碳化铀 | 12070-09-6

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 中文名称: 碳化铀
• 中文别名: 一碳化铀
• 英文名称: uranium carbide
• 英文别名: uranium monocarbide；copper；methane;uranium
• CAS: 12070-09-6
• 化学式: CU
• 分子量: 250.04
• InChiKey: QRKOGTOMYRGNOR-UHFFFAOYSA-N

物化性质

• 熔点：
  2790°C
• 密度：
  13.630
• 稳定性/保质期：

  灰色、硬而脆的金属性化合物，属于NaCl型立方晶系，边长a为4.9605 Å（1 Å = 0.1 nm）。其密度为13.61 g/cm³，熔点约为2525±30℃。铀的一碳化物具有良好的导热性，并且熔点和硬度都很高，适合作为核燃料。在1000℃以上时，其组成呈非整比状态，1400℃时C/U比值范围为0.94～1.00，2200℃时为0.90～1.92；此外，氧和氮在其中的溶解度也较高。这种化合物较为活泼，容易与水蒸气、氧气反应而被氧化。因此，在处理粉末样品时，必须在惰性气体环境中进行。

计算性质

• 辛醇/水分配系数(LogP)：
  0.64
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

铀通过口服、吸入和皮肤途径被少量吸收。体内的铀通常以铀酰离子（UO2）2+ 的形式存在，与阴离子如柠檬酸盐和碳酸氢盐或血浆蛋白结合。铀优先分布到骨骼、肝脏和肾脏。进入体内的铀大部分不被吸收，并通过尿液和粪便从体内排出。

Uranium is absorbed in low amounts via oral, inhalation, and dermal routes. Uranium in body fluids generally exists as the uranyl ion (UO2)2+ complexed with anions, such as citrate and bicarbonate, or plasma proteins. Uranium preferentially distributes to bone, liver, and kidney. The large majority of uranium that enters the body is not absorbed and is eliminated from the body via the urine and faeces. (L248)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

铀与血液中的碳酸氢盐或血浆蛋白结合，但一旦进入肾脏，它就会被释放并与肾小管壁上的磷酸盐配体和蛋白质形成复合物，造成损害。铀还可能抑制肾近端小管中的依赖钠传输和不依赖钠传输的ATP利用以及线粒体的氧化磷酸化。铀通过损害肺泡上皮II型细胞引起呼吸系统疾病。铀诱导c-Jun N端激酶（JNK）和p38丝裂原活化蛋白激酶（p38 MAPK）的激活，进而诱导肿瘤坏死因子α（TNF-α）的分泌，在肺部产生炎症反应。研究表明，铀盐的水溶性越大，毒性越强。铀产生的电离辐射损伤DNA，导致基因突变和染色体畸变。这可以启动和促进致癌作用，并干扰繁殖和发育。（L249，A160）

Uranium is combined with either bicarbonate or a plasma protein in the blood but once in the kidney, it is released and forms complexes with phosphate ligands and proteins in the tubular wall, causing damage. Uranium may also inhibit both sodium transport-dependent and independent ATP utilization and mitochondrial oxidative phosphorylation in the renal proximal tubule. Uranium causes respiratory diseases by damaging alveolar epithelium type II cells in the lungs. Uranium induces c-Jun N-terminal kinase (JNK) and p38 mitogen-activated protein kinase (p38 MAPK) activation, which in turn induces tumor necrosis factor alpha (TNF-alpha) secretion and generates and inflammatory response in the lungs. Studies have shown that the more soluble the uranium salt, the more toxic it is. Ionizing radiation produced by uranium damages the DNA, resulting in gene mutations and chromosomal aberrations. This can both both initiate and promote carcinogenesis, and interfere with reproduction and development. (L249, A160)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

铀：第1组，对人类有致癌性（L135）

Uranium: Group 1, carcinogenic to humans (L135)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

铀主要损害肾脏，但也可能损害肺部、中枢神经系统和免疫系统。铀的放射性被认为会损害DNA，导致致癌效应以及生殖和发育损害。

Uranium primarily damages the kidney, but may also damage the lungs, central nervous system, and immune system. Uranium's radioactivity is believed to damage the DNA, resulting in carcinogenic effects and reproductive and developmental damage. (L248, L249)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L249）；吸入（L249）；皮肤给药（L249）

