Semi-analytical modelling of linear scan voltammetric responses for soluble-insoluble system: The case of metal deposition

Abstract

The absence of general theoretical models describing linear sweep voltammetry (LSV) or cyclic voltammetry (CV) responses for soluble-insoluble systems such as one-step electrodeposition reactions under quasi-reversible condition makes it difficult to extract quantitative kinetic information from experimental voltammograms. In this work, a semi-analytical method for modelling LSV responses for one–step electrodeposition process is described, for a case where instantaneous nucleation takes place, such as metal deposition on same metal. Voltammetric peaks were analyzed following variation of both dimensionless rate constants and charge transfer coefficients in a broad range. Therefore, kinetic curves for electron transfer processes were established and fitted perfectly by sigmoidal Boltzmann function and linear models. With these models, LSV or CV experimental data can be used to measure electrodeposition reactions kinetics whatever the degree of reversibility. The Cu(I)/Cu(0) couple in acetonitrile was selected as an experimental example. The model developed in this work predicts accurately the current response for Cu electrodeposition reaction and an excellent experiment–theory agreement was found.