; = <1T4 . The Poljak system can be formulated even more practically by converting equation (111.84) algebraically as follows : (I II.85a} (IU.85b)
using Kircbhotrs law. The practical course of calculation is then that with equation (lli.8Sb) for each wall the total radiation is expressed as a function of the temperature of that wall (l/>~ = .aT 4 ) and of the still unknown net transport 4>~- With the relations for the total radiation of each wall thus obtained the foreign radiation f>'( on each waiJ can be calculated. These ¢;' values used in equation (UI.85a) then give the net energy fluxes t/>~ for each wall as functions of the wall temperatures. In order to calculate the foreign radiation >'(" for a wall with number k, we must know the fractions Ejk which indicate which part of the total radiation of wall j directly reaches wall k. These view factors Fare calculated by cumbersome integrations (summation o~·er small surface elements) and we have to take into account that the radiation intensity depends on the angle cjJ between the direction of the radiation and the norm~ to the surface (approximately proportional to cos
223
A 1/ A 2 of the radiation which is emitted by wall 2 reaches wall 1 ;·the fraction (1 - AdA 2 ) again reaches walll). With these data we can now ·calculate the net radiation transport between two bodies of which the one (1) is completely enclosed by the other (2). The foreign radiation over wall 1 ( =A 1 >f'1 ) is then equal to F21 times the total radiation of wall 2 ( = F21 A 2 cf>;). It follows that the energy flux of the radiation Qn the smallest wall ( = rfJi'1 ) equals the total energy flux of the radiation emitted by the larger surface ( = cf>;). So, using equation (III.85): .A._,
'¥111
=
A., II -
o/1
A.,~l
'+'12
=
A., II
o/1
-
~II
o/2
=
.A._II
'f'z l
-
l -
a
a ·l
1
.A._ JI
o/:2
+ 1 -a Q2.A._II '¥1'12 2
Between the net radiation transport of body 1 (¢; 1A 1) and that of body 2 (
cp;1A1 +
>~2A2 = 0
because the energy lost by wall 1 most be taken up by wall 2 (law of energy conservation). From the two latter relations we find for the net radiation transport from body 1 :
~
l
+ 1 -a
a1 1
+ A1 A
2
1-
a
a2) cplld = cp"zt. _
2
1'!) 2
(III.S6)
This is an important relation which is often used for calculating radiation
transport If the temperature difference {T1 - T2 ) is not too great, (Ji - T~) can be expressed approximately as 4 P(T1 - T2) . In these cases a heat transfer coefficient for radiation Cl.r can be defined, which according to equation (Ill.86) equals:
a2 ) a,.="W_"7'1 l 3 ~ 1 + 1 - a 1 + -A1 -1 ---= .A
a1
A2
a2
1
(III.86a)
This means that at room temperature a,. is about 6 Wjm 2 oc and can therefore not be neglected with respect to free convection. At higher temperatures a,. ~ increases considerably and hence so does the radiation contribution to the total heat transport.
II 1.9. I. Problems 1. A long rod (diameter l ·l em, emission coefficient 0·8) with a temperature of 327°C is suspended in quiet air of 2rc. Calculate the contribution of free convection and radiation to the total heat transfer coefficient. Assume the air to be an ideal gas with a density of l·Okgjm3 at 27°C.
Answer : horizontal rod: 46 % free convection 54 % radiation vertical rod :
29 % free convection 71% radiation
224 *2. A small ceramic sphere (diameter 1 em), e.g. of a thermocouple holder, is situated in the middle of a long tube with a diameter of 20 em. Air of l50°C is passed through the tube at a mean velocity of 20 m/s. The temperature of the tube wall is l00°C. Calculate the temperature of the sphere.
