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Tyrrell
The University
Sheffield, England
Ad0lf Fick
397
' Where the terms "atom" and "molecule" are used in a sense
other than a modern one, they areput hetween quotation marks.
398
Fick thus obtained the "Grundgesetz" for the diffusion process solely by analogy with the laws of Fourier
and Ohm, and could give no a priori reason for the
choice of the solution density gradient as the driving
force for diffusion. I n applying this law to real systems, he specified that the volume change on mixing
the diffusing solutions must be ignored; this proviso
enabled him to pass from the solution density gradient
to the concentration gradient as the driving force, concentration being expressed as weight units per unit
volume. He also pointed out that the density gradient had to be of such a kind that the heavier layers
of liquid lay below the lighter ones.
The mathematical development of the basic law proceeded as follows:
A quantity nf salt will he transferred into the elementary layer
between the planes z and z d z (where the concentration is y)
from that between x
d z and z
2 d z (wbere the concentration
d y l d z . d z ) equal to -Q k d y l d z dt, where Q is the crossis y
sectional area of the layer, and k s. constant dependent on the
nature of the substances. Naturally, an amount of water equal
in volume to this amount of salt enters from the upper into the
lower layer. Exactly by the method used for the development of
Fourier's law oneobtains from this basic law of diffusion flow, the
differential equation,
ay/st = - k(a2 y / a r z
+ 1/Q d ~ / d zs y / a z )
(3)
Medium
column
Short
column
T ("c)
( x 109
( x lo5)
( x 105)
14.8-15.8
20
2W21
1.12
1.29
1.37
1.12
...
1 .07
1.27
1 .29
Tmw
...
Modern differential coefficients ( 2 5 W ( X 10-4'
0.5 M
2.0 M
4.0 M
1.474
1.514
1.58a
399
data, and did many quantitative messurements designed to support Graham's conclusion (1) that the
amount of salt transferred into distilled water in unit
time was proportional to the weight of salt contained
in the solution from which the transfer took place.
Fick's reply to these criticisms forms the substance of
his third, and last, paper on diusion (6) and he claimed
that since, in his own experiments, the concentration
varied along the column from saturated solution a t the
base to pure solvent a t the top, the effect of concentration changes were automatically taken into account;
Fick does not seem to have realized that his assumption
about the constancy of the concentration gradient
in the colun~nwas the weak point in this argument.
As for the suggestion that the concentration gradient
was involved to some other power than the first, he
claimed that the observed constancy of his experimental
coefficients would not have been found if any other
assumption than this had been used. Later work has
shown that the diffusion coefficient usually varies appreciably with concentration, and Nernst (6) took the
gradient of osmotic pressure as the driving force for
diffusion. This is equivalent to taking this force as the
gradient of chemical potential, proposed independently
by Gibbs (7) (1899) and later by Schreiner (8) (1922)
and by Hartley (9) (1931) to whom is due the main
credit for the specific application of this conception t o
the diusion problem. This conclusion has been
confirmed by the application of steady-state thermodynamics to the problem (10). For dilute electrolyte
solutions the correction introduced into the original
diusion law4 suggests that D ( l
b In y/b in m ) ~ ;
should be independent of concentration and be equal to
the theoretical limiting Nernst value ( 6 ) which can be
calculated from the mobilities of the constituent ions.
Experiment has shown that this quotient is not quite
independent of concentration but does tend to the
limiting value a t low dilutions. The observed deviation
is due to neglect of certain interionic attraction terms,
as can be seen clearly from the thermodynamic treatment (11). These can be calculated successfully for
I : l electrolytes by a kinetic thecry due to Onsager and
Fuoss (10) which is, however, rather less successfnl for
other classes of electrolytes and breaks down for concentrated solutions. While detailed evidence is rather scanty as yet, for certain classes of nonelectrolyte
pairs insertion of the thermodynamic term does give
a quotient which is constant within experimental error.
For others. D (1
b in f/b 1nN) $; varies much
more with changing concentration than does D itself (18). Qualitatively, such variations are often
attributed to the formation of complex species in the
solution, each with its own characteristic diffusion coefficients (18), but ideas of this kind have not yet led to
400
quantitative developments. Indeed, a fully sahfactory explanation of the observed values of diusion
coefficient and of their variation with concentration
would not appear to be an immediate prospect.
More than a century of experience has shown that
the value of Fick's contribution to the study of diusion
in liquids, and also in its later application to gases, lies
preeminently in the stimulus i t gave, and is still giving,
t o accurate experimental work, and in the provision of
a concise and easily appreciated form for the expression
of experimental data. A glance a t Graham's extensive,
and almost unreadable, descriptions of quantitative
studies on diffusion, will show how great a contribution
this was. The original concept has been extended to
cover the phenomenon of self-diffusion, and, for a
binary mixture, a full description of the transport of
matter within the system requires three diffusion
coefficients, one for inter-diiusion of the two components, and two self-diffusion coefficients. Fick's hope
that diffusion coefficients could be calculated from considerations of the repulsive and attractive forces between molecules of the same, and of different, species
bore no fruit a t the time or for many years afterwards.
Hydrodynamic theories, like the Stokes-Einstein theory
held, and in many ways still hold, the field; but increasing attention is being paid to the statistical mechanical
description of transport processes in liquids (14) which,
it can reasonably he hoped, will eventually be successful
in realizing the ambitious program set out by Fick in
1855.
Literature Cited
(1) GRAHAM.
T.. Phil. Trans. Rou. Soc. L a d n . 140. 1. 805
(1850);. 141,483 (1851); is:, 183 (1861); A m . c&. 77,
58, 129 (1851); 80, 197 (1851).
FICK,A,, "Gesammelte Schriften," Stahelverlag, Wiirshurg,
1903-04, R. Fick, editor. (The papera referred to here
are reprinted in volume 1 of this four volume work. The
portrait here reproduced is also taken from this work.)
CLACK,
B., Proc. Phys. Soc., 21, 374 (1908); 24,40 (1912);
33. 259 11921).
27. 56 (1914): 29.. 49 (1916):
.
BEIL&&_
F R . : ' A ~ Chem..
~.
lbb. 165 (1856)
: h a . , 102; 97 ?1857j, (also reprinted in
(5j FICK,A., ~ n n C
reference (2)).
(6) NERNST,
W., Z. physik. Chernie, 2 , 613 (1888).
(7) "The Scientific Papers of J. Willard Gibb~," Longmars,
Green, snd Co. New York, 1906, p. 429. (Letter dated
1899, to Wilder D. Bancroft).
E., TidSskr. Kjemi, Bwgvesa Met., 2, 151
(8) SCHREINER,
(1922); ef. L m , O., S v m k Ka. Tidskr., 72, l(1960).
(9) HARTLEY,
GI S., Phil. Mag., (7) 12,473 (1931).
(10) ONSAGER,
L., AND FUOSS,R., J . Phys. Chem., 62,404 (1958).
H.J . V., "Diffusion and Heat Flow in Liquids,"
(11 ) TYRRELL,
Butterworth, London, 1961, chsp. 4.
D.K., HALL,J. R.,AND BABB,A. L., J . Phys.
(12) ANDERSON,
Chem., 62, 404 (1958).
A. W., AND IRANI,R., J. Phys. Chem., 64, 199
(13) ADAMSON,
11960).
(14) BEARMA,R. J., J. Phys. Chem., 65, 1961 (1961); RICE,
H. L., Ann. Rev. Phys. Chem., 11, 187
S. A,, AND FRISCH,
F. C., AND RAPFEL,H., Advan. Chem.
(1962); COLLINS,
Phys., 1,135 (1958).