卤代苯甲酸在水-乙醇混合溶剂中和在气相中的质子迁移反应的比较(英文)

A Study of the Proton Transfer of Five Halobezoic Acids in Water-ethanol Mixtures Compared with the Same Process in the Gaseous Phase

将在水 乙醇混合溶剂中从卤代苯甲酸到苯甲酸的质子迁移过程与在气相中的同一过程进行了比较 .用一个热力学循环计算了在从气相初始状态到混合溶剂某一组成X时该质子迁移过程的热力学函数的变化 ,即δΔPig→X.这一项的值被作为质子迁移过程中卤代苯甲酸分子 ,离子和溶剂间的相互作用的外部贡献的一种量度 .但是 ,对于邻位卤代苯甲酸 ,由于位阻效应的存在 ,δΔPig→X值不能作为外部贡献的量度 .

A study of the proton transfer process from halobenzoic acids to benzoic acid in water-ethanol mixtures compared with the same process in the gaseous phase is presented. A thermodynamic cycle was used to calculate in solvent X a proton transfer process which refers to an initial gaseous thermodynamic state, i.e. δΔPiR-X. By using these values, it is possible to calculate the 'external' interactions of the above cited processes for meta and para halobenzoic acids. But for the ortho halobenzoic acids, the values of δΔPiR-X can not be used to represent the corresponding 'external' interactions due to steric effect.