Theory of A.c. Polarization and A.c. Polarography and Voltammetry of Two-step Surface Redox Reactions

Abstract
Theoretical expressions are presented of the a.c. polarization and of the a.c. polarography and voltammetry for a two-step surface redox reaction (Oad+n1e\ightleftharpoonsSad,Sad+n2e\ightleftharpoonsRad) in which the charge transfer reactions take place exclusively between the adsorbed reactants Oad, Sad, and Rad, and all the reactants are adsorbed so strongly that the amount of O, S, or R brought to or removed from the electrode surface can be neglected. The interaction between the adsorbed reactants is assumed to be expressed by Frumkin’s a-parameters. The effect of the double layer impedance is taken into account. Several simplified cases are discussed in detail.

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