The surface excess of electric polarization at electrified interphases

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Abstract
It is known that the thermodynamic properties of electrified interphases between metals and dilute solutions of nonspecifically adsorbed 1–1 valent electrolytes, once corrected for the so called ‘‘diffuse layer’’ on the basis of the Gouy–Chapman (GC) theory, yield pseudothermodynamic quantities which are independent of the electrolyte concentration. It is shown that, as a line of principle, the latter quantities can be interpreted on the basis of molecular models of the interphase from which ions are excluded. To this end a ‘‘polarization surface excess’’ is introduced for which analytical expressions are provided both for nonprimitive dipole–wall models in the framework of the mean spherical approximation and for monolayer lattice models in the framework of the mean field approximation. Predictions of these two different models are critically compared.

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