高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (11): 1852.

• 研究论文 • 上一篇    下一篇

时间参量法(Ⅵ)——连续一级反应的热动力学研究

陈勇, 汪海东, 李延团, 曾宪诚   

  1. 四川大学化学学院, 成都 610064
  • 收稿日期:2000-04-12 出版日期:2001-11-24 发布日期:2001-11-24
  • 通讯作者: 曾宪诚(1939年出生),男,教授,博士生导师,从事热动力学及人工酶催化研究.
  • 基金资助:

    国家自然科学基金(批准号:29873031)资助

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

CHEN Yong, WANG Hai-Dong, LI Yan-Tuan, ZENG Xian-Cheng   

  1. Faculty of Chemistry, Sichuan University, Chengdu 610064, China
  • Received:2000-04-12 Online:2001-11-24 Published:2001-11-24

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,验证了连续一级反应时间参量法的正确性.

关键词: 热动力学, 热动力学研究法, 时间参量法, 连续一级反应

Abstract: 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 tm, 2 tm and 3 tm 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 /dt by using the time parameter tm, the peak height Δ m at time tm 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.

Key words: Thermokinetics, Thermokinetic research method, Time parameter method, Consecutive first order reactions

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