Copper monosulfide

Last updated
Copper monosulfide
Sulfid mednaty.PNG
Names
IUPAC name
Copper sulfide
Other names
Covellite
Copper(II) sulfide
Cupric sulfide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.884 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-271-2
PubChem CID
RTECS number
  • GL8912000
UNII
  • InChI=1S/Cu.S Yes check.svgY
    Key: BWFPGXWASODCHM-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Cu.S/rCuS/c1-2
    Key: BWFPGXWASODCHM-BLKBWTQCAT
  • [Cu]=S
Properties
CuS
Molar mass 95.611 g/mol
Appearanceblack powder or lumps
Density 4.76 g/cm3
Melting point above500 °C (932 °F; 773 K) (decomposes) [1]
0.000033 g/100 ml (18 °C)
6 x 10−37 [2]
Solubility soluble in HNO3, NH4OH, KCN
insoluble in HCl, H2SO4
-2.0·10−6 cm3/mol
1.45
Structure
hexagonal
Hazards
GHS labelling:
GHS-pictogram-pollu.svg
H413
P273, P501
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 1 mg/m3 (as Cu) [3]
REL (Recommended)
TWA 1 mg/m3 (as Cu) [3]
IDLH (Immediate danger)
TWA 100 mg/m3 (as Cu) [3]
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).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Copper monosulfide is a chemical compound of copper and sulfur. It was initially thought to occur in nature as the dark indigo blue mineral covellite. However, it was later shown to be rather a cuprous compound, formula Cu+3S(S2). [4] CuS is a moderate conductor of electricity. [5] A black colloidal precipitate of CuS is formed when hydrogen sulfide, H2S, is bubbled through solutions of Cu(II) salts. [6] 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 [7] and photovoltaics. [8]

Contents

Manufacturing

Copper monosulfide can be prepared by passing hydrogen sulfide gas into a solution of copper(II) salt.

Alternatively, it 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.

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. [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 CuSe (klockmannite). The covellite unit cell contains 6 formula units (12 atoms) in which:

The formulation of copper sulfide as CuIIS (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. [6]
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. [6] [20] ) describing CuS as containing both CuI and CuII i.e. (Cu+)2Cu2+(S2)2−S2−. An alternative formulation as (Cu+)3(S2−)(S2)− was proposed and supported by calculations. [21] The formulation should not be interpreted as containing radical anion, but rather that there is a delocalized valence "hole". [21] [22] Electron paramagnetic resonance studies on the precipitation of Cu(II) salts indicates that the reduction of Cu(II) to Cu(I) occurs in solution. [23]

Covellite-xtal-CM-3D-balls.png

Covellite-Cu1-coordination-3D-balls.png Covellite-Cu2-coordination-3D-balls.png Covellite-S1-coordination-3D-balls.png Covellite-S2-coordination-3D-balls.png
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 disulfide unit

See also

Related Research Articles

<span class="mw-page-title-main">Pyrite</span> Iron (II) disulfide mineral

The mineral pyrite ( PY-ryte), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula FeS2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral.

<span class="mw-page-title-main">Chalcopyrite</span> Copper iron sulfide mineral

Chalcopyrite ( KAL-kə-PY-ryte, -⁠koh-) is a copper iron sulfide mineral and the most abundant copper ore mineral. It has the chemical formula CuFeS2 and crystallizes in the tetragonal system. It has a brassy to golden yellow color and a hardness of 3.5 to 4 on the Mohs scale. Its streak is diagnostic as green-tinged black.

<span class="mw-page-title-main">Bornite</span> Sulfide mineral

Bornite, also known as peacock ore, is a sulfide mineral with chemical composition Cu5FeS4 that crystallizes in the orthorhombic system (pseudo-cubic).

