Abstract
A theoretical treatment is given of the effect of Langmuirian adsorption on Nernstian, diffusion-limited electrode reactions at a plane electrode under potentiostatic conditions. Relaxation currents generally consist of three components, an instantaneous initial conversion of adsorbed reactant to product, the same diffusional component that would be observed in the absence of adsorption, and a time-distributed adsorptive component due to interconversion between adsorbed and diffusing species. The magnitude, sign, and time-constant associated with the time-distributed adsorptive component vary widely with experimental conditions. In favorable situations the magnitudes of both adsorptive components can be determined conveniently by extrapolation of two separate linear segments of a chronocoulometric plot of charge vs. square root of time to time zero. This feature and other prominent effects of adsorption are shown to be qualitatively independent of the detailed form of the adsorption isotherms.
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