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Diffusion in Three-component Gas Mixtures

H. 1. TOOR
Carnegie Institute of Technology, Pittsburgh, Pennsylvania

A solution to the Stefan-Maxwell diffusion equations for equimolal countercurrent mine the important characteristics of
diffusion in a three-component gas mixture is obtained which is similar in form to Gilli- the diffusion process and to develop
land's equation for diffusion of two gases through a third inert gas. The important features approximate equations which will show
of both types of diffusion are investigated and the conditions under which the following these characteristics and still retain, as
phenomena occur are determined: (1) diffusion barrier (the rate of diffusion of a component
is zero even though its concentration gradient is not zero) ; (2) osmotic diffusion (the rate far as possible, the familiar forms of the
of diffusion of a component is not zero even though its concentration gradient is zero); binary-diffusion equations,
(3) reverse diffusion (a component diffuses against the gradient of its concentration).
A generalized driving force which describes these phenomena is introduced, and approxi-
mate equations are developed which give the individual rates of diffusion directly. SOLUTIONS OF THE MAXWELL
DIFFUSION EQUATIONS

PART I general restrictions are the stagnant-gas It is simplest and mos informative to
Almost all the theories of mass transfer case and the equimolal countercurrent obtain directly the desired solution for
are based to some extent on molecular diffusion case. The former sets the rate of equimolal diffusion.
diffusion (5, 6, 18). Although binary- diffusion of one component equal to zero For a three-component system Equa-
diffusion theory is well understood, the by placing a barrier to the transfer of this tion (1)can be written for each component,
theory for multicomponent diffusion is component (which will be called an and since the summation of the mole
less satisfactory, even though the basic absorption barrier), and the latter usually fractions is 1,the equation for component
diffusion equations have long been sets the total net rate equal to zero by an C can be eliminated. At a constant total
available. This paper will be restricted to energy balance. pressure D t i = Di,and the equations
the study of steady state diffusion in the These two restricted types of diffusion become
simplest multicomponent gas, the ternary. appear to be of most utility in multi-
The equations for diffusion in ideal component systems as well as in binary
multicomponent gases were developed by systems. The case of one stagnant gas
Stefan (16, 17) and Maxn-ell (11, 12). corresponds to absorption in which one
For ideal binary gas mixtures the more component of the mixture is insoluble in
rigorous Chapman-Enskog (9)equations the liquid phase, and equimolal counter-
can be shown to reduce to the Maxwell current diffusion (hereafter referred to as
equations when the temperature and equimolal digusion) corresponds to dis-
total pressure are constant. Similarly, tillation of a multicomponent mixture.
under the same conditions the Curtiss- Equimolal diffusion is closely approxi-
Hirschfelder (4) extension of the Chap- mated (14) when the distillation column
man-Enskog equations can be shown to is adiabatic, molal heats of vaporization
reduce to the Maxwell-Stefan equations are approximately the same for all
for ideal multicomponent gas mixtures. components, etc.
Gilliland (15) solved the diffusion Since D i i P is independent of P i t can
The predictions of the Maxwell equations be seen that the diffusion rates are
for three-component mixtures have been equations for a ternary system by setting
the rate of diffusion of one of the com- independent of the total pressure and
shown to be in good accord with experi- proportional to l / R T x , where J: is the
ment for various types of diffusion (?',lo). ponents equal to zero, and Hoopes (10)
solved the same equation with the rates length of the diffusion path. This is also
For the general n-component system true for an n-component mixture.
there are n Maxwell equations of the form of transfer unrestricted. Hoopes also
presented a solution for the case of For equimolal diffusion
equimolal diffusion. Solutions for other
special cases of ternary diffusion have N = Ara + NBf Nc = 0 (1)
been obtained by Benedict and Boas ( I )
and with this restriction Equations (2)
and Cichelli, Weatherford, and Bowman
and (3) reduce to
(3).
The integrated equations, even for a
When the total pressure is constant, as three-componen t system, are highly com-
assumed in the equation, the number of plex and numerical results usually can
equations is reduced to n - 1. For steady be calculated from the equations only
state diffusion in the x direction only, by trial-and-error. In addition, the
these n - 1 differential equations can be physical significance of the equatioiis is
solved to give n - 1 algebraic equations not a t all apparent. Wilke (19) has
relating the rates of diffusion of the n developed approximate methods of solv-
different molecular species. Therefore the ing Maxwell's equations, but his method
resulting equations will be indeterminate, necessitates a trial-and-error solution
and one more restriction is necessary to and consequently does not bring out the
make the system determinate. This important features of the diffusion
restriction is obtained by fixing the rate process.
of diffusion of any one of the components This paper will be concerned with the Part of the solution to these equations
or by relating any two or more of the two types of diffusion in three-component may be obtained directly by first multi-
diffusion rates. gas mixtures: diffusion of two gases plying both sides of Equation ( 5 ) by
For a binary system the two simplest through a third stagnant gas and equi- (l/DAB) - ( l / D s c ) , both sides of Equa-
and most useful special cases of these molal diffusion. The object is to deter- tions (6) by (l/DAB) - ( l / D A c ) , and

Page 198 A.1.Ch.E. Journal June, 1957


then adding the resulting equations: If y A and y B are assumed small, Equa- However, they also yield the additional
tions (2) and (3) may be integrated equation
separately:

