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Abstract:
Model calculations are presented that yield in a straightforward manner the quantitative dependence of the specific adsorption of ions at electrode surfaces on the applied electrode potential (electrode charge). Furthermore, the double-layer capacitance and the potential at the outer Helmholtz plane (ø2) are obtained. The derivation is based on Devanathan's three-capacitor model for the interfacial electric-potential distribution. A convenient correction function for the ø1 potential accounting for the discreteness-of-charge effect is derived, largely on the basis of recent work by Conway et al. The results are shown to be in very good agreement with published work by Lawrence and Parsons on the double layer between Br− electrolyte and the mercury electrode.