Comparison of linear sweep and staircase voltammetries using walsh series

Abstract

Theories of linear sweep voltammetry and staircase voltammetry are shown to be equivalant for a reversible system under semi-infinite linear diffusion. This equivalence is demonstrated by using a Walsh series approximation for the potential profile involved in the integrals which arise in the theory for linear sweep voltammetry. The resulting approximate expression for the current in linear scan voltammetry, which can be made arbitrarily exact, is identical to the exact expression for the current in staircase voltammetry. Quantitative agreement for comparable experiments is obtained when the current in staircase voltammetry is sampled at one-quarter of each pulse interval. These conclusions do not take into account complications due to charging currents.