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
2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学
为研究2,4-二硝基甲苯(2,4-DNT)的热危险性及其分解反应的特征, 利用差示扫描量热仪(DSC)对该物质进行了动态扫描测试, 得到其起始分解温度T0范围为272.4-303.5℃, 分解热ΔHd约为2.22 kJ·g-1. 在此基础上, 采用瑞士安全技术与保障研究所提出的快速鉴别法(瑞士方法)及数值模拟技术, 对其分解反应的特性参数进行了推算, 结果表明其分解具有自催化性. 采用Malek法分析了该物质分解反应的最概然机理函数并得出了相关动力学参数, 表明其分解具有自催化性且符合Sestak-Berggren 双参数自催化模型(SB模型), 这与瑞士方法所得结论一致. 采用等温DSC测试获得了该物质的‘钟形’热解曲线, 从而验证了两种方法的结论.
English
Identification and Thermokinetics of Autocatalytic Exothermic Decomposition of 2,4-Dinitrotoluene
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 (ΔHd) 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.
-
-
[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.]
(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) 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.](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) 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.](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) 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.](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) 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.](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) 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.](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) 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(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) 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.](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) 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.](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) 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(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) 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.](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) 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(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) 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.](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) 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(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) Tanaka, G.;Weatherford, C. Int. J. Quantum Chem. 2008, 108 (15), 2924. doi: 10.1002/qua.v108:15(15) Tanaka, G.;Weatherford, C. Int. J. Quantum Chem. 2008, 108 (15), 2924. doi: 10.1002/qua.v108:15
-
[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(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) 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(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) Lenz, A.; Pohl, A.; Ojamae, L.; Persson, P. Int. J. QuantumChem. 2012, 112 (7), 1852. doi: 10.1002/qua.v112.7(18) Lenz, A.; Pohl, A.; Ojamae, L.; Persson, P. Int. J. QuantumChem. 2012, 112 (7), 1852. doi: 10.1002/qua.v112.7
-
[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(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) 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(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) Zeman, S. Thermochimica Acta 1997, 290 (2), 199. doi: 10.1016/S0040-6031(96)03078-X(21) Zeman, S. Thermochimica Acta 1997, 290 (2), 199. doi: 10.1016/S0040-6031(96)03078-X
-
[22]
(22) Chervina, S.; Bodman, G. T. Process Saf. Prog. 2002, 16 (2), 94(22) Chervina, S.; Bodman, G. T. Process Saf. Prog. 2002, 16 (2), 94
-
[23]
(23) Bou-Diab, L.; Fierz, H. J. Hazard. Mater. 2002, 93 (1), 137. doi: 10.1016/S0304-3894(02)00044-4(23) Bou-Diab, L.; Fierz, H. J. Hazard. Mater. 2002, 93 (1), 137. doi: 10.1016/S0304-3894(02)00044-4
-
[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.](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) 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.](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) 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.](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) 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.]
(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.]
-
[1]
-
扫一扫看文章
计量
- PDF下载量: 1129
- 文章访问数: 1674
- HTML全文浏览量: 58

下载: