摘要
十氢化萘作为航空燃料中大分子烃的重要替代组分,其燃烧反应机理建立的重要性不可忽视。碳氢燃料的低温燃烧反应研究受到越来越广泛地关注。Boehma等人~1对十氢化萘的高中低温段反应进行了实验测量,Ranzi等人~2建立了十氢化萘的集总反应机理。现在迫切地需要十氢化萘低温燃烧反应的理论反应路径的计算。Violi等人~3对十氢化萘的开环裂解初始反应在BH&HLYP/6-31G(d,p)水平上进行了计算,但精度过低,也没有考虑氧的参与。本研究对十氢化萘的顺反异构体中低温燃烧的反应路径,在BH&HLYP/cc-pvdz水平上进行几何结构优化以及频率计算,用CBS-QB3方法做单点能计算。对相关基元反应,基于原子化焓方法计算得到了焓变,变分过渡态理论计算得到了高压极限反应速率常数,用RRKM/ME理论计算得到了压力依赖反应速率常数。计算所得的反应速率常数和所预测的反应路径可望应用于十氢化萘机理建立和模拟研究。
As an important arrogant of macromolecular hydrocarbon of aviation fuel, Decalin plays a critical role in establishing scientific combustion mechanism. Decalin was tested in experiments in a wide range of temperature by Hanson et al., Boehman et al. and He et al. Ranzi et al. established lumped reaction mechanism of decalin through previous experiments. Now a better understanding of theoretical kinetic modeling of decalin is in need. Ring-opening cracking initial reactions in BH&HLYP/6-31G(d,p) level were calculated by Violi et al. whose method is low precision and lack of oxidation reactions of decalin. This study detects cis-trans isomers of decalin in BH&HLYP/cc-pvdz level by doing optimization calculation and frequency calculation. Single point energy was calculated with CBS-QB3 method. Enthalpy change is based on the atomization enthalpy method. The high pressure limit rate constants for reactions were obtained by the transition state theory. The rate constants in the fall-off range for pressure-dependent reactions were obtained by RRKM/ME theory. Calculating the reaction rate constant and the predicted path could be applied to improve the kinetic modeling of decalin in the future studies.
引文
[1]Y.Yang;A.L.Boehman.Combust.Flame.2010,157:496-505.
[2]M.A.Oehlschlaeger;H.S.Shen;A.Frassoldati;S.Pierucci;E.Ranzi.Energy&Fuel.2009,23:1664-1472.
[3]K.Chae,A.Violi.J.Org.Chem.2007,72:3179-3185.