时间参量法(Ⅵ)——连续一级反应的热动力学研究  

Time-parameter Method(Ⅵ) Studies on Thermokinetics for Consecutive First-order Reactions

作　　者：陈勇[1] 汪海东[1] 李延团[1] 曾宪诚[1] 

机构地区：[1]四川大学化学学院,成都610064

出　　处：《高等学校化学学报》2001年第11期1852-1855,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 98730 31)资助

摘　　要：根据化学反应热动力学的基本原理 ,推导了连续一级反应的积分和微分热动力学方程 ,建立了连续一级反应热动力学时间参量法的数学模型 ,通过对己二酸二乙酯和邻苯二甲酸二乙酯皂化反应的热动力学研究 。According to the theoretical basis of thermokinetics, the integral and differential thermokinetic equations of consecutive first order reaction have been deduced, and the mathematical models of the time parameter method for consecutive first order reaction have been established in this paper. Only needing the characteristic time parameter t m, 2 t m and 3 t m and the corresponding thermoanalytical data from the same curve, the rate constants of the two steps can be determined simultaneously. Additionally, a novel method to determine the values of d Δ /d t by using the time parameter t m, the peak height Δ m at time t m and the total area of the curve, rather than by the use of slop from thermoanalytical curve at time t with differential method, is proposed. The thermokinetics of saponifications of diethyl phthalate and diethyl adipate in aqueous ethanol solvent has been studied and the validation of the theory and method of the time parameter method for consecutive first order reactions is verified by the experimental results.

关 键 词：热动力学 时间参量法 连续一级反应 皂化反应 已二酸二乙酯 化学反应 邻苯二甲酸二乙酯 

分 类 号：O643.1[理学—物理化学] O621.256.5[理学—化学]