Electrical properties and kinetics of electrode reactions

Abstract

A common basis for investigations of the properties of electrode reactions is provided. The basic equations of electrostatics and electrodynamics and the assumption that elec-trode reactIOns are relaxatIOn processes, are used to develop the equations for the electrical behavior of electrode systems. Thus electrode reaction pro cesses are characterized as two states separated by an energy barrier. The application of static and a lternating fi elds to electrode syste ms is interpreted in terms of th e kinetic parameters of t he electrode reactions. The equations for impedance are applied to silver and cadium e lectrode systems reported in the li terature. The agreement of experiment and theoretical expectation is excellent. The equation s are also applied to t he interpretation of the impedance of LeClanche cells. The kinetic analysis of a simple unimolecuJar reaction is used to illustrate the kinetic in-te rpretation of experi mental information. This simple analysis may be extended to more co mplex reactions.