Although these are the equations for


binary equimolal diffusion, as well as the
limiting forms for diffusion of one dilute This indicatcs, as expected, that Nc
This may be integrated in terms of the gas through a second stagnant gas, could not be arbitrarily set equal to
variable Equation (13) applies to a system con- zero, as all the degrees of freedom were
sisting of A and C, and Equation (14) removed by fixing N = 0. Thus Equation
applies to a system consisting of B and (15) gives the rate of transfer of com-
C. Thus, when gases A and B are dilute ponents A and B when N c = 0 but
from x = 0 where Y A = y A , and y e = y B , they diffuse through the third gas with N c = 0 only when the mole fractions are
to x = x where Y A = y A , and y e = ~ J B , no interaction among themselves. related in such a way that they satisfy
(8)
. .
The differences in mole fraction in these Equation (16). This result throws light on
to give equations can be conveniently considered Gilliland's solution to the ternary diffu-
to be the driving forces for diffusion in sion problem where N c is fixed equal to
-
1 - -1
-)ATA 1 binary systems, and with this picture the zero. As pointed out by Wilke ( I 9 ) ,
D A c (DAB D B , first terms on the right of the equations Equations (11) and (12) are always
may be considered to be reciprocal resist- satisfied by N A f N B = 0 and there are
ances. Since mole fraction is proportional usually a t least two solutions to the
to concentration in ideal gases, this is the equations. Consequently, as NA ap-
P 1 I same as considering a concentration
-
-_ _
RTx [(z -
-
difference to be the driving force.
proaches N B , i t becomes more and more
difficult to determine the correct solution.

(z 1 - 1
Z G ) ( Y B i - ?JB2)] (9) DIFFUSION BARRIER
This difficulty occurs because when
N.4 + N B = 0, Gilliland's equation is a
special case of equimolal diffusion.
Equimolal Diffusion
The second part of the solution may be Although the same physical situation
obtained by use of the Laplace Trans- +
If Nc is set equal to zero, N A NB = 0 is described regardless of the order in
form. ( I S ) , and the result is from Equation (4), and the equimolal which the limit N A + N B = Nc = 0 is
approached, Gilliland's solution in the
limit gives Equation (15), but it fails to
give Equation (16). It can be shown by
substituting N A + N B = Nc = 0 into
the original differential equations, (2)
and (3), that Equations (15) and (16) are
the correct solutions for this situation.
Therefore, when Nc is fixed equal to
-
- -_ In zero, by a solubility barrier, for example,
RTx 1 1
equimolal diffusion of the remaining two
components occurs when Equation (16)
is satisfied and the rate is given by
Equation (15). Equation (16) thus com-
plements Gilliland's solution. When it is
Equations (9) and (10) together +
not satisfied, the solution N A NB= 0
is a ficticious one.
When N is set equal to zero, by an
energy balance, for example, then when
trial a i d error; N c is then fixed by Equa- 1 Equation (16) is satisfied Nc goes to zero
tion (4). N A = -L%'B = and Equation (15) gives the rate of
The parametric solution to the ternary- diffusion of the other two components.
diffusion problem obtained by Gilliland The interesting result is that if component
(15) when one gas is stagnant ( N c = 0) C is not in equilibrium its rate of diffu-
is given below:
.- p I n 2Ye (15) sion, even if there is no apparent barrier
RTx YC, to its transfer, will be zero if the com-
(11)

Vol. 3, No. 2 A.1.Ch.E. Journal Page 199


ponents are distributed so that Equation ,4 point on any of the curves gives the which cannot diffuse because of a solu-
(16) is satisfied. compositions of that component at the bility barrier. If N B is set equal to zero in
(The concept of equilibrium is being terminal points when that component is Equation ( l l ) ,
stopped from diffusing by a diffusion
used in a restricted sense to indicate the
condition nhen y$> = Y , ~ ; i.e., the barrier. The 45-deg. line indicates the
ordinary binary driving force is zero. absence of a diffusion barrier, for this
line corresponds to no diffusion when
This is really a pseudoequilibrium for each Equations (11) and (12) together also
component.) Using the ordinary concept ye, = yc,. The difference between any
of diffusion in a binary gas, one might of thc curves and the 45-deg. line there- yield
say the resistance of the gas to the fore gives the driving force, yc, - ye,,
transfer of component C is infinite, and for the component which is not diffusing.
This difference can be considered in a
this condition will be defined as a difusion
sense as the strength of the diffusion and so a diffusion barrier exists here also.
burrier to differentiate it from the solu-
barrier. The curves show that the maxi- Gas C therefore cannot diffuse because
bility barrier, which exists in gas absorp-
tion. mum strength of the diffusion barrier for of a solubility barrier and when Equation
The physical situation is clarified ifhydrogen, the light component, is con- (21) holds, gas B cannot diffuse because
siderably less than the maximum strength of a diffusion barrier.
one considers the theoretical situation in
which the two independent restrictions, of the barriers for the two heavier com- It can be shown (10) that Equations
+
N c = 0 arid ibrA N B = 0, are simul- ponents. (20) and (21) are the solutions to the
taneously placed in the system. Maxwell's Just as in Gilliland's equation, the diffusion equations, (2) and ( 3 ) ,when
equations then yield Equations (15) and equations for equimolal diffusion also and S c arc both set equal t o zmo.
contain a solution Tnhich is usually Therefore, nhen two of the three gases
(16); thr first equation gives the rates of
diffusion and the second describes the fictitious for it can be seen that Equation arc stagnant, the stagnant gas roncentra-
manner in which the gases arrange (10) is always satisfied by tions adjust themsrlves t o satisfy Equa-
themselves. If either of the original tion (2l), and the diffusion rate is given
restrictions is placed separately on the by Equation (20). If only one gas is
system, the preceding situation is repro- initially stagnant o\+ing t o a solubility
duced identically if a second restriction barrier, the system containing two
is that the compositions must satisfy stagnant gases can be exactly reproduced
Equation 16). by fixing the compositions of the com-
When D,, = D B Cit can be shom-n that
the only physically possible solution to Under these conditions Equation (9) gives ponents a t both ends of the diffusion
path so that Equation (21) is satisfied.
Equation (16) is y, = ycl, and so The fact that two stagnant gases will
Equation (15) does not go to infinity, but partially separate when a third gas is
becomes indeterminate under this restric- passed through them, as shown by
tion. The rates of diffusion of A and B Equation (2l), is the basis of the sweep-
under these conditions are shown below diffusion separation process (5).Hellund
to be given by Equations (43) and (44). (9) has considered the unsteady state
Figure (1) shows some concentration analogue of the sweep-diffusion process
relationships which cause diffusion bar- using his extension of the Chapman-
riers in the system H,, HLO, and Con. Enskog theory.
These curves were determined from Figure 2 shows some concentration
Equation (16) by use of binary diffusion
coefficients from Table 1. The curves arcAs before, this solution is true for only relationships when H20 is restrained by
one particular relationship among the a diffusion barrier. The terminal concen-
mole fractions and here the extra equation trations of the diffusing coniponent have
TABLE1 must be obtained by solving the original bcen fixed a t 0 a t point 1 and 0.5 a t
differential equations with restrictions point 2. The conditions when CO? is
BIKARY-DIFFTSIOX COEFFIC~IEXTS given by Equations (17) and (4). The diffusing and H2 is stagnant arc shown
(sq. cm./sec.) solution gives Equation (18) and the by curve a, and curve b shows the con-
additional relationship ditions nhen H, is diffusing and CO, is
1 = COT D,, = 0.9220 stagnant. It ran be seen that CO, is
3 = HZO Dzk = 2.7064 more effective than H, in stopping the
k = H2 D,k = 3.1576
diffusion of the H20.
Approximate values a t 40°C. arid 155 \17hen y B , approaches 1, y, approaches
mm. Hg, from Wilke ( 2 9 ) .

