Abstract
Summary The kinetics and stoichiometry of the electroreduction of PtCl62− and PtCl42− at platinum electrodes are consistent with a negtive shift in the potential ϵ2 of the outer Helmholtz plane of PtCl62− ions brought about by the adsorption of chloride ions, and with competition between chloride and PtCl42− for adsorption sites in formation of an adsorbed Pt(II) intermediate species. The present data pertaining to Pt(IV) compounds are suggestive of ligand-bridged charge transfer, whereas reduction of PtCl42− appears to require short-range interaction between the electrode and the entire reactant complex.
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