Description of Solid-to-Solid Redox Processes Based on the Voltammetry of Immobilized Particles Methodology: A Logistic Approximation

A semiempirical model to describe the voltammetry of nontopotactic solid-to-solid redox processes occurring in the voltammetry of immobilized particles (VIMP) electrochemistry is described. It is applied to the reduction of solid metal compounds to the corresponding metal in contact with suitable electrolytes. The model is based on the assumption that the transferred charge is a logistic function of the applied potential, a situation that applies for reversible redox processes involving strongly adsorbed reactants. The model satisfactorily applies to reproduce linear potential scan curves recorded for graphite electrodes modified with different lead compounds (PbO, PbCl2·2H2O, lead-tin yellow, lead white) in contact with 0.10 M H2SO4 aqueous solution.