independent of the total pressure. All


the subsequent calculations are based on
these same diffusion coefficients. Equa-
tion (16), which gives the conditions for
N e = 0, mas applied to each of the com-
ponents in turn. Two of the four inde-
pendent variables were removed by The solution to the equimolal diffusion
setting the mole fraction of one of the
diffusing gases equal to zero a t point 1
and setting the mole fraction of the other satished. is reduced to a binary gas and this binary
diffusing gas equal t o zero a t point 2. system is indeterminate as the removal of
One Gas Stagnant the stagnant gas removes the deter-
This allows the compositions a t points 1
and 2 to be given by one point on a curve The previous results suggest the possi- minancy condition. Since Equation (21)
and also shons the greatest effect of the bility of a diffusion barrier when two gives the conditions under which N B = 0,
diffusion barrier. gases are diffusing through a third gas it yields y R z = 0.5 when y e , = 1.0, the

Page 200 A.1.Ch.E. Journal June, 1957


only composition a t point 2 which can becomes greater than yAl the direction of
exist in this binary system. diffusion is unchanged, but the direction
Figure 3 shows the diffusion-barricr of the driving force is reversed so that
conditions when the terminal concentra- the diffusion is again in the direction of
tions of the stagnant gas are held con- the driving force. T h e n ya, equals 1 the
stant. There are six different combinations system is reduced to a binary gas con-
of COz, H20 and H2, all of which are sisting of COZ and Hz. A T n = --SB and
shown. The strength of the diffusion the rates are the same as those given by
barrier clearly increases as the mass of the usual equation for binary equiniolal
the restrained and diffusing components diffusion.
increases. The same conclusions can be reached
analytically for the special case of diffu-
GENERALIZED DRIVING FORCE
sion in which two of the binary-diffusion
coefficients are equal. [See Equation (36).]
When a diffusion barrier exists for a No diffusion barrier occurs for H,O
particular component, it cannot diffuse and Hz because of the may the coniposi-
Fig. 1. Diffusion-barrier conditions for com- even though it is distributed nonuniformly tions were fixed.
ponent C, equimolal diffusion. in the gas. This can be pictured as a There are two separation processes
Ha = C CO, = C H2O = C dynamic equilibrium between the ten- which take advantage of the phenomenon
dency of the restrained component to
-1 - 2 - 1 - 2- -
1 2
diffuse in the direction of decreasing
of diffusion from regions of low to high
HZO CO, H2 HZO HZ COz concentrations. They differ from them-
concentration because of the usual con- selves, and froin the conditions considered
Hz Hz Cot COz Ha0 HzO
centration driving force and the ten- here, by the restrictions placed on N .
dency of the component to be forced in One has becn defined as mass di$usion ( I )
the reverse direction by interactions with or atmolgsis, and the other as sweep
the othcr two diffusing components. diflusion ( 3 ) .
A small increase in the driving force
a t this point, therefore, should allow i t It seems useful to define as reverse
to overcome the interactions and cause diffusion the diffusion of a constituent of
the transfer to take place in the direction a multicomponent gas from a region
of the driving force (high to low concen- where its concentration is low to a region
trations) and a small decrease in the where it is high when i t is caused by the
Y5
driving force should make the transfer action of the other constituents of the
Fig. 2. Diffusion-barrier conditions for com- take place in the direction opposite to gas. The region in which reverse diffusion
ponent B; component C is stagnant. the driving force. takes place is indicated in Figure 4.
YA, = IJA, = 0.5 I n one sense the diffusion-barrier
YC, = 1 - YB, Y r 3 = 0.5 - YB, concentrations of the restrained com-
Equimolal Diffusion
ponent correspond to a zero concentration
Curve Component
A B C This conclusion has been tested numer- gradient in a binary gas. When the
U co, &O Hi ically for equimolal diffusion by use 6f restrained component is a t the concen-
b H, Hz0 COa Equations (9), (lo), (4), and (16). trations corresponding to a diffusion
Figure 4 shows the rate of diffusion of barrier, its rate of transfer is zero, just
COPas a function of its mole fraction a t as i t is zero in a binary gas when yl = y2.
point 2, when its mole fraction a t point 1 In the ternary gas mixture the diffusion
is constant at 0.5. It is assumed for of a component is from point 1 to point 2
simplicity that the mole fraction of when the concentration of the component
HzO is zero a t point 1 and the mole a t 1 is greater than the concentration a t 1
fraction of Hais zero a t point 2. The rates corresponding to the diffusion barrier,
of diffusion of HzO and Haare also shown just as the diffusion in a binary system is
on the figure. The dotted lines are from 1 to 2 when y1 is greater than the
approximate equations developed in a value corresponding to zero concentration
later section. gradient y2. As the displacement from
It can be secn that the rate of diffusion the barrier condition increases, the rate
of COz is close to a linear function of of diffusion increases; therefore, the
y A , . At y A , = 0.159, N A is zero, as this driving force in a ternary gas which
is the diffusion-barrier concentration. As should correspond to yl - y2 in a binary
yA,, decreases from this value, the driving gas is, for component i ,
force y A 1 - Y A , increases and overcomes
the interactions and Na increases in the
Ya positive direction. As YA, increases from or
Fig. 3. Diffusion-barrier conditions for com- the diffusion-barrier value, the driving
ponent B; component C is stagnant. force decreases, the interactions over-
come the driving force, and the diffusion
YA, = 0.7 - YB? Y A ~ - 0.8 - YB,
increases in the negative direction. The where ysl* is the mole fraction which
yc, = 0.3 Yc, - 0.2
direction of diffusion is now opposite to would have to exist a t point 1 for a
Curve Components the direction of the driving force. diffusion barrier to exist for component
A B C As ya, continues increasing the driving i when the mole fractions a t point 2 are,
a Ha0 HP coz force decreases and the magnitude of held constant and yi,* is the mole fraction
b coz Hz H?O
N A increases. At y A 2 = 0.5 = ya, the necessary a t point 2 for a diffusion barrier
C Hz HzO coz driving force is now zero but N , is not to exist when the mole fractions a t point 1
d CO, Ha0 H2
e Hz coz HzO zero. This point is labeled osmotic di$u- are held constant.
f Hz0 cos H% sion and is considered later. When Y A , Equation (16), when A and C are

