Journal of Electroanalytical Chemistry, Vol.633, No.1, 45-56, 2009
Re-examination of the potential step chronoamperometry method through numerical inversion of Laplace transforms. II. Application examples
In the first part of this work, we proposed the so-called GS-, FE- and FT-PSCA algorithms to investigate a wide range of electrode geometry and chemical, electrochemical and one-dimensional mass-transport processes by the potential-step chronoamperometry (PSCA) method. Each algorithm provides a full explicit formulation of Faradaic current with respect to time, applied potential and electrochemical parameters (initial concentrations, geometrical parameter(s), standard potential, electrochemical and chemical rate constants and diffusion coefficients). Application examples relative to diffusion equations with spherical electrode geometry are presented in this second article by way of illustration of the potentialities of GS- and FT-PSCA algorithms. First, the case of one-step electrochemical reactions at spherical and hemispherical electrodes of any radius is investigated when both implicated species are soluble in the electrolytic solution. The numerical solution obtained from GS-PSCA algorithm is favourably compared to previous results in the electrochemical literature. Next, we use the FT-PSCA algorithm for investigating spherical diffusion with amalgamation reaction. Finally, the characteristic features of chronoamperograms and sampled-current voltammograms pertaining to the above reaction are examined and discussed. (C) 2009 Elsevier B.V. All rights reserved.
Keywords:Potential step;Chronoamperometry;Sampled-current voltammetry;Modelling;Numerical inversion of Laplace transforms