Abstract
The formal potentials and kinetic parameters for the electrode process Cr2+ + 2e−⇄Cr0 occurring at mercury electrode in solutions of LiClO4 + LiCl(aH2O = 0.741) and LiClO4 + LiI(aH2O = 0.853) were determined from analysis of irreversible anodic and cathodic chronocoulometric charge-potential curves. The interaction of Cr(II) with I− ions was found to be stronger (K1 = 1.6 M−1) than the very weak interaction with Cl− ions (K1 < 0.1 M−1). Double-layer properties were established for the solutions studied. On the basis of the rate constants, transfer coefficients, electrode reaction orders, double-layer properties and charges of the activated complex determined, a mechanism for the electrode reaction of the Cr2+/Cr(Hg) redox couple was proposed.
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