无机化学学报

碱性介质中二(碲酸根)合铜(Ⅲ)酸根氧化乙二醇一乙醚的反应动力学及机理(英文)

Kinetics and Mechanism of Oxidation Ethylene Glycol Monoethylether by Ditelluratocuprate(Ⅲ) in Alkaline Medium

作者	单位
单金缓	河北大学化学与环境科学学院,保定 071002
王莉	中国乐凯胶片厂,保定 071051
魏海英	河北大学化学与环境科学学院,保定 071002
申世刚	河北大学化学与环境科学学院,保定 071002
孙汉文	河北大学化学与环境科学学院,保定 071002

摘要: 在碱性介质中用分光光度法研究了二过碲酸合铜(Ⅲ)配离子(DTC)氧化乙二醇一乙醚(EGE)的反应动力学及机理。反应速率表明:反应对DTC为准一级,对EGE为分数级;在保持准一级条件([EGE]》[DTC])下,表观速率常数随着OH^-浓度的增加而增大,随着TeO₄^2-浓度的增加而减小;有负的盐效应。据此提出了包括配离子和EGE形成络合物的前期平衡的反应机理,由假设反应机理推出的速率方程能很好的解释全部实验现象,进一步求得速控步的速率常数和活化

关键词: 二碲酸合铜(Ⅲ)离子乙二醇一乙醚氧化还原反应动力学及机理

基金项目:

Abstract: The kinetics of the oxidation of ethylene glycol monoethyl ether (EGE) by ditelluratocuprate(Ⅲ) complex (DTC) was studied in alkaline medium with spectrophotometry. The reaction rate showed pseudo-first order de-pendence in oxdation and fractional order in EGE.It was found that the pseudo-first order(under the condition:[EGE]》[DTC]) rate constants kobs increased with the increase in [OH^-] and decrease in [TeO₄^2-]. There is a negative salt effect. A mechanism involving a preequilibrium of a adduct formation between the complex and EGE was proposed. The rate equation derived from the mechanism can explain all the experimental results. The acti-vation parameters along with the rate constants of the rate-determining step were calculated.

Keywords: ditelluratocuprate(Ⅲ) ethylene glycol monothylether redox reaction kinetics and mechanism

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单金缓,王莉,魏海英,申世刚,孙汉文.碱性介质中二(碲酸根)合铜(Ⅲ)酸根氧化乙二醇一乙醚的反应动力学及机理(英文)[J].无机化学学报,2002,18(2):143-146.

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