On second order effects in a glavanic cell : Part II. A unified treatment of the theoretical principles of the second order techniques for the study of electrode processes and for electrochemical analysis

Abstract

A general formalism is developed for the theory of the second order contribution to the non-linear behaviour of an electrochemical cell. The derivations result into a set of linear relationships for both the faradaic process and the double-layer charging process, which can be combined to deduce the ultimate cell response under various experimental conditions. The treatment is applicable to any accepted input waveform and gives a clear insight in the close connection between the so-called potentiostatic and galvanostatic approach. As an example the second harmonic distortion and the rectification effect arising from a single harmonic perturbation are briefly discussed. The implications of the treatment for the study of charge transfer kinetics are indicated in a general way, i.e. without specifying an a priori model, but in terms of operational parameters.