Method for the study of asymmetry in fast electrode processes

Abstract

A method is described for the detailed study of the second harmonic component of the faradaic current I₂ cos (2ωt+π) arising from a sinusoidal variation in the overpotential V₁ cos ωt at an electrode. The characteristics of the second harmonic current are discussed. These are related to asymmetry in the electrode processes involved which can be interpreted in terms of non-linearity in the components of the faradaic impedance. The method is applied to the reaction V³⁺_aq+ e^–= V²⁺_aq at a dropping mercury electrode in aqueous perchlorate media at 25°C.