THEORY OF DIFFUSIOX IN LIQUIDS 981

A THEORY OF DIFFUSIOS I S LIQUIDS

ALLEN E. STEARK
Department of Chemistry, I'nzversity of .Missouri, Columbia, Mtssourt
AND
EDWIT bI. IRISH AND HESRY ETRISG
Frick Chemacal Laboratory, Princeton Cnaversaty, Prznceton, N e w Jersey
Receaved J a n u a r y 88, 1940

INTRODUCTION
Although for the diffusion of large molecules through a solvent com-
posed of smaller molecules the Stokes-Einstein law of diffusion has been
found to describe satisfactorily the experimental results, it is unsatis-
factory in principle in case6 where solute and solvent molecules are-nearly
the same size. Eyring (3) has pointed out that the process of diffusion is
the same as that for viscous flow, except that in diffusion the two mole-
cules passing each other may have different properties, whereas for viscous
flow, in a pure liquid a t least, the two molecules passing each other are
alike. The relation between the diffusion coefficient and the specific
velocity constant given for an activated rate process was

where X is the distance between two equilibrium positions of the diffusing

molecule, and k' is the number of times per second that a particular
molecule is engaged in passing a neighbor in any particular direction,-
say the direction of diffusion.
The expression developed for viscosity was (3)
7 = XikT/X2X&k' (2)
where X has the same significance as in equation 1, namely, the distance
between equilibrium positions in the direction of flow, XI is the perpendicu-
lar distance between adjacent layers of molecules, hz is the distance
between adjacent molecules in the direction of flow, X 3 is the distance
between molecules in the plane of flow and normal to the direction of
flow, and k' is the specific rate constant.
Taylor (18), using the combination
D = kTXi/X2Xsq

of equations 1 and 2, found that it gave much more reasonable results

than the Stokes-Einstein relation,
D = kT/6~7
when the molecules diffusing into each other were similar.
982 ALLEN E. BTEARN, EDWIN hl. IRISH AND HENRY EYRING

Since viscosity was shown to exhibit an exponential variation with

temperature ( 2 ) , it follows that diffusion should exhibit a like tempera-
ture variation. For solid diffusion such a variation with temperature has
long been recognized, but up until this time diffusion in liquids has fre-
quently been considered as a linear function of temperature. The diffi-
culty of measuring diffusion rates has restricted the advancement of
investigation into this problem, and even Cohen and Bruins (l),whose
data on the diffusion of tetrabromoethane in tetrachloroethane seem as
yet the best available for determining the variation of diffusion rate with
temperature, plot their rate values against both the first and the second
powers of the temperature.
From absolute reaction rate theory (4) we may write for k’ in equation 1

where 3$and F,, are the partition functions of the reacting system in the
activated and the normal state, respectively, AF* AS’, and AHt are,
respectively, the standard free energy, entropy, and heat increases when
the activated complex is formed from the reactants, Eo is the difference
in energy between the lowest level in the normal and in the activated
state, k is the Boltzmann constant, and h is the Planck constant. We
have taken the transmission coefficient as unity. The heat of activation
is calculated from the relation
d Ink’ -
AH’ = R T ~ -
dT
From equations 1, 3, and 4 we obtain

If we assume that the degree of freedom corresponding to flow is a trans-

lational one, and that the partition functions for other degrees of freedom
are the same for the initial and activated states, then

where q is the free volume for one molecule. Capital letters are used for
the volume, V , and the free volume, V, , when a mole is indicated.
 THEORY OF DIFFUSION IN LIQUIDS 983

If the unit process in diffusion (or in viscous flow) is the passing of two
molecules in the sense of a partial rotation of a double molecule (lo), extra
space must be provided, though this may not necessarily have to be a
hole the full size of a molecule. Therefore the energy of activation for
diffusion will be some fraction of the energy of vaporization; AE.,t. =
AEvap./n. Considering the data of Cohen and Bruins (l), Taylor (18)
concluded that in diffusion the size of the hole required is approximately
the arithmetic mean of that required by the two pure substances in their
respective viscous flows.
Substituting equation 7 into equation 5 and writing AEVa,,./nfor Eo ,
we obtain

For A, in the case of a pure liquid, we take (V/N)’I3,where N is Avo-

gadro’s number. The free volume characteristic of a pure liquid has been
estimated in various ways. Eyring and Hirschfelder ( 5 ) developed the
relation

where AEvap,= AH,,,, - A ( p V ) . Kincaid and Eyring (13) find

uj/3 = 211/3 5
UIiq.

where I’ is the velocity of sound.’

