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Abstract
A theoretical study of the E-DIM reaction with adsorption of the reactants is presented. The electrochemical reaction E can have a heterogeneous (Eh) or surface (Es) character, whereas the dimerization can occur in a volume near the electrode (DIMv) or on its surface (DIMs). Four paths are possible: EhDIMv, EhDIMs, EsDIMh or EsDIMs. The dependence of the variations of the characteristic parameters (e.g.E1/2 in polarography or RDE voltammetry,Ep in LSV), the measurement time (τ,RT/Fv), the concentrationcT or the surface concentrationГT is different in each case, and can thus be used to determine the nature and the sequence of the paths and to calculate the dimerization reaction rate constant.
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