Abstract
The analytical solutions of the non-steady-state concentrations of species at a planar microelectrode are presented. These simple new approximate expressions of concentrations are valid for all values of time and possible values of rate constants. Analytical equations are given to describe the current when the homogeneous equilibrium position lies heavily in favour of the electroinactive species. Working surfaces are presented for the variation of limiting current with a homogeneous kinetic parameter and equilibrium constant. Moreover, in this work we employ the Homotopy perturbation method to solve the boundary value problem.
Highlights
One of the major achievements in electroanalytical chemistry in the 1980s was the introduction of microelectrodes, i.e., electrodes whose characteristic dimension is on the order of a few m
The electroinactive species A is in dynamic equilibrium with the electroactive species B via a homogeneous chemical step
The decay of species A is described by the first order forward rate constant k f and the reverse of this process is described by the rate constant kb, which is first order for the CE mechanism
Summary
One of the major achievements in electroanalytical chemistry in the 1980s was the introduction of microelectrodes, i.e., electrodes whose characteristic dimension is on the order of a few m (the radius in the case of disc and hemispheres, band width in the case of bands, etc.). We are interested in finding the mass transport limiting current response for the CE mechanism at a microelectrode. Oldham [2] made use of an analytical expression of CE mechanism at a hemispherical electrode. There have been many previous theoretical descriptions of the diffusion limiting current for the CE mechanism. To the best of the author’s knowledge, no purely analytical expressions for the non-steady-state concentrations of these CE mechanisms have been reported. The purpose of this communication is to derive approximate analytical expressions for the non-steady-state concentrations of the species for all values of m1 , m2 , k1 , k2 , k3 and k4 using Homotopy perturbation method
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