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

作     者：Yulei Guan Ying Zhang Chunhai Yi Bolun Yang 

作者机构：Department of Chemical Engineering State Key Laboratory of Multiphase Flow in Power Engineering Xi'an Jiaotong University Xi'an Shannxi 710049 China 

出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)

年 卷 期：2013年第31卷第8期

页      面：1087-1094页

核心收录：

学科分类：07[理学] 08[工学] 070104[理学-应用数学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 0701[理学-数学] 

基　　金：support of this work by the National Basic Research Program of China (973 Program) 国家教育部高等学校博士学科点专项科研基金 国家自然科学基金 

主　　题：free radical initial decomposition mechanism computational chemistry hydrogen-abstraction bimol-ecular 

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.