Oral (L249) ; inhalation (L249) ; dermal (L249)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

摄入铀可能会导致呕吐和腹泻。

Ingestion of uranium may cause vomiting and diarrhea. (L248)

来源:Toxin and Toxin Target Database (T3DB)

安全信息

• 危险等级：
  7
• 危险品运输编号：
  UN 2912

制备方法与用途

合成制备方法 制法1

将(UO₃+C)微球体在真空条件下加热至973K，直至系统达到1mPa的真空度，以确保(UO₃+C)微球按照如下反应完全转化为(UO₂+C)微球，并保持C/UO₂摩尔比为3.0： [ UO_3(s) + 0.5C(s) \rightarrow UO_2(s) + 0.5CO_2(g) ] 随后，在真空条件下以1K/min的速率将样品从1473K加热至1773K，或在通入氩气流的情况下以0.75K/min的速率使样品从1523K加热至1900K。此过程会使氧化物转化为碳化物： [ UO_2(s) + 3C(s) \rightarrow UC(s) + 2CO(g) ]

制法2

按化学计量比取适量的氢化铀粉末与碳粉，在惰性气体中充分混合后加压成型为片状，参照三碳化二铀制备方法2。在真空或精制的惰性气体中加热样品，待氢分解析出后，迅速升温至1200℃并保持1～2小时即可得到UC产品。这种方法也可在较低温度下进行，且能准确控制成分，但反应可能不够彻底。

反应信息

• 作为反应物：
  描述：

  碳化铀 、 亚硝酸 以 硝酸 为溶剂， 生成 uranyl
  参考文献：
  名称：

  Physicochemical behavior of uranium and technetium in some new stages of the nuclear fuel cycle

  摘要：

  Recently published results of the cooperative studies executed by the Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences (IPCE RAS), Research Center Vallee du Rhone (CEA, France), Institute of Nuclear Physics Orsay and University Bordeaux I [Centre Nationale de Recherches Scientifiques (CNRS), France] are reviewed. The review includes data obtained for the first time on the electrochemical properties and anodic dissolution of uranium monocarbide considered among possible bases of the fuel for the reactors of the IVth generation. The results of the investigations in the field of the synthesis of tetraalkyl ammonium pertechnetates, their physicochemical properties and thermal decomposition with formation of Tc metal and Tc monocarbide are summarized. The electrochemical reactions with participation of Tc ions in various oxidation states and their application in the nuclear fuel cycle are described. The behavior of technetium in natural waters near the locations of the radwastes long-term storage and in the areas surrounding nuclear power plants in RF and France was studied.

  DOI：

  10.1134/s107036320805037x
• 作为产物：
  描述：

  铀 、 甲烷 以 not given 为溶剂， 生成 碳化铀
  参考文献：
  名称：

  Crystal structure and electronic properties of the new compounds, U6Fe16Si7 and its interstitial carbide U6Fe16Si7C

  摘要：

  The new compounds U6Fe16Si7 and U6Fe16Si7C were prepared by arc-melting and subsequent annealing at 1500 degrees C. Single-crystal X-ray diffraction showed that they crystallize in the cubic space group Fm (3) over barm (No. 225), with unit-cell parameters at room temperature a = 11.7206(5)angstrom for U6Fe16Si7 and a = 11.7814(2)angstrom for U6Fe16Si7C. Their crystal structures correspond to ordered variants of the Th6Mn23 type. U6Fe16Si7 adopts the Mg6Cu16Si7 Structure type, whereas U6Fe16Si7C crystallizes with a novel "filled" quaternary variant. The inserted carbon is located in octahedral cages formed by six U atoms, with U-U interatomic distances of 3.509(1)angstrom. Insertion of carbon in the Structure of U6Fe16Si7 has a direct influence on the U-Fe and Fe-Fe interatomic distances. The electronic properties of both compounds were investigated by means of DC Susceptibility, electrical resistivity and thermopower. U6Fe16Si7 is a Pauli paramagnet. Its electrical resistivity and thermopower point Out that it cannot be classified as a simple metal. The magnetic susceptibility Of U6Fe16Si7C is best described over the temperature range 100-300K by using a modified Curie-Weiss law with all effective magnetic moment of 2.3(2)mu(B)/U, a paramagnetic Weiss temperature, theta(p) = 57(2) K and a temperature-independent term chi(0) = 0.057(1)emu/mol. Both the electrical resistivity and thermopower reveal metallic behavior. (C) 2007 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jssc.2007.07.030
• 作为试剂：
  描述：

