Image charges and dispersion forces in electric double layers: The dependence of wall-wall interactions on salt concentration and surface charge density

Abstract

The interaction pressure between two planar charged walls is calculated for a range of conditions. The diffuse electric double layers between the two wall surfaces are treated with ion - wall dispersion forces and ionic image charge interactions taken into account. Both these interactions are due to dielectric discontinuities at the surfaces. Ion - ion and ion - image charge correlations are explicitly included. The ion-wall dispersion interactions can give rise to appreciable ion specific effects, which are particularly strong when the counterions to the surfaces are highly polarizable. The mechanisms of these effects are investigated, and their influence on the net interaction pressure between the walls is studied for a range of surface charge densities, strengths of the anion - wall dispersion interaction and bulk electrolyte concentrations. When the strength of the anion - wall dipersion interaction is increased, the pressure generally becomes less repulsive (or more attractive) for positive surfaces. The opposite happens in general for negative surfaces but to a much lesser extent. The effects are largest for large surface charge densities and high electrolyte concentrations. The image charge interactions give rise to a considerable depletion attraction between the walls for low surface charge densities. © 2007 American Chemical Society.