<span class="mw-page-title-main">Cadmium sulfide</span> Chemical compound

Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow salt. It occurs in nature with two different crystal structures as the rare minerals greenockite and hawleyite, but is more prevalent as an impurity substituent in the similarly structured zinc ores sphalerite and wurtzite, which are the major economic sources of cadmium. As a compound that is easy to isolate and purify, it is the principal source of cadmium for all commercial applications. Its vivid yellow color led to its adoption as a pigment for the yellow paint "cadmium yellow" in the 18th century.

<span class="mw-page-title-main">Covellite</span> Sulfide mineral

Covellite is a rare copper sulfide mineral with the formula CuS. This indigo blue mineral is commonly a secondary mineral in limited abundance and although it is not an important ore of copper itself, it is well known to mineral collectors.

<span class="mw-page-title-main">Polysulfide</span>

Polysulfides are a class of chemical compounds derived from anionic chains of sulfur atoms. There are two main classes of polysulfides: inorganic and organic. The inorganic polysulfides have the general formula S2−
n. These anions are the conjugate bases of polysulfanes H2Sn. Organic polysulfides generally have the formulae R1SnR2, where R = alkyl or aryl.

<span class="mw-page-title-main">Chalcogenide</span>

A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.

Sulfur compounds are chemical compounds formed the element sulfur (S). Common oxidation states of sulfur range from −2 to +6. Sulfur forms stable compounds with all elements except the noble gases.

<span class="mw-page-title-main">Silicon disulfide</span> Chemical compound

Silicon disulfide is the inorganic compound with the formula SiS2. Like silicon dioxide, this material is polymeric, but it adopts a 1-dimensional structure quite different from the usual forms of SiO2.

<span class="mw-page-title-main">Thorium(IV) sulfide</span> Chemical compound

Thorium(IV) sulfide (ThS2) is an inorganic chemical compound composed of one thorium atom ionically bonded to two atoms of sulfur. This salt is dark brown and has a melting point of 1905 °C. ThS2 adopts the same orthorhombic lattice structure as PbCl2.

<span class="mw-page-title-main">Ammonium tetrathiomolybdate</span> Chemical compound

Ammonium tetrathiomolybdate is the chemical compound with the formula (NH4)2MoS4. This bright red ammonium salt is an important reagent in the chemistry of molybdenum and has been used as a building block in bioinorganic chemistry. The thiometallate (see metallate) anion has the distinctive property of undergoing oxidation at the sulfur centers concomitant with reduction of the metal from Mo(VI) to Mo(IV).

Copper sulfides describe a family of chemical compounds and minerals with the formula CuxSy. Both minerals and synthetic materials comprise these compounds. Some copper sulfides are economically important ores.

<span class="mw-page-title-main">Copper(I) sulfide</span> Chemical compound

Copper(I) sulfide is a copper sulfide, a chemical compound of copper and sulfur. It has the chemical compound Cu2S. It is found in nature as the mineral chalcocite. It has a narrow range of stoichiometry ranging from Cu1.997S to Cu2.000S. Samples are typically black.

<span class="mw-page-title-main">Titanium disulfide</span> Inorganic chemical compound

Titanium disulfide is an inorganic compound with the formula TiS2. A golden yellow solid with high electrical conductivity, it belongs to a group of compounds called transition metal dichalcogenides, which consist of the stoichiometry ME2. TiS2 has been employed as a cathode material in rechargeable batteries.

Phosphorus selenides are a relatively obscure group of compounds. There have been some studies of the phosphorus - selenium phase diagram and the glassy amorphous phases are reported. The compounds that have been reported are shown below. While some of phosphorus selenides are similar to their sulfide analogues, there are some new forms, molecular P2Se5 and the polymeric catena-[P4Se4]x. There is also some doubt about the existence of molecular P4Se10.

<span class="mw-page-title-main">Rhenium disulfide</span> Chemical compound

Rhenium disulfide is an inorganic compound of rhenium and sulfur with the formula ReS2. It has a layered structure where atoms are strongly bonded within each layer. The layers are held together by weak Van der Waals bonds, and can be easily peeled off from the bulk material.

