The location of the reaction site and discreteness-of-charge effects in electrode kinetics

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Abstract
Discreteness-of-charge effects for simple heterogeneous electron transfer reactions, namely, the self-image effect, the exclusion disc effect, and the effect of local attractive ion–ion interactions, are considered for a variety of reaction sites in the double layer, both in the presence and in the absence of ionic specific adsorption. An expression is derived for the local activity coefficient of the activated complex; this quantity is shown to be a function of both the potential drop across the inner layer and the adsorbed charge density due to specifically adsorbed ions when the standard state is chosen on the basis of the reaction conditions considered in the classical Frumkin theory (reaction site at the outer Helmholtz plane). The consequences of discreteness-of-charge effects for reactions occuring in three different double layer environments of increasing complexity are described. These effects are discussed on the basis of data obtained earlier for the electroreduction of periodate anion in the presence of specifically adsorbed anions.

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