32

The Diffusion of Potassium Chloride in Aqueous Solution

By J. W. M c B ain , F.R.S., and Dr. C. R. D aw so n *
{Received June 27, 1934)

Diffusion is one of the simplest and most significant properties of

substances in solution, and yet it has received comparatively little atten­
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tion for lack of a ready method of obtaining even moderately accurate

data. The state of this subject is strikingly revealed when one plots,
as in fig. 1, the data of International Critical Tablesf and of Landolt-
Bornstein Tabellenf for potassium chloride, which presumably comprise
the best measurements available for any one substance. It is evident
that a very arbitrary choice would be required to deduce quantitative
information from these conflicting numbers obtained at such great
expense of time and trouble.
The device introduced by Northrop and Anson§ of arranging that
diffusion should take place between two homogeneous bodies of liquid
through a porous partition of sintered glass (or of alundum) appears to
provide a very simple, rapid, and reproducible method of obtaining
diffusion data for electrolytes, non-electrolytes, mixtures and colloids,
under very varied conditions.||
The present communication records measurements of the diffusion
coefficient of potassium chloride at 25° over a range of concentration
from 0-1 to 2-0 N. The measurements include both “ integral ” values
for diffusion into water, and “ differential,” or “ true,” or “ instan­
taneous coefficients for diffusion into a second solution of slightly less
concentration.
E xperimental
The diffusion cells used * are shown in fig. 2. The simpler one A
may be used for most purposes, but the double-ended one B possesses
* Experiments by C. R. D.
t Vol. 5, p. 68 (1929). *
l 5th ed., vol. 1, p. 246 (1923) ; 5th ed., ‘Erganzungsbandll/part 1, p. 189(1931)
§ ‘ J. Gen. Physiol.,’ vol. 12, p. 543 (1929). For further standardization and
development of technique, see McBain and Liu, ‘ J. Amer. Chem. Soc.,’ vol. 53,
p. 59 (1931) ; Dawson, ibid., vol. 55, p. 432 (1933).
|| Compare M. E. Laing McBain, ‘ J. Amer. Chem. Soc.,’ vol. 55, p. 545 (1933) •
McBain and Dawson, ibid., vol. 56, p. 52 (1934); McBain, Dawson and Barker,
vol. 56, p. 1021 (1934); Scherp, ‘ J. Gen. Physiol.,’ vol. 16, p. 495 (1933).
H Made for us by the Jena Glaswerk Schott und Gen. through the Fish-Schurman
Corporation of New York.
 The Diffusion 33
o f Potassium Chloride
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1.05 AT C = 0 .2 5

CONC., GM. EQ UIV /LITER

F ig . 1—The data of International Critical Tables (I.C.T.) and of Landolt-Bornstein

Tabellen (L.B.T.) for the diffusion coefficient in cm2/sec o f potassium chloride
at 18°.* O Clack, true diffusion; o Clack, integral diffusion; A Oholm;
□ Zuber; 0 Graham-Stephan, L.B.T. 12-5°; 4^ Schuhmeister, L.B.T. 10°;
A Thovert, L.B.T. 17*5°; ■ Cohen and Bruins, I.C.T. 20°.

* In several cases indicated, data at other temperatures are arbitrarily converted

to 18° by multiplying by the ratio o f the absolute temperatures and dividing by the
ratio of the viscosities of water at the two temperatures. The value of the diffusion
coefficient of decinormal potassium chloride at 20°, 1-448 cm2/day, as obtained by
Cohen and Bruins, is misprinted in the Landolt-Bornstein Tabellen. The theoretical
limiting value from the universally accepted Nernst equation for infinite dilution is
indicated upon the figure; it is 1-674 from the data of I.C.T., or 1-682 from the
more recent mobility value of Maclnnes, Shedlovsky, and Longsworth (‘ J. Amer.
Chem. Soc.,’ vol. 54, p. 2758 (1932)).

