Theoretical treatment of high-frequency, large-amplitude ac voltammetry applied to ideal surface-confined redox systems

Large-amplitude ac voltammetry, where the applied voltage is a large-amplitude sinusoidal waveform superimposed onto a dc ramp, is a powerful method for investigating the reaction kinetics of surface-confined redox species. Here we consider the large-amplitude ac voltammetric current response of a quasi-reversible, ideal, surface-confined redox system, for which the redox reaction is described by Butler–Volmer theory. We derive an approximate analytical solution, which is valid whenever the angular frequency of the sine-wave is much larger than the rate of the dc ramp and the standard kinetic rate constant of the redox reaction. We demonstrate how the third harmonic and the initial transient of the current response can be used to estimate parameters of the electrochemical system, namely the kinetic rate constant, the electron transfer coefficient, the adsorption formal potential, the initial proportion of oxidised molecules and the linear double-layer capacitance.

► Theory of ac voltammetry on ideal surface-confined redox systems. ► Analytical description of the harmonics and transient of the current response. ► Solution valid for high frequency, large-amplitude sinusoidal input voltage. ► Protocol for determining system parameters from experimental current responses.