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.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2003年第4期690-693,共4页
Chemical Journal of Chinese Universities
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 )
