1981
DOI: 10.1139/v81-275
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The location of the reaction site and discreteness-of-charge effects in electrode kinetics

Abstract: This paper is dedicated to Dr. Sam Levine on the occasion of his 70th birthday W. R. FAWCETT. Can. J. Chem. 59, 1844(1981. 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 coeffi… Show more

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Cited by 40 publications
(41 citation statements)
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“…In the present case, a negatively charged anion is reduced at a negatively charged electrode in an atmosphere composed predominantly of cations at the oHp with anions on the inner Helmholtz plane (iHp). It follows that one expects some interaction between the reacting species and its atmosphere in the diffuse layer (4,5,14,15,21). According to the theory of discreteness-of-charge effects (14), the change in the corrected logarithm of the rate constant, y with respect to its value in the absence of adsorbed anions at constant 4"' -4d is given by…”
Section: Kineticmentioning
confidence: 99%
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“…In the present case, a negatively charged anion is reduced at a negatively charged electrode in an atmosphere composed predominantly of cations at the oHp with anions on the inner Helmholtz plane (iHp). It follows that one expects some interaction between the reacting species and its atmosphere in the diffuse layer (4,5,14,15,21). According to the theory of discreteness-of-charge effects (14), the change in the corrected logarithm of the rate constant, y with respect to its value in the absence of adsorbed anions at constant 4"' -4d is given by…”
Section: Kineticmentioning
confidence: 99%
“…g is a dimensionless factor related to the degree that repulsive interactions between adsorbed anions are screened; it is given by (25) where Cd is the differential capacity of the diffuse layer and K2, the integral capacity of the region between the iHp and the oHp. od is the charge density of cations in the diffuse layer whose distance from the reactant is such that attractive interaction is possible and a,, the interaction parameter in the activated state (14). od and a, both vary with electrode potential, od being strongly dependent on the value of 4d.…”
Section: Kineticmentioning
confidence: 99%
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“…The transfer coefficient is termed apparent because the actual potential experienced by the reactant may differ from id for a variety of reasons which are generally termed discreteness-of-charge effects [125][126][127].…”
mentioning
confidence: 99%