  氮 在 碳化铀 氢气 作用下， 生成 氨
  参考文献：
  名称：

  Haber, F.; Maschke, A., Zeitschrift fur Elektrochemie, 1915, vol. 21, p. 128

  摘要：

  DOI：

文献信息

• Reactions of uranium mononitride, thorium monocarbide and uranium monocarbide with nitric acid and other aqueous reagents
  作者：Leslie M. Ferris

  DOI：10.1016/0022-1902(68)80393-8

  日期：1968.10

  Uranium mononitride was inert at 80° in water, 3–12 M HCl, 1 M H2SO4, 1 M NaOH, 1 M NaNO3, and 5 M NH4NO3; however, it did react in 1–2·5 M Al(NO3)3. The nitride reacted with 0·5–15·8 M HNO3 to give gaseous mixtures of N2, N2O, NO, and NO2 (NO2 was produced only when the acid concentration was 6 M or higher). In reactions of thorium monocarbide with 0·1 to 1 M HNO3 at 90°, both hydrolysis (yielding

  一氮化铀在80°C的水中，3–12 M HCl，1 MH 2 SO 4，1 M NaOH，1 M NaNO 3和5 M NH 4 NO 3呈惰性。但是，它确实在1-2·5 M Al（NO 3）3中反应。氮化物与0·5-15·8 M HNO 3反应，生成N 2，N 2 O，NO和NO 2的气态混合物（仅当酸浓度为6 M或更高时才产生NO 2）。在90°下，一碳化ide与0·1至1 M HNO 3的反应中，水解（主要产甲烷）和氧化（主要产CO 2，N 2），和氮氧化物）的碳化物发生; 在较高的HNO 3浓度下，仅发生氧化。UC或ThC与4和6 M NH 4 F在80°下的主要反应为：
• Equilibria of uranium carbides in the molten fluoride solutions of UF3 and UF4 contained in graphite at 850°K
  作者：L.M. Toth、L.O. Gilpatrick

  DOI：10.1016/0022-1902(73)80239-8

  日期：1973.5

  of dilute molten fluoride solutions of UF4 with UC, U2C3 and UC2 at 850°K has been investigated to establish that a UC2 phase, possibly oxygen stabilized, is the stable carbide phase in contact with dilute UF3-UF4 solutions contained in graphite. The carbides were identified by X-ray powder patterns. Lattice parameters for these carbides are included. UF3 and UF4 concentrations in solution were measured

  研究了UF 4与UC，U 2 C 3和UC 2在850°K下的稀熔融氟化物溶液的平衡，以建立UC 2相（可能是氧稳定的）是与稀UF 3接触的稳定碳化物相。-UF 4溶液包含在石墨中。通过X射线粉末图案鉴定出碳化物。这些碳化物的晶格参数也包括在内。通过近红外可见分光光度法测量溶液中的UF 3和UF 4浓度。平衡商Q =（UF 3）4 /（UF 4）根据以下反应，与熔融氟化物溶液接触的每种碳化物均计算为3：4UF3 + xC⇄3UF4 + UCϰ
• Infrared Spectra and Quantum Chemical Calculations of the Uranium Carbide Molecules UC and CUC with Triple Bonds
  作者：Xuefeng Wang、Lester Andrews、Per-Åke Malmqvist、Björn O. Roos、António P. Gonçalves、Cláudia C. L. Pereira、Joaquim Marçalo、Claude Godart、Benjamin Villeroy

  DOI：10.1021/ja102475t

  日期：2010.6.23

  Laser evaporation of carbon-rich uranium/carbon alloys followed by atom reactions in a solid argon matrix and trapping at 8 K gives weak infrared absorptions for CUO at 852 and 804 cm(-1). A new band at 827 cm(-1) becomes a doublet with mixed carbon 12 and 13 isotopes and exhibits the 1.0381 isotopic frequency ratio, which is appropriate for the UC diatomic molecule, and another new band at 891 cm(-1)

