| Revision as of 15:21, 9 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 469066348 of page Copper(I)_chloride for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 13:02, 20 November 2024 edit 5.178.188.143 (talk) →HistoryTag: Visual edit |
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{{Chembox |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{chembox |
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| verifiedrevid = 455130451 |
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| verifiedrevid = 470447484 |
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| ImageFile = Copper(I) chloride pure.jpg |
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| ImageFile1 = Nantokite-unit-cell-3D-balls.png |
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| ImageSize = 230px |
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| ImageName = Sample of copper(I) chloride |
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| ImageName1 = Unit cell of nantokite |
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| IUPACName = Copper(I) chloride |
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| ImageFile1 = Copper(I)-chloride-from-xtal-unit-cell-3D-bs-17.png |
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| ImageSize1 = 180px |
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| OtherNames = Cuprous chloride |
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| ImageName1 = Unit cell of nantokite |
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| Section1 = {{Chembox Identifiers |
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| IUPACName = Copper(I) chloride |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| OtherNames = Cuprous chloride |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 56403 |
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| ChemSpiderID = 56403 |
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| InChI = 1/ClH.Cu/h1H;/q;+1/p-1 |
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| InChI = 1/ClH.Cu/h1H;/q;+1/p-1 |
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| StdInChIKey = OXBLHERUFWYNTN-UHFFFAOYSA-M |
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| StdInChIKey = OXBLHERUFWYNTN-UHFFFAOYSA-M |
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| CASNo = 7758-89-6 |
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| CASNo = 7758-89-6 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| PubChem = 62652 |
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| RTECS = GL6990000 |
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| UNII = C955P95064 |
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| EINECS = 231-842-9 |
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| PubChem = 62652 |
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| RTECS = GL6990000 |
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| EINECS = 231-842-9 |
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| Gmelin = 13676 |
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| Beilstein = 8127933 |
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| DrugBank = DB15535 |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = CuCl |
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| Formula = CuCl |
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| MolarMass = 98.999 g/mol |
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| MolarMass = 98.999 g/mol<ref name=crc>{{RubberBible92nd|page=4.61}}</ref> |
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| Appearance = white powder, slightly green from oxidized impurities |
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| Appearance = white powder, slightly green from oxidized impurities |
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| Density = 4.145 g/cm<sup>3</sup> |
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| Density = 4.14 g/cm<sup>3</sup><ref name=crc/> |
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| Solubility = 0.0062 g/100 mL (20 °C) |
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| Solubility = 0.047 g/L (20 °C)<ref name=crc/> |
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| SolubilityProduct = 1.72 x 10<sup>-7</sup> |
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| SolubilityProduct = 1.72×10<sup>−7</sup> |
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| MeltingPtC = 423 |
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| MeltingPt = 426 °C (703 K) |
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| MeltingPt_ref = <ref name=crc/> |
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| BoilingPt = 1490 °C (1760 K) (decomp.) |
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| BoilingPtC = 1490 |
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| SolubleOther = insoluble in ] <br> ]; soluble in concentrated ], ] |
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| BoilingPt_notes = (decomposes)<ref name=crc/> |
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| RefractIndex = 1.930<ref>Pradyot Patnaik. ''Handbook of Inorganic Chemicals''. McGraw-Hill, 2002, ISBN 0-07-049439-8</ref> |
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| SolubleOther = insoluble in ], <br> ];<ref name=crc/> soluble in concentrated ], ] |
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| RefractIndex = 1.930<ref>Patnaik, Pradyot (2002) ''Handbook of Inorganic Chemicals''. McGraw-Hill, {{ISBN|0-07-049439-8}}</ref> |
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| MagSus = -40.0·10<sup>−6</sup> cm<sup>3</sup>/mol<ref>{{RubberBible92nd|page=4.132}}</ref> |
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| BandGap = 3.25 eV (300 K, direct)<ref>{{cite journal|doi=10.1016/0038-1098(96)00020-8|title=Electron-phonon interaction at the direct gap of the copper halides|journal=Solid State Communications|volume=98|pages=27–30|year=1996|last1=Garro|first1=Núria|last2=Cantarero|first2=Andrés|last3=Cardona|first3=Manuel|last4=Ruf|first4=Tobias|last5=Göbel|first5=Andreas|last6=Lin|first6=Chengtian|last7=Reimann|first7=Klaus|last8=Rübenacke|first8=Stefan|last9=Steube|first9=Markus|issue=1|bibcode=1996SSCom..98...27G}}</ref> |
