Citation: BAO Shi-Long, CHEN Wang-Hua, CHEN Li-Ping, GAO Hai-Su, LÜ Jia-Yu. Identification and Thermokinetics of Autocatalytic Exothermic Decomposition of 2,4-Dinitrotoluene[J]. Acta Physico-Chimica Sinica, ;2013, 29(03): 479-485. doi: 10.3866/PKU.WHXB201212141 shu

Identification and Thermokinetics of Autocatalytic Exothermic Decomposition of 2,4-Dinitrotoluene

1.
Department of Safety Engineering, Institute of Chemical Technology, Nanjing University of Technology and Science, Nanjing 210094, P. R. China

Received Date: 28 September 2012
Available Online: 14 December 2012
Fund Project: 国家自然科学基金(51204099)资助项目 (51204099)

The thermal stability and autocatalytic decomposition of 2,4-dinitrotoluene (2,4-DNT) is investigated under dynamic and isothermal conditions using differential scanning calorimetry (DSC). The temperature range of initial exothermic temperature (T₀) is 272.4-303.5℃, and its decomposition enthalpy (ΔH_d) is about 2.22 kJ·g^-1. An identification method based on a numerical simulation technique from the Swiss Institute for the Promotion of Safety and Security (Swiss method) is used to determine the characteristic parameters of the decomposition reaction, revealing that the decomposition of 2,4-DNT is potentially autocatalytic. The Malek method is used to determine the most probable mechanism function and kinetic parameters of 2,4-DNT decomposition. The Sestak-Berggren model with two parameters is suitable to describe the autocatalytic decomposition of 2,4-DNT, which is consistent with the results of the Swiss method and isothermal experimental results. Isothermal DSC experiments confirmed that the decomposition of 2,4-DNT is autocatalytic.
- Autocatalytic decomposition reaction,
- Differential scanning calorimeter,
- Rapid identification,
- Malek method,
- Decomposition kinetics
1. [1]
  
