化学学报 ›› 2012, Vol. 0 ›› Issue (05): 585-590 .DOI: 10.6023/A1106104 上一篇    下一篇

研究论文

烷基环己烷夺氢反应类的动力学研究

王苏川a, 李军a, 朱权a, 李泽荣b, 李象远a   

  1. a 四川大学化工学院 成都 610065;
    b 四川大学化学学院 成都 610064
  • 收稿日期:2011-06-10 修回日期:2011-10-10 出版日期:2012-03-14 发布日期:2012-03-17
  • 通讯作者: 朱权 E-mail:qzhu@scu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 91016002, 20903067)和留学回国人员科研启动基金(No. 20111139-10-10)资助项目.

Investigations on the Kinetics for the Reaction Class of Hydrogen Abstractions from Substituted Cyclohexane by Hydrogen Atom

Wang Suchuana, Li Juna, Zhu Quana, Li Zerongb, Li Xiangyuana   

  1. a College of Chemical Engineering, Sichuan University, Chengdu 610065;
    b College of Chemisitry, Sichuan University, Chengdu 610064
  • Received:2011-06-10 Revised:2011-10-10 Online:2012-03-14 Published:2012-03-17
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Project Nos. 91016002, 20903067) and the Ministry of Education Returned Scientific Research Foundation (Project No. 20111139-10-10).

应用反应类过渡态理论(RC-TST)研究了氢自由基抽取烷基环己烷氢的反应类, 给出了该类反应的动力学参数.通过研究该反应类中的14 个代表反应, 分析得到了RC-TST 方法所需要的各种参数, 建立了该类反应的线性能量关系式(LER). 应用RC-TST/LER 方法计算得到速率常数与TST/Eckart 方法计算结果吻合很好, 分析表明RC-TST/LER 方法对于准确预测夺氢反应类的速率常数十分有效, 可以节约大量计算成本.

关键词: 环己烷, 氢提取, 反应类过渡态理论, 速率常数, 线性能量关系

This work presents an application of the reaction class transition state theory (RC-TST) to predict kinetics parameters for hydrogen abstraction reactions of the substituted cyclohexane. All parameters for the RC-TST method of this reaction class were derived from the 14 representative reactions in this class. And the linear energy relationship (LER) was also established. The rate constants for selected reactions predicted by the RC-TST/LER are in good agreement with those calculated with TST/Eckart method. Compared with results from the TST/Eckart calculations, the RC-TST/LER method is found to be quite efficient and time-saving.

Key words: cyclohexane, hydrogen abstraction, reaction class transition state theory, rate constant, linear energy relationship