高等学校化学学报 ›› 1983, Vol. 4 ›› Issue (5): 600.

• 论文 • 上一篇    下一篇

定标粒子理论在动力学介质效应上的应用

金家骏, 陈民生, 张楚柏   

  1. 华东工程学院三系
  • 收稿日期:1981-09-02 修回日期:1983-04-01 出版日期:1983-10-24 发布日期:1983-10-24

THE APPLICATION OF SCALED PARTICLE THEORY IN KINETIC MEDIUM EFFECTS

Jin Jiajun, Chen Minsheng, Zhang Chubo   

  1. East China Engineering Institute, Nanjing
  • Received:1981-09-02 Revised:1983-04-01 Online:1983-10-24 Published:1983-10-24

摘要: 应用定标粒子溶液理论,导出了动力学介质效应公式,分析计算了乙酸乙酯皂化反应的介质效应,并与本文实验值相比较,结果,规律一致,数值相近。溶剂体系为水-乙醇和水-二甲亚砜。由于反应体系中包含有极性分子及离子,故在计算相互作用自由焓时,对定标粒子理论作适当补充,包括了色散能、诱导能、取向能和静电作用能。

Abstract: This paper is a theoretical analysis for the medium effects on alkaline hydrolysis of ethyl acetate by the scaled particle theory, according to our own experimental results. The composition of solvent is from 0% to 90% volume percentage of ethyl alcohol aqueous solution or of DMSO aqueous solution, and takes the pure water as the standard solvent. The medium effects are well predicted by the theory. Calculated values of lg(k/k*) are the reaction rate constants and agree with experiment. The term , partial mole intenal free enthalpy in the resulting equation for the rate constants, includs the all interreaction energy of solvent molecules with solute molecules, that are, orientation energy, induction energy and dispersion energy. It will be added by electronic energy when the interreaction is from the polar molecules-ions.

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