General theory of charge regulation and surface 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 calculation of the differential capacitance for several models of the specific ion-surface non-electrostatic interactions providing a thermodynamic insight into the characteristics of the differential capacitance. The packing considerations due to surface adsorbed ions will be shown to be more relevant then the bulk packing constraints for ions vicinal to the surface, and to set in prior to the conditions where the bulk packing constraints would become relevant.