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Concept
Electrochemical reaction mechanism
Summary
In electrochemistry, an electrochemical reaction mechanism is the step-by-step sequence of elementary steps, involving at least one outer-sphere electron transfer, by which an overall electrochemical reaction occurs.
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.
The reaction above would be called an EC reaction.
The production of in the reaction above by the "following" chemical reaction produces a species directly at the electrode that could display redox chemistry anywhere in a CV plot or none at all. The change in coordination from to often prevents the observation of "reversible" behavior during electrochemical experiments like cyclic voltammetry. On the forward scan the expected diffusion wave is observed, in example above the reduction of to .
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