Implementation of a statistically supported heuristic approach to alternating current voltammetric harmonic component analysis: re-evaluation of the macrodisk glassy carbon electrode kinetics for oxidation of ferrocene in acetonitrile

Elena Mashkina, Alan Bond

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Sinusoidal large amplitude ac voltammetric techniques generate very large data sets. When analyzed in the frequency domain, using a Fourier transform (FT)-band filtering- inverse FT sequence, the data may be resolved into the aperiodic dc, fundamental, second, and higher order ac harmonics. Each of these components exhibit a different level of sensitivity to electrode kinetics, uncompensated resistance and capacitance. Detailed simulations illustrate how the heuristic approach for evaluation of each data subset may be implemented and exploited in the assessment of the electrode, kinetics for the fast Fc reversible arrow Fc(+) + e (Fc = ferrocene) oxidation process at a glassy carbon macrodisk electrode. The simulations presented in this study are based on the Butler-Volmer model and incorporate consideration of the uncompensated resistance (R(u)), double-layer capacitance (C(dl)), rate constant (k(o)), and charge transfer coefficient (alpha). Error analysis of the heuristically evaluated simulation-experiment comparison is used to assist in establishing the best fit of data for each harmonic.
Original languageEnglish
Pages (from-to)1791 - 1799
Number of pages9
JournalAnalytical Chemistry
Issue number5
Publication statusPublished - 2011

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