Some remarks to the derivation of the “generalized Lippmann equation”

Abstract

AbstractIn the present communication, an attempt is made to demonstrate (once again) some of the problems with the derivation of the “generalized Lippmann equation” considered to be valid by many researchers for solid electrodes and to address the problems in the framework of the Gibbs model of the interface by using only the basic principles of thermodynamics. By surveying the relevant literature, it has been shown that during the derivation of the equation, it was completely ignored that the Gibbs-Duhem equation (i.e., the electrocapillary equation) is a mathematical consequence which follows directly from the homogeneous degree one property of the corresponding thermodynamic potential function; consequently, the resulting expression cannot be correct. Some alternative approaches have also been considered. The adequacy of the open system and the partly closed system approach has been critically discussed, together with the possibility of introducing new thermodynamic potential functions.