摘要
用ＰＭ３－ＭＯ法对２－叠氮－１，３，５－三硝基苯的热解机理进行了计算研究，基于统计热力学和过渡态理论求得该反应的热力学和动力学参数。结果表明，“氧化呋咱”机理下的热解活化能（１０３．７５０ｋＪ／ｍｏｌ）比Ｃ—ＮＯ２均裂反应活化能（２０５．４１５ｋＪ／ｍｏｌ）小得多，且反应动力学参数的计算值与ＤＳＣ实测值相符。４００Ｋ以下Ｃ－ＮＯ２均裂反应的ΔＧθ值为负，热力学上可能发生，但速率常数为０ｓ－１。
The PM3 MO method has been employed to study the pyrolysis mechanism of picryl azide in this paper.Thermodynamical and kinetic parameters have been calculated with statistical method and transition state theory.The results show that the activation energy of “furoxan mechanism”(103 750kJ/mol)is much smaller than that(205 415kJ/mol)of C NO 2 homolysis.The calculated kinetic parameters(activation energy,frequency factor,and reaction rate constant) for “furoxan mechanism” are in very good agreement with the corresponding results from DSC experiments.From 200K to 400K,although the C NO 2 homolysis can occur thermodynamically (Δ G θ<0 ),its rate constant is 0s -1 .
出处
《爆炸与冲击》
EI
CAS
CSCD
北大核心
1999年第1期39-43,共5页
Explosion and Shock Waves
基金
中国工程物理研究院科学基金
关键词
三硝基苯
热解反应
热力学参数
动力学参数
Azido 1,3,5 trinitrobenzene, pyrolysis, PM3 method, thermodynamical parameters, kinetic parameters
