硝酸酯类的量子化学研究一一硝化甘油的热解机理

兵工学报 ›› 1992, Vol. 13 ›› Issue (1): 41-46.

硝酸酯类的量子化学研究一一硝化甘油的热解机理

肖鹤鸣、王大喜

华东工学院

收稿日期:1990-04-01 修回日期:1991-01-01 上线日期:2014-12-25
通讯作者: 肖鹤鸣

Quantum Chemical Studies on the Nitrate Esters—Trinitroglycerin and Mechanisms of Its Thermal Decomposition

Xiao Heming, Wang Daxi

East China Institute of Technology

Received:1990-04-01 Revised:1991-01-01 Online:2014-12-25
Contact: Xiao Heming

摘要/Abstract

摘要： 用量子化学方法对硝化甘油(NG)及其热解机理进行了研究。用能量梯度全优化计算获得NG的平衡几何构型，其生成热(-363.34kJ／mol)与实验值(一370.82kJ／mol)相一致。计算发现NG分子中O- NO2键的Wiberg键级(WON)最小，推测NG在热解过程中O- N02键有可能优先断裂。计算出NG热裂解和β-H转移消除反应位能曲线。求得β-H转移消除反应活化能为177.32kJ／mol讲，介于实验测定值107.86～209.20kj／mol之间。

关键词: 量子化学, 硝化甘油, 平衡几何构型, 热解机理

Abstract: Trinitroglycerin (NG) and its thermal decomposition have been studied with the quantum-chemical method. The equilibrium geometry is obtained by optimization using MINDO/3 energy gradient method. Calculated heat of formation ( — 363. 34kJ/mol) agrees fairly well with the result of experiment (—370. 82kJ/mol). It is found that Wiberg bond order of the O—N02 bond is smallest among all the bond types of NG. This suggests that the O — N02 bond is liable to be among the foremost to break during decomposition. The potential energy curves of the decompositions and β-H transition elimllation reaction were calculated for NG. The activation energy of the elimiiation reaction was found to be 177. 32kJ/mol which lies between the experimental values (107. 86?209. 20kJ/mol).

Key words: quantum chemistry, trinitrogiycerin, equilibrium geometry, decomposition mechanism

肖鹤鸣、王大喜. 硝酸酯类的量子化学研究一一硝化甘油的热解机理[J]. 兵工学报, 1992, 13(1): 41-46.

Xiao Heming, Wang Daxi. Quantum Chemical Studies on the Nitrate Esters—Trinitroglycerin and Mechanisms of Its Thermal Decomposition[J]. Acta Armamentarii, 1992, 13(1): 41-46.

[1]	齐晓飞1，张晓宏1，李吉祯1，刘芳莉1，宋振伟1，张军平2. NC/NG共混体系的分子动力学模拟研究[J]. 兵工学报, 2013, 34(1): 93-99.
[2]	胡国胜，王大喜. l,l'-DM-5,5'-AT和2,2'-DM-5,5'-AT热分解机理的量子化学研究[J]. 兵工学报, 2005, 26(4): 453-459.
[3]	胡国胜，王大喜. l,l'-DM-5,5'-AT和2,2'-DM-5,5'-AT结构及其热稳定性的量子化学研究[J]. 兵工学报, 2005, 26(4): 460-464.
[4]	林信云. 用分析仪快速测定硝化甘油化学安定性的试验研究[J]. 兵工学报, 1992, 13(4): 21-27.
[5]	王大喜、邓森元、刘靖疆. 某些二元硝胺水解机理的量子化学研究[J]. 兵工学报, 1989, 10(2): 19-25.