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26 views11 pagesPhysica A235
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/ 11
PHYSICA ‘'
Physica A 235 (1997) 159-169 SS
Phase separation of binary liquid mixtures of hard
spheres and Yukawa particles
R. Garibay-Alonso**, J.M. Méndez-Alcaraz*!, R. Klein”
* Instituto de Fisica, Universidad Auténoma de San Luis Potosi, Alvaro Obregon 64,
78000 San Luis Potosi, S.L.P., Mexico
Fakultdt fir Physik, Universitat Konstanz, Postfach 560, 78434 Konstanz, Germany
Abstract
By solving the Orstein-Zernike equation together with the Rogers-Young closure relation
for the correlation functions of binary liquid mixtures of hard spheres and Yukawa particles
we calculate the concentration-concentration structure factor, S.c(k), for different values of the
diameter ratio and molar fraction of the mixtures. For hard spheres much larger than the Yukawa
particles, and for large values of the molar fraction of the latter, we find a divergence of the
value of S.c(k) at k = 0, which signals the limit of thermodynamic stability with respect to
phase separation. At the same time, from the form of the partial radial distribution functions of
systems near to the instability we conclude that the phase separated systems are composed of
cone phase rich in hard spheres, whose structure may be interpreted in terms of bridge formation,
immersed in an other rich in Yukawa particles
PACS: 61.20.Gy: 64.70.Ja; 82.70.Dd
Keywords: Phase separation; Binary liquid mixtures; Structure of liquids; Colloidal mixtures
1, Introduction
The phase behavior of fluid binary mixtures has recently been widely studied, both
theoretically and experimentally. The structure of the homogenous fluid phase is well
described by the integral equations theory of liquid mixtures, based on the Omstein—
Zemike equation and its closure relations [1], and it is therefore interesting to study
whether these theories can predict a stability limit for the real systems. For the case
of mixtures of hard spheres, it was shown that phase separation does not occur for all
concentrations and size ratios within the Percus-Yevick closure [2]. By using instead
* Corresponding author.
Permanent address: Instituto de Fisica, CINVESTAV-IPN, Apdo. Postal 14-740, 07000 México, D. F.
0378-4371/97/$17.00 Copyright © 1997 Elsevier Science B.V. All rights reserved
PIT $0378-4371(96 )00337-8 160 R Garibay-Alonso et al. Physica A 235 (1997) 159-169
the thermodynamically self-consistent closure suggested by Rogers and Young [3],
Biben and Hansen [4,5] demonstrated that binary mixtures of hard spheres can exhibit
a phase separation, provided the sizes are sufficiently different and the partial packing
fractions of the two species are roughly comparable. These conclusions have more re-
cently been supported by different theoretical approaches [6,7], and experimental results
[8-10]
The physical origin of the entropically driven phase separation of asymmetric hard
sphere mixtures is the osmotic depletion effect [11,12]: When two large particles ap-
proach each other, small spheres are expelled from the closing gap, leading to an un-
compensated osmotic pressure difference between the gap and the outer surface. This
induces an effective attractive interaction between the large spheres, which eventually
separates the system into two phases. Formally, the solution of the Ornstein-Zernike
equation with the Rogers~Young closure relation provides the partial radial distribution
functions g,(r) between like (i = j = 1,2) and unlike (i # j) species, from which
the concentration-concentration structure factor S..(k) can be calculated. This quan-
tity describes the correlations between the fluctuations of the local composition, which
diverge at k = 0 when the spinodal line, which marks the limit of thermodynamic sta-
bility with respect to phase separation, is approached. In this form, the spinodal line
can be calculated.
In this paper we investigate the effects on the above-mentioned phase behavior due
to replacing the short-range interaction among the small particles by long-range repul-
sions; the small hard spheres are replaced by charged hard spheres interacting through
repulsive Yukawa potentials. Such systems represent simple models of colloidal mix-
tures of charged and uncharged spherical particles [13]. In contrast to binary mixtures
of hard spheres, where the phase separation is entirely of entropic nature, energetic con-
siderations have to be included for these systems because of the range of the Yukawa
potential, In a very asymmetric mixture of large uncharged particles and small charged
ones, it can be expected that charged particles will have a tendency to be in close con-
tact with the large ones, since the latter represent a big volume without charge. This
will in turn reduce the number of close contacts between the big uncharged particles
as compared to the situation in the absence of charge on the small spheres. If there
are many more small charged spheres than big uncharged ones, one may expect that a
fraction of the charged spheres will be in the neighborhood of the surfaces of the large
particles. As a result, the large particles will effectively behave as weakly charged, so
that there will be a weak effective repulsion between them. By increasing further the
molar fraction of small charged spheres and the size difference between both species,
the osmotic depletion effect will eventually take over, reducing the effective repulsion
between the large particles. The system is expected to exhibit a qualitatively similar
phase instability, like in binary mixtures of very asymmetric hard spheres, but the val-
ues of the molar fraction and diameter ratio, at which the instability occurs, will be
different.
In the following sections, after presenting the theoretical scheme we use for our
calculations, we analyze the partial structures of different species in the mixtures as R. Garibay-Alonso et al. | Physica A 235 (1997) 159-169 161
functions of the composition and of the diameter ratio of the particles, when the spin-
odal instability is approached. It allows us to understand better the above-mentioned
phase behavior, and to get an idea of the composition and structure of the separated
phases. Finaly, we determine the corresponding spinodal line, as it is signaled by the
divergence of S.(k) at k = 0.
2. Theoretical scheme
The structure of binary liquid mixtures is described by the pair correlation functions
9y(7). i,j = 1,2, which are proportional to the probability of finding a particle of
species j at a distance r from a particle of species i. The calculation of these functions
for a system with given pair interaction potentials u,(r) is performed by solving the
Omstein-Zernike (OZ) equation [1]
Gr) — 1 = clr) +> xe [aalr) — Nocy(r), w
a
which relates gj(r) and the direct correlation functions c,(r), through the convolution
product denoted by ©, together with approximate relations between these functions and
u(r). Among the different possibilities existing in the literature, we are using here the
Rogers—Young (RY) closure relation [3],
{i 4 exPl(ul”)
g(r) = exp[—Bui(r)]
Yue =1 \ a
with
fil) =
exp(— my 7), GB)
since it is the only known one able to predict the spinodal instability of highly asym-
metric hard spheres suspensions [4,5].
As already known, RY is just mixing the Percus-Yevick (PY) closure relation,
for small values of r, and the hypernetted-chain (HNC) closure relation, for large
values of r, The meaning of aj' is the distance for which RY changes from PY
to HNC. A good choice for a is the simple scaling form a = a/di), where the
parameters dj; are the structure scales of the system. This quantity is the diameter of
the particles for monodisperse hard sphere systems, and the mean distance between
particles for monodisperse repulsive Yukawa systems. However, the most simple form
ay = a is often sufficient to obtain reliable results, if the different values of dij are
similar. This is the case in our mixtures, where the diameter of the hard spheres is
comparable to the mean distance between small charged particles. Then, we take the
same value x in the calculation of all partial structures (aj; = 0; i,j = 1,2), and
determine it by requiring equal values for the isothermal compressibility calculated
from the compressibility equation and from the virial equation of state [13] 162 R. Garibay-Alonso et al. | Physica A 235 (1997) 159-169
The interaction potential between hard spheres, wyr(r), and between hard spheres
and Yukawa particles, uyy(r), is taken as
unn(r)= +00, r< on,
=0, r>on, @)
and
uyy(r)= +00, 1 < ony,
=0, r>ony. (6)
The interaction potential between Yukawa particles is given by
uyy(r) = +00, r