文献类型：期刊文献

中文题名：临界溶剂化作用对水解反应动力学的影响

英文题名：Effects of Critical Solvation on Hydrolysis Kinetics

作者：袁佩青[1];程振民[1];刘涛[1];袁渭康[1]

机构：[1]华东理工大学反应工程国家重点实验室,上海200237

年份：2003

卷号：24

期号：4

起止页码：690

中文期刊名：高等学校化学学报

外文期刊名：Chemical Journal of Chinese Universities

收录：CSTPCD;;Scopus;北大核心:【北大核心2000】；CSCD:【CSCD2011_2012】；

基金：国家重点基础研究发展规划 (973)项目 (项目编号 :G2 0 0 0 0 480 10 )

语种：中文

中文关键词：临界溶剂化作用;水解反应;动力学;过渡态;醋酸甲酯

外文关键词：Solvation; Near critical water; Hydrolysis

摘要：用过渡态及 Kirkwood介电模型考察近临界水中醋酸甲酯 ( Me Ac)水解动力学 .实验结果表明 ,临界溶剂化作用使本体系在 62 3 K附近出现反应活化体积 ( ΔV≠ )极负值现象 ,同时反应表观活化能降低至( 2 3 .5± 8.2 9) k J/ mol.利用 lnkc 与反应场的线性关系可修正压力因素对水解动力学的影响 ,并证实了近临界水介质中 Me Ac水解
The work presented in this paper focuses on employing Transition State Theory and Kirkwood dielectric model to interpret the solvation effects on hydrolysis of methyl acetate under near or supercritical conditions. The experimental data show that the apparent activation energy of hydrolysis is (23.5±8.29) kJ/mol, which is much lower than that obtained by using the conventional technique, the intricate solvation effects observed in the experiment may cause a minimum activation volume at the temperature near to the critical temperature, and the reaction field shows a good linear relationship with ln k c, which can be utilized to correct the effect of pressure on reaction kinetics, also S N2 reaction mechanism can be validated from several aspects.