Effect of large-amplitude alternating current modulation on apparent reversibility of electrode processes

We examined the effect of a large-amplitude high-frequency alternating potential modulation on direct currents associated with irreversible, quasi-reversible, and reversible electron-transfer processes occurring at microelectrodes under voltammetric conditions. All irreversible processes appear to be accelerated by the superimposed ac modulation, and under certain conditions this may even lead to an electrochemical etching of noble metal electrodes. In the case of electrode processes which are reversible on the time scale of a dc polarization, but quasi-reversible on the time scale of the ac modulation, the distortion of voltammograms caused by the ac modulation can provide useful information about the kinetics of fast electron-transfer processes. For completely reversible electrode processes the effect of the large-amplitude ac modulation is essentially trivial; the distortion of voltammetric curves causes broadening of analytical signals without providing any useful information.