A New Formulation of the Frequency Factor in the Expression for the Rate Constant of Interfacial Charge Transfers

Jaime González Velasco*

 

Universidad Autónoma de Madrid. Facultad de Ciencias. Cantoblanco.28049 Madrid. Spain

Received 20 July 2006; accepted 17 July 2007

 

 

Abstract

A new way for deriving the fundamental equation of the electrochemistry has been developed in the potential range in which Butler-Volmer behaviour is found. In this approach the frequency factor is considered to be a function of the potential instead of the activation energy. The frequency factor is calculated by means of a classical statistical mechanics treatment giving rise to a new definition for the symmetry factor. A new expression for the standard rate constant in adiabatic heterogeneous charge transfer reactions has been derived.

 

Keywords: heterogeneous charge transfer, standard rate constant, potential dependent frequency factor.

 

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* Corresponding author. E-mail address: Jaime.gonzalez@uam.es