Answer :
l47°C
3. Check that if between two large flat walls with equal emission coefficients a third equal waU is placed the net heat transport by radiation is halved. An example of this type of radiation shield is the layers of aluminium foil in the walls of refrigerators and cold store rooms. 4. The maximum intensity of sunlight occurs at a wavelength of approximately 0·5 x 10- 6 m. Calculate the surface temperature of the sun. Comments on problems Problem 2 In steady-state conditions, heat transport by radiation from the sphere must equal convective transport to the sphere. Thus : ( ex)
(T, - TJ = a.,(7;
- Tw)
thus ( a ) = 183 Wfm 2 oc (equation 111.68). Assuming 7; ~ T, , 'f = (T, + TJ/2 = 125°C ~ 400°K. Thus,employingequation(lll.86a) we find (a 1 = 0·9, A1/A2 « 1): Now Re
= 7000,
CHAPTER IV
Mass Transport
In this chapter the transport of matter will be treated. The starting point of our analysis is the law of conservation of matter, which reads for a substance A (see paragraph 1.1): (IV.l)
The following pages are no more than an elaboration of this law.
Apart from agreement in the description of the transport of matter and heat transfer, there are distinct differences as, for example :
(a) The 'production' of mass (by chemical reaction) is usually a compJjcated function of the molar concentrations of the reactants (and of the temperature), whereas the production of impulse and heat is seldom a strong function of concentration or temperature. (b) The interface between two media between which matter is transferred (e.g. between two liquids or a gas and a liquid) is usually mobile, contrary to the interface between two media between which heat is transferred (usually a solid wall). (c) The order of magnitude of the diff~sion coefficients ID of liquid and solid substances is much smaller than, for example, the thermal diffusivity or the kinematic viscosity (for gases at 20° C and 1 atm, D ~ 10- 5 m 2/ s ; for liquids at 20°C , D ~ 10- 9 m 2 j s ; and for solid substances D varies widely between 10- 10 and 10- 1 5 m 2f s). This means forliquids and solid substances that in the first place the penetration of matter in a given time takes place over (much) smaller distances than the penetration of heat or momentum ; that in the second place already with convective currents of low velocities, wruch frequently occur in the case of mobile interfaces, the convective transport exceeds the diffusion transport in the direction of flow. From the foregoing there appears to be a dilemma in the description of the mass transport. We formulated a law of conservation of mass because mass is the most characteristic property of matter. Accordingly we defined the diffusion coefficient in paragraph 1.2, equation (I.13), as the proportionality constant
226
between the mass flux and the gradient in the mass concentration: ,~.,
= -ll}
'+'mA, :r.
A
dpA
(IV.2a)
(Fick)
d;c
In addition, production rates in chemical reactions are functions of the molar concentrations, which we. shall indicate by cA, etc. (kmolfm 3). So we can imagine that for many calculations it offers advantages to define the diffusion coefficient as the ratio between the mole ftux (kmoljm 2 s) and the gradient in
the molar concentration :
,.~,.,
'+'mol A,x
=-
dcA
n LY A
(IV.2b}
(Fick)
dx
Both thus defined diffusion coefficients are in principle different (although in practice they are often almost equal) and in applying them we should realize on which concentration the description is based. The diffusion coefficient has been defined in such a way that the net transport through a fixed plane (in Figure 1.6 the plane n = constant) is zero. If we restrict ourselves to binar'y systems (with components A and B) for practical purposes two cases can be distinguished in which the net transport is zero:
A For every unit of mass A which diffuses through a fixed plane a unit of mass B moves in the opposite direction by diffusion ('barocentric' system). B. For every mole A a mole B moves in the other direction through the plane.
sub A. Net mass flow
= 0. p = constant
For the diffusion transport of substance A we can write : ¢':rrA,:r
=-
[)AB :A
whereas for the transport of substance B applies: A.."
'f'w.B,x
= - 0
BA
dps
dx
where ¢':nA.x is the mass flux of A (kgjm 2 s) in the x-direction for a net mass flow = 0 ; PA is the mass concentration of A (kgfm )). Because the conditions have been such that: ,/,."
