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Laboratoire d'Electrochimie Moleculaire, LEM, Paris

UMR CNRS - Université Paris Diderot - Paris France

   
 
Master Frontiers in Chemistry | UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie Université de Paris Master Chimie Sorbonne Paris Cité UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie
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Université Paris Diderot
Université de Paris CNRS, Centre National de la Recherche Scientifique
 
 


Le LEM - Publications: Abstracts

Publication 671

Phys. Chem. Chem. Phys., 12 (40),13061 - 13069, 2010
DOI: 10.1039/c0cp00017e
 

doi

Reorganization energies and pre-exponential factors in the one-electron electrochemical and homogeneous oxidation of phenols coupled with an intramolecular amine-driven proton transfer

Cyrille Costentin, Marc Robert, and Jean-Michel Savéant

Laboratoire d’Electrochimie Moléculaire, UMR CNRS 7591, Université Paris Diderot, 15 rue Jean-Antoine de Baïf, 75205 Paris Cedex 13, France


Temperature variations of the kinetics of the electrochemical and homogeneous oxidation of the title compounds give rise to Arrhenius plots, the slopes of which give access to the heavy-atom (including solvent) reorganization energies. Information on the role of proton transfer in the dynamics of the concerted proton–electron transfer reaction (CPET) is potentially contained in the pre-exponential factor. Previous analyses of the problem were based on equalling the pre-exponential factor in the absence of barrier for proton transfer with the collision frequency. Taking into account that the reaction may take place at various distances from the electrode surface increases the value of this limiting pre-exponential factor. Strategies are discussed for evaluating the impact of proton transfer in the CPET kinetics by comparing the experimental pre-exponential factor with pre-exponential factors characterizing simple outersphere electron transfers.

 
   
 
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