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Improvement and estimation of precision in the cyclic voltammetric determination of rate constants and activation parameters of coupled homogeneous first order reactions. Halide cleavage in anion radicals of chloroanthracenes

Journal of Electroanalytical Chemistry
Publication Date
DOI: 10.1016/0022-0728(93)80127-4


Abstract The variation of the cathodic peak potential with the scan rate (0.3-0.4 mV precision on each determination, 1 mV reproducibility over the whole set of experiments) allows the determination of the rate constant of the title reaction with a relative error of 3%–11%. The results are consistent with those derived from anodic-to-cathodic peak current ratios. Simulation of the whole voltammogram confirms the absence of significant systematic errors that could arise from the assumptions underlying the analysis of kinetic data. Activation parameters derived from weighted regression Arrhenius plots of the data points taken at 5 or 6 temperatures are determined with an uncertainty of 4–8 kJ mol −1 for the activation energy and 12-20 J K −1 mol −1 for the activation entropy.

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