Issue 5, 2012

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

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.

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

Article information

Article type
Communication
Submitted
26 Sep 2011
Accepted
28 Nov 2011
First published
16 Dec 2011

Phys. Chem. Chem. Phys., 2012,14, 1581-1584

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

C. Costentin, C. Louault, M. Robert, V. Rogé and J. Savéant, Phys. Chem. Chem. Phys., 2012, 14, 1581 DOI: 10.1039/C2CP23050J

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