For more concentrated solutions the change in activity coefficients of
the components with concentration will affect the free energy of activa-
tion. This effect can be calculated for the simple case of molecules of
approximately equal size as follows: Let AF: be the height of the energy
barrier in figure 1. Then if y1 and y~ are, respectively, the activity coeffi-
cients of constituents 1 and 2, the rate a t which constituent 1 will sur-
1 There seems t o be no significant difference in the values of the free volumes
whether calculated from equation 11 or equation 12 except in the case of water.
For five organic liquids the ratio of v;/*from equation 12 t o t h a t from equation 11
averages 0.95 a n d varies from about 0.85 t o 1.07, whereas for water this ratio is
about 2.5 (cf. reference 8). I n the case of t h e values of free volume used later in
this paper, we specify in all cases whether they were obtained from equation 11 or
equation 12.
984 ALLEN E. STEARN, EDWIN M. IRISH AND HENRY EYRING

mount the barrier in the forward direction (left t o right) will depend not
only 'on AF: but also on the differences in y1 and y z on the opposite sides
of the barrier. For a symmetrical barrier the additional free energy, due

DISTANCE X

FIQ.1. Potential energy curve for diffusion

to non-ideality of the solution, needed by constituent 1 to reach the top

of the barrier in the forward direction will be
R T d In y1 dN1 X _-
R T d In y2 dN2 X
dN1 &5 - dN2 dx 2

- R T d In yl dN1
- -X R T d In y2 dN1
-X
dN1 dx 5 -I- dN2 dx 2
where N1 and NZ are the mole fractions of constituents 1 and 2, and
dN1 = -dNz.
We set

and
A F ~
-kT
e - 0
RT = B
h
We may then write for the net rate' of constituent 1in the forward direction
2 When the effect of GIonly is considered, we obtain the form of activity coeffi-

cient effect given by L. Onsager and R. M.Fuoss (J. Phys. Chem. 36, 2687 (1932)).
 THEORY OF DIFFUSION IN LIQUIDS

Since

(GI - G2) << RT

we may expand the exponential in equation 14 and, neglecting higher
powers of the exponent, write

Xoting that nl dN,/dx = N 1 dnl/dx, provided the molecules are about

the same size so that n1 +
n2 can be assumed constant, and that

can be neglected compared to unity, we obtain

D1 = X2B(1 + Ni(G1 + Gz)/RT) (16)
Replacing GI, GZ, and B by their respective values and noting that
XZB = D! (equations 1 and 4)
we have

From the Duhem-Margules relation

. d In YI - d In YZ
dlnN1 dlnN1
equation 18 becomes
DI = D;(1 + d In rz/dN2)
986 ALLEN E. STEARN, EDWIN M. IRISH AND HENRY EYRINO

If we intraduce the relation (9)

1 2
l n w = -hNi
2
we may also write
Di = D!(1 -W 1 )

true when N 1 is small. Similarly, when N Z is small we have

1
In y1 = -p,N:
2
which when substituted in equation 20 gives
Di = Di(1 - PzNi)
For large spherical molecules moving with a velocity u in a solution
Stokes has shown that the force acting on such a molecule is
f = 6rrur) (22)
where r is the radius of the molecule and 7 is the viscosity of the solution.
For a solution containing nl of these large molecules per cubic centimeter,
the total force acting on all these molecules in a column of solution of
unit cross section and length 61: is
df = 671~7un162 (33)
Now for a perfect solution p = nlkT, so that the osmotic force acting on
the same column of solution is
dn
-df = --'6xkT
dx (24)

For an actual solution we have

where the second term is due to the change of activity coefficients with
concentration. The factor Vl/P, , the ratio of partial molal volumes,
arises from the fact that when one large molecule flows from its initial
position, enough small molecules must then flow in to fill the resulting
hole. Noting that dN1 = - d N 2 , where N i is the mole fraction and, since