"f'rnA.x
+
A-,•1
'f'mB .x
=
0
whereas :
PA
+ p8
= p =constant
or dpA
+ dp8
= 0
it follows from these relations that DAB . DnA. In other words, the definitions have been determined in such. a way that the diffusion coefficients of A in B and of B in A have the same numerical value. These definitions are used for describing the dlffusion transport in solid substances and liquids ; here, in the
227
case of not too high concentrations of, for example, A in B the density may be assumed to be constant. · sub B . Net mole ftux =
o. the total concentr~tion c =constant (kmoljm 3 )
Now we can write for the mole flux. (kmol/m 2 s) in the x-direction: n
dcA dx
A." 'f'mol A..x
= -
A." 'YmolB.x
= -:- 0)BA dc dx
11..11 AB
and : 8
and cB are molar concentrations (lcmoljm 3); for ideal gases and constant pressure and temperature their sum total is constant and equals c. These definitions are very suitable for describing the diffusion transport in gases. In the case of equimolar diffusion :
cA
A." 'f'mol A.x
A." 0 + '#'mol B,;r =
Also, here, the diffusivities have been defined in such a way that : _[]) AB
= . O)BA
According to the two definitions the dimension of II) is (length)2/ time, so that Din the MKS system is expressed in (m2 /s). This was likewise the case for the two other transport coefficients v (kinematic viscosity) and a (thermal diffusivity). However, in the case of diffusion it is .advisable to distinguish between two cases: p = constant and c = constant For these cases []) has to be defined using respectively the gradient of the mass or of the molar concentration. . IV.l. Stationary diffosion and mass transfer John noticed that, before m had left his office, the lawyer who had disappeared had prepared a pot ofcoffee. A cup on his desk was still half .fuU and from the scale on the sides. caused by evaporacton ofrhe wacer, he could see that the cup had been .filled to 1 em below the rim. He estimated rhe cup co be 8 em high. remembered the pages to come and concluded that the lawyer muse have left h is office approximately 17
days before.
IV.J.l . Stationary diffusion During most practical cases of diffusion neither the net mass flux nor the ~et mole flux discussed in the foregoing paragraph will be zero. A practical example in which the net mole flux is almost zero is the distillation in which, for every mole of the light component which passes into the gas phase, approximately one mole of the heavy component enters the liquid. However, on absorption and extraction of one component from a mixture the net transfer is invariably
~
:_ t;A·'
I
' ;~ ij'
. I
,,
228
, I
It
~
~·
.
unequal to zero. AI~() guring a chemical reaction e.g. at a catalyst ·s urface, the mole fluxes of-the re~9.~~t$ ~o be f~d. ~n(:i the mole fluxes of the product ·to be discharged are usu~UY y~~gll~ ·<~~g, ·in ~ 9.tm~ri~tign). When describing q}~ m~ ifi:iil~f~r til th~§~ ~@.~s ~!lgw~Qc~ ll1l!st b~ m~qe for the entrain~ent of &pbstilP.f~1i fP ~h~ ~PW ~~~q b.Y th~ ma-s~ tnm&fer as SIJCh. Fqr ~ biJl~ry mi~tl.q-e J1lO.Vliig wit~ fl velocity v relative to .a plane X = constant, t}le steady-state diffusion flux of component A relative to this velocity is·:
(vA
v)cA
-
de A
= - 0 dx
Tht~ rate of molar transport relative to ·t he plar~
>':not A t
VC
=
'
" ! :·
.
I.~
I
mol A,;.;
\,
. .
