At the present time, the general area of mechanism analysis of organic electrode processes is being subjected to serious challenge. In the past it has been customary to assume that the reaction of electrode generated intermediates that can be described by two or three letter symbols designating electron transfer at the electrode (E) or homogenous chemical (C) reactions. Mechanism were frequently proposed on the basis of Cyclic voltammograms or the best fit of experimental data to theoretical working curves derived from models based on the simple mechanisms. Reinvestigations of number of electrode processes have indicated that nature is far more complex than the EC type models which are the basis for theoretical data, because a cyclic voltammogram gives qualitative information about non-redox processes occurring before or after the redox reaction. Cyclic Voltammetry may be used to study E, EC, ECE, EC', and adsorption mechanisms.
It is concluded that the most reliable procedure in electrode mechanism analysis is to make use of as many variables as possible in studying the reactions. This will usually include variable temperature, variable concentration, isotopic studies as well as the conventional variation of electrochemical parameters. Mechanism based on the electrode studies may in future enjoy lifetimes as great as those proposed on the basis of careful homogenous kinetic studies.
