高等学校化学学报

高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (9): 1275.

• 研究论文 • 上一篇    下一篇

水及含水混合溶剂中动力学盐效应的理论研究

王风云, 俞柏恒, 陈民生, 叶静娴, 金家骏   

  1. 南京理工大学化工学院化学系, 南京 210014
  • 收稿日期:1992-10-29 修回日期:1993-02-10 出版日期:1993-09-24 发布日期:1993-09-24
  • 通讯作者: 王风云.
  • 作者简介:第一作者:男, 33岁, 硕士, 教授.

Theoretical Prediction for the Reaction Rates in Salt-Aqueous Binary and Salt-Aqueous-Nonaqueous Ternary Systems

WANG Feng-Yun, YU Bo-Heng, CHEN Min-Sheng, YE Jing-Xian, JIN Jia-Jun   

  1. Department of Chemistry, Nanjing University of Science and Technology, Nanjing, 210014
  • Received:1992-10-29 Revised:1993-02-10 Online:1993-09-24 Published:1993-09-24

PDF (PC)

被引次数

1

摘要： 从溶质-溶剂间的造腔、静电、非静电、排斥及氢键等相互作用出发,本文根据过渡状态理论计算了乙酸乙酯皂化反应在一系列浓度的H2O-NaCl、H2O-KCl、H2O-BaCl2、H2O-SrCl2水-盐二元体系中和氯代叔丁烷溶剂解反应在一定组成的H2O-DMSO-MX、H2O-Me2CO-MX、H2O-MeOH-MX、H2O-EtOH-MX(MX=NaCl,NaNO3,LiClO4)水-有机溶剂-盐三元体系中的动力学速率常数,大多数溶剂体系的计算结果与文献值颇相符.还讨论了理论公式、计算结果及各相互作用项的贡献.

关键词: 混合溶剂, 乙酸乙酯, 氯代叔丁烷, 盐效应, 速率常数

Abstract: Considering the contributions from the cavity formation, non-electrostatic (induction and dispersion), electrostatic (i.e.ion-ion, ion-dipole, dipole-dipole), repulsion (hard-sphere and electrostatic) and the hydrogen bond interactions between the solute and the solvent particles, this paper is a prediction of the rate constants for alkaline hydrolysis reaction of ethyl-acetate in a series of H2O-NaCl, H2O-KCl, H2O-BaCl2, H2O-SrCl2 systems, and for solvolysis reaction of t-BuCl in some compositions of H2O-DMSO-MX, H2O-Me2CO-MX, H2O-MeOH-MX, H2O-EtOH-MXsystems (where MX = NaCl, NaNO3, LiClO4).For most of the systems, the calculated results are in good agreement with those from literatures.Adiscussion on the formula used, the results obtained and the contributions from each interactions is given at the end briefly.

Key words: Mixed solvent, Ethyl-acetate, t-BuCl, Salt effect, Reaction rate constant

TrendMD: