The use of electrochemical methods for investigating kinetics and mechanisms

The fact that electrochemical processes are tied to electron transfer processes makes electrochemical methods generally less applicable for kinetics and mechanism studies than, for instance, spectroscopic methods. On the other hand, if the reaction under scrutiny involves a radical or radical-like species, electrochemical methods are invaluable tools that often provide a wealth of mechanistic detail. A major advantage of electrochemical methods for kinetics and mechanism studies is that intermediates (radical ions, radicals, etc.) may be formed and their chemical reactions studied at the same electrode in the same operation. 

Many electrochemical methods have been developed to serve different purposes, but it is beyond the scope of this chapter to cover them all, so the presentation is purposefully highly 

The application of any electrochemical method is usually initiated by preliminary investigations the aim of which is to provide information about the reactivity of the primary intermediate as well as other possible intermediates formed during the course of the reaction. Also, it is necessary initially to know the stoichiometry of the electrochemical reaction, including the number of electrons transferred of course, it is necessary to know the produces) of the reaction if this information is not available already. Preliminary experiments leading to this kind of information are briefly described in the appendix at the end of this chapter. 

---