Mn(Ⅲ)/Mn(Ⅱ)体系电极过程的研究  

A STUDY ON THE ELECTRODE PROCESS OF Mn(Ⅲ)/Mn(Ⅱ) SYSTEM

作　　者：张国衡[1] 刘淑兰[1] 齐欣[2] 

机构地区：[1]天津大学应用化学系 [2]天津大学化学系

出　　处：《天津大学学报》1989年第4期65-72,共8页Journal of Tianjin University(Science and Technology)

摘　　要：研究了用于间接有机电合成的Mn(Ⅲ)/Mn(Ⅱ)体系的电化学热力学和动力学。证实Mn(Ⅲ)离子在浓H_2SO_4溶液中将形成络合离子,以MnSO_4^+形式存在。提出了Mn(Ⅲ)/Mn(Ⅱ)在浓H_2SO_4溶液中电解氧化还原时与前人不同的电极反应历程,即在阳极氧化过程中存在着前置化学转化步骤。阐明在不同过电位条件下,电子转移步骤、扩散传质步骤和前置化学转化步骤均可分别成为电极过程的控制步骤。This paper studies the electrochemical thermodynamics and kinetics of the system Mn(Ⅲ)/Mn(Ⅱ) used in the indirect electrosynthesis of organic compounds. Experiment results show that Mn(Ⅲ) forms complex ions in concentrated sulphuric acid and the ions exist in the form of MnSO_4^+. The mechanism of the electrolytic redox reaction of Mn(Ⅲ)/Mn(Ⅱ) in H_2SO_4 solution proposed is different from that of the previous work in that there exists a preceding chemical reaction in the process of anodic oxidation of Mn(Ⅱ) to Mn(Ⅲ). Electron transfer, mass transport or preceding chemical reaction can become the rate-controlling step of the electrode process depending on the magnitude of the overpotential.

关 键 词：电极过程 有机电合成 电化学 

分 类 号：O646.54[理学—物理化学]