Analytical formulae for chronoamperometry of a charge neutralisation process under conditions of linear migration and diffusion |
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Affiliation: | 1. Laboratoire de Génie Chimique, CNRS, Université de Toulouse, 4 allée Emile Monso, 31432 Toulouse, France;2. IRSTEA-Unité de Recherche Hydrosystèmes et Bioprocédés, 1 rue Pierre-Gilles de Gennes, CS 10030, 92761 Antony, France;1. School of Environmental Studies, China University of Geosciences, Wuhan 430074, China;2. College of Resources and Environment, Yangtze University, Wuhan 430100, China |
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Abstract: | The electrochemical reaction of the charge neutralisation of a binary electrolyte ion, at a planar electrode, is a rare example for which analytical formulae for potential step chronoamperometry can be obtained, under conditions of migration-diffusion transport in semi-infinite, one-dimensional space domain. This has been previously shown by Myland and Oldham [Electrochem. Commun. 1 (1999) 467], assuming equal diffusion coefficients. In the present work, a more general analytical solution is obtained, for the case of unequal diffusion coefficients. The effect of the diffusion coefficient ratio DR/DC, of the electroactive ion R and the counter-ion C, on the limiting chronoamperometric current, is examined. The effect increases with the growing ratio |zR/zC| of the electric charges of these ions, and becomes nonnegligible for |zR| greater than or equal about 2, and for typical departures of DR/DC from unity. Among other things, the formulae obtained can be useful for testing digital simulation methods for the Nernst–Planck equations. |
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