Abstract
A numerical method is used to characterize the steady-state voltammetry at microdisk electrodes of a new electrocatalytic reaction. This reaction, which occurs for the oxidation of N,N-dimethylphenylenediamine (DMPD, A) in the presence of H2S (X) is believed to proceed via the following route: A − 2e- ⇄ B, B + X → BX (k2), B−X − 2e- ⇄ [BX]2+. Due to the presence of a reagent restricted homogeneous kinetic step, the reaction is labeled EC2XE. The numerical method for simulating this reaction scheme is based on the finite-difference formulation of coupled mass transport and kinetic equations in oblate spherical coordinates. The method is illustrated for not only the EC2XE but also the EC‘ reaction and is applicable to the simulation of steady-state limiting currents at microdisk electrodes. Iterative solutions are calculated using a Gauss−Newton scheme to overcome nonlinear homogeneous kinetic terms. The spatial convergence of the simulation for both reactions is investigated by considering the form of the...
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