Abstract
The electrode reaction Cu(I)/Cu(Hg) in complex chloride, bromide and iodide solutions with DMSO as solvent has been studied at the equilibrium potential by the faradiac impedance method and a cyclic current-step method. The kinetic data refer to the ionic strength 1 M with ammonium perchlorate as supporting electrolyte and to the temperature 25°C. Double-layer data have been obtained from electrocapillary measurements. From the results for the chloride system at [Cl −]>15 m M it is concluded that the charge transfer is catalysed by ligand bridging at the amalgam and the following parallel reactions predominate: Cl ads −-Cu ++e −(am)Cl ads −+Cu(am) Cl ads −-Cu 2Cl j 2−j+e −(am)Cl ads −+Cu(am)+CuCl j 1−j At lower [Cl −] and in the whole ligand concentration range available in the bromide and iodide systems the impedance measurements indicate a rate-controlling adsorption step. It is suggested that uncharged complex CuL (L −=halide ion) then forms an adsorbed two-dimensional network on the amalgam surface.
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