VOL. CXLVIII.— A. D
 34 J. W. McBain and C. R. Dawson
important advantages. In it the diffusion columns may be established
within the sealed-in membrane of sintered glass by preliminary diffusion.
Then each of the solutions in contact with the membrane may be replaced
by a fresh solution of accurately known composition without disturbing
the diffusion columns, and the experiment thus begins at a known time
with solutions of accurately known composition with the diffusion
columns fully set up.
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It is characteristic of this porous membrane method that, when the

heavier solution is above the membrane and the lighter one below, gravity

F ig . 2—Diffusion cells with diffusion columns in sintered glass membranes. (A)

Single cell tightly fastened into beaker. (B) Symmetrical double-ended cell.

is found to be effective in keeping both bodies of liquid automatically

stirred. Reference should be made to previous communications cited
for the experimental precautions and technique observed. It will be
noted that an essential improvement in A has been made by placing a
piece of rubber tube, packed tightly in between the cell and the beaker,
to eliminate evaporation and to ensure a more complete protection of the
membrane from outside thermal changes. Often mercury was poured
on top of the rubber ring.
In the present work the most exacting requirement, especially in
measuring diffusion between two solutions of high concentration, was
accuracy of analysis. An error of 0 T% in estimating potassium chloride
yields an error of 20% in the diffusion coefficient of 2-0 N diffusing into
 The Diffusion o f Potassium Chloride 35
1 •9 N potassium chloride, although for 2 •0 N diffusing into water this
error would be only 0-1% of the diffusion coefficient. In other work we
are accustomed to use a Zeiss interferometer for determining differences
of the order of 10~7 grams per cubic centimetre in low concentrations of
solution, but the interferometric method usually becomes untrustworthy
and inaccurate in concentrated solutions even when great care is taken.
Hence the gravimetric method of analysis of evaporation to dryness
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was employed, eliminating the tendency of potassium chloride crystals to

“ creep ” during evaporation, loss by “ spitting,” and retention of water
by the solid. Solutions were weighed into tared, flat bottomed, narrow
necked 100 cc flasks of very thin glass with hollow stoppers made from
bottoms of test tubes ground in. The solutions were evaporated at 60° in
an electrically regulated air oven; the crystals were then dried by slowly
raising the temperature to 180° and then the flasks were transferred to
a thermostat at 310° for 20 hours. The method is simpler than that
briefly described by Geffcken and Kohner* and the accuracy attained
was found to be comparable with theirs. Analysis of about 75 cc of
concentrated solution yielded 10 to 11 grams of potassium chloride,
agreeing in duplicate experiments to within 0-2 mg. While solutions
were primarily measured by weight, the concentration was likewise
recorded as grams KC1 per cubic centimetre of solution, in accordance
with the requirements of Fick’s definition of diffusion coefficient.
Potassium chloride was Kahlbaum’s “ zur Analyse.” Calculation was
based upon the logarithmic formula of McBain and Liu. The experi­
ments lasted from 24 to 70 hours, and the solutions on both sides of the
membranes were analysed.
The porosity of the glass membranes was that designated by the makers
as G4, with average pore diameter 2 to 5 x 10~4 cm. The cell com­
partment usually contained 100 cc, but some smaller cells of 30 cc capacity
were also used. The basis of all measurements with these cells is the
cell constant determined with 0 •1 N potassium chloride at 20°, for which
Cohen and Bruinsf have established the value D = 1 -448 cm2/day.

T he D ata

Our data are assembled in Tables I and II. The measurements in

Table I for diffusion into water, giving integral diffusion coefficients over
the whole intervening range, are comparatively easy as compared with
* ‘ Z. phys. Chem.,’ B, vol. 1, p. 458 (1928).
t ‘ Z. phys. Chem.,’ vol. 113, p. 159 (1924).
 36 J. W. McBain and C. R. Dawson
those of Table II where in each experiment the solution above the mem­
brane was originally more concentrated than that below the membrane
by exactly 0-1 N. For comparison with our results Table I includes
those published by Liu,f which are seen to be in remarkable agreement.
Furthermore, two results are included in Table I which were obtained
with 30 cc cells equipped with sintered glass membranes of porosity
“ G5,” which are bacteria-tight. These are very inconvenient to use
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because they take an hour or so to fill or rinse when sucking the solution
through the dense membrane. However, the result is in exact agreement
with that obtained with G4 membranes.

