摘要
采用量子化学从头算方法全优化计算了1,1′二甲基5,5′偶氮四唑(1,1′DM5,5′AT)和2,2′二甲基5,5′偶氮四唑(2,2′DM5,5′AT)热分解反应位能曲线,探讨了它们的热分解机理。研究发现热分解按开环和脱氮两步完成,推测的机理可由取代四唑的热分解实验和理论研究所支持。计算得到1,1′DM5,5′AT两步反应的活化能分别为243.5、64.01kJ/mol;2,2′DM5,5′AT两步反应的活化能分别为152.3、44.67kJ/mol.二者的热分解活化能都表明开环反应是速度控制步骤。前者的两步反应的活化能均大于后者的活化能。从动力学性质显示前者比后者有更好的稳定性。
The potential curves of thermal decomposition for 1, 1＇-dimethy-5, 5＇-azotetrazole （1, 1＇-DM-5, 5＇-AT） and 2, 2＇-dimethyl-5, 5＇-azotetrazole （2, 2＇-DM-5, 5＇-AT） were calculated by use of ab initio calculation of quantum chemistry method, their decomposition mechanisms were explored. The thermal decompositions were accomplished in two steps, that is, opening ring and denitrification. Predicting mechanisms can be supported by the thermal decomposition experimental and theoretical results for substitution of tetrazole. The decomposition activation energies of two steps are 243.5 and 64.01 kJ/mol respectively for 1, 1＇-DM-5, 5＇-AT. The decomposition activation energies of two steps are 152.3 and 44.67 kJ/mol respectively for 2, 2＇-DM-5, 5＇-AT. Opening ring reaction for two compounds controls the decomposition rate. The two-step decomposition activation energies of 1, 1＇-DM-5, 5＇-AT are larger than that of 2, 2＇-DM-5, 5＇-AT. The thermal stability of 1, 1＇-DM-5, 5＇-AT is better than 2, 2＇-DM-5, 5＇-AT, as indicated by dynamics.
出处
《兵工学报》
EI
CAS
CSCD
北大核心
2005年第4期453-459,共7页
Acta Armamentarii
关键词
物理化学
量子化学
二甲基偶氮四唑
热稳定性
热分解机理
位能曲线
physicochemistry
quantum chemistry
dimethyl azotetrazole
thermal stability
thermal decomposition mechanism
potential curve
