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(中国乐凯胶片厂,保定071051)在碱性介质中用分光光度法研究了二过碲酸合铜?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(犤EGE犦犤DTC犦)下,表观速率常数随着OH-浓度的增加而增大,随着TeO42-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参数。
(China Lucky Film Factory, Baoding 071051) The kinetics and mechanism of the oxidation of ethylene glycol monoethyl ether (EGE) by di-tungstate copper complex ion (DTC) was studied spectrophotometrically in alkaline medium. The reaction rate indicated that the reaction was quasi-one-order for DTC and fractional for EGE, while the apparent rate constant increased with the increase of OH-concentration while maintaining quasi-first-order conditions (犤 EGE 犦 犤 DTC,) Decrease in concentration of TeO42-; negative salt effect. Based on this, the pre-equilibrium reaction mechanism including complex ion and EGE formation reaction was proposed. The rate equation derived from the hypothesized reaction mechanism can well explain all the experimental phenomena and further obtain the rate constants and activation parameters of the velocity-controlled step.