Electrical Properties and Kinetics of Electrode Reactions

A common basis for investigations of the properties of electrode reactions is provided. The basic equations of electrostatics and electrodynamics and the assumption that electrode reactions are relaxation processes, are used to develop the equations for the electrical behavior of electrode systems. Thus electrode reaction processes are characterized as two states separated by an energy barrier. The application of static and alternating fields to electrode systems is interpreted in terms of the kinetic parameters of the electrode reactions. The equations for impedance are applied to silver and cadium electrode systems reported in the literature. The agreement of experiment and theoretical expectation is excellent. The equations are also applied to the interpretation of the impedance of LeClanché cells. The kinetic analysis of a simple unimolecular reaction is used to illustrate the kinetic interpretation of experimental information. This simple analysis may be extended to more complex reactions.