH ions consisting of Al in two thirds of the octahedral sites. BCF Crystal Growth Theory See Burton, Cabrera, Frank (BCF) Crystal Growth Theory. Beer’s Law Law used for characterizing the optical absorption properties of a material. The absorption of light in a medium depends on the concentration of the absorbing ion and is expressed as follows: I / I0 = e( J cx )

where I is the transmitted intensity, I0 is the initial intensity, J is the extinction coefficient or absorption observed per unit concentration per unit length, c is the concentration of the absorbing ion, and x is the optical path length. Beer’s law is also described as the BeerLambert equation. Beevers–Ross Sites One of three possible sites for sodium ions in the conduction plane of Galumina (modified spinel structure). The three possible sites for the sodium ions are (a) a midoxygen position, m, (b) the BeeversRoss site, br, and (c) the anti-Beever–Ross site, abr. © 2005 by CRC Press

The sodium ion in the br site is coordinated to three oxygens in the oxide plane A (below), three in the plane C (above), and three in the conduction plane (plane B). Bentoite A silicate salt with an Si:O ratio of 1:3 that contains two bridging oxygens, two nonbridging oxygens, and the silicate anion in the ring/cyclic form (e.g., Si3O6 9 ). Beryl A silicate salt, Be3Al2Si6O18, with a composition similar to bentoite, except that the formula 6 of the silicate ion is Si6O12 18 instead of Si 3O 9 . Bethe Lattice The polymerization of a monomer that results in branching without forming any rings. Since the lattice contains no loops, the density increases without limit as the polymerization process proceeds. Also known as Cayley tree. BET Method See Brunauer, Emmett, and Teller method. Biaxial Crystal An anisotropic, low-symmetry crystal in which the index ellipsoid has three unequal axes and two directions along which the wave velocity is independent of the polarization direction. In convergent light between polarizers, biaxial crystals show a pattern that is different from uniaxial crystals. Rhombohedral crystals are biaxial in nature. See also uniaxial crystals. Bidendate Ligand Bifunctional ligands that bond with the metal through two functional groups. Ketonates are common examples of bidendate ligands that bond with metals through the two ester oxygens in the ligands. Benzoate is one such ligand. O CH3 C O Benzoate ligand

Bifunctional Monomers with a functionality of 2, which is the number of bonds that monomers can form. For example, (H3C)2Si(OCH3)2 is bifunctional because of the ability of two OCH3 groups to react and bond with other species. Bimodal Size Distribution Size distribution (bimodal pore size distribution or bimodal particle size distribution) composed of two average sizes of small and large pores or particles. For example, a system containing monomers and polymers with no oligomers has a bimodal particle size distribution. Binary Systems A two-component system with three independent variables: pressure, temperature, and composition. In solid-state compounds, the vapor pressure usually does not vary substantially with the temperature; hence, the vertical axis in the phase diagram is used as a temperature axis, and the horizontal axis is used for composition in binary phase diagrams. See also condensed phase rule. Binders Polymers and colloidal particles that are adsorbed on particle surfaces to bridge between ceramic particles for interparticle flocculation. In ceramic processing, binders improve the wetting and change the viscosity and sedimentation characteristics of the slurry for ease of processing. Soluble silicates and polyalkyl glycols are common binders used in ceramic processing. Biochip The integration of biomolecules with inorganic substrates, in particular, microelectronic substrates used for drug discovery, diagnostics, sequencing, and biosensing. For example, DNA chips (microarrays), protein arrays, lab-on-a-chip, microfluidics, etc. Biomaterials Biocompatible inorganic or polymeric materials for prolonged use as medical devices implanted within the human body (e.g., prosthetics, microelectronic blood monitors, timed internal drug delivery, etc.). Biomimetic materials chemistry Human-made devices, systems, and materials that imitate or copy nature in design, fabrication, or function (e.g., self-assembly, neural networks, organicinorganic composites, etc.). © 2005 by CRC Press

Birefringence A condition in an anisotropic optical material in which an incident beam is split into two transmitted beams with opposite polarization and with different velocities and hence different refractive indices. Calcite, for example, exhibits birefringence. These types of optical crystals find applications in polarizers, analyzers, compensators, and phase contrast microscopes. Centrosymmetric crystals, however, do not exhibit birefringence. Biuret Test An analytical test used for determining the presence of a peptide linkage in a compound. The alkaline solution of biuret HN(CONH2)2 reacts with CuSO4 to produce a characteristic violet color that indicates the presence of a peptide linkage in the compound. This forms the basis of the biuret test, in which excess NaOH and small amounts of CuSO4 are added to the unknown material. Bivariant System A system in which two variables are required to describe the system. In a binary phase diagram of refractories, the phase rule P + F = C + 2 is modified to P + F = C + 1 owing to the absence of vapor pressure of the solid phases in the system. In the condensed phase rule P + F = C + 1, P is the number of phases, F is the number of degrees of freedom, and C is the number of components needed to describe the system. For example, in the Al2O3 Cr2O3 system, C = 2 and P = 1; hence, F = 2 (i.e., temperature and composition are the only two variables required to describe this system). See also binary systems and condensed phase rule. Body-Centered Lattice A cubic lattice that contains an atom or an ion in the center of the cube in addition to the corner lattice points. F-Iron is an example of a body-centered lattice. See also lattice. Boehmite Aluminum oxohydroxide L-AlO(OH) with cubic close packing of O and (OH) anions and aluminum cation occupancy in octahedral sites. Boltzmann Constant See magnetic susceptibility and magnetic moment. Bond Order See valence sum rule. Bond Percolation The percolation model used to describe the polycondensation process in solgel systems in which bonds are formed at random between-lattice sites resulting in cyclic species in addition to linear and branched species. The percolation threshold in bond percolation is different from that in site percolation, because each bond joins only two sites, whereas one site can link with several bonds depending upon the geometry of the lattice. Bonds Any one of five types of chemical bonds: covalent, ionic, a combination of these two types, intermediate, or van der Waals. Covalent bonds are formed by overlapping orbitals of the elements (or sharing of their electrons). Covalent bonds are highly directional bonds formed between elements of the same or similar electronegativities. For example, CH bonds in CH4 are covalent bonds. Ionic bonds are formed by complete transfer of electrons from the orbital on one element to the other. Ionic bonds are formed between elements with a large difference in electronegativities. For example, KCI exhibits ionic bonding in which potassium is the electron donor and chlorine is an electron acceptor. Although KCI can be regarded as an almost completely ionic structure and CH4 can be regarded as a completely covalent structure, many compounds exhibit an intermediate structure with both ionic and covalent bond characters. Intermediate bonding can be characterized by an ionic electron configuration associated with an increased electron concentration along the line between atom centers (i.e., consisting of some orbital overlapping with more directionality). van der Waals bonds are weak attractive forces between atoms or molecules resulting from fluctuating dipole moments that arise owing to the changing positions of the electrons in neighboring atoms or molecules. See also van der Waals forces. Borate Glasses Amorphous glassy materials with MO · xB2O3 composition, in which M is an alkali metal. The structure of borate glasses contains a mixture of BO3 triangles and BO4 tetrahedra, depending on the composition. Borate glasses are of little commercial importance owing to their high water solubility. © 2005 by CRC Press

Borax The borate composition Na2B4O7 · 4H2O used as a fluxing agent in manufacturing refractories. Borazine A boronnitrogen compound (B3N3H6) that has a regular-plane hexagonal ring structure with alternate boron and nitrogen atoms. The physical properties of borazine closely resemble those of the isoelectronic compound benzene; however, the chemical properties of borazine are distinctively nonaromatic. Bordeaux Copper sulfate pentahydrate (blue vitrol) compound (CuSO4 · 5H2O) that is used as a fungicide to protect crops and in electroplating processes. Borosilicate Glasses Glasses composed of SiO2 and B2O3 oxides. The structure is a combination of borate (BO3 triangles) and silicate (SiO4 tetrahedra) glasses. Boundary Stresses Stresses generated between the grain boundaries of each component in a multicomponent system or between different crystallographic orientations in a single-component system. When two powder components are mixed, heated, and then cooled to produce a ceramic part, stresses are generated by the differential thermal expansion coefficient of the two materials. The grain boundary stresses cause cracking and separation at the boundaries. The boundary stresses in an anisotropic single-component system are caused by heating and cooling cycles. This technique of heating and cooling is used in crushing quartzite rock to obtain oriented quartz crystals. Bragg’s Law The law that describes the diffraction phenomenon in which a crystal is regarded as a multiple-layer system, with each layer acting as a semitransparent mirror. Incident x-rays are either reflected by the top layer or transmitted to the lower layers and subsequently reflected. Bragg’s law determines the conditions under which the two reflected beams are in phase. The extra distance traveled by the incident beam to the lower layers is equal to the multiple of the wavelength of light and can be expressed by nQ = 2d sin V,

where d is the spacing between the planes (d-spacing) and V is the incidence angle. Brass An alloy of copper and zinc (CuZn), with a superstructure in which Cu occupies the bodycentered position in the cube and Zn occupies the corners of the cube. Bravais Lattice A lattice system that is a combination of a crystal system (cubic, tetragonal, trigonal, hexagonal, monoclinic, orthorhombic, triclinic, etc.) and a lattice-type [rhombohedral (R), body-centered (I), primitive (P), face-centered (F), etc.] system. For example, NaCl is a face-centered cubic crystal. See also individual crystal systems. Bridgman Method A method used for preparing oriented single crystals from melts by flowing the melt in a gradient furnace where solidification occurs at the cool end of the furnace. This method is also known as directional solidification. Brookite A titanium oxide polymorph. Brown-Ring Complex A nitrosyl complex of iron [Fe(H2O)5NO]2+ formed during the qualitative analysis of nitrates. Brucite Magnesium hydroxide, Mg(OH)2, a source for producing MgO used in brick manufacturing. In the brucite structure, magnesium is hexa-coordinated in a CdI2 structure with OH bonds perpendicular to the layers and strong hydrogen bonding (OH …. O) between them. Brunauer, Emmett, and Teller (BET) method A nitrogen adsorption technique for measuring surface area, pore size, and pore size distribution in the solid state material (powder or monolithic samples). In this method, the sample is first evacuated to remove any gases in the pores. Then nitrogen gas is slowly adsorbed into the pores, and the weight gain in the sample measured as a function of increasing nitrogen pressure. Based on this information, other data such as surface area, types of pores ( meso- or micropores), and pore size distribution are derived. The BET equation is © 2005 by CRC Press

1/ W ( P0 / P)  1 = 1/ WmC + C  1/ WmC ( P / P0 )

where W is the weight of the gas adsorbed at a relative pressure P/P0 and Wm is the weight of the monolayer of surface coverage. C is the BET constant and is related to the energy of adsorption in the first adsorbed layer. See also surface area. Buckminsterfullerene A spherical caged C60 molecule arranged in a soccer ball shape with 20 hexagons and 12 pentagons, also called a buckyball. At 30°K, rubidium-doped buckyballs (Rb3C60) are superconducting. Buckyballs have been proposed as drug delivery molecules owing to their small size (1 nm diameter) and low toxicity. See also fullerene and nanotechnology. Buffer Solution A solution that contains a moderately weak acid (e.g., HC2H3O2) and its conjugate base (e.g., C2 H 3O 2 ) to neutralize any added acid or base to the solution, maintaining the pH of the solution close to the desired solution pH. In the absence of the weak acid or its conjugate base, addition of small amounts of acid or base dramatically changes the pH of the solution. The solution retains its buffering action as long as the quantities of added acid or base are much less than the quantities of weak acid and its conjugate base. Bulk Modulus The ratio of isotropic pressure, P, applied on the sample to the relative volume change, )V/V, in the sample as expressed below: K =  P / )V / V

where K is bulk modulus. K can also be expressed as K = E / 3(1  2S)

where E is Young’s modulus and S is Poisson’s ratio (ratio of the decrease in thickness to the increase in length). When S is equal to half, the material is incompressible. Burger Vectors The vector, b, that characterizes the dislocation in a crystal lattice. For example, in an edge dislocation, b is perpendicular to the line of dislocation and is parallel to the direction of the dislocation motion and the direction of the shear. Burton, Cabrera, Frank (BCF) Crystal Growth Theory The theory of crystal growth based on the motion of step edges across a surface. Mobile surface adatoms are incorporated at step edges, typically at kink sites, causing the step edge to propagate laterally across the surface. See also terrace-step-kink model. Butoxy An alkoxy ligand with the formula –OR, where R is butyl, C4H9. There are four types of butoxy ligands: n-butoxy (OCH2CH2CH2CH3), sec-butoxy (H3COCHCH2CH3), isobutoxy [OCH2CH(CH3)2], and tert-butoxy [OC(CH3)3]. O CH2 CH2 CH2 CH3 n-Butoxy

CH3 O CH2 CH CH3 iso-Butoxy

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O CH CH2 CH3 CH3 sec-Butoxy

CH3 O C CH3 CH3 tert-Butoxy

C Cab-o-Sil Trade name for fumed silica powder produced by Cabot. See also aerosil. Cacodylic Acid A dimethylarsenic acid, (CH3)2ASO(OH), used in agriculture as an herbicide. Cadmium Iodide Structure See CdI2 structure. Calamine A zinc ore, also known as Smithsonite, with the chemical formula ZnCO3. Calcination A ceramic process that involves converting metal salt precursors, such as carbonates, oxalates, alkoxides, sulfates, nitrates, and acetates or oxides, into desired crystalline oxides or other nonoxide single or multicomponent compounds. The variables involved in this process include temperature, pressure, gaseous atmosphere, and calcination time. The variables determine the crystallinity, grain, size, and other physical properties of the final material. For example, when basic magnesium carbonate (MgCO3) is calcined at 550°C, a pseudomorphed MgO is formed, whereas when calcination is performed at 900°C, crystalline MgO (approaching cubic) is produced. In another example, BaCO3 and TiO2 are calcined at 1100°C to form perovskite BaTiO3. Calcite A sedimentary deposit of CaCO3. Capillary Pressure The pore pressure that develops during the drying and densification of ceramic and glassy materials. When the liquid phase wets the solid particles or phase, each interparticle space becomes a capillary in which substantial pressure develops owing to the surface tension of the liquid. Capillary pressure (P) can be represented by P = L(1/ r1 + 1/ r2 )

For circular pores, capillary pressure is given by P = 2L cos V / r

where L is the surface tension of the liquid, V is the wetting angle, and r is the pore radius for circular pores, with r1 and r2 the principle radii of curvature of meniscus. Carbides Ceramic composition composed of a metal cation and a carbide anion, commonly used for refractory and structural applications. There are three classes of carbides: ionic, covalent, and interstitial. Ionic carbides include metal cations from group IA, IIA, and IIIA in the periodic table and are extremely unstable under atmospheric conditions. Silicon carbide (SiC) and boron carbide (B4C) are the only two covalent carbides known. Interstitial carbides are normally composed of transition metal cations, such as Ti, Zr, Nb, Ta, Cr, Mo, and W. Among the above carbides, SiC, B4C, and WC are the most widely used. Carbon Nanotubes A form of carbon structurally obtained by rolling a graphitic sheet of carbon into a tube (~1–2 nm diameter), which can be several microns long. Nanotubes are formed using either cathodic or across carbon electrodes, pulsed laser evaporation of a carbon target, or chemical vapor deposition methods. The chirality of the tube determines whether the electrical properties are metallic or semiconducting. Nanotubes come in single wall nanotube (SWNT) or multiwalled nanotube (MWNT) forms whose ends are often capped with half a buckyball. Carbon nanotubes have been formed into nanoscale transistor and wire components. They have also been used in nanocomposites when mixed with a polymer matrix. See also buckminsterfullerene, fullerene. Carbonates Metal salts used as precursors for ceramics, glasses, and metallic materials. Some examples of carbonate precursors include MgCO3, CaCO3, and PbCO3. Carnegieite Sodium aluminum silicate, NaAlSiO4, with a less open framework structure than pure silica. © 2005 by CRC Press

Cassiterite Crystals produced by hydrothermally treating silica with 10% SnO2 at 300°C. This material reduces the coarsening effect and helps produce silica material with high surface area. Catalysts Materials that increase the efficiency of the reaction or the rate of reaction and that are regenerated at the end of the reaction. Several ceramic materials such as inorganic oxides are used for catalyzing organic and inorganic reactions. For higher catalytic efficiency, large catalytic surface area is required. The catalysts are produced and used in a variety of forms including powder, membrane, sheet, and wire. TiO2 is one of the most common catalysts used in the petroleum industry. Cathode An electrode in which reduction occurs in an electrochemical cell [e.g., copper deposition: Cu2+(aq) + 2e– q Cu(s)]. See also anode. Cathodic Sputtering A standard method of electroplating the metal substrate in which two metal electrodes are dipped in an electrolyte solution and an external field is applied across the electrodes, resulting in film deposition caused by the migration of metal ions to the cathode. Cathodoluminesence The emission of light by a material as a result of absorbing energy from cathode rays or electrons. Cayley Tree A growing polymer that branches without forming any rings. It is also referred to as the Bethe lattice. The Cayley tree has been used to explain the gelation process in certain sol-gel systems. CdI2 Structure A structure similar to the rutile structure in which iodide ions are arranged in a hexagonal close-packed structure and half of the octahedral sites are filled by Cd2+ ions. However, this structure differs from the rutile structure in the three-dimensional arrangement. The CdI2 structure is layered, with octahedral sites filled by cations on alternate layers, whereas the rutile structure has a more rigid three-dimensional structure. Celsian Barium aluminosilicate, composition containing BaO · Al2O3 · 2SiO2. Cement Silicate material that solidifies (sets or hardens) owing to a chemical reaction with water. Although cements have been used since ancient times, many types of cement such as Portland cement are commonly used today. Portland cement is composed of strong cementitious materials such as Ca2SiO4 and Ca3SiO5 that are produced by mixing and heating (~1500°C) a variety of clay, lime sand, and oxides together. The oxide contents of Portland cement include 63% CaO, 20% SiO2, 6% Al2O3, 3% Fe2O3, 2% SO3, 2% MgO, 1% K2O + Na2O, and 3% others. Cement Clinker In cement production, partially fused lumps produced as a result of raw materials mixing and oxidation at ~1500°C, which are then crushed and mixed with gypsum to form powder. Cementite The iron-carbide phase, Fe3C (cementite), which is thermodynamically unstable and decomposes to iron and graphite. However, the kinetic decomposition of cementite is slow. Center of Symmetry The point at which any part of a molecule can be reflected through its center to produce an identical arrangement present on the other side. For example, an AlO6 octahedron is centrosymmetric. Ceramer The combination or hybrid of ceramic (inorganic) and polymeric (organic) materials. They can be prepared by reacting the monomeric precursors at a molecular level to yield a highly homogeneous material with chemical bonding between organic and inorganic components. Sometimes materials prepared by physically mixing the raw materials are also referred to as ceramers. Ceramers may have improved properties over their ceramic or polymer counterparts alone. For example, glass polymer composites are more flexible than glass and can withstand higher temperatures than organic polymers. Ceramics The art and science of preparing inorganic solid articles including monoliths, powders, films, fibers, and composites from inorganic raw materials or precursors and studying the structure and properties relationships. Ceramic materials are inorganic and can be classified into oxides, borides, carbides, nitrides, other chalcogenides, and their composites in crystalline and amorphous forms. They do not exhibit metallic properties and are brittle in nature. Ceramic products are used as refractory, electronic, optical, abrasive, structural, and magnetic materials. © 2005 by CRC Press

Ceria A dioxide of cerium CeO2. Cermet The combination of ceramic and metal materials that is generally used as refractories. The resultant material possesses properties of both metal and ceramic components. NiTiC, for example, is a refractory cermet used in high-temperature abrasive applications. Cesium Chloride Structure See CsCl structure. Chalcogenide Glasses Glasses composed of amorphous sulfur, selenium, and tellurium by themselves or in combination with other elements such as silicon and germanium. Selenium in an amorphous thin film form is a chalcogenide glass used in the photocopying industry. Si and Ge chalcogens are widely used in the semiconductor industry. Charge Density Wave Normally uniform distribution of conduction electrons is coupled with phonon variations to result in the periodic variation of charge density in one dimension. Electron motion is cooperative in this direction, giving rise to unusual properties such as highly nonlinear electrical behavior. Charge-Determining Ions Adsorbed ions that control the charge of the surface of a particle in a suspension and provide a repulsive electrostatic barrier between the particles. Charge Transfer Spectrum An absorption spectrum that results from the promotion of an electron from a localized orbital of one atom to a higher energy localized orbital on an adjacent atom. For example, the intense yellow color of chromates results from an electron transfer from an oxygen atom in a (CrO4)2– in a tetrahedral environment to the central chromium ion in an octahedral environment. Chelate In metal organic compounds, the ligand that can bond to the metal through two or more sites. In sol-gel science, acetylacetonates are frequently used as chelating ligands to substitute alkoxy ligands in metal alkoxides. The acetylacetonates are bonded to the metal via two ester oxygen atoms. By using chelating ligands in place of alkoxy ligands, the hydrolysis and condensation reactions in the sol-gel process are slowed down. Examples of Chelates R R = Alkyls, aryls

O M O R

CH3 CH3

CH3 HC C CH3 C O O C O Al CH O O C C O CH3 HC C CH3

Aluminum (III) pentanedionate

H3C H7C3iO H3C

CH3 O O Ti OiC3H7 O O CH3

Titanium (IV) diisopropoxy bis pentanedionate

Chemical Diffusion The diffusive motion of an atom under a chemical concentration gradient (i.e., a gradient in the chemical potential of the species) typically occurring in a solid. See also self-diffusion, surface diffusion. Chemical Etching A process of removing a thin surface layer by dissolving the film in a chemically active solution. The chemical etching of the sample surface can be achieved by reactive solvents (e.g., hydrocarbons and halogenated hydrocarbons) or aqueous solutions (acids, © 2005 by CRC Press

bases, and neutral solutions). Chemical etching is performed in scanning electron microscopy (SEM) for exposing the microstructure of the bulk sample (for revealing features such as grain boundaries), and in the semiconductor industry chemical etching is used for several purposes, such as film bonding and adhesion and photolithographic pattern formation. It is also used for cleaning surfaces prior to film deposition. Chemical Mechanical Polishing (CMP) A form of wet etching commonly employed in the microelectronics industry to planarize a surface. The polishing slurry is a combination of abrasive media and a chemical etchant, which are added to a polishing cloth under an applied load. Chemical Shifts The position of a peak in a molecular spectrum relative to the internal and external standard to obtain local structural information on the molecule under consideration. The positions of the peaks are referred to as chemical shifts in nuclear magnetic resonance (NMR) spectroscopy, Mossbauer spectroscopy, and electron spectroscopy for chemical analysis (ESCA). Chemical Vapor Deposition (CVD) A vapor transport method used to deposit films on a variety of substrates. Vapors of various sources (reactants) are transported in a controlled manner (for stoichiometry) to react in the CVD chamber and deposit films on the heated substrates. The precursors may react in the gas phase or react or decompose on the heated substrate to form the desired film compositions. The decomposition or reaction may be achieved by pyrolysis, photolysis, or chemical reactions. In many cases, the film growth from vapor deposition results in epitaxial films (highly oriented along the substrate crystalline lattice). See also metallorganic chemical vapor deposition, sputtering, evaporation, electron beam evaporation, and vapor phase epitaxy. Chemisorption Adsorption of an atom or molecule on a surface through formation of a chemical bond between the adatom and the solid surface. They typically possess energies on the order of 100 to 400 kJ/mol. The adsorbate–adsorbate interactions are often small compared to the adsorbate–substrate interactions, resulting in an adlayer structure partially determined by the underlying substrate lattice. The long-range ordering of the adlayer is usually determined by adsorbate–adsorbate interactions. See also physisorption. Chemorheology Viscoelastic behavior induced in cross-linked polymeric systems in a reactive environment. For example, stress relaxation and flow result when crosslinks are oxidized or hydrolyzed by the atmosphere. See also viscoelasticity. Chimie Douce French term for a chemical method used for preparing metastable phases from chemical precursors mixed at a molecular level instead of a solid-state reaction route. The crystal structure of the new metastable phase closely resembles that of the precursors. For example, TiO2(B), a new polymorph of titania prepared by hydrolysis and subsequent heat-treatment of the K2Ti4O9 precursor, has a structure composed of TiO6 octahedra; however, they are linked to each other in a manner different from rutile, anatase, and brookite phases but similar to the K2Ti4O9 phase. China Clay Pure kaolin with an approximate formula Al2O3 · 2SiO2 · 2H2O. This clay begins to melt at 1595°C and is converted into a complete melt at 1800°C. Chip An unpackaged semiconductor device or die cut from a wafer, which contains the integrated circuit elements such as transistors and resistors. Chiral Molecule An optically active molecule that is not superimposable on its mirror image. A molecule’s chiral counterpart often possesses different chemical activity and function, and each will rotate plane-polarized light in a different direction. Chrome Refractory Chrome, Cr2O3, is a refractory oxide that melts at 2275°C. Cr2O3 is also referred to as chromium sesquioxide. Chromophore A combination of ions that cause absorption in the visible region (whereas ions themselves do not) and, hence, impart color. CdS chromophore is yellow; however, neither Cd2+ nor S2 alone causes visible absorption. © 2005 by CRC Press

Clausius–Claypeyron Equation The quantitative statement of le Chatelier’s principle in reference to the pressure dependence of phase transition as a function of temperature, which is given by dP / dT = )H / T )V

where dP/dT is a change in pressure with temperature, )H is the change in enthalpy, and )V is the change in volume as a function to temperature T. For example, KCl changes from rock salt structure to CsCl structure at 19.6 kbar and at room temperature with )H of 8.03 kJ/mol and )V of 4.11 cm2. In another example, the melting point of water decreases or the boiling point of water increases for each mega pascal of applied pressure. Clay A sheetlike mineral composed of aluminum silicate hydrate, aluminum-sodium silicate hydrate, and aluminum-potassium-magnesium silicate hydrate. Hence, the major components in the clay are aluminosilicates. Clinoenstatite A mineral, magnesium silicate, MgSiO3. Close-Packed Structures The structures resulting from the most efficient approach to pack spheres in three dimensions by stacking close-packed layers on top of each other. These layers consist of spheres that are surrounded by and are in contact with six other spheres. There are two types of structures: hexagonal and cubic close packed. In hexagonal and cubic close-packed structures, the void volume is only 26%, compared with 48% in a simple cubic structure. See also cubic close packing. Cluster–Cluster Growth Model A model used to describe the cluster growth process that results from aggregation of clusters with one another rather than addition of monomers to clusters. The fractal objects thus produced are more porous than those resulting from monomer–cluster-type aggregation. The kinetics of aggregation may be limited by the rate of condensation or diffusion, and this affects the fractal dimensions of the aggregate. See also fractal. Clusters Nanoscale particles typically containing tens to a few thousand atoms, which exhibit size-dependent electrical and optical properties owing to their large surface area to volume ratio and quantum size effects. Clusters are often studied on materials substrates. See also quantum dots. Coacervates In colloidal suspensions, the concentrated regions of particles that are not bound to one another. The surface tension associated with coacervates may help these regions of particles adopt a spheroidal shape. Coadsorption The simultaneous adsorption of two or more different types of atoms or molecules onto a substrate. Coating Typically a thick film added to the surface of another material for mechanical, chemical, or thermal protection; as a cosmetic finish; or as a reflective or light adsorbing layer. Coatings are typically on the order of several microns to millimeters in thickness. Coatings can be formed naturally via oxidation or corrosion or synthetically applied via chemical and physical deposition methods, the latter including dip coating, vapor deposition, laser ablation, sputtering, plasma spray, electrodeposition, etc. Coagulation See flocculation. Coarsening A process of dissolution and reprecipitation driven by differences in solubility between the particle surfaces with different radii of curvature, sometimes also referred to as Ostwald ripening. Because of the difference in solubility, the smaller particles dissolve more easily and the solute precipitates in regions of lower curvature (necks and crevices with lower solubility), filling small pores with larger particles growing at the expense of smaller ones. Coercive Field The electric or magnetic field required to polarize the electric or magnetic dipoles in a material. These materials normally possess electric or magnetic hysteresis; i.e., when the field is removed, the materials retain a certain percentage of the polarization or magnetization. © 2005 by CRC Press

Coercivity The magnitude of the reverse field required to achieve demagnetization or depolarization. The magnitude of the applied field in electrical and magnetic materials is denoted by Ec and Hc, respectively. Magnetically soft materials possess low coercivity. Coesite A polymorph of SiO2 with a density of 2.90 g/cm3 that forms at 30 to 40 kbar of pressure. Colossal Magnetoresistance (CMR) Similar to giant magnetoresistance, but the resistance of a multilayer composite drops even more sharply under the application of an externally applied magnetic field. CMR has been predominantly observed in manganese-based perovskite oxides, lanthanum-strontium-manganite (LSMO), lanthanum-calcium-manganite (LCMO), and the double perovskite strontium-iron-molybdate (SFMO). The CMR effect arises because of strong mutual coupling of spin, charge, and lattice degrees of freedom. See also anisotropic magnetoresistance, magnetoresistance, and giant magnetoresistance. Cole–Cole Plots Plots of the imaginary part of the dielectric permittivity versus the real part as a function of frequency forms a semicircular arc that provides information relating to dielectric relaxation phenomenon occurring within a dielectric material. The permittivity measurements are collected over a range of frequencies, including radio, audio, and microwave frequencies. Colloid A suspension with the dispersed phase characterized by large surface area and a size range of 1 to 1000 nm, such that the gravitational forces are negligible and the interactions between particles are dominated by short-range forces (van der Waals forces) and surface charges. The fine, dispersed phase in colloids normally exhibits Brownian motion. The dispersed and the continuous phase combination in a colloid may include solid-in-gas (e.g., sprays), gas-in-liquid (e.g., beer), liquid-in-liquid (e.g., milk), solid-in-liquid (e.g., paints), and solid-in-solid. Colloidal processing is used in preparing a variety of slurries for tape casting processes employed in ceramics and for producing monodispersed or polydispersed ceramic particles via nucleation, growth, and ultracentrifugation or spray drying steps. A variety of gels, films, and fibers have also been produced by colloidal processing. Color The coloring constituents in most ceramic materials consist of transition elements with incomplete d shells, such as V, Cr, Mn, Fe, Co, Ni, Cu, and some rare earth elements with incomplete f shells. The colors commonly produced by various metals are listed in Table 2.1. In addition to the individual ions and oxidation states, the color of a compound can be affected by the ionic environment. See also color center. Table 2.1

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Element

Color

Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Cerium Praseodymium Neodymium Samarium Europium Terbium Dysprosium Holmium Erbium Thulium

Yellow Green Green Purple Yellow, green/blue, green Blue Yellow/brown/purple Green/blue Yellow/brown Green Purple, red/blue Pale yellow Dark yellow Very pale yellow Yellow Peach Pink Green

Color Center Color spots arising from defects in the crystal lattice. There are a variety of color centers, including F-center, H-center, and V-center. An F-center is an example of a color center in alkali halide crystals produced as a result of a trapped electron in an anion vacancy. A greenish yellow F-center can be produced by heating sodium chloride in sodium metal vapors. This process involves absorption of sodium atoms that subsequently ionize the crystal surface. Na+ stays at the surface, and Cl ions tend to move to the surface to neutralize the sodium ions. In the meantime, electrons diffuse into the lattice to fill the anion vacancies. The energy required for the electron to transfer from one energy level to another falls in the visible region of the electromagnetic spectrum, thus producing the characteristic color. The color results from the host crystal, not the source of the electron. For example, NaCl heated in K vapors still produces yellow color centers, whereas KCl heated in Na vapors produces violet color centers. An H– center is produced, for example, when an anion site in NaCl is replaced by Cl 2 , whereas a V– center is produced when two anion sites are filled by Cl 2 . Colorimetry See spectrophotometric analysis. Combinatorial Chemistry Combinatorial chemistry is often called high throughput chemistry, as it uses efficient parallel synthesis. Large sets of chemically similar reagents (such as amino acids, peptides, oligomers, etc.) are mixed in minute amounts in binary chemical reactions to produce hundreds to thousands of products that are then screened for relevant properties such as biological activity; chemical reactivity; and electrical, magnetic, or optical properties. The fundamentals of combinatorial chemistry tend to apply regardless of the application, including synthesis of the compound library, mixture of solutions or solids, the running of a large number of screens, and a rapid and reliable analysis technique. Robotics are often used to automate many of the steps, including mixture of the compounds and rapid analysis. The largest impacts of combinatorial chemistry to date have been in drug discovery, materials development, and biology. Screening for new materials with improved properties has also benefited from combinatorial chemistry techniques. Compatible Phases The phases of the material that are stable in each others’ presence. Complexation The process of forming an associated species from positively charged molecules or particles in the solute and a variety of anions from the solution. Composite A combination of different types of materials to obtain synergetic properties unattainable by one material alone. Ceramic processing and sol-gel processing have been used to prepare ceramic–ceramic, ceramic–metal (cermet), and ceramic–polymer (ceramer) composite materials. Composites normally include two phases: matrix and reinforcements. In composites, the two phases are typically physically bonded by conventional ceramic processing or can be chemically bonded at the molecular level by chemical processes such as sol-gel. Compound Semiconductor Inorganic and organic compounds that possess semiconducting properties. For example, GaAs, InSb, and GaP (III-V compounds) are compound semiconductors. Compressive Strength The applied compressive load (stress) on a material at failure. Concrete Composition formed when cement is mixed with water and other components that quickly set. See also cement. Condensation In the polymerization process, the reaction in which the reactants bond and as a result liberate a small molecule in addition to the products. In the sol-gel process, when metal alkoxides are hydrolyzed, the OH group on the metal organic species thus produced condenses with another OH group or alkoxy (OR) group on another metal organic species, and a condensed product is formed, releasing a water or an alcohol molecule. This is a common example of a condensation reaction in sol-gel processing. Condensed Phase Rule A Gibb’s phase rule defined by the following equation: P+F =C+2

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where P is the number of phases in equilibrium, C is the number of components needed to describe a system, and F is the number of degrees of freedom (number of variables such as pressure, temperature, and composition). However, in refractory systems with high melting temperatures, the vapor pressure of solid and liquid phases is negligible in comparison with atmospheric pressure, and the phase rule equation is modified to a condensed phase rule: P + F = C +1

In the Al2O3Cr2O3 system, C = 2 and P = 1; therefore, F = 2. That is, the two variables temperature and composition are required to describe the system. See also bivariant system. Conditional Glass Formers Oxides that do not form glass when their melt is cooled rapidly; however, glass can be formed when these oxides are combined with another non-glass–forming oxide. The liquid composition of CaOAl2O3 forms glass, whereas CaO and Al2O3 independently do not form glass. Conductance (Conductivity) The ease at which an electric current passes through a material (or liquid); the inverse of resistance. Conductivity is related to an electron’s or hole’s mobility under an applied electric field. Conduction Band The energy band in a semiconducting or insulating material that contains the conduction electrons involved in electron transport. In an intrinsic semiconductor, electrons must be thermally or optically excited from filled states in the valence band to empty states in the conduction band in order for electrical conductivity to be possible. Conduction Electrons Electrons in the conduction band that are involved in electron transport. Conductor (Electronic) A material with partially filled valence (hole doping) or conduction (electron doping) bands (i.e., a semiconductor) or with delocalized electrons such as metals. See also band theory and insulator. Consolute Temperature The temperature at which a liquid melts or crystalline solution cools and separates into two phases. Constructive Interference In optical experiments, the process of combining two or more light beams (waves) with the same frequency or wavelength that are in phase to form a wave whose amplitude is the sum of the amplitudes of the incident waves. Contact Angle The angle between the solid surface and the tangent to the liquid surface at the contact point in which a liquid is wetting the solid surface (also called wetting angle). The contact angle might vary between 0 and 180° for various liquids on solid surfaces. Water is the most commonly used liquid to determine the contact angle of the solid surface to evaluate the hydrophobicity or hydrophilicity of the surface. If the contact angle is closer to 0 or 180°, the surface is characterized as sticky (hydrophilic) or slick (hydrophobic), respectively. Contrast Ratio In optics, a factor that determines the opacifying power of a material. Hence, high opacity results in high reflectance, and a high scattering coefficient results in a high contrast ratio. Controlled Valency Semiconductors Transition metal compounds that normally conduct electricity because of multiple oxidation states that have only one valency or one oxidation state of the element stabilized, resulting in semiconducting properties. For example, pale green NiO (Ni2+) is an intrinsic semiconductor owing to internal d–d transitions. However, when the semiconductor is oxidized at 1000°C, some Ni2+ sites are oxidized to Ni3+ (black). The conduction occurs through electron transfer from Ni2+ to Ni3+. Coordination Compound Compound or complex formed when a ligand (Lewis base) is attached to a metal (Lewis acid) by means of a lone pair of electrons. For example, [Co(NH3)6]Cl3 and K3[Cr(CN)6] are coordination compounds with NH3 and CN as ligands (Lewis bases) to Co and K metal cations, respectively. Coordination Number The maximum number of neighbors with opposite charge that an ion can achieve. For example, in TiO2 the coordination number of Ti4+ is six (i.e., it has six O2 neighbors). © 2005 by CRC Press

In colloidal chemistry, for a particle in a suspension, the coordination number is the average number of nearest neighbors/particles. Coprecipitation Methods An alternative chemical method to ceramic batching and milling for producing preceramic powder. In this method, the metal salt precursors are mixed at a molecular level in a solution to precipitate a fine powder that is calcined (solid state reaction) at relatively lower temperatures to yield ceramic products. See also calcination. Cord and Striae Inclusions present in amorphous materials. Cords are attenuated amorphous inclusions in the glass (resulting from an inhomogeneous melt) that have properties (such as index of refraction) different from the material surrounding the glass. Striae are low-intensity cords that are especially deleterious in optical glasses. Cordierite A mineral composition with magnesia, alumina, and silica (2MgO · 2Al2O3 · 5SiO2) commonly used as an electrical insulator. It can be synthesized as a glass-ceramic material. Coring In a multicomponent system, a condition in which the central part of the crystal has a specific composition, but in areas radially surrounding this central part, the crystal becomes rich in another composition. This occurs in natural minerals and rocks and in manufactured steel parts. Coring can be deleterious to the mechanical properties of the metal and is preferably removed by reheating the metal below the solidus temperature. Corrosion The chemical degradation or deterioration of a material generally in the presence of a reactive liquid or gas. Aqueous electrochemical reactions are the most common causes of corrosion in aqueous or humid environments; however, high temperature gases can also degrade a surface. The atomic and molecular mechanisms of corrosion are quite complex and are still actively being studied. The corrosion of a material can also be carefully controlled to shape, pattern, or clean a material, as in electrochemical machining of metal parts and wet chemical etching of semiconductors. See also chemical mechanical polishing, etching. Corundum A single crystal of alumina, Al2O3. Counter Electrode (or Auxiliary Electrode) An electrode in a three-electrode configuration that is used only to complete the electrochemical circuit so that current can be applied to the working electrode. The counter electrode must be inert under the voltage and electrolyte conditions, must pass sufficient current to the solution, and must not create nonuniform current distributions at the working electrode. Typical counter electrodes are made from gold, platinum, or graphite. See also cyclic voltammetry, reference electrode. Counterions Ions of opposite charge. In colloidal chemistry, the charge-determining ions in the double layer are on the surface, and the counterions are in the solution in the vicinity of the particle and contribute to the repulsive barrier between the particles. Coupling Agents Chemicals that provide a means of chemically modifying the film or particle surfaces. The coupling agents normally contain two or three types of ligands and groups. At least one of the groups reacts with surface groups, bonding the coupling agent to the surface, and the other groups and ligands provide surface functionality not previously available. Coupling agents may be applied to improve adherence of the film to the surface or may be applied in cases in which the film and the substrate are not chemically compatible. The same approach can be applied to solid particles in suspension to produce stable emulsions. In this fashion, desired surface properties can be easily modified by applying coupling agents. Some examples for commonly used coupling agents that couple polymeric and silica surfaces are vinyltrimethoxysilane, phenyl-trimethoxysilane, and epoxytrimethoxysilane. OCH3 CH2 CH Si OCH3 OCH3 Vinyltrimethoxysilane

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Covalent Crystals Crystals with a repetitious structure consistent with the strong directional nature of the covalent bond. For example, CH4 is not a covalent crystal; however, diamond is a covalent crystal with a three-dimensional network created by covalent bonds. Crack See fracture. Crazing A common glaze defect produced when the thermal expansion coefficients of the underlying materials and the glaze are mismatched. As a result, during heating or cooling, the tensile forces produce defects, such as fissures. Creep A deformation produced in crystalline materials as a result of applied stress. Creep is one of the important properties studied to evaluate the mechanical properties of structural and refractory materials. Creep Fracture A macroscopic fracture that begins with a local microscopic creep, which then produces considerable grain boundary stress, resulting in propagation of deformation. Creep fracture normally occurs at high temperatures; the rate of crack growth increases with temperature. Cristobalite A crystalline silica (SiO2) polymorph (with a density of 2.334 g/cm3) produced by heating tridymite to 1470°C. Critical Concentration In the growth of particles from solution, a concentration at which nucleation is extremely rapid. The supersaturation in suspension is normally increased via change in temperature of pH until a critical concentration is reached in which the nucleation rate rises abruptly. The precipitation of particles reduces the supersaturation below the critical concentration. Under these conditions, nucleation is unlikely, and the particle grows until the concentration is reduced to the equilibrium solubility. Critical Cooling Rate The minimum cooling rate needed to quench the melt to produce a glassy material. Critical Flaw The size of a flaw that continues to grow uncontrollably under the applied load and causes fracture. Critical Point During the drying process, the point at which shrinkage stops. The liquid surface tension creates capillary stress in the pores that causes the gel to collapse and shrink; however, the solid network (gel or particle packing) stiffens during shrinkage and eventually can withstand the capillary pressure. Critical Point Gelation See gel point. Critical Pressure and Temperature The pressure and temperature at which the liquid converts into the vapor phase without undergoing density change. At and above the critical temperature and pressure of the liquid, the surface tension of the liquid is zero. In the case of drying gellike materials, pressure and temperature are increased in such a way that the phase boundary is not crossed. See also supercritical drying. Critical Radius The minimum radius of a seed particle in a suspension or a melt required to begin the crystallization process. See also nucleation and growth. Crosslinks Links that join chains to form a three-dimensional network when a polyfunctional unit with two or more reactive groups (with a functionality of two or more) is present. For example, Si(OH)4 has a functionality of four and can lead to complex branching of the polymer via crosslinking. Crown Ethers See macrocyclic polyethers. Crystal Chemistry Chemistry that includes the description and classification of crystal structures, basis of crystallizing a particular phase, and relationships between the crystalline phase and their chemical and physical properties. Crystallography differs from crystal chemistry in that it involves approaches to solve crystal structures. Crystal Defects Defects that originate from imperfect placement of atoms or ions in various lattice positions. Since perfect placement of atoms is only possible at absolute zero temperature, many defects are produced in crystals at practical temperatures. Examples of low-defect (<1%) crystals are diamond and quartz. The defect could involve the displacement of an atom or ion © 2005 by CRC Press

or a vacancy or presence of guest ions and atoms in the lattice. All these defects lead to a change in properties of perfect crystals, which could be used in many applications such as p and n conductors. See Schottky defect, Frenkel defect, color center, dislocation, stacking faults. Crystal Growth Methods Methods used to grow crystals from vapors, liquids, and solid phases. Growth of crystals from vapors or liquids results in larger crystal sizes. In crystal growth, the kinetics and morphology of crystallization are greatly influenced by the interface between the crystal and the phase that it is growing from, in addition to the temperature and supersaturation conditions. See Czochralski method, Bridgman method, Stockbarger method, zone melting, flux growth of crystals, epitaxial growth, Verneuil flame fusion method, vapor phase transport, and hydrothermal processing. Crystalline Glazes Glassy silicates are normally used as glazes for ceramic bodies or as porcelain enamels for iron, aluminum, and other compositions to provide smooth, glossy surfaces, to prevent leaching, and to close the pores in the system. Crystalline glazes are composed of combinations of CaO, SiO2, Al2O3, and other oxides. Crystallization The process of forming a crystal with both short- and long-range order via the nucleation and growth process. Crystals can grow from solutions (supersaturation), melts, or amorphous materials and can be converted into crystal by applying appropriate temperatures and pressures. Crystallographic Point Group A point group that defines the symmetry of the crystal. Elements of the point group include rotation axes, inversion axes, and mirror planes. For example, a triclinic unit cell has one rotation axis and one inversion axis and no mirror planes. Crystalloid Ordered structure formed as a result of slow drying of an ordered arrangement of particles (tactoids), decreasing the repulsive forces and forming an irreversible interparticle bond. Crystal Systems Seven independent unit cell shapes possible in three-dimensional crystal structures. The seven crystal systems are cubic, tetragonal, orthorhombic, hexagonal, trigonal, monoclinic, and triclinic. See individual crystals systems for their definitions. CsCl Structure The cubic unit cell with anions at the corners and cations at the body center coordinated with eight anions. The coordination number of the anion is also eight. This is, however, not a body-centered structure since corner species are different from body-centered species. Many compound crystal structures are defined as cesium chloride (CsCl) structures such as CsBr, CuZn, AuMg, NH4Cl, TlI, and MgSr. Cubic Close Packing (ccp) A close packing of spheres in which three close-packed layers (A, B, and C) are positioned such that the spheres of layer B lie in the hollow space of layer A and the spheres of layer C lie in the hollow space of the combined layers A and B. This pattern is repeated, creating a ccp structure, ABCABCABC…. See also close-packed structures and hexagonal close packing. Cubic Symmetry A unit cell in which all three lattice parameters (a, b, and c) are equal and at right angles, (i.e., the angles F, G, and L are equal to 90°). Cubic symmetry is also characterized by four threefold rotation axes. Crystals of copper, silver, and sodium chloride exhibit cubic symmetry. Cuprite A name for cuperous oxide, Cu2O, with a cubic close-packed arrangement of Cu+ ions and tetrahedral O–2 ions in the unit cell structure where the coordination number of Cu+ is 2 (linear). Curie Temperature The temperature, Tc, above which the ferroelectric behavior of the ferroelectric material disappears. Above the Curie temperature, the material becomes paraelectric or nonferroelectric. Below the Curie temperature, spontaneous polarization develops causing elementary dipoles to become aligned with the same orientation. For example, Tc values for BaTiO3 and LiNbO3 are 120 and 1210°C, respectively. CVD See chemical vapor deposition. Cyclic Voltammetry The cyclic linear sweeping of the electric potential of the working electrode surface while monitoring the current. It is most often used to determine electrode kinetics and © 2005 by CRC Press

mechanisms of electrode reactions. See also working electrode, counter electrode, reference electrode). Czochralski Method A method used to grow a single crystal from a melt of the same composition. A seed crystal is placed on the surface of the melt, and as the seed crystal is pulled out of the melt, the melt solidifies on the surface of the seed, resulting in a rod-shaped crystal with an orientation similar to the original seed. This method is used to grow single crystals of semiconductors such as Si, Ge, and GaAs.

D Dalton A Dalton (D) is 1/12 the mass of a 12C atom. 1000 D = 1 kD (kilodalton). DCCA See drying control chemical additive. Dealkalization The process of strengthening alkali glasses and crystalline ceramics by developing surface compression through chemical processes. In this process, the alkali glass is dealkalized by heating it to high temperatures in an acidic environment (SO2 or SO3), which results in a surface skin with low thermal expansion coefficient and high durability. However, the process is self-limiting since the dealkalized surface tends to prevent further diffusive loss of alkali oxide. Debye Forces The attractive forces between the permanent dipole and induced dipole contributing toward van der Waals forces between atoms or particles. Debye–Huckel Attractive Forces Long-range attractive forces between defects of opposite charges (vacancies and interstitials). In materials with Frenkel or Schottky defects, the number of defects increases abruptly at higher temperatures. This may result from the long-range-type Debye–Huckel attractive forces between defects of opposite charges, which reduces the energy of formation of defects at higher temperatures. 1 ¬ 2JJ oVs ¼ ½ ­® enebulk ½¾

Debye Length The penetration depth, d, of electrostatic surface effects given by d = ­

2

where J is the dielectric constant of the material, J o is the permittivity of free space, Vs is the height of the space charge potential at the interface, e is the charge of an electron, and nebulk is the bulk electron concentration. Defect Chemistry The study of ionic, hence charged, point defect chemistry in solids. Most common point defects are vacancies, aliovalent (or differently charged) substituents, and interstitials. Their equilibrium concentration in solids is often determined by temperature, partial pressure, and dopant concentration and can be monitored by high temperature four-point probe electrical characterization. Defect chemistry in solids is important in a variety of areas including solid-oxide fuel cells, oxygen sensors, ion implantation, thermal annealing, and diffusional processes. Deflocculation A particle separation process in suspensions, which results in a substantial increase in fluidity for improved processibility. Charged species are attached on the surface of the particles in a suspension to increase and impart interparticle repulsive forces and, hence, to disperse the particles for easy processibility. Dehydroxylation A process involving the elimination of the surface and bulk hydroxyl groups (present as silanol groups in silica systems) through condensation and restructuring during thermal treatment and drying of wet gels. The dehydroxylation process can be studied with infrared and Raman spectroscopy. Delayed Elastic Strain One of three types of strain created when stress is applied to a viscoelastic material; the other components are instantaneous elastic strain and viscous strain. With constant applied stress delayed elastic strain gradually approaches a constant value proportional to the stress, then recovers completely when the stress is removed. See also creep. © 2005 by CRC Press

Dendritic Growth A term used for treelike growth with abundant branching in which the growth rate is constant over time (i.e., it does not decay with time) since the tip of growth, for example, in the gelation process, is always advancing toward fresh liquid with low solute content. Hence, the crystal growth is constant, even when the compositions of the crystal and liquid are different. Density Mass per unit volume. The bulk density of a sample is the total mass divided by the total volume occupied by the sample, that is, including pores. The green density is the density (mass/volume) of the compacted material before sintering. The skeletal density of a sample is the mass of the sample divided by the volume of the solid phase only (i.e., the pore volume is subtracted from the total volume). Desorption The removal of adsorbate atoms or molecules from a material surface. Desorption rates typically increase with increasing temperature and can be first or second order in nature. For a first order desorption process, the peak desorption temperature is independent of the initial coverage (i.e., surface concentration) of the adsorbate. In a second order desorption process, the peak temperature depends on the initial coverage of the adsorbate. Destructive Interference Interference that occurs when two light beams are out-of-phase by a fraction of one wavelength. If the two beams are out-of-phase by half of a wavelength, cancellation occurs. See also constructive interference. Devitrification A term used for crystallization of glass, an exothermic process. See crystallization. Devitrite A sodium calcium silicate mineral with the formula Na2O · 3CaO · 6SiO2. Diamagnetism The magnetic effect observed in materials in which ions have closed electronic shells, that is, an absence of unpaired electrons. Hence, materials that do not contain transition and rare earth metals with unpaired electrons are diamagnetic. The magnetic susceptibility, H, of diamagnetic materials with an electronic radius of about 1 Å ranges between 10–5 and 10–6, and their H does not change with temperature or magnetic field. Diamond A polymorph of graphite that has a three-dimensional covalent network of carbon atoms. Diamond is very inert at room temperature and is thermally stable up to 4000 K at 150 kbar. Diamond can be regarded as having a sphalerite structure, with half of the carbon atoms in a cubic close-packed (ccp) array and the other half in tetrahedral interstitial sites. The structure can be classified as eutactic because the ccp array atoms and interstitial atoms cannot be distinguished since they are all carbon atoms. Diaspore An F-aluminum hydroxide with the formula AlO(OH). Dielectric Materials Electrically insulating materials. The amount of charge stored in a dielectric material compared with free space is the dielectric constant or relative dielectric permittivity. Good dielectric materials normally possess high dielectric strength (i.e., they withstand high voltages without degradation and loss of insulating capabilities) or low dielectric loss, quantified by tan I, which is related to the amount of electrical energy lost through heat dissipation within an alternating field. Dielectric materials are also used in capacitors (i.e., charge storage devices) common in electronic insulation. Differential Scanning Calorimetry (DSC) A quantitative thermal analysis method that allows measurement of enthalpy changes occurring in a sample as a function of temperature or time. The DSC technique can provide information on exothermic and endothermic reactions involving organic burnout, dehydration, phase transformation, crystallization, and melting processes. Differential Thermal Analysis (DTA) A thermal analysis method used to measure the difference in temperature, )T, between a sample and an inert reference material as a function of temperature. This qualitative or semiquantitative thermal analysis determines the exothermic and endothermic reactions involving organic burnout, dehydration, phase transformation, crystallization, and melting processes. Diffraction Techniques Techniques used for molecular characterization of solid state materials, including x-ray diffraction (phase identification, quantitative phase analysis, unit cell parameters, solid-solution lattice parameters, crystal structure, particle size, and crystal defects), electron © 2005 by CRC Press

diffraction (unit cell, space group, and phase), and neutron diffraction (crystal structure, magnetic structure, inelastic scattering, solt modes, and phase transitions). Diffusion A random-walk process by which molecules are transported down a gradient in chemical potential. Diffusion Controlled Growth A growth process in which the growth rate is controlled by transport at the interface. For example, the rate of crystal growth may depend on the rate of diffusion of atoms to the crystal–liquid interface or diffusion of the heat of fusion away from the interface. Diffusion-limited aggregation is a type of diffusion controlled growth, in which the growth rate of the cluster is controlled by the rate of diffusion of monomers or particles to the periphery or the surface of the aggregate. As a result, the density of the final product reduces radially from the center. Dihedral Angle The angle between two crystalline grains with a second phase present, determined by the balance of grain boundaries and interfacial energies. When the second phase is liquid, during the grain-growth process in sintering kinetics, a small dihedral angle provides small grain-to-grain contact and large liquid penetration between the grains, which results in more rapid grain growth and a large final grain size. In this case, the dihedral angle is governed by the surface tension properties of crystal and liquid present in the system. Dilation Symmetry The property of a fractal object, where the overall structure of the object looks similar at any level magnification. Dilatometry A thermal analysis method used to measure the change in linear dimension of a sample as a function of temperature that is frequently used for measuring the thermal expansion coefficient of materials. Dilatometry is also known as thermomechanical analysis (TMA). Dimer The bonding of two identical monomers into a single molecule. Diode A pn junction device that conducts electricity well in one direction but not the other. Diopside A calcium magnesium silicate, CaMg(SiO3)2, lamp phosphor material that exhibits a blue color when activated by titanium. Dip Coating A film deposition process in which a substrate is dipped into and withdrawn from a coating solution at a given speed to allow drainage, solvent evaporation, and drying of the wet film. To accommodate straight and curved surfaces, the substrates can be dip coated at an angle of 90° or between 45 and 90°, respectively, to the liquid coating medium surface. Dip coating can be performed in a batch or continuous process. This method is frequently applied in the sol-gel process to produce thin films of oxides and other compositions. Diphasic Gel Multicomponent gels composed of two phases. The oxide-type gel with metal salts dispersed in the gel is an example of a diphasic gel. When heat-treated in a reducing atmosphere, these gels yield amorphous materials with dispersed metallic particles called cermets. Dislocation An important class of crystal defects in metals and ceramics. These are stoichiometric line defects (not point defects) responsible for the relative weakness of pure metals, which provides metal ductility and malleability. Two types of dislocations, edge and screw dislocations, are described elsewhere. Dispersion A stable colloidal suspension with long-range attraction (transitory dipole London forces) and short-range repulsion between the particles. These repulsive forces are either created by inherent surface charges on the particles (electrostatic repulsion) or by artificially incorporating additives to the system (steric repulsion). See also Gouy layer. Displacive Phase Transition The phase transition that involves distortion of bonds rather than bond breaking, resulting in minimal structural changes. For this reason, displacive phase transitions occur very easily with zero or low activation energy and hence are difficult to prevent. Dissolution-Reprecipitation The particle growth process in suspension, also referred to as Ostwald ripening, in which smaller particles (normally less than 5 nm in diameter) tend to dissolve and reprecipitate on surfaces with less positive curvature (such as large particles). The variables that affect the particle growth process include system composition, solution pH, particle size, and temperature. © 2005 by CRC Press

Distribution Coefficient The factor that determines the distribution of solute in a crystal growth process from a melt. When the crystal grows into an impure melt, the solute is redistributed. This results from the difference in equilibrium concentration of solute at the interface (CS) and the adjacent liquid (CL), and hence, the distribution coefficient, KO, can be expressed as K o = CS / CL

Dolomite An alkaline carbonate solid solution with the formula CaCO3 · MgCO3. Domains Regions in an otherwise crystallographically and chemically homogeneous solid in which strain, electric dipoles, or magnetic dipoles spontaneously orient in different yet crystallographically related directions, hence ferroelastic, ferroelectric, and ferromagnetic domains. These domains are separated by domain walls, which can also be twin walls. Domains can often be reoriented under the application of suitably large unidirectional potentials, stresses, or magnetic fields. See also ferroelectric materials, domain wall, ferroic materials. Domain Wall The boundary between two differently oriented domain regions in ferroic materials. Donor A dopant (e.g., phosphorus doped silicon) whose excess positive site charge is compensated by the formation of electrons in the conduction band leading to an n-type conductor. See also acceptor, dope, n-type, p-type. Dope The introduction of impurity ions (i.e., dopants) into a material. Doping is widely used in the semiconductor industry to control the electrical conductivity behavior of a material (see also acceptor, donor, n-type, p-type). Double Alkoxide A two-component alkoxide precursor used for producing two-component ceramic or glass compositions. The double alkoxide consists of two metals and a sufficient number of alkoxide groups. For example, MgAl2(OR)8, where R is an alkyl or aryl group, is a double alkoxide. Double Layer See Gouy layer. Drain Casting A ceramic-casting process in which a porous mold is filled with a suspension or slurry to form a monolithic part and the liquid is either sucked out through the porous mold over time, or, if only thinner walls are required, the excess liquid is poured out to form a monolithic part with thinner walls. See also slip. Drying Control Chemical Additive (DCCA) Cosolvents used in chemical processes such as the sol-gel process. Some studies have suggested that these cosolvents may affect the concentration of the reactants and their reactivity, thereby influencing the gelation kinetics and the gel-drying process. However, DCCA effects have not been conclusive. Drying Stress Stresses generated during drying as a result of a gradient in pressure in the liquid inside the system. Drying stresses may cause warping and cracking, which is minimized by slow evaporation of liquid, low viscosity of the pore liquid, and high permeability of the drying body. For example, in gel drying, the surface of the gel becomes stiffer and less permeable than it is on the inside, causing shrinkage gradients that result in stress. However, in practice, the difference in shrinkage rate from the surface to the center is not large when drying is slow and controlled. Dry Pressing A simple compacting process to from a ceramic shape from dry or slightly damp powder with organic binders. This process is conducted at sufficiently high pressures to form dense, strong pieces. Dry pressing is currently used to produce green bodies for tiles, spark plugs, and nuclear fuel pellets at a very low cost. DSC See differential scanning calorimetry. DTA See differential thermal analysis. Ductile The ability of a material to undergo plastic deformation when mechanically stressed. © 2005 by CRC Press

Dumbbell-Shaped Interstitial Crystal defects that originate when an interstitial atom dislocates another neighboring atom, resulting in two atoms on distorted interstitial sites. Also referred to as split interstitial.

E Edge Dislocation A dislocation that arises in a crystal when a plane of atoms extends only part of the way through the structure. EDS See evaporative decomposition of solution. EDS (Energy Dispersive Spectrum) See electron microscopy with microanalysis (EMMA). EELFS See extended energy loss fine structure spectroscopy. EELS See electron energy loss spectroscopy. Effective Nuclear Charge The reduced positive charge of a nucleus felt by an electron in the atomic orbital owing to the shielding effect of the other electrons in the atom or by a foreign electron from a neighboring atom. This charge is the basis of covalent and ionic bond formation. Efflorescence The process in which destructive precipitation occurs as the concentration of solute increases dramatically in pores during the drying process. In a related phenomenon, calcium carbonate crystals grow on the surface of the brick when Ca(OH)2 reacts with ambient CO2 during the brick-making process. Elastic Deformation A reversible deformation process below the yield point (stress) of the material; that is, no permanent deformation occurs. Elastic Modulus The ratio of stress to strain during elastic deformation where the initial extension is completely recovered when the stress is removed. Elastomer A polymer that can undergo large reversible elastic displacements. Polydimethylsiloxane (PDMS), or silicone, is an example of a biocompatible and widely used elastomer in the biotechnology field. See also microcontact printing. Electrochemical Cell Typically, a two or three electrode cell designed to measure the potential of reduction–oxidation reactions. A two-electrode cell consists of an anode and cathode immersed in an electrolyte (liquid or solid) and electrically connected by a wire. The cell potential is composed of the two half-cell reactions of the anode and cathode. A three-electrode cell consists of a working, counter, and reference electrode and is used for precise measurement of cell potentials, particularly at the working electrode. Sodium–sulfur batteries and lithium batteries are examples of electrochemical cells. See also electrolytic cell, galvanic cell, anode, cathode, counter electrode. Electrochemical Double Layer Liquid molecules become polarized in response to the surface space charge of a material. The electric field induced on the liquid side of the interface is called the Helmholtz layer and can play an important role in molecular and charge transport to and from the interface, especially during electrochemically induced oxidation and reduction processes. Electrochemical Reduction Method An approach used to prepare crystalline solids by reducing one of the species in the mixture in an electrochemical cell. The mixture is normally in a melt form composed of a metal oxide, alkali borate, and alkali halide contained in an inert crucible with inert electrodes, such as platinum and graphite. For example, CaTi2O4 is prepared by this reduction method from CaTiO3 and CaCl2 at 850°C in an electrochemical cell. Electrochromic Materials Materials containing multivalent transition metals with unpaired electrons that change color when an external field is applied. Electrochromic materials absorb the applied energy to oxidize or reduce the metal centers in the materials. The transition metal oxides with metals in different oxidation states have different colors, hence producing changes in color. For example, WO3 and V2O5 are electrochromic materials with transition metals that can exist in two oxidation states, +4 and +5.2 © 2005 by CRC Press

Electrode Potential (or Half-Cell Potential) The potential of an electrode in solution with respect to the normal hydrogen electrode (NHE). The overall cell potential of two electrodes is obtained by combining the two-electrode or half-cell potentials. Electroless Deposition of Films A film deposition method in which two electrodes are dipped in an electrolyte, and a thin film is deposited on one of the electrodes without application of an external field. This process is mainly limited to metal films. Nickel films for the electronics industry are often deposited by this method. Electroluminescence A process in which light is emitted from a material as a consequence of absorbing electrical energy. The III–V compound semiconductors (e.g., GaP, GaN) are electroluminescent materials.3 Electrolyte Solid or liquid materials that conduct electricity via transport of ions in the electrochemical cells. Sodium chloride solutions containing Na+ and Cl– ions and solid state V2O5 comprising V4+ and V5+ oxidation states are, for example, liquid and solid electrolytes, respectively. Electrolytic Cell A two- or three-electrode cell in which a potentiostat is used to supply an external potential to an electrode. This can drive both oxidation and reduction processes (i.e., a single electrode can be both an anode or a cathode depending on the applied potential). Electrorefining, electrodeposition, and battery recharging are all examples of electrolytic cells. See also galvanic cell. Electromagnetic Spectrum The spectrum that covers an enormous span of frequency, wavelength, and energy, including nuclear magnetic resonance (NMR; averages at 108 Hz), electron spin resonance (ESR; averages at 1010 Hz), microwave (averages at 109 Hz), infrared (IR; averages at 1013 Hz or 1 kJ/mol), visible (averages at 1015 Hz or 102 kJ/mol), ultraviolet (UV; averages at 1016 Hz or 104 kJ/mol), x-ray (averages at 1018 Hz or 106 kJ/mol), and gamma ray (averages at 1021 Hz) frequencies.4 Electron Beam (or e-Beam) Evaporation Similar to the thermal evaporation technique, but the material in the crucible is evaporated with an electron beam that localizes the heating and reduces contamination. Unlike thermal evaporation, it can be used for physically depositing films of insulating and multicomponent materials. See also evaporation. Electron Diffraction One method of characterizing crystalline solids used in conjunction with transmission electron microscopy (TEM) when no other technique is available to analyze crystals smaller than 0.05 mm. The more frequently used x-ray diffraction technique requires crystals 0.05 mm or larger; however, smaller samples can be analyzed by this method since the electron diffraction technique makes use of wave properties of electrons that scatter with higher efficiency than x-rays. The electron diffraction spectrum provides information on crystallinity, phase, unit cell, space group, crystal structure, crystal defects, surface structure, polycrystalline texture, and elemental analysis of a material. Electronegativity A measure of the net attractive force experienced by an outermost electron interacting with the nucleus in an atom within a molecule. For example, sulfur, S (3s23p4), is less electronegative than chlorine, Cl (3s23p5), but more electronegative than Si (3s23p2). Also, C in sp-, sp2-, and sp3-hybridized states has different values for electronegativity. Electron Energy Loss Spectroscopy (EELS) An electron spectroscopy technique that measures the loss in kinetic energy of the primary electron beam to provide information on the electronic structure, bond type, elemental constitution, local and surface structures, and surface defects of the material. This technique is useful for lighter elements such as carbon and nitrogen and therefore complements the x-ray fluorescence spectroscopy more useful for heavier elements. Electronic Conductivity Conductivity that results from electrons that are not paired owing to multivalency of transition metals or owing to doping processes. Electronic conductivity is common in many glasses with multivalent transition metals (e.g., vanadium and iron phosphate, S, Se, Te alone or in combination with P, As, Sb, or Bi) and semiconductors such as Si, Ge, Ga, and As. In addition, certain oxide semiconductors that are either doped to create extrinsic defects © 2005 by CRC Press

or that are annealed in conditions such that the oxides become nonstoichiometric (e.g., Cu2-xO) exhibit electronic conductivity. Electron Microscopy (EM) A qualitative technique that provides microstructural (shapes and dimensions) information for materials over a wide range of magnification. EM can be used to study the features in millimeter dimensions; however, it is most frequently used for structural information in the following ranges: 100 Å to 10 µm (scanning electron microscopy, SEM), and 3 to 1000 Å (transmission electron microscopy, TEM). See also descriptions for each type of electron microscopy. Electron Microscopy with Microanalysis (EMMA) The materials characterization technique that includes both electron microscopy for microstructural characterization and microanalysis for chemical analysis. In addition to observing the microstructure (back scattered and secondary electrons) when a material is bombarded with high-energy electrons, x-rays are generated that have characteristic emission spectra of elements present that determine the chemical composition of the material. By scanning either the wavelength (wavelength dispersive spectroscopy, WDS) or the energy (energy dispersive spectroscopy, EDS) of the emitted x-rays, it is possible to identify the elements present in the materials. EDS is used for identifying elements heavier than sodium (Na). A quantitative analysis by these methods is possible using a suitable calibration procedure. Electron Nuclear Double Resonance (ENDOR) A spectroscopy technique that involves a combination of ESR (electron spin resonance) and NMR (nuclear magnetic resonance) techniques to record hyperfine and superhyperfine splittings in the ESR spectrum for studying the local atomic structure in a compound. In this technique, the NMR frequencies of the nuclei adjacent to a paramagnetic center are scanned to record the fine structures associated with the interactions between the ligands and the paramagnetic ion. This technique is often applied to study the crystal defects, radiation damage, and doping in materials. Electron Probe Microanalysis (EPMA) A materials characterization technique similar to EMMA (electron microscopy with microanalysis), except that EPMA is more specific to WDS (wavelength dispersive spectroscopy)-type microanalysis in which specific sections of the surface are probed and characterized, instead of full-surface scan characterization.4a See wavelength dispersive spectroscopy and electron microscopy with microanalysis. Electron Spectroscopy for Chemical Analysis (ESCA) A qualitative electron spectroscopy technique that provides information on the chemical composition of and the local atomic environment in the compound by measuring the ionized electron energy ejected from the shells of the atom in the compound as a result of the bombardment with ionizing radiation or highenergy particles. ESCA is a surface technique suited to determining the presence of an element rather than the percentage composition of elements in the material tested; hence, it can be used as a semiquantitative technique to reveal the distribution of elements on the surface. The ESCA spectrum is a plot of peak intensities as a function of binding energies. The peaks correspond to specific elements with differentiation among types of bonding; for example, in the methyl acetate (CH3COOCH3) spectrum, four separate carbon peaks are observed. Electron Spin Resonance (ESR) A technique that detects changes in the electron spin configuration of a compound possessing unpaired electrons (e.g., transition metal compounds) as a function of the applied magnetic field. ESR spectra represent the first derivative of absorption associated with the electron spin transition plotted as a function of the applied magnetic field. The electron spin transitions occur at close to 1010 Hz frequency and provide information on the elemental constitution, electronic structure, local structure, and bond type of a material. The ESR technique can, for example, reveal the oxidation state of an element. Chromium in a CrO43– ion exhibits four hyperfine lines indicative of a Cr5+ characteristic pattern. Electro-Optic Materials Materials that exhibit an electro-optic effect by producing a change in the optical properties (e.g., index of refraction, birefringence) as a result of an applied electric © 2005 by CRC Press

field. Some electro-optic materials include LiNbO3, LiTaO3, KNbO3, (Sr,Ba)Nb2O6, Ca2Nb2O7, and KH2PO4. Electrophoresis The electron transport mechanism in a colloidal system in which charged particles move toward oppositely charged electrodes as a result of an applied electric field. This method is frequently used for depositing films on conductive substrates. Electroplating The deposition of ions from liquids under the application of an external potential. For example, copper cations can plate on a surface when the electrode is made sufficiently negative [Cu2+(aq) + 2e- q Cu(s)]. See also cathodic sputtering and electroless deposition of films. Electrosteric Stabilization The condition in which the electrostatic repulsion in a colloid is enhanced by steric effects (i.e., by covering the particles with adsorbed layers to discourage close approach between particles). Elemental Analysis A technique used to determine the elemental constitution of a material. Elemental analyses include a variety of techniques, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), infrared (IR), ultraviolet (UV), visible, electron, x-ray, and Mossbauer spectroscopy. Energy dispersive spectroscopy (EDS) and wavelength dispersive spectroscopy (WDS) techniques are used for elemental analyses in conjunction with scanning electron microscopy (SEM). Accurate quantitative elemental analysis is normally performed by atomic absorption (AA) and inductively coupled plasma (ICP) spectroscopies. See also individual analysis techniques. Elemental Semiconductor Elements such as silicon, germanium, and gray tin that conduct electricity and that exhibit an increase in electrical conductivity with increasing temperature. In Group IV of the periodic table, as the atomic weight increases, the elements change from insulators (diamond) to semiconductors (Si, Ge, gray Sn) and to metals (white Sn, Pb). All Group IV elements are tetrahedrally surrounded by four other elements. Ellipsometry A technique for measuring the thickness of adsorbed films on surfaces by monitoring the change in the polarization characteristics of a reflected circular polarized beam of light directed at the surface. EM See electron microscopy. Emerald A beryllium aluminum silicate mineral with the formula Be3Al2Si6O18. Emerald contains approximately 2% chromium, which gives it a green color. Emission Spectrography An elemental analysis technique for studying the radiation emitted by a sample when it is introduced into an electrical discharge. This technique is only useful for metals and metalloids and has a wide range of sensitivity from fractional parts per million to percent. The elements in a sample are identified by comparing the emission spectrograph of a sample with standard spectra of pure elements (metals and metalloids). EMMA See electron microscopy with microanalysis. Emulsion A colloidal system containing two liquids with solute droplets of one liquid suspended in another liquid. Water-in-oil and oil-in-water are common emulsions. In microemulsions, the size of the solute droplets is in the micron or submicron range. ENDOR See electron nuclear double resonance. Enstatite A magnesium silicate mineral, MgSiO3. Enthalpy For a system doing only expansion work, the enthalpy, H = U + PV, where U is the internal energy of the system, P is pressure, and V is volume. At constant pressure, the enthalpy change is equal to the heat input, q. Entropy The degree of disorder in a system. As the disorder of a system increases, the entropy, S, increases, which is thermodynamically favorable. Epitactic Reactions A reaction pertaining to a condition in which a similarity exists in molecular structure (oxide ion lattice arrangement) between the reactants and the products at the interface only. See also topotactic reactions. © 2005 by CRC Press

Epitaxial Growth Crystal growth from the seed that possesses two-dimensional structural similarity with the seed. In the epitaxial growth of a thin layer, the film is highly oriented with the lattice parameters matching to within a few percent of that for the substrate. See also heteroepitaxy, homoepitaxy. EPMA See electron probe microanalysis. ESCA See electron spectroscopy for chemical analysis. ESR See electron spin resonance. Esterification A process by which the hydroxy group on a metal is exchanged for an ester (e.g., alkoxy or aryloxy) group. A general esterification reaction follows: } M OH + ROH q M OR + H 2O

where M is a metal and R is an alkyl or aryl group. Esterification is also referred to as alcoholysis. Etching Controlled removal of material by either wet chemical or dry vacuum-based methods. Wet etching is still used in the microelectronics industry for less critical fabrication tasks such as wafer cleaning and large feature patterning. Wet etchants can be highly materials selective, so that they etch stop when the substrate or other thin film barrier material is reached. While generally inexpensive, wet methods can suffer from contamination, lack of directional etching, poor process control, and the generation of large quantities of waste. An example of a wet chemical etch is the use of a mixture of acetic acid, phosphoric acid, and nitric acid to remove aluminum. Chemical mechanical polishing and electrochemical etching are other types of wet etching methods. Dry etching has a physical component (e.g., ion bombardment) but often is combined with a chemical part and includes methods such as plasma etch, ion milling or ion beam etching (IBE), reactive ion etching (RIE), chemically assisted ion beam etching (CAIBE), and for MEMS devices, deep reactive ion etching (DRIE). Dry etching is often highly directional and better suited for the patterning of small features (f1 µm) but can damage the material being etched. See also chemical and thermal etching. Ethene (Ethylene) Ligand An alkene ligand with a double bond and a formula, CH2 = CH2. The metal ions are normally bonded to ethene via the U bond. H H

C C

H M H

Ethene (ethylene) ligand

Ethoxy Ligand An alkoxy ligand with the structure –OCH2CH3, normally bonded to metal via an oxygen atom to form metal organic compounds. Ethyl Ligand An alkyl ligand with the formula –CH2CH3, normally bonded via the carbon atom of a CH2 group to form organometallic compounds. Ettringite A calcium mineral, Ca2Al2(OH)12(SO4)3 · 26H2O. Eucryptite A lithium aluminum silicate with the formula LiAlSiO4. Eutactic Structures An ionic structure in which the ions are not necessarily in contact with each other in cubic packed arrays. For example, Cu2O has a eutactic structure with a cubic closepacked array of Cu+ ions with tetrahedral O2– ions. The coordination number of Cu+ is 2 (linear). Eutactic System A multicomponent system in which intermediate compounds or solid solutions are formed in the solid state. Instead, a mixture of the components is present. In the liquid state, at high temperatures, however, a complete range of single-phase liquid solutions occurs. At © 2005 by CRC Press

intermediate temperatures, regions of partial melting appear, containing a mixture of a crystalline phase and a liquid that contains a different composition of the crystalline phase. Eutectic Composition The composition of a multicomponent system (e.g., a mixture of SiO2 and Al2O3) at which the eutectic temperature occurs. Eutectic Temperature The lowest temperature at which a liquid exists in a multicomponent system. See also eutectic composition. Evaporation A low vacuum physical vapor deposition technique for depositing primarily metals. A crucible of the metal is resistively heated until metal vapor is formed. This vapor then deposits on every available surface within line-of-sight, including wafers. Surfaces are often metallized through a liftoff technique in which a metal is evaporated onto a patterned photoresist. The resist is then removed, leaving behind the patterned metal film. Evaporative Decomposition of Solution (EDS) An aerosol technique used to prepare fine powders by spraying salt solutions into a furnace, in which the liquid droplets of the salt solution dry and decompose. The resulting particles can be oxides or nonoxides such as sulfides and nitrides. Oxide particles are formed when air or oxygen is used as the gaseous atmosphere. Similarly, nitride and sulfide particles are formed when a gaseous atmosphere such as nitrogen or ammonia, respectively, and H2S are used. EXAFS See extended x-ray absorption fine structures. Exciton Band The spectroscopic absorption associated with the promotion of an electron from a lower energy to a higher energy localized orbital within the same atom. The electronhole pair remains closely associated and is called the exciton, which can be represented as an excited state of an atom or ion. Such transitions, for example, include dd or ff transitions in transition metal compounds and transitions associated with defects (trapped electrons or holes) in color centers. Extended Energy Loss Fine Structure Spectroscopy (EELFS) The spectroscopy related to the fine structure in the EELS spectrum of a material. This technique is also the electron analogue of the x-ray technique, EXAFS. See also electron energy loss spectroscopy (EELS) and extended x-ray absorption fine structures (EXAFS). Extended X-ray Absorption Fine Structures (EXAFS) An x-ray spectroscopy technique for molecular characterization used to study local structure. This technique is applicable to crystalline or amorphous materials. The structure is examined by the variation in absorption as a function of energy or wavelength, extending from the absorption edge to higher energies up to 1 keV. This technique provides information on local structure (e.g., bond distances) of materials. In particular, EXAFS is useful for amorphous materials such as glasses and gels that are difficult to study using standard diffraction techniques. Extrinsic Defects Crystal defects originating from impurities in the material. For example, doping NaCl with Ca2+ ions increases the number of cation vacancies, resulting in extrinsic defects. Extrinsic Semiconductors Materials with conductivity controlled by the addition of dopants. For example, Si can be converted into an extrinsic semiconductor by doping it with an element from Group III (e.g., B3+) or V (e.g., As5+, P5+) in the periodic table. See also n-type, p-type, dope. Extrusion A method for forming near net-shape ceramic and plastic parts in which a homogeneous slurry or a paste is forced through a small orifice of steel or a carbide die to produce tubes, rods, and other near net-shape parts. After extrusion, the green part is further processed (e.g., sintering in the case of extruded ceramics) to complete the material fabrication.

F Face-Centered Cubic (fcc) A close-packed cell consisting of spheres (atoms or ions) at the corners of the cube and at the center of each face, such that each sphere is connected to 12 other spheres at the 4 corners of the adjacent cells. © 2005 by CRC Press

Fast Ion Conductors (FIC) The ionic conductivities of these solid electrolytes are several orders of magnitude greater than normal ionic conductors (XFIC > 102 ohm1cm1). Examples of FIC materials include Y-doped ZrO2 and Na+-doped G-alumina. Unlike ionic conductors whose defect concentrations, and hence charge carrier concentrations, are strongly temperature dependent, FIC materials often have temperature independent carrier concentrations owing to large numbers of structurally inherent defect sites such as vacancies. See also ionic conduction. Fatigue Fractures In ceramics, fractures resulting from repeated cyclic stresses caused by nucleation or extensions of cracks within an intensely cold-worked area at the specimen surface. However, static fatigue is caused by preferential stress corrosion at the tip of a crack under a static applied stress. See also fracture. Faujasite A sodium calcium aluminosilicate zeolite with a cavity framework and the chemical formula [NaCa0.5(Al2SiO5O14)] · 10H2O. Fayalite An iron silicate with the formula Fe2SiO4 and a melting point of approximately 1200°C. F-Center See color centers. Feldspar An aluminosilicate mineral with a framework structure that can be chemically classified as a member of the ternary system, NaAlSi3O8KAlSi3O8CaAl2Si2O8. See also orthoclase. Fermi Energy For a metal at absolute zero, the Fermi energy corresponds to the highest filled electronic state in the valence band. For an intrinsic semiconductor at 0K, it falls midway between the valence and conduction bands. The Fermi energy’s temperature dependence controls the statistical distribution of electrons and holes in a semiconductor. Ferrielectric Materials Materials that are antiferroelectric in one direction, but in another direction the electric dipoles are not completely canceled and there is a net dipole moment in the absence of an electric field. Lithium ammonium tartate monohydrate and Bi4Ti3O12 are examples of ferrielectric materials. Ferrimagnetic Materials Materials that possess a residual magnetic moment in the absence of a magnetic field. This results from unequal moments of two sublattices close to each other in a material in which the antiferromagnetically arranged spins do not completely cancel out. Ferrites Mixed metal oxides containing Fe2O3 and other metal oxides. Most ferrites are magnetic in nature. Many ferrites can be described by the general formula M II Fe 2IIIO 4 , with spinel or inverse spinel structures. Barium ferrite, BaFe12O19, with the magnetoplumbite structure is an example of a magnetic ferrite. Ferrocene A dicyclopentadienyliron, [Fe(M5C5H5)2], with a sandwich-type structure. This organometallic compound forms orange crystals that melt at 174°C and are thermally stable up to 500°C.

Fe

Ferrocene

Ferroelastic Materials Ferroelastics are strain analogues of ferroelectric materials in which strain spontaneously develops into different orientation domains. Some ferroelectrics (e.g., BaTiO3) can be simultaneously ferroelastic and ferroelectric. Ferroelectric Materials Crystalline materials that possess a permanent spontaneous electric polarization (electric dipole moment per cubic centimeter) that can be reversed by an external electric field. Owing to the distortion of a perfect cubic structure, ferroelectric materials exhibit an electric dipole moment, and the applied electric field causes polarization of the material. © 2005 by CRC Press

After the removal of the electric field, the materials still possess remanent polarization. This type of behavior is referred to as ferroelectric hysteresis. Ferroelectric materials normally have large permittivities. For example, barium titanate (BaTiO3), lead titanate (PbTiO3), and lead zirconate titanate Pb(Zr,Ti)O3 are ferroelectric in nature. Ferroic Materials The broad class of materials that order into domains of different orientations of either spontaneous strain, polarization, magnetization, or combinations thereof, hence ferroelastics, ferroelectrics, and ferromagnetics. Ferromagnetic Materials Materials that possess magnetic moment owing to complete ordering of magnetic spins in the absence of a magnetic field. In some ferromagnetic materials, individual ions are strongly coupled and aligned parallel, resulting in a net magnetic moment. The typical magnetic susceptibility, H, of ferromagnetic materials ranges from 10–2 to 10–6 and decreases with increasing temperature. Ferromagnetic property is exhibited by certain metals, alloys, transition metal compounds, and rare earth and actinide elements. Fiber Drawing In a sol-gel solution, as polymerization proceeds, the solution viscosity increases, and in a certain range of viscosities, fibers can be drawn directly from the viscous liquid system. Similarly, fibers can be drawn from a glass melt at a given viscosity and temperature. The fibers thus produced can be further processed into short fibers, mats, etc. and are commonly used as filtration media, insulation, reinforcements in refractory and structural materials and as fiberoptic devices. Fiber-Optic Devices Devices that use an optical waveguiding mode for transmitting information, for illumination, and other purposes. A glass rod can transmit light around corners as a result of total internal reflection. If an image is incident on one end of the rod, it is seen at the other end as an area of approximately uniform intensity (an average of incident light). If the rod is replaced by a bundle of fibers, each fiber transmits (with a resolution equal to the individual fiber diameters) only a part of the image incident on it. Hence, a bundle of fiber can transmit a full image. A simple fiber-optic communication system has a modulated light source, which feeds into a fiber, which delivers into a receiver that decodes the optical signal and converts it to electronic form for use by equipment at the receiving end. Fiber-optic technology has widespread applications in the communications area (telephones, cable, and computer links) because of the high rate of data transmission. Fick’s Law An empirical law used to study an atom’s mobility in a condensed phase during microstructural changes and chemical reactions that states that diffusive flux, JD (mol/cm2 · s), is proportional to the concentration gradient, Ic/Ix: JD =  DcIc / Ix

where Dc is the chemical diffusion coefficient (cm2/s), c is the concentration in mol/cm3, and x is the direction of diffusion. Film A thin layer form of a material. Thin and thick films can be coated on a variety of substrates by numerous processes including sol-gel, chemical vapor deposition (CVD), sputtering, ionimplantation, laser ablation, electrophoresis, and electroplating. These films are used for optical (colored, antireflective, optical memory), electronic (ferroelectric, conductive, superconductors), protective (corrosion and scratch resistant, passive), and foam-type (membranes) applications. During the sintering process in cermics, films can also form at the grain boundaries and interfaces. Filtration Medium Inert materials with controlled porosity and pore sizes. Polymers and glass fibers are the most frequently used materials for filtration purposes. However, porous ceramic materials can also be prepared in membrane form by conventional ceramic processes (fibers and foams) and by the sol-gel process (membranes with fine porosity). These separation media are © 2005 by CRC Press

usually composed of metal oxides such as titania, alumina, and silica. Ceramic membranes are normally used for higher temperature applications. Fischer (Karl) Reagent See KarlFischer reagent. Fish Scaling The poor coating condition on metal, ceramics, or glass relating to breakout or peeling actions of films upon cooling the surface. Fixed Bed Reactor A common catalytic reactor that consists of tube and parallel arrays of tubes filled with solid catalyst particles. The fixed bed reactors are used for a variety of oxidation reactions and synthesis of new compounds. One of the drawbacks associated with the fixed bed reactor is that the fixed solid phase in the reactor exhibits variable temperatures at different locations because of limited mixing of reactants resulting in lower yield reactions. See also fluid bed reactor. Flame Hydrolysis A commercially used process of producing fine oxide powders by oxidizing metal halides in the flame. Although metal halides react vigorously with water, oxidation occurs faster than hydrolysis at flame temperatures. For example, titania is prepared from TiCl4 in H2/O2 or CH4/O2 flames and can be represented by the following equation: TiCl4 + O2 q TiO2 + 2Cl2

This method has also been used for fabricating high-purity glass preforms used in producing optical fibers for telecommunications. Flame Oxidation See flame hydrolysis. Flame Photometry An elemental analysis technique that measures the emission spectra produced when solutions containing metals are introduced into a flame. This technique is particularly useful for analyzing alkali and alkaline earth metals. However, the sensitivity of the technique for transition metals is low. The spectra obtained from this method are much less complicated than those generated by emission spectrography. Flocculation The process of aggregating finely dispersed particles into larger units called flocs or coagula. In suspension, flocculation is achieved by collapsing the repulsive double layers of particles by using flocculent additives such as electrolytes or surfactants. For example, a suspension of quartz particles at pH 4 can be flocculated by a variety of high-molecular-weight cationic binders. See also deflocculation. Flory–Stockmayer Theory The theory that predicts the gel point and the molecular size distributions of polymers constructed from monomers, each of which may be connected to f other monomers, where f is the functionality of the monomer or oligomer. This theory assumes that no cyclic species are formed and that the polymerization process proceeds in a statistically random fashion.5 Fluid Bed Reactor A reactor in which the fluid passes through a bed of fine solid particles and the velocity of the fluid and the gas bubbles in the fluid agitate the bed continuously like a boiling liquid. Unlike the fixed bed reactor, because of the continuous mixing in this reactor, the heat is uniformly distributed throughout the reactor. Fluid bed reactors are used for a variety of organic and inorganic reactions. If the mobile phase in the reactor is replaced by gas, it can be used as a dryer in addition to a reactor. In the two modes, where the mobile phase is liquid or gas, the reactions occur between solid and liquid or solid and gas phases. This technique has been used for converting metals into metal oxides, sulfides, and nitrides by heating the fine metal particles to high temperatures under the appropriate gaseous environment. Fluoroapatite See apatite. Fluorescent Materials The photoluminescence materials that emit light owing to the decay of electrons from an excited state (as a result of absorbing photons or light, often ultraviolet) to the ground state over a short period of time. (The elapsed time between excitation and emission processes is on the order of <10–8 s.) CaF2 is a fluorescent material. © 2005 by CRC Press

Fluorinating Agents Chemical agents that fluorinate reactants and materials. Fluorine gas (F2) is one of the strongest and most expensive fluorinating agents because of the handleability problems associated with it. Following is a list of strong fluorinating agents with the fluorinating power steadily diminishing: ClF3 > BrF3 > IF7 > ClF > BrF3 > IF5. Other hard oxidizing fluorinating agents include AgF2, CoF3, MnF3, PbF4, CeF4, BiF5, and UF6. Moderate fluorinating agents include HgF2, SbF5, SbF3/SbCl5, AsF3, CaF2, and KSO2F. Mild fluorinating agents are the monofluorides of H, Li, K, Na, Rb, Cs, Ag, and Tl and compounds such as SF4, SeF4, CoF2, SiF4, and NaSiF6. Fluorite Crystal Structure The crystal structure of CaF2 is a generic fluorite structure assigned to many crystals. The face-centered cubic structure is similar to CsCl structure; however, only half of the cation sites are filled, and it consists of a void in the center of the unit cell. See also CsCl structure. Fluorspar Calcium fluoride, CaF2, that emits light when it is heated. See also fluorescent materials. Flux Growth of Crystals Method of growing crystals that involves adding noncrystallizing components (fluxing agents) to reduce the melting temperature of the source (solid reactants). Addition of salt (NaCl) to ice, for example, lowers the melting point of ice below 0°C, resulting in a low temperature eutactic at 21°C. Foams Materials with high porosity in which the pores can be closed or open. Several polymeric materials (polystyrene, polyurethane, phenols, etc.) can be prepared as foams. Inorganic and organic aerogels are sometimes referred to as foams. Formamide A protic solvent with the formula HCHONH, used in many sol-gel reactions as a drying control chemical additive (DCCA). Forsterite A magnesia-silica mineral with the formula 2MgO, SiO2, or Mg2SiO4. This mineral is frequently used as a dielectric material. Fractal A fractal object is self-similar in that subsections of the object are similar in some sense to the whole object and the subsection contains no less detail than the whole. Fractal growth theory has been applied to study the growth processes in the sol-gel and other colloidal processes used for fabricating solid state materials.6 Fracture A process of crack growth. Most ceramics and glasses fail in a brittle manner in which fracture occurs with little or no plastic deformation. Most glasses below the softening temperature are brittle, and the appearance of the fracture surface is called conchoidal. However, in crystalline ceramic materials, brittle fracture generally occurs by cleavage over particular crystallographic planes. At high temperatures when the grain boundaries in crystalline materials shear, they might fail intergranularly. In ductile ceramics, when a section is continuously thinned, cup- or conetype fractures result. Free Energy Free energy is the measure of a system’s ability to do useful work. The Gibb’s free energy, G, combines the enthalpy, H, and entropy, S, of a system into one thermodynamic function: )G = )H  T)S, where T is temperature. The sign of )G describes whether a system is in equilibrium ()G = 0) or whether a physical or chemical change is spontaneous or favorable ()G < 0) or nonspontaneous and unfavorable ()G > 0). Freeze-Drying The process of removing liquid from a system by freezing the liquid followed by subliming the frozen liquid. By removing the liquid through this approach, the solid–liquid interface is avoided and a solid state material with high porosity, fine pores, and intricate structure is formed under vacuum. Freeze-drying is a commonly used process in the food industry and has also been used in preparing fine ceramic powders. Frenkel Defect A stoichiometric defect (structural imperfection) in a crystal in which the atoms or ions move from normal sites to interstitial sites such that the number of vacant sites is equal to the interstitial atoms. For example, AgCl commonly has a Frenkel defect that causes Ag+ ions to move to interstitial sites surrounded by four Cl– ions and four Ag+ ions. © 2005 by CRC Press

Fuel Cell Solid state electrochemical cells that convert chemical energy (i.e., fuels) directly into electrical energy and no energy is expended to produce heat before producing power. In a fuel cell, the electrochemical reaction between two chemicals, a fuel and an oxidant, produces a flow of current when power is demanded by an external load. By eliminating moving parts and the heat stage, fuel cells can be a more efficient energy system than other systems. For example, a hydrogen–oxygen fuel cell produces electricity and water when hydrogen gas and oxygen gas react electrochemically in the cell containing two porous electrodes and an electrolyte.7 Fuller’s Earth Any natural clay-type material that decolorizes minerals. Fuller’s earth is normally composed of clay materials such as montmorillonite and kaolinite. See also kaolin. Fullerene A closed, convex caged carbon molecule containing both hexagonal and pentagonal faces. The most common carbon fullerene is spherical C60 and is called a buckminsterfullerene or buckyball. Spherical carbon structures can theoretically form at even numbers of carbon above 32 and include the common C60 and C70 forms (see Table 2.2). Carbon nanotubes, a fourth allotrope of carbon, are essentially giant linear fullerenes whose ends are closed with hemispherical caps or half a bucky ball. Proposed uses of fullerenes include medical drug delivery and electronic, catalytic and optical applications. See also buckminster fullerene, carbon nanotubes. Table 2.2 Dimensionality of Carbon Allotropes Carbon Allotrope

Crystalline Dimensionality

Diamond

Three

Graphite

Two

Nanotube (fullerene) Buckyball (fullerene)

One Zero

Comments fcc structure with four of eight tetrahedral sites also filled; an insulator with high thermal conductivity Hexagonal array of sheets; bonds within the planes are strong directional covalent bonds. Coupling between the sheets is due to weaker van der Waal’s forces. Covalent bonding of carbon in hexagonal arrays, but sheets are wrapped into a tubular form Covalently bonded carbon in hexagonal and pentagonal coordination with the sheet wrapped around a point

Fumed Silica See aerosil or cab-o-sil. Functionality The number of bonds that a monomer can form. Functionality is normally represented as f. For example, Si(OCH3)4 has four reactive groups; hence, the functionality is 4. Funicular State During drying, the pore liquid state in which the liquid is continuous along the pore walls but does not fill the pore space; i.e., the liquid and vapor phase are continuous. See also pendular state. Fused Silica Amorphous silicon dioxide (SiO2) formed from a melt by the quenching process.

G Galena Lead sulfide mineral with the formula PbS. Galena is also called lead glance. Galvanic Cell A two- or three-electrode cell in which the oxidation–reduction reactions occur spontaneously, thus generating an electrical current. Batteries and fuel cells are examples of galvanic cells. See also electrolytic cell. Garnets A large family of complex oxides with the general formula A3B2X3O12, where A is the large ion with a radius of ~1 Å and a coordination number of 8 in a distorted cubic environment and B and X are smaller ions that occupy octahedral and tetrahedral sites, respectively. Many garnets are important ferrimagnetic materials. Some examples of garnets include Ca3Al2Si3O12, Ca3Fe2Si3O12, Y3Fe5O12, and Mg3Al2Si3O12. Garnierite A nickel ore in the form of a silicate, with the formula (Ni,Mg)6Si4O10(OH)8. © 2005 by CRC Press

Gas Chromatography (GC) A chromatographic technique that identifies and separates various volatile components in a sample using a porous solid phase column as an adsorbent and a mobile gas phase to carry the components through the column. The results are plotted with the detector response as a function of time. The two most common detection techniques are FID (flame ionization detection) and TCD (thermal conductivity detection). The FID and TCD detectors involve measurement of change in the thermal conductivity of hydrogen flame by the organic vapors and direct thermal conductivity measurement of the eluted components, respectively. GC can be used for both qualitative and quantitative analysis of samples. Lower-molecular-weight compounds with compact structures and lower boiling points normally elute first, depending upon the affinity of the packing used in the chromatographic column. For example, in a nonpolar capillary column, methanol elutes before methoxyethanol. The quantitative analysis is based on the area under the peak and comparison with standards.8 Gehlenite A lime-rich aluminosilicate phase with the formula Ca2Al2SiO7. Gel A solid-state network with liquid trapped in the pores. As monomer polymerization proceeds, the viscosity of the solution increases, and after a point the liquid stops flowing, forming a gel. There are various ways to prepare inorganic gels; the two most common methods are the solgel process and the hydrothermal process. Most gels can be classified as particulate- (colloidal) or polymeric-type gels. Although the gel formation process can be reversible in a particulate system, it can be irreversible, as in the case of polymeric systems. Several oxide gels, such as silica, titania, and alumina, have a large organic component in the solid-state network with an aqueous or nonaqueous solvent filled in the pores. Gel Permeation Chromatography (GPC) See size exclusion chromatography (SEC). Gel Point The degree of reaction at which the viscosity of the sol, owing to polymerization or connectivity, increases drastically such that the liquid stops flowing. For example, in the sol-gel process, during sol-to-gel transition the liquid stops flowing and it forms a gel at the gel point. Getter A material used to remove a trace gas molecule, often oxygen, from a high temperature furnace or vacuum chamber. For example, materials such as carbon and zirconium are often used as oxygen getters to remove trace oxygen from high temperature processes. Certain high pressure, high temperature lamps also use getters to remove trace corrosive gases that form during operation from inside the lightbulb. Giant Magnetoresistance (GMR) The change in the electrical resistance of a material in response to an applied magnetic field. GMR devices are often made from multilayers of alternating ferromagnetic and conducting layers, 4 to 6 nm and 3 to 5 nm thick, respectively (e.g., NiFe or Au-Co alloys with a metallic conductor such as Cu), with the magnetic moments antiferromagnetically ordered, which leads to a high resistance state as the electron spins are anti-parallel to the magnetic dipoles. When a magnetic field is applied, the magnetic dipoles align with the field and the electron spins are also aligned parallel to these magnetic dipoles, leading to less scatter and a corresponding sharp drop in the resistance. Applications of GMR include magnetic field sensors and read-write heads for computer disks. See also anisotropic magnetoresistance, magnetoresistance, colossal magnetoresistance. Gibbsite An aluminum hydroxide with the formula Al(OH)3. The structure consists of a cubic close-packed (ccp) arrangement of (OH) ions within layers of edge-shared Al(OH)6 octahedra that are vertically stacked via H bonds. Glass An amorphous solid with a short-range order (local elemental environment) and without a long-range order or periodicity in the arrangement of the atoms. Glasses can be formed by supercooling the liquid melt or raw materials (powders) at a rapid rate to avoid crystallization or they can be prepared by polymerizing the monomeric precursors at room temperature via the sol-gel process. These glasses can be colored by adding the appropriate transition metals in the precursor solution or melt. The glasses can be made photosensitive and photochromic by adding optical sensitizers (e.g., cerium ions) or organic or inorganic compounds (e.g., Zn, Cd, Hg, Cu, Ag), respectively. Photosensitive glasses change color when they are exposed to light (ultra© 2005 by CRC Press

violet or x-ray) by reducing metal ion in the glass. Photochromic glasses change color when they are exposed to light but return to their original color when light is removed (e.g., sunglasses that automatically adjust to different light intensities). Glass-Ceramic Materials Crystalline materials with long-range order that are produced by the controlled crystallization (using nucleating agents) of appropriate glass compositions. These materials consist of 95 to 98% small crystals by volume and very small amounts of amorphous glass; as a result, they are much stronger than glass and can withstand pressures of as much as 30,000 psi in comparison to only 10,000 psi for glass compositions. For example, Li2OAl2O3 SiO2 is a glass ceramic with higher mechanical strength than SiO2 glass. Glycerate Metal salts derived from glyceric acid (HOOCCH(OH)COOH) that contains two carboxylic acid groups and one alcohol group. O C OH H C OH C O O Glycerate

Goethite An iron hydroxide with the formula F-FeOOH. Gouy Layer The outer diffused layer of opposite charge beyond the tightly bound layer surrounding the positively or negatively charged suspended particles in a dispersion or in a colloid. Also referred to as diffused double layer. Graded Refractive Index (GRIN) Glass Glasses composed of layers with increasing refractive indexes toward the center to minimize reflection at the surface. These glasses are also referred to as antireflective glasses. In these materials, the refractive index toward the surface of the glass is close to air, and the refractive index toward the center is close to that of dense glass. Grain Boundaries The interface or the plane of contact between two crystals of the same material resulting from the sintering process in which the fine particles neck and coalesce to form microscopic crystals. Grain Growth The process by which the grain size of a strain-free material increases continuously as a result of the attachment of smaller grains to larger grains or, in some cases, attachment of two or more larger grains. The grain growth is normally driven by the difference in the energy between large- and small-grain-size products. Materials produced from small-grain–large-grain attachment are denser compared with materials produced from attachment of large grains, which are porous. Graphite An intercalate solid with a layer structure composed of carbon only. Owing to the layer structure, graphite can be used as a solid lubricant or as an intercalating host for species such as alkali cations, halide anions, ammonia, and oxysalts. Green Density The density (mass/total volume) of the compacted ceramic powder before sintering. Grignard Reagents Organomagnesium halides with the general formula RMgX, where R is an organic group and X is a halide ion. Grignard reagents have been used in synthesizing numerous alcohols, acids, hydrocarbons, amides, and other exotic compounds. Group 0 to VIII Elements Group 0 Elements Elements in a group of the periodic table, consisting of inert gas elements with the outer shell electron configuration of ns2np6. Examples of Group 0 elements include He, Ar, Xe, and Kr. These elements are also referred to as Group VIIIA elements. © 2005 by CRC Press

Group 1A Elements Elements in a group of the periodic table consisting of extremely reactive alkali metals from lithium (Li) to francium (Fr) with the outer shell electron configuration of ns1. See also alkali metals. Group IB Elements Elements in a group of the periodic table consisting of transition metals including copper, silver, and gold with the outer shell electron configuration of nd10(n + 1)s1. These elements are also called coinage metals because they were used for currency. Group IIA Elements Elements in a group of the periodic table consisting of alkaline earth metals from beryllium (Be) to radium (Ra), with the outer shell electron configuration of ns2. See also alkaline earth metals. Group IIB Elements Elements in a group of the periodic table consisting of transition metals, including zinc, cadmium, and mercury, with the outer shell electron configuration of nd10(n + 1)s2. Group IIIA Elements Column of elements in the periodic table including boron (B) to thallium (Tl), with the outer shell electron configuration of ns2np1. Group IIIB Elements Elements in a group of the periodic table consisting of transition metals, including Sc, Y, La, and Ac, with the outer shell electron configuration of nd1(n + 1)s2. Group IVA Elements Column of elements in the periodic table including C to Pb, with the outer shell electron configuration of ns2np2. Group IVB Elements Elements in a group of the periodic table consisting of transition elements, including Ti, Zr, and Hf, with the outer shell electron configuration of nd2(n + 1)s2. Group VA Elements Column of elements in the periodic table beginning with nitrogen and ending with bismuth, with the outer shell electron configuration of ns2np3. Group VB Elements Elements in a group of the periodic table consisting of transition metals, including V, Nb, and Ta, with the outer shell electron configuration of nd3(n + 1)s2, except for Nb (4d45s1). Group VIA Elements Column of elements in the periodic table beginning with oxygen and ending with polonium, with the outer shell electron configuration of ns2np4. Group VIB Elements Transition metals including Cr, Mo, and W of the periodic table, with the outer shell electron configuration of nd5(n + 1)s1, except for W (5d46s2). Group VIIA Elements Elements in a group of the periodic table consisting of halogens, including F, Cl, Br, I, and At, with the outer shell electron configuration of ns2np5. Group VIIB Elements Elements in a group of the periodic table consisting of transition metals, including Mn, Tc, and Re, with the outer shell electron configuration of nd5(n + 1)s2, except for Tc (4d65s1). Group VIII Elements Elements in a group of the periodic table consisting of transition metals, including Fe, Ru, Os; Co, Rh, Ir; Ni, Pb, and Pt, with the outer shell electron configurations of nd6(n + 1)s2; nd7(n + 1)s2; and nd8(n + 1)s2, respectively, except for Ru(4d75s1), Rh(4d85s2), Pd(4d10), and Pt (5d96s7). Gypsum Calcium sulfate (CaSO4 · 2H2O) mineral used by ancient Egyptians to produce concrete.

