REPETITIVE CYCLIC VOLTAMMETRY OF IRREVERSIBLE SYSTEMS

The fact that repetitive cyclic voltammograms of irreversible systems tend towards a non-zero steady-state limit can be explained in terms of interference of natural convection. Simulations of the current-potential responses obtained for the reduction of 1-bromonaphthalene in acetonitrile under these conditions, and also when the electrode is rotated, show good agreement between theory and experiment. The parameter controlling the shape of the cyclic voltammetric responses and the rate of their decay towards the steady-state limit is the ratio of the thickness of the diffusion-convection layer to that of a diffusion layer controlled by the scan rate.