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• W2092148680 abstract "The prospects of utilizing electrochemical kinetic measurements at lower temperatures for evaluating reliably the standard rate constants ks of rapid redox couples in non-aqueous media, specifically using microelectrode voltammetry, have been examined by means of digital simulations together with experiment. Cyclic voltammetric measurements were made between 200 and 300 K at a gold microdisk, for ferrocenium-ferrocene (Fc+/0), o-nitrotoluene0/− and nitromesitylene0/− redox couples in acetone, propionitrile and butyronitrile, at a gold microdisk with scan rates from 100 to 104 V s−1. The latter two couples were selected as examples of systems that exhibit rapid but yet still unambiguously measurable ks values at ambient temperatures; the more facile Fc+/0 system has been suspected to yield immeasurably fast electrode kinetics using conventional techniques under these conditions. Sample simulated voltammograms were generated between 200 and 300 K for a sequence of activation enthalpies ΔHex‡ for electron exchange, accounting also for known temperature-dependent diffusion coefficients, solution resistance and double-layer capacitance. As long as ΔHex‡ > 10 kJ mol−1, the use of diminished temperatures in such solvents is predicted to facilitate the reliable evaluation of ks. This expectation is in harmony with experiment: ks for Fc+/0 is apparently evaluated readily at lower temperatures, yielding ΔHex‡ = 20 kJ mol−1. The temperature-dependent electrode kinetic data for Fc+/0 are compared briefly with some expectations of contemporary theory." @default.
• W2092148680 created "2016-06-24" @default.
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• W2092148680 date "1992-01-01" @default.
• W2092148680 modified "2023-10-10" @default.
• W2092148680 title "The evaluation of rate constants for rapid electrode reactions using microelectrode voltammetry: virtues of measurements at lower temperatures" @default.
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• W2092148680 doi "https://doi.org/10.1016/0022-0728(92)85011-q" @default.
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