General theory of charge regulation and surface differential capacitance.

Abstract

A generalization of the mean-field approach will be derived that will take into account the ion-ion as well as ion-surface non-electrostatic effects on an equal footing, being based on the bulk and surface equations of state in the absence of electrostatic interactions. This approach will be applied to the analysis of a single planar surface with dissociable sites with several models of the specific ion-surface non-electrostatic interactions, providing a general thermodynamic insight into the characteristics of the surface differential capacitance. The ion-surface interactions and ion-ion packing considerations at the surface will be shown to be more relevant than the bulk packing constraints for ions vicinal to the surface, as well as to set in prior to the conditions where the bulk packing constraints would become relevant.