碱性介质中二过碘酸合铜(III)配离子氧化四氢糠醇的动力学及机理

本文采用分光光度法研究了二过碘酸合铜(III)配离子在碱性介质中氧化四氢糠醇的动力学及机理. 结果表明反应对[Cu(III)]是一级, 对四氢糠醇是1.3级. 反应速率随体系中[OH^-]的增大而增大, 随过碘酸浓度的增大而减小, 反应体系加入硝酸钾盐时,速率增大, 有正盐效应. 在氮气保护下, 体系能够诱发丙烯酰胺聚合. 提出了一种含有自由基过程的反应机理, 据此导出了一个能够解释本文全部实验事实的速率方程. 求得了速率控制步骤的速率常数, 并给出了相应的活化参数.

Kinetics and mechanism of oxidation of tetrahydrofurfuryl alcohol by diperiodatocuprate (III) in alkaline medium

The kinetics of oxidation of tetrahydrofurfuryl alcohol by potassium diperiodatocuprate (III) has been studied spectrophotometrically in alkaline medium. The order in [Cu(III)] is found to be unity and that in alcohol to be 1.3. The rate increases with increasing in [OH-] and decreases with increasing in [KIO4]. There is a pos. salt effect of addition of KNO3. Under the protection of nitrogen gas, the reaction system can induce polymerisation of acrylamide. A plausible mechanism involving free radicals has been proposed. The activation parameters of the rate determing step have been calculated