Vol. 3, No. 2 A.1.Ch.E. Journal Page 201


interchanged, gives for component A
2 0 1 I

12

0 8
and either ya, or yA, can be considered
t o be the starred value. When yA, is 0 4
taken as yA,*,Equation (22) becomes for
component A 0

-0 4

-0 8
and when ya9 is taken as ya,* Equation
(23) yields for componcnt A -1 2

6A(YA, - YA,) (26) -I 6

There are similar equations for the other -2 0


two componcrits obtained by interchang-
0 01 02 0 3 0 4 0 5 06 07 0 8 09 10
ing subscripts in the above equations. It
can be shown that YAZ

Fig. 4. Diffusion rates as a function of yA2,equimolal diffusion.

It is immaterial whether Equation (25)


or (26) is considered to represent the
generalized driving force; so, for simpli-
city, the second one will be used. The
function defined by Equation (26)
satisfies the necessary conditions for a
driving force. First, it gives the correct
direction of diffusion; when i t is positive driving force is of opposite sign to the from a diffusion barrier as a measure of
the direction of diffusion is positive and binary driving force, and this would be the driving force.
when it is negative the direction of expected to be the case in general. Figure 6 shows the rates of diffusion of
diffusion is negative. Second, the rate of The reciprocal slopes of the curves in CO, and HzO through stagnant Hz as a
diffusion is zero when the function is Figure 5 are a measure of the generalized function of the mole fraction of COz a t
zero. Since the relationship between the resistances to the diffusion of each com- point 2. The solid curves were calculated
rate of diffusion and the generalized ponent (the generalized driving force from Equations (11) and (12) and the
driving force must be single valued, the divided by the diffusion rate). The mean dotted ones are approximations developed
first two conditions require that the rate slopes of the lines decrease with increasing in a later section. The terminal concentra-
of diffusion be a monatonic increasing molecular weight, an indication, a t least tions are fixed as shown in the figure. The
function of the generalized driving force. for this example, that the generalized inert-gas concentrations are fixed a t both
A final condition which i s desirable but resistances increase with the mass of the ends of the diffusion path, and the con-
not necessary is that the rate of diffusion component. Since the curves for CO, centrations of CO, and HzO are fixed
should be proportional, or approximately and HzO have opposite curvatures, their only a t point 1.
proportional, to the driving force. The generalized resistances approach each These curves bear a resemblance to
rate of diffusion of each of the three other when the generalized driving forces those shown in Figure 4 for equimolal
components is plotted against its gener- are small. diffusion, although the conditions are
alized driving force in Figure 5. The I n general, the relationship between quite different. There is no diffusion
curves were obtained by the use of the rates of diffusion and the generalized barrier for HzO, as its concentration a t
Figure 4 and Equations (24) and (26) driving forces would not be expected to point 1 is zero, but the CO, diffusion
and the curves are close to straight lines. be as linear as in this particular case, barrier occurs at y e , = 0.152. A t this
In this eusmple no diffusion barrier and so the generalized resistances for each point the tendency for COz to diffuse in
occurs for Hz and H20 since the com- component would vary more with the the direction of decreasing COz concen-
position of both components is fixed a t composition of the system. I n this instance tration is just balanced by collisions with
zero a t one or the other end of the diffu- the generalized driving force has the same HzO, which is diffusing in the opposite
sion path. The rates of diffusion of these utility as the one used in the diffusion of direction.
two components are roughly proportional one gas through a second inert gas, I n this system, contrary to the equi-
to their binary driving forces, and their quantitatively i t can be somewhat mis- molal one previously discussed, there is a
generalized driving forces are essentially leading, but i t always gives the correct net molal transfer for all values of ye,.
the same as their binary ones. However, direction of diffusion and the correct zero N A never equals - N g since Equation
CO,, for which a diffusion barrier exists, condition. (16), the criterion for this condition,
diffuses quite independently of its binary cannot be satisfied by any physically
driving forcc, and its diffusion rate is One Gas Stagnant
possible value of y B 2 in this example.
closely proportional to its generalized The gencralized-driving-force viewpoint When yB, is less than the diffusion-
driving force. It can be seen that reverse can also be applied to transfer when one barrier concentration, NB is positive and
diffusion takes place when the generalized gas is stagnant by using the displacement in the direction of decreasing CO, con-

