Electrochimica Acta, Vol.53, No.26, 7711-7719, 2008
The mathematical models of kinetics of the E, EC, ECE, ECEC, ECE-ECE and ECEC-ECEC processes with potential-dependent transfer coefficient as a rationale of isoalpha points
It has been proven that including elementary potential-dependent transfer coefficient (alpha) into mathematical model of E, EC, ECE, ECEC, ECE-ECE and ECEC-ECEC mechanisms leads to creation of set of cyclic voltammetry curves with the intersection point called isoalpha point. The isoalpha points have been detected by the use of the models of particular mechanisms with and without partial derivative alpha/partial derivative E parameter included or through different alpha values introduction. The point of intersection unknown in electrode kinetics so far, seems to exemplify an electrochemical analog of isosbestic point in absorption spectroscopy or isopotential point in electrochemistry. Moreover, an example of the experimental data that demonstrates the presence of the isoalpha point has been provided. The presented phenomenon can be of importance for solid state and modified electrodes. (C) 2008 Elsevier Ltd. All rights reserved.
Keywords:cyclic voltammetry;mathematical modeling;transfer coefficient-potential variation;E;EC;ECE;ECEC;ECE-ECE;ECEC-ECEC mechanism;isopotential point;isoalpha point