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| Section3 = {{Chembox Structure |
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|Section3={{Chembox Structure |
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| CrystalStruct = ] |
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| CrystalStruct = ], ] |
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| SpaceGroup = F{{overline|4}}3m, No. 216<ref name=str>{{cite journal|doi=10.1103/PhysRevB.50.5868|title=High-pressure polymorphism of the copper(I) halides: A neutron-diffraction study to ~10 GPa|journal=Physical Review B|volume=50|issue=9|pages=5868–5885|year=1994|last1=Hull|first1=S.|last2=Keen|first2=D. A.|pmid=9976955|bibcode=1994PhRvB..50.5868H}}</ref> |
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| PointGroup = |
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| LattConst_a = 0.54202 nm |
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| UnitCellFormulas = 4 |
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| UnitCellVolume = 0.1592 nm<sup>3</sup> |
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| Section7 = {{Chembox Hazards |
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|Section7={{Chembox Hazards |
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| ExternalMSDS = |
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| ExternalSDS = |
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| GHSPictograms = {{GHS07}}{{GHS09}} |
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| EUClass = Harmful ('''Xn''')<br/>Dangerous for the environment ('''N''') |
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| GHSSignalWord = Warning |
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| EUIndex = 029-001-00-4 |
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| RPhrases = {{R22}}, {{R50/53}} |
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| HPhrases = {{H-phrases|302|410}} |
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| PPhrases = {{P-phrases|264|270|273|301+312|330|391|501}} |
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| SPhrases = {{S2}}, {{S22}}, {{S60}}, {{S61}} |
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| NFPA-H = 3 |
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| NFPA-H = 3 |
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| NFPA-R = 0 |
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| NFPA-R = 0 |
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| NFPA-F = 0 |
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| NFPA-F = 0 |
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| FlashPt = Non-flammable |
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| FlashPt = Non-flammable |
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| LD50 = 140 mg/kg |
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| LD50 = 140 mg/kg |
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| PEL = TWA 1 mg/m<sup>3</sup> (as Cu)<ref name=PGCH>{{PGCH|0150}}</ref> |
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| REL = TWA 1 mg/m<sup>3</sup> (as Cu)<ref name=PGCH/> |
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| IDLH = TWA 100 mg/m<sup>3</sup> (as Cu)<ref name=PGCH/> |
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| Section8 = {{Chembox Related |
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| OtherAnions = ]<br/>] |
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| OtherAnions = ]<br>]<br/>] |
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| OtherCations = ]<br/>] |
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| OtherCations = ]<br>] |
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| OtherCompounds =] |
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] |
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'''Copper(I) chloride''', commonly called '''cuprous chloride''', is the lower ] of ], with the formula CuCl. The substance is a white solid sparingly soluble in water, but very soluble in concentrated ]. Impure samples appear green due to the presence of ] (CuCl<sub>2</sub>). |
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==History== |
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Copper(I) chloride was first prepared by ] and designated '''rosin of copper''' in the mid-seventeenth century from ] ("Venetian sublimate") and copper metal:<ref name="Boyle1666">{{cite book|last=Boyle|first=Robert|title=Considerations and experiments about the origin of forms and qualities|year=1666|place=Oxford|url=https://quod.lib.umich.edu/e/eebo/A29017.0001.001?rgn=main;view=fulltext|pages=286–288}}</ref> |
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:HgCl<sub>2</sub> + 2 Cu → 2 CuCl + Hg |
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In 1799, ] first differentiated two different chlorides of copper. He prepared CuCl (which he called '''white muriate of copper''') by heating CuCl<sub>2</sub> at red heat in the absence of air, causing it to lose half of its combined chlorine followed by removing residual CuCl<sub>2</sub> by washing with water.<ref name="Proust1799">{{cite journal |last=Proust |first=J. L. |year=1799 |title=Recherches sur le Cuivre |url=https://books.google.com/books?id=ZBki5255ZXgC&pg=PA47 |journal=] |volume=32 |pages=26–54}}</ref> |
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An acidic solution of CuCl was formerly used to analyze carbon monoxide content in gases, for example in Hempel's gas apparatus where the CuCl absorbs the carbon monoxide.<ref name="martin">{{cite book|last = Martin|first = Geoffrey|year = 1922|title = Industrial and Manufacturing Chemistry|url = https://archive.org/details/in.ernet.dli.2015.73073/|edition = Part 1, Organic|location = London|publisher = Crosby Lockwood|pages=408}}</ref> This application was significant during the nineteenth and early twentieth centuries when ] was widely used for heating and lighting.<ref name="Lewes1891">{{cite journal|last=Lewes|first=Vivian H.|journal=Journal of the Society of Chemical Industry|year=1891|title=The Analysis of Illuminationg Gases|volume=10|pages=407–413|url=https://books.google.com/books?id=oSEAAAAAMAAJ&pg=PA408}}</ref> |
