Understanding the Initial Decomposition Pathways of the n-Alkane/Nitroalkane Binary Mixture  

作　　者：Yulei Guan Ying Zhang Chunhai Yi Bolun Yang 

机构地区：[1]Department of Chemical Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, Shannxi 710049, China

出　　处：《Chinese Journal of Chemistry》2013年第8期1087-1094,共8页中国化学（英文版）

摘　　要：Addition of nitroalkanes into n-alkanes can lower the activation barriers of free-radical production and acceler- ate the decomposition of n-alkanes at relatively low temperatures. Four initial decomposition mechanisms of the n-butane/nitroethane binary mixture were proposed for the promoting effect and considered theoretically at the B3LYP, BB1K, BMK, MPW1K, and M06-2X levels with MG3S basis set. Energetics above was compared to high-level CBS-QB3 and G4 calculations. Calculated results confirm the feasibility of the four initial decomposition pathways： （I） the C--NO2 bond rupture of nitroethane to produce ethyl and .NO2, （II） HONO elimination from nitroethane followed by decomposition to .OH and .NO, （1II） rearrangement of nitroethane to ethyl nitrite which further dissociates into CH3CH20. and .NO, and （IV） direct hydrogen-abstraction ofnitroethane with n-butane.Addition of nitroalkanes into n-alkanes can lower the activation barriers of free-radical production and acceler- ate the decomposition of n-alkanes at relatively low temperatures. Four initial decomposition mechanisms of the n-butane/nitroethane binary mixture were proposed for the promoting effect and considered theoretically at the B3LYP, BB1K, BMK, MPW1K, and M06-2X levels with MG3S basis set. Energetics above was compared to high-level CBS-QB3 and G4 calculations. Calculated results confirm the feasibility of the four initial decomposition pathways： （I） the C--NO2 bond rupture of nitroethane to produce ethyl and .NO2, （II） HONO elimination from nitroethane followed by decomposition to .OH and .NO, （1II） rearrangement of nitroethane to ethyl nitrite which further dissociates into CH3CH20. and .NO, and （IV） direct hydrogen-abstraction ofnitroethane with n-butane.

关 键 词：free radical initial decomposition mechanism computational chemistry hydrogen-abstraction bimol-ecular 

分 类 号：O159[理学—数学] TQ325.304[理学—基础数学]