( N being Avogadro's number here), that

 THEORY O F DIFFUSION IN LIQUIDS 987

using the Duhem-Margules relation and simplifying,

Equating expressions 23 and 26 and noting that un1 = dnlldt, we obtain

so that

For large molecules which are not spherical, the right-hand side of equa-
tioG 28 would have to be multiplied by another factor which would depend
on the shape. For example, in the case of a prolate ellipsoid with the
ratio of the short to the long axis a/b, this factor has been found to have
the form (16)
(a/b)"l" In 1 + 4 1 - (a/b)2
1 - (a/b)2
4 alb
Diffusion, like every other rate process, has a specific rate constant
which depends on the mechanism, Le., the nature of the activated complex.
Whether the mechanisms that lead to equations 20 and 28 are correct can
be ascertained only by comparison with experiment. They should be com-
pared with equation 19 for a unimolecular mechanism in the accompany-
ing article by Stearn and Eyring. With sufficient data, using these
equations, it should be possible to choose definitely between a bimolecular
and a unimolecular or some still more complicated mechanism.

COMPARISON WITH EXPERIMENTAL DATA

As a test of equation 9 we use the data of Cohen and Bruins (1) on the
diffusion of tetrabromoethane in tetrachloroethane. They employed
liquid mixtures up to a mole fraction of tetrabromoethane of 0.0783, and
we have used this concentration for calculating the average values of the
quantities occurring in equation 9. For these different quantities the
following average values are chosen: For X and #l" we take the weighted
arithmetical mean of the values characteristic of the pure constituents, e.g.,
L e . = N A + N2Xa
988 ALLEN E. BTEARN, EDWIN M. IRISH AND HENRY EYRING

For m we use the reduced mass of the two passing molecules, and for
AE,.,, we use the geometric mean of the energies of vaporization of the
two pure constituents, Le.,
+
AEvF.P.ave,= ( N N ' A E ~ ~ ~N. ~z d Z E J 2
The heat of vaporization of tetrachloroethane is known, and, by assuming
the same Trouton constant for tetrabromoethane, its theoretical heat of
vaporization can be calculated a t its boiling point, and from this can be
obtained the corresponding energy of vaporization. For the temperature
coefficient of the energy of vaporization we use the relation developed by
Kincaid and Eyring (12)
AE,/AE, = V,/V,
where the subscripts B and T refer respectively to boiling point and the
temperature of interest, and V is the molal volume. The results are

TABLE 1
Diffuszon of tetrabromoethane in tetrachloroethane
A' x 1016 v;'a x 100 AEvap. RATIO
(AVERAQE) (AVEBAQE) (AVZRAQE) Dobad./Doaled.

'A.
273.44
280.7
3.124
3.140
6.45
6.69
kr.-cal.
9.852
9.784
cm.2 8ec.-l
0.351
0.419
I1 cm.2 8 e c - l

0.61
0.77
0.55
0.54
288.0 3.155 6.92 9.719 0.497 0.92 0.54
298.0
308.61
324.1
3.174
3.195
3.230
7.25
7.59
8.13
9.624
9.525
9.383
0.611
0.741
0.954
1
~
1.14
1.42
1.89
0.54
0.52
0.51

given in table 1. Values of u:'~ for the constituents were obtained with
the use of equation 11, and from the results of Ewe11 and Eyring (2) and
in agreement with Taylor (18), we take n = 3.
The constancy of the ratio Dobad./Doalcd (column 7) shows that the
calculated values of D reproduce the experimental temperature coefficient
very closely. This ratio is less than unity, a fact which has been found
generally true for diffusion in organic liquids, and which is commented on
below.
Aqueous digusion
Few data are available which suffice for obtaining satisfactory tempera-
ture coefficients in the case of aqueous diffusion. There areriumerous
cases where the value of the diffusion coefficient is reported for two tem-
peratures, usually differing by not much more than 10 degrees. For such
cases it was not thought advisable to attempt to calculate values for n.
However, the value of n for the viscous flow of water varies (2) from 2.0
 THEORY OF DIFFUSION IN LIQUIDS 989

