硝化纤维素生成焓、键离解能及爆轰性能的理论研究

俞进阳 陈利平 朱卫华 彭金华

俞进阳, 陈利平, 朱卫华, 彭金华. 硝化纤维素生成焓、键离解能及爆轰性能的理论研究[J]. 高压物理学报, 2014, 28(5): 604-610. doi: 10.11858/gywlxb.2014.05.015
引用本文: 俞进阳, 陈利平, 朱卫华, 彭金华. 硝化纤维素生成焓、键离解能及爆轰性能的理论研究[J]. 高压物理学报, 2014, 28(5): 604-610. doi: 10.11858/gywlxb.2014.05.015
YU Jin-Yang, CHEN Li-Ping, ZHU Wei-Hua, PENG Jin-Hua. Heats of Formation, Bond Dissociation Energies and Detonation Properties of Nitrocellulose[J]. Chinese Journal of High Pressure Physics, 2014, 28(5): 604-610. doi: 10.11858/gywlxb.2014.05.015
Citation: YU Jin-Yang, CHEN Li-Ping, ZHU Wei-Hua, PENG Jin-Hua. Heats of Formation, Bond Dissociation Energies and Detonation Properties of Nitrocellulose[J]. Chinese Journal of High Pressure Physics, 2014, 28(5): 604-610. doi: 10.11858/gywlxb.2014.05.015

硝化纤维素生成焓、键离解能及爆轰性能的理论研究

doi: 10.11858/gywlxb.2014.05.015
详细信息
    作者简介:

    俞进阳(1986—), 女,博士研究生,主要从事烟火药剂热分析动力学研究.E-mail:jyyu009@sina.com

    通讯作者:

    陈利平(1986—), 女,博士,讲师,主要从事化工工艺热危险性研究.E-mail:clp2005@hotmail.com

  • 中图分类号: O641

Heats of Formation, Bond Dissociation Energies and Detonation Properties of Nitrocellulose

  • 摘要: 运用密度泛函理论方法结合等键反应,研究了硝化纤维素(NC)单体的生成热及其不同位置上氧硝基键(ONO2)的键离解能,基于半经验的Kamlet-Jacobs方程估算了其爆速与爆压。结果表明:B3LYP和B3P86两种方法得到的计算结果较为接近,生成热均为负值,其大小与氧硝基的数目有关,与氧硝基的取代位置无关。理论计算得到的氧硝基键的键离解能与含氮量无关,而是与实际断裂的氧硝基键的数目相关。爆速和爆压的计算表明,NC单体中所含氧硝基的数量增多,会降低其爆速和爆压。

     

  • 图  纤维素单体的分子结构

    Figure  1.  Molecular frameworks of cellulose monomer

    表  1  B3LYP/6-311G**和B3P86/6-311G**水平上纤维素、NC及参考物质的E0EZPHTQHOF

    Table  1.   Calculated E0, EZP, HT and QHOF at the B3LYP/6-311G** and B3P86/6-311G** levels

    Compd. B3LYP/6-311G** B3P86/6-311G**
    E0/
    (eV)
    EZP/
    (kJ/mol)
    HT/
    (kJ/mol)
    QHOF/
    (kJ/mol)
    E0/
    (eV)
    EZP/
    (kJ/mol)
    HT/
    (kJ/mol)
    QHOF/
    (kJ/mol)
    2NC 24 269.269 502.18 42.48 -1 708.365 97 24 326.686 503.31 41.76 -1 724.355 8
    3NC 24 269.257 499.41 43.84 -1 708.620 75 24 326.688 503.16 43.48 -1 723.069 3
    6NC 24 269.586 502.05 42.30 -1 739.236 79 24 327.012 505.67 41.99 -1 753.208 7
    23NC 29 834.172 503.69 50.58 -2 142.300 26 29 902.091 505.80 49.21 -2 069.079 2
    26NC 29 834.482 506.85 48.62 -2 171.02571 29 902.091 511.37 48.10 -2 098.078 6
    36NC 29 834.249 505.74 49.92 -2 148.29317 29 902.198 510.33 49.30 -2 074.766 9
    236NC 35 399.175 510.51 56.06 -2 583.119 75 35 477.650 516.08 55.28 -2 473.410 9
    Cellulose 18 704.328 497.38 36.16 -1 272.35[15] 18 751.239 500.04 36.05 -1 272.35[15]
    HNO3 7 639.939 61.65 11.82 -173.23[15] 7 655.146 62.83 11.68 -173.23[15]
    H2O 2 080.242 53.73 9.93 -241.83[15] 2 085.080 54.20 9.93 -241.83[15]
    下载: 导出CSV

