Page 228 - Introduction to Colloid and Surface Chemistry

Colloid stability 217

between the particles, the result of which is a weakening of V A. In
most practical situations relating to colloid stability this retardation
effect is not likely to be important.
The major problem in calculating the van der Waals interaction
between colloidal particles is that of evaluating the Hamaker
constant, A. Two methods are available.
The first of these methods is the London-Hamaker microscopic
approach, which has already been mentioned. In it Hamaker
constants are evaluated from the individual atomic polarisabilities
and the atomic densities of the materials involved. The total
interaction is assumed to be the sum of the interactions between all
interparticle atom pairs and is assumed to centre around a single
oscillation frequency. These assumptions are essentially incorrect.
The influence of neighbouring atoms on the interaction of a given
pair of atoms is ignored, van der Waals interaction energies
calculated in accord with the microscopic approach are likely to be in
error but the error involved is not likely to be so great as to prejudice
general conclusions concerning colloid stability.
95 102
The other method is the macroscopic approach of Lifshiftz ' -
103,198,199 j n Wj 1j cj 1 th e interacting particles and the intervening
medium are treated as continuous phases. The calculations are
complex, and require the availability of bulk optical/dielectric
properties of the interacting materials over a sufficiently wide
frequency range.
The values of A calculated by microscopic and by macroscopic
methods tend to be similar in the non-retarded range. The
macroscopic approach predicts a smaller retardation effect (i.e.
better applicability of equations 8.8-8.10 for relatively large values of
H) than the microscopic approach 104 .
Hamaker constants for single materials usually vary between about
10-20 j an(j j0-i9 j s ome examples are given in Table 8.3. Where a
range of values is quoted for a given material, this reflects different
methods of calculation within the basic microscopic or macroscopic
method.
The presence of a liquid dispersion medium, rather than a vacuum
(or air), between the particles (as considered so far) notably lowers
the van der Waals interaction energy. The constant A in equations
(8.8)-~(8.10) must be replaced by an effective Hamaker constant.
Consider the interaction between two particles, 1 and 2, in a
dispersion medium, 3. When the particles are far apart (Figure 8. la),