Abstract
The impedance spectral response of electrochemical systems to multi sine (MS) potential perturbations was simulated using numerical techniques. The MS waves comprised of odd harmonic waves and were applied to a simple electron transfer reaction, and a reaction with an adsorbed intermediate. The governing equations were solved without linearization. Two choices of frequency sets with phases corresponding to the minimum crest factor were employed. The effects of large amplitude perturbations, potential instability, noise and solution resistance were investigated. The EIS data were subjected to Kramers Kronig transforms (KKT). The results show that (i) if large amplitude perturbations are used, the spectra acquired using MS appear to be noisy and they violate KKT, (ii) potential drifts and noise effects are successfully identified by KKT and (iii) in the presence of a significant solution resistance, the kinetic equations must be employed along with the equivalent circuit model to estimate the kinetic parameters.
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