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1,4 - 二硝基哌嗪(DNP)的热分解及动力学研究

Thermal decomposition and kinetics studies on 1,4-dinitropiperazine (DNP).

作者信息

Yan Qi-Long, Li Xiao-Jiang, Wang Han, Nie Li-Hua, Zhang Ze-Yi, Gao Hong-Xu

机构信息

Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.

出版信息

J Hazard Mater. 2008 Mar 1;151(2-3):515-21. doi: 10.1016/j.jhazmat.2007.06.019. Epub 2007 Jun 12.

Abstract

DNP, a nitramine, has been studied with regard to the kinetics and mechanism of thermal decomposition, using thermogravimetry (TG), differential thermal analysis (DTA), infrared (IR) spectroscopy, and differential scanning calorimetry (DSC). The IR spectra of DNP have also been recorded and the kinetics of thermolysis has been followed by non-isothermal TG. The activation energy of the solid-state process was determined using Flynn-Wall-Ozawa method. The actual reaction mechanism obeyed nucleation and growth model, Avramie Erofeev function (n=1) with integral form Galpha=-ln(1-alpha) (alpha=0.10-0.65). Ea and A were determined to be 116.51 kJ/mol and 10(10.52) s(-1). The T/Jump FT-IR analysis showed that CH2O, NO2, and NO are produced in larger amounts than CO2 and HCN. The cleavage of the N-N and C-N bond appears to be the primary step in the thermolysis of DNP.

摘要

二硝基苯酚(DNP)是一种硝胺,已使用热重分析法(TG)、差示热分析(DTA)、红外(IR)光谱法和差示扫描量热法(DSC)对其热分解动力学和机理进行了研究。还记录了DNP的红外光谱,并通过非等温TG跟踪热解动力学。使用弗林-沃尔-小泽方法确定了固态过程的活化能。实际反应机理符合成核和生长模型,即具有积分形式Galpha = -ln(1 - alpha)(alpha = 0.10 - 0.65)的阿弗拉米-埃罗菲耶夫函数(n = 1)。确定活化能Ea和指前因子A分别为116.51 kJ/mol和10(10.52) s(-1)。T/Jump傅里叶变换红外光谱分析表明,生成的甲醛(CH2O)、二氧化氮(NO2)和一氧化氮(NO)的量比二氧化碳(CO2)和氰化氢(HCN)更多。N-N键和C-N键的断裂似乎是DNP热解的主要步骤。

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