Reorganization energy and pre-exponential factor from temperature-dependent experiments in electron transfer reactions. A typical example: the reduction of tert-nitrobutane

Literature Information

Publication Date 2011-12-16
DOI 10.1039/C2CP23050J
Impact Factor 3.676
Authors

Cyrille Costentin, Cyril Louault, Marc Robert, Vincent Rogé, Jean-Michel Savéant


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Abstract

The electrochemical one-electron reduction of tert-nitrobutane in N,N′-dimethylformamide is a typical reaction, which has been shown to follow the quadratic model of outersphere electron transfer. The variation of the standard rate constant with temperature allows a separate determination of the reorganization energy and of the pre-exponential factor. The value found for the former is in agreement with independent estimates of the solvent and intramolecular reorganization energies. The value of the latter, significantly larger than the collision frequency, implies that the reaction starts to take place before close contact with the electrode surface.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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