CHINESE JOURNAL OF ENERGETIC MATERIALS
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含能五唑离子盐的能量性能预估
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1.南京理工大学化工学院, 江苏 南京 210094;2.国家民用爆破器材质量监督检验中心, 江苏 南京 210094;3.甘肃银光化学工业集团有限公司, 甘肃 白银 730900

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国家自然科学基金资助(21771108);江苏省研究生科研与实践创新计划项目资助(KYCX19_0308)


Prediction of the Energetic Performance of Pentazolate Salts
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1.School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094, China;2.China National Quality Supervision Testing Center for Industrial Explosive Material, Nanjing 210094, Jiangsu, China;3.Gansu Yinguang Chemical Industry Group Co., Ltd.,Baiyin 730900, China

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    摘要:

    为了在同一水平上比较含能五唑离子盐的密度、生成热、爆速和爆压,采用密度泛函理论,对近两年合成的五大类16个非金属N5ˉ离子盐进行了研究。结果表明在MP2/6-311++G(d,p)理论水平上,根据Born-Haber能量循环计算的五唑离子盐的生成热为95.2~1362.0 kJ·mol-1,三唑类N5ˉ离子盐的平均生成热最高。这些五唑离子盐的密度为1.395~1.650 g·cm-3(298.15 K),远远低于理论预测的全氮化合物的密度。通过Kamlet-Jacobs公式计算的爆速和爆压结果与EXPLO5的计算结果吻合良好,大部分五唑含能离子盐的爆速为6500~8000 m·s-1;爆压为15~26 GPa,低于RDX的爆速和爆压。N5ˉ的缩二胍盐、羟胺盐和肼盐的理论爆轰性能突出,它们的爆速(8622~9032 m·s-1)与RDX持平或者略高,爆压(29.5~32.3 GPa)均低于RDX,并未展现出全氮阴离子衍生物的明显优势,也远未达到对它们超高能量的预期。

    Abstract:

    In order to compare the densities, heats of formation, detonation velocities, and detonation pressures of the energetic pentazolate salts at the same level, density functional theory (DFT) method was used to study the sixteen N5ˉ based nonmetallic energetic salts synthesized in the past two years. According to the Born-Haber energy cycle, the calculated heats of formation of the pentazolate salts are between 95.2 kJ·mol-1 and 1362.0 kJ·mol-1 at the MP2/6-311++G(d,p) level. The average heat of formation of the salts formed by the triazole-containing cation and N5ˉ is the highest among the five types of N5ˉ salts. The densities(at 298.15 K) of these pentazolate salts range from 1.395 g·cm-3 to 1.650 g·cm-3, which are much lower than the theoretical densities of all-nitrogen compounds. The detonation velocities and detonation pressures calculated by the Kamlet-Jacobs formula agree well with the calculation results from EXPLO5. Most of the N5ˉ-containing ionic salts have detonation velocities between 6500 m·s-1 and 8000 m·s-1 and detonation pressures between 15 GPa and 26 GPa, which are lower than RDX. The theoretical detonation performance of biguanidinium, hydroxylammonium, and hydrazinium pentazolates are outstanding. Their detonation velocities (8622-9032 m·s-1) are equal or slightly higher than that of RDX, and their detonation pressures (29.5-32.3 GPa) are lower than that of RDX. Thus, their predicted performance are not revolutionary. They do not exhibit the distinct advantages of all-nitrogen anion derivatives, and are far from the expectation of their ultra-high energy.

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引用本文

许元刚,李冬雪,田丽莉,等.含能五唑离子盐的能量性能预估[J].含能材料, 2020, 28(8):718-723. DOI:10.11943/CJEM2019208.
XU Yuan-gang, LI Dong-xue, TIAN Li-li, et al. Prediction of the Energetic Performance of Pentazolate Salts[J]. Chinese Journal of Energetic Materials, 2020, 28(8):718-723. DOI:10.11943/CJEM2019208.

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历史
  • 收稿日期: 2019-07-26
  • 最后修改日期: 2020-03-14
  • 录用日期: 2019-09-03
  • 在线发布日期: 2020-03-11
  • 出版日期: 2020-08-25