Material characteristics kinetic barriers

Finally, it should be noted that non-Butler-Volmer behaviour may be observed in the analysis of cyclic voltammetric data. For example, particularly in the presence of low concentrations of supporting electrolyte, electron transfer kinetics of charged species may be significantly modified due to the double layer or Frumkin effects [79]. Under these conditions, (i) the potential experienced by the reactant at the point of closest approach to the electrode can be different from the applied potential, and (ii) an additional energy barrier for the approach of charged reactants to the electrode may exist. Corrections to account for Frumkin effects have been proposed. Deviations from Butler-Volmer behaviour may also be interpreted in terms of the Marcus theory [80]. A further interesting case of non-Butler-Volmer voltammetric characteristics is observed with semiconducting elecfrode materials [81]. 

From the above discussion, it is clear that various kinetic criteria (reaction orders, Tafel slopes, and log/-AGads plots on different electrode materials, where appropriate) can be used to determine the reaction mechanism and the coverage conditions. For reactions involving protons, the separation factors (H-T or H-D) can also be used as another criterion, since the barrier heights vary characteristically with mechanism because of the relatively large zero point energy difference between the isotopes and their different quantum mechanical tunneling properties. This is evaluated in Refs. 50 and 51, and may be used to confirm other evidence. 

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