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# H. J. V.

## Tyrrell The Origin and Present Status of

The University
Sheffield, England
Fick's Diffusion Law

## A serious experimental study of the

diffusion of one solution into another was first under-
Ludwig, sixteen years older than he, was Professor of
Anatomy, and another brother, Heinrich, seven years
taken by Thomas Graham (I), who devised a number his senior, and later Professor of Commercial Law a t
of experimental techniques for studying the phenom- Ziirich, was then privatdozent. Adolf's original inten-
enon and obtained a great deal of qualitative and tion was to take mathematics, but Heinrich, with
quantitative data. His achievements in this field great perception, suggested that he should read for a
have perhaps been overrated and he is more justly medical degree, studying mathematics as a subsidiary
remembered for his distinction between crystalloids subject, since his aptitude for this would be of ines-
and colloids in terms of the different rates a t which they timable value if he pursued a career in medical re-
pass through membranes, and for his description of the search. This judgement was later fully vindicated,
process of dialysis. A far more important name in the because Adolf Fick became an outstanding figure in
early literature of the subject is that of Adolf Fick that small group of nineteenth century physiologist8
(1829-1901). "Fick's Laws of diffusion" and the
"Fickian frame of reference" are terms which fre-
quently appear in modern papers on transport prop-
erties. Virtually all experimental papers on diffusion
are concerned, in the first instance, with the deter-
mination of diffusion coefficients defined in a manner
similar to that proposed by Fick, namely.
J = -D dcldz (1)

## where J is the one-dimensional flow in moles or grams

per unit area per unit time across a reference plane, D
is the diffusion coefficient,and c is the concentration in
moles or grams per unit volume. An equation of this
Form is often termed Fick's first law, and the derived
equation.

