Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. II. Electrode Systems

Abstract

In certain electrode processes involving electron transfer mechanisms, a portion of the dielectric polarization is not in electrostatic equilibrium with the charge distribution. In the present paper expressions are deduced for the properties of such systems. These properties include the electrostatic free energy, entropy and energy, and the spatial dependence of the inner potential. The method of images provides a convenient means for determining the electrode charge distribution, due account being taken of its quantum limitations. These expressions have been used to formulate a quantitative theory of overvoltage for electron transfer electrode processes.