On the interaction of colloidal particles IV. general mathematical theory for two identical particles

Abstract

A general theory of the interaction of two charged identical colloidal particles of arbitrary shape is developed. An expression for the Helmholtz free energy of the electric double layers is obtained by the methods of statistical mechanics. The condition that there is equilibrium between the ions adsorbed on the surfaces of the colloidal particles and those dissolved in the dispersion medium is accounted for by requiring that the free energy of the whole system be a minimum with respect to variation of the ionic density on the surfaces. The theory presented here is a further development of the work of Verwey and Overbeek. The conclusions of this paper are that in dilute sols, to which the present investigations are restricted, the results of these authors require extension in two directions. First, there is a correction to the mutual energy of two particles, due to the Coulomb interaction of the ions in the bulk of the solution. Secondly, no special assumption concerning the relation between the surface potential (or charge) and interparticle separation need be introduced. The equations set up to determine the free energy of interaction at the same time yield the ‘adsorption isotherm’ for the ion type which is common to the solution and the surface of the particle.