## Fick's second law. Furthermore, attempts to obtain

semiempirical equations to predict values of diffusion Ad0lf Fick
coefficients from other physical properties have a long
history, while a priori calculations of transport coef- who applied the concepts and methods of physics to the
ficients, including diffusion coefficients, in liquids study of living organisnls, and thereby laid the founda-
from statistical-mechanical considerations have at- tions of modern physiology. He was graduated
tracted considerable attention from modern theore- as a doctor of medicine from Marburg in 1851, and
ticians. Clearly, Fick's ideas have proved fruitful for early in 1852 was invited by his friend and teacher
more than a century, almost as fruitful in fact as the from earlier days in hlarburg, Carl Ludwig, then Pro-
very similar ideas of Ohm in the field of electrical fessor of Anatomy and Physiology in Ziirich, to take
conduction, and of Fourier in that of heat conduction. up a post as Assistant (Prosektor) in the Anatomy Dc-
Yet his paper on diffusion is usually misquoted; partment there. The contact with Ludwig was re-
his name, unlike those of Fourier and Ohm does not sponsible for Fick's interest in diffusion, since Ludwig,
appear in general works of reference in English, such as in common with several other physiologists of the
"Encylopaedia Rrittanica" or "Chamber's Encyclopae- period, had been interested in diffusion through mem-
dia," and the details of his career are unknown to branes for some years previously.
most physical scientists, though net to physiologists. Fick's principal paper on diffusion entitled "Ueber
This paper is not intended as a biographical memoir Diffusion" appeared in Poggendorff's Annalen in 1856
but rather as a review of the ideas which led Fick to (94, p. 59). It was clearly intended t o be read by
his conception of the basic diffusion law (Grundgesetz) physical scientists. Following a not uncommon prac-
and an assessment of its present importance. tice, he comnlunicated the same results in a modiied
Fick, the youngest of nine children, showed a strong form to the Zeitschrift fur rationelle Medicin (6, 28%
mathematical bent a t school in Cassel, where he (1955)) (2) in order to bring his ideas to the attention
graduated from the gymnasium in 1847. He proceeded of physiologists and medical men generally. The paper
to the University of Marburg where his eldest brother in A n n a l a begins with the remark that hydrodiffusion
Volume 41, Number 7, July 1964 / 397
through membranes is an important physiological problem and solved it in the same way, rather than by
problem which should also be of great interest to the applying the essentially correct explanation given by
physicist. After quoting several references to earlier Dalton of the interdiiusion of two gases (that the proc-
work in this field, Fick stated that he had himself car- ess was akin to the expansion of a gas into a vacuum)
ried out experiments of this kind but with limited suc- to the case of liquid diffusion, though he mentions this
cess. Smce it was not possible to carry the work fur- possibility in afootnote. The revolution brought about
ther he proposed t o describe the results as far as they by the kinetic theory of gases can be seen from the
went, and to draw attention to the analogy, which had standpoint taken up by Fick in a series of six popular
formerly been neglected, between diffusion through lectures "Die Naturkriifte in ihrer Wechselsbeziehung"
membranes and the "simple spreading of a soluble sub- published in 1869, where his views on this subject are
stance in its solvent." The quantitative aspects of essentially those held today (2).
Graham's work were strongly criticized and Fick went Fick's reasoning can best be followed from this point
on to announce his intention of discovering the basic by direct quotation:
law governing the transfer of material from one layer
The first task would now he ta establish the basic law far this
of solvent to the next. To do this he began by devising mode of motion [i.e., of diffusion] from the general laws of mo-
a model to be used in describing the state of matter tion, and this should, I hope, d m be possible without knowing
taken up by a single substance and the process of the the functions f(r) and q(r). My attempts to do this have how-
diffusion of one substance into another. It was con- ever had no success. On the other hand, when first considering
ceived in terns of attractive and repulsive forces be- this hasic law, it occurred to me that a very similar supposition
has, in my opinion, been fully proved hy experiment. In fact, it
tween particles. A single substance was assumed to might be added, that from the outset, nothing is more probable
be made up of two kinds of "atoms,"' "ponderable than this; the spreading of a. dissolved suhstance in a solvent,