a t 0°C. to 2.8 a t 50°C. For room temperatures, where most aqueous

diffusion data have been obtained, n for water is about 2.4. The data of
Scheffer and Scheffer (17) on the diffusion of mannite in water between
0” and 70°C. were found to give a good straight line when log D was
plotted against 1 / T . Its slope gave AEaCt.= 4047 cal., and this, with
the average AE,,,, for water between 0 and 70”C., gives a value for n of
2.41. We therefore use the value 2.4 for n for water. In table 2 we
compare values of D calculated by means of equation 9 with the experi-
mental values of Scheffer and Scheffer. Besides the average value of
n = 2.4, which we use through the temperature range, we use the average
AEvap.for water of 9700 cal.
T e have calculated D using both equation 11 and equation 12 to obtain
the free volumes. As was pointed out above, these two equations seem
TABLE 2
Diffusion of inannzte in water

0.4 * cm.3 8ec.-l cm.2 8ec.-1 cm.1 8ec.-l

273.0 0.26 0.096 2.7 0.26 1 .o
296.2 0.61 0.179 3.4 0.43 1.4
305.9 0.75 0.226 3.3 0.52 1.4
316.4 0.97 0.288 3.4 0.63 1.5
325.3 1.14 0.349 3.3 0.74 1.5
335.0 1.35 0.424 3.2 0.89 1.5
343.2 1.56 0,498 3.1 1.05 1.5

to give about the same values for most liquids, but not for water. In
either case the constancy of the ratio D o b . d . / D o a l o d . indicates how well the
calculated values of D reproduce the temperature coefficient. In the case
of this aqueous solution it will be seen that the ratio D o b a d . / D c a l c d is greater
than 1. This is found to be generally true for diffusion in water, in con-
trast to values less than 1 for diffusion in organic liquids. That this ratio
differs consistently from unity is a t least partly due to a factor in equa-
tion 9 which has not been considered. For the case of a liquid with a
structure such as water, rotation in the normal state will be hindered more
strongly than in the activated state. Thus in cancelling out all but one
term in the partition functions corresponding to the two states this factor
is overlooked (13). This would lead to a calculated value too low. For
liquids without such pronounced structure rotation may, on the other
hand, be less hindered in the normal state, and the neglect of this factor
would then lead to calculated results which are too high.
In table 3 we have collected data for a variety of solutes diffusing in
 990 . .
ALLEN E STEARN. EDWIN M IRISH AND HENRY EYRING

water . These have been obtained from the Landolt-Bornstein Tabelbn.

and su5ce for our purpose. For calculating the value of D we use the

TABLE 3
Data for a variety of solutes diffusing in water

T uno
Do~.lDmbzi.

PQ crnl .A. cm.1 #&.-I cm.1 aa.-1

Methyl alcohol . . . . . . 0.25 291 1.37 0.386 3.5
Ethyl alcohol . . . . . . . . 0.25 291 1.10 0.382 3.0
Propyl alcohol . . . . . . . 0.25 291 0.98 0.346 2.8
Butyl alcohol . . . . . . . . 0.25 291 0.88 0.343 2.6
Amyl alcohol . . . . . . . . 0.25 291 0.88 0.338 2.6
0.25 291 0.99 0.353 2.8

Phenol . . . . . . . . . . . . . . 0.25 291 0.80 0.338 2.4

0.125' 293 0.83 0.36 2.3
Pyrogallol . . . . . . . . . . . 0.25 291 0.66 0.329 2.0
Resorcinol . . . . . . . . . . . 0.125 293 0.76 0.358 2.1
Hydroquinone . . . . . . . 0.25 293 0.77 0.358 2.2
Saligenin . . . . . . 0.25. 293 0.72 0.353 2.0

Urea . . . . . . . . . . . . . . . . 0.25' 293 1.18 0.377 3.1

Acetamide . . . . . . . . . . . 0.25. 293 1.0 0.377 2.7
Alloxan . . . . . . . . . . . . . 0.125* 293 0.66 0.350 1.9
Urethan . . . . . . . . . . . . . 0.25 29 1 0.87 0.338 2.6
Dicyandiamide . . . . . . 0.2' 293 1.04 0.365 2.8
Antipyrine . . . . 0.25 291 0.56 0.324 1.7
Caffeine. . . . . . . . . . . . . 0.05' 293 0.57 0.343 1.7