=-
((jJ"
[DdCA
dx +
mol A,x
+
x = constant is then, since . . ..
if>" . m ol
B,.x)
CA C
{1V.3a)
:' . , ·,.. . , ··;. ,.... whereas'!ihe mass ·tra:nsport is given by : \,
first right-hand teqn in these equations repre~nts the mass flux resulting from diffusio'n, whereas the secopd is a. m~a~!ll'~ the mass flux result~ng fro~ ~o~~~ mola~ flow, Equations (11I~3a) and (IIIJb) can only be solved if the rel.atio~ b.~twe~n' Hi~'fripl~at ff.~x~s of Aand B;s kl}gwn. We cari di~tinguish two exJreJ11~ s~wat1ons: . .. . i •
Th~
term
of
I
(a) 4>';.. +
•
) . :, •
::-: • : \ . . . :;-;, . .
.
·.~ ~..
.. '
..'i
:
.
:~· :·~-~ · ~"! ~
..
••
i
• !.
:\
l
~
:
,
1 l ~..!~ _1 :·. .. ~~ ··:·. . ~~~{L:.: '· i.' ·.~ 1
I :.:\ 1 \,
•
·\
•
\
:l.
~. ~. ' . .
••
• • •
In;·practice,. sit.'"l;lti.on.s; be,tw.een . these .extr,em~s,:"w.ill ofteq ·o9cur, but sine¥ ~he qiff~rence~ P~tw~ep ~s~s (a).an~(~) ~t;~.o.ftF9.&JA~U, it is ~earl:y 1atways p~.ssible to>ptoduce :a good es:timate·of the:molar flu,x by making a ahoice between these ca~es~ :.l n)the·following, we~.will.anatyse 'the t:Wo extreme:.cases. st~~ed ·in.greater ,_ ' •
•
•
de~u.
•
•
:·
•-
· ·.. .
:1 ~ '':...,(
•
- ·~/· ··. :-
·• •
-.
••
-·
-. • "
•••
' ,.. •
•
~
•
•
'
. ,,
(aj ~Etl~iiiJD.lar· d.iif:J!..siPn, ;·= 0.
••
•
·
.
~quation {IV.,3~ can now· be simpljfied t~ :
~f :we
consiq¢.r. one-dimension.a l
station~ry , diffusion
in the x-direction, the
mass balance (IV.l) yields (there is no production of A) :
. or ¢':nolA,;= coqstant for every plane
.e quation · yields, ; with
! .
'
··
..
':
=constant. Solution' of this the boundary conditions · cA= cA·; at x ' x 1 and X
.'i
229
c: .~
~c:
&I
u c: 0
u
l
- - Distance
Figure IV.l Concentration profile during equimolar diffusion (drawn line) and during diffusion through a stagnant fluid (dotted line)
cA
= cA 2 at
x = x 2, the concentration -distribution : CA- CAl
X -
X1
(IV5t
We see that the concentration distribution (Figure IV.l) is linear. · The mole flux of A is found ·after substitution of dc.Jdx in equation (IV.4) by the value calculated'from equation (IV.5) to be : (IV.6)
So, during equimolar diffusion the mole flux (and analogously also 'the mass flux) is directly proportional to the concentration gradient llcjAx. We notice that mass transport by equimolar diffusion is analogous to the transport of heat by conduction. For one--dimensional beat conduction we had found in paragraph 111.1 .1 (equation II1.2a): A-"
'+-' H
= - /,• T2 -
T1
x 2 - Xt
=-
peP~ - pcPT2 Q--"' - - - - - . _ _ _
x2-
xl
This equation is identical to equation (IV.6) if we replace the molar diffusivity 10 by the thermal diffusivity a and the molar concentrations c (moljm 3 ) by the 'heat co ncentratio ns, pc PT ('W jm 3 ). We can therefore also ad apt the relations found for stationary heat conduction around cylinders and spheres to diffusion. Using equations (lll.6) and (Ill. 8) we find for equimolar diffusion
230 between coaxial cylinders with diameters D 1 and D 2 and concentrations CAl and C Al : (IV.7) and for equimolar diffusion between concentric spheres (diameters D 1 and D 2 , concentrations cA 1 and cA2) : >mol A
2-nD D
= R) D2 -1 D21 (cAl
-
CA z)
(IV.8)
(b) Diffusion through a stagnant body. cb':notB = 0 This process can be observed, for example, during selective absorption oi extraction of material A from a mixture of A and B. For this situation equation (JV.3a) can be simplified to: _
A."
