Chemistry:Copper monosulfide

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Copper monosulfide
Names
IUPAC name
Copper sulfide
Other names
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 215-271-2
RTECS number
  • GL8912000
UNII
Properties
Cu3S3
Molar mass 95.611 g/mol
Appearance black powder or lumps
Density 4.76 g/cm3
Melting point above 500 °C (932 °F; 773 K) (decomposes)[2]
3.3×10−5 g/100 ml (18 °C)
Solubility product (Ksp) of CuS
 6×10−37 (25 °C)[1]
−2.0×10−6 cm3/mol
1.45
Structure
hexagonal
Hazards
GHS pictograms GHS09: Environmental hazard
H413
P273, P501
NIOSH (US health exposure limits):Template:Chembox NIOSH (set)/formatPocketGuideLink
PEL (Permissible)
 TWA 1 mg/m3 (as Cu)
REL (Recommended)
 TWA 1 mg/m3 (as Cu)
IDLH (Immediate danger)
 TWA 100 mg/m3 (as Cu)
Related compounds
Other anions
 Copper(II) oxide
Other cations
 zinc sulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Copper monosulfide is a chemical compound of copper and sulfur with the formula Cu
3S(S
2).[3] It occurs in nature as the dark indigo blue mineral covellite.[3] It is one of a number of binary compounds of copper and sulfur (see copper sulfide for an overview of this subject), and has attracted interest because of its potential uses in catalysis[4] and photovoltaics.[5] It is a moderate conductor of electricity.[6]

Manufacturing

A black colloidal precipitate of copper monosulfide is formed when hydrogen sulfide, H
2S, is bubbled through solutions of Cu(II) salts.[7] This is the basis of its industrial production. Special forms of CuS for certain applications can be prepared by melting an excess of sulfur with copper(I) sulfide or by precipitation with hydrogen sulfide from a solution of anhydrous copper(II) chloride in anhydrous ethanol. Nanoparticles of CuS can be prepare by reaction of dissolved copper(II) chloride with thioglycolic acid.[8]

The reaction of copper with molten sulfur followed by boiling sodium hydroxide and the reaction of sodium sulfide with aqueous copper sulfate will also produce copper sulfide.

CuS structure and bonding

Copper sulfide crystallizes in the hexagonal crystal system, and this is the form of the mineral covellite. There is also an amorphous high pressure form[9] which on the basis of the Raman spectrum has been described as having a distorted covellite structure. An amorphous room temperature semiconducting form produced by the reaction of a Cu(II) ethylenediamine complex with thiourea has been reported, which transforms to the crystalline covellite form at 30 °C (86 °F).[10]
The crystal structure of covellite has been reported several times,[11][12][13] and whilst these studies are in general agreement on assigning the space group P63/mmc there are small discrepancies in bond lengths and angles between them. The structure was described as "extraordinary" by Wells[14] and is quite different from Copper(II) oxide, but similar to Copper(II) selenide (or referred to as Klockmannite). The covellite unit cell contains 6 formula units (12 atoms) in which:

  • 4 Cu atoms have tetrahedral coordination (see illustration).
  • 2 Cu atoms have trigonal planar coordination (see illustration).
  • 2 pairs of S atoms are only 207.1 picometers apart[13] indicating the existence of an S-S bond (a disulfide unit).
  • the 2 remaining S atoms form trigonal planar triangles around the copper atoms, and are surrounded by five Cu atoms in a pentagonal bipyramid (see illustration).
  • The S atoms at each end of a disulfide unit are tetrahedrally coordinated to 3 tetrahedrally coordinated Cu atoms and the other S atom in the disulfide unit (see illustration).

The formulation of copper sulfide as CuII
S (i.e. containing no sulfur-sulfur bond) is clearly incompatible with the crystal structure, and also at variance with the observed diamagnetism[15] as a Cu(II) compound would have a d9 configuration and be expected to be paramagnetic.[7]{{page needed|date=July 2025} Studies using XPS[16][17][18][19] indicate that all of the copper atoms have an oxidation state of +1. This contradicts a formulation based on the crystal structure and obeying the octet rule that is found in many textbooks (e.g.[7] [20] and CuII
 i.e. (Cu+
)
2Cu2+(S
2)2−S2−. An alternative formulation as (Cu+
)
3(S2−)(S
2)−
 was proposed and supported by calculations. The formulation should not be interpreted as containing radical anion, but rather that there is a delocalized valence "hole".[3][21] Electron paramagnetic resonance studies on the precipitation of Cu(II) salts indicates that the reduction of Cu(II) to Cu(I) occurs in solution.[22]

200px

120px 120px 120px 120px
ball-and-stick model of part of
the crystal structure of covellite		 trigonal planar
coordination of copper		 tetrahedral
coordination of copper		 trigonal bipyramidal
coordination of sulfur		 tetrahedral
coordination of sulfur-note[clarification needed] disulfide unit

