热动力学对比参量法──简单级数反应  

Thermokinetically Reduced Parameter Method ──Simple Order Reaction

作　　者：陈勇[1] 蒋福宾[2] 谢家庆[3] 曾宪诚[1] 

机构地区：[1]四川大学化学学院,成都610064 [2]广西大学化学化工学院 [3]自贡师范高等专科学校化学系

出　　处：《高等学校化学学报》2000年第4期609-609,共1页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金! (批准号 :2 9873 0 3 1)

摘　　要：根据化学反应动力学和热动力学基本理论 ,建立了简单级数反应的热动力学对比参量方程 ,提出了一种新的热动力学研究法——对比参量法 .利用该法可以从一张热谱图上同时解析出化学反应的速率常数、半衰期和热动力学体系的冷却常数 .According to the theoretical basis of thermokinetics and chemical kinetics, the thermokinetically reduced parameter equation for simple order reaction has been derived and a novel thermokinetic research method, reduced parameter method, has been proposed in this paper. The mathematical models for determining the kinetic parameters and rate constants have been established. The method has simple principle and concise expression form. It only needs two time points and corresponding thermoanalytical data obtained from the same thermoanalytical curve measured by a calorimeter, both the half life time and the rate constant of studied reaction can conveniently be calculated. In the light of the reduced parameter method, a method to determine the cooling constants of calorimetric system by using the thermoanalytical data of reaction studied has been developed, which decrease the experimental errors of determining the kinetic parameter due to the difference of dynamic properties between the calorimetric measurement and the electric calibration. In order to test the validith of the reduced parameter method, the thermokinetics of the oxidation reaction of isopropyl alcohol by N bromosuccinimide(NBS) in aqueous acetic acid solvent, the saponification of ethyl acetate in aqueous ethanol solvent and the ring opening reaction of epichlorohydrin by hydrobromic acid in aqueous solution have been studied, respectively, the rate constants calculated with this method of reactions studied are in agreement with those published in the literature, and the reduced parameter method is therefore believed to be correct. [WT5HZ]

关 键 词：热动力学 对比参量法 简单级数反应 

分 类 号：O642.1[理学—物理化学] O643.1[理学—化学]