Abstract
The kinetics of electroreduction of Co(NH 3) 5F 2+ cation have been studied at a Hg electrode in solutions of NaNO 3 + NaF with an ionic strength of 0.2 M. The acceleration of the reduction due to adsorption of nitrate ions could not be rationalized on the basis of the change in the average potential on the outer Helmholtz plane. Under most conditions, the acceleration was less than that predicted by the classical theory, the magnitude of the difference increasing with the extent of adsorption and with shift in electrode potential in the positive direction. The results obtained can be explained in terms of changes in the potential profiles near the electrode caused by adsorbed anions with consideration of discreteness-of-charge effects.
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