Educational Voltammetry, Part VIII: Mathcad Simulation Protocol of an electrochemical reaction coupled with an irreversible regenerative chemical reaction (the EC’ or electrochemical-catalytic mechanism) at stationary planar electrode under conditions of square-wave voltammetry

Square wave voltammetry (SWV) offers unique advantages for mechanistic studies because its waveform combines a staircase ramp with rapid potential oscillations and it provides sensitivity to kinetic regimes through adjustable parameters (step increment, amplitude and frequency). In this instalment, we analyze, simulate and interpret voltammetric responses for the EC′ mechanism i.e. an electrochemical reaction where the oxidised species reacts irreversibly with a co reactant to regenerate the starting redox form, producing catalytic current amplification. The study is carried out at a stationary planar electrode under purely diffusional transport, using the Butler–Volmer formalism for electron transfer and a pseudo first order rate for the regenerative chemical step. We derive the dimensionless kinetic parameters that govern the response (K for electron transfer, and Kchem related to the rate of regenerative chemical step), while evaluating the numerical recursive formulas to compute forward, reverse and net currents of the square-wave voltammograms for this mechanism. A step-by-step Mathcad protocol is provided so students and researchers can reproduce square wave voltammograms, explore how scan rate and catalytic rate constant shape the voltammetric profile, and recognize diagnostic features that distinguish EC′ mechanisms from simple EC or CE pathways. This resource bridges theory and practice and serves as an accessible introduction to simulating catalytic electrochemical processes with SWV.