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- W1965863895 abstract "The electrode reactions of 26 compounds have been studied by cyclic voltammetry at mercury electrodes using acetonitrile as solvent and either 0.10 M tetraethylammonium perchlorate (TEAP) or 0.10 M tetra-n-heptylammonium perchlorate (THpAP) as supporting electrolyte. The standard potentials of the compounds ranged from −0.07 to −2.90 V vs. the Ag/AgNO3 reference electrode. In several of the redox couples studied, the charge on the ionic partner was localized on a few atoms which is expected to cause the outer reorganization energy to be high, giving small electron transfer rate constants. However, is some instances it does not appear that the degree of charge localization is great enough to account fully for the small rate constants. It is argued that the inner reorganization energy should not be ignored in such cases. The rate constants observed for THpAP were always smaller than those for TEAP when the values were small enough to measure in at least one electrolyte. This general result was explained by a suppression of the probability of electron transfer by an adsorbed film containing mainly tetra-n-heptylammonium ions. The interpretation was supported by measurement of the activation parameters for nitroethane in the two electrolytes. The activation enthalpies were almost identical but the preexponential factor for THpAP was only 1/44 that for TEAP." @default.
- W1965863895 created "2016-06-24" @default.
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- W1965863895 date "1987-05-01" @default.
- W1965863895 modified "2023-10-16" @default.
- W1965863895 title "Heterogeneous electron transfer kinetics for a variety of organic electrode reactions at the mercury-acetonitrile interface using either tetraethylammonium perchlorate or tetraheptylammonium perchlorate electrolyte" @default.
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- W1965863895 doi "https://doi.org/10.1016/0022-0728(87)80282-6" @default.
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