Glucose . . . . . . . . . . . . . 0.25 291 0.57 0.324 1.7

Salicin . . . . . . . . . . . . . . 0.06. 293 0.49 0.341 1.5
Maltose . . . . . . . . . . . . . 0.25 291 0.41 0.317 1.3
0.25 291 0.41 0.317 1.3
Sucrose . . . . . . . . . . . . . . 2.0 293 0.57 0.338 1.7
Raffinose . . . . . . . . . . . . 0.25 291 0.64 0.312 2.0

Acetylene . . . . . . . . . . . 291 1.76 0.391 4.5

Carbon dioxide . . . . . . 291 1.46 0.367 4.0
Nitrogen . . . . . . . . . . . . 291 1.62 0.396 4.1
Hydrogen . . . . . . . . . . . 291 3.59 1.04 3.5

Dyes (various) 0.008' 291 . 17 to 0.51 ea . 0.31 0.5 t o 1.9

Proteins (various) 280 t o 290 .04 t o 0.1: ca . 0.3 D . l to 0.4

* These concentrations are in moles per liter .
properties of water itself (except for the reduced mass of the passing
molecules) to substitute into equation 9. and we have compared aur calcu-
 THEORY OF DIFFUSION IN LIQUIDS 991

lated values with experimental ones for the most dilute solutions for which
data were available.
Non-aqueous diflm'on
In tables 4 and 5 are collected representative data for non-aqueous
diffusion. Table 4 shows diffusion behavior for several solutes diffusing in
the same solvent. while table 5 has data for the same solute diffusing in
TABLE 4
&fusion i n benzene
T = 280.5"A.
I
(IoLVT1 Dobd . X 101 D&d . X 101
(WWATION 8)
.
cm.f a&.-' m.2 aw.-1

Phenyl bromide . . . . . . . . . . . . . . . . . . 1.45 3.39 0.43

Phenyl iodide . . . . . . . . . . . . . . . . . . . . 1.35 3.27 0.42
o-Dichlorobenzene . . . . . . 1.62 3.44 0.48
m-Dichlorobenzene . . . . . 1.57 3.44 0.45
p-Dichlorobenzene . . . . . . 1.42 3.44 0.42
1,2,4-Trichlorobenzene. 1.34 3.33 0.40
1,2,4,5-Tetrachlorobenzene. . . . . . . . 1.24 3.27 0.38
Hexachlorobenzene . . . . . . . . . . . . . . . . 1.02 3.13 0.33
Bromocy clohexane . . . . . . . . . . . . . . . . 1.38 3.38 0.42
Naphthalene . . . . . . . . . . . . . . . . . . . . . 1.19 3.52 0.34
Phenanthrene . . . . . . . . . . . . . . . . . . . . 0.95 3.34 0.29
a-Bromonaphthalene . . . . . . . . . . . . . 1.07 3.26 0.33
a-Bromophenanthrene . . . . . . . . . . . 0.95 3.17 0.30
Methyl iodide . . . . . . . . . . . . . . . . . . . . . 2.06 3.46 0.59
Ethyl iodide . . . . . . . . . . . . . . . . . . . . . . 1.77 3.39 0.53
n-Propyl bromide . . . . . . . . . . . . . . . . . 1.71 3.55 0.48
n-Propyl iodide . . . . . . . . . . . . . . . . . . . 1.67 3.36 0.50
n-Butyl bromide . . . . . . . . . . . . . . . . . . . 1.68 3.48 0.48
n-Butyl iodide . . . . . . . . . . . . . . . . . 1.53 3.31 0.45
n-Amyl bromide . . . . . . . . . . . . . . . . . . 1.42 3.42 0.42
n-Amyl iodide . . . . . . . . . . . . . . . . . . 1.41 3.28 0.43
Octyl bromide . . . . . . . . . . . . . . . . . . . . 1.17 3.29 0.36
Ethylene chloride . . . . . . . . . . . . . . . . . 1.77 3.71 0.48
Iodoform . . . . . . . . . . . . . . . . . . . . . . . . . 1.12 3.04 0.37
Carbon tetrachloride . . . . . . . . . . . . . . 1.51 3.40 0.43
Carbon tetrabromide . . . . . . . . . . . . . . 1.12 3.08 0.37

