从DSC曲线数据计算/确定含能材料自催化分解反应动力学参数和热爆炸临界温升速率的方法

引用本文: 胡荣祖, 赵凤起, 高红旭, 姚二岗, 张海, 王尧, 常象宇, 赵宏安. 从DSC曲线数据计算/确定含能材料自催化分解反应动力学参数和热爆炸临界温升速率的方法[J]. 物理化学学报, 2013, 29(08): 1623-1631. doi: 10.3866/PKU.WHXB201305282 shu

Citation: HU Rong-Zu, ZHAO Feng-Qi, GAO Hong-Xu, YAO Er-Gang, ZHANG Hai, WANG Yao, Chang Xiang-Yu, ZHAO Hong-An. Method to Determine the Kinetic Parameters of the Autocatalytic Decomposition Reaction and Critical Rate of Temperature Rise of Thermal Explosion of Energetic Materials from DSC Curves[J]. Acta Physico-Chimica Sinica, 2013, 29(08): 1623-1631. doi: 10.3866/PKU.WHXB201305282 shu

从DSC曲线数据计算/确定含能材料自催化分解反应动力学参数和热爆炸临界温升速率的方法

胡荣祖 ^1, ,
赵凤起 ^1, ,
高红旭 ^1, ,
姚二岗 ^1, ,
张海 ^2, ,
王尧 ^3, ,
常象宇 ^3, ,
赵宏安 ^4,

基金项目:
国家自然科学基金(21173163)资助项目 (21173163)

摘要:

为应用热爆炸临界温升速率(dT/dt)_{T_b}评价含能材料(EMs)的热安全性, 得到计算(dT/dt)_{T_b}值的基本数据, 用合理的假设, 由Semenov的热爆炸理论和9 个自催化反应速率方程[dα/dt=Aexp(-E/RT)α(1-α) (I), dα/dt=Aexp(-E/RT)(1-α)ⁿ(1+K_catα) (II), dα/dt=Aexp(-E/RT)[α^a-(1-α)ⁿ)] (III), dα/dt=A₁exp(-E_a1/RT)(1-α)+A₂exp(-E_a2/RT)α(1-α) (IV), dα/dt=A₁exp(-E_a1/RT)(1-α)^m+A₂exp(-E_a2/RT)αⁿ(1-α)^p (V), dα/dt=Aexp(-E/RT)(1-α) (VI), dα/dt=Aexp(-E/RT)(1-α)ⁿ (VII), dα/dt=A₁exp(-E_a1/RT)+A₂exp(-E_a2/RT)(1-α) (VII), dα/dt=A₁exp(-E_a1/RT)+A₂exp(-E_a2/RT)α(1-α) (IX)]导出了计算(dT/dt)_{T_b}值的9 个表达式. 提出了从不同恒速升温速率(β)条件下的差示扫描量热(DSC)曲线数据计算/确定EMs自催化分解反应的动力学参数和自催化分解转向热爆炸时的(dT/dt)_{T_b}的方法. 由DSC曲线数据的分析得到了用于计算(dT/dt)_{T_b}值的β→0 时的onset 温度(T_e0),热爆炸临界温度(T_b)和相应于T_b时的转化率(α_b). 分别用线性最小二乘法和信赖域方法得到方程(I)和(VI)及方程(II)-(V)和方程(VII)-(IX)中的自催化分解反应动力学参数. 用上述基础数据得到了EMs的(dT/dt)_{T_b}值. 结果表明: (1) 在非等温DSC条件下硝化棉(NC, 13.54% N)分解反应可用表观经验级数自催化反应速率方程dα/dt=10^15.82exp(-170020/RT)(1-α)^1.11+10^15.82exp(-157140/RT)α^1.51(1-α)^2.51描述; (2) NC (13.54% N)自催化分解转向热爆炸时的(dT/dt)_{T_b}值为0.103 K·s^-1.

