化学学报 ›› 1989, Vol. 47 ›› Issue (11): 1120-123. 上一篇    下一篇

研究论文

氮氧自由基研究:XXI,水溶液中哌啶氮氧自由基单电子还原反应机理的极谱研究

张发;刘有成   

  1. 兰州大学化学系
  • 发布日期:1989-11-15

Stueies on nitroxides:XXI. The mechanism for the one-electron reduction electrode reaction of piperidine nitroxides in aqueous solution studied by polarography

ZHANG FA;LIU YOUCHENG   

  • Published:1989-11-15

本文采用取样直流极谱, 常规脉冲极谱, 微分脉冲极谱和交流极谱考察了,2,2,6,6-四甲基-4-羟基哌啶 -1-氧和2,2,6,6-四甲基-4-氧哌啶 -1-氧由基及2,2,6,6-四甲基哌啶 -1-氧自由基在水溶液中的还原反应, 并研究了它们的还原经历电化学过程 。

关键词: 哌啶 P, 水溶液, 反应机理, 还原, 脉冲极谱法, 极谱分析, 氮氧自由基, 单电子转移反应

The experimental results obtained from sampled d.c. polarog. (SDCP), normal pulse polarog. (NPP), differential pulse polarog. (DPP), and a.c. polarog. (ACP) with 2,2,6,6-tetramethyl-4-hydroxypiperidinyl-1-oxy; 2,2,6,6-tetramethyl-4-oxopiperidinyl-1-oxy; and 2,2,6,6-tetramethyl-piperidinyl-1-oxy in aqueous solution showed that these nitroxides can be reduced on the electrode with the formation of the corresponding hydroxylamines as their products. The half-wave potentials and the peak potentials increased with a decrease in the pH of the medium. A linear relation between the peak potentials of ACP of the nitroxides and the pH of the medium was found with a slope of -0.03 V/pH unit. The ratio between the total limiting current of NPP and that of SDCP is independent of the pH and the nitroxides studied. A heterogeneous electron transfer followed by protonation in a homogeneous medium (EC) is proposed for the reductive process.

Key words: PIPERIDINE P, AQUEOUS SOLUTION, REACTION MECHANISM, REDUCTION, PULSE POLAROGRAPHY, POLAROGRAPHIC ANALYSIS, NITRO-OXY RADICAL, SINGLE ELECTRON TRANSFER REACTION

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