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Detection of Electrochemically Adsorbed Surface Films by Reflectance Spectra

Abstract

THE rate of electrochemical reaction can be strongly influenced by adsorbed species on the electrode surface, and a knowledge of the degree of surface coverage and the heat of adsorption of the species is in many cases essential for a correct interpretation of the reaction mechanism. The surface coverage by chemisorbed oxygen and hydrogen on many metals has been determined electrochemically by pulse1 or rapid potential sweep methods2, where the quantity of electricity required to either reduce or oxidize the surface film has been determined. In general, these methods can be simply applied only if the current flowing during the time of measurement can be attributed to a single reaction. In many cases, however, it is desirable to know the surface coverage with an intermediate during the progress of a reaction or with the products of a simultaneous reaction, and under these conditions only a small fraction of the total current can be attributed to the formation of an adsorbed species. In some cases it may be possible to relate the experimentally measured pseudocapacitance to surface adsorption but here, also, assumptions have to be made on the relative rates of reaction3.

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References

  1. Slygin, A., and Frumkin, A., Acta physicochim. U.R.S.S., 3, 791 (1935).

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  2. Will, F. G., and Knorr, C. A., Z. Elektrochem., 64, 258 (1960).

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  3. Conway, B. E., Gileadi, E., and Dzieciuch, M., Electrochim. Acta, 8, 143 (1963).

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KOCH, D. Detection of Electrochemically Adsorbed Surface Films by Reflectance Spectra. Nature 202, 387–388 (1964). https://doi.org/10.1038/202387a0

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