Journal of Electroanalytical Chemistry, Vol.471, No.1, 14-25, 1999
The voltammetric reduction of some benzenesulfonyl fluorides, simulation of the ECE mechanism and determination of the potential variation of the transfer coefficient by using the compounds with two reducible groups
The cyclic voltammetry reduction process of benzenesulfonyl fluoride (BSF) and m-benzenedisulfonyl difluoride (m-BDF) was investigated in 0.3 M TBAP in DMF. A numerical model of the process was developed consistent with the ECE mechanism of BSF reduction and consecutive ECE-ECE reduction of m-BDF. The values of elementary kinetic parameters were determined. The value of partial derivative alpha(l)/partial derivative E for -SO2F reduction in m-BDF was found to be 0.44 +/- 0.02 V-1. The ECE-ECE system is probably the first recognized example of elementary a kinetic discrimination between two identical two-electron processes.
Keywords:ELECTROCHEMICAL TRANSFER-COEFFICIENT;LINEAR SWEEP VOLTAMMETRY;ELECTRON-TRANSFER;CHEMICAL-REACTIONS;CHARGE-TRANSFER;REACTIVITY;DEPENDENCE;KINETICS;ELECTROREDUCTION;SELECTIVITY