    表  2  硝化纤维素中O—N键的键离解能

    Table  2.   Bond dissociation energies of O—N in NC

    Compd. Position E0/(eV) EZP/(kJ/mol) HT/(kJ/mol) EBD, 0/(kJ/mol) EBD, ZPE/(kJ/mol)
    2NC 2 -18 686.040 480.588 3 461.36 124.60 106.01
    3NC 3 -18 685.575 475.6731 456.65 168.25 147.72
    6NC 6 -18 685.990 -478.547 1 459.41 160.01 139.60
    2 -24 250.881 -482.686 3 463.38 130.62 112.54
    23NC 3 -24 250.601 480.444 7 461.23 157.62 137.40
    2, 3 -18 667.615 438.893 8 421.34 258.80 222.91
    2 -24 251.253 485.602 7 466.18 124.64 106.20
    26NC 6 -24 250.880 483.225 2 463.90 160.61 139.89
    2, 6 -18 667.657 440.360 8 422.75 284.65 247.01
    3 -24 251.076 485.372 1 465.96 119.15 101.60
    36NC 6 -24 250.674 483.5039 464.16 158.00 138.65
    3, 6 -18 667.497 440.427 4 422.81 277.54 241.07
    2 -29 815.963 490.142 7 470.54 122.93 105.19
    3 -29 816.051 489.122 3 469.56 114.44 95.72
    6 -29 815.606 487.905 8 468.39 157.38 137.49
    236NC 2, 3 -24 232.425 444.5719 426.79 230.07 192.81
    2, 6 -24 232.336 445.2715 427.46 285.95 249.36
    3, -24 232.327 441.7939 424.12 286.75 246.82
    2, 3, 6 -18 649.333 399.0945 383.13 388.73 331.04
    下载: 导出CSV

    表  3  预测NC的爆轰性能

    Table  3.   Predicted detonation properties of NC

    Compd. V/(cm3/mol) N/(mol/g) M/(g/mol) Q/(J/g) ρ/(g/cm3) D/(km/s) p/(GPa)
    2NC 139.46 0.037 23.17 2 111.802 1.61 4.37 3.87
    3NC 154.13 0.037 23.17 2 017.193 1.46 4.09 3.68
    6NC 104.62 0.037 23.17 1 537.060 2.15 4.95 3.81
    23NC 145.71 0.031 26.82 782.902 1.85 3.57 2.28
    26NC 169.93 0.031 26.82 337.127 1.59 2.60 1.38
    36NC 137.79 0.031 26.82 689.925 1.96 3.60 2.20
    236NC 176.48 0.031 29.54 -257.978 1.78 - -
    下载: 导出CSV
  • [1] 堵平, 廖昕, 王泽山.表面处理对单基药燃烧性能的影响[J].含能材料, 2010, 18(3): 348-350.

    Du P, Liao X, Wang Z S. Effect of surface treatment on burning performance of single-base gun propellant[J]. Chinese Journal of Energetic Materials, 2010, 18(3): 348-350. (in Chinese)
    [2] 刘波, 王琼林, 刘少武, 等.提高改性单基药燃烧性能的研究[J].火炸药学报, 2010, 33(4): 82-85. http://www.cqvip.com/Main/Detail.aspx?id=35239343

    Liu B, Wang Q L, Liu S W, et al. Study on improvement o f combustion performance of the modified single base propellant[J]. Chinese Journal of Explosives and Propellants, 2010, 33(4): 82-85. (in Chinese) http://www.cqvip.com/Main/Detail.aspx?id=35239343
    [3] 吕智星, 贺增弟, 萧忠良, 等.单基发射药氧平衡调节探讨[J].含能材料, 2010, 18(5): 587-591. http://d.wanfangdata.com.cn/Periodical/hncl201005025

    Lü Z X, He Z D, Xiao Z L, et al. Adjustment of oxygen balance for single-base propellant[J]. Chinese Journal of Energetic Materials, 2010, 18(5): 587-591. (in Chinese) http://d.wanfangdata.com.cn/Periodical/hncl201005025
    [4] 杨慧群, 王泽山, 魏晓安.废旧单基药爆轰性能的实验研究[J].火炸药学报, 2005, 28(2): 32-34. http://www.cnki.com.cn/Article/CJFDTotal-BGXB200502010.htm

    Yang H Q, Wang Z S, Wei Y A. The experimental study on detonation of wasted single base propellant[J]. Chinese Journal of Explosive & Propellants, 2005, 28(2): 32-34. (in Chinese) http://www.cnki.com.cn/Article/CJFDTotal-BGXB200502010.htm
    [5] 王琼林, 刘少武, 于慧芳, 等.高性能改性单基发射药的制备与性能[J].火炸药学报, 2007, 30(6): 68-71. http://www.cqvip.com/Main/Detail.aspx?id=26371994