'PmolA,x- -
c
0 C-
dcA
dx
CA
(IV.9)
Application of the mass balance (equation IV.l) yields, again, that under stationary conditions and no production of A the molar flux of A through aU planes x =constant must be the same. So :
de A - = constant
dx
The above equation can be integrated and, applying the boundary conditions x 1 , cA 1 and x 2, cA2, we find for ~he concentration distribution: C -
CA
C-
CAl
=,1
CA>) (x-.xl)/(xl -.x!)
C-
\c- CAl
(IV.lO)
This concentration distribution is also shown in Figure IV.l for materials A (e.g. solvent) and B (e.g. solute). With the aid of equation (IV.lO) we find from equation (IV.9) for the molar flux for diffusion through a stagnant body : ,~,.,.
_
'f'moiA,x -
In c - cA 2
Oc X2 -
C -
X1
CAl
(IV.ll)
If cA is at all places much smaller than the total concentration c, the logarithmic factor in this relation can be approximated by : }n C C -
CA2 ~ _
CA2 -
CAL
CA l
C
and we find :
(IV.12)
the same result as for equimolar diffusion.
231
Mass transport through a stagnant fluid is a factor of I' _ JD-
C CAl -
} CA2
n
C -
CA2 _
C -
CAl
-
1
+
1
2
CAt
+
CA2
2
+ ...
bigger than during equimolar diffusion. The correction factor fD is named after Stefan; if trus factor is applied to equations (IV. 7) and (IV .8) these equations will also correctly describe, for the geometries considered, diffusion through a stagnant fluid. ·
I V.J.2. Mass transfer coefficients Analogous to the introduction o f the heat transfer coefficient ex in paragraph 111.1.3 whlch was defined by: dT
ex =
T... - ( T ) = -
A dx
x=O
Tw - ( T )
we can now introduce a mass transfer coefficient k which is defined as the ratio of the mass flux and the concentration gradient (which constitutes the driving force) in o n e phase :
kA
=
A.." '+'mol,A
cAo - (cA)
dx
_ _ rn.
-
!LJIA
x•O
cA, - (cA)
(IV.l3)
Here, 4>':no1A is the mass flux o f A into phase Band cA, - ( cA) is the difference between the concentration at the interface and the average concentration of A in phase B (mean cup concentration). For diffusion from a sphere into an infu1ite stagnant medium we ·find, combining equations (IV.13) and (IV.8) (the latter for the case D 2 ~ ex:>):
The dimensionless number kAD/ 0 is called the Sherwood number Sh, which plays the same role in mass transfer as the Nusselt number in heat transfer. For diffusion from a sphere into a stagnant infinite fluid Sh = 2, analogous to Nu = 2 for heat conduction. The dimension of the mass transfer coefficient is the same as that of velocity, distance{unit of time.* If a certain component is exchanged between two mobile phases (e.g. gas absorption, extraction, distillation, etc.) we encounter an overall mass transfer coefficient K which is composed of the partial transfer coefficients in the different
* In mass transfer with gases the partial pressure
instead of the molar concentration is often used for calculations. A mass transfer coefficient is theo defined as: 4J:C<>1A = kr{pA.w - PA.r)
since for ideal gases c = p/ RT, k, = kJ R T.
232
phases. Contrary to heat transfer (paragraph·111.2.2), however, in the case of mass transfer it is not possible to calculate the overall coefficient by summing up the partial resistances (1/ k) to the total resistance (1/ K). This is due to the fact that the concentrations in both pbases are generally not equal if the two phases are in equilibrium. Figure IV.2 shows an interface between two fluid phases through which a stationary mass flux