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Abstract
CrBr 2+ and CrI 2+ complexes formed during the electrooxidation of Cr 2+ on mercury electrodes in the presence of Br − and I − ions, respectively, aquate with rates ca. 10 3 higher than those measured by the spectrophotometric method in the bulk of the solution. The entropies of activation of these reactions are large and negative, which indicates that the transition states are highly organized. Changes in the H + concentration did not influence the rate of aquation. Since Cr 2+ ions are not oxidized on Pt, Au, glassy carbon or pyrolytic graphite electrodes, this high instability was explained in terms of the adsorption of the transition state on mercury during the inner-sphere electron transfer.
Published Version
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