several solvents. For table 4 the common solvent was benzene. and since
the solutions were dilute we use the properties of benzene to obtain the
values for substituting in equation 9 (except reduced mass) . For viscous
flow of benmme Ewell and Eyring (2) find n = 3. which value we usc in
equation 9. ';u is the value given by equation 12.
In table 5 we also use the properties of the pure solvents to obtain the
values for substituting in equation 9. using equation 11 to obtain the
992 ALLEN E . STEARN. EDWIN M . IRISH AND HENRY EYRING

values of 21:'~ . In treating the data included in table 5. the choice of n

presents a problem . We have where possible used the value of n found
by Ewell and Eyring to hold for the viscous flow of the solvent in question .

TABLE 5

Diffusion of bromobenzene in various solvents . T = 280.5"4.

k g 4 . m . 2 am.-' em.2 8ec-1
Ether., . . . . . . . . . . . . . . . . . . . . . . . . . . 6.16 4* 3.50 16.5 0.21
Benzene., . . . . . . . . . . . . . . . . . . . . . . 7.69 3' 1.41 3.1 0.45
Toluene . . . . . . . . . . . . . . . . . . . . . . . . 8.5 4' 1.59 7.4 0.22
Cyclohexane . . . . . . . . . . . . . . . 7.59 3* 1 .16 3.34 0.34
Hexane . . . . . . . . . . . . . . . . . . . . . . . 7 .0 4* 2.59 13.26 0.20
m-Xylene . . . . . . . . . . . . . . . . . . . . . 9.77 4 1.52 4.90 0.31
m-Cymene . . . . . . . . . . . . . . . . . . . 10.3 4 1.18 4.09 0.29

Diffusion of bromoform in various solvents . T = 293"A .

Acetone . . . . . . . . . . . . . . . . . . . . . . . 7.27 4* 2.69 11.97 0.23
Ether . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1 4* 3.39 17.3 0.20
Benzene . . . . . . . . . . . . . . . . . . . . . 7.45 3' 1.69 3.71 0.45
Methyl alcohol.,. . . . . . . . . . . . . . . . 8.44 3 1.93 2.64 0.71
Ethyl alcohol . . . . . . . . . . . . . . . . . . . 9.97 3 0.97 1.25 0.77
Propyl alcohol . . . . . . . . . . . . . . . . 9.99 3 0.77 1.22 0.63
Amyl alcohol . . . . . . . . . . . . . . . . . 10.6 3 0.52 0.94 0.56

Diffusion of iodine in various solvents . T = 293"A.

Dibromoethane . . . . . . . . . . . . . . . . 8.25 3.5' 0.83 3.82 0.22
Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . 7.45 3* 1.93 3.79 0.50
Carbon tetrachloride . . . . . . . . . . . . 8 .0 3* 1.37 2.39 0.59
Toluene . . . . . . . . . . . . . . . . . . . . . . . . 7.99 4* 1.96 9.26 0.21
Chloroform . . . . . . . . . . . . . . . . . . . . . . 7.08 4' 2.12 10.08 0.21
Ethyl acetate . . . . . . . . . . . . . . . . . 7.78 4' 2.15 9.79 0.22
Heptane . . . . . . . . . . . . . . . . . . . . . . 7.59 4* 2.77 11.39 0.24
Carbon disulfide . . . . . . . . . . . . . . . . 6.60 4* 3.12 12.41 0.25
m-Xylene . . . . . . . . . . . . . . . . . . . . . . . 8.80 4 1.68 7.23 0.23
Isoamyl acetate . . . . . . . . . . . . . . . . . 9 .00 4 1.24 6.75 0.19
Bromobenzene . . . . . . . . . . . . . . . . . . . 8.80 3 1.20 1.71 0.71
* Values found by Ewell and Eyring .

