苯基与乙炔加成反应动力理论研究  

Kinetic Study of Phenyl and Acetylene Addition Reaction

作　　者：王朝晖 张凤[1] WANG Zhao-Hui;ZhANG Feng(National Synchrotron Radiation Laboratory,University of Science and Technology of China,Hefei 230029,China)

机构地区：[1]中国科技大学国家同步辐射实验室,合肥230029

出　　处：《工程热物理学报》2020年第5期1222-1228,共7页Journal of Engineering Thermophysics

基　　金：国家自然科学基金(No.91541112);中央高校基本科研基金专项资金资助(No.WK2320000038)。

摘　　要：使用RRKM-主方程计算了乙炔加成到苯基上的反应的详细温度压力依赖速率常数,计算结果表明在HACA机理中,乙炔与苯基的加成反应具有强烈的压力依赖效应。在一个大气压或者更低的压力下,当温度高于1800 K时,C8H7自由基如2-苯基乙烯基和2-乙烯基苯基将不能稳定存在。因此在这种条件下,Bittner-Howard HACA路径和改性的Frenklach HACA路径都将不能发生,只有在相对高压或者低温的条件下,这些路径才是可行的。而原始的Frenklach HACA路径除了在高温段具有绝对的优势地位外,在一个大气压或者更低的压力,温度1200 K以上时都具有重要的影响。Detailed temperature and pressure dependent rate constants of phenyl and acetylene addition reaction were calculated under RRKM-ME theory.Results show that pressure dependence has strong influence on the reaction in HACA mechanism.C8H7 radicals,such like 2-phenyl-vinyl radical and 2-vinyl-phenyl radical,are not stable under 1 atm or lower pressure and 1800 K or higher temperature and Bittner-Howard HACA route and modified-Frenklach HACA route are both important at this situation.Only at relatively high pressure and lower temperature,Bittner-Howard HACA route and modified-Frenklach HACA route will be relatively important.However,the traditional Frenklach HACA route is not only dominate at high temperature,but also important at 1 atm or lower pressure and 1200 K or higher temperature.

关 键 词：氢-提取-乙炔-加成(HACA)机理 燃烧动力学模型 多环芳烃 速率常数 RRKM/主方程 

分 类 号：O643.12[理学—物理化学]