Evaluation of the Koutecky-Koryta approximation for voltammetric currents generated my metal complex systems with various labilities

H.P. van Leeuwen, J. Puy, J. Galceran, J. Cecília

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47 Citations (Scopus)

Abstract

The voltammetric response of metal complex systems with various labilities is analyzed by rigorous numerical simulation with the Finite Element Method of the time-dependent concentration profiles of the different species. The ensuing exact fluxes and the corresponding currents are compared to those derived from the Koutecký–Koryta (KK) approximation which assumes a discontinuous transition in the concentration profiles from non-labile to labile behavior. The results indicate a relatively far-reaching correctness of the KK approximation in the complete kinetic range from non-labile to labile complexes, as long as the kinetic flux is computed from the effective concentration of the complex in the reaction layer. Some approximate analytical expressions for this concentration are provided. The KK approximation is shown to be applicable for any metal-to-ligand ratio, provided that the thickness of the reaction layer is expressed in terms of the ligand concentration at the electrode surface
Original languageEnglish
Pages (from-to)10-18
JournalJournal of Electroanalytical Chemistry
Volume526
DOIs
Publication statusPublished - 2002

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