Electrode mechanisms with coupled chemical reaction — Amplitude effect in square-wave voltammetry

Abstract

This article presents the theoretical prediction of square-wave amplitude effect on electrode reaction mechanisms coupled with chemical reaction under conditions of square-wave voltammetry. A systematic change in simulated voltammograms occurs following a change in the applied square-wave amplitude parameter. The obtained results help to assess the generated impact on the peak potential separation of square-wave forward and backward components from conventional and potential corrected voltammograms as well as on the so-called ‘amplitude-based quasireversible maximum’ acquired during the analysis of the net response peak height. In most cases, these features are independent of the parameters of coupled chemical reaction, and electrode kinetics can be estimated without their prior knowledge. Some characteristic criteria can be deduced from the observed trends, which can serve as a means to elucidate electron transfer kinetics. Under these conditions, even nonexperts in the square-wave voltammetry technique can characterize the studied experimental systems.