| 二(过碘酸根)合铜(Ⅲ)酸根离子氧化二乙醇胺的反应动力学及机理 |
| KINETICS AND MECHANISM OF OXIDATION OF DIETHANOL-AMINE BY DIPERIODATOCUPRATE(Ⅲ) ION IN ALKALINE MEDIUM |
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| 摘要: 在25～40℃区间用分光光度法在碱性介质中研究了二(过碘酸根)合铜(Ⅲ)酸根配离子(DPC)氧化二乙醇胺(DEA)的反应动力学。结果表明，反应对DPC为一级，对二乙醇胺是1.7～1.9级。准一级速率常数kobs随［OH-］增大而增大，随［IO-4］ex(外加的IO-4离子浓度)的增加而减小，也随［KNO3］增大而减小，有负盐效应。在氮气保护下，反应体系能引发丙烯腈聚合。提出了含有自由基过程的反应机理。经此导出的速率方程圆满地解释了全部实验事实，并计算出速控步骤的速率常数及相应的活化参数。 |
| 关键词: 二(过碘酸根)合铜(Ⅲ)酸根 二乙醇胺 氧化还原 动力学及机理 |
| 基金项目: |
| Abstract: The kinetics of oxidation of diperiodatocuprate(Ⅲ) complex ion was studied spectrophotometrically between 25℃ and 40℃ in alkaline medium. The reaction rate showed first order dependance in oxidant and 1.7～1.9 order in diethanolamine. It was found that the pesudo first order (［DEA］［DPC］)rate constant, kobs increases with the increase of ［OH-］ and decreases with the increase of ［IO-4］ex. There is a negative ionic strength effect. Under the protection of nitrogen the reaction system can induce polymerization of acrylonitrile. A reasonable mechanism involving free redical has been proposed. All the experimental phenomena can be explained by the equation derived from the mechanism. The rate constant of the rate-determining step and corresponding the activation parameters have also been obtained. |
| Keywords: diperiodatocuprate(Ⅲ) diethanolamine redox reaction kinetics and mechanism |
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| 宋文玉,降青梅,王安周.二(过碘酸根)合铜(Ⅲ)酸根离子氧化二乙醇胺的反应动力学及机理[J].无机化学学报,1999,15(4):441-445. |
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