  (1) Sun, J. H.; Lu, S. X.; Sun, Z. H. Chin. Saf. Sci. J. 2003, 13 (4), 44.[孙金华, 陆守香, 孙占辉. 中国安全科学学报, 2003, 13 (4), 44.]
2. [2]
  (2) Wu, Z. Z.; Zhang, S. Z.; Zhang, Y.; Shi, C.; Liu, N.; Yang, G. L.J. Saf. Sci. Tech. 2011, 7 (7), 5. [吴宗之, 张圣柱, 张悦, 石超, 刘宁, 杨国梁. 中国安全生产科学技术, 2011, 7 (7), 5.]
3. [3]
  (3) Zhao, L. J.;Wu, P.; Xu, K. Chin. Saf. Sci. J. 2009, 19 (7), 165.[赵来军, 吴萍, 许科. 中国安全科学学报, 2009, 19 (7), 165.]
4. [4]
  (4) Stoessel, F. Thermal Safety of Chemical Process: RiskAssessment and Process Design; Science Press: Beijing, 2009;pp 56, 271-287; translated by Chen,W. H., Peng, J. H., Chen,L. P. [Stoessel, F. 化工工艺热安全, 风险评估与工艺设计.陈网桦, 彭金华, 陈利平译. 北京: 科学出版社, 2009: 56,271-287.]
5. [5]
  (5) Guo, M. C.; Chu, S. J.; Feng, C. G.; He, G. B. Explo. Sho. Wav.1995, 15 (2), 107. [郭明朝, 楚士晋, 冯长根, 何光斌. 爆炸与冲击, 1995, 15 (2), 107.]
6. [6]
  (6) Jia, H. P.; Bai, M. L. Acta Armamentarii 1993, No. 4, 53. [贾会平, 白木兰. 兵工学报, 1993, No. 4, 53.]
7. [7]
  (7) Zhang, H.; Xia, Z. M.; Guo, P. J.; Hu, R. Z.; Gao, S. L.; Ning,B. K.; Fang, Y.; Shi, Q. Z.; Liu, R. J. Hazard. Mater. 2002, 94 (3), 205. doi: 10.1016/S0304-3894(02)00118-8
8. [8]
  (8) Hu, R. Z.; Guo, P. J.; Song, J. R.; Zhang, H.; Xia, Z. M.; Ning,B. K.; Fang, Y.; Shi, Q. Z.; Liu, R.; Lu, G. E.; Jiang, J. Y. Chin.J. Explo. Prop. 2003, 26 (2), 53. [胡荣祖, 郭鹏江, 宋纪蓉,张海, 夏志明, 宁斌科, 房艳, 史启祯, 刘蓉, 路桂娥,江劲勇. 火炸药学报, 2003, 26 (2), 53.]
9. [9]
  (9) Hu, R. Z.; Ning, B. K.; Yang, Z. Q.; Song, J. R.; Gao, S. L.; Shi,Q. Z.; Lu, G. E.; Jiang, J. Y. Chin. J. Explo. Prop. 2004, 27 (2),67. [胡荣祖, 宁斌科, 杨正权, 宋纪蓉, 高胜利, 史启祯, 路桂娥, 江劲勇. 火炸药学报, 2004, 27 (2), 67.]
10. [10]
  (10) Ning, B. K.; Hu, R. Z.; Zhang, H.; Xia, Z. M.; Guo, P. J.; Liu,R.; Lu, G. E.; Jiang, J. Y. Thermochimica Acta 2004, 416 (1-2),47. doi: 10.1016/j.tca.2003.11.029
11. [11]
  (11) Zhao, F. Q.; Guo, P. J.; Hu, R. Z.; Zhang, H.; Xia, Z. M.; Gao,H. X.; Chen, P.; Luo, Y.; Zhang, Z. Z.; Zhou, Y. S.; Zhao, H. A.;Gao, S. L.; Shi, Q. Z.; Lu, G. E.; Jiang, J. Y. Chin. J. Chem.2006, 24 (5), 631. [赵凤起, 郭鹏江, 胡荣祖, 张海, 夏志明,高红旭, 陈沛, 罗阳, 张志忠, 周彦水, 赵宏安, 高胜利,史启祯, 路桂娥, 江劲勇. 化学学报, 2006, 24 (5), 631.]
12. [12]
  (12) Gao, H. X.; Zhang, H.; Zhao, F. Q.; Hu, R. Z.; Ma, H. X.; Xu,K. Z.; Yi, J. H.; Xu, S. Y.; Gao, Y. Acta Phys. -Chim. Sin. 2008,24 (3), 453. [高红旭, 张海, 赵凤起, 胡荣祖, 马海霞, 徐抗震, 仪建华, 徐司雨, 高茵. 物理化学学报, 2008, 24 (3),453.] doi: 10.3866/PKU.WHXB20080318
13. [13]
  (13) Ou, X. R.; Zhang, C. M. J. Occu. Saf. Heal. 2005, 15 (2), 159.[欧新荣, 张承明. 劳工安全卫生研究季刊, 2005, 15 (2), 159.]
14. [14]
  (14) Chen, J. R.; Cheng, S. Y.; Yuan, M. H.; Kossoy, A. A.; Shu, C.M. J. Therm. Anal. Calorim. 2009, 96 (3), 751. doi: 10.1007/s10973-009-0023-6
15. [15]
  (15) Tanaka, G.;Weatherford, C. Int. J. Quantum Chem. 2008, 108 (15), 2924. doi: 10.1002/qua.v108:15
16. [16]
  (16) nzalez, A. C.; Lamon, C.W.; McMillen, D. F.; lden, D. M.J. Phys. Chem. 1985, 89 (22), 4809. doi: 10.1021/j100268a030
17. [17]
  (17) Neri, G.; Musolino, M. G.; Milone, C.; Pietropaolo, D.; Galvagno,S. Applied Catalysis A: General 2001, 208 (1), 307. doi: 10.1016/S0926-860X(00)00717-1
18. [18]
  (18) Lenz, A.; Pohl, A.; Ojamae, L.; Persson, P. Int. J. QuantumChem. 2012, 112 (7), 1852. doi: 10.1002/qua.v112.7
19. [19]
  (19) Dontsova, K. M.; Pennington, J. C.; Hayes, C.; Šimunek, J.;Williford, C.W. Chemosphere 2009, 77 (4), 597. doi: 10.1016/j.chemosphere.2009.05.039
20. [20]
  (20) Wang, S. X.; Tan, Z. C.; Shi, Q.; Di, Y. Y.; Zhang, H. T.; Xu, F.;Sun, L. X.; Zhang, T. J. Chem. Thermodynamics 2005, 37 (4),349. doi: 10.1016/j.jct.2004.09.018
21. [21]
  (21) Zeman, S. Thermochimica Acta 1997, 290 (2), 199. doi: 10.1016/S0040-6031(96)03078-X
22. [22]
  (22) Chervina, S.; Bodman, G. T. Process Saf. Prog. 2002, 16 (2), 94
23. [23]
  (23) Bou-Diab, L.; Fierz, H. J. Hazard. Mater. 2002, 93 (1), 137. doi: 10.1016/S0304-3894(02)00044-4
24. [24]
  (24) Hu, R. Z.; Gao, S. L.; Zhao, F. Q.; Shi, Q. Z.; Zhang, T. L.;Zhang, J. J. Thermal Analysis Kinetics, 2nd ed.; Science Press:Beijing, 2008; pp 149-165. [胡荣祖, 高胜利, 赵凤起, 史启祯, 张同来, 张建军. 热分析动力学(第二版). 北京: 科学出版社, 2008: 149-165.]
25. [25]
  (25) Tang, Z.; Ren, Y.; Yang, L.; Zhang, T. L.; Qiao, X. J.; Zhang, J.G.; Zhou, Z. N. Chin. J. Explo. Prop. 2011, 34 (1), 19.[汤崭, 任雁, 杨利, 张同来, 乔小晶, 张建国, 周遵宁.火炸药学报, 2011, 34 (1), 19.]
26. [26]
  (26) Zhou, H. J.; Yin, G. Q.; Huang, D. Y.; Li, C. J.; Guo, Q. B.Insulating Materials 2011, 44 (6), 48. [周红军, 尹国强,黄东莹, 李翠金, 郭清兵. 绝缘材料, 2011, 44 (6), 48.]
27. [27]
  (27) Sun,W. B.; Zhang, C. C. J. Wuhan Univ. Tech. 2009, 31 (6),28. [孙文兵, 张超灿. 武汉理工大学学报, 2009, 31 (6), 28.]
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