Abstract
Abstract The reduction of Cr(III) at a dropping mercury electrode is studied in the presence of highly concentrated NaCl, NaI and Na2SO4 solutions. Thermodynamic analyses of the interface in the supporting electrolyte solutions are also performed in order to account for the double-layer contributions to the reaction rates. The results can be rationalized better fi the relative surface excesses are corrected for the amount of adsorbed water and if the discharge plane is situated outside the OHP. The reactivities in NaI solutions are higher than those in NaClO4 at the same concentration but they are equal when compared at the same water activity. Lower rate constants are observed in NaCl and Na2SO4 solutions, which are explained on the basis of ion-pair associations in the bulk of the solution.
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