关键词:

English

Method to Determine the Kinetic Parameters of the Autocatalytic Decomposition Reaction and Critical Rate of Temperature Rise of Thermal Explosion of Energetic Materials from DSC Curves

1.
1 Science and Technology on Combustion and Explosion Laboratory, Xi’an Modern Chemistry Research Institute, Xi’an 710065, P. R. China;
2 Department of Mathematics/Institute of data analysis and computation chemistry, Northwest University, Xi’an 710069, P. R. China;
3 Institute for Information Science and System Science, Xi’an Jiaotong University, Xi’an 710049, P. R. China;
4 College of Communication Science and Engineering, Northwest University, Xi’an 710069, P. R. China
Received Date: 08 April 2013
Available Online: 09 July 2013
Fund Project:
国家自然科学基金(21173163)资助项目

Abstract:

To evaluate the thermal safety of energetic materials (EMs) using the critical rate of temperature rise of thermal explosion (dT/dt)_{T_b} and obtain basic data used to calculate (dT/dt)_{T_b}, nine expressions to calculate (dT/dt)_{T_b} for EMs were derived from Semenov thermal explosion theory and nine autocatalytic reaction rate equations, dα/dt=Aexp(-E/RT)α(1-α) (I), dα/dt=Aexp(-E/RT)(1-α)ⁿ(1+K_catα) (II), dα/dt=Aexp(-E/RT)[α^a-(1-α)ⁿ] (III), dα/dt=A₁exp(-E_a1/RT)(1-α)+A₂exp(-E_a2/RT)α(1-α) (IV), dα/dt=A₁exp(-E_a1/RT)(1-α)^m+A₂exp(-E_a2/RT)αⁿ(1-α)^p (V), dα/dt=Aexp(-E/RT)(1-α) (VI), dα/dt=Aexp(-E/RT)(1-α)ⁿ (VII), dα/dt=A₁exp(-E_a1/RT)+A₂exp(-E_a2/RT)(1-α) (VII) and dα/dt=A₁exp(-E_a1/RT)+A₂exp(-E_a2/RT)α(1-α) (IX), using reasonable hypotheses. A method to determine the kinetic parameters in the nine autocatalytic decomposition reaction rate equations and (dT/dt)_{T_b} of EMs when autocatalytic decomposition converts into thermal explosion from difference scanning calorimetry (DSC) curves at different heating rates (β) was presented. The onset temperature (T_e0) corresponding to heating rate β→0, the critical temperature of thermal explosion (T_b) and the conversion degree (α_b) corresponding to T_b used in the calculation of (dT/dt)_{T_b} were obtained from analysis of DSC curves. The kinetic parameters of the autocatalytic decomposition reactions in Eqs.(I) and (VI), and Eqs.(II)-(V), (VII)-(IX) were estimated by the linear least-squares method and trust region approach, respectively. The values of (dT/dt)_{T_b} for EMs were obtained from basic DSC data. Results show that (1) under non-isothermal DSC conditions, the autocatalytic decomposition reaction of nitrocotton (NC) (13.54% N) can be described by the apparent empiric-order equation dα/dt=10^15.82exp(-170020/RT)(1-α)^1.11+10^15.82exp(-157140/RT)α^1.51(1-α)^2.51; (2)The value of for NC (13.54% N) when autocatalytic decomposition converts into thermal explosion is 0.103 K·s^-1.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

从DSC曲线数据计算/确定含能材料自催化分解反应动力学参数和热爆炸临界温升速率的方法

English

Method to Determine the Kinetic Parameters of the Autocatalytic Decomposition Reaction and Critical Rate of Temperature Rise of Thermal Explosion of Energetic Materials from DSC Curves

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

从DSC曲线数据计算/确定含能材料自催化分解反应动力学参数和热爆炸临界温升速率的方法

English

Method to Determine the Kinetic Parameters of the Autocatalytic Decomposition Reaction and Critical Rate of Temperature Rise of Thermal Explosion of Energetic Materials from DSC Curves

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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