atoms" attracting one another by gravitational forces, provided that it is not affected by the exceptional influence of
and "aether atoms" which repelled one another with a molecular farce^,^ takes place according to the same law which
Fourier has suggested for the spreading of heat in a conductor,
force proportional to the product of their masses and and which Ohm has already applied to the spreading of elec-
to an inverse power of the distance r between them tricity, where it is, of course, not quite correct.' It is only neces-
which was greater than 2, indicated by f(r). Likewise, sary to replace, in Fourier's law, the words "quantity of heat"
the two types of "atoms" were assumed to attract one with the words "quantity of dissolved substance," and the word
another with a force, also proportional t o the product of "temperature" by "solution density." The conductivity, in our
case, corresponds ta a constant dependent on the affinity (ver-
their masses, which fell off less rapidly with increasing wmdsehaft) of the two substances.
separation than f(r). This distance function was
termed ~ ( r ) . According to Fick, a model of this kind Fick thus obtained the "Grundgesetz" for the diffu-
leads to a system in which each "ponderable atom'' sion process solely by analogy with the laws of Fourier
acts as the center of a sphere of "aether atoms," the and Ohm, and could give no a priori reason for the
density of the latter falling off as the distance from the choice of the solution density gradient as the driving
central "atom" increases. Such aggregates he termed force for diffusion. I n applying this law to real sys-
"molecules." Diffusion is discussed in terms of two tems, he specified that the volume change on mixing
assemblies, one of "molecules" of species A, and the the diffusing solutions must be ignored; this proviso
other of species B, placed side by side. Assuming that enabled him to pass from the solution density gradient
the attraction between "n~olecules" of unlike species is to the concentration gradient as the driving force, con-
greater than that between those of like species, "mole- centration being expressed as weight units per unit
cules" of species A will be drawn into the region formerly volume. He also pointed out that the density gra-
occupied by those of B and vice versa, until the "mole- dient had to be of such a kind that the heavier layers
cules" of each species are distributed uniformly over of liquid lay below the lighter ones.
the whole region. The model can be used to explain why The mathematical development of the basic law pro-
"molecules" of A and B do not coalesce entirely; the ceeded as follows:
gravitational attraction of the two species of "ponder- A quantity nf salt will he transferred into the elementary layer
able" atoms is balanced before this can occur by the in- +
between the planes z and z d z (where the concentration is y)
creasing repulsive forces between the surrounding from that between x + d z and z +2 d z (wbere the concentration
spherical shells of "aether atoms." The most im- is y + d y l d z . d z ) equal to -Q k d y l d z dt, where Q is the cross-
sectional area of the layer, and k s. constant dependent on the
portant aspects of this to modern eyes are the very nature of the substances. Naturally, an amount of water equal
clear recognition of the part played by molecular motion in volume to this amount of salt enters from the upper into the
(using molecule in the modern sense) in diffusion proc- lower layer. Exactly by the method used for the development of
esses, and the use of a model in which the macroscopic Fourier's law oneobtains from this basic law of diffusion flow, the
differential equation,
properties of matter depend upon the balance of at-
tractive and repulsive forces between microscopic ay/st = - k(a2 y / a r z + 1/Q d ~ / d zs y / a z ) (3)
particles, an idea which is of central importance in all where Q is aasumed to be n function of the height of the plane
modern theoretical treatments of similar problems. It
is of considerable historical interest to note that, a t
this date, Fick found it necessary to introduce a spe- This proviso, which Fick did not discuss further, could be
cial hypothesis to explain the random distribution stretched to cover all deviations from the hssic law. It is ao
of A and B "molecules" which was the final result of the general, however, that it can he regarded on Fick's part as seien-
tifie caution rather than as exceptional prescience.
diffusion process. Graham was faced with the same =Fick gives no indication of what he has in mind here. In
fact, Ohm's law is obeyed more exactly than Fourier's law in the
sense that the electrical conductivity of a substance is less de-
' Where the terms "atom" and "molecule" are used in a sense pendent on the potentid gradient than is the thermal conductivity
other than a modern one, they areput hetween quotation marks. on the temperature gradient.

