Influence of Electrode Roughness on Stripping Voltammetry: Mathematical Modeling and Numerical Simulation

Electrodes with rough surfaces inevitably have practical importance from both applied and fundamental points of view including electroanalysis where stripping voltammetry is a popular technique due to its simplicity and high sensitivity. The diffusional domain approach is used to model stripping voltammetry at rough electrodes: two models of the electrode Surface, "rough" and "scratched", are considered. Electron transfer is described by three models which correspond to cases of stripping of a monolayer, a thin layer, and a bulk layer, The shape of the votammograms strongly depends on the model of the electron transfer but is not always sensitive to the precise model of the electrode surface; the conditions under which this is the case are identified, and generic roughness effects on stripping voltammetry are quantified. We conclude that electrode roughness can have a significant effect on the stripping of the metals from the solid electrode especially in respect of the voltammetric waveshape.