Voltammetric Response of a Two-Step EC’EC’ Double Regenerative Mechanism: First MATHCAD Protocol for Square-Wave Voltammetric Analysis

A two-step electrode mechanism in which each electron-transfer step is followed by an irreversible regenerative chemical reaction (EC′EC′) is theoretically analyzed under conditions of square-wave voltammetry (SWV). For the first time, a complete MATHCAD simulation protocol is developed and presented in open free format, which is related to theoretical modeling the voltammetric behavior of such a doubly catalytic system, enabling systematic variation of all kinetic, thermodynamic, and instrumental parameters. The model accounts for semi-infinite planar diffusion and electron transfer governed by Butler–Volmer kinetics, while the rates of both irreversible chemical regenerations are expressed through dimensionless catalytic parameters. Simulated voltammograms reveal the characteristic catalytic peak enhancement, potential shifts, and dependence of net peak currents on the kinetic strength of both regenerative steps. This mechanism is electrochemically important because it describes systems such as enzyme-mediated redox cascades, catalytic metal complex recycling, two-step reduction of polyphenols (like resveratrol, quercetin, and rutin, for example), electrocatalytic sensing interfaces, and other biochemically important multi-electron transformations. The provided MATHCAD file enables open, reproducible, and fully interactive exploration of this mechanistic class.