H Haematite An iron oxide with the formula Fe2O3. Halates Two-element anions with the formula XO3 , where X is a halogen. Some examples of halates include ClO3 and IO3 . In addition, the formula for halites is XO 2 and the formula for hypohalates is OX–. Half-Cell Reactions The separate oxidation and reduction reactions that take place at the two electrodes (anode and cathode) in an electrochemical cell. One can measure the electrode potential of individual half cells with reference to the standard hydrogen electrode, thus allowing © 2005 by CRC Press

the potential difference between any two half cells to be readily calculated. See also, anode, cathode, electrode potential. Halide Ion Conductors Halides with a fluorite (CaF2) structure that can be classified as solid electrolytes at high temperatures owing to their high anion (halide) conductivity. For example, PbF2 has low conductivity at room temperature; however, above 500°C, its ionic conductivity sharply increases to ~5 <–1 cm–1. Halides The salts of metals derived from halogens (elements from Group VIIA of the periodic table). For example, TiCl4, SiCl4, and BaCl2 are metal chlorides and LiF, NaF, and MgF2 are metal fluorides, which are all classified as halides. Hall Effect The Hall effect can be used to distinguish between electron and hole conduction in a solid by applying orthogonal magnetic and electric fields and measuring the electric field in the third orthogonal direction. Hapticity The number of carbon atoms in an organic ligand attached to the metal in a compound. For example, an alkyl ligand is a M1-monohapto, an alkene ligand is a M2-dihapto, and cyclopentadiene is a M5-pentahapto since the number of carbon atom sites for metals in the ligands increased from 1 to 2 to 5. Hardness A measure of resistance to deformation, scratching, and erosion. The hardness of a material is normally tested by indentation techniques known as Vickers (HV) or Knoop (HK) or Rockwell superficial (HR). See hardness values for a variety of materials in Chapter 4, Section V. Hausmannite Manganese oxide with the formula Mn3O4. Heat Capacity The energy required to raise the temperature of the material by a unit degree or an increase in energy per degree of temperature increase. Helium Pycnometry See pycnometry. Helium Scattering Inelastic He atoms with high thermal energies excite surface vibrational modes and also diffract to yield surface-phonon dispersion spectra (Rayleigh waves). Helmholtz Layer See electrochemical double layer. Hematite An iron oxide F-Fe2O3 compound. Hemimorphite A zinc silicate with the formula [Zn4Si2O7(OH)2] · H2O. Heteroepitaxy The thin film growth of a different material than the substrate, which is either commensurate, strain-relaxed incommensurate, or pseudomorphic. Commensurate growth occurs when the substrate is lattice matched to the growing film, and thus no strain is developed at the interface or in the growing film. Incommensurate growth occurs when there is no lattice match between the substrate and the growth layer, and thus defects (often dislocations) are created near the interface that often propagate into the growing film. Pseudomorphic growth occurs when there is some lattice mismatch, but the growing film can accommodate the strain up to a critical thickness before defects occur. See also epitaxial growth, homoepitaxy. Heterogeneous Nucleation The process of forming a critical nucleus (a fine solid particle) from a liquid solution or a melt with another substance to facilitate nucleation. Normally, heterogeneous nucleation is much easier to attain since most materials consist of atomic defects and the nucleation occurs preferentially at defect sites and locations with high local free energy. See also nucleation and growth. Heterojunction The atomic-level interface between two (typically semiconducting) materials. If the two materials form a solid solution with each other, the interface can be either extremely sharp with very few defects or can be chemically graded over some distance. Heteropoly Blues Chemicals with a characteristic intense blue color created by mildly reducing 1:12 and 2:18 heteropolymolybdates and heteropolytungstates. In the polymetallates, for example, [CoIIW12O40]6–, the heteroatom, cobalt, is situated inside the cavities or baskets formed by WO6 octahedra. These chemicals can be used as dyes and pigments or can also be used in the quantitative determination of Si, Ge, P, and As elements. Heterostructures Microelectronic devices made of more than one material, typically using heteroepitaxy to grow chemically dissimilar materials on top of each other. © 2005 by CRC Press

Hexagonal Close Packing (hcp) An arrangement of atoms in which each sphere is surrounded by six spheres, and these close-packed layers are stacked with an A, B, A, B,… type arrangement. The spheres of the B layers lie on the holes of the A layers. See also cubic close packing. Hexagonal Symmetry A unit cell in which three equal axes are coplanar at 120°, the fourth axis is at right angles to these axes, the angles F and G are equal to 90°, and L is equal to 120°. Crystals of zinc, cadmium, and quartz (SiO2) exhibit hexagonal symmetry. High-Resolution Electron Microscopy (HREM) An electron microscopy technique used for lattice imaging at the angstrom level. For more information on the types of HREMs, see transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). Homoepitaxy The thin film growth of the same material as the substrate; hence they are lattice matched and do not induce strain in the growing film. See also epitaxial growth, hetereoepitaxy. Homogenous Nucleation The process of forming a critical nucleus (fine solid particles) in which the crystal grows from the liquid without assistance from other sources (i.e., all parts of the parent phase are identical). See also nucleation and growth. Hopping Semiconductor A semiconductor material composed of elements with two oxidation states that can be switched by thermal activation. Nickel oxide (NiO) is a hopping semiconductor with the oxidation states Ni2+ and Ni3+. Hot Pressing A densification technique used frequently for ceramic and composite materials in which external pressure and temperature are applied to obtain materials with near theoretical density. Typically, the sample is placed in a graphite cylindrical die and heated to a high temperature while a high uniaxial load is applied by a piston. For example, when beryllia is hot pressed at 1600°C, the bulk density increases from 2.55 to 2.91 g/cm3, forming a stronger material. See also isostatic pressing. Hydration The process of surrounding a particle or a molecule with a water molecule as an electron-rich species around the electron-deficient species via electrostatic attraction. Hydrazido Ligand A ligand derived from hydrazine (N2H4). For example, (NNH2)2– and (NNH3)1– are hydrazido ligands. Hydrides Compounds (MxHy) formed by combining hydrogen with other electropositive elements. Many of these hydrides are volatile and flammable and are frequently used in chemical vapor deposition processes to fabricate films (e.g., arsine, AsH3). Hydrogen Bond The polar interaction between a hydrogen atom and electronegative atoms that influences the properties and structures of substances. The hydrogen bond strength ranges between 10 and 60 kJ/mol of H-bonds. Properties of several substances suggest that in addition to normal chemical bonding between atoms and ions, there is further interaction involving a hydrogen atom placed between two or more other groups of atoms or ions. This further interaction is often due to hydrogen bonding. Hydrolysis The exchange reaction in which an alkoxy group (OR, where R is an alkyl or aryl group) or other reactive groups attached to the metal are replaced by a hydroxy group (OH on water) in an aqueous or nonaqueous media. For producing glass or ceramics by the sol-gel process, hydrolysis and condensation reactions occur with metal organic monomers and oligomers during polymerization to form gels. Hydrolysis }MOR + H2O°}MOH + ROH Esterification Hydrophilic “Water-loving” species in which layers of water molecules can be strongly adsorbed on the surface of a particle or compound via hydrogen bonds and van der Waals forces. © 2005 by CRC Press

Hydrophilic surfaces exhibit low contact angles (0 to 40°) with water and high surface energies. Hydrophilic surfaces also tend to attract polar species. An example of a hydrophilic surface is a chemically etched glass. Hydrophobic “Water-hating” species in which the surface of the particle or compound repels water molecules. Hydrophobic surfaces tend to attract nonpolar species and repel polar species. The contact angles with water for hydrophobic surfaces can be as high as 150°. Long-chain hydrocarbons and fluoride groups provide hydrophobic surfaces. Hydrothermal Processing Processing that uses water under high pressure and temperature to speed up the reactions between solids. In this method, materials are exposed to steam at high pressures and temperature in a pressure vessel. The temperatures are normally higher than 100°C (above the boiling point of water), and pressures are a few hundred (5 to 15 × 10–3 MPa) to a few thousand psi (5 to 15 × 10–2 MPa) corresponding to the vapor pressure of water at the reaction temperature. Several materials including fine powders and single crystals are prepared by hydrothermal processes, in which crystallization can occur at lower temperatures by creating extreme conditions of high pressure. Hydrothermal processes can also be used for leaching, material separation, and purification. Hydroxo Ligand Ligand (} M OH) also referred to as hydroxy ligand, formed by hydrolysis or hydroxylation of metal organic compounds and metal salts. Hypercritical Drying See supercritical drying. Hysteresis A nonlinear memory effect observed in many materials. A material is said to have hysteresis when an external stress or field (e.g., electric or magnetic) or other force is applied, a strain or change in properties (e.g., polarization, magnetization) is observed, and the material still possesses a residual effect after the external stress or field is removed. Hysteretic behavior is observed in phase transitions, thermal cycling, mechanical stress-strain relationships, electrical polarization, and magnetization behavior.

I Ilmenite A group of phases with the composition ABO3, where A is Fe, Co Ni, Cd, or Mg and B is Ti, Rh, or Mn. The structure of ilmenites is an approximately a hexagonal closed packed array of oxide ions, with cations occupying two thirds of the octahedral sites. Along the c-axis, cations A and B occupy the octahedral sites in alternate layers of the three-dimensional structure. Incongruent Melting Point At the incongruent melting point (or peritectic point), a solid melts to form a new solid phase and a liquid. For example, MgSiO3 incongruently melts at 1557°C to form a solid Mg2SiO3 plus a liquid containing about 61% SiO2. Inductive Effect During polymerization processes (e.g., sol-gel process), phenomena that occur when the rate of condensation or other reactions is affected indirectly by the functional groups attached to the metal center. For example, the bulkier (butoxy) group on the precursor tends to condense slower than smaller groups (methoxy) in a polymerization reaction. Inductively Coupled Plasma (ICP) Spectroscopy An elemental analysis technique in which samples are injected into the core of the plasma causing vaporization, atomization, ionization, and excitation of the sample constituents and the resultant species are detected by atomic emission spectroscopic (AES), atomic fluorescence spectroscopic (AFS), or mass spectroscopic techniques. The advantages of ICP-related techniques compared to other elemental analysis techniques include the ability to conduct multielement analysis, high sensitivity (2 to 3 orders of magnitude higher), high accuracy (1 to 3% with a standard), and the ability to conduct isotopic analysis.8a Inelastic Scattering A condition in which a set of particles is deflected by collision with other particles, causing a net energy loss. For example, the inelastic scattering condition is satisfied © 2005 by CRC Press

when particle A collides with particle B of finite mass and particle A loses energy but no energy is transferred to particle B. Inert Gases Also referred to as noble gases; the elements of Group VIIIA or 0 in the periodic table. These elements have completely filled outer shell electron configurations and, as a result, are very unreactive. However, some compounds of inert gases have been formed with elements from the halogen group. See also Group 0 elements. Infrared (IR) Spectroscopy The vibrational spectroscopy technique, in which pairs or groups of bonded atoms are excited to higher energy by absorption of radiation of appropriate frequency, and as the frequency varies, the quantity of radiation absorbed changes. The IR spectra are plots of change in intensity of absorption as a function of frequency or wave number, which provide molecular information on the local structures, bond type, and elemental composition. The IR frequency ranges from 0.8 to 15 µm, where the near IR range falls between 0.8 and 3 µm, the mid-IR range is between 3 and 6 µm, and far IR falls in the 6 to 15 µm range. IR spectroscopy is most frequently used for distinguishing between aromatic and aliphatic groups, for identifying functional groups in the molecule (OH, CO, COOH, CN, NH2, etc.), and for identifying metal heteroatom (X) bonds, where X can be O, Cl, S, N, B, etc. Inosilicates Chain metasilicates [SiO32 ]h formed by corner sharing of [SiO4] tetrahedra. Instantaneous Elastic Strain The reversible strain that develops immediately after stress is applied to a viscoelastic material. The strain developed has two other components: delayed elastic and viscous. See also viscoelasticity. Insulator (electronic) A material that does not conduct electricity because its energy bands are either completely full or completely empty or the band gap is greater than several electron volts. See also band theory and conductor. Intercalation Compounds Layered porous structures with the ability to absorb and bond with the extra atoms or ions of the absorbed species. The interlayer spacing in the intercalate compound varies with the adsorbed species. These compounds are used in adsorption, ion exchange, and separation-type processes. Some examples of intercalation compounds include graphite, MoS2-type compounds, hydroboric acid, and clays. Interconnected Pores In porous materials, the pores that are not closed and are often referred to as open pores. Interconnects Metal connections used in multilayer metallization of microelectronic devices to electrically connect one layer of the device to another layer above or below. Common low resistivity interconnect materials include aluminum and copper. Interface Site Factor The fraction of sites for the attachment of atoms or ions during phase transformation in the nucleation and growth process. Intermolecular Forces Nonbonding forces (e.g., dispersion or van der Waals forces, dipoledipole, hydrogen bonding) that account for the attractive interactions between molecules and between inorganic surfaces and molecules. Interplanar d-Spacing The distance between two adjacent planes in a three-dimensional array of atoms. In x-ray diffraction patterns, the material composition, phase, and crystallinity of a material is identified by the d-spacings corresponding to the Bragg’s diffraction angle. Interstices In crystal structures, the holes (space between anion spheres) created by the anion arrangement of close-packed arrays that are normally occupied by cations. Interstitial Solid Solutions The solid solutions arising from the introduction of a foreign species (defect) into sites that are normally vacant in the crystal structure. See also solid solution. Intrinsic Defects Defects present in pure materials without intentional introduction of foreign species. For example, the displacement of an Ag+ ion in the AgCl structure is an intrinsic defect. See also Frenkel and Schottky defects. Intrinsic Semiconductors Pure materials (undoped) with a band gap small enough to thermally excite the electrons from the valence band to the conduction band. For example, silicon is an intrinsic semiconductor with a small band gap (1.1 eV) between conduction and valence bands. © 2005 by CRC Press

For every electron thermally excited across the band gap to the conduction band there are an equal number of electron holes remaining in the valence band. See also extrinsic, dopant. Ion Exchange Reactions The reversible exchange of ions of the same charge (positive or negative) between a solution (normally aqueous) and an insoluble solid in contact with it. Porous clays with layered structures frequently exhibit cation exchange in the anion array of open layers or interconnected channels. For example, in the G-alumina structure, the sodium ion can be exchanged with other cations such as Li+, K+, Rb+, Ag+, Cu+, Tl+, NH +4 , In+, Ga+, NO+, and H3O+. Ion Implantation At acceleration energies above about 10 keV, charged ions penetrate many atomic layers into a material and rearrange its crystal structure. By controlling implant energy, dose, species, and postimplant annealing, ion implantation can be used in conjunction with patterned masks to electrically isolate or pattern select regions of thin films or to create embedded devices such as resistors. Since no material is removed by ion implantation (as opposed to ion beam etching), the film remains planar, although it may swell. Ionic Conduction The transfer of electric charge with charged ions, vacancies, or interstitials, typically in solids at high temperatures (e.g., ZnO, ZrO2). The defect concentration of vacancies, in particular, is temperature dependent. These materials can be used as oxygen sensors, ion pumps, or components of fuel cells. See also fast ion conductors. Ionic Structures Structures that result mostly from ionic bonding with complete transfer of electrons. In ionic structures, there is some degree of covalent bonding (shared electrons) between the atoms. For example, NaCl, LiF, and BaCl2 have ionic structures with cations and anions surrounded by the opposite charges. These ionic structures can conduct electricity via ions (e.g., halides and oxides), and, as a result, they are also called ionic conductors. Ionization Energy (IE) The energy required to remove electrons from the outermost electron shells of the atom. Ion Scattering Spectroscopy See secondary ion mass spectrometry. IROX A commercial coating composed of TiO2 and Pd, used for architectural glass. IROX coatings alter reflection, absorption, and transmission characteristics of the glass. Isobutoxy Isobutoxy is an alkoxy ligand to a metal center consisting of a secondary carbon, i.e., OCH2CH(CH3)2. See also butoxy. Isocyanate A compound containing a ligand with the carbon–nitrogen bond RN=C=O, where R is an alkyl or an aryl group. Isoelectric Point (IEP) A condition of a suspension in which the electrical mobility of the particles in the sol is zero. In a silica colloidal suspension, the IEP is close to a pH of 2. At the IEP of a sol, the polymerization process is slow and the sols are more stable. Isomers Compounds that have the same chemical formula but different structures. There are several types of isomers, including conformational (e.g., square planar and tetrahedral geometry), geometric (e.g., cis and trans), optical or enantiomers (e.g., levo and dextro), ionization (e.g., anions inside or outside of the coordination sphere), linkage (ambidendate), coordination, polymerization, and ligand isomers. Isostatic Pressing The process of compacting a material at constant pressure. Isostatic pressing is commonly used in producing compacted ceramic powder prior to sintering. When isostatic pressing is carried out at high temperatures, it is often referred to as hot isostatic pressing (HIP). See also hot pressing. Isotopes Elements with the same atomic numbers (number of electrons or protons) but with different atomic weights (number of protons and neutrons). In other words, the number of neutrons in the nuclei are different in the isotopes. For example, hydrogen and deuterium are isotopes (1H and 2H). Isotropic Isotropic materials are centrosymmetric such that bulk physical properties are uniform in all crystallographic directions: they have no net directionality. For example, most cubic materials such as sodium chloride and most metals are isotropic. See also anisotropic. ISS (Ion Scattering Spectroscopy) See secondary ion mass spectrometry. © 2005 by CRC Press

ITO Indium–tin oxide compositions. ITO systems normally contain 80% or more of In2O3 and 20% or less of SnO2 and are frequently used as antistatic, thermal, and electrically conductive coatings. ITO coatings have numerous uses as electrode materials, especially because the coatings are transparent at visible and infrared wavelengths.

K Kalsilite A member of the family of aluminosilicates, with the chemical formula KAlSiO4 and a framework structure. Kaolin Also known as kaolinite or china clay. An aluminosilicate with the formula Al4Si4O10(OH)3 and a layer-type structure. Karl–Fischer Reagent A chemical composition containing I2, SO2, pyridine, and 2-methoxyethanol in a 1:1:3:1 molar ratio, which is used for quantitative analysis of water present in small quantities in samples. The following reaction leads to a 1:1 stoichiometry between H2O and I2: 3OCH 2CH 2OH H 2O + I 2 + SO2 + 3 pyridine ( py) CH  q[ pyH ][CH 3OCH 2OSO3 ]

This technique has been used as an analytical tool to study the hydrolysis and condensation reactions in the sol-gel process by measuring the amount of water present at progressive stages. Keatite A synthetic form of vitreous silica with a density of 3.010 g/cm3. Keesom Forces The forces between two permanent atomic dipoles that contribute to the van der Waals forces between atoms. Examples of permanent atomic dipoles are polar molecules containing heteroatoms such as HCl and H2O that influence the electron distribution in the molecules. See also van der Waals forces. Keggin Structure A polymetallate cage structure with the formula [Xn+M12O40](8–n)–, where M is W or Mo and X is Si, Ge, P, As, Ti, Zr, etc. The polymetallate structures normally consist of metal oxide octahdera (MO6) joined by shared edges such that the opposite sides are displayed. The groups of octahedra are then attached to each other by corners creating cavities for X ions. Kernite A borate mineral with the formula Na2B4O7 · 4H2O. Kieselguhr The term originating from the German words Kiesel (flint) and Guhr (earthy deposit). Kieselguhr is mainly composed of silica. Kinematic Viscosity The viscosity, v, is the measure of the resistive flow of a fluid under gravity and is given by v = M/W

where M is the dynamic coefficient and W is the fluid density. The kinematic viscosity is expressed in square centimeters per second (or centistokes) and can be converted to absolute viscosity (centipoise) by multiplying v by the fluid density.9 Kinetic Molecular Theory Gas molecules are considered to have a kinetic energy distribution whose average speed increases with temperature. This kinetic energy gives rise to gas pressure. Kinetic molecular theory can also be used to describe molecular collision frequency, the equilibrium behavior of liquids and gases, and the growth of thin films by vapor deposition. Kink Monoatomic step edges are typically not atomically straight but contain kink sites, which are the termination points of extra (or missing) rows of atoms along the step edge. They are important as adatom incorporation points during crystal growth and thin film deposition. See also terrace-step-kink model. © 2005 by CRC Press

Knudsen Diffusion The movement of molecules under conditions in which the pores of a gel or structure are so small that the vapor molecules collide with the walls more often than with each other. Koch Cluster A large cluster defect extending symmetrically in three dimensions (unlike point defects such as Frenkel or Schottky defects) that has been proposed for a wustite, Fe1-xO, structure containing a deficiency of iron. The oxide ions occupy the corners and the face centers of the cube, and the edge centers and one body center octahedral sites (which are occupied by iron in FeO) are empty; however, four of the eight possible tetrahedral sites contain Fe3+ ions such that a unit cell can be divided into eight smaller unit cells where anions are present on the three corners and one cation is present at the face center position of the four cells only. Kurrol’s Salt A crystalline compound derived from heating sodium polyphosphate. The salt structure consists of unbranched chains of corner-shared [PO4] units.

L Labile Ligands to the metal centers in organometallic or metal organic precursors that are considered reactive and exchange or react readily with another component in the reaction. For example, hydroxyl (OH) groups on metals in the sol-gel process are labile, since they either condense with another OH group or an alkoxy group (OR) or can be replaced by an alkoxy group (esterification). Ladder Polymers Like organic polymers, inorganic polymers that comprise an uninterrupted series of rings connected by links around which rotation cannot occur except by bond breaking. Since all bonds are equally strong in ladder polymers, they tend to have high thermal stability compared with simple polymers. Several silicones form ladder polymers in which the tetrahedral symmetry around the silicon atom is maintained. Ph Si Ph O O Si O Si O O O Ph Si Ph

Ph Ph Si Ph Si Ph O O O O Si Si O O Si Si O O O O O O Si Ph Si Ph Ph Ph

Ph = C6H5

Ladder Polymer (hypothetical Phenylsilicone Resin)

Lamellar Structures Layered structures of compounds with open porosity such as graphite, MoS2, boric acid, and some ion-exchange materials. See also intercalation compounds, selfassembled monolayer. Langmuir A unit of gas exposure (1.33 x 104 Pa-sec or 10-6 torr-sec) that will cover a surface with a monolayer of gas molecules, assuming a sticking coefficient of unity. See also sticking probability. Langmuir Adsorption Isotherm 6=

Kp 1+ Kp

A measure of fractional coverage of a gas adsorbate on a surface, 6, as a function of gas partial pressure, p, at constant temperature, where K is an equilibrium constant. This model assumes that (a) adsorption is finished upon completion of a full monolayer; (b) any gas molecule that © 2005 by CRC Press

strikes an already adsorbed gas molecule is reflected back from the surface; (c) the surface is homogeneous; and (4) the adsorbed species are noninteracting. See also BET method. Langmuir Film A monomolecular film of water-insoluble amphiphilic molecules that form on water with the hydrophilic group oriented toward the water. For example, octadecanoic acid in benzene will form a Langmuir film in water. The benzene solution spreads on the water surface, then evaporates and leaves the octadecanoic acid behind. See also amphoteric behavior, LangmuirBlodgett film. Langmuir-Blodgett (LB) Film The transfer of one or more layers of self-assembled monomolecular film (also called Langmuir film) from the surface of a liquid to a solid surface upon repeated immersion and emersion of the solid into the liquid. LB films have been proposed as possible resists or as nanoscale dielectrics in the field of molecular electronics. Lanthanides Also referred to as rare earths. Lanthanides are elements in a row of the periodic table that includes lanthanum (La) to lutetium (Lu). Laser Materials Ceramic or glass compositions used as hosts for solid-state lasers and as window materials for gas lasers. Lasers are materials that luminesce when they are excited. Laser stands for light amplification by stimulated emission of radiation. Examples of solid-state laser compositions include Cr-doped single-crystal alumina; Nd-doped crystalline YAG (Y3Al5O12); and Nd-, Yb-, Ho-, or Tm-doped glasses. Examples of window materials for gas lasers include Al2O3 (1- to 2-µm operation range), alkaline earth halides (e.g., CaF2, ~5-µm operation), alkali halides, and some Group II to VI compounds (e.g., ZnSe, CdTe, ~10-µm operation). Lasers have been used for producing fine particles, for film deposition (e.g., laser ablation film deposition technique), and for sintering or densifying ceramics close to theoretical densities at a much faster rate than traditional furnace heating techniques. See also solid-state laser. Lattice The repetition of atoms, ions, or molecules in a crystal, forming an array of points. See also crystal systems. Lattice Defects A defect cluster in a three-dimensional arrangement of atoms. See Koch cluster. Lattice Diffusion During the sintering process, the diffusion process that brings the materials from the convex regions of the particles to the neck region (point of contact) through the crystal lattice. However, this process does not densify the material, but coarsens the neck region and enlarges the pore sizes in the system. The material transport during sintering normally occurs via four paths: surface diffusion, lattice diffusion, evaporation, and boundary diffusion. Layer Structures See lamellar structures and intercalation compounds. Leatherhard Point A critical point during the clay-drying process in which the material stops shrinking and is able to withstand the capillary pressure of the residual liquid. Beyond the leatherhard point, additional energy is required to densify the material by collapsing the pores. Leaving Group Ligands or parts of ligands normally classified as anions or Lewis bases that are displaced from a complex by breaking the bond with the cations or Lewis acids owing to the reaction between the components or ligand substitution by another group. In sol-gel reactions, H2O acts as a good leaving group during condensation reactions to form metal oxides. LEFM See linear elastic fracture mechanism. Lepidocrocite An iron hydroxide with the formula L-FeOOH. Lepidoidal Silica The flakes formed as a result of freezing silica sol. Lever Principle The graphic presentation (phase diagram) of the composition of a multicomponent system. To determine the fraction of phase A present in the system, the distance from the phase A to the overall system composition (A + B) is divided by the distance from the phase A boundary to the phase B boundary. Lewis Acid Substances that accept electrons (metal centers). For example, metals in organometallic or metal organic compounds are Lewis acids. Lewis Base Substances that donate electrons (ligands). For example, butoxy, methoxy, propoxy, and acetylacetonate ligands are Lewis bases to the metal center in metal organic compounds. © 2005 by CRC Press

Ligand Groups that are mostly composed of organic materials with no metals or metalloids and that attach to the metal center in a chemical compound or a polymer. For example, alkyl, aryl, and alkoxy are ligands to metals in organometallic and metal organic compounds. Ligands can be classified into uni-, bi-, tri-, quadri-,… dendate, corresponding to the number of donor atoms (1, 2, 3, 4,…) in the ligand. Unidendate ligands include methoxy-, ethoxy-, and isopropoxytype ligands, whereas bidendate ligands are frequently chelating ligands (see chelates) such as acetates and ketonates. Ambidendate ligands possess more than one donor atom and can coordinate through either one or the other. Bridging ligands are those in which a donor atom in the ligand is shared between two metal or metalloid centers, whereas in terminal ligands, the donor atoms are not shared. Light Emitting Diode (LED) A forward biased diode in which the recombination of electrons and holes emits photons with a narrow wavelength distribution (often monochromatic) under the application of an electric potential. Multilayers of GaAsP (GAP) or doped GaN are common LED materials. LEDs consume less energy, generate less heat, and have longer lives than standard incandescent lights. See also organic light emitting diode. Light Scattering A phenomenon where the path of light is changed as a result of collision with particles. Light-scattering methods are used for measuring particle sizes in colloidal systems. Lime Calcium oxide (CaO). Limonite An iron ore with the formula 2Fe2O3 · 3H2O. Lime Stone A calcium carbonate mineral with the formula CaCO3. Linear Elastic Fracture Mechanism (LEFM) The fracture mechanism in which the crack of the material is large enough and the stress intensity has reached the critical intensity factor such that as the crack growth proceeds, the speed of fracture increases, reaching the speed of sound. Line Defects See dislocation. Linkage Isomer See isomers. Liquid Chromatography A chromatographic technique that identifies the components in the liquid mixture, particularly high-molecular-weight components and thermally unstable compounds. This technique is useful for separating high-molecular-weight compounds. See size exclusion chromatography for further details. Liquid Crystal Fluids that consist of stiff rod-like organic molecules that possess some longrange order. They can be used as flat panel displays by sandwiching them between separately addressable transparent electrodes. An applied bias potential can control the orientation and degree of long-range order and hence control the refractive index and color of the display. Examples of liquid crystals include cholesterol benzoate, DNA, and cellulose. Liquid Phase Sintering In ceramics, after the formation of a green body, the sintering process in which a liquid phase is introduced to invade the grain boundary between particles to help dissolve the solid phase and to provide the transport mechanism. The liquid helps lubricate the particles to slip them into a denser phase. This sintering process provides the material with a route to densify further after green body formation. Lisicon An inorganic solid electrolyte with the highest ionic conductivity identified so far at medium temperatures of 100 to 500°C. The chemical formula of the electrolyte is Li12ZnGe4O16 with a X of 10–1 <–1 cm–1 at 300°C, where the material conducts electricity through the transport of Li+ ions within the crystalline structure. Lisicon is a useful material for batteries. Litharge A lead oxide ore with the formula PbO. Lithia A lithium oxide with the formula Li2O. Lithography The process by which a pattern is transferred to a substrate or surface, often by shining photons through a patterned photo- or shadow-mask onto a photosensitive material such as photoresist. The exposed photoresist is then developed (removed) to reveal the underlying surface, which can be removed or patterned using etching techniques or ion implantation. When used repeatedly with one or more photomasks, etching processes, and thin film depositions, lithography is used to fabricate complex three-dimensional microelectronic devices. Resolution © 2005 by CRC Press

and minimum feature size are typically limited by the wavelength of the radiation used — hence, the development of higher energy electron beam and x-ray lithographies. The drive for even smaller feature sizes (<100 nm) has led to the development of nanolithography, which makes use of such nanofabrication techniques as self-assembly, scanning probe microscopes, molecular electronics, carbon nanotubes, etc. See also nanolithography, photolithography, photoresist, soft lithography. Littleton Point During the annealing process, the point at which the viscosity of the material reaches 107.6 P. See also annealing. Load-Bearing Capacity A qualitative determination of the strength of the refractory material as a function of temperature. Either a fixed deformation (~10%) or a rate of deformation (~1%/10° temperature rise) is considered an end point (deformation) temperature, indicating the loadbearing capacity of a material. London Forces The forces between two transitory atomic dipoles that produce the van der Waals attractive forces between the particles in colloids. Examples of transitory atomic dipoles are nonpolar molecules such as O2 and N2, which produce electrostatic dipole owing to random relative motion of electrons and nuclei of the atoms involved. Long-Range Order A three-dimensional infinite order in the lattice of crystalline materials in addition to the short-range local (atomic) order. For example, crystalline silica (e.g., quartz) possesses a long-range order (hexagonal close packing) in addition to a short-range tetrahedral arrangement of oxide anions around the silicon atom (characteristic of amorphous silica). Low Energy Electron Diffraction (LEED) LEED uses low energy (<500 eV) monochromatic electrons that elastically backscatter from near-surface atoms, yielding surface structural information. Lubricants Fluids or semi-fluids that reduce friction between two moving surfaces by either minimizing or eliminating their contact. An ideal lubricant must also keep the system clean, cool the components, dampen shock, transfer energy, and prevent corrosion. Ludox A commercial colloidal silica commonly used as a nucleating agent and also for forming silicate gels by the sol-gel process.

M Macrocyclic Polyethers Also called crown ethers. Large cycle ethers composed of a repeating ethylene (CH2CH2) unit separated by heteroatoms (such as donor oxygen atoms) to provide a coordination polyhedra appropriate to the cation size in a metal organic precursor. Other heteroatoms included in crown ethers are nitrogen, sulfur, and phosphorus. All crown ethers are potential ligands in inorganic precursors (metal organic) for preparing solid state inorganic materials. In typical examples, the size of the hole in the crown ether can vary from 100 to 500 pm, with a total of 14 to 21 heteroatoms and 4 to 7 oxygen atoms. Macrodefect-Free (MDF) Cement An advanced cement produced in a controlled fashion in which large pores or voids (~1 mm) are absent and the flexural strength (~70 MPa) and fracture energies (~1 kJ/m) are much higher than those of the conventional Portland cement. MDF cements are composed of multicomponent oxides such as Al2O3, SiO2, CaO, MgO, and some phosphates. Macromolecule Macromolecules are large molecules formed by polymerizing monomers with a molecular mass greater than ~1000 Da. A macromolecule is also called a polymer in certain cases. For example, polyamides, long-chain silicates, polypeptides, proteins, and nucleic acids can be classified as macromolecules. Macropores Pores with radii larger than 1000 Å. In some articles, pores larger than or equal to 500 Å are classified as macropores. The macropore analysis of a material is performed by a Brunauer, Emmett, and Teller (BET) nitrogen adsorption method. See also meso- and micropores. © 2005 by CRC Press

Maddrell’s Salt One of the crystalline phosphates formed as a result of heating long chain polyphosphates. For example, cyclic trimetaphosphate, a Maddrell’s salt, is formed by heating anhydrous NaH2PO4 to 250°C. Magic Angle Spinning (MAS) NMR Spectroscopy A type of nuclear magnetic resonance (NMR) spectroscopy used for determining the molecular structure of solids only, in which the samples rotate at a high velocity and at a critical angle of 54.74° to the applied magnetic field. The standard NMR technique, however, is frequently used for liquid samples to determine their molecular structures with high resolution. In liquid NMR spectra, it is possible to obtain information on bonding, coordination number, next-nearest neighbors, etc. In contrast, MAS NMR spectra resolution is not high enough to provide the level of information available in the liquid NMR techniques. See also nuclear magnetic resonance (NMR) spectroscopy. Magneli Phases Intensely colored metal oxide phases formed as intermediates during reduction of MO3 to MO2, where M can be W or Mo. A series of MnO3n-1 stoichiometries are possible between the MO3 structure consisting of corner-shared MO octahedra and the rutile structure consisting of edge-shared MO6 octahedra. The transition between the two structures occurs via crystallographic shear. Magnetic Bubbles The bubble-like domain structure in magnetic materials that can be observed under a polarizing microscope. The magnetic bubbles result from stress-induced magnetization in the direction perpendicular to the surface. The stress originates from cooling certain garnet (magnetic) compositions to room temperature, which are deposited epitaxially on nonmagnetic surfaces. Magnetic Ceramics Materials that possess any magnetic properties such as magnetic dipole moment, magnetic polarization, and spontaneous magnetization. Ferrites, garnets, and ilmenites (all are multicomponent iron oxides) are classes of magnetic ceramic materials. See Chapter 4 for property information on magnetic ceramics. Magnetic Force Microscopy (MFM) A subclass of scanning probe microscopy (SPM) that uses a ferromagnetically coated tip to measure the spatial variation in magnetic forces near the surface of a material. Magnetic Moment (M) The total pole strength, m, of a magnet/material and length, 1, of the magnetized body in M = ml

Magnetic Susceptibility (␹) A magnetic property of a material defined by H = I /H

where I is the intensity of magnetization and H is the magnetic field. Magnetic susceptibility is a dimensionless quantity and is measured relative to the permeability of a vacuum. See also ferromagnetic materials. Magnesite A magnesium mineral with the formula MgCO3. Magnetite An iron oxide with the formula Fe3O4. Magnetocrystalline Anisotropy The energy required to rotate the orientation of the magnetization from the preferred direction within the unit cell of a magnetic crystal. For example, the preferred (easy) direction in an iron structure is parallel to the axes of the cubic unit cell. For use as permanent magnets, materials (e.g., iron) are required to have high magnetocrystalline anisotropy. Magnetoplumbite An iron mineral with the formula PbFe12O19. © 2005 by CRC Press

Magnetoresistance (MR) The change in a material’s electrical resistance under the application of an applied magnetic field. See Table 2.3 for comparison of percent change in electrical resistance for different types of MR materials. See also anisotropic magnetoresistance, giant magnetoresistance, colossal magnetoresistance.

Table 2.3 Type of Magnetoresistance MR AMR GMR CMR

% Increase in Resistance 1% 20% 200% 100,000%

Magnetostriction The ability of many magnetic materials to change shape as a result of magnetization. For example, a small change in the length of a magnetic material resulting from zero to saturated (all spins aligned) magnetization indicates that the material is magnetostrictive. Magnus Salt The platinum chloroamine salts. For example, the Magnus green salt is [Pt(NH4)4][PtCl4] with a square planar arrangement of anions and cations stacked to produce a linear chain of platinum (Pt). Malachite A copper mineral with the formula Cu2CO3(OH)3. Malathion A diphosphate ester, (CH3O)2P(S)SC(CH2CO2C2H5)HCO2C2H5. Manganocene A cyclopentadiene sandwich compound of manganese with a structure similar to ferrocene. See also ferrocene. Martensitic Transformation A crystalline transformation that occurs in various metallic and ceramic crystalline systems, by which a shearing mechanism creates plates of product crystal within the parent crystal. Although the composition of the parent and the plate is similar, the crystal structures are slightly different. The transformation process is not completed at a defined temperature but occurs over a wide range of temperatures. Zirconia undergoes martensitic transformation from monoclinic to tetragonal phases, and vice versa, when it is heated to temperatures of 600 to 1200°C. Mask A pattern usually made in a chrome metal film on glass or quartz, which acts as a photographic negative for transferring a chip design or pattern to a substrate. See also lithography. Mass Spectrometry (MS) A spectrometric technique used for identifying the molecular species through the fragmentation pattern (intensity vs. atomic mass unit fragments) obtained as a result of electron impact (EI), chemical ionization (CI), ion trap (IP), and other such processes. This technique is used to identify the organic and inorganic compounds up to an approximate limit of 5000 atomic mass units (amu). Information can also be derived about the functional groups and structures of molecules and the presence of heteroatoms. However, the technique has limitations in quantitative analysis. The MS technique can be coupled with other techniques such as gas chromatography (GC) to separate and identify various species in the mixture. Mean Free Path In Brownian motion, the mean of the path length covered by a species or particle before it collides with another species or particle. Meissner Effect The complete exclusion of an external magnetic field as a material becomes superconducting. A perfect diamagnetic material would not exclude an already applied magnetic field. See also diamagnetism. Membranes Freestanding films with pore sizes of less than 50 nm used for filtration purposes. Membranes can be prepared by the sol-gel process or other ceramic leaching processes. Glassy and ceramic membranes have the advantage of operating at higher temperatures than polymeric © 2005 by CRC Press

membranes. Membranes are used for filtering solid particles from liquids and gases and for purifying or separating a gas from a mixture of gases. Meniscus In a cylindrical capillary, a liquidvapor interface with a hemispherical shape and a radius of curvature of a/cos V, where a is the radius of the tube and V is the contact angle of the liquid. Mercaptons A class of sulfur compounds with the formula RSH, where R is an alkyl or aryl group. Mercury Porosimetry A technique used for measuring porosity, pore size distribution, pore shapes, and surface area of a sample with a minimum pore size of 18 Å. This technique involves evacuating all gases from the porous sample and filling the pores with mercury under vacuum with a maximum applied pressure of 60,000 psi. Pressure is a applied to force the mercury into interparticle voids and intraparticle pores, and the intruded volume is measured as a function of applied pressure to obtain information about the pore size and porosity content of the material. Mesopores Transitional pores with radii between 20 and 500 Å. The mesopore size normally falls between macro- and micropore sizes.10 Metal Organic Compound A compound in which organic ligands are attached to metal or metalloid atoms via heteroatoms other than carbon. Alkoxides and ketonates are examples of metal organic compounds in which alkoxy (OR) and ketonates [OC(CH3)CHC(CH3)O] ligands are bonded to metal via the oxygen atoms. Metal Organic Compounds H CH3 C O CH3 H3C H C O Ti O C H H3C CH3 O C H3C CH3 H H3C

OCH3 OCH3 Al OCH3

Aluminum (III) methoxide

Titanium (IV) isopropoxide

Aluminum (III) pentanedionate

CH3 CH3

CH3 HC C CH3 C O O C O Al CH O O C C O CH3 HC C CH3

Metal Organic Decomposition (MOD) A material synthesis method (for thin films or powders) by which metal organic or organometallic compounds are either decomposed themselves or dissolved in solvents, then decomposed to form a film on a substrate or a powder composition without the use of vacuum or gel powder techniques. For example, a carbosilane oligomer mixture dissolved in a solvent is deposited on a substrate and heat-treated from 600 to 800°C to form an SiC film.11 Metallization The electrical interconnection or wiring of various microelectronic devices (e.g., transistors) to form a functioning device. Metallization controls a circuit’s impedance losses, device speed, and thermal management. Miniaturization of microelectronic circuitry is often © 2005 by CRC Press

limited by the ability to pattern planar and interconnected (between different layers) wiring. Copper is currently the state-of-the-art metallization material in the microelectronics industry, with a resistivity of 1.7 µ<-cm, although carbon nanotubes are being considered for nanoelectronic metallization applications. Metallorganic Chemical Vapor Deposition (MOCVD) The use of gaseous organometallic and metal hydride species to grow high quality epitaxial thin films (often of III-V compounds such as GaAs and GaN) with atomically sharp interfaces. MOCVD is similar to vapor phase epitaxy (VPE) and molecular beam epitaxy (MBE). Metals Elements that conduct electricity very easily, with values of conductivity, X, in the range of 104 to 106 <–1 cm–1. The high conductivity results from electrons present in the conduction band. See also band theory. Metaphosphates Phosphate compounds with a structure similar to metasilicates, where PO4 tetrahedra are linked, forming chain and cyclic structures. See metasilicates.  Metasilicates Silicate salts in which SiO32 –(SiO3 )2n ions share two corners of the polyhedra to n form ring and chain structures. See also orthosilicate and pyrosilicate. Metasilicates O

O Si

O O O Si Si O O O O O Si Si O O O O O Si O O O

(SiO3)2-2

O Si

O Si

O Si

O Si O O O O O O O O (SiO3)n-2n

Metastable Phases Phases that are only partially thermodynamically stable but are kinetically stable. Metastable phases are also called nonequilibrium phases. A titanium oxide polymorph, TiO2(B), is a metastable phase of TiO2 and has a structure similar to its presursor, K2Ti4O9, instead of the structures of other TiO2 polymorphs, rutile, anatase, and brookite. Also, hexagonal WO3 is a metastable form of tungsten oxide, whereas the stable form of WO3 is monoclinic. Methoxy An alkoxy ligand with the formula OCH3, by which methyl is an alkyl ligand with the formula CH3. Methoxy ligand normally bonds to metal in metal organic compounds via the oxygen atom. Micas An number of aluminosilicate clay minerals including muscovite [KAl2(OH)2(Si3Al)O10] and phlogopite [KMg3(OH)2(Si3Al)O10]. Micelles The general term for an individual body of an aggregate with a globular, cylindrical, or platelike shape. These shapes are often formed by the ordering of long chain amphiphilic molecules, which try to effectively isolate the hydrophobic chains (or tails) from aqueous solutions, thus forming bilayers with the hydrophilic head groups in contact with the liquid. Microcontact Printing A soft lithographic method for applying submicron scale or larger patterns of monomolecular layers to surfaces. First, a negative topographic mold is made on a hard © 2005 by CRC Press

surface such as silicon by using standard lithographic techniques. Next, a liquid polymer such as polydimethylsiloxane (PDMS) is poured over the mold, allowed to harden, and then slowly removed to reproduce the features of the master. The PDMS stamp can be coated with an ink of self-assembled monolayers (SAMs; e.g., alkanethiols) or other organic or biomolecules, which when brought into contact with a surface (e.g., gold, glass, etc.), allow the transfer of molecules only to those parts of the stamp that touch the surface. This pattern can then be used to chemically etch the exposed regions of the surface, control the self-assembly of other alkanethiols with different tail group chemistry, or allow selective electrodeposition at exposed regions. MicroElectroMechanical System (MEMS) Mechanical elements such as gears, actuators, mirrors, and microfluidic passages fabricated on a substrate using variations of common microelectronic fabrication techniques. See also nanoelectromechanical system. Microfluidics The flow of liquids and gases in channels that are generally 10 to 100 µm wide and are often fabricated using standard MEMS or soft lithographic techniques. Micropores Pores with radii smaller than 15 Å. This size of pores in materials is frequently analyzed by the Brunauer, Emmett, and Teller (BET) nitrogen adsorption method or scanning electron microscopy (SEM). See also macro- and mesopores. Microprobe Mapping See electron probe microanalysis (EPMA). Microstructure The information on the phase distribution, grain size and shape, domains, and defects constitutes the microstructure of a material. The microstructure of suspensions, gels, powders, monolithic parts, films, and fibers can be studied by a variety of techniques, including microscopy and light scattering. See also optical microscopy, scanning electron microscopy, and transmission electron microscopy. Microsyneresis The process of phase separation in a suspension by which the polymers or agglomerates cluster together, creating regions of free liquid. The driving force for affinity of the polymer or agglomerate for itself increases compared with the affinity for the pore liquid, thereby promoting phase separation. Miller Index Three numbers (a, b, c) assigned to each lattice plane in a crystal structure, where the lattice planes are imaginary and simply provide a reference grid to which the atoms or ions in the crystal structure may be referred. For example, Miller indices (101) and (100) correspond to the planes through the diagonal of a cube (with b = 0) and the side face (a) of the cube, respectively. Mineralizer Any compound added to an aqueous solution to speed up the crystallization process. For example, quartz has low solubility in water; hence, to grow large crystals of quartz, a small amount of NaOH mineralizer is added to the aqueous solution of quartz to facilitate crystallization. Addition of a mineralizer is very common in hydrothermal processing to produce crystalline materials. Mirror Plane A symmetry plane in a molecule or ion in which two halves created by the mirror plane are interconvertible by the imaginary process of reflection across the plane. Mixed Alkali Effect The effect corresponding to the lower mobility of each cation in glass compositions containing two or more alkali ions, as compared with the mobility of pure cationic species themselves. The mixed alkali composition results in reduced mechanical loss and increased dielectric loss in several glasses. See also dielectric materials. Mixed Conductors Mixed conductors are generally ionic compounds at high temperatures, in which electrical current is carried by a mixture of conduction electrons (or holes) and mobile charged ions. See also transference number. Mixed Valence Compounds Compounds in which the metal center exists in two oxidation states. For example, KCr3O8 is a mixed valence compound in which Cr exists in III and VI oxidation states; the formula can be more accurately written as KCrIII(CrVIO4)2. Mobility The average drift velocity at which electrons, holes, or ions move through a material under the application of an applied field. It is measured in units of cm2/V-sec. Modulus of Elasticity The ratio of applied stress (tensile) to the normal strain. © 2005 by CRC Press

Modulus of Rigidity The ratio of applied stress (shear) to the strain. Mohr’s Salt An iron salt with the formula (NH4)2SO4FeSO4 · 6H2O, which is used as a standard reducing agent in volumetric analysis. Molarity A solution concentration unit for the number of moles of solute in one liter of total solution. Molality A solution concentration unit for the number of moles of solute in one kilogram of solvent. Molecular Beam Epitaxy (MBE) An utlrahigh vacuum (UHV) physical deposition technique for making high quality epitaxial thin films at relatively low temperatures compared with vapor phase epitaxy (VPE) and metallorganic chemical vapor deposition (MOCVD). The gas sources for MBE, which include electron beam sources and gas sources, are often brought to high temperatures to ensure volatization of the species; however, the substrate upon which the film is depositing is kept at significantly lower temperatures to reduce dopant and impurity diffusion. Molecular Electronics The use of small organic molecules as electronic components such as rectifiers, amplifiers, data storage arrays, or molecular wires. For example, small molecules can be carefully placed between electrodes and shown to behave like diodes. Molecular Sieves Aluminosilicates with a three-dimensional network of AlO4 and SiO4 tetrahedra linked by shared oxygens. Since the pores in the cages can be tailored in size and shape (one-, two-, or three-dimensional), these cage materials are used as sieves; hence the name. For example, the commercial molecular sieve 13X, produced by Linde, has an oxide formula Na2O · Al2O3 · 2.5 · SiO2 · 6H2O with a 10-Å pore size and is commonly used for absorbing water in an organic system.12 See also zeolites. Molecular Tectonics The use of nonbonding intermolecular attractive forces to induce selfassembly of molecules into one-, two-, or three-dimensional supramolecular structures or networks. See also nanotechnology. Molten Salts Liquid inorganic compounds that are often at high temperatures and are typically used as etchants and electrolytes and for materials synthesis. Monazite Lanthanide minerals with the general formula MIIIPO4, where M can be Ce, La, Y, Th, or their combinations. Monoclinic Symmetry A unit cell in which the cell parameters a, b, and c are unequal (a | b | c) and F and L angles are equal to 90° (F = L = 90°), but angle G is not equal to 90° (G | 90°). The unit cell also exhibits a twofold rotation axis. At room temperature, the zirconia (ZrO2) crystal structure can be described by monoclinic unit cells. Crystals of gypsum (CaSO4 · 2H2O) also exhibit monoclinic symmetry. Monodispersed Particles A system (e.g., suspension) containing particles of approximately equal size. As a result, the particle size distribution of the suspension is very sharp. Uniform particle size is said to facilitate preparation of stable suspensions, as well as dense, uniform compact powders for sintering purposes. Monolayer A single layer of atoms (or molecules) that is chemisorbed or physisorbed onto a material’s surface (i.e., the substrate). These monolayers tend to form ordered arrays (or induce ordered surface reconstructions) and posses a direct crystallographic relationship to the underlying substrate surface lattice. The properties of real surfaces are often determined by the presence of an adsorbed atomic monolayer. A full monolayer is often defined as one atom or molecule for each unit cell of the unreconstructed surface. Monolayer Capacity The ability of a solid surface to adsorb a certain number of moles of a gas per unit gram of solid corresponding to a monolayer of gas molecules on a solid surface. This method is frequently used in the BET technique to measure the surface area of powders and monolithic materials. Monolith An object cast as a single piece with dimensions normally greater than a few millimeters. Monomer A compound or particle with a minimum functionality of 2 to form polymers (i.e., a compound with the ability to form two bonds). A silica particle with reactive surface groups © 2005 by CRC Press

can be a monomer for a silica aggregate, or Si(OCH3)2(CH3)2 can be a molecular monomer for a silica chain polymer. Monomer–Cluster Aggregation A growth pathway for oligomers and polymers to grow in size in a suspension by preferentially condensing the monomer with the cluster rather than with other monomers via physical or chemical bonding. Monomolecular Films Monolayers composed of large organic molecules. Monomolecular films can be formed when a low concentration of an insoluble substance of lower surface energy is placed on another substance (e.g., a solid) of higher surface energy. The insoluble substance will spread out to form a layer one molecule thick provided that the interfacial energy is also low. Monomolecular films are also called Langmuir films. For example, long chain organic molecules often form a monomolecular layer on water. Monomolecular films can also be applied to surfaces using microcontact printing and self-assembly. Montmorillonite A clay with a layered structure and the formula [Al1.67Na (or Mg)0.33] (Si2O5)2(OH)2. Montmorillonite has been extensively used as adsorbent, ion exchange material, and catalytic support. Morphology The particle size, shape, microstructure (surface characteristics), porosity, and particle size distribution of a material system. Mossbauer Spectroscopy Spectroscopy in which the absorption of monochromatic L-rays by the sample is monitored as a function of energy (or source velocity), resulting in a spectrum with poorly resolved peaks. The spectra provide information on local structure in a solid-state material, such as oxidation state, coordination number, and bond character. The spectroscopy is based on the principle that if the source and the sample are the same, a single-line spectrum is obtained; however, if the source is slightly different or is moved at a certain velocity with respect to the sample, then a multiple-peak spectrum is obtained. Mossbauer spectroscopy has been limited to mainly 57Fe, 119Sn, 129I, 99Ru, and 121Sb nuclei that emit and absorb L-rays. This technique has been applied in mineralogy to distinguish between Fe2+ and Fe3+ cations and to check the purity and crystallinity of the materials. Mullite An aluminosilicate refractory with the formula 3Al2O3 · 2SiO2. See Chapter 3 for material properties. MultiChip Module (MCM) The integration or packaging of two or more chips into a larger device. Multicomponent Systems Systems containing more than one type of a compound. In these multicomponent systems, two components may be chemically bonded, which in some cases may change the coordination numbers of the atoms involved. For example, silica is a singlecomponent system, whereas mullite, 3Al2O3 · 2SiO2, is a multicomponent or two-component system containing alumina and silica in a molar ratio of 3 to 2. Muriatic Acid Also called marine acid. The name is occasionally used for hydrochloric acid (HCl), a mineral acid. Muscovite A mica composition with the formula KAl2(OH)2(Si3Al)O10.

N n-Butoxy See butoxy. n-type Electrons are the primary charge-carrying species in an n-type material (e.g., P doped Si). Nanobiotechnology The use of micro- and nano-fabrication methods to study biosystems, including the fabrication of inorganic-biological hybrid systems for the investigation of directed cell growth, biosensors, and protein chips or microarrays. Conversely, nanobiotechnology is also the use of biological systems as models to develop better micro- and nano-scale devices (e.g., biomimetics). © 2005 by CRC Press

Nanocomposites Similar to composites, but one or more of the filler materials have at least one of their physical dimensions at the nanoscale. For example, nanotubes are used as fillers in polymers to increase their electrostatic interactions with certain types of paints. See also nanotechnology. NanoElectroMechanical System (NEMS) Similar to microelectromechanical systems (MEMS), but one or more of the device components have nanoscale dimensions. Nanofabrication Fabrication techniques such as e-beam lithography, self-assembly, and scanning probe manipulation, which are used to form structures and devices at the nanoscale. See also nanolithography. Nanolithography The ability to physically fabricate structures, patterns, or devices in which at least one of the three dimensions of the system is less than 100 nm. Methods include but are not limited to self-assembly, scanning probe manipulation, and miniaturization of standard lithographic techniques. Nanotechnology The use of physical, chemical, and biological fabrication techniques to make structures, patterns, or devices in which one or more of the system’s three dimensions are less than 100 nm. If successfully applied to integrated circuit design, it promises huge increases in device speed and storage density. The development of nanotechnology has been greatly facilitated through the enabling technology of scanning probe microscopy, which allows one to observe, characterize, and manipulate objects at the nanoscale. Areas of nanotechnology include molecular electronics, self-assembly, quantum dots, and nanotubes. Nanotribology Nanotribology is the application of tribology to the nanometer scale of only a few molecules and is of fundamental and practical importance in MEMS, NEMS, and data storage devices. Nanotubes Nanoscale diameter tubes with high aspect ratios typically made from carbon, hence carbon nanotubes. (Boron nitride and tungsten disulfide nanotubes have also been fabricated.) Depending on shape, chirality, and doping, these tubes’ electronic properties can range from insulating to semiconducting to metallic. Their small size suggests that they could be used as components (e.g., nanowires) in fabrication of nanoscale devices such as transistors. See also fullerene, carbon nanotube. Nephelauxetic (Cloud Expanding) Series The series of ligands arranged with increasing ionic sizes and increasing covalent character of the bond between the ligand and the metal center: F –, – – – – H2O, NH3, C2O 2 4 , et (ethylenediamine), Cl , CN , Br , and I . The order of the series is more or less independent of the metal ion involved. Nepheline An aluminosilicate with the formula Na3KAl4Si4O16. Nernst Equation This equation relates the electrochemical potential of a cell, E, to the concentration of electroactive species in solution E = Eo – (kT/ne)lnQ where Eo is the electrochemical potential of the cell under standard conditions of 1 molar concentration and pressures of 1 atm, k is the Boltzmann constant, T is temperature, n is the number of electrons transferred per electroactive species [e.g., n = 2 for Cu2+(aq) species], e is the charge of an electron, and Q is the reaction quotient for the two half cell reactions of the electrochemical cell. Neso-Silicate A type of silicate in which the SiO4 tetrahedra are discrete and no oxygen atoms are shared in the structure (i.e., monomers). For example, orthosilicates, such as Si(OCH3)4 and Si(OC2H5)4, are neso-silicates. Neutron Diffraction Unlike x-ray diffraction, in which the x-rays scatter off of the electron shells, neutrons scatter from the nucleus. In x-ray diffraction, the scattering amplitude has a monotonic relationship with atomic number: the higher the atomic number, the larger the number of electrons and the larger the x-ray scattering amplitude. What makes neutron diffraction so powerful is that there is generally no linear relationship between the atomic mass of the element © 2005 by CRC Press

and the scattering cross-section of the nucleus toward neutrons. Hence, neutron diffraction can detect small amounts of hydrogen in a sample composed of high atomic mass elements, as the nuclear scattering amplitude of hydrogen is quite large compared with most other elements. Nextal® Fibers Alumina fibers produced by the 3M Company with diameters in the range of 8 to 12 µm. Nextel fibers are extensively used in composite fabrication. Nitramide A weak nitrogen acid, H2NNO2, that decomposes into N2O and H2O by a basecatalyzed reaction. Nitridation The process of converting MX bonds to MN bonds, where M is a metal or metalloid atom and X is an oxygen atom or other such ligand (chloride, sulfide, etc.). Nitridation is normally performed in ceramic materials to convert MO bonds to MN bonds to form nitrides from oxides. The conversion continues until nitrogen achieves a trigonal coordination with the surrounding metal sites. Nitrogen plasma, ammonia, and other such reagents are used for the nitridation process. Nitrides Ceramic materials with the general formula MxNy, where M is a metal or metalloid. Most nitrides are structurally robust and thermally conductive with better oxidation and corrosion resistance properties at higher temperatures (above 1000°C) than other high-temperature ceramics. Common examples of such nitrides include Si3N4, AlN, and BN. Nitrogen Ligands Ligands that contain nitrogen atoms such as nitrates (NO3 ), nitride (N3–), azides ( N3 ), nitriles or cyanides (CN–), nitrite ( NO 2 ), isocyanides (NC–), amide ( NH 2 ), imide (NH2–), nitrosyl (NO), nitroxyl (HNO), and orthonitrate (NO4)3. Nitroprusside Ion The iron-nitrogen anion [Fe(CN)5NO]2–. NMR Spectroscopy See nuclear magnetic resonance spectroscopy. Noble Metals Generally unreactive, highly stable metals such as gold, platinum, palladium, rhodium, ruthenium, silver, iridium, and copper. Their relative inertness makes them ideal for jewelry and microelectronic applications. Nonaqueous Solutions that contain solvents other than water or a mixture of water and other solvents. The nonaqueous solvents include alcohols, alkanes, ketones, ethers, and other aliphatic and aromatic compounds. Noncrystalline See also amorphous and glass. Materials that possess only short-range order (local atomic environment) but no long-range three-dimensional order. Amorphous silica or silica glass is an example of a noncrystalline material. Nonoxide Materials Ceramic or glassy materials that contain no oxide ions. The nonoxides normally include borides (e.g., AlB, TiB2), carbides (e.g., SiC, TaC), nitrides (BN, Si3N4), and sulfides (e.g., ZnS, PbS). Selenides and tellurides can also be classified under nonoxide compositions. Nonradiative Transitions In phosphor and luminescent-type materials, the transition associated with the transfer of excess energy from an excited ion to the host lattice in the form of vibrational energy. In this way, the excited ion returns to the ground state without emitting any light. Nonstoichiometric Defects Defects that arise from change in a crystal’s composition; that is, in a crystal lattice, a nonstoichiometric defect results from ejection of an atom or introduction of a foreign atom. For example, NaCl doped with CaCl2 results in a nonstoichiometric crystal with the formula Na1–2xCaxVNaxCl, where VNax represents a cation vacancy. In this compound, the cubic close-packed structure of NaCl is retained; however, some cation sites are vacant. Nuclear Magnetic Resonance (NMR) Spectroscopy A spectroscopy technique that uses an external magnetic field to provide information on the molecular structure of the compounds containing NMR-active nuclei (with nonzero nuclear spins that are multiples of 1/2). For example, 1H, 2H, 6Li, 7Li, 13C, and 29Si are NMR-active nuclei. The molecular structure information derived from the spectroscopic studies includes the local atomic environment (i.e., connectivities and bond types). NMR primarily identifies types and positions of hydrogen, carbon, and other heteroatoms (e.g., sulfur, nitrogen, silicon, chlorine, phosphorous, lead) in a molecule. This method is useful at a percent concentration level but not at trace levels. For © 2005 by CRC Press

example, in a silicone mixture, 29Si NMR provides information on the ratios of silicon centers, Q0, Si(R)4; Q1, (R)3SiO; Q2, OSi(R)2O; Q3, (R)Si(O)3; and Q4, Si(O)4. Nucleation and Growth The process of forming a critical particle radius, called critical nucleus, to begin the growth process via aggregation. In colloidal suspensions, several critical nuclei form after the threshold concentration (supersaturation) is reached. Once the particles are formed, they grow in size via several growth processes. The monomer-cluster growth pathway provides a means for a large particle to grow continuously, resulting in bimodal or broad particle size distribution. Monomer-monomer or cluster-cluster growth pathways, however, may provide a more monodispersed particle size distribution. See homogeneous and heterogeneous nucleation.

O Octahedral Sites Interstitial sites in the close-packed structure coordinated to three anions in each layer. Octahedral sites are placed midway between the anion layers, coordinating with a total of six anions. Octahedral sites can also be defined as sites that coordinate to four coplanar anions and to two anions on each apex, above and below the plane. Olation In the sol-gel process, the term that refers to the condensation reaction in which a bridged hydroxy bond is formed. Oligomer An intermediately sized molecule much larger than a monomer and much smaller than a polymer. For example, Si4O3(OCH3)10 is an oligomer (tetramer), whereas Si(OCH3)4 is its monomer, and SixOx–1(OCH3)2x+2 (where x is large) is its polymer. Olivine A silicate mineral with the formula (Mg, Fe, Mn)2IISiO4, where Mg2SiO4 is the major component containing Fe and Mn cation impurities. Olivine derives its name from the olive green color of FeII. An olivine consists of SiO4 tetrahedra and MO6 octahedra. MII includes all three metals with only partial occupancy of each metal cation in the octahedral sites. One-Dimensional Conductors Compounds that conduct electricity in only one direction. For example, in the compound K2[Pt(CN)4], the CN– ligands are in the square planar geometry stacked with a linear chain of Pt atoms in the direction perpendicular to the square plane, and the Pt d 2z orbital overlap accounts for the conductivity along the PtPt chain. Onyx An impure form of crystalline silica (F-SiO2). Opacifiers Materials (particles, whiskers, fibers, etc.) that obstruct the transmission of light through a transparent sample. The opacification effect is achieved by selecting an appropriate amount of an opacifier with a specified particle size and refractive index. High opacity requires that the light be diffused, reflected, or scattered before it reaches the underlayer. For maximum diffused reflectivity, the opacifier particles should normally have an index of refraction much higher than that of the matrix or a particle size nearly the same as the incident light wavelength or a high-volume fraction of the opacifier. Titania particles are the most commonly used opacifiers. Opal An exceedingly complex crystalline aggregate of partially hydrated silica. Optical Coatings Films that change the absorption or transmission and reflectance characteristics of the substrate. Optical coatings can be produced for color effect, antireflective properties, electro-optic properties, or optical memory applications. See also individual types of optical coatings. Optical Isomers Also called enantiomers. Pairs of molecules that are nonsuperimposable mirror images of each other. Enantiomers are chiral (i.e., they possess the property of handedness), where one of them rotates the plane of polarized to the left (levo or L or –) and the other to the right (dextro or D or +). Chromium oxalate anion [Cr(oxalate)3]2– exhibits dextro and levo enantiomers. See also isomers. Optical Microscopy A technique that uses a light source for obtaining morphological information on samples with a resolution between 1 µm and 1 mm. The two basic optical microscopes are © 2005 by CRC Press

polarizing and reflecting light. In polarizing microscopy, the samples studied are often fine powders or thin slices, whereas in reflecting light microscopy, the samples studied are normally solid lumps that are opaque. Optical Properties The properties of glasses and ceramic materials characterized by an index of refraction and dispersion, reflection, absorption/transmission, scattering, reflectance, translucency, and color. Optical Rotatory Dispersion (ORD) Curve The plot in which the extinction coefficient (specific optical rotatory power) is plotted as a function of the wavelength of light. The ORD curve analysis method is used for establishing the absolute configuration of a particular enantiomer (optical isomer). See also optical isomers. Optical Waveguides Devices (e.g., fibers or films) that exhibit total internal reflection when the light propagates within the devices with minimal loss in optical transmission. Optical fibers where the core of the fiber has a higher refractive index than the cladding are the most widely used optical waveguides. Thin films when deposited on lower refractive index substrates can also act as optical waveguides. The fewer the defects in the film or fiber, the lower the optical transmission loss. Silica-based optical fibers are used for providing better and more efficient transmission of telephone signals. Optically Active Compounds Compounds with crystal structures in which a center of symmetry is absent. As a result, the polarization of a light beam propagating through an optically active medium will always be modified. The optical activity is confined to only 15 of the 21 noncentrosymmetric point groups. Optoelectronics The integration of light with microelectronic devices, including fibers, waveguides, lasers, LEDs, and optical sensors. Orbital Reduction Factor A factor introduced in the electrostatic model for transition metal compounds to account for the reduction in orbital contribution caused by electron (d orbital) delocalization from a metal to a ligand. This factor assists in interpreting the physical properties of the transition metal compounds since there is much evidence that covalency plays an important role in bonding. Organic Light Emitting Diode (OLED) Thin films of organic molecules or polymers that can emit light with a low applied voltage. Polyphenylene vinylene (PPV) is an example of a polymer based OLED material. OLEDs, which are thinner and consume less energy, are expected to replace liquid crystal displays (LCD) for flat panel displays. Organically Modified Silicates (Ormosils) A class of ceramers representing a variety of molecular hybrids between silicates and organic polymers produced by reacting and polymerizing their respective precursors. For example, epoxy, methacrylates, silicones, and other such polymers have been incorporated in silica sol-gel networks at the precursor level to form ormosils. Organic Matrices Matrices in gel or solid state forms frequently used for trapping precipitates and crystallites of inorganic compositions. When these compositions are heat-treated, the organic matrix is decomposed, leaving the inorganic precipitates or crystallites behind. Pechini used this method to produce multicomponent oxides by mixing the metal alkoxides or hydroxides together with a polyhydroxy alcohol and a chelating agent, citric acid. Organic Radical Extremely reactive organic species containing unpaired electrons. However, organic radicals are different from anions and cations and are produced as an intermediate species in a reaction. In ceramics and glass production by chemical processes, intermediate species are frequently produced from the organic ligands in the precursors used during the reactions, such as the CH3 radical in compositions containing a methyl ligand or methanol solvent. Organic Removal Also called organic burnout. The process of removing organics by heattreating the material produced in the chemical processing of ceramics or glasses. The organic components may include materials such as organic ligands, solvents, binders, and other organic additives. © 2005 by CRC Press

Organometallic Compounds Compounds containing metal or metalloids and ligands in which there is at least one close metal-carbon bond present. For example, compounds with a bond between a metal and a carbon atom of CO, CO2, CS2, CH3, and CN– ligands are classified as organometallic compounds. Inorganic salts, such as NaCN and sodium acetate, and other ligands, such as alkoxy (OCH3), C5H5N, P(C6H5)3, and S(CH3)2, in which the donor atom is not carbon are excluded from this class of compounds. Organophosphorus Compounds Compounds containing organic ligands and phosphorus. Some examples include phosphine ligands (PR3, where R is an alkyl or aryl), alkoxy or aryloxy phosphines [P(OR)3, where R is an alkyl or aryl], and their combinations, phosphate esters, and polyphosphazenes [(P = N)xR2, where R is a halogen, alkyl, aryl, alkoxy, or aryloxy]. Orpiment An arsenic compound, arsenic sulfide, As2S3. Orthoclase A framework aluminosilicate with the formula KAlSiO3O8. Orthophosphate A phosphorus-containing compound analogous to orthosilicate. Orthorhombic Symmetry A unit cell in which the cell parameters a, b, and c are unequal (a | b | c) but angles F, L, and G are equal to 90° (F = L = G = 90°). The unit cells also exhibit three twofold axes or mirror planes. Crystals of gallium and calcium titanate (CaTiO3 perovskite) exhibit orthorhombic symmetry. Orthosilicate A silicate structure in which the oxygen in the SiO4 tetrahedra is not shared and they are independent of another, that is, a silicate molecular monomer. For example, MgSiO3, CaSiO3, and Si(OC2H5)4 are orthosilicates with no sharing between tetrahedra. See also nesosilicate. Osmate A purple osmium salt solution in water with the formula K2[OsVIO2(OH)4], where anions occupy the corners of the octahedra. Osmiamate The most stable OsVIII complex, with the formula [OsO3N]–. Osmocene An osmium sandwich compound analogous to ferrocene. See also ferrocene. Osmosis The process of diffusion driven by a chemical potential gradient. Transport of pure liquids from mixtures or solutions through a selective membrane has been accomplished by this process. In the gel-drying process, the gel network acts as a membrane, and with appropriate selection of solutions, the osmosis process can be effectively used to dry the gels with minimal stress development. Osmotic pressure is the pressure required to stop osmosis occurring in a system. Ostwald Ripening The coarsening of precipitates dispersed in solids or liquids, in which the smaller particles are sacrificed for the growth of larger, more stable particles. This process is driven by the reduction in free energy. Overlayer See monolayer, adlayer. Oxalic Acid An organic acid with the formula HOOCCOOH, which contains two carboxylic acid groups. This acid has been used as a drying control chemical additive in gels to produce narrower pores and a larger pore-size distribution. Oxidation The process corresponding to loss of electrons from an atom. This term can also describe reactions involving the removal of hydrogen or the addition of an oxygen atom. Oxidation State The charge remaining on the element when all the atoms in a compound or molecule have been removed in their ion form. For example, the oxidation state of Si in SiO2 is +4 since the two oxygen anions have 2– charge on each, resulting in a charge of +4 on Si. Similarly, in KMnO4, the charge on Mn is +7, which can be calculated as 1  (K+ + 4O2–) = Mn7+. Oxoalkoxides Metal organic precursors (monomers or oligomers) to metal oxides, with the general formula MxOy(OR)z, where M is a metal and R is an alkyl or aryl group. For example, Ti7O4(OC2H5)20 is a titanium oxoethoxide. Oxolation A condensation reaction in which an oxo bridge, O, is formed between two metal centers. The oxolation reactions result in the formation of oxoalkoxides. Oxo Ligand An oxygen ligand that bonds to a metal atom, forming an M = Otype bond. © 2005 by CRC Press

Oxonium Ion Also called hydronium ion. An oxonium ion is a cation with the formula H3O+ that forms as a result of self-protolysis of water, or, in many cases, the protolysis is assisted by other proton-donating reactants in the mixture. Oxygen Concentration Cells A zirconia (or other oxide) solid electrolyte cell with porous metal electrodes used for measuring oxygen concentrations in samples with partial pressures as low as 10–16 atm at temperatures between 500 and 1000°C. Oxygen concentration cells are used for analyzing exhaust gases and pollution, measuring oxygen consumption during respiration, etc.

P p-Type Electrical conduction in a p-type solid is dominated by hole carriers (e.g., B doped Si is a p-type material). Package A protective enclosure (e.g., ceramic, polymer) that provides environmental, electrical, mechanical, and thermal stability to a microelectronic chip or sensor. Paraelectric Materials with randomly oriented electric dipoles and with zero net dipole moment in the absence of an electric field. When an external electric field is applied, the dipoles tend to orient in a direction parallel to the field, converting the paraelectric material to ferroelectric material. For example, if the BaTiO3 crystal has an ideal cubic or perovskite structure, it is paraelectric with a net dipole moment equal to zero. The transition from ferroelectric to paraelectric behavior of BaTiO3 occurs at approximately 110°C.13 See also ferroelectric. Paramagnetic Materials that contain magnetic atoms or ions whose spins are isolated from their magnetic environment and can more or less freely change their directions. At finite temperatures, the spins are thermally agitated and take random orientations. When an external magnetic field is applied, the average orientation of the spins is slightly changed where a weak magnetization is induced in a direction parallel to the applied magnetic field. In some materials, the applied external field can align the electron dipoles parallel in domains, resulting in ferromagnetism. Magnetic behavior is normally restricted to transition metals and lanthanides with unpaired d and f electrons.14 See also ferromagnetism. Parathion A monothiophosphate ester pesticide, (C2H5O)2P(S)OC6H4NO2. Particle Coarsening or Growth See coarsening and Ostwald ripening. Particle Size Measurement A variety of methods used for determining the particle size of a powder, including x-ray diffraction (XRD), small-angle x-ray scattering (SAXS), electron microscopy (EM), centrifugal analysis, sedimentation, and light-scattering techniques. See the definitions of individual techniques. Pauling’s Rules Five rules generalized by Pauling to interpret the crystal structure of ionic compounds: 1. A coordination polyhedron of anions is formed around each cation in the structure. 2. The coordination number (number of anions surrounding the cations) is determined by the ratio of the radii of cation and anion. The most stable structure has the maximum permissible coordination number. 3. In a stable structure, only the corners and faces of the unit cell are shared. If an edge is shared, the length of the edge decreases, causing an increase in the repulsive forces between the cations. 4. The polyhedra formed around cations of low coordination number and high charge tend to be linked by corners (not edges or faces), since the separation between cations decreases as the coordination number decreases. 5. The number of different constituents (cations and anions) in a structure tends to be small. Pechini Method A method involving precipitation of metal salts in an organic matrix and thermal decomposition of the mixture to yield metal oxide systems. For example, Ti, Nb, and Zr © 2005 by CRC Press

hydroxides or alkoxides are dissolved in an organic matrix of polyhydroxy alcohol and citric acid, a chelating agent, then thermally decomposed to yield a Ti, Nb, and Zr oxide multicomponent system. Barium titanate (BaTiO3) has also been produced by this method. See also organic matrices. Peltier Effect The Peltier effect is the converse of the Seebeck effect. An electric potential externally applied to a junction between two materials with dissimilar work functions can result in a temperature difference that removes heat and can be used in refrigeration. Pendular State During the gel-drying process, the condition corresponding to the pore liquid in the gel being trapped in isolated pockets with no continuity. Pentagonal Bipyramidal The geometry of a molecule consisting of cations in the center, coordinated to seven anions in the polyhedron with five anions in the x-y plane (pentagonal) and two anions above and below the x-y plane in the z-direction. A pentagonal bipyramid has a D5h point group. For example, the [ZrF7]3– anion has a pentagonal bipyramidal symmetry. Peptization The process of redispersing the coagulated colloid. Peptization is normally achieved by washing the coagulated precipitate or reestablishing the surface charge for creating repulsive forces between the particles. Percolation The formation of gel; near the gel point, bonds form randomly between the clusters (polymers of aggregates), linking them together to form a network. The gel point corresponds to the percolation threshold in which a single cluster is formed, connecting the whole network. Percolation Theory A theory used to describe the gelation process in the wet chemical processing of ceramic and glassy materials, which includes formation of linear, branched, and cyclic oligomers and polymers. In percolation theory, to simulate the gelation process, a square lattice is used where circles are placed in empty grids, and they are randomly connected by bonds to form clusters. If the two neighboring sites are filled by circles and joined by a bond, the process is called site percolation. If the sites are initially filled and the bonds are formed at random, then the process is referred to as bond percolation. The percolation threshold is reached when the average cluster size reaches infinity (i.e., each circle is connected to any other circle in the grid through one of the many passages). Perhalate Anions consisting of halogen (X) and oxygen atoms with the general formula XO 4 . Examples include perbromate, perchlorate, and periodate. Periclase Magnesium oxide, MgO. Peritectic Point The invariant point in the phase diagram of two components, A and B, in which three phases, A, AB, and liquid, exist at the same time. The liquid composition, however, cannot be represented by combinations of solids A and B; that is, sometimes a solid compound does not melt to form a liquid of its own composition but instead dissociates to form a new solid phase and a liquid. At the eutactic point, however, the liquid composition can be represented by two solid compositions, such as A and AB. Permanent Magnets Materials that ideally maintain their magnetization constant when subjected to internal or external demagnetization fields or to a change in temperature. Permanent magnets possess high saturation magnetization, high coercive field, high remanent magnetization, high Curie temperature, and high magnetocrystalline anisotropy. Material composition is normally based on Fe, Co, and Ni; for example, the SmCo alloy is a permanent magnet.14 Permanganate Dark green manganese (VII) salt, with the anion formula MnO 4 . Permeability The ability of pores or openings to permit gases and liquids to pass through, represented by volume per unit time, or the property of a magnetic material that determines the degree to which it modifies the magnetic flux of the magnetic field in the region occupied by the material. Perovskite A structure based on the cubic close packing of anions in multicomponent oxides, with the formula ABO3. Larger A cations occupy corners of the cubic unit cell, oxygen atoms occupy the cube edge centers, and smaller B cations occupy the body center of the cube (octahedral site). Below the Curie point, the cations are displaced, resulting in tetragonal, © 2005 by CRC Press

orthorhombic, or rhombohedral distortions of the unit cell and thus creating dipole moments and spontaneous polarization. Examples of perovskite materials include PbTiO3, SrTiO3, and BaTiO3. A and B sites in the structure can be shared by two or more different atoms, as in the case of (Pb,La)(Zr,Ti)O3. Peroxoanions Anions, (OOX)x–, that contain an OO bond in addition to single-element anions, (X)x-, where X is B, P, N, S, or another such element. Examples include peroxoborates, peroxonitrates, peroxophosphates, and peroxosulfates. Peroxy Ligands Oxygen ligands that contain an O2 (OO) bond. These ligands bond through both oxygen atoms, and their bond length increases from an O2 bond length. See also superoxo complexes. O O M

M

O

O

M

Peroxo Complexes

Phase A physically distinct and mechanically separable homogeneous portion of the system. For example, in a CaCO3SiO2 system, there are two distinct phases: CaCO3 and SiO2. Also, in a magnesium silicate system, MgSiO3 is in a different phase from Mg2SiO4, even though they both contain MgO and SiO2. Phase Diagram Plots of system composition as a function of temperature or pressure. Phase diagrams provide graphical information about the existence of various compositions over a given range of temperatures or pressures. Phase Rule Rule that describes the various phases of the system as a function of temperature, pressure, or composition. The phase rule for a system is given by the following equation: P+F =C+2

where P is the number of phases present at the equilibrium stage, C is the number of components (e.g., MgO is a one-component system and Al2O3SiO2 is a two-component system), and F is the number of degrees of freedom or independent variables (temperature, pressure, composition). For example, a boiling water system consists of one component (C), H2O, and two phases, liquid and vapor (P); hence, F = 1. Therefore, only temperature or pressure is required as an independent variable to define the system. Phase Transition The process of transforming from one polymorph or phase to another. For example, transformation of graphite to diamond is a phase transition. This transition involves a change in structure only, without any changes in the composition. Phenacite A name given to beryllium silicate, with the formula Be2SiO4. Pholgopite An aluminosilicate with the formula KMg3(OH)2(Si3Al)O10, where Mg2+ occupies octahedral sites between silicate sheets and K+ ions are 12 coordinated. Phonon A quantum of lattice vibrational energy in a solid that gives rise to its specific heat capacity. Phosgene A highly toxic gas with the formula COCl2. Phosphazene See organophosphorus compounds. Phosphorescence A type of photoluminescence in which a material emits light owing to the decay of an electron from an excited state (reached by absorbing light energy) to the ground state over a longer period of time (>10–8 s). Phosphors are widely used in fluorescent lamps, cathode ray tubes, and scintillation counters. Some phosphor examples include Mn-activated Zn2SiO4 and [Ca5(PO4)3(Cl,F):Sb3+Mn2+]. Photochromic Materials See glass. © 2005 by CRC Press

Photoconductors Materials that begin conducting electricity or exhibit an increase in electrical conductivity as a result of light irradiation. Amorphous selenium is an excellent photoconductor and is used in the photocopying process (or xerography). Photodiode A diode that converts light to electrical energy. Photoelectron An electron emitted from the near-surface region of a material into a vacuum after excitation by x-rays or other energy appropriate photons. The electron has a kinetic energy, Ekin = hS  E B , where hS is the energy of the incident x-ray and E B is the binding energy of the electron. See also x-ray photoelectron spectroscopy. Photolithography The use of light to selectively expose a photosensitive film, typically a polymeric photoresist, through a patterned mask. The mask image is optically projected onto the photoresist, and the exposed (or unexposed) areas are removed chemically. Exposed regions of the underlying substrate can then be either patterned by using wet chemical or dry etching techniques, or otherwise selectively modified chemically or physically. Photoluminescence The process involving emission of light by a material as a result of absorbing light irradiation. See also fluorescent materials and phosphorescence. Photon A quantum of electromagnetic radiation with energy E = hS, where h is Planck’s constant (6.6 x 1034 Js) and S is the frequency. Photons of well-controlled energy distributions are powerful probes of materials and surface properties. Photoresist A photosensitive mask, often polymer based, that is selectively exposed to light (or electrons or x-rays). The exposed regions can be either more or less soluble than the unexposed regions, respectively, called positive and negative photoresists. pH Scale The scale that measures the concentration of a hydrogen ion in the solution, as follows: pH =  log[ H + ]

A pH value of >7 indicates that the solution is basic, a pH of <7 indicates that the solution is acidic, and a pH of 7 indicates that the solution is neutral. Phyllosilicates Type of silicates that form continuous sheets by sharing three oxygen atoms in the anion tetrahedra. See also metasilicates. Physical Vapor Deposition Thin film deposition techniques in which a chemical change of the vapor does not occur (e.g., evaporation, electron beam evaporation, sputtering, pulsed laser deposition). For example, in pulsed laser deposition, a high energy laser is directed at a bulk target composed of the chemical species desired in the final thin film. The resulting high energy gaseous species ejected from the target deposit onto a substrate forming a thin film. See also chemical vapor deposition. Physisorption Adsorbate–adsorbate and adsorbate–substrate interactions are mediated by dispersion (van der Waal’s) and electrostatic (dipole–dipole) forces that are weaker than chemical bonds (see chemisorption). In physisorption (or physical adsorption), adlayer packing density is mediated by physical interactions between the adsorbate atoms or molecules, which tend to yield incommensurate adlayer structures that often do not correspond to the underlying substrate lattice. Enthalpies of adsorption are on the order of 10 to 100 kJ/mol. Piezocaloric Materials Materials that exhibit a second-order effect where heat is indirectly produced under an applied stress. For example, lead zirconium titanate [Pb(Zr,Ti)O3 or PZT] composition exhibits piezocaloric properties. Piezoelectric Materials Noncentrosymmetric crystals that develop net electric polarization under mechanical stress or develop strain under an applied electric field. The ferroelectric materials, like KH2PO4, that exhibit piezoelectricity in the unpolarized phase can simulate a very large piezoelectric modulus. The ferroelectric materials that do not exhibit piezoelectric behavior in the paraelectric phase can be polarized to produce piezoelectricity with low strain (~1%). © 2005 by CRC Press

Examples of such piezoelectric crystals include ZnS, ZnO, PbZrO3, PbTiO3, and Pb(Zr,Ti)O3. They have been used as infrared detectors and transducers. Pigments Dispersed particles used as additives for changing color, specular and diffuse reflectance, direct and diffused transmission, and selective absorption characteristics of a material (monolithic, film, suspension, etc.). Titania (TiO2) pigments are frequently used in paints to provide color and to change other optical properties. See also opacifiers. Pitting Localized uneven corrosion of a surface resulting in the formation of pits ranging from nanoscale to macroscopic sizes. Pitting can occur by several means including localized corrosion in liquids, plasmas, or by sand (or grit) blasting. pK Scale The scale that determines the degree of dissociation of polar substances, such as acids (pKa) and bases (pKb). The pK scale was devised to simplify the large variation in dissociation constants (K) of substances and is given by the following equations: pK a =  log K a and pK b =  log K b

For example, the pKa values of water and acetic acid are 13.997 and 4.756, respectively, indicating a higher dissociation ability of water. The pKb values of aniline and ammonium hydroxides are 9.42 and 4.75, respectively. Plagioclase Feldspar A family of aluminosilicates, including members such as albite, NaAlSi3O8, and anorthite, CaAl2Si2O8. Planarization Planarization of a surface is important in the microelectronics industry because it allows subsequently deposited films to remain planar and thus grow with fewer defects. If a thin film is deposited over ramps, vias (i.e., holes), or other surface asperities, current-limiting defects (dislocations and strained regions) can occur because epitaxial growth is not maintained. Planarization or flattening of a surface, including the removal of surface asperities, can be achieved by a number of methods through etching, chemical mechanical polishing, and ion implant patterning. Planar Defects Two-dimensional defects in a crystalline structure involving a layer (or plane). Planar defects are sometimes referred to as extended defects. Twin boundaries in ferroelectric materials are examples of planar defects. Plasma The mixture of reactive species including atoms, ions, electrons, and photons produced by DC arc or radio frequency discharge at temperatures higher than 8000 K. Reactive plasmas are frequently used to prepare films, powders, and composites with high purity. Plaster of Paris Calcium compound (CaSO4 · 1/2H2O) formed as gypsum (CaSO4 · 2H2O) that loses three quarters of the water of crystallization by heating. Plastic Deformation Irreversible deformation produced by applying a load at a constant rate where the stressstrain curve is observed to provide information on yield strength and tensile strength. Plastic Flow The condition that occurs in materials above their yield points where the crystal suffers an irreversible elongation. Point Counting In microscopy, the calculation method used for measuring the volume fraction of a phase by spreading a grid of points on the micrograph and counting the fraction of the total point count. Point Defects The defects in a crystal structure that involve dislocation or absence of atoms, ions, or pairs of ions. See Frenkel and Schottky defects. Point Group Also called a symmetry group. A complete set of symmetry operations that can be performed on a molecule: an operation involving rotation around an axis (Cn), the reflection plane (X), an inversion point (i), rotation followed by reflection (Sn), and an identity operation (E). For example, the C2v point group has three elements of symmetry: E (identity operation), C2 (rotation axis), and 2Xv (reflection plane). © 2005 by CRC Press

Point of Zero Discharge (PZC) A point at which the surface charge on the particle in a colloidal system is zero. In silica colloidal suspensions, PZC lies close to a pH of 2. See also isoelectric point. Polarizability A condition caused by the displacement of charge in a material. There are four variations of polarizability: electronic, ionic, dipolar, and space charge. Electronic polarizability is caused by slight displacement of the electron cloud in an atom relative to the nucleus, which contributes to the dielectric constant of the materials (e.g., diamond). The ionic polarizability results from a relative displacement of ions in the solids. Dipolar polarizability occurs in permanent electric dipoles (e.g., HCl) and arises from the change in orientation of the dipoles in the presence of an external field. Space polarizability arises in materials that are not perfect dielectrics but exhibit long-range migration of ions or atoms (e.g., materials with point defects, NaCl). Polaron The association of an electronic carrier and its polarization field. Polycrystalline Materials that do not grow as a single large crystals but grow as an aggregate of smaller crystals (grains or particles). They are produced in powder, film, fiber, and monolithic forms. Polydispersed Particles A collection of particles in a colloid or a solid-state system consisting of a broad range of particle sizes. However, in a monodispersed particle system, the particles have similar sizes or have a narrow particle size distribution. The polydispersity of the system is frequently studied by Brunauer, Emmett, and Teller and scanning election microscopy methods. Polyfunctional A species that contains more than one reactive functional group (f > 1). For example, the precursors (CH3)2Si(OH)2, (CH3)1Si(OH)3, and Si(OH)4 have a functionality, f, of 2, 3, and 4, respectively, and are classified as polyfunctional. A particle surface, however, may contain more than four functional groups and could be classified as a polyfunctional species. Polymer A large molecule formed from several monomers or oligomers. For example, (OH) [Si(R2)OSi(R2)(OH)]n is a silicone polymer. The process of converting monomers or oligomers to polymers is called polymerization. Polymerization normally proceeds by additiontype or condensation-type reactions. Polymorph Materials with the same chemical composition but with different crystalline structures. Diamond and graphite are polymorphs since their chemical composition is the same (carbon), but their molecular structures are different (i.e., diamond has a three-dimensional structure and graphite has a layered structure). Polythiazyl See (SN)x polymer and sulfur compounds. Polythionates See sulfur compounds. Polytypes Polymorphic materials that differ in their structures in one dimension only. The order in which the two-dimensional layers are stacked may also result in polytypes. The wurtzite and sphalerite forms of ZnS are polytypes differing only in the order in which sheets of tetrahedra are arranged in two structures. SiC is probably the richest material in terms of polytype diversity, with at least 74 identified structures with repeat or unit cell distances up to 150 nm. Pore-Size Distribution The range of pore sizes in a porous material system. A porous material may be composed of a range of pore sizes, and the pore size distribution can be calculated by differentiating the pore volume adsorbed with respect to the pore sizes in the adsorption and desorption isotherms measured in BET-type nitrogen adsorption methods. The pore size distribution can also be determined by electron microscopy studies. Pore Volume The total volume of all the pores in a sample, which is measured by the amount of gas adsorbed by the sample. Porosity The volume fraction of the pores in a material. Invariably, all ceramic materials have some porosity in the finished product, which can vary between 0 to 99% of the total volume. For example, certain structural materials have densities close to their theoretically calculated densities; hence, the porosity is close to 0. However, some ceramic foams (e.g., aerogels and © 2005 by CRC Press

reticulate ceramics) that are frequently used for high-temperature filtration and thermal insulation have porosities as high as 99%. Portland Cement See cement. Potash Feldspar A potassium aluminosilicate with the formula K2O · Al2O3 · 6SiO2. Powder Synthesis Preparation of powders by a variety of methods, including wet chemical, aerosols, solid-state reaction, and vapor phase methods. For wet chemical methods, see sol-gel process, hydrothermal processing, and colloid. For dry processing methods, see spray drying, flame hydrolysis, and fluid bed reactor. Pozzolanic Cement A cement similar to Portland cement except that it uses natural or synthetic reactive silica (volcanic or fuel ash) that forms calcium silicate hydrate gels at room temperature in contrast to high temperature requirements of Portland cements, causing the final product to be more inert to chemical attack and mechanically stronger. See also cement. Precipitation The process that involves particle or cluster growth in colloidal systems via a nucleation and growth mechanism, in which a solid phase eventually falls out of the solution. See nucleation and growth. Precursor Methods See coprecipitation methods, sol-gel process, and metal organic decomposition. Protective Films Coatings that perform the function of abrasion resistance, corrosion resistance, electronic passivation (dielectric), and planarization (smoothness) and impart hardness to the surface. Protic Solvents Solvents that contain a labile or removable proton. For example, H2O, CH3OH, and HCONH2 are protic solvents. Protoenstatite A magnesium silicate crystal with the formula MgSiO3. Prussian Blue Water-soluble iron cyanide compounds with the formula FeIIIx[FeII(CN)6]y and a characteristic blue color. Pseudosymmetric Crystals Partially symmetric crystals in which the unit cell may be geometrically symmetric but does not possess the essential symmetry elements. For example, a crystal may be pseudocubic if the unit cell is geometrically cubic but does not have four threefold axes, which is an essential symmetry element of a cubic cell. This type of pseudocubic cell has lower symmetry such as tetragonal symmetry. An example of a pseudo-symmetric crystal is CaC2 in comparison with a cubic crystal, NaCl. PTC Thermistors (Positive Temperature Coefficient Thermally Sensitive Resistor) Ferroelectric materials that exhibit a large increase in electrical resistivity with increases in temperature in contrast to normal nonmetallic behavior (where resistivity decreases with increasing temperatures). These materials are used as thermal resistor switches. BaTiO3 is an example of a PTC thermistor. Pulsed Laser Deposition (PLD) A high vacuum physical deposition technique in which a laser is used to volatize the target material, which then deposits onto a substrate. Similar to sputtering, it can be used to deposit insulating and multicomponent materials. PLD is also called laser sputter deposition or laser ablation deposition. Pycnometry A method used to measure the density of large samples (10 to 100 g) by a gas displacement (e.g., He gas) procedure. In this technique, the sample is compressed in a gasfilled chamber by a piston until a defined pressure (e.g., 2 atm) is reached. The volume of the sample is obtained by the difference in the position of the piston when the sample is in the chamber and when the chamber is empty and contains only gas compressed to the same pressure. Hence, the density is given by mass/volume of the sample in g/cm3 units. Pyrex® A sodium borosilicate glass composition with 4% Na2O, 16% B2O3, and 80% SiO2. The glass transition temperature (550°C) of pyrex is higher than that for borate glass; however, it is the same as the window-glass transition temperature. Pyrex Process The process involving dissolution of uranium (U) and plutonium (Pu) elements in 7 M HNO3 to produce a solution containing UVI and PuIV ions. © 2005 by CRC Press

Pyroelectric Noncentrosymmetric crystals that exhibit change in electric polarization as a function of temperature. Like ferroelectric materials, pyroelectric materials possess net spontaneous polarization; however, unlike ferroelectrics, the direction of polarization in pyroelectrics cannot be reversed by an applied electric field. Zinc oxide is a common example of a pyroelectric crystal. Pyrogenic Particles Particles produced by vapor phase methods at high temperatures using furnaces, lasers, electron beams, plasmas, or flames. Pyrolysis The high-temperature reaction in which the molecule or precursor is fragmented at a molecular level. Pyrogenic particles are essentially produced by the pyrolysis process. For example, zirconia is prepared from zirconium butoxide by the pyrolysis process: Zr (OC4 H 9 )4 q ZrO2 + alcohol + olefin

Pyrope A type of garnet (a magnetic material) with the formula Mg3Al2Si3O12. Pyrophyllite An aluminosilicate with the formula [Al2(OH)2Si4O10]. Pyrosilicate Crystalline silicates containing Si 2O6 7 ions (two ion tetrahedra are shared at the corner). Pyroxene Polysilicates composed of chains of (SiO3)2n– anions. Examples include MgSiO3 and Na2SiO3. Pyrrhotite Iron sulfide compounds with the general formula Fe1-xS.

Q Qualitative Chemical Analysis A subdiscipline of analytical chemistry that determines the constituents of a sample. For example, qualitative analysis can be used to determine the elemental impurities in the sample or to identify various metals in an alloy. The most useful methods of qualitative molecular analysis include NMR (nuclear magnetic resonance), IR (infrared), and UV (ultraviolet) spectroscopies and MS (mass spectrometry). Quantitative Chemical Analysis A subdiscipline of analytical chemistry that determines the molecular composition of a sample. A molecular formula can be obtained from the quantitative analysis of a sample. However, quantitative analysis does not differentiate between isomers and polymorphs. The most useful methods of quantitative molecular analysis include atomic absorption, NMR (nuclear magnetic resonance), MS (mass spectrometry), IR (infrared), and UV (ultraviolet) spectroscopies, x-ray diffraction, thermal analysis and combinations thereof. Quantum Dots Nanometer-scale metal or semiconducting structures or clusters for spatially confining a small defined number of electrons or holes. Altering the size of the dot or changing its local electrostatic environment changes the number of confined electrons or holes. A quantum dot laser emits photons of different wavelengths depending on dot size. Other optical properties (e.g., photoluminescence) of quantum dots also vary with dot size. Quantum Numbers The arrangement of electrons in an atom is described by four quantum numbers that determine the spatial distribution, energy, and properties of the element/atom. The principal quantum number, n, defines the energy level of the electron (n = 1, 2, 3, 4, etc.). The orbital quantum number, l, defines the electron charge distribution and its orbital angular momentum (1 = n  1 = 0, 1, 2, and 3, which corresponds to the orbitals s, p, d, and f, respectively). The magnetic quantum number, m, provides the direction of the electron (m = 21 + 1, for orbital s, m = 0, i.e., spherical orbital shape; for orbital p, m = 3, i.e., three orientations of the orbital). The spin angular momentum quantum number ms is associated with the property of the wave function of the electron, and an electron can have two values ±1/2. Quartz Crystal The crystalline form of silica produced at high temperatures and pressures. The low quartz or F-quartz is stable up to 573°C, and quartz or G-quartz is stable between 573 and © 2005 by CRC Press

867°C. High quartz has a structure that can be viewed as silica tetrahedra chains formed by sharing oxygens, and low quartz has slightly distorted SiOSi angles of 150° instead of a normal angle of 144°. Quartzite A silica mineral with 98% SiO2 and 2% CaO. Quasicrystal Materials usually composed of three or more elements (e.g., Cd-Mg-RE, where RE is a rare-earth element) exhibiting quasiperiodic crystalline structure. For example, many quasicrystals exhibit usually forbidden symmetries such as fivefold rotation axes.

R Radioactive Decay Series Four types of radioactive decay series in which radioactive elements decay by emitting a variety of radiation particles, such as F and G. The four series include (a) 232 208 Th to 82 Pb), in which the atomic weight of elements is a multiple of four the thorium series (90 241 209 Pu to 83 Bi) , in which the atomic weight of the elements can (4n); (b) the neptunium series (94 238 206 U to 82 Pb) , in which the atomic weight of be represented by 4n + 1; (c) the uranium series (92 235 207 U to 82 Pb) , in which the elements can be represented by 4n + 2; and (d) the actinium series (92 the atomic weight of the elements can be represented by 4n + 3. Raman Spectroscopy A spectroscopy that complements infrared (IR) spectroscopy in recording various vibrational modes in a molecule. In IR spectroscopy, change in the dipole is involved with the change of vibration. However, Raman spectroscopy does not involve change in dipole. Raman spectra are plots of intensity of light scattering as a function of frequency or wave number in which a monochromatic light source (laser), normally in the ultraviolet region, is used. Raman spectroscopy is used for examining compounds such as O2 and N2 with no changeable dipole. This technique has also been used for studying polymer crystallinity, tacticity, and amorphous character. Rapid Thermal Annealing The process of annealing a material (film, powder, fiber, or monolith) with a very high rate of temperature increase of the order of ~100 to 1000°C/s. This process not only increases the product throughput, but in many cases also assists in avoiding the crystallization of undesired phases that form through the transition temperatures to crystallize the desired phases. This technique is frequently used in the semiconducting industry. In ferroelectrics, for example, the undesired low-density pyrochlore crystallizes at a lower temperature (500°C) than a high-density perovskite phase (>600°C) in ferroelectric materials (e.g., PbTiO3). By rapidly annealing the sample through the 500°C temperature range, crystallization of the pyrochlore phase is avoided. RTA limits significant interdiffusion at heterostructure interfaces and of ion implant profiles by using lasers or lamps to avoid long temperature ramps and timeat-temperature of standard furnace annealing. RTA is also used to electrically activate ionimplanted dopant species, heal implant damage, and recrystallize thin films after deposition, all while maintaining sharp interfaces between different materials. Rare Earths Lanthanides elements from lanthanum (La) to lutetium (Lu) with partially filled f orbitals. Some examples of rare earths include cerium (Ce), gadolinium (Gd), and erbium (Er) with outer shell electron configurations of 4f26s2, 4f75d6s2, and 4f126s2, respectively. Realgar An arsenic sulfide compound, As4S4. Reconstruction See surface reconstruction. Recrystallization The process of regenerating strain-free grains by the nucleation and growth phenomenon in a plastically deformed matrix. Redispersion See peptization. Red Lead A lead oxide with the formula Pb3O4. Reedmergnerite A sodium borosilicate composition with the formula NaBSi3O8, which is produced by forming a gel rather than by melting a glass. © 2005 by CRC Press

Reference Electrode An electrode in a three-electrode configuration with a well known and stable electrode potential, which is used as a reference point for the working electrode. Typical reference electrodes are Ag/AgCl, the standard hydrogen electrode (SHE), and the calomel electrode. See also cyclic voltammetry, counter electrode, working electrode) Reinecke’s Salt A chromium salt with the formula NH4[Cr(NH3)2(NCS)4] · H2O. Reflected Light Microscopy See optical microscopy. Reflection High Energy Electron Diffraction (RHEED) Monoenergetic electrons (1 to 20 keV) are scattered from surfaces at low (or glancing) angles to yield information on surface and thin film structures. Refractive Index The ratio of velocity of light in two media when the light passes through from a vacuum to a denser material/medium with a drop in the light velocity. Refractive index , n = vvacuo / vmaterial

Changes in the light velocity between the two media also cause bending of the light ray at the interface. Refractive indices are important parameters for optical applications such as gradient index films (antireflective) and optical waveguides (optical communication applications). Refractories Materials that possess high strength, mechanical stability and chemical inertness at high temperatures (approximately 1400°C and higher). Materials such as ZrO2, Al2O3, SiC, BN, and TaC are classified as refractories. Some of the oxide materials have played an important historic role in the steel, glass, and cement industries by providing the furnace lining to melt raw materials. Carbides, nitrides, and borides are relatively new refractory materials used in advanced composite applications (e.g., aerospace, cutting tools, and electronics). Rehydration A process normally associated with surfaces involving water adsorption followed by dissociative chemisorption. The materials or surfaces that are rehydrated were previously dehydroxylated to remove water. If the dehydration process is conducted at high temperatures, all of the hydroxyls are removed, and the surface is rendered hydrophobic. As a result, the materials and surfaces cannot be rehydrated. For rehydration, residual hydroxyl groups or hydrophilic groups at the surface are required. Remanent Magnetization The property of a ferromagnetic material to retain magnetization even after the external magnetic field is removed. These ferromagnetic materials exhibit hysteretic behavior. Remanent Polarization The property of a ferroelectric material to retain polarization even after the external electric field is removed. These ferroelectric materials exhibit hysteretic behavior. Resistance (Resistivity) A material’s (or liquid’s) resistance to the flow of electrical current or the inverse of a material’s conductivity. Electrons or holes with zero or extremely low mobilities under an applied electric field have high resistances. Rest Potential (Also called, equilibrium potential or open-circuit potential.) The rest potential of a three-electrode electrolytic cell is the measured electrical potential (or electromotive force) between the working and reference electrodes when there is no applied voltage. See also cyclic voltammetry, counter electrode, working electrode. Reversible Electrode An electrode that allows conduction via both electrons and the mobile ions of the solid electrolyte. For example, molten sodium is a suitable reversible electrode for measuring DC conductance in G-alumina, since the reversible reaction Na+ + e ž Na occurs at the sodium–G-alumina interface where the Na+ ion can move across from the electrode to the solid electrolyte and vice versa. Solid-solution electrodes are a type of reversible electrode composed of framework or layered-type structures in which a small cation can be chemisorbed or desorbed. For example, in the TiS2 electrode, an alkali cation, such as lithium (Li), can push into the layers within the TiS2 structure and form LixTiS2 solid solutions, and the reaction can be reversed when the lithium ion (Li+) diffuses out. © 2005 by CRC Press

Rheology The science of deformation and flow of matter. In rheology, a variety of polymer properties including viscosity, elasticity, and viscoelasticity are studied to describe the mechanical and flow properties of the material. Rhodocene A rhodium compound analogous to ferrocene. See ferrocene. Rhombohedral Symmetry A unit cell whose three parameters, a, b, and c, are equal (a = b = c) and are inclined equally but not at right angles (a = G = L | 90°). The rhombohedral unit cell exhibits three twofold axes or mirror planes (essential symmetry elements). Crystals of arsenic, bismuth, and calcite (CaCO3) exhibit rhombohedral symmetry. Rochelle Salt A ferroelectric material with the formula KNaC4H4O6 · 4H2O and Curie temperature between –18 and +20°C. Rock Salt Structure Structures in which the large anions are arranged in a cubic close-packed array and all the octahedral sites are occupied by the cations. Many halides, oxides, and sulfides crystallize into rock salt structures. Some examples include MgO, CaO, BaO, MnO, alkali halides, and alkaline earth sulfides. In oxides, both cations and anions have a coordination number of 6. Roller Quenching A quick glass preparation method in which the melt is propelled onto a cooled, rotating drum, forming a thin ribbon of glass. Rotation Axis A symmetry element, an axis in a molecular structure around which the polyhedron is rotated to result in identical positions of the atoms involved. For example, in SiO4 tetrahedra, rotation about the two axes, C2 or C3, by 180 or 120° (360°/n) produces an identical orientation. See also point group. O Si O O O

O O

n=3

Si

O O

n=2

Rotation Axes (Symmetry Elements)

Ruby A crystalline alumina (Al2O3) doped with Cr3+ (0.5 to 2%). The ruby composition has been recently used in laser applications. See also laser materials. Ruthenocene A ruthenium compound analogous to ferrocene. See also ferrocene. Rutherford Backscattering Spectroscopy (RBS) A quick and nondestructive technique for measuring large atomic mass impurity concentration profiles in lower atomic mass thin films (e.g., As or Sb impurities in Si). High energy (~1 MeV) helium ions directed normal to a surface will penetrate a thin film deeply until backscattered from an impurity atom. The measured energy of the backscattered He ion is characteristic of the mass of the impurity and its depth in the film. Rutile Structure A structure that can be regarded as a distorted hexagonal close packing of tetragonal close packing of oxide anions, with half of the octahedral sites filled by cations. The octahedra link up by sharing one pair of opposite edges to form infinite parallel chains that are linked up by the octahedra corners to form a three-dimensional network. Titania, TiO2, is the most common example of the rutile structure; other examples include GeO2, PbO2, SnO2, and MnO2.

