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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.
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Randles et al. (1968) studied this question.
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