HXCO（X＝F、Cl）解离和异构通道中的取代基效应  

The Substitution Effects on Dissociation and Isomerization of HXCO(X=F,Cl)

作　　者：陈德展[1] 陈宝吉 居冠之[1] 

机构地区：[1]山东师范大学化学系,南京大学化学化工学院

出　　处：《Chinese Journal of Chemical Physics》1995年第4期347-353,共7页化学物理学报（英文）

摘　　要：本文在２００～１３００Ｋ温度范围内，计算了ＨＸＣＯ、ＸＣＯＨ和ＨＣＯＸ解离和异构化反应的Ｇｉｂｂｓ自由能改变、热效应、速度常数以及Ｗｉｇｎｅｒ校正系数，讨论了取代基对反应的热力学和动力学参量的影响。结果表明：（１）取代基对反应的热力学量和速度常数影响较大，但影响结果因反应机理不同而异；（２）当反应所断裂化学键不直接连接取代基，则取代基对隧道效应影响较小；（３）仅用电子能量判断分子的稳定性是不可靠的．Abstract The changes of Gibbs' free energy (△G°), heat of reaction (△H °), rate constants, and Wigner's correCtion for dissociation and isomerization of HXCO, XCOH and HCOX have been calculated over the temperature interval 200-1300K.The influence of the substitute on the thermodynamic and kinetic properties has been analysed. Main results are as follows:(1)the substitute has great influence on the △G°, △H°,and the rate, the effects varing with the mechanism of reaction.(2)If the reaction do not involve the chemical bond which links the substitute, the suboitution effect on tunneling is much weak.(3)the molecular stability judged only by electronic energy is unreliable.

关 键 词：甲醛卤代物 解离 取代基效应 

分 类 号：O623.511[理学—有机化学]