Theory of square-wave voltammetry of two-step electrode reaction with kinetically stabilized intermediate

Abstract

Square-wave voltammograms of quasireversible EE mechanism with thermodynamically unstable intermediate may consist either of a single peak, or of two peaks if the second electron transfer appears quasireversible at the lowest frequency and irreversible at the highest frequency. The development of the second peak depends on the critical dimensionless kinetic parameter which was calculated in this paper. This parameter can be used for the estimation of standard rate constant of the second electrode reaction.