Theory and application of cyclic voltammetry for measurement of fast electrode kinetics at microdisk electrode

摘要

An analytical expression describing voltammetric behaviors responses at microdisk electrode for various diffusion conditions and degrees of reversibility is reported in this paper. Results of theoretical calculation made it possible to use cyclic voltammetry to evaluate heterogeneous rate constants under intermediate diffusion conditions. At relatively low scan rate, the distortion of current-voltage can be reduced due to small iR drops and charging current. The effects of transfer coefficient, α, kinetic parameter, λ(=k~0r/4D), and switching potential, ξ_s, on potential peak separation are discussed in detail. The relationship obtained in this paper between potential peak separation and λ is in good agreement with that in Ref. 14, whose authors have got their results by using digital simulation technique. After the experiment of Fe(CN)_6~(4-) oxidation, k~0 and α were obtained by the theory of this paper. The result agrees with that in Ref. 19.