Page 202 A.1.Ch.E. Journal June, 1957


centration. When yfl, is between the total net diffusion rate, g.- condition holds, Equation (15) is indeter-
diffusion-barrier concentration and yB1, mole/(sq. cm.) (sec.) minate and the diffusion equations reduce
0.7, N g is negative and reverse diffusion diffusion rate for component to Equations (43) and (44). When DAC
takes place. When y e , is greater than yo, i, g.-mole/(sq. cm.) (sec.) does not equal D f l c , thc rates of diffusion
the diffusion is again in the direction of total pressure, atm. are given by the general equations.
of decreasing GOn concentration. When gas constant, (cc.) (atni.)/(g.- From the generalized-driving-force
yB, = 0.8, the system reduces to a binary mole) (OK.) viewpoint, N c = 0 for ye, - ye, = 0
one in which CO, is diffusing through temperature, OK. only when the generalized driving force,
stagnant Hz and the rate of diffusion of distance in direction of diffu- &ye, - yc,, is equal to the usual binary
GOz is given by the binary equation. sion or length of diffusion driving force, that is, when ye, = yc, and
Since the diffusion phenomena when path, cm. Equation (30) or (31) is satisfied. The
one gas is stagnant are similar to the mole fraction of Component i point a t which osmotic diffusion occurs
phenomena when the transfer is equi- value of y i when component i is shown in Figures 4 and 5.
molal, the generalized driving force given is restrained by a diffusion The phenomenon of diffusion of a com-
by Equation (23) applies here also. The barrier ponent which is in equilibrium was pre-
only difference is that yi,* is now given Yim = log mean of yi dicted by Hellund (8), who extended the
by Equation (21). Thus for component B, Chapman-Enskog equations to a ternary
Greek letters system and obtained a solution for diffu-
D A C / D AB
6, 6,, 6,, (ac= functions used in equimolal sion in the unsteady state. He named the
= SB’ (28) phenomenon osmotic diJusion by ar.:ilogy
YRI diffusion equations, defined
by Equations (35), (24), (59), to liquids.
and the generalized driving force for and (60), respectively
One Gos Stagnant
component B is obtained by combining 6’, Sir, IS^', (ac’ = functions used in stag-
Equations (23) and (28), nant-gas diffusion equations, When N e is fixed equal to zero by a
defined by Equations (49), solubility barrier, N B is zero when
(28), (65), and (66), respec- Equation (21) holds. If component B
tively is in equilibrium, y B I = y B , and the
The equation for component A is ob- condition for N f l = 0 becomes yc, = yc,.
tained by interchanging the A and B Subscripts
This is the condition which reduces the
subscripts in the preceding equations. A , B, C = components of a mixture generalized driving force to the binary
SA’ and 6,’ are related to each other in i, j , k = indexes which refer to com- driving force as well as the condition for
the same way as 6; and 6i [Equation (27)]. ponents A , B, or C complete equilibrium, and so in this
As before, the generalized driving force 1, 2 = terminal conditions of the system a component which is in equi-
gives the correct direction of diffusion diffusion path librium will always diffuse unless the
as well as the correct zero condition. entire system is in equilibrium. The point
The rate of diffusion of both compo- at which osmotic diffusion occurs is
nents is shown plotted against their PART I1 shown in Figures 6 and 7.
generalized driving forces in Figure 7. I n general, reverse diffusion, both in
The data are from Figure 6 and Equa- OSMOTIC DIFFUSION equimolal diffusion and diffusion with
tions (28) and (29). The generalized It has been shown that a component one gas stagnant, would be expected to
driving force for component A , HzO, not in equilibrium under certain con- occur when the generalized driving force
reduces to the binary one because of the ditions may not diffuse even if there is no lies between zero and the value corre-
terminal concentrations which were used barrier to its diffusion, and i t has also sponding to osmotic diffusion.
and the rate of diffusion of HzO is been shown for a particular example that
approximately proportional to this quan- the converse is true, i.e., that a component
tity. The generalized driving force for TWO DIFFUSION COEFFICIENTS EQUAL
which is in equilibrium may diffuse.
GO2,however, is markedly different from By setting two of the three binary
the binary one, and only the generalized Equimolal Diffusion diffusion coefficients equal to each other,
driving force has the characteristics of a one may obtain simplified forms of the
driving force. It has already been demonstrated that
Equation (16) must be satisfied for N c diffusion equations.
The generalized resistances to the
diffusion of the two components are not to equal zero when N = 0. If component Equimolal Diffusion
the same although they approach one C is in equilibrium, yc, = yc,, and since
the sum of the mole fractions a t any If DAC = D f l c Equations (9) and (10)
another as the generalized driving forces reduce to
approach zero, and the generalized point is equal to 1, Equation (16) is
resistance for GOzis greater than that for satisfied with these restrictions only if
Hz0. one of the following conditions is satisfied:
Simplified approximate equations for
the rates of diffusion, developed in a later YAx = Y A z (30)
section both when the diffusion is equi- and consequently
molal and when one gas is stagnant, allow
analytic confirmation of the conclusions Ye1 = Yfl.