S Saffil Fibers Alumina and zirconia fibers produced by the ICI company for various applications. The alumina and zirconia fibers ( ~3 µm) are heat resistant up to 1400 and 1600°C, respectively, © 2005 by CRC Press

and have extreme chemical resistance to hot alkali and acids except for hot sulfuric acid. They are used in high-temperature insulations, filtration, and catalysis supports. Saltpeter Potassium nitrate, KNO3. Sandwich Molecules The general class of organometallic compounds in which the metal cation is bonded to and sandwiched between aromatic rings. Examples of sandwich molecules include ferrocene, uranocene, and rhinocene, in which the respective metals are sandwiched between two cyclopentadiene rings. See also individual metallocenes. Sanidine An aluminosilicate with the formula KAlSi3O8. Sapphire The single crystal form of alumina (Al2O3), which possesses high strength, high optical transmittance, excellent thermal and chemical stability, high thermal conductivity, and excellent biocompatibility. Sapphirine An aluminosilicate with the composition 2MgO · 2Al2O3 · 5SiO2. Saturated Steam Curve In a pressure-temperature phase diagram of water, the curve along which vapor is composed of saturated steam that is in equilibrium with liquid water and above which the vapor phase is absent and liquid water is effectively under compression. Saturation Magnetization In a ferromagnetic material, the condition in which the spins of the magnetic domain are all parallel at a given applied magnetic field. This also corresponds to the highest magnetization point in the hysteresis loop. Saturation Polarization (Ps) In a ferroelectric material, the level of polarization where the dipole orientations are all parallel at a given applied field above the coercive field. This also corresponds to the highest polarization value in the hysteresis loop. In BaTiO3, Ps is 0.26°C/m2 at 23°C. Saturation Solubility Curve In the phase diagram (composition vs. temperature) of a system, the curve along which crystals can exist with their melts and above which only liquid melt exists. Scanning Electron Microscopy (SEM) The electron microscopy technique that images the surface of the sample by collecting the backscattered and secondary electrons to provide information on the morphological properties and elemental composition of the sample surface. This technique is useful for surface features in the range of 100 Å to 10 µm, and it provides magnification in the range of 20× to 100,000×. Scanning Force Microscope (SFM) Also called an atomic force microscope (AFM) and is part of a broader class of instruments called scanning probe microscopes. An SFM measures the intermolecular forces between a nanoscale tip and a surface, giving rise to surface topography with lateral resolution ranging from the atomic to the hundreds of microns and resolution normal to a surface on the order of 0.1 Å or less. An SFM can quantitatively measure frictional forces, capillary forces, and other nanoscale tip–sample interactions. An SFM tip can also be used to manipulate matter at a surface at the nanoscale, hence its use as a nanolithography tool. Scanning Probe Microscope (SPM) The broad term for a class of surface characterization instruments in which an atomically sharp tip or probe is brought close to, or in contact with, a surface. An appropriate tip–sample transfer function is then monitored as the tip is moved across the surface in a controlled fashion. Transfer functions include electron tunneling current (scanning tunneling microscope), intermolecular forces (scanning force microscope), magnetic moment (magnetic force microscope), capacitance, and friction or lateral forces (scanning force microscope). These probes are capable of imaging individual atoms and point defects and other nanoscale surface properties and have been key to the development of the nanotechnology field. See also scanning tunneling microscope, scanning force microscope, and magnetic force microscope. Scanning Transmission Electron Microscopy (STEM) The electron microscopy technique that combines the scanning feature of scanning electron microscopy (SEM) with the high resolution of transmission electron microscopy (TEM). Scanning Tunneling Microscope (STM) The quantum mechanical tunneling of electrons from a sharp metal tip to a conductive or semiconductive surface at tip–sample separations on the order of angstroms as the tip is rastered across a surface. An STM is one type of scanning probe © 2005 by CRC Press

microscopy instrument. The tunneling current is an exponential function of the tip–sample distance and thus an extremely sensitive probe of atomic scale surface topography and surface electron density of states. An STM can also be used as a nanolithography tool to manipulate and pattern matter on surfaces. Scattering The process by which a part of the incident light is diffused, reflected, or scattered in an optically heterogeneous system containing particles or secondary phase with a mismatched refractive index. Scheelite A tungsten ore with the formula CaWO4. Schonites See Tutton salts. Schottky Barrier An interfacial blocking charge potential between two materials of different work functions. The Schottky barrier impedes electron flow in one direction and enhances flow in the other direction. A doped interface between two identical materials can also lead to space charge build-up that impedes electron flow in both directions. This type of interface engineering is used in the microelectronics industry for fabricating diodes, metal–semiconductor contacts, varistors, thermistors, and other boundary modified devices. Schottky Defect A point defect in an ionic crystal composed of a pair of cation and anion vacant sites (stoichiometric) in the lattice. This defect normally occurs in alkali halides in which an alkali cation and a halide ion are missing as an ion pair (i.e., the cation and anion vacant sites are next to each other or both ions are missing, with vacant sites distributed at random in the three-dimensional array). However, in both cases, the crystal on the whole is electroneutral. In 1 mg of NaCl, approximately 104 Schottky defects account for its optical and electrical properties. Schulze–Hardy Rule The rule that qualitatively predicts the concentration of the electrolyte required to cause flocculation in a colloidal suspension. Coagulation results from reducing the double-layer repulsion in a suspension, which in turn is caused by increasing the concentration of the electrolyte (i.e., the counterions) or by changing the solution pH. The following formula is used to predict the flocculation concentration, cf: c f = CJ3 K 5T 5 / A2e6 z 6

where C is a constant (weakly dependent on the anioncation charge ratio), k is Boltzmann’s constant, T is the temperature, A is the Hamaker constant of the particles (expressed in joules), e is the electron charge, and z is the valence of the counterion. This rule fails when the electrolyte causes reactions or when it is chemisorbed on the surface of the particle. Screw Dislocation Like edge dislocation, a line dislocation in a crystal lattice in which the crystal has gone through a slip in front of the line but not behind the line. This line dislocation involves rotation in addition to translation motion. Secondary Ion Mass Spectrometry (SIMS) A technique for elemental surface analysis of materials where the sample is bombarded with ionized inert gas and the molecular ions or fragments of ions displaced from the surface are analyzed by mass spectrometry. The displaced ions may be positively or negatively charged. In a companion technique, ion scattering spectroscopy (ISS), the energy of the scattered ions is measured instead. Both techniques provide information on the relative amounts of elements present on the surface. Seebeck Effect The temperature-dependent contact potential at the junction of two materials with dissimilar work functions. These junctions can be used to make thermocouples and refrigerators (Peltier effect). Seeding The process of introducing a controlled number of nuclei/particles with a defined size into a suspension or into a liquid melt to begin the nucleation and growth phenomenon (i.e., heterogeneous nucleation). The seeding process has been frequently used in glass and ceramic manufacturing and in producing suspensions or powders with controlled particle sizes. Recently, © 2005 by CRC Press

the process was applied for crystallizing films at relatively lower temperatures by providing nucleation sites. Self Assembled Monolayer (SAM) A monolayer, typically a monomolecular layer, formed on an inorganic surface through the process of self-assembly. Self-Assembly The ability of molecules to interact and aggregate to form ordered structures. Examples of self assembly include the formation of lipid bilayers (cell walls), DNA replication, self-assembled monolayers of alkanethiols (sulfur-terminated long chain hydrocarbons) on metal surfaces, and supramolecular chemistry. Self-assembly is being used as a nanofabrication tool to design and form nanoscale inorganic/organic/biological hybrid structures and devices on inorganic surfaces. Self-assembly typically avoids the high temperatures found in microfabrication techniques and as in biology, it can often be carried out at or near room temperature. For example, gold nanoparticles can be self-assembled into clusters using short single-stranded DNA. Self-Diffusion Random walk diffusive motion of an atom in a solid in the absence of any kind of gradient such as concentration, temperature, or pressure. See also chemical diffusion, surface diffusion. Semiconductors Materials in which the valence and conduction bands are very close together and the electrons in the valence band can be easily excited into the conduction bands. Elemental semiconductors, such as Si and Ge, are the most commonly used semiconductors. In addition, compounds composed of elements in Groups II and VI and Groups II and V, a few chalcogenides, and many nonstoichiometric oxides are excellent semiconductors that are prepared by either doping or annealing under certain conditions to create defects. The conductivity, X, of the semiconductors is in the range of 10–5 to 103 <–1 cm–1. Some examples of ceramic semiconductors include Cu2-xO, SrTiO3–x, Zn1+xO, and Hg2–xS. Sensors A device such as chemical sensors, biosensors, motion detectors, and accelerometers that can detect changes in a property. Serpentine A magnesium silicate mineral with the formula 3MgO · 2SiO2 · 2H2O. Shear Modulus The stressstrain ratio of instantaneous elastic shear stress in which strain develops from twisting of the material without volume change. Shear modulus, G, is related to Young’s modulus, E, by the following formula: G = 2(1 + v) E

where v is Poisson’s ratio defined as the ratio between the strain in the direction of the applied stress and the strain perpendicular to the applied stress. Shivering Failure in glazes under compressive stress. Shoup Process A method developed by Shoup for large-scale production of monolithic gels (mainly silica), in which a sol of Ludox• particles (silica nucleating agent) is mixed with potassium silicate at a high pH and gelation is produced by adding formamide (HCONH2). When formamide is added to the water sol, it is hydrolyzed and produces ammonium hydroxide (a weak base), reducing the system pH from 11.8 to 10.8. The reaction conditions can be adjusted such that pore and particle sizes are controlled and large blocks of silica gels (30 × 30 × 9 cm) can be dried without cracking. Sialons (SiAlON) A multicomponent system containing silicon (Si), aluminum (Al), oxygen (O), and nitrogen (N) elements. The sialon structure is based upon the Si3N4 parent structure. Sialons are frequently used in high-temperature ceramic applications. Siderite A carbonate ore for iron with the composition FeCO3. Silicon Compounds Compounds containing a silicon element that are organized into four common classes: © 2005 by CRC Press

Silanes are silicon hydrides or molecules with one or more hydrogens replaced by organic or halide ligands. Silicon hydrides have the general formula SinH2n+2. Silicates are salts made up of SiO4 anion and alkali or alkaline earth cations. They occur naturally and can also be synthesized. Potassium silicate (KSiO3), sodium silicate (NaSiO3), and metasilicates are some examples of silicates. Silicones are similar to silicates except for the local environment around silicon. In silicones, silicon is bonded to only two oxygen atoms instead of all four oxygen atoms as in the case of silicates, with the other two valencies satisfied by organic ligands such as alkyls and aryls. Several polyalkylsiloxanes, (Si(R2)OSi(R2)O)n, where R is an alkyl group, and hexamethylcyclotrisiloxane are examples of silicones. Siloxanes are similar to silicones in that the two silicon valencies are satisfied by two oxygen atoms, and out of the other two valencies, at least one is satisfied by ligands other than alkyl and aryls, such as alkoxy and aryloxy. A polydiphenylsiloxane methoxy terminated polymer is an example of a siloxane compound. Sillimanite A aluminosilicate mineral with the formula Al2SiO5. Silylation The process of substituting an active hydrogen (normally in a hydroxyl) with an organosilyl group or ligand. This type of reaction has been exploited in preparing ceramers, water-repellent surfaces, and silicones with tailored properties. Simple Cubic Structure A structural array in which spheres are packed together such that one sphere touches only four other spheres in the same plane: one above and one below the plane. In addition, interstitial sites are surrounded by eight spheres. This packing constitutes a void volume of 48%. SIMS See secondary ion mass spectrometry. Sintering The process of densifying a polycrystalline or amorphous body with or without the aid of a liquid phase. In the sintering process, the compacted ceramic is heated close to the solidus (melting temperature) to effectively bond the grains in the compacted powder for maximum density. Extensive studies have been conducted to investigate the effects of pore sizes and shapes, grain sizes and shapes, and porosity on the sintering process and the properties of the densified material. Size Exclusion Chromatography (SEC) Also called gel permeation chromatography (GPC). A type of chromatography in which a porous material is used as a stationary phase, a liquid as a mobile phase, and the molecules in the eluant are separated by their size. The porous material normally has pores in the range of 50 to 3000 Å, and the smaller molecules in the eluant penetrate the pores more readily than the larger molecules. As a result, the smaller molecules travel faster through the column than the larger excluded molecules. The SEC technique also provides qualitative information on the molecular weight of the eluted compounds. Often, the components with same molecular weight, but with different structure and shapes, elute at different times, providing information on the shape of the molecule. Hence, this technique provides information on the molecular weight and size of the components in a mixture when compared with a standard with known amounts of the components. Skeletal Density The density of a solid component in the system, excluding pores, or the theoretical density of a completely compacted system with no porosity. For example, the skeletal density of a silica system is 2.2 g/cm3, whereas the bulk density of a silica system may be much less than this skeletal density. See also density. Slip The process of movement of a dislocation in a crystalline lattice. See also dislocation. An aqueous slurry of ceramic particles is also traditionally called a slip. A nonaqueous slurry of ceramic particles can be referred to as a slip. Slip casting Generally a ceramic forming technique in which a slurry or suspension of solid particles is poured over or into a porous mold. The water is adsorbed by the mold, leaving behind a dense compact of solid particles (green body) in the shape of the mold. The mold is © 2005 by CRC Press

removed and the green body is heat-treated to induce sintering and densification to form the final product. Small-Angle X-ray Scattering (SAXS) A light-scattering technique used for detecting particles or inhomogeneities on a scale of 10 to 1000 Å in colloids and macromolecular systems. In this method, a diffracted beam is detected at angles very close to the incident beam, and the diffracted beam appears as a small shoulder on the intense undiffracted beam centered at 0° 2V. The SAXS technique has been frequently used to determine the particle sizes in sols and to study the particle growth pattern in sol-gel and colloidal processing. (SN)x Polymer Also called polythiazyl. A sulfur nitride polymer with a planar sulfur and nitrogen backbone chain polymer structure. This polymer is more stable than its precursor, S2N2. Polythiazyl decomposes explosively at 240°C and sublimes under vacuum at 135°C. Polythiazyl has properties similar to metals at liquid helium temperatures, and below 0.26 K it behaves as a superconductor. N

S N S N

S N S N

S S N

Thiazyl Polymer: (SN)x

Sodium–Sulfur Cell A battery system that provides high-energy power to a mass ratio and consists of a molten sodium cathode and sulfur anode separated by a G-alumina solid electrolyte. The normal cell design is composed of a tube closed at one end with sodium inside the tube and sulfur outside the tube, and the outer casing of the cell is composed of stainless steel, which is used as a current collector. The cell is operated between 300 and 350°C, and the cell discharge reaction is given by the following: 2 Na + xS q Na2 S x

Soft Lithography Nonphotolithographic method for replicating patterns from the submicron to the macroscopic. A patterned substrate or master often serves as the pattern negative (e.g., etched silicon or patterned photoresist). An elastomer such as PDMS (polydimethylsiloxane) is molded over the rigid master to make a miniature stamp, which can then be inked with a protein or organic solution and stamped onto another substrate to reproduce the pattern. Soft lithography is typically a top-down method for patterning monomolecular layers of organic or biological molecules (e.g., alkanethiols and proteins) at the micron scale. The substrate does not have to be completely flat, so curved surfaces can be patterned. Also, the elastomer can be fabricated with microfluidic pathways for guiding small amounts of fluid on a chip. Benefits of this technique include the minimization of the use of cleanrooms, rapid prototyping, and patterning of curved surfaces. See also microcontact printing. SOG See spin-on glass. Sol A colloidal suspension of solid particles (1 to 1000 nm) in liquid. Solar Cells A semiconductor p or n junction device that converts the radiant energy of sunlight into electrical energy. Individual solar cells are used as light detectors in cameras, and when they are connected in parallel or in series, they can be used to obtain the required value of current and voltage for generating electric power. Single-crystal silicon is the most commonly used solar cell. Solarization The phenomenon of material darkening under radiation that might result from trapped impurities or vacancies in the materials. Sol-Gel Process A chemical route to a variety of glass and ceramic compositions, in which precursors are mixed to form sols (clear to cloudy) that undergo polymerization, forming a gel © 2005 by CRC Press

when the liquid stops flowing. By controlling the reaction conditions (such as solution pH, type of precursors and solvents, reaction temperature, and additives), a variety of physical forms can be produced including films, fibers, microspheres, and monoliths. Oxides are the materials most commonly prepared by the sol-gel process; however, other materials such as nitrides, carbides, borides, and other chalcogenides are also prepared by this process. The sol-gel process has certain advantages and disadvantages compared with conventional processes. The advantages include the ability to precisely control the stoichiometry, the possibility of producing multicomponent materials not previously available, and the ability to produce high-purity materials for electronics and optics without much investment in equipment. However, the drawbacks associated with the sol-gel process are solvent waste, large-volume shrinkage during drying, and high precursor costs. Hence, for each application, the advantages and disadvantages have to be considered in comparison with other processes. Among the sol-gel products, films have gained considerable interest owing to the versatility of the sol-gel process in producing multicomponent homogeneous compositions with ease. Solid Electrolyte Also called fast ion conductors or superionic conductors. Crystalline materials that conduct electricity through the transport of mobile ions in the crystalline structure. The crystal structures of solid electrolytes often consist of open tunnels or layers for mobile ions to movearound, and their conductivity ranges between 10–3 and 101 <–1 cm–1. Conductivities are typically higher than those for regular ionic solids and lower than those for liquid electrolytes. Most solid electrolytes are functional or have sufficient ionic conductivity only at elevated temperature. For example, solid electrolytes, lithium sulfate (Li2SO4), and silver iodide (AgI) are poor ionic conductors at 25°C, but at 542 and 146°C, respectively, their crystal structures change to F-polymorphs with ionic conductivity of ~1 <–1 cm–1. Solid Solution A crystalline phase of a multicomponent material in which at least one atomic site can be filled by more than one atomic species. Hence, compositions can be varied by substituting the ions or by introducing an interstitial atom/ion to occupy the site previously vacant in the lattice. For example, a series of compositions with Cr2O3 and Al2O3 are considered substitutional solid solutions, where Cr and Al have the same charge. Interstitial solid solutions are exemplified by a Pd-H system, where H occupies the sites normally vacant in the palladium lattice. Solid-Solution Electrodes See reversible electrode. Solid State Battery A cell in which both electrodes and electrolytes are solids. See also solid electrolyte. Solid-State Laser Luminescent solids in which the light is artificially amplified by stimulated emission of radiation (laser). This process involves pumping numerous active centers into excited states with reasonably long lifetimes. A condition is then reached in which more active centers are in excited states than in ground states, and a population inversion occurs with an intense pulse of coherent light being emitted. Lasers are exploited in many applications such as photography, surgery, and communications and are used in several types of equipment that involve precise measurements. See also laser materials. Solid-State Reactions The process by which two or more solid materials (powders or monoliths) are mixed and heated to higher temperatures (1000 to 1500°C) or pressures to yield a new solid state product. These reactions do not occur at room temperature over a normal timescale. For example, when MgO and Al2O3 are combined, they yield MgAl2O4 at ~1200°C and not below that temperature. Solidus In a phase diagram, the lowest temperature at which liquids can exist in equilibrium over the given composition range. In the CaO–SiO2 system, solidus occurs at 1460°C. Solubility The ability of a solute to dissolve in a solvent at a given temperature. Solubility is expressed in mass percentage, molarity, or other measures of composition. As the concentration of the solute in the solvent increases, the solution becomes saturated and the solute no longer dissolves in the solvent. © 2005 by CRC Press

Solute The component of a solution that is dissolved in the solvent. For example, in an aqueous solution of sodium chloride, water is the solvent and NaCl is the solute. See also solvent, solubility. Solvent The component of a solution that dissolves the solute. See also solute, solubility. Sonogel The gel produced by the sol-gel process using ultrasonic agitation. Sorel Cements Oxychloride cements (e.g., magnesium oxychloride) used for decorative purposes (e.g., flooring, stucco) in the building industry. Sorel cements have a gel-like texture before setting, which provides acoustic, elastic, and weather-resistant properties. Soro-Silicates Silicates in which discrete Si2O7 polyhedra exist with only one oxygen atom shared in the solid-state structure. Soro-silicates are rare, and one example of such compounds is Sc2Si2O7. Space Charge The net electric charge within a given volume. In systems with both positive and negative charges, the space charge represents the excess of the total positive charge diffused through the volume under study over the total negative charge. Space Groups A symmetry group defined by the point group, crystal system, and space symmetry that describes the structure of all crystalline materials. Triclinic, monoclinic, orthorhombic, and tetragonal are space groups that define crystallinity of materials. See crystal systems, point groups, and space symmetry. d-Spacing In the x-ray diffraction of a polycrystalline material, the perpendicular distance between any pair of adjacent planes in the set of planes of a given structure. The d-spacings are characteristic of each set of planes (hkl) in a polycrystalline material, which assists in identifying the phase or the cell structure of the material under study. Space Lattice See crystal systems. Space Symmetry In polycrystalline materials, the long-range symmetry (incremental translational steps) in the infinite repeating structure in addition to molecular/crystal symmetry. The two elements of space symmetry include the screw axis and the glide plane. The screw axis combines translation and rotation operations, whereas the glide plane combines translation and reflection operations. Spanning Cluster In the sol-gel process, the term used for a continuous gel network created when the gel point is reached and the liquid stops flowing. Specific Heat Capacity See heat capacity. Spectrochemical Series A series arranged in ascending order by the ability of certain anions or ligands to coordinate with a given metal ion. The specific ligands and the order of the coordinating ability of the ligands is I  < Br _ < Cl  < NO3 < F  < OH  < C2O42 < H 2O < NH 3 ~ pyridine < bipyridine << CNI 

Spectrophotometric Analysis A qualitative analysis method applicable to elements or compounds that when reacted with organic or inorganic reagents produce materials that absorb light at specific wavelengths. If the compounds are colored, then the analysis can be carried out visually (colorimetry). Spectroscopic Techniques Several techniques used to characterize materials at a molecular level, involving absorption or emission of energy. See individual techniques such as absorption edge fine structure (AEFS), auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS), electron spectroscopy for chemical analysis (ESCA), electron spin resonance (ESR), extended x-ray absorption fine structures (EXAFS), infrared (IR) spectroscopy, Mossbauer spectroscopy, nuclear magnetic resonance (NMR), Raman spectroscopy, ultraviolet photoelectron spectroscopy (UPS), ultraviolet visible (UV-Vis) spectroscopy, and x-ray fluorescence (XRF). Sphalerite Also called zinc blend. A zinc sulfide (ZnS) compound that is a polytype of a wurtzite structure. © 2005 by CRC Press

Spherulites A spherical cluster of dendrites formed during the gelation process. Spin Coating A coating process that involves flooding or dropping the solution on the clean substrate and spinning the substrate at a defined speed to coat the substrate and dry the film. The substrates are normally held by vacuum during the solution deposition and spinning processes. The spin-coating process can be divided into four stages: deposition, spin-up, spin-off, and evaporation. Excess liquid/solution is deposited on the substrate, and during the spin-up stage, the liquid flows radially outward; and during the spin-off stage, the liquid flows to the perimeter and drops. As the film thins down, the liquid runoff slows down, and evaporation begins, increasing the concentration and viscosity of the deposited film. Factors that affect the film properties include liquid composition, viscosity of the solution, spin rate, and the atmosphere (relative humidity, temperature, etc.) during the spinning process. The advantage of the spincoating process is its ability to form very uniform films with minimum defects; however, this process is limited to smaller substrates. Spin coating is most widely used in the semiconductor industry for coating silicon wafers. See also spin-on glass. Spinel A class of compounds with the general formula ABO4, which are magnetic in nature and have a cubic closed array of oxide ions, with cations A and B occupying tetrahedral and octahedral sites, respectively. The parent spinel is MgAl2O4, and there are over 100 other spinels, with a few produced as sulfides, selenides, and tellurides instead of oxides. Some examples of spinels include Mg2TiO4, LiAlTiO4, LiNiVO4, and Na2WO4. See their magnetic properties in Chapter 4. Spinodal Decomposition A continuous type of phase transformation that begins with small variations in composition over a large spatial extent resulting in interconnected structures of different chemical composition. Spinodal decomposition occurs near the boundaries of a miscibility gap or the spinodes for two liquids and is common in multicomponent silicate glasses and gives rise to an interconnected, tendril-like microstructure. Sputtering A low-vacuum physical deposition technique for making high quality thin films. A low-pressure sputtering chamber typically consists of a parallel plate plasma reactor, with the negatively charged cathode composed of the target material. An inert gas is formed into a plasma by a large DC voltage potential between the electrodes or an RF coil that causes the target element(s) to vaporize and be transported to the anode or substrate where a film is formed. Sputtering is particularly well suited for depositing insulating and multicomponent films of high crystalline quality. Spinodes Inflection points in the phase diagram of a system in which phase separation or decomposition occurs suddenly. Spin-On Glass (SOG) Sol-gel-type coatings spun on glass that are frequently used as insulating layers in the semiconductor industry and for controlling optical properties in architectural glass. Splat Quenching A process used for producing glassy metals by which liquid droplets are propelled at high velocities onto a cold surface and the liquid solidifies in a fraction of a second. Split Interstitial A defect cluster in which the interstitial atom in a lattice causes displacement of another atom to an interstitial site in the lattice; hence, two atoms are affected and are on interstitial sites. This defect is also called a dumbbell-shaped interstitial. The split interstitial defect is commonly exhibited by platinum metal. Spodumene A lithium aluminosilicate composition with the formula LiAlSi2O6. Spontaneous Polarization Polarization in which the dipole moments in a noncentrosymmetric ferroelectric system align parallel to an applied electric field, resulting in a net dipole moment. Spray Drying The process of producing highly dispersed liquid droplets (~5 µm or as large as 600 µm) in a high temperature zone (760°C), by using high pressure nozzles, pneumatic nozzles, or high speed rotating disks. The spray-drying process can be used for both thin liquids or viscous sludges (<1500 cp). The drying gas flow direction can be concurrent or countercurrent to the direction of the spray. This method is frequently used for drying colloidal suspensions of © 2005 by CRC Press

ceramic particles in aqueous and organic liquids. At high temperatures, the spray-drying technique can also be used for producing fine particles by metal organic decomposition. Sputtering A low-vacuum physical-deposition technique for making high quality thin films. A low pressure sputtering chamber typically consists of a parallel plate plasma reactor, with the negatively charged cathode composed of the target material. An inert gas is formed into a plasma by a large DC voltage potential between the electrodes or by an RF coil. The charged gas ions bombard the target element(s), which vaporize and are transported to the anode or substrate, where a film is formed. Sputtering is particularly well suited for depositing insulating and multicomponent films of high crystalline quality. See cathodic sputtering. Square Antiprismatic Coordination The coordination polyhedron that defines the symmetry of the molecule in which the anions occupy the corners of the two staggered squares, with an octavalent cation coordinated to eight anions in a sandwich-type structure. Zr(acac)4 exhibits such coordination. Square Planar Coordination The coordination polyhedron that defines the symmetry of the molecule in which the anions occupy the corners of the square in a plane, and the tetravalent cation is coordinated to anions in the same plane. Examples of such coordination are exhibited by PdO and PtO compounds. Square Pyramidal Coordination The coordination polyhedron that defines the symmetry of the molecule in which the anions occupy the corners of the square in a plane and the pentavalent cation is coordinated to four anions in the same plane and one above the plane. The VO(acac)2 compound exhibits such coordination. Stacking Disorder In many materials, the defect developed in structures involving reversal of stacking of a few layers in the three-dimensional structure. For example, in a …ABCABCABCACBABCABC… structure, CB layers are once reversed during stacking, resulting in transposition of the layers. Stacking Faults Faults that occur in a three-dimensional structure when one or more layers are missing or have moved to the adjacent interstitial sites. Standard Hydrogen Electrode (SHE) A platinum electrode in contact with a 1 molar H+ solution and bathed by hydrogen gas at 1 atm. An SHE is often used as a reference electrode in a three-electrode electrochemical cell and is often considered the standard reference electrode for defining half-cell potentials of other electrode materials. Stannates Tin salts with the general formula MxSnO3. Step Edges These can range in height on surfaces from monoatomic in metals, to unit cell height in binary compounds such as semiconductors, to multiple unit cells (or atoms) in height if step bunching occurs. These step edges and their structures (curved vs. faceted and number of kink sites) often mediate surface growth, dissolution, and other surface structure–dependent properties. See also terrace-step-kink model. Stereograms Graphical representations of the point group of a crystalline material. Stereograms are used to indicate the crystalline orientation of the material with respect to the crystal faces. Stereograms are represented by a circle with an axis perpendicular to the plane and passing through the center. Steric Effects The spatial effects of the ligands attached to the metal on the rate of reaction; that is, the size and shape of the group attached to the metal can alter the rate of reaction of the group or can alter the rate of reaction of more reactive groups or ligands in the vicinity. For example, in the sol-gel process, the condensation reaction might be retarded if the alkyl in the alkoxy groups attached to the metal are bulky like neopentyl in comparison to a nonbulky methyl group. Stern Layer In a colloidal suspension, the tightly bound layer on the surface of the particles formed between the surface charge on particles and the loosely held counterions from the solvent. See also double layer. Stibine An antimony trihydride, SbH3, compound. © 2005 by CRC Press

Stibnite An antimony sulfide, Sb2S3, composition. Sticking Probability The surface adsorption rate divided by the surface collision rate; it often decreases with increasing surface coverage and higher temperature. Stiction An electrostatic or even chemical interaction between initially free surfaces formed during etching of MEMS (or NEMS) devices. At a few nanometers separation, two surfaces often experience an attractive van der Waal’s interaction, which makes them adhere together. With the development of devices with smaller and smaller moving parts in close proximity (several nanometers or less), surface engineering will be required either during or after the etching and fabrication processes to allow parts to freely slide past each other and to reduce wear. See also nanotribology. Stishovite A polymorph of silica with a very high density (4.28 g/cm3). Stishovite is produced by applying 90,000 to 120,000 atm pressure to quartz. Stober Process A widely used method for preparing monodispersed silica spheres, developed by Stober, Fink, and Bohn. In this method, tetraethoxyorthosilicate (TEOS) is hydrolyzed in a basic solution of water and ethanol to a TEOS ratio of 20:1. The stoichiometric ratio of TEOS to H2O is 2:1 to produce SiO2 and is represented by the following equation: Si(OC2 H 5 )4 + 2 H 2O q SiO2 + 4C2 H 5OH

The reaction conditions (high pH and excess water) are suitable for producing a compact structure in contrast to polymeric type structures. The particles produced have a very narrow size distribution with an average particle size of ~0.7 µm. The concentration of TEOS is maintained below 0.2 M to produce monodispersed silica particles. This method has now been extended to other compositions such as TiO2, ZrO2, and B2O3. Stochastic A process that possesses a random or probabilistic nature. The individual molecular motions of an ideal gas can be thought of as stochastic processes even though their averaged behavior is predictable. Stockbarger Method A crystal growth process similar to the Bridgman method, except that the temperature gradient is maintained for the melt through the crystallization process. See Bridgman method. Stoichiometric Defects In a crystal lattice, the point defects originating from the displacement of an atom or ion in the lattice or from the absence or addition of a cation–anion pair in the lattice such that the overall crystal composition remains unchanged. Schottky and Frenkel defects are examples of stoichiometric defects. Stokes Shift In the luminescene process, a shift in the wavelength of the emitted light from the adsorbed light wavelength toward higher wave numbers that correspond to the difference in the energy of the emitted light and the adsorbed light. The energy of the emitted light is normally lower than the energy of the adsorbed light. Since energy, E, is equal to hS or hc/Q, where h is Plank’s constant, c is the speed of light, S is the frequency, and Q is the wavelength of light, loss in energy corresponds to increases in the wavelength of the emitted radiation. Strain The relative change in a material’s dimensions under the application of an applied stress. Stress A load (force per unit area) applied to a material. A sufficiently large stress will cause a strain, and eventually mechanical failure of a material. Striae See cord and striae. Subgrain Boundaries The grain boundary between the two grains in the same crystal that indicates the relative angular orientation of the grains. Sublimation Temperature The temperature at which solids transform directly to vapor phase without passing through the transient liquid phase. Many compounds do not exhibit melting or boiling processes; however, they are purified and separated by the sublimation process. For © 2005 by CRC Press

example, Si8O12(OCH3)8, a silsesquioxane, does not melt, but is purified by sublimation. Chemicals such as iodine and sulfur are also purified by the sublimation process. Substitutional Solid Solutions See solid solution. Sulfur Compounds Compounds containing sulfur atom(s). Sulfur compounds include sulfanes, sulfur halides, sulfur–oxygen compounds, sulfur–nitrogen compounds, and thiols. Sulfanes are hydrides of sulfur. For example, H2S is a sulfane or is commonly known as hydrogen sulfide. Many polysulfanes have been synthesized with higher boiling points, such as H2S2, H2S4, H2S5, and H2S8. Sulfur halides are fluorides, chlorides, bromides, and iodides of sulfur. Many of these could be mixed halides also. Sulfur–oxygen compounds are the most common sulfur compounds, such as SO2, SO3, and many oxyacids. Both oxides and oxyacids can bond with metals as ligands. Sulfur–nitrogen compounds are mostly unsaturated cyclic rings with alternating sulfur and nitrogen atoms. They have been used as suitable ligands to metals. Thiols are sulfur analogues of alcohols in which oxygen is replaced by a sulfur atom. In addition to sulfanes, thiols are excellent reactants for producing sulfides. Superalloy Solution-strengthened or precipitation-hardened alloys typically based on either nickel, iron, or cobalt (e.g., Ni-Al, NiCoCrAlY, etc.). Their high strength, oxidation resistance, and corrosion resistance, particularly at elevated temperatures, make them well suited for gas turbine applications including jet engines and power generation. Superconductors Materials that conduct electricity without any electrical resistance and exhibit large diamagnetism. Superconductors are characterized by unusual magnetic effects, substantial alteration of thermal properties, and quantum effects normally associated with atomic or subatomic levels. Aluminum (Al), indium (In), zinc (Zn), and their alloys are metal superconductors at low temperatures. However, ceramic oxides (such as yttrium-barium-copper oxides) exhibit superconductivity at relatively higher temperatures (e.g., 40 to 92 K). Supercritical Drying The process by which a gel is dried by removing the liquid trapped in the solid-state network at temperatures and pressures above the critical point of the liquid. Since the surface tension of the liquid is zero at and above the critical point, the liquid is removed without causing any structural collapse or volume shrinkage. See also critical pressure and temperature. Superionic Conductors See solid electrolyte. Superlattice Bulk or surface lattice structures that are different (often larger) than the bulk or unreconstructed surface-terminated unit cell. A bulk superlattice structure can be formed if point defects possess long-range order over many unit cells. For example, superconducting YBa2Cu3O6+x can form superlattices depending on the oxygen stoichiometry, x. An example of a surface superlattice adlayer structure would occur when an adsorbate atom occupies every other available surface adsorption site: a partial monolayer. Superoxo Complexes Dioxygen–metal compounds with 1:1 stoichiometry of O2:M (metal) in which the metal is bonded to one or both oxygen atoms and the O2 bond length increases slightly but is less than in peroxo complexes. O M

O M

O

O

M

Superoxo Complexes

Supramolecular chemistry The controlled assemblage of large molecules through intermolecular forces to form one-, two-, or three-dimensional networks with unique structures and properties. See also self-assembly. © 2005 by CRC Press

Surface Area The characteristic of a powder or material that determines its reactivity and performance and is affected by the size and shape of the primary particles. The surface area of a given material is expressed in square meters per gram. The higher the surface area, the more reactive, active, or adsorptive the powder will be, depending upon the composition. For example, a powder with a surface area of 500 m2/g will adsorb more species than a powder with a surface area of only 100 m2/g. A material with a known cross-sectional area can be determined by the monolayer capacity of an adsorbent (nitrogen gas) in a nitrogen adsorption Brunauer, Emmett, and Teller (BET) method. The surface area, A, of a material is given by A = N 0 mX

where m is the experimental monolayer value (mol/gsolid) for an adsorbent (N2) of a crosssectional area X (m2) and N0 is Avogadro’s number. A is normally determined by nitrogen adsorption using the BET method. This equation is valid for flat surfaces only; however, a more accurate BET surface area, St, is determined by St = Wm NA / M

where Wm is the weight adsorbed in a monolayer, M is the molecular weight of the adsorbate, and A is the cross-sectional area of the adsorbate molecule. See also Brunauer, Emmett, and Teller (BET) method. Surface Charge The build-up of charge at solid surfaces, particularly on insulators. The induced electric field can extend many hundreds of layers into the bulk of the material and also several layers into a liquid in contact with the charged surface. See also electrochemical double layer, Shottky barrier, Gouy layer. Surface Chemistry The study of chemical processes that occur at surfaces such as catalysis, chemical synthesis, biomolecule interactions, adhesion, energy conversion, electrochemistry, tribology, film growth, and corrosion. Surface Concentration There are typically of the order of 1015 sites/cm2 or atoms/cm2 on a surface that are available as possible atomic adsorption sites. The surface concentration of adatoms is also the number of adatoms per unit area. Fractional coverage is the ratio of adatoms on the surface to the maximum theoretical number of adatoms that could form an ordered surface monolayer. The latter depends on the initial surface structure and the size and interaction forces of the adatom. Surface Diffusion Random walk motion of surface point defects (e.g., vacancies and adatoms) along a materials surface. Two-dimensional defects such as step edges and kink sites also take part in atom motion at surfaces. Surface diffusion is often highly anisotropic and can depend on crystal orientation, step edge density, and direction of adatom motion relative to step edges (i.e., diffusion is often greater parallel to step edges than normal to step edges). Surface diffusion can also involve the motion of adsorbates. Surface Energy Also frequently called surface tension. The free energy of a surface is almost always positive, as surface atoms always have fewer nearest neighbors than corresponding bulk atoms. In other words, the creation of a new surface is energetically unfavorable, thus requiring the addition of chemical or physical energy. The atomic structure of a surface can also raise or lower its surface energy by packing more or less efficiently. For example, hexagonally packed (111) low index planes of fcc metals typically have lower surface energies (and are generally less reactive) than more open orientations occurring in the square (100) or rectangular (110) faces. A reduction in surface free energy is a driving force for the spheroidization of soap bubbles, faceting of solids, sintering, adsorption, and passivation. © 2005 by CRC Press

Surface Enhanced Raman Spectroscopy (SERS) Rough (or highly stepped) surfaces tend to concentrate the electric fields of Raman scattering to make it a surface sensitive chemical probe, especially at solid–liquid interfaces. Surface Flatness A term used in the microelectronics industry to describe wafer flatness across the entire wafer. A surface can be essentially atomically smooth yet still be bowed or buckled at the macroscopic level. Nonflat substrates do not function properly in much microelectronics fabrication equipment and can yield higher defective devices. See also surface roughness. Surface Modification Also referred to as surface treatment. The chemical modification of the surface by gaseous, liquid, or solid reactions. In the Brunauer, Emmett, and Teller (BET) method of surface area determination, the gases can access a large part of the solid-state material, and the surface can be chemically modified using reactive gases. Similarly, in silica gels, the surface Si–O–Si groups or Si–OH groups can be nitridated by using ammonia and other nitrogencontaining gases. The surfaces can also be chemically modified by reacting the surface active groups with liquids such as coupling agents, hydrophobing agents, and other such materials to change the surface properties. Surface Nucleation Heterogeneous nucleation that occurs on the surface of a material as a result of contaminants on the surface. Nucleations normally occur within the liquid surfaces because of lower energy associated with them compared with crystalvapor interfaces. However, in several systems, the surface contamination provides nucleating sites and promotes heterogeneous nucleation. Surface Reconstruction The outermost atoms in a solid have lower coordination numbers than corresponding bulk atoms; hence the bond lengths between the first and second layers of a material tend to contract or relax, leading to smaller bond distances than in the bulk. This relaxation can be sufficient to change the surface structure to one that is fundamentally different from what one would expect if the bulk crystal structure abruptly terminated at the surface. These reconstructions can also be adsorbate induced and electrochemically induced. Surface Roughness The root mean square (RMS) peak-to-valley roughness value is found by measuring RMS height deviations from a mean atomically flat reference point. Scanning probe microscopy and profilometers are often used to measure surface roughness. Surface roughness is important in thin film growth epitaxy, surface chemical reactivity, and optical properties. See also surface flatness. Surface Structure The ideal crystallographic structure of a material surface can be obtained by simply terminating the bulk Bravais lattice along a particular lattice plane. [For example, a (111) surface of a fcc crystal has a hexagonal close packed atomic arrangement identical to the fcc (111) lattice plane.] Adsorbate monolayer structures often possess a direct crystallographic relationship to this idealized substrate structure. However, just like bulk crystal structures, a surface is often far from ideal and can contain point defects such as vacancies and adatoms, line defects, step edges, and kinks. It may also lower its energy by reconstructing to a different structure. Surface Tension The property of a liquid defined as a force acting on the surface of a liquid to minimize the area of the surface. Surface tension is expressed in dyn/cm or erg/cm2. The surface tension of a liquid is directly proportional to the contact angle of the liquid against a solid surface. The higher the contact angle, the higher the surface tension of the liquid. Surface roughness and contamination of surfaces can drastically change the contact angles of liquids at given surfaces. Surface Thermodynamics Atoms on a surface have fewer nearest neighbors than in the bulk and thus typically behave markedly differently from bulk atoms. Surface thermodynamics describes the equilibrium behavior of these surface atoms with corresponding surface enthalpies, entropies, and free energies. These surface values can have markedly different values and temperature dependencies than the bulk thermodynamic values. Surface thermodynamics can © 2005 by CRC Press

be used to account for surface tension, wetting, capillary forces, surface heat capacities, surface nucleation, and adsorption isotherms. Surfactants Additives composed of varying proportions of polar and nonpolar groups used in two-phase systems to provide a homogenous emulsion. Although surfactants are present in small quantities, they exert a marked effect on the surface behavior of the system. Surfactants form interfaces between solidsolid, solidliquid, solidgas, liquidliquid, and liquidgas phases. In many systems containing oil and water (water-in-oil or oil-in-water) or containing insoluble solids in a liquid medium, surfactants are used to form homogeneous emulsions. Depending upon the system under consideration, the type of surfactant used in producing a homogeneous emulsion can change drastically. There are two types of surfactants: ionic and nonionic. Nonionic surfactants are characterized by their HLB (hydrophobic–lipophilic balance) number to indicate polarity in the compound. A higher HLB number indicates a higher polarity of the surfactant, whereas a lower HLB number indicates the lipophilic (nonpolar) nature of the surfactant. For example, an ethylene glycol fatty acid ester has an HLB number of 2.6, whereas polyoxoethylene fatty alcohol has an HLB number of 15.4. However, ionic surfactants such as sodium oleate (NaOOCC15H31) ionize in an aqueous medium to provide low-energy interfaces, forming a solution or an emulsion. Symmetry Elements See point group. Syneresis The process of spontaneous shrinkage of the solid-state network of the gel, resulting from condensation reactions in a sol-gel-type process. The shrinkage results from the collapse of the solid-state network as a result of the surface tension of liquid removed from the pores of the gel during drying.

T Tactoids The ordered arrangement (nonspheroidal) of colloidal particles in a suspension that are not rigidly bonded to one another, but the colloidal suspension has non-Newtonian viscosity. Unlike coacervates with spheroidal arrangements, the nonspheroidal arrangement of tactoids can be explained by the anisotropy in the double layer surrounding the particles. See also coacervates and crystalloid. Talc Mineral with an infinite silicate sheet structure with the formula Mg3(OH)2Si4O10. Tap Volume The volume occupied by the loose powder packed or shaken in a dry container. Tactosilicates Three-dimensional silicates with a framework structure in which all four oxygens attached to the silicon center are shared with other polyhedrons. Teflon Also known as polytetrafluoroethylene (PTFE). A thermosetting polymer produced from a tetrafluoroethene monomer that is stable up to 325°C. Teflon has a very low coefficient of friction and is a highly inert material. These properties of Teflon are used in nonstick inert coatings for a variety of applications. TEM See transmission electron microscopy. Temperature Diffuse X-ray Scattering A temperature-dependent x-ray scattering technique used to identify the crystal imperfections in a material. Imperfections in the crystals cause diffuse scattering at angles other than Bragg’s angles in the x-ray diffraction patterns. At higher temperatures, diffuse scattering increases and the effect of imperfections in the crystals is enhanced, reducing the intensities of the powder lines in the pattern with a constant total diffracted intensity. Tempering of Glass Strengthening of glass rendered by chemical or thermal treatment of the material. In both cases, treatments at high temperatures below the softening point of glass are performed by introducing chemical species into the glass and by heating and cooling the glass at very high rates. These treatments produce blunt flaws or surface compressions in the structure owing to intergranular voids or changes in surface characteristics that provide excellent resistance to shock damage of glass by preventing crack propagation. © 2005 by CRC Press

Tenorite A name given to a copper oxide, CuO, compound. Tensile Strength A maximum nominal tensile stress developed during increasing load application. It is calculated from the maximum applied load and original unstrained sectional area. Ternary Systems Systems composed of three components. For example, K2OAl2O3SiO2 is a ternary system composed of K2O, Al2O3, and SiO2 components. Several such ternary systems exist in ceramic science and glass technology on commercial scales. Terrace-Step-Kink Model A model for the growth of thin films from vapor onto a vicinal surface. A terrace is the perfectly terminated crystallographic face between two monoatomic step edges. A kink site is where a step edge forms an angle with itself corresponding to a missing atom or row of atoms. In the terrace-step-kink model, the adatom reaches the terrace between two step edges, then diffuses to a step edge where it is captured before diffusing along the edge until a high energy, but low coordination number, kink site is reached. The adatom is then chemically incorporated into the growing surface at the kink site. See also BCF Crystal Growth Theory. tert-Butoxy See butoxy. Tetraalkoxysilane The general class of metal alkoxide represented by the formula Si(OR)4, where R is methyl, ethyl, propyl, butyl, pentyl, etc., and their isomers. TMOS (tetramethoxyorthosilicate or tetramethoxy silane) and TEOS (tetraethylorthosilicate or tetramethoxy silane) are the two most common alkoxysilanes. Tetraalkoxytitanate Titanium analogue of tetraalkoxysilane. See tetraalkoxysilane. Tetrafunctional Monomers or polymers containing four reactive functional groups (f = 4). For example, tetraalkoxysilanes and tetraalkoxytitanates are tetrafunctional monomers. Tetragonal Symmetry Crystal symmetry in which the unit cell consists of one fourfold rotation axis with unit cell parameters a = b | c, and F = G = L = 90°. Examples of crystals with tetragonal structures include tin, rutile (TiO2), G-spodumene (LiAlSi2O6), lead titanate (PbTiO3), and barium titanate (BaTiO3). Tetrahedron A polyhedron system composed of five atoms with one cation in the center of the cube and four anions occupying diagonal corners of the cube. A tetrahedron possesses a threefold rotation axis along each MX direction (i.e., diagonal of the cube). In tetrahedral complexes, the cations have a coordination number of 4. Si(OCH3)4 is an example of a tetrahedral monomer, where M = Si and X = OCH3. TGA See thermogravimetric analysis. Thermal Analysis Analysis of a system that determines the change in physical or chemical properties of the material as a function of temperature. A variety of techniques are used for thermal analysis of a system, including thermogravimetric analysis (TGA), differential thermal analysis (DTA), differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and dilatometry. See individual thermal analysis techniques. Thermal Conductivity The property of a material that determines the amount (or rate) of heatenergy transferred across a boundary (sample) as a result of a thermal gradient. The thermal conductivity of a material depends on several factors such as composition, porosity, pore shapes and sizes, type of gases trapped in the structure, density, and transparency. The total thermal conductivity (Kt) of the system is given by Kt = K s + K g + Kr + Kc

where Ks is solid conductivity, Kg is gas conductivity, Kr is the radiative factor, and Kc is the convective factor. The thermal conductivity, Kt, is measured in watts per meter Kelvin, i.e., the rate of heat-energy flow (Q) across a slab of a given area (A), and thickness (x) per unit temperature difference across the slab (dT). © 2005 by CRC Press

Kt = Qx / A š dT

Thermal Decomposition One of the methods of preparing metal oxide thin films and microspheres/powders from organometallic compounds, metal organic compounds, and metal salts by decomposing the precursors at a given temperature. Examples of ligands in the above metal precursors could include triethanolamine, nitriloacetic acid, ketonates, alkyls, and alkoxides. The thermal decomposition method normally involves dissolving or hydrolyzing the aforementioned compounds in solvents and heating them to high temperatures to produce solid-state materials. Some carbides, nitrides, and chalcogenides have also been prepared by this method, which involves using appropriate environments (e.g., ammonia, nitrogen, H2S, etc.) to form nitrides and sulfides, among others, during the decomposition process. Thermal Etching In certain ceramic materials, the process of removing the surface layer by oxidation or by using other reactions at high temperatures. In many cases, it is the consequence of ceramic processing; however, in others, thermal etching is intentionally performed for functions similar to chemical etching processes. See also chemical etching. Thermal Expansion Coefficient The property of a material that determines the changes in linear dimensions or volume associated with changes in temperature. The coefficient of linear thermal expansion, a, is the change in linear dimension (dl) per unit length (l) per unit change in temperature (dT): a = dl / l š dT

The coefficient of volume thermal expansion, F, is the change in volume (dv) per unit volume (v) per unit change in temperature (dT): F = dv / v š dT

See also thermomechanical analysis. Thermal Oxidation An oxidation method by which several metals or a variety of monomers are oxidized in air at high temperatures to form oxides. For example, metallic aluminum forms an aluminum oxide layer on the surface when it is heated in air. The same method can be used for producing metal nitrides by substituting air with ammonia or nitrogen. Thermistors Thermally sensitive resistors. Thermistors are controlled valency semiconductors with electrical resistivity that vary drastically with temperature. Controlled valency semiconductors are created by limiting the number of ions that have multiple valence states in a given material. Li0.05Ni0.95O is a thermistor operable up to 200°C that exhibits Arrhenius-type conductivity. Oxides with spinel structures, for example, ZnMn2O4 and FeMn2O4, are also used as thermistor materials. Thermistors are used in devices to measure and control temperatures. Thermogravimetric Analysis (TGA) A method of measuring weight change (normally loss) as a function of increasing temperature and time. TGA can be used to study the behavior of a solid system as a function of atmosphere in addition to temperature and time variables. TGA is normally used for measuring the weight loss associated with the decomposition process and for determining the decomposition temperature. Thermomechanical Analysis (TMA) A technique involving measurement of the change in linear dimension as a function of temperature. This procedure measures the thermal expansion coefficient of a material by dilatometric equipment. See also dilatometry. Thermophoresis Phenomenon that describes the movement of suspended particles in a fluid under the influence of an applied thermal gradient. The particles normally move in the direction of the lower temperature region. This method has been frequently used for coating surfaces that are not electrically conductive. © 2005 by CRC Press

Thermoplastic A material, often a polymer, that can be repeatedly reshaped under suitably high temperatures and pressures. Thermoset A material, often a polymer, that once shaped at high temperatures and pressures, cannot be softened and reshaped later. Thiazyl Halides Compounds containing nitrogen, sulfur, and halides, in which the halogen atom is connected to sulfur and not to nitrogen. Thiazyl halides are nonlinear compounds with the formula N } S  X, where X is a halogen atom. Thick Film Materials film or coating thicker than ~1 µm. Thick films are often used for chemical, physical, or thermal protection of the underlying bulk material. Thin Film Materials film with thicknesses typically less than 1 µm often used for microelectronic applications. These films are typically grown or formed by methods such as chemical vapor deposition, physical vapor deposition, self-assembly, and electrochemical deposition techniques. Thiocarbonyl A sulfur-containing ligand analogous to a carbonyl (CO) ligand. The chemical formula of thiocarbonyl is CS. Thiocyanate A ligand-containing carbon, nitrogen, and sulfur, in which the metal is bonded via the nitrogen atom. In certain cases, they can also bond via the sulfur atom, hence producing an ambidendate ligand. The chemical formula of a thiocyanate ligand is RSC}N, where R is an alkyl or aryl group. Thioethers Sulfur analogous to ethers with the general formula RSR. In thioether, sulfur atoms can bond to the metal center. Thionates The salts derived from thionic acids (H2SnO6). For example, K2S3O6 is a potassium trithionate. Thionitrosyls Sulfur ligands analogous to nitrosyl ligands (NO). The chemical formula of thionitrosyls can be represented as NS. Thixotropic Liquids that do not run or drip. Many titanates used in the paint industry are modified by substituting chelating ligands, such as ketonates, for alkoxy to produce thixotropic properties. Thortveite A scandium silicate mineral with the formula Sc2Si2O7, which contains discrete {Si2O6-7 } units. Tie-Lines In a phase diagram, an isotherm that determines the composition of the system at given conditions; the region where both solid and liquid phases exist. The composition of the two phases in equilibrium is determined by drawing a tie-line or an isotherm at the temperature of interest. The composition is given by the points of intersection of this tie-line with the liquidus and solidus curve in the phase diagram. Time–Temperature Transformation (TTT) Diagrams Diagrams that provide information on the phase transition and rate of reactions of a system as a function of temperature to study the kinetics of phase transformation. In the plot, the y-axis is normally used for temperature and the x-axis for time, and various compositions are depicted on this plot. Titanocene The titanium analogue of ferrocene. See ferrocene. TMA See thermomechanical analysis. Tolman’s Cone Angle The solid angle at the metal atom of the cone in a three-coordinated phosphorus ligand in coordination compounds, for example, P(C6H5)3. The cone is normally swept out by the van der Waals radii of the groups attached to the phosphorus atom. Topotactic Reactions The reactions in which the structural similarity in terms of crystalline orientation exists between the product and the reactants at the interface and through the bulk of the crystalline product. See also epitactic reactions. Toughness Property of a material that defines the resistance of the material to fracture or to extended cracking under conditions of strain (i.e., load or impact). Tracer Diffusion Method A technique to measure the conductivity of a solid electrolyte. For example, in sodium G-alumina, a thin film containing radioactive Na+ is deposited on the crystal and placed in a furnace. The radioactive Na+ begins to diffuse into the bulk of the crystal as a result of a random diffusion process. After a limited time, the crystal is removed from the furnace © 2005 by CRC Press

and cut into thin sections parallel to the original painted surface. The radioactivity of the thin section is measured and mapped for calculating the diffusion coefficient, D, of Na+. From this value, the conductivity of the solid electrolyte crystal can be calculated using the NernstEinstein equation. trans-Effect A kinetic effect that controls the ability of the ligands in a compound to labilize the ligands trans to themselves. The order in which the ability of the ligands to labilize the transposition in a complex increases is given by the trans-series: F  , OH  , H 2O, NH 3 , pyridine < Cl  < Br  < I  ,  SCN  , NO2 , C6 H 5 < S = C ( NH 2 )2 , CH 3 < H  , PR3 , AsR3 < CN  , CO,, C2 H 4

The trans-effect has been explained in terms of U and X bonding of the ligands of the metal center. The ligands that are excellent U-electron acceptors (e.g., C2H4 or CO) will remove the U-electron density from the metal, reducing the electron density at the site directly opposite (i.e., trans) to the ligand. This makes the trans-position more prone to nucleophilic attack. Transference Number The fraction of charge carried by either ionic or electronic contributions to the overall conductivity. See also mixed conductors. trans-Influence A thermodynamic effect, with results similar to the trans-effect (i.e., affecting the lability of the ligand in the trans-position). This influence is explained in terms of the Xdonation capability of the ligand. A strong X-donor is expected to produce an axial polarization of the metal, with the lone pair inducing the positive charge on the near side of the metal and a subsequent negative charge on the far side of the metal. This would weaken the metalligand bond at the trans-position, making it labile. Hence, the properties of the ligands low in the transseries can be explained by the X effect (trans-influence), and ligands high in the trans-series can be explained by the U effect (trans-effect). Transition Metals The series of elements involving partially filled 3d, 4d, and 5d orbitals following the alkaline earth metals. These elements possess characteristic properties, such as lustrous nature and high thermal and electrical conductivity, with high melting and boiling points. Transition metals are generally hard and strong materials. Many of them display multiple oxidation states that vary in steps of one rather than two, as in the case of main group elements. Transition metals readily form coordination compounds with Lewis bases. Translucency The optical property of a material characterized by only the fraction of incident light being scattered, with most of the light transmitted and none absorbed. Opal glasses are good examples of translucent materials. Transmission Electron Microscopy (TEM) The electron microscopy technique that images electrons transmitted through and scattered by the sample under investigation to study highresolution microscopic features with an upper working limit of 0.1 µm. TEM allows the study of the lattice structure at the angstrom level by imaging electrons transmitted through a thin sample. TEM uses electron beam energies ranging from 50 to 500 kV and provides magnification multiples in the range of 1400 to 200,000. TEM samples must be prepared such that the sample sections to be analyzed are thin enough for the electron beam to pass through. Transparency The optical property of a material characterized by a condition in which most of the incident light is transmitted through the material without being absorbed or scattered. Transparent materials are homogeneous, and if two phases exist in the material, the solute phase has the same refractive index as the matrix, or the solute phase particles are smaller than the wavelength of light avoiding any scattering or absorption of light. Transparent Electrode An optically transparent electrode that can conduct electricity. Transparent electrodes (e.g., indium tin oxide: ITO) are used in such applications as light emitting diodes © 2005 by CRC Press

(LEDs), which require an electrical bias to generate photons that must then pass through the electrode. Tribology The mechanical properties of surfaces in relative motion to each other such as friction, lubrication, wear, stiction, and adhesion. A monolayer of adsorbates at the interface between two solids can drastically modify tribological properties. With the advent of MEMS, a molecular understanding of tribology, so-called nanotribology, is extremely important. See also MEMS, NEMS, stiction, nanotribology. Triclinic Symmetry A crystal system in which the unit cell parameters a, b, and c are not equal (a | b | c) and the angles F, G, and L are not equal to 90° (F | G | L | 90°). Crystals of sodium aluminosilicate, orthoclase (KAlSi3O8), and potassium chromate (K2CrO7) exhibit triclinic symmetry. Tridymite One of the polymorphs of silica with a density of 2.298 g/cm3, which is formed at 870°C from G-quartz and is stable up to 1470°C. Trifunctional Monomers or polymers containing three reactive functional groups (f = 3). For example, Ti(OC3H7)3(C3H7) is a trifunctional monomer. Trigonal Bipyramidal The coordination polyhedron that defines the symmetry of the molecule in which the anions (ligands) occupy the corners of the triangle (equatorial positions) and two axial positions, above and below the triangular plane. The cation or the metal occupies the center of the equatorial plane coordinated to all five anions. Fe(CO)5 is an example of such coordination. Trigonal bipyramidal molecules possess D3h symmetry. Trigonal Prismatic Coordination polyhedron that defines the symmetry of the molecule in which the anions occupy the corners of the two nonstaggered triangles with a hexavalent cation coordinated to six anions in a sandwich-type structure. Trigonal prismatic compounds possess D3h symmetry. MoS2 and WS2 are examples of such coordination. Triple Point A point in the phase diagram at which three phases exist in equilibrium. Trona A sodium bicarbonate compound, Na3H(CO3)2 · 2 · H2O. Tropylium Another name for a cycloheptatrienyl ligand. H H

Tropylium

Turbidity The property of a suspension system defined by the fraction of scattered light over transmitted light. The higher the scattering, the higher the turbidity. Turbidity results from optical heterogeneity in the system in which the solute phase has a refractive index mismatch or the solute particle sizes are larger than the wavelength of light. See also opacifiers and translucency. Turnbull’s Blue An intense blue complex in a precipitate form produced by mixing K3[FeIII(CN)6] and aqueous FeII. Tutton Salts Double sulfates M 2I Cu(SO4)2 · 6H2O that contain [Cu(H2O)6]2+. These salts belong to a more general class of sulfates with MI (e.g., KI) and MII (MgII) cations instead of a single cation, referred to as Schonites. Twinning A deformation process in crystallography in which the crystal planes slip or glide over one another or are homogeneously sheared. A two-dimensional transformation or growth defect in noncubic crystals. Transformation (or deformation) twins may move under appropriately applied stresses, electric fields, or magnetic fields. See also ferroelectrics. © 2005 by CRC Press

U Ultrahigh Vacuum (UHV) UHV vacuum conditions are less than 1.33 × 107 Pa or 109 torr, which are the conditions required to maintain a clean surface for about 1 hour. Ultraviolet Photoelectron Spectroscopy (UPS) An electron spectroscopy technique that involves measuring the kinetic energy of the outer electrons emitted from the valence shell of an element as a consequence of ultraviolet irradiation. UPS allows identification of the elemental composition, electron structure, and bond-type information in the sample. See also electron spectroscopy for chemical analysis (ESCA) and x-ray photoelectron spectroscopy (XPS). Ultraviolet Visible (UV-Vis) Spectroscopy Spectroscopy associated with the electron transition in the outermost shells in the range of ~104 to 105 cm1 or ~102 to 103 kJ mol1. The UV-vis spectra exhibit absorbance as a function of wavelength, energy, or frequency. The UV range falls between 0.1 and 0.4 µm, and the visible transitions occur between 0.4 and 0.75 µm. Four types of transitions that result in UV-vis spectra include exciton band (promotion of an electron from a localized orbital to a higher energy localized orbital on the same atom), charge transfer spectra (promotion of an electron from a localized orbital on one atom to a higher energy localized orbital on another atom), conduction band (promotion of an electron from a localized orbital to a conduction band), and semiconduction (promotion of an electron from a valence band to a conduction band). (See also definitions of individual types of transitions.) UV-vis spectroscopy provides information on the local structure of an atom in a material and provides some indication of elemental composition and bond type. In particular, UV spectroscopy is useful in identifying functional groups, aromaticity, and molecular structures with unsaturated bonds (U-bonds) and lone pairs in organic and polymeric materials. Uniaxial Crystal Low symmetry crystal belonging to either the hexagonal or tetragonal crystal systems which has an index ellipsoid with only two unequal axes. See also biaxial crystals. Unit Cell In solid-state chemistry, the repeat unit structure that defines the symmetry of the crystal structure represented by a three-dimensional arrangement of atoms and ions. For example, zirconia can stabilize monoclinic (room temperature to ~800°C), tetragonal (~1000 to 1120°C), or cubic (~1500° and higher) unit cell structures at different temperatures. Univariant Condition The condition in which a system in equilibrium in the phase diagram can be completely described by a single variable, pressure, or temperature. For example, the water steam system can be described in terms of change in pressure or temperature. The phase rule, P + F = C + 2, for the watersteam system produces F = 1 (univarient) since P = 2 (liquid and vapor), C = 1 (H2O). UPS See ultraviolet photoelectron spectroscopy. Uranocene A uranium compound analogous to ferrocene. See ferrocene. Uvarovite A member of the garnet family (magnetic materials) with the molecular formula Ca3Cr2Si3O12. UV-Vis Spectroscopy See ultraviolet visible spectroscopy.

V Vacancy Pair The anion and cation vacancy pairs on the nearest neighboring sites observed in crystal structures with Schottky defects. Vacuum Evaporation A common technique used for depositing thin solid films in which the source is heat-evaporated or bombarded by electrons, and the gaseous material is deposited on the substrates. The process is normally conducted inside a bell jar, where the substrates are attached to the top of the bell jar. As the gas rises, it deposits on the cold or hot substrates present. Metal films have been deposited on ceramic, glass, or metal surfaces by vacuum evaporation techniques such as sputtering and physical vapor deposition (PVD) processes. © 2005 by CRC Press

Valence Band An energy band in a material that contains the valence electrons. Valence Electrons Electrons in the outermost occupied shell of an atom, which usually participate in interatomic bonding. See also band gap, conduction band. Valence Sum Rule Rule stating that the valence of an atom is equal to the sum of bond valences for all the bonds that the atom forms. For example, a double bond would be counted as two bonds. In SiO2, silicon bonds to four oxygen atoms; hence, the silicon valence is 4. In AlCl3, aluminum is bonded to three chlorine atoms; hence, the valence of aluminum in this compound is 3. In complex systems, the oxidation state characterizes an atom better than its valence. Vanadocene A vanadium compound analogous to ferrocene. See ferrocene. van der Waals Forces Attractive forces between the atoms with direct proportionality to the polarizability of the atoms and inverse proportionality to the sixth power of their separation. van der Waals forces result from three types of forces, including Keesom, Debye, and London forces. See the definitions of individual forces. Vapor Phase Epitaxy (VPE) VPE uses gaseous inorganic metal compounds (e.g., GaCl3) to grow epitaxial thin films on substrates. The VPE procedure includes formation of the metal carrier gases, transport to and adsorption of the gas on the substrate, surface diffusion, then decomposition of the species to form the desired material and by-products that must be eliminated from the surface. VPE typically occurs at or near atmospheric pressures and at high temperatures to ensure high vapor pressures of the carrier gases. See also, MOCVD, MBE. Vapor Phase Oxidation See flame hydrolysis and pyrolysis. Vapor Phase Transport (Vapor Growth) A method developed for synthesizing new compounds and single crystals from vapors and for purifying compounds in the vapor phase. The process normally involves vacuum sealing a quartz tube with the solid reactant or the impure solid or sealing the reactant with a gaseous transporting media and heating the tube such that a temperature gradient is maintained from one end of the tube to the other. As a result, the pure product is deposited at the cooler end. Chromium metal is purified in this manner, where Cr reacts with iodine gas and deposits CrI2 at the cooler end. CrI2 is then heated to a much higher temperature and decomposes to pure Cr metal. Vaska’s Compound An iridium compound [IrCl(CO)(P(C6H5)3)] named after its discoverer. Vermiculite A magnesium silicate clay compound with a three-layer structure. The chemical composition of vermiculite is [Mg3(OH)2(Si4O10)] × H2O. Verneuil Flame Fusion Method A method used for growing crystals of high melting oxides by melting the starting material (five powder) in a high temperature torch and slowly dropping the melt on the surface of the seed crystal. Vibration Spectroscopy See infrared and Raman spectroscopies. Vicinal Surface A materials surface that is slightly misaligned from a principal crystallographic low index direction. The greater the deviation, the greater the number of monoatomic step edges with a corresponding change in surface energy. The separation of the step edges (or the width of the terraces), L, is given by h/sin()V), where h is the step height and )V is the crystal misorientation from the nearest low index face. Vicinal surfaces are often used to promote epitaxy (and thus reduce strain) of deposited films. Viscoelasticity The property of a material defined by the ratio of applied force to the rate of deformation. The deformation in this case is reversible but is time dependent and is associated with distortion of polymeric chains owing to rotation around the chemical bonds in the molecular structure. Viscosity The property of a liquid defined by the ratio of the applied force to the rate of the flow of the liquid. If the liquid is contained between two plates separated by distance d, each of area A, the viscosity (M) of the liquid is given by the following relationship: M = Fd / Av

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where F is the shearing force and v is the velocity of the liquid. Viscosity is expressed in poise (P), which has the dimensions of g/cmšs. For example, the viscosity of water is 1 cP, and the viscosity of glass at the annealing point is 107.6 P. Viscous Fingering A process by which portions of an interface surge ahead of the advancing front of the viscous flow. Vitrification The process of densifying glasses or ceramics by melting the solid (dried gel or loose powder). The liquid produced as a result of melting fills in the pores developed during the early sintering process to densify the solid further. Vycor Glass A type of glass that contains less silica than Pyrex. Vycor glass is composed of 5% Na2O, 20% B2O3, and 75% SiO2. See also Pyrex.

W Wadsley Defect Defect occurring in oxygen-deficient metal oxide structures composed of blocks of normal defect-free oxide structures separated by crystallographic shear (CS) planes containing oxygen deficiency defects. This defect corresponds to a random distribution of the CS planes in the crystallographic structure. Wafer Generally a single crystalline semiconducting disk from which integrated circuits are fabricated, although wafer can be used to refer to any material used as a substrate. Silicon wafers are sliced from large single crystal boules grown from a melt. Typically, a wafer must be exceptionally pure; have well-defined electrical, mechanical, and thermal properties; be globally flat and atomically smooth; and have lattice parameters that closely match those of the material to be grown on it. Waveguide A material structure, such as a glass fiber, that confines and directs a propagating electromagnetic wave. See also optoelectronics. Wavelength Dispersive Spectroscopy (WDS) An analytical technique used during scanning electron microscopic study to determine the elemental (metal) composition of the sample by scanning the wavelength of x-rays emitted from the sample caused by the bombardment of electrons from the electron beam. The x-rays emitted are characteristic of the elements in the sample. WDS, often used in conjunction with scanning electron microscopy (SEM), can be used for elemental analyses for elements with atomic numbers greater than 3. WDS See wavelength dispersive spectroscopy. Wetting of Solid Surfaces See contact angle. Whisker A high aspect ratio single-crystalline form of a material sometimes used in making mechanically strong composites. A whisker’s extremely high crystalline perfection makes it much stronger than the material’s bulk form, which can contain strength limiting grain boundaries, impurities, and dislocations. White Arsenic Oxide of arsenic (As2O3). White Lead Basic lead carbonate. White lead has been used traditionally in the paint industry as pigment; however, since lead-containing compounds have been found to be toxic, usage of white lead has been reduced. Wolframite A tungsten ore with the formula (Fe,Mn)WO4. Wollastonite A calcium silicate phosphor with the formula CaSiO3. Working Electrode The electrode in a three-electrode cell upon which the desired electrochemical reactions are made to occur. The working electrode may be the site of the measurement of electrochemical kinetics and mechanisms or it may be used to analyze components in the electrolyte. The working electrode can serve as either the anode or cathode, depending on the polarity of the applied voltage. See also cyclic voltammetry, counter electrode, reference electrode. © 2005 by CRC Press

Work Function The energy needed to remove the most loosely bound valence electron from a solid surface into a vacuum with zero kinetic energy at absolute zero. Work function is sensitive to surface structure (e.g., step edge density) and crystal orientation. Adsorbates can both increase and decrease the work function of a surface. The work function difference of two solids gives rise to a contact potential that in turn depends on temperature (the Seebeck effect). When an external potential is applied to the junction, heat removal can occur and can be used in refrigeration (Peltier effect). Wurtzite Structure A structure that consists of a hexagonal close-packed arrangement of anions in which only half of the tetrahedral sites (or vacancies) are filled by the cations. Examples of compounds with such structures include BeO and ZnS. III )O and a overall stoichiometry Wustite A nonstoichiometric iron oxide with the formula (Fe1II3x Fe 2x of Fe1–xO, where 0 < × f 0.1. The oxide has a rock salt structure with cation vacancies and complex defects.

X XANES X-ray absorption near-edge spectroscopy. See x-ray spectroscopies. Xerogel Dried gels produced by removing the liquid in the gel by evaporation. During the evaporation process, the capillary pressure caused by the surface tension of the liquid causes the network structure (polymeric or particulate) to collapse, resulting in large volume shrinkage from the gel to xerogel stage. However, xerogel contains some porosity (10 to 50%) and requires sintering to produce a dense glass or ceramic end product. Xerography A photocopying process. See photoconductors. Xonotlite A calcium silicate with the formula Ca6Si6O17(OH)2. XPS See x-ray photoelectron spectroscopy. X-ray Absorption Near Edge Spectroscopy (XANES) See x-ray spectroscopies. X-ray Fluorescence See x-ray spectroscopies. X-ray Lithography Similar to optical lithography but uses shorter wavelength x-rays, which allows smaller structures to be patterned on a wafer. X-ray Photoelectron Spectroscopy (XPS) An electron spectroscopy technique that involves measuring the kinetic energy of the inner or outer shell electrons emitted from the valence shell of an atom in a sample as a consequence of x-ray irradiation. XPS makes possible identification of the elemental composition, electronic structure, and bond-type information of the sample. See also ultraviolet photoelectron spectroscopy (UPS) and electron spectroscopy for chemical analysis (ESCA). X-ray Spectroscopies The spectroscopy techniques in the x-ray region (104 to 106 kJ/mol) of the electromagnetic spectrum used frequently for structural analysis of solids. There are four types of X-ray spectroscopic techniques: 1. X-ray diffraction techniques utilize a monochromatic beam of x-rays diffracted by the sample and the diffraction pattern (intensity of peaks or spots plotted as a function of d-spacing or Bragg’s angle, V). X-ray diffraction is used to study the crystal structure, crystal phase, particle size (in the case of powder samples), lattice parameters, and crystal defects of the material. This technique can be used for the determination of percent crystallinity in ceramic materials. 2. X-ray emission techniques utilize the characteristic x-rays emitted by the elements as a result of high-energy electron bombardment. X-ray emission spectra are used for the chemical analysis of the sample, the local structure, and the coordination number of an atom in a sample composition. © 2005 by CRC Press

3. X-ray fluorescence (XRF) spectroscopy is a type of x-ray emission spectroscopy used frequently for chemical analysis of solids containing heavier elements that exhibit x-ray fluorescence. Since XRF is normally used for heavier elements (atomic numbers >10), it complements the electron energy loss spectroscopy (EELS) technique, which is used for lighter elements. 4. X-ray absorption measures the absorption of the x-ray by the samples at energies close to absorption edges to study the local structure, for example, extended x-ray absorption fine structures (EXAFS) and x-ray absorption near-edge spectroscopy (XANES). This technique requires a synchroton radiation source. X-ray absorption is a qualitative technique that reveals the contours and location of high-atomic-weight elements in the presence of low atomic-weight-matrices or voids in solid sample. See also extended Xray absorption fine structures (EXAFS). XRF See x-ray spectroscopies.

Y YAG A yttrium aluminum garnet, Y3Al5O12, which is frequently used as a host material for a neodymium laser (Nd3+ ion). See also laser materials. Yellow Cake Uranium dioxide, UO2. Yield Point The point at which the applied stress causes irreversible plastic flow or elongation in a material. YIG A yttrium iron garnet, Y3Fe5O12, which is ferrimagnetic in nature. Ylide A compound with a carbanion attached directly to a heteroatom carrying a high positive charge. Triphenylphosphonium methylide, (C6H5)3P = CH2, is a representative example of a ylide compound. Yoldas Process The wet chemical process developed for producing a transparent monolithic alumina named after the inventor, B. Yoldas. In this process, 1 mol of aluminum butoxide is hydrolyzed with 100 mol of water at 80°C to precipitate fibrillar boehmite, Al(OH)3, followed by peptization with 0.07 mol of HCl or HNO3 to yield a stable alumina sol. By subsequent evaporation and drying steps, sol is converted into a gel, and gel is dried to a transparent alumina monolith by calcination and sintering processes at temperatures between 500 and 1200°C. Young’s Modulus The ratio of normal tensile stress (X) to normal strain (J), which is expressed as E = X/J

The Young’s modulus (E) is calculated as the slope from the stress–strain plot.

Z Zachariasen’s Rules A set of rules developed by Zachariasen to describe the ability of oxides to form glassy materials with an extended three-dimensional network structure and no longrange order. These rules include the following: 1. An oxygen atom is linked to no more than two cations. 2. The coordination number of the cations must be small (4 or less). 3. The coordination polyhedra formed by oxygen atoms around cations share corners, not edges or faces. 4. At least three corners of each polyhedra should be shared. © 2005 by CRC Press

Na2O, MgO, and B2O3 follow the above rules and form glassy solid state materials. However, Al2O3 does not form glassy materials since aluminum has a coordination number of 6, which is high compared with Na, Mg, and B in other oxides. Zeise’s Salt The platinum compound, k[Pt(h2  C2H4)Cl3]H2O, named after the chemist W. Zeise, who first isolated the compound. Zeolites Hydrated aluminosilicate framework structures that contain large channels and cavities (4 to 12 Å), ion-exchangeable cations, and loosely held water molecules, permitting reversible dehydration. The general formula for a zeolite can be represented as X1y+ ,2+ Al 3x+ Si14+xO 2 · nH 2O, where X is a cation (e.g., Na+, K+, Ca2+, and Ba2+). Zeolites are synthesized from fresh aqueous supersaturated gels at relatively high pH levels under high pressures and varying temperatures (hydrothermal processing conditions). The size of the cages selectively allows several organic and inorganic species to enter the zeolite structure. This behavior allows zeolites to be used in several applications such as catalysis, ion-exchange reactions, and adsorbents for a variety of chemical species. Sodalite, Na4(Al3Si3O12)Cl, and ZK-5, Na24(Al24Si72O192) · 90H2O, are examples of zeolites. When zeolites are used for sieving action, they are called molecular sieves. See also molecular sieves. Zeotrope A solution of two or more liquids that changes in composition as the solution is boiled, since one of the liquids evaporates preferentially over the others because of higher volatility. For example, an acetone and ethanol solution is a zeotrope, since acetone evaporates preferentially over ethanol because of higher volatility during the evaporation process. See also azeotrope. Zeta-Potential The surface charge on the particle associated with the plane of shear located in the Gouy layer of the particle in a suspension. The potential of the plane of shear (zeta-potential), _, is given by _ = q / Da(1 / 1 + ka) where q is the net charge inside the plane of shear, D is the dielectric constant, a is the particle radius at the plane of shear, and 1/k is the effective thickness of the double layer. Zeta-potential determines the potential required for the movement of charged particles through a continuous medium or the movement of a continuous medium over a charged surface. See also Gouy layer. Zinc Blend Structure A structure with a cubic close-packed arrangement of anions in which only half of the tetrahedral holes are filled by cations. ZnS, BeO, and SiC have a zinc blend structure. Zircon A zirconium silicate, ZrSiO4. Zone Melting The process of growing crystals in a thermal gradient system in which the source (charge) is only partially melted at any one time. As the charge comes in contact with the seed crystal, it is melted, and the container with seed crystal is pulled through the furnace to cause oriented solidification onto the seed.

GENERAL REFERENCES Atkins, P.W., Physical Chemistry, The English Language Book Society and Oxford University Press, London, 1978. Ball, P., Made to Measure, Princeton University Press, Princeton, NJ, 1997. Bard A. and Faulkner, L., Electrochemical Methods: Fundamentals and Applications, Academic Press, New York, 1980. Billmeyer, F.W., Textbook of Polymer Chemistry, John Wiley & Sons, New York, 1984. Bradley, D.C., Mehrotra, R.C., and Gaur, D.P., Metal Alkoxides, Academic Press, New York, 1978. Brinker, C.J. and Scherer, G.W., Sol-Gel Science, Academic Press, New York, 1990.

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Campbell, S.A., The Science and Engineering of Microelectronic Fabrication, Oxford University Press, New York, 1996. Cotton, F.A. and Wilkinson, G., Inorganic Chemistry, John Wiley & Sons, New York, 1980. Engineered Materials Handbook, Vol. 4: Ceramics and Glasses, ASM International, The Materials Information Society, Materials Park, OH, 1991. Gordon, A.J. and Ford, R.A., The Chemist’s Companion: A Handbook of Practical Data, Techniques, and References, John Wiley & Sons, New York, 1972. Gould, R.F., Ed., Contact Angle: Wettability and Adhesion, Advances in Chemistry Series, American Chemical Society, Washington, DC, 1964. Greenwood, N.N. and Earnshaw, A., Chemistry of Elements, Pergamon Press, New York, 1984. Hendrickson, J.B., Cram, D.J., and Hammond, G.S., Organic Chemistry, McGraw-Hill Kagakusha, London, 1970. Hoch, H.C., Jelinski, L.W., and Craighead, H.G., Eds., Nanofabrication and Biosystems: Integrating Materials Science, Engineering, and Biology, Cambridge University Press, New York, 1996. Kingery, W.D., Bowen, H.D., and Uhlman, D.R., Introduction to Ceramics, 2nd ed., John Wiley & Sons, New York, 1976. Klien, L., Sol-Gel Technology, Noyes, Park Ridge, NJ, 1988. Lowell, S. and Shields, J.E., Powder Surface Area and Porosity, 2nd ed., Chapman and Hall, New York, 1984. Mark, J.E., Allcock, H.R., and West, R., Inorganic Polymers, Prentice Hall, Englewood Cliffs, NJ, 1992. McGraw-Hill Encyclopedia of Science and Technology, 7th ed., Vol. 120, McGraw-Hill, New York, 1992. Moulson, A.J. and Herbert, J.M., Electroceramics: Materials, Properties, Applications, Chapman and Hall, New York, 1990. Parker, S.P., McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed., McGraw-Hill, New York, 1989. Pierson, H.D., Handbook of Chemical Vapor Deposition: Principles, Technology, and Applications, Noyes, Park Ridge, NJ, 1992. Poole, C.P. and Owens, F.J., Introduction to Nanotechnology, John Wiley & Sons, New York, 2003. Robinson, J.W., Undergraduate Instrumental Analysis, Marcel Dekker, New York, 1987. Shinoda, K. and Freeberg, S., Emulsions and Solubilizations, John Wiley & Sons, New York, 1986. Somorjai, G.A. Introduction to Surface Chemistry and Catalysis, John Wiley & Sons, New York, 1994. Terrett, N.K., Combinatorial Chemistry, Oxford University Press, New York, 1998. Tsujii, K., Surface Activity: Principles, Phenomena, and Applications, Academic Press, San Diego, CA, 1998. West, A.R., Solid State Chemistry and Its Applications, John Wiley & Sons, New York, 1984.

SELECTED REFERENCES 1. Fricke, J., Aerogels, Sci. Am., 258, 92, 1988. 2. Colton, R. J. et al., Photochromism and electrochromism in amorphous transition metal oxides, Acc. Chem. Res., 11, 170, 1978. 3. Dean, P.J. et al., Eds., Electroluminescence, Springer-Verlag, New York, 1977. 4. Hecht, J. et al., Understanding Fiber Optics, Howard W. Sams, Indianapolis, 1987, pp. 115. 4a. Reed, S.J.B., Electron Microprobe Analysis, 2nd Ed., Cambridge University Press, New York, 1993, p.13. 5. Flory, P.J., Principles of Polymer Chemistry, Cornell University Press, Ithaca, NY, 1953, Ch. 8, 9. 6. Crilly, A.J. et al., Fractals and Chaos, Springer-Verlag, New York, 1991, p. 7. 7. Adams, D.R., Fuel Cells: A Technical and Economic Analysis of Development and Opportunities in Electrochemical Cells, Harvard Business School, Cambridge, MA, 1960, p. 9. 8. Karasek, F.W. et al., Basic Gas-Chromatography-Mass Spectroscopy, Principles and Techniques, Elsevier, New York, 1988, p. 183. 8a. Montaser, A. et al., Inductively Coupled Plasmas in Analytical Atomic Spectrometry, 2nd Ed., VCH, New York, 1992. 9. Standard test method for kinematic viscosity of transparent and opaque liquids, ASTM Method, 5.01, D44594, 1996. 10. Surface area, pore size/volume distribution measurement, Ceram. Ind., 11, 1994.

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11. Vest, R.W. and Vest, G.M., Metal-Organic Decompostion for Dielectric Films, Report to the Office of Naval Research, Nov. 30, 1991. 12. Breck, D.W., Zeolites Molecular Sieves, Wiley Interscience, New York, 1974. 13. Richerson, D.W., Modern Ceramic Engineering, Marcel Dekker, New York, 1992, p. 276. 14. Chikazumi, S. et al., Physics of Magnetism, Robert E. Krieger, Malabar, FL, 1986, p. 8.

© 2005 by CRC Press

CHAPTER 3 Physical Properties of Inorganic Materials Precursors

© 2005 by CRC Press

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Aluminum Compounds I. Aluminum Alkoxides and Ketonates Alumatrane Al(-OCH2CH2)3NAluminum acetylacetonate derivative: See 2,4-pentadionate derivatives Aluminum (III) n-butoxide Al(O–nC4H9)3 Aluminum (III) s-butoxide Al(O–sC4H9)3 Aluminum (III) s-butoxide bis(ethylacetoacetate) Al(OC4H9)2(-OC(OC2H5)CH(CH3)CO-) Aluminum (III) t-butoxide Al(O–tC4H9)3 Aluminum (III) di-s-butoxide ethylacetoacetate Al(O-sC4H9)2(-OC(OC2H5)CH (CH3)CO-) Aluminum (III) diisopropoxide ethylacetoacetate Al(O-iC3H7)2(-OC(OC2H5)CH (CH3)CO-) Aluminum (III) ethoxide Al(O–C2H5) Aluminum (III) ethoxyethoxy ethoxide, 15% in ethoxydiethylene glycol Al(O–C2H2OC2H2OC2H4)3 Aluminum (III) hexafluoro pentanedionate Al(OC(CF3)CH(CF3)CO)3 Aluminum (III) 3-hydroxy-2-methyl-4pyronate Al(–OC(CH3)CO(CH2)2CO–)3 Aluminum (III) isopropoxide Al(O–iC3H7)3

173.15

—

—

280/13

s/—

1.05

246.32

242/0.7

102

—

s/none

—

246.32

200–206/30

—

—

1/none

0.9671

358.39

—

—

—

l/none

1.10

246.32

156/2

241–246

—

s/none

—

302.34

—

—

—

l/—

1.03

274.49

—

—

—

l/—

1.05

Flash point: 50°C Viscosity: 1000–1200 cSt

1, p. 61

162.17

189/3

157–159

—

s/white

1.142

Degree of association: (4)

426.47

—

—

—

—/—

1.01

Miscible in methanol

1, p. 61; 4, p. 47 1, p. 61

648.17

—

70–73

—

s/—

—

450.29

—

240 (d)

—

—/—

—

204.25

135–138/10

118.5

—

s/white

1.035

Soluble ethanol, toluene

1, p. 60

)Hvap = 29.9 kCal/mol; degree of 1, p. 60; 4, association: (4) p. 47 1.438 (n0); )Hvap = 21.5 kCal/mol; 1, p. 60 flash point: 27°C Flash point: 77°C 1, p. 61 )Hvap = 21.5Kcal/mole )Hvap = 21.6 kCal/mol; Degree of 1, p. 61; 1, association: (2.4) p. 47 — 1, p. 61

Decomposes at 170°C, soluble in 1, p. 62 toluene, carbon tetrachloride, )Hvap = 14.3 kcal/mol Decomposes at 240°C; soluble in 1, p. 62 H2O at pH = 4.5–8 )-vap: 21.5 kCal/mol; degree of association: (3)

1, p. 62; 4, p. 47

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Aluminum n-nitrosophenylhydroxylamine Al(-ON(NO)C6H5)3 Aluminum 9-octadecenylaceto-acetate diisopropoxide (-OC(O(C18H35)CHC(CH3)O-)Al (O-iC3H7)2 Aluminum phenoxide (C6H5O)3Al Aluminum (III) n-propoxide Al(O–nC3H7)3 Aluminum (III) 2,4-pentanedionate Al(OC(CH3)CH(CH3)CO)3

483.3

—

—

168(d)

s/—

—

496.7

—

—

—

s/—

0.99

306.3

—

265

—

s/—

1.23

204.25

232.5/0.5

—

—

s/none

324.31

315

189

150/1

Aluminum (III) 2,2,6,6,-tetramethyl 3,5-heptanedionate Al(OC(C(CH3)3)CH(C(CH3)3)CO)3

576.8

—

235

75/0.02

s/—

—

Soluble (alcohol, ether, toluene, 1, p.63 benzene, pentanedione); insoluble (H2O); )Hform = 428.5 kcal/mol; )Hsub = 4.58 kcal/mol; )Hcomb = 1900 kcal/mol; — 1, p. 63

Di-s-butoxyaluminoxytriethoxysilane ((sC4H9O-)2Al-OSi(OC2H5)3 Sodium aluminum dicaprolactam bis(2-methoxyethoxide) C18H34N2O6AlNa Sodium aluminum hydride bis(2methoxyethoxide) NaAl(H)2(OCH2CH2OCH3)2 Triethyl(tri-s-butoxy)dialuminum (C4H9O)3Al2(C2H5)3

352.48

—

—

—

—/—

1.0

Flash point: 23°C

1, p. 64

424.45

—

20

225(d)

l/—

1.11

Flash point = 21°C

1, p. 64

202.16

—

—

—

l/—

1.036

Flash point: 4°C

1, p. 64

360.49

183/40

20

—

l/—

1.11

Flash point: 21°C

1, p. 64

140.20

—

—

—

l/—

—

Decomposes on distillation

2, p. 583

124.16

103/0.1

—

—

l/—

—

Degree of association: (2)

2, p. 583

262.33

—

87

—

s/—

—

Degree of association: (2)

2, p. 583

s/white-pale yellow

— 1.213

1, p. 63

Flash point: 21°C Miscible in isoproponal, toluene

— Degree of association: (4)

1, p. 63

1, p. 63 4, p. 47

II. Aluminum Alkyls Diethyl(butenyl) aluminum (C2H5CH = CH)Al(C2H5)2 Diethyl(methylacetylenyl) aluminum (CH3C } } C)Al(C2H5)2 Diphenyl(butylacetylenyl) aluminum (C4H9C } C)Al(C6H5)2

Some density numbers are provided with temperatures (in degrees centigrade) in parentheses. Note: µ = magnetic moment; n20 = refractive index at 20°C; d = decomposes; HC = hydrocarbons; s = solid; 1 = liquid; sp = sparingly; ROH = alcohol; Ph = Phenyl (C6H5); )Hform = heat of formation; )Hvap = heat of vaporization; )Hcomb = heat of combustion; Et = ethyl; Cp = C5H5 (cyclopentadiene).

© 2005 by CRC Press

Compound Diphenyl(phenylacetylenyl) aluminum (C6H5C } C)Al(C6H5)2 Trimethyl aluminum Al(CH3)3 Triethyl aluminum Al(C2H5)3 Tribenzyl aluminum Al(CH2C6H5)3 Triisobutyl aluminum Al(i-C4H9)3 Tri-n-butyl aluminum Al(n-C4H9)3 Tri-t-butyl aluminum Al(t-C4H9)3 Tricyclopentadienyl aluminum Al(C5H4)3 Triethylene aluminum Al(CH = CH2)3 Diisobutylaluminumhydride Al(O–iC4H9)2H Tri-m-methylphenyl aluminum Al(m-C6H4CH3)3 Tri-o-methylphenyl aluminum Al(o-C6H4CH3)3 Tri-p-methylphenyl aluminum etherate Al(p–C6H4CH3)3.O(C2H5)2 Triphenyl aluminum Al(C6H5)3 Tri-n-propyl aluminum Al(i–C3H7)3 Triacetylenyl aluminum etherate Al(C } CH)3O(C2H5)2 Tri(methylacetylenyl) aluminum etherate Al(C } CCH3)3. O(C2H5)2 Tri(ethylacetylenyl) aluminum Al(C } CC2H5)3.O(C2H5)2

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

282.32

—

144

—

s/—

—

72.09

126

15.4

—

l/—

0.752

—

6, p. 70

114.7

194

-52.5

—

l/—

0.835

—

6, p. 70

303.38

—

118

—

s/—

—

Degree of association: (1)

2, p. 583

198.33

4

—

l/—

0.787

Degree of association: (1)

198.33

130 73/5 98/1

27

—

l/—

0.816

Degree of association: (2)

1, p. 64; 6, p. 70 6, p. 70

198.33

20/0.001

—

—

l/—

—

Degree of association: (1)

6, p. 70

222.27

—

60

—

s/—

—

Degree of association: (2)

2, p. 583

108.12

55/1

—

—

l/—

—

Degree of association: (2–3)

2, p. 583

142.22

140/4

70

—

l/—

0.78

—

6, p. 70

300.38

—

168

—

s/—

—

—

2, p. 583

300.38

—

195

—

s/—

—

—

2, p. 583

374.50

—

125

—

s/—

—

Degree of association: (1–2)

2, p. 583

258.30

—

237

—

s/—

—

Degree of association: (1–2)

2, p. 583

156.25

85/2

84

—

l/—

0.817

Degree of association: (2)

2, p. 583

176.19

—

34

—

s/—

—

Degree of association: (1)

2, p. 583

218.27

—

78

—

s/—

—

Degree of association: (1)

2, p. 583

260.36

—

—

—

l/—

—

Degree of association: (1)

2, p. 583

State/Color

Densitya (g/cc)

Miscellaneous Degree of association: (2)

Reference 2, p. 583

© 2005 by CRC Press

III. Aluminum Alkyl Alkoxides Diethyl aluminum methoxide (C2H5)2AlOCH3 Diethyl aluminum ethoxide (C2H5)2AlOC2H5 Diethyl aluminum t-butoxide (C2H5)2AlO–tC4H9

116.14

76/4

—

—

l/—

s/—

0.909 (40) 0.850 (30) —

Degree of association: (3)

2, p. 584

130.17

109/10

4.5

—

l/—

Degree of association: (2)

2, p. 584

158.22

88/0.0001

70

—

Degree of association: (2)

2, p. 584

101.13

—

57

—

l/—

—

Degree of association: (3)

2, p. 584

115.15

33/0.001

—

—

l/—

—

Degree of association: (3)

2, p. 584

129.18

66/0.15

6

—

l/—

—

Degree of association: (2)

2, p. 584

(195.06)x

—

—

—

—

—

Degree of association: (4), cubic array for Al and N

2, p. 584

104.10

106/3

—

—

l/—

—

Degree of association: (4)

2, p. 583

120.56

127/50

85

—

l/—

Degree of association: (2)

2, p. 583

92.50

126

21

—

l/—

Degree of association: (2)

2, p. 583

135.96

150

—

—

l/—

0.961 (25) 0.996 (30) —

Degree of association: (2)

2, p. 583

183.96

111/50

—

—

l/—

—

Degree of association: (2)

2, p. 583

216.65

—

148

—

s/—

—

Degree of association: (2)

2, p. 583

126.95

115/50

32

—

l/—

Degree of association: (2)

2, p. 583

173.99

—

95.5

—

s/—

1.207 (50) —

Degree of association: (2)

2, p. 583

103.12

50–5/0.05

11

—

l/—

0.78

Pyrophoric

1, p. 59

IV. Aluminum Alkyl Amides Diethyl aluminum amide (C2H5)2AlNH2 Diethyl aluminum metylamide (C2H5)2AlNH(CH3) Diethyl aluminum dimethylamide (C2H5)2AlN(CH3)2 Diphenylaluminitride compound (C6H5AlNC6H5)8x V. Aluminum Alkyl Halides Diethyl aluminumfluoride (C2H5)2AlF Diethyl aluminumchloride (C2H5)2AlCl Dimethyl aluminumchloride (CH3)2AlCl Dimethyl aluminumbromide (CH3)2AlBr Dimethyl aluminumiodide (CH3)2AlI Diphenyl aluminumchloride (C6H5)2AlCl Ethyl aluminum dichloride (C2H5)AlCl2 Phenyl aluminum dichloride (C6H5)AlCl2 VI. Aluminum Alkyl Hydrides Alane-dimethylethylamine AlH3š(CH3)2NCH2CH3

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Compound Alane-trimethylamine AlH3š(CH3)3N Diethyl aluminumhydride (C2H5)2AlH Diisobutylaluminumhydride (iC4H9)2AlH Dimethyl aluminumhydride (CH3)2AlH Diphenyl aluminumhydride (C6H5)2AlH

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

89.01

76

—

—

l/—

—

86.11

77/1

60

—

l/—

142.22

140/4 114/1

70 80

—

l/—

58.06

55/9

17

—

l/—

0.808 (20) 0.78 0.798 (25) —

182.20

—

157.5

—

s/—

—

240.15

—

—

—

—

—

390.33

—

—

—

s/white

—

562.78

—

—

—

—

—

459.44

—

413-5

—

s/—

—

Soluble in chloroform

1, p. 62

282.23

—

—

—

s/—

—

Soluble in chloroform

1, p. 63

877.42

—

103

—

s/—

1.01

204.12

—

—

—

s/white

—

366.03

—

—

—

s/—

—

474.18

—

—

—

s/—

—

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Pyrophoric

1, p. 59

Degree of association: (3)

2, p. 583

Degree of association: (3)

6, p. 70; 2, p. 583

Degree of association: (3)

6, p. 70; 2, p. 583 2, p. 583

Degree of association: (2, and 4 in vapor)

VII. Aluminum Salts Aluminum acrylate (CH2CHCOO)3Al Aluminum benzoate (C6H5COO)3Al Aluminum 5-chloro-8hydroxyquinolinate (C9H5ClNO)3Al Aluminum 8-hydroxyquinolinate Al(-OC9H6N-)3 Aluminum methacrylate (CH2C(CH3)COO)3Al Aluminum stearate (C17H35COO)3Al Aluminum triacetate (CH3COO)3Al Aluminum trifluoroacetate (CF3COO)3Al Aluminum trifluoromethane- sulfonate (CF3SO3)3Al

— Slightly soluble in water —

— Decomposes on melting — Hygroscopic

1, p. 60 11, p. 73 1, p. 61

1, p. 63 11, p. 73 1, p. 63 1, p. 64

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Antimony Compounds I. Antimony Alkoxides Antimony (III) n-butoxide Sb(O–nC4H9)3 Antimony (III) ethoxide Sb(OC2H5)3 Methacryloxydiphenylantimony CH2C(CH3)COOSb(C6H5)2 Antimony (III) isopropoxide Sb(O–iC3H7)3 Antimony (III) methoxide Sb(OCH3)3

341.10

133–135/0.4

—

—

l/—

256.93

94/10

—

—

l/—

1.265 (25) 1.524

Soluble in benzene, butanol

361.03

—

112-4

—

l/—

—

298.80

68/3

—

—

l/—

—

—

7, p. 1

214.80

—

123–124

—

s/—

—

—

27, p. 18

208.94

160

29.0

—

l/—

1.324

Pyrophoric

6, p. 72

166.86

80.6

87.6

—

l/—

1.528

Pyrophoric

6, p. 72

353.07

377

53

—

l/—

1.4343

1, p. 68

271.43

104/24

—

—

l/yellow

—

Soluble in toluene, ether, chloroform —

207.69

115–120/60

—

—

l/—

—

Low solubility in water

2, p. 685; 8, p. 1891 5, p. 206

296.59

—

42

—

s/—

—

Low solubility in water

5, p. 206

390.59

—

110

—

s/—

—

Low solubility in water

5, p. 206

269.76

—

62

—

s/—

—

Low solubility in water

5, p. 206

452.66

—

69

—

s/—

—

Low solubility in water

5, p. 206

187.27

158

—

—

l/—

—

Low solubility in water

5, p. 206

231.72

178

89

—

s/—

—

Low solubility in water

5, p. 206

278.72

—

86

—

s/—

—

Low solubility in water

5, p. 206

— Soluble in acetone

1, p. 67 1, p. 67 1, p. 67

II. Antimony (III) Alkyls/Aryls Triethyl antimony Sb(C2H5)3 Trimethyl antimony Sb(CH3)3 Triphenylantimony (C6H5)3Sb Bis(tert-butyl) antimony chloride (t-C4H9)2SbCl Methyl antimony dichloride (CH3)SbCl2 Methyl antimony dibromide (CH3)SbBr2 Methyl antimony diiodide (CH3)SbI2 Phenyl antimony dichloride (C6H5)SbCl2 Phenyl antimony diiodide (C6H5)SbI2 Dimethyl antimony chloride (CH3)2SbCl Dimethyl antimony bromide (CH3)2SbBr Dimethyl antimony iodide (CH3)2SbI

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

311.41

—

68

—

s/—

—

Low solubility in water

5, p. 206

355.87

—

86

—

s/—

—

Low solubility in water

5, p. 206

402.87

—

69

—

s/—

—

Low solubility in water

5, p. 206

382.32

—

175

—

—

152.83

60.7 (extrapolated)

—

—

Crystalline solid/— 1/clear

—

Decomposes to (CH3)2Sb2 and H2above 0°C

507.28

—

169–170

—

—

Square pyramid

2, p. 695; 8, p. 1901

Penta-p-tolyl antimony (p-CH3C6H4)5Sb

577.41

—

189

—

—

Trigonal bipyramid

2, p. 695; 8, p. 1902

Tetramethyl antimony iodide (CH3)4SbI

308.79

—

—

—

—

Polymeric chain, decomposes at 288–302°C

2, p. 696; 8, p. 1887

Tetraphenylantimony fluoride (C6H5)4SbF Tetraphenylantimony chloride (C6H5)4SbCl Tetraphenylantimony bromide (C6H5)4SbBr

449.17

—

—

—

Crystalline solid/clear (in hexane) Crystalline solid/clear (in hexane) Crystalline solid/— (in ethanol) —/—

—

Trigonal bipyramid

2, p. 696

465.63

—

—

—

—/—

—

Trigonal bipyramid

2, p. 696

510.08

—

210–215

—

—

Trigonal bipyramid

2, p. 696; 8, p. 1899

Trimethylantimony (CH3)3SbF2 Trimethylantimony (CH3)3SbCl2 Trimethylantimony (CH3)3SbBr2 Triphenylantimony (C6H5)3SbF2

difluoride

204.85

—

—

—

Crystalline solid/— (in ethanol) —/—

—

Trigonal bipyramid

2, p. 696

dichloride

237.76

—

—

—

—/—

—

Trigonal bipyramid

2, p. 696

dibromide

326.66

—

—

—

—/—

—

Trigonal bipyramid

2, p. 696

difluoride

391.06

—

—

—

—/—

—

Compound Diphenyl antimony chloride (C6H5)2SbCl Diphenyl antimony bromide (C6H5)2SbBr Diphenyl antimony iodide (C6H5)2SbI

State/Color

Densitya (g/cc)

Miscellaneous

Reference

III. Antimony (V) Alkyls/Aryls Diphenylantimony trichloride (C6H5)2SbCl3 Dimethylantimony hydride (dimethyl stibbine) (CH3)2SbH Pentaphenyl antimony (C6H5)5Sb

—

—

2, p. 696; 8, p. 1894 2, p. 696; 8, p. 1886

2, p. 696

© 2005 by CRC Press

Triphenylantimony dichloride (C6H5)3SbCl2

423.97

—

143

—

—

—

Crystalline solid/— (in methanol) s/—

Triphenylantimony dibromide (C6H5)3SbBr2 Triphenylantimony diiodide (C6H5)3SbI2 Triphenyl methyl antimony floride (C6H5)3CH3SbF

512.88

—

212–214

606.88

—

387.10

Toxic

2, p. 696; 8, p. 1897

—

—

—

—

—/—

—

—

—

—

_

—/—

—

253.98

50/0.5

—

—

l/—

1.3

298.88

—

—

—

—/—

1.22

Soluble in ethylene glycol

1.21

Trigonal bipyramid

2, p. 696; 8, p. 1897 2, p. 696 2, p. 696

IV. Antimony Alkyl Amide Tris(dimethylamino)antimony ((CH3)2N)3Sb

—

1, p. 68

V. Antimony (III) Salt Antimony acetate (CH3COO)3Sb

1, p. 67

Arsenic Compounds I. Arsenic Alkoxide Arsenic triethoxide As(OC2H5)3

210.07

166

—

—

l/—

Tetramethyl arsenic methoxide (CH3)4AsOCH3

166.10

—

—

—

—/—

—

1.6 mm vapor pressure at 25°C; 1, p. 68 soluble in hexane; )Hform = 169 kCal/mol — 2, p. 700

150.10

—

—

—

—/—

—

Decomposes at 100°C

2, p. 697

120.03

50–52

87

—

l/—

1.124

Flammable

6, p. 73

162.11

140

91

—

l/—

1.152

Flammable

6, p. 73

306.24

233/14

59

—

s/—

1.225

II. Arsenic Alkyls Pentamethyl arsene As(CH3)5 Trimethyl arsene As(CH3)3 Triethyl arsene As(C2H5)3 Triphenylarsine (C6H5)3As

—

1, p. 69

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

207.15

55/10

—

—

77.95

55

—

134.06

101–106

134.06

Densitya (g/cc)

Miscellaneous

l/—

1.1248

—

1, p. 69

—

l/—

—

—

3, p. 77

—

—

l/—

—

Flammable

6, p. 73

65

—

—

l/—

—

Flammable

6, p. 73

140.44

107

—

—

l/—

—

Low solubility in water

5, p. 206

184.90

129

—

—

l/—

—

231.90

156

—

—

l/—

—

Low solubility in water

2, p. 684; 5, p. 206 5, p. 206

259.95

230

—

—

l/—

—

Low solubility in water

5, p. 206

264.59

333

38

—

s/—

—

Low solubility in water

5, p. 206

309.04

356

55

—

s/—

—

Low solubility in water

5, p. 206

356.04

—

40.5

—

s/—

—

Low solubility in water

5, p. 206

141.98

94.3

—

—

l/—

—

Low solubility in water

5, p. 206

174.89

155.3

—

—

l/—

—

Low solubility in water

5, p. 206

263.79

192

—

—

l/—

—

Low solubility in water

5, p. 206

357.79

122.7/11

—

—

l/—

—

Low solubility in water

5, p. 206

State/Color

Reference

III. Arsenic Alkyl Amide Tris(dimethylamino)arsine ((CH3)2N)3As IV. Arsenic Alkyl Hydride Arsine AsH3 Diethyl arsenic hydride (C2H5)2AsH Tertiary butyl arsine (t-C4H9)SbH2 V. Alkyl Arsenic Halides Dimethyl arsenic chloride (CH3)2AsCl Dimethyl arsenic bromide (CH3)2AsBr Dimethyl arsenic iodide (CH3)2AsI Diethyl arsenic iodide (C2H5)2AsI Diphenyl arsenic chloride (C6H5)2AsCl Diphenyl arsenic bromide (C6H5)2AsBr Diphenyl arsenic iodide (C6H5)2AsI Ethylarsenic difluoride C2H5AsF2 Ethylarsenic dichloride C2H5AsCl2 Ethylarsenic dibromide C2H5AsBr2 Ethylarsenic diiodide C2H5AsI2

—

© 2005 by CRC Press

Methylarsenic difluoride CH3AsF2 Methylarsenic dichloride CH3AsCl2 Methylarsenic diiodide CH3AsI2 Phenylarsenic difluoride C6H5AsF2 Phenylarsenic dichloride C6H5AsCl2 Phenylarsenic dibromide C6H5AsBr2 Phenylarsenic diiodide C6H5AsI2

127.95

76.5

—

—

l/—

—

Low solubility in water

160.86

132.5

—

—

l/—

—

Low solubility in water

2, p. 684; 5, p. 206 5, p. 206

343.77

>200

—

—

l/—

—

Low solubility in water

5, p. 206

190.02

110/48

42

—

s/—

—

Low solubility in water

5, p. 206

222.93

254

—

—

l/—

—

Low solubility in water

5, p. 206

311.84

285

—

—

l/—

—

Low solubility in water

5, p. 206

405.84

310

89

—

s/—

—

Low solubility in water

5, p. 206

Barium Compounds I. Barium Alkoxides Barium II, 6,6,7,7,8,8,8 heptafluoro2,2–dimethyl-3,5octanedionate,dihydrate Ba(OC((CF2)2CF3CHCO(C(CH3)3)2. 2H2O Barium hexafluoropentanedionate (OC(CF3)CH(CF3)CO)2Ba Barium II isopropoxide Ba(OCH(CH3)2)2 Barium methoxypropoxide Ba(OCH2CH(CH3(OH3)2 Barium 2,4-pentanedionate Ba(OC(CH3)CH(CH3)CO)2 Barium II 2,2,6,6, tetramethyl 3,5heptanedionate, hydrated Ba(OC(C(CH3)3)CH(C(CH3)3)CO)2

727.70

—

194–196

190/0.05

s/—

—

—

1, p. 69

551.44

—

—

220(d)

s/—

—

—

1, p. 69

255.52

—

>130

—

s/amber

—

—

1, p. 70

315.55

—

—

—

—/—

—

Flash point: 35°C

1, p. 70

335.53

—

>320

—

—/—

—

1, p. 70

503.89

—

175–185

225/0.05

—/—

—

Starts dehydrating at 123°C in vacuum Employed as MOCVD precursor for super-conducting films (see Chapter 1 for MOCVD definition)

293.30

—

—

—

s/—

—

2, p. 225

279.27

—

—

—

s/—

—

Reactive and decomposes in moisture Reactive and decomposes in moisture

1, p. 70

II. Alkyl Barium Halides Ethylbarium iodide Ba(C2H5)I Methylbarium iodide Ba(CH3)I

2, p. 225

© 2005 by CRC Press

Compound n-propylbarium iodide Ba(n-C3H7)I Barium acetate (CH3COO)2Ba Barium acrylate (CH2CHCOO)2Ba Barium methacrylate (CH2C(CH3)COO)2Ba Barium neodecanoate (C6H13C(CH3)2COO)2Ba

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

307.32

—

—

—

s/—

—

255.43

—

—

—

s/—

2.47

279.44

—

—

s/—

—

307.54

—

—

—

s/—

—

—

1, p. 70

479.83

—

—

—

s/—

—

—

1, p. 70

s/—

—

—

12 12

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Reactive and decomposes in moisture Soluble in water

2, p. 225

Soluble in water

1, p. 69

1, p. 69

Beryllium Compounds I. Beryllium Alkoxides 155.24

—

112

100/10–3

71.08

—

>360

—

s/white

—

—

207.22

270

108

—

s/white

1.168

)Hsub: 8.51 kCal/mol; slightly soluble in H2O; soluble in acid and organic compounds; decomposes in hot H2O

123.24

—

16

—

l/—

—

Diethylberyllium Be(C2H5)2

67.14

93–95/4 194

12 13 to 11

—

l/none

—

Diisopropylberyllium Be(C(CH3)2)2

95.19

280

9.5

—

l/none

—

Beryllium t-butoxide Be(O-tC4H9)2 Beryllium methoxide Be(OCH3)2 Beryllium 2,4-pentanedionate Be(OC(CH3)CH(CH3)CO)2

1, p. 71; 10

II. Beryllium Dialkyls Dibutylberyllium monomeric Be(C(CH3)3)2(tert-C4H9)

Decomposes at 280–305°C; 2, p. 127; monomeric; highly toxic and eight volatile Decomposes at 85°C; 2, p. 126; pyrophoric; dimeric in benzene; 5, p. 96; monomeric in dioxane; soluble 10 in organic solvents Decomposition starts starts at 2, p. 127; 40–50°C; dimeric in benzene 5, p. 96; 10

© 2005 by CRC Press

Dimethylberyllium Be(CH3)2

Crystalline solid/white

—

Hsub = 40.8 kJ/mol; thermal decomposition starts at 202°C

—

—/—

—

17

—

1/none

—

Monomeric but dimeric in solution; not separable from ether Decomposition starts at 40–50°C; soluble in organic solvents

—

244–248

—

Crystalline solid/—

—

131.22

—

40

—

s/—

—

171.29

—

—

—

—/—

—

87.3

—

—

—

—/—

—

139.24

—

177–189

40–50/103

—/—

—

153.27

—

213–215

—

s/—

209.38

—

84–86

—

249.36

—

—

125.22

—

97.16

—

39.08

—

217–220

200

151.30

—

—

95.19

244–246

Diphenylberyllium Be(C6H5)2

163.22

t-Butyl, cyclopentadienyl beryllium (C5H5)Be(t-C4H9)

Dineopentylberyllium ((CH3)3CCH2)2Be in ether Di-n-propylberyllium Be(CH2CH2CH3)2

2, p. 125; 5, p. 95; 10 2, p. 128

5, p. 97; 10

III. Beryllium Aryls )Hform = 153.1 ± 2.5 kJ/m; thermal decomposition: 240–250°C; soluble in benzene and ether —

2, p. 128

Insoluble in benzene; exists in polymeric forms Insoluble in benzene; exists in polymeric forms

2, p. 128

—

Degree of association: (2); decomposition starts at 108°C Degree of association: (2)

2, p. 134; nine 2, p. 134

s/colorless

—

Degree of association: (2)

—

—/—

—

Degree of association: (2)

2, p. 134; 10 2, p. 134

—

—

—/—

—

Degree of association: (2)

2, p. 134

199

—

Crystalline solid/ colorless

—

Degree of association: (4)

2, p. 134; nine

10

IV. Beryllium Alkynyls Di(t-butyl)acetylideberyllium Be((H3C)3CC C)2 Dimethylacetylideberyllium Be(H3CC C)2

2, p. 128

V. Organoberyllium Alkoxides RBeOR’ in Benzene t-Butyl,t-butoxyberyllium (t-C4H9)Be(O–tC4H9) t-Butyl,t-butymethoxy beryllium (t-C4H9)Be(OCH2(t-C4H9)) t-Butyl (t-butyl beryllium pivalate (t-C4H9)Be(OCH(tC4H9)2) t-Butyl diphenylmethoxy beryllium (t-C4H9)Be(OCH(C6H5)2) t-Butylisopropoxyberyllium (t-C4H9)Be(Oi-C3H7) t-Butylmethoxyberyllium (t-C4H9)Be(OCH3)

