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• W2014204029 abstract "The reduction mechanism of [Ni(CN)4]2− at the dropping mercury electrode was studied varying the concentration and the cation type of supporting electrolyte. It has been found that both have a strong effect on the limiting current, i1, and the half-wave potential. This means that according to the experimental conditions, the electron transfer and/or a chemical reaction may be the rate-determining steps. From the analysis of the limiting current data as a function of ψ0, it was found that in the chemical reaction preceding the electron transfer, the sum of the charges of all the particles that react to give the electroactive complex is equal to −2. Since in the experimental conditions used, the only complex present in the solution is the tetracyanonickelate ion with two negative charges, it results from z=−2 that this particle is reduced at the mercury electrode without any association. On the other hand, also the dissociation of [Ni(CN)4]2−, which is in accordance with z=−2, must be disregarded owing to the very small effect of the CN− concentration on i1. An intramolecular rearrangement as suggested by Vlček may be considered responsible for the chemical rate-determining step. The strong influence of the type of cation in the double layer region does not allow the correct determination of the equilibrium constant and the reaction rate constant, which must be very large." @default.
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• W2014204029 date "1969-02-01" @default.
• W2014204029 modified "2023-09-26" @default.
• W2014204029 title "Supporting electrolyte effect on the [Ni(CN)4]2-electrochemical reduction" @default.
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• W2014204029 doi "https://doi.org/10.1016/s0022-0728(69)80124-5" @default.
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