Extraction of Electron Transfer Kinetics from Cyclic Voltammetric Signals. Comparison with Other Techniques

Extraction of Electron Transfer Kinetics from Cyclic Voltammetric Signals. Comparison with Other Techniques 

How electron transfer kinetics may be investigated by means of an electrochemical method such as cyclic voltammetry is the question we address now, starting with the case where the reactants are immobilized on the electrode surface, as in the beginning of Section 1.2. The key equations are those that relate the surface concentrations rA and rB to the current. The first of these expresses the Faradaic consumption of A and production of B as the current flows  

The cyclic voltammetric responses depend on the manner in which the rate constants are related to the electrode potential. We start with cases in which the Butler-Volmer law applies  

Combining the two key equations after normalization, the following expression of the dimensionless cyclic voltammograms is obtained  

During the cathodic scan, ( m, = t, where m, = (F/TZT)(Ej — EP) is a dimensionless expression of the location of the staring potential In practice, the scan is started much before the peak, and therefore 

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