Limitations in Electrochemical Determination of Mass-Transport Parameters: Implications for Quantification of Electrode Kinetics Using Data Optimisation Methods

摘要: Voltammetric quantification of the electrode kinetics for quasi-reversible reaction requires detailed experiment–theory comparisons. Ideally, predicted data derived from theoretical model are fitted to experimental by adjusting reversible potential (E0), heterogeneous electron transfer rate constant at E0 (k0), and charge coefficient α, with mass-transport other parameters exactly known. However, relevant mass transport that include area (A), diffusion (D), concentration (c), usually subject some uncertainty. Herein, we examine consequences having different combinations errors present in A, D, c estimation E0, k0, α on basis a.c. (alternating current) voltammetric comparisons facilitated use a computer-assisted parameter optimisation algorithm. In most cases, experimentally reasonable (<10 %) do not introduce significant recovered values. pernicious situation may emerge when slight overestimation D or is included results erroneous identification redox process as one report apparently quantifiable kinetic k0 α.