Study on Electrochemical Methods of Controlled Convolution ——A simple electron transfer reaction followed by a homogeneous catalytic reaction(Ⅰ)

采用控制卷积量的电化学实验方法，对伴有后续均相催化反应的电极过程进行了处理，得到恒半积分法、半积分扫描法和半微分扫描法的理论曲线，并对亚铁氰化钾——抗坏血酸体系进行了实验验证，获得后续均相催化反应的动力学速率常数，与文献值吻合．A simple electron transfer reaction followed by a homogeneous catalytic reaction is studied in this paper by three kinds of controlled convolution electrochemical experimental methods, which are the constant semi integral (CSI), linear semi integral sweep (LSIS) and linear semi differential sweep (LSDS). According to the three methods, the following equations can be obtained: CSI: πmΨ iI 1(τ)-1=ξe θ LSIS: π2bI 2(τ)-1=ξe θ LSDS: 3π8dI 3(τ)-1=ξe θ Where mΨ i=m i/nFAD 1/2 oC * o, b=D 1/2 ov/nFAk 02 C * o, d=cD 3/2 o/nFAk 04 C * o, m i, v and c are constant value of semi integral, sweep rate of semi integral and sweep rate of semi differential, respectively. With these equations, the theoretical curves of the above three methods can be computed. Experiments of the ferrocyanide ascorbic acid catalytic system have confirmed that kinetic rate constant in catalytic reaction is in good agreement with the previously reported values.作者联系地址：湖南师范大学化学系,湖南大学化学化工系Author's Address: Dept. of Chem., Hunan Normal Univ., Changsha 410081 Chem. Engiv. and Chem. Dept., Hunan Univ., Changsha 41008