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硫化銅

硫化銅
IUPAC名
Copper(II) sulfide
硫化铜
别名 靛铜矿
硫化铜(II)
识别
CAS号 1317-40-4 ?
PubChem 14831
SMILES
 
  • [Cu+2].[S-2]
RTECS GL8912000
性质
化学式 CuS
摩尔质量 95.611[1] g·mol⁻¹
外观 黑色六方晶体[1]
密度 4.76 g/cm3[1]
熔点 507°C[1](转化为硫化亚铜 [1][3]
溶解性 难溶[1]
溶度积Ksp 8.0 x 10-34
溶解性 难溶于稀酸,强碱溶液,乙醇[1]溶于硝酸氰化钾
折光度n
D
1.45 [2]
结构
晶体结构 六方[1]
相关物质
其他阴离子 氧化铜
其他阳离子 硫化锌
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

硫化铜是一种的化合物,化学式CuS,在自然界中以深蓝色的靛铜矿形式存在。它是一种中等导电性的导体[4] 硫化氢气体通入铜盐溶液时可形成硫化铜的胶状沉淀。[5] 目前也有研究發現硫化铜可用在催化[6] 和光电性[7] 的應用上。

结构

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硫化铜(靛铜矿)以六方晶系形式结晶,也存在一种不定型的高压形式,[8] 是以拉曼光譜學为基础,被描述为一种扭曲的靛铜矿形式的结构。由铜(II)乙二胺配合物硫脲在常温下反应也可得一种不定型的半导体硫化铜,在30°C时转化为靛铜矿结构。[9]
硫化铜的晶体结构被多次报道。[10][11][12] Wells形容此结构“特别”,[13] 它与氧化铜的晶体结构很不相同,但与硒化铜(CuSe)的结构相似。硫化铜晶胞包含6个CuS(12个原子),其中

  • 4个铜原子成四面体结构。
  • 2个铜原子成平面三角形结构。
  • 2对硫原子的距离仅207.1 pm,[12] 证明了S-S键(二硫键)的存在。
  • 剩下的两个硫原子形成围绕铜原子的三角形结构,并且这两个硫原子也被5个构成五角双锥结构的铜原子围绕。
  • 二硫键中的两个硫原子中的一个与3个四面体构型的铜原子配位。

硫化铜CuIIS(不含硫硫键)与晶体结构不相符合,与观测到的抗磁性不吻合,[14] 因为Cu(II)化合物具d9排布,应为顺磁性物质。[5]
使用XPS技术的研究[15][16][17][18] 表明所有的铜原子均具有+1的氧化态。这与许多课本中的八隅律相违背。[5] 通常课本认为CuS同时具有CuI和CuII,也就是(Cu+)2Cu2+(S2)2–S2–。另外一种化学式(Cu+)3(S2–)(S2)则收到了计算数据的支持。[19] 这种化学式不应被认为是含有自由离子,而是存在价“空洞”。[19][20] 对Cu(II)盐沉淀的电子顺磁共振研究也显示出溶液中Cu(II)被还原至Cu(I)的过程的存在。[21]

部分结构的球棍模型
铜原子的三角形构型
铜原子的四面体构型
硫原子的三角双锥构型
二硫键的四面体构型

参见

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参考

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  1. ^ 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 CRC Handbook of Chemistry and Physics 97th Edition. 2016-06-24: 4–60. ISBN 1-4987-5428-7 (英语). 
  2. ^ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0070494398
  3. ^ Blachnik, R.; Müller, A., The formation of Cu2S from the elements I. Copper used in form of powders, Thermochimica Acta, 2000, 361 (1–2): 31–52, doi:10.1016/S0040-6031(00)00545-1 
  4. ^ Wells A.F. (1962) Structural Inorganic Chemistry 3d edition Oxford University Press
  5. ^ 5.0 5.1 5.2 Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4. 
  6. ^ Kuchmii, S.Y.; Korzhak A.V., Raevskaya A.E.,Kryukov A.I. Catalysis of the Sodium Sulfide Reduction of Methylviologene by CuS Nanoparticles. Theoretical and Experimental Chemistry (New York: Springer). 2001, 37 (1): 36–41. doi:10.1023/A:1010465823376. 
  7. ^ Mane, R.S.; Lokhande C.D. Chemical deposition method for metal chalcogenide thin films. Materials Chemistry and Physics. June 2000, 65: 1–31. doi:10.1016/S0254-0584(00)00217-0. 
  8. ^ Peiris, M; Sweeney, J.S.; Campbell, A.J.; Heinz D. L. Pressure-induced amorphization of covellite, CuS. J. Chem. Phys. 1996, 104: 11–16. doi:10.1063/1.470870. 
  9. ^ Grijalva, H.; Inoue, M.; Boggavarapu, S.; Calvert, P. Amorphous and crystalline copper sulfides, CuS. J. Mater. Chem. 1996, 6: 1157–1160. doi:10.1039/JM9960601157. 
  10. ^ Oftedal, I. Z. Kristallogr. 1932, 83: 9–25.  缺少或|title=为空 (帮助)
  11. ^ Berry, L. G. The crystal structure of covellite CuS and klockmannite CuSe. American Mineralogist. 1954, 39: 504. 
  12. ^ 12.0 12.1 Evans, H.T. Jr.; Konnert J. Crystal structure refinement of covellite. American Mineralogist. 1976, 61: 996–1000. 
  13. ^ Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN 0-19-855370-6
  14. ^ Magnetic susceptibility of the elements and inorganic compounds 互联网档案馆存檔,存档日期2012-01-12.
  15. ^ Nakai, I.; Sugitani, Y.; Nagashima, K.; Niwa, Y. X-ray photoelectron spectroscopic study of copper minerals. Journal of Inorganic and Nuclear Chemistry. 1978, 40 (5): 789–791. doi:10.1016/0022-1902(78)80152-3. 
  16. ^ Folmer, J.C.W.; Jellinek F. The valence of copper in sulfides and selenides: An X-ray photoelectron spectroscopy study. Journal of the Less Common Metals. 1980, 76 (1-2): 789–791. doi:10.1016/0022-5088(80)90019-3. 
  17. ^ Folmer, J.C.W.; Jellinek F., Calis G.H.M. The electronic structure of pyrites, particularly CuS2 and Fe1−xCuxSe2: An XPS and Mössbauer study. Journal of Solid State Chemistry. 1988, 72 (1): 137–144. doi:10.1016/0022-4596(88)90017-5. 
  18. ^ Goh, S.W.; Buckley A.N., Lamb R.N. Copper(II) sulfide?. Minerals Engineering. 2006年2月, 19 (2): 204–208. doi:10.1016/j.mineng.2005.09.003. 
  19. ^ 19.0 19.1 Liang, W.; Whangbo M, -H. Conductivity anisotropy and structural phase transition in Covellite CuS. Solid State Communications. 1993年2月, 85 (5): 405–408. doi:10.1016/0038-1098(93)90689-K. 
  20. ^ Nozaki, H; Shibata, K; Ohhashi,N. Metallic hole conduction in CuS. Journal of Solid State Chemistry. 1991年4月, 91 (2): 306–311. doi:10.1016/0022-4596(91)90085-V. 
  21. ^ Luther, GW; Theberge SM, Rozan TF, Rickard D, Rowlands CC, Oldroyd A. Aqueous copper sulfide clusters as intermediates during copper sulfide formation.. Environ. Sci. Technol. 2002年2月, 36 (3): 394–402. doi:10.1021/es010906k. 
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硫化銅
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