    Wang Q L, Liu S W, Yu H F, et al. Preparation and properties test of high performance modified single base gun propellant[J]. Chinese Journal of Explosive & Propellants, 2007, 30(6): 68-71. (in Chinese) http://www.cqvip.com/Main/Detail.aspx?id=26371994
    [6] 王煊军, 王泽山.增能钝感单基药热分解性能研究[J].弹道学报, 1997, 9(1): 22-26. http://epub.cnki.net/grid2008/docdown/docdownload.aspx?filename=DDXB701.004&dbcode=CJFD&year=1997&dflag=pdfdown

    Wang X J, Wang Z S. Thermal decomposition performance of energy increased and deterred single-base propellant[J]. Journal of Ballistics, 1997, 9(1): 22-26. (in Chinese) http://epub.cnki.net/grid2008/docdown/docdownload.aspx?filename=DDXB701.004&dbcode=CJFD&year=1997&dflag=pdfdown
    [7] 张辰.硝化纤维素的酯化反应和安定处理研究[D].南京: 南京理工大学, 2007: 3-5.

    Zhang C. The study of esterification reaction and stability treatment of NC[D]. Nanjing: Nanjing University of Science and Technology, 2007: 3-5. (in Chinese)
    [8] 梁晓琴, 蒲雪梅, 田安民. 1, 2, 4, 5-四嗪含氮取代基衍生物结构和性质的理论研究[J].有机化学, 2011, 31(3): 328-335. http://d.wanfangdata.com.cn/Periodical/yjhx201103008

    Liang X Q, Pu X M, Tian A M. Theoretical studies on structures and properties of 1, 2, 4, 5-tetrazine derivations substituted by substituent groups containing nitrogen[J]. Chinese Journal of Organic Chemistry, 2011, 31(3): 328-335. (in Chinese) http://d.wanfangdata.com.cn/Periodical/yjhx201103008
    [9] 张婧婧, 高洪伟, 卫涛, 等.高能量密度材料3, 3′-偶氮-1, 2, 4, 5-四嗪衍生物的分子设计[J].物理化学学报, 2010, 26(12): 3337-3344. http://www.cqvip.com/Main/Detail.aspx?id=36263947

    Zhang J J, Gao H W, Wei, T, et al. Molecular Design of 3, 3′-Azobis-1, 2, 4, 5-tetrazine-based high-energy density materials[J]. Acta Physico-Chimica Sinica, 2010, 26(12): 3337-3344. (in Chinese) http://www.cqvip.com/Main/Detail.aspx?id=36263947
    [10] Gong X D, Xiao H M. Ab initio and density functional methods studies on the conformations and thermodynamic properties of propyl nitrate[J]. J Molecul Struct-Theochem, 2000, 498: 181-190. doi: 10.1016/S0166-1280(99)00259-6
    [11] 李良, 谭碧生, 彭汝芳, 等. 1, 1, 3, 3-四硝基环丁烷生成热和爆轰参数的计算[J].西南科技大学学报, 2010, 25(4): 5-8. http://www.cqvip.com/QK/91897B/201004/36621451.html

    Li L, Tan B S, Peng R F, et al. Calculations of standard heat of formation and detonation parameters of 1, 1, 3, 3, -tetranitrocyclobutane[J]. Journal of Southwest University of Science and Technology, 2010, 25(4): 5-8. (in Chinese) http://www.cqvip.com/QK/91897B/201004/36621451.html
    [12] 李彦军, 宋婧, 李春迎, 等.几种新型六氮杂异伍兹烷衍生物结构与性能的理论预测——高能量密度化合物的寻求[J].化学学报, 2009, 67(13): 1437-1446. http://d.wanfangdata.com.cn/Periodical/hxxb200913007

    Li Y J, Song J, Li C Y, et al. Theoretical predictions on the structures and properties for several novel hexaazaisowurtzitane Derivatives-Looking for HEDC[J]. Acta Chimica Sinica, 2009, 67(13): 1437-1446. (in Chinese) http://d.wanfangdata.com.cn/Periodical/hxxb200913007
    [13] He W D, Zhou G, Li J S, et al. Molecular design of analogues of 2, 6-diamino-3, 5-dinitropyrazine-1-oxide[J]. J Molecul Structure: Theochem, 2004, 668(2/3): 201-208.
    [14] Valiron P, Mayer I. Hierarchy of counterpoise corrections for N-body clusters: Generalization of the Boys-Bernardi scheme[J]. Chem Phys Lett, 1997, 275(1): 46-55. http://www.sciencedirect.com/science/article/pii/S0009261497006891
    [15] Dean J A. Lance's Handbook of Chemistry[M]. 13th ed. New York: McGraw-Hill, INC, 1985: 1457-1544.
    [16] 张芳沛, 程新路, 刘子江, 等.硝酸丙酯键离解能和热解机理的密度泛函理论研究[J].高压物理学报, 2005, 19(2): 189-192. http://d.wanfangdata.com.cn/Periodical/gywlxb200502016