© 2005 by CRC Press

Compound t-Butyltriphenylmethoxy beryllium (t-C4H9)Be(OC(C6H5)3) Ethyl,t-butoxyberyllium (C2H5)Be(O-tC4H9) Ethyl, t-butylmethoxy beryllium (C2H5)Be(OCH(tC4H9)2) Ethyl, t-heptoxylberyllium (C2H5)Be(OC(tC4H9)3) Isobutylneopentoxyberyllium (i-C4H9)Be(OCH2(t-C4H9)) Isobutyl (di-t-butylmethoxy) beryllium (i-C4H9)Be(OCH(t-C4H9)2) Isopropylmethoxyberyllium (i-C3H7)Be(OCH3) Methylbenzoxyberyllium (CH3)Be(OCH2C6H4) Methyl, t-butoxyberyllium (CH3)Be(OC(CH3)3) Methyl, t-butyl(methyl) methoxy beryllium (CH3(Be(OC(CH3)(t-C4H9))2 Methyl diphenylmethoxy beryllium (CH3)Be(OCH(C6H5)2) Methylethoxyberyllium (CH3)Be(OC2H5) Methylmethoxyberyllium (CH3)Be(OCH3) Methyl,n-propoxyberyllium (CH3(Be(OCH2CH2CH3) Methyl,i-propoxyberyllium (CH3)Be(OCH(CH3)2) Methyltritytoxyberyllium (CH3)Be(OC(C6H5)3) Phenylmethoxyberyllium (C6H5)Be(OCH3)

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

325.46

—

141–143

—

s/colorless

—

Degree of association: (2)

111.19

—

—

—

—/—

—

Degree of association: (2–4)

2, p. 134; 10 2, p. 134

181.32

—

147–8

—

—

Degree of association: (2)

2, p. 134

237.43

—

—

—

s/none or colorless —/—

—

Degree of association: (3)

2, p. 134

153.27

—

—

—

—/—

—

Degree of association: (3)

2, p. 134

209.38

—

171–172

—

s/colorless

—

Degree of association: (2)

83.13

—

133–135

—

—

Degree of association: (4)

130.17

—

—

—

s/white plates —/—

—

Degree of association: (4)

2, p. 134; 10 2, p. 134; nine 2, p. 134

97.16

—

93

—

s/—

—

Degree of association: (4)

181.32

—

89–91

—

—

Degree of association: (2)

207.28

—

97–108

—

—

Degree of association: (2)

2, p. 134; nine

69.11

—

28–30

—

Solid needles/ colorless Star-like crystalline solid s/—

—

Degree of association: (4)

55.08

—

23–25

70/103

s/—

—

83.13

—

38–40

—

s/—

—

83.13

—

134–136

100/103

s/—

—

283.37

—

—

—

—/—

—

Degree of association: (4); highly toxic; tetrameric in C6H6 Degree of association: (4); crystalline plates Degree of association: (4); crystalline Degree of association: (2)

2, p. 134; nine 2, p. 134; 8, p. 436 2, p. 134; nine 2, p. 134; nine 2, p. 134

117.15

—

—

v

—/—

—

AU: : all opening parens need closing parens

State/Color

Densitya (g/cc)

Miscellaneous

Degree of association: (4); soluble in ether; resistant to hydrolysis

Reference

2, p. 134; nine 2, p.134; 10

2, p. 134; 10

© 2005 by CRC Press

Phenyltriphenylmethoxy beryllium (C6H5)Be(OC(C6H5)3) Phenylacetylide,t-butoxy beryllium (H4C6C } C)Be(Ot-C4H9)

345.45

—

—

—

—/colorless

—

Degree of association: (2)

2, p. 134

160.24

—

—

—

—/—

—

Degree of association: (F)

2, p. 134

186.30

—

—

—

—/—

—

Degree of association: (2)

2, p. 134

304.48

—

128–130

—

—

261.42

—

—

—

s/orange red —/—

—

Degree of association: (2)

2, p. 136

110.20

—

—

—

—/—

—

Degree of association: (2)

2, p. 136

82.15

—

—

—

—/—

—

Degree of association: (3)

2, p. 136

206.29

—

—

—

—/—

—

Degree of association: (2)

2, p. 136

324.47

—

—

—

—/—

—

Degree of association: (2)

2, p. 136

96.18

—

—

1/none

—

Degree of association: (3)

96.18

100 (decomposes) —

—

—

—/—

—

Degree of association: (3)

2, p. 136; 10 2, p. 136

68.12

—

55–56

—/—

—

124.23

—

—

Decomposes at > ~60 —

—/—

—

Degree of association: (3); highly toxic Degree of association: (2)

2, p. 136; 8, p. 436 2, p. 136

192.27

—

—

—

—/—

—

Degree of association: (2)

2, p. 136

206.29

—

—

—

—/—

—

Degree of association: (2)

2, p. 136

234.35

—

—

—

—/—

—

Degree of association: (2)

2, p. 136

130.19

—

—

—

—/—

—

Degree of association: (3)

2, p. 136

VI. Organoberyllium Amides RBeNR’R” in Benzene t-Butyl,methylbenzylamide beryllium (t-C4H9)Be(N(CH3)(CH2C6H5)) Di-t-butyl,phenylbenzylberyllium (t-C4H9)2Be(N(C6H5)(CHC6H5) t-Butyl,phenylpropylenephenylamide beryllium (t-C4H9)Be(N(C6H5)(C6H4CH = CHCH2)) Ethyl,diethylamide beryllium (C2H5)Be(N(C2H5)2) Ethyl,dimethylamide beryllium (C2H5)Be(N(CH3)2) Ethyl,diphenylamide beryllium (C2H5)Be(N(C6H5)2) Ethyl(phenylbenzyl amide) beryllium (C2H5)Be((C6H5)N(CH(C6H5) (C2H4C6H5)) Isopropyldimethylamide beryllium (iC3H7)Be(N(CH3)2) Methyl,diethylamide beryllium (CH3)Be(N(C2H5)2) Methyl,dimethylamide beryllium (CH3)Be(N(CH3)2) Methyl,di-n-propylamide beryllium (CH3)Be(N(n-C3H7)2) Methyl,diphenylamide beryllium (CH3)Be(N(C6H5)2) Methyl,phenyltolylamide beryllium (CH3)Be(N(C6H5)(C6H4CH3)) (Methyl,phenylmethylamide) beryllium (CH3)Be((p-CH2C6H5)N(CH(CH3) (C6H5))) Phenyl,dimethylamdie beryllium (C6H5)Be(N(CH3)2)

—

10

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

254.34

—

—

—

—/—

—

Degree of association: (2)

2, p. 136

t-Butylberyllium hydride (t-C4H9)BeH

67.14

—

—

—

s/white

—

Highly toxic, glassy

Ethylberyllium hydride (C2H5)BeH

39.08

—

—

—

s/white

—

Highly toxic

Methylberyllium hydride CH3BeH

25.05

—

—

—

s/white

—

Polymeric glass

n-Pentylberyllium hydride (n-C5H11)BeH Phenylberylliumhydride (C6H5)BeH o-Tolylberylliumhydride (o-C6H4CH3)BeH m-Toluylberylliumhydride (m-C6H4CH3)BeH

81.16

—

—

—

s/white

—

—

87.13

—

—

—

s/white

—

—

2, p. 142; 8, p. 437; 12 2, p. 142; 8, p. 436; 12 2, p. 142; 8, p. 436; 12 2, p. 142; 12 2, p.142

101.07

—

—

—

s/white

—

—

2, p.142

101.07

—

—

—

s/white

—

—

2, p.142

—

59–60

—

s/none

—

Decomposes above 70°C; sublimable crystals from BeCl2 and CpNa; unstable in air; reacts violently with H2O; highly toxic

s/—

—

—

Compound Phenyl,diphenylamdie amide beryllium (C6H5)Be(N(C6H5)2)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

VII. Organoberyllium Hydrides

VIII. Dicyclopentadienylberyllium Compounds Dicyclopentadienylberyllium Be(C5H5)2

139.20

2, p. 144; 8, p. 438

Bismuth Compounds I. Bismuth Alkoxides and Thioalkoxides Bismuth hexafluoropentanedionate Bi(COCF3CHCF3CO)3

830.14

110/0.05

95-7

—

1, p. 72

© 2005 by CRC Press

Bismuth methoxyethoxy ethoxide Bi(OC2H4OC2H4OCH3)3 Bismuth t-pentoxide Bi(O–tC5H11)3 Bismuth tetramethylheptanedionate Bi(-OC(C(CH3)3)CHC(C(CH3)3)O-)3 Phenylbishmuth bisthiophenol C6H5Bi(SC6H5)2

555.40

—

—

—

s/—

—

—

1, p. 72

470.39

—

63/404

—

s/—

—

—

1, p. 72

758.74

160/0.1

112-6

>295(d)

s/—

—

—

1, p. 72

504.42

—

—

—

—/—

—

—

2, p. 690

274.50

—

116

—

s/—

—

Low solubility in water

5, p. 206

443.10

—

158

—

s/—

—

Low solubility in water

5, p. 206

398.64

—

185

—

s/—

—

Low solubility in water

5, p. 206

490.10

—

134

—

s/—

—

Low solubility in water

5, p. 206

383.82

—

214

—

s/—

—

Low solubility in water

5, p. 206

294.92

—

242

—

s/—

—

Low solubility in water

5, p. 206

477.82

—

225

—

s/—

—

Low solubility in water

5, p. 206

445.89

—

206

—

s/—

—

Low solubility in water

5, p. 206

440.30

100/0.2

77

—

s/—

1.585

—

1, p. 69

638.61

—

—

—

s/—

1.21

—

1, p. 72

722.71

—

—

—

s/—

—

—

1, p. 72

362.11

—

—

—

s/—

—

II. Bismuth Alkyl/Aryl Halides Dimethyl bismuth chloride (CH3)2BiCl Diphenyl bismuth bromide (C6H5)2BiBr Diphenyl bismuth chloride (C6H5)2BiCl Diphenyl bismuth iodide (C6H5)2BiI Methyl bismuth dibromide CH3BiBr2 Methyl bismuth dichloride CH3BiCl2 Methyl bismuth diiodide CH3BiI2 Phenyl bismuth dibromide C6H5BiBr2 Triphenylbismuth (C6H5)3Bi III. Bismuth Salts Bismuth 2-ethylhexanoate (C4H9CH(C2H5)COO)3Bi Bismuth neodecanoate (C6H13C (CH3)2COO)3Bi Bismuth salicylate (HOC6H4COO)BiO

Soluble acetic acid

1, p. 72

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Boron Compounds I. Boron Alkoxides Boratrane B(-OCH2CH2)3NBoron allyloxide B(OCH2CHCH2)3 Boron t-butoxide B(O—tC4H9)3 Boron n-butoxide B(O-nC4H9)3

156.98

—

235-237

—

s/—

—

—

1, p. 73

182.03

72/12

—

—

s/—

0.919

—

1, p. 73

230.16

101/74

18-19

—

l/—

0.811

1, p. 73

230.16

230–235

70

—

l/—

0.853

Boron ethoxide B(OC2H5)3 Boron isopropoxide B(O-iC3H7)3 Boron methoxide B(OCH3)3 Boron methoxyethoxide B(OCH2CH2OCH3)3 Boron propoxide B(OC3H7)3 Boron n-propoxide B(O-nC3H7)3 Boron trimethylsiloxide B(OSi(CH3)3) 3 n20 = 1.3860Boron vinyldimethylsiloxide B(OSi(CH3)2CHCH2)3 Diphenylborane 8-hydroxyquinolinate (C6H5)2BOC9H6N

145.80

117-8

85

—

l/—

—

188.08

139-41

—

—

l/—

0.815

n20 = 1.389 Flash point: 29°C Vapor pressure of 10 mm at 106°C; )Hform = 292 kcal/mol; viscosity: 2.0 cSt; n20 = 1.141 n20 = 1.389; )Hform = 251 kcal/ mol —

103.91

68–69

34

—

l/—

0.915

236.07

123-125/1.5

—

l/—

1.029

)Hform = 224 kcal/mol; viscosity: 0.4 cSt; n20 = 1.3568 n20 = 1.4138

187.80

—

—

—

—/—

1, p. 73; 4, p. 52 1, p. 74; 4, p. 52 4, p. 53

188.08

175

—

—

l/—

0.857

273.38

184

35

—

l/—

0.825

)Hvap = 10.1 kcal/mol

1, p. 74

314.41

78/15

—

—

l/—

0.872

n20 = 1.4163

1, p. 74

309.18

100/0.1

203-205

—

s/yellow

69.94

47/2.5

—

—

l/—

—

)Hform = 272 kcal/mol —

1, p. 73

1, p. 735, 52 1, p. 74

1, p. 74

—

—

1, p. 75

0.7383 (35)

—

2, p. 255

II. Alkylboron Compounds Isobutylborane (i-C4H9)BH2

© 2005 by CRC Press

n-Butylborane (n-C4H9)BH2 sec-Butylborane (s-C4H9)BH2 Butyldibromoborane (C4H9)BBr2 Butyldichloroborane (C4H9)BCl2 Butyldifluoroborane (C4H9)BF2 Dibutylchloroborane (C4H9)2BCl Diethylbromoborane (C2H5)2BBr Diethylchloroborane (C2H5)2BCl Dimethylbromoborane (CH3)2BBr Dimethylchloroborane (CH3)2BCl Dimethylethylborane (CH3)2B(C2H5) Dimethylfluoroborane (CH3)2BF Dimethyliodoborane (CH3)2BI Dimethylhydroxyborane (CH3)2BOH Dimethylmethoxyborane (CH3)2B(OCH3) Diphenylchloroborane (C6H5)2BCl Ethyldichloroborane (C2H5)BCl2 Ethylhydroxyborane (C2H5)2BOH Methyldibromoborane (CH3)BBr2 Methyldichloroborane (CH3)BCl2 Methyldiethylborane (CH3)B(C2H5)2

69.94

—

—

—

—/—

—

2, p. 255

—

2, p. 255

l/—

0.7853 (33) 0.7561 (36) —

69.94

68/2.5

—

—

l/—

227.73

150

—

—

—

2, p. 255

138.83

107.9

—

—

l/—

—

—

2, p. 255

105.92

35

—

—

l/—

—

2, p. 255

173

—

—

l/—

0.851 (25) —

160.49

—

2, p. 255

148.84

101

81.0

—

l/—

—

—

2, p. 254

104.39

78.5

84.6

—

l/—

—

2, p. 255

120.78

31.6

128.9

—

l/—

0.85091 (26.5) —

—

2, p. 254

76.33

4.9

—

—

Gas/—

—

—

2, p. 254

69.74

25.5

<160

—

Gas/—

—

—

2, p. 254

59.88

42

147.3

—

Gas/—

—

—

167.78

68.8

107.5

—

l/—

—

—

2, p. 254

57.89

0/36 torr

—

—

Gas/—

—

—

2, p. 254

71.91

21

—

—

Gas/—

—

—

2, p. 254

200.47

271

—

—

l/—

—

—

2, p. 255

110.18

50

—

—

l/—

—

—

2, p. 254

85.94

50

—

l/—

0.7921

—

2, p. 255

185.65

80 (decomposes) 60

110.6

—

l/—

—

—

2, p. 254

96.75

11.1

127.1

—

l/—

—

—

2, p. 254

83.97

61

135.5

—

l/—

—

—

2, p. 254

© 2005 by CRC Press

Compound Methyldifluoroborane (CH3)BF2 Methyldihydroxyborane (CH3)B(OH)2 Methyldimethoxyborane (CH3)B(OCH3)2 Phenyldichloroborane (C6H5)BCl2 Phenyldifluoroborane (C6H5)BF2 n-Propyldifluoroborane (n-C3H7)BF2 n-Propyldihydroxyborane (n-C3H7)B(OH)2 Tribenzylboron B(CH2C6H5)3 Triisobutylboron B(i-C4H9)3 Tri-n-butylboron B(n-C4H9)3 Tri-sec-butylboron B(s-C4H9)3 Tri-t-butylboron B(t-C4H9)3 Triethylborane B(C2H5)3 Tri-n-hexylboron B(n-C6H13)3 Trimethylborane B(CH3)3 Triphenylborane B(C6H5)3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

63.84

63

130.4

—

g/—

—

59.86

110(d)

95(d)

—

s/—

—

—

2, p. 254

87.91

53.5

—

—

l/—

—

—

2, p. 255

158.82

175

0

—

l/—

—

—

2, p. 255

125.91

70

—

—

l/—

—

—

2, p. 255

91.90

36

—

—

l/—

—

—

2, p. 255

87.91

—

106

—

s/—

—

—

2, p. 255

284.21

229/16

47

—

s/—

—

—

2, p. 255

182.16

188

—

—

l/—

182.16

208

—

—

l/—

182.16

—

—

—

—/—

182.16

181.5

—

—

l/—

07380 (25) 0.7687 (20) 0.7583 (33) 0.7687 (20) —

98.00

95.4

92.9

—

l/—

0.6774

266.32

133/1.5 torr

99.1

—

l/—

55.91

20.5

160

—

Gas/—

0.7761 (33.5) 0.7994 (20) 0.625

242.13

195 245

142 136

—

s/—

State/Color

Densitya (g/cc)

—

Miscellaneous )Hvap = 832.6 kJ/mol

Reference 2, p. 254

)Hform = 337.6 ± 5 kJ/mol (liquid); 279.9 ± 5.4 kJ/mol (gas)

2, p. 255

)Hform = 345.2 ± 10.5 (liquid); 283.2 ± 10.9 (gas) )Hform = 305.4 ± 25.1, (liquid), 245.6 ± 25.1 (gas) —

2, p. 255

—

2, p. 255 2, p. 255 2, p. 254

)Hform = 485.3 ± 9.6, (liquid), 396.6 ± 10.5 (gas)

2, p. 255

)Hvap = 142.7, 23 (liquid) 112.6, 23 (gas) —

2, p. 254 2, p. 255

© 2005 by CRC Press

Triisopentylboron Bi-C5H11)3

224.24

119

—

—

l/—

l/—

0.7452 (33) 0.76 (23.4) 0.7721 (20) 0.7676 (25) —

—

2, p. 255

Tri-n-pentylboron B(n-C5H11)3

224.24

—

26.5

—

l/—

—

2, p. 255

Triisopropylborane B(iC3H7)3 Tris(pentafluorophenyl)boron (C6H5F)3B Tri-n-propylborane B(nC3H7)3

140.08

147.4

52.5

—

—

2, p. 255

511.99

—

126–131

—

s/—

1.585

—

1, p. 75

140.08

156

65.6

—

l/—

0.7204 (24.7) 0.7631 (20) —

—

2, p. 255

Tritolyboron B(C6H4CH3)3

284.21

—

175

—

s/—

—

2, p. 255

120.78

—

98

—

Gas/—

—

—

2, p. 255

76.33

76.4

109.6

—

l/—

—

—

2, p. 255

59.88

23.8

164 to 157

—

Gas/—

—

—

2, p. 255

67.93

17.1

—

—

Gas/—

—

—

2, p. 255

197.66

—

95

—

—/—

—

—

2, p. 255

108.76

46.0

111.1

—

l/—

—

—

2, p. 255

75.85

39.1

133.4

—

Gas/—

—

—

2, p. 255

79.94

51.7

—

—

l/—

—

—

2, p. 255

176.11

72/2

—

—

l/—

0.7857 (20)

—

2, p. 255

III. Alkylene Boron Compounds Diethylenebromoboride (CH2 = CH)2BBr Diethylenechloroboride (CH2 = CH)2BCl Diethylenefluoroboride (CH2 = CH)2BF Dimethylethyleneboron (CH3)2B(CH = CH2) Ethylenedibromoboride (CH2 = CH)BBr2 Ethylenedichloroboride (CH2 = CH)BCl2 Ethylenedifluoroboride (CH2 = CH)BF2 Methyldiethyleneboron (CH3)B(CH = CH2)2 Tributeneboron B(CH2CH = CHCH3)3

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Cadmium Compounds I. Cadmium Alkoxides/Ketonates Cadmium diethyldithiocarbamate ((C2H5)2NCS2)2Cd Cadmium 2,4-pentanedionate Cd(–OC(CH3)CH(CH3)CO–)2 Dimethylcadmium (CH3)2Cd

408.94

—

63–69

—

s/—

1.48

310.64

—

—

—

s/yellow

142.88

105.5

4.5

—

l/—

1.986

446.53

—

158

—

s/—

—

—

2, p. 853

194.56

—

—

—/—

—

—

2, p. 853

226.64

103.5/12.5

Decomposes at >0 48

—

l/none

—

242.60

—

—

—/—

—

170.53

64/1

Decomposes at >250 21

—

l/none

—

142.88

105.6

4.5

—

l/none

1.985

294.68

—

115

—

s/—

266.62

—

174

—

205.64

84/21

83

Decomposes at >190

—

Soluble in toluene, chloroform — )Hform = 15.2kcal/mole

1, p. 79 1, p. 79 1, p. 79

II. Diorganocadmium Compounds Bis(pentafluorophenyl)cadmium (C6F5)2Cd Diallylcadmium Cd(CH2CH = CH2)2 Di-n-butylcadmium Cd(n-C4H9)2 Dicyclopentadienylcadmium Cd(C5H5)2 Diethylcadmium Cd(C2H5)2 Dimethylcadmium Cd(CH3)2 Di-2-methylphenylcadmium Cd(C6H4CH3)2 Diphenylcadmium Cd(C6H5)2 Di-n-propylcadmium Cd(n-C3H7)2

Monomeric, light sensitive; explodes at >180°C —

2, p. 853

2, p. 853

—

Monomeric, light sensitive, explodes at >180°C Pyrophoric, monomeric, vapor phase: 28/20°C; light sensitive; explodes at >180°C —

2, p. 853

s/—

—

—

2, p. 853

—

l/none

—

Monomeric, light sensitive, explodes at >180°C

2, p. 853

—

—/—

—

Degree of association: (2)

2, p. 857

2, p. 853

2, p. 853

III. Organocadmium Alkoxides/Aryloxides and Thioalkoxides Methyl-t-butoxycadmium (CH3)Cd(O-tC4H9)

200.56

—

© 2005 by CRC Press

Methylethoxycadmium (CH3)Cd(OC2H5) Methylmethoxycadmium (CH3)Cd(OCH3) Methylisopropoxycadmium (CH3)Cd(O–iC3H7) Methylthio-t-butoxylcadmium (CH3)Cd(S-tC4H9) Methylthiophenyloxy cadmium (CH3)Cd(SC6H5) Methylthioisopropoxyl cadmium (CH3)Cd(S-iC3H7)

172.51

—

158.48

—

186.53

—

316.34

—

400.22

—

269.37

Decomposes at >90 Decomposes at >70 —

—

—/—

—

Degree of association: (4)

—

—/—

—

—

—/—

—

Degree of association: (4)

2, p. 857

—

2, p. 857 2, p. 857

—

—/—

—

Degree of association: (4)

2, p. 857

—

—/—

—

Degree of association: (4)

2, p. 857

—

Decomposes at >100 Decomposes at >35 —

—

—/—

—

Degree of association: (5)

2, p. 857

230.49

—

254–256

—

s/—

2.01

Soluble in water

1, p. 79

202.45

—

—

—

s/—

—

Soluble in water

1, p. 79

Soluble in hot ethanol

1, p. 80

IV. Cadmium Salts Cadmium acetate (CH3COO)2Cd Cadmium formate (HCOO)2Cd

Calcium Compounds I. Calcium Alkoxides and Ketonates Calcium ethoxide Ca(OC2H5)2 Calcium 6,6,7,7,8,8,8—heptafluoro—2,2—Dim ethyl—3,5—octanedionate Ca(OC(CF3CF2CF2)CHC(C(CH3)3)O)2 Calcium hexafluoropentanedionate Ca(OC(CF3)CH(CF3)CO)2 Calcium methoxide Ca(OCH3)2 Calcium methoxyethoxide Ca(OC2H4OCH3)2 Calcium 2,4-pentanedionate Ca(OC(CH3)CH(CH3)CO)2.2H2O Calcium 2,2,6,6-tetramethyl-3,5heptanedionate Ca(OC(C(CH3)3)CH(C(CH3)3)CO)2

130.2

—

—

—

—/—

—

630.43

205/0.1

90–95

—

s/—

—

—

1, p. 81

454.18

180/0.07

135–140

—

s/—

—

—

1, p. 81

102.15

—

—

s/—

—

—

1, p. 81

190.25

—

Decomposes at >170 —

—

l/—

—

238.30/ 274.33 406.63

—

Decomposes at 175 221–224

—

s/white

—

d = 1.0 g/cc; 20% in methoxyethanol Dihydrate, 95%

—

s/—

—

Soluble in ethanol, toluene

—

1, p. 81 1, p. 81; 3, p. 75 1, p. 81

© 2005 by CRC Press

Compound

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

98.20

—

—

—

—/—

—

70.15

—

—

—

—/—

—

194.29

—

—

—

—/—

—

—

—/—

—

—

2, p. 231

—

2, p. 231; 8, p. 454

Formula Weight

State/Color

Densitya (g/cc)

Miscellaneous

Reference

II. Dialkyl and Diaryl Calcium Compounds Diethylcalcium Ca(C2H5)2 Dimethylcalcium Ca(CH3)2 Diphenylcalcium Ca(C6H5)2

Unstable in solution at room temperature Reacts with pyridine; unstable in solution at room temperature Stable in solution at room temperature; soluble in tetrahydrofuran and ether; decomposes at >80°C

2, p. 230 2, p. 230 2, p. 231; 8, p. 454

III. Dialkenyl, Dialkynyl and Di-F-arylalkyl Calcium Compounds Diacetylcalcium Ca(C CH)2 Bis(phenylacetylyl)calcium Ca(C } CC6H5)2 Dipropenylcalcium Ca(CH = CHCH3)2 Divinyl calcium Ca(CH = CH2)2

90.14

—

—

242.34

—

—

123.23

—

—

—

s/clear

—

94.17

—

—

—

—/—

—

Decomposes at 320°C, white microcrystal powder; insoluble in C6H6; soluble in tetrahydrofuran and liquid NH3 Soluble in tetrahydrofuran, pyrophoric, powder form Soluble in tetrahydrofuran

170.27

—

—

265

s/colorless to faintly yellow

—

Glows in air

2, p. 233; 8, p. 453

158.17

160

—

—

—/—

1.5

Soluble in water and methanol

1, p. 80

182.18

—

—

—

—/—

1.442

326.48

—

—

—

—/—

—

Decomposition s/white at ~320

2, p. 231; 8, p. 453 8, p. 453

IV. Dicyclopentadienyl Calcium Compounds Dicyclopentadienylcalcium Ca(C5H5)2

V. Calcium Salts Calcium acetate Ca(CH3COO)2 Calcium acrylate Ca(CH2CHCOO)2 Calcium 2—ethylhexanoate Ca(C4H9CH(C2H5)COO)2

—

1, p. 80

Soluble in xylene

1, p. 80

© 2005 by CRC Press

Calcium formate Ca(HCOO)2 Calcium D—gluconate Ca(CH2OH(CHOH)4COO)2 Calcium lactate Ca(CH3CH(OH)COO)2 Calcium methacrylate Ca(CH2C(CH3)COO)2

130.12

—

—

—

—/—

2.02

—

430.38

—

—

—

—/—

—

218.22

—

—

—

s/white

—

—

1, p. 81

210.24

>160

—

—

—/—

—

—

1, p. 81

Soluble in water

1, p. 80 1, p. 80

Cerium Compounds I. Cerium Alkoxides and Ketonates Cerium ter-butoxide Ce(OC(CH3)3)4 Cerium IV ethylthioethoxide Ce(OC2H4SC2H5)4 Cerium ethoxide Ce(OC2H5)4 Cerium III 6,6,7,7,8,8,8—heptafluoro— 2,2—dimethyl—3,5—octanedionate (—OC(C3F7)CHC(C(CH3)3)O—)3Ce Cerium tert-heptaoxide Ce(OC(CH3)(C2H5C3H7n))4 Cerium tert-heptaoxide Ce(OC(C2H5)3)4 Cerium tert-hexoxide Ce(OCCH3(C2H5)2)4 Cerium methoxide Ce(OCH3)4 Cerium IV methoxyethoxide Ce(OC2H4OCH3)4 Cerium octyloxide Ce(OC8H17)4 Cerium III 2,4-pentanedionate Ce(OC(CH3)CH(CH3)CO)3 Cerium tert-pentoxide Ce(OC(CH3)2C2H5)4 Cerium IV isopropoxide solution Ce(O–iC3H7)4.C3H7OH

432.58

140–150/0.1

—

—

l/—

—

560.82

—

—

—

—/—

—

—

1, p. 161

320.36

>200 (in vacuo)

—

l/—

—

—

—

4, p. 73

1025.64

—

142

—

s/—

—

—

1, p. 160

600.90

150/0.05

—

—

l/—

—

Molecular complexity: 1.0

4, p. 70

600.90

154/0.05

—

—

l/—

—

Molecular complexity: 1.1

4, p. 70

544.79

140/0.06

—

—

l/—

—

264.26

>2000 (in vacuo)

>280

—

s/yellolw

—

440.46

—

—

—

—/—

657.01

—

—

—

l/orange-red

—

437.45

—

131–132

—

—

488.69

240/0.1

—

—

s/light yellow l/—

—

Molecular complexity: 2.4

4, p. 70

376.47/ 436.57

—

>200 (decomposes)

—

s/yellow

—

Soluble in pyridine

1, p. 161

1.02

Molecular complexity: 2.5

— Hydrolyzed in air; insoluble in methanol — Decomposes at 240–260°C —

4, p. 70

4, p. 70 4, p. 73; eight, Vol. 3, p. 53 1, p. 161 8, Vol. 3, p. 53 1, p. 161

© 2005 by CRC Press

Compound Cerium isopropoxide Ce(OCH(CH3)2)4 Cerium n-propoxide Ce(O-nC3H7)4 Cerium IV 2,2,6,6—tetramethyl— heptanedionate Ce(OC(C(CH3) 3)CHC(C(CH3) 3)O)4 Cerium IV thenoyltrifluoroacetonate Ce(OC(SC4H3)CH(CF3)CO)4

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

376.47

160–170/0.5

—

—

l/—

—

376.47

—

—

l/—

—

—

4, p. 73

873.2

>200 (in vacuo) —

250(d)

140/0.05

s/red

—

—

1, p. 161

1024.84

—

—

—

—

—

Soluble in toluene, methanol

1, p. 161

Extremely moisture sensitive

2, p. 193; 8, p. 466

State/Color

Densitya (g/cc)

Miscellaneous Molecular complexity: 3.1

Reference 4, p. 70

II. Cycloaryl Cerium Compounds Bis(M8-1,3,5,7-cyclooctatetraene) cerate (1-) or dicyclooctatetraenecerate (1-) Ce(C8H8)2 Cerium III tris(bis(trimethylsilylamide)) Ce(N(Si(CH3)3)2)3 Dicerium, triscyclooctatetraene Ce2(C8H8)3

348.422

—

>345 (C16H16CeK)

—

s/pale green

—

621.28

95–9/104

—

—

l/—

—

529.69

—

—

—

—

Stable to 250°C; highly oxygen sensitive; soluble in tetrahydrofuran

2, p. 189; 8, p. 467

Tetraindenyl cerium Ce(C9H7)4 Triyclopentadienyl cerium Ce(C5H5)3 Tricyclopentadienyl cerium chloride (C5H5)3CeCl

600.74

—

—

—

Microcrystal line powder/ green —/—

—

Stable in aqueous solution

2, p. 189

335.40

—

435

—

Hydrolyzed by water

370.86

—

—

s/orange crystals s/dark brown

317.26

—

308

—

s/—

—

Soluble in water and methanol

1, p. 160

569.74

—

>275

—

s/—

—

Soluble in THF, toluene

1, p. 160

544.29

—

—

—

—/—

—

—

1, p. 161

736.36

—

—

—

—/—

—

—

1, p. 161

200–250 (in vacuo) Decomposes at 176

—

—

1, p.161

2, p. 189; 8, p. 466 Insoluble in aromatic HC; soluble 2, p. 189; in most other organic solvents 8, p. 466

III. Cerium Salts Cerium III acetate Ce(CH3COO)3 Cerium III 2—ethylhexanoate (C4H9CH(C2H5)COO)3Ce Cerium III oxalate Ce(—O2CCO2—)3Ce Cerium IV trifluoromethanesulfonate (CF3SO3)4Ce

© 2005 by CRC Press

Cesium Compounds I. Cesium Alkoxides and Ketonates Cesium methoxide CH3OCs Cesium pentanedionate Cs(-OC(CH3)CHC(CH3)O-)

163.94

—

—

—

—/—

0.85

—

1, p. 82

232.02

—

—

—

—/—

—

Soluble in water

1, p. 82

191.95

—

190–196

—

—/—

—

Soluble in water

1, p. 82

177.92

—

45

—

s/—

—

Soluble in water

1, p. 82

Crystalline solid/ brownblack 1/brownblack Crystalline solid/ red-brown Crystalline solid/black s/none

—

)Hform = 142 kJ/mol

2, pp. 980–988

—

)Hform = 66 kJ/mol

—

)Hform = 302 kJ/mol

2, pp. 980–988 2, pp. 980–988

—

)Hform = –41 kJ/mol

II. Cesium Salts Cesium acetate CH3COOCs Cesium formate HCOOCs

Chromium Compounds I. Chromium Alkoxides and Ketonates Miscellaneous Organochromium Compounds Bis(M6–benzene)chromium (0) Cr(M6–C6H6)2

208.22

—

280–281

—

Bis(M6–hexaethylbenzene) chromium Cr(M6–(C2H5)6C6)2 Bis(M6–napthalene)2 chromium Cr(M6–C10H8)2

544.87

—

—

—

308.34

—

160 (decomposition)

—

Bis(M6–trimethylbenzene) chromium (0) Cr(M6–1,3,5–(CH3)3C6H3)2 Chromium hexacarbonyl Cr(CO)6

244.34

—

114–116

—

220.06

—

130 (with decomposition) 150/2

25/0.1

AlkoxidesChromium III benzoyacetonate (-OC(CH3)CHC(C6H5)O-)3Cr

535.54

—

—

—

—/—

1.77

—

2, pp. 980–988 2, p. 785

1.63 torr vapor phase at 50°C, 58.9 torr vapor phase at 100°C; low solubility in polar and nonpolar solvents; insoluble in H2O — 1, p. 83

© 2005 by CRC Press

Compound Chromium III hexafluoropentanedionatetetrahydrofuran (-OC(CF3)CH(CF3)CO-)3Cr Chromium III isopropoxide 10–12% solution in isopropanol/tetrahydrofuran Cr(O–iC3H7)3 Chromium III 2,4-pentanedionate Cr(OC(CH3)CH(CH3)CO)3 Chromium III 2,2,6,6-tetramethylheptanedionate Cr(OC(C(CH3)3)CH((CH3)3C)CO)3 Chromium III trifluoropentanedionate Cr(-OC(CH3)CH(CF3)CO-)3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

673.17

—

—

—

—/—

229.26

—

—

—

349.36

340

214

601.82

180/0.1

511.24

Densitya (g/cc)

Miscellaneous

—

—

1, p. 83

-/green

0.80

—

1, p. 83

—

s/violet

1.35

216–219

—

—

150–152

—

Crystalline solid/dark purple s/red-violet

340.17

—

—

—

—/—

603.32

—

—

—

s/blue—

481.62

—

—

—

State/Color

Reference

Soluble in H2O and toluene; )Hform = 353.7 kcal/mol Soluble in hot ethanol

1, p. 84; 3, p. 75 1, p. 84

—

Soluble in toluene, acetone, hot ethanol

1, p. 84

1.79

—

1, p. 82

—

—

1, p. 83

—/—

1.01

—

1, p. 83

0.84

—

II. Chromium Salts Chromium II acetate (CH3COO)2Cr Chromium III acetate hydroxide (CH3COO)2CrOH —/GreenChromium III 2—ethylhexanoate (C4H9CH(C2H5)COO)3Cr

Cobalt Compounds I. Cobalt Alkoxides and Ketonates Cobalt carbonyl methoxide 10% in methanol Co(CH3OH)6[Co(CO4)]2 Cobalt II 2,4-pentanedionate Co(OC(CH3)CH(CH3)CO)2

593.13

—

—

—

l/rose

257.18

—

166–169

—

Cobalt III 2,4-pentanedionate Co(OC(CH3CH(CH3)CO)3

356.24

340

216

—

s/blueviolet, pink with water s/dark green

—

1.43

Stored in CO

27, p. 22

)Hsub = 15kcal/mol; soluble in H2O, toluene

1, p. 84

Soluble in H2O, toluene

1, p. 85; 3, p. 75

© 2005 by CRC Press

II. Dinuclear Cobalt Carbonyls Sublimes with decomposition at 90 —

—

s/blue

—

)Hsub = 1749 kJ/mol

2, p. 7

801.77

Melts with decomposition at 60 —

—

s/blue

—

Decomposes slowly in air

2, p. 9

171.98

47 ± 3

—

Solid-liquid/ white to pale yellow

—

Ebarrier = 28kJ/mol; )Hform = 611 kJ/mol

2, p. 10

341.95

—

26.2 to 33 (starts decomposing as it melts) 51

—

s/orange

—

172.97

48.6–50

0.5–0

—

l/dark red

—

Hform° (g) = 117 kJ/mol; )Hsub = 2, p. 4 653.3 kJ/mol 2, p. 25 Decomposes slowly in air; insoluble in and decomposed by H2O; soluble in most organic solvents

598.55

—

79–81

—

s/orange

—

340.00

—

—

—

l/light amber

—

189.99

110

30

—

l/light amber

—

—

2, p. 63

239.98

—

10–13

—

l/light amber

—

—

2, p. 63

177

—

—

—

—/—

—

—

1, p. 84

s/—

1.882

Dodecacarbonyltetracobalt Co4(CO)12

571.86

Hexadecacarbonylhexacobalt Co6(CO)16 Hydridotetracarbonylcobalt CoH(CO)4 Octacarbonyldicobalt Co2(CO)8 Tricarbonylnitrotosylcobalt (NO)Co(OC)3

III. Fluorocarbon–Cobalt (I) Compounds Diphenylphospinemethylcobalt (I) [Co(CH3)(P(C6H5)3)2] Tetracarbonylheptafluoropropylcobalt (I) Co(C3F7)(CO)4 Tetracarbonylpentafluoroethyl cobalt Co(C2F5)(CO)4 Tetracarbonyltrifluoromethyl cobalt (I) Co(CF3)(CO)4

—

2, p. 68 2, p. 63

Oil

V. Cobalt Salt Cobalt (II) acetate (CH3COO)2Co

Copper Compounds I. Copper Alkoxides and Ketonates Copper II acetate (CH3COO)4Cu2(OH2)2

181.63

—

115

—

Soluble in water, methanol

1, p. 89

© 2005 by CRC Press

Compound Copper II allyoxyethoxytrifluoroacetoacetate Cu(OC(CF3)CHCOOC2H4OCH2 CHCH2) Copper II benzoylacetonate (cupric phenylbutanedionate) Cu(OC(C6H5)CH(CH3)CO)2 Copper II benzoyltrifluoroacetonate Cu(OC(C6H5)CH(CF3)CO)2 Copper II dimethylaminoethoxide Cu(OCH2CH2N(CH3)2)2 Copper 1,3-diphenyl-1,3propanedionate Cu(-OC(C6H5)CHC(C6H5)O-)2 Copper II ethoxide Cu(OC2H5)2 Copper II ethylacetoacetate Cu(-OC(OC2H5)CH(CH3)CO-)2 Copper II 6,6,7,7,8,8,8-heptafluoro-2,2dimethyl-3,5-octanedionate Cu(-OC(OCF2CF2CF3)CH ((CH3)3C)CO-)2 Copper I hexafluoropentante dionate-2butyne complex (OC(CF3)CH(CF3)CO)Cu (CH3CCCH3) Copper I hexafluoropentantedionatecyclooctadiene complex (-OC(CF3)CH(CF3)CO-) Cu-cycloC8H12 Copper I hexafluoropentantedionatevinyltrimethylsilane complexcopper II hexafluoropentanedionate (OC(CF3)CH(CF3)CO)Cu(Si(CH3)3 CHCH2)

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

541.89

—

72–74

—

s/—

385.91

—

195–196

—

s/blue

493.85

—

241–244

—

239.80

—

512.07

—

184–185 (decomposes) 310–320(d)

153.67

—

321.81

State/Color

Densitya (g/cc) 1.882

Miscellaneous

Reference

Soluble in methanol, toluene, THF

1, p. 89

—

Soluble in xylene

1, p. 89

s/—

—

—

1, p. 89

—

s/—

—

—

s/—

—

—

s/blue

—

—

120 (decomposes) 192–193

—

s/blue green

—

653.90

100/0.1

70

—

s/blue purple

—

324.68

40/0.1

68–73

—

s/—

—

378.77

—

82–83

>60/0.1

s/whitegreen

—

385.87

50/50

—

—

l/—

—

1 mm vapor phase at 90°C; precursor for superconductor Soluble in THF, toluene

Decomposes during melting; precursor for superconductor Soluble in ethanol and warm methanol —

—

Decomposes at >150°C; precursor for Cu2O

—

1, p. 89 1, p. 89

1, p. 89 1, p. 90 1, p. 90

1, p. 90

1, p. 90

1, p. 90

© 2005 by CRC Press

Copper II hexafluoropentanedionatedihydrate Cu(-OC(CF3)CH(CF3)CO-)2 Copper II 8—hydroxyquinolinate Cu(-OC9H8N-)2 Copper II methacryloxyethyl acetoacetate (-OC(OC2H4OCOC(CH3)CH2) CHC(CH3)CO-)2Cu Copper II methoxide Cu(OCH3)2 Copper II methoxyethoxyethoxide Cu(OC2H4OC2H4OCH3)2 Copper II 2,4-pentanedionate Cu(-OC(CH3)CH(CH3)CO-)2 Copper II 2,2,6,6-tetramethyl-3,5heptanedionate Cu(-OC(C(CH3)3)CH(C(CH3)3)CO-)2 Copper II trifluoropentanedionate Cu(-OC(CF3)CH(CH3)CO-)2 Copper II 2,2,6-trimethyl-3,5heptanedionate Cu(-OC(C(CH3)3)CH(CH(CH3)2)CO-)2

477.64

—

130

100/0.5

s/blue-green

—

0.003 mm vapor phase at 25°C

1, p. 91

351.85

—

270

—

s/—

1.68

Soluble in warm acetic acid; slightly soluble in chloroform Soluble in methanol

1, p. 91

483.90

—

106–107

—

s/—

—

125.61

—

206

—

s/—

—

—

1, p. 91

301.83

—

—

—

—/—

1.042

—

1, p. 91

261.76

—

238–240; 230

78/0.05

s/pale blue

—

430.09

—

198 (decomposes)

—

s/—

—

369.70

140/0.1

198–199

—

s/purple

—

428.06

—

166–7

—

s/purple

—

Soluble in H2O, toluene, dimethylsulfoxide; decomposes while melting Decomposes while melting; precursor for CuO in MOCVD process )Hsub = 12.1 kcal/mol; soluble in ethanol, toluene Soluble in hexane

102.60

—

—

—

—

—

164.67

—

—

—

130.66

—

—

—

Powder/ orange s/bright yellow s/canary yellow

303.98

—

260

—

s/—

1.75

Soluble in acetone, toluene

1, p. 89

349.96

—

252(d)

—

s/—

—

Slightly soluble in acetone

1, p. 90

1, p. 91

1, p. 92; 3, p. 75 1, p. 92

1, p. 92 27, p. 25

II. Copper Acetylides (Castro Reax) Copper methylacetylide Cu–C } C–CH3 Copper phenyl acetylide Cu–C } C–C6H5 Copper propylacetylide Cu–C } C–C3H7

— —

Soluble in pyridine —

1, p. 691; 8, p. 573 1, p. 691; 8, p. 576 1, p. 691; 8, p. 574

III. Copper Alkyl Thiol Copper II dimethyldithiocarbamate Cu(S2CN(CH3)2)2 IV. Copper Salts Copper II 2—ethylhexanoate C4H9CH(C2H5)COO)2Cu

© 2005 by CRC Press

Compound Copper II formate (HCOO)2Cu Copper II methacrylate (CH2C(CH3)COO)2Cu Copper II trifluoroacetate (CF3COO)2Cu Copper II trifluoromethanesulfonate (CF3SO3)2Cu

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

153.58

—

130(d)

—

s/—

1.81

Soluble in water

1, p. 90

233.71

—

208

—

s/—

1.81

Soluble in acetone

1, p. 91

289.57

—

—

—

—/—

—

—

1, p. 92

361.68

—

—

—

—/—

—

—

1, p. 93

1, p. 25

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Dysprosium Compounds I. Dysprosium Alkoxides Dysprosium 2,4-pentanedionate Dy(–OC(CH3)CH(CH3)CO–)2 Dysprosium 2,2,6,6-tetramethyl-3,5Heptanedionate Dy(-OC(C(CH3)3)CHC(C(CH3)3)O-)3

459.83

—

134–137

—

s/—

—

—

712.31

—

182–185

—

s/—

—

)Hsub = 31.9 kcal

1, p. 162

357.78

—

302

220 (in vacuo)

Crystalline solid/ yellow

—

Soluble in tetrahydrofuran; hydrolyzed by water

1, p. 584

339.64

—

120(d)

—

s/—

2.47

Soluble in water

1, p. 162

609.71

—

—

—

s/—

—

s/pale pink

—

II. Dysprosium Alkyl Tricyclopentadienyl dysprosium Dy(C5H5)3

III. Dysprosium Salts Dysprosium acetate (CH3COO)3Dy Dysprosium trifluoromethane sulfonate (CF3SO3)3Dy

—

1, p. 162

Erbium Compounds I. Erbium Alkoxides and Ketonates Erbium III 6,6,7,7,8,8,8- heptafluoro2,2-dimethyl-3,5-octanedionate Er(-OC(C3F7)CH((CH3C)CO-)3

1052.79

—

157–163

130/0.01

)Hsub = 37 kcal/mol

1, p. 163

© 2005 by CRC Press

Erbium hexafluoropentanedionate Er(-OC(CF3)CH(CF3)CO-)3 Erbium 2,4-pentanedioante Er(–OC(CH3)CH(CH3)CO–)3 Tricyclopentadienyl erbium Er(C5H5)3 Erbium 8-hydroxyquinolinate Er(OC9H8N)3 Erbium methoxyethoxide Er(OC2H4OCH3)3 Erbium 2,2,6,6-tetramethyl-3,5heptanedionate Er(-OC(C(CH3)3)CH(C(CH3)3)CO-)3

788.42

—

110–120

—

s/—

—

—

1, p. 163

464.59

—

125–132

—

—

—

1, p. 163

362.54

—

285

200

—

600.22

—

—

280(d)

Hydrolyzed by water; soluble in tetrahydrofuran Soluble in THF, CH2Cl2

2, p. 186; 8, p. 587 1, p. 163

392.52

—

—

—

s/off-white to light pink Crystalline solid/pink s/bright yellow —/—

15% in methoxyethanol

1, p. 163

717.08

—

168–169

160/0.1

s/pink

—

)Hsub = 35.7 kcal/mol

1, p. 163

648.43

165/0.04

173

—

s/pink

—

Soluble in hexane, toluene THF, dimethoxyethane

1, p. 163

344.38

—

>330

—

s/—

2.11

—

1, p. 162

— 1.02

II. Erbium Alkylamide Erbium tris(bis(trimethylsilylamide)) Er(N(Si(CH3)3)2)3 III. Erbium Salt Erbium acetate (CH3COO)3Dy

Europium Compounds I. Europium Alkoxides and Ketonates Europium (III) 6,6,7,7,8,8,8-heptafluoro- 1037.49 2,2-dimethyl-3,5-octanedionate Eu(–OC(CF2CF2CF3)CH(C(CH3)3) CO–)3 701.77 Europium 2,4-pentanedionate Eu(–OC(CH3)CH(CH3)CO–)3 701.77 Europium 2,2,6,6-tetramethyl-3,5heptanedioante Eu(–OC(C(CH3)3)CH(C(CH3)3)CO–)3 818.51 Europium (III) thenoyltrifluroacetonate 869.52 Eu(-OC(C4H3S)CH(CF3)CO-)3.3H2O Europium 1,3-diphenyl-1,3propanedionate Eu(-OC(C6H5)CHC(C6H5)O-)2

821.72

—

209–213

—

s/—

—

—

1, p.164

—

187–189

—

s/—

—

—

1, p. 165

—

187–189

—

s/—

—

)Hsub = 39.5 kcal/mol

1, p. 165

—

134–140

—

—

Soluble toluene, methanol

1, p. 165

—

—

210–220(d)

s/red; turns yellow on hydration s/—

—

—

1, p. 164

© 2005 by CRC Press

Compound Europium 1,3-Diphenyl-1,3propanedionate-1,10-phenanthroline (-NC12H8N-)Eu(-OC(C6H5) CHC(C6H5)O-)2

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

1001.92

—

172–173

—

s/—

—

282.15

—

—

s/—

—

—

2, p. 187

633.13

82–84/10-4

159–162

400–420 (in vacuo) —

s/orange

—

—

1, p. 165

329.1

—

—

—

s/white

—

—

1, p. 164

377.20

—

—

—

—/—

—

—

1, p. 164

State/Color

Densitya (g/cc)

Miscellaneous Soluble in toluene

Reference 1, p. 164

II. Alkyleuropium Compounds Bis(cyclopentadienyl) europium Eu(C5H5)2 Europium tris(bis(trimethylsilylamide)) Eu(N(Si(CH3)3)2)3 III. Europium Salts Europium acetate (CH3COO)3Eu Europium III methacrylate (CH2C(CH3)COO)3Eu

Ferric/Ferrous Compounds (see section on iron compounds) Gadolinium Compounds I. Gadolinium Alkoxides and Ketonates Gadolinium 6,6,7,7,8,8,8 heptafluoro2,2-dimethyl-3,5-octanedionate Gd(OC((C3F7)2CF3CHCO(C(CH3)3)3 Gadolinium 2,4-pentanedionate trihydrate Gd(–OC(CH3)CH(CH3)CO–)3.3H2O Gadolinium (III) 2,2,6,6tetramethylheptanedionate Gd(–OC(C(CH3)3)CH(C(CH3)3)CO–)3

1042.79

—

138

—

—/—

—

—

1, p. 166

454.58 508.63

—

135–143

—

s/—

—

—

1, p. 166

707.07

—

167–70

—

Crystalline solid/offwhite

—

)Hsub = 38.6 kcal/mmol

1, p. 166

352.53

—

—

200–205

s/—

—

Air and moisture sensitive, isolated as a tetrahydrofuran adduct

2, p. 180; 8, p. 964

II. Alkyl Gadolinium Compounds Tricyclopentadienyl gadolinium Gd(C5H5)3

© 2005 by CRC Press

III. Gadolinium Salts Gadolinium acetate (CH3COO)3Gd Gadolinium III diethylenetriamine pentaacetic acid Gd(OCOCH2N((CH2)2NCH2COO)CH2 COOH)2

406.45

—

—

—

s/white

1.611

547.58

—

129

—

s/—

—

— Soluble in water

1, p. 165 1, p. 166

Gallium Compounds I. Gallium Alkoxides and Ketonates Gallium (III) ethoxide Ga(OC2H5)3 Gallium 2,2,6,6,Tetramethyl 3,5-Heptanedionate Ga(-OC(C(CH3)3)CH(C(CH3)3)CO-)3

204.90

—

144–145

180–190/0.5

s/—

—

—

1, p. 97

619.54

—

219–220

170/0.2

s/—

—

—

1, p. 97

201.95

125/0.01

91

—

s/—

—

—

1, p. 98

551.59

—

—

—

—/—

—

—

1, p. 98

367.05

—

194–195

140/10

s/—

1.42

158.83

—

162–162.3

—

s/—

192.94

—

36–37

—

164.88

—

68–69

261.65

—

—

II. Gallium Alkyl Amides Tris(dimethylamino)gallium Ga(N(CH3)2)3 Gallium tris(bis(trimethylsilylamide)) Ce(N(Si(CH3)3)2)3 Gallium (III) 2,4-pentanedionate Ga(–OC(CH3)CH(CH3)CO–)3

)Hform = 352.8 kcal/mol; )Hcomb = 1903 kcal/mol

1, p. 97

—

Dimeric or polymeric in solution

2, p. 717

s/—

—

—

—

s/—

—

—

Crystalline solid/—

—

Degree of association (1.3–1.7) in benzene or cyclohexane Dimeric in vapor phase; formulated as an oxobridge molecule

2, p. 686; 8, p. 958 2, p. 686; 8, p. 955 2, p. 713

III. Alkylcyclopentadienyl Compounds Acetoxydimethyl gallium (CH3)2Ga(OOCCH3) Diethylcyclopentadienyl gallium (C2H5)2Ga(C5H5) Dimethylcyclopentadienyl gallium (CH3)2Ga(C5H5) Dimethylmethoxygallium [(CH3)2Ga(OCH3)]2

© 2005 by CRC Press

Compound Tri-i-butyl gallium (iC4H9)3Ga Triethylgallium (C2H3)3Ga Trimethylgallium (CH3)3Ga Trimethylgallium-trimethyl arsenic adduct (CH3)3Ga.As(CH3)3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

241.07

—

—

—

l/—

—

Pyrophoric

6, p. 77

156.91

143

82.3

—

l/—

1.0576

Pyrophoric

6, p. 77

114.83

55.7

15.8

—

l/—

1.10

234.86

121

24

—

l/—

—

163.29

60–62

—

—

—/—

1.135

—

1, p. 97

502.18

—

—

—

s/—

—

—

1, p. 97

State/Color

Densitya (g/cc)

Miscellaneous

Reference

)Hform = 79.8 6.3 kJ/mol (l); 2, p. 691; )Hform = 46.8 6.7 kJ/mol (g); 6, p. 77 )Hvap = 32.6 kJ/mol, pyrophoric Pyrophoric 6, p. 77

IV. Gallium Alkyl Halide Diethylgallium chloride (CH3CH2)2GaCl V. Gallium Salt Gallium 8-hydroxyquinolinate Ga(-OC9H6N-)3

Germanium Compounds I. Germanium Alkoxides and Ketonates Di-n-butyldiacetoxygermane (nC4H9)2Ge(OOCCH3)2 Degree of polymerization = 1.0Diethyldiethoxygermane (C2H5)2Ge(OCCH2CH3)2 Ethyltriethoxygermane CH3CH2Ge(OCH2CH3)3 Germanium (IV) n-butoxide (tetra-nbutoxygermane) Ge(O–nC4H9)4 Germanium (IV) ethoxide (tetraethoxygermane) Ge(O–nC2H5)4

n20 = 1.4452

304.90

127/5

—

—

l/—

1.444

1, p. 103

220.85

72–73/13

—

—

l/—

1.4250

236.83

180

—

—

l/—

1.1105

n20 = 1.4178

365.05

143/8

—

—

l/—

1.017

252.84

185–186

72

—

l/—

1.134

n20 1, p. 107 0 = 1.4255; viscosity = 0.2 cSt; flash point: 112°C; surface tension: 24 dyn/cm n20 = 1.4049; viscosity at 20°C: 1, p. 108; 0.2 cSt; flash point: 62°C; 4, p. 45 degree of polymerization: 1.0

—

1, p. 104

1, p. 105

© 2005 by CRC Press

1, p. 109

—

n20 = 1.4015; flash point: 34°C; surface tension: 22.5 dyn/cm; reacts with H2S to form GeS2 n20 = 1.4141; viscosity: 1.3 cSt; surface tension: 20.8 dyn/cm; flash point: 68°C Soluble in water

l/—

—

—

1, p. 109

—

l/—

1.068

—

—

l/—

—

85/85

—

—

l/—

1.4805

228.81

79/0.01

—

—

l/—

—

256.87

145/10

—

—

l/—

1.180

282.91

147–150/2.2

91–92

—

s/—

—

—

1, p. 105

76.62

88

165

—

Gas/—

65–66/0.01

60

—

—/—

Ignites in air; )Hvap = 3.36 kcal/ mol; )Hform = 21.6 kcal/mol n20 = 1.4960

1, p. 115

319.55

1.53 (142) —

335.55

88–90/2

—

—

l/—

1.147

n20 = 1.4612

1, p. 105

235.39

137–138

40

—

—/—

—

n20 = 1.4564; flash point: 14°C

1, p. 105

607.82

—

340

271/1

s/—

—

623.82

—

182–183

—

s/—

—

216.80

64–67/7

—

—

l/—

1.13

196.73

145–146

18

—

l/—

1.325

308.94

109/30

—

—

l/—

1.025

187.76

—

156–157

—

s/—

429.35

104–110/2

62 to 59

—

190.81

163

—

t-Butylgermane H3Ge(tC4H9) Cyclopentadienyltrimethylgermane C5H5Ge(CH3) 3 Diphenylgermane (C6H5)2GeH2

132.73

45–46

182.79

Diphenyldimethylgermane (C6H5)2Ge(CH3)2 Fluorenyltrimethylgermane (C12H8)CGe(CH3)3 Germane GeH4 Hexaethyldigermane (C2H5)3Ge2(C2H5)3 Hexaethyldigermoxane (C2H5)3GeOGe(C2H5)3 Hexamethyldigermane (CH3)3Ge2(CH3)3 Hexaphenyldigermane (C6H5)3Ge2(C6H5)3 Hexaphenyldigermoxane (C6H5)3GeOGe(C6H5)3 Methacryloxymethyltrimethylgermane CH2C(CH3)COOGe(CH3)3

Germanium (IV)methoxide (tetramethoxygermane) Ge(O–CH3)4 Germanium (IV) isoproroxide (tetraisopropoxygermane) ((CH3)2CO-)4Ge Hydroxygermatrane N(CH2CH2)3GeOH Tetrakis(trimethylsiloxy)germane ((CH3)3SiO)4Ge Triethylmethoxygermane (C2H5)3GeOCH3

1, p. 108

1, p. 106

n20 = 1.436

1, p. 112

Source for Ge

1, p. 102; 3, p. 186 1, p. 103

II. Alkylgermanium Compounds

—

n25 = 1.5921; slowly decomposes 1, at room temperature p. 66105; 3, p. 988 n20 = 1.5730 1, p. 105

—

1, p. 105

1, p. 106

Soluble in THF

1, p. 106

n20 = 1.4469 Flash point: 63°C Soluble in acetonitrile

1, p. 106

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Phenylgermane C6H5GeH2 Phenyltrimethylgermane (C6H5)Ge(CH3)3 Tetra-n-butylgermane Ge(nC4H9)4

151.71

40/22

—

—

l/—

1.2371

n20 = 1.5353

2, p. 500

194.80

183

—

—

l/—

1.117

1, p. 107

301.05

274

—

—

l/—

0.929

Tetraethylgermane Ge(C2H5)4

188.84

163–164

93

—

l/—

1.134 (72°C)

Tetramethylgermane Ge(CH3)4

132.73

43.5

88

—

l/—

0.975 1.006

Tetra-n-pentylgermane Ge(nC5H11)4

357.15

173/4

—

—

l/—

0.927

Tetraphenylgermane Ge(C6H5)4

381.02

—

231–34

210/1

s/—

—

Tetra-n-propylgermane Ge(nC3H7)4

244.95

86–87/5

73

—

l/—

0.954

Tetra-4-tolylgermane Ge(4–C6H4CH3)4 Tri-n-butylgermane HGe(nC4H9)3

437.12

—

224–227

—

s/—

—

n20 = 1.5045 Flash point: 53°C n20 = 1.4561; flash point: 90°C; viscosity: 3 cSt; surface tension: 26 dyn/cm; dielectric constant: 2.33 n20 = 1.4428; viscosity: 0.9 cSt; )Hvap = 9 kcal/mol; surface tension: 24 dyn/cm; )Hform = 45.3 kcal/mol; dielectric constant: 1.97 n20 =1.3882, )Hvap = 6.3 kcal/mol; viscosity: 0.3 cSt; surface tension: 24 dyn/cm; critical temprature and pressure: 493 K and 27.7 atm; flammable; liquid n20 = 1.4592; viscosity: 0.4 cSt; surface tension: 27 dyn/cm; dieletric constant: 2.30 N20 = 1.58 Soluble in acetone, benzene, hot toluene )Hform = 208.6 kcal/mol )Hsub = 37.5 kcal/mol N20 = 1.4510; toxic )Hform = 69.6 kcal/mol )Hform = -2144.5 kcal/mol Dielectric constant: 1.92 Viscosity: 1.1 cSt; surface tension: 25 dyne/cm —

244.94

123/20

—

—

l/—

0.916

Compound

State/Color

Densitya (g/cc)

Miscellaneous

N20 = 1.4508

Reference

1, p. 108

1, p. 108

2, p. 499; 1, p. 109; 6, p. 79

1, p. 109

2, p. 499 1, p. 109

2, p. 499 1, p. 110

2, p. 499; 1, p. 110 1, p. 110

© 2005 by CRC Press

Triethylgermane HGe(C2H5)3 Trimethylgermane HGe(CH3)3 Trimethylphenylgermane Ge(CH3)3(C6H5) Triphenylgermane HGe(C6H5)3

1.004 –1.0075 1.013

n20 = 1.4382–1.4330; flash point: 1, p. 112; 5°C 2, p. 500 n20 = 1.3890; )Hvap = 6.10 kcal/ 1, p. 113 mol N20 = 1.5045 27, p. 77

160.78

122

—

—

l/—

118.70

26–27

123

—

—/—

194.80

183

—

—

l/—

1.17

304.92

128–136/102

41–41.5

—

s/—

—

200.85

181–182

—

—

l/—

1.000

N20 = 1.4594

1, p. 101

158.77

101

—

—

l/—

0.995

N20 = 1.4333; flash point: 16°C

1, p. 101

276.86

—

49

—

s/—

—

236.88

105/10

—

—

l/—

1.105

n20 = 1.482; tends to polymerize 1, p. 107

144.74

70.6/735

—

—

l/—

0.9970

n20 = 1.4153

2, p. 499

186.82

152

—

—

l/—

1.005

n20 = 1.4501

1, p. 114

170.78

88–89/38

—

—

l/—

1.2043

n20 = 1.5185

2, p. 499

327.09

135/0.045

—

—

l/—

1.0104

n20 = 1.4918

2, p. 499

200.85

75/13

—

—

l/—

1.0401

n20 = 1.4720

2, p. 499

220.02

154–157

—

—

l/—

1.5274

1, p. 101

272.12

111–118

35–37

—

s/—

—

n20 = 1.4928 Flash point: 55°C —

201.62

174–175

—

—

l/—

1.382

1, p. 102

406.23

78–79/4

35–37

—

l/—

—

n20 = 1.4810 Flash point: 51°C —

—

2, p. 500; 8, p. 995

III. Alkenyl Germanium Compounds Allyltriethylgermane (C2H5)3Ge(CH2CH = CH2) Allyltrimethylgermane (CH3)3Ge(CH2CH = CH2) Diphenyldiacetylgermane (C6H5)2Ge(C } CH)2 Tetraallylgermane Ge(CH2CH = CH2)4 Trimethylallylgermane (CH3)3Ge(CH = CH2) Vinyltriethylgermane (CH2 = CH)Ge(C2H5)3

—

2, p. 499

IV. Cycloalkylgermanium Compounds Cylclopropylcyclobutylgermane (–CH2CH2CH2–)Ge(–CH2(CH2)2CH2-) Diethylcyclo(tetradecyl)germane (C2H5)2Ge(–CH2(CH2)12CH2-) Ethylbutylcyclopropylgermane (C2H5)(C4H9)Ge(–CH2CH2CH2–) V. Germanium Alkyl Halides Allyltrichlorogermane Cl3Ge(CH2CHCH2) Benzyltrichlorogermane C6H5CH2GeCl3 Bis(chloromethyl)dimethylgermane (ClCH2)2Ge(CH3)2 Bromomethyltribromogermane BrCH2GeBr3

1, p. 101

1, p. 102

© 2005 by CRC Press

Compound n-Butyltrichlorogermane (CH3(CH2)3)GeCl3 t-Butyldimethylchlorogermane (CH3)3CGe(CH3)2Cl tert-butyltrichlorogermane (tC4H9)GeCl3 Carboxyethyltrichlorogermane HOOC(CH2)2GeCl3 Choromethyltrimethylgermane (CH3)3Ge(CH2Cl) 3-Chloropropyltrichlorogermane (Cl(CH2)3)GeCl3 Di-n-butyldichlorogermane (nC4H9)2GeCl2 (Dichloromethyl)trimethylgermane (Cl2CH)Ge(CH3)3 Diethylchorogermane (C2H5)2Ge(Cl)H Diethyldichlorogermane (C2H5)2GeCl2 Dimethyldichlorogermane (CH3)2GeCl2 Diphenyldichlorogermane (C6H5)2GeCl2 Ethyliodogermane (C2H5)Ge(I)H2 Ethyltribromogermane (C2H5)GeBr3 Ethyltrichlorogermane (C2H5)GeCl3 Methyltrichlorogermane (CH3)GeCl3 Phenyldifluorogermane (C6H5)Ge(F2)H Phenyldimethylchlorogermane (C6H5)Ge(CH3)2Cl

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

236.07

184

—

—

l/—

1.451

n20 = 1.4760

1, p. 102

195.24

147–154

93–94

—

l/—

2.9706

n20 = 1.6327

1, p. 102

236.07

169–170

94.5

—

s/—

—

—

1, p. 102

252.06

—

83–85

—

s/—

—

—

1, p. 103

167.17

113–114

—

—

l/—

256.50

78–79/8

—

—

l/—

257.73

242

—

—

l/—

1.208

n20 = 1.4724

1, p. 103

201.62

149–150

—

—

l/—

1.334

n20 = 1.4653

1, p. 104

179.19

137/760

—

—

l/—

1.2409

n20 = 1.4572

2, p. 500

201.64

175

39

—

l/—

1.374

1, p. 104

173.57

124

22

—

l/—

1.493

297.71

223/12

9

—

l/—

1.41

230.57

138

—

—

l/—

2.0277

n20 = 1.4700 Flash point: 52°C n20 = 1.4600 Flash point: 21°C n20 = 1.5975 Flash point = 160°C n20 = 1.5612

341.36

200

—

—

l/—

—

208.03

144

33

—

l/—

1.604

n20 = 1.4745; flash point: 51°C

1, p. 105

193.98

110–111

—

—

l/—

1.706

n20 = 1.4685; flash point: 10°C

1, p. 106

188.70

—

38

—

s/—

—

—

2, p. 500

215.23

80/5

—

—

l/—

1.41

—

1, p. 107

State/Color

Densitya (g/cc)

Miscellaneous

1.189–1. n20 = 1.4389–1.4419 21 1.664 n20 = 1.5070

—

Reference

2, p. 499; 1, p. 103 1, p. 103

1, p. 104 2, p. 500 1, p. 104 2, p. 500 2, p. 500

© 2005 by CRC Press

Phenyltrichlorogermane (C6H5)GeCl3 Phenyltriiodogermane (C6H5)GeI3 Tri-n-butylbromogermane (nC4H9)3GeBr Tri-n-butylchlorogermane ((nC4H9)3GeCl Trichlorogermane Cl3GeH Decomposesat >140°3(Trichlorogermyl)propionylchloride OC(Cl)CH2CH2GeCl3 Triethylbromogermane (C2H5)3GeBr Triethylchlorogermane (C2H5)3GeCl Trifluoromethyltriiodogermane CF3GeI3 Trimethylbromogermane (CH3)3GeBr Trimethylchlorogermane (CH3)3GeCl Trimethyliodogermane (CH3)3GeI Light sensitiveTri-n-butylchlorogermane ((nC4H9)3GeCl Trichlorogermane Cl3GeH Decomposes at >140°3(Trichlorogermyl)propionylchloride OC(Cl)CH2CH2GeCl3 Triethylbromogermane (C2H5)3GeBr Triethylchlorogermane (C2H5)3GeCl Trifluoromethyltriiodogermane CF3GeI3 Trimethylbromogermane (CH3)3GeBr Trimethylchlorogermane (CH3)3GeCl

n20 = 1.5536

256.06

226–228

—

—

l/—

1.584

1, p. 107

530.41

—

55–56

—

s/—

—

323.84

143–4/10

—

—

l/—

1.195

n20 = 1.4809

1, p. 110

279.38

269–270

—

—

l/—

1.054

1, p. 110

179.97

75

71

—

l/—

1.930

n20 = 1.4652 Flash point: 94°C Flash point: 12°C

270.48

89–91/7

—

—

l/—

1.751

n20 = 1.5115

1, p. 111

239.68

190–191

32

—

l/—

1.412

n20 = 1.4829

1, p. 111

195.23

176

—

—

l/—

1.175

1, p. 111

522.31

42/0.001

—

—

l/—

—

n20 = 1.4643 Flash point: 38°C n20 = 1.6571

197.60

113–114

25

—

l/—

1.549

1, p. 112

153.15

102

14

—

l/—

1.249

244.60

133–135

—

—

l/—

1.796

n20 = 1.4713 Flash point: 37°C n20 = 1.4337 Flash point = 1°C n20 = 1.5189

279.38

269–270

—

—

l/—

1.054

1, p. 110

179.97

75

71

—

l/—

1.930

n20 = 1.4652 Flash point: 94°C Flash point: 12°C

270.48

89–91/7

—

—

l/—

1.751

n20 = 1.5115

1, p. 111

239.68

190–191

32

—

l/—

1.412

n20 = 1.4829

1, p. 111

195.23

176

—

—

l/—

1.175

1, p. 111

522.31

42/0.001

—

—

l/—

—

n20 = 1.4643 Flash point: 38°C n20 = 1.6571

197.60

113–114

25

—

l/—

1.549

1, p. 112

153.15

102

14

—

l/—

1.249

n20 = 1.4713 Flash point: 37°C n20 = 1.4337 Flash point = 1°C

—

2, p. 500

1, p. 111

1, p. 112

1, p. 113 1, p. 113

1, p. 111

1, p. 112

1, p. 113

© 2005 by CRC Press

Compound Trimethylfluorogermane (CH3)3GeF Trimethyliodogermane (CH3)3GeI Light sensitiveTriphenylbromogermane (C6H5)3GeBr Triphenylchlorogermane (C6H5)3GeCl Triphenylgermane (C6H5)3GeH Tris(trifluoromethyl)iodogermane (CF3)3GeI Tris(trimethylsilyl)germane ((CH3)3Si)3GeH Vinyltrichlorogermane CH2CHGeCl3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

136.69

76/746

—

—

l/—

1.2300

n20 = 1.3863

2, p. 500

244.60

133–135

—

—

l/—

1.796

n20 = 1.5189

1, p. 113

383.81

—

138-9

—

s/—

—

339.36

285/12

117

—

s/—

—

304.91

128–129/0.03

41–43

—

s/—

406.51

72

40

—

293.17

80/5

—

205.99

128

188.84

State/Color

Densitya (g/cc)

Miscellaneous

—

Reference

1, p. 113 1, p. 113

1.6187

Soluble in methylene chloride, hot toluene —

l/—

2.074

n20 = 1.3580

1, p. 114

—

l/—

0.937

n20 = 1.4974

1, p. 114

—

—

l/—

1.652

n20 = 1.4815

1, p. 114

70–75/15

—

—

l/—

0.9782

n20 = 1.4428

1, p. 104

132.73

74

—

—

l/—

1.039

n20 = 1.4208

1, p. 104

90.65

34.1

154

—

g/—

—

302.04

105–109/0.2

—

—

l/—

0.982

222.66

—

—

380

s/—

2.56

217.88

35–37/0.2

—

—

l/—

—

—

2, p. 500

372.73

—

—

—

—/—

—

—

27, p. 63

1, p. 113

VI. Germanium Alkyl Hydride Compounds Di-n-Butylgermane (n-C4H9)2GeH2 Diethylgermane (C2H5)2GeH2 Methylgermane CH3GeH3

—

1, p. 106

VII. Miscellaneous Organogermanium Compounds 3-Aminopropyltributylgermane (NH2(CH2)3)Ge(nC4H9)3 Ammoniumhexafluorogermanate (NH4)2GeF6 Amino triisopropylgermane (iC3H7)3GeNH2 Bisammoniumtris(oxalato)germanate (NH4)2Ge(C2O4)3

n20 = 1.4700 flash point: >100°C n20 = 1.425

1, p. 101 27, p. 63

© 2005 by CRC Press

Bis[Bis(Trimethylsilyl)amino] germanium II Ge(N(Si(CH3)3)2)2 Carboxyethylgermanium sesquioxide HOOCCH2CH2GeO1.5 Carboxytriphenylgermane (C6H5)3Ge(COOH) Dibutyl germanium 2,3-butanedionate (C4H9)2Ge(–OC(CH3)C(CH3)O–) Diethyl(cyclothiopropyl)germane (C2H5)2Ge(–C(CH2)2S–) Dimethylamino triethylgermane (C2H5)3Ge(N(CH3)2) Dimethylamino trimethylgermane (CH3)3Ge(N(CH3)2) Ethyltrimethoxy germane (C2H5)Ge(OCH3)3 Methacryloxytriethylgermane (CH2 = CH(CH3)COO)Ge(C2H5)3 Methyltriethoxygermane (CH3)Ge(OC2H5)3 Tri-n-butylacetoxygermane (nC4H9)3Ge(OOCCH3) Tris(dimethyl)amino ethylgermanium (C2H5)Ge(N(CH3)2)3 Triethyl(diethyl)phosphinogermane (C2H5)3Ge(P(C2H5)2) Trimethyl(ethyl)thiogermane (CH3)3Ge(SC2H5)

393.36

60/0.4

32–33

—

s/orangeyellow

—

—

339.32

—

—

—

s/—

—

348.92

—

187–190

—

s/—

—

272.91

90–94/1.5

—

—

l/—

—

n20 = 1.4555

2, p. 500

202.84

107/23

—

—

l/—

1.2102

n20 = 1.5241

2, p. 500

217.86

176

—

—

l/—

1.0235

n20 = 1.4498

2, p. 500

161.71

102–104

—

—

l/—

—

n20 = 1.4246; Flash point: 10°C

1, p. 104

194.75

154

—

—

l/—

1.2446

n20 = 1.4178

2, p. 500

244.85

69–70/5

—

—

l/—

1.144

n20 = 1.4564

1, p. 106

222.80

166–167

—

—

l/—

1.128

n20 = 1.4128

1, p. 107

302.97

146–149/15

—

—

l/—

1.051

n20 = 1.4538

1, p. 110

233.88

191

46

—

l/—

248.87

120/15

—

—

l/—

1.049 (22) —

n20 = 1.4845

2, p. 500

178.82

148

—

—

l/—

1.10

n20 = 1.4779

2, p. 500

Decomposes at 320°C —

—

1, p. 102

1, p. 103 2, p. 499

2, p. 500

Gold Compounds I. Gold Alkoxides and Ketonates Gold(diethyl)2,4-pentanedionate (C2H5)2Au(–OC(CH3)CHC(CH3)O–)

354.20

—

9–10

—

s/—

—

—

27, p. 27

530.36

—

124–125

—

s/—

—

—

2, p. 768

II. Acetoalkylgold (I) Complexes Acetoethylgold triphenylphosphine Au(CH2COC2H5)(P(C6H5)3)

© 2005 by CRC Press

Compound Acetomethylgold triphenylphosphine (Au(CH2COCH3)(P(C6H5)3)) Acetophenylgold triphenylphosphine Au(CH2COC6H5)(P(C6H5)3)

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

516.33

—

144–145

—

578.40

—

125–126

486.30

—

392.23

Densitya (g/cc)

Miscellaneous

s/—

—

—

2, p. 768

—

s/—

—

—

2, p. 768

123–125

—

s/—

—

—

2, p. 768

—

68

—

s/—

—

—

2, p. 770

536.36

—

164

—

s/—

—

—

2, p. 770

550.39

—

161–162

—

s/—

—

—

2, p. 770

524.35

—

100 (d)

—

s/—

—

—

2, p. 773

622.90

—

99–100

—

s/—

—

—

2, p. 784

829.33

—

87

—

s/—

—

—

2, p. 784

897.25

—

78–79

—

s/—

—

—

2, p. 784

360.23

—

5

—

s/—

—

—

2, p. 784

318.15

—

23–26

—

s/—

—

—

2, p. 784

State/Color

Reference

III. Vinyl Gold (I) Complexes Gold vinyltriphenylphosphine Au(CH = CH2)(P(C6H5)3) IV. Aryl Gold (I) Complexes Gold phenyltriethylphosphine C6H5Au(P(C2H5)3) Gold phenyltriphenylphosphine C6H5AuP(C6H5)3 Gold 4–xyleneyltriphenylphosphine 4–CH3C6H4AuP(C6H5)3 V. Cyclopentadienylgold (I) Complexes Gold cyclopentadienyltriphenylphosphine Au(M1–C5H5)(P(C6H5)3) VI. Arylgold (III) Complexes Gold trichlorophenyl, tetrabutylamine ((C4H9)4N)(AuCl3(C6H5)) Gold tribromophenyl, tetrabutylamine ((C4H9)4N))(AuBr3(C6H(C6H5)) Gold triiodophenyl, tetrabutylamine ((C4H9)4N)(AuI3(C6H5)) VII. Trialkylgold (III) Complexes Gold trimethyl, triethylphosphine Au(CH3)3(P(C2H5)3) Gold trimethyl, trimethylphosphine Au(CH3)3(P(CH3)3)

© 2005 by CRC Press

VIII. Miscellaneous Complexes of Gold Cycloheptenylgoldchloride (C7H10)AuCl Cyclohexenylgoldchloride (C6H8)AuCl cis-Cyclooctaenegoldchloride (cis-C8H12)AuCl Cyclopentadienylgoldchloride (C5H5)AuCl trans-Cyclodecenegoldchloride (trans-C10H16)AuCl trans-Cyclooctenegoldchloride (trans-C8H12)AuCl Triethylphosphinegold I chloride (C2H5)3PAuCl

326.58

—

—

—

—/—

—

Decomposes at 93–80°C

2, p. 813

312.55

—

—

—

—/—

—

Decomposes at 60°C

2, p. 813

340.60

—

—

—

—/—

—

Decomposes at 93–96°C

2, p. 813

297.51

—

—

—

s/—

—

368.66

—

—

—

—/—

—

Decomposes at 55–60°C; 2, p. 813; soluble in organic polar solvents 8, p. 194 Decomposes at 93–96°C 2, p. 813

340.60

—

—

—

—/—

—

Decomposes at 115°C

2, p. 813

350.57

—

85–87

—

s/—

—

Soluble in methylene chloride

2 p. 118

Hafnium Compounds I. Hafnium Alkoxides and Ketonates Hafnium n-butoxide Hf(O-nC4H9)4 Hafnium tert-butoxide Hf(O-tC4H9)4 n20 = 1.4240Hafnium di-n-butoxide (bis-2,2-pentanedionate) (-OC(CH3)CH(CH3)CO-)2Hf (O-nC4H9)2 Hafnium ethoxide Hf(OC2H5)4 Hafnium 2-ethylhexoxide tetraoctylhafnate Hf((OCH2CH(C2H5)C4H9)4 Hafnium 2,4–pentanedionate Hf(–OC(CH3)CH(CH3)CO–)4 Hafnium tetramethylheptanedionate Hf(-OC(C(CH3)3)CH(C(CH3)3)CO-)4 Hafnium trifluoropentanedionate Hf(-OC(CF3)CH(CH3)CO-)4

470.95

280–285/0.01

—

—

l/—

1.32

—

470.65

90/5

—

—

l/—

1.16

522.58

—

—

—

—/—

—

358.73

180–200/13

178–180

—

s/—

—

678.40

—

—

—

—/—

—

—

1, p. 28; 4, p. 45 2. p. 119

574.91

—

193

82/0.001

s/—

—

—

1, p. 119

911.57

—

315

180/0.1

s/—

—

Soluble in toluene, hexane

790.82

—

128–129

115/0.05

s/—

—

Soluble in acetone, cyclohexane 1, p. 119

)Hvap = 16.3 kcal/mol —

Degree of polymerization: 3.6

1, p. 118 1, p. 118 1, p. 119

2. p. 119

© 2005 by CRC Press

Compound Hafnium trifluoropentanedionate Hf(–OC(CF3)CH(CH3)CO–)4

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

790.82

—

128–129

—

s/—

—

Soluble in acetone

1, p. 119

478.84

—

—

—

—/—

—

Pentagonal, bipyramid

2, p. 562

851.27

—

—

—

—/—

—

—

2, p. 562

731.33

—

—

—

—/—

—

—

2, p. 562

809.12

—

—

—

—/—

—

—

2, p. 562

438.868

—

120

~120 (in vacuo)

s/pale yellow

—

—

2, p. 562

354.80

—

—

—

—

—

2, p. 584

379.59

—

230–233

—

s/pale yellow s/—

—

—

1, p. 119

420.08

—

—

—

s/—

—

—

1, p. 120

State/Color

Densitya (g/cc)

Miscellaneous

Reference

II. Monocyclopentadienyl Hafnium (IV) Compounds Hafniumacetylacetonate (Hf(Hacac)3) Hf(–OC(CH3)CH2C(CH3)O–)3 Hafniumbenzoylacetonate Hf(Hbzac)3 Hf(–OC(C6H5)CH2C(C6H5)O–)3 Hafniumdipivalylmethane Hf(Hdpm)3 Hf(–OC(C(CH3)3)CH2C(CCH3)3O–)3 Hafniumbenzoylbenzoate Hf(Hbzbz)3 Hf(OC(C6H5)C(C6H5)O)3 Tetracyclopentadienylhafnium Hf(C5H5)4 III. Miscellaneous Hafnium Compounds Hafnium dimethylamide Hf(N(CH3)2)4 Hafnocene dichloride (C5H5)2HfCl2 Pentamethylcyclopentadienyl-hafnium trichloride (CH3)5C5HfCl3

Holmium Compounds I. Holmium Alkoxides and Ketonates Holium acetate (CH3COO)3Ho orangeHolmium II 6,6,7,7,8,8,8 heptafluoro-2,2-dimethyl-3, 5-octanedionate Ho(-OC(C3F7)3CHC(C(CH3)3O-)3 Holmium 2,4-pentanedionate Ho(–OC(CH3)CH(CH3)CO–)4

342.07

—

—

—

s/pink-

—

—

1, p. 166

1050.45

—

103–111

—

s/pale yellow

—

—

1, p. 166

462.26

—

—

—

—/—

—

—

1, p. 166

© 2005 by CRC Press

Holmium 2,2,6,6,Tetramethyl 3,5-Heptanedionate, hydrated Ho(OC(C(CH3)3)CH(C(CH3)3)CO)3 Tricyclopentadienyl holmium Ho(C5H5)3

714.75

—

179–181

—

—/—

—

360.21

—

295

230

Yellow

—

—

Soluble in tetrahydrofuran; hydrolyzed by water

1, p. 167

8, p. 1137

Indium Compounds I. Indium Alkoxides and Ketonates Indium hexafluoropentanedionate (-OC(CF3)CH(CF3)CO-)2In Indium methoxyethoxide 15–18% in methoxyethanol In(–OC2H4OCH3)3 Indium methyl(trimethyl)acetylacetate In(–OC(OC(CH3)3)CH(CH3)CO–)4 Indium Trifluoropentanedionate In(-OC(CF3)CH(CH3)CO-)2 Indium 2,4–pentanedionate In(–OC(CH3)CH(CH3)CO–)3

735.97

—

—

—

—/—

—

340.08

—

—

—

—/—

1.02

586.37

—

—

—

574.06

—

118–119

—

Resinous solid/— s/—

412.15

—

186

260–280

s/—

1.41

180.34

—

218–219

—

s/—

—

—

1, p. 120

159.92

—

88

—

s/—

1.568

—

1, p. 121

179.91

—

—

150

s/—

—

Attacked by air; polymeric

310.10

—

—

—

Yellow

—

Thermal decomposition to CpIn in vacuo above 150°C

187.98

—

—

—

l/—

—

Pyrophoric

— —

—

1, p. 121

Isolated as solution

1, p. 121

Soluble in acetone, methanol, warm toluene, ethylacetate Soluble in xylene, hot methoxyethanol )Hform = 335.8 kcal/mol; soluble in water; )Hcomb = 1903 kcal/ mol

1, p. 121 1, p. 121 1, p. 121

II. Indium Alkyls Dimethylindium chloride (CH3)2InCl Trimethylindium (CH3)3In III. Cyclopentadienyl Indium Compounds Cyclopentadienylindium (C5H5)In Triscyclopentadienylindium (C5H5)3In

2, p. 685; 8, p. 1146 2, p. 685

IV. Trialkyl/aryl Indium Compounds Diethylmethylindium CH3(C2H5)2In

6, p. 80

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Dimethylcyclopentadienylindium (CH3)2In(C5H5)

209.98

—

195

—

s/white

—

Dimethylethylindium (CH3)2(C2H5)In Triethylindium (C2H5)3In Trimethylindium (CH3)3In

173.96

—

—

—

l/—

—

202.01

184

32

—

l/—

159.93

134 (70/72)

88

—

361.26

—

208

244.09

178

236.01

Compound

Triphenylindium (C6H5)3In Tripropylindium (C3H7)3In Trimethylindium-trimethylphosphine adduct (CH3)3In.P(CH3)3

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Polymeric in solid state; air stable; insoluble in organic solvents; soluble in dimethylformamide Pyrophoric

2, p. 687; 8, p. 1148

1.260

Pyrophoric

6, p. 80

s/—

1.568

—

s/—

1.501

)Hform = 122.0 5.9 kJ/mol; )Hform (g) = 170.5 6.3 kJ/mol; )Hvap = 48.5 kJ/mol; H2O reactive —

2, p. 693; 5, p. 139; 6, p. 80 5, p. 139

51

—

l/—

1.501

—

—

44.5

—

s/—

—

Flammable

6, p. 80

—

—

—

s/—

—

Polymeric (linear)

2, p. 717; 8, p. 1144

s/copperbrownIridium s/yelloworange

—

—

s/yellow

—

6, p. 80

5, p. 139

V. Organometallic Carboxylates of Indium Dimethylindiumacetate (CH3)2In(OOCCH3)

203.93

Iridium Compounds I. Iridium Alkoxides and Ketonates Iridium I dicarbonyl pentanedionate (-OC(CH3)CH(CH3)CO-)Ir(CO)2

347.35

—

—

100/0.05

(III) 2,4-pentanedionate Ir(-OC(CH3)CH(CH3)CO-)3

489.53

—

—

260/1

258–280

Decomposes at 290–319

—

Soluble in methanol, ethyl acetate

1, p. 122

2 p. 122

II. Mononuclear Iridium Compounds (Vaska Compounds) (Bistriphenylphosphine)iridium bromocarbonyl IrBr(CO)(P(C6H5)3)2

821.72

—

—

2, p. 543; 8, p. 1183

© 2005 by CRC Press

(Bistriphenylphosphine)iridium chlorocarbonyl IrCl(CO)(P(C6H5)3)2 (Bistriphenylphosphine)iridium fluorocarbonyl IrF(CO)(P(C6H5)3)2 (Bistriphenylphosphine)iridium iodocarbonyl IrI(CO)(P(C6H5)3)2

780.26

—

327–328

—

s/lemon yellow

—

Stable in air; takes up O2 in solution

2, p. 543; 8, p. 1184

763.81

—

208–211

—

s/yellow

—

Air sensitive

2, p. 543; 8, p. 1185

871.72

—

270–296.5, >300

—

s/yellow

—

—

2, p. 543; 8, p. 1185

511.124

—

—

—

—/brown

—

—

452.67

—

242

—

s/yellow

—

—

2, p. 604; 8, p. 1162 2, p. 604; 19

679.41

—

275

—

s/orange

—

—

590.51

—

290

—

—

773.41

—

290–310

—

Crystalline solid/ yellow s/red

—

—

2, p. 606; 8, p. 1163

2, p. 606; 8, p. 1179

III. Cyclopentadienyl Iridium Compounds Cyclopentadienyliridiumdiodide Ir(C5H5)I2 Cyclopentadienyl, methylbis(dithian) iridium (C5H5)Ir(CH3)(SC2H2S)2 Triphenylphosphine,cyclopentadienyl iridiumdibromide Ir(C5H5)Br2(P(C6H5)3) Triphenylphosphine,cyclopentadienyliridiumdichloride Ir(C5H5)Cl2(P(C6H5)3) Triphenylphosphine,cyclopentadienyliridiumdiiodide Ir(C5H5)I2(P(C6H5)3)

Insoluble

2, p. 604

2, p. 604; 8, p. 1178 2, p. 604

IV. Cyclopentadienyl, C1 Carbonyl Iridium Compounds Cyclopentadienyldicarbonyl iridium Ir(C5H5)(CO)2

313.335

—

—

—

–/yellow

—

Cyclopentadienylmethyl iridiumdicarbonyl Ir(C5H5)(CH3)(CO)2 Triphenylphosphine,cyclopentadienyl, iridiumcarbonyl Ir(C5H5)(CO)(P(C6H5)3)

328.37

—

—

—

–/yellow

—

Volatile in vacuum; stable in air for short time; very soluble in organic solvents; insoluble in H2O; µ = 3.45 D Volatile in vacuum

547.615

—

160, 180–183

—

s/bright orange

—

Strongly nucleophilic

—

79–84

—

s/white

—

2, p. 606

V. Cyclopentadienyl, C2 Alkene Iridium Compounds Cyclopentadienyl,diethylenemethyl iridium Ir(C5H5)(CH3)(C2H4)2

328.46

—

2, p. 608

© 2005 by CRC Press

Compound Cyclopentadienyl, methylcyclohexadiene iridium IrC5H5CH3(1,3–C6H8) Cyclopentadienyl, methylcyclooctadiene iridium IrC5H5CH3(1,5–C8H12) Cyclopentadienyl, octadiene iridium Ir(C5H5)(1,5–C8H12) Cyclopentadienyl, octatriene iridium Ir(C5H5)(1,3,5–C8H10) Cyclopentadienyl, octatetraene iridium Ir(C5H5)(1,3,5,7–C8H8) ((1,2,3,4-M)-1,3,5,7-Cyclohexadiene) (M5–2,4–cyclopentadien–yl)iridium IrC5H5(1,3–C6H8)

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

352.48

—

65–67

—

380.53

—

170–171

365.497

—

363.482

Densitya (g/cc)

Miscellaneous

s/white

—

—

2, p. 608

—

s/white

—

—

2, p. 608

122–127

—

s/white

—

—

—

80

s/pale green

—

361.466

—

114–166

—

s/white

—

—

337.44

—

—

—

s/white

—

—

State/Color

Soluble in organic solvents; volatile —

Reference

2, p. 608; 8, p. 1167 2, p. 608; 8, p. 1167 2, p.608; 8, p. 1167 2, p. 608; 8, p. 1165

Iron Compounds I. Iron Alkoxides and Ketonates Iron (III) benzoylacetonate Ferric phenylbutanedionate Fe(–OC(C6H5)CH(CH3)CO–)3 Iron (III) ethoxide Fe(OC2H5)3 Iron (III) 2,4-pentanedionate Ferric Acetylacetonate Fe(–OC(CH3)CH(CH3)CO–)3

539.39

—

216

—

s/—

—

Soluble in xylene

1, p. 125

191.03

155/0.1

120

—

s/—

—

Soluble in benzene, hot ethanol

1, p. 125

353.18

—

176–179

—

s/red brown

Iron (III) trifluoropentanedionate Fe(–OC(CF3)CH(CH3)CO–)3

515.09

—

110–112

—

s/—

—

186.04

249

171

100

Crystalline solid/ orangeyellow

—

1.33

Soluble in water (1.5g/l), toluene 1, p. 126 (204 g/l), ethanol (32 g/l); )Hform = 355.2 kcal/mol; )Hsub = 4.67 kcal/mol )Hsub = 20.8 kcal/mol 1, p. 126

II. Alkyl Iron Compounds Bis(cyclopentadienyl)iron (ferrocene) (C5H5)2Fe

Nonhazardous; soluble in ether, 6, p. 82 benzene, methanol, and most HC; monomeric; thermally stable; does not react with water

© 2005 by CRC Press

Iron III dimethyldithiocarbamate Fe(S2CN(CH3)2)3 Iron III diphenylpropanedionate tris(Dibenzoylmethanato) iron Fe(-OC(C6H5)CH(C6H5)CO-)3 Iron III tetramethylheptane-dionate Fe(-OC(C(CH3)3)CH(C(CH3)3)CO-)3

416.51

—

180

—

s/—

—

—

725.61

—

260–265

—

s/—

—

515.09

—

110–112

—

s/—

—

—

1, p. 126

173.94

—

—

—

—/—

—

—

1, p. 125

269.01

—

—

—

s/—

—

311.10

—

—

—

s/—

—

Soluble in acetone, THF

1, p. 125 1, p. 125

III. Iron Salts Iron II acetate (CH3COO)2Fe Iron III acrylate (CH2CHCOO)3Fe Iron III methacrylate (CH2C(CH3)COO)3Fe

Decomposes 190–200°C; soluble in warm ethanol Decomposes 215–220°C; soluble in methylmethacrylate

1, p. 125

1, p. 167

1, p. 125

Lanthanum Compounds I. Lanthanum Alkoxides and Ketonates Lanthanum (III) isopropoxide La(O–iC3H7)3 Lanthanum 6,6,7,7,8,8,8 heptafluoro2,2-dimethyl-3, 5-octanedionate La(OC((CF2)2CF3CHCO(C(CH3)3)3 Lanthanum methoxyethoxide La(-OC2H4OCH3)3 Lanthanum 2,4-pentanedionate La(–OC(CH3)CH(CH3)CO–)3 Lanthanum 2,2,6,6-tetramethyl-3,5heptanedionate La(–OC(C(CH3)3)CH(C(CH3)3)CO–)3

316.18

170/0.04

120–128

—

—/—

—

Soluble in isopropanol (60 g/l)

1024.44

—

—

—

—/—

—

)Hsub = 34.7 kcal/mole; soluble in 1, p. 167 acetonitrile, chloroform

364.17

—

—

—

—/—

1.01

436.24

—

140–143

—

s/—

—

Soluble in toluene (0.4 g/l)

1, p. 168

688.72

210/0.2

230–234

—

s/—

—

Hsub = 34.3 kcal/mol

1, p. 168

316.04

—

120(d)

—

s/—

1.64

Soluble in water

1, p. 167

620.07

—

145–149

100–102/10—4 l/—

0.937

n20 = 1.4974

1, p. 167

—

1, p. 167

II. Miscellaneous Lanthanum Compounds Lanthanum acetate (CH3COO)3La Lanthanum tris(bis-(trimethylsilyl)amide) La(N((Si(CH3)3)2)3

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Lead Compound I. Lead Alkoxides and Ketonates 379.33

—

75

797.55

—

75–80

621.29

—

135–140

—

269.27

—

—

—

s/pale yellow s/white

549.69

—

—

—

—/—

1.11

405.41

—

—

120/0.01

s/—

499.49

—

132

—

s/—

373.91/ 409.91 443.37

—

—

—

—

573.75

130/0.1

126–128

Hexamethyldilead (CH3)6Pb2

504.61

—

38

—

Hexaphenyldilead (C6H5)6Pb2 Tetra-n-butyllead 95% (nC4H9)4Pb

877.03

—

225

435.65

140/1

—

Lead (II) acetate (CH3CO2)2Pb Lead II 6,6,7,7,8,8,8 heptafluoro-2,2dimethyl-3, 5-octanedionate Pb(-OC3F7CH(C(CH3)3)O-)2 Lead (II) hexafluoropentanedionate Pb(–OC(CF3)CH(CF3)CO–)2 Lead methoxide [Pb(OCH3)2]n Lead (II) neodecanoate, 60% in naptha Pb(–OOCC(CH3)2C6H13)4 Lead (II) 2,4-pentanedionate Pb(–OC(CH3)CH(CH3)CO–)2 Lead (IV) propionate, 90% Pb(–OOCCH2CH3)4 Lead stannate, dihydrate Pb(–OOCCH3)4 Lead tetraacetate Pb(–OOCCH3)4 Lead (II) 2,2,6,6-tetramethyl,3,5heptanedionate Pb(–OC(C(CH3)3)CH(C(CH3)3)CO–)2

280 s/— (decomposes) — s/—

>950 —/— (decomposes) 175 —/— (decomposes) — s/—

2.55

Soluble in H2O; 20°C: 356 g/l

1, p. 131

—

)Hvap = 20.5 kcal/mol

1, p. 131

—

Soluble in methanol, toluene, acetone Polymeric; air sensitive

1, p. 132

—

Flash point: 40°C

9(suppl.), p. 45 1, p. 132

—

Soluble in hot toluene

1, p. 132

—

Contains Pb II propionate

1, p. 132

—

Photosensitive

27, p. 97

2.28

—

1, p. 132

—

Soluble in toluene; )Hvap = 17.9 kcal/mol

1, p. 132

Crystalline solid/ yellow

—

2, p. 634; 8, p. 1466

—

s/—

—

—

l/—

1.324

Soluble in benzene; )Hform = 161.8163.0 kJ/mol; decomposes slowly at room temperature Does not decompose below 200°C n20 = 1.5119; decomposes at >145°

II. Organolead Compound

2, p. 667; 8, p. 1481 1, p. 133

© 2005 by CRC Press

Soluble in toluene; )Hform = 52.7 2, p. 634; kJ/mol; nD20 = 1.5198; 8, p. 1468 decomposes at 233–267°C Soluble in toluene; )Hform = 136.3 2, p. 634 kJ/mol; nD20 = 1.5120; decomposes at 240–371°C, 25 mmHg )Hform = 515 kJ/mol, highly toxic; 2, p. 635, soluble in chloroform, dioxane 654; 8, p. 1479; 1, p. 133 )Hform = 28.9 kJ/mol 2, p. 635

Tetraethyllead (C2H5)4Pb

323.45

198–202

130.2

—

l/—

1.650

Tetramethyllead (CH3)4Pb

267.34

110

30.2

—

—/—

1.995

Tetraphenyllead (C6H5)4Pb

515.62

240

227.7

Trimethyl-tert-butyllead (CH3)3Pb(tC4H9)

309.42

—

—

—

—/—

—

1,1-Diphenyl-1-plumbacyclohexane (C6H5)2Pb(C2H4(C6H5)2)

336.48

—

—

—

l/—

—

Decomposes on exposure to light and air to resinous solid; discolors on standing

2, p. 642

1-Plumbacycopentane Pb(CH2(C6H5)2)

375.44

145–165/0.5

—

—

—/—

—

Distills unchanged at 145–165°C/0.5 torr

2, p. 642

483.22

—

—

—

l/clear

—

270 —/— (decomposes)

—

III. Heterocyclic Lead Compounds

IV. Perfluorinated Lead Compounds Trifluoromethyllead Pb(CF3)4

—

2, p. 643; eight(sup pl.), p. 47

V. Miscellaneous Functionally Substituted Lead Compounds Triphenyl,lead(dimethyl)acetamide (C6H5)3Pb(OCN(CH3)2 Triphenyl,leadethylacetate (C6H5)3Pb(OOCC2H5)

510.60

—

—

—

—/—

—

Can be stored indefinitely

2, p. 646

511.59

—

—

—

—/—

—

Decomposes slowly at room 2, p. 646 temperature and rapidly at 100°C to (Ph4)Pb, CO, and (Et)2 carbonate

—

—

Decomposes at 20 to 50

—/—

—

Disproportionates explosively at room temperature; air and light sensitive

VI. Compounds with Lead Bonding to Hydrogen Dimethyllead dihydride (CH3)2PbH2

239.29

2, p. 648; 8, p. 1460

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Tributyllead hydride (C4H9)3PbH

379.55

—

—

—

—/—

—

Trimethyllead hydride (CH3)3PbH

253.31

—

~106

Decomposes at 20 to 50

—/—

—

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference

May be stored for few days in the 2, p. 648; dark at 0°C; air and light 8, p. 1473 sensitive Decomposes at 37°C to H2 and 2, p. 648; hexamethyl-dilead; at higher 8, p. 1461 temperature, products are tetramethyllead and Pb; low thermal stability; air and light sensitive

VII. Compounds with Lead Bonding to Oxygen Diethyllead dihydroxide (C2H5)2Pb(OH)2

299.338

—

—

—

s/none

—

Triethyllead hydroxide (C2H5)3PbOH

310.384

—

—

—

s/white (in ethanol)

—

Triethyllead-tert-butylperoxide (C2H5)3PbOO–tC4H9

383.50

—

—

—

s/—

—

Trimethyllead-tert(CH3)3PbOO–tC4H9

341.418

—

81–83

—

s/white

—

Triphenyllead hydroxide (C6H5)3PbOH

455.52

—

—

Decomposes at 300

s/white

—

Triphenyllead-tert-butylperoxide (C6H5)3PbOO–tC4H9

527.630

—

99–101

—

s/white

—

Soluble in H2O; forms hexahydrate, which effloresces to Et2PbO Decomposes at ~50°C in vacuo to Et4Pb and Et2Pb(OH)2; disproportionates on heating Decomposes at ~50°C in vacuo to Et4Pb and Et2Pb(OH)2; disproportionates on heating Thermally unstable, can be stored at low temperature without decomposition Thermally stable; decomposes without melting at 300°C; polymeric chain structure Thermally stable; decomposes without melting at 300°C; polymeric chain structure

2, p. 654; 8, p. 1466 2, p. 648; 8, p. 1465 2, p. 656

2, p. 656; 8, p. 1466 2, p. 654; 8, p. 1476 2, p. 656; 8, p. 1478

VIII. Compounds with Lead Bonding to Nitrogen Tri-n-butyllead,diethylamide (nC4H9)3PbN(C2H5)2

450.68

—

—

—

s/—

—

Triisobutyllead,diethylamide (iC4H9)3PbN(C2H5)2

450.68

—

—

—

s/—

—

Very moisture sensitive; monomeric; freely soluble in aprotic solvents Very moisture sensitive; monomeric; freely soluble in aprotic solvents

2, p. 663

2, p. 663

© 2005 by CRC Press

Triethyllead,diethylamide (diethyl(triethylplumbyl)amine) (C2H5)3PbN(C2H5)2 Triphenyllead,diethylamide (C6H5)3PbN(C2H5)2

366.514

—

—

—

s/—

—

Very moisture sensitive; monomeric; freely soluble in aprotic solvents Very moisture sensitive; monomeric; freely soluble in aprotic solvents Very moisture sensitive; monomeric; freely soluble in aprotic solvents

2, p. 663; 8, p. 1470

510.65

—

—

—

s/—

—

Tripropyllead,diethylamide (C3H7)3PbN(C2H5)2

408.60

—

—

—

s/—

—

379.33

—

75

280(d)

s/—

2.55

349.34

—

—

—

s/—

—

493.60

—

—

—

—/—

1.56

377.36

—

62

—

s/—

—

397.38

—

—

—

—/—

1.700

499.49

—

132

—

s/—

—

443.37

—

—

175(d)

—/—

2.28

433.22

—

72–76

—

s/—

—

Soluble in THF, acetone trifluoroacetic acid

1, p. 133

1, p. 136

1, p. 136 4, p. 47

2, p. 663

2, p. 663

IX. Lead Salts Lead (II) acetate (CH3CO2)2Pb Lead II acrylate (CH2CHCOO)2Pb Soluble in warm ethanol, methanol, waterLead II 2-ethylhexanoate Pb(C4H9CH(C2H5)COO)2 Lead II methacrylate Pb(CH2C(CH3)COO)2 Lead (II) methanesulfonate (CH3SO3)2Pb Lead (IV) propionate, 90% Pb(-OOCCH2CH3)4 Soluble in propionic acidLead (IV) tetraacetate Pb(-OOCCH3)4 Lead (II) trifluoroacetate (CF3COO)2Pb

Soluble in H2O (625g/l), 1, p. 131 methanol (60g/l), ethanol (33g/l) Decomposes at 190-200° 1, p. 131 Soluble in toluene

1, p. 131

Soluble in methanol acetone, THF N20 = 1.4320

1, p. 132 1, p. 132

Contains Pb II propionate

1, p. 132

—

1, p. 132

Lithium Compounds I. Lithium Alkoxides and Diketonates Lithium t-butoxide (CH3)3COLi Lithium ethoxide LiO-C2H5 Lithium isopropoxide LiO-CH(CH3)2

80.05

—

—

110/0.01

s/—

—

52.00

—

—

—

—/—

0.82

Sublimes as hexamer; hexamer in benzene Soluble in ethanol

66.03

—

—

—

—/—

—

—

1, p. 136

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

37.97

—

500 (d)

—

106.05

—

250

192.24

—

Allylithium CH2CHCH2Li

48.01

Butyllithium nC4H9Li

Cyclopentadienyllithium C5H5Li

Compound Lithium methoxide CH3OLi Lithium 2,4-pentanedionate Li(OC(CH3)CH(CH3)CO) Lithium tetramethylheptanedionate Li(-OC(C(CH3)3)CH(C(CH3)3)CO-)

Densitya (g/cc)

Miscellaneous

s/—

—

—

—

s/—

—

Soluble in methanol

1, p. 136

265–268

—

s/—

—

Soluble in methanol, acetone

1, p. 136

—

—

—

s/clear

—

2, p. 47, 99; 8, p. 1211

64.06

80–90/104

76

—

l/—

72.04

—

—

—

s/white

—

174.17

—

—

—

Yellow to red in solution

—

21.98

—

—

—

s/—

—

84.05

—

—

—

s/—

—

Electrochemical oxidation potential: 1.40 V at 62°; air sensitive and may ignite in air; soluble in ether; sp soluble in HC Electrochemical oxidation potential: 1.41 V at 62°C; air sensitive and may ignite in air; stable at room temperature; tetrameric in ether; hexameric in HC Electrochemical oxidation potential: 0.37 V at 62°C; air sensitive and may ignite in air; soluble in tetra-hydrofuran; sparingly soluble in ether Electrochemical oxidation potential: 1.37 V at 62°C; air sensitive and may ignite in air Electrochemical oxidation potential: 0.72 V at 62°C; air sensitive; spontaneous ignition in air; tetrameric in ether and tetrahydrofuran Electrochemical oxidation potential: 0.34 V at 62°C; air sensitive and may ignite in air; soluble in ether; insoluble in HC; dimeric in ether

State/Color

Reference 1, p. 136

II. Alkyl and Aryl Lithium

Diphenylmethyl lithium(lithiodiphenylmethane) (C6H5)2CHLi Methyllithium (CH3)Li

Phenyl lithium (C6H5)Li

0.765

2, p. 47; 8, p. 1213

2, p. 47; 8, p. 1214

2, p. 47; 8, p. 1226 2, p. 47; 8, p. 1207

2, p. 47; 8, p. 1217

© 2005 by CRC Press

Phenylmethl lithium (benzyl lithium) (C6H5)CH2Li

98.07

—

—

—

Crystalline solid/clear (in ether)

—

Electrochemical oxidation potential: 1.33 V at 62°C; air sensitive and may ignite in air; insoluble in hexane; soluble in ether Electrochemical oxidation potential: 1.33 V at 62°C; air sensitive and may ignite in air Electrochemical oxidation potential: 1.57 V at 62°C; air sensitive and may ignite in air