reached in this section. or


and
D A =~ DBc (31)
NOTATION
The first condition is trivial, as it gives
Dii = diffusion coefficient for binary the obvious result that there is no transfer
mixture of components i and j , if there is complete equilibrium in the
sq. cm./sec. system. The second condition shows that
D, = mean diffusion coefficient de- N c = 0 only when the diffusivity of A
fined by Equation (56), sq. through C equals the diffusivity of B
cm./sec. through C (when yc, = yCJ. When this

Vol. 3, No. 2 A.1.Ch.E. Journal Page 203


equating the last two equations yields this proportionality does not exist. It
can be shown that the generalized resist-
ance in Equations (36) and (37) is always
positive, finite, and nonzero, as indeed is
where nesessary if the driving-force viewpoint is
to be meaningful.
The rate of diffusion of component C,
so that components A and B deviate from which is given by the binary-diffusion
the binary rate of diffusion of gas A and equation, (38), apparently is not a
Substituting Equation (34) into Equation B by their mole fractions in the mixture function of its generalized driving force.
(32) leads to A and B, and the composition of the gas To determine the cause of this incon-
A and B is unchanged by the diffusion sistancy it is necessary to consider the
NA Y e , - YC? through component C. original derivation of the generalized
-
(1 - Y c J - 6(1 - Ye,) As DAB approaches DAC, 6 approaches driving force. Applying Equation (24)
1 and Equations (36) and (37) approach to component C with DAC = DBe yields
the binary equimolal equations (13) and
(14), as expected. When ye, approaches 6 c --yc,
ye,, Equations (36) and (37) reduce to YCI
and

and ye,, which can be taken as yc,*, is


the mole fraction of C at point 2, which
causes a diffusion barrier. If this equation
Equation (32) with the equimolal con- is combined with Equation (23) as usual,
dition gives it does not yield the binary driving force
which appears in Equation (38), because
there is only one solution to Equation
(45) which has any physical significance
This is the equation for equimolal and that solution is yc, = ye,, or ye,* =
diffusion in a binary system consisting ye,. Therefore, 6c must always be 1 and
of A and C. Hence the rate of diffusion of Equation (23) does yield yc, - ye, as
component C is the same as i t would be and this is the special case discussed pre- the generalized driving force for this
if A and B were one gas; indeed, as far viously where ATcis zero and N A = - N,. limit. There can be no diffusion barrier
as C is concerned A and B are the same The presence of component C under these for component C and the only condition
gas, for their interactions with C were conditions merely causes the rates of for zero diffusion is ye, = ye,.
assumed identical. Equation (32) shows diffusion of the other two components to
that the hypothetical gas consisting of deviate from the binary rates by a con-
One Gas Stagnant
A and B also diffuses through C as if it stant amount.
were the second gas in a binary mixture. When gas C is dilute, the equations When DAC = DBc Equations (11) and
In a sense the ternary mixture has further simplify to the equimolal diffu- (12) yield
been reduced to a binary one in which sion equations for the binary system
part of the molecules of one component consisting of A and R. When A and B
are tagged to distinguish them from the are dilute, yc approaches 1 and the
other part of the same component. The binary equimolal diffusion equations are
diffusion coefficient DAB then represents again obtained, although in this case the and
the coefficient of self-diffusion of com- diffusion coefficient DAC or DBc replaces
ponents A and B. Although the net rate the coefficient DAB, giving Equations (13)
of diffusion of the tagged and untagged and (14). If either A or B alone is dilute,
molecules, A and B, follows the binary the rate of diffusion of the other com-
equation, the individual components ponent is given by Equation (13) or (14).
deviate from the binary equation as Equations (36) and (37) are very
shown by Equations (36) and (37). closely related to the idea of a generalized and by equating these the counterpart of
If the composition of the gas A and B driving force. The last terms on the right Equation (34) is abtained,
is the same at both ends of the diffusion of the equations are special cases of the
path, generalized driving force defined by
Equations (24) and (26) since aA and 6B
(39) are both equal to 6. The remaining terms
on the right of the equations are therefore where
reciprocals of t4e generalized resistances
and Equations (36) and (37) show that

N A - YA. - YA>/(YA, + Y B J
for this special case. The generalized
resistance is the same for components A 6‘ = p)
D A C / D AB

(49)
N B YB, YB,/(YA, + ye,) (40) and B and, for any particular system,
is a function of the concentration of and so
Equation (32) then yields component C only. When the terminal
concentrations of component C are held
constant, the generalized resistance is
constant and the diffusion rates are
directly proportional to the generalized
driving forces, but when the concentra-
tions of component C are allowed to vary

Page 204 A.1.Ch.E. Journal June, 1957


2.a
In Y C
YC3
N, = I .6
(1 - Ye,) - 6’(1 - Y C J
1.2

0.8

Equation (46) shows that the hypo-


thetical gas A + B diffuses through the
0 4

stagnant gas C a t the same rate that one x o


gas diffuses through a second inert gas,
but Equations (50) and (51) indicate -0 4
that components A and B individually do
not follow the binary equations. -0 8
When the ratio of A to B is the same
at both ends of the diffusion path, -1 2

