N2O5/HNO3体系中硝解DADN的反应动力学

doi:10.3969/j.issn.0438-1157.2013.04.021

化工学报 ›› 2013, Vol. 64 ›› Issue (4): 1269-1275.DOI: 10.3969/j.issn.0438-1157.2013.04.021

• 催化、动力学与反应器 • 上一篇下一篇

N₂O₅/HNO₃体系中硝解DADN的反应动力学

何志勇¹, 罗军¹, 吕春绪¹, 徐容², 李金山²

1. 南京理工大学化工学院,江苏南京 210094;
2. 中国工程物理研究院化工材料研究所,四川绵阳 621900

收稿日期:2012-06-28 修回日期:2012-10-30 出版日期:2013-04-05 发布日期:2013-04-05
通讯作者: 罗军
作者简介:何志勇(1975—),男,博士研究生,高级工程师。
基金资助:
国家自然科学基金项目(10976014)。

Nitrolysis kinetics of DADN by N₂O₅/HNO₃

HE Zhiyong¹, LUO Jun¹, LV Chunxu¹, XU Rong², LI Jinshan²

1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, Jiangsu, China;
2. Institute of Chemical Materials, CAEP, Mianyang 621900, Sichuan, China

Received:2012-06-28 Revised:2012-10-30 Online:2013-04-05 Published:2013-04-05
Supported by:
supported by the National Natural Science Foundation of China(10976014).

摘要/Abstract

摘要： 采用高效液相色谱跟踪检测了不同温度条件下N₂O₅/HNO₃体系硝解DADN时反应底物、中间体和产物浓度随时间的变化情况。通过对303、313、323、333 K温度下实验数据的分析,计算得到各步的反应速率常数,并最终求得DADN到SEX和SEX到HMX两步的反应活化能分别为2.3996×10⁴ J·mol^-1和1.6598×10⁴ J·mol^-1,指前因子分别为2.2000×10⁴ h^-1和6.5178×10² h^-1。同时,通过柱分离得到的中间产物经结构鉴定为SEX,对其硝基机理进行了分析,实验证明DADN的硝解反应分两步进行,是一级连串反应过程,控制步骤是SEX到HMX。

关键词: N₂O₅, DADN, SEX, HMX, 硝解, 反应动力学

Abstract: Concentrations of reactant, intermediate, product were measured by HPLC during nitrolysis of DADN(1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane) by N₂O₅/HNO₃ at temperatures of 303, 313, 323, and 333 K.Based on the mechanism of the nitrolysis reaction(first-order consecutive reaction), the kinetic parameters were calculated from these data obtained.The activation energies were 2.3996?10⁴ J穖ol^-1 for the first step(DADN to SEX(1-acetyl-3,5,7-trinitro-1,3,5,7-tetrazacyclooctane)) and 1.6598?10⁴ J穖ol^-1 for the second step(SEX to HMX(high melt point explosive)), and the pre-exponential factors were 2.2000?10⁴ h^-1 and 6.5178?10² h^-1, respectively.The reaction rate constant is larger for the fist step than for the second one. In order to check the intermediate in nitrolysis reaction of DADN, an experiment was carried out to separate and identify the intermediate(also by-product).The results indicate that this intermediate is SEX.

Key words: N₂O₅, DADN, SEX, HMX, nitrolysis, reaction kinetics

中图分类号:

O626

何志勇, 罗军, 吕春绪, 徐容, 李金山. N₂O₅/HNO₃体系中硝解DADN的反应动力学[J]. 化工学报, 2013, 64(4): 1269-1275.

HE Zhiyong, LUO Jun, LV Chunxu, XU Rong, LI Jinshan. Nitrolysis kinetics of DADN by N₂O₅/HNO₃[J]. CIESC Journal, 2013, 64(4): 1269-1275.

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N₂O₅/HNO₃体系中硝解DADN的反应动力学

Nitrolysis kinetics of DADN by N₂O₅/HNO₃

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