微电极对多步电极反应(EE反应)稳态过程的研究

本文推导了微盘及微球电极上EE反应的一般稳态电流表达式; 对ErEr,EqEr, EiEr, ErEq, ErEi, EiEi及EqEq各反应机理进行了详细讨论; 并以亚硫酰氯的还原反应为特例进行了研究及动力学常数的测定。

The kinetic study of multistep electrode processes at microelectrodes under steady-state conditions

A general current-potential expression for the first order EE reactions at disk and spherical microelectrodes on the basis of the equal fluxes under steady-state conditions was derived. According to the classification for the voltammetric experiments that presented in our previous work, the characteristics of the ErEr, EqEr, EiEr, ErEq, ErEi, EiEi, EqEq and EE∞ mechanisms are also discussed. Obviously, it expressed the electrode processes in concept more concisely. In this work, we also presented some methods for the determination of kinetic parameters in various systems and examplified by the reduction of thionyl chloride (SOCl2) in dimethyl formamide (DMF).