硝化甘油自催化初始分解反应机理研究  

Research on auto-catalytic initial decomposition reaction mechanism of nitroglycerin

作　　者：丁超 吴婉娥 裴海潮 王明良[2] 

机构地区：[1]火箭军工程大学,陕西西安710025 [2]深圳大学化学与化工学院,广东深圳518060

出　　处：《化学推进剂与高分子材料》2017年第6期78-81,共4页Chemical Propellants & Polymeric Materials

摘　　要：采用密度泛函理论在B3LYP/6–31+G(d,p)水平上对推断的硝化甘油自催化分解反应进行了模拟计算。计算结果表明:NO_2自由基催化硝化甘油的分解反应第一步分为2种,即α和β位夺氢催化反应,2种反应的反应能垒分别为105.337 kJ/mol和124.381 kJ/mol,证明α夺氢反应更易发生;α位夺氢的反应速率常数为1.701 4×10^(–26)cm^3/(mol·s),大约是β位夺氢反应的10 000倍,拟合的表观活化能相对要低18.36 kJ/mol,验证了能量结论,即α夺氢反应更加快速。The simulating calculation for the deduced auto-catalytic decomposition reaction of nitroglycerin was carried out by using the density functional theory at B3LYP/6-3 1＋G（d, p） level. The calculating results show that the first step of decomposition reaction of nitroglycerin catalyzed by NO2 free radical is divided into two types, namely a-position and fl-position catalytic hydrogen abstraction reactions. The reaction energy barriers of above two reactions are 105.337 kJ/mol and 124.381 kJ/mol respectively, proving that the a-position hydrogen abstraction reaction is more likely to occur. The rate constant of the a-position hydrogen abstraction reaction is 1.701 4× 10.26 cm3/（mol.s） which is about 10 000 times of that of β-position hydrogen abstraction reaction. The fitting apparent activation energy relatively lowers 18.36 kJ/mol. The energy conclusions were verified, namely, the a-position hydrogen abstraction reaction is more quick.

关 键 词：密度泛函理论 硝化甘油 催化分解 反应速率常数 NEPE固体推进剂 

分 类 号：V512[航空宇航科学与技术—航空宇航推进理论与工程]