FREQUENCY-ANALYSIS OF A TEMPERATURE PERTURBATION TECHNIQUE IN ELECTROCHEMISTRY .1. THEORETICAL ASPECTS

In this paper, some models of reaction mechanisms related to heterogeneous electrochemical reactions (limited or not by mass transport) are investigated in terms of a transfer function between the response of the current or the potential and a temperature perturbation. This quantity is analysed in the frequency domain. A redox process is first considered in two cases: where the reactions are the rate-limiting step and where the diffusion is the rate-limiting step. Then the case of a two-step reaction mechanism involving one adsorbed reaction intermediate is reported. The transfer function obtained in each case is then calculated. One of the models is in good agreement with results already published in the literature for experimental conditions similar to those taken into account here.