2, p. 47; 8, p. 1219

Tri(phenylmethyl) lithium (C6H5)3CLi

96.06

—

—

—

Crystalline solid/red

—

Vinyl lithium H2C = CHLi

33.99

—

—

—

s/—

—

167.33

114–116/1

—

—

l/—

—

—

1, p. 135

107.13

—

—

—

—/—

—

—

1, p. 136

78.00

—

—

—

—/—

—

—

1, p. 135

92.03

—

—

—

—/—

—

—

1, p. 136

156.01

—

—

—

—/—

—

104.15

—

—

—

—/—

0.829

—

1, p. 137

—/—

—

—

1, p. 168

Crystalline solid/clear

—

—

8, p. 1232

2, p. 47; 8, p. 1227 2, p. 47; 8, p. 1208

III. Alkyl Amide Lithium Compounds Lithium bis(trimethylsilyl)amide LiN(Si(CH3)3)2 Lithium diisopropylamide LiN(CH(CH3)2)2 IV. Lithium Salts Lithium acrylate CH2CHCOOLi Lithium methacrylate CH2C(CH3)COOLi Lithium trifluoromethanesulfonate CF3SO3Li Lithium (trimethylsilyl)acetylide LiCCSi(CH3)3)

Hygroscopic

1, p. 137

Lutetium Compounds I. Lutetium Alkoxides and Diketonates Lutetium 2,4-pentanedionate Lu[OC(CH3)CH(CH3)CO]2 Tricyclopentadienyl lutetium Lu(C5H5)3

472.30

—

—

—

370.25

—

295

260 (in vacuo)

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Magnesium Compounds I. Magnesium Alkoxides and Diketonates 98.43

—

—

Sublimes

—

Trimeric in ether; soluble in ether, 8, p. 1244 sp soluble in benzene

—

Crystalline solid (in ether)/— s/—

Magnesium ethoxide Mg(OC2H5)2 Magnesium hexafluoropentanedionate Mg(-OC(CF3)CH(CF3)CO-)2 Magnesium methoxide Mg(OCH3)2 Magnesium methoxyethoxide Mg(-OC2H4OCH3)2 Magnesium methyl carbonate CH3OCO2MgOCH3.xCO2

114.44

—

270

—

—

—

—/—

—

Soluble in ethanol: 0.9 g/l; soluble in methanol: 31 g/l —

438.41

—

1, p. 138

86.38

—

—

—

l/—

0.815

N20 = 1.3380; flash point: 7°C

1, p. 139

174.47

—

—

—

—/—

1.03

—

1, p. 139

130.39

—

—

—

—/—

1.103

1, p. 139

222.53/ 258.56

—

259

—

s/ivory white

—

142.47

—

—

—

s/—

—

330.47

—

—

—

—/—

—

Flash point: 57°C, soluble form; CO2 removed at high temperature Solubility: in H2O = 11 g/1, in ethanol = 5 g/l, in toluene = 01 g/l Solubility: propanol = 0.3 g/l, in methanol = 4 g/l —

Magnesium 2,4-pentanedionate, dihydrate Mg(OC(CH3)CH(CH3)CO)2 Magnesium n-propoxide Mg(OCH2CH2CH3)2 Magnesium trifluoropentanedionate Mg(-OC(CH3)CH(CF3)CO-)2

Bis(cyclopentadienyl)magnesium (C5H5)2Mg

154.49

—

176

—

s/amber brown

—

Bis(methylcyclopentadienyl)magnesium (C5H4CH3)2Mg Diethyl magnesium (C2H5)2Mg

182.55

—

29

—

s/—

—

82.43

—

—

—

s/—

—

Ethylmagnesiumethoxide C2H5MgOCH3

1, p. 138

1, p. 139

1, p. 139 1, p. 140

II. Alkyl Magnesium Compounds H2O reactive; pyrophoric; 6, p. 83; 5, sp. soluble in CS2, CCl4, CHCl3; p. 241 moderately soluble in benzene, ether, C6H12; very soluble in pyridine, tetrahydrofuran H2O reactive; soluble 6, p. 83 Polymeric; pyrophoric; decomposes at 176°C

3, p. 72; 8, p. 1224

© 2005 by CRC Press

Dimethyl magnesium (CH3)2Mg

54.37

—

—

Sublimes

—

Trimeric in ether; soluble in ether; 8, p. 1244 sp soluble in benzene

—

Crystalline solid (in ether)/— s/—

Diphenyl magnesium (C6H5)2Mg

178.52

—

—

—

—

—

—/—

—

Decomposes at 280°C; pyrophoric; reacts violently with water Soluble in ether

Diisopropyl magnesium ((CH3)2CH)2Mg

110.48

—

166.43

—

>220(d)

—

s/—

—

202.46

—

41

—

s/white

—

Soluble in warm methanol, water, 1, p. 138 toluene Soluble in water 1, p. 138

194.48

—

250–252

—

s/—

—

Soluble in warm toluene

1, p. 139

322.45

—

—

—

—/—

—

Hygroscopic

1, p. 140

27, p. 32; 4, p. 111 1, p. 142

8, p. 1253

8, p. 1248

III. Magnesium Salts Magnesium acrylate (CH2CHCOO)2Mg Magnesium lactate (CH3CH(OH)COO)2Mg Magnesium methacrylate Mg(CH2C(CH3)COO)2 Magnesium trifluoromethanesulfonate (CF3SO3) 2Mg

Manganese Compounds I. Manganese Alkoxides and Diketonates Manganese II methoxide 95% Mn(OCH3)2 Manganese II 2,4-pentanedionate 95% Mn(–OC(CH3)CH(CH3)CO–)2

117.01

—

—

—

-/purple

—

Soluble in methanol

253.16

—

>180

—

s/beige

1.6

Manganese III 2,4-pentanedionate Mn(–OC(CH3)CH(CH3)CO–)3

352.27

—

172

—

s/—

—

Solubility: in H2O = 12 g/l, in ethanol = 22 g/l; hydrolyzes in H2O; trimeric Soluble in benzene, ethyl 1, p. 142 acetate; )Hform = 325 kcal/mol

389.98

—

154–155

—

s/yellow

—

446.00

—

152

—

s/—

196.00

—

24.6

—

l/none

II. Managanese Carbonyls Dimanganesedecacarbonyl Mn2(CO)10 Dimanganesedodecacarbonyl Mn2(CO)12 Manganesehydridepentacarbonyl MnH(CO)5

—

Decomposition in an open system occurs at 110°C —

2, p. 7 3, p. 63

—

Volatile

2, p. 67

© 2005 by CRC Press

Compound Tricarbonyl(methylcyclopentadienyl) maganese (CO)3CH3C5H4Mn

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

218.09

232.22

1.5

—

l/—

198.15

—

—

—

Crystalline solid/deep red

—

173.02

—

—

—

s/pale pink

—

266.31

—

131

—

s/yellow

—

218.09

233

—

—

l/—

State/Color

Densitya (g/cc) 1.38

Miscellaneous Flammable; poisonous

Reference 6, p. 84

III. Manganese Aryl Compounds (M6-Benzene)( M5-cyclopentadienyl) manganese (C6H6)Mn(C5H5)

—

8, p. 1268

IV. Miscellaneous Manganese Compounds Manganese II acetate (CH3COO)2Mg Manganese II ethylenebis(dithiocarbamate) -(NHCS2MnS2CNHC2H4)nMethylcyclopentadienylmanganese tricarbonyl C5H4(CH3)Mn(CO)3

1.38

N20 = 1.589

1, p. 141 —

N20 = 1.5840; flash point: 96°C

1, p. 142

1, p. 142

Mercury Compounds I. Mercury Carboxylates and Alkoxides Ethyl mercury acetate C2H5HgOOCCH3

288.70

—

69–69.8

—

Crystalline solid (in CCl4)— s/—

—

Mercury II acetate (CH3COO)2Hg Methyl mercury acetate CH3HgOOCCH3)

318.70

—

178–180

—

274.67

—

125.5–127.5

—

Crystalline solid/—

—

Methyl mercury ethoxide CH3HgOC2H5 Phenylmercuric acetate C6H5HgOOCCH3

260.69

—

24.25

—

—/—

—

Soluble in water, ethanol, ethyl 1, p. 142 acetate Very soluble in water, ethanol, 8, p. 1040 acetic acid; soluble in ethylacetate, pyridine, benzene, CCl4, CS2; moderately soluble in ether Strong desiccant 8, p. 1042

336.75

—

150

—

s/—

2.4

Soluble in benzene, acetic acid

3.29

—

8, p. 1050

1, p. 142

© 2005 by CRC Press

Phenyl mercury methoxide C6H6HgOCH3

308.73

—

144–145

—

—/—

—

Dimeric in benzene

8, p. 1078

Bisdodecene mercury (n-C12H25)2Hg Bistetrafluorophenyl mercury (C6HF4)2Hg Bis(2-thienyl)mercury (C4H3S)2Hg

539.25

—

44.5–45

—

s/—

—

Soluble in benzene

2, p. 901

498.73

—

—

300/vacuum

s/—

—

—

366.85

—

202

—

—

—

Bistolyl mercury (CH3C6H4)2Hg

382.86

—

—

—

—

2, p. 902; 16

Bistrifluoromethylmercury (CF3)2Hg

338.60

—

—

—

—

2, p. 902; 16

Cyclopentadienylmercury (C5H5)2Hg

330.78

—

—

—

3, p. 73; 8, p. 1100

Diethylmercury (C2H5)2Hg Dimethylmercury (CH3)2Hg

258.71

159

—

—

l/—

—

230.66

92.5

—

—

l/—

3.069

Di(1-naphthyl)mercury (1-C10H8)2Hg Diphenylmercury (C6H5)2Hg Methyl mercury azide CH3HgN3

456.94

—

243

—

s/—

—

354.80

—

125

—

s/—

—

257.64

—

130

—

s/—

—

295.53

—

172

—

s/—

—

251.08

—

170

—

s/—

—

241.64

—

—

—

Needle shaped crystal

—

Soluble in benzene; sensitive to light, moisture, and heat; turns gray on storage; decomposes at 83–84°C Slowly deposits Hg; toxic; soluble in benzene Flammable; toxic; stable at room temperature; nD = 1.5413; soluble in benzene Thermally stable; soluble in benzene Thermally stable; soluble in benzene Leaflets in ethanol; soluble in MeOH, hot EtOH, Me2CO, CCl4; detonates by shock with difficulty Plates in ethanol, dipole moment: 3.16 D Plates in ethanol, dipole moment: 3.16 D Monoclinic in solid shape

II. Alkyl Mercury Compounds

Methyl mercury bromide CH3HgBr Methyl mercury chloride CH3HgCl Methyl mercury cyanide CH3HgCN

Crystalline solid (in benzene)/ — — Solid monoclinic crystals Purified by Crystalline sublimation in solid/— vacuo — Crystalline solid/ yellow

2, p. 902; 14 2, p. 902; 8, p. 1084

2, p. 901 2, p. 901; 6, p. 85; 8, p. 1036 2, p. 901 2, p. 901 2, p. 904; 8, p. 1031

2, p. 904; 8, p. 1030 2, p. 904; 8, p. 1084 2, p. 904; 15

© 2005 by CRC Press

Compound Methyl mercury iodide CH3HgI

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

342.53

—

145

—

State/Color

Densitya (g/cc)

s/none

—

Miscellaneous Rectangular plate crystals

Reference 2, p. 904

Molybdenum Compounds I. Molybdenum Alkoxides and Diketonates Molybdenum V ethoxide Mn(OC2H5)5 Molybdenum VI oxide bis(2,4pentanedionate); Molybdenyl acetylacetonate OMo(OC(CH3)CH(CH3)CO)2

321.25

—

—

—

—/—

—

—

1, p. 143

326.17

—

181

—

s/yelloworange

—

—

1, p. 143

264.00

—

150

258.08

—

—

276.19

—

—

60–100/high vacuum ~100/103

321.06

—

—

~100/103

II. Molybdenum Carbonyls Molybdenum hexacarbonyl Mo(CO)6

Decomposes at 180

Solid/white Crystalline solid/ colorless

1.96

s/yellow or orange —/green

—

3, p. 63; 2, Octahedral; volatile; air stable; p. 1081 hydrophobic; decomposes without melting at 150°C yet melts reversibly under vacuum at 146°C; very slightly soluble in nonpolar solvents and polar organic solvents; insoluble in water; odorless; diamagnetic; )Hsub = 68.2–73.6; )Hcomb = –2116 to –2123; )Hform = –960 to –991; )H° = 297–326; )Hm = 26.8

III. Molybdenum Arene Compounds Benzenetricarbonyl molybdenum M6-C6H6Mo(CO)3 Bis(trimethylbenzene) molybdenum Mo(M-1,3,5-Me3C6H3)2 Bis(chlorobenzene) molybdenum Mo(M-ClC6H5)2

—/light green

2, p. 1214

—

Air stable in solid state; air sensitive in solution Air sensitive

—

Air sensitive; pyrophobic

2, p. 1205

2, p. 1205

© 2005 by CRC Press

Dibenzyl molybdenum Mo(M-CH2-C6H6)2

252.17

—

—

~100/103

—

103

—

—/green

—

Air sensitive

2, p. 1205

s/—

—

—

1, p. 143

IV. Miscellaneous Molybdenum Compound Molybdenyl II diethyldithiocarbamate Mn(S2CNH(C2H5) 2)2

424.48

Neodymium Compounds I. Neodymium Alkoxides and Diketonates Neodymium 6,6,7,7,8,8,8-heptafluoro2,2-dimethyl-3,5-octanedionate (OC(C3F7)CHC(C(CH3)3)O)3Nd Neodymium hexafluoropentanedionate Nd(OC(CF3)CH(CF3)CO)3 Neodymium methoxyethoxide Nd(-OC2H4OCH3)3 Neodymium III 2,4-pentanedionate Nd(OC(CH3)CH(CH3)CO)3 Neodymium 2,2,6,6-tetramethyl-3,5heptanedionate Nd(OC(C(CH3)3)CH(C(CH3)3)CO)3 )Hsub = 37.9 kcal/molNeodymium III trifluoropentanedionate Nd(OC(CF3)CH(CH3)CO)3

1029.77

—

82-3

—

s/—

—

—

1, p. 169

765.39

—

—

—

—/—

—

—

1, p. 169

369.50

—

—

—

l/pale blue

—

—

1, p. 169

441.57

—

150–152

—

s/—

1.618

—

1, p. 170

694.06

—

209-212

150/0.1

s/—

—

603.48

—

140–142

—

s/—

—

—

1, p.170

321.38

—

—

—

—

—

1, p. 169

369.48

—

>200(d)

—

657.97

—

—

—

—/light purple —/pale purple —/—

—

380

200–250 (in vacuo)

Crystalline solid/pale blue

—

Decomposes > 270°C

1, p. 170

II. Neodymium Salts Neodymium acetate (CH3COO)3Nd Neodymium methacrylate (CH2C(CH3)COO)3Nd Neodymium neodecanoate (C6H13C(CH3)2COO)3Nd

— —

Slightly soluble in THF —

1, p. 169 1, p. 170

III. Miscellaneous Neodymium Compounds Tricyclopentadienylneodymium (C5H5)3Nd

339.52

Soluble in tetrahydrofuran; hydrolyzed in water

8, p. 1318

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Nickel Compounds I. Nickel Alkoxides and Diketonates Nickel hexafluoropentanedionate Ni(OC(CF3)CH(CF3)CO)2 Nickel II methoxide Ni(OCH3)2 Nickel II 2,4-pentanedionate Ni(OC(CH3)CH(CH3)CO)2

472.82

—

213

—

s/green

—

—

1, p. 145

120.76

—

—

—

—

—

4, p. 111

256.88

—

208

—

—/pale green s/green (turns turquoise on absorption of 3 mol H2O)

Nickel II 2,2,6,6-tetramethyl-3,5heptanedionate Ni(OC(C(CH3)3)CH(C(CH3)3)CO)2

425.23

—

223–225

90–110/0.1

279.09

—

—

—

542.05

—

210–220

303.59

—

153.59

1.455

n20 = 1.57–164; trimeric compound; solubility: H2O = 11.0 g/l, toluene = 85 g/l, ethanol = 27 g/l; )Hsub = 16.5 kcal/mol

1, p. 145

s/—

—

—

1, p. 145

—

—

2, p. 110

—

s/yelloworange s/red

—

—

1, p. 144

—

—

s/purple

—

60/30

—

—

l/red

—

176.78

—

—

—

—/—

—

467.43

—

86

—

s/green

1.26

299.12

—

>290

—

—/—

1.77

II. Organonickel Compounds Bis(cyclooctadiene)nickel Ni(C8H14)2 1,3-Bis(diphenylphosphino)propanenickel II chloride ((C6H5)2P(-C3H6-)P(C6H5)2)NiCl2 Cyclopentadienylnickle carbonyl (NiCO(M-C5H5))2 Cyclopentadienylnickel nitrosyl ONNi(M-C5H5) Nickel diacetate Ni(OOCCH3)2 Nikel di-n-butyldithiocarbamate Ni(S2CNH(C4H9) 2)2 Nickel dimethyldithiocarbamate Ni(S2CNH(CH3) 2)2

Diamagnetic; decomposes at >115°C Stable; distilled at ~60°C at 30 mmHg without decomposition —

2, p. 199

Soluble in toluene, CHCl3, warm acetone —

1, p. 144

2, p. 209 2, p. 110

1, p. 144

© 2005 by CRC Press

Nickel tetracarbonyl Ni(CO)4 Nickelocene (Ni(M-C5H5))2

170.73

43

25, 17.2

188.88

—

173–174

Decomposes >35°C 50/0.1

Tolyl(pentafluorobenzyl) nickle Ni(C6F5)2(M-CH3C6H5)

484.95

—

137–140

—

s/red

176.78

—

—

—

—/green

1.744

184.77

—

180–200(d)

—

s/—

2.15

—

l/colorless

1.32

Very toxic

s/dark green

1.47

Paramagnetic; )Hform = 262; soluble in most organic solvents; magnetic susceptibility —

—

2, p. 4; 3, p. 63 2, p. 189–191

2, p. 229

III. Nickel Salts Nickel II acetate Ni(OOCCH3)2 Nickel formate (HCOO)2Ni

— Soluble in water

2, p. 110 1, p. 144 1, p. 79

Niobium Compounds I. Niobium Alkoxides and Diketonates Niobium V n-butoxide Nb(O-nC4H9)5

458.48

197/0.15

—

—

l/—

4, p. 71, 72

—

Molecular complexity: 2.01 (in benzene), 1.74 (toulene), 1.13 (ROH) n20 = 1.5160; flash point: 74°C; molecular complexity: 2.02 (in benzene), 1.89 (toluene), 1.34 (ROH) Molecular complexity: 2.11 (in benzene), 1.90 (in toluene), 1.34 (in ROH) Molecular complexity: 2.00 (in benzene) Molecular complexity: 1.16

Niobium V ethoxide Nb(OC2H5)5

318.22

142/0.1 156/0.05

5–6

—

—/pale yellow

Niobium V methoxide Nb(OCH3)5

248.08

153/0.1

—

—

l/—

—

Niobium V n-pentoxide Nb(O-n-C5H11)5 Niobium V sec-pentoxide Nb(OCH(C2H5)2)5 Niobium V sec-pentoxide Nb(OCH(nC3H7)CH3)5 Niobium V pentaoxide Nb(OCH2CH2CH(CH3)2)5 Niobium V n-propoxide Nb(O-n-C3H7)5

528.62

223/0.15

—

—

l/—

—

528.62

138/0.1

—

—

l/—

528.62

137.5/0.1

—

—

l/—

—

Molecular complexity: 1.03

4, p. 71

528.62

199/0.1

—

—

l/—

—

Molecular complexity: 1.81

4, p. 71

374.24

166/0.05

—

—

l/—

—

4, p. 71, 72

—

—

l/—

—

Molecular complexity: 1.02 (in benzene), 1.79 (toluene), 1.29 (ROH) Molecular complexity: 1.00

Niobium V isopropoxide Nb(OCH(CH3)2)5

374.24

60–70/0.1

1.258

1, p. 146; 4, p. 72

4, p. 71, 72

4, p. 71, 72 4, p. 71

4, p. 71

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

374.24

110–120/0.3

—

—

Bis(M2-benzene)niobium (C6H6)2Nb

249.13

—

—

Bis-cyclopentadienyl dimethyl niobium IV (C5H5)2Nb(CH3)2 Biscyclopentadienyltribromo niobium (C5H5)2NbBr3

253.17

—

—

462.81

—

—

Biscyclopentadienyltrihrydrido niobium (C5H5)2NbH3

226.12

—

—

Cyclopentadienyltetrachloro niobium (C5H5)NbCl4 Dimethyltrichloroniobium NbCl3(CH3)2 Methyltetrabromoniobium NbBr4CH3

299.81

—

—

229.34

—

—

—

427.56

—

—

—

Methyltetrachloroniobium NbCl4CH3

249.75

—

—

—

273.58

—

—

—

Compound Niobium V tert-propoxide Nb(OC(CH3)3)5

State/Color l/—

Densitya (g/cc) —

Miscellaneous Molecular complexity: 1.00

Reference 4, p. 71

II. Niobium Alkyl Compounds 80 Crystalline (decomposes) solid/redpurple 80/10-4 Crystalline solid/redbrown — Crystalline solid/redbrown (in CHCl3) — Crystalline solid/ yellow (in toluene) — s/—

—

—

8, p. 1312

—

Explodes at 128°

2, p. 737; 21

—

Decomposes at 260°C; stable in 2, p. 766; dry air; soluble in polar solvents; 8, p. 1311 hydrolyzed by water

—

Soluble in aromatic solvents; 2, p. 774; decomposes at 80°C in solution 8, p. 1311

—

s/yelloworange Crystalline solid/ orangebrown Crystalline solid/ orangebrown

—

Decomposes at 180°C; slightly soluble in organic solvents —

—

Air and moisture sensitive

Crystalline solid/ brown (in toluene)

—

—

—

2, p. 763; 8, p. 1310 2, p. 733; 21 2, p. 733; 20

2, p. 733; 15

III. Niobium Alkyls and Derivatives (IV) Biscyclopentadienyl chloromethyl niobium IV (C5H5)2NbClCH3

Soluble in toluene

2, p. 736; 8, p. 1312; 18

© 2005 by CRC Press

Biscyclopentadienyl dibenzothiolato niobium IV (C5H5)2Nb(C6H4S)2

441.43

—

135–140

—

Biscyclopentadienyl dibenzyl niobium IV (C5H5)2Nb(CH2C6H5)2

405.36

—

140–142

—

Bis(methylcyclopentadienyl) dimethylniobium IV (CH3C5H4)2Nb(CH3)2 Biscyclopentadienyl dineopentyl niobium IV (C5H5)2Nb(CH2C(CH3)3)2 Biscyclopentadienyl diphenyl niobium IV (C5H5)2Nb(C6H5)2

281.22

—

—

—

Crystalline solid/green (in CH2Cl2 and petroleum ether) Crystalline solid/blackred —/—

—

—

2, p. 736; 8, p. 1315

—

—

2, p. 735; 17

—

—

2, p. 735; 17

365.38

—

—

—

—/—

—

—

2, p. 735

377.31

—

—

—

—/—

—

—

2, p. 736

327.25

—

—

—

—

—

2, p. 751; 23

—

—

—

—

—

20

238.13

—

—

—

Crystalline solid/redbrown Crystalline sold/purple —/—

405.36

—

—

2, p. 736

266.18

—

—

—

—/—

—

—

2, p. 736

249.13

—

—

120/0.01

s/—

—

—

8, p. 1313

813.97

—

—

—

l/yellow

—

—

1, p. 147

538.05

—

—

—

—/—

—

IV. Niobium Alkyls and Derivatives (III) Biscyclopentadiene,cyclooctatetraene(c ot) niobium (C5H5)2Nb(h2-C8H8) Biscyclopentadienyl dibenzyl niobium (C5H5)2Nb(CH2C6H5)2 Biscyclopentadienyl methyl niobium III (C5H5)2NbCH3 Biscyclopentadienyl methylethylene niobium III (C5H5)2NbCH3C2H4 (Cycloheptatrienyl)(cyclopentadienyl) niobium (C7H7)Nb(C5H5) V. Niobium Salts Niobium 2-ethylhexanoate (C4H9CH(C2H5)COO)5Nb Niobium oxalate Nb(OOCCOOH)5

Soluble in water, methanol

1, p. 147

© 2005 by CRC Press

Compound

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

342.24

—

90/103

—

266.14

—

75/103

328.21

—

120/103

Formula Weight

Densitya (g/cc)

Miscellaneous

s/green

—

—

20

—

s/green

—

—

18; 20

—

s/green

—

—

20

l/colorless

—

Very volatile

s/yellow

—

s/pale yellow

—

Air stable; slightly soluble in organic solvents Air stable, readily sublimes

s/—

—

s/yelloworange

—

State/Color

Reference

VI. Miscellaneous Niobium Carbonyl Compounds Biscyclopentadienyl benzylcarbonyl niobium (C5H5)2(CH2C6H5)Nb(CO) Biscyclopentadienyl methylcarbonyl niobium (C5H5)2Nb(CH3)(CO) Biscyclopentadienyl phenylcarbonyl niobium (C5H5)2(C6H5)Nb(CO)

Osmium Compounds I. Osmium Carbonyl Compounds Osmium pentacarbonyl Os(CO)5 Trinuclear-osmiumtetracarbonyl (Os(CO)4)3 Trinuclear-osmiumtetracarbonyldihydride (CO)4HOs–(CO)4Os–Os(CO)4H

330.25

—

15

—

906.72

—

—

908.74

—

95–98

403 K in vacuo —

2, p. 968; 3, p. 63 2, p. 971 2, p. 972

Palladium Compounds I. Palladium Alkoxides and Diketonates Palladium 1,1,1,5,5,5-hexafluoro-2,4pentanedionate Pd(OC(CF3)CH(CF3)CO)2 Palladium 2,4-pentanedionate Pd(OC(CH3)CH(CH3)CO)2

520.51

—

100

70/70

304.92

—

>205

—

Soluble in methylene chloride, 1, p. 147 methanol, toluene, acetone, ethylacetate; )Hfus = 10.2 cal/g Solubility: toluene = 6.5 g/l, 2, p. 240; pentanedionate = 8 g/l 1, p. 148

© 2005 by CRC Press

II. Miscellaneous Palladium Compounds Palladium II acetate Pd(OOCH3)2 Palladium acetate Pd3(OOCH3)6

224.49

—

—

—

673.53

—

—

—

Palladium trifluoroacetate Pd(OOCF3)2 Tetrakis(triphenylphosphine)-palladium [(C6H5)3P]4Pd

332.43

—

—

—

1155.58

—

—

—

—/orangebrown Crystalline solid/ orange-red —/—.

—

—

—

1, p. 148

—/yellowbrown

—

—

1, p. 148

Flash point: 70°C n20 = 1.4216 Pyrophoric

1, p. 148

Flash point: 90°C n20 = 1.4080 Flash point: 44°C n20 = 1.43

1, p. 149

Flash point: 38°C

1, p. 149

—

—

1, p. 147

Trinuclear in solution and soluble 2, p. 239 1, in organic solvents p. 147

Phosphorus Compounds I. Alkyl Phosphorus Compounds Diethylphosphatoethyltriethoxysilane (C2H5O)2P(O)CH2CH2Si(OC2H5)3 Diethylphosphorushydride (C2H5)2PH Diethylphosphite (C2H5O)2P(O)H Diethyl(trimethylsiloxycarbonyl)methyl)phosphonate (C2H5O)2P(O)CH2C(O)OSi(CH3)3 Dimethyl(trimethylsilyl)phosphite (CH3O)2P(O)Si(CH3)3 tert-Butyl phosphine PH2(t-C4H9) Triethylphosphate (C2H5O)3PO Triethylphosphorus (C2H5)3P Trimethylphosphorus (CH3)3P Triphenylphosphine oxide (C6H5)3PO Tris(trimethylsilyl)phosphate ((CH3)3SiO)3PO Tris(trimethylsilyl)phosphite ((CH3)3SiO)2P

328.41

141/2

—

—

l/—

1.031

90.11

85

—

—

l/—

—

138.11

50–51/2

—

—

l/—

1.072

268.33

93/0.0005

—

—

l/—

1.059

182.23

73–77/56

—

—

l/—

0.954

90.11

—

—

—

—/—

182.16

215

57

—

l/—

1.072

118.16

127

88

—

l/—

0.801

76.08

37.8

85

—

l/—

—

278.28

—

151–154

—

s/—

—

314.54

85–87/4

2–4

—

l/—

0.959

298.55

90–92/20

—

—

l/—

0.893

—

— Flash point: 116°C n20 = 1.4050 Pyrophoric, vapor pressure of 108 mm at 20°C Pyrophoric —

6, p. 86

1, p. 149

3, p. 72 1, p. 150 3, p. 72; 6, p. 86 6, p. 86 1, p. 151

n20 = 1.4090; flash point: >110°C; 1, p. 151 )Hvap = 9.7 kcal/mol N20 = 1.4090 1, p. 151 Flash point: 66°C )Hvap = 9.7 kcal/mol

© 2005 by CRC Press

Compound

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

284.18

—

>340(d)

—

—/—

1.396

Soluble in THF, CH2Cl2, methanol

1, p. 148

186.20

280

—

—

l/—

1.070

n20 = 1.6250

1, p. 149

316.46

160/1

—

—

l/—

—

376.50

182/1.3

—

—

l/—

1.05

232.31

—

—

—

—/—

1.14

276.45

—

—

—

—/—

0.989

298.45

—

—

—

—/—

—

Formula Weight

State/Color

Densitya (g/cc)

Miscellaneous

Reference

II. Miscellaneous Alkyl Phorphous Compounds 1-Butyl-3-methyllimidazolium hexafluorophosphate (CH3)(C3H3N2)C4H9)PF6 Diphenylphosphine (C6H5)2PH 2-(Diphenylphosphino)ethyldimethylethoxysilane (C6H5)2PC2H4Si(CH3)2OC2H5 2-(Diphenylphosphino)ethyltriethoxysilane (C6H5)2PC2H4Si(OC2H5)3 Sodium di(isobutyl)dithiophosphinate ((CH3)2CHCH2)2PS2Na Tetrabutylphosphinium hydroxide (nC4H9)4POH Vinyl(diphenylphosphinoethyl)dimethylsilane (C6H5)2PCH2CH2Si(CH3)2(CHCH2)

—

Flash point: 134°C

— n20 = 1.4120

1, p. 149

1, p. 149

1, p. 150 3, p. 150

—

1, p. 151

Platinum Compounds I. Platinum Alkoxides and Diketonates 393.31

—

250–252

—

s/pale yellow

—

Soluble in methylene chloride

1, p. 153

Bis[(1,2,5,6–M)-1,5-cyclooctadiene platinum Pt(C8H12)2

411.47

—

—

—

—

Can be handled in air but solutions are oxygen sensitive

2, p. 425; 8, p. 1584

Bis(dibenzylideneacetone)platinum Pt(C6H5CH = CHCOCH = CHC6H5)2

663.68

—

—

—

Crystalline solid (in petroleum ether)/— —/deep purple

—

Air stable

2, p. 622

Platinum 2,4-pentanedionate Pt(OC(CH3)CH(CH3)CO)2 II. Organoplatinum Compounds

© 2005 by CRC Press

Bispentanedionate,trimethyl platinum ((CH3)3Pt(OC(CH3)CHC(CH3)O))2 Dimethylplatinum II cyclooctadiene C8H12Pt(CH3)2 Tetra(triphenylphosphine)platinum Pt(P(C6H5)3)4 Trisdibenzylideneacetone platinum Pt(C6H5CH = CHCOCH = CHC6H5)3 Triethyleneplatinum Pt(C2H4)3

438.40

—

—

—

—/—

—

333.34

—

103–105

—

s/—

—

1244.24

—

—

s/yellow

—

897.97

—

159–160 (in vacuo) —

—

–/yellow

—

279.24

—

—

—

Crystalline solid (in pentane/—

—

2, p. 588

Soluble in acetone, CO2, toluene, pentane Air sensitive; dissociates in benzene —

1, p. 152 2, p. 627; 8, p. 1628 2, p. 622

—

Volatile; can be stored in ethane at 20°C

2, p. 620; 8, p. 1564

—

Plutonium Compounds Bisbutylcyclooctatetraene plutonium Pu(BunC8H7)2 Biscyclooctatriene plutonium Pu(C8H8)2

564.52

—

—

—

—/—

—

452.30

—

—

—

s/cherry red

—

Bisethylcyclooctatetrane plutonium Pu(C2H5C8H7)2 Tricyclopentadienyl plutonium (C5H5)3Pu

508.41

—

—

—

—/—

—

439.284

—

—

140–165 (in vacuo)

s/moss green

2, p. 235

Soluble in tetrahydrofuran, toluene, benzene, CCl4; air sensitive; diamagneitc —

2, p. 232; 8, p. 1631

—

Soluble in tetrahydrofuran; decomposes at >195°C; extremely air sensitive

8, p. 1631

Solubility: hexane = 1.8 g/l, t-butanol = 140 g/l, tetrahydrofuran = 220 g/l; bulk density = 500 g/l; hygroscopic Soluble in ethanol, ether; bulk density: 0.65 g/ml Soluble in methanol

1, p. 154

2, p. 235

Potassium Compounds I. Potassium Alkoxides and Diketonates Potassium t-butoxide KO-t-C4H9 Potassium ethoxide 95% KOC2H5 Potassium methoxide CH3OK Potassium 2-methyl-2-butoxide KOC(CH3)2CH2CH3 Potassium 2,4-pentanedionate, hemihydrate K(OC(CH3)CH(CH3)CO)

112.21

275

220

—

—/—

—

84.16

—

250

—

s/—

—

70.14

—

—

—

s/—

—

126.24

—

—

—

s/—

0.80

138.21/ 147.22

—

250

—

s/—

—

1, p. 154 1, p. 155

Flash point: 18°C

1, p. 155

Soluble in water, methanol

1, p. 155

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

222.37

—

—

—

Solid powder/ light brown

—

Soluble in ethanol; ionic

Butylpotassium C4H9K

96.21

—

—

—

s/—

—

Methylpotassium CH3K Potassium bis(trimethylsilyl)amide K(N(Si(CH3)3)2)

54.13

—

—

—

—

199.49

—

—

—

Crystalline solid/— l/—

Amorphous solid; decomposes 2, p. 55; 8, below melting point; insoluble in p. 1199 and unreactive toward all solvents Ionic crystal; insoluble 2, p. 55

0.877

Flash point: 7°C; soluble in toluene

1, p. 155

98.15

—

292

—

s/—

1.57

1, p. 153

110.15

—

194

—

s/—

—

Soluble in water (725g/l), methanol (200g/l) —

1, p. 154

160.22

—

—

—

—/—

—

Soluble in water, methanol

1, p. 154

84.12

—

167.5

—

s/—

1.91

Soluble in water, ethanol

1, p. 154

124.18

—

—

—

—/—

—

246.32

—

>300(d)

—

—/—

—

114.21

—

173–176

—

s/—

—

—

1, p. 156

152.12

—

143–145

—

s/—

—

—

1, p. 156

188.17

—

—

—

—/—

—

128.29

—

134–138

—

s/—

—

140.30

—

—

—

s/—

—

Compound Potassium 2,2,6,6-tetramethylheptanedionate K(OC(C(CH3)3)CH((C(CH3)3)CO)

State/Color

Densitya (g/cc)

Miscellaneous

Reference 1, p. 155

II. Alkyl Potassium

III. Potassium Salts Potassium acetate CH3COOK Potassium acrylate CH2CHCOOK Potassium benzoate C6H5COOK Potassium formate HCOOK Potassium methacrylate CH2C(CH3)COOK Potassium sulfopropylmethacrylate CH2C(CH3)COOC3H6SO3K Potassium thioacetate CH3C(S)OK Potassium trifluoroacetate CF3COOK Potassium trifluoromethanesulfonate CF3SO3K Potassium trimethylsilanolate (CH3)3SiOK Potassium vinyldimethylsilanolate CH2CHSi(CH3)2OK

— Soluble in water (700g/l)

Hygroscopic

1, p. 155

1, p. 156 —

Soluble in THF

1, p. 154

1, p. 156 1, p. 156

© 2005 by CRC Press

Praseodymium Compounds I. Praseodymium Alkoxides and Diketonates Praseodymium III 6,6,7,7,8,8,8heptafluoro-2,2-dimethyl-3,5octanedionate Pr(OC(CF2CF2CF3)CH(C(CH3)3)CO)3 Praseodymium 2,4-pentanedionate Pr(OC(CH3)CH(CH3)CO)3 Praseodymium hexafluoropentanedionate (OC(CF3)CH(CF3)CO)3Pr Praseodymium methoxyethoxide Pr(-OC2H4OCH3)3 Praseodymium 2,2,6,6,tetramethyl 3,5heptanedionate Pr(OC(C(CH3)3)CH(C(CH3)3)CO)3 Tricyclopentadienyl praseodymium (C5H5)3Pr

1026.45

—

215–219

—

s/—

—

—

1, p. 171

438.24

—

143–146

—

s/—

—

—

1, p. 171

762.06

—

—

—

s/light green

—

—

1, p. 171

366.17

—

—

—

l/pale green

1.01

—

1, p. 171

690.72

—

212–214

150/1

336.19

—

420

200–250 (in vacuo)

s/—

—

)Hsub = 39.5 kcal/mol

1, p. 171

Crystalline solid/pale green

—

Soluble in tetrahydrofuran; hydrolyzes in water

8, p. 1548

s/yelloworange

—

Air and moisture sensitive; soluble in tetrahydrofuran; hydrolyzes in water

2, p. 180; 8, p. 1546

—

Volatile; cubic

3, p. 64; 2, p. 163

Promethium Compounds I. Promethium Cyclopentadienyls Triscyclopentadienyl promethium Pm(C5H5)3

342.28

—

—

200–250 140–260 (in vacuo)

Rhenium Compounds I. Carbonyl Compounds Dirhenium decacarbonyl Re2(CO)10

652.52

—

170

250 s/colorless (decomposes)

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Biscyclopentadienyl hydrodorhenium ReH(M-C5H5)2

317.40

—

161–162

80/0.01

Cyclopentadienyl tricarbonyl rhenium Re(CO)3(M-C5H5)

335.33

—

112

Hexamethyl rhenium Rh(CH3)6 Methyltrioxorhenium VII CH3RhO3 Pentamethyl cyclopentadienyl tricarbonyl rhenium Re(CO)3(M-C5(CH3)5) Propylenyl rhenium tetracarbonyl Re(M-C3H5)(CO)4

276.42

—

—

249.23

—

111

405.47

—

151

—

339.32

—

32–35

—

323.39

—

79–81

65–75/1

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference

—

Air sensitive; soluble in organic solvents, insoluble in water

2, p. 206; 8, p. 1642

—

Can be sublimed in vacuum

2, p. 207; 8, p. 1641

—

Soluble in hexane

8, p. 1638

—

—

1, p. 179

Crystalline solid/white (in hexane) Crystalline solid/ yellow (in hydrocarbons) s/—

—

—

2, p. 207; 8, p. 1644

—

—

2, p. 231; 8, p. 1040

—

Soluble in hydrocarbons, chloroform, THF

1, p. 179

II. Miscellaneous Rhenium Compounds

Trimethylsilylperrhenate O3RhOSi(CH3)3

Crystalline solid/ yellow — Crystalline solid (in hexane)/— 10–12 Crystalline (decomposes) solid/green 65/0.001 —/—

Rhodium Compounds I. Rhodium Alkoxides and Diketonates Rhodium II acetate (CH3COO)2Rh2(CH3COO)2 Rhodium dicarbonyl 2,4-pentanedionate (CO)2Rh(OC(CH3))CH((CH3)CO) Rhodium III 2,4-pentanedionate Rh(OC(CH3)CH(CH3)CO)3 Soluble in chloroform, ether, pentane, acetoneRhodium trifluoropentanedionate Rh(-OC(CF3)CH(CH3)CO-)3

441.99

—

—

—

—/—

—

Soluble in water

1, p. 180

258.04

—

90/0.1

s/—

—

400.24

—

144–147 (155) 263–264

240/1

s/yellow

—

Exhibits semiconducting properties Decomposes at >280°C

1, p. 180; 8, p. 1668 1, p. 180

562.14

—

185–186

—

s/yellow

—

Soluble in methanol, chloroform

1, p. 181

© 2005 by CRC Press

II. Alkyl Complexes of Rhodium Tris(dibutylsulfide)rhodium trichloride ((C4H9)2S)3RhCl3 Tris(triphenylphosphine)rhodium I ((C6H5)3P)3RhCl3

648.16

—

—

—

—/—

0.91

Soluble in toluene

1, p. 180

925.23

—

>170(d)

—

s/—

—

Soluble in warm acetone, chloroform, ethanol

1, p. 180

Cyclopentadienyl cyclooctadiene rhodium (C5H5)Rh(C8H12)

276.18

—

108

—

Crystalline solid/ orangeyellow (in CH2Cl2) Platelets/ yellow Solid (prism)/ yellow

—

Soluble in ether

8, p. 1681

Diethylenerhodiumacetylacetonate Rh(OC(CH3)CHC(CH3)O)C2H4)2 Tri(U-allyl)rhodium Rh(C3H4)3

258.12

—

144–146

—

—

Best stored at 0°C

—

Decomposes at 130°C

2, p. 438; 8, p. 1677 8, p. 1671

226.12

—

80–85

40/0.01

Hygroscopic

1, p. 181

III. Alkylene Complexes of Rhodium

Rubidium Compounds Rubidium acetate CH3COORb Rubidium 2,4-pentanedionate RuOC(CH3)CH(CH3)CO

144.52

—

246(d)

—

s/—

—

184.58

—

200

—

s/—

—

—

1, p. 181

Ruthenium Compounds I. Ruthenium Alkoxides and Diketonates Ruthenium III 2,4-pentanedionate Ru(OC(CH3)CH(CH3)CO)3

398.40

—

226

—

s/red-brown

—

Ruthenium III oxoacetate (Ru3O(OOCCH3)6(H2O)3)OOCCH3

786.57

—

>200(d)

—

s/green

—

Soluble in acetone, methanol, 2, p. 652; cyclohexane, methylene 1, p. 182 chloride 2, p. 652 Soluble in water, methanol, THF 1, p. 182

231.26

—

199–200

—

Crystalline solid/light yellow (in CCl4)

—

Sublimes under vacuum

II. Ruthenium Alkyls and Aryls Biscyclopentadienyl ruthenium Ru(M-C5H5)2

2, p. 652; 8, p. 1780

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Cyclooctatetraene ruthenium tricarbonyl Ru(CO)3(h4-C8H8)

289.25

—

75–76

47/0.05

Propylenyl ruthenium dicarbonyl Ru(CO)2(M-C3H5)2

239.24

—

<25

—

Ruthenium di(pentadionate)dicarbonyl Ru(OCC(CH3)CH(CH3)CO)2(CO)2 Rutheniumpentacarbonyl Ru(CO)5

355.31

—

—

—

241.12

—

22

50 (decomposes)

Tris(triphenylphosphine)rhuthenium II dichloride ((C6H5)3P)3RuCl2

958.85

—

—

—

Compound

Densitya (g/cc)

Miscellaneous

Reference

Crystalline solid/ orange-red

—

—

Crystalline solid/pale yellow —/pale yellow 1/colorless

—

2, p. 655; 8, p. 1783; 26 2, p. 655; 8, p. 1771

—/black

State/Color

Sublimes under vacuum

—

—

—

—

Very volatile; )Hform = 1053 kJ/ mol; readily loses CO to make Ru3(CO)12; sensitive to light —

2, p. 708 2, p. 662; 3, p. 63; 8, p. 1764 1, p. 182

Samarium Compounds I. Samarium Alkoxides and Diketonates Samarium 2,4-pentanedionate Sm(OC(CH3)CH(CH3)CO)3 Samarium III isopropoxide Sm(OiC3H7)3 Samariam III 2,2,6,6tetramethylheptanedionate Sm(OC(C(CH3)3)CH((CH3)3C)CO)3 Samariam III thenoyltrifluoroacetonateSm(OC(C4H3S)CH(CF3)CO)3

447.68

—

146–147

—

s/—

—

—

1, p. 172

286.62

—

—

—

—/—

—

—

1, p. 172

700.11

—

191–193

—

s/pale yellow

—

816.90

—

—

—

—/—

—

321.62

—

—

Sublimable

s/pale yellow

—

)Hsub = 36.0 kcal/mol —

1, p. 172

1, p. 172

II. Samarium Allyls Biscyclopentadienyl,propylenyl samarium Sm(C5H5)2(C3H5)

Air and moisture sensitive; thermally stable

2, p. 196

© 2005 by CRC Press

III. Samarium Alkene Complexes Samarium, 3–hexyne Sm(C6H10)

232.51

—

—

—

s/brown

—

Samarium trisbutadiene Sm(C4H6)3

312.63

—

—

—

—

Tri-U-cyclopentadienyl samarium Sm(C5H5)3

345.64

—

365

200–250 (under vacuum)

Crystalline solid/deep brown Crystalline solid/ orange

327.53

—

—

—

—/—

1.94

—

1, p. 172

597.56

—

—

—

—/—

—

—

1, p. 172

—

Tetrahydrofuran soluble materials, 220 (thermal decomposition) Air and moisture sensitive

Soluble in tetrahydrofuran; hydrolyzed by water

2, p. 206

2, p. 205

8, p. 2150

IV. Samarium Salts Samarium (III) acetate (CH3COO)3Sm Samarium (III) trifluoromethanesulfonate (CF3SO3) 3Sm

Scandium Compounds I. Scandium Alkoxides and Diketonates Scandium III 2,2,6,6teramethylheptanedionate Sc(OC(C(CH3)3)CH(CH3)3)C)CO)3

594.77

—

150–152

—

s/—

—

Soluble: ethyl acetate modulus and low coefficient for thermal expansion

1, p. 173

286.27

—

—

—

—/—

—

—

2, p. 185

240.24

—

—

200–250

s/—

—

216.22

—

—

—

—/—

—

II. Scandium Cyclopentadienyls Biscyclopentadienyl scandium pentadionate Sc(C5H5)2(OCC(CH3)CH(CH3)CO) Triscyclopentadienyl scandium Sc(C5H5)3

Air and moisture sensitive

2, p. 180

III. Scandium Allyls Biscyclopentadienyl propenyl scandium Sc(C5H5)2(C3H5)

—

2, p. 196

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Biscyclopentadienyl(diphenylphosphinidenio)bis(methylene) scandium Sc(C5H5)2(CH2)2P(C6H5)2 Tricyclopentadienyl scandium Sc(C5H5)3

388.38

—

—

—

Crystalline solid/pale yellow

—

More air sensitive crystals, soluble in ether

2, p. 204; 8, p. 1906

240.24

—

240

Crystalline solid/—

—

Soluble in pyridine, dioxane; decomposes in water

8, p. 1905

Trisphenylethynyl scandium Sc(C CC6H5)3

348.34

—

>250

200–250 (under vacuum) —

s/dark brown

—

Pyrophoric in air; soluble in tetrahydrofuran

2, p. 197; 8, p. 1906

492.16

—

—

—

—/—

—

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference

IV. Scandium Hydrocarbyls

V. Scandium Salt Scandium trifluoromethanesulfonate (CF3SO3) 3Sc

—

1, p. 173

Selenium Compounds I. Selenium (II) Alkyl and Aryls Diethylselenide (C2H5)2Se Dimethylselenide (CH3)2Se Diphenylselenide (C6H5)2Se Di-n-propylselenide (n-C3H7)2Se Ethyl seleniumhydride (C2H5)SeH Phenyl selenium bromide C6H5SeBr Phenyl seleniumhydride (C6H5)SeH Propylseleniumhydride (C3H7)SeH

137.08

108

—

—

l/—

1.230

Poison

109.03

57–58

—

—

l/—

1.4077

Poison

233.17

301

2.5

—

l/none

1.1427

Unpleasant odor

5, p. 227; 6, p. 88 5, p. 227; 6, p. 88 5, p. 227

165.14

159

—

—

l/none

1.1427

Unpleasant odor

5, p. 227

109.03

53.2

—

—

l/none

1.3594

Unpleasant odor

5, p. 227

235.97

134/35

62

—

s/none

—

157.07

183.6

—

—

l/none

1.4865

Unpleasant odor

5, p. 227

123.06

84

—

—

l/none

1.302

Unpleasant odor

5, p. 227

—

5, p. 227

© 2005 by CRC Press

II. Selenium (IV) Alkyl/Aryl Halides Diethyl selenium dibromide (C2H5)2SeBr2 Dimethyl selenium dibromide (CH3)2SeBr2 Dimethyl selenium dichloride (CH3)2SeCl2 Diphenyl selenium dichloride (C6H5)SeCl2 Methyl selenium tribromide CH3SeBr3 Phenyl selenium tribromide C6H5SeBr3

296.89

—

37

—

s/none

—

—

5, p. 227

268.84

—

82

—

s/none

—

—

5, p. 227

179.94

—

59.5

—

s/none

—

—

5, p. 227

304.08

—

180

—

s/none

—

—

5, p. 227

333.71

—

75

—

s/none

—

—

5, p. 227

395.78

—

105

—

s/none

—

—

5, p. 227

Silicon Compounds I. Silicon Alkoxides and Diketonates Hydroxyethoxysilatrane HOCH2CH2OSi(-OCH2CH2)3NPolydimethylsiloxane polymers (SiC2H60)x Silicon di-t-butoxide diacetate (t-C4H9O)2Si(OOCCH3)2 Tetraacetoxysilane Si(OOCCH3)4 Tetra-n-butoxysilane (n-C4H9O)4Si

235.32 —

>205(d)

1.05

—

—

—

l/clear

—

292.40

102/5

4

—

—/—

1.0196

264.26

148/6

111–115

—

s/—

—

320.54

115/3

<80

—

l/—

0.899

Tetraethoxysilane (TEOS) (C2H5O)4Si

208.33

169

77

—

l/—

0.9335

Tetraisopropoxysilane Si(OCH(CH3)2)4 Tetrakis(2-ethylbutoxy)silane Si(OCH2CH(CH2CH3)2)4

264.44

185–186

—

—/—

0.8772

432.76

166–171/2

—

—/—

0.892

Soluble in water

1, p. 213

Crystallizes at 60°C; glass transition at 123°C n20 = 1.4040; flash point: 95°C

2, p. 345 1, p. 203

Flash point: >110°C

1, p. 226

n20 = 1.4128; flash point: 78°C; viscosity: 2.33 cSt; )Hvap = 14.8 kcal/mol; surface tension = 22.8 dyn/cm n20 = 1.3818; toxic; flash point: 46°C; )Hvap = 11.0 kcal/mol; viscosity: 0.8 cSt Flash point: 58°C; )Hvap = 11,700 kcal/mol n20 = 1.430; flash point: 116°C; viscosity (38°): 4.35 cSt; surface tension: 22.8 dyn/cm

13, p. 194; 1, p. 226

13, p. 195; 1, p. 227 1, p. 227 1, p. 228

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Tetrakis(2-ethylhexoxy)silane Si(OCH2CH(CH2CH3)C4H9)4

544.97

194/1

<73

Tetramethoxysilane (CH3O)4Si

152.22

121–122

4–5

Tetraphenoxysilane (C6H5O)4Si Tetra-n-propoxysilane (n-C3H7O)4Si

400.51

236–237/1

264.44

Tri-t-butoxysilanol HOSi(OC(CH3)3)3 Triethylacetoxysilane (C2H5)3SiOOCCH3 Triisopropoxysilane HSi(OCH(CH3)2)3 Vinyltriacetoxysilane CH2CHSi(OOCCH3)3

Compound

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

n20 = 1.4388; flash point: 188°C; viscosity (38°): 6.89 cSt; surface tension: 26.7 dyn/cm; )Hvap = 16.9 kcal/mol; n20 = 1.3688; toxic; viscosity; 0.5 cSt; flash point: 20°C; )Hform = 30 kcal/mol; )Hvap = 11.25 kcal/ mol; )Hcomb = 694 kcal/mol n20 = 1.554 (at 60°C); viscosity (55°C): 6.6 cSt n20 = 1.4012; flash point: 95°C; viscosity: 1.66 cSt; surface tension: 23.6 dyn/cm; )Hcomb = 1694 kcal/mol —

1, p. 228

13, p. 205

—

n20 = 1.4190; surface tension: 24.5 dyn/cm n20 = 1.3839

l/—

1.167

n20 = 1.423; flash point: 88°C

13, p. 226; 1, p. 240

—

l/—

1.086

Flash point: 4°C

1, p. 189

—

—

—/—

—

—

1, p. 189

117–118

—

—

l/—

1.201

1, p. 189

184.74

75–76/15

—

—

l/—

1.016

n20 = 1.4460; flash point: 31°C; )Hvap = 9.4 kcal/mol n20 = 1.509

225.58

140–142/100

—

—

l/—

1.288

n20 = 1.5257; toxic

13, p. 108

197.95

58–59/16

—

—

l/—

—

n20 = 1.4624; flash point: 47°C

1, p. 192

—/—

0.880

—

l/—

1.032

48–49

—

—/—

224–225

<80

—

l/—

1.141 (60) 0.9158

264.44

—

65–66

—

—/—

174.31

173–174

—

—

l/—

206.35

35/5

—

—

—/—

232.26

112–113/1

—

—

141.07

97

—

252.86

—

175.52

— 0.893

4, p. 108; 13, p. 198 1, p. 228 13, p. 200 4, p. 108; 13, p. 201; 1, p. 230 1, p. 231

1, p. 234

II. Halosilane Compounds Allyldichlorosilane CH2CHCH2Si(Cl)2H m-Allylphenylpropyldimethylchlorosilane m-CH2CHCH2(C6H4)(CH2)3Si(CH3)2Cl Allyltrichlorosilane CH2CHCH2SiCl3 Benzyldimethylchlorosilane C6H5CH2Si(CH3)2Cl Benzyltrichlorosilane C6H5CH2SiCl3 Bis(chloromethyl)dichlorosilane (ClCH2)2SiCl2

13, p. 108

© 2005 by CRC Press

3-Bromopropyltrichlorosilane BrCH2CH2CH2SiCl3 3-Bromopropyltrimethoxysilane BrCH2CH2CH2Si(OCH3)3 11-Bromoundecyldimethylchlorosilane BrCH2(CH2)10Si(CH3)2Cl 11-Bromoundecyltrichlorosilane BrCH2(CH2)10SiCl3 11-Bromoundecyltrimethoxysilane BrCH2(CH2)10Si(OCH3)3 13-(Carbomethoxy)decyldimethylchlorosilane CH3OOC(CH2)10Si(CH3)2Cl n-Butyldimethylchlorosilane n-C4H9Si(CH3)2Cl tert-Butyldimethylchlorosilane (CH3)3CSi(CH3)2Cl tert-Butylmethyldichlorosilane (CH3)3CSi(CH3)Cl2 Isobutyltrichlorosilane (CH3)2CHCH2–SiCl3 n-Butyltrichlorosilane CH3CH2CH2CH2SiCl3 t-Butyltrichlorosilane (CH3)3CSiCl3 1-Chloroethyltrichlorosilane (95%) CH3CHClSiCl3 2-Chloroethylsilane ClCH2CH2SiH3 2-Chloroethyltrichlorosilane (95%) ClCH2CH2SiCl3 2-Chloroethyltriethoxysilane ClCH2CH2Si(OC2H5)3 2-(Chloromethyl)allyltrimethoxysilane CH2C(CH2Cl)CH2Si(OCH3)3 ((Chloromethyl)phenylethyl)dimethylchlorosilane ClCH2C6H4CH2CH2Si(CH3)2Cl ((Chloromethyl)phenylethyl)methyldichlorosilane ClCH2C6H4CH2CH2Si(CH3)Cl2

256.43

85–86/16

—

—

l/—

1.618

n20 = 1.4910; flash point: 88°C

1, p. 198

243.17

130/45

—

—

l/—

1.293

n20 = 1.440; Flash point: 82°C

1, p. 198

327.80

170/1

—

—

l/—

—

—

1, p. 198

368.64

172/1

—

—

l/—

1.26

—

1, p. 198

355.39

150/0.8

—

—

l/—

1.119

n20 = 1.4559

1, p. 198

292.92

133/0.3

—

—

l/—

0.950

n20 = 1.4483; flash point: 105°C

1, p. 198

150.72

138

—

—

l/—

0.8751

n20 = 1.4205

13, p. 124

150.72

124–126

91.5

—

—/—

0.81

171.14

147–148

—

—

l/—

1.042

n20 = 1.431

13, p. 126

191.56

140

—

—

l/—

1.15

n20 = 1.4335

13, p. 165

191.56

142–143

—

—

l/—

1.161

n20 = 1.436; flash point: 7°C

13, p. 126

191.56

132–133

98–99

—

s/—

—

197.95

136–137

—

—

l/—

1.393

94.61

69–71

—

—

l/—

0.904

197.95

152–153

—

—

l/—

1.419

226.77

88–89/9

—

—

l/—

210.73

128/70

—

—

247.24

134–135/20

—

267.66

120–125/0.6

—

—

13, p. 124

—

2, p. 10; 13, p. 126 n20 = 1.456; dipole moment: 2.30 13, p. 126 —

1, p. 199

l/—

1.009 (25) 1.09

n20 = 1.4640; flash point: 28°; dipole moment: 1.51 n20 = 1.4130 (at 25°C); flash point: 66° Flash point: 89°C

1, p. 199

—

l/—

1.00

n20 = 1.5223; flash point: 87°C

1, p. 199

—

l/—

1.21

Flash point: 104°C

1, p. 199

13, p. 126; 1, p. 199 13, p. 126

© 2005 by CRC Press

Compound ((Chloromethyl)phenylethyl) trichlorosilane ClCH2C6H4CH2CH2SiCl3 ((Chloromethyl)phenylethyl) trimethoxysilane ClCH2C6H4CH2CH2Si(OCH3)3 (p-Chloromethyl)phenyltrimethoxysilane p-ClCH2C6H4Si(OCH3)3 Chloromethyltriethoxysilane ClCH2Si(OC2H5)3 3-Chloropropylmethyldimethoxysilane ClCH2CH2CH2SiCH3(OCH3)2 3-Chloropropyltrimethoxysilane ClCH2CH2CH2Si(OCH3)3 2-(4-Chlorosulfonylphenyl)ethyltrichlorosilane (50%) 4-ClSO2C6H4CH2CH2SiCl3 3-Cyanopropyltrichlorosilane NCCH2CH2CH2SiCl3 11-Cyanoundecyltrichlorosilane NC(CH2)11SiCl3 Cyclohexyldimethylchlorosilane C6H11Si(CH3)2Cl Cyclohexyldimethylsilane C6H11Si(CH3)2H Cyclohexyltrichlorosilane C6H11SiCl3 n-Decylmethyldichlorosilane n-C10H21Si(CH3)Cl2 n-Decyltrichlorosilane n-C10H21SiCl3 Dibenzyloxydichlorosilane (90%) (C6H5CH2O)2SiCl2 Di-tert-butylchlorosilane (t-C4H9)2Si(Cl)H Di-n-butyldichlorosilane (95%) (n-C4H9)2SiCl2

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

288.08

111–112/1.5

—

—

l/—

1.32

Flash point: >100°C

1, p. 200

274.82

115/1.5

—

—

l/—

1.09

n20 = 1.4930; flash point: 130°C

1, p. 200

246.77

134–143/10

—

—

l/—

1.13

n20 = 1.4965; flash point: 183°C

1, p. 200

212.75

90–91/25

—

—

l/—

1.048

n20 = 1.407; flash point: 47°C

1, p. 200

182.72

70–72/11

—

—

l/—

1.0250

n20 = 1.4253; flash point: 80°C

1, p. 200

198.72

100/40

—

—

l/—

1.077

1, p. 200

338.11

—

—

—

l/—

1.37

n20 = 1.4183; flash point: 78°C; viscosity: 0.56 cSt —

202.54

93–94/8

—

—

l/—

1.302

n20 = 1.465; flash point: 75°C

1, p. 201

314.76

162–164/1

—

—

l/—

1.075

—

1, p. 201

176.76

202; 52–53/2

—

—

l/—

—

—

13, p. 136

142.32

159

—

—

l/—

—

n20 = 1.4508

13, p. 136

217.60

90–91/10

—

—

l/—

1.222

n20 = 1.4774

13, p. 136

255.31

111–114/3

—

—

l/—

0.9600

n20 = 1.4490

13, p. 138

275.72

133–137/5

—

—

l/—

1.0540

n20 = 1.4528

13, p. 138

313.26

140-5/1

—

—

l/—

1.22

178.78

82–84/45

—

—

l/—

0.88

n20 = 1.4414; flash point: 39°

13, p. 139

213.22

212

—

—

l/—

0.991

n20 = 1.4448

13, p. 139

State/Color

Densitya (g/cc)

Miscellaneous

—

Reference

1, p. 200

1, p. 202

© 2005 by CRC Press

Di-n-butylmethylchlorosilane (n-C4H9)2Si(CH3)Cl (Dichloromethyl)(chloromethyl)dimethylsilane (Cl2CH)(ClCH2)Si(CH3)2 Dichlorosilane H2SiCl2

192.80

193–198

—

—

l/—

0.8656

n20 = 1.4325

13, p. 139

191.56

184

—

—

l/—

1.209

n20 = 1.4753

1, p. 203

101.01

8.3

112

—

—/—

1.22 (7)

13, p. 142

Diethyldichlorosilane (C2H5)2SiCl2 Dimethyl,t-butylchlorosilane (t-C4H9)(CH3)2SiCl Dimethyldichlorosilane (CH3)2SiCl2

157.11

130

96.5

—

—/—

1.050

150.72

—

—

—

—/—

—

)Hvap = 6.5 kcal/mol; )Hform = 75 kcal/mol; flash point: <37°C; specific heat: 0.268 cal/g/°C n20 = 1.431; toxic; )Hvap = 10.0 kcal/mol; dipole moment: 2.4 —

129.06

7071

76

—

—/—

1.0637

96.15

23

87.8

—

—/—

—

124.64

77

—

—

l/—

347.10

159/0.1

28–30

—

s/—

0.9527 (25) —

253.20

309310

—

—

l/—

1.222

220.29

156/50

—

—

l/—

232.78

295

—

—

l/—

1.145 (17) 1.128

244.80

125/0.5

—

—

l/—

185.17

165166

—

—

423.62

218220/0.5

—

129.06

7476

122.67

91

Dimethyldifluorosilane (CH3)2SiF2 Dimethylmethoxychlorosilane (90%) (CH3)2Si(OCH3)Cl Dimethyl-noctadecylchlorosilane CH3(CH2)17Si(CH3)2Cl Diphenyldichlorosilane (C6H5)2SiCl2 Diphenyldifluorosilane (C6H5)2SiF2 Diphenylmethylchlorosilane (C6H5)2Si(CH3)Cl Diphenylvinylchlorosilane (C6H5)2Si(HCCH2)Cl Din-propyldichlorosilane (95%) (C3H7)2SiCl2 n-docosylmethyldichlorosilane CH3(CH2)21Si(CH3)Cl2 Ethyldichlorosilane CH3CH2SiCl2H Ethyldimethylchlorosilane C2H5Si(CH3)2Cl

13, p. 142

2, p. 10; 13, p. 124 n20 = 1.4055, toxic; DHvap = 8.0 2, p. 10; kcal/mol; DHcomb = -491 kcal/ 13, p. mol; viscosity: 0.47 cSt; flash 146; 1, p. point: –10°C; surface tension = 205 20.1 dyn/cm; specific heat: 0.22 cal/g/°C Specific heat: 0.26 cal/g/°C 13, p. 147 n20 = 1.3865

13, p. 147 13, p. 147; 1, p. 220 13, p. 150

1.104

Flash point: 201°C; waxy, low melting solid n20 = 1.582; toxic; DHvap = 15.0 kcal/mol; flash point: 157°C n20 = 1.5221; DHvap = 12.9 kcal/ mol n20 = 1.5742; viscosity: 5.3 cSt; DHvap = 149 kcal/mol; flash point: >112°C n20 = 1.579

l/—

1.017

n20 = 1.4411

—

l/—

—

107

—

—/—

1.093

—

—

—/—

0.8756

13, p. 150 13, p. 151

13, p. 152 13, p. 152

—

13, p. 153

n20 = 1.4129; viscosity: 0.53 cSt; 13, p. 155 surface tension = 21.7 dyn/cm n20 = 1.4050 13, p. 155

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Ethylmethyldichlorosilane CH3CH2Si(CH3)Cl2 Ethyltrichlorosilane CH3CH2SiCl3

143.09

100

—

—

l/—

1.0632

n20 = 1.420

163.51

100101

106

—

—/—

1.237

(Heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane CF3(CF2)7CH2CH2Si(CH3)2Cl (Heptadecafluoro-1,1,2,2-tetrahydrodecyl)methyldichlorosilane CF3(CF2)7CH2CH2Si(CH3)Cl2 (Heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane CF3(CF2)7CH2CH2SiCl3 n-Heptyltrichlorosilane n-C7H15SiCl3 n-Hexadecyltrichlorosilane n-C16H33SiCl3 Hexenyldimethylchlorosilane CH2CH(CH2)4Si(CH3)2Cl n-Hexylmethyldichlorosilane CH3(CH2)5Si(CH3)Cl2 n-Hexyltrichlorosilane CH3(CH2)5SiCl3 n-Hexyltrifluorosilane CH3(CH2)5SiF3 3-iodopropyltrimethoxysilane ICH2CH2CH2Si(OCH3)3 3-isocyanatopropyldimethylchlorosilane OCNCH2CH2CH2Si(CH3)2Cl 3-Methacryloxypropyldimethylchlorosilane CH2C(CH3)COO(CH2)3Si(CH3)2Cl Methacryloxypropylmethyldichlorosilane CH2C(CH3)COO(CH2)3Si(CH3)Cl2 Methacryloxypropyltrichlorosilane CH2C(CH3)COO(CH2)3SiCl3

540.72

197–198

—

—

l/—

—

n20 = 1.426; toxic; flash point: 13, p. 156 27°C; viscosity: 0.48 cSt; )Hvap = 9.0 kcal/mol — 1, p. 210

561.14

205–207

26–27

—

l/—

1.63

581.56

216–218

—

—

l/—

1.703

n20 = 1.3490

1, p. 211

233.64

211212

—

—

l/—

1.087

n20 = 1.4439 (at 25°C)

13, p. 160

359.88

202/10

—

—

l/—

0.98

n20 = 1.4592; flash point: 154°

176.76

183–184

—

—

l/—

0.895

n20 = 1.4423; flash point: 48°

13, p. 161 1, p. 211 1, p. 213

199.19

204206

—

—

l/—

0.993

n20 = 1.4390

13, p. 164

219.61

191192

—

—

l/—

1.107

n20 = 1.3473

13, p. 164

170.25

8891

—

—

l/—

—

n20 = 1.3473

13, p. 164

290.17

79–80/2

—

—

l/—

1.475

n20 = 1.4714; flash point: 78°

1, p. 214

177.71

62–66/0.6

—

—

l/—

—

Flash point: 70°

1, p. 215

220.77

78/1

—

—

l/—

1.012

n20 = 1.451; flash point: 85°

1, p. 216

241.19

75/2

—

—

l/—

1.108 (25)

n20 = 1.4552 (at 25°C)

13, p. 169

261.61

96–98/1

—

—

l/—

1.251

n20 = 1.4650; flash point: >94°C

1, p. 216

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference 13, p. 156

—

1, p. 211

© 2005 by CRC Press

Methoxyethoxyundecyltrichlorosilane CH3OCH2CH2O(CH2)11SiCl3 Methyldichlorosilane CH3SiHCl2

363.83

—

—

—

—/—

—

—

1, p. 217

115.03

4142

93

—

—/—

1.105

Methyldiiodosilane CH3SiHI2 Methyldodecyldichlorosilane CH3(CH2)11Si(CH3)Cl2 Methyl-n-octadecyldichlorosilane CH3(CH2)17Si(CH3)Cl2 Methyl-n-octyldichlorosilane CH3(CH2)7Si(CH3)SiCl2 Methylphenyldichlorosilane C6H5Si(CH3)Cl2 (2-Methyl-2-phenylethyl)methyldichlorosilane C6H5CH(CH3)CH2Si(CH3)Cl2 Methyl-n-propyldichlorosilane CH3CH2CH2Si(CH3)Cl2 Methyltrichlorosilane CH3SiCl3

312.97

—

—

—

—/—

—

283.36

124127/3

—

—

l/—

0.955

367.52

185/2.5

—

—

l/—

0.930

227.25

94/6

—

—

l/—

0.976

N20 = 1.444

13, p. 174

191.13

205206

—

—

l/—

1.187

13, p. 174

233.21

104–105/9

—

—

l/—

1.1165

N20 = 1.5180; toxic; )Hvap = 11.5 kcal/mol; flash point: 82°C N20 = 1.5152

157.11

125

—

—

l/—

N20 = 1.425 (at 25°C)

13, p. 175

149.48

66.4

78

—

—/—

1.04 (25°C) 1.275

Methyltrifluorosilane CH3SiF3 p-Nonylphenoxypropyldimethylchlorosilane p-CH3(CH2)8C6H4OCH2CH2CH2Si (CH3)2Cl n-Nonyltrichlorosilane n-C9H19SiCl3 n-Octadecylmethoxydichlorosilane CH3(CH2)17Si(OCH3)Cl2 n-Octadecyltrichlorosilane CH3(CH2)17SiCl3 7-Octenyltrichlorosilane CH2CH(CH2)6SiCl3 n-Octyldimethylchlorosilane n-C8H17Si(CH3)2Cl n-Octyltrichlorosilane n-C8H17SiCl3

100.11

30

73

—

—/—

—

355.04

181/0.75

—

—

l/—

0.963

261.69

116/10

—

—

l/—

1.064

383.51

144–147/1.5

—

—

l/—

—

—

387.93

160162/3

22

—

—/—

n20 = 1.4602; flash point: 189°C

245.65

223–224

—

—

l/—

0.950 (22°C) 1.07

206.83

222225

—

—

1/

0.794

247.67

224226

—

—

l/—

1.074

n20 = 1.422; toxic; flash point: 2, p. 11; 32°C; viscosity: 0.60 cSt; )Hvap 13, p. 172 = 7.0 kcal/mol; )Hcomb = 39 kcal/mol — 2, p. 11 n20 = 1.453

13, p. 173 —

13, p. 173

1, p. 218

n20 = 1.4110; toxic; flash point: 13, p. 175; 15°C; viscosity: 0.37 cSt; )Hvap 1, p. 219 = 7.4 kcal/mol — 13, p. 176 —

N20 = 1.450

1, p. 220

13, p. 178 1, p. 221

n20 = 1.4578; flash point: 94°C

13, p. 179; 1, p. 221 1, p. 222

n20 = 1.4328 (at 25°C); flash point: 97°C n20 = 1.447; flash point: 96°C

13, p. 181; 1, p. 222 13, p. 181

© 2005 by CRC Press

Compound Pentafluorophenylpropylmethyldichlorosilane C6F5(CH2)3Si(CH3)Cl2 Phenethyltrichlorosilane C6H5CH2CH2SiCl3 Phenylallyldichlorosilane C6H5Si(CH2CHCH2)Cl2 4-Phenylbutyldimethylchlorosilane C6H5(CH2)4Si(CH3)2Cl 4-Phenylbutylmethyldichlorosilane C6H5(CH2)4Si(CH3)Cl2 4-Phenylbutyltrichlorosilane C6H5(CH2)4SiCl3 Phenyldichlorosilane C6H5SiHCl2 Phenyldimethylchlorosilane C6H5Si(CH3)2Cl Phenylethyldichlorosilane C6H5Si(C2H5)Cl2 Phenylmethylchlorosilane C6H5SiHCH3Cl Phenylmethylvinylchlorosilane C6H5Si(HCCH2)(CH3)Cl Phenyltrichlorosilane C6H5SiCl3 Phenyltrifluorosilane C6H5SF3 Phenylvinyldichlorosilane C6H5Si(CHCH2)Cl2 Isopropylchlorosilane (i-C3H7)2SiHCl n-Propyldimethylchlorosilane CH3CH2CH2Si(CH3)2Cl n-Propyltrichlorosilane CH3CH2CH2SiCl3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

323.16

128–129/20

—

—

239.60

93–96

—

217.17

100102/8

226.83

Densitya (g/cc)

Miscellaneous

1/

1.378

—

—

l/—

1.240

n20 = 1.5185; flash point: 91°C

1, p. 224

—

—

—/—

N20 = 1.535 (at 25°C)

13, p. 183

85–87/0.6

—

—

l/—

1.168 (25°C) 0.964

247.24

105–109/1.5

—

—

l/—

1.09

Flash point: >110°C

1, p. 224

268.66

—

—

—

l/—

—

Flash point: >110°C

1, p. 224

177.10

6566/10

—

—

l/—

1.212

N20 = 1.526

13, p. 183

170.71

192193

—

—

l/—

1.032

13, p. 184

205.16

225226

—

—

l/—

1.184

156.69

113/100

—

—

l/—

1.054

n20 = 1.5082; viscosity: 1.4 cSt; )Hvap = 11.4 kcal/mol; flash point: 61°C n20 = 1.5321; )Hvap = 11.9 kcal/ mol N20 = 1.571

13, p. 185

182.72

7980/34

—

—

l/—

1.034

n20 = 1.5197

13, p. 185

211.55

201

—

—

l/—

1.329

13, p. 186

162.19

101102

—

—

l/—

203.14

8487/1.5

—

—

l/—

n20 = 1.534 (at 25°C)

13, p. 187

150.72

137; 5455/45

—

—

l/—

1.201 (26.5°C) 1.196 (25°C) 0.872

n20 = 1.525 (at 25°C); toxic; flash point: 91°C; viscosity: 1.08 cSt; )Hvap = 11.4 kcal/mol n20 = 1.4110

136.70

113114

—

—

l/—

0.873

n20 = 1.414

177.53

123125

—

—

l/—

1.1851

n20 = 1.429; flash point: 2°C; )Hvap = 8.7 kcal/mol

State/Color

Reference 1, p. 223

n20 = 1.4979; flash point: >110°C 1, p. 224

—

13, p. 185

13, p. 186

2, p. 11; 8, p. 1982 13, p. 188 13, p. 188

© 2005 by CRC Press

Tetraethylsilane (C2H5)4Si

144.33

153155

82

—

—/—

Thexyltrichlorosilane (CH3)2CHC(CH3)2SiCl3 p-Tolylmethyldichlorosilane p-CH3C6H5Si(CH3)Cl2 p-Tolyltrichlorosilane p-CH3C6H5SiCl3 Tri-t-butoxychlorosilane (95%) (t-C4H9O)3SiCl Tri-n-butylchlorosilane (90%) (n-C4H9)3SiCl Trichlorosilane HSiCl3

219.61

70-2/15

—

—

l/—

—

205.16

161165/7

—

—

l/—

1.1609

225.58

218220

—

—

l/—

1.28

282.88

97/12

—

—

l/—

—

234.88

9394/4

—

—

l/—

0.879

n20 = 1.4472

13, p. 202

135.45

31.9

128

—

—/—

1.342

13, p. 203

240.59

—

—

—

l/—

0.93

n20 = 1.402; toxic; )Hvap = 6.7 kcal/mol; )Hform = 115.2 kcal/ mol; flash point: 13°C; surface tension: 14.3 dyn/cm Flash point: 4°C; hazy liquid

1, p. 231

198.72

156157

—

—

l/—

n20 = 1.388 (at 25°C)

13, p. 204

440.70

189–191

—

—

l/—

1.012 (25°C) 1.473

n20 = 1.3453; flash point: 52°C

1, p. 231

461.12

189–190

—

—

l/—

1.550

n20 = 1.3500; flash point: 51°C

1, p. 231

481.55

84–85/17

—

—

l/—

1.639

n20 = 1.3521; flash point: 54°C

1, p. 232

182.27

133–134

—

—

l/—

0.94

195.17

6667/24

50

—

—/—

1.140

n20 = 1.4561

13, p. 205

150.72

144–145

—

—

l/—

0.896

134.27

110111

—

—

l/—

—

n20 = 1.4313; flash point: 30°C; )Hvap = 9.8 kcal/mol nD = 1.39

319.04

154155/5

—

—

l/—

0.871

2, p. 11; 13, p. 206 2, p. 11; 8, p. 1983 13, p. 207

4-[2-(Trichlorosilyl)ethylpyridine 4-(C5H4N)CH2CH2SiCl3 Triethoxychlorosilane (95%) (C2H5O)3SiCl (Tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylchlorosilane CF3(CF2)5CH2CH2Si(CH3)2Cl (Tridecafluoro-1,1,2,2-tetrahydrooctyl)methyldichlorosilane CF3(CF2)5CH2CH2Si(CH3)Cl2 (Tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane CF3(CF2)5CH2CH2SiCl3 Triethoxyfluorosilane FSi(OC2H5)3 Triethylbromosilane (C2H5)3SiBr Triethylchlorosilane (C2H5)3SiCl Triethylfluorosilane (C2H5)3SiF Tri-n-hexylchlorosilane (n-C6H13)3SiCl

0.762

n20 = 1.4246; flash point: 32°; viscosity: 0.9 cSt; )Hvap = 9.9 kcal/mol; )Hform = 41 kcal/mol; )Hcomb = 1597 kcal/mol —

13, p. 195; 1, p. 227

n20 = 1.5330

13, p. 202

n20 = 1.5224 (at 25°C)

13, p. 202

—

—

n20 = 1.456

1, p. 231

13, p. 202

1, p. 232

© 2005 by CRC Press

Compound Trimethylbromosilane (CH3)3SiBr Trimethylchlorosilane (99.9%) (CH3)3SiCl Trimethylfluorosilane (CH3)3SiF Trimethylsilyliodide (95%) (CH3)3SiI Triphenylbromosilane (C6H5)3SiBr Triphenylchlorosilane (C6H5)3SiCl Triphenylfluorosilane (C6H5)3SiF (Triphenylmethyl)methyl-dichlorosilane (C6H5)3CSi(CH3)Cl2 Triisopropylchlorosilane ((CH3)2CH)3SiCl Tri-n-propylchlorosilane (CH3CH2CH2)3SiCl 10-Undecenyldimethylchlorosilane CH2CH(CH2)9Si(CH3)2Cl 10-Undecenyltrichlorosilane CH2CH(CH2)9SiCl3 Undecyltrichlorosilane CH3(CH2)10SiCl3 Vinyl(chloromethyl)dimethylsilane CH2CHSi(CH3)2(CH2Cl) Vinyldimethylchlorosilane CH2CHSi(CH3)2Cl Vinylethyldichlorosilane CH2CHSi(CH3CH2)Cl2 Vinylmethyldichlorosilane CH2CHSi(CH3)Cl2

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

153.09

80

44

—

—/—

1.173

108.64

57.6

57.7

—

l/—

0.8580

92.19

1618

74

—

—/—

200.09

106107

—

—

l/—

0.793 (0°C) 1.470

195.17

6667/24

50

—

l/—

1.140

294.85

207210/12

9192

—

—

278.40

207210/12

6162

—

Solid crystal/ white —/—

—

—

13, p. 221

357.35

—

196–197

—

s/—

—

—

1, p. 236

192.80

80/10

—

—

l/—

0.9027

192.80

199201

—

—

l/—

0.882

246.90

100/2

—

—

—/—

0.871

287.74

100–102/0.8

—

—

l/—

1.04

Flash point: 105°C

1, p. 238

289.75

155160/15

—

—

l/—

1.019

Flash point: 107°C

1, p. 238

134.68

121–122

—

—

l/—

0.893

Flash point: 14°C

13, p. 238

120.65

8282.5

—

—

l/—

n20 = 1.414 (at 15°C)

13, p. 225

155.10

118120

—

—

l/—

0.884 (25°C) 1.07

n20 = 1.439; flash point: 6°C

13, p. 225

141.1

9293

—

—

l/—

1.087

n20 = 1.4270; toxic; flash point: 4°C; viscosity: 0.70 cSt

13, p. 225

State/Color

Densitya (g/cc)

Miscellaneous

Reference

n20 = 1.4211; )Hform = 70.3 kcal/ 13, p. 210 mol; flash point: 32°C n20 = 1.3885; viscosity: 0.47 cSt; 13, p. 210; )Hvap = 6.6 kcal/mol; flash point: 1, p. 235 27°C; )Hcomb = 714 kcal/mol; )Hform = 84.5 kcal/mol — 13, p. 210 n20 = 1.474; flash point = 2°C; )Hform = 52.2 kcal/mol nD = 1.4561 Toxic

n20 = 1.4515 (at 25°C); flash point: 62°C n20 = 1.440; flash point: 70°C —

13, p. 216 2, p. 11; 13, p. 205 13, p. 220

13, p. 207 13, p. 221 1, p. 238

© 2005 by CRC Press

III. Alkyl Silanes Allyldimethylsilane (90%) CH2CHCH2Si(CH3)2H Allyltrimethylsilane CH2CHCH2Si(CH3)3 Bis(dimethylamino)diethylsilane ((CH3)2N)2Si(C2H5)2 Bis(dimethylamino)dimethylsilane ((CH3)2N)2Si(CH3)2 Bis(dimethylamino)methylsilane ((CH3)2N)2Si(CH3)H Bis(dimethylamino)vinylmethylsilane ((CH3)2N)2Si(CH3)(CHCH2) Di(t-butylamino)silane ((CH3)3CNH)2SiH2 Di-t-butylsilane ((CH3)3C)2SiH2 Ethynyltrimethylsilane HCCSi(CH3)3 Methyltri-n-octylsilane (CH3(CH2)6CH2)3SiCH3 n-Octyldimethyl(dimethylamino)silane CH3(CH2)6CH2Si(CH3)2N(CH3)2 Tetraallylsilane (CH2CHCH2)4Si Tetravinylsilane (95%) (CH2CH)4Si 3-Trimethylsilylpropynal HCOCCSi(CH3)3 1-Trimethylsilylpropyne CH3CCSi(CH3)3 Tris(dimethylamino)methylsilane CH3Si(N(CH3)2)3 Tris(dimethylamino)silane HSi(N(CH3)2)3 Vinyldimethylsilane CH2CHSi(CH3)2H Vinyl(trifluoromethyl)dimethylsilane CH2CHSi(CH3)2CF3

100.24

69–70

—

—

l/—

0.705

114.26

85–86

—

—

l/—

0.7193

n20 = 1.4029; toxic; flash point:  1, p. 189 20°C n20 = 1.4074; flash point: 7°C 1, p. 190

174.36

62–63/15

—

—

l/—

0.837

n20 = 1.4362; flash point: 30°C

1, p. 193

146.31

128–129

98

—

l/—

0.810

n20 = 1.4169; flash point: 7°C

1, p. 193

132.28

112–113

—

—

l/—

0.798

n20 = 1.414; flash point: 3°C

1, p. 193

158.32

146–147

—

—

l/—

—

Flash point: 4°C

1, p. 193

174.36

167

—

—

l/—

0.816

Flash point: 30°C

1, p. 203

144.33

128

38

—

l/—

0.74

—

1, p. 203

98.22

52

—

—

l/—

0.709

n20 = 1.3880; flash point: 34°C

1, p. 210

382.79

210/5

—

—

l/—

0.813

215.45

94–96/10

—

—

l/—

0.80

n20 = 1.4520; flash point: >110°C; 1, p. 220 viscosity (54°C) = 1500 cSt Flash point: 69°C 1, p. 223

192.37

91/10

—

—

l/—

0.8345

n20 = 1.4864; flash point: 77°C

1, p. 226

136.27

130–131

—

—

l/—

0.815

1, p. 226

128.14

52/30

—

—

l/—

0.86

n20 = 1.4610; flash point: 18°C; viscosity: 0.6cSt; )Hcomb = 1293 kcal/mol; )Hform = 5.2 kcal/mol —

112.25

99–100

69

—

l/—

0.758

n20 = 1.4091; flash point: 3°C

1, p. 236

175.35

55–56/17

11

—

l/—

0.850

n20 = 1.432; flash point: 30°C

1, p. 237

161.32

145–148

—

—

l/—

0.838

Flash point: 25°C

1, p. 237

86.20

36–37

—

—

l/—

0.6744

n20 = 1.3885

1, p. 238

154.21

80

—

—

l/—

0.978

n20 = 1.3549; flash point: –10°C

1, p. 240

1, p. 236

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

213.31

110–114/0.6

—

—

l/—

1.19

Flash point: 180°C

1, p. 191

150.30

72/15

—

—

l/—

0.949

n20 = 1.5040

13, p. 108

164.32

190191

—

—

l/—

0.893

n20 = 1.4941

13, p. 108

274.39

195–199/0.5

64

—

s/—

1.19

Flash point: >110°C

1, p. 192

202.41

8182/17

—

—

l/—

0.826

n20 = 1.432 (at 25°C)

13, p. 112

146.31

128129

98

—

—/—

356.50

210/1

13

—

l/—

0.810 (22°C) 1.13

n20 = 1.417 (at 22°C); flash point: 13, p. 112 7°C Flash point: 150°C 1, p. 194

260.41

180/4

78–81

—

s/—

—

116.28

8183

—

—

l/—

0.701

234.41

80/0.075

—

—

l/—

—

158.36

155

—

—

l/—

—

102.25

7778

—

—

l/—

88.22

56

–132

—

290.78

—

181

348.93

—

174.31

101/15

State/Color

Densitya (g/cc)

Miscellaneous

Reference

IV. Aryl Silanes Aminophenyltrimethoxysilane NH2C6H6Si(OCH3)3 Benzyldimethylsilane C6H5CH2Si(CH3)2H Benzyltrimethylsilane C6H5CH2Si(CH3)3 Bis(p-aminophenoxy)dimethylsilane (p-NH2C6H4O)2Si(CH3)2 Bis(diethylamino)dimethylsilane (CH3)2Si(N(C2H5)2)2 Bis(dimethylamino)dimethylsilane (CH3)2Si(N(CH3)2)2 Bis(n-methylbenzamido)ethoxymethylsilane (C6H5CON(CH3))2Si(CH3))C2H5 Bis(phenylethynyl)dimethylsilane (C6H5CC)2Si(CH3)2 tert-Butyldimethylsilane tC4H9Si(CH3)2H p(t-Butyldimethylsiloxy)styrene pCH2CHC6H4OSi(CH3)2C(CH2)3 Di-tert-butylmethylsilane (tC4H9)2Si(CH3)H Diethylmethylsilane (C2H5)2Si(CH3)H Diethylsilane (C2H5)2SiH2 Dimethylcyclopentasilane ((CH3)2Si)5 Dimethylcyclohexasilane ((CH3)2Si)6 Dimethyldiisothiocyanatosilane (CH3)2Si (NCS)2

— n20 = 1.4005

1, p. 195 13, p. 124

—

1, p. 198

n20 = 1.4293 (at 25°C)

13, p. 140

0.700

n20 = 1.398

13, p. 143

l/—

0.6837

13, p. 143; 1, p. 204

—

s/—

—

253

—

s/—

—

—

—

l/—

1.14

n20 = 1.3921; flash point: 20°; viscosity: 0.4 cSt; )Hvap = 7.18 kcal/mol; )Hcomb = 951 kcal/ mol; )Hform = 37 kcal/mol Transitions from brittle to plastic crystalline phase at 39°C Transitions from brittle to plastic crystalline phase at 77°C —

2, p. 385 2, p. 385 13, p. 147

© 2005 by CRC Press

60.17

20

150

—

Gas/—

3-(2,4-Dinitrophenylamino)propyltriethoxysilane (NO2)2C6H5NH(CH2)3Si(OC2H5)3 Diphenylmethylsilane (C6H5)2Si(CH3)H Diphenylphosphinoethyldimethylethoxysilane (C6H5)2P(CH2)2Si(CH3)2OC2H5 2-(Diphenylphosphino)ethyltriethoxysilane (C6H5)2P(CH2)2Si(OC2H5)3 Diphenylsilane (C6H5)2SiH2 Diphenylsilanediol (C6H5)2Si(OH)2

387.46

—

2730

—

l/—

—

198.34

266267

—

—

l/—

0.997

316.46

160/1

—

—

l/—

1.004

n20 = 1.569; flash point: >112°C; 13, p. 151 )Hvap = 15.4 kcal/mol n20 = 1.5630 1, p. 207

376.50

182/1.3

—

—

l/—

1.05

Flash point: 134°C

1, p. 207

184.31

9597/13

—

—

1/colorless

0.9969

n20 = 1.5795; flash point: 98°C

216.32

—

138–142(d)

—

s/—

—

Divinyldimethylsilane (CH3)2Si(CHCH2)2 Ethyldimethylsilane (CH3)2Si(C2H5)H Hexamethyldisilane (CH3)6Si2 Methylsilane CH3SiH3

112.25

82

—

—

l/—

0.7337

Flash point: 53°C; )Hform = 250 kcal/mol; )Hcomb = 1500 kcal/ mol n20 = 1.4176; flash point: 8°

13, p. 151; 1, p. 207 1, p. 207

88.22

4546

—

—

l/—

0.668

n20 = 1.3783

13, p. 153 1, p. 207 13, p. 155

146.38

112113

12.514

—

—/—

0.729

Flammable

6, p. 89

46.14

57

157

—

Gas/—

0.628 (58)

13, p. 175; 1, p. 219

Methylphenylsilane C6H5Si(CH3)H2 Methyltri-n-decylsilane (nC10H21)3SiCH3 n-Octadecylsilane CH3(CH2)17SiH3 n-Octylsilane nC8H17SiH3 n-Octyltris(trimethylsiloxy)silane CH3(CH2)7Si(OSi(CH3)3)3 Pentafluorophenyltriethoxysilane C6F5Si(OC2H5)3 Phenyldimethylsilane C6H5Si(CH3)2H

122.24

139140

—

—

l/—

0.889

flash point: <-40°; )Hvap = 4.6 kcal/mol; )Hcomb = 624 kcal/ mol; )Hform = 7 kcal/mol n20 = 1.506

466.95

261262/4

—

—

l/—

—

Viscosity: 14.3 cSt at 38°C

13, p. 175

284.60

195/15

29

—

—/—

—

Flash point: >110°C

144.33

162163

—

—

1/—

0.746

399.81

7980/0.12

—

—

l/—

—

n20 = 1.4100 (at 25°)

13, p. 179; 1, p. 221 13, p. 181; 1, p. 223 13, p. 181

330.33

130/10

—

—

1/

1.24

n20 = 1.4180

1, p. 223

136.27

156157

—

—

l/—

0.8891

n20 = 1.4995; flash point: 35°

13, p. 184

Dimethylsilane (CH3)2SiH2

0.68 (80°C)

)Hvap = 5.5 kcal/mol; )Hcomb = 13, p. 148; 624 kcal/mol; )Hform = 23 kcal/ 1, p. 206 mol; flash point <30°C Flash point: >110°C 1, p. 206

n20 = 1.425; flash point: 36°

13, p. 174

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

162.31

80/20

—

—

l/—

0.892

n20 = 1.5048

13, p. 184

148.28

5657/7

—

—

l/—

0.891

n20 = 1.5115

13, p. 185

108.21

120

64 to 68

—

l/—

0.8681

1, p. 224

196.37

88/15

—

—

l/—

—

n20 = 1.5125; flash point: 8°; )Hvap = 8.31 kcal/mol Flash point: 39°C

150.30

169170

—

—

l/—

0.872

269.43

105/0.9

—

—

l/amber

252.38

98/0.1

—

—

256.55

230232

—

144.33

153155

88.22

Tetraphenylsilane (C6H5)4Si p-Tolyltrimethoxysilane (95%) pCH3C6H4Si(OCH3)3 Triethylazidosilane (C2H5)3SiN3 Triethylsilane (C2H5)3SiH Tri-n-hexylsilane (nC6H13)3SiH

Compound Phenyldimethylvinylsilane C6H5Si(CH3)2CHCH2 Phenylmethylvinylsilane C6H5Si(CH3)(CHCH2)H Phenylsilane C6H5SiH3 Phenylthiomethyltrimethylsilane (CH3)3SiCH2SC6H5 Phenyltrimethylsilane C6H5Si(CH3)3 2-(4-Pyridylethyl)triethoxysilane (4-C5H4N)CH2CH2Si(OC2H5)3 Styrylethyltrimethoxysilane (95%) CH2CHC6H5CH2CH2Si(OCH3)3 Tetra-n-butylsilane (nC4H9)4Si Tetraethylsilane (C2H5)4Si

Tetramethylsilane (CH3)4Si

State/Color

Densitya (g/cc)

Miscellaneous

Reference

13, p. 186 13, p. 187

1.00

n20 = 1.4908; viscosity: 1.1 cSt; flash point: 44°C n20 = 1.4624

l/—

1.02

n20 = 1.505; flash point: 97°C

1, p. 225

—

l/—

0.799

n20 = 1.4465

13, p. 194

82

—

1/clear

0.762

2, p. 10; 13, p. 195

26.626.7

99

—

1/clear

0.6411

336.51

228/3

236237

—

—/—

1.078

212.32

75–8/8

—

—

l/—

1.033

nD = 1.4246; )Hvap = 9.9 kcal/mol; viscosity: 0.40/9 cSt; flash point = 28°C; )Hfus = 1.6 k/mol; )Hform = 55.4 k/mol; )Hcomb = 920 kcal/mol nD = 1.3588; )Hvap = 6.4 kcal/mol; )Hfus = 1.6 kcal/mol; )Hform = 55.4 kcal/mol; flash point: 27°C; viscosity: 0.4 cSt )Hform = 58.7 kcal/mol; )Hcomb = 3215.5 kcal/mol n20 = 1.4726; flash point: 94°C

157.29

104/95

—

—

l/—

—

116.28

107108

157

—

—/—

0.731

284.60

160161/5

—

—

l/—

0.799

1, p. 225

13, p. 200; 1, p. 230

13, p. 200 1, p. 231 13, p. 205

n20 = 1.4123; viscosity: 4.9 cSt; flash point: 3°C; surface tension: 20.7 dyn/cm; )Hform = 41 kcal/mol n20 = 1.4480

6, p. 89; 13, p. 206

13, p. 207

© 2005 by CRC Press

227.33

105/0.3

—

—

l/—

74.20

6.7

135.9

—

—/—

Trimethylethylsilane (CH3)3SiC2H5 Trimethyl (m-neopentylphenyl) silane m-C5H12C6H4Si(CH3)3 Trimethyl (p-neopentylphenyl) silane p-C5H12C6H4Si(CH3)3 Trimethylsilylazide (CH3)3SiN3 Tri-n-octylsilane (nC8H17)3SiH Triphenylsilane (C6H5)3SiH Triphenylvinylsilane (C6H5)3SiCHCH2 Triisopropylsilane ((CH3)2CH)3SiH Tri-n-propylsilane (CH2CH2CH2)3SiH (m,p-Vinylbenzyloxy)trimethylsilane CH2CHC6H5CH2OSi(CH3)3 Vinyldiethylmethylsilane CH2CHSi(C2H5)2CH3 Vinylphenyldimethylsilane C6H5Si(CHCH2)(CH3)2 Vinyltrichlorosilane CH2CHSiCl3

102.25

62

—

—

l/—

0.68

221.44

80/2

—

—

l/—

—

Flash point: <-20°; vapor 13, p. 211 pressure: 1218mm (20°); )Hvap 1, p. 236 = 5.8 kcal/mol; )Hcomb = 766 kcal/mol; )Hform = 39 kcal/mol nD20 = 1.382 2, p. 10; 8, p. 1971 n20 = 1.4852 10

221.44

70/1.2

—

—

l/—

—

n20 = 1.4876

10

115.21

9596

95

—

—/—

0.876

n20 = 1.416; flash point: 23°C

13, p. 213

368.76

163165/0.15

—

—

l/—

0.821

n20 = 1.454

13, p. 220

260.41

160165/3

424

—

—/—

—

Flash point: 76°C

13, p. 221

286.45

—

5861

—

s/—

—

—

13, p. 221

158.36

16970

—

—

l/—

0.7726

n20 = 1.4358; flash point: 35°C

13, p. 207

158.36

173

—

—

l/—

0.758

n20 = 1.427

13, p. 221

206.35

56-60/0.15

—

—

l/—

0.96

n20 = 1.537

1, p. 238

128.29

118

—

—

l/—

0.7503

n20 = 1.4230

13, p. 225

162.30

82/20

—

—

l/—

0.8919

n20 = 1.5048

1, p. 239

161.49

93

95

—

—/—

1.243

100.24

55

–132

—

l/—

0.6903

n20 = 1.429; toxic; flash point: 13, p. 226 21°C; viscosity: 0.50 cSt; )Hform = 1381 kcal/mol; )Hvap = 7.9 k/mol n20 = 1.3910; flash point: 20°C; 13, p. 227; )Hcomb = 987.3 kcal/mol 1, p. 241

250.37

60/0.2

—

—

l/—

0.983

Vinyltrimethylsilane CH2CHSi(CH3)3

1.06

n20 = 1.4755; Flash point: >110°C 1, p. 234

2-(Trimethoxysilylethyl)pyridine (2-CH3C5H4N)CH2CH2Si(OCH3)3 Trimethylsilane (CH3)3SiH

0.638 (6.7°C)

V. Alkoxysilanes Acetoxyethyltriethoxysilane CH3COOCH2CH2Si(OC2H5)3

n20 = 1.410

1, p. 188

© 2005 by CRC Press

Compound Acetoxymethyltriethoxysilane CH3COOCH2Si(OC2H5)3 Acetoxypropyltrimethoxysilane CH3COOCH2CH2CH2Si(OCH3)3 (3-Acryloxypropyl)methyldimethoxysilane CH2CHCOOCH2CH2CH2Si(CH3) (OCH3)2 (3-Acryloxypropyl)trimethoxysilane CH2CHCOOCH2CH2CH2Si(OCH3)3 Acryloxytrimethylsilane CH2CHCOOSi(CH3)3 3-(N-Allyamino)propyltrimethoxysilane CH2CHCH2NHCH2CH2CH2Si(OCH3)3 Allydimethoxysilane CH2CHCH2SiH(OCH3)2 O-Allyoxy(polyethyleneoxy)trimethylsilane CH2CHCH2(OCH2CH2)nOSi(CH3)3 Allyoxyundecyltrimethoxysilane CH2CHCH2O(CH2)11Si(OCH3)3 Allytrimethoxysilane CH2CHCH2Si(OCH3)3 (Aminoethylaminomethyl)phenethyltrimethoxysilane H2NCH2CH2NHCH2C6H4CH2CH2Si (OCH3)3 N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane H2NCH2CH2NHCH2CH2CH2Si(CH3) (OCH3)2 N-(2-aminoethyl)-3-aminopropyltrimethoxysilane H2NCH2CH2NHCH2CH2CH2Si(OCH3)3 N-(6-aminohexyl)aminopropyltrimethoxysilane H2N(CH2)6NHCH2CH2CH2Si(OCH3)3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

236.34

106/15

—

—

l/—

1.042

n20 = 1.4092

1, p. 188

222.31

92/2

—

—

l/—

1.062

n20 = 1.4146; flash point: 93°C

1, p. 188

218.33

65/0.35

—

—

l/—

1.0

n20 = 1.431

1, p. 188

234.32

68/0.4

—

—

l/—

1.0

n20 = 1.4112; flash point: 26°C

1, p. 188

144.25

64–65/100

—

—

l/—

0.8939

n20 = 1.4155; flash point: 123°C

1, p. 188

219.36

106–109/25

—

—

l/—

0.989

—

1, p. 188

132.23

107–109

—

—

l/—

—

470–560

107–109

—

—

l/—

1.040

332.56

175–179/5

—

—

l/—

—

162.26

146–148

—

—

l/—

0.963

n20 = 1.4036; flash point: 46°C

298.46

126–130/0.2

—

—

l/—

1.02

n20 = 1.5083; flash point: >110°C 1, p. 190

206.36

265

—

—

l/—

0.975

n20 = 1.4447; flash point: 90°C

1, p. 190

226.36

140/15

—

—

l/—

1.019

n20 = 1.450; flash point: 150°C; viscosity: 6.5 cSt

1, p. 190

278.47

160–163/0.15

—

—

l/—

1.11

n20 = 1.4501; flash point: >110°C 1, p. 190

State/Color

Densitya (g/cc)

Miscellaneous

Reference

n20 = 1.4450

1, p. 189

Viscosity: 20–25 cSt

1, p. 189

—

1, p. 189 1, p. 189

© 2005 by CRC Press

N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane H2NCH2CH2NH(CH2)11Si(OCH3)3 N-3-[(amino(polypropylenoxy)]aminopropyltrimethoxysilane H2N(CH2CH(CH3)O)2CH(CH3)NHCH2 CH2CH2Si(OCH3)3 3-Aminopropyldimethylmethoxysilane H2NCH2CH2CH2Si(CH3)2OCH3 3-Aminopropylmethyldiethoxysilane H2NCH2CH2CH2Si(OC2H5)2CH3 Aminopropylsilanetriol H2NCH2CH2CH2Si(OH)3 3Aminopropyltriethoxysilane H2NCH2CH2CH2Si(OC2H5)3 3Aminopropyltrimethoxysilane H2NCH2CH2CH2Si(OCH3)3 Benzyltriethoxysilane C6H5CH2Si(OC2H5)3 Bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane (HOCH2CH2)2NCH2CH2CH2Si(OC2H5)3 tert-Butoxytrimethylsilane (CH3)3SiOC(CH3)3 n-Butylaminopropyltrimethoxysilane C4H9NHCH2CH2CH2Si(OCH3)3 tert-Butyldiphenylmethoxysilane (t-C4H9)(C6H5)2SiOCH3 n-Butyltrimethoxysilane CH3CH2CH2CH2Si(OCH3) 3 2-Cyanoethylmethyldimethoxysilane NCCH2CH2S(OCH3)2CH3 2-Cyanoethyltriethoxysilane NCCH2CH2Si(OC2H5)3 2-Cyanoethyltrimethoxysilane NCCH2CH2Si(OCH3)3 3-Cyanopropyltriethoxysilane NCCH2CH2CH2Si(OC2H5)3 3-Cyanopropyltrimethoxysilane NCCH2CH2CH2Si(OCH3)3

334.57

—

—

—

—/—

—

337–435

—

—

—

—/—

—

161.32

78–79/24

—

—

l/—

191.34

85–88/8

—

—

137.21

—

—

221.37

122123/30

179.29

—

1, p. 190

3–4 propyleneoxy units

1, p. 191

0.857

n20 = 1.427; flash point: 73°C

1, p. 191

l/—

0.916

n20 = 1.4272; flash point: 68°C

1, p. 191

—

l/—

1.06

Flash point: >110°C

1, p. 191

—

—

l/—

0.951

13, p. 106; 1, p. 191

80/8

—

—

l/—

1.027

n20 = 1.4225; )Hvap = 11.8 kcal/ mol; viscosity: 1.6 cSt; flash point: 104°C n20 = 1.4240; flash point: 83°C

254.40

170175/70

—

—

l/—

0.986

—

13, p. 108

309.48

—

—

—

l/—

0.92

n20 = 1.409; flash point: 24°C

1, p. 194

146.30

104

—

—

l/—

0.761

N20 = 1.3913

13, p. 124

235.40

238

—

—

l/—

0.947

Flash point: 110°C

1, p. 198

270.45

—

4951

—

s/—

—

Flash point: >110°C

13, p. 125

178.30

1645

—

—

l/—

0.9312

n20 = 1.3979; flash point: 49°C

13, p. 126

159.26

89–90/8

—

—

l/—

0.9862

n20 = 1.4192

1, p. 201

217.34

224–225

—

—

l/—

0.9792

n20 = 1.4140; flash point: 86°C

1, p. 201

175.26

112/15

—

—

l/—

1.079

n20 = 1.4126; flash point: 88°C

1, p. 201

231.37

79–80/0.6

—

—

l/—

0.961

1, p. 201

189.29

90–92/7

—

—

l/—

1.026

n20 = 1.4174; flash point: 74°C; viscosity: 2.3 cSt —

1, p. 191

1, p. 201

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

11-Cyanoundecyltrimethoxysilane NC(CH2)11Si(OCH3)3 [2-(3-Cyclohexenyl)ethyl]trimethoxysilane (C6H9)CH2CH2Si(OCH3)3 Di-n-butyldimethoxysilane (nC4H9)2Si(OCH3)2 Diethylaminomethyltriethoxysilane (C2H5)2NCH2Si(OC2H5)3 Diethylphosphatoethyltriethoxysilane (C2H5O)2POCH2CH2Si(OC2H5)3 Diethyldiethoxysilane (C2H5)2Si(OC2H5)2 Diisobutyldimethoxysilane ((CH3)2CHCH2)2Si(OCH3)2 Diisopropyldimethoxysilane ((CH3)2CH)2Si(OCH3)2 (N,N-dimethylaminopropyl) trimethoxysilane (CH3)2NCH2CH2CH2Si(OCH3)3 Dimethyldiethoxysilane (CH3)2Si(OC2H5)2

301.59

160/1

—

—

230.38

109/6

—

204.39

125/50

249.43

Densitya (g/cc)

Miscellaneous

l/—

0.933

—

1, p. 201

—

l/—

1.02

Flash point: 80°C

1, p. 201

—

—

l/—

0.861

Flash point: 103°C

1, p. 203

74–76/3

—

—

l/—

0.9336

n20 = 1.4142

1, p. 204

328.41

141/2

—

—

l/—

1.031

n20 = 1.4216; flash point: 70°C

1, p. 204

176.33

157

—

—

l/—

0.862

n20 = 1.402

13, p. 143

204.39

120/6

—

—

l/—

0.87

Flash point: 102°C

1, p. 204

176.33

85–87/50

—

—

l/—

0.875

n20 = 1.4178; flash point: 43°C

1, p. 204

207.34

106/30

—

—

—/—

0.948

n20 = 1.4150; flash point: 99°

1, p. 204

148.28

114115

97

—

—/—

0.8395

13, p. 147; 1, p. 205

Dimethyldimethoxysilane (CH3)2Si(OCH3)2

120.22

82

–80

—

l/—

0.8646

Dimethylethoxysilane (CH3)2Si(OC2H5)H (2,2-Dimethyl-1-methylenepropoxy)trimethylsilane (CH3)3CC(CH2)OSi(CH3)3 Diphenyldiethoxysilane (C6H5)2Si(OC2H5)2 Diphenyldimethoxysilane (C6H5)2Si(OCH3)2

104.22

54–55

—

—

l/—

0.757

172.35

140–142

—

—

l/—

0.798

n20 = 1.3805; flash point: 11°; toxic; )Hvap = 9.8 kcal/mol; )Hform = 200 k/mol; )Hcomb = 1119 kcal/mol; viscosity: 0.53 cSt n20 = 1.3708; )Hform = 171 kcal/ mol; )Hcomb = 832 kcal/mol; viscosity: 0.44cSt n20 = 1.3683; flash point: 15°; toxic n20 = 1.4090; flash point: 24°

272.42

167/15

—

—

l/—

1.0329

244.36

161/15

—

—

l/—

1.0771

Compound

State/Color

Reference

13, p. 147 1, p. 205 13, p. 147 1, p. 206 1, p. 206

n20 = 1.5269s; flash point: 175˚C 13, p. 150 1, p. 207 n20 = 1.5447; flash point: 13, p. 150 >110˚C; viscosity: (25˚) 8.4 cSt

