文献类型：期刊文献

英文题名：Effects of critical solvation on hydrolysis kinetics

作者：Yuan, PQ; Cheng, ZM; Liu, T; Yuan, WK

机构：[1]E China Univ Sci & Technol, Shanghai 200237, Peoples R China

年份：2003

卷号：24

期号：4

起止页码：690

外文期刊名：CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000182512000033)】；

语种：英文

外文关键词：solvation; near-critical water; hydrolysis

摘要：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 Inkappa(c), which can be utilized to correct the effect of pressure on reaction kinetics, also S(N)2 reaction mechanism can be validated from several aspects.