Such values are marked in the table with an asterisk . Values used for
other solvents may be somewhat arbitrary. though they have been assigned
values which are considered probable from analogy to chemically related
liquids for which these values of n are known .
 THEORY OF DIFFUSION IN LIQUIDS 993

Effect of concentration
We compare available data with results calculated from a modification
of equation 20. Besides the "gradient" effect on diffusion covered by the
factor
d In yi
(l + N z d I n N i )
there is a concentration effect on AFf due to the change in AEvap.with
concentration. If we arbitrarily take a solution dilute with respect to
constituent 2 as a standard or reference state, for which we can use
TABLE 6
Ratio of the two limiting diffueion rules of the dilute constituents i n a binUTy solution

comIlwIw 1 ! CONSTITUENT2

Ethyl acetate Ethyl benzoate 0.46 0.48

Acetone Ethyl benzoate 0.41 0.42
Ethyl benzoate Xitrobenzene 0.66 0.79
Acetone Nitrobenzene 0.26 0.30
Ethyl acetate Nitrobenzene 0.30 0.34
Benzene Bromobenzene 0.68 0.72
Benzene Nitrobenzene 0.26 0.44
Benzene Carbon tetrachloride 1.1 1.0

AElysp,,X i , and Vj!3,for the reference value of the diffusion coefficient,

we would then have

In the limiting case we may compare D for the diffusion of constituent 1

in practically pure constituent 2 with that for the diffusion of constituent 2
in practically pure constituent 1. Equation 29 then becomes

In table 6 values of the ratio D1-12/D2-tlfrom diffusion data, obtained for

several non-aqueous liquid pairs from the Landolt-Bornstein Tabellen, are
compared with values of this ratio calculated from equation 30. We take
n = 3 in all cases.
In order to test equation 29 it is necessary to have partial-pressure data
or their equivalent for obtaining activity coefficients. Available data
permit only rough average values of DI/Dref,through finite, and sometimes
fairly wide, composition ranges. In figure 2 we plot D l / D r e f calculated
,
from equation 29 against N2 for several liquid pairs. The plot is never
994 ALLEN E. BTEARN, EDWIN M. IRISH AND HENRY EYRING

extended beyond Nz = 0.5, in order to avoid multiplying the errors in yi

too muqh for small values of N z (and large values of 1/Ns). These calcu-

I- -I

I
N2 - I
a t-Nt
I

FIG.2. Comparison of experimental values of D,/Dls!. (circles) with those calcu-

lated from equation 29, through composition ranges of N t = 0 t o N S = 0.5 (heavy
horizontal straight lines) for the following liquid pairs:
cmvm CONETITWENT 1 CORgllTUENT 2
~

A. . . . . . . . . . Propyl alcohol Water

B.......... Water Propyl alcohol
c. . . . . . . . . . Water Methyl alcohol
D. . . . . . . . . . Methyl alcohol Water
E. . . . . . . . . . Carbon tetrachloride Nitrobenzene
F. . . . . . . . . . Water Ethyl alcohol
G. . . . . . . . . . Ethyl alcohol Water
H. . . . . . . . . . Benzene Carbon tetrachloride
I, . . . . . . . . . Carbon tetrachloride Benzene

lated values are compared with experimental values of Dj/Dref.obtained

from measurements of Gerlach (7), of Munter (15), and of Franke (6).
Partial-pressure data for the system carbon tetrachloride-nitrobenzene
 THEORY OF DIFFUBION IN LIQUIDS 995

were obtained from the measurements of Linebarger (14), and for the other
systems from the International Critical Tables. The average calculated
values of Dl/Drof,are shown in the figure by straight lines covering the
particular composition range for which they were calculated. The experi-
mental values are denoted by circles. We have arbitrarily assumed perfect
solutions for all compositions within 1 mole per cent of a pure constituent,
an assumption which is apparently not true in some of the cases. The
average values of A’, Vj’3,and AEIRP. were calculated as described earlier
in this paper, and for d In r / d In N we used the mean of the value of this
coefficient for each constituent in the range covered. In spite, however,
of the incompleteness of the data and the necessary crudeness of handling,
the obvious correlations in figure 2 between the trends of the experimental
points and the calculated averages of DI/Dref,indicate the general sound-
ness of equation 29.
James, Hollingshead, and Gordon (11) have recently published results
for the diffusion of hydrochloric acid in water which agree very well with a
formula due to Gordon (8). His formula has the same dependence on thc
gradient in activity as our own in the range of low mole fractions of hydro-
chloric acid for which agreemcnt is found. Further precise experimental
diffusion measurements covering the temperature variations will make it
possible to assign diffusion mechanisms from a comparison of the observed
rates with those calculated from the absolute rate theory using only
thermodynamic data.
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