烷基环己烷夺氢反应类的动力学研究

摘要

Abstract 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.%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.