光谱电化学法测准可逆体系电子转移速率常数

Determination of Heterogeneous Electron Transfer Kinetic Parameters of Quasi Reversible Processes by Spectroelectrochemistry Technique

采用单电势跃——计时吸收光谱法（ＳＰＳ－ＣＡ）测量了准可逆体系的电子转移速率常数。首先通过测Ｋ３Ｆｅ（ＣＮ）６—Ｋ４Ｆｅ（ＣＮ）６体系的标准速率常数ｋｓ０′，证实了理论公式、实验方法及数据处理的合理性，而后以ＳｎＯ２－Ｉｎ２Ｏ３膜玻璃电极为工作电极，分别测定了亚甲基蓝还原和无色亚甲蓝氧化的电子转移速率常数及该体系的ｋｓ０′，结果较为理想。

Single potential step chronoabsorptometry(SPS CA) method for determining the heterogeneous electr on transfer kinetic parameters of quasi reversible electrode reactions was described The present method was experimentally verified using the modle ferricyanide ferrocyanide system Then,by determining the kinetic parameters of reduction of methylene blue and oxidation of leuco methylene blue,the formal heterogeneous electron transfer rate constant k s 0′ of the system were obtained respectively and the two values were in agreement