    Zhang F P, Cheng X L, Liu Z J, et al. Density functional studies on the bond dissociation energy and pyrolysis mechanism of propyl nitrate[J]. Chinese Journal of High Pressure Physics, 2005, 19(2): 189-192. (in Chinese) http://d.wanfangdata.com.cn/Periodical/gywlxb200502016
    [17] 宋晓书, 余春日, 令狐荣锋, 等.多硝基苯酸酯炸药分子键离解能与撞击感度关系研究[J].原子与分子物理学报, 2008, 25(6): 1357-1361. http://d.wanfangdata.com.cn/Periodical/yzyfzwlxb200806011

    Song X S, Yu C R, Linghu R F, et al. Study on correlation between the bond dissociation energies and impact sensitivities in polynitro benzoate molecules[J]. Journal of Atomic and Molecular physics, 2008, 25(6): 1357-1361. (in Chinese) http://d.wanfangdata.com.cn/Periodical/yzyfzwlxb200806011
    [18] 王凤武, 曾秀琳, 方文彦, 等.硝酸酯的热分解性能[J].应用化学, 2010, 27(3): 308-312.

    Wang F, Zeng X L, Fang W Y, et al. Thermal decomposition characteristics of nitrates[J]. Chinese Journal of Applied Chemistry, 2010, 27(3): 308-312. (in Chinese)
    [19] 苏欣纺, 陈恒杰, 程新路.三硝基甲烷键离解能和生成焓的理论计算[J].原子与分子物理学报, 2006, 23(4): 721-724. http://d.wanfangdata.com.cn/Periodical/yzyfzwlxb200604027

    Su X F, Chen H J, Cheng X L. Theoretical calculation of bond dissociation energy and enthalpy of formation for trinitromethane[J]. Chinese Journal of Applied Chemistry, 2006, 23(4): 721-724. (in Chinese) http://d.wanfangdata.com.cn/Periodical/yzyfzwlxb200604027
    [20] 张芳沛, 张红, 刘子江, 等.含能材料中键离解能的密度泛函理论计算[J].原子与分子物理学报, 2005, 22(1): 168-170. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=yzyfzwlxb200501034

    Zhang F P, Zhang H, Liu Z J, et al. Calculations of bond dissociation energies and dipole moments in eneretic materials density functional methods[J]. Journal of Atomic and Molecular Physics, 2005, 22(1): 168-170. (in Chinese) http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=yzyfzwlxb200501034
    [21] 邵菊香, 程新路, 杨向东, 等. C—H, C—N, C—O, N—N的键离解能和键长的计算[J].原子与分子物理学报, 2006, 23(1): 80-84. http://www.cqvip.com/Main/Detail.aspx?id=21275720

    Shao J X, Cheng X L, Yang X D, et al. Calculations of bond dissociation energies and bond lengths of C—H, C—N, C—O, N—N[J]. Journal of Atomic and Molecular Physics, 2006, 23(1): 80-84. (in Chinese) http://www.cqvip.com/Main/Detail.aspx?id=21275720
    [22] Kamlet M J, Jacobs S J. Chemistry of detonations. I. A simple method for calculating detonation properties of C-H-N-O explosives[J]. J Chem Phys, 1968, 48: 23-35. doi: 10.1063/1.1667908
    [23] 贡雪东, 肖鹤鸣.多元硝酸酯热解反应的理论研究[J].物理化学学报, 1998, 14(1): 33-38.

    Gong X D, Xiao H M. Theoretical studies on the pyrolysis of polynitric esters[J]. Acta Physico-Chimica Sinica, 1998, 14(1): 33-38. (in Chinese)
    [24] 董海山, 胡荣祖, 姚朴, 等.含能材料热谱集[M].北京: 国防工业出版社, 1998: 159-164.

    Dong H S, Hu R Z, Yao P, et al. Thermograms of Energetic Materials[M]. Beijing: National Defence Industry Press, 1998: 159-164. (in Chinese)
    [25] Yu J Y, Chen L P, Peng J H. Thermal hazard research of smokeless fireworks[J]. J Thermal Analys Calorimet, 2012, 109(3): 1151-1156. doi: 10.1007/s10973-012-2367-6
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  • 收稿日期:  2012-08-28
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