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

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: 8 April 2013
Available Online: 28 May 2013
Fund Project: 国家自然科学基金(21173163)资助项目 (21173163)

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.
- Critical rate of temperature rise,
- Non-isothermal DSC,
- Thermal explosion,
- Nitrocotton,
- Trust region approach
1. [1]
  
  (1) Deng, Y. Chem. J. Chin. Univ. 1985, 6 (7), 621. [邓郁. 高等学校化学学报, 1985, 6 (7), 621.]
2. [2]
  (2) Semenov, N. N. On Some Problem of Kineties and Reactivity;Ind., AN SSSR: Moscow, 1958; p 421.
3. [3]
  (3) Hu, R. Z.; Gao, S. L.; Zhao, F. Q.; Shi, Q. Z.; Zhang, T. L.;Zhang, J. J. Thermal Analysis Kinetics; Science Press: Beijing,2008; pp 322-334. [胡荣祖, 高胜利, 赵凤起, 史启桢, 张同来, 张建军. 热分析动力学. 北京: 科学出版社, 2008:322-334.]
4. [4]
  (4) Hu, R. Z.; Zhang, H.; Xia, Z. M.; Guo, P. J.; Gao, S. L.; Shi, Q.Z.; Lu, G. E.; Jiang, J. Y. Chin. J. Energ. Mater. 2003, 11 (3),130. [胡荣祖, 张海, 夏志明, 郭鹏江, 高胜利, 史启桢, 路桂娥, 江劲勇. 含能材料, 2003, 11 (3), 130.]
5. [5]
  (5) Wang, Y.; Feng, C. G.; Zheng, X. Chin. J. Energ. Mater. 2000, 8 (3), 119. [王耘, 冯长根, 郑晓. 含能材料, 2000, 8 (3),119.]
6. [6]
  (6) Hu, R. Z.; Guo, P. J.; Song, J. R.; Zhang, H.; Xia, Z. M.; Ning,B. K.; Fang, Y.; Shi, Q. Z.; Liu, R.; Luo, G. E.; Jiang, J. Y. Chin. J. Explo. Prop. 2003, 26 (2), 53.
7. [7]
  (7) Ning, B. K.; Hu, R. Z.; Zhang, H., Xia, Z. M.; Guo, P. J.; Liu,R.; Luo, G. E.; Jiang, J. Y. Thermochim. Acta 2004, 416 (1-2),47. doi: 10.1016/j.tca.2003.11.029
8. [8]
  (8) Hu, R. Z.; Guo, P. J.; Gao, S. L.; Zhang, H.; Xia, Z. M.; Ning,B. K.; Fang, Y.; Shi, Q. Z.; Liu, R. Chinese Journal of Polymer Science 2003, 21 (3), 285.
9. [9]
  (9) Guo, P. J.; Hu, R. Z.; Zhang, H., Xia, Z. M.; Song, J. R.; Gao, S.L.; Ning, B. K; Liu, R.; Lu, G. E.; Jiang, J. Y. Chem. Res. Chin. Univ. 2004, 20 (2), 163.
10. [10]
  (10) Zhang, H.; Xia, Z. M.; Guo, P. J.; Hu, R. Z.; Gao, S. L.; Ning,B. K.; Fang, Y.; Shi, Q. Z.; Liu, R. Journal of Hazardous Materials 2002, 94 (3), 205. doi: 10.1016/S0304-3894(02)00118-8
11. [11]
  (11) Eisenreich, N. Beitrag Zur Kinetic ThermischerZersetzungseaktionen (Thermoanalytische Auswertung DerZersetzung Von Nitrocellulose). Ph. D. Dissertation, TechnicalUniversity of Munich, Munich, 1978.
12. [12]
  (12) Eisenreich, N.; Pfeil, A. Thermochim. Acta 1983, 61 (1-2), 13.doi: 10.1016/0040-6031(83)80300-1
13. [13]
  (13) Hu, R. Z.; Song, Q. C.; Xie, J. J.; Liang, Y. J. Explosion and Shock Waves 1987, 7 (3), 217. [胡荣祖, 松全才, 谢俊杰, 梁燕军. 爆炸与冲击, 1987, 7 (3), 217.]
14. [14]
  (14) Thomas, F. C.; Li, Y. Y. SIAM Journal on Optimization 1996, 6 (2), 418. doi: 10.1137/0806023
15. [15]
  (15) Ozawa, T. Bulletin of the Chemical Society of Japan 1965, 38 (1), 1881.
16. [16]
  (16) Zhang, T. L.; Hu, R. Z.; Xie, Y.; Li F. P. Thermochim. Acta1994, 244 (3), 171.
17. [17]
  (17) Hu, R. Z.; Yang, Z. Q.; Ling, Y. J. Thermochim. Acta 1988, 123,135. doi: 10.1016/0040-6031(88)80017-0
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