较快一级化学反应的热动力学研究法—热弛豫法  

Thermokinetic Research Method for Faster First- order Reactions -- The Thermal Relaxation Method

作　　者：孟祥光[1] 曾宪诚[1] 程四清[1] 陈勇[2] 

机构地区：[1]四川大学化学学院, [2]后勤工程学院油料应用工程系,

出　　处：《化学学报》2001年第12期2132-2137,共6页Acta Chimica Sinica

基　　金：国家自然科学基金

摘　　要：分析了非稳态传热情况下热导式热量计的动态性能,通过对热输出信号的剖析,建立了热导式热量计冷却常数的经验动态模型.通过对热弛豫现象的分析,建立了可用于研究快速化学反应的热动力学研究法--热弛豫法,应用此种量热研究法可用于研究速率常数小于5 s-1的一级化学反应.研究了25℃下乙酸甲酯、甲酸乙酯和甲酸甲酯在水溶液中的皂化反应,其计算结果与文献值相吻合,从而验证了热弛豫法的正确性.The transient heat transport property of conduction calorimeter is dissected and the experimental time-dependent cooling constant model of the conduction calorimeter is established in this paper. The thermal relaxation method proposed in this paper can be used to determine the faster reactions whose first-order rate constant could be less than 5 s(-1) with the calorimetric technique. In order to test the validity of this method, the saponification of methyl acetate, ethyl formate and methyl formate in aqueous solution at 25 degreesC has been studied. The rate constants calculated with this method are in agreement with those in the literatures. Therefore, the thermal relaxation method is believed to be correct.

关 键 词：热弛豫法 热动力学研究法 非稳态传热 一级反应 热导式热量计 化学反应 

分 类 号：O643.1[理学—物理化学]