Cyclic Square Wave Voltammetry of Single and Consecutive Reversible Electron Transfer Reactions

In this report, theory for cyclic square wave voltammetry for single and consecutive reversible electron transfer reactions is presented and experimentally verified. The impact of empirical parameters on the shape of the current−voltage curve is examined. Diagnostic criteria enabling the use of this waveform as a tool for mechanistic analysis of electrode reaction processes are also presented. Since this waveform effectively discriminates against capacitance currents, cyclic square wave voltammetry will enable acquisition of mechanistic information at analyte concentration levels lower than that possible with cyclic voltammetry.