Voltammetric Measurement of Bimolecular Electron-Transfer Rates in Low Ionic Strength Solutions
CORNELL UNIV ITHACA NY BAKER LAB
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Electrochemical investigations of homogenous chemical reactions that are coupled to an initial electron-transfer step are frequently based on methods in which the mass-transfer coefficient of a reactant or intermediate is experimentally varied relative to the inherent rate of the chemical reaction. Common methods employed in studying coupled chemical reactions include the rotating disk electrode RDE, rotating ring-disk electrode RRDE, and cyclic voltammetry. In the RDE and RRDE experiments, the rate of mass-transfer is proportional to the square-root of the electrode rotation rate so that the mass- transfer rate may be adjusted to a value comparable to the rate of the chemical reaction. The dependence of the limiting current in this experimental regime may be analyzed, using appropriate kinetic equations, to determine the rate constant of a chemical reaction.
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