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 i n DMF. A numerical model of the process was developed consistent with the E CE mechanism of BSF reduction and consecutive ECE-ECE reduction of m-BDF. T he values of elementary kinetic parameters were determined. The value of pa rtial 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 firs t recognized example of elementary a kinetic discrimination between two ide ntical two-electron processes. (C) 1999 Elsevier Science S.A. All rights re served.