T able I— T he D iffusion of Potassium C hloride from A queous

Solutions into W ater at 25°. “ I ntegral ” D iffusion C o­
efficients in cm2/ day
Cone. N Mean
001 1-724 1•710 1•708 1•714
002 Liu 1•687
01 1-638 1 •629 1•626 1•630 1•635 1•631 1-628 1-630 1-633 1•631
01 Liu 1•631 1•631
0-2 1-632 1•615 1•612 1•620
0-5 1-601 1 596 1 ■592 1•596
0-5 Liu 1 •580 1 •567 1 •572 1•573
10 1-647* 1 ■649* 1 •667* 1 •644 1•655 1•651 1-652 1-656 1-653 1•653
20 1-688 1 ■700 1 •704 1 •700 1•695 1•696 1•697
20 “ G5 ” 1 ■693 1■702 1 ■698
* Earlier technique.

T able II—T he D iffusion of P otassium C hloride at 25° in H igher

C oncentrations between A queous Solutions D iffering by
0-1 N. “ T r u e ” D iffusion C oefficients in cm2/ day
Concentration of more concentrated solution Mean
0 (Calculated from Machines, etc.) 1-722
0-1 N (From Table I) 1-631
0-2 1-636 1-612 1-629 1-629 1-615 1-615 1-623
0-5 1-594 1-586 1-576 1-585
10 1 620 1-610 1-596 1-609
1-5 1-741 1-736 1-691 1-723
20 201 4 2 002 1-999 1-996 1 -'991 1-986 1-998

D iscussion
In the first place, the data are independent of the membranes used,
being the same for alundum membranes of two different porosities as for
t McBain and Liu, loc. cit.
 The Diffusion o f Potassium Chloride 37
glass membranes of four pore sizes (15 to 20,2 to 5, 5 to 10, and 1 •5 x 10-4
cm respectively), the average pore size exceeding twenty thousand ionic
diameters. If there is a dependence of diffusion upon proximity to the
solid, the effect is evidently eliminated by the method of determining the
cell constant with decinormal potassium chloride itself.
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-LIMIT

> 1.0 I
CONIC., GM. EQUIV/LITER

F ig. 3—Integral and differential values of the diffusion coefficient of potassium

chloride in aqueous solution at 25°. O integral; A differential; □ integral
(Liu).

Next, the data are displayed in fig. 3. For the first time differential
and integral values have been derived from the same apparatus. Com­
paring them with the previous records of fig. 1, the integral values most
nearly resemble those of Oholm up to 0 •5 N, but above that ours increase
noticeably whilst his remain constant. The increase must occur because
the differential coefficient is rapidly increasing. This is most nearly
 38 J. W. McBain and C. R. Dawson
reminiscent of the data of Clack with which they nearly agree at about
0-5 N, but his values are seen to rise linearly with higher concentrations
whilst ours definitely do not. Thus for a portion of the upper range of
concentrations our results would fall below his, but afterwards they rise
to a value nearly 10% higher than would correspond to his. In lower
concentrations it appears quite possible that if we had used a narrower
bracket than our arbitrary difference of 0 T N, our differential diffusion
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coefficients would have been somewhat lower. Had this work not been
unexpectedly interrupted, we should have continued the curve of true
diffusion into more dilute solutions and should have checked the integral
value for 0-2 N ; the experiments were, in fact, completed, but the
analyses were destroyed by an accident. We, therefore, cannot draw
the “ true ” diffusion curve for lower concentrations in fig. 3. In com­
paring Clack’s graph with ours it may be noted that his individual results
diverge from each other by several units in the second decimal. In
a general way, but only to a first approximation, our results like his
conform with the theoretical treatment of Onsager and Fuoss.*
The relation between the integral and differential coefficient is not
quite simple because the diffusion gradient within the membrane is not
linear.f This was very clearly seen in the measurement of soap solutions
by M. E. Laing McBain {loc. cit.) where there was but little difference
between the two owing to the preponderating effect of the slower stages of
diffusion. With rising concentration the integral values must follow
the trend of the differential values, but more and more slowly.
A point to be noted is that our diffusion coefficients, in common with
all other experimental methods calculated by Fick’s Law, refer to linear
measure corresponding to a constant volume of solution and not to an
immobile solvent. Onsager and Fuoss* discard the Fick definition.
Except where the partial specific volume of the solute is zero, the solution
out of which diffusion is taking place must be either contracting or
expanding, causing a corresponding bodily displacement of the solution
to maintain constant volume or constant height referred to the containing
vessel. For potassium chloride the contraction is 0-36 per gram in the
lower concentrations, rising to 0-40 and 0-47 in 1 and 2 N solutions,
respectively. This effect is extraneous to that of hydration, which is
exactly parallel with the well-known effects in electrolytic transport of
ions, and in both cases diminishes the apparent movement of the ions
with reference to the solvent.