-1 6

-2 0

6,#, - YI2
Fig. 5. Diffusion rates as a function of the generalized driving forces, equimolal diffusion.
YA, = 0.5 YA I
YE, = 0 YE, = 1 - YA.
yex = 0.5 Ycx = 0
A B C
Yc, - Ye, c02 H,O Hz
Ycin = (54)
In Y C
YC, I .o
At this limit the diffusion rates when one
0.8
gas is stagnant differ from the rates for
equimolal transfer by the term ycm, just
as in binary diffusion. Under these con- 0.6
ditions the composition of the gas A B +
is unchanged by its diffusion through gas 0.4
C.
Equations (50) and (51) differ from 0 2
/ analogous equimolol equations in
th
thTt they do not reduce to the binary 0
equations when all the diffusion coeffi-
cients are equal.
-0.8
when yc, approaches ye,, Equations
(,YO) and (51) reduce to Equations (43)
-0 4
ahd (44), as do the equimolal equations,
since N A = -NB. When the diffusing
gases are dilute, Equations (13) and (14) 215 -0.6

are again obtained, and when only one


of the diffusing gases is dilute, the binary -0.8
stagnant gas equation applies to the
other gas. -1 .o
When the stagnant gas is dilute, the
limiting forms of the equations depend, -I .2
in this case, on how the limit is ap-
proached. This would be expected since -I .4
when component C is removed, the
restriction which makes the system -I .6
determinate is removed and the resulting
binary system is indeterminate. Thus,
-I .8
when ye, = ye, = 0, Equation (47)
reduces to the general equation for -2.o
binary diffusion, 3

Fig. 6. Diffusion rates as a function of yE,; Ha is stagnant.


!/A,= 0 !/A, = 0.8 - YE,
= 0.7 YE,
yc, = 0.3 yes = 0.2
A B C
H,O COa Hz

Vol. 3, No. 2 A.1.Ch.E. Journal Page 205


and another restriction is now needed to
define N A and hTB.
The last terms on the right of Equa-
tions (50) and (51) are special cases of the
generalized driving force defined by
Equations (28) and (29) and the remain-
ing terms on the right are the generalized
resistances, which are the same for both
components. This generalized resistance is
positive, finite, and nonzero for all con-
ditions of physical significance.

APPROXIMATE DIFFUSION EQUATIONS

Since the equations developed in the


last two sections apply to a ternary gas
in which two of the three binary-diffusion
coefficients are equal, i t seems possible
that they could be modified to approxi-
mate the general equations when all the
diffusion coefficients arc unequal.
a; Y$ - K.
Equimolal Transfer
Fig. 7. Diffusion rates as a function of the generalized driving forces; HPis stagnant.
The simplest useful modifications of
Equations (35) to (37) are obtained by Y.4, = 0 YA, = 0.8 - YB,
replacing D A Cin Equation (35) by yal = 0.7 Y Bs
yc, = 0.3 yc, = 0.2
A B C
HzO COZ H2

so that this example this region is extremely components, calculating H P by difference


narrow. could lead to large relative errors in N c .
If more accurate values are desired I n order to test the methods under
near the diffusion barrier, the approximate other conditions, the test examples set
generalized driving force in Equation (57) up by Wilke ( 1 9 ) were used. The system
may be replaced by the true generalized is HP, COP, and HPO, as before, and the
driving force given by Equations (24) results obtained by use of Equations (56)
where and (26). Thus, for component A to (60) and (4),defined as method 1, in
most cases check those calculated from
the exact equations within 10%. They
are tabulated in Tables 2 and 3.* How-
(59) ever, when the gencralizcd driving force
and ;
This equation is not symmetrical with for HP,which is the recommended choice
respect to positions 1 and 2. The equation for component C, is much smaller than
can be made symmetrical by replacing the other generalized driving forces, this
6, by F A in Equation (BO), although method causes large errors. (The directioR
Once ATA and N B are obtained, N c can better results are obtained by taking the
be determined from Equation (4). Al- as well as the magnitude is incorrect.)
average of the two values given by inter- This is due to the fact that H2is obtained
though the equations are symmetrical changing points 1 and 2 in Equation (61),
with respect to A and B, they are not by difference. Calculating HPdirectly by
symmetrical with respect to C. Therefore, this method also gives poor results
because the generalized driving forces are
the results obtained from them depend
small. I n this case Equation (62) is a
on which of the three components is
much better approximation since it uses
chosen to be component C. The most
accurate results should be obtained when the correct generalized driving force
The equation can be written for the (method 2). With both methods, the
component C is chosen so that DAc and
DBc are the two diffusion coefficients other components by interchanging sub- maximum error is 207& although the
which are closest to each other, since this scripts. It is a good approximation when absolute errors are generally very small.
choice makes the system approximate as tho generalized driving force is not too At present the recommended procedure
closely as possible the conditions under large, as i t gives the correct zero condi- for equimolal diffusion is to use method 1
which Equations (57) and (58) are exact. tion, but it is usually less accurate than in all cases where the generalized driving
The preceding approximate equations (57) when the generalized driving force force is not small and method 2 if the
are compared with the exact ones in is large. For the conditions of Figure 4 generalized driving force for a component
Figure 4, where thc approximate equa- it is actually a better approximation to is small. The results may be checked for
tions are shown by dotted lines. The N A than Equation (57) over :t large part
consistency by use of Equations (4) and
error for COPis very small and the diffu- of the range of YA,. (9) without solving the general equations.
sion-barrier conditions predicted by Equa- The difference between the approxi- The errors in the approximate mcthods
tion (57) arc close to the true diffusion- mate and true diffusion rates for HPO is should increase as the difference between
barrier conditions. This may not be the larger than that for COPand the rate of the diffusion coefficients increases.
case in general, and when y A , is between diffusion of HPis fixed by the equimolal *Tables 2, 3, and 4 have been deposited as docu-
the approximate and exact diffusion condition, Equation (4). Consequently if ment 5210 with the American Documentation
Institute, Photoduplication Service, Library of
barrier values the direction of diffusion H2 were diffusing a t a relatively low rate Congress, Washington 25, D. C.. and may be ob-
tained for $2.50 for photoprints o r $1.75 for 35-mm.
given by Equation (57) is incorrect. I n compared with that of the other two microfilm.