<span class="mw-page-title-main">Thiosilicate</span> Inorganic silicon compound

In chemistry and materials science, thiosilicate refers to materials containing anions of the formula [SiS2+n]2n−. Derivatives where some sulfide is replaced by oxide are also called thiosilicates, examples being materials derived from the oxohexathiodisilicate [Si2OS6]6−. Silicon is tetrahedral in all thiosilicates and sulfur is bridging or terminal. Formally such materials are derived from silicon disulfide in analogy to the relationship between silicon dioxide and silicates. Thiosilicates are typically encountered as colorless solids. They are characteristically sensitive to hydrolysis. They are from the class of chalcogenidotetrelates.

<span class="mw-page-title-main">Iridium disulfide</span> Chemical compound

Iridium disulfide is the binary inorganic compound with the formula IrS2. Prepared by the direct reaction of the elements, the compound adopts the pyrite crystal structure at high pressure. At normal atmospheric pressures, an orthorhombic polymorph is observed.. The high- and low-pressure forms both feature octahedral Ir centers, but the S–S distances are pressure dependent. Although not practical, IrS2 is a highly active catalyst for hydrodesulfurization.

<span class="mw-page-title-main">Palladium(II) sulfide</span> Chemical compound

Palladium(II) sulfide is a chemical compound of palladium and sulfur with the chemical formula PdS. Like other palladium and platinum chalcogenides, palladium(II) sulfide has complex structural, electrical and magnetic properties.

Sulfidostannates, or thiostannates are chemical compounds containing anions composed of tin linked with sulfur. They can be considered as stannates with sulfur substituting for oxygen. Related compounds include the thiosilicates, and thiogermanates, and by varying the chalcogen: selenostannates, and tellurostannates. Oxothiostannates have oxygen in addition to sulfur. Thiostannates can be classed as chalcogenidometalates, thiometallates, chalcogenidotetrelates, thiotetrelates, and chalcogenidostannates. Tin is almost always in the +4 oxidation state in thiostannates, although a couple of mixed sulfides in the +2 state are known,

References

  1. ↑ 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.
  2. ↑ 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. Bibcode:1986JChEd..63..687M. doi:10.1021/ed063p687.
  3. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  4. ↑ Liang, W., Whangbo, M.H. (1993) Conductivity anisotropy and structural phase transition in Covellite CuS Solid State Communications, 85(5), 405-408
  5. ↑ Wells A.F. (1962) Structural Inorganic Chemistry 3d edition Oxford University Press
  6. 1 2 3 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  7. ↑ 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. S2CID   91893521.
  8. ↑ 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.
  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. Bibcode:1996JChPh.104...11P. doi:10.1063/1.470870.
  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. S2CID   101164006.
  12. ↑ Berry, L. G. (1954). "The crystal structure of covellite CuS and klockmannite CuSe". American Mineralogist. 39: 504.
  13. 1 2 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 edition Oxford Science Publications ISBN   0-19-855370-6
  15. ↑ Magnetic susceptibility of the elements and inorganic compounds Archived 2012-01-12 at the Wayback Machine
  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. Bibcode:1988JSSCh..72..137F. doi:10.1016/0022-4596(88)90017-5.
  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.
  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. 1 2 Liang, W.; Whangbo M, -H (February 1993). "Conductivity anisotropy and structural phase transition in Covellite CuS". Solid State Communications. 85 (5): 405–408. Bibcode:1993SSCom..85..405L. doi:10.1016/0038-1098(93)90689-K.
  22. ↑ Nozaki, H; Shibata, K; Ohhashi,N. (April 1991). "Metallic hole conduction in CuS". Journal of Solid State Chemistry. 91 (2): 306–311. Bibcode:1991JSSCh..91..306N. doi:10.1016/0022-4596(91)90085-V.
  23. ↑ 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. Bibcode:2002EnST...36..394L. doi:10.1021/es010906k. PMID   11871554.
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