Abstract
The electrode reactions of the Ca(II)/Ca(Hg) system in aqueous 0.10–2.0 mol dm −3 Ca(ClO 4) 2 solutions were investigated using potentiostatic pulse techniques and dc polarography. The reduction of Ca(II) was found to be irreversible under polarographic conditions and accompanied by hydrogen evolution. It was shown, however, that the water reduction process does not influence the kinetics of Ca amalgam formation. The oxidation of in situ generated diluted Ca amalgam was found to be controlled both by diffusion and charge transfer kinetics. In various solutions standard rate constants not reported earlier in the literature (−log k app s = 4.08–4.20) and formal potentials (− E o = 2.200-2.143 V vs. SSCE) for the Ca(II)/Ca(Hg) couple were determined and discussed critically. Possible mechanisms of H 2O reduction are discussed.
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