Repulsive interface forces in overlapping electric double layers in electrolyte solutions

Abstract

The historical development of the problem of the electric interaction of particles in electrolyte solutions is comprehensively discussed. The existing approaches are divided into force-based methods, where the mechanical (ponderomotive) forces of the electric field are directly calculated, and energy-based methods calculating the free energy of the colloid system (at least the part of the free energy which is determined by the repulsive forces of electrical nature). The fundamental works of Langmuir, Derjaguin, Levine, Verwey and Overbeek are discussed in detail. At the same time, new original methods are proposed: the method of effective displacements; the formula of free energy of overlapping double layers. Special attention is paid to the analysis of electrostriction forces in liquids, particularly in electric double layers. The non-contradictory application of the concepts of classic macroelectrostatics is shown to result in the need to take into account electrostriction forces in overlapping double layers. The main formulas are given for force and energy of repulsion in flat surfaces with a constant density of the electric charge on them. These formulas are derived with electrostriction forces taken into account. A number of the theoretical results are new. Some experiments are discussed in measuring repulsive forces in colloid systems. A qualitative agreement is established between the experimental results of Ottewill et al. and the theory of electrostriction forces in double layers.