Abstract
The electrode reaction Cd(II)/Cd(Hg) in complex chloride, bromide and iodide solutions with dimethyl sulfoxide as solvent has been studied by a cyclic current-step method. The ionic strength was 1 M with ammonium perchlorate as supporting electrolyte. The φ 2-potential of the double-layer has been determined by electrocapillary measurements. The results indicate that the overall charge transfer proceeds step-wise and is accompanied by a fast disproportionation of the intermediate Cd(I). In the chloride system it is not possible to detect that the complexes formed take part in the electrode reaction, while in the bromide and iodide systems Cd 2+ as well as the complexes CdX + and CdX 2 contribute to the exchange current density. It is suggested that the rate constant of the step CdX j 2− j /Cd(I) depends on the possibility of ligand bridging at the amalgam by X − and on the total enthalpy change at the formation of CdX j 2− j from the solvated Cd 2+.
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