Page 206 A.1.Ch.E. Journal June, 1957


One Gas Stagnant It is interesting to note here that depends both on whether an actual region
In this case the approximate diffusion exists in which steady state molecular
equations are obtained by replacing DAC 6, ’= d G T (68) diffusion controls the transfer rate (i.e.,
the usual laminar film) and on what
in Equation (49) by Dm; so from Equa- ~s Equation (67) is exact when N~ = 0,
tions-(49) t o (51) : percentage of the total resistance to
it should bc a good approximation when transfer resides in this region if it does
the generalized driving force is small. If nv;c+

where

to (66), is generally very accurate- is infinite as far as one component is


and appreciably more so than the analogous concerned, and the film then completely
method for equimolal diffusion. The stops the transfer of this component.
average error is a few per cent and the Thus a laminar film may be controlling in
maximum error is 18c7,. This error is very the usual sense for one component only
small compared with the total diffusion while the transfer of the other components
rate. Method 2, which uses the correct is controlled by some other resistance in
Since there are only two diffusion rates generalized driving force, Equation (67), the syytem.
which are unknown, there is no problem is in general less accurate than method 1
with the third component as there was in in these examplrs. The results are in
equimolal diffusion. The equations are Table 4.* NOTATION
now completely symmetrical, but here The recommended procedure for calcu-
there is no freedom in choosing the The notation for4his article appears on
lating the rates of diffusion of two gases
constituent which is t o be considered as Page 203.
through a third stagnant gas is to use
coniponent C: it must be the stagnant gas. method 1 except whcn the generalized
Therefore, the accuracy of the approxi- driving force is very small, a point a t LITERATURE CITED
mate equations would be expectcd to which method 2 should be more reliable.
decrease as the dissimilarity between the Wilke’s (In) approximate methods for 1. Benedict, Manson, and Arnold Boas,
two diffusing gases increases. Chvn. Eng. Progr., 47, 51 (1951).
solving Maxwell’s equations have not 2. Chapmhn, S., arid T. G. Cowling,
The approximate equations are com- bren checked extensively, but it appears
pared with Gilliland’s equation in Figure “R/IathcmaticalTheory of Non-Uniform
that the equations are not inconsistent Gases.” Cambridge University Press,
6, where H2 is the stagnant gas. When with the phenomena discussed above if Camhridge (1939);
ye, = 0.8, the system reduces to a binary the negative partial film pressure factors 3. Cichelli. M. T.. W. D. Weatherford,
gas and the approximate equations are nhich occur in the procedure are not ,Jr., and J. R. Bowman, Chem. Eng.
exact a t this point. At yB, = 0, the rejected as he suggested, but are retained. Progr., 47, 63 (1051).
approximate equations differ very slightly This makes the average effective diffusion 4. Curtiss, C. F., and J. 0. Hirschfelder,
from the exact ones, but betwecn these coefficient used by Wilke negative in the J . Chem. Phys., 17, 550 (1949).
two extremes the error is larger because 5. Danckwerts, P. V , Znd. Eng. Chem., 43,
reverse diffusion region.
of the curvature in the correct curves. 1460 (1951).
6. ---, A . Z. Ch. E. Journal, 1, 456
The diffusion rates are reproduced
(1955).
quite well by the approximate equations, CONCLUSIONS
7. Fairbanks, D. F., and C. R. Wilke,
except for C 0 2 near its diffusion barrier. Znd. Eng. C h e w , 42, 471 (1950).
I t is clrar that in general there are
Thcx diffusion barrier predicted by the 8. Hellund, F,. J., Phy. Rev., 57,737 (1940).
marked qualitative as well as quantitative
approximate equations occurs a t a value 9. Zbid., p. 743.
differrnces between binary and ternary 10. Hoopes, J. W., Jr., Ph.D. thesis, Cohm-
of yHgslightly different from the correct
diffusion. The approximate Equations bia Univ., New Yorlr (1951).
diffusion barrier, so that in this region the
(57) and (63) show explicity that in both 11. MsLxwell, J. C., Scienlifc Papers, 2,
percentage error in N O can be very large,
equimolal diffusion and diffusion of two p. 57, Dover Publications, Inc., New
although the absolute error is small. In
gases through a third stagnant gas, the Yorlr (1952).
addition, when y B , is between the values
usual concept of a driving force, 12. Zbid., p. 625.
corresponding to the two diffusion bar-
(yA1- y A , ) , is inapplicable and the rate 13. Pipes, 1,. A., “Applied Mathematics for
riers, the approximate equation gives the Engineers and Physicists,” McGraw-
of transfer of one component is not only
wrong direction of diffusion for CO,.
If the correct generalized driving force
a function of its own concentration -
Hill Book ComDanv, Inc., New York
“ I

(1946).
gradient but is :&o a function of the 14. Robinson, C. S., and E. R. Gilliland,
is used to replace the approximate one
concentrations of the other components. Elements of Fractional Distillation,” 2
in Equation (63), the equation can be
This interaction is the cause of the diffu- ed., McGraw-Hill Book Company,
made to yield the correct diffusion-
sion barriers, reverse diffusion. and Inc., New York (1950).
barrier conditions, and when the equa-
osmotic diffusion which are predicted by 15. Sherwood, T. I<., “Absorption and
tion is made symmetrical as in the Extraction,” 1 ed., McGraw-Hi!l Book
the more rigorous diffusion equations as
equimolal case, Compsny, Inc., New York (1949).
wrll as by the ne!? approximate equations.
Hon- great an effect these results have 16. Stefan, J., Sitzber. Akad. Wiss. Wien.,
on mass transfer in operations such as 63 (Abt. 11), 63 (1871).
17. Zbid., 65 (Abt. 11), 323 (1872).
ternary distillation or in the absorption 18. Whitman, W. G., Chem. & M e t . Eng.,
of two gases from a third stagnant gas 29, 147 (1923).
19. Wilke, C. It., Chem. Enq. Progr., 46,
The equation for AT, is similar. *See footnote on page 206. 95 (1950).

Vol. 3, No. 2 A.1.Ch.E. Journal Page 207