应用化学 ›› 2010, Vol. 27 ›› Issue (03): 308-312.DOI: 10.3724/SP.J.1095.2010.90163

• 研究论文 • 上一篇    下一篇

硝酸酯的热分解性能

王凤武,曾秀琳*,方文彦,李芬   

  1. (淮南师范学院化学系 淮南 232001)
  • 收稿日期:2009-03-06 修回日期:2009-05-18 出版日期:2010-03-10 发布日期:2010-03-10
  • 通讯作者: 曾秀琳,女,博士,讲师; E-mail:zengxlnj@yahoo.com.cn; 研究方向:物质结构和安全性能
  • 基金资助:
    安徽省自然科学基金(KJ2008B009)资助项目

Thermal Decomposition Characteristics of Nitrates

WANG Feng-Wu, ZENG Xiu-Lin*, FANG Wen-Yan, LI Fen   

  1. (Department of Chemistry,Huainan Normal University,Huainan 232001)
  • Received:2009-03-06 Revised:2009-05-18 Published:2010-03-10 Online:2010-03-10
  • Contact: WANG Feng-Wu WANG

摘要:

分别在B3LYP/6-31G*和MP2/6-31G*的理论水平下,计算得到硝酸正丙酯、硝酸异丙酯、硝酸异辛酯和二缩三乙二醇二硝酸酯4种硝酸酯的O-NO2键离解能(BDE)。 采用常压DSC和高压DSC实验方法,研究了4种硝酸酯的热分解过程,获得热分解反应动力学参数。 常压下4种物质的热分解反应发生在气相区,当压力增大至2 MPa时,4种物质直接发生液相分解反应。 4种硝酸酯的O—NO2键离解能在很大程度上符合由实验分析得到的活化能,表明4种硝酸酯的热分解反应只是单分子O—NO2键的均裂反应。

关键词: 硝酸酯,密度泛函理论,键离解能(BDE),高压DSC,热分解,活化能

Abstract:

At B3LYP/6-31G* and MP2/6-31G* levels, the bond dissociation energies(BDEs) of O—NO2 bond in four nitrates such as n-propyl nitrate(NPN), isopropyl nitrate(IPN), 2-ethylhexyl nitrate(EHN), and tri-ethylene glycol dinitrate(Tri-EGDN) were calculated. The thermal decomposition characteristics of NPN, IPN, EHN, and Tri-EGDN were investigated by means of ambient-pressure DSC and high-pressure DSC. Kinetic parameters of thermal decomposition were obtained. The results show that the thermal decomposition of four nitrates under ambientpressure occurred in gas phase. When the pressure increased up to 2 MPa, their decomposition processes occurred in liquid phase. According to the fact that the calculated results of O—NO2 BDEs of the four nitrates are in good agreement with the experimental results of apparent activation energies obtained from DSC, we deduce that the thermolysis of the four nitrates is only unimolecular homolytic cleavage of the O—NO2 bonds.

Key words: nitrates, density functional theory (DFT), bond dissociation energy (BDE), high-pressure DSC, thermal decomposition, activation energy

中图分类号: