Copper monosulfide: Difference between revisions

|Watchedfields = changed

|verifiedrevid = 440734948

|ImageFile = Sulfid měďnatý.PNG

|IUPACName = Copper sulfide

|OtherNames = [[Covellite]]<br/>Copper(II) sulfide<br/>Cupric sulfide

|Section1={{Chembox Identifiers

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChemSpiderID = 14145

|InChI = 1/Cu.S/rCuS/c1-2

|SMILES = [Cu]=S

|InChIKey = BWFPGXWASODCHM-BLKBWTQCAT

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChI = 1S/Cu.S

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = BWFPGXWASODCHM-UHFFFAOYSA-N

|CASNo = 1317-40-4

|CASNo_Ref = {{cascite|correct|CAS}}

|UNII_Ref = {{fdacite|correct|FDA}}

|UNII = KL4YU612X7

|PubChem = 14831

|RTECS = GL8912000

|EC_number = 215-271-2

|Section2={{Chembox Properties

|Formula = CuS

|MolarMass = 95.611 g/mol

|Appearance = black powder or lumps

|Density = 4.76 g/cm³

|MeltingPt= above

|MeltingPtC = 500

|MeltingPt_notes = (decomposes)<ref name = "Blachnik">{{Cite journal | last = Blachnik | first = R. |author2=Müller, A. | year = 2000 | title = The formation of Cu₂S from the elements I. Copper used in form of powders | journal= Thermochimica Acta | volume = 361 | issue = 1–2 | pages= 31–52 | doi= 10.1016/S0040-6031(00)00545-1 }}</ref>

|Solubility = 0.000033 g/100 ml (18 °C)

|SolubilityProduct = 6 x 10⁻³⁷<ref>{{cite journal | title=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 | author=Rollie J. Myers | journal=J. Chem. Educ. | year=1986 | volume=63 | issue=8 | pages=687 |doi=10.1021/ed063p687| bibcode=1986JChEd..63..687M }}</ref>

|SolubleOther = soluble in [[nitric acid|HNO₃]], [[ammonium hydroxide|NH₄OH]], [[potassium cyanide|KCN]] <br> insoluble in [[hydrochloric acid|HCl]], [[sulfuric acid|H₂SO₄]]

|RefractIndex = 1.45

|MagSus = -2.0·10⁻⁶ cm³/mol

}}

|Section3={{Chembox Structure

|CrystalStruct = hexagonal

}}

|Section4={{Chembox Hazards

|GHSPictograms = {{GHS09}}

|HPhrases = {{H-phrases|413}}

|PPhrases = {{P-phrases|273|501}}

|PEL = TWA 1 mg/m³ (as Cu)<ref name=PGCH>{{PGCH|0150}}</ref>

|REL = TWA 1 mg/m³ (as Cu)<ref name=PGCH/>

|IDLH = TWA 100 mg/m³ (as Cu)<ref name=PGCH/>

}}

|Section5={{Chembox Related

|OtherAnions = [[Copper(II) oxide]]

|OtherCations = [[zinc sulfide]]

}}

}}

'''Copper monosulfide''' <!-- No, it is NOT copper (II), please read the article before changing that --> 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).<ref name ="Liang & 1993">Liang, W., Whangbo, M.H. (1993) ''Conductivity anisotropy and structural phase transition in Covellite CuS'' Solid State Communications, 85(5), 405-408</ref> CuS is a moderate conductor of electricity.<ref name ="Wells">Wells A.F. (1962) ''Structural Inorganic Chemistry'' 3d edition Oxford University Press</ref> A black colloidal precipitate of CuS is formed when [[hydrogen sulfide]], H₂S, is bubbled through solutions of Cu(II) salts.<ref name = "Greenwood">{{Greenwood&Earnshaw}}</ref> 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<ref>{{cite journal

| author2=Korzhak A.V.|author3=Raevskaya A.E.|author4=Kryukov A.I.

| doi = 10.1023/A:1010465823376| s2cid = 91893521

}}</ref> and [[photovoltaics]].<ref>

| author2=Lokhande C.D.

| date=June 2000

| title = Chemical deposition method for metal chalcogenide thin films

| issue = 1| pages = 1–31

==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.

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<ref>{{cite journal

|author2=Sweeney, J.S. |author3=Campbell, A.J. |author4=Heinz D. L.

| year = 1996

| issue = 1| pages = 11–16

| doi = 10.1063/1.470870 |bibcode = 1996JChPh.104...11P }}</ref> which on the basis of the [[Raman spectroscopy|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.<ref>{{cite journal

| first = H. |author2=Inoue, M. |author3=Boggavarapu, S. |author4=Calvert, P.

| issue = 7| pages = 1157–1160

| title = Die Kristallstruktur des Covellins (CuS)

| issue = 1–6

| doi = 10.1524/zkri.1932.83.1.9

| s2cid = 101164006

}}</ref><ref>{{cite journal

| author2=Konnert J.

| pages = 996–1000}}</ref> 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<ref>Wells A.F. (1984) ''Structural Inorganic Chemistry'' 5th edition Oxford Science Publications {{ISBN|0-19-855370-6}}</ref> 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:

* 2 pairs of S atoms are only 207.1 pm apart<ref name= "Evans"/> 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 formulation of copper sulfide as Cu^IIS (i.e. containing no sulfur-sulfur bond) is clearly incompatible with the crystal structure, and also at variance with the observed diamagnetism<ref>[http://www-d0.fnal.gov/hardware/cal/lvps_info/engineering/elementmagn.pdf Magnetic susceptibility of the elements and inorganic compounds] {{webarchive|url=https://web.archive.org/web/20120112012253/http://www-d0.fnal.gov/hardware/cal/lvps_info/engineering/elementmagn.pdf |date=2012-01-12 }}</ref> as a Cu(II) compound would have a d⁹ configuration and be expected to be paramagnetic.<ref name = "Greenwood"/> <br />

| first = I. |author2=Sugitani, Y. |author3=Nagashima, K. |author4=Niwa, Y.

| author2=Jellinek F.

| issue = 1–2

| author2=Jellinek F.|author3=Calis G.H.M

| doi = 10.1016/0022-4596(88)90017-5|bibcode = 1988JSSCh..72..137F }}</ref><ref>{{cite journal

| author2=Buckley A.N.|author3=Lamb R.N.

| date=February 2006

| doi = 10.1016/j.mineng.2005.09.003}}</ref> 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.<ref name = "Greenwood"/><ref>{{Cotton&Wilkinson6th}}</ref>) describing CuS as containing both Cu^I and Cu^II i.e. (Cu⁺)₂Cu²⁺(S₂)²⁻S²⁻. An alternative formulation as (Cu⁺)₃(S²⁻)(S₂)⁻ was proposed and supported by calculations.<ref name = "Liang">{{cite journal

| author2=Whangbo M, -H

| date=February 1993

| doi = 10.1016/0038-1098(93)90689-K|bibcode = 1993SSCom..85..405L }}</ref>

The formulation should not be interpreted as containing radical anion, but rather that there is a delocalized valence "hole".<ref name = "Liang"/><ref>{{cite journal

| first = H |author2=Shibata, K |author3=Ohhashi,N.

| date=April 1991

| doi = 10.1016/0022-4596(91)90085-V|bibcode = 1991JSSCh..91..306N }}</ref>

[[Electron paramagnetic resonance]] studies on the precipitation of Cu(II) salts indicates that the reduction of Cu(II) to Cu(I) occurs in solution.<ref>{{cite journal

| author2=Theberge SM|author3=Rozan TF|author4=Rickard D|author5=Rowlands CC|author6=Oldroyd A.

| date=February 2002

| pmid = 11871554|bibcode = 2002EnST...36..394L }}</ref>

{| class="wikitable" style="margin:1em auto; text-align:center;"

|

[[Image:Covellite-xtal-CM-3D-balls.png|200px]]

|[[Image:Covellite-Cu1-coordination-3D-balls.png|120px]]||[[Image:Covellite-Cu2-coordination-3D-balls.png|120px]]||[[Image:Covellite-S1-coordination-3D-balls.png|120px]]||[[Image:Covellite-S2-coordination-3D-balls.png|120px]]

|<small>[[ball-and-stick model]] of part of<br>the crystal structure of [[covellite]]</small>||<small>trigonal planar<br>coordination of copper</small>||<small>tetrahedral<br>coordination of copper</small>||<small>trigonal bipyramidal<br>coordination of sulfur</small>||<small>tetrahedral<br>coordination of sulfur-note disulfide unit</small>

*[[Copper(I) sulfide]], Cu₂S

{{reflist|30em}}

{{Sulfides}}

{{Disulfides}}

[[Category:Copper(II) compounds]]

[[Category:Disulfides]]