## 398 / Journol o f Chemical Education

above the base. If this is constant, the differential equation tem is described more completely in the paper in the
becomes, Zeitschrift jfir ratimelle Medicin; and there Fick used
the terms, still in current use, "stationary state" and
"dynamic equilibrium" to describe conditions within
the column. The amount of solute diffusing out a t the
Fick's notation is here retained without any modifica- top of the column when the stationary state had been
tion. attained was measured, and the concentration gradient
The equation now referred to as Fick's first law has taken to he the ratio of the solubility of the salt to the
the form (1); the "basic law" referred to by Fick as a height of the column. This is only true if the diffusion
modification of Fourier's law, is not exactly this, and coefficient is independent of the concentration, and Fick's
was never written down explicitly in the Annalen "constants" are therefore averaged diffusion coefficients.
paper. Equation (4) would now he called Fick's He does not seem to have considered the possibility
second law for the restricted case where the diffusion that the "constant" might vary in this way possibly
coefficient, written ask by Fick, is independent of con- because this would not strictly he consistent with his
centration. Further points of particular interest are "basic law of Diffusion." Three columns of different
that Fick was fully aware of the mutual nature of the heights were used, and the coefficients derived from
diffusion process, migration of one component in one experiments on each were considered t o be sufficiently
direction being balanced by the migration of an equal concordant for the diffusion law to be taken as experi-
volume of the other component in the opposite direc- mentally established. Other experiments were done
tion. The plane of reference, with respect to which the with a cone-shapedcolumninorder toestablish thevalid-
(one-dimensional) flows are measured, while not ity of an equation related to equation (2). The table
specifically discussed, is obviously one across which no shows some of his results on columns of uniform cross
net volume transfer occurs. If there is no change in section, recalculated to modern units; some accurate
volume on mixing as Fick assumed, this reference plane differential diffusion coefficients for sodium chloride in
will also he fixed with respect to the containing vessel. water are also shown. It is worth mentioning that an
This is probably the most useful way in which to de- improved form of this method was used over fifty years
fine a diffusion coefficient, and Fick's contribution in later by Clack (3) who measured the local concentration
this respect can hardly he overrated. However, it gradient a t successive horizontal planes in diffusion
will be apparent that the detailed molecular model columns which had been allowed to reach the steady
which was to provide the basic law contributed noth- state, and corrected for the solvent counterflow;
ing to its development, and the only real justification for many years they provided the best available diffu-
for equations (3) and (4) would he a demonstration sion data for electrolytes in water.
that the quantity k (i.e., in modern terms, the diffusion
coefficient) is, in fact, independent of the concentration Fick's Average Diffusion Coefficients for Aqueous Sodium
gradient. This was the next task t o which Fick turned Chlorides
his attention.
Tmw Medium Short
The first possibility considered was that of integrat- colunk column column
ing equation (4) subject to appropriate boundary con- T ("c) ( x 109 ( x lo5) ( x 105)
ditions in order to find the concentration y as a function 14.8-15.8 1.12 1.12 1 .07
of position x and time, a procedure which is the basis 20 1.29 ... 1.27
of ahnost all methods in common use a t the present 2W21 1.37 ... 1 .29
time. Fick rejected this possibility because of the Modern differential coefficients ( 2 5 W ( X 10-4'
computational labor involved if the law were to be 0.5 M 1.474
tested adequately, even for those cases where an in- 2.0 M 1.514
tegral solution could be obtained in closed form; 4.0 M 1.58a
this was the reason for not presenting any such solu- Values are recalculated to cm' seo-lunits. A value of 1.50.X
tions. A second method, found to be unsatisfactory, 10-6 at 25' would correspond approximately to 1.34 X lo-' at
20' and 1.20 X 10"at l 5 T .
was to establish a diffusion boundary in a tall cylindri- 1 STOKE% R. H.,J . Am. Chem. Soc., 72, 2243 (1950).
cal vessel by introducing concentrated sodium chloride
solution beneath a water layer, allowing the diiusion
process to continue for a definite period, then sampling Although Fick stated that his results had confirmed
layers a t different levels in the liquid column, and ana- the basic law, subsequent work has shown that, as in
lyzing. Ay/Ax, and A2x/Ay2 could in principle be the case of so many simple physical "hws," Fick's
obtained from these measurements, but the experi- "Grnndgesetz" is not correct in the general sense that its
mental errors were such that their ratio (k) was vari- author clearly hoped that it would he. His views did
able. However, the qualitative change of concentration not escape criticism a t the t i e . Beilstein (4) sug-
with the coordinate x was that expected. A more suc- gested that the effect of varying the concentration had
cessful technique was then devised. A column was not been adequately investigated, and that there was
set up with sodium chloride crystals a t the bottom and no more reason for choosing the first power of the con-
pure water, constantly renewed, a t the top. The con- centration gradient as the driving force rather than some
centration distribution along the column was allowed power of it other than this. I n particular, Beilstein
to become that characteristic of a time-independent state proposed that the density gradient in Fick's formula-
in which the flow of solute (and, in the reverse direc- tion should be replaced by (density)"'/x, a curious sug-
tion, of solvent) was the same across any horizontal gestion later treated with some scorn by Fick (6).
