物理化学学报 >> 2008, Vol. 24 >> Issue (04): 576-580.doi: 10.1016/S1872-1508(08)60025-X

研究论文 上一篇    下一篇

三硝基间苯三酚5-氨基四唑盐的晶体结构及热分解

胡晓春; 张同来; 乔小晶; 杨利; 张建国; 崔燕; 张进   

  1. 北京理工大学机电工程学院, 爆炸科学与技术国家重点实验室, 北京 100081; 防化指挥工程学院三系, 北京 102205; 防化研究院六所, 北京 102205
  • 收稿日期:2007-12-05 修回日期:2007-12-12 发布日期:2008-04-07
  • 通讯作者: 张同来 E-mail:ztlbit@bit.edu.cn

Crystal Structure and Thermal Decomposition of 5-Aminotetrazole Trinitrophloroglucinolate

HU Xiao-Chun; ZHANG Tong-Lai; QIAO Xiao-Jing; YANG Li; ZHANG Jian-Guo; CUI Yan; ZHANG Jin   

  1. State Key Laboratory of Explosion Science and Technology, School of Mechano-Electronic Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China; The 3rd Department, Institute of Chemical Defense, Beijing 102205, P. R. China; The 6th Department, Research Institute of Chemical Defense, Beijing 102205, P. R. China
  • Received:2007-12-05 Revised:2007-12-12 Published:2008-04-07
  • Contact: ZHANG Tong-Lai E-mail:ztlbit@bit.edu.cn

摘要: 制备得到标题化合物并对其进行了元素分析与红外光谱分析. 用X射线衍射方法测得其晶体结构属于正交晶系, 空间群Pbca, 晶胞参数a=0.6624(2) nm, b=1.7933(4) nm, c=2.3117(5) nm, V=2.7458(9) nm3, Z=4, Dc=1.849 g·cm-3. 其分子式可写作(ATZ)TNPG·2H2O. 5-氨基四唑阳离子(ATZ+)和三硝基间苯三酚阴离子(TNPG-)通过氢键在b轴和c轴方向上联成二维层面, 然后在a轴方向通过不同层中的水分子之间的氢键联接起来. 用差示扫描量热法(DSC), TG-DTG结合傅立叶变换红外光谱(FT-IR)分析了其热分解过程. 在氮气气氛下用10 ℃·min-1的升温速率测定发现,该化合物经历一个峰温为76 ℃的吸热过程及一个峰温为203 ℃的放热过程. 前者为脱除结晶水的过程, 后者为产物中的TNPG-与ATZ+的热分解过程, 放热的焓变为-212.10 kJ·mol-1. 对该过程估算动力学参数: 采用Kissinger法得活化能E=132.1 kJ·mol-1, ln (A/s-1)=12.54, r=0.9990; 采用Ozawa-Doyle法得E=133.1 kJ·mol-1, r=0.9992.

关键词: 三硝基间苯三酚, 5-氨基四唑, TNPG, 制备, 晶体结构, 热分解

Abstract: 5-Aminotetrazole trinitrophloroglucinolate ((ATZ) TNPG) was prepared and characterized by elemental analysis and FT-IR spectroscopy. The crystal structure was determined by X-ray diffraction analysis and it belonged to orthorhombic systemand Pbca space group with a=0.6624(2) nm, b=1.7933(4) nm, c=2.3117(5) nm, V=2.7458(9) nm3, Z=4, and Dc=1.849 g·cm-3. The molecular formula was confirmed to be (ATZ)TNPG·2H2O. 5-Aminotetrazole cation (ATZ+) and trinitrophloroglucinol anion (TNPG-) were linked into 2-Dlayers along b-axis and c-axis by hydrogen bonds. Then the layers were linked along a-axis by hydrogen bonds between the water molecules belonging to different layers. The thermal decomposition mechanism of the compound was studied by differential scanning calorimetry (DSC), thermogravimetry-thermogravimetric analysis (TG-DTG), and Fourier transform-infrared (FT-IR) spectroscopy techniques. Under nitrogen atmosphere with a heating rate of 10 ℃·min-1, the compound experienced one endothermic process with peak temperature of 76 ℃ and one exothermal process with peak temperature of 203 ℃. The former was confirmed to be a dehydrate process. The latter was the decomposition of TNPG- and ATZ+ in the compound. The exothermic enthalpy change of this process was -212.10 kJ·mol-1. The kinetic parameter calculation from Kissinger’s method were, E=132.1 kJ·mol-1, ln (A/s-1)=12.54 with r=0.9990, and the calculation results from Ozawa-Doyle’s method were, E=133.1 kJ·mol-1 with r=0.9992.

Key words: Trinitrophloroglucinol, ATZ, TNPG, Preparation, Crystal structure, Thermal decomposition

MSC2000: 

  • O641