硝酸异丙酯与Cl原子、OH和NO_(3)自由基反应的机理及动力学  

Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl,OH and NO_(3) Radicals

作　　者：孙翠红[1] 吕立强[1] 刘迎 王妍 杨静 张绍文 SUN Cuihong;LYU Liqiang;LIU Ying;WANG Yan;YANG Jing;ZHANG Shaowen(College of Chemical Engineering,Shijiazhuang University,Shijiazhuang 050035,China;School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 100081,China)

机构地区：[1]石家庄学院化工学院,石家庄050035 [2]北京理工大学化学与化工学院,北京100081

出　　处：《高等学校化学学报》2022年第2期70-76,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21673018,21603152);河北省人力资源与社会保障厅项目(批准号:A202001079);河北省高等学校科学技术研究项目(批准号:Z2018015);石家庄学院河北省杂环类化合物技术创新中心项目(批准号:SG2021122)资助。

摘　　要：采用CCSD(T)//M06-2X/6-311++G(d,p)方法,结合传统过渡态理论,研究了硝酸异丙酯与Cl原子、OH及NO_(3)自由基的反应机理和动力学.两个反应物单体首先形成氢键复合物,随后X(X=Cl原子、OH和NO_(3)自由基)提取硝酸异丙酯中叔碳的α-H原子或甲基的β-H原子,室温下,以X提取α-H原子为主.反应的主要历程为Cl原子(OH或NO_(3)自由基)提取(CH_(3))_(2)CHONO_(2)的α-H原子,生成HCl(H_(2)O或HNO_(3))分子和(CH_(3))_(2)CONO_(2)自由基,后者分解为丙酮和NO_(2).结果表明,在200~500 K温度范围内,随着温度的升高,丙酮和NO_(2)的产率降低;在室温下,硝酸异丙酯与Cl原子、OH和NO_(3)自由基反应的速率常数分别为3.933×10^(-11),1.182×10^(-13)和7.134×10^(-19)cm^(3)·molecule^(-1)·s^(-1).计算所得硝酸异丙酯与OH自由基反应的动力学数据与实验结论一致.The reaction mechanism of(CH_(3))_(2)CHONO_(2) with X(X=Cl,OH and NO_(3) radical)was studied at M06-2X/6-311++G(d,p)level of theory,and the energy of the stationary points was calculated by CCSD(T)method.The kinetics of the reaction was calculated by the conventional transition state theory.The hydrogen bonded complexes are formed firstly by isopropyl nitrate and X radical,and X radical can abstract theα-H orβ-H atoms from(CH_(3))_(2)CHONO_(2).Theα-H abstraction is the main channel,and the main products are(CH_(3))_(2)CO+NO_(2)+HCl(H_(2)O or HNO_(3)).The yield ofα-H abstraction products decreases as the temperature increases from 200 K to 500 K for IPN+OH reaction.The overall rate constant for the reaction of(CH_(3))_(2)CHONO_(2) with Cl atom,OH and NO_(3) radical at 300 K is 3.933×10^(−11),1.182×10^(−13),and 7.134×10^(−19) cm^(3)·molecule^(−1)·s^(−1),respectively.The theoretical kinetics data is in consistent with the previous experimental values for the reaction of OH with isopropyl nitrate.

关 键 词：硝酸异丙酯 自由基 反应机理 动力学 

分 类 号：O641[理学—物理化学] O643.12[理学—化学]