摘要
用PM3－MO方法，基于热力学、统计热力学和反应速率过渡态理论，对2，4，6－三叠氮基－1，3，5－三硝基苯（TATNB）的热解反应机理进行了计算研究，求得各基元反应的反应物、产物和过渡态的全优化几何构型、电子结构和反应的热力学、动力学参数。结果表明，N－N_2断裂和C－NO_2自由基均裂反应活化能较高，TATNB的各步热解优先取“氧化呋咱”机理，且生成4，6－二叠氮基－3，5－二硝基本并氧化呋咱的第一步反应为速率控制步骤。还讨论了温度对TATNB热解的影响。
The thermolysis meeanism of 2, 4, 6-triando - 1, 3, 5-trinitrobere(TATNB)has been studied with PM3-MO method and by prindples of thermodynamies, statistical thermodyamics and transition state theory of reaction rate. The fully optimized geometries and electronic structures of reactant, thansition state, and product, and the thermodynamical and kinetic palametere for every elementary reacton of TATNB pyrolysis have been obtained. The calculated results show:(1) the activation energy of N-N_2 bond cleavage or C-NO_2 bond homlysis for TATNB pyrolysis is much larger than that of cydisation, so TATNB decomposes through the 'furoxan mechanism ,; (2) the first step that TATNB deremposes to 4, 6-diazido3, 5-dinitrobenzofuroxan is the controlling step. In addition, the influence of temerature on the TATNB thermolysis has been discussed.
基金
中国工程物理研究院科技基金!960539
关键词
三叠氮基
均三叠氮基
三硝基苯
热解
TATNB
BTF
2, 4, 6-triazido-1, 3, 5-trinitrobenzene
Pyrolysis
PM3 method
Thermodynamical parameters
Kinetic parameters