© 2005 by CRC Press

Diphenylmethylethoxysilane (C6H5)2SiCH3(OC2H5) Docosenyltriethoxysilane CH2CH(CH2)20Si(OC2H5)3 Dodecyltriethoxysilane CH3(CH2)10CH2Si(OC2H5)3 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilane (3,4-OC6H9)CH2CH2Si(OC2H5)3 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane (3,4-OC6H9)CH2CH2Si(OCH3)3 Epoxyhexyltriethoxysilane H2C(O-)CHCH2CH2CH2CH2Si (OC2H5)3 N-ethylaminoisobutyltrimethoxysilane CH3CH2NHCH2CH(CH3)CH2Si(OCH3)3 m,p-Ethylphenethyltrimethoxysilane CH3CH2C6H5CH2CH2Si(OCH3)3 Ethyltriacetoxysilane CH3CH2Si(OOCCH3)3 Ethyltrimethoxysilane CH3CH2Si(OCH3)3 (3-Glycidoxypropyl)methyldiethoxysilane H2C(O)CHCH2O(CH2)3Si(OC2H5)2CH3 (3-Glycidoxypropyl)methyldimethoxysilane H2C(O)CHCH2O(CH2)3Si(OCH3)2CH3 (Heptadecafluoro-1,1,2,2tetrahydrodecyl)-triethoxysilane CF3(CF2)7CH2CH2Si(OC2H5)3 n-Hexadecyltriethoxysilane n-C16H33Si(OC2H5)3 n-Hexyltrimethoxysilane CH3(CH2)5Si(OCH3)3 N-(hydroxyethyl)-Nmethylaminopropyltrimethoxysilane HOCH2CH2N(CH3)(CH2)3Si(OCH3)3 Isobutylisopropyldimethoxysilane (CH3)2CHCH2Si(OCH3)2CH(CH3)2

n20 = 1.544; flash point: 165˚C; viscosity: (25˚) 4.9 cSt —

13, p. 151

n20 = 1.4330; flash point: >110°C; n20 = 1.449; flash point: 146°C;

1, p. 208

1.065

n20 = 1.4455; flash point: 104°C; viscosity: 5.2 cSt

1, p. 208

l/—

0.960

n20 = 1.4254; flash point: 99°C;

1, p. 209

—

l/—

0.952

Flash point: 91°C

1, p. 209

—

—

l/—

0.996

n20 = 1.4776

1, p. 209

107–108/8

7–9

—

l/—

1.143

n20 = 1.4123; flash point: 106°C; 1, p. 209

150.25

124–125

—

—

l/—

0.9488

1, p. 209

248.39

122–126/5

—

—

l/—

0.978

n20 = 1.3838; flash point: 27°C; viscosity: 0.5 cSt n20 = 1.431; flash point: 122°C; viscosity: 3.0 cSt

220.34

100/4

—

—

l/—

1.02

n20 = 1.431; flash point: 105°C; viscosity: 3.0 cSt

1, p. 210

610.38

103–106/3

—

—

l/—

1.407

n20 = 1.3419

1, p. 211

388.70

159161/1

—

—

l/—

n20 = 1.4370

13, p. 161

206.35

202203

—

—

l/—

0.8870 (14°C) —

237.37

—

—

—

l/—

0.99

n20 = 1.417; flash point: 16°C

1, p. 214

190.36

93/37

—

—

l/—

0.867

Flash point: 50°C

1, p. 214

242.39

100–102/0.3

—

—

l/—

1.018

470.88

187–195/0.05

—

—

l/—

—

332.60

152–153/3

—

—

l/—

0.8842

288.46

114–117/0.4

—

—

l/—

1.015

246.38

95–97/0.25

—

—

l/—

262.42

115–119/1.5

—

—

221.37

95/10

—

254.40

93–96/4

243.28

—

1, p. 208

1, p. 208

1, p. 210

13, p. 164

© 2005 by CRC Press

Compound Isobutyltrimethoxysilane (CH3)2CHCH2Si(OCH3)3 3-Isocyanatopropyltriethoxysilane OCN(CH2)3Si (OC2H5)3 3-Isocyanatopropyltrimethoxysilane OCN(CH2)3Si (OCH3)3 3-Isooctyltrimethoxysilane (CH3)3CCH2CH(CH3)CH2Si (OCH3)3 3-Mercaptopropyltrimethoxysilane HSCH2CH2CH2Si(OCH3)3 3-Mercaptopropylmethyldimethoxysilane HSCH2CH2CH2Si(OCH3)2CH3 3-Mercaptopropyltriethoxysilane HSCH2CH2CH2Si(OC2H5)3 O-(methacryloxyethyl)-N(triethoxysilylpropyl)urethane H2CC(CH3)COOCH2CH2OOCNH (CH2)3Si(OC2H5)3 Methacryloxyethoxytrimethylsilane H2CC(CH3)COOCH2CH2OSi(CH3)3 Methacryloxymethyltriethoxysilane H2CC(CH3)COOCH2Si(OC2H5)3 Methacryloxymethyltrimethoxysilane H2CC(CH3)COOCH2Si(OCH3)3 Methacryloxypropylsilatrane H2CC(CH3)COOCH2CH2CH2Si (-OCH2CH2)3N Methacryloxypropyltrimethoxysilane H2CC(CH3)COO(CH2)3Si(OCH3)3 Methacryloxytrimethylsilane H2CC(CH3)COOSi(CH3)3 2-[Methoxy(polyethyleneoxy)propyl]trimethoxysilane CH3O(CH2CH2O)6-9(CH2)3Si(OCH3)3 3-Methoxypropyltrimethoxysilane CH3OCH2CH2CH2Si(OCH3)3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

178.30

154

—

—

l/—

0.9330

247.37

130/20

—

—

l/—

205.29

95–98/10

—

—

234.41

90/10

—

196.34

93/40

180.34

Densitya (g/cc)

Miscellaneous

Reference

0.99

n20 = 1.3960; flash point: 42°C; viscosity: 0.8 cSt n20 = 1.419; flash point: 80°C

13, p. 165; 1, p. 214 1, p. 215

l/—

1.06

n20 = 1.4219

1, p. 215

—

l/—

0.887

1, p. 215

—

—

l/—

1.051

96/30

—

—

l/—

1.00

n20 = 1.4176; flash point: 52°C; viscosity: 2 cSt n20 = 1.4502; toxic; flash point: 96°C; viscosity: 2 cSt n20 = 1.4502; toxic; flash point: 93°C

238.38

210

—

—

l/—

Flash point: 88°C

13, p. 168

377.51

—

—

—

l/—

0.993 (25°C) 1.051

n20 = 1.446

1, p. 215

202.32

65/0.9

—

—

l/—

0.928

n20 = 1.4280; flash point: 76°C

1, p. 215

262.38

65–8/2

—

—

l/—

—

220.30

48–50/2

—

—

l/—

1.07

l/—

1.17

301.41

State/Color

— n20 = 1.4271

13, p. 168 1, p. 215 1, p. 215

1, p. 216 1, p. 216

—

n20 = 1.4310; flash point: 92°C; viscosity: 2cSt n20 = 1.4716; flash point: 32°C

1, p. 216

248.35

78–81/1

—

—

l/—

1.045

1, p. 217

158.27

51–52/20

—

—

l/—

0.885

460–590

—

—

—

l/—

1.076

n20 = 1.403; Flash point: 88°C; viscosity: 29cSt

1, p. 218

194.30

98-9/40

—

—

l/—

0.995

Flash point: 53°C

1, p. 218

1, p. 217

© 2005 by CRC Press

174.31

57/15

—

—

l/—

0.858

n20 = 1.4150; flash point: 43°C

1, p. 218

177.32

93/25

—

—

l/—

0.9173

n20 = 1.4224; flash point: 80°C

1, p. 218

193.32

106/30

—

—

l/—

0.978

n20 = 1.4194; flash point: 82°C

1, p. 218

134.25

9495

—

—

l/—

n20 = 1.3275

13, p. 173

106.20

61

136

—

—/—

0.829 (25°C) 0.861

n20 = 1.360

13, p. 173

302.57

140/0.5

—

—

l/—

—

—

13, p. 173

386.73

197/2.0

—

—

l/—

—

—

13, p. 174

210.35

117118/31

—

—

l/—

0.963

n20 = 1.4690

13, p. 174

182.29

199200

—

—

l/—

0.993

13, p. 174

220.25

87–8/3

40

—

l/—

1.175

n20 = 1.4694; toxic; flash point: 76°C n20 = 1.4083; flash point: 85°C

178.30

142

—

—

l/—

0.8948

13, p. 176; 1, p. 219

Methyltrimethoxysilane CH3Si(OCH3)3

136.22

102103

78

—

l/—

0.955

Methyl tri-n-propoxysilane CH3Si(O-nC3H7) 3 Methyltris(methylethylketoxime)silane (CH3(CH3CH2)CNO)3SiCH3 n-Octadecyltriethoxysilane CH3(CH2)17Si(OC2H5)3 n-Octadecyltrimethoxysilane nC18H37Si(OCH3)3 Octyldimethylmethoxysilane CH3(CH2)7CH3Si(CH3)2OCH3 n-Octylmethyldimethoxysilane CH3(CH2)7CH2Si(OCH3)2 n-Octyltriethoxysilane n-C8H17Si(OC2H5)3

220.38

8384/13

—

—

l/—

0.88

n20 = 1.3832; toxic; flash point: 30°C; viscosity: 0.6 cSt; )Hcomb = 1831 kcal/mol n20 = 1.3696; toxic; flash point: 8°C; viscosity: 0.50 cSt; )Hcomb = 1142 kcal/mol n20 = 1.4085

301.46

110–1/2

22

—

l/—

0.982

n20 = 1.4548; flash point: 90°C

1, p. 220

416.76

165169/2

—

—

l/—

0.87

374.68

170/0.1

13–17

—

l/—

0.885

n20 = 1.439; flash point: 140°C

202.42

221–223

—

—

l/—

0.813

n20 = 1.4230; flash point: 82°C

218.41

107108/10 87–89/5 9899/2

—

—

l/—

0.858

n20 = 1.4190; flash point: 94°C

<40

—

l/—

0.8750

n20 = 1.4160; flash point: 100°C; viscosity: 1.9 cSt

1-Methoxy-1-(trimethylsiloxy)-2-methyl1-propene (CH3)2CC(OCH3)OSi(CH3)3 N-methylaminopropylmethyldimethoxysilane CH3NHCH2CH2CH2Si(CH3)(OCH3)2 N-methylaminopropyltrimethoxysilane CH3NHCH2CH2CH2Si(OCH3)3 Methyldiethoxysilane CH3Si(OC2H5)2H Methyldimethoxysilane CH3Si(OCH3)2H Methyldodecyldiethoxysilane CH3(CH2)11Si(OC2H5)2CH3 Methyl-n-octadecyldiethoxysilane CH3(CH2)17Si(OC2H5)2CH3 Methylphenyldiethoxysilane C6H5Si(OC2H5)2CH3 Methylphenyldimethoxysilane C6H5Si(OCH3)2CH3 Methyltriacetoxysilane CH3Si(OCOCH3)3 Methyltriethoxysilane CH3Si(OC2H5)3

276.48

—

1, p. 219

13, p. 176; 1, p. 219 13, p. 176

13, p. 179 13, p. 179; 1, p. 221 13, p. 181; 1, p. 222 13, p. 181; 1, p. 223 13, p. 181; 1, p. 223

© 2005 by CRC Press

Compound

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

157–198/1.5

—

—

180.32

93/25

—

182.36

93/12

Formula Weight

Densitya (g/cc)

Miscellaneous

l/—

—

—

1, p. 223

—

l/—

0.9263

13, p. 184

—

—

l/—

0.967

n20 = 1.4799; toxic; viscosity: 1.3 cSt n201.535; flash point: 30°C

State/Color

Reference

Perfluorododecyl-1H, 1H, 2H, 2Htriethoxysilane CF3(CF2)9CH2CH2Si(OC2H5)3 Phenyldimethylethoxysilane C6H5Si(CH3)2OC2H5 Phenylthiotrimethylsilane C6H5SSi(CH3)3 Phenyltriethoxysilane C6H5Si(OC2H5)3

710

240.37

112113/10

—

—

l/—

0.996

Phenyltrimethoxysilane C6H5Si(OCH3)3 O-(propargyloxy)-N(triethoxysilylpropyl)urethane HCCCH2OOCNHCH2CH2CH2Si (OC2H5)3 n-Propyltriethoxysilane CH3CH2CH2Si(OC2H5)3 n-Propyltrimethoxysilane CH3CH2CH2Si(OCH3)3 Sodium methylsiliconate CH3Si(OH)2ONa 3-Thiocyanatopropyltriethoxysilane NCSCH2CH2CH2Si(OC2H5)3 (Tridecafluoro-1,1,2,2tetrahydrooctyl)triethoxysilane CF3(CF2)5CH2CH2Si(OC2H5)3 Triethoxysilane (C5H5O)3SiH

198.29

211

25

—

l/—

1.064

303.43

110–120/0.2

—

—

l/—

0.99

206.36

179–180

—

—

l/—

0.8916

n20 = 1.3956; flash point: 57°C

164.27

142

—

—

l/—

116.12

—

—

—

l/—

0.9318 (25°C) 1.24

n20 = 1.3880 (at 25°); flash point: 13, p. 188 35°C Viscosity: 10 cSt 1, p. 225

263.43

95/0.1

—

—

l/—

1.03

n20 = 1.4460; flash point: 112°C

1, p. 231

510.36

86/1.5

<38

—

l/—

1.351

n20 = 1.3436; flash point: 84°C; viscosity: 3 cSt

1, p. 232

164.28

131–132

170

—

l/—

0.8753

13, p. 204; 1, p. 232

234.37

—

—

—

—/—

n20 = 1.3767; flash point: 26°; toxic; )Hcomb = 1100 kcal/mol; viscosity: 0.6 cSt; )Hform = 221 kcal/mol; surface tension: 22.3 dyn/cm —

274.43

134/2

—

—

l/—

n20 = 1.452; flash point: >110°C; viscosity: 5 cSt

1, p. 233

Triethoxysilylbutyraldehyde HCOCH2CH2CH2Si(OC2H5)3 N-(3-triethoxysilylpropyl)-4,5dihydroimidazole (C3H5N2)CH2CH2CH2Si(OC2H5)3

— 1.005

13, p. 186

n20 = 1.4718; toxic; flash point: 13, p. 186; 96°C; viscosity: 1.7 cSt; surface 1, p. 224 tension: 28 dyn/cm n20 = 1.4734; flash point: 86°C; 13, p. 186; viscosity: 2.1 cSt 1, p. 224 n20 = 1.4461; flash point: 93°C 1, p. 225

1, p. 225

1, p. 232

© 2005 by CRC Press

Triethoxysilylpropylethylcarbamate C2H5OOCNHCH2CH2CH2Si(OC2H5)3 N-(3-triethoxysilylpropyl)gluconamide HOCH2(CHOH)4CONH(CH2)3Si (OC2H5)3 N-(triethoxysilylpropyl)-0-polyethylene oxide urethane H(OCH2CH2)5OOCNH(CH2)3Si (OC2H5)3 3-(triethoxysilyl)propylsuccinic anyhdride (C4H3O3)(CH2)3Si(OC2H5)3 (3,3,3-Trifluoropropyl)trimethoxysilane CF3CH2CH2Si(OCH3)3 Trimethoxysilane (CH3O)3SiH (3-Trimethoxysilylpropyl)diethylenetriamine (CH3O)3Si(CH2)3NHCH2CH2NHCH2 CH2NH2 N-(3-trimethoxysilylpropyl)pyrrole C4H4N(CH2)3Si(OCH3)3 N-trimethoxysilylpropyl-N,N,Ntrimethylammonium chloride (CH3O)3Si(CH2)3N(CH3)3Cl Trimethylethoxysilane (CH3)3SiOC2H5 Trimethylmethoxysilane (CH3)3SiOCH3 Trimethyl-n-propoxysilane n-C3H7OSi(CH3)3 Triphenylethoxysilane (C6H5)3SiOC2H5 Uriedopropyltriethoxysilane H2NCONH(CH2)3Si(OC2H5)3 Uriedopropyltrimethoxysilane H2NCONH(CH2)3Si(OCH3)3 Vinyldimethylethoxysilane CH2CHSi(CH3)2OC2H5

293.44

124–126/0.5

—

—

l/—

1.015

Flash point: 95°C

1, p. 233

399.51

—

—

—

l/—

0.951

n20 = 1.4111; flash point: 8°C

1, p. 233

400–500

—

—

—

l/—

1.09

n20 = 1.4540; viscosity: 75–125 cSt

1, p. 233

304.41

135/0.2

—

—

l/—

1.070

n20 = 1.4405; viscosity: 20 cSt

1, p. 233

218.25

144

—

—

l/—

1.137

n20 = 1.3546; flash point: 38°C

1, p. 234

122.20

8687

114

—

—/—

0.860

265.43

114–118/2

—

—

l/—

1.030

n20 = 1.3687; toxic; )Hcomb = 640 13, p. 208 kcal/mol; )Hform = 143 kcal/mol; flash point: 9°C n20 = 1.4590; flash point: 137°C 1, p. 234

229.35

105–107/1

—

—

l/—

1.017

n20 = 1.463; flash point: >110°C

1, p. 235

257.83

—

—

—

l/—

0.927

n20 = 1.3966; flash point: 11°C

1, p. 235

118.25

7576

—

—

l/—

0.757

104.22

5758

—

—

l/—

0.7560

n20 = 1.374; )Hvap = 8.0 kcal/mol; 13, p. 210 flash point: 18°C n20 = 1.3678; flash point: 30°C 13, p. 211

132.28

100–101/735

—

—

l/—

0.768

n20 = 1.384

13, p. 211

304.46

—

6365

—

s/—

—

13, p. 220

264.40

—

97

—

l/—

0.92

)Hvap = 20.2 kcal/mol; )Hcomb = 10,962.9 12.6 kJ/mol; )Hform = 671.1 12.6 kJ/mol n20 = 1.386; flash point: 14°C

222.32

217–225

—

—

l/—

1.150

n20 = 1.386; flash point: 99°C

1, p. 238

130.26

99100/170

—

—

l/—

0.790

n20 = 1.3983; flash point: 3°C

13, p. 225

1, p. 238

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Vinylmethyldiethoxysilane (CH2CH)Si(OC2H5)2CH3 O-(vinyloxyethyl)-N(triethoxysilylpropyl)urethane CH2CHOCH2CH2OOCNH(CH2)3Si (OC2H5)3 Vinyloxytrimethylsilane H2CCHOSi(CH3)3 Vinyltriethoxysilane CH2CHSi(OC2H5)3

160.29

133134

—

—

l/—

0.858

335.47

60–65/0.1–0.2

—

—

l/—

—

—

116.23

74–75

—

—

l/—

0.77

n20 = 1.3880; flash point: 10°C

190.31

160161

—

—

l/—

0.903

Vinyltriisopropenoxysilane CH2CHSi(OC(CH3)CH2)3 Vinyltriisopropoxysilane CH2CHSi(O-iC3H7)3 Vinyltrimethoxysilane CH2CHSi(OCH3)3 Vinyltriphenoxysilane CH2CHSi(OC6H5)3 Vinyltris-t-butoxysilane CH2CHSi(OtC4H9)3 Vinyltris(2-methoxyethoxy)silane CH2CHSi(OCH2CH2OCH3)3 Vinyltris(methyethylketoximino)silane CH2CHSi(ONC(CH3)CH2CH3)3

226.35

73–75/12

—

—

l/—

0.934

n20 = 1.3960; toxic; flash point: 13, p. 227; 44°C; viscosity: 0.70 cSt; )Hvap 1, p. 240 = 6.8 kcal/mol; )Hform = 463.5 kcal/mol n20 = 1.4360 1, p. 240

232.39

179–181

—

—

l/—

0.8659

n20 = 1.3961; flash point: 51°C

1, p. 240

148.23

123

—

—

l/—

0.970

334.45

210/7

—

—

l/—

13, p. 227; 1, p. 241 13, p. 227

274.47

54/2

—

—

l/—

1.130 (25) 0.869

n20 = 1.3930; toxic; flash point: 28°C; viscosity: 0.6 cSt n20 = 1.562 (25)

280.39

284–286

—

—

l/—

1.0336

n20 = 1.4271; flash point: 115°C 1, p. 241

313.47

113/0.1

22

—

l/—

0.982

Flash point: 91°C

1, p. 241

194.30

127130/44

—

—

l/—

1.006

n20 = 1.4907

13, p. 184

234.37

106107/1

—

—

l/—

—

n20 = 1.5068; flash point: 105°

13, p. 184; 1, p. 216

Compound

State/Color

Densitya (g/cc)

Miscellaneous n20 = 1.4000; flash point: 16°C

—

Reference 13, p. 225; 1, p. 239 1, p. 239

1, p. 239

13, p. 227

VI. Ketoxysilanes Phenyldimethylacetoxysilane (95%) C6H5Si(CH3)2OOCCH3 (Phenyldimethylsilyl)methylmethacrylate C6H5Si(CH3)2CH2OOCC(CH3)CH2

© 2005 by CRC Press

Silver Compounds I. Silver Alkoxides and Diketonates 403.05

—

160

—

s/—

—

423.1

—

118–189

—

s/—

—

206.98

—

82–86

—

s/—

—

Light sensitive; decomposes slowly at >70°C

1, p. 249

256.14

—

172–175

—

s/—

—

Soluble in pyridine

1, p. 248

Silver butylacetyllide C4H9C}CAg

189.01

—

—

—

—/—

—

2, p. 723; 8, p. 4

Silver phenylacetylide C6H5C}CAg

209.00

—

—

—

—/—

—

More stable than alkyl/aryl analogues; soluble in chloroform, CCl4, ppyridine, benzene More stable than alkyl/aryl analogues; soluble in chloroform, CCl4, U^WNINSJ; UTQ^µJWNH NS SFYZWJ

Phenyl silver [Ag(C6H5)]n

184.97

—

74 (decomposes)

—

s/—

—

Styrenylsilver Ag(CH = CHC6H5)

211.01

—

—

—

—/—

—

Silver I 6,6,7,7,8,8,8-Heptafluoro-2,2dimethyl-3,5-octanedionate AgOC(C3F7)CHC(C(CH3)3)O Silver hexafluoropentanedionatecyclooctadiene OC(CF3)CH(CF3)COAg-cycloC8H12 Silver (I) 2,4-pentanedionate Ag(OC(CH3)CH(CH3)CO)

Light sensitive

1, p. 248

—

1, p. 248

II. Silver Alkyl Thiol Amide Silver diethyldithiocarbamate AgS2CN(CH2CH3)2 III. Silver Alkylenyls

2, p. 723

IV. Arylsilver compounds Polymeric; not very sensitive to 8, p. 4 oxygen, water; slightly sensitive to light; slightly soluble in benzene, CHCl, pyridine; insoluble in aliphatic hydrocarbons Light, air, and moisture sensitive; 2, p. 719 complete decomposition requires several days at room temperature or hours in boiling ethanol

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

166.92

—

—

—

—/—

3.259

178.93

—

—

—

—/—

—

—

1, p. 248

320.90

—

292–294

—

s/—

—

—

1, p. 248

196.94

—

120–122

—

s/—

—

192.95

—

—

—

—/—

—

—

1, p. 249

279.13

—

106–116

—

s/—

—

—

1, p. 249

279.07

—

—

—

—/—

—

Soluble in acetonitrile

1, p. 249

220.88

—

251–253

—

s/—

—

Soluble in dimethyl-acetamide

1, p.249

State/Color

Densitya (g/cc)

Miscellaneous

Reference

V. Silver Salts Silver acetate CH3COOAg Silver acrylate CH2CHCOOAg Silver heptafluorobutryrate C3F7COOAg Silver lactate CH3CH(OH)COOAg Silver methacrylate CH2C(CH3)COOAg Silver neodecanoate C6H13C(CH3)2COOAg Silver p-toluenesulfonate p-CH3C6H4SO3)Ag Silver trifluoroacetate CF3COOAg

Soluble in water

Soluble in water

1, p. 248

1, p. 249

Sodium Compounds I. Sodium Alkoxides and Diketonates Sodium bis-2-(allyloxymethyl)-butoxide 10% in toluene CH2CH3(CH2CHCH2OCH2)2CCH2ONa Sodium bis(2-propenoxyethyl)ethoxide 10% in toluene (CH2CHCH2OCH2CH2)2CHCH2ONa Sodium n-butoxide 20% in n-butanol NaO-n-C4H9 Sodium t-butoxide NaOC(CH3)3 Sodium ethoxide 95% NaOC2H5 Sodium Hexafluoropentanedionate Na(-OC(CF3)CH(CF3)CO-)

236.28

—

—

—

s/—

—

—

1, p. 251

236.28

—

—

—

s/—

—

—

27, p. 37

96.11

—

—

—

—/—

0.86

Flash point: 36°C

1, p. 251

96.11

—

263270

—

s/—

1.104

1, p. 251

68.05

—

260

—

s/—

—

Soluble in diglyme, THF (33g/l), cyclohexane Solubility: ethanol, 20° 250 g/l

230.04

—

230

—

s/—

—

1, p. 252

Soluble in water, methanol, warm 1, p. 252 methoxypropanol, propanol

© 2005 by CRC Press

Sodium hexafluoropentanedionate NaOC(CF3)CH(CF3)CO Sodium methoxide 95% NaOCH3 Sodium methoxyethoxide 20% NaOCH2CH2OCH3 Sodium methylacetoacetate Na-OC(CH3O)CH(CH3)COSodium methoxide 25% in methanol NaOCH3 Sodium 2-methyl-2-butoxide Sodium t-pentyloxide NaOC(CH3)2C2H5 Sodium 2, 4-pentanedionate Na(OC(CH3)CH(CH3)CO) Sodium isopropoxide 15% in isopropanol (frozen solution) NaOCH(CH3)2 Sodium n-propoxide 20% CH3CH2CH2ONa

230.04

—

230

—

s/—

—

Soluble in water, methanol, 1, p. 252 propanol Soluble in methanol, 20°(330g/l) 1, p. 253

54.02

—

>300(d)

—

s/—

—

116.09

—

—

—

—/—

—

—

1, p. 253

138.10

—

—

—

—/—

—

—

1, p. 253

54.02

—

—

—

—/—

0.945

110.13

—

200 (decomposes)

—

s/—

—

122.09

—

210

—

s/—

—

82.08

—

7075

—

s/—

0.82

82.08

—

—

—

—/—

38.02

—

—

—

s(Powder)/ —

—

Decomposes without melting; burns explosively in air, irritant; corrosive

8, p. 1305

82.03

—

324(d)

—

s/—

—

Soluble in methanol (210g/l)

1, p. 250

229.24

—

—

—

—/—

—

—

1, p. 250

94.04

—

230(d)

—

s/—

—

—

1, p. 250

144.12

—

—

—

—/—

1.25

—

1, p. 251

237.36

—

—

—

—/—

1.09

232.31

—

—

—

—/—

1.14

n20 = 1.3700; flash point: 29°C; viscosity (25°C): 2025 cSt —

1, p. 253 1, p. 254

—

1, p. 254

Flash point: 12°C

1, p. 252

0.866 Flash point: 23°C (solution in propanol)

1, p. 254

II. Alkyl Sodium Methyl sodium CH3Na

III. Sodium Salts Sodium acetate CH3COONa Sodium 2-acrylamido-2-methylpropane CH2CHC(O)ONHC(CH3)2CH2SO3Na Sodium acrylate CH2CHCOONa Sodium allylsulfonate CH2CHCH2SO3Na Sodium di-n-butyldithiocarbamate NaS2CN((CH2)3CH3)2 Sodium di(isobutyl)dithiophosphinate NaS2P(CH2CH(CH3)2)2

Soluble in water —

1, p. 251 1, p. 251

© 2005 by CRC Press

Compound Sodium dimethyldithiocarbamate NaS2CN(CH3)2 Sodium formate HCOONa Sodium fumarate NaOOCHCHCOONa Sodium itaconate NaOOCC(CH2)CH2COOH Sodium maleate cis-NaOOCHCHCOONa Sodium methacrylate CH2C(CH3)COONa Sodium phenoxide C6H5ONa Sodium thiophenoxide C6H5SNa Sodium trifluoroacetate CF3COONa Sodium trifluoromethanesulfonate CF3SO3Na Sodium trimethylsilanolate (CH3)3SiONa Sodium vinylsulfonate CH2CHSO3Na

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

143.21

—

—

—

68.02

—

253

160.04

—

174.06

Densitya (g/cc)

Miscellaneous

—/—

—

—

1, p. 252

—

s/—

1.92

—

1, p. 252

>300

—

s/—

1.92

—

1, p. 252

—

—

—

—/—

—

—

1, p. 253

160.04

—

—

—

—/—

—

—

1, p. 253

108.07

—

310

—

s/—

2.703

116.10

—

—

—

—

132.17

—

>300(d)

—

—/white to reddish s/

Soluble in warm methanol, water, 1, p. 253 hot dimethylacetamide Decomposes in CO2 1, p.,254

—

Soluble in water

1, p. 254

136.0

—

207 (d)

—

s/—

—

Soluble in trifluoroacetic acid

1, p. 254

172.05

—

253–255

—

s/—

—

—

1, p. 255

112.18

—

147–150

—

s/—

—

—

1, p. 255

130.11

—

—

—

l/yellow

State/Color

1.206

Soluble in water, methanol

Reference

1, p. 255

Strontium Compounds I. Strontium Alkoxides and Diketonates Strontium hexafluoropentanedionate Sr(OC(CF3)CH(CF3)CO)2 Strontium methoxypropoxide 20% Sr(OCH(CH3)CH2OCH3)2 Strontium 2,4-pentanedionate Sr(OC(CH3)CH(CH3)CO)2

501.75

—

220/0.02

s/—

—

—

260 (decomposes) —

297.84

—

—/—

0.99

285.84

—

220

—

s/—

—

— Soluble in methoxypropanol

1, p. 256 1, p. 256

Solubility in water at 30°C: 21 g/l 1, p. 256

© 2005 by CRC Press

Strontium isopropoxide ((CH3)2CHO)2Sr Strontium 2,2,6,6-tetramethyl-3,5heptanedionate Sr(OC(C(CH3)3)CH(C(CH3)3)CO)2

205.80

—

130

—

s/—

—

—

1, p. 256

453.94

—

110–112

230/0.05

s/—

—

—

1, p. 256

—

II. Dialkyl and Diaryl Strontium Compounds Dibenzylstrontium (Sr(CH2C6H5)2

269.89

—

—

—

Dimethylstrontium Sr(CH3)2 Diphenylstrontium Sr(C6H5)2

117.69

—

—

—

s/yellow-red (in solution) —/—

241.83

—

—

—

s/orange

—

—

Soluble in ether tetrahydrofuran; 2, p. 231; decomposes at ambient 8, p. 2221 temperature Unstable in solution at room 2, p. 230 temperature Unstable in solution at room 2, p. 230; temperature; sp soluble in 8, p. 2221 tetrahydrofuran

III. Dialkenyl and Dialkynl Strontium Compounds Bisphenyl ethynyl strontium Sr(C}CC6H5)2

289.88

—

—

—

s(powder)/ white

—

Diallyl strontium Sr(CH2CH = CH2)2 Strontium divinyl Sr(CH = CH2)

169.77

—

—

—

—

114.67

—

—

—

s(powder)/ colorless —/orangeyellow

205.72

—

—

—

—

Thermally stable; decomposes at 2, p. 231; >360ºC; insoluble in benzene; 8, p. 2221 soluble in tetrahydrofuran and liquid ammonia Pyrophoric; soluble in 8, p. 2221 tetrahydrofuran Soluble in tetrahydrofuran 2, p. 231; 8, p. 2221

IV. Strontium Salt Strontium acetate (CH3COO)2Sr

s/—

2.099

—/—

—

Dehydrates at >150°C

1, p. 256

Sulfur Compounds I. Sulfur Alkyls Diethylsulfur S(C2H5)2

90.18

—

—

—

—

3, p. 72

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Tantalum Compounds I. Tantalum Alkoxides and Diketonates Tantalum V n-butoxide Ta(O-n-C4H9)5

546.51

217/0.15

—

—

l/—

1.310

n20 = 1.48302

1, p. 257 4, p. 71

Tantalum V t-butoxide Ta(O-C(CH3)3)5 Tantalum V ethoxide Ta(OC2H5)5

546.52

96/0.1

—

—

1/—

—

Molecular complexity: 2.02 Flash point: 66°C Molecular complexity: 1.00

406.26

145/0.1

18–19

—

l/—

1.58

Molecular complexity: 1.98

1, p. 257

Tantalum V-1-ethylpropoxide Ta(O-CH(C2H5)2)5 Tantalum V methoxide Ta(OCH3)5 Tantalum 1-methyl butoxide Ta(O-CH(CH3)(nC3H7))5 Tantalum 3-methyl butoxide Ta(OCH2CH2CH(CH3)2)5 Tantalum n-pentoxide Ta(O-n-C5H11)5 Tantalum n-propoxide Ta(O-n-C3H7)5 Tantalum isopropoxide Ta(O-CH(CH3)2)5 Tantalum tetraethoxide dimethylaminoethoxide (C2H5O)4TaOCH2CH2N(CH3)2) Tantalum V tetraethoxidepentanedionate (OC2H5)4Ta(-OC(CH3)CH(CH3)CO-) Tantalum V trifluoroethoxide Ta(OCH2CF3)5

616.66

146/0.15 153/0.1

—

—

1/—

—

Soluble in toluene, ethanol Molecular complexity: 1.02

4, p. 71 4, p. 71

50

—

—/—

—

Molecular complexity: 1.98.

616.66

189/10; 130/0.2 148/0.1

—

—

1/—

—

Molecular complexity: 0.99

1, p. 258; 4, p. 71 4, p. 71

616.66

210/0.1

—

—

1/—

—

Molecular complexity: 1.98

4, p. 71

616.66

239/0.02

—

—

1/—

—

Molecular complexity: 2.01

4, p. 71

476.39

184/0.15

—

—

1/—

—

Molecular complexity: 1.95

4, p. 71

458.24

122/0.1

—

—

1/—

—

Molecular complexity: 1.00

4, p. 71

449.33

125/1

—

—

l/—

1.5

—

1, p. 258

460.30

95/0.5

44–45

—

s/—

1.5

—

1, p. 258

676.14

70/2

110

—

s/—

1.9

—

1, p. 258

336.12

4, p. 71

© 2005 by CRC Press

II. Miscellaneous Tantalum Compounds Bismethylcyclopentadienyldimethyltantalum (CH3C5H4)2Ta(CH3)2 Tantalum pentakis(dimethylamide) Ta(N(CH3)2)5 Trimethyl dichlrotantalum (CH3)3TaCl2

369.26

100–102

90/10–4

—

401.33

—

>150

100/0.01

296.96

Volatile

—

—

Crystalline solid/deep red s/—

—

—

21

—

—

1, p. 258

s/pale yellow

—

Air and moisture sensitive; very soluble in organic solvent

8, p. 2225; 22

Crystalline solid/ yellow (in toluene) Crystalline solid/—

—

Air sensitive

2, p. 206; 8, p. 2234

—

Crystallized by subliming in high vacuum

2, p. 207; 8, p. 2234

Technetium Compounds I. Technetium Carbonyls Biscyclopentadienyl hydridotechnetium TcH(M-C5H5)2

229.20

—

—

—

Cyclopentadienyl technetiumtricarbonyl Tc(CO)3(M-C5H5)

247.13

—

87.5

—

Tellurium Compounds I. Alkyl Tellurium Compounds Bistrifluoromethyl ditelluride (CF3)2Te2 Dibenzyltelluride (C6H5CH2)2Te Di-n-butyltelluride (C4H9)2Te Di-t-butyltelluride (C4H9)2Te Diethyltelluride (C2H5)2Te Dimethyltelluride (CH3)2Te Dimethylditelluride (CH3)2Te2 Di-i-propyltelluride (C3H7)2Te

393.21

—

73

—

1/—

—

Thermally unstable

27

272.39

—

—

—

1/—

—

Flammable

6, p. 90

241.82

—

—

—

1/—

—

Flammable

6, p. 90

241.82

132–135

—

—

1/—

1.334

Flammable

6, p. 90

185.72

137–138

—

—

1/—

1.599

Flammable

6, p. 90

157.68

82

10

—

1/—

—

Flammable

6, p. 90

270.24

—

—

—

1/—

—

Flammable

6, p. 90

213.77

49

—

—

1/—

—

Flammable

6, p. 90

© 2005 by CRC Press

Compound Di-n-propyltelluride (C3H7)2Te Tellurium IV diethyldithiocarbamate Te(S2CN(CH2CH3)2) Tellurium IV ethoxide Te(OC2H5)4

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

213.77

—

—

—

1/—

—

720.69

—

108–109

—

s/—

1.55

307.84

88–90/2

—

—

l/dark brown

1.52

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Flammable

6, p. 90

Soluble in toluene, carbon disulfide Light sensitive Decomposes t > 100°C

1, p. 260 1, p. 260

Terbium Compounds I. Terbium Alkoxides and Diketonates Terbium 2,4-pentanedionate trihydrate Tb(–OC(CH3)CH(CH3)CO–)3 Terbium 2,4-pentanedionate trihydrate Tb(-OC(CH3)CH(CH3)CO-)3 Terbium 2,2,6,6-tetramethyl-3,5heptanedionate Tb(-OC(C(CH3)3)CH((CH3)3C)CO-)3

456.25/ 510.31 456.25/ 510.31 708.74

—

169–173

—

s/—

—

Hygroscopic

1, p. 173

—

169–170

—

s/—

—

1, p. 173

—

155–156

—

s/—

—

Soluble in tetrahydrofuran; hygroscopic )Hsub = 33.8 kcal/mol; soluble in toluene, THF

354.21

—

316

230 (under vacuum)

Crystalline solid/ colorless

—

336.06

—

—

—

—/—

—

—

1, p. 173

II. Organoterbium Compounds Tricyclopentadienyl terbium Tb(C5H5)3

Soluble in tetrahydrofuran; hydrolyzed by water

8, p. 2232

III. Terbium Salt Terbium acetate (CH3COO)3Tb

—

1, p. 173

Thallium Compounds I. Thallium Alkoxides and Diketonates Thallium benzoylacetonate Tl(–OC(C6H5)CH(CH3)CO–) Thallium I ethoxide TlOC2H5

365.55

—

103–104

—

s/—

249.43

—

3

—

l/hazy

3.493

Soluble in benzene

1, p. 261

n20 =1.6714; decomposes at 130°C

1, p. 261

© 2005 by CRC Press

Thallium hexafluoropentanedionateOC(CF3)CH(CF3)COTl Thallium 2,4-pentanedionate Ti(–OC(CH3)CH(CH3)CO–) Thallium 2,2,6,6-tetramethyl-3,5Heptanedionate Tl(OC(C(CH3)3)CH(C(CH3)3)CO)

411.42

—

126–128

140/0.1

s/—

—

—

1, p. 261

303.50

—

—

100/105

—/—

—

—

1, p. 261

387.62

—

159–164

110/1

s/—

—

—

1, p. 261

Cyclopentadienyl, dimethyl thallium (CH3)2TlC5H5

299.55

—

—

—

Crystalline solid/ colorless

—

Air sensitive, fluxional molecule

Dimethyl thallium methylacetylide (CH3)2(CH3C}C)Tl Dimethyl thallium phenylacetylide (CH3)2(C6H5C}C)Tl

273.51

—

—

—

—/—

—

335.58

—

—

—

—/—

—

Triethyl thallium (C2H5)3Tl Trimethyl thallium (CH3)3Tl

291.57

74/25

43/1

249.49

76/85

38.5

Tri(methylvinyl)thallium (CH3CH2 = CH)3Tl

330.62

—

—

Triphenyl thallium (C6H5)Tl

435.70

—

188–189

Isolated by vacuum sublimation —

Trispentachlorophenyl thallium (C6Cl5)3Tl Trispentafluorophenylthallium (C6F5)3Tl Tristetrachlorophenyl thallium (2,3,5,6-Cl4C6H)3Tl

952.38

—

280

435.70

—

849.04

—

II. Triorganothallium Compounds

>125 s/— (decomposes) >90 s/— (decomposes)

1.952 —

Crystalline solid/ colorless s/—

—

—

s/white

—

139–141

—

s/—

—

209

—

Crystalline solid/ colorless

—

—

2, p. 727; 8, p. 2298; 16; 27 Dimeric in solution 2, p. 727; 17; 27 Toxic 2, p. 727; 8, p. 2310; 17 Light sensitive; may be explosive 2, p. 726; 5, p. 141 Light sensitive; dissociation 2, p. 726; energy for first TI-C: 152 kJ/mol; 5, p. 141; may be explosive; purified by 25 vacuum sublimation Air and light sensitive; 25 decomposes at room temperature If temperature greater than 2, p. 726; melting point, it decomposes 5, p. 141 into Tl and Ph2 — 2, p. 727; 23 — 2, p. 727 —

2, p. 727; 14, p. 11

© 2005 by CRC Press

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

269.48

—

>270

—

s/—

—

283.50

—

109–10

—

s/—

—

249.39

—

101

—

s/off white

494.81

—

—

—

—/—

—

—

325.57

—

27–28

—

s/—

—

—

Biscyclohexyl thallium chloride (cyclo-C6H11)2TlCl

406.14

—

210–230 (explodes)

—

s/—

—

Bis(trans-methylethylenyl) thallium chloride (trans-CH3CH = CH)2TlCl Bis(cis-methylethylenyl) thallium chloride (cis-CH3CH = CH)2TlCl Di/(n-butyl)thallium chloride n-(C4H9)2TlCl Di/(sec-butyl)thallium chloride s-(C4H9)2TICl Di(isobutyl)thallium chloride i-(C4H9)2TlCl Diethyl thallium chloride (C2H5)2TlCl

321.98

—

>310

—

s/—

—

333.99

—

>310

—

s/—

—

354.07

—

—

s/—

—

354.07

—

—

s/—

—

354.07

—

240–250 (explodes) 150 (explodes) —

—

—/—

—

297.96

—

205–206 (decomposes)

—

s/—

—

314.36

—

295 (decomposes)

—

s/—

—

Stable; very high melting point; not very soluble in H2O, alcohol, or other common solvents Stable; very high melting point; not very soluble in H2O, alcohol, or other common solvents Stable; very high melting point; not very soluble in H2O, alcohol, or other common solvents More soluble than lower alkyl analogues Decomposes more easily when heated Decomposes more easily when heated Low solubility in H2O, alcohol; soluble in pyridine, aqueous NH3 Low solubility in H2O alcohol; soluble in pyridine, aqueous NH3

Compound

Formula Weight

State/Color

Densitya (g/cc)

Miscellaneous

Reference

III. Miscellaneous Organothallium Compounds Cyclopentadienylthallium C5H5Tl Methylcyclopentadienyl thallium C5H4TlCH3 Thallium formate HCOOTl Triethylthallium trimethylamine (C6H5)3TlN(CH3)3 Trimethyl thallium (trimethyl phospine) (CH3)3TlP(CH3)3

4.97

Soluble in polar solvents; stable in air, H2O —

2, p. 749

Soluble in water, methanol

1, p. 261

2, p. 750

2, p. 728; 26 2, p. 728

IV. Organohalo Thallium Compounds

Dimethyl thallium bromide (CH3)2TIBr

2, p. 731

2, p. 731

2, p. 731

2, p. 731 2, p. 731 2, p. 731 2, p. 731

2, p. 731

© 2005 by CRC Press

Dimethyl thallium chloride (CH3)2TICl

269.91

—

>280 (decomposes)

—

s/—

—

Dimethylthallium fluoride (CH3)2TIF Dimethyl thallium iodide (CH3)2TlI

253.45

—

—

—

s/—

—

373.37

—

264–266 (decomposes)

—

s/—

—

Di(pentachlorophenyl) thallium chloride (C6Cl5)2TlCl Di(pentafluorophenyl) thallium chloride (C6F5)2TlCl Dipentylthallium chloride ((CH3)3CCH2)2TlCl Diphenyl thallium chloride (C6H5)2TiCl

738.50

—

314

—

s/—

—

573.95

—

237–279

—

s/—

—

382.12

—

>340

—

s/—

—

394.05

—

>310

—

s/—

—

326.01

—

198–202

—

s/—

—

326.01

—

—

s/—

—

363.57

—

198–202 (decomposes) 123–5 (decomposes)

—

s/—

—

More soluble than other diphenyl analogues Stable and soluble in H2O, alcohol, other common solvents Stable; very high melting point; not very soluble in H2O, alcohol, or other common solvents More soluble than lower alkyl analogues Decomposes more easily when heated; toxic —

363.557

—

149–151 (decomposes)

—

s/—

—

—

283.93

—

>250

—

s/—

—

441.30

—

149

—

s/—

—

352.39

—

—

s/—

—

—

2, p. 742

663.96

—

235 (decomposes) —

—

—/—

—

Stable in air, H2O

2, p. 749

441.70

—

—

—

—/—

—

Unstable; ignites spontaneously in air

2, p. 749

337.51

—

102–103 (decomposes)

—

s/—

—

—

2, p. 742

Di-n-propyl thallium chloride n-(C3H7)2TlCl Di(isopropyl)thallium chloride i-(C3H7)2TlCl Fluorophenyl, n5-cyclopentadienyl thallium (3-FC6H4)C5H4Tl Fluorophenyl, n5-cyclopentadienyl thallium 4-FC6H4C5H4Tl Methyl, ethyl thallium chloride CH3(C2H5)TlCl Phenylthallium dibromide C6H5TlBr2 Phenylthallium dichloride C6H5TlCl2 Pentabromocyclopentadienyl thallium C5Br5Tl Pentachlorocyclopentadienyl thallium C5Cl5Tl

Low solubility in H2O, alcohol; soluble in pyridine, aqueous NH3 Toxic Low solubility in H2O, alcohol; soluble in pyridine, aqueous NH3 —

2, p. 731

2, p. 731; 8, p. 2281 2, p. 731

2, p. 731 2, p. 731 2, p. 731 2, p. 731

2, p. 731 2, p. 731; 8, p. 2294 2, p. 750

2, p. 750

Stable; very high melting point; 2, p. 731 not very soluble in H2O, alcohol, or other common solvents — 2, p. 742

V. Organo Acetate Thallium Compounds Methyl thallium diacetate CH3Tl(OOCCH3)2

© 2005 by CRC Press

Compound Phenyl thallium di(trifluoro acetate) C6H5Tl(OOCCF3)2

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

507.52

—

184–189

—

Densitya (g/cc)

Miscellaneous

s/—

—

—

State/Color

Reference 2, p. 742

Thorium Compounds I. Thorium Alkoxides and Diketonates Thorium-t-butoxide Th(OC(CH3)3)4 Thorium 1-diethyl propoxide Th(OC(C2H5)3)4

524.50

160/0.1

—

—

1/–

—

Molecular complexity: 3.4

692.82

148/0.05

—

—

1/—

1.2230

Thorium 1-dimethyl propoxide Th(OC(CH3)2C2H5)4 Thorium ethoxide Th(OC2H5)4 Thorium 1-ethyl, 1-methyl butoxide Th(OCCH3(C2H5)(n-C3H7))4 Thorium 1-ethyl, 1-methyl propoxide Th(OCCH3(C2H5)2)4 Thorium 1-ethyl(1,2 di-methylpropoxide) or Thorium heptoxide Th(OCCH3(C2H5)(i-C3H7))4 Thorium methoxide Th(OCH3)4 Thorium 2,4-pentanedionate Th(–OC(CH3)CH(CH3)CO–)4 Thorium n-propoxide Th(O-n-C3H7)4 Thorium isopropoxide Th(OCH(CH3)2)4

580.61

208/0.3

—

—

1/—

—

Molecular complexity: 1.0; 4, p. 70; surface tension: 22.0; viscosity: 109 0.4920 cSt Molecular complexity: 2.8 4, p. 70

412.28

300/0.05

—

—

1/—

—

Degree of polymerization: 6.0

4, p. 45

692.82

153/0.1

—

—

1/—

—

Molecular complexity: 1.7

4, p. 70

636.71

148/0.1

—

—

1/—

—

692.81

139/0.05

—

—

1/—

—

356.17

—

—

>300/0.05

s/—

—

628.49

—

159–161

160/8

s/—

—

468.39

—

—

—

—/—

—

468.39

200–210/0.1

—

—

1/—

—

Molecular complexity: 3.8

440.34

160/0.03

>190 (decomposes)

—

s/bright yellow

—

Soluble in (CH3)2SO; air sensitive 2, p.195; 8, p.2239

— Molecular complexity: 1.0

— Soluble in toluene —

4, p. 70

4, p. 70 4, p. 70

4, p. 72 27, p. 41 4, p.72 4, p.70

II. Organothorium Compounds Biscyclooctatetraene thorium Th(C8H8)2

© 2005 by CRC Press

Tetraallyl thorium Th(C3H4)4 Tricyclopentadienyl thorium Th(C5H5)3

396.33

—

427.32

—

0 (decomposes) >270 (decomposes)

— —

s/dark yellow s/purple

—

Soluble in benzene

8, p. 2238

—

Soluble in tetrahydrofuran; insoluble in benzene

8, p. 2239

Thulium Compounds I. Thulium Alkoxides and Diketonates Thulium 2,4-pentanedionate, trihydrate Tm(–OC(CH3)CH(CH3)CO–)3 Thulium 2,2,6,6-tetramethyl-3,5heptanedionate Tm(–OC(C(CH3)3)CH(C(CH3)3)CO–)3

466.26/ 520.31 718.75

—

—

—

s/—

—

—

1, p. 174

—

169–172

—

s/—

—

—

1, p. 174

346.07

—

—

—

—/—

—

—

1, p. 174

II. Thulium Salt Thulium acetate (CH3COO)3Tm

Tin Compounds I. Tin Alkoxides and Diketonates Bis(2-ethylhexanoate)tin Tin II Octoate Sn(OOCCH(C2H5)C4H9)2 Bis(Tri-n-butyltin)acetylenedicarboxylate (nC4H9)3SnOOCC2COOSn(nC4H9)3 Diacetonxytin 95% Stannous Acetate Sn(OOCCH3)2

405.11

—

—

—

—/—

1.28

92.11

—

176–177(d)

—

s/—

—

236.79

—

180–183

—

s/—

2.31

Di-n-butyldiacrylatetin (CH2CHCOO)2Sn(nC4H9)2 Di-n-butyldi-n-butoxytin (CH3(CH2)3O)2Sn(nC4H9)2 Di-n-butyldimethacrylatetin (CH2C(CH3)COO)2Sn(nC4H9)2 Di-n-butyl dineodecanoate (CH3(CH2)5C(CH3)2COO)2Sn(nC4H9)2

375.02

—

—

—

—/—

1.175

379.15

136–138/0.05

—

—

l/—

1.122

403.09

—

54–58

—

s/—

1.175

575.44

—

—

—

—/—

1.09

Toxic; flash point: >110°C; soluble in xylene, cyclic siloxanes —

1, p. 266

1, p. 267

Reducing agent; promotes dye 1, p. 269 uptake by fabrics; soluble in acetic acid, water; decomposes at >238°C n20 = 1.4771 1, p. 271 n20=1.4721; flash point: 116°C; soluble in hexane — —

1, p. 271 1, p. 272 1, p. 272

© 2005 by CRC Press

Compound Dioctyldineodecanoatetin (CH3(CH2)6CH2)2Sn(OOCC(CH3)2 C6H13)2 Tetraisopropoxytin isopropanol adduct ((CH3)2CHO)4Sn Tin IV t-butoxide 95% Tetra-t-butoxytin Sn(Ot-C4H9)4 Tin dichloride bis(2,4-pentanedionate) Cl2Sn(–OC(CH3)CH(CH3)CO–)2 Tin 1,1-dimethyl butoxide (tin hexoxide) Sn(OC(CH3)2CH2CH2CH2)4 Tin II ethoxide Sn(OC2H5)2 Tin IV ethoxide Sn(OC2H5)4 Tin II methoxide Sn(OCH3)2 Tin 1-methyl, 1-ethyl propoxide (tin hexoxide) Sn(OCCH3(C2H5)2)4 Tin II oxalate Sn(OOC)2 Tin II 2,4-pentanedionate Stannous acetylacetonate Sn(–OC(CH3)CH(CH3)CO–)2 Tin sodium ethoxide 95% NaSn2(OC2H5)9 Tin tetra-ter-amyloxide, tin tetra(1-methyl butyl) Sn(Ot-Am)4

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

687.66

—

—

—

—/—

355.05

131/1.6

—

—

l/—

—

411.14

99/4

—

—

1/—

—

387.83

202–203

199

—

s/—

—

498.3

—

—

—

1/—

1.0499

208.81

—

200

—

s/—

298.93

—

—

—

180.76

—

242–246

—

488.5

—

—

—

206.72

—

—

316.90

100–105/0.02

25 to 19

665.91

—

>250

—

s/—

—

425.4

—

—

—

—/—

331.11

88–92/0.2

—

—

1/—

State/Color

Densitya (g/cc) 1.03

Miscellaneous

Reference

n20=1.4680 Flash point: 140°C

1, p. 274

Soluble in hydrocarbons, warm isopropanol —

1, p. 278

—

1, p. 278

1, p. 266

Viscosity: 0.0986 cSt

4, p. 108

—

Insoluble in ethanol

1, p. 280

—/—

—

Degree of polymerization: 4.0

4, p. 45

Solid (polymeric) /white 1/—

—

280 s/— (decomposes) — 1/bright yellow

1.1768

3.56 —

—

1, p. 280

Viscosity: 0.4127 cSt

4, p. 108

Solubility: H2O: 0.5 g/1

1, p. 280

—

1, p. 280

Soluble in ethanol, hexane

1, p. 277

1.0984

Surface tension: 21.7 dyn/cm; viscosity: 0.1664 cSt

4, p. 108

1.068

n20 = 1.4846; flash point: 103°C

1, p. 265

II. Alkyl Organotin Compounds Allyltri-n-butyltin (C4H9)3SnCH2CHCH2

© 2005 by CRC Press

Allyltrimethyltin (CH3)3SnCH2CHCH2 Biscyclopentadienyl tin Sn(C5H5)2 Bisphenyl tin cyclobutane (C6H5)2Sn(C4H8) Bis(tri-n-butylstannyl)acetylene (nC4H9)3SnCCSn(nC4H9)3 Bis(tri-n-butyltin)oxide Hexabutyldistannoxane (C4H9)3SnOSn(C4H9)3 Bis(triethyltin)oxide (C2H5)3SnOSn(C2H5)3 Diallyldi-n-butyltin (C4H9)2Sn(CH2CHCH2)2 Di-n-Butylbis(1-thioglycerol)tin Dibutylbis(2,3-dihydroxypropylmercaptan (C4H9)2Sn(SCH2CH(OH)CH2OH)2 Diallyldi-n-butyltin (CH2CHCH2)2Sn(C4H9)2 Di-n-butylbis(dodecylthio)tin 95% Dibutyltindilaurylmercaptide (C4H9)2Sn(S(CH2)11CH3)2 Di-n-butyltin oxide ((C4H9)2SnO)n Di-n-Butyltin Sulfide ((C4H9)2SnS)n Diethyldibutyl tin (C2H5)2Sn(C4H9)2 Dimethyl tin cyclopentane (CH3)2Sn(C5H10) Dioctyltin oxide (SnO(nC8H17)2)n Diphenyldiethyl tin (C2H5)2Sn(C6H5)2 Divinyldi-n-butyltin (CH2CH)2Sn(C4H9)2 1-ethoxyvinyltri-n-butylin C2H5OC(CH2)Sn(C4H9)3

204.87

125–129

—

—

1/—

248.88

—

—

—

329.01

—

33

—

Crystalline solid/white s/none

604.10

140–145/0.1

—

—

l/—

1.170

596.08

180/2

—

—

1/—

1.170

427.75

125/4

—

—

l/—

1.377

315.07

93/0.1

—

—

l/—

1.100

447.24

—

22

—

l/—

1.39

315.07

93/0.1

—

—

l/—

1.100

635.67

160/10

—

—

1/—

1.04

248.92

—

>150(d)

—

s/—

1.58

264.98

—

90–98

—

s/off-white

1.42

291.04

205–208/760

—

—

1/none

—

218.89

63/15

—

—

1/none

—

361.13

—

245-8

331.02

—

154–156

287.01

—

60/0.4

—

l/—

1.122

361.14

85–86/1

—

—

l/—

1.069

245–248 s/— (decomposes) — s/none

1.255 — —

1.30 —

n20 = 1.4734

1, p. 265

Air sensitive; soluble in aprotic solvents Stable to 200ºC

3, p. 72; 8, p. 2184 2, p. 553, 535 n20 = 1.4930; flash point: >110°C 1, p. 266 n20 = 1.4864, viscosity: 25º: 4.8 cSt; flash point: 168°C; surface tension at 25ºC: 30.6 dyn/cm Toxic

1, p. 267

n20 = 1.500 Flash point: 101°C n20 = 1.5691 Flash point: 176°C

1, p. 269

n20 = 1.500 Flash point: 101°C n20 = 1.4992; soluble in toluene, heptane; flash point: >204ºC

1, p. 269

1, p. 267

1, p. 270

1, p. 270

Autoignition temperature: 280ºC; 1, p. 273 polymeric infusion solid Trimeric; soluble in THF, hot 1, p. 273 toluene 2, p. 533, Stable to 200ºC 535 2, p. 533, Stable to 200ºC 535 — 1, p. 275 Stable to 200º n20=1.4749; soluble in hexane, THF Toxic n20 = 1.4760

2, p. 533, 535 1, p. 275 1, p. 275

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Ethynyltri-n-butyltin Tributylstannylacetylene Sn(nBu)3CCH Hexa-n-butylditin Bis(tributyl)tin (Sn(nBu)3)2 Hexamethylditin (Sn(CH3)3)2 Propynyltri-n-butyltin (C4H9)3SnCCCH3 Tetraallytin Sn(CH2CHCH2)4 Tetra-n-butyltin Sn(C4H9)4

315.07

71/0.2

—

—

1/—

1.092

n20 = 1.4760; flash point: 73ºC

1, p. 275

580.08

197–198/1

—

—

1/—

1.148

n25 = 1.5990

1, p. 275

327.59

85–88/45

23–24

—

—/—

1.570

1, p. 276

329.09

277

—

—

l/—

1.082

Flash point: 61ºC; inflames in air at 182ºC —

282.98

—

—

1/—

1.179

n20 = 1.5385; flash point: 75ºC

347.15

69–70/1.5; 128–130/760 145/10

97

—

—/—

1.057

Tetra(chloromethyl)tin (ClCH2)4Sn Tetraethyltin (C2H5)4Sn

316.61

—

49–49.5

—

s/none

234.94

181; 63–65/12

112

—

1/—

1.187

Tetramethyltin (CH3)4Sn

178.83

74-5

53

—

1/—

1.291

Tetra-n-Octyltin Sn(C8H17)4 Tetra-n-pentyltin (CH3(CH2)3CH2)4Sn Trimethyltin hydride Sn(CH3)3H Tetraoctenyl tin (C8H15)4Sn Tetra-n-octyltin Sn(C8H17)4 Tetra(pentachlorophenyl)tin (Cl5C6)4Sn

571.58

224/1

—

—

l/—

0.961

403.11

135/0.25

—

—

l/—

1.016

164.80

59

—

—

1/—

—

Easily oxidized

563.52

268/10

—

—

1/none

—

Stable to 200ºC

571.58

224/1

—

—

1/—

1116.01

—

446–447 (decomposes)

—

s/none

Compound

State/Color

Densitya (g/cc)

—

0.961 —

Miscellaneous

Reference

1, p. 277

2, p. 532; 1, p. 277 n20 = 1.4742, flash point: 107ºC; 2, p. 532; surface tension at 23º: 30.1 dyn/ 1, p. 278 cm; viscosity at 25º: 4.2 cSt 2, p. 532, Stable to 200ºC 535 Flammable; n20 = 1.4725; highly 2, p. 532; toxic; flash point: 53°C 1, p. 278; 6, p. 92 Flammable; n20 = 1.4410; )Hvap: 2, p. 532; 6.8 kcal/mol; )Hform, (gas) 27º: 1, p. 279; 13.6 kcal/mol; Hcomb: 903.5 6, p. 92 kcal/mol; flash point: –12ºC; toxic n20 = 1.4677; decomposesat 1, p. 279 >270°C — 1, p. 279

n20 = 1.4677 Stable to 200ºC

3, p. 72; 8, p. 2165 2, p. 532, 535 1, p. 279 2, p. 532, 535

© 2005 by CRC Press

Tetraisopropyltin Sn(CH(CH3)2)4 Tetra-n-propyltin (C3H7)4Sn Tetratolyl tin (C6H5CH2)4Sn Tetravinyltin (CH2 = CH)4Sn Tin tetra(methyl acetylide) (CH3C}C)4Sn Tin tetracyclopentadienyl (C5H5)4Sn Tri-n-butylmethyltin (C4H9)3SnCH3 Triphenylbutyl tin C4H9Sn(C6H5)3 Vinyltri-n-butyltin (C4H9)3SnCHCH2

n20 = 1.4851

1, p. 278

—

Stable to 200ºC

s/none

—

Stable to 200ºC

—

s/none

—

Stable to 200ºC

139–150

—

s/none

—

Stable to 200ºC

—

81–82

—

s/none

—

Stable to 200ºC

305.07

122–4/11

—

—

l/—

2, p. 532, 535 2, p. 532, 535 2, p. 532, 535 2, p. 532, 535 2, p. 532, 535 1, p. 282

407.12

—

60–62.5

—

s/none

317.09

104–106/3.5

—

—

1/—

1.085

716.02

—

119–123

—

s/—

—

732.07

—

141–143

—

s/—

—

1076.89

—

142–145

—

s/—

—

427.11

420–425

224–227

—

s/none

421.06

—

150–155

—

s/—

—

—

1, p. 265

391.10

—

71–73

—

s/—

—

—

1, p. 265

355.13

132–133/1

—

—

1/—

1.12

n20 = 1.5150

1, p. 269

391.17

—

—

—

—/—

1.116

n20 = 1.5320

1, p. 276

291.04

89/4

—

—

1/–

291.04

131

—

—

1/none

483.22

—

41.5–43

—

226.87

160

55–57

274.92

—

379.07

1.124

1.090 —

— Stable to 200ºC n20 = 1.4776

2, p. 533, 535 1, p. 284

III. Tin Aryls Bis(triphenyltin)oxide Hexaphenyldistannoxane (C6H5)3SnOSn(C6H5)3 Bis(triphenylntin)sulfide (C6H5)3SnSSn(C6H5)3 Bis[tris(2-methyl-2-phenylpropyl)]tin oxide (((C6H5)C(CH3)2CH2)3Sn)2O Tetraphenyltin Sn(C6H5)4

1.490

Antifouling agent; soluble in THF 1, p. 267

—

Toxic; soluble in warm toluene, THF Flash point: 231ºC; stable to 200º; soluble in hot toluene

2, p. 532, 535; 1, p. 268 1, p. 268

1, p. 279

IV. Tin Alkyl and Aryl Compounds Acryloxytriphenyltin (C6H5)3SnOOCCHCH2 Allytriphenyltin (C6H5)3SnCH2CHCH2 Cyclopentadienyltri-n-butyltin C5H5Sn(C4H9)3 Phenyethynyltri-n-butyltin C6H5CCSn(C4H9)3

© 2005 by CRC Press

Compound Phenyltri-n-butyltin (C6H5)Sn(C4H9)3 Tetra-p-tolyltin (p-CH3C6H4) 4Sn Tri-p-tolylchlorotin (p-CH3C6H4)3SnCl Tri-p-tolyhydroxytin (p-CH3C6H4)3SnOH

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

367.13

130/0.2

—

—

1/—

1.125

483.22

—

236–237

—

s/—

—

—

1, p. 279

427.56

—

108

—

s/—

—

—

1, p. 284

409.11

—

108–109

—

s/—

—

—

1, p. 284

340.97

—

—

—

—/—

—

—

1, p. 269

687.46

—

25

>215(d)

370.99

—

—

351.01

—

447.23

State/Color

Densitya (g/cc)

Miscellaneous n20 = 1.5155

Reference 1, p. 277

V. Tin Alkyl Ketonates Carbomethoxyethyltriethoxytin CH3OOCCH2CH2Sn(OC2H5)3 Di-n-butylbis(2-ethylhexylmaleate)tin (C4H9CH(C2H5)CH2OOCCHCHCOO)2 Sn(C4H9)2 Di-n-butylbis(2-methylmaleate)tin (CH3OOCCHCHCOO)2Sn(C4H9)2 Di-t-butyldiacetoxytin (CH3COO)2Sn(tC4H9)2 Dimethylhydroxy(oleate)tin 90% (CH3)2Sn(OH)OOC(CH2)7C2H2(CH2)7CH3 1,3-Diacetoxy-1,1,3,3-tetrabutyltin oxide (C4H9)2(CH3COO)Sn–O–Sn (OOCCH3)(C4H9)2 Di-n-butylbis(2,4-pentanedionate)tin (C4H9)2Sn(OC(CH3)CH(CH3)CO)2 Di-n-butylbis(2-ethylhexanoate)tin (C4H9)2Sn(OOCCH(C2H5)C4H9)2 Di-n-butylbis(2-ethylhexanoxy)tin Dibutyltindioctoate (C4H9)2Sn(OOCCH(C2H5)C4C9)2 Di-n-butylbis(2,4-pentanedionate)tin (C4H9)2Sn(OC(CH3)CH(CH3)CO)2 Di-n-butyldiacetoxytin Dibutyltindiacetate C4H9Sn(OOCCH3)2

l/—

1.145

Flash point = 123°C

1, p. 270

—

—/—

1.36

1, p. 270

104

—

s/—

—

n20 = 1.5005 Flash point: 135°C —

—

—

—

1/—

1.15

n20 = 1.492; viscous liquid; toxic

1, p. 274

599.94

—

56–58

—

s/—

—

Soluble in acetone, THF

1, p. 269

431.13

132/0.4

25–26

—

l/—

1.21

n20 = 1.4653; flash point: 91°C

1, p. 270

519.34

—

—

—

l/—

0.97

Flash point: 26°C

1, p. 270

519.34

215–220/2

54–60

—

—/—

1.070

n20 = 1.4653

1, p. 270

431.13

132/0.4

—

—

1/—

1.2

Flash point: 91ºC

1, p. 270

351.01

142–145/10

10

—

1/—

1.320

n20 = 1.4773; flash point: 143ºC; toxic

1, p. 271

1, p. 271

© 2005 by CRC Press

n-Butyltris(2-ethylhexanoate)tin C4H9Sn(OOCHCH(C2H5)C4H9)3 Di-n-butyldilauryltin Dibutyltin dilaurate (C4H9)2Sn(OOC(CH2)10CH3)2

605.43

—

—

—

—/—

1.105

n20 = 1.4650; flash point: >110ºC 1, p. 268

631.55

—

22–24

—

s/—

1.066

1, p. 272

Di-n-butyl(maleate)tin ((C4H9)2SnOOCCHCHCOO)n

346.98

—

103–105

—

s/white

1.318

Di-n-butyl-S,Sebis(isooctylmercaptoacetate)tin 95% (C4H9)2Sn(SCH2COOiC8H17)2 Dimethyl-S,Sebis(isooctylmercaptoacetate)tin 80% Bis(isooctylthioglycolate)dimethyltin (CH3)2Sn(SCH2COOiC8H17)2 Dimethyldineodecanoatetin Dimethyl tin dineodecanoate (CH3)2Sn(OOCC(CH3)2C6H13)2 Dioctyldilauryltin 95% Dioctyltindilaurate (C8H17)2Sn(OOC(CH2)10CH3)2 Tetraacetoxytin (CH3COO)4Sn Tin II oleate (CH3(CH2)7CHCH(CH2)7COO)2Sn Tri-n-butylacetoxytin (C4H9)3SnOOCCH3 Tri-n-butylbenzoyloxytin 95% (C4H9)3SnOOCC6H5

639.54

—

—

—

—/—

1.120

n20 = 1.4708; flash point: 231°C; viscosity at 25°C: 31–34 cSt; toxic; soluble in benzene, acetone, ether n20 = 1.502; flash point: 204ºC; polymeric solid; white powder; soluble in benzene, organic esters Flash point: 140ºC; toxic

555.38

—

—

—

—/—

1.17

Flash point: 127ºC; viscosity at 25º: 50 cSt; toxic

1, p. 273

491.26

—

6

—

s/—

1.14

n20 = 1.470; flash point: 153ºC

1, p. 274

743.89

—

17–18

—

s/—

0.998

Flash point: 70ºC; toxic

1, p. 274

354.87

—

232–234

—

s/—

—

—

1, p. 277

381.71

—

—

—

—/—

1.06

—

1, p. 280

349.08

—

85–87

—

s/—

1.27

411.14

166–168/1

—

—

1/—

1.193

409.05

—

123

—

s/—

—

Toxic; soluble in toluene, 1, p. 281 methanol n20 = 1.5157; flash point: >110ºC; 1, p. 281 toxic; solubility in H2O at 20ºC: 0.02 g/l; viscosity at 25ºC: 9 cSt Solubility in H2O: 9 mg/l; toxic 1, p. 283

612.14

208/1

—

—

l/—

—

n20 = 1.518

Triphenylacetoxytin (C6H5)3SnOOCCH3

1, p. 272

1, p. 273

VI. Haloalkyl Tin Bis(tri-n-butyltin)sulfide (C4H9)3SnSSn(C4H9)3

1, p. 267

© 2005 by CRC Press

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

77–79/0.2 (decomposes)

—

—

1/—

—

245.27

—

130–139(d)

—

s/—

1.26

241.33

108/30

—

—

l/—

—

282.17

93/10

63

—

—

1.693

Butyl trifluoride tin C4H9SnF3

232.80

—

337–338

—

s/—

—

Butyl triiodide tin C4H9SnI3

556.52

154/5

—

—

1/—

—

Carbomethoxyethyltrichlorotin CH3OOCCH2CH2SnCl3 Chloromethyltrimethyltin ClCH2Sn(CH3)3 Diallyldibromotin (CH2CHCH2)2SnBr2 Dibenzyldibromo tin (C6H5CH2)2SnBr2

312.14

174/4

69

—

s/—

—

213.29

70/57

—

—

—/—

1.507

360.65

77–79/2

—

—

l/—

1.864

460.76

—

123–124

—

s/—

—

Formula Weight

Boiling Point (°C/mmHg)

Butyltribromide tin C4H9SnBr3

415.52

Butylchlorodihydroxytin C4H9Sn(OH)2Cl Butyldimethylchlorotin C4H9Sn(CH3)2Cl n-Butyltrichlorotin C4H9SnCl3

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Soluble in organic solvents; 2, p. 553 monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition — 1, p. 268 n20 = 1.4922

1, p. 268

n20 = 1.5229; toxic; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution in nonconducting solvents; close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition —

2, p. 553; 1, p. 268

n20 = 1.4863

2, p. 553

2, p. 553

1, p. 268 1, p. 269

—

1, p. 269

Soluble in organic solvents; 2, p. 553 monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition

© 2005 by CRC Press

Dibenzyldichloro tin (C6H5CH2)2SnCl2

371.86

—

163

—

s/—

—

Dibenzyl diiodide tin (C6H5CH2)2SnI2

554.76

—

88

—

s/—

—

Dibutyldibromo tin (C4H9)2SnBr2

392.73

96/0.1

20

—

Solid–liquid/ —

—

Di-n-butylbutoxychlorotin C4H9OSnCl(C4H9)2 Di-n-butyldibromotin Br2Sn(C4H9)2 Di-n-butyldicholorotin (n-C4H9)2SnCl2

341.48

—

35–38

—

s/—

1.2

392.74

150/10

20

—

l/—

1.739

303.83

153/5

39–41

—

s/—

1.36(50)

Di-t-butyldichlorotin (t-C4H9)2SnCl2 Di-n-butyldifluorotin (C4H9)2SnF2

303.83

66/3

42–43

—

s/—

—

270.92

—

157–159

—

s/—

—

Dibutyl diiodide tin (C4H9)2SnI2

486.73

145/6

—

—

1/—

—

Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition —

2, p. 553

2, p. 553

2, p. 553

1, p. 270

Flash point: >110°C; soluble in 1, p. 271 hexane n50 = 1.499; toxic; flash point: 2, p. 553; 168ºC; soluble in organic 1, p. 271 solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas — 1, p. 271 Toxic; insoluble in most organic 2, p. 553; solvents and H2O; monomer in 1, p. 272 vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; 2, p. 553 monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Diethyldibromo tin (C2H5)2SnBr2

336.62

—

63

—

s/—

—

Diethyldichloro tin (C2H5)2SnCl2

247.72

—

84

—

s/—

—

Diethyldiflouro tin (C2H5)2SnF2

241.81

—

310–320

—

s/—

—

Diethyl diiodo tin (C2H5)2SnI2

430.62

—

44

—

s/—

—

Dimethylbis(dodecylthio)tin (CH3(CH2)10CH2S)2Sn(CH3)3 Dimethyldibromo tin (CH3)2SnBr2

557.58

—

—

—

—/—

1.08

308.57

—

75–77

—

s/—

—

Dimethyldichlorotin (CH3)2SnCl2

219.67

185–190

103–105

—

s/—

—

Compound

State/Color

Densitya (g/cc)

Miscellaneous Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition —

Reference 2, p. 553

2, p. 553

2, p. 553

2, p. 553

1, p. 273

Soluble in organic solvents and 2, p. 553 H2O; monomeric, vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Toxic; soluble in organic solvents 2, p. 553; and H2O; monomer in vapor and 1, p. 274 dilute solution (in nonconducting solvents); close to tetrahedral in gas

© 2005 by CRC Press

Dimethyl diiodide tin (CH3)2SnI2

402.57

—

43–44

—

s/—

—

Dioctyldichlorotin 95% (C8H17)2SnCl2

416.04

175/1

46–48

—

s/—

1.15

Dioctyldifluoro tin (C8H15)2SnF2

379.10

—

125–127

—

s/—

—

Dioctyl diiodide tin (C8H15)2SnI2

594.91

225–230/1

—

—

1/—

—

Diphenyldibromo tin (C6H5)2SnBr2

432.71

—

37

—

s/—

—

Diphenyldichlorotin 95% (C6H5)2SnCl2

343.81

—

41–43

333–337 s/— (decomposes)

—

Diphenyldifluoro tin (C6H5)2SnF2

310.90

—

>300

—

s/—

—

Diphenyldiiodo tin (C6H5)2SnI2

526.71

—

72–73

—

s/—

—

Soluble in organic solvents and H2O; monomeric, vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Toxic; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Toxic; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents) Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition

2, p. 553

2, p. 553; 1, p. 274

2, p. 553

2, p. 553

2, p. 553

2, p. 553; 1, p. 275

2, p. 553

2, p. 553

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Dipropyldibromo tin (C3H7)2SnBr2

364.68

—

49

—

s/—

—

Dipropyldichloro tin (C3H7)2SnCl2

275.77

—

81

—

s/—

—

Dipropylfluoro tin (C3H7)2SnF2

242.86

—

262–270

—

s/—

—

Dipropyl diiodide tin (C3H7)2SnI2

458.68

270–273

—

—

1/—

—

Divinyldichlorotin (CH2CH)2SnCl2 Ethyl tribromide tin C2H5SnBr3

243.69

54–56/3

—

—

l/—

1.122

387.46

46/0.1

—

—

1/—

—

Ethyl trichloride tin C2H5SnCl3

254.11

86/12

—

—

1/—

—

Compound

State/Color

Densitya (g/cc)

Miscellaneous Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition —

Reference 2, p. 553

2, p. 553

2, p. 553

2, p. 553

1, p. 275

Soluble in organic solvents; 2, p. 553 monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; 2, p. 553 monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas

© 2005 by CRC Press

Ethyl trifluoride tin C2H5SnF3

204.75

—

269–272

—

s/—

—

Ethyl triiodide tin C2H5SnI3

528.47

181–184.5/19

—

—

1/—

—

Methyl tribromide tin CH3SnBr3

373.44

—

55

—

s/—

—

Methyltrichlorotin CH3SnCl3

240.08

171

43–48

—

s/—

—

Methyl trifluoride tin CH3SnF3

190.72

—

321–327

—

s/—

—

Methyl triiodide tin CH3SnI3

514.44

—

85

—

s/—

—

Phenyl tribromide tin C6H5SnBr3

435.51

182–3/29

—

—

1/—

—

Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents and H2O; distill at low pressure to avoid thermal decomposition; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Toxic; solute in H2O and organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in organic solvents and H2O; monomer in vapor and in dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents and H2O; monomeric, vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition

2, p. 553

2, p. 553

2, p. 553

2, p. 553; 1, p. 276

2, p. 553

2, p. 553

2, p. 553

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Phenyl trifluoride tin C6H5SnF3

252.79

—

~220

—

s/—

—

Phenyl triiodide tin C6H5SnI3

576.51

—

31–32

—

s/—

—

Propyl trichloride tin C3H7SnCl3

268.14

98–99/12

—

—

1/—

—

Propyl trifluoride tin C3H7SnF3

218.77

—

296–299

—

s/—

—

Propyl triiodide tin C3H7SnI3

542.49

200/16 (decomposes)

—

—

1/—

—

Octyltrichlorotin 95% C8H17SnCl3 Phenyltrichlorotin C6H5SnCl3

338.28

150–160/10

—

—

1/—

—

302.16

141–143/25 128/15

—

—

1/—

1.839

2-thienyltri-n-butylin C4H3SSn(C4H9)3 Tin II hexafluoropentanedionate (-OC(CF3)CHC(CF3)O-)2Sn

373.17

155/0.1

—

—

l/—

1.175

532.78

125/2

71–72

—

l/—

—

Compound

State/Color

Densitya (g/cc)

Miscellaneous Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Toxic

Reference 2, p. 553

2, p. 553

2, p. 553

2, p. 553

2, p. 553

1, p. 276

n20 = 1.5851; soluble in organic 2, p. 553; solvents; monomer in vapor and 1, p. 277 dilute solution (in nonconducting solvents); close to tetrahedral in gas n20 = 1.518 1, p. 280 Flash point: 106°C — 1, p. 280

© 2005 by CRC Press

Tribenzylbromo tin (C6H5CH2)3SnBr

471.99

—

125–128

—

s/—

—

Tribenzylchloro tin (C6H5CH2)3SnCl

427.54

—

142–144

—

s/—

—

Tribenzylfluoro tin (C6H5CH2)3SnF

411.09

—

242

—

s/—

—

Tribenzyliodo tin (C6H5CH2)3SnI

518.99

—

102–103

—

s/—

—

Tri-n-butylbromo tin 95% (C4H9)3SnBr

369.95

163/12; 120–122/2

—

—

1/—

1.338

Tri-n-butylchlorotin (C4H9)3SnCl

325.49

171–173/25 152–156/14

—

—

l/—

1.186

Tri-n-butylfluorotin (C4H9)3SnF

309.04

—

248–52

—

s/—

1.28

Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition n20 = 1.5070; toxic; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid decomposition n20 = 1.4905; toxic; flash point: 120ºC; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Toxic; insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas

2, p. 553

2, p. 553

2, p. 553

2, p. 553

2, p. 553; 1, p. 281

2, p. 553; 1, p. 281

2, p. 553; 1, p. 282

© 2005 by CRC Press

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

172/10; 108/0.07

—

—

l/—

1.460

285.79

222–224; 224/760

—

—

l/—

1.630

Triethylchloro tin (C2H5)3SnCl

241.33

210

—

—

l/—

—

Triethylfluoro tin (C2H5)3SnF

224.87

—

302

—

s/—

—

Triethyliodo tin (C2H5)3SnI

332.78

234

—

—

l/—

—

Trimethylbromo tin (CH3)3SnBr

243.70

—

2627

—

s/—

—

Formula Weight

Boiling Point (°C/mmHg)

Tri-n-butyliodotin 95% (C4H9)3SnI

416.94

Triethylbromotin (C2H5)3SnBr

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference

n20 = 1.5300; stabilized with copper powder; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas n20 = 1.5260; flash point: 99ºC; highly toxic; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition

2, p. 553; 1, p. 282

2, p. 553; 1, p. 283

2, p. 553

2, p. 553

2, p. 553

2, p. 553

© 2005 by CRC Press

Trimethylchloro tin (CH3)3SnCl

199.25

154

379

—

s/—

—

Trimethylfluoro tin (CH3)3SnF

182.79

—

375 (decomposes)

—

s/—

—

Trimethyliodo tin (CH3)3SnI

290.70

6768/15

—

—

l/—

—

Tri-n-octylchlorotin (CH3(CH2)6CH2)3SnCl Tri-n-pentylchlorotin (CH3(CH2)3CH2)3SnCl Triphenylbromo tin (C6H5)3SnBr

493.82

—

—

—

—/—

1.041

Flash point: 97°C; toxic; soluble in organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents and H2O; monomeric in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition n20 = 1.478

367.57

120/0.25

—

—

—/—

1.137

n20 = 1.4860

1, p. 283

429.91

—

124–125

—

s/—

—

2, p. 553

Triphenylchlorotin 95% (C6H5)3SnCl

385.46

244/13.5

106; 105

—

s/—

—

Triphenylfluorotin 95% (C6H5)3SnF

368.99

—

—

357 s/— (decomposes)

—

Triphenyliodo tin (C6H5)3SnI

476.91

—

122124

Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Flash point: 70°C; toxic; soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Toxic; insoluble in most organic solvents and H2O; monomer in vapor and in dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition

—

s/—

—

2, p. 553; 1, p. 283

2, p. 553

2, p. 553

1, p. 283

2, p. 553; 1, p. 284

2, p. 553; 1, p. 284

2, p. 553

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Tripropylbromo tin (C3H7)3SnBr

327.86

126127/12

—

—

l/—

—

Tripropylchloro tin (C3H7)3SnCl

283.41

98100/4

—

—

l/—

—

Tripropylfluoro tin (C3H7)3SnF

266.95

—

275

—

s/—

—

Tripropyliodo tin (C3H7)3SnI

374.86

147148/20

—

—

l/—

—

268.91

—

—

s/—

294.99

136139/1.2

220225 (decomposes) —

—

351.10

99100/0.1

—

321.03

—

291.00 292.97

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Insoluble in most organic solvents and H2O; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas Soluble in organic solvents; monomer in vapor and dilute solution (in nonconducting solvents); close to tetrahedral in gas; distill at low pressure to avoid thermal decomposition

2, p. 553

—

—

2, p. 579

l/—

1.286

n20 = 1.4854; flash point: 110°C

1, p. 272

—

l/—

—

—

2, p. 579

124126

—

s/—

—

—

2, p. 579

—

220224

—

s/—

—

—

2, p. 579

—

223226.5

—

s/—

—

—

2, p. 579

2, p. 553

2, p. 553

2, p. 553

VII. Tin Alkyl Alkoxides Butyl trimethoxy tin C4H9Sn(OCH3)3 Di-n-butyldimethoxytin (C4H9)2Sn(OCH3)2 Dibutyldipropoxy tin (C4H9)2Sn(OC3H7)2 Dibutyl tin(2-methyl, 3-methylbutanedionato) (C4H9)2Sn(OCH(CH3)CH(CH3)O) Dibutyl tin propoxide (C4H9)2SnOCH2CH2CH2 Dibutyl tin butanedianato (C4H9)2Sn(OCH2CH2O)

© 2005 by CRC Press

Dimethyl dimethoxy tin (CH3)2Sn(OCH3)2 Ethyl trimethoxy tin C2H5Sn(OCH3)3 Tri-n-butylethoxytin (C4H9)3SnOC2H5 Tri-n-butylmethoxytin (C4H9)3SnOCH3

210.83

—

8687

—

s/—

—

—

2, p. 579

240.85

—

—

s/—

—

—

2, p. 579

335.10

92/0.1

230235 (decomposes) —

—

l/—

1.098

n20 = 1.4672; flash point: 40°C

1, p. 281

321.07

97/0.06

—

—

l/—

1.169

n20 = 1.4745; flash point: 98°C; sensitive to moisture, CO2

Tributyl pentoxy tin (C4H9)3SnOCH2C(CH3)3 Triethyl ethoxy tin (C2H5)3SnOC2H5 Trimethyl methoxy tin (CH3)3SnOCH3 Trimethyl phenoxy tin (CH3)3SnOC6H5 Trioctyl benzoxy tin (C8H15)3SnOCH2C6H5 Triphenyl ethoxy tin (C6H5)3SnOC2H5

377.18

122/0.3

—

—

l/—

—

—

2, p. 577, 579; 1, p. 282 2, p. 579

250.94

8284/11

—

—

l/—

—

—

2, p. 579

194.83

—

75

—

s/—

—

—

2, p. 579

256.90

109/8

—

—

l/—

—

—

2, p. 579

538.28

225/0.2

—

—

l/—

—

—

2, p. 579

395.07

—

112

—

s/—

—

—

2, p. 579

439.47

112/0.05

37–38

—

s/—

1.136

1, p. 266

369.07

—

77

—

s/—

—

n20 = 1.5140 Flash point: 56°C —

316.96

—

4448

—

s/—

—

—

2, p. 554

349.08

—

144145

—

s/—

—

—

2, p. 554

292.97

—

188.5190

—

s/—

—

—

2, p. 554

334.11

86/0.1

—

—

l/—

—

207.87

126

—

—

l/—

1.274

264.92

—

194196

—

s/—

457.26

—

106107

—

s/—

VIII. Organotin Nitrogen Compounds Bis[bis(bistTrimethylsilyl)amino]tin II Sn(N(Si(CH3)3)2) 2 Butylphenyltin diisothiocyanide C4H9(C6H5)Sn(NCS)2 Dibutyltin diisocyanide (C4H9)2Sn(NCO)2 Dibutyltin diisothiocyanide (C4H9)2Sn(NCS)2 Diethyltin diisothiocyanide (C2H5)2Sn(NCS)2 Dimethylaminotri-n-butyltin (CH3)2NSn(C4H9)3 Dimethylaminotrimethyltin (CH3)2NSn(CH3)3 Dimethyltin diisothiocyanide (CH3)2(NCS)2 Dioctyltin diisothiocyanide (C8H15)2Sn(NCS)2

2, p. 554

n20 = 1.4737

1, p. 273 1, p. 273

—

n20 = 1.4630 Flash point: 1°C —

—

—

2, p. 554

2, p. 554

© 2005 by CRC Press

Compound Diphenyltin diisothiocyanide (C6H5)2Sn(NCS)2 Dipropyltin diisothiocyanide (C3H7)2Sn(NCS)2 Tetrakis(diethylamino)tin ((C2H5)2N)4Sn Tetrakis(dimethylamino)tin ((CH3)2N)4Sn Tri-n-butylcyanotin (C4H9)3SnCN Tributyl stannyl (dimethyl) amine (C4H9)3SnN(CH3)2 Tributyl stannyl (phenyl) amine (C4H9)3SnNHC6H5 Tributyltin thiocyanide (C4H9)3SnNCS Triethyl stannyl (dimethyl) amine (C2H5)3SnN(C2H5)2 Triethyltin thiocyanide (C2H5)3SnNCS Trimethyl azide (CH3)3SnN3 Trimethyltin thiocyanide (CH3)3SnNCS Trimethyl tin (dimethyl) amine (CH3)3SnN(CH3)2 Triphenyl stannyl (phenyl) amine (C6H5)3SnNHC6H5 Triphenyl tin azide (C6H5)3SnN3 Triphenyltin thiocyanide (C6H5)3SnNCS Tripropyltin thiocyanide (C3H7)3SnNCS

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

389.06

—

176177

-

321.02

—

135136

407.20

90/0.05

294.99

Densitya (g/cc)

Miscellaneous

s/—

—

—

2, p. 554

—

s/—

—

—

2, p. 554

—

—

l/—

1.104

53–55/0.1

—

—

l/—

1.169

316.06

—

105–107

—

s/—

—

334.11

86/0.1

—

—

l/—

—

—

2, p. 599

382.16

—

—

s/—

—

—

2, p. 599

348.11

155/0.4

140 (decomposes) —

—

l/—

—

—

2, p. 554

278.01

72/2

—

—

l/—

—

—

2, p. 599

263.95

—

33

—

s/—

—

—

2, p. 554

205.81

—

119121.5

—

s/—

—

—

2, p. 554

221.87

—

104106

—

s/—

—

—

2, p. 554

207.87

126

—

—

l/—

—

—

2, p. 599

442.13

—

9596

—

s/—

—

—

2, p. 599

392.03

—

115116

—

s/—

—

—

2, p. 554

408.08

—

172173

—

s/—

—

—

2, p. 554

306.03

1268/0.2

—

—

l/—

—

—

2, p. 554

State/Color

n20 = 1.4800

Reference

1, p. 278 —

Toxic

1, p. 278 1, p. 281

© 2005 by CRC Press

IX. Organotin Carboxylates Acryloxytri-n-butylin (C4H9)3SnOOCCHCH2 Bis(neodecanoate)tin C6H13C(CH3)2COO)2Sn Butyl tin triacetate C4H9Sn(OOCCH3)3 Dibutyl tin diacetate (C4H9)2Sn(OOCCH3)2 Ethyl tin tribenzoate C2H5Sn(OOCC6H5)3 Methacryloxytri-n-butyltin CH2CHC(CH3)COOSn(nC4H9) Phenyl tin tripropionate C6H5Sn(OOCC2H5)3 Tributyl tin acetate (C4H9)3SnOCOCCH3 Tributyl tin benzoate (C4H9)3SnOOCC6H5 Tributyl tin formate (C4H9)3SnOOCH Triethyl tin acetate (C2H5)3SnOOCCH3 Trimethyl tin acetate (CH3)3SnOOCCH3

361.09

—

69–70

—

s/—

—

—

1, p. 265

461.23

—

—

—

—/—

1.16

—

1, p. 266

352.94

—

46

—

s/—

—

—

2, p. 565

351.01

144.5145.5/10

—

—

l/—

—

—

2, p. 565

511.10

—

67.5

—

s/—

—

—

2, p. 565

375.17

—

17–20

—

s/—

1.565

415.01

—

76

—

s/—

—

349.08

—

85

—

s/—

—

—

2, p. 565

411.15

166168/1

—

—

l/—

—

—

2, p. 565

335.05

120125/0.7

—

—

l/—

—

264.92

—

134–135

—

s/—

—

222.84

—

196.5197.5

—

s/—

—

Trimethyl tin formate (CH3)3SnOOCH

208.81

—

146

—

Crystalline solid/white

—

Triphenyl tin acetate (C6H5)3SnOOCCH3 Triphenyl tin benzoate (C6H5)3SnOOCC6H5 Tripropyl tin acetate (C3H7)3SnOOCCH3

409.05

—

121–122

—

s/—

—

471.12

—

84–85.5

—

s/—

—

307.00

—

99100

—

s/—

—

354.06

156157/1

—

—

l/—

—

n20 = 1.4811; soluble in hydrocarbons —

1, p. 276 2, p. 565

Soluble in organic solvents polymeric Soluble in organic solvents

2, p. 565

Low solubility in organic solvents; polymeric; soluble in cyclohexane at 90°C Soluble in CHCl3 and cyclohexane; sp soluble in CCl4; low solubility in organic solvents Relatively more soluble than alkyl analogues Relatively more soluble than alkyl analogues Relatively more soluble than alkyl analogues

2, p. 565

2, p. 565

2, p. 565; 8, p. 2167 2, p. 565 2, p. 565 2, p. 565

X. Organotin Nitrates Tributyl tin nitrate (C4H9)3SnNO3

—

2, p. 569

© 2005 by CRC Press

Compound Trimethyl tin nitrate (CH3)3SnNO3 Triphenyl tin nitrate (C6H5)3SnNO3

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

225.80

—

140

—

s/—

—

412.01

—

184186

—

s/—

—

—

2, p. 569

416.82

—

—

—

—/—

—

—

1, p. 281

439.11

156–157/0.08

31–34

—

s/—

—

320.96

—

6769

—

s/—

—

—

2, p. 571

242.89

—

112

—

s/—

—

—

2, p. 571

491.17

—

228229

—

s/—

—

—

2, p. 571

507.17

—

254256

—

s/—

—

—

2, p. 571

262.95

9899/5

—

—

l/—

—

—

2, p. 581

220.87

8486/25

—

—

l/—

—

—

2, p. 581

282.94

8989.5/1.5

—

—

l/—

—

—

2, p. 581

305.03

105106/2

—

—

l/—

—

—

2, p. 581

291.00

—

—

—

—/—

—

—

2, p. 581

178.83

98100

—

—

l/—

—

State/Color

Densitya (g/cc)

Miscellaneous Deliquescent

Reference 2, p. 569

XI. Organotin Sulphonates/Sulphites Tin II trifluoromethanesulphonate (CF3SO3)2Sn Tri-n-butyl(trifluoromethanesulphonate)tin CF3SO3Sn(C4H9)3 Trimethyl tin (phenyl) sulphonate (CH3)3SnOSO2(C6H5) Trimethyl tin (methyl) sulphite (CH3)3SnOSOCH3 Triphenyl tin (phenyl) sulphite (C6H5)3SnOSOC6H5 Triphenyl tin (phenyl) sulphonate (C6H5)3SnOSO3(C6H5)

Flash point: >110°C

1, p. 283

XII. Organotin Enolates Triethyl tin (1-methylvinyloxide) (C2H5)3SnOC(CH3) = CH2 Trimethyl tin (1-methylvinyloxide) (CH3)3SnOC(CH3) = CH2 Trimethyl tin (1-phenylvinyloxide) (CH3)3SnOC(C6H5) = CH2 Tripropyl tin (1-methylvinyloxide) (C3H7)3SnOC(CH3) = CH2 Tripropyl tin vinyloxide (C3H7)3SnOCH = CH2 XIII. Organotin Hydrides Butyl tin trihydride C4H9SnH3

Monomeric in solution; less 2, p. 586 stable compared with mono and dihydrides

© 2005 by CRC Press

Dibutyl tin chlorohydride (C4H9)2SnClH Dibutyl tin dihydride (C4H9)2SnH2 Dimethyl tin hydride (CH3)2SnH2 Diphenyl tin bromohydride (C6H5)2SnBrH Diphenyl tin hydride (C6H5)2SnH2 Ethyl tin bromodihydride C2H5SnH2Br Methyl tin dihydride CH3SnH2 Phenyl tin bromodihydride C6H5SnH2Br Phenyl tin trihydride C6H5SnH3

269.38

—

35 to 33

—

—/—

—

234.94

70/12

—

—

1/—

—

Monomeric in solution

2, p. 586

150.78

35

—

—

l/—

—

Monomeric in solution

2, p. 586

353.81

—

—

—

s/white

—

Stable only at 78°C

274.92

8993/0.3

—

—

l/—

—

Monomeric in solution

2, p. 586; 8, p. 2188 2, p. 586

229.67

—

—

s/—

—

135.74

014

~65 (decomposes) —

—

l/—

—

277.72

—

—

s/—

—

—

2, p. 586

198.82

5764/106

~65 (decomposes) —

—

l/—

—

2, p. 586

Tri-n-butyltin hydride (C4H9)3SnH Triethyl tin hydride (C2H5)3SnH Trimethyl tin hydride (CH3)3SnH Trioctyl tin hydride (C8H15)3SnH Triphenyl tin hydride (C6H5)3SnH

291.05

—

—

l/—

1.082

206.88

80/0.4; 7681/ 0.7 39/12; 148150

—

—

l/—

—

Monomeric in solution; less stable compared to mono- and dihydrides n20 = 1.4731; flash point: 40°C; monomeric in solution Monomeric in solution

164.80

59

—

—

l/—

—

Monomeric in solution

2, p. 586

453.32

164166/103

—

—

l/—

—

Monomeric in solution

2, p. 586

3351.01

165/0.3; 157/ 0.15

2628

—

l/—

1.374

n20 = 1.632; sensitive to air and light; monomeric in solution

248.96

7678/12

—

—

l/—

—

Monomeric in solution

2, p. 586; 1, p. 284; 8, p. 220 2, p. 586

612.13

208/1

—

—

l/—

—

Not readily hydrolyzed

2, p. 605

443.81

127129/1.5

—

—

l/—

—

Not readily hydrolyzed

2, p. 605

732.07

—

144144.5

—

s/—

—

Tripropyl tin hydride (C3H7)3SnH

—

— Monomeric in solution

2, p. 586

2, p. 586 2, p. 586

2, p. 586; 1, p. 282 2, p. 586

XIV. Organotin Sulfides Bis(tributyltin) sulfide ((C4H9)3Sn)2S Bis(triethyltin) sulfide ((C2H5)3Sn)2S Bis(triphenyltin) sulfide ((C6H5)3Sn)2S

—

2, p. 605

© 2005 by CRC Press

Compound Dibutyl tin bis(methylthiolate) (C4H9)2Sn(SCH3)2 Dimethyl tin bis(methylthiolate) (CH3)2Sn(SCH3)2 Ethyl tin tris(methylthiolate) C2H5Sn(SCH3)3 Methyl tin tris(ethylthiolate) CH3Sn(SC2H5)3 Trimethyl tin methylthiolate (CH3)3SnSCH3 Trimethyl tin isopropylthiolate (CH3)3SnSi-C3H7 Triphenyl tin phenylthiolate (C6H5)3SnSC6H5

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

327.11

81/0.1

—

—

l/—

242.95

44/0.05

—

—

1/colorless

1.547

nD20 = 1.6003

289.04

66/0.001

—

—

l/—

1.548

nD20 = 1.6232

317.09

90/0.05

—

—

l/—

1.469

nD20 = 1.5972

211.77

163

—

—

l/—

1.43

nD20 = 1.5303

305.72

2425/0.01

—

—

l/—

—

522.73

—

9899.5

—

s/colorless (in water)

—

375.17

—

17–20

—

s/—

226.88

160–163

—

—

427.54

—

142–144

403.60

—

367.02

—

State/Color

Densitya (g/cc)

Miscellaneous

—

—

2, p. 605

—

2, p. 605; 8, p. 2169 2, p. 605; 8, p. 2171 2, p. 605; 8, p. 2177 2, p. 605; 8, p. 2168 2, p. 605

Reference

Soluble in organic solvents

2, p. 605; 8, p. 2207

1.565

n20 = 1.4811

1, p. 276

l/—

1.257

1, p. 280

—

s/—

—

n20 = 1.4914 Flash point: 40°C Soluble in ethyl acetate

129–130

—

s/—

—

128

—

s/—

—

—/—

1.08

XV. Miscellaneous Tin Compounds Methacryloxytri-n-butyltin H2CC(CH3)COOSn(C4H9)3 Soluble in hydrocarbonsTetravinyltin Sn(CHCH2)4 Tribenzylchlorotin (C6H5CH2)3SnCl Tricyclohexychlorotin (C6H11)3SnCl Triphenylhydroxytin (C6H5)3SnOH

Soluble in ethanol, ether, toluene, chloroform Toxic; soluble in warm THF

1, p. 281 1, p. 283 1, p. 284

Titanium Compounds I. Titanium Alkoxides and Diketonates O-Allyloxy(polyethyleneoxy)triisopropoxytitanate (iC3H7O)3Ti-(OCH2CH2)10CH2CHCH2

660–780

—

—

—

—

1, p. 289

© 2005 by CRC Press

(2-Methacryloxyethoxy)triisopropoxytitanate (CH2C(CH3)COOCH2CH2O-)Ti (OiC3H7)3 Methyltitanium triisopropoxide (iC3H7O)3TiCH3 Titanium allylacetoacetatetriisopropoxide (iC3H7O)3Ti (-OC(OCH2CHCH2)CHC(CH3)O-) Titanium bis(triethanolamine)diisopropoxide 80% in isopropanol (OiC3H7)2Ti-(N (CH2CH2OH)3)2 (mixed chelates) Titanium isobutoxide Tetraisobutyl titanate Ti(OiC4H9)4 Titanium n-Butoxide Tetrabutyltitanate (nC4H9)4Ti Titanium di-n-butoxide (Bis-2,4-pentanedionate) (-OC(CH3)CHC(CH3)O-)2 Ti(OnC4H9)2 Titanium 1,2-dimethyl propoxide(titanium pentoxide) Ti(OCH(CH3)CH(CH3)2)4 Titanium 1,1-dimethyl propoxide(titanium pentoxide) Ti(OC(CH3)2C2H5)4 Titanium 2,2-dimethylpropoxide (titanium pentoxide) Ti(OCH2C(CH3)2CH3)4 Titanium iisopropoxide bis(Ethylacetoacetate) (C3H7O)2Ti (OC(OC2H5)CH (CH3)CO)2

354.29

—

—

—

—/—

1.05

—

1, p. 292

240.18

50–52/0.02

10

—

l/—

—

—

1, p. 289

358.25

—

—

—

—/—

1.06

—

1, p. 289

462.42

—

—

—

—/—

1.065

n20 = 1.488; flash point: 12°C; 1, p. 289 viscosity at 25°C: 90 cSt; soluble in H2O and isopropanol

340.36

141/1

—

—

l/—

1.02

n20= 1.495; )Hform = 403 kcal/mol

340.36

142.7/5 135/1 98/0.1

40

—

l/—

0.998

392.32

—

—

—

—/—

1.085

Flash point: 76°C; toxic; viscosity 1, p. 290; at 25°C: 67 cSt; dipole moment: 4, p. 47, 1.68; )Hform = 399 63 kcal/mol; n20 = 1.493; degree of polymerization: 1 Flash point: >110°C 1, p. 290 Viscosity (25°): 3545 cSt

396.45

131/0.5

—

—

l/—

—

Degree of polymerization: 1.0

4, p. 47, 63

396.45

98/0.1; 142.7/5

—

—

l/—

—

Degree of polymerization: 1.0

4, p. 47, 63

396.45

105/0.05

—

—

l/—

—

Degree of polymerization: 1.3

4, p. 47, 63

452.02

—

—

—

—/—

1.05

Toxic; viscosity at 25°C: 4555 cSt; flash point: 27°C

1, p. 290

1, p. 291

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Titanium diisopropoxide bis (Tetramethylheptanedionate) (-OC(C(CH3)3)CHC(C(CH3)3)CO-)2 Ti(OiC3H7)2 Titanium diisopropoxy (bis-2,4pentanedionate) 75% in isopropanol (C3H7O)2Ti (OC(CH3)CH(CH3)CO)2 Titanium ethoxide Ti(OC2H5)4

532.60

150/0.1

170–177

—

364.26

—

—

228.14

122/1; 103/0.1

Titanium 2-ethylhexoxide Tetraoctyltitanate Ti[OCH2CH(C2H5)C4H9]4 Titanium 1-ethylpropoxide (titanium pentoxide) Ti(OCH(C2H5)2)4 Titanium lactate (CH3CH(OH)COO)2Ti Titanium methoxide 95% Tetramethyl titanate Ti(OCH3)4 Titanium methacrylate triisopropoxide CH2C(CH3)COO-Ti(OiC3H7)3 Titanium methacryloxyethylacetoacetate triisopropoxide (-OC(OCH2CH2OOCC(CH3)CH2) CH(CH3)CO-)Ti(OiC3H7)3 Titanium methoxypropoxide 95% Tetramethoxypropyl titanate Ti(OCH(CH3)CH2OCH3)4 Titanium 3-methylbutoxide (titanium pentoxide) Ti(O(CH2)2CH(CH3)2)4

564.79

Compound

Densitya (g/cc)

Miscellaneous

s/—

—

—

—

—/—

0.992

n20 = 1.4935; flash point: 12°C; viscosity at 25°C: 11 cSt

—

—

l/—

1.107

194/0.25

—

—

l/—

0.937

n20 = 1.5043; flash point: 28°C; 1, p. 291; 4, p. 45, molecular complexity: 2.4; 63 surface tension at 25°C: 23.1 dyn/cm; degree of polymerization: 2.4; viscosity at 25°C: 40 cSt; )Hvap = 21.6 kcal/ mol; )Hform = 349 kcal/mol Viscosity at 25°C: 120130 cSt; 1, p. 291 flash point: 60°C; n20 = 1.482

396.45

112/0.05

—

—

l/—

—

404.16

—

—

—

—/—

1.27

172.04

—

210

170/0.01

s/—

302.18

—

—

—

438.38

—

—

404.35

136/0.12

396.45

148/0.1

State/Color

Reference 1, p. 290

1, p. 290

Degree of polymerization: 1.0

4, p. 47, 63

n20 = 1.475

1, p. 292

—

Flash point: 10°C

1, p. 292

—/—

—

—

1, p. 292

—

—/—

—

—

1, p. 292

—

—

l/—

1.10

—

1, p. 292

—

—

l/—

—

Degree of polymerization: 1.2

4, p. 47, 63

© 2005 by CRC Press

Titanium 1-methylbutoxide (titanium pentoxide) Ti(OCH(CH3)C3H7n ) 4 Titanium 2-methylbutoxide (titanium pentoxide) Ti(OCH2CH(CH3)C2H5)4 Titanium methylphenoxide 95% Tetramethylphenyl titanate Ti(O2CH3C6H4)4 Titanium n-nonoxide 95% Tetranonyl titanate Ti(OnC9H19)4 Titanium oxide bis-(pentanedionate) (-OC(CH3)CH(CH3)CO-)2TiO Titanium oxide bis(tetramethylheptanedionate) (-OC(C(CH3)3)CHC(CH3)3C) CO-)2TiO Titanium n-pentoxide Tetrapentyl titanate Ti(O(CH2)4CH3)4 Titanium isopropoxide Tetraisopropyl titanate Ti(iOC3H7)4 Titanium n-propoxide Tetra-n-propyl titanate Ti(nOC3H7)4 Titanium sec-propoxide Tetra-s-propyl titanate Ti(OCH(CH3)2)4 Titanium stearyloxide Ti(OC18H37)4 Titanium tetrakis (bis 2,2-(Allyloxymethyl)butoxide) Ti(OCH2C(CH2OCH2CHCH2)2 CH2CH3)4 Titanium triisostearoylisopropoxide (iC3H7O)Ti(OiC18H37)3 Titanium trimethacrylate mMethoxyethoxyethoxide (CH2C(CH3)COO-)3 TiOCH2CH2OCH2CH2OCH3

396.45

135/1.0

—

—

l/—

—

Degree of polymerization: 1.0

4, p. 47, 63

396.45

154/0.5

—

—

l/—

—

Degree of polymerization: 1.1

4, p. 47, 63

476.40

—

—

—

—/—

1.055

Flash point: 40°C

1, p. 292

620.85

226/1

—

—

l/—

0.93

n20 = 1.486; flash point: 60°C

1, p. 292

262.12

—

184

—

s/—

—

—

1, p. 292

430.42

—

120

—

s/—

—

—

1, p. 293

396.45

175/0.8

—

—

l/—

—

284.25

58/1

1519

—

—/—

0.937

284.25

137/5

—

—

l/—

0.955

284.25

49/0.1

—

—

l/—

—

1125.84

—

55–60

—

s/—

0.91

—

1, p. 293

901.06

—

—

—

—/—

1.08

—

1, p. 293

957.37

—

—

—

l/—

0.95

Flash point: 93°C; n20 = 1.481

1, p. 293

422.28

—

—

—

—/amberred

1.11

Flash point: 49°C Miscible in toluene, isopropanol

1, p. 293

Degree of polymerization: 1.4

4, p. 47, 63

n20 = 1.4654; flash point: 25°C; 1, p. 291 molecular complexity: 1.4; toxic; )Hvap = 14.7 kcal/mol; )Hform = 377 kcal/mol Viscosity at 25°C: 150165 cSt; 1, p. 293 surface tension: 25.4 dyn/cm; n20 = 1.498 Degree of polymerization: 1.4 4, p. 63

