Corresponding author: Rolando Guidelli

 The transfer coefficient a is a quantity that is commonly employed in the kinetic investigation of electrode processes. An unambiguous definition of the transfer coefficient, independent of any mechanistic consideration and exclusively based on experimental data, is proposed. The cathodic transfer coefficient a_c is defined as -(RT/F)(dln j_c/dE), where j_c is the cathodic current density corrected for any changes in the reactant concentration on the electrode surface with respect to its bulk value, E is the applied potential and R, T and F have their usual significance. The anodic transfer coefficient a_a is defined similarly, by simply replacing j_c  with the anodic current density and the minus sign with the plus sign. This recommendation aims at clarifying and improving the definition of the transfer coefficient reported in the 3^rd edition of the IUPAC “Green Book”.

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Professor Rolando Guidelli
University of Florence
Department of Chemistry “Ugo Schiff”
Via della Lastruccia 3
I-50014 Sesto Fiorentino (Firenze), Italy
guidelli@unifi.it

Project: 2011-038-1-100