crosssection irrespective of the value of x. The sys- He attacked the accuracy of Fick's experimental
Volume 41, Number 7, July 1964 / 399
data, and did many quantitative messurements de- quantitative developments. Indeed, a fully sahfac-
signed to support Graham's conclusion (1) that the tory explanation of the observed values of diusion
amount of salt transferred into distilled water in unit coefficient and of their variation with concentration
time was proportional to the weight of salt contained would not appear to be an immediate prospect.
in the solution from which the transfer took place. More than a century of experience has shown that
Fick's reply to these criticisms forms the substance of the value of Fick's contribution to the study of diusion
his third, and last, paper on diusion (6) and he claimed in liquids, and also in its later application to gases, lies
that since, in his own experiments, the concentration preeminently in the stimulus i t gave, and is still giving,
varied along the column from saturated solution a t the t o accurate experimental work, and in the provision of
base to pure solvent a t the top, the effect of concentra- a concise and easily appreciated form for the expression
tion changes were automatically taken into account; of experimental data. A glance a t Graham's extensive,
Fick does not seem to have realized that his assumption and almost unreadable, descriptions of quantitative
about the constancy of the concentration gradient studies on diffusion, will show how great a contribution
in the colun~nwas the weak point in this argument. this was. The original concept has been extended to
As for the suggestion that the concentration gradient cover the phenomenon of self-diffusion, and, for a
was involved to some other power than the first, he binary mixture, a full description of the transport of
claimed that the observed constancy of his experimental matter within the system requires three diffusion
coefficients would not have been found if any other coefficients, one for inter-diiusion of the two compo-
assumption than this had been used. Later work has nents, and two self-diffusion coefficients. Fick's hope
shown that the diffusion coefficient usually varies ap- that diffusion coefficients could be calculated from con-
preciably with concentration, and Nernst (6) took the siderations of the repulsive and attractive forces be-
gradient of osmotic pressure as the driving force for tween molecules of the same, and of different, species
diffusion. This is equivalent to taking this force as the bore no fruit a t the time or for many years afterwards.
gradient of chemical potential, proposed independently Hydrodynamic theories, like the Stokes-Einstein theory
by Gibbs (7) (1899) and later by Schreiner (8) (1922) held, and in many ways still hold, the field; but increas-
and by Hartley (9) (1931) to whom is due the main ing attention is being paid to the statistical mechanical
credit for the specific application of this conception t o description of transport processes in liquids (14) which,
the diusion problem. This conclusion has been it can reasonably he hoped, will eventually be successful
confirmed by the application of steady-state thermody- in realizing the ambitious program set out by Fick in
namics to the problem (10). For dilute electrolyte 1855.
solutions the correction introduced into the original
diusion law4 suggests that D ( l +b In y/b in m ) ~ ; Literature Cited
should be independent of concentration and be equal to (1) GRAHAM. T.. Phil. Trans. Rou. Soc. L a d n . 140. 1. 805
the theoretical limiting Nernst value ( 6 ) which can be (1850);. 141,483 (1851); is:, 183 (1861); A m . c&. 77,
calculated from the mobilities of the constituent ions. 58, 129 (1851); 80, 197 (1851).
FICK,A,, "Gesammelte Schriften," Stahelverlag, Wiirshurg,
Experiment has shown that this quotient is not quite 1903-04, R. Fick, editor. (The papera referred to here
independent of concentration but does tend to the are reprinted in volume 1 of this four volume work. The
limiting value a t low dilutions. The observed deviation portrait here reproduced is also taken from this work.)
is due to neglect of certain interionic attraction terms, CLACK, B., Proc. Phys. Soc., 21, 374 (1908); 24,40 (1912);
as can be seen clearly from the thermodynamic treat- 27. 56 (1914): 29.. 49 (1916):
. 33. 259 11921).
BEIL&&_ F R . : ' A ~ Chem..
~. lbb. 165 (1856)
ment (11). These can be calculated successfully for (5j FICK,A., ~ n n C : h a . , 102; 97 ?1857j, (also reprinted in
I : l electrolytes by a kinetic thecry due to Onsager and reference (2)).
Fuoss (10) which is, however, rather less successfnl for (6) NERNST, W., Z. physik. Chernie, 2 , 613 (1888).
other classes of electrolytes and breaks down for con- (7) "The Scientific Papers of J. Willard Gibb~," Longmars,
Green, snd Co. New York, 1906, p. 429. (Letter dated
centrated solutions. While detailed evidence is ra- 1899, to Wilder D. Bancroft).
ther scanty as yet, for certain classes of nonelectrolyte (8) SCHREINER, E., TidSskr. Kjemi, Bwgvesa Met., 2, 151
pairs insertion of the thermodynamic term does give (1922); ef. L m , O., S v m k Ka. Tidskr., 72, l(1960).
a quotient which is constant within experimental error. (9) HARTLEY, GI S., Phil. Mag., (7) 12,473 (1931).
For others. D (1 + b in f/b 1nN) \$; varies much (10) ONSAGER,
(11 ) TYRRELL,
L., AND FUOSS,R., J . Phys. Chem., 62,404 (1958).
H.J . V., "Diffusion and Heat Flow in Liquids,"
more with changing concentration than does D it- Butterworth, London, 1961, chsp. 4.
self (18). Qualitatively, such variations are often (12) ANDERSON, D.K., HALL,J. R.,AND BABB,A. L., J . Phys.
attributed to the formation of complex species in the Chem., 62, 404 (1958).
solution, each with its own characteristic diffusion co- (13) ADAMSON, A. W., AND IRANI,R., J. Phys. Chem., 64, 199
11960).
efficients (18), but ideas of this kind have not yet led to (14) BEARMA,R. J., J. Phys. Chem., 65, 1961 (1961); RICE,
S. A,, AND FRISCH, H. L., Ann. Rev. Phys. Chem., 11, 187
7 is the activity coefficient on the molality scale, and f that (1962); COLLINS, F. C., AND RAPFEL,H., Advan. Chem.
on the mole fraction scale. Phys., 1,135 (1958).