Abstract
The application of the boundary element method (BEM) as an efficient and powerful method for the analysis of the time-dependent electrochemical processes at multiple electrode configurations is presented. The paper describes the theory and numerical details required for developing one-, two- and three-dimensional transient diffusion models for chronoampermetric simulations under diffusion control. The benefits of the BEM approach are discussed, including the reduction in dimensionality brought about by the formulation procedure and complete elimination of the need for domain discretisation with the time-domain convolution approach. The versatility and efficiency of the numerical procedures are examined with respect to a number of electrode geometries. Results are presented for chronoamperometric simulations at microband, microhemishpere, microcylinder and microdisc electrodes compared to appropriate analytical theory. The three-dimensional simulations focus on the modelling of double-electrode configurations (microdisc and microhemisphere) operating in a generator–collector mode. The influence of electrode separation on the transient current response is presented and normalised working curves currently unavailable via analytical methods are provided.
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