焓-熵补偿的热力学解释  

Thermodynamic Interpretation of Enthalpy-Entropy Compensation

作　　者：赖国华[1] 周仁贤[1] 韩晓祥[1] 郑小明[1] 

机构地区：[1]浙江大学催化研究所

出　　处：《化学通报》2005年第12期928-934,共7页Chemistry

摘　　要：采用热力学方法考察了相变过程、化学反应以及其它相关过程中可能存在的焓熵补偿。补偿效应可以简单地分为两种类型———温度扰动引起的补偿和其它参数引起的补偿。温度扰动引起的补偿方程如下:ΔH(T2)=ΔCpΔCT1ΔS(T2)+ΔH(T1)-ΔCpΔCT1ΔS(T1)其它参数引起的补偿方程具有相同的形式:ΔH=TΔS-ΔVβ讨论了补偿温度、多参数扰动及补偿效应成立的条件。结果表明,焓变和熵变存在着热力学上的固有联系,其是否表现出线性补偿关系则与体系的细致过程有关。The enthalpy-entropy compensation was thermodynamically examined in the phase changes, chemical reactions and other analogous processes. The compensation may be simply divided into two types. One results from the disturbance of the temperature, and another results from the disturbance of the other parameters. The equation of the compensation caused by the temperature disturbance was given as follows：△H（T2）=△Cp/△CT1△S（T2）＋[△H（T1）-△Cp/△CT1△S（T1）] The equation of the compensation caused by the disturbance of other parameters had an identical form ：△H=T△S-△V/β The compensation temperature, the multiple parameters disturbance, and the conditions of the linear enthalpy-entropy compensation were discussed. It is clear that there is an intrinsic relation between enthalpy and entropy thermodynamically, but whether the enthalpy-entropy compensation is linear is related to the detail process of the system.

关 键 词：解释 焓-熵补偿 线性关系 

分 类 号：O642[理学—物理化学]