* ‘ J. Phys. Chem.,’ vol. 36, pp. 2769, 2759 (1932).

t Cf. Barnes, ‘ Physics,’ vol. 5, p. 4 (1934).
 The Diffusion o f Potassium Chloride 39
The most remarkable aspect of the diffusion of potassium chloride, as
observed by Clack and ourselves, is the greatly enhanced mobility of ions
in concentrated solution. Thus the true diffusion coefficient, after
passing through a minimum in lower dilutions, attains in concentrated
solutions values greatly surpassing that for infinite dilution. As pointed
out by McBain and Liu ( loc.cit.) two of the three chief facto
mining the electrical mobility of ions have very little influence upon
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diffusion. This is particularly true of the present case where both ions move
with almost equal velocity in the same direction. A number of authors*
from various lines of evidence have inferred that in concentrated solution
the free motion of water molecules is greatly restricted through strong
polarization and orderly arrangement. Furthermore, “ hydration ” of
the ions becomes increasingly influential as the proportion of solvent
becomes less. Likewise, the viscosity of the solution increases between
normal and twice normal, although only by 0-7%, being then practically
the same as that of water. Nevertheless, the ions are evidently much
freer to move than they are in pure water. This phenomenon is even
more striking when it is recalled that the activity coefficient is so much
less in these concentrated solutions.
The only apparent explanation is that the ions carry with them less
water in concentrated solution than they do in dilute solution. That
their movement is accompanied by water is well known from the results
of migration determinations in which an indifferent reference substance
is displaced during electrolysis.!
S um m ary
The highly conflicting values given in standard tables for the diffusion
coefficient of potassium chloride are compared with integral and
differential results obtained with the porous membrane method, using
sintered glass discs. Of the former those of Oholm are most nearly
correct, and of the latter the data of Clack are most nearly in conformity
with the new data. In concentrated solution the ions of potassium
chloride are much more mobile even than at infinite dilution. This
very rapid and simple method appears to be amongst the most precise
and trustworthy yet available, and it is readily adapted to the study of
all problems of diffusion.
* C/., for example, Porter and Swain, ‘ J. Amer. Chem. Soc.,’ vol. 55, p. 2792
(1933); Urban, ‘ J. Phys. Chem.,’ vol. 36, p. 1122 (1932).
t Nernst, Lotmar, Garrard, and Oppermann, ‘ Nach. Ges. Wiss. Gott.,’ pp. 68-89
(1900); Buchbock, ‘ Z. phys. Chem.,’ vol. 55, p. 563 (1906); Washburn, ‘ Tech.
Quart.,’ vol. 21, p. 288 (1908); ‘ J. Amer. Chem. Soc.,’ vol. 31, p. 322 (1909); Taylor
aqd Sawyer, * J. Chem. Soc.,’ p. 2095 (1929).