  富碳铀/碳合金的激光蒸发，然后是固体氩基质中的原子反应，并在 8 K 下捕获，在 852 和 804 cm(-1) 处为 CUO 提供微弱的红外吸收。827 cm(-1) 处的新谱带变成了混合碳 12 和 13 同位素的双峰，并显示出 1.0381 同位素频率比，这适用于 UC 双原子分子，而 891 cm(-1) 处的另一个新谱带给出了具有 1.0366 同位素频率比的三波段混合同位素谱，这是线性 CUC 分子的特征。具有动力学相关性的 CASPT2 计算发现 C[三键]U[三键]C 基态为线性 3Sigma(u)+，具有 1.840 A 键长和分子轨道占有率，有效键阶为 2.83。
• Coupling XRD, EXAFS, and ¹³C NMR to Study the Effect of the Carbon Stoichiometry on the Local Structure of UC_1±<i>x</i>
  作者：U. Carvajal Nuñez、L. Martel、D. Prieur、E. Lopez Honorato、R. Eloirdi、I. Farnan、T. Vitova、J. Somers

  DOI：10.1021/ic402144g

  日期：2013.10.7

  diffraction (XRD), 13C nuclear magnetic resonance (NMR), and extended X-ray absorption fine structure (EXAFS). XRD determines phase uniqueness and the increase of the lattice parameter versus the carbon content. In contrast, 13C NMR detects the different carbon environments in the lattice and in this study, clearly identifies the presence of discrete peaks for carbon in the octahedral lattice site in UC and

  通过X射线衍射（XRD），13 C核磁共振（NMR）和扩展X射线吸收研究了一系列通过电弧熔化制备的碳化铀样品，其C / U比在0.96至1.04范围内精细结构（EXAFS）。XRD确定相的唯一性以及晶格参数相对于碳含量的增加。相比之下，1313 C NMR检测到晶格中的不同碳环境，在这项研究中，可以清楚地识别出UC中八面体晶格位点中碳的离散峰以及与超化学计量样品中过量碳相关的另一个峰。对于所有化学计量不足的成分，均检测到与碳缺乏水平不同相关的两个峰。始终通过13 C NMR检测到一个以上的碳环境。这举例说明了获得理想的化学计量的一碳化铀UC 1.00的难度。在13碳化铀的C MAS光谱显示出碳含量对峰的加宽和奈特位移的影响。在低化学计量和超化学计量的样品之间会发生突然的光谱变化。通过EXAFS获得的结果突显了不同化学计量之间的细微差异，在超化学计量样品中，EXAFS结果与多余的碳原子在四面体间隙位置一致。
• Thermodynamics of nitrogen-rich uranium sesquinitride formation by reaction of uranium monocarbide with ammonia
  作者：K. Nishimaki、M. Hirota、T. Nakagawa、T.A. Yamamoto、M. Miyake、M. Katsura

  DOI：10.1016/s0925-8388(98)00180-7

  日期：1998.6

  Abstract According to our thermodynamic analysis, the flowing NH 3 possesses high nitrogen and hydrogen activities due to its instability with respect to the dissociation equilibrium, NH 3 ⇄(1/2)N 2 +(3/2)H 2 . As the extent of dissociation of NH 3 into N 2 and H 2 , α , is lower, nitrogen and hydrogen activities exhibited by unstable gaseous mixture of NH 3 , N 2 and H 2 become higher. The reaction

  摘要 根据我们的热力学分析，流动的NH 3 由于其解离平衡NH 3 ⇄(1/2)N 2 +(3/2)H 2 的不稳定性而具有较高的氮和氢活性。由于NH 3 离解成N 2 和H 2 的程度α越低，NH 3 、N 2 和H 2 的不稳定气体混合物表现出的氮和氢活性变得越高。UC 与 NH 3 流在 600、700、800 和 900°C 下的反应实验是在两个不同的 α 值下进行的。一些运行使用 1 g UC 作为起始材料，而其他运行使用 2 g UC。在这四个温度中的每一个温度下，除了使用的 UC 量不同外，在相同的实验条件下进行了两次运行。实验结果表明，解离程度 α ，在使用2g UC的情况下比在使用1g UC的情况下更大可能表明NH 3 解离的程度受作为起始材料的UC的量的很大影响。发现由具有较低α的NH 3 、N 2 和H 2 组成的气相在给定温度下产生具有较高N/U比的U 2 N 3+