CH_(3)ONO与OH自由基的反应机理及动力学研究  

Study on the Reaction Mechanism and Kinetics of CH_(3)ONO with OH Radical

作　　者：赵晓霞 刘子忠[1,2,3] 赵瑞生 许天孜 ZHAO Xiao-xia;LIU Zi-zhong;ZHAO Rui-sheng;XU Tian-zi(College of Chemistry and Environmental Science,Inner Mongolia Normal University,Hohhot 010022,China;Key Laboratory of Green Catalysis of Inner Mongolia Autonomous Region,Hohhot 010022,China;Inner Mongolia Center of Applied Mathematics,Hohhot 010022,China)

机构地区：[1]内蒙古师范大学化学与环境科学学院,内蒙古呼和浩特010022 [2]内蒙古自治区绿色催化重点实验室,内蒙古呼和浩特010022 [3]内蒙古自治区应用数学中心,内蒙古呼和浩特010022

出　　处：《内蒙古师范大学学报（自然科学版）》2022年第6期614-621,共8页Journal of Inner Mongolia Normal University(Natural Science Edition)

基　　金：国家自然科学基金资助项目(21063009);内蒙古自治区高等学校科学研究资助项目(NJZY19023)。

摘　　要：采用Gaussian 09程序,在CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(2df,2p)理论水平下模拟了CH_(3)ONO+OH自由基的反应机理,并计算了各通道的反应速率常数。结果表明,CH_(3)ONO与OH自由基反应共有六条反应路径,其中有四条反应路径分两步反应完成。从反应势垒来看,cis-CH_(3)ONO+OH自由基反应比trans-CH_(3)ONO+OH自由基反应更容易在大气中反应,而且氢提取路径优于OH自由基加成路径。在298 K时H提取路径和OH自由基加成路径的反应速率常数比为k_(H)/k_(OH)=218.68,氢提取机制是CH_(3)ONO与OH自由基反应的主要机制,反应主产物为CH_(2)O、NO和H_(2)O。In this paper,we used Gaussian 09 to simulate the reaction mechanism of CH_(3)ONO+OH at the theoretical level of CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(2df,2p),and the reaction rate constants of each channel were calculated.The results showed that there were six reaction paths between CH_(3)ONO and OH radical,four of which were completed in two steps.From the reaction energy barrier,cis-CH_(3)ONO+OH reaction was easier to react in atmosphere than trans-CH_(3)ONO+OH reaction,and the hydrogen extraction path was better than the OH radical addition path.At 298K,the rate constant ratio of H extraction path and OH radical addition path was k_(H)/k_(OH)=218.68.Hydrogen extraction mechanism was the main mechanism of the reaction between CH_(3)ONO and OH radical,and the main products were CH_(2)O,NO and H_(2)O.

关 键 词：亚硝酸甲酯 氢提取 反应机理 动力学 

分 类 号：O622[理学—有机化学]