Elementary steps like proton coupled electron transfer and the movement of electrons between an electrode and substrate are special to electrochemical processes. Electrochemical mechanisms are important to all redox chemistry including corrosion, redox active photochemistry including photosynthesis, other biological systems often involving electron transport chains and other forms of homogeneous and heterogeneous electron transfer. Such reactions are most often studied with standard three electrode techniques such as cyclic voltammetry(CV), chronoamperometry, and bulk electrolysis as well as more complex experiments involving rotating disk electrodes and rotating ring-disk electrodes. In the case of photoinduced electron transfer the use of time-resolved spectroscopy is common.
When describing electrochemical reactions an "E" and "C" formalism is often employed. The E represents an electron transfer; sometimes EO and ER are used to represent oxidations and reductions respectively. The C represents a chemical reaction which can be any elementary reaction step and is often called a "following" reaction. In coordination chemistry common C steps which "follow" electron transfer are ligand loss and association. The ligand loss or gain is associated with a geometric change in the complexes coordination sphere.
Plots of forward and reverse peak ratios against modified forms of the scan rate often identify the rate of the chemical reaction. It has become a common practice to model such plots with electrochemical simulations. The results of such studies are of disputed practical relevance since simulation requires excellent experimental data, better than that routinely obtained and reported. Furthermore, the parameters of such studies are rarely reported and often include an unreasonably high variable to data ratio (ref?). A better practice is to look for a simple, well documented relationship between observed results and implied phenomena; or to investigate a specific physical phenomenon using an alternative technique such as chronoamperometry or those involving a rotating electrode.
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