Fourier transformed large amplitude square−wave voltammetry as an alternative to impedance spectroscopy: Evaluation of resistance‚ capacitance and electrode kinetic effects via an heuristic approach

Abstract

A detailed simulation of Fourier transformed large amplitude square-wave voltammetry is presented in the frequency domain for the process Red reversible arrow Ox+e(-). The simulation takes into account the influence of the electrode kinetics (Butler - Volmer model), uncompensated resistance (R-u) and double layer capacitance (C-dl). Of particular significance is the prediction that the even harmonic responses are only detected in the presence of quasi-reversibility or uncompensated resistance, and also are essentially devoid of charging current.