二(原碲酸根)合铜(Ⅲ)酸根离子氧化环已酮的反应动力学及机理

Kinetics and Mechanism of Oxidation of Cyclohexanone by Diorthotelluraocuprate(Ⅲ) Complex Ion in Alkaline Medium

在碱性介质中用分光光度法研究了二（原碲酸根）合铜 ?酸根离子 (DTC)于 25～ 40℃区间氧化环已酮的反应动力学。结果表明反应对 DTC为一级，对环已酮的表观反应级数也是一级。准一级速率常数 kobs随 [OH－ ]增大而增大，随 []ex(ex表示外加的 )的增加而减小，并且有弱的负盐效应。在氮气保护下，反应能引发丙烯酰胺的聚合。提出了含有自由基过程的反应机理，据此导出的速率方程圆满地解释了全部实验事实，并计算出平衡常数、速控步骤的速率常数及相应的活化参数。

The kinetics of oxidation of cyclohexanone by Diorthotelluraocuprate? complex ion was studied spectrophotometrically in alkaline medium in a temperature range of 25～ 40℃ .The reaction rate showed first order dependence both in oxidant and cyclohexanone.It was found that the pesudo first order([C6H10O] [DTC]) rate constant kobs increases with the increase in [OH－ ] and decreases with the increase in [].A week negative ionic strength effect was observed.Under the protection of nitrogen the reaction system can induce polymerization of acrylamide.A reasonable mechanism involving free radical has been proposed.All the experimental phenomena can be explained by the equation derived from the mechanism.The preequilibrium constants and rate constants of the determining step along with the activation parameters were evaluated.