© 2005 by CRC Press

Compound Titanium tris(dioctylphosphato)isopropoxide ((C8H17O)2PO2-)3TiOiC3H7 Titanium tris(dodecylbenzenesulfonate) isopropoxide (C12H23(C6H4)SO3-)3TiOiC3H7

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

1191.33

—

—

—

l/amber

1.04

Flash point: 63°C

1, p. 294

1077.40

—

—

—

—/dark amber

1.08

Viscosity: 8000 cSt

1, p. 294

346.35

70/5° 10–3

—

—

Liquid oil/ yellow

—

—

2, p. 340

332.32

—

—

—

—

2, p. 340

332.32

102/1

—

124.5125.5/ l/yellow 0.5 (decomposes) — l/colorless

—

—

2, p. 340

521.50

—

—

—

—/yellow

—

248.16

106107/3

—

—

l/colorless

—

413.46

177181/1

—

—

l/pale yellow

—

—

2, p. 340

206.08

88/1.5

5012

—

s/white

—

—

2, p. 340

495.63

—

—

—

s/yellow

—

446.26

—

—

—

s/yelloworange

—

434.37

—

6566

—

s/yellow

—

476.45

—

6465

—

Solid crystals/ yellow

—

State/Color

Densitya (g/cc)

Miscellaneous

Reference

II. Titanium Alkyl/Aryl Alkoxides and Aryloxides tert-butylcyclopentadienyl titanium triisopropoxide (Ti(OiC3H7)3(M-C5H4C(CH3)3) Cyclopentadienyl titanium tri-n-butoxide (Ti(OC4H9n)3C5H5) Cyclopentadienyl titanium tri-tertbutoxide (Ti(OC4H9t)3C5H5) Cyclopentadienyl titaniumtri(4dimethylamino)phenoxide (Ti(OC6H4N(CH3)24)3C5H5) Cyclopentadienyl titanium triethoxide (Ti(OC2H5)3C5H5 Cyclopentadienyl titaniumtri-n-hexoxide (Ti(On-C6H13)3C5H5 Cyclopentadienyl titanium trimethoxide Ti(OCH3)3C5H5 Cyclopentadienyl titanium tri(4chloro)phenoxide Ti(OC6H4Cl-4)3C5H5 Cyclopentadienyl titanium tri(4fluoro)phenoxide Ti(OC6H4F-4)3C5H5 Cyclopentadienyl titanium tri(3methyl)phenoxide Ti(OC6H4CH3-3)3C5H5 Cyclopentadienyl titanium di(2,4methyl)phenoxide Ti(OC6H3(CH3)2-2,4)3C5H5

Characterized by nuclear magnetic resonance and infrared spectroscopies —

Characterized by nuclear magnetic resonance and infrared spectroscopies Characterized by nuclear magnetic resonance and infrared spectroscopies —

—

2, p. 340

2, p. 340

2, p. 340

2, p. 340

2, p. 340

2, p. 340

© 2005 by CRC Press

Cyclopentadienyl titanium di(3,5methyl)phenoxide Ti(OC6H3(CH3)2-3,5)3C5H5) Cyclopentadienyl titanium tri(4methyl)phenoxide Ti(OC6H4CH3-4)3C5H5 Cyclopentadienyl titanium tri(3nitro)phenoxide Ti(OC6H4NO2-3)3C5H5 Cyclopentadienyl titanium tri(4nitro)phenoxide Ti(OC6H4NO2-4)3C5H5 Cyclopentadienyl titanium triphenoxide Ti(OC6H5)3C5H5

476.45

—

8081

—

s/yellow

—

—

2, p. 340

434.37

—

—

—

—/yellow

—

527.28

—

—

—

s/yellow

—

527.28

—

—

—

s/yellow

—

392.29

—

102104

—

s/yellow

—

Cyclopentadienyl titanium tri-npropoxide (Ti(OC3H7n)3C5H5 Cyclopentadienyl titanium triisopropoxide Ti(OC3H7i)3C5H5 Cyclopentadienyl titanium tri(trifluoromethylethoxide) Ti(OCH2CF3)3C5H5 Ethyl cyclopentadienyl titanium triethoxide Ti(OC2H5)3(M-C5H4C2H5) Methyl cyclopentadienyl titanium triethoxide Ti(OC2H5)3(h-C5H4CH3) Methyl cyclopentadienyl titanium triisopropoxide Ti(OC3H7i)3(h-C5H4CH3) Pentamethyl cyclopentadienyl titanium triethoxide Ti(OC2H5)3(h-C5(CH3)5) Pentamethyl cyclopentadienyl titanium triphenoxide Ti(OC6H5)3(h-C5(CH3)5) Titanium methyl triethoxide TiCH3(OC2H5)3 Titanium methyl triisopropoxide TiCH3(O(C3H7)i)3

290.24

106107/0.51

—

—

l/colorless

—

290.24

8082/0.5

—

—

l/colorless

—

—

2, p. 340

410.07

72/0.01

—

—

l/yellow

—

—

2, p. 340

276.21

101102/2

—

—

l/—

—

—

2, p. 341

262.18

8081/1

—

—

l/—

—

—

2, p. 340

304.27

56/103

—

—

Liquid oil/ yellow

—

—

2, p. 340

318.29

115117/1

—

—

l/yellow

—

—

2, p. 341

430.43

214216/1

—

—

l/—

—

—

2, p. 341

198.10

—

—

—

l/dark red

—

Soluble in benzene

2, p. 447

240.18

102(50/0.01)

—

—

l/yellow

—

Soluble in benzene

2, p. 447

Characterized by nuclear magnetic resonance and infrared spectroscopies Characterized by infrared spectroscopies

2, p. 340

Characterized by nuclear magnetic resonance and infrared spectroscopies Characterized by nuclear magnetic resonance and infrared spectroscopies —

2, p. 340

2, p. 340

2, p. 340; 8, p. 2266 2, p. 340

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Titanium phenyl triisobutoxide TiC6H5(OC4H9i)3 Titanium phenyl triisopropoxide TiC6H5(OC3H7i)3

344.33

—

—

—

—/—

—

302.25

—

8890

—

—

Titanium pentafluorophenyl triisopropoxide Ti(C6F5)(OC3H7i)3 Titanium 4-toulyl tributoxide Ti(C6H4CH3–4)(OC4H9)3

392.20

—

133135

—

Solid crystal/ white or light yellow s/white

—

358.36

—

—

—

—/—

—

257.00

—

—

—

Crystals/ yellow

—

—

2, p. 343

339.11

136145/0.8

—

—

l/yellow

—

—

2, p. 343

283.00

118119/1

—

—

l/—

—

—

2, p. 343

238.55

109111/1

—

—

l/—

—

—

2, p. 343

222.10

—

—

—

—/—

—

305.04

—

114116

—

s/yellow

—

—

2, p. 343

424.63

—

—

2124 s/yellow (decomposes)

—

—

2, p. 343

334.64

—

3942

—

—

2, p. 343

Compound

State/Color

Densitya (g/cc)

Miscellaneous Could be only isolated as an impure compound —

—

Obtained as a solution only

Reference 2, p. 447 2, p. 447

2, p. 447

2, p. 447

III. Alkoxides and Related Complexes of Titanium Cyclopentadienyl tert-butoxy titanium dichloride TiCl2(OC4H9i)C5H5 Cyclopentadienyl dibutoxy titanium bromide (TiBr(OC4H9)2C5H5 Cyclopentadienyl diethoxy titanium bromide TiBr(OC2H5)2C5H5 Cyclopentadienyl diethoxy titanium chloride TiCl(OC2H5)2C5H5 Cyclopentadienyl diethoxy titanium fluoride TiF(OC2H5)2C5H5 Cyclopentadienyl (2,6 dimethyl) phenoxy titanium dichloride TiCl2(OC6H3(CH3)2-2,6)C5H5 Cyclopentadienyl di(4-nitro) phenoxy titanium chloride TiCl(OC6H4NO2-4)2C5H5 Cyclopentadienyl diphenoxy titanium chloride (TiCl(OC6H5)2C5H5)

—

s/orange

Characterized by infrared spectroscopy

2, p. 343

© 2005 by CRC Press

Cyclopentadienyl di-n-propoxy titanium chloride TiCl(OC3H7n)2C5H5 Cyclopentadienyl diisopropoxy titanium chloride (TiCl(OC3H7i)2C5H5) Cyclopentadienyl ethoxy titanium dibromide (TiBr2(OC2H5)C5H5) Cyclopentadienyl ethoxy titanium dichloride (TiCl2(OC2H5)C5H5 Cyclopentadienyl ethoxy titanium difluoride TiF2(OC2H5)C5H5 Cyclopentadienyl methoxy titanium dichloride (TiCl2(OCH3)C5H5 Cyclopentadienyl isopropoxy titanium dichloride TiCl2(OC3H7i)C5H5 Cyclopentadienyl (2,4,6-trimethyl) phenoxy titanium dichloride TiCl2(OC6H2(CH3)3-2,4,6)C5H5 Methyl cyclopentadienyl diethoxy titanium chloride TiCl(OC2H5)2(h-C5H4CH3) Pentamethyl cyclopentadienyl diethoxy titanium chloride TiCl(OC2H5)2(C5(CH3)5) Pentamethyl cyclopentadienyl ethoxy titanium dichloride TiCl2(OC2H5)(C2(CH3)5) Pentamethyl cyclopentadienyl titanium trichloride (CH3)5C5TiCl3 Pentamethylcyclopentadienyltitanium trimethoxide (CH3)5C5Ti(OCH3)3 Titanium chloride triisopropoxide (-OiC3H7O)3TiCl Titanium dichloride diethoxide (C2H5O)2TiCl2

266.60

—

—

132145/1 Liquid oil/ (decomposes) yellowgreen — l/—

—

—

2, p. 343

266.60

8284/0.5

—

—

—

2, p. 343

317.84

—

5053

—

s/—

—

—

2, p. 343

228.94

—

4849

—

s/yellow

—

—

2, p. 343

196.03

120123/1

—

—

l/—

—

—

2, p. 343

214.91

—

93–96

—

—

—

2, p. 343

242.97

—

113114

—

Solid crystal/ yellow —/—

—

—

2, p. 343

319.07

—

107108

—

s/yelloworange

—

—

2, p. 343

252.58

143145/2

—

—

l/—

—

—

2, p. 344

308.68

125/2

—

—

l/—

—

—

2, p. 344

263.04

—

4647

—

s/—

—

—

2, p. 344

289.47

—

225

—

s/—

—

—

1, p. 289

276.21

285

—

—

l/yellow

1.081

n20 = 1.5540 Flash point: 61°C

1, p. 289

260.62

63–66/0.1

34–36

—

s/—

1.091

Flash point: 22°C

1, p. 290

208.91

142/18

40–50

—

s/—

—

—

1, p. 290

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

352.07

—

—

—

—/—

1.04

Flash point: 22°C

1, p. 290

249.00

—

288–289

—

s/—

1.600

—

1, p. 294

Biscyclopentadienyl titanium di(trifluoro acetate) Ti(O2CCF3)2(C5H5)2 Cyclopentadienyl titanium triacetate Ti(OCOCH3)3C5H5

404.10

—

175179

—

s/—

—

Prepared from aqueous solution 2, p. 378

290.11

—

115117

—

s/orange

—

Cyclopentadienyl titanium tri(phenyl acetate) Ti(OCOC6H5)3C5H5

476.32

—

—

Decomposes

—/yellow

—

Cyclopentadienyl titanium tri(trifluoro acetate) (Ti(OCOCF3)3C5H5)

452.02

—

—

179181 s/orange (decomposes)

—

Pentamethyl cyclopentadienyl titanium triacetate Ti(OCOCH3)3(h-C5(CH3)5)

360.24

—

136138

Pentamethyl cyclopentadienyl titanium tri(trifluoroacetate) Ti(OCOCF3)3(M-C5(CH3)5)

522.16

—

—

Reasonably soluble in polar solvents; less stable than biscyclopentadienyl analogues; readily hydrolyzed Reasonably soluble in polar solvents; less stable than biscyclopentadienyl analogues; readily hydrolyzed Reasonably soluble in polar solvents; less stable than biscyclopentadienyl analogues; readily hydrolyzed Reasonably soluble in polar solvents; less stable than biscyclopentadienyl analogues; readily hydrolyzed Reasonably soluble in polar solvents; less stable than biscyclopentadienyl analogues; readily hydrolyzed

146/0.2

—

Compound Titanium iodide triisopropoxide (iC3H7O)3TiI Titanocene dichloride (C5H5)2TiCl2

State/Color

Densitya (g/cc)

Miscellaneous

Reference

IV. Titanium Carboxylates

—

s/yellow

243246 s/orange (decomposes)

—

—

2, p. 348

2, p. 348

2, p. 348

2, p. 348

2, p. 348

V. Tris(amido) Titanium Aryl Compounds Tris(diethyl amido) (M-cyclopentadienyl) titanium Ti(N(C2H5)2)3(C5H5)

329.37

—

l/red-brown; oil/red

—

Reasonably soluble in polar 2, p. 351 solvents; less stable than biscyclopentadienyl analogues; readily hydrolyzed

© 2005 by CRC Press

Tris(dimethyl amido) (M-tertbutylcyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H4(C4H9)t)

301.31

70/103

—

—

Solid crystal/ yellow

—

Tris(dimethyl amido) (Mcyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H5)

245.20

95/0.05

—

—

Liquid oil/ red

—

Tris(dimethyl amido) (M-di-tertbutylcyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H3(C4H9)2t)

357.42

90/5 × 103

—

—

Liquid oil/ red

—

Tris(dimethyl amido) (M-diethylmethyl cyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H4(C2H5)2CH)

315.34

85/103

—

—

Liquid oil/ red

—

Tris(dimethyl amido) (M-diphenylmethyl cyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H4(C6H5)2CH

411.43

—

—

—

Solid crystal/ yellow

—

Tris(dimethyl amido (Methylcyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H4C2H5)

273.26

78/103

—

—

Liquid oil/ red

—

Tris(dimethyl amido (Mmethylcyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H4CH3)

259.23

84/0.02

—

—

l/red oil (or low melting point)

—

Tris(dimethyl amido (M-methyl, tert-butyl cyclopentadienyl) titanium Ti(N(CH3)2)3(M-C5H3CH3(C4H9)t)

315.34

70/103

—

—

Liquid oil/ red

—

Tris(dimethyl amido (M-isopropyl cylcopentadienyl) titanium Ti(N(CH3)2)3(M-C5H4CH3(C3H7)i)

287.28

64/<103

—

—

Liquid oil/ red

—

Tris(piperidyl amido) (M-tert-butyl cyclopentadienyl) titanium Ti(NC5H10)3(M-C5H4(C4H9)t)

421.51

155/102

—

—

Liquid impure oil/ red

—

Reasonably soluble in polar solvents; less stable than biscyclopentadienyl analogues; readily hydrolyzed Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C

2, p. 351

2, p. 351

2, p. 351

2, p. 351

2, p. 351

2, p. 351

2, p. 351

2, p. 351

2, p. 351

2, p. 351

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Tris(piperidyl amido) (Mcyclopentadienyl) titanium Ti(NC5H10)3(M-C5H5)

365.40

100/103

—

—

Solid crystal/ yellow

—

Tris(piperidyl amido) (M-methyl cyclopentadienyl) titanium Ti(NC5H10)3(M-C5H4CH3)

379.42

110/103

—

—

Liquid oil/ red

—

Tris(piperidyl amido) (M-isopropyl cyclopentadienyl) titanium Ti(NC5H10)3(M-C5H4(C3H7)i)

407.48

110/103

—

—

l/red

—

337.88

—

—

248.98

—

289291

216.07

—

—

431.88

—

315317

445.35

—

142145

—

333.14

—

170172

417.30

—

349.10

—

Compound

State/Color

Densitya (g/cc)

Miscellaneous

Reference

Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C Miscible in nonpolar solvents; stable to O2; readily hydrolyzed by moisture; decomposes below 150°C

2, p. 351

—

—

2, p. 362

—

—

2, p. 362

—

—

2, p. 351

—

—

2, p. 362

Crystalline solid/—

—

—

2, p. 367

—

s/—

—

—

2, p. 367

200.5201

—

—

—

2, p. 367

~210

—

Solid crystal/redbrown Solid crystal/ dark brown

—

—

2, p. 367

2, p. 351

2, p. 351

VI. Titanium Halocyclopentadienyl Compounds Bis(cyclopentadienyl) titanium dibromide TiBr2(C5H5)2 Bis(cyclopentadienyl) titanium dichloride TiCl2(C5H5)2 Bis(cyclopentadienyl) titanium difluoride TiF2(C5H5)2 Bis(cyclopentadienyl) titanium diiodide TiI2(C5H5)2 Bis(M-(dimethyl butyl)methylcyclopentadienyl) titanium dichloride TiCl2(M-C5H4C(C4H9)(CH3)2)2 Bis(M-(dimethyl) methylcyclopentadienyl) titanium dichloride TiCl2(M-C5H4C(H)(CH3)2)2 Bis(M-(ethyl)(tetramethyl) cyclopentadienyl) titanium dichloride TiCl2(M-C5(CH3)4(C2H5))2 Bisindenyl titanium dichloride TiCl2(M-C9H7)2

290313 s/dark red (decomposes) —

s/red

238280 s/yellow (decomposes) — s/black

© 2005 by CRC Press

Bis(M-methylcyclopentadienyl) titanium dichloride TiCl2(M-C5H4CH3)2 Bis(M-methylcyclopentadienyl) titanium difluoride TiF2(M-C5H4CH3)2 Bis(M-pentamethyl cyclopentadienyl) titanium dichloride TiCl2(M-C5(CH3)5)2

277.03

—

223225

244.12

—

189191

389.24

—

—

—

Solid crystal/ dark red — Solid crystal/ yellow 273 Solid (decomposes) crystal/redbrown

—

—

2, p. 367

—

—

2, p. 367

—

—

2, p. 367

VII. Miscellaneous Titanium Biscyclopentadienyl Compounds Biscyclopentadienyl titanium diacetate Ti(O2CCH3)2(C5H5)2 Biscyclopentadienyl titanium dibenzeneoate Ti(O2CC6H5)2(C5H5)2 Biscyclopentadienyl titanium di(chloroacetate) Ti(O2CCH2Cl)2(C5H5)2 Biscyclopentadienyl titanium di(trichloro) acetate Ti(O2CCCl3)2(C5H5)2 Biscyclopentadienyl di(dicyanoamide) titanium Ti(N(CN)2(C5H5)2 Biscyclopentadienyl titanium dibutyrate Ti(O2CC3H7)2(C5H5)2 Biscyclopentadienyl titanium di(heptafluorobutyrate) Ti(O2CC3F7)2(C5H5)2 Biscyclopentadienyl diisocyanato titanium Ti(NCO)2(C5H5)2 Biscyclopentadienyl titanium di(2-methyl acrylate) Ti(O2CC(CH3) = CH2)2(C5H5)2 Biscyclopentadienyl titanium di(pentafluoro) propionate Ti(O2CC2F5)2(C5H5)2 Biscyclopentadienyl titanium dipropionate Ti(O2CC2H5)2(C5H5)2

296.16

—

126130

—

s/—

—

Prepared from aqueous solution 2, p. 378

420.30

—

188

—

s/—

—

365.05

—

9899

—

s/—

—

Prepared from aqueous solution 2, p. 378

502.83

—

192194

—

s/—

—

Prepared from aqueous solution 2, p. 378

310.15

—

8590

—

s/orangered

—

328.24

—

8284

—

s/—

—

Prepared from aqueous solution 2, p. 378

604.13

—

110111; (141142)

—

s/—

—

Prepared from aqueous solution 2, p. 378

262.10

—

275277

—

s/orangered

—

348.23

—

13550

—

s/—

—

Prepared from aqueous solution 2, p. 378

504.12

—

112113

—

s/—

—

Prepared from aqueous solution 2, p. 378

324.21

—

114116

—

s/—

—

Prepared from aqueous solution 2, p. 378

—

—

—

2, p. 378

2, p. 371

2, p. 371

© 2005 by CRC Press

Compound Biscyclopentadienyl diselenioisocyanato titanium Ti(NCSe)2(C5H5)2 Biscyclopentadienyl dithioisocyanato titanium Ti(NCS)2(C5H5)2 Biscyclopentadienyl triazide titanium Ti(N3)2(C5H5)2 Bis(methylcyclopentadienyl) diisocyanato titanium Ti(NCO)2(M-C5H4CH3)2 Bis(methylcyclopentadienyl) diseleniothiocyanato titanium Ti(NCSe)2(M-C5H4CH3)2 Bis(methylcyclopentadienyl) dithioisocyanato titanium Ti(NCS)2(M-C5H4CH3)2 Bis(methylcyclopentadienyl) diazide titanium Ti(N3)2(M-C5H4CH3)2 Cyclopentadienyl, methylcyclopentadienyl diisocyanato titanium Ti(NCO)2C5H5(M-C5H4CH3) Cyclopentadienyl, methylcyclopentadienyl diselenioisocyanato titanium Ti(NCSe)2C5H5(M-C5H4CH3) Cyclopentadienyl, methylcyclopentadienyl dithioisocyanato titanium Ti(NCS)2C5H5(M-C5H4CH3) Cyclopentadienyl, methylcyclopentadienyl triazide titanium Ti(N3)2C5H5(M-C5H4CH3)

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

388.02

—

—

294.22

—

303307

—

262.11

—

145146

—

290.16

—

416.08

Densitya (g/cc)

Miscellaneous

—

—

2, p. 371

s/maroon

—

—

2, p. 371

s/orange

—

—

2, p. 371

—

123126 s/red (decomposes) orange

—

—

2, p. 371

—

—

219223 s/dark (decomposes) brown

—

—

2, p. 371

322.28

—

220222

s/maroon

—

—

2, p. 371

288.15

—

—

113116 s/orange (decomposes)

—

—

2, p. 371

276.13

—

145

—

s/orange

—

—

2, p. 371

402.05

—

191

—

s/brown

—

—

2, p. 371

308.25

—

168

—

s/dark green

—

—

2, p. 371

276.14

—

170

—

s/yellow

—

—

2, p. 371

State/Color

140 s/green (decomposes)

—

Reference

© 2005 by CRC Press

VIII. Aryltitanium (IV) Thioalkoxides Biscyclopentadienyl titanium di(4-chlorothiophenoxide) Ti(SC6H4Cl-4)2(C5H5)2 Biscyclopentadienyl titanium di(4-methyl thiophenoxide) Ti(SC6H4CH3-4)2(C5H5)2 Biscyclopentadienyl titanium dithiobenzeneyloxide Ti(SCH2C6H5)2(C5H5)2 Biscyclopentadienyl titanium dithioethoxide Ti(SC2H5)2(C5H5)2 Biscyclopentadienyl titanium dithiohydroxide Ti(SH)2(C5H5)2 Biscyclopentadienyl titanium dithiomethoxide Ti(SCH3)2(C5H5)2 Biscyclopentadienyl titanium dithiophenoxide Ti(SC6H5)2(C5H5)2 Biscyclopentadienyl titanium di(thio-2phenyl ethoxide) Ti(SCH2CH2C6H5)2(C5H5)2 Biscyclopentadienyl titanium di(thio-npropoxide) Ti(S(C3H7)n)2(C5H5)2 Bis cyclopentadienyl titanium thiobenzeneoyl chloride TiCl(SCH2C6H5)(C5H5)2 Biscyclopentadienyl titanium thioethoxy chloride TiCl(SC2H5)(C5H5)2 Biscyclopentadienyl titanium (thiomethoxy) chloride TiCl(SCH3)(C5H5)2 Biscyclopentadienyl titanium thiophenoxychloride TiCl(SC6H5)(C5H5)2

465.29

—

178–182

—

s/—

—

—

2, p. 379

424.45

—

198–199.5

—

s/red-violet

—

—

2, p. 379

424.45

—

172–178

—

s/—

—

—

2, p. 379

296.28

—

107–117

—

s/—

—

—

2, p. 384

244.21

—

—

150–160 s/— (decomposes)

—

—

2, p. 384

272.26

—

184–185

—

s/red-violet

—

—

2, p. 384

396.40

—

199–206

—

s/deep red

—

—

2, p. 379

452.51

—

92–94

—

s/—

—

—

2, p. 379

328.37

—

88–93

—

s/—

—

—

2, p. 379

336.71

—

—

134–135.5 s/— (decomposes)

—

—

2, p. 384

274.64

—

—

108 s/— (decomposes)

—

—

2, p. 384

260.62

—

—

117 s/— (decomposes)

—

—

2, p. 384

322.69

—

—

140 s/— (decomposes)

—

—

2, p. 384

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

Reference

IX. Alkyl/Aryl Cyclopentadienyl Titanium Compounds Biscyclopentadienyl (benzyl)titanium chloride Ti(CH2C6H5)(Cl)(C5H5)2 Biscyclopentadienyl (n-butyl)titanium chloride Ti(C4H9)n(Cl)(C5H5)2 Biscyclopentadienyl (i-butyl) titanium chloride Ti(C4H9)i(Cl)(C5H5)2 Biscyclopentadienyl diethyl titanium Ti(C2H5)2(C5H5)2 Biscyclopentadienyl dimethyl titanium Ti(CH3)2(C5H5)2

304.65

—

107

—

s/blue-black

—

—

2, p. 400

270.64

—

84.7

—

s/red-brown

—

—

2, p. 400

270.64

—

70.5

—

s/red-brown

—

—

2, p. 400

236.19

—

—

—

—

2, p. 397

208.14

—

—

Biscyclopentadienyl ethyl titanium chloride TiC2H5(Cl)(C5H5)2 Biscyclopentadienyl heptafluorophenyl titanium chloride Ti(C6F5)(Cl)(C5H5)2 Biscyclopentadienyl heptafluorophenyl titanium fluoride Ti(C6F5)(F)(C5H5)2 Biscyclopentadienyl pentafluorophenyl titanium ethoxide Ti(C6F5)(OC2H5)(C5H5)2 Biscyclopentadienyl pentafluorophenyl titanium methoxide Ti(C6F5)(OCH3)(C5H5)2 Biscyclopentadienyl (n-pentyl) titanium chloride Ti(C6H11–n)(Cl)(C5H5)2 Biscyclopentadienyl (neopentyl)titanium chloride Ti(CH2C(CH3)3)(Cl)(C5H5)2

242.58

—

88.7

40 s/orange(decomposes) red 97 Solid (decomposes) crystal/ orange — s/red-brown

380.58

—

187–188; 201–203

—

364.13

—

240

—

390.19

—

117

376.16

—

284.66

284.66

—

Air stable but sensitive to light; 2, p. 397 should be stored in refrigerator

—

—

2, p. 400

s/pale orange

—

—

2, p. 401

—

—

2, p. 401

—

Crystalline solid/ yellow s/yellow

—

—

2, p. 401

144–145

—

s/—

—

—

2, p. 401

—

52.0

—

s/red-brown

—

—

2, p. 400

—

95.0

—

s/graybrown

—

—

2, p. 400

© 2005 by CRC Press

Biscyclopentadienyl 2-phenylethyl titanium chloride Ti(CH2CH2C6H5)(Cl)(C5H5)2 Biscyclopentadienyl (phenyl) titanium chloride TiC6H5(Cl)(C5H5)2 Biscyclopentadienyl (n-propyl) titanium chloride Ti(C3H7)n(Cl)(C5H5)2 Biscyclopentadienyl titanium diphenylacetylide Di(phenylethynyl) titanocene Ti(C}CC6H5)2(C5H5)2 Biscyclopentadienyl vinyl titanium chloride Ti(CH = CH2)(Cl)(C5H5)2

318.68

—

139

—

s/red-brown

—

—

2, p. 400

290.63

—

121

—

—

—

2, p. 401

256.61

—

74.5

—

s/redbrown, orange s/red brown

—

—

2, p. 400

380.32

—

—

—

—

—

2, p. 402

240.57

—

153

—

—

—

2, p. 402

Bis(2,6-difluoro-3-(1-hydropyrrol-1-yl) phenyl)titanocene (C5H5)2Ti(C10H6F2N)2 Tetrabenzyl titanium Ti(CH2C6H5)4 Tetrabutyl titanium Ti(C4H9)4 Tetraethyl titanium Ti(C2H5)4 Tetramethyl titanium Ti(CH3)4

534.4

—

160–170

—

s/orangeyellow

—

412.41

—

~70

—

—

—

2, p. 459

276.34

—

—

—

Crystalline solid/red —/—

—

—

2, p. 459

164.13

—

—

—

—/—

—

—

2, p. 459

108.02

—

—

Tetrapentyl titanium(Tetra(2,2-dimethyl propyl titanium) Ti(CH2C(CH3)3)4 Tetra(pentafluorophenyl) titanium Ti(C6F5)4

212.17

—

—

716.11

—

—

Tetraphenyl titanium Ti(C6F5)4

356.30

—

—

Titanium diethyldithiocarbamate (CH3CH2)2NCS2)4Ti

640.97

—

198–200(d)

Crystalline solid/ orangebrown s/red-brown

X. Titanium Alkyls/Aryls

>78 Crystalline (decomposes) solid/ yellow ~105 Crystalline (decomposes) solid/ yellow — Crystalline solid/ yellow ~45 Crystalline (decomposes) solid/ yellow — s/red

—

Soluble in acetone, toluene, methylethylketone

Very unstable compound

1, p. 289

2, p. 459

—

—

2, p. 459

—

—

2, p. 459

—

—

2, p. 459

—

Soluble in CH2Cl2, toluene

1, p. 290

© 2005 by CRC Press

Compound Titanium tetrakis(diethylamide) ((CH3CH2)2N-)4Ti N20 = 1.536Titanium tetrakis(dimethylamide) ((CH3)2N-)4Ti

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

336.4

133/1.2

—

—

l/—

0.938

224.20

50/0.5

—

—

—/—

0.96

—

1, p. 293

—

—

1, p.296

1.3

—

1, p.296

State/Color

Densitya (g/cc)

Miscellaneous Flash point: 165°C

Reference 1, p. 293

Tungsten Compounds I. Tungsten Alkoxides and Diketonates 409.15

110–115/1

—

—

454.21

105–110/0.05

105–115

—

M-Benzene tungsten tricarbonyl W(CO)3(M-C6H6)

345.99

—

140–145

—

Cyclooctatetraene tungsten tricarbonyl W(CO)3(M6C8H10)

372.03

—

—

—

Trisdiethyl acetylide tungsten carbonyl Carbonyl tris(3-hexyne) tungsten W(CO)(M-C2H5C CC2H5)3 Trisdiphenyl acetylide tungsten carbonyl W(CO)(M-C6H5C CC2H5)3

458.30

—

55–56

—

746.56

—

—

—

Tungsten hexacarbonyl W(CO)6

351.91

Decomposes

169

—

Tungsten V ethoxide 95% W(OC2H5)5 Tungsten VI ethoxide 95% W(OC2H5)6

1/purpleblack s/light yellow

II. Tungsten Carbonyls Crystalline solid/ yellow Crystalline solid/redbrown Crystalline solid/pale yellow Prismatic crystal/ yellow s/white; crystal/ colorless

—

Air stable; soluble in organic solvents

2, p. 1359; 8, p. 2391

—

Soluble in hexane

2, p. 1368; 8, p. 2395

—

—

2, p. 1375; 8, p. 2403

—

—

2, p. 1375

2.65

Volatile, octahedral, odorless, diamagnetic, air-stable crystal; melts with decomposition at ~150ºC; hydrophobic; stable to oxidation; slightly soluble in polar and nonpolar solvents, sublimes under vacuum

2, p. 1256; 3, p. 63

© 2005 by CRC Press

III. Tungsten Aryl Compounds Bis-M6– benzene tungsten W(M-C6H6)2 Tungsten VI phenoxide W(OC6H5)6

340.08

—

—

—

747.53

—

72–76

—

Crystalline solid/green s/dark red

—

—

—

Soluble in THF, toluene

Soluble in tetrahydrofuran, cyclohexane; slightly soluble in pentane Soluble in tetrahydrofuran, benzene; slightly soluble in pentane —

2, p. 1356; 8, p. 2397 1, p. 296

Uranium Compounds I. Uranium Alkoxides and Diketonates Tricyclopentadienyl uranium n-butoxide (C5H5)3U(O-n-C4H9)

506.43

—

149–151

120 (in vacuo)

Crystalline solid/green

—

Tricyclopentadienyl uranium ethoxide (C5H5)3U(OC2H5)

478.37

—

210–213

—

Crystalline solid/green

—

Uranium VI oxide 2,4-pentanedionate UO2(–O–C(CH3)CH(CH3)CO–)2

468.25

—

—

—

—/—

—

8, p. 2353

8, p. 2353

27, p. 44

II. Alkyl and Aryl Compounds of Uranium Tetraethyl uranium U(C2H5)4 Tetrakis (M3-2-propenyl) uranium U(CH2–CH = CH2)4 Tricyclopentadiene uranium U(C5H5)3 Triscyclopentadienyl n-butyl uranium U(C5H5)3n-C4H9

354.28

—

—

—

—/—

—

402.32

—

—

—

—/dark red

—

433.31

—

—

—

—

490.43

—

130 (decomposes)

—

Triscyclopentadienyl 2-methylallyl uranium U(C5H5)32-(CH2C(CH3) = CH2) Triscyclopentadienyl p-methylbenzeneyl uranium U(C5H5)3p-(CH3C6H4) Triscyclopentadienyl uranium phenylacetylide U(C5H5)3C}CC6H5

488.41

—

—

—

524.45

—

200 (decomposes)

—

534.44

—

183–185 (decomposes)

—

Crystalline solid/— Crystalline solid/dark red Crystalline solid/deep red-brown Crystalline solid/dark violet Crystalline solid/ yellow green

—

—

Unstable at room temperature; volatile Pyrophoric; reacts with alcohol to yield mixed complexes Forms complexes and adducts with solvents Soluble in benzene, toluene, ether, hot hexane; smokes on exposure to air Soluble in toluene, air sensitive

2, p. 241 2, p. 239; 8, p. 2351 2, p. 213 2, p. 243; 8, p. 2354 2, p. 243; 8, p. 2353

—

Soluble in benzene, tetrahydrofuran; air sensitive

2, p. 243; 8, p. 2356

—

Soluble in hexane, tetrahydrofuran, water; sensitive to oxygen

2, p. 243; 8, p. 2357

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Triscyclopentadienyl uranium ethynyl U(C5H5)3(C}CH)

458.34

—

—

—

Uranocene biscyclo octatetraene uranium U(M-C8H8)2

446.33

—

—

180/0.03

Compound

State/Color

Densitya (g/cc)

s/yellowgreen

—

Plates/ green

—

Miscellaneous

Reference

Soluble in tetrahydrofuran, 2, p. 243; toluene, sensitive to oxygen and 8, p. 2353 moisture Sp soluble in organic solvents; 2, p. 31, flammable in air but stable to 95; 8, water p. 2352

Vanadium Compounds I. Vanadium Alkoxides and Diketonates Vanadium IV oxide bis(benzoylacetonate) (-OC(C6H5)CHC(CH3)O-)2VO Vanadium IV oxide bis(hexafluoropentanedionate) (-OC(CF3)CH(CF3)CO-)2VO Vanadium IV oxide bis(2, 4pentandionate) or Vanadylacetylacetonate VO(OC(CH3)CH(CH3)CO)2 Vanadium III 2, 4-pentanedionate V(OC(CH3)CH(CH3)CO)3 Vanadium triisobutoxide oxide OV(OiC4H9)3 Vanadium triisopropoxide oxide VO(OiC3H7)3 Vanadium tri-n-propoxide oxide VO(O–n-C3H7)3

389.31

—

218

—

s/—

—

Soluble in xylene

1, p. 297

481.04

—

—

—

—/—

—

—

1, p. 298

265.16

—

243–246

—

s/blue-green

348.26

—

178–190

—

s/brown

286.29

105/1.5

10 to 5

—

242.21

80–82/2

11 to 14

242.21

100–102/2

350.29

322.28

1.52– 1.74

Solubility in water: 13 g/l, methanol: 64 g/l

1, p. 298

—

Solubility in water: 2 g/l; toxic

1, p. 298

—/—

1.011

1, p. 298

—

—/—

1.029

Flash point: 64°C; n20 = 1.487; viscosity (38°): 3 cSt n20 = 1.481; flash point: 58ºC

1, p. 298

—

—

1/—

1.077

n20 = 1.500; flash point: 62ºC

1, p. 298

—

58–60

—

Crystalline solid/green

—

Air sensitive

2, p. 666

—

105–110 (decomposes)

—

s/orange

—

Air sensitive

2, p. 666

II. Vanadium Carbonyl Compounds Cyclopentadienyl (diphenylacetylide) vanadium carbonyl V(CO2)(C6H5C}CC6H5)(C5H5) Cyclopentadienyl bis(diphenylacetylide) vanadium carbonyl V(CO)(C6H5C}CC6H5)2(C5H5)

© 2005 by CRC Press

Cyclopentadienyl tetracarbonyl vanadium V(CO)4(C5H5) Cyclopentadienyl thiocarbonyl vanadium tricarbonyl V(CO)3(CS)(C5H5) Vanadium hexacarbonyl V(CO)6

228.08

—

139

80–100/0.5

Crystalline solid/ orange s/yellow (in hexane)

—

244.14

—

69–72

—

219.00

Decomposes

65

—

s/black; crystalline solid/ yellowgreen

—

—

Air sensitive; sublimes; soluble in 2, p. 663; arene solvents 8, p. 2369 —

2, p. 665; 8, p. 2369

Volatile; very unstable; 2, p. 651; octahedral; yellow-orange in 3, p. 63 solution; soluble in benzene and toluene

III. Miscellaneous Vanadium Alkyl/Aryl Compounds Biscyclopentadienyl vanadium 2methylpropylenyl V(2-CH3C3H4)(C5H5)2 Biscyclopentadienyl vanadium pentafluorophenyl VC6F5(C5H5)2 Biscyclopentadienyl vanadium phenyl VC6H5(C5H5)2 Biscyclopentadienyl vanadium-n-propyl VC3Hn7(C5H5)2 n-Butyl vanadium trisdiethylamine VC4Hn9(N(C2H5)2)3 Dibenzene vanadium V(M-C6H6)2

236.23

—

65

—

s/black

—

—

2, p. 677

348.19

—

208

—

s/blue-black

—

—

2, p. 677

258.24

—

92

—

s/black

—

—

2, p. 677

224.22

—

41

—

—

—

2, p. 677

324.45

—

—

—

—

—

120–125 (in vacuo)

Dicyclopentadienyl vanadium V(C5H5)2

181.13

—

277 under nitrogen decomposes >300 167–168

—

Crystal/ violet

—

Ethyl vanadium trisdiethylamine VC2H5(N(C2H5)2)3

296.39

71–73/0.001

—

—

1/dark green

—

Phenylvanadium trichloride C6H5VCl3

234.41

—

—

—

—/—

—

n-Propyl vanadium trisdiethylamine VC3Hn7 (N(C2H5)2)3

310.42

—

—

—

1/dark green

—

Air sensitive; can be vacuum distilled Soluble in organic solvents; )H°f = 322(6) and 36(10); thermally stable; insoluble in CCl4, methanol )H°f = 123 and 142 kJ/mol; air sensitive; soluble in tetrahydrofuran, benzene Air sensitive, can be vacuum distilled; stable to 115°C, soluble in hydrocarbons; paramagnetic Decomposes to lower V halides and biphenyl, used as a catalyst for vinylchloride polymers Air sensitive, can be vacuum distilled

2, p. 660

207.17

s/greenblack 1/dark green Liquid or solid/redbrown

—

2, p. 689; 8, p. 2373

2, p. 673, 142(8); 8, p. 2371 2, p. 660; 8, p. 2375

2, p. 659

2, p. 660

© 2005 by CRC Press

Compound Tetramethyl vanadium V(CH3)4 Tetraphenyl vanadium V(C6H5)4

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

111.08

—

—

—

—/—

—

359.36

—

—

—

—/—

—

State/Color

Densitya (g/cc)

Miscellaneous Thermally unstable and cannot be isolated Thermally unstable and cannot be isolated

Reference 2, p. 660 2, p. 660

Ytterbium Compounds I. Ytterbium Alkoxides and Diketonates 470.37

—

122–129

—

s/—

—

1058.58

—

165–168

—

s/—

—

794.19

—

—

—

s/—

—

722.86

—

167–169

—

s/—

—

Biscylopentadienyl ytterbium(n-butyl acetylide) (C5H5)2YbC}CC4Hn9 Biscyclooctatetraene methyl ytterbium (C5H5)2 YbCH3

384.37

—

—

—

—/—

—

636.53

—

—

—

Crystal/ orange

—

Cyclooctatetraene ytterbium Yb(C8H8)

277.19

—

>500

—

s/pink

—

Ytterbium 2,4-pentanedionate Yb(OC(CH3)CH(CH3)CO)3 Ytterbium 6,6,7,7,8,8,8 heptafluoro-2,2dimethyl-3,5-octanedionate Yb(OC(nC3F7)CH(C(CH3)3)CO)3 Ytterbium Hexafluoropentanedionate (OC(CF3)CH(CF3)CO)3Ba Ytterbium 2,2,6,6-tetramethyl-3,5heptanedionate Yb(-OC(C(CH3)3)CHC(C(CH3)3O-)3

— )Hsub = 37 kcal/mol — )Hsub = 31.9 kcal/mol

1, p. 174 1, p. 175

1, p. 175 1, p. 175

II. Ytterbium Alkyl/Aryl Compounds —

2, p. 203

Degree of association: 2; soluble 2, p. 203; in benzene, toulene, CH2Cl2; air 8, p. 2415 and moisture sensitive; decomposes at >165ºC Air and moisture sensitive; stable 2, p. 194; to 500ºC in vacuum; insoluble 8, p. 2415 in ammonia or etheral solvents yet exposure brings strong color changes; pyridine, dimethylformamide will dissolve it, yielding deep red solutions; decomposed by water

© 2005 by CRC Press

Tricyclopentadienyl ytterbium Yb(C5H5)3

368.22

—

273 (decomposes)

150 (in vacuo)

Ytterbocene Yb(C5H5)2 Ytterbium 3-hexyne Ytterbium diethylacetylide Yb(C2H5–C}C-C2H5)

303.30

—

—

255.19

—

—

400 (in vacuo) —

Crystalline solid/dark green s/red

—

Soluble in tetrahydrofuran; hydolyzed by water

8, p. 2416

—

Soluble in tetrahydrofuran

8, p. 2415

s/brown

—

Soluble in tetrahydrofuran; decomposes at 220ºC

2, p. 206

Yttrium Compounds I. Yttrium Alkoxides and Diketonates Yttrium 6,6,7,7,8,8,8 heptafluoro-2,2dimethyl-3,5-octanedionate Y(OC(nC3F7)CH(C(CH3)3)CO)3 Yttrium Hexafluoroisopropoxide diammonia Y(OCH(CF3)2)3 Yttrium hexafluoropentanedionate Y(-OC(CF3)CH(CF3)CO-)3 Yttrium methoxyethoxide 15–18% in methoxyethanol Y(OCH2CH2OCH3)3

974.45

—

97–102

—

s/—

—

—

1, p. 175

590.0

—

—

—

s/—

—

—

1, p. 175

710.1

—

166–70

100/0.2

s/—

—

—

1, p. 176

314.17

—

—

—

—/—

1.01

Yttrium 2,4-pentanedionate Y(OC(CH3)CH(CH3)CO)3 Yttrium isopropoxide 95% Y(OiC3H7)3

386.23

—

130–133

—

s/—

266.17

—

—

200–210/1

Yttrium 2,2,6,6-tetramethylheptanedionate Y(-OC(C(CH3)3)CH(C(CH3)3)CO-)3 Ytrrium 2,2,6,6-tetramethylheptanedionate Y(–OC(C(CH3)3)CH(C(CH3)3)CO–)3

638.72

—

169–73

638.72

—

570.06

—

Prepared as solution

1, p. 176

—

Soluble in toluene, acetone

1, p. 176

—/—

—

1, p. 176

95/0.05

s/—

—

Solubility: isopropanol, 30 g/l; toluene >200 g/l; molecular complexity: 1.6 Soluble in acetone Decomposes>290°C

169–173

—

s/—

—

—

1, p. 176

180–184

105/10–14

s/—

—

—

1, p. 177

1, p. 175

II. Yttrium Alkyl Amide Yttrium tris(bis(trimethylsilylamide)) Y(N(Si(CH3)3)2)3

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

284.19

—

295

200–250 (in vacuo)

266.04

—

285

—

s/—

—

314.14

—

110

—

s/—

—

—

1, p. 176

427.95

—

138–142

—

s/—

—

—

1, p. 176

536.11

—

—

—

—/—

—

—

1, p. 177

State/Color

Densitya (g/cc)

Miscellaneous

Reference

III. Organoyttrium Compounds Tri-U-cyclopentadienyl yttrium Y(C5H5)3

Crystalline solid/pale yellow

Soluble in tetrahydrofuran; hydrolyzed by water

8, p. 2410

Soluble in water (90g/l)

1, p. 175

IV. Yttrium Salt Yttrium Acetate (CH3COO)3Y Yttrium methacrylate (CH2C(CH3)COO)3Y Yttrium trifluoroacetate (CF3COO)3Y Yttrium trifluoromethanesulfonate (CF3SO3)3Y

Zinc Compounds I. Zinc Alkoxides and Diketonates t-Butyl t-butoxyzinc C4Ht9ZnOC4Ht9 Ethyl pentafluorophenoxy zinc C2H5ZnOC6F5 Ethyl phenoxy zinc C2H5ZnOC6F5 Ethyl zinc acetylacetonate C2H5Zn(OC(CH3)CHC(CH3)O) Methyl methoxy zinc CH3ZnOCH3 Phenyl triphenyl methoxy zinc C6H5ZnOC(C6H5)3 Zinc N,N-dimethylaminoethoxide Zn-(OCH2CH2NMe2)2 Zinc 8-hydroxyquinolinate Cu(-OC9H8N-)2

195.61

—

169

—

s/—

—

Degree of association: 3

2, p. 838

277.50

—

114

—

s/—

—

Degree of association: 2

2, p. 838

187.55

—

177

—

s/—

—

Degree of association: 4

2, p. 838

229.58

—

95

—

s/—

—

Degree of association: 2

2, p. 838

111.45

—

—

s/—

—

Degree of association: 4

2, p. 838

401.81

—

—

s/—

—

Degree of association: 2

2, p. 838

241.63

—

190 (decomposes) 236 (decomposes) —

170/104

—/—

—

—

1, p. 300

353.68

—

>350

—

s/—

—

—

1, p. 300

© 2005 by CRC Press

Zinc methoxyethoxide 90% Zn-(OCH2CH2OCH3)2 Zinc 2,4-pentanedionate Zn(OC(CH3)CH(CH3)CO)2

215.54

—

—

—

—/—

—

Slowly decomposes at >130ºC

1, p. 300

263.59

—

136–8

110/1

s/—

—

Solubility in H2O: 6.9 g/l, in methanol: 135 g/l; trimeric

1, p. 300

335.66

—

—

Sinters at 107ºC

—

—

Crystalline solid/— s/—

—

399.50

112 (decomposes) 91–93

—

179.61

61/4

57

—

1/none

—

179.61

34/12

28.8

—

s/none

—

231.69

65/104

55

—

s/—

—

203.63

45/104

36

—

s/none

—

123.50

118

28

—

1/none

1.2065

Di-n-hexylzinc (C6H13)2Zn Dimethylzinc (CH3)2Zn

235.72

258

—

—

1/—

95.45

46

42; 29

—

1/none

Di-2-methylphenylzinc (2-CH3C6H4)2Zn Di-3-methylphenylzinc (3-CH3C6H4)2Zn Di-4-methylphenylzinc (4-CH3C6H4)2Zn Di-2,6-dimethylphenylzinc (2,6-(CH3)2C6H3)2Zn Dipentylzinc (C5H11)2Zn Diphenylzinc (C6H5)2Zn

247.65

—

70

—

s/—

—

247.65

—

53

—

s/—

—

247.65

—

168

—

s/—

—

275.70

—

166

—

s/—

—

207.66

231

—

—

1/none

—

219.59

280–285 (decomposes)

107

—

—/—

—

Soluble in nonprotic organic solvents )H°f (l) = 104.2 kJ/mol; soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Pyrophoric; )H°f (l) = 16.74 kJ/ mol; air and moisture sensitive; soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Pyrophoric; )H°f (l) = 25.1 kJ/mol; air and moisture sensitive; soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Soluble in nonprotic organic solvents Soluble in nonprotic organic solvents

2, p. 669; 8, p. 2443 2, p. 827

II. Zinc Alkyl/Aryls Bis(benzeneoyloxymethyl)zinc (C6H5COOCH2)2Zn Bis(pentafluorophenyl)zinc (C6F5)2Zn Di-n-butylzinc (C4H9)2Zn Di-t-butylzinc ((CH3)3C)2Zn Dicyclohexylzinc (C6H11)2Zn Dicyclopentylzinc (C5H9)2Zn Diethylzinc (C2H5)2Zn

— 1.386

2, p. 827, 832 2, p. 827 2, p. 827 2, p. 827 2, p. 827, 832; 6, p. 93 2, p. 827 2, p. 827, 832; 6, p. 93 2, p. 827 2, p. 827 2, p. 827 2, p. 827 2, p. 827 2, p. 827

© 2005 by CRC Press

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

Di-n-propylzinc (C3Hn7)2Zn

151.56

139

81 to 84

—

1/none

—

)H°f (l) = 57.7 kJ/mol; pyrophoric; air and moisture sensitive; soluble in nonprotic organic solvents

2, p. 827, 832

Diisoprpylzinc (i-C3H7)2Zn or ((CH3)2CH)2Zn Ethyl-n-propylzinc (C2H5)Zn(n-C3H7) Phenyl(phenylethynyl)zinc C6H5C}C-ZnC6H5

151.56

40/12

—

—

1/none

—

2, p. 827

137.53

27/10

—

—

1/—

—

243.61

—

132.5–133.5 (decomposes)

—

Crystalline solid/—

—

165.58

38–43/3

—

—

1/—

—

2, p. 827

267.64

—

—

—

Crystalline solid/—

—

Pyrophoric; air and moisture sensitive Soluble in nonprotic organic solvents Very soluble in tetrahydrofuran; soluble in ether, benzene; turns yellow on storage; readily hydrolyzed; forms ethrates Soluble in nonprotic organic solvents Polymeric in solid state; aggregate in pyridine solution; soluble in dimethylsulfoxide, dimethylformamide; slightly soluble in pyridine; insoluble in ether, tetrahydrofuran, HC; decomposes at 200ºC without melting; readily hydrolyzes

183.46

—

242–244

350(d)

s/—

1.735

Soluble in water

1, p. 299

207.50

—

>250

—

s/—

1.600

351.79

—

—

—

—/—

1.18

Flash point: 127°C

1, p. 300

155.41

—

—

—

—/—

2.21

Solubility in water 52g/l

1, p. 300

235.53

—

250(d)

—

s/—

1.48

Soluble in warm acetic acid

1, p. 300

407.89

—

—

—

—/—

1.10

Compound

n-Propyl-n-butylzinc (n-C3H7)Zn(n-C4H9) Zinc diphenyl acetylide Bis(phenylethynyl) zinc (C6H5C}C-)2Zn

State/Color

Densitya (g/cc)

Miscellaneous

Reference

2, p. 827 2, p. 829; 8, p. 2441

8, p. 2442

III. Zinc Salts Zinc acetate (CH3COO)2Zn Zinc acrylate (CH2CHCOO)2Zn Zinc 2-ethylhexanoate (C4H9CH(C2H5)COO)2Zn Zinc formate (HCOO)2Zn Zinc methacrylate (CH2C(CH3)COO)2Zn Zinc neodecanoate (C6H13C(CH3)2COO)2Zn

—

—

1, p. 299

1, p. 300

© 2005 by CRC Press

Zinc 2,2,6,6-tetramethyl-3,5heptanedionate Zn(-OC(C(CH3)3)CHC(C(CH3)3)O-)2 Zinc undecylenate (CH2CH(CH2)8COO)2Zn

431.92

144/0.1

132–134

—

s/—

—

1, p. 301

431.92

—

116–119

—

s/—

—

—

1, p. 301

233.23

—

—

—

—/—

—

—

2, p. 669

235.68

—

37

—

s/—

—

—

2, p. 829

271.75

143–144/1

—

—

1/—

—

—

2, p. 829

237.65

105–106/2.5

—

—

1/—

—

—

2, p. 829

262.66

—

106

—

s/—

—

Degree of association: 2

2, p. 841

239.65

—

43

—

s/—

—

2, p. 843

279.63

—

>300

—

s/—

—

Degree of association: “associated” Polymer

127.51

—

—

s/—

—

Polymer

2, p. 843

189.58

—

—

s/—

—

Polymer

2, p. 843

155.56

—

90 (decomposes) 60 (decomposes) 90–105

—

s/—

—

Degree of association: 6

2, p. 843

287.67

—

—

—

1/—

—

2, p. 843

327.67

—

179

—

s/—

—

Degree of association: “associated” Degree of association: >7

2, p. 843

386.15

—

12–13

—

l/—

0.957

Flash point: 40°C

1, p. 299

474.13

—

104–110

—

s/

1.21

Soluble in toluene, CS2, CHCl3

1, p. 299

361.91

—

178–181

—

s/red

1.48

—

1, p. 299

305.80

—

250–252

—

s/—

1.71

—

1, p. 300

IV. Miscellaneous Zinc Compounds Bis(dichloromethyl)zinc Zn(CHCl2)2 Di-3-dimethylaminopropylzinc Zn(CH2CH2CH(N(CH3)2)2 Di3-ethylmercaptopropylzinc Di3-ethyl thiopropylzinc Zn(SCH2CH2CH2(C2H5))2 Di4-methoxybutylzinc Zn(H2CCH2CH2CH(OCH3))2 Ethyl diphenylamide zinc C2H5ZnN(C6H5)2 Ethyl zinc dibutyl phosphide C2H5ZnP(C4H9)2 Ethyl zinc dephenylphosphide C2H5ZnP(C6H5)2 Methyl zinc thiomethoxide CH3ZnSCH3 Methyl zinc thiophenoxide CH3ZnSC6H5 Methyl zinc thioisopropoxide CH3ZnSC3Hi7 Phenyl zinc dibutyl phosphide C6H5ZnP(C4H9)2 Phenyl zinc diphenylphosphide C6H5ZnP(C6H5)2 Zinc bis[bis(trimethylsilyl)amide] Zn(N(Si(CH3)3)2)2 Zinc di-n-butyldithiocarbamate (C4H9)2NCS2)2Zn Zinc diethyldithiocarbamate (CH3CH2)2NCS2)2Zn Zinc dimethyldithiocarbamate (CH3)2NCS2)2Zn

2, p. 843

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

State/Color

Densitya (g/cc)

Miscellaneous

—

—

Reference

Zirconium Compounds I. Zirconium Alkoxides and Diketonates Zirconium acetylacetonate Zr(–OC(CH3)CHC(CH3)O–)3 Zirconium n-butoxide 80% in n-butanol Zr(O–N-C4H9)4 Zirconium t-butoxide Zr(OtC4H9)4 Zirconium di-n-butoxide (Bis-2,4pentanedionate) (-OC(CH3)CHC(CH3)O-)2Zr(OnC4H9)2 Zirconium dichloride bis(pentanedionate) (-OC(CH3)CH(CH3)CO-)2ZrCl2 Zirconium diisopropoxide bis(2,2,6,6tetramethyl-3,5-heptanedionate) (-OC(C(CH3)3)CH(C(CH3)3CO-)2 Zr(OiC3H7)2 Zirconium dimethacrylate dibutoxide (CH2C(CH3)COO)2Zr(OnC4H9)2 Zirconium 2dimethylpropoxide(zirconium pentoxide) Zr(OCH2C(CH3)3)4 Zirconium 1,2dimethylpropoxide(zirconium pentoxide) Zr(OCH(C3H7i )CH3)4 Zirconium 1,1dimethylpropoxide(zirconium pentoxide) Zr(OC(C2H5)(CH3)2)4 Zirconium ethoxide Zr(OC2H5)4

388.55

—

—

—

—/—

2, p. 562

383.68

260/0.1

—

—

l/—

1.07

383.68

70/2

>250(d)

—

s/—

0.96

435.66

—

—

—

—/—

1.05

360.35

—

180–182

—

s/—

—

575.94

140/0.1

110

—

s/—

—

—

1, p. 302

379.55

—

—

—

—/—

—

—

1, p. 302

439.79

188/0.2

—

—

l/—

—

Degree of polymerization: 2.4

4, p. 47

439.79

156/0.01

—

—

l/—

—

Degree of polymerization: 2.0

4, p. 47

439.79

95/0.1

—

—

l/—

—

Degree of polymerization: 1.0

4, p. 47

271.47

180/13

171–173

—

—/—

—

)Hvap: 30.2 kCal/mol; molecular complexity: 3.0; degree of polymerization: 3.6

1, p. 302; 4, p. 45

n20 = 1.4565; flash point: 30°C; molecular complexity: 3.4 Flash point: 85°C; )Hvap = 14.8 kcal/mol Miscible in isopropanol

1, p. 301

Soluble in toluene

1, p. 302

1, p. 301 1, p. 302

© 2005 by CRC Press

Zirconium 2-ethylhexoxide (C4H9CC(C2H5)HCH2O)4Zr Zirconium hexafluoropentanedionate Zr(-OC(CF3)CH(CF3)CO-)4 Zirconium methacryloxyethylacetoacetate tri-n-propoxide (-OC(OCH2CH2OC(O)C(CH3)CH2) CH(CH3)CO-)Zr(OnC3H7)3 Zirconium 2-methyl-2-butoxide Zirconium t-pentyloxide, Zirconium t-amyloxide Zr(OC(CH3)2C2H5)4 Zirconium 1-methylbutoxide(zirconium pentoxide) Zr(OCH(C2H5)2)4 Zirconium 1-methylbutoxide(zirconium pentoxide) Zr(OCH(C3Hn7)CH3)4 Zirconium 3-methylbutoxide(zirconium pentoxide) Zr(O(CH2)2CH(CH)3)2)4 Zirconium 2-methyl butoxide (Zirconium pentoxide) Zr(OCH2CH(C2H5)CH3)4 Zirconium 2,4-pentanedionate Zr(OC(CH3)CH(CH3)CO)4 Zirconium n-pentoxide Zr(O(CH2)4CH3)4 Zirconium isopropoxide 70–75% in heptane Zr(O–i-C3H7)4 Zirconium n-propoxide 70% in propanol Zr(O–n-C3H7)4 Zirconium 2,2,6,6-tetramethyl-3,5heptanedionate Zr(-OC(C(CH3)3)CH(C(CH3)3COO-)4 Zirconium trifluoropentanedionate Zr(–OC(CF3)CH(CH3)CO–)4 Zirconocene diethoxide Dicyclopentadienylzirconium Diethoxide Zr(OC2H5)2(C5H5)2

591.13

—

55–60

—

s/—

1.00

—

919.47

225

41–43

—

s/—

—

481.68

—

60–65

—

s/—

0.978

—

1, p. 303

436.79

138/5

—

—

l/—

0.961

)Hvap = 16.3 kCal/mol; molecular complexity: 1.0

1, p. 303

439.79

178/0.5

—

—

l/—

—

Degree of polymerization: 2.0

4, p. 47

439.79

175/0.05

—

—

l/—

—

Degree of polymerization: 2.0

4, p. 47

439.79

247/0.1

—

—

l/—

—

Degree of polymerization: 3.3

4, p. 47

439.79

238/0.1

—

—

l/—

—

Degree of polymerization: 3.7

4, p. 47

487.66

—

186–188

—

s/—

—

439.79

256/0.01

—

—

l/—

—

Solubility: H2O = 4.5 g/l; ethanol: 1, p. 303 30 g/l; toluene: 54 g/l; toxic; bulk density: 500 g/l — 4, p. 47

327.56

160/0.1

—

—

l/—

—

327.56

208/0.1

—

—

l/—

1.05

824.30

—

308–310

185/0.1

s/—

703.54

—

125–128

—

311.52

—

52–57

—

Soluble in pentane

1, p. 302 1, p. 302

)Hvap = 31.5 kCal/mol; molecular 1, p. 302 complexity: 3.0 n20 = 1.457; flash point: 16°C

1, p. 303

—

Soluble in hexane

1, p. 303

s/—

—

—

1, p. 304

s/—

—

—

27, p. 47

© 2005 by CRC Press

Compound

Formula Weight

Boiling Point (°C/mmHg)

Melting Point (°C)

Sublimation Temperature (°C/mmHg)

659.99

—

—

—

431.55

—

225–230(d)

293.39

—

215.31

Densitya (g/cc)

Miscellaneous

—/—

1.27

—

—

—/—

—

>250(d)

—

s/—

1.69

—

160(d)

—

s/—

State/Color

Reference

II. Zirconium Salts Zirconium 2-ethylhexanoate (C4H9CH(C2H5)COO)4Zr Zirconium methacrylate (CH2C(CH3)COO-)4Zr Zirconyl dimethacrylate (CH2C(CH3)COO-)2ZrO Zirconyl propionate (CH3CH2COO-)2ZrO

1, p. 302

Soluble in isopropanol, THF

1, p. 303

Soluble in ethylacetate

1, p. 304

—

Soluble in ethylacetate, ethanol

1, p. 304

—

Characterized by infrared 2, p. 561; spectroscopy; could exist in 8, p. 2453 oligomeric form; decomposes at 178°C

—

Characterized by infrared spectroscopy; could exist in oligomeric form —

III. Miscellaneous Zirconium Compounds Cyclopentadienyl zirconium triacetate Triacetoxy cyclopentadienyl ziroconium Zr(O2CCH3)3(M-C5H5)

333.45

—

~170

—

Cyclopentadienyl zinc tripivalate Zr(O2CC(CH3)3t ) 3 (M -C5H5)

459.69

—

—

—

Crystalline solid/white (in benzene, petroleum ether) s/—

Dimethylzirconocene (C5H5)2Zr(CH3)2 Dimethyl[bis(cyclopentadienyl)- silyl]zirconium dichloride (CH3)2Si(C5H5)2ZrCl2 Tetracyclopentadienyl zirconium Zr(C5H5)4

251.38

—

170

—

s/—

—

348.46

—

—

—

—/—

—

—

1, p. 301

351.60

—

—

—

—/—

—

—

2, p. 562

Zirconocene dichloride (C5H5)2ZrCl2

292.32

—

242–245

—

s/white

—

—

1, p. 304

2, p. 561

1, p. 301

REFERENCES 1. The Gelest Inc. Catalog, Gelest, Inc., Bensalem, PA, 2001. 2. Comprehensive Organometallic Chemistry: The Synthesis, Reactions, and Structures of Organometallic Compounds, edited by G. Wilkinson, F. G. Stone, and E. W. Abel, Pergamon Press, New York, 1982, Vol. 1–9. 3. H. D. Pierson, Handbook of Chemical Vapor Deposition: Principles, Technology, and Applications, Noyes, Park Ridge, NJ, 1992. 4. D. C. Bradley, R. C. Mehrotra, and D. P. Gaur, Metal Alkoxides, Academic Press, New York, 1978. 5. E. G., Rochow, D. T. Hurd, and R. N. Lewis, The Chemistry of Organometallic Compounds, John Wiley & Sons, New York, 1957. 6. Organometallics for Vapor Phase Epitaxy, Morton Thiokol Catalog, Morton Thiokol CVD, Woburn, MA, 1987. 7. The Chemat Catalog, Chemat Technology, Northridge, CA, 1993. 8. Dictionary of Organometallic Compounds, Chapman and Hall, New York, 1984, Vol. 1–4 and Suppl. 1–4. 9. G. E. Coates et al., Alkylberyllium alkoxides and some of their reactions with bases, J. Chem. Soc. (A), 477, 1968. 10. R. A. Andresen et al., Reactions of beryllium with carbonyl and azomethine groups: additions, reductions, complex formation, and ortho-metallation, J. Chem. Soc. Dalton Trans., 1171, 1974. 11. CRC Handbook of Physics and Chemistry, edited by D. R. Lide, 73rd ed., CRC Press, Boca Raton, FL, 1992–1993. 12. N. A. Bell et al., The addition of alkylberyllium hydrides to some unsaturated compounds, J. Chem. Soc. (A), 1969, 1966. 13. Silicon Compounds, Register and Review, edited by R. Anderson, B. C. Arkles, and G. L. Larson, 4th ed., Petrarch Systems, Bristol, PA, 1987. 14. D. S. Brown et al., The crystal and molecular structure of bis(2,3,4,5-tetrafluorophenyl)mercury, J. Organometallic Chem., 194, 131–135, 1980. 15a. J. C. Mill et al., The crystal structure of methylmercury (II) cyanide, J. Organometallic Chem., 14, 33–41, 1968. 16. D. J. Brauer et al., Vibrational spectra of normal coordinate analysis of CF3 compounds. XIX. Molecular structure and vibration spectra of bis(trifluoromethyl)mercury, J. Organometallic Chem., 135, 281–299, 1977. 17. P. B. Hitchcock et al., Metallocene derivates of early transition elements. Part 1. Niobium IV chlorides, chloroalkyls, and dialkyls and the crystal and molecular structure of [Nb(M-C5H5)2(Ch2Ph)2], J. Chem. Soc. Dalton Trans., 180, 1981. 18. E. E. H. Otto et al., Ligand exchange and ligand migration reactions involving dicyclopentadienylniobium (III) carbonyl derivatives, J. Organometallic Chem., 170, 209–216, 1978. 19. C. P. Verkade et al., Organoniobium compounds containing cyclooctatetraene as a ligand, J. Organometallic Chem., 154, 317–321, 1978. 20. R. S. Threlkel et al., Migratory insertion reactions of carbenes. Kinetics and mechanisms of migratory insertion reactions of zirconoxy carbene complexes of niobocene hydride and alkyls, J. Am. Chem. Soc., 2550, 1981. 21. L. E. Manzer, Preparation of the paramagnetic alkyls Cp2NbMe2 and (MeCp)2TaMe2 and some sixand eight-coordinate phosphine derivatives of Nb(IV), Inorg. Chem., 16 (3), 525, 1977. 22. G. W. A. Fowles et al., Reaction of dimethylzinc and tantalum(V) chloride and some coordination compounds of methyltantalum(V) chloride, dimethyltantalum(V) chloride and methylniobium(V) chloride, J. Chem. Soc. Dalton Trans., 961, 1973. 23. S. Numat et al., Preparation and some reactions of tris(polychlorophenyl)thallium(III) compounds, J. Organometallic Chem., 102, 259–263, 1975. 24. A. G. Lee, Cyclopentadienyl- and phenylethyinyl-dimethylthallium, J. Chem. Soc. (A), 2157, 1970. 25. J. P. Maher et al., Proton magnetic resonance spectra of thallium trialkyls, chemical exchange, and the formation of a mixed tri(methyl, vinyl)thallium, Proc. Chem. Soc., 5534, 1963.

© 2005 by CRC Press

26. B. G. Gowenlock et al., The organometallic chemistry of the alkaline-earth metals. Part 3. Preparation and properties of alkylhalogen metal compounds and related species of calcium, strontium, and barium, J. Chem. Soc. Dalton Trans., 657, 1978. 27. These compounds originally appeared in The Gelest Inc. Catalog (Ref. 2), Gelest, Inc., Bensalem, PA, 1992, but were no longer in the 2001 catalog.

© 2005 by CRC Press

0910_book.fm Page 295 Wednesday, September 22, 2004 9:01 AM

CHAPTER 4 Properties of Solid-State Inorganic Materials I. GENERAL PROPERTIES

© 2005 by CRC Press

Density (g/cc)

Ac2O3 Ac2S3

502 550.19

9.19 6.75

AlB2 Al4C3 AlN Al2O3 α-Al2O3 γ-Al2O3 Al2Se3 Al2S3

48.6 143.96 40.99 101.96 101.96 101.96 290.84 150.16

Am2O3 AmO2

Crystalline Form

Miscellaneous

Hexagonal Cubic

White, insoluble in water

3.19 2.36 3.26 3.965 3.97 3.5–3.9 3.437 2.02

Hexagonal Hexagonal Hexagonal Hexagonal Rhombohedral Microcrystalline powder Powder Hexagonal

Copper red; melts at 1654°C Yellow-green; dissolves in dilute acid White; dissolves in acid; alkali Colorless; soluble in acid; alkali Colorless; soluble in acid; alkali; insoluble in water White; soluble in acid; alkali Light brown; dissolves in acid Yellow; soluble in acid; insoluble in acetone; smell of H2S

534.26 275.13

— 11.68

Cubic or hexagonal Cubic

Red-brown; soluble in acid Black; soluble in acid

SbN Sb2O5 Sb2O4 Sb2O3

135.76 323.50 307.50 291.05

Antimony selenide Antimony (penta)sulfide Antimony (tri)sulfide

Sb2Se3 Sb2S5 Sb2S3

480.38 403.82 339.69

Antimony telluride

Sb2Te3

626.30

— 3.80 5.82 5.2 5.67 — 4.12 4.64 4.12 6.5

Powder Powder Powder Cubic Rhombohedral Crystalline Powder Rhombohedral Amorphous —

Orange powder; decomposes on melting; dissolves in cold H2O Yellow; very slightly soluble in H2O and acid; alkali White; n0 = 2.0; very slightly soluble in H2O and acid; alkali White; slightly soluble in H2O; soluble in acid; alkali Colorless; slightly soluble in H2O; soluble in acid, alkali Gray; very slightly soluble in H2O; soluble in concentrated HCl Yellow; insoluble in H2O and ethanol; soluble in HCl Black; n0 = 3.2; very slightly soluble in H2O; soluble in ethanol Yellow-red; very slightly soluble in H2O; soluble in ethanol Gray; soluble in HNO3; aqua regia

As2O5

229.04

4.32

Amorphous

White deliquescent; soluble in H2O; ethanol, acid, alkali

Actinium Materials Actinium sesquioxide Actinium sesquisulfide Aluminum Materials Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum

(di)boride carbide nitride oxide oxide oxide selenide sulfide

Americium oxide Americium (di)oxide Antimony Materials Antimony Antimony Antimony Antimony

nitride (penta)oxide (tetra)oxide (tri)oxide

Arsenic Materials Arsenic (penta)oxide

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Americium Materials

0910_book.fm Page 296 Wednesday, September 22, 2004 9:01 AM

Molecular Weight

Formula

296

© 2005 by CRC Press

Material

197.84

Arsenic selenide Arsenic sulfide

As2Se3 As2S3

386.72 213.97

Arsenic (penta)sulfide Arsenic (tri)sulfide

As2S5 As2S3

310.16 246.04

BaB6 BaC2 Ba3N2 BaO

202.19 161.35 440.00 153.33

Barium (per)oxide

BaO2

Barium selenide Barium telluride

3.74 3.87 4.15 4.75 α 3.51 β 3.25 — 3.43

Amorphous Cubic Monoclinic Crystalline Monoclinic — — Monoclinic

Soluble in H2O, alkali Colorless; n0 = 1.76; soluble in H2O, ethanol, acid, alkali Colorless; n0 = 1.8−2.0; soluble in H2O, ethanol, acid, alkali Brown; insoluble in cold H2O, acid; dissolves in hot H2O; soluble in base Red-brown; insoluble in H2O; soluble in K2S, bicarbonate n0 = 2.4−2.6 Yellow; insoluble in H2O; soluble in alkali, HNO3 Yellow red; n0 = 2.4−2.8; soluble in water, ethanol, alkali

4.36 3.75 4.783 5.72

Cubic Tetragonal — Cubic

169.33

4.96

—

BaSe BaTe

216.29 264.93

5.02 5.13

Cubic disk Cubic disk

Metallic black; insoluble in H2O and HCl; soluble in HNO3 Gray; dissolves in acid; reacts with H2O Yellow brown; dissolves in H2O Colorless, yellowishwhite powder; soluble in dilute acid and alkali; insoluble in acetone, NH3 Whitish gray powder; soluble in dilute acid; insoluble in acetone; very slightly soluble in H2O White; n0 = 2.268; dissolves in H2O, HCl Yellow-white; nD = 2.440; dissolves in acid

Be2C Be3N2 BeO BeS

30.04 55.05 25.01 41.07

1.90 — 3.01 2.36

Hexagonal Cubic Hexagonal Regular

Yellow; decomposes on melting; reacts with H2O; soluble in acid Colorless; dissolves in H2O, acid and concentrated alkali White; n0 = 1.719, 1.733; soluble in concentrated H2SO4, fused KOH Dissolves in H2O

Bismuth (mono)oxide Bismuth (penta)oxide Bismuth (tri)oxide

BiO Bi2O5 Bi2O3

224.98 497.96 465.96

Bismuth (mono)sulfide

BiS

241.04

7.15 5.10 8.9 8.20 8.55 7.6–7.8

Powder — Rhombohedral Cubic Rhombohedral Powder

Dark gray powder; dissolves in H2O, dilute acid; soluble in dilute KOH Red or brown; insoluble in H2O; soluble in KOH Yellow; insoluble in H2O; soluble in acid Gray-black; insoluble in H2O; soluble in acid White to light yellow; n0 = 1.91; insoluble in H2O; slightly soluble in acid Dark gray powder; decomposes on boiling; very slightly soluble in H2O

B 4C BN

55.26 24.82

2.52 2.25

Rhombohedral Hexagonal

Black; insoluble in H2O, acid; soluble in fused alkali White; insoluble in cold H2O; dissolves slightly in hot H2O; slightly soluble in hot acid

Barium Materials Barium Barium Barium Barium

(hexa)boride carbide nitride oxide

Beryllium Materials Beryllium Beryllium Beryllium Beryllium

carbide nitride oxide sulfide

Bismuth Materials

Boron Materials

297

(Tetra)boron carbide Boron nitride

0910_book.fm Page 297 Wednesday, September 22, 2004 9:01 AM

As2O3

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Arsenic (tri)oxide

B 2O 3 BP B2Se3 B 2S 5 B 2S 3

69.62 41.78 258.50 181.92 117.80

2.46 ± 0.01 — — 1.85 1.55

BrO2 Br2O Br3O8

111.91 175.81 367.71

— — —

Cadmium oxide

CdO

128.41

Cadmium phosphide Cadmium selenide Cadmium telluride

Cd3P2 CdSe CdTe

Boron Boron Boron Boron Boron

oxide phosphide (tri)selenide (penta)sulfide (tri)sulfide

Crystalline Form

Miscellaneous

Rhombohedral Powder Powder Tetragonal Vitreous

Colorless; n0 = 1.61, 1.64; soluble in H2O Maroon; insoluble in H2O, all solvents Yellow-gray powder; dissolves in H2O Colorless; dissolves in H2O, ethanol White; dissolves in H2O, ethanol

— — —

Light yellow Dark brown White

399.18 191.37 240.01

6.95 8.15 5.60 5.81 5.850

Amorphous Cubic Tetragonal Powder; hexagonal Cubic

Brown; insoluble in H2O and alkali Brown; insoluble in H2O and alkali; soluble in acid Green; soluble in dilute HCl; soluble in concentrated HNO3 Green-brown or red; insoluble in H2O; dissolves in acid Black; insoluble in H2O and acid; dissolves in HNO3

Ca3N2 CaO2 Ca3P2 CaSe CaS CaTe

148.25 72.08 182.19 119.04 72.14 167.68

2.63 2.92 2.51 3.57 2.5 4.873

Hexagonal Tetragonal Lumps Cubic Cubic Cubic

Brown crystal; dissolves in H2O; soluble in dilute acid White; n0 = 1.895; slightly soluble in H2O; soluble in acid Gray; soluble in acid; insoluble in ethanol, benzene n0 = 2.274 Colorless; n0 = 2.137; dissolves in H2O, acid n0 = 2.51, 2.58

CeB6 CeB4 CeC2 Ce2O3 CeO2

204.98 183.36 164.14 328.24 172.12

— 5.74 5.23 6.86 7.132

Cubic Tetragonal Hexagonal Trigonal Powder

Ce2S3

376.42

5.020

Powder

Metallic blue, insoluble in H2O, HCl; decomposes upon boiling — Red; dissolves in H2O; soluble in acid Gray-green; insoluble in H2O, HCl; soluble in H2SO4 Brownish white; insoluble in H2O and dilute acid; soluble in H2SO4, HNO3 Red crystals; purple powder; insoluble in H2O; soluble in dilute acid

Bromine Materials Bromine (di)oxide Bromine (mono)oxide (Tri)bromine octoxide Cadmium Materials

Calcium Calcium Calcium Calcium Calcium Calcium

nitride (per)oxide phosphide selenide sulfide telluride

Cerium Materials Cerium Cerium Cerium Cerium Cerium

(hexa)boride (tetra)boride carbide (III) oxide (IV) (di)oxide

Cerium (III) sulfide

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Calcium Materials

0910_book.fm Page 298 Wednesday, September 22, 2004 9:01 AM

Density (g/cc)

Formula

298

© 2005 by CRC Press

Molecular Weight

Material

CsN3 Cs2O Cs2O2 Cs2O3 Cs2S2 Cs2S6 Cs2S5 Cs2S4 Cs2S3

174.93 281.81 297.81 313.81 329.93 458.17 426.11 394.05 361.99

— 4.25 4.25 4.25 — — 2.806 — —

Needle Needle Needle Cubic Amorphous — — — Leaf

Colorless; deliquescent Orange; very soluble in H2O; soluble in acid Pale yellow; soluble in H2O, acid Chocolate brown crystals; dissolves in H2O; soluble in acid Dark red Brownish red — Yellow Yellow

CrB Cr3C2 CrN CrO2 CrO Cr2O3 CrO3 CrP CrS Cr2S3

62.81 180.01 66.00 83.99 68.00 151.99 99.99 82.97 84.06 200.17

6.17 6.68 5.9 — — 5.21 2.70 5.7 4.85 3.77

Orthorhombic/crystalline Rhombohedral Cubic/amorphous Powder Powder Hexagonal Rhombohedral Crystalline Powder/hexagonal Powder

Silver; insoluble in H2O Gray; insoluble in H2O Insoluble in H2O Brown-black; insoluble in cold H2O; soluble in HNO3 Black; insoluble in H2O, dilute HNO3 Green; n0 = 2.551; insoluble in H2O, acid, alkali Red; deliquescent; decomposes upon boiling; soluble in H2SO4, HNO3 Gray-black; insoluble in cold H2O; soluble in HNO3 Black; insoluble in cold H2O; very soluble in acid Brown-black; insoluble in H2O; soluble in HNO3

Cobalt (mono)boride Cobalt (II) oxide Cobalt (III) oxide

CoB CoO Co2O3

69.74 74.93 165.86

7.25 6.45 5.18

Cobalt Cobalt Cobalt Cobalt Cobalt

Co3O4 Co2P CoSe CoS2 Co2S3

240.80 148.84 137.89 123.05 214.05

6.07 6.4 7.65 4.269 4.8

Prism Cubic Hexagonal Rhombohedral Cubic Need Hexagonal Cubic Crystalline

Dissolves in H2O; soluble in HNO3 Pink, insoluble in H2O, soluble in acid Black-gray; insoluble in H2O, ethanol Soluble in acid Black; insoluble in H2O; very slightly soluble in acid Gray; insoluble in H2O; soluble in HNO3 Yellow; soluble in HNO3; insoluble in ethanol Black; soluble in HNO3; insoluble in H2O Black crystal; dissolves in acid

Cu2C2 CuN3 Cu(N3)2

151.11 105.57 147.59

— 3.26 2.604

Amorphous Crystalline Crystalline

Red; explosive; soluble in acid Colorless; very explosive; dissolves in concentrated H2SO4 Brown-red/yellow; explosive; very soluble in dilute acid

Chromium Compounds Chromium (mono)boride Trichromium (di)carbide Chromium (mono)nitride Chromium (di)oxide Chromium (II) monoxide Chromium (III) (sesqui)oxide Chromium (tri)oxide Chromium (mono)phosphide Chromium (II) (mono)sulfide Chromium (III) (sesqui)sulfide Cobalt Compounds

(II, III) oxide phosphide (mono)selenide (di)sulfide sesquisulfide

Copper Compounds

299

Copper (III) acetylide Copper (I) azide Copper (II) azide

0910_book.fm Page 299 Wednesday, September 22, 2004 9:01 AM

Compounds azide oxide (per)oxide (tri)oxide (di)sulfide (hexa)sulfide (penta)sulfide (tetra)sulfide (tri)sulfide

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Cesium Cesium Cesium Cesium Cesium Cesium Cesium Cesium Cesium Cesium

Density (g/cc)

Cu3B2 Cu3N CuO

212.26 204.64 79.55

8.116 5.84 6.3−6.49

(Tri)copper phosphide

Cu3P

221.61

6.4−6.8

Copper (I) selenide Copper (II) selenide

Cu2Se CuSe

206.05 142.51

6.749 5.99

Copper telluride

Cu2Te

254.69

7.27

Cubic Hexagonal plates (Unstable) Hexagonal

Dy2O3

373.00

7.81

Powder

White

Er2O3

382.52

8.640

Powder; trigonal to cubic at 1300

Rose red; insoluble in H2O; soluble in acid

Eu2O3

351.92

7.42

Powder

Pale rose

Formula

Copper boride Copper nitride Copper (II) oxide

Crystalline Form

Miscellaneous

— Powder Bulk powder or monoclinic crystals —

Yellow Dark green powder; dissolves in H2O, acid Insoluble in H2O; ethanol; soluble in acid, KCN, NH4Cl Gray-black; insoluble in H2O, HCl; soluble in HNO3; decomposes upon melting Black; dissolves in HCl Green-black; insoluble in H2O; slightly soluble in HCl, NH4OH Blue-black; insoluble in acid

Dysprosium Compounds Dysprosium oxide

Erbium oxide

Europium Compounds Europium oxide Gadolinium Compounds Gadolinium oxide Gadolinium sulfide Gallium Compounds Gallium nitride Gallium (α)-(sesqui)oxide Gallium (β)-(sesqui)oxide

Gd2O3 Gd2S3

362.50 410.70

7.407 6.1

Amorphous powder Cubic

White; hygroscopic; soluble in acid Yellow; hygroscopic; dissolves in acid, H2O

GaN Ga2O3 Ga2O3

83.73 187.44 187.44

6.1 6.44 5.88

Dark gray; sublimes at 800°C; insoluble in H2O, dilute acid White; insoluble in H2O; soluble in alkali; n0 = 1.92, 1.95 Insoluble in H2O; soluble in alkali

Gallium Gallium Gallium Gallium Gallium

Ga2O GaSe GasSe3 Ga2Se GaS

155.44 148.68 376.32 218.40 101.78

4.77 5.03 4.92 5.02 3.86

Powder Hexagonal Rhombohedral; monoclinic Powder Leaf — — Crystalline

(sub)oxide (mono)selenide (sesqui)selenide (sub)selenide (mono)sulfide

Black-brown; insoluble in H2O; soluble in acid, alkali Dark red-brown; greasy Red-brown; brittle; hard Blue Yellow; insoluble in H2O; soluble in acid, alkali

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Erbium Compounds

0910_book.fm Page 300 Wednesday, September 22, 2004 9:01 AM

300

© 2005 by CRC Press

Molecular Weight

Material

235.62

3.65 4.18 5.44 5.57

Crystalline or amorphous — Soft crystalline Brittle crystalline

Yellow crystal; white amorphous; dissolves in H2O, acid; soluble in alkali Dark gray; dissolves in H2O; soluble in acid, alkali Black Black

Gallium (sub)sulfide Gallium (mono)telluride Gallium (sesqui)telluride

Ga2S GaTe Ga2Te3

171.50 197.32 522.24

Ge3N2 Ge3N4 GeO2 GeO2 GeO GeSe2 GeS2 GeS

245.78 273.80 104.59 104.59 88.59 230.51 136.71 104.65

— 5.25 4.228 6.239 — 4.56 2.94 3.31 4.01

Crystalline Powder Hexagonal Tetragonal Powder Rhombohedral Powder/orthorhombic Amorphous Rhombohedral pyramid

Black White to light brown; insoluble in H2O, acid, alkali Colorless; n0 = 1.650; soluble in acid, alkali; insoluble in HCl Insoluble in H2O, HCl; slightly soluble in NaOH Black crystalline powder; n0 = 1.607; insoluble in H2O, acid, alkali Orange; slightly soluble in acid, alkali White; soluble in alkali, ethanol, acid Yellow-red Black; insoluble in H2O; soluble in HCl, alkali

Au2O3 Au2P3 Au2Se2 Au2S Au2S3 AuTe2

441.93 486.85 630.81 425.99 490.11 452.17

— 6.67 4.65 — 8.754 8.2–9.3

— — — Powder Powder Rhombohedral Monoclinic Triclinic

Insoluble in H2O; soluble in HCl, concentrated HNO3 Gray; insoluble in HCl, dilute HNO3 — Brown-black; insoluble in acid Brown-black; insoluble in H2O, alkali Insoluble in H2O — Yellow

HfC Hf N HfO2

190.50 192.50 210.49

12.20 — 9.68

— Cubic Cubic

Insoluble in cold H2O Yellow-brown White; insoluble in H2O

Iridium dioxide Iridium (sesqui)oxide

IrO2 Ir2O3

224.22 432.44

11.665 —

Crystalline or tetragonal —

Iridium selenide

IrSe2

350.14

—

Black tetragonal or blue crystal; insoluble in acid, alkali Blue-black crystals; insoluble in H2O alkali; soluble in acid; decomposes at 1000οC Insoluble in acid

Germanium Compounds (Tri)germanium (di)nitride (Tri)germanium (tetra)nitride Germanium (di)oxide (soluble) Germanium (di)oxide (insoluble) Germanium (mono)oxide Germanium selenide Germanium (di)sulfide Germanium (mono)sulfide

Gold Compounds Gold Gold Gold Gold Gold Gold

(III) oxide phosphide selenide (I) sulfide (III) sulfide (di)telluride

Hafnium Compounds Hafnium carbide Hafnium nitride Hafnium oxide Iridium Compounds

301

Crystalline or powder

0910_book.fm Page 301 Wednesday, September 22, 2004 9:01 AM

Ga2S3

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Gallium (sesqui)sulfide

IrS2 IrS Ir2O3

256.34 224.28 480.62

IrTe3 FeB Fe3C Fe4N Fe2N Fe3O4

Crystalline Form

Miscellaneous

8.43 — 9.64

— — —

575.02

9.5

Crystalline

Brown-black; insoluble in H2O, acid Blue-black; decomposes upon boiling; insoluble in H2O, acid Brown-black; decomposes upon melting; slightly soluble in H2O; soluble in HNO3 Dark gray; insoluble in H2O, acid

Iridium telluride Iron Compounds Iron boride Iron carbide Iron nitride Iron nitride Iron oxide

66.66 179.55 237.39 125.70 231.54

7.15 7.694 6.57 6.35 5.18

Crystalline Cubic — — Cubic or powder

Iron (mono)phosphide

FeP

86.82

(Di)iron phosphide (Tri)iron phosphide Iron (di)sulfide

Fe2P Fe3P FeS2

142.67 198.51 119.97

Iron (II) sulfide Iron (III) sulfide

FeS Fe2S3

87.91 207.87

LaB6 LaC2 La2S3

203.77 162.93 373.99

Lead azide Lead (di)oxide Lead (mono)oxide

Pb(N3)2 PbO2 PbO

291.24 239.20 223.20

Lead (red)oxide Lead (sesqui)oxide Lead (sub)oxide

Pb3O4 Pb2O3 Pb2O

685.60 462.40 430.40

Rhombohedral

Gray; insoluble in H2O Gray; insoluble in H2O; soluble in acid — Gray; insoluble in H2O; soluble in acid Black cubic or red to black powder; n0 = 2.42; insoluble in H2O, ethanol; soluble in concentrated acid —

Crystalline or powder — Cubic Rhombohedral Hexagonal —

Blue-gray; insoluble in H2O, dilute acid Gray; insoluble in H2O Yellow; dissolves in dilute acid; HNO3 Yellow; insoluble in dilute acid; dissolves in HNO3 Black-brown; dissolves in hot H2O; soluble in dilute acid Yellow-green; decomposes upon melting; dissolves in acid

2.61 5.02 4.911

Cubic Crystalline Crystalline; hexagonal

Purple metallic; decomposes upon boiling; insoluble in H2O, HCl Yellow; dissolves in H2O; soluble in H2SO4 Red-yellow; dissolves in H2O; soluble in acid

— 9.375 9.53 8.0 9.1 — 8.342

Needles or powder Tetragonal Tetragonal Rhombohedral Tetragonal Powder; amorphous Amorphous

Colorless; very soluble in acetone, acid; insoluble in NH4OH Bronze-black, insoluble in H2O, ethanol; soluble in dilute HCl Yellow; soluble in HNO3, alkali Yellow; n0 = 2.51, 2.6; insoluble in H2O; soluble in alkali Red; insoluble in H2O and ethanol, soluble in hydrocarbon, hot HCl Orange-yellow; insoluble in H2O; dissolves in hot H2O, acid Black; decomposes upon melting; insoluble in H2O; soluble in acid, alkali

6.07 (5.2) 6.56 6.74 5.0 4.87 4.74 4.3

Lanthanum Compounds Lanthanum (hexa)boride Lanthanum carbide Lanthanum sulfide Lead Compounds

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Iridium (di)sulfide Iridium (mono)sulfide Iridium (sesqui)sulfide

0910_book.fm Page 302 Wednesday, September 22, 2004 9:01 AM

Density (g/cc)

Formula

302

© 2005 by CRC Press

Molecular Weight

Material

362.07 286.16

— 8.10

Unstable Cubic

Black; flammable; dissolves in H2O, dilute acid Gray; insoluble in H2O; soluble in HNO3

Lithium azide Lithium carbide Lithium nitride

LiN3 Li2C2 Li3N

48.96 37.90 34.83

— 1.65 —

Colorless White; dissolves in H2O; soluble in acid Red-brown amorphous, black-gray crystal

Lithium oxide Lithium sulfide

Li2O Li2S

29.88 45.94

2.013 1.66

Crystalline; hygroscopic Crystalline/powder Amorphous; cubic; crystalline Crystalline/cubic Cubic

Lu2O3

397.93

9.42

Cubic crystalline

—

Magnesium boride Magnesium nitride

MgB4 Mg3N2

89.17 100.93

— 2.712

— Powder mass

Magnesium Magnesium Magnesium Magnesium Magnesium

MgO2 Mg3P2 MgSe MgS MgTe

56.30 134.86 103.27 56.37 151.91

— 2.055 4.21 2.84 3.86

Powder Cubic crystalline Powder/crystalline Cubic Hexagonal crystalline

Blue; dissolves in H2O; slightly soluble in acid Green-yellow powder; dissolves in H2O; soluble in acid; decomposes at 270οC White; insoluble in H2O; soluble in acid Yellow-green; dissolves in H2O Light gray; n0 = 2.44; dissolves in H2O, acid Pale red-brown; n0 = 2.271; dissolves in H2O; soluble in acid White; dissolves in H2O, acid

Crystalline Crystalline powder Tetragonal Tetragonal; rhombohedral Rhombohedral; powder Oil; hygroscopic Cubic Cubic (tetragonal) —

Lithium Compounds

White; n0 = 1.644 White to yellow; cubic; deliquescent; very soluble in H2O

Lutetium Compounds Lutetium oxide Magnesium Compounds

(per)oxide phosphide selenide sulfide telluride

Manganese Compounds (di)boride (mono)boride carbide (II, III) oxide

MnB2 MnB Mn3C Mn3O4

76.56 65.75 176.83 228.81

6.9 6.2 6.89 4.856

Manganese Manganese Manganese Manganese Manganese

(di)oxide (hepta)oxide (mono)oxide (III) (sesqui)oxide (tri)oxide

MnO2 Mn2O7 MnO Mn2O3 MnO3

86.94 221.87 70.94 157.87 102.94

5.026 2.396 5.43−5.46 4.50 —

Manganese (mono)phosphide (Tri)manganese (di)phosphide

MnP Mn3P2

85.91 226.76

5.39 5.12

— —

Gray-violet; dissolves in H2O; soluble in acid — Dissolves in H2O; soluble in acid Black; n0 = 2.46; insoluble in H2O; soluble in HCl Black, brown-black powder; insoluble in H2O, HNO3; soluble in HCl Dark red oil; hygroscopic; explosive; dissolves in H2O; soluble in H2SO4 Green; n0 = 2.16; insoluble in H2Ol soluble in acid Black; insoluble in H2O, acetone, acid; soluble in acid Reddish; deliquescent; decomposes upon melting; soluble in alkali, H2O, H2SO4 Dark gray; insoluble in H2O; slightly soluble in HNO3 Dark gray; insoluble in H2O; slightly soluble in dilute HNO3

303

Manganese Manganese Manganese Manganese

0910_book.fm Page 303 Wednesday, September 22, 2004 9:01 AM

PbP5 PbSe

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Lead phosphide Lead selenide

MnSe MnS2

133.90 119.06

Hg(N3)2 Hg3N2 Hg2O HgO Hg2S HgS

Manganese selenide Manganese (IV) sulfide

Crystalline Form

Miscellaneous

5.55 3.463

Cubic Cubic

Gray; insoluble in H2O; dissolves in dilute acid Black; n0 = 2.69; decomposes upon melting; insoluble in H2O; dissolves in HCl

485.22 629.78 417.18 216.59

— — 9.8 1.1

Crystalline Powder Powder Rhombohedral

433.24 232.65

— 8.10

— Crystalline hexagonal/powder Cubic/amorphous powder

White; explodes in light Brown; explodes on melting; dissolves in acid, H2O Black or brownish-black; insoluble in H2O; soluble in HNO3 Yellow, red; n0 = 2.37, 2.5, 2.65; soluble in acid; insoluble in ethanol, alkali Black; decomposes upon melting; insoluble in H2O, ethanol Red; n0 = 2.854 3.201; insoluble in HNO3

Mercury Compounds Mercury Mercury Mercury Mercury

(I) azide nitride (I) oxide (II) oxide

Mercury (I) sulfide Mercury (II) sulfide

7.73

Black; insoluble in H2O, HNO3; soluble in alkali

Molybdenum (di)boride Molybdenum (mono)boride (Di)molybdenum boride Molybdenum (mono)carbide (Di)molybdenum carbide Molybdenum (di)oxide

MoB2 MoB Mo2B MoC Mo2C MoO2

117.56 106.75 202.69 107.95 203.89 127.94

7.12 8.65 9.26 8.20 8.9 6.47

Rhombohedral Tetragonal Tetragonal Hexagonal Hexagonal prism Tetragonal or monoclinic

Molybdenum (penta)oxide

Mo2O5

271.88

Molybdenum (sesqui)oxide Molybdenum phosphide Molybdenum (di)sulfide

Mo2O3 MoP2 MoS2

239.88 157.89 160.06

— 3.6 — 5.35 4.80

Powder Colorless/powder — Powder Hexagonal

Molybdenum (sesqui)sulfide Molybdenum (tetra)sulfide

Mo2S3 MoS4

288.06 224.18

5.91 —

Needles Powder

Molybdenum (tri)sulfide

MoS3

192.12

—

Plates

— — — Gray; insoluble in H2O, alkali; slightly soluble in acid White; slightly soluble in acid; insoluble in alkali Lead gray; insoluble in H2O; slightly soluble in hot concentrated H2SO4; insoluble in alkali, HCl, HF Violet-black; soluble in hot acid Dark blue; soluble in acid; insoluble in benzene Blue; opaque; insoluble in H2O, acid, alkali Black; soluble in acid; insoluble in concentrated HCl Black luster; insoluble in H2O; soluble in acid; insoluble in dilute acid, concentrated H2SO4 Steel gray; insoluble in concentrated HCl Brown; decomposes upon melting; insoluble in H2O, acid; soluble in hot H2SO4 Black; decomposes upon melting or boiling; soluble in H2O, alkali

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Molybdenum Compounds

0910_book.fm Page 304 Wednesday, September 22, 2004 9:01 AM

Density (g/cc)

Formula

304

© 2005 by CRC Press

Molecular Weight

Material

NdC2

168.26

5.15

Hexagonal leaf

Neodymium nitride Neodymium oxide Neodymium sulfide

NdN Nd2O3 Nd2S3

158.25 336.48 384.66

— 7.24 5.179

Powder Powder Powder

NpO2 Np3O3

269.05 839.14

Nickel boride Nickel carbide Nickel (mono)oxide (Di)nickel phosphide (Penta)nickel (di)phosphide (Tri)nickel (di)phosphide Nickel selenide Nickel (mono)sulfide Nickel (sub)sulfide

NiB Ni3C NiO Ni2P Ni5P2 Ni3P2 NiSe NiS Ni3S2

69.50 188.08 74.69 148.35 355.40 238.01 137.65 90.75 240.19

Nickel (II, III) sulfide

Ni3S4

304.31

4.7

Cubic

Niobium boride Niobium carbide

NbB2 NbC

114.53 104.92

6.97 7.6

Hexagonal Cubic/powder

Niobium nitride Niobium (di)oxide Niobium (mono)oxide Niobium (penta)oxide (Sesqui)niobium (tri)oxide

NbN NbO2 NbO Nb2O5 Nb2O3

106.91 124.91 108.91 265.81 233.81

8.4 5.9 7.30 4.47 —

Cubic — Cubic Rhombohedral —

Yellow; decomposes upon melting; dissolves in H2O; soluble in dilute acid; insoluble in concentrated HNO3 Black; dissolves in H2O Light blue; red fluorescence; soluble in acid Olive green; decomposes upon melting; insoluble in cold H2O; dissolves in hot H2O; soluble in dilute acid

Neptunium Compounds Neptunium (di)oxide (Tri)neptunium (octa)oxide

11.11 —

Cubic Cubic

Apple green; insoluble in H2O; soluble in concentrated acid Brown; soluble in HNO3

Prisms Powder Cubic Crystalline Needles/tablet crystals — Cubic Trigonal/amorphous —

Dissolves in H2O; soluble in HNO3 Dark gray Green-black; n0 = 2.1818 (red); soluble in acid; insoluble in H2O Gray; insoluble in H2O, acid — Dark green-black White or gray; insoluble in H2O, acid, HCl Black; soluble in HNO3 Pale, yellowish, bronze metallic luster; insoluble in cold H2O; soluble in HNO3 Gray-black; insoluble in cold H2O; soluble in HNO3

Nickel Compounds 7.39 7.957 6.67 6.31 — 5.99 8.46 5.3–5.65 5.82

Niobium Compounds — Black, lavender-gray powder; insoluble in cold H2O; soluble in HNO3, HF Black; insoluble in cold H2O, HNO3 Black; insoluble in H2O, acid Black; insoluble in H2O; soluble in acid, alkali White; insoluble in H2O acid; soluble in alkali Blue-black

0910_book.fm Page 305 Wednesday, September 22, 2004 9:01 AM

Neodymium carbide

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Neodymium Compounds

305

Molecular Weight

Density (g/cc)

Crystalline Form

Miscellaneous

Crystalline Powder — — Monoclinic Cubic

Osmium Compounds Osmium (di)oxide

OsO2

222.20

Osmium Osmium Osmium Osmium

OsO Os2O3 OsO4 OsS2

206.20 428.40 254.20 254.32

11.37 7.71 — — 4.906 9.47

Osmium (tetra)sulfide

OsS4

318.44

—

—

Osmium telluride

OsTe2

445.40

—

Crystalline

Brown; insoluble in H2O, acid Black; insoluble in H2O; soluble in dilute Black; insoluble in H2O Dark brown; decomposes upon melting; insoluble in H2O, acid Colorless Black; decomposes upon melting; insoluble in H2O, alkali; soluble in HNO3 Brown-black; decomposes upon melting; insoluble in cold H2O; soluble in dilute HNO3 Gray-black; insoluble in acid; dissolves in dilute HNO3

PdO PdSe PdSe2 PdS4 PdS Pd2S PdTe2

122.24 185.38 264.34 170.54 138.48 244.90 361.62

9.70 — — 4.7–4.8 6.6 7.303 —

Mass/powder — Hexagonal Crystalline Tetragonal — Crystalline/hexagonal

Greenish blue or amber/black powder; insoluble in H2O Dark gray; insoluble in cold H2O Olive gray; insoluble in H2O, alkali Dark brown; decomposes upon melting; insoluble in H2O Brown-black; insoluble in H2O, HCl Green-gray; insoluble in H2O; slightly soluble in acid Silvery crystal; insoluble in H2O, alkali; soluble in HNO3

Phosphorus (penta)oxide Phosphorus (sesqui)oxide

P 2O 5 P 4O 6

141.94 219.89

2.39 2.135

Monoclinic/powder Powder/crystalline

Phosphorus (tetra)oxide Phosphorus (tri)oxide

P 2O 4 P 2O 3

125.95 109.95

2.54 2.135

Rhombohedral Powder

Phosphorus (penta)selenide (Tetra)phosphorus (tri)selenide (Tetra)phosphorus (hepta)sulfide Phosphorus (penta)sulfide

P2Se5 P4Se3 P 4S 7

456.75 360.78 348.32

— 1.31 2.19

Needles Crystalline Crystalline

White; very deliquescent; monoclinic; soluble in H2SO4 Colorless or white powder; monoclinic crystal; deliquescent; dissolves in hot H2O Colorless; deliquescent; dissolves in hot H2O Colorless or white powder or monoclinic; deliquescent; dissolves in hot H2O Dark red-black; decomposes upon melting; dissolves in cold H2O Orange-red Light yellow

P 2S 5

222.25

2.03

Crystalline

Phosphorus (sesqui)sulfide

P 4S 3

220.08

2.03

Rhombohedral

(mono)oxide (sesqui)oxide (tetra)oxide (di)sulfide

Palladium Compounds (mono)oxide selenide (di)selenide (di)sulfide (mono)sulfide (sub)sulfide (di)telluride

Phosphorus Compounds

Gray–yellow crystal; deliquescent; insoluble in cold H2O; dissolves in hot H2O; soluble in alkali Yellow; insoluble in cold H2O; dissolves in hot H2O

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Palladium Palladium Palladium Palladium Palladium Palladium Palladium

0910_book.fm Page 306 Wednesday, September 22, 2004 9:01 AM

Formula

306

© 2005 by CRC Press

Material

(II) (mono)oxide (IV) (di)oxide (II,IV) oxide (tri)oxide phosphide (di)selenide (tri)selenide (IV) (di)sulfide (II) (mono)sulfide (sesqui)sulfide telluride

PtO PtO2 Pt3O4 PtO3 PtP2 PtSe2 PtSe3 PtS2 PtS Pt2S3 PtTe2

211.08 227.08 649.24 243.09 257.03 353.00 431.96 259.20 227.14 486.34 450.28

14.9 10.2 — — 9.01 7.65 7.15 7.66 10.04 5.52 —

— — — Powder — Crystalline/amorphous Flakes Powder Tetragonal — Hexagonal

Violet-black; insoluble in H2O acid; soluble in HCl Black; insoluble in H2O acid Decomposes upon melting; insoluble in H2O, acid Reddish brown; soluble in HCl, H2SO4 Metallic shine; insoluble in H2O, acid Black or gray; slightly soluble in acid Blue; insoluble in H2O, concentrated acid Black-brown; insoluble in H2O; soluble in acid Black; decomposes upon melting; insoluble in H2O, acid, alkali Gray; decomposes upon melting; insoluble in H2O, acid Gray

PuN PuO2

253.06 271.05

14.25 11.46

Cubic Cubic

Black; soluble in acid Yellowish-green; slightly soluble in acid

PoO2 PoS

240.98 401.10

— —

Tetragonal —

Red Purple; insoluble in ethanol

KN3 K 3N K 2O K 2O 2 KO2 K 2O 3 K2Se K 2S 2 K 2S K 2S 5 K 2S 4 K 2S 3 K2Te

81.12 131.30 94.20 110.20 71.10 126.20 157.16 142.32 110.26 238.50 206.44 174.38 205.80

2.04 — 2.32 — 2.14 — 2.851 — 1.805 — — — 2.51

Tetragonal — Cubic Amorphous Cubic — Cubic Crystalline Cubic Crystalline Crystalline Crystalline Cubic

Colorless; soluble in ethanol Greenish black; decomposes upon melting; dissolves in cold H2O Colorless; hygroscopic; very soluble in H2O White; deliquescent; decomposes upon boiling Yellow leaf; decomposes upon boiling Red; dissolves in dilute H2SO4 White; turns red in air; hygroscopic Red-yellow; soluble in cold H2O; dissolves in hot H2O Yellow-brown; deliquescent; soluble in H2O Orange; hygroscopic; very soluble in H2O Red-brown; soluble in cold H2O Bright yellow; soluble in cold H2O; dissolves in hot H2O Colorless; hygroscopic; soluble in H2O

Plutonium Compounds Plutonium nitride Plutonium (di)oxide Polonium Compounds Polonium (di)oxide Polonium (mono)sulfide Potassium Compounds Potassium azide Potassium nitride Potassium (mono)oxide Potassium (per)oxide Potassium (super)oxide (Sesqui)potassium (tri)oxide Potassium selenide Potassium (di)sulfide Potassium (mono)sulfide Potassium (penta)sulfide Potassium (tetra)sulfide Potassium (tri)sulfide Potassium telluride

0910_book.fm Page 307 Wednesday, September 22, 2004 9:01 AM

Platinum Platinum Platinum Platinum Platinum Platinum Platinum Platinum Platinum Platinum Platinum

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Platinium Compounds

307

Molecular Weight

Density (g/cc)

Crystalline Form

Miscellaneous

Praseodymium Compounds Praseodymium carbide

PrC2

164.93

5.10

Crystalline

Praseodymium (di)oxide (Sesqui)praseodymium oxide Praseodymium selenate Praseodymium sulfide

PrO2 Pr2O3 Pr2(Se)4)3 Pr2S3

172.91 329.81 710.69 378.00

6.82 7.07 4.30 5.042

Powder Amorphous — Powder

Yellow; decomposes upon melting; dissolves in H2O; soluble in dilute acid Bright blue Yellow-green; decomposes upon melting soluble in acid — Brown; dissolves in hot H2O; soluble in dilute acid

PaO2 Pa2O5

263.03 542.07

— —

Cubic Cubic

Black Black

Rhenium (di)oxide Rhenium (hepta)oxide

ReO2 Re2O7

218.21 484.41

11.4 6.103

Black; insoluble in H2O; soluble in concentrated HCl Yellow; hygroscopic; very soluble in H2O; soluble in alkali, acid

