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.
出处
《化学推进剂与高分子材料》
CAS
2017年第6期78-81,共4页
Chemical Propellants & Polymeric Materials
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
density functional theory
nitroglycerin
catalytic decomposition
reaction rate constant
NEPE solid propellant
