Effect of molecular interactions at the interface: Part I. The metal/aqueous electrolyte interface

Abstract

A model for solvent structure at the electrode-electrolyte interface in the presence of nonadsorbing ions is described. The basic assumptions of this model are: (a) solvent molecules can exist in an unassociated form and as associates (dimers), (b) both monomers and dimers can take any orientation, but with different probabilities, (c) the electric charge of the electrode influences the structure of the associates and the equilibrium between two forms of aggregation of the solvent molecules. Computed results for the mercury-aqueous NaF solution interface (inner layer capacity curve calculated at several temperatures, entropy, and temperature coefficient of the surface potential of solvent dipoles) are very close to the experimental data.