关键词: 溶剂化, 近临界水, 水解

Abstract: 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 kc, which can be utilized to correct the effect of pressure on reaction kinetics, also S_N2 reaction mechanism can be validated from several aspects.

Key words: Solvation, Near critical water, Hydrolysis