Rhenium (per)oxide Rhenium (tri)oxide Rhenium (di)sulfide

Re2O3 ReO3 ReS2

500.41 234.21 250.33

8.4 6.9–7.4 7.506

— Plates or hexagonal or powder — Cubic Hexagonal

Rhenium (hepta)sulfide

Re2S7

596.83

4.866

Powder

Rhodium (di)oxide Rhodium (sesqui)oxide

RhO2 Rh2O3

134.90 253.81

— 8.20

Brown; insoluble in H2O, acid, alkali Gray; insoluble in H2O, acid, KOH

Rhodium (mono)sulfide Rhodium (sesqui)sulfide

RhS Rh2S3

134.97 302.00

— 6.40

— Crystalline or amorphous Crystalline —

RuO2 RuO4 RuS2

133.07 165.07 165.19

6.97 3.29 6.99

Tetragonal Needles, rhombohedral Cubic

Dark blue; decomposes upon melting; insoluble in H2O, acid Yellow; soluble in acid, alkali Gray-black; insoluble in H2O, acid

Protactinium Compounds Protactinium (di)oxide Protactinium (penta)oxide Rhenium Compounds

Rhodium Compounds

Gray-black; decomposes upon melting; insoluble in H2O, acid Black; decomposes upon melting; insoluble in H2O, acid

Ruthenium Compounds Ruthenium (di)oxide Ruthenium (tetra)oxide Ruthenium sulfide

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

White; very soluble in H2O; soluble in alkali Red, blue; insoluble in H2O; soluble in HNO3 Black; decomposes at 1000οC; insoluble in H2O, alkali, HCl; soluble in HNO3 Black; decomposes upon boiling; insoluble in H2O; soluble in HNO3

0910_book.fm Page 308 Wednesday, September 22, 2004 9:01 AM

Formula

308

© 2005 by CRC Press

Material

174.38 348.72 396.90

5.86 8.347 5.729

Hexagonal Powder —

Yellow; dissolves in H2O, acid White to yellowish; insoluble in cold H2O; very soluble in acid Yellowish pink; dissolves in hot H2O, dilute acid

ScO2

137.91

3.864

Powder

White; insoluble in H2O; soluble in hot acid

SeC2 Se4N4 SeO2 SeO3 SeS2

102.98 371.87 110.96 126.96 143.08

2.682 — 3.95 3.6 —

Liquid Amorphous Tetragonal Tetragonal —

SeS

11.02

3.056

Powder or tablets

Yellow; n0 = 1.845; insoluble in cold H2O Orange-yellow, brick red; hygroscopic; decomposes upon boiling Colorless-white; poisonous; soluble in ethanol, methanol White, deliquescent, very soluble in H2O Bright red-yellow; decomposes upon boiling; insoluble in cold H2O; dHNO3 Orange-yellow; insoluble in H2O

Silicon carbide Silicon (di)oxide

SiC SiO2

40.10 60.08

Hexagonal or cubic Cubic or tetragonal Amorphous Rhombohedral Hexagonal

Colorless to black; n0 = 2.654, 2.697; insoluble in H2O, acid Colorless; n0 = 1.487, 1.484; insoluble in H2O Colorless; vitreous; n0 = 1.4588, insoluble in H2O Colorless; n0 = 1.469, 1.470, 1.471; insoluble in H2O Colorless; n0 = 1.544, 1.553; insoluble in H2O

Silicon (mono)oxide Silicon (di)sulfide Silicon (mono)sulfide

SiO SiS2 SiS

44.08 92.21 60.15

3.217 2.32 2.19 2.26 2.635− 2.660 2.13 2.02 1.853

Cubic Needles, rhombohedral Needles

White; insoluble in H2O White; dissolves in cold H2O; soluble in dilute alkali Yellow; dissolves in H2O, alkali

AgN3 Ag2C2 Ag2O Ag2O2 Ag2Se

149.89 239.76 231.74 247.74 294.70

— — 7.143 7.44 8.0

Rhombohedral prism Precipitate Cubic Cubic Cubic or plates

Ag2S

247.80

7.326 7.317

Rhombohedral Cubic

White; explosive; insoluble in cold H2O White; insoluble in cold H2O; soluble in acid Brown-black; soluble in acid Gray-black; insoluble in cold H2O; soluble in acid Gray; decomposes upon boiling; insoluble in cold H2O; soluble in hot HNO3 Gray-black; decomposes upon boiling; soluble in acid Black; decomposes upon boiling; soluble in acid

Scandium Compounds Scandium oxide Selenium Compounds Selenium Selenium Selenium Selenium Selenium

carbide nitride (di)oxide (tri)oxide (di)sulfide

Selenium (mono)sulfide Silicon Compounds

Silver Compounds Silver Silver Silver Silver Silver

azide acetylide oxide (per)oxide selenide

309

Silver sulfide

0910_book.fm Page 309 Wednesday, September 22, 2004 9:01 AM

SmC2 Sm2O2 Sm2S3

Samarium carbide Samarium (sesqui)oxide Samarium (III) sulfide

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Samarium Compounds

Silver telluride

Ag2Te

343.34

NaN3 Na2C2 Na3N Na2O Na2O2 Na3P Na2Se Na2S Na2S5 Na2S4 Na2Te

Density (g/cc)

Crystalline Form

Miscellaneous

8.5

Cubic

Gray, insoluble in H2O

65.01 70.00 82.98 61.98 77.98 99.94 124.94 78.04 206.28 174.22 173.58

1.846 1.575 — 2.27 2.805 — 2.625 1.856 — — 2.90

Hexagonal Powder — — Powder — Crystalline Crystalline — Cubic Crystalline/powder

Colorless White; dissolves in H2O; soluble in acid Dark gray; dissolves in cold H2O White to gray; deliquescent; dissolves in H2O Yellowish white; soluble in cold H2O; dissolves in hot H2O Red; decomposes upon melting White to red; deliquescent; dissolves in cold H2O White; deliquescent; dissolves in acid Yellow; soluble in acid Yellow; hygroscopic; decomposes upon boiling; soluble in cold H2O White; very hygroscopic; dissolves in air; very soluble; dissolves in H 2O

SrB6 SrC2 Sr3N2 SrO SrO2 SrSe SrS

152.48 111.64 290.87 103.62 119.62 166.58 119.68

3.39 3.2 — 4.7 4.56 4.38 3.70

Cubic Tetragonal — Cubic Powder Cubic Cubic

SrTe

215.22

4.83

Cubic

Black; insoluble in H2O, HCl Black; dissolves in H2O, acid Dissolves in H2O; soluble in HCl Gray-white; n0 = 1.810 White; dissolves in cold H2O White; n0 = 2.220; dissolves in H2O; soluble in HCl Colorless to light gray; n0 = 2.107; insoluble in cold H2O; dissolves in hot H2O acid White; n0 = 2.408

(Tetra)sulfur (di)nitride (Tetra)sulfur (tetra)nitride Sulfur (di)oxide

S 4N 2 S 4S 4 SO2

156.25 184.27 64.06

Liquid or solid — Gas; liquid

Red liquid or gray solid; insoluble in cold H2O Orange-red; dissolves in cold H2O Colorless; soluble in acid; suffocating odor; soluble in acid

Sulfur (hepta)oxide Sulfur (mono)oxide Sulfur (sesqui)oxide

S 2O 7 SO S 2O 2

176.12 48.06 112.12

1.901 2.22 2.927 1.434 — — —

Needles or liquid Gas Crystalline

Viscous liquid; dissolves in H2O; soluble in H2SO4 Colorless; decomposes on melting, boiling, H2O Blue-green; dissolves in H2O; soluble in fumed H2SO4

Sodium Compounds Sodium Sodium Sodium Sodium Sodium Sodium Sodium Sodium Sodium Sodium Sodium

azide carbide nitride (mono)oxide (per)oxide phosphide selenide (mono)sulfide (penta)sulfide (tetra)sulfide telluride

Strontium Strontium Strontium Strontium Strontium Strontium Strontium

(hexa)boride carbide nitride oxide (per)oxide selenide (mono)sulfide

Strontium telluride Sulfur Compounds

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Strontium Compounds

0910_book.fm Page 310 Wednesday, September 22, 2004 9:01 AM

Formula

310

© 2005 by CRC Press

Molecular Weight

Material

SO4 SO3 (SO3)2 SO3

96.06 80.06 160.12 80.06

TaB2 TaC TaN Ta2N5 Ta2O4 Ta2S4

202.57 192.96 194.95 441.89 425.89 490.14

Tellurium (di)oxide

TeO2

159.60

Tellurium (mono)oxide

TeO

143.60

Tellurium (tri)oxide

TeO3

175.60

Tellurium sulfide

TeS2

191.72

Tb2O3 Tb4O7

365.85 747.70

Thallium azide Thallium (I) oxide Thallium (III) oxide

TlN3 Tl2O Tl2O3

246.40 424.77 456.76

Thallium selenide Thallium (I) sulfide

Tl2Se Tl2S

487.73 440.83

Thallium (III) sulfide

Tl2S3

504.93

— 1.97 — 1.920 2.29

— Fibrous needles Asbestos-like fiber Liquid Solid

White; dissolves in dilute H2SO4 Silky; stable; dissolves in H2O Metastable; dissolves in H2O Vitreous; orthorhombic; dissolves in H2O Metastable

— Cubic Hexagonal Rhombohedral Powder Powder/crystalline

— Black; insoluble in H2O; slightly soluble in acid Bright bronze or black; insoluble in H2O; slightly soluble in acid Colorless; insoluble in H2O; acid Dark gray; insoluble in H2O; acid Black; insoluble in H2O, HCl

5.67 5.91 5.682

Tetragonal Rhombohedral Amorphous

5.0752 6.21 —

Amorphous Crystalline Amorphous/powder

White; insoluble in H2O; soluble in acid, alkali n0 = 2.00, 2.18, 2.35 Black; decomposes upon boiling; insoluble in H2O; soluble in dilute acid Yellow amorphous, gray crystal; insoluble in H2O, acid Dissolves in concentrated HCl Red-black; insoluble in cold H2O, acid

Solid Solid

White; soluble in dilute acid Dark brown or black; insoluble in H2O; soluble in hot concentrated acid

Tetragonal — Hexagonal Amorphous prisms Leaf Tetragonal

Yellow Black; deliquescent; soluble in acid Insoluble in H2O, alkali; soluble in acid Colorless Gray; insoluble in cold H2O; soluble in acid Blue-black; decomposes upon boiling; soluble in acid; insoluble in alkali Black; decomposes upon boiling; insoluble in H2O; soluble in hot H2SO4

Tantalum Compounds Tantalum Tantalum Tantalum Tantalum Tantalum Tantalum

diboride carbide nitride (penta)oxide (tetra)oxide sulfide

11.15 13.9 16.30 8.2 — —

Tellurium Compounds

Terbium Compounds Terbium oxide Terbium (per)oxide

— —

Thallium Compounds — 9.52 10.19 9.65 9.05 8.46 —

Amorphous

0910_book.fm Page 311 Wednesday, September 22, 2004 9:01 AM

(tetra)oxide (α)trioxide (β)trioxide (γ)trioxide

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Sulfur Sulfur Sulfur Sulfur

311

Density (g/cc)

Crystalline Form

Miscellaneous

ThB6 ThB4 ThC2 Th3N4 ThO2 ThS2

296.90 275.28 256.06 752.14 264.04 296.16

6.4 7.5 8.96 — 9.86 7.30

Cubic Tetragonal prisms Tetragonal Powder/crystalline Cubic Crystalline

Dark violet-black metallic; insoluble in H2O, alkali, acid; soluble in HCl Insoluble in H2O; soluble in acid Yellow, dissolves in cold H2O, very slightly soluble in concentrated acid Dark brown powder, black crystal; dissolves in H2O; soluble in HCl White; n0 = 2.20; insoluble in H2O, dilute acid, alkali Dark brown-black; insoluble in cold H2O

Tm2O3

385.87

—

Powder

Greenish white

Tin (II) (mono)oxide Tin (IV) (di)oxide Tin (mono)phosphide

SnO SnO2 SnP

134.69 150.69 149.66

6.446 6.95 6.56

Cubic (tetragonal) Tetragonal —

Tin (tri)phosphide (Tetra)tin (tri)phosphide Tin (II) selenide Tin (II) sulfide Tin (IV) sulfide Tin (II) telluride Tin (IV) telluride

SnP3 Sn4P3 SnSe SnS SnS2 SnTe SnTe2

211.61 567.68 197.65 150.75 182.81 246.29 373.89

4.10 5.181 6.179 5.22 4.5 6.48 —

Crystalline Crystalline Crystalline Cubic, monoclinic Hexagonal Crystalline Precipitate

Black; insoluble in H2O; soluble in acid, alkali White; n0 = 1.997, 2.093; insoluble in H2O Silver-white; decomposes on melting, boiling; insoluble in H2O HNO3; soluble in HCl Insoluble in H2O, HCl; dissolves in HNO3 White; insoluble in H2O Steel gray; insoluble in H2O; dissolves in acid Gray-black; dissolves in HCl, alkali Golden yellow; insoluble in acid Gray; decomposes upon boiling; insoluble in H2O Black flocculated percipitate; insoluble in H2O; dissolves in dilute acid, alkali

Formula

Thorium Compounds Thorium Thorium Thorium Thorium Thorium Thorium

(hexa)boride (tetra)boride carbide nitride (di)oxide sulfide

Thulium Compounds Thulium oxide Tin Compounds

Titanium (di)boride Titanium carbide Titanium (di)oxide

TiB2 TiC TiO2

69.50 59.89 79.88

4.5 4.93 4.17 3.84 4.26

Hexagonal Cubic Rhombohedral Tetragonal Tetragonal

Titanium (mono)oxide Titanium (sesqui)oxide

TiO Ti2O3

63.85 143.76

4.93 4.6

Prisms Hexagonal

— Gray metallic; insoluble in H2O; soluble in HNO3 White; n0 = 2.583, 2.586, 2.741 Brown-black; n0 = 2.554, 2.493 Colorless; n0 = 2.616, 2.903; for all three forms: insoluble in H2O, acid, soluble in alkali, H2SO4 Yellow-black; insoluble in HNO3; soluble in dilute H2SO4 Violet-black; insoluble in H2O, acid; soluble in H2SO4

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Titanium Compounds

0910_book.fm Page 312 Wednesday, September 22, 2004 9:01 AM

312

© 2005 by CRC Press

Molecular Weight

Material

78.85 112.00 79.94

3.95 3.22 4.05

— Hexagonal Hexagonal

Titanium (sesqui)sulfide

Ti2S3

191.94

3.584

Hexagonal

Gray metallic; insoluble in H2O, acid Yellow; dissolves in HCl, soluble in dilute acid Reddish bronze; insoluble in cold H2O, acid; soluble in concentrated H2SO4 Grayish black; insoluble in H2O, dilute acid; soluble in concentrated acid

WB2 WC W 2C WN2 WO2 W 2O 5 WO3 WP WP2 W 2P WS2 WS3

205.47 195.86 379.71 211.86 215.85 447.70 231.85 214.82 245.80 398.67 247.97 280.03

10.77 15.63 17.75 — 12.11 — 7.16 8.5 5.8 5.21 7.5 —

Octahedral Hexagonal Hexagonal Cubic Cubic Triclinic Rhombohedral/powder Prism Crystalline Prism Hexagonal Powder

Silvery; insoluble in H2O Black; insoluble in cold H2O Black; insoluble in cold H2O Brown, dissolves in H2O Brown; insoluble in H2O; soluble in acid, KOH Blue-violet; insoluble in H2O, acid Yellow-orange powder; insoluble in H2O, acid; soluble in hot alkali Gray; insoluble in cold H2O, alkali, HCl Black; decomposes upon melting; insoluble in H2O Dark gray; decomposes upon melting; insoluble in acid Dark gray; insoluble in cold H2O; soluble in fused alkali Chocolate brown; soluble in H2O, alkali

UB2 UC2 UN UO2 UO3

259.65 262.05 252.04 270.03 286.93

12.70 11.28 14.31 10.96 7.29

Hexagonal Crystalline Powder Rhombohedral/cubic Crystalline

Uranium (sesqui)oxide Uranium (di)sulfide

U 2O 3 US2

842.08 302.15

8.30 7.96

Uranium (mono)sulfide Uranium (sesqui)sulfide

US U 2S 3

270.09 572.24

10.87 —

Amorphous powder Rhombohedral needles

— Metallic; dissolves in H2O, dilute inorganic acid Brown; insoluble in HCl, H2SO4 Brown-black; insoluble in H2O; soluble in acid Yellow-red; decomposes upon melting; insoluble in cold H2O; soluble in acid Olive green to black; insoluble in H2O; soluble in acid Gray-black; slightly dissolves in cold H2O; soluble in concentrated HCl; dissolves in HNO3 Black, insoluble in acid Gray black, insoluble in dilute acid

VB2 VC VN VO

72.56 62.95 64.95 66.94

Hexagonal Cubic Cubic Crystalline

— Black; insoluble in cold H2O, acid; soluble in HNO3 Black; insoluble in cold H2O Light gray; insoluble in H2O; soluble in acid

Tungsten Compounds Tungsten (di)boride Tungsten carbide (Di)tungsten carbide Tungsten (di)nitride Tungsten (di)oxide Tungsten (penta)oxide Tungsten (tri)oxide Tungsten (mono)phosphide Tungsten (di)phosphide (Di)tungsten phosphide Tungsten (di)sulfide Tungsten (tri)sulfide Uranium Compounds Uranium Uranium Uranium Uranium Uranium

(di)boride (di)carbide (mono)nitride (di)oxide (tri)oxide

— Tetragonal

Vanadium Compounds (di)boride carbide nitride oxide

5.10 5.77 6.13 5.758

313

Vanadium Vanadium Vanadium Vanadium

0910_book.fm Page 313 Wednesday, September 22, 2004 9:01 AM

Tip TiS2 TiS

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Titanium phosphide Titanium (di)sulfide Titanium (mono)sulfide

Molecular Weight

Density (g/cc)

Crystalline Form

Miscellaneous

(di)oxide (penta)oxide (sesqui)oxide (mono)sulfide

VO2 V 2O 5 V 2O 3 VS

82.94 181.88 149.88 83.00

4.339 3.357 4.87 4.20

Crystalline Rhombohedral Crystalline Hexagonal

Vanadium (penta)sulfide

V 2S 5

262.18

3.0

Powder

Vanadium (sesqui)sulfide

V 2S 3

198.06

4.72

Plates/powder

Blue; insoluble in H2O; soluble in acid, alkali Yellow to red; n0 = 1.46, 1.52, 1.76; soluble in acid, alkali Black; soluble in H2O, HNO3, alkali Black plates; decomposes upon melting; soluble in acid; insoluble in HCl, alkali Black to green; decomposes upon melting; insoluble in cold H2O; soluble in HNO3, alkali Green to black; insoluble in cold H2O; slightly soluble in alkali, acid

Yb2O3

394.08

9.17

Cubic

Colorless; insoluble in H2O; soluble in hot dilute acid

YC2 Y 2O 3

112.93 225.81

4.13 5.01

Microcrystalline Cubic/powder

Yellow; dissolves in cold H2O Colorless to yellowish; soluble in acid; insoluble in alkali

Zn3N2 Zn3P2 ZnSe ZnS ZnS ZnTe

224.15 258.09 144.34 97.44 97.44 192.98

6.22 4.55 5.42 3.98 4.102 6.34

Cubic Tetragonal Cubic Hexagonal Cubic Cubic

Gray; dissolves in cold H2O; soluble in HCl Dark gray; poisonous; dissolves in cold H2O; soluble in dilute acid Yellowish to reddish; n0 = 2.89; insoluble in cold H2O; soluble in acid Colorless; n0 = 2.356, 2.378; very soluble in acid Colorless; n0 = 2.368; very soluble in acid Insoluble in H2O; slowly dissolves in acid

Zirconium (di)boride Zirconium carbide

ZrB2 ZrC

112.84 103.23

6.085 6.73

Hexagonal Cubic

Zirconium nitride Zirconium oxide

ZrN ZrO2

105.23 123.22

7.09 5.89

Crystalline Monoclinic

Zirconium phosphide

ZrP2

153.17

4.77

—

Zirconium sulfide

ZrS2

155.34

3.87

Crystalline

— Gray metallic; insoluble in cold H2O; slightly soluble in concentrated H2SO4 Yellow-brown; insoluble in H2O; soluble in concentrated acid Colorless to yellow brown; n0 = 2.13, 2.19, 2.20; insoluble in H2O; soluble in acid Gray; brittle; insoluble in cold H2O; very soluble in concentrated hot H2SO4 Steel gray crystal; hexagonal; insoluble in H2O, acid

Ytterbium Compounds Ytterbium (III) oxide Yttrium Compounds

Zinc Compounds Zinc nitride Zinc phosphide Zinc selenide Zinc α-sulfide Zind β-sulfide Zinc telluride Zirconium Compounds

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Yttrium carbide Yttrium oxide

0910_book.fm Page 314 Wednesday, September 22, 2004 9:01 AM

Vanadium Vanadium Vanadium Vanadium

Formula

314

© 2005 by CRC Press

Material

0910_book.fm Page 315 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

II. ELECTRICAL PROPERTIES

© 2005 by CRC Press

315

Aluminum (III) oxide or alumina (Al2O3)

Dielectric Strength (kV/mm)

—

—

Dielectric Loss at ~1 MHz (tan )

Curie, Tc, or (Neel, Tn) Temp. (°C)

References and Miscellaneous

—

—

24.00

—

5.10

—

—

—

—

5.30

—

—

1, p. 308

—

—

3.30

—

—

1, p. 306

—

—

11.40

—

—

1, p. 306

—

—

34.00

—

1, p. 306; 5, p. 933

—

—

19.23

—

—

1, p. 306

—

—

0.01–0.02; 0.01–0.02 at 1 kHz for thin films

135; 115−140 for thin films

—

—

1,000−5,000; 1,200−1,600 at 1 kHz; 550−1800 at 1 kHz for thin films 43.00

—

—

1, p. 306; 4, p. 180; 5, p. 868; 7, p. 1113; 8, p. 192; 10, p. 965; 12; Eg = 2.5−3.2 eV 1, p. 306

—

—

18.00

—

—

1, p. 306

—

—

10,000−20,000

—

—

7, p. 1113; 8, p. 192

(1−3) × 10−4; 4 × 10−4 for thin film

—

1, p. 306; 3, p. TD25, TD27; 6, p. 710; 7, p. 1108; 13

10; ∼2,000 (single crystal)

8.8−10.0

1 × 10−3 to 2 × 10−4

—

∼1010−1013

10; 23.6 for thick film

8.60−12.3, 10.10 (γ-Al2O3)

1 × 10−3 to 1 × 10−5

—

>1015

24; 9.5 for thin film

6.4−6.8

1 × 10−3

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

—

1, p. 306; 12, p. 63; Eg = 1.6 eV 3, p. TD25, TD27, TD29, TD30; 6, p. 709; 7, p. 1108 1, p. 306; 2, p. 233; 3, p. TD25, TD27; 4, p. 180; 5, p. 868, 933; 6, p. 710; 7, p. 1108; 8, p. 192; 9, p. 400; 11−13; Eg > 8 eV 1, p. 308

2 × 109−1011

Antimony bromide (SbBr3) Antimony chloride (SbCl3) Arsenic boride (AsBr3) Barium chloride (BaCl2) Barium oxide (BaO) Barium sulfide (BaS) Barium titanate (BaTiO3) Barium zirconate (BaZrO3) Barium-tin IV oxide (barium stannate) (BaSnO3) Barium−zirconiumtitanate (BaZrxTi1–xO3) Berrylium oxide (BeO)

Dielectric Constant at ~25°C and ~1 MHz

0910_book.fm Page 316 Wednesday, September 22, 2004 9:01 AM

Aluminum antimonide (AlSb) Alumium nitride (AIN)

Resistivity (
·m at ~25°C)

316

© 2005 by CRC Press

Material

Boron nitride (BN)

1010 to 1.7 × 1011; 3 × 102 at 1000οC

Cadmium bromide (CdBr2) Cadmium oxide (CdO) Cadmium sulfide (CdS) Cadmium telluride (CdTe) Calcium carbonate (CaCO3) Calcium fluoride (CaF2) Calcium oxide (CaO)

Calcium titanate (CaTiO3) Cesium chloride (CsCl) Cesium iodide (CsI) Chromium boride (CrB2) Chromium oxide (Cr2O3)

— —

135.00

10−3−10−1

— 112 at 1 kHz

—

31−39

—

3−4.11; 7.1 at i.r

—

—

2, p. 231

—

—

1, p. 306

—

—

5, p. 851; 6, p. 707; 7, p. 806; 9, p. 400; 11; 12; Eg = 1.64 eV 3, p. TD29; 5, p. 868; 6, p. 709; 11−14; Eg = 4.8 eV 1, p. 306

3.4−11

—

—

—

8.60

—

—

67.3 at 795οC; 7.13 at 1000οC; 0.326 at 1200οC —

—

17.2 at 4.5 × 108 Hz

—

—

5, p. 868; 13; Eg = 2.1 eV

—

9.53−10.33 at 104 Hz

—

—

—

—

7−10.60 at i.r.

—

—

—

—

7.80−8.50

—

—

3, p. TD30; 5, p. 868; 12; 14; Eg = 2.42 eV 1, p. 306; 5, p. 868; 12; 14; Eg = 1.45 eV 2, p. 233

—

—

6.25−6.79

—

—

41.75 × 103 at 930οC; 10.4 × 102 at 1235οC; 20.45 at 1370οC —

—

0.10−11.80

—

—

—

160−165

—

—

—

—

6.34−7.2

—

—

7, p. 1113; 8, p. 192; 14 1, p. 306; 14

—

—

5.60; 6.31 at 1 kHz —

—

—

1, p. 306; 14

—

—

6, p. 707; 7, p. 799

9.2 at 450 MHz; 11.9−13.3 at 1 kHz

—

—

9, p. 400; 12−14

—

3 × 102; 1.3 × 101 at 350ο C; 7.8 × 10–1 at 750οC; 4.0 × 10−1 at 1000οC; 2.2 × 10−1 at 1200οC

—

Note: Eg = band gap; 1 kV/mm = 0.0393 V/mil; i.r. (infrared) frequency range = 0.7 to 15 µm or (0.33−5) × 1014 Hz.

317

21−30 × 10−8

2, p. 233; 5, p. 868; Eg = 12 eV 1, p. 306; 12; 13

0910_book.fm Page 317 Wednesday, September 22, 2004 9:01 AM

3−570

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Bismuth sulfide (Bi2S3) Bismuth titanate (Bi4Ti3O12) Boron carbide (B4C)

1 × 106; 1.0 at 300οC

—

10−50

—

(80–100) × 10−6

Dielectric Loss at ~1 MHz (tan )

Curie, Tc, or (Neel, Tn) Temp. (°C)

References and Miscellaneous

12.90

—

—

7.5−10

—

—

—

—

1, p. 306; 5, p. 868; 13; 14; Eg = 4 eV 2, p. 231; 5, p. 868; 13; 14; Eg = 2.1 eV 2, p. 231

Dielectric Constant at ~25°C and ~1 MHz

—

—

—

—

9.80

—

—

1, p. 306

6000

—

10.68−18.1

—

—

2, p. 231; 13; 14

(0.30–83) × 10−6

—

—

—

2, p. 231

—

11

>1012

14

— 60 × 10−4

10.6

—

—

15.69 at i.r.

—

—

—

—

12.95

—

—

—

—

11.1

—

—

(10−2) × 10−8

—

—

—

—

1, p. 307; 12; 14; Eg = 0.8 eV 1, p. 307; 5, p. 868; 12; Eg = 1.4 eV 5, p. 868; 12; 14; Eg = 1.3−2.25 eV 6, p. 707; 7, p. 799; 12

10.9 × 10−7 − 60 × 10−8

—

—

—

—

6, p. 708; 7, p. 810; 12

—

—

17.88 at i.r.

—

—

—

—

14.55 at i.r.

—

—

—

—

—

—

1, p. 307; 12; 14; Eg = 0.18 eV 1, p. 307; 12; 14; Eg = 0.47 eV 2, p. 231

(1−150) × 10−3 (marcasite) (1.2−600) × 10−3 (pyrite) — 4 × 10−2; 10.38 at 700οC; 8.23 × 10−1 at 1,000οC

—

14.20

—

(−87 to −83)

—

25.0

—

575-(γ−Fe2 O3), 675-(α and γ forms)

1, p. 307; 2, p. 256; 13−14 2, pp. 233, 256; 5, pp. 868, 993; 9, p. 400; 13; Eg = 3.1 eV

0910_book.fm Page 318 Wednesday, September 22, 2004 9:01 AM

Iron II oxide (FeO) Iron III oxide (Fe2O3)

Dielectric Strength (kV/mm)

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Cobalt oxide (CoO) Copper I oxide (Cu2O) Copper I sulfide (Cu2S) Copper II chloride (CuCl2) Copper II oxide (CuO) Copper II sulfide (CuS) Cordierite (2MgO. 2Al2O3. 5SiO2) Gallium antimonide (GaSb) Gallium arsenide (GaAs) Gallium phosphide (GaP) Hafnium boride (HfB2) Hafnium carbide (HfC) Indium antimonide (InSb) Indium arsenide (InAs) Iron disulfide (marcasite-FeS2) (Pyrite-FeS2)

Resistivity (
·m at ~25°C)

318

© 2005 by CRC Press

Material

10–3−4.0

—

20 —

—

(575−580)

—

(−216 to −205)

2, pp. 231, 256; 5, p. 851; 13, 14 2, pp. 231, 256; 14

—

—

<6,000

—

−70

8, p. 211

—

—

<4,000

—

−140

8, p. 211

—

—

<250

—

32

8, p. 211

—

—

<12,000

—

114

8, p. 211

—

—

<1,000 <9,000

—

−30; −95

8, p. 211

—

—

15,000−20,000

–12

7, p. 1113; 8, pp. 192, 211; 10, p. 965

—

—

<7,000

—

−98

8, p. 211

—

—

<250

—

39

8, p. 211

—

—

<4000

—

−120

8, p. 211

—

—

<2500

—

−180

8, p. 211

107 at 100οC; 2.67 × 103 at 470οC —

—

25.90; 22 at 4.5 kHz

—

—

1, p. 30; 13

—

280 at i.r.

—

—

6.8 × 10−6 to 9.0 × 10−2

—

17.9; 200 ± 35 at i.r.

—

—

(20−200) × 10−6

—

450 at i.r.

—

—

—

—

200.00 at 1 kHz

—

—

5, p. 868; 12; 14; Eg = 0.26−0.50 eV 2, pp. 231, 233; 5, p. 868; 12; Eg = 0.35− 0.4 2, p. 231; 5, p. 868; Eg = 0.25−0.30 eV 1, p. 307

—

—

7; (max. value of 20,000 reported)

—

0.03 at 1 kHz (thin film)

140

8, p. 211; 14

0910_book.fm Page 319 Wednesday, September 22, 2004 9:01 AM

—

319

Lead telluride (PbTe) Lead titanate (PT-TbTiO3) Lead zinc-niobate (PznPb(Zn1/3Nb2/3)O3

10−4 to 5.2 × 10−5

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Iron II, III oxide (Fe3O4) Iron II titanate (FeTiO3) Lead cobalt-niobate (Pb(Co1/3Nb2/3)O3) Lead cobalt-tantalate (Pb(Co1/3Ta2/3)O3) Lead cobalttungstate (Pb(Co1/2W1/2)O3) Lead iron-niobate (Pb(Fe1/2Nb1./2)O3) Lead iron-tungstate (Pb(Fe2/3W1/2)O3) (Pb(Fe2/3W1/3)O3) Lead magnesium niobate (PMN-Pb (Mg1/3Nb2/3)O3) Lead magnesiumtantalate (Pb(Mg1/3Ta2/3)O3 Lead magnesiumtungstate (Pb(Mg1/2W1/2)O3 Lead nickel-niobate (Pb(Ni1/3Nb2/3)O3 Lead nickel-tantalate (Pb(Ni1/3Ta2/3)O3 Lead oxide (PbO) Lead selenide (PbSe) Lead sulfide (PbS)

—

—

200.00

—

—

—

—

1300−3400 at 1 kHz (ceramic); ∼160 (thin film at 1 kHz) 303−5700; 120−200 (thin film at 1 kHz)

—

—

10.60−11.05

—

—

9.00

Dielectric Loss at ~1 MHz (tan )

Curie, Tc, or (Neel, Tn) Temp. (°C)

—

—

0.004−0.02 (ceramic); 0.034 (thin film) at 1 kHz) 0.4−6.0; 0.042 −0.044 (thin film at 1 kHz)

References and Miscellaneous 1, p. 307; 14

193−328 (ceramic); 300 (film)

3, p. TD29; 7, p. 1121; 10, pp. 955, 965

−25 to 355

3, p. TD29; 7, p. 1127; 8, pp. 192, 433; 10, p. 964

— 2 × 10−4

—

1, p. 307; 14

—

4, p. 180; 5, pp. 868, 933; 14; Eg = 12 eV 3, p. TD30; 7, pp. 1121, 1129 7, p. 1121; 14

—

—

εs = 67.2; 37−39 (single crystal) 41−53 at 105 Hz

108−1016 (max. value of 1016 reported); 1012−1013 at 300οC; 9 × 1011 at 500οC; 104−105 at 1,000οC >1012; 103 at 1,000οC

—

3.2−9.8

3 ×10−4

—

4, pp. 180, 306; 5, p. 868, 933; 6, p. 710; 7, p. 1113; 9, p. 400; 12; 14; Eg > 7.8 eV

6.2−6.5

1−3 × 10−4

—

3, p. TD29; 5, p. 933; 7, p. 759; 11

—

—

8, p. 192

—

—

2, p. 231

—

2, p. 231; 14

—

—

∼50 (single crystal)

Dielectric Constant at ~25°C and ~1 MHz

10

—

20 —

—

1210

—

618

10−20

—

0.16−1.0

—

8 at 6 × 1010 Hz

—

0.007−30

—

104 at 104 Hz

—

1 × 106

—

18.1; 12.8 at 6 × 1010 Hz

—

(−189)

2, pp. 231, 257; 14

—

13

0910_book.fm Page 320 Wednesday, September 22, 2004 9:01 AM

Magnesium silicate (ForsteriteMg2SiO4) Magnesium tantalate (MgTiO3) Manganese disulfide (MnS2) Manganese III oxide (Mn2O3) Manganese oxide, dioxide (MnO2) Manganese oxide, mono (MnO)

Dielectric Strength (kV/mm)

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Lead zirconate (PZ-PbZrO3) Lead zirconatetitanate (PZT-Pb(Zr,Ti)O3) Lead-lanthanum zirconate-titanate (PLZT−Pb,La (Zr,Ti)O3) La/Zr/Ti = 2-12/10-65/10-90 Lithium chloride (LiCl) Lithium fluoride (LiF) Lithium niobate (LiNbO3) Lithium tantalate (LiTaO3) Magnesium oxide (MgO)

Resistivity (
·m at ~25°C)

320

© 2005 by CRC Press

Material

Silicon nitride (Si3N4) Silicon oxide (SiO2)

9.40; 14 at 1012 Hz

—

—

1, p. 307; 14

—

—

3.20; 6.5 at 1012 Hz

—

—

1, p. 307; 14

(21.5−35) × 10−8; 4 × 10–6 at 1700οC

—

—

—

—

6, p. 712; 7; 12

0.12−7.5

—

—

—

—

2, p. 231

—

—

3, p. TD25; 5, p. 933; 6, p. 711; 7, p. 1108; 11 2, p. 231

—

1, p. 308; 5, p. 933; 14

—

1, p. 308

— —

2, p. 233; 5, pp. 868, 933; 14; Eg = 7 eV 1, p. 308; 14

—

10, p. 965; 14

—

1, p. 308

—

—

1, p. 308; 14

—

—

1, p. 308; 14

—

1, p. 308; 3, p. TD27; 4, p. 306; 5, pp. 851, 868; 6, p. 708; 9, p. 400; 11; 12; 14; Eg = 2.8−3 eV for α-SiC 3, p. TD25; 6, p. 709; 11; 14 2, p. 235; 3, p. TD29, TD30; 4, p. 180; 6, p. 710; 8, p. 192; 9, p. 400; 13

>1011

9.8

3 × 10−3

5.4−6.5

(2−4) × 10−7

—

—

—

4.78−4.90

—

—

4.96

—

—

4.39−6.20

—

—

6.05

—

—

—

—

700; 300 at 10 kHz (thin film) 7.75

—

—

—

—

10−3−102

1010−1014 107−1016; 104 at 700οC; 2 × 103 at 900οC

0.7 (thin film)

— 50 (single crystal)

—

6.73; 4.87 at 5 × 103 Hz 4.91 at 5 × 103 Hz 9.7−10.20 at i.r.; 40 (thin film); 42 (2% BeO)

7.0; 4.2 at 1 kHz for film 3.8 (fused) 4.1−4.34 α-SiO2

— 2 × 10−4 — 1 × 10−4 — 0.04 at 10 kHz (thin film) —

5 × 10−2 (thin film)

—

—

—

—

321

—

0910_book.fm Page 321 Wednesday, September 22, 2004 9:01 AM

Nickel sulfide (NiS) Potassium bromide (KBr) Potassium carbonate (K2CO3) Potassium chloride (KCl) Potassium fluoride (KF) Potassium niobate (KNbO3) Potassium phosphate (K3PO4) Rubidium carbonate (Rb2CO3) Rubidium chloride (RbCl) Silicon carbide (SiC)

—

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Mercury I chloride (Hg2Cl2) Mercury II chloride (HgCl2) Molybdenum disilicide (MoSi2) Molybdenum disulfide (MoS2) Mullite (3Al2O3. 2SiO2)

Dielectric Constant at ~25°C and ~1 MHz

Dielectric Loss at ~1 MHz (tan )

Curie, Tc, or (Neel, Tn) Temp. (°C)

References and Miscellaneous

—

—

—

—

—

5, p. 868; Eg = 2.8 eV

—

—

1, p. 308; 13; 14

—

—

2, p. 231

—

—

1, p. 308; 14

—

2, p. 233; 4, p. 180; 5, p. 933; 14 1, p. 308; 14

∼10−1

—

(1.5−2.0) × 10−3

—

8.80 —

—

—

8.75

—

—

5.70−6.20

—

—

11.31−11.50

—

—

320; 332 at 1 kHz

2 × 10−4 — <0.001

—

(33−68) × 10−8

—

—

—

—

7, p. 1113; 8, p. 192; 14 6, p. 707; 7, p. 799; 12

2 × 10−6 to 3 × 10−3

—

—

—

—

9, p. 400; 12

103

—

45.00

—

—

1, p. 309; 13

—

—

31.90−32.20

—

—

1, p. 309; 14

—

—

147.00

—

—

1, p. 309; 14

—

—

2.87

—

—

1, p. 308

—

23.4−24.0 (9−14, Ref.14) —

—

—

2, pp. 231, 233; 13; 14

—

—

6, p. 707; 7, p. 799; 12

4, p. 306; 6, p. 708; 7, p. 810; 12 6, p. 709

(1−4) × 104; 2.56 at 1000οC (8.7−15) × 10−8 (poly-crystalline); (6.6−6.7) × 10−8 (mono-crystalline) 10−8−10−3 (1.11−13.00) × 10−7

—

—

—

—

—

—

—

—

—

—

0910_book.fm Page 322 Wednesday, September 22, 2004 9:01 AM

Titanium carbide (TiC) Titanium nitride (TiN)

Dielectric Strength (kV/mm)

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Silver iodide (AgI) Silver oxide (Ag2O) Silver sulfide (Ag2S) Sodium carbonate (Na2CO3) Sodium chloride (NaCl) Strontium sulfide (SrS) Strontium titanate (SrTiO3) Tantalum boride (TaB2) Tantalum carbide (TaC) Tantalum oxide (Ta2O5) Thallium chloride (TlCl) Tin antimonide (SnSb) Tin IV chloride (SnCl4) Tin IV oxide (SnO2) Titanium boride (TiB2)

Resistivity (
·m at ~25°C)

322

© 2005 by CRC Press

Material

Tungsten disilicide (WSi2) Tungsten pentaoxide (W2O5) Tungsten trioxide (WO3) Uranium oxide (Uraninite-UO) Ytterbium oxide (Yb2O3) Yttrium oxide (Y2O3) Zinc oxide (ZnO) Zinc selenide (ZnSe) Zinc sulfide (ZnS) Zinc telluride (ZnTe) Zirconium bromide (ZrB2) Zirconium carbide (ZrC) Zirconium nitride (ZrN) Zirconium oxide (ZrO2)

(33.4−54.9) × 10–8

—

4.5 × 10−6

—

2.0 × 103

—

1.5−4,200

—

108 at 390οC

—

5.4 × 104 at 730οC

—

Zirconium oxide (stabilized-ZrO2) Zirconium silicate (ZrSiO4)

1.03; 0.026 at 1,000οC —

5.91−7.87

∼50 (single crystal) —

2.7 × 10−3 to 1.2 × 104

—

—

—

2 × 10−4 to 1.6 × 10−3

—

—

—

—

2, pp. 231, 233; 4, p. 180; 5, pp. 868, 933; 7, p. 1113; 8, p. 192; 9, pp. 400; 12; 14; Eg = 3.05−3.8 eV 6, p. 712

—

—

—

1, p. 309

—

—

1, p. 309; 13; 14

—

—

2, p. 231; 14

5.0−12.6; 5.0 at 1 kHz for film 10−14

—

—

1, p. 309; 13; 14

—

—

1, p. 309; 13; 14

8.2−18; 8.84 (single crystal) 9.12 at 104 Hz

— —

—

7.88−69.9; 8.3 at 104 Hz 10.10

—

—

3, p. TD30; 7, p. 1121; 12; 14 5, p. 868; 14; Eg = 2.6 eV 2, pp. 231, 233; 14

—

—

1, p. 309; 14

85.8−170 (rutile) 425 (anatase)

20.2−29.1 (300, Ref. 14) 24 at 5 × 105 Hz

1,200

(9.2−10) × 10−8

—

—

—

—

(61−70) × 10−8

—

—

—

—

(1.15−16.0) × 10−7

—

—

—

—

6, p. 707; 7, p. 800 6, pp. 709; 7, pp. 810; 9, p. 400; 12 6, p. 709

3 × 1011; 3 × 104 at 300οC; 10−1−102 at 1000οC ∼1013; 0.37 × 10−2−23 at 700−2200οC 1012

—

—

—

9, p. 400; 13; 14

—

—

6, p. 710; 11

—

—

11, 12

12.5

9.5 10

— 9.4−12.7

0910_book.fm Page 323 Wednesday, September 22, 2004 9:01 AM

108−1012; 3 × 105 at 500οC; 8.5 × 102 at 1200οC

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Titanium oxide (TiO2)

323

0910_book.fm Page 324 Wednesday, September 22, 2004 9:01 AM

324

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

REFERENCES 1. Y. S. Touloukian, W. R. Judd, and R. F. Roy, Physical Properties of Rocks and Minerals, Vol. II−2, McGraw-Hill, New York, 1981. 2. R. S. Carmichael, Practical Handbook of Physical Properties of Rocks, Vol. 1, CRC Press, Boca Raton, FL, 1992. 3. Ceramic Source, Vol. 8, American Ceramic Society, Westerville, OH, 1992−1993. 4. L. H. Van Vlack, Physical Ceramics for Engineers, Addison-Wesley, Reading, MA, 1964. 5. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2nd ed., John Wiley & Sons, New York, 1976. 6. J. Shackelford and W. Alexander, The CRC Materials Science and Engineering Handbook, CRC Press, Boca Raton, FL, 1992. 7. Engineered Materials Handbook, Vol. 4, Ceramics and Glasses, ASM International, Materials Park, OH, 1991. 8. Electronics Ceramics: Properties, Devices, and Applications, edited by L. M. Levinson, Marcel Dekker, New York, 1987. 9. S. C. Carniglia and G. L. Barna, Handbook of Industrial Refractories Technology: Principles, Types, Properties, and Applications, Noyes, Park Ridge, NJ, 1992. 10. S. L. Swartz, Topics in electronics, IEE Trans. Electr. Insul., 25(5), 935, 1990. 11. CRC-Elsevier Materials Selector, Vol. 2, edited by N. A. Waterman and M. F. Ashby, CRC Press, Boca Raton, FL, 1991. 12. Materials Handbook, Ceram. Ind., 144(1), 57, 1995. 13. The Oxide Handbook, edited by G.V. Samsonov, IFI/Plenum, New York, 1973. 14. CRC Handbook of Physics and Chemistry, edited by D. R. Lide, 73rd ed., CRC Press, Boca Raton, FL, 1992−1993, pp. 9−57.

© 2005 by CRC Press

0910_book.fm Page 325 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

III. MAGNETIC PROPERTIES

© 2005 by CRC Press

325

0910_book.fm Page 326 Wednesday, September 22, 2004 9:01 AM

326

Material Aluminum oxide (Al2O3) Antimony oxide (Sb2O3) Antimony sulfide (Sb2S3) Barium-iron III oxide (BaFe12O19) Barium oxide (BaO) Beryllium oxide (BeO) Bismuth oxide (Bi2O3) Bismuth sulfide (Bi2S3) Calcium carbonate (CaCO3) Calcium oxide (CaO) Cerium oxide (CeO2) Cesium oxide (CsO2) Chromium I oxide (CrO2) Chromium III oxide (Cr2O3) Cobalt-barium-iron III oxide (Co2Ba3Fe24O41) Cobalt chloride (CoCl2) Cobalt-iron III oxide (CoFe2O4) Cobalt oxide (CoO) Cobalt IV sulfide (CoS2) Copper-iron III oxide (CuFe2O4) Copper II oxide (Cu2O) Copper III oxide (CuO) Copper-iron II sulfide (CuFeS2) or CuFe2S3) Copper sulfide (CuS) Dysprosium-iron III oxide (3Dy2O3⋅5Fe2O3) Dysprosium oxide (Dy2O3) Erbium-iron III oxide (3Er2O3⋅5Fe2O3) Erbium oxide (Er2O3)

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Saturation Magnetization (Ms) (emu/g)

Curie, TC, or Neel (TN) Temperatures (K)

Magnetic Susceptibility (k) in 10–6 emu/g at ~25°C

—

—

−0.36

10

—

—

−0.24

10

—

—

−0.25

10

—

723

—

2

—

—

−0.20

10

—

—

−0.48

10

—

—

−0.18

10

—

—

−0.24

10

—

—

−0.38

5, 10

—

—

−0.27

10

—

—

0.15

10

—

—

9.30

10

—

392−397

—

5, 11

—

308

12.90

10, 11

—

683

—

—

38 (25)

97.51

80

793

—

—

−280 (291)

65.39 at 260 K

—

122

2.47

25

728

—

—

—

−0.14

—

458

3.00−3.25

—

823 (CuFeS2)

—

6

—

—

−0.02

10

—

563

—

—

—

240.22 at 287 K

—

556

—

—

13

193.25

References

2 1, 4, 10 2 1, 4, 10, 11 6, 10 2 5, 10 6, 10, 11

2, 4 10, 11 2, 4 10, 11

Note: Unit conversions: intensity of magnetization: emu = 1/4π ⋅104 Wb ⋅ m2; magnetic moment: emu = 1/4π 1010 Wb ⋅ m.

© 2005 by CRC Press

0910_book.fm Page 327 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

Material Europium oxide (Eu2O3) Gadolinium III-iron III oxide (3Gd2O3⋅5Fe2O3) Gadolinium oxide (Gd2O3) Gallium oxide (Ga2O) Gallium sulfide (Ga2S) Germanium oxide (GeO2) Germanium sulfide (GeS2) Hafnium oxide (HfO2) Holmium oxide (Ho2O3) Holmium III-iron III oxide (3Ho2O3⋅5Fe2O3) Indium oxide (In2O3) Indium sulfide (In2S3) Iridium oxide (IrO2) Iron-barium oxide (Fe2BaFe15O27) Iron II chloride (FeCl2) Iron II carbonate (FeCO3) Iron II-chromium III oxide (FeCr2O4) Iron II fluoride (FeF2) Iron II oxide (FeO) Iron III oxide (Fe3O4) Iron III oxide (α-Fe2O3) Iron III oxide (γ-Fe2O3) Iron II silicate (FeSiO3 or Fe2SiO4) Iron II sulfide (FeS) Iron II titanate (FeTiO3 or Fe2TiO4) Lanthanum chromate (LaCrO3) Lanthanum III-iron III oxide (LaFeO3) Lanthanum III-manganese II oxide (LaMnO3)

© 2005 by CRC Press

327

Saturation Magnetization (Ms) (emu/g)

Curie, TC, or Neel (TN) Temperatures (K)

Magnetic Susceptibility (k) in 10–6 emu/g at ~25°C

—

—

28.70

—

564

—

—

18

146.76

10, 11

—

—

−0.22

10

—

—

−0.21

10

—

—

−0.33

10

—

—

−0.39

10

—

—

−0.11

10

—

14

233.16

10, 11

—

567

—

—

—

−0.20

10

—

—

−0.30

10

—

—

1.00

10

—

728

—

2

—

48 (24)

116.37

—

(40)

97.53−98

—

88

—

—

−117 (79)

101.23

1, 4, 10

—

−570 (198)

100.21

1, 4, 10

92.0

858

92.3

2, 5, 11

0.5

948−950

105

5, 11

73.5−92

848−853

—

—

(40) − FeSiO3 (126) − Fe2SiO4 −857 (613)

73 − FeSiO3 100 − Fe2SiO4 12.22

4, 5, 10

0.87 − FeTiO3

5

—

(68) − FeTiO3 (120) − Fe2TiO4 (320)

—

3

—

(720)

—

3

—

(100)

—

3

— —

References 10 2, 4

2, 4

1, 4, 10 5, 10 5

2, 5, 6 5

0910_book.fm Page 328 Wednesday, September 22, 2004 9:01 AM

328

Material Lanthanum oxide (La2O3) Lanthanum sulfide (La2S3) Lead-iron III oxide (PbFe12O19) Lead oxide (PbO) Lead sulfide (PbS) Lithium-iron III oxide (Li0.5Fe2.5O4) Lutetium III-iron III oxide (3Lu2O3⋅5Fe2O3) Magnesium-iron III oxide (MgFe2O4) Magnesium oxide (MgO) Magnesium sulfate (MgSO4) Manganese-iron-barium oxide (Mn2Ba2Fe12O22) Manganese carbonate (MnCO3) Manganese fluoride (MnF2) Manganese-iron III oxide (MnFe2O4) Manganese II oxide (MnO) Manganese IV oxide (MnO2) Manganese (II, III) oxide (Mn3O4) Manganese selenide (MnSe) Manganese sulfide (MnS) Manganese telluride (MnTe) Molybdenum oxide (MoO3) Molybdenum sulfide (MoS3) Neodymium-cobalt boride (Nd2Co14B) Neodymium-iron boride (Nd2Fe14B) Neodymium-iron carbide (Nd2Fe17C) Neodymium oxide (Nd2O3) Nickel chloride (NiCl2) Nickel-iron III oxide (NiFe2O4) Nickel II oxide (NiO)

© 2005 by CRC Press

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Saturation Magnetization (Ms) (emu/g)

Curie, TC, or Neel (TN) Temperatures (K)

Magnetic Susceptibility (k) in 10–6 emu/g at ~25°C

—

—

−0.24

10

—

—

−0.10

10

—

725

—

2

—

—

−0.19

10

—

—

−0.34 to −0.35

65

943

—

2

—

549

—

2

27

713

—

2

—

—

−0.25

10

—

—

−0.37 to −0.42

—

563

—

—

(30)

99.17−100

5, 10

—

(67)

115.93

1, 10

80

573

400

2, 5

—

−610 (122)

68.37

1, 4, 10, 11

—

(84−92)

26.23

4, 5, 10, 11

—

42

54−54.19

—

−361 (247)

—

—

−528 (160−165)

65 (for α form)

—

(307)

—

1

—

—

0.02

10

—

—

−0.33

10

—

1000

—

7

—

585

—

8

—

552

—

9

—

—

30.31

10

—

68.2(50)

47.42

1, 4, 10

50

858

—

—

(513−525)

8.83

References

5, 10

5, 10 2

2, 5, 10 4 1, 4, 6, 10

2, 5 1, 10, 11

0910_book.fm Page 329 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

Material Nickel II sulfide (NiS) Niobium oxide (Nb2O5) Platinum oxide (Pt2O3) Plutonium oxide (PuO2) Praseodymium oxide (Pr2O3) Praseodymium sulfide (Pr2S3) Rhenium oxide (ReO3) Rhodium oxide (Rh2O3) Rubidium oxide (RbO2) Ruthenium oxide (RuO2) Samarium III-iron III oxide (3Sm2O3⋅5Fe2O3) Samarium oxide (Sm2O3) Selenium oxide (SeO2) Silicon oxide (SiO2) Silver oxide (Ag2O) Sodium chloride (NaCl) Strontium-iron III oxide (SrFe12O19) Strontium oxide (SrO) Tantalum oxide (Ta2O5) Terbium III-iron III oxide (3Tb2O3⋅5Fe2O3) Terbium oxide (Tb2O3) Thallium oxide (T12O3) Thorium oxide (ThO2) Thulium III-iron III oxide (3Tm2O3⋅5Fe2O3) Thulium oxide (Tm2O3) Tin oxide (SnO2) Titanium oxide (TiO2) Tungsten oxide (WO3) Tungsten sulfide (WS2)

© 2005 by CRC Press

329

Saturation Magnetization (Ms) (emu/g)

Curie, TC, or Neel (TN) Temperatures (K)

Magnetic Susceptibility (k) in 10–6 emu/g at ~25°C

—

263

2.0−2.1

—

—

−0.04

10

—

—

−0.09

10

—

—

2.64

10

—

57

27.27

10, 11

—

—

28.49

10

—

—

0.07

10

—

—

0.41

10

—

—

13.00

10

—

—

1.22

10

—

578

—

2

—

—

5.70

10

—

—

−0.25

10

—

—

−0.49

5, 6, 10

—

—

−0.58

10

—

—

−0.52

5, 10

—

733

—

2

—

—

−0.34

10

—

—

−0.07

10

—

568

—

2

—

24

214.13

—

—

0.17

10

—

—

−0.06

10

—

549

—

—

42

133.32

10, 11

—

—

−0.27

10

—

—

0.07

5, 10

—

—

−0.07

10

—

—

23.59

10

References 5, 6, 10

10, 11

2, 4

0910_book.fm Page 330 Wednesday, September 22, 2004 9:01 AM

330

Material Uranium oxide (UO2) Uranium sulfide (US2) Vanadium IV oxide (V2O4) Ytterbium sulfide (Yb2S3) Yttrium III-iron III oxide (3Y2O3⋅5Fe2O3) Yttrium oxide (Y2O3) Yttrium sulfide (Y2S3) Zinc-iron III oxide (ZnFe2O4) Zinc oxide (ZnO) Zinc sulfide (ZnS) Zirconium oxide (ZrO2)

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Saturation Magnetization (Ms) (emu/g)

Curie, TC, or Neel (TN) Temperatures (K)

Magnetic Susceptibility (k) in 10–6 emu/g at ~25°C

—

30

8.74

10, 11

—

—

10.45

10

—

−720 (343)

0.70 (V2O5)

—

—

41.38

10

—

553

—

2

—

—

0.20

10

—

—

0.37

10

—

(9.5)

6754

2, 5

—

—

−0.57

10

—

—

−0.26

6, 10

—

—

−0.11

6, 10

References

4, 10, 11

REFERENCES 1. C. Kittle, Introduction to Solid State Physics, 5th ed., John Wiley & Sons, New York, 1976. 2. R. S. Tebble and D. J. Craik, Magnetic Materials, Wiley-Interscience, New York, 1969. 3. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Cermics, 2nd ed., John Wiley & Sons, New York, 1976. 4. J. E. Thompson, The Magnetic Properties of Materials, CRC Press, Boca Raton, FL, 1968. 5. R. S. Carmichael, CRC Handbook of Physical Properties of Rocks, Vol. 2, CRC Press, Boca Raton, FL, 1992. 6. Y. S. Touloukian, W. R. Judd, and R. F. Ray, CINDAS Physical Properties of Rocks and Minerals, Vol. II-2, 1981. 7. G. J. Cong and F. Grandjean, Eds., Supermagnets, Hard Magnetic Materials, Kluwer Academic, The Netherlands, 1991. 8. J. F. Herbst, R2FE14B materials: intrinsic properties and technological aspects, Rev. Mod. Phys., 63, 4, 1991. 9. K. H. J. Bschow, Structure and properties of ternary Fe-rich rare earth carbides, in Supermagnets, Hard Magnetic Materials, edited by G. J. Long and F. Grandjean, Kluwer Academic, The Netherlands, 1991, pp. 527−552. 10. CRC Handbook of Physics and Chemistry, edited by D. R. Lide, 73rd ed., CRC Press, Boca Raton, FL, 1992−1993, pp. 9−57. 11. The Oxide Handbook, edited by G. V. Samsonov, IFI/Plenum, New York, 1973, p. 289.

© 2005 by CRC Press

0910_book.fm Page 331 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

IV. OPTICAL PROPERTIES

© 2005 by CRC Press

331

1.65

0.021

—

1, p. 662

Colorless/rhombohedral

1.64

0.010

—

1, p. 662

Colorless to white, amorphous

1.76

—

0.2−7

Colorless to white, rhombohedral

∼1.82

−0.008

0.14−7.5

Yellow or red/monoclinic

2.66

—

0.6−13

Colorless or white, cubic

1.473

—

0.13−15

—

—

0.75−12

Aluminosilicate crystals (sillimanite — Al2O3⋅SiO2) Aluminosilicate crystals (mullite — 3Al2O3⋅2SiO2) Aluminum oxide (Al2O3) Aluminum oxide-sapphire (Al2O3) Arsenic trisulfide glass (As2S3) Barium fluoride (BaF2) Barium fluoride/calcium fluoride (BaF2/CaF2) Barium titanate (BaTiO3) Borosilicate glass (0.67SiO/0.16K2O− 0.07BaO/0.07B2O Cadmium borate (Cd2B2O5) Cadmium selenide (CdSe) Cadmium sulfide (CdS) Cadmium telluride (CdTe) Calcium aluminate glass (CaAl2O4) Calcium carbonate (calcite- CaCO3) Calcium fluoride (polycrystalline — CaF2) Calcium fluoride (single crystal — CaF2) Calcium silicate (CaSiO2)

White/rhombohedral

— —/mostly tetragonal at room temperature or hexagonal Colorless to white, amorphous

2.37−2.44

−0.53

∼0.6−7.0

1.47−1.51

—

—

White/rhombohedral (orange-red, emission with Mn activator) Green brown or red/hexagonal (red at low temperature Yellow orange/hexagonal

—

—

—

2.54 at 1064 nm

−0.02

∼0.7−24.0

2.33 at 633 nm

−0.01

0.55−16

Black/cubic

2.60−2.82

—

White/amorphous

<1.6

—

0.9−31; 70% in 4−15 range (i.r) 0.4−5.5

Colorless/rhombohedral

1.65

0.17

0.2−5.5

—/cubic

1.43 at 1064 nm

—

0.13−11.8

Colorless/cubic

1.434 at 589 nm; 1.433 at 633 nm ∼1.61

—

0.13−12

—

—

Colorless, but yellow to orange (emission with Pb, Mn activators)/monoclinic

References and Miscellaneous

1, pp. 648, 662; 6 1, pp. 648, 652; 2, pp. 4−36; 8 1, pp. 648, 662; 2, pp. 4−41 1, pp. 648, 663; 2, pp. 4−42; 6; 8 1, p. 648 1, p. 662; 2, pp. 4−43; 5, p. 960 1, p. 662; 3, p. 205

1, p. 691; Uused as phosphor 3, p. 209 1, pp. 648, 662; 2, pp. 4−47; 3, p. 209 1, pp. 648, 662; 2, pp. 4−47; 5, p. 960; 6 1, p. 648; 2, pp. 4−47 1, pp. 648, 662; 2, pp. 4−47 1, p. 648 1, pp. 648, 662; 2, pp. 4−48; 8 1, p. 691; 2, pp. 4−49; used as phosphor

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Refractive Index

0910_book.fm Page 332 Wednesday, September 22, 2004 9:01 AM

Transmission Range (µm) for 2-mm-Thick Sample

Color/Crystalline Form

332

© 2005 by CRC Press

Birefringence

Material

Lithium fluoride (LiF) Lithium iodide (LiI)

—

1, p. 669; 2, pp. 4−50

−0.016

0.12−8.0

—

0.2−55

1.787

—

0.25−70

1, p. 691; 6; 8; used as phosphor 1, pp. 648, 652; 2, pp. 4−51 1, p. 648; 2, pp. 4−52

Green/hexagonal

2.551

—

—

Purple blue/amorphous Dark gray/cubic

— 3.34 at ∼1.9 µm

— —

— 1.0−15.0

Gray-white/metallic, cubic

4.0 at 10.6 µm

—

1.8−23

Red brown to black/trigonal

3.01

—

—

1, pp. 648, 652; 2, p. 4−60 3, p. 209; 7

Yellow/monoclinic

2.3−2.6

—

—

3, p. 209; 6

Colorless/rhombohedral

1.76

—

0.29−15

1, p. 648; 2, pp. 4−67

—/tetragonal

2.4−2.6 (thin film)

—

—

Yellowish/—

2.56

—

—

5, p. 791; electrooptic coefficient: 28− 81 pm/V in thin film 5, p. 975

Yellow/tetragonal

2.61

—

—

Blue/metallic, cubic

3.912 4.1 at 3 µm

—

3.0−7.0

Colorless to white/tetragonal

2.66

—

5, p. 975; 9, p. 135

Colorless to white/tetragonal or rhombohedral

2.5−2.6 (thin film)

0.008 at 633 nm —

—

White/cubic

1.392 at 633 nm

—

0.12−8.5

White/cubic

∼1.95 at 633 nm

—

—

5, p. 791; electrooptic coefficient: 10− 24 pm/V in thin film 1, pp. 648, 662; 2, pp. 4−70 1, p. 663; 2, pp. 4−70

2.35

White/tetragonal; deep blue (emission) Colorless/cubic

1.45−1.47; 1.92 at 600 nm ∼1.7

—/rhombohedral

3, p. 209; 7 3, p. 209 5, p. 960

1, p. 662; 2, pp. 4−68; 7 1, p. 662; 2, pp. 4−69

333

Note: The optical spectrum range: UV = 0.1−0.4 µm; Vis = 0.4−0.75 µm; near IR = 0.7−3.0 µm; mid IR = 3−6 µm; far IR = 6−15 µm; extreme IR = 15−100 µm.

0910_book.fm Page 333 Wednesday, September 22, 2004 9:01 AM

Lead magnesium-niobate (PbMg1/3Nb2/3O3) Lead oxide (litharge — PbO) Lead sulfide (PbS) Lead titanate (PbTiO3) Lead zirconate-titanate (PbZr0.53Ti0.47O3)

—

Colorless/cubic or orthorhombic

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Calcium titanate (CaTiO3) Calcium tungstate (CaWO4) Cesium bromide (CsBr) Cesium iodide (CsI) Chromium oxide (Cr2O3) Cobalt-containing glasses Gallium arsenide (GaAs) Germanium (Ge) Iron III oxide (Fe2O3) Lead chromate (PbCrO4) Lead fluoride (PbF2) Lead lanthanum zirconate-titanate (Pb,La(Zr,Ti)O3)

0.35−5.5

0.004 at 600 nm

—

—

0.21−6.0

—

0.45−9

1, pp. 648, 662; 5, pp. 960, 971; 8; 10, p. 332 electro-optic coefficient: 2.3 (r13), 12.0 (r33) pm/V in thin film, 30.0 (r33) pm/V in crystal 5, pp. 960, 971; 11, p. 1674; electro-optic coefficient: 0.32 pm/V in thin film, 30.0 (r33) pm/V in crystal 1, p. 662; 2, pp. 4−71; 6 1, p. 648; 8

−0.11 at 633 nm —

0.15−9.6

1.73 at 633 nm

—

0.25−9.5

—/tetragonal

1.476

—

—

1, pp. 648, 662; 2, pp. 4−72; 8 8

Black/rhombohedral; or brown black/amorphous White/triclinic

1.216 (Li)

—

—

3, p. 209; 7

1.525

0.007

—

1, pp. 662; 2, pp. 4−84

Colorless/tetragonal

1.47−1.51

0.04

—

2; 5, p. 960

Colorless/cubic

1.559 at 589 nm

—

0.2−38

1, p. 648; 2, pp. 4−84

Colorless/cubic

1.490 at 589 nm

—

0.21−25

1, p. 648; 2, pp. 4−85

Colorless or white/cubic or granular

1.677 1.666 at 589 nm

—

0.25−47

1, p. 648; 2, pp. 4−87

Birefringence

Lithium niobate (LiNbO3)

Transparent/rhombohedral

2.20−2.31; 2.28 at 633 nm

Lithium tantalate (LiTaO3)

Transparent/rhombohedral

2.18 at 600 nm

Magnesium aluminate (Spinel — MgAl2O4) Magnesium fluoride (polycrystalline-MgF2) Magnesium fluoride (single crystal—MgF2) Magnesium oxide (polycrystalline — MgO) Magnesium oxide (single crystal — MgO) Manganese fluoride (MnF2) Manganese oxide (MnO2) Potassium aluminosilicate crystal (orthoclase — KAlSi3O8) Potassium dihydrogen phosphate (KH2PO4) Potasium bromide (KBr) Potassium chloride (KCl) Potassium iodide (KI)

Colorless/cubic —/tetragonal

1.718−1.723; 1.72 at 589 nm 1.38 at 1.06 µm

Colorless/tetragonal

1.378 at 633 nm

Colorless/—

—

Colorless/cubic

0.3−9.5

1, p. 648; 2, pp. 4−72; 8 1, p. 648; 7

0910_book.fm Page 334 Wednesday, September 22, 2004 9:01 AM

−0.084 at 633 nm

Refractive Index

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

References and Miscellaneous

Color/Crystalline Form

334

© 2005 by CRC Press

Transmission Range (µm) for 2-mm-Thick Sample

Material

2.17; 2.28; 2.33

0.16 max.

0.4−4.5

5, p. 975; 12

Steel gray/cubic

3.49 at 1.5 µm

—

1.2−15

Colorless to black/hexagonal or cubic

2.68 at 0.5 µm

0.043

—

1, pp. 648, 662; 2, pp. 4−94 1, p. 662; 2, p. 4−94

Colorless/amorphous

1.458

—

0.16−4

Colorless/hexagonal

0.009

0.18−4.2

Silver bromide (AgBr) Silver chloride (AgCl) Sodium aluminosilicate crystal (albite — NaAlSi3O8) Sodium chloride (NaCl) Sodium fluoride (NaF) Sodium iodide (NaI) Strontium fluoride (SrF2) Strontium titanate (SrTiO3) Thallium bromide (TlBr) Thallium bromoiodide (Tl(Br, I)) Thallium chloride (TlCl) Thallium chlorobromide (Tl(Cl,Br)) Tin oxide (SnO2)

Pale yellow/—

1.54−1.55 (quartz at 589 nm); 1.47 (tridymite); 1.48 (cristobalite) 2.253

1, pp. 648−662; 2, pp. 4−95 1, pp. 648, 662; 2, pp. 4−95; 3, p. 203; 5, p. 960; 7

—

0.45−40

1, p. 648; 2, pp. 4−95

White/cubic

2.071

—

0.4−30

1, p. 648; 2, pp. 4−95

Colorless/triclinic

1.529

0.008

—

1, p. 662; 2, pp. 4−96

Colorless/cubic

∼1.54

—

0.2−25

Colorless/cubic or tetragonal

1.336

—

0.14−15

Colorless/cubic

1.775

—

0.25−25

1, pp. 648, 652; 2, pp. 4−98; 3, pp. 203 1, pp. 648, 662; 2, pp. 4−99; 3, pp. 203 1, p. 648; 2, pp. 4−99

Colorless/cubic or white/powder

~1.45

—

—

1, p. 663; 2, pp. 4−102

Colorless to white/cubic

2.39 at 633 nm 2.4−2.8

—

0.39−6.8

1, p. 648, 662; 6

—

0.38−40

1, p. 648; 2, pp. 4−105

—

—

0.55−50

1, p. 648

2.247

—

0.42−30

1, p. 648; 2, pp. 4−105

—

—

0.4−35

1, p. 648

2.0−2.09

—

—

Yellowish white/cubic — White, but discolors in air/— — White/tetragonal (also hexagonal and rhombohedral)

1, p. 669; 2, pp. 4− 108; 3, p. 209; 7; used as opacifier

0910_book.fm Page 335 Wednesday, September 22, 2004 9:01 AM

Colorless/orthorhombic crystal

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Potassium niobate (KNbO3) Silicon (Si) Silicon carbide (SiC) Silicon oxide (fused — SiO2) Silicon oxide (quartz — SiO2)

335

Birefringence

Transmission Range (µm) for 2-mm-Thick Sample

References and Miscellaneous

Titanium oxide (TiO2)

White/rhombohedral

2.71 (rutile); 2.52 (anatase)

0.287

0.43−6.2

Yttrium aluminate (YAlO3) Yttrium aluminate (Y3Al5O12-YAG) Yttrium oxide (Y2O3) Yttrium vanadate (YVO4) Zinc fluoride (ZnF2) Zinc selenide (ZnSe) Zinc silicate (Zn2SiO4)

Colorless/orthorhombic

1.94−1.97

—

0.3−5.8

1, pp. 648, 662, 669; 2, pp. 4−108; 3, p. 209; 6; 7 8

Colorless/cubic

1.823

—

0.3−5.5

8

Colorless to yellowish white/cubic

1.91−1.92

—

0.23−9.2

Red (emission with Eu activator)/tetragonal —/tetragonal

1.86−1.88

—

0.35−4.8

1.497

—

—

1, pp. 648, 662; 2, pp. 4−11; 7; 8 1, p. 691; 8; used as phosphor 8

Yellowish-reddish/cubic

2.62−2.89

—

0.48−22

Green/trigonal (emission with Mn activator)

1.694−1.723

—

—

Zinc sulfide (ZnS)

White to gray/cubic

2.37−2.4

—

0.6−14.5

Zinc telluride (ZnTe) Zirconium oxide (ZrO2) Zirconium silicate (Zircon — ZrSiO4)

Red/cubic

2.79−3.56

—

—

White-yellow-brown/monoclinic (often doped to form cubic zirconia) Various colors/tetragonal

2.2

—

—

0.055

≥0.44

1.95 at 589 nm

1, pp. 648, 662; 2, pp. 4−113 1, pp. 691; 2, pp. 4− 113; 6 Used as phosphor 1, pp. 648, 669; 2, pp. 4−113; 3, p. 209; 5, p. 960; 6 2; 5, p. 960; 6 1, p. 669; 2, pp. 4− 113; 3, p. 209; 7 1, p. 662; 2, pp. 4−113

0910_book.fm Page 336 Wednesday, September 22, 2004 9:01 AM

Refractive Index

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Color/Crystalline Form

336

© 2005 by CRC Press

Material

0910_book.fm Page 337 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

337

REFERENCES 1. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2nd ed., John Wiley & Sons, New York, 1976. 2. CRC Handbook of Physics and Chemistry, edited by D. R. Lide, 73rd ed., CRC Press, Boca Raton, FL, 1993. 3. L. H. Van Vlack, Physical Ceramics for Engineers, Addison-Wesley, Reading, MA, 1964. 4. Ceramic Source, Vol. 8, American Ceramic Society, Westerville, OH, 1992−1993. 5. S. L. Swartz, Topics in electronic ceramics, IEEE Trans. Electr. Insul., 25(5), 935, 1990 6. Materials Handbook, Ceram. Ind., 144(1), 57, 1995, Business News Publishing, Troy, MI. 7. The Oxide Handbook, edited by G. V. Samsonov, IFI/Plenum, New York, 1973. 8. CRC Handbook of Laser Science and Technology, Vol. 1, Lasers and Masers, edited by M. J. Weber, CRC Press, Boca Raton, FL, 1982. 9. S. Singh, J. P. Remeika, and J-R. Potopowicz, Nonlinear optical properties of ferroelectric lead titanate, Appl. Phys. Lett., 20(3), 135−137, 1972. 10. D. S. Smith and H. D. Riccius, Refractive indices of lithium niobate, Optics Communications, 17(3), 332−335, 1976. 11. W. L. Bond, Measurement of the refractive indices of several crystals, J. Appl. Phys., 36(5), 1674− 1677, 1965. 12. B. Zysset, I. Biaggio, and P. Gunter, Refractive indices of orthorhombic KNbO3. I. Dispersion and temperature dependence, J. Opt. Soc. Am. B., 9(3), 386, 1992.

© 2005 by CRC Press

0910_book.fm Page 338 Wednesday, September 22, 2004 9:01 AM

338

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

V. STRUCTURAL PROPERTIES

© 2005 by CRC Press

3.19

—

—

—

—

—

∼3.20

37−51

—

—

34−54

300

Aluminum oxide (α-Al2O3) single crystal polycrystalline

∼3.97 3.73−3.8

53−60 44−55

30−45 (TS); 40−150 (MR)

23−24

41−80 33−51

370−550

Aluminosilicate (Glass-3Al2O3⋅2SiO2 or Al6Si2O13)

2.6−3.156

10.8−25

—

—

190

Not available 4.36

45

—

—

19.6−29.0 for densities between 2.6 and 2.9 —

—

500 (K); 5 (M)

2, p. 126; 8−11

56

—

—

—

—

3025 (K)

Not available ∼3.03

—

—

—

—

—

3166 (K)

1, pp. 796, 798; 5, pp. 4−42 1, p. 796

40−55

15−20 (TS); 20−40 (MR)

22.0

26−35

200−300

1300 (K); 64−67 (R45N)

42−65

50 (MR); 22.5 (TS) at 980οC

27

44−70

400−414

2800 (K); 2200 (K) at 1000g; 2400−3700 (V)

Material Aluminum boride (AlB2) Aluminum nitride (AlN)

Apatite (Ca5P2O12F) Barium boride (BaB6) Beryllium boride (BeB2) Beryllium oxide (BeO) Boron carbide (B4C)

Flexural Strength (ksi)

Compressive Strength (ksi)

Hardnessa 985 (K) 1225−1230 (K); 5−5.5 (M); 94−95 (R15N) — thick film 2000−2050 (K); 9 (M); 78−90 (R45N) V at 500 g 1300−1500

—

(K): Knoops hardness in kg/mm2 at 100 g load; (M): Mohs hardness number; (V): Vicker’s hardness in kg/mm2; (R): Rockwell’s hardness number. Note: 1 Pa = N/m2 = 9.8 × 106 kg/mm2 = 6.894 × 106 ksi = 6.894 × 103 psi

References 1, p. 796; 5, p. 4−36 1, p. 819; 7, p. 417; 8−11

1, pp. 752, 759; 2, pp. 118, 126; 3, p. 44; 4, pp. 777, 805; 6, p. TD39; 7, p. 417; 8−11 1, p. 850; 5, pp. 4−37; 7, p. 417; 8−11

2, p. 118; 4, pp. 777, 791; 7, p. 417; 8−11 1, p. 805; 2, p. 12; 3, p. 44; 4, pp. 777, 791; 7, p. 417; 8−11 339

a

∼2.52

Shear Modulus (106 psi)

0910_book.fm Page 339 Wednesday, September 22, 2004 9:01 AM

Elastic Modulus (106 psi)

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Density (g/cc)

Modulus of Rupture (MR) or Tensile Strength (TS) in ksi

Shear Modulus (106 psi)

Flexural Strength (ksi)

Compressive Strength (ksi)

7−15 (MR)

—

45

90−385 (K); 2 (M)— hexagonal

1, p. 819; 3, p. 44; 4, pp. 777, 779; 7, p. 417; 8−11

—

141 (V)

1, p. 850; 5, pp. 4−45 1, pp. 796, 798; 5, pp. 4−47 2, p. 126; 5, pp. 4−47 2, p. 126; 5, pp. 4−48 1, pp. 796, 798; 8−11 1, p. 796; 8−11

Hardnessa

∼2.25

Boron oxide (Glass-B2O3) Calcium boride (CaB6) Calcium carbonate (Calcite-CaCO3) Calcium fluoride (CaF2) Cerium boride (CeB6) Chromium boride (CrB2)

2.46

2.5

—

—

7.7−14.2 with grain; 6.4−15.4 against grain —

2.30

65

—

20

—

—

1689−2744 (K)

2.71

—

—

—

—

—

150 (K); 4 (M)

2.9−3.3

—

—

—

—

—

200 (K); 4 (M)

Not available 5.6

55

—

—

—

—

3166 (K) at 32 g

31

—

—

88

190

∼6.66

54

—

40

400

7.25

—

30 (TS); 100 (MR) —

—

—

—

1125−1700 (K); <2110 (K) at 50 g; 1800 (V) at 50 g 1400 (V) at 50 g; 86−89 (RA) 1126 (K) at 50 g

2.0−2.53

20−22

—

6.5

17–35

—

2.8

21.0

10 (MR)

—

21.8

—

835.6 (V); 672.5 (V)—glass ∼880 (K); 7.5 (M)

6.24

6.2

—

—

—

—

∼246 (K)

2.32

—

—

—

—

—

50 (K); 2 (M)

11.20

72.5

—

—

5 ± 10

—

2400 (K) at 160 g — polycrystal; 3800 (K) at 160 g — single crystal

Chromium carbide (Cr3C2) Cobalt boride (CoB) Cordierite (2MgO⋅2Al2O3⋅5SiO2) Forsterite (Mg2SiO4) Germanium oxide (Glass-GeO2) Gypsum (CaSO2(OH)4) Hafnium boride (HfB2)

15; 6.2−13.8 with grain; 5.9−15.2 against grain

References

1, p. 810; 11, 12 1, p. 796; 5, pp. 4−54 1, pp. 759, 761; 8−11 1, p. 759; 3, p. 44; 8−11 1, pp. 850−851; 5, pp. 4−61 2, p. 126; 5, pp. 4−49 1, pp. 796, 798; 9

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Boron nitride (BN)

0910_book.fm Page 340 Wednesday, September 22, 2004 9:01 AM

Elastic Modulus (106 psi)

340

© 2005 by CRC Press

Material

Density (g/cc)

Modulus of Rupture (MR) or Tensile Strength (TS) in ksi

—

—

40

—

7.15

50

—

—

—

—

1790−1870 (K); 2533−3202 (V) at 50 g 1618−1899 (K)

2.61

69.5

—

—

18.0

—

2040 (K)

3.3−3.9

35−42

12.3−13 (MR)

16

16−35

270

3.53−3.65

30.5−46

14−15 (MR); 13.9 (TS)

11−19

∼13

120−217

1.66

25 (estimate)

—

—

—

80

—

2, p. 118; 3, p. 44; 4, pp. 777, 791, 805; 7, p .417; 11 7, p. 417

Not available 9.3

—

—

—

—

—

∼1970 (K)

1, p. 797

97.5−MO2B5

—

—

—

—

1, pp. 797−798; 8−11

Molybdenum carbide (MO2C) Molybdenum silicide (MoSi2)

8.9−9.2

77.3

—

—

—

—

2181−2321 (K) at 50 g or MO2B5; 8−9 (M) or MO2B 1500 at 50 g

∼6.24

59

100 (TS); 40−60 (MR

—

—

100−350

Mullite (0.72Al2O3-28SiO2) Niobium boride (NbB2)

3.03−3.16

7−32

13

72

—

6.97−7.2

92.4

7−39 (TS); 12 (MR) —

—

—

—

1120 (V); 7.5 (M); 71 (R45N) 2603 (K); 8 (M)

Niobium carbide (NbC) Orthoclase (KAlSi3O8) Potassium silicate (KSiO3)

7.80−7.85

49.0

—

—

40

—

2000 at 50 g

2.56

—

—

—

—

—

600 (K); 6 (M)

2.01

0.053

0.6 (MR)

—

—

1.6−2.4

Iron boride (FeB) Lanthanum boride (LaB6) Magnesium aluminate (spinel-MgAl2O4) Magnesium oxide (periclase-MgO)

Magnesium silicate (Mg2SiO4) Manganese boride (Mn3B4) Molybdenum boride (MO2B)

1785 (K); 8 (M) 5.5−6.5 (M)

—

—

1, p. 810; 12

1, pp. 796, 798; 5, pp. 4−65 1, pp. 797, 798; 5, pp. 4−66 7, p. 417; 8−11

1, p. 81; 5, pp. 4−76 3, p. 44; 4, pp. 777, 791; 8−11 1, pp. 759, 761; 3, pp. 44; 8−11 1, pp. 797−798; 5, pp. 4−79; 8−11 1, p. 810, 12 2, p. 126; 5, pp. 4−84 6, p. TD34

0910_book.fm Page 341 Wednesday, September 22, 2004 9:01 AM

51−61

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

∼12.76

Hafnium carbide (HfC)

341

Silicon nitride (Si3N4)

Silicon oxide (Glass-SiO2)

Silicon oxynitride (Si2ON2) Talc (Mg3Si4O10(O H)12) Tantalum boride (TaB2) Tantalum carbide (TaC) Thorium boride (ThB4) Thorium oxide (ThO2)

3.1−3.22

33−70

24−25 (MR)

23−29

33−85

200−667

37−48 (17 reaction bonded)

21 (TS); 143 (MR)

—

65−174 (22 reaction bonded)

145

3.2−3.4 (2.2reaction bonded Si3N4) ∼2.6

7.5−16.1 (fiber)

Flexural Strength (ksi)

Compressive Strength (ksi)

References 1, pp. 806−808; 2, pp. 118, 126; 3, p. 44; 4, pp. 777, 791; 6, p. TD39; 7, p. 417; 8−12 1, p. 815; 5, pp. 4−95; 6, p. TD39; 8−12

6−15

100−200

7.5 (MR)

—

65−70

—

1600 (K

—

—

—

—

—

20 (K); 1 (M)

2, p. 126; 11

11.15

36−37

—

—

—

—

1, pp. 797−798; 5, pp. 4−104; 8−11

∼14.53

41.3

2−4 (TS)

—

40

—

8.5

21

—

—

20

—

2615 ± 120 (K); 2537 (K) at 30 g; 2533 (K) at 50 g; 89 (RA) 825 (K); 1800−1952 (K) at 50 g; 9+ (M) —

9.7−9.9

20−35

12.0 (MR)

13.5−14.5

8.7−30

199−213

2.1−2.9

39−40

2.6−2.8

Up to 300

2500−3000 (K); 3000−3500 (V) at 25 g; 9.1 (M); 2853−4483 (K or V) — cubic chemical vapor deposition ∼2200 (K); 1400−1700 (V); 900−1000 (V) at 500 g (reaction bonded Si3N4) 710−1000 (K); 1040−1260 (V) at 500 g; 7 (M) ∼633 (V); 6 (M); 480 (K)

—

10.5

4.5−9.6 (fiber)

Hardnessa

1, p. 755; 2, p. 126; 4, p. 805; 8−11 1, pp. 755, 850− 851; 3, p. 44; 4, pp. 777, 791, 805; 6, p. TD35; 10 1, p. 819; 8−11

∼2.2

16−40 (TS); 128−1306 (TS−fiber) 3−10 (TS); 15.5 (MR)

Shear Modulus (106 psi)

945 (K); 6.5 (M)

1, p. 810; 8−12

1, p. 798; 5, p. 106 3, p. 44; 5, pp. 4−107; 8−12

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Silicon oxide (quartz-SiO2)

Elastic Modulus (106 psi)

0910_book.fm Page 342 Wednesday, September 22, 2004 9:01 AM

Silicon carbide (SiC)

342

© 2005 by CRC Press

Material

Density (g/cc)

Modulus of Rupture (MR) or Tensile Strength (TS) in ksi

77−80

Titanium carbide (TiC)

4.25−4.94

45−65.4

—

35−54

190−800

160 (TS;) 73.5 (MR)

—

60

—

∼4.24 (rutile) ∼3.89 (anatase) 3.4−3.6

41 (rutile)

8−10 (TS); 69−103 (rutile–TS); 8 (MR) —

14−16.5

13−49

35.5; (117−136 for rutile polycrystals)

—

—

—

16.0

112

—

—

—

—

15.5−17.2

60.5−101

50 (TS); 80 (MR)

—

80

—

12.70 (UB2)

64 (UB4)

—

—

60 (UB4)

Uranium oxide (UO2) Vanadium boride (VB2)

∼10.96

25−31

0.14−0.28

5.10

38−39

Vanadium carbide (VC) Zirconium boride (ZrB2)

5.71−5.81

61.2

6.085

Zirconium carbide (ZrC)

6.44−6.56

Titanium oxide (TiO2) Topaz (SiAl2F2O4) Tungsten boride (W2B5) Tungsten carbide (WC)

Uranium boride

—

—

2710−3377 (K); 3250 ± 100 (K) − single crystal; 3400 (V) at 50; 9+ (M) 2400−2800 (K); 1905 (K) at 1000 g; 2900− 3200 (V) at 50 g; 2850−3390 (V) at 100 g; 9+ (M) 713−1121 (K); 8.8−10.4 (Krutile)

1, pp. 797−798; 5, pp. 4−108; 8−11

1, p. 810; 2, p. 118, 126; 3, p. 4; 4, pp. 777, 791; 8−12 1, p. 755; 3, p. 44; 8−11

1250−1500 (K); 8 (M) 2533−2633 (K)

2, p. 126; 11

1, pp. 806, 810; 2, p. 126; 8−12

—

1800−2150 (K); 2400 (V) at 50 g; 1730 (V) at 100 g; 92 (RA) 1477 (K) (UB2)

9.4−15

139

600 (K); 6−7 (M)

—

—

—

2110−2814 (K)

—

—

—

—

2900 at 50 kg

50−73

—

—

29−54

—

50.5−60

11.7−14.5 (TS)

—

25

—

1560−2603 (K); 2100 (K) at 160 g; 2000 (K) at 160 g— single crystal; 2200 (V) at 50 g; 87−89 (RA) 2138 (K); 2836−3640 (V) at 100 g; 92.5 (RA); 8−9 (M)

15.9 (TS); 12.0 (MR) —

1, p. 798; 8−11

1, pp. 797−798; 5, pp. 4−109 3, p. 44; 8−12 1, pp. 797−798; 5, pp. 4−110; 8−11 1, p. 810 1, p. 79; 5, pp. 4−113; 8−11

1, p. 810; 8−12

0910_book.fm Page 343 Wednesday, September 22, 2004 9:01 AM

4.5

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Titanium boride (TiB2)

343

Elastic Modulus (106 psi)

5.56−6.1

21.7−36.2

19.9 (TS)

8.7−14.0

28.4−35.5

298.5

1200 (K); 6.5 (M),

3.5−4.7

20−30

12 (MR)

—

23.9

100

827 (K); 7.5−8 (M)

∼6.0

29−30.5

130 (MR)

13.5 (with CaO)

116−218

Shear Modulus (106 psi)

Flexural Strength (ksi)

Compressive Strength (ksi)

Hardnessa

261−420; 300 (stabilized with CaO)

1019−1121 (V) partially stabilized; 1019−1529 (V) fully stabilized; 83 (R45N)

References 6, p. TD39; 11; 12 3, p. 44; 7, p. 417; 8−11 1, pp. 756, 782; 7, p. 417; 8−11

0910_book.fm Page 344 Wednesday, September 22, 2004 9:01 AM

Zirconium oxide (ZrO2) Zirconium silicate (zircon-ZrSiO4) Stabilized zirconia (0.97ZrO2-0.03Y2O3)

344

© 2005 by CRC Press

Material

Density (g/cc)

Modulus of Rupture (MR) or Tensile Strength (TS) in ksi

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

0910_book.fm Page 345 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

345

REFERENCES 1. ASM Engineered Materials Handbook, Vol. 4, Ceramics and Glases, ASM International, Materials Park, OH, 1991. 2. L. H. Van Vlack, Physical Ceramics for Engineers, Addison-Wesley, Reading, MA, 1964, Chapter 8. 3. W. D. Kingery, Property Measurements at High Temperatures, John Wiley & Sons, New York, 1959. 4. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, John Wiley & Sons, New York, 1976. 5. CRC Handbook of Physics and Chemistry, edited by D. R. Lide, 73rd ed., CRC Press, Boca Raton, FL, 1992−1993. 6. Ceramic Source, Vol. 8, American Ceramic Society, Westerville, OH, 1993. 7. S. C. Carniglia and G. L. Barna, Handbook of Industrial Refractories Technology: Principles, Types, Properties, and Applications, Noyes, Park Ridge, NJ, 1992. 8. Z. D. Jastrzebski, The Nature and Properties of Engineering Materials, 2nd ed., John Wiley & Sons, New York, 1977. 9. CRC–Elsevier Materials Selector, Vol. 2, edited by N. A. Waterman and M. F. Ashby, CRC Press, Boca Raton, FL, 1991. 10. Materials Handbook, Ceram. Ind., 144(1), 57, Business News Publishing Company, Troy, MI, 1995. 11. The Oxide Handbook, edited by G. V. Samsonov, IFI/Plenum, New York, 1973. 12. M. Swain, Ed., Materials science and technology: a comprehensive treatment, in Structure and Properties of Ceramics, Vol. 11, edited by R. W. Cahn, P. Haasen, and E. J. Kramer, VCH Publishers, New York, 1994.

© 2005 by CRC Press

0910_book.fm Page 346 Wednesday, September 22, 2004 9:01 AM

346

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

VI. SUPERCONDUCTING COMPOUNDS

© 2005 by CRC Press

0910_book.fm Page 347 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

Compound

T c, K

Crystal Structure

La–Ba–Cu–O System BaxLa5–xO5(3–y) (La0.9Ba0.1)2CuO4–y, at 1 GPa (La1–xSrx)2CuO4 (La0.9Sr0.1)2CuO4 (La0.925Sr0.075)2CuO4 (La0.925BA0.075)2CuO4

30−35 52.5 34−37 30−36 33−38.5 ∼30

D4h D4h Tetragonal D4h Tetragonal Tetragonal

X–Ba–Cu–O System YBa2Cu3O7–x YBa2Cu3O7 LaBa2Cu3O7–x LaBa2Cu3O6 NdBa2Cu3O7-x SmBa2Cu3O7–x EuBa2Cu3O7–x GdBa2Cu3O7–x DyBa2Cu3O7–x HoBa2Cu3O7–x ErBa2Cu3O7–x TmBa2Cu3O7–x TmBa2Cu3O7 YbBa2Cu3O7–x LuBa2Cu3O7–x Y0.75Sc0.25Ba2Cu3O7–x Y0.5Sc0.5Ba2Cu3O7–x Y0.5La0.5Ba2Cu3O7–x Y0.25Eu0.75Ba2Cu3O7–x Y0.1Eu0.9Ba2Cu3O7–x Pr0.1Eu0.9Ba2Cu3O7–x Eu0.75Sc0.25Ba2Cu3O7–x Y(Ba0.75Sr0.25)2Cu3O7–x LaBa2Cu3O7–x La(Ba0.5Ca0.5)2Cu3O7–x

92−94 90 59.2 80 78.3 88.6 91.1 90.9 91.8 91.1 90.7 90.5 101 89.3 72.6 91 90 87 95 94.5 82 93 87 60 79

D2v (a = 3.820 Å, b = 3.893 Å, c = 11.688 Å) — Orthorhombic — Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic — Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic

10−22 110 ∼85 ∼110

Tetragonal D4h Tetragonal Tetragonal

∼60 ∼120 ∼108 ∼50 ∼85 ∼120 ∼30 ∼105 ∼125 ∼115

Tetragonal Tetragonal Tetragonal Tetragonal Tetragonal Tetragonal Tetragonal D4h Tetragonal Tetragonal

∼30 ∼20 ∼24

Tetragonal Tetragonal Tetragonal

Bi–Sr–Ca–Cu–O System Bi2Sr2CuO6 Bi2Sr2CaCuO8 Bi2–xPbxSr2Ca1–xyxCu2O8 Bi2–xPbxSr2Ca2Cu3O10 Tl–Ba–Ca–Cu–O System TlBa2CaCu2O7 TlBa2Ca2Cu3O9 Tlba2Ca3Cu4O11 TlSr2CaCu2O7 Tl0.5Pb0.5Sr2CaCu2O7 Tl0.5Pb0.5Sr2Ca2Cu3O9 Tl2Ba2CuO6 Tl2Ba2CaCu2O8 Tl2Ba2Ca2Cu3O10 Tl2Ba2Ca2Cu4O12 Nd–Ce–Sr–Cu–O System Nd2–x–zCexSrzCuO4–y Nd2Ce0.5Sr0.5Cu1.2Oy Nd2–xCexCuy

© 2005 by CRC Press

347

0910_book.fm Page 348 Wednesday, September 22, 2004 9:01 AM

348

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Compound

T c, K

Crystal Structure

Miscellaneous (Ca,La)2CuO4 Cu(La,Sr)2O4

18 39

K2NiF4 —

SOURCES 1. The CRC Materials Science and Engineering Handbook, edited by J. Shackelford and W. Alexander, CRC Press, Boca Raton, FL, 1992, pp. 97−100. 2. Ceramic Source, Vol. 8, American Ceramic Society, Westerville, OH, 1992−1993. 3. Electronic Ceramics: Properties, Devices, and Applications, edited by L. M. Levinson, Marcel Dekker, New York, 1987. 4. CRC Handbook of Chemistry and Physics, 73rd ed., edited by D. R. Lide, CRC Press, Boca Raton, FL, 1992−1993, pp. 12−71.

© 2005 by CRC Press

0910_book.fm Page 349 Wednesday, September 22, 2004 9:01 AM

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

VII. THERMAL PROPERTIES

© 2005 by CRC Press

349

α-Aluminum oxide(Al2O3) Single crystal Polycrystalline

2200 (under 4 atm N2), sublimes at 1 atm 2025 ± 15

~20°C

Thermal Conductivity (W/mK) 100°C

Coefficient of Thermal Expansion (10–6/K) at 25–400°C 25–1000°C

1000°C

50−2008

—

20−60

4.6

4.4−5.7

3.97

39−54

30.14; single crystal: 34.58− 46.68 at 100οF

6.15−6.28 (fused)

6.8−7.4

8.0−8.3

219.77; single crystal: 4.36−5.50 at 100οF —

20.30−20.51

8

9.0

14.8−20.9

4.0−5.6

5.0−5.6

3.73−3.8

24−26

1, p. 819; 9, p. 3785; 11; 800J/kgC (Cp) at 25οC; 1570 J/kgC (Cp) at 1000οC 1, p. 752; 3, pp. 12−144, 15−35; 2, pp. 595, 642; 5, p. 44; 6, p. 158; 8, p. TD39; 9, p. 378; 11−14; 0.20 cal/g⋅mol⋅K (Cp) 3, pp. 12−44, 15−35; 2, pp. 595, 642; 5, p. 44; 11−14

Beryllium oxide (BeO)

2650

2.93−3.03

242−270

Boron carbide (B4C)

2450 (3500: boiling point)

2.45−2.52

26−69

Boron nitride (hexagonal-BN)

Sublimes at ∼3000

2.25

17−58; 70.8 for sintered BN

16.7−29.0

13−25; 28.3 for sintered BN

0.4−7.72

0.77−7.51

Calcium carbonate (CaCO3)

1339

2.71

—

—

—

Calcium oxide (CaO) Cereium oxide (CeO2) Copper oxide (CuO) Cordierite (2MgO⋅2Al2O3⋅5 SiO2) Forsterite (2MgO-SiO2)

2572−2614

3.25−3.38

25.1

15.2

7.8−9.12

−6 (⊥ to c axis); 25 (|| to c axis) —

1, p. 805; 3, p. 12−143; 2, p. 595 5, p. 44; 9, p. 378; 11; 12; 14; 0.226 cal/g 1, p. 819; 4, p. 5277; 5, p. 44; 9, p. 378; 11; 12; 780 J/kgC (Cp); 2, p. 594, 3, pp. 4−47

13.6

9, p. 378; 13

2600−2800

7.13

—

64

8.5 ± 0.55

Decomposes at 1026 —

6.3−6.49

1.01

—

—

—

2.53−2.7

3.5

Polycrystalline: 11.5 at 100οF Polycrystalline: 17.6 at 100οF —

—

0.10

0.28

3, pp. 15−35, 4−51; 10, p. 150; 11−13 3, pp. 15−35, 4−57; 11−13 11−12

1910

2.8−3.22

3.3

—

—

10.6

12.5

6, p. 158; 11; 0.22 cal/g⋅mol⋅K

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

3.20−3.26

References and Miscellaneous Information

0910_book.fm Page 350 Wednesday, September 22, 2004 9:01 AM

Aluminum nitride (AlN)

Density (g/cc)

350

© 2005 by CRC Press

Material

Melting Point (°C)

2.32

2.1 ± 1.8

128 (−1.5H2O)

—

20−42

—

Hafnium boride (HfB2) Hafnium carbide (HfC) Kaolin (0.45Al2O30.53SiO2) Lead oxide (PbO) Magnesium aluminate (spinel-MgAl2O4) Molybdenum carbide (MO2C) Molybdenum silicide (MoSi2)

3060−3249

51.5

—

—

—

6.3

3900

11.2 (hexagonal) 12.20−12.76

7, p. 429; 10, p. 170; 11−12; 1010 ± 50 J/kg⋅C (Cp) 1, p. 794; 3; 12

—

—

—

6.6

—

1, p. 810; 3; 12

1682−1760

2.67−2.72

—

—

1.88

—

4.3

6, p. 158; 12; 0.254 cal/g⋅mol⋅K (Cp)

886−888

9.3−9.7

—

—

—

—

2135

3.3−3.60

1.7

Polycrystalline: 2.8 at 100οF —

6.61

8.1

8.8−9

3, pp. 15−35, 4−68; 12 6, p. 141; 9, p. 378; 11

2310−2687

8.9–9.18

—

—

—

7.8

—

1, p. 810; 11−12

1870−2037 (with some decomposition) 1810−1838

6.2−6.31

31.40

31.30

12.5

8.0

9.2

3, pp. 12−145; 5, p. 44; 12

2.82−3.16

4.1−6.2

3.9

1.84

3.7−4.2

4.5−5.5

3036

6.97

16.74

—

23.5

—

8.0−8.6

3500

7.6−7.85

14.23

—

—

6.7

—

770−776

1.98

7.12

—

—

∼35

—

976

2.01

0.88

—

—

7.0

—

3; 6, p. 158; 11; 12; 0.20 cal/g⋅mol⋅K (Cp) 1, pp. 790, 795; 3, pp. 12−142, 4−79; 12 1, p. 810; 3, pp. 12−143; 12 4, p. 525; 3, pp. 4−85; 10, p. 138 8, p. TD34

Sublimes/ dissociates at 2700−2816

3.1−3.22

50−200

13−110; single crystal: 89.90 at 100οF

26−57

4−4.5

4.02−5.10

Mullite (0.60Al2O30.36SiO2) Niobium boride (NbB2) Niobium carbide (NbC) Potassium chloride (KCl) Potassium silicate (K2SiO3) Silicon carbide (SiC)

1, p. 808; 5, p. 44; 6, p. 158; 8, p. TD39; 9, p. 378; 11; 12; 0.67 J/g⋅K

Note: Thermal conductivity units: 1 Btu ⋅ in/h ⋅ ft2 ⋅ F = 6.9381 Wm/K; Cp = specific heat

0910_book.fm Page 351 Wednesday, September 22, 2004 9:01 AM

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PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Gypsum (CaSO4⋅2H2O)

351

~20°C

Thermal Conductivity (W/mK) 100°C

Coefficient of Thermal Expansion (10–6/K) at 25–400°C 25–1000°C

1000°C

References and Miscellaneous Information

3.2−3.44

14−43

—

4−10

3.0−3.3

2.8−5.2

1, p. 815; 3, pp. 4−95; 8, p. TD39; 9, p. 378; 11; 12; 680−800 J/kgC

2.19−2.2

1.46−1.5

2.01

2.0−2.51

9−20.93

0.50−0.60

Silicon oxide (SiO2-quartz)

1610

2.66

12.55

—

17

—

Sodium chloride (NaCl) Silver chloride (AgCl) Tantalum boride (TaB2)

801

2.17

7.12

0.5−0.8; Single crystal: 5.88−11.06 at 100οF —

—

∼39

∼66 (at 600οC)

455

5.56

1.09

—

—

∼30

—

4, p. 527; 2, pp. 595, 642; 3, pp. 15−35; 6, pp. 141, 148; 9, p. 378; 12; 795.3 J/kgC (Cp) at room temperature 4, p. 527; 2, pp. 595, 642; 3, pp. 15−35; 6, pp. 141, 148; 9, p. 378 4, p. 525; 3, pp. 4−98; 10, p. 142 4, p. 525; 4, pp. 4−95

3000

11.15−12.6

10.88−16.0

—

16.1

—

8.2−8.4

3880−4820 (incongruent melting point) 3070−3300

13.9−14.53

22.18−29

—

38.4

5−8.2

9.76−9.86

>0.10

2.9−3.3

—

9.2−9.3

Titanium boride (TiB2) Titanium carbide (TiC)

2871−2900

4.5

25.3−115

10.35; Polycrystalline: 13.8 at 100οF —

>69

8.1

5.8−8.2

3160

4.25−4.93

17.2−20.50

25.12

5.86

4.12−7.7

7.4

Titanium oxide (TiO2)

1840−1854

3.8: anatase; 4.24: rutile

5−10.4

6.53−8.4; Single crystal: 5.5− 9.7 at 100F

3.35

6.8−8.5

7.0−8.7

Silicon oxide (SiO2-fused)

Tantalum carbide (TaC) Thorium oxide (ThO2)

1, p. 793, 795; 3, pp. 12–142; 10, p. 160; 12; 48.12 J/mol⋅K (Cp) 1, p. 810; 3, p. 12−143; 9, p. 378; 12 3, pp. 12−144, 15−35; 2, pp. 595, 642; 5, p. 44; 11−13 1, p. 795; 3, p. 4− 108; 11 1, p. 810; 2, pp. 595, 642; 3, pp. 12−143; 6, p. 143; 9, p. 378; 12 1, p. 755; 2, p. 594; 3, pp. 12−144, 15−35; 5, p. 44; 11− 13

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

Dissociates in air at 1800 and at 1850 under 1 atm N2 1600−1713

0910_book.fm Page 352 Wednesday, September 22, 2004 9:01 AM

Silicon nitride (Si3N4)

Density (g/cc)

352

© 2005 by CRC Press

Material

Melting Point (°C)

15.50−15.7

—

—

—

5.2−7.1

—

1, p. 810; 3; 11−12

2878 ± 20

10.96

14.6

9.80−14.2

2.8−3.35

—

10.0

Vanadium boride (VB2)

2100−2427

5.10

42.3

—

42.0

—

7.6−8.3

Vanadium carbide (VC)

2810 (burns in O2 or air but is stable to 2500 in N2) 2410−2685

5.71−5.81

—

—

—

7.2

—

3, pp. 12−144; 2, pp. 595, 642; 3; 11−13 1, pp. 793, 795; 3, pp. 12−142; 11; 46.92 J/mol⋅K (Cp) 1, p. 810; 3; 12

4.50−5.03

2.0−3.3

8.36

—

9.6−10.4

9.3

—

—

5−6 at 0°C (crystal)

64.4

—

5.5−5.9

Ytteria (Y2O3) Zinc oxide (ZnO)

Sublimes at 1800

5.61

0.6

Zirconium boride (ZrB2)

3038−3040

6.09

57.9

Polycrystalline: 23.5−29.0 at 100οF —

Zirconium carbide (ZrC)

3540−3570 (pyrophoric at room temperature) 2677−2700

6.44−6.73

20.50

—

—

6.7

—

5.70−6.1

1.7−3.3

1.95; single crystal: 4.1−4.2 at 100οF; 1.7

2.13−2.2

—

1.92

1.92

4.2−11, 10 at 0οC 7.5−13 (cubic & tetragonal); 1.1–14 (monoclinic) 4.2−4.5

Zirconium oxide (ZrO2) Single crystal polycrystalline

Zirconium silicate (Zircon-ZrSiO4)

2550

4.5−4.7

2.1

2.1

1.4−4.2

1, p. 756; 2, p. 595; 3, pp. 4−111; 11−13, 0.11−0.12 cal/gK (Cp) 3, pp. 15−35, 4−112; 6, p. 144; 11−13 1, pp. 793, 795; 3, pp. 12−142; 48.37 J/mol⋅K (Cp) 1, p. 810; 3, pp. 12−144; 12

3, pp. 12−144, 15−35; 2, p. 595; 8, p. TD39; 6, p. 143; 9, p. 378; 14

6, pp. 141, 158; 4; 11; 12; 0.132 cal/g⋅mol⋅K (Cp)

0910_book.fm Page 353 Wednesday, September 22, 2004 9:01 AM

2865

PROPERTIES OF SOLID-STATE INORGANIC MATERIALS

© 2005 by CRC Press

Tungsten carbide (WC) Uranium oxide (UO2)

353

0910_book.fm Page 354 Wednesday, September 22, 2004 9:01 AM

354

INORGANIC MATERIALS CHEMISTRY DESK REFERENCE

REFERENCES 1. ASM Engineering Materials Handbook, Vol. 4, Ceramics and Glasses, ASM International, The Materials Information Society, Materials Park, OH, 1991. 2. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2nd ed., John Wiley & Sons, New York, 1975. 3. CRC Handbook of Physics and Chemistry, edited by D. R. Lide, 73rd ed., CRC Press, Boca Raton, FL, 1993. 4. R. A. Flim and P. K. Trojan, Engineering Materials and Their Applications, Houghton Mifflin, Boston, 1975. 5. W. D. Kingery, Property Measurements at High Temperatures, John Wiley & Sons, New York, 1959. 6. L. H. Van Vlack, Physical Ceramics for Engineers, Addison-Wesley, Reading, MA, 1964, Chapter 9. 7. Y. S. Touloukian, W. R. Judd, and R. F. Ray, CINDAS Physical Properties of Rocks and Minerals, Vol. II-2, 1981. 8. Ceramic Source, Vol. 8, American Ceramic Society, Westerville, OH, 1992−1993. 9. S. C. Carniglia and G. L. Barna, Handbook of Industrial Refractory Technology: Principles, Types, Properties, and Applications, Noyes, Park Ridge, NJ, 1992. 10. R. S. Krishanan, R. Srinivasan, and S. Devanarayanan, Thermal Expansion of Crystals, Pergamon, New York, 1979. 11. CRC-Elsevier Materials Selector, Vol. 2, edited by N. A. Waterman and M. A. Ashby, CRC Press, Boca Raton, FL, 1991. 12. Materials Handbook, Ceram. Ind., 144(1), 57, 1995. 13. The Oxide Handbook, edited by G. V. Samsonov, IFI/Plenum, New York, 1973. 14. M. Swain, Materials science and technology: a comprehensive treatment, in Structure and Properties of Ceramics, Vol. 11, edited by R. W. Cahn, P. Haasen, and E. J. Kramer, VCH Publishers, New York, 1994.

© 2005 by CRC Press