Large amplitude AC voltammetry - A comparison between theory and experiment

Recently a published theory advocates the abandonment of the classical limi tation that the applied voltage signal, V, in reversible AC voltammetry, be small compared with RT/nF: We have performed experiments designed to test the validity of the theoretical predictions. The AC voltammetric peak heigh ts and areas have been measured as a function of V. for both the fundamenta l and harmonic frequencies. As well, the shapes of the AC voltammograms hav e been compared with predictions. In general, experiment agrees well with t heory Though our experiments have not yet addressed a range of concentratio ns, they do have strong implications for electroanalytical applications of AC voltammetry.