See also

References

  1. ↑ Rollie J. Myers (1986). "The new low value for the second dissociation constant for H2S: Its history, its best value, and its impact on the teaching of sulfide equilibria". J. Chem. Educ. 63 (8): 687–690. doi:10.1021/ed063p687. Bibcode: 1986JChEd..63..687M. 
  2. ↑ Blachnik, R.; Müller, A. (2000). "The formation of Cu2S from the elements I. Copper used in form of powders". Thermochimica Acta 361 (1–2): 31–52. doi:10.1016/S0040-6031(00)00545-1. 
  3. ↑ 3.0 3.1 3.2 Liang, W.; Whangbo, M.-H. (February 1993). "Conductivity anisotropy and structural phase transition in Covellite CuS". Solid State Communications 85 (5): 405–408. doi:10.1016/0038-1098(93)90689-K. Bibcode: 1993SSCom..85..405L. 
  4. ↑ Kuchmii, S.Y.; Korzhak A.V.; Raevskaya A.E.; Kryukov A.I. (2001). "Catalysis of the Sodium Sulfide Reduction of Methylviologene by CuS Nanoparticles". Theoretical and Experimental Chemistry (New York: Springer) 37 (1): 36–41. doi:10.1023/A:1010465823376. 
  5. ↑ Mane, R.S.; Lokhande C.D. (June 2000). "Chemical deposition method for metal chalcogenide thin films". Materials Chemistry and Physics 65 (1): 1–31. doi:10.1016/S0254-0584(00)00217-0. 
  6. ↑ Wells, Alexander Frank (1984). Structural Inorganic Chemistry (5th ed.). Oxford University Press. p. 1142. ISBN 0-19-855370-6. https://archive.org/details/structuralinorga0000well_m8i1/page/1142/mode/2up?q=covellite. 
  7. ↑ 7.0 7.1 7.2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 1181. ISBN 978-0-08-037941-8. 
  8. ↑ "Copper Sulfide Nanoparticles for Photothermal Ablation of Tumor Cells". Nanomedicine. https://www.tandfonline.com/doi/abs/10.2217/nnm.10.85. 
  9. ↑ Peiris, M; Sweeney, J.S.; Campbell, A.J.; Heinz D. L. (1996). "Pressure-induced amorphization of covellite, CuS". J. Chem. Phys. 104 (1): 11–16. doi:10.1063/1.470870. Bibcode: 1996JChPh.104...11P. 
  10. ↑ Grijalva, H.; Inoue, M.; Boggavarapu, S.; Calvert, P. (1996). "Amorphous and crystalline copper sulfides, CuS". J. Mater. Chem. 6 (7): 1157–1160. doi:10.1039/JM9960601157. 
  11. ↑ Oftedal, I. (1932). "Die Kristallstruktur des Covellins (CuS)". Z. Kristallogr. 83 (1–6): 9–25. doi:10.1524/zkri.1932.83.1.9. 
  12. ↑ Berry, L. G. (1954). "The crystal structure of covellite CuS and klockmannite CuSe". American Mineralogist 39: 504. 
  13. ↑ 13.0 13.1 Evans, H.T. Jr.; Konnert J. (1976). "Crystal structure refinement of covellite". American Mineralogist 61: 996–1000. 
  14. ↑ Wells, A. F. (1984). Structural inorganic chemistry (5th ed.). Oxford [Oxfordshire] : New York: Clarendon Press; Oxford University Press. ISBN 0-19-855370-6. 
  15. ↑ Magnetic susceptibility of the elements and inorganic compounds
  16. ↑ Nakai, I.; Sugitani, Y.; Nagashima, K.; Niwa, Y. (1978). "X-ray photoelectron spectroscopic study of copper minerals". Journal of Inorganic and Nuclear Chemistry 40 (5): 789–791. doi:10.1016/0022-1902(78)80152-3. 
  17. ↑ Folmer, J.C.W.; Jellinek F. (1980). "The valence of copper in sulfides and selenides: An X-ray photoelectron spectroscopy study". Journal of the Less Common Metals 76 (1–2): 789–791. doi:10.1016/0022-5088(80)90019-3. 
  18. ↑ Folmer, J.C.W.; Jellinek F.; Calis G.H.M (1988). "The electronic structure of pyrites, particularly CuS2 and Fe1−xCuxSe2: An XPS and Mössbauer study". Journal of Solid State Chemistry 72 (1): 137–144. doi:10.1016/0022-4596(88)90017-5. Bibcode: 1988JSSCh..72..137F. 
  19. ↑ Goh, S.W.; Buckley A.N.; Lamb R.N. (February 2006). "Copper(II) sulfide?". Minerals Engineering 19 (2): 204–208. doi:10.1016/j.mineng.2005.09.003. Bibcode: 2006MiEng..19..204G. 
  20. ↑ Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5 
  21. ↑ Nozaki, H; Shibata, K; Ohhashi, N. (April 1991). "Metallic hole conduction in CuS". Journal of Solid State Chemistry 91 (2): 306–311. doi:10.1016/0022-4596(91)90085-V. Bibcode: 1991JSSCh..91..306N. 
  22. ↑ Luther, GW; Theberge SM; Rozan TF; Rickard D; Rowlands CC; Oldroyd A. (February 2002). "Aqueous copper sulfide clusters as intermediates during copper sulfide formation.". Environ. Sci. Technol. 36 (3): 394–402. doi:10.1021/es010906k. PMID 11871554. Bibcode: 2002EnST...36..394L. 

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