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E. J. W. VERWEY
Natuurkundig Laboratorium der N . V . Philips’ Gloeilampenfabrieken,
Eindhoven, Holland
Received November 14, 1946
FIG.1. Potential energy us. distance for two parallel plates in a solution of monovalent
ions, for different values of the double-layer potential, 2, measured in units k T / e (see text).
those for two flat plates, so that, especially if the particles are not extremely
small, the case of two plates can often be used as a first approximation. For
large values of the double-layer potential we may then derive a very simple
expression for the eiectrolyte concentration for which the maximum in the
potential curve touches the axis of abscissas, Le., an approximate value of the
electrolyte concentration for which the maximum will be insufficient to prevent
agglomeration. This concentration is known as the flocculation value, and it is
a well-known fact that it depends strongly on the valency of the ions with a
r
-,?OH I
FIG.2 . Potential energy of interaction us. distance between centers of two spherical
particles (in units of particle radius a = 10-6 cm., for z = l ) ,showing the influence of elec-
trolyte concentration.
trophoretic data. We know now that the {-potentials calculated in this way are
more or less incorrect, because we cannot neglect the relaxation effect in electro-
phoresis. The interesting phenomena discussed by Stamberger (coagulation
by stirring (7)) must be directly associated with this effect, as it seems rather
certain that they must be explained by a local decrease of the potential barrier
betxeen the particles caused by a lagging behind of the charge in the liquid
phase when a particle is in motion with respect to the surrounding liquid.
The theory may be especially useful in considering in more detail the phenom-
ena of thixotropy and tactoid formation as discussed by Heller (5). It seems
worthwhile to study more closely the significance of the quantity {"/Kput for-
ward by Eilers and Korff, and discussed in the present symposium in the paper
by Graham (3).
For further details ive refer to the papers previously cited (8-12). There we
have also considered extensively the work of previous authors, including some
who have been mentioned above. We wish to add that an essentially correct
theory for the interaction of tvio double layers can be found in earlier papers (2)
by the Russian author Deryagin, though worked out in an unsatisfactory manner.
It should also be mentioned that Langmuir, in the last part of his well-known
paper (6) on tactoids and coacervation, gives a correct expression for the re-
pulsive force between tvio plates, which can be directly derived from our more
general theory.
SUMMARY
The theory of the interaction of the double layers has been reviewed in relation
to the stability of lyophobic colloids. It is concluded that the interaction must
be associated with an increase of the free energy, leading to a repulsion between
the particles. The repulsive potential calculated from a consideration of the
free energy for certain special cases has been combined with the London-van der
Waals attractive potential calculated by Hamaker to obtain curves of potential
us. distance. Predictions based on these curves appear to agree well withvarious
experimental data. For example, the influence of electrolyte concentration and
of the valencies of the ions on flocculation is satisfactorily explained in terms of
the theory, although many complicated phenomena remain to be correlated
with it.
REFERESCES
(1) BERSAL,J. D . , A S D F a X K V C H E s , I.: J. Gen. Physiol. 26, 111-20, 147 (1941).
(2) DERYAGIN, B.: Acta Physicochim. U.R.S.S. 10, 333 (1939); Trans. Faraday SOC.36,
203 (1940).
(3) GRAHAM, D . P . : The Contribution of Solvation to the Stability of Anthraquinone Vat
Dye Suspensions; Paper S o . 32 of the Symposium on the Stability of Colloidal Dis-
persions, !vh&cb was held under the auspices of the Division of Colloid Chemistry at
the 110th Meeting of the American Chemical Society, Chicago, Illinois, September
19-16.
(4) H.~MAKER, H . C.: Chem. Weeliblad 36, 47 (1938); (English language) Symposium on
Lyophobic Colloids.
( 5 ) HELLER,W.:Thixotropy, Tactoid Formation, Syneresis, and Other Colloid Phe-
636 C. W. CARR, W. F. JOHKSOK .4KD I. M. KOLTHOFF
nomena, and their Dependence on Colloid Stability; Paper So. 27 of the Symposium
on the Stability of Colloidal Dispersions, which was held under the auspices of the
Division of Colloid Chemistry a t the 110th RIeeting of the American Chemical
Society, Chicago, Illinois, September, 1916.
(6) LANGMUIR, I.: J. Chem. Phys. 6,873 (1938).
(7) STAMBERGER, P. : Flocculation of Lyophobic Dispersions by Slow Mechanical Stirring;
Paper S o . 33 of the Symposium on the Stability of Colloidal Dispersions, which was
held under the auspices of the Division of Colloid Chemistry a t the 110th 3Ieeting
of the American Chemical Society, Chicago, Illinois, September, 1946.
(8) VERWEY, E. J. W . : Chem. Xeekblad 39, 563 (1912).
(9) VERWEY, E . J. W.: Contribution to a symposium held by the Xederlandsche Chemische
Vereniging on July 3-4, 1944.
(10) VERWEY, E. J. W . : Philips Research Reports 1.33 (1945).
(11) VERWEY, E. J. W., A K D OVERBEEK, J. TH.G . : Trans. Faraday Soc., in press.
(12) VERWEY,E. J. W., ABD OVERBEEK, J. TH. G., with the collaboration of K . van Xes:
Theory of the Stability of Lj/ophobic Colloids, in press. Elsevier Publishing Company,
Amsterdam, Holland.