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==Synthesis== |
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Copper(I) chloride is produced industrially by the direct combination of copper metal and chlorine at 450–900 °C:<ref>{{Cite book|title=Kirk-Othmer Encyclopedia of Chemical Technology|last=Richardson|first=H. W.|year=2003|isbn=0471238961|chapter=Copper Compounds|doi=10.1002/0471238961.0315161618090308.a01.pub2}}</ref><ref name="Ullmann">{{Cite book|title=Ullmann's Encyclopedia of Industrial Chemistry|author1=Zhang, J. |author2=Richardson, H. W.|year=2016|isbn=978-3-527-30673-2|chapter=Copper Compounds|pages=1–31 |doi=10.1002/14356007.a07_567.pub2}}</ref> |
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:{{chem2|2 Cu + Cl2 -> 2 CuCl}} |
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Copper(I) chloride can also be prepared by ] copper(II) chloride with ], or with ascorbic acid (]) that acts as a ]:<ref>{{cite book |last1= Glemser |first1= O. |last2= Sauer |first2= H. |year= 1963 |chapter= Copper(I) Chloride |title= Handbook of Preparative Inorganic Chemistry |edition= 2nd |editor-first= G. |editor-last= Brauer |publisher= Academic Press |location= New York |volume= 1 |page= 1005 }}</ref><ref>{{cite journal |author1=Tuğba Akbıyık |author2=İnci Sönmezoğlu |author3=Kubilay Güçlü |author4=İzzet Tor |author5=Reşat Apak |title=Protection of Ascorbic Acid from Copper(II)−Catalyzed Oxidative Degradation in the Presence of Fruit Acids: Citric, Oxalic, Tartaric, Malic, Malonic, and Fumaric Acids |journal=International Journal of Food Properties |date=2012 |volume=15 |issue=2 |pages=398–411 |doi=10.1080/10942912.2010.487630 |s2cid=85408826 |language=en}}</ref> |
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:{{chem2|2 CuCl2 + SO2 + 2 H2O -> 2 CuCl + H2SO4 + 2 HCl}} |
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:{{chem2|2 CuCl2 + C6H8O6 -> 2CuCl + 2HCl + C6H6O6}} |
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Many other reducing agents can be used.<ref name="Ullmann" /><gallery mode="packed"> |
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Image:Copper(I)chloride crystal 01.jpg|White copper(I) chloride crystals on copper wire |
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File:Copper(I) chloride.jpg|Copper(I) chloride partially oxidized in air |
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</gallery> |
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==Properties== |
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Copper(I) chloride has the cubic ] crystal structure at ambient conditions. Upon heating to 408 °C the structure changes to hexagonal. Several other crystalline forms of CuCl appear at high pressures (several GPa).<ref name=str/> |
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Copper(I) chloride is a ]. It is classified as soft according to the ]. Thus, it forms a series of ] with soft ]s such as ]: |
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: CuCl + 1 P(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub> → 1/4 {CuCl}<sub>4</sub> |
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: CuCl + 2 P(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub> → CuCl<sub>2</sub> |
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: CuCl + 3 P(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub> → CuCl<sub>3</sub> |
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CuCl also forms complexes with ]s. For example ] CuCl<sub>2</sub><sup>−</sup> forms in concentrated ].<ref>{{cite journal |author1=J. J. Fritz |title=Chloride complexes of copper(I) chloride in aqueous solution |journal=J. Phys. Chem. |date=1980 |volume=84 |issue=18 |pages=2241–2246 |doi=10.1021/j100455a006 |language=en}}</ref> Chloride is displaced by ] and ].<ref name="Ullmann" /> |
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Solutions of CuCl in ] absorb ] to form colourless complexes such as the chloride-bridged dimer <sub>2</sub>. The same hydrochloric acid solutions also react with ] gas to form . ]cal solutions of CuCl react with acetylenes to form the explosive ], Cu<sub>2</sub>C<sub>2</sub>. ]es of CuCl can be prepared by reduction of ] by ] in the presence of the alkene in ] solution. Complexes with ]s such as ] are particularly stable:<ref name="Nicholls">Nicholls, D. (1973) ''Complexes and First-Row Transition Elements'', Macmillan Press, London.</ref> |
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Upon contact with ], copper(I) chloride slowly undergoes ]:<ref name="GreenwoodEarnshaw">{{Greenwood&Earnshaw2nd|page=1185}}</ref> |
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: 2 CuCl → Cu + CuCl<sub>2</sub> |
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In part for this reason, samples in air assume a green coloration.<ref>Pastor, Antonio C. (1986) {{US Patent|4582579}} "Method of preparing cupric ion free cuprous chloride" Section 2, lines 4–41.</ref> |
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==Uses== |
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The main use of copper(I) chloride is as a precursor to the ] ]. For this purpose aqueous copper(I) chloride is generated by ] and then air-oxidized:<ref name="Ullmann" /> |
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: Cu + CuCl<sub>2</sub> → 2 CuCl |
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: 4 CuCl + O<sub>2</sub> + 2 H<sub>2</sub>O → Cu<sub>3</sub>Cl<sub>2</sub>(OH)<sub>4</sub> + CuCl<sub>2</sub> |
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Copper(I) chloride catalyzes a variety of ], as discussed above. Its affinity for ] in the presence of ] is exploited in the COPure<sup>SM</sup> process.<ref>{{cite journal |author1=Xiaozhou Ma |author2=Jelco Albertsma |author3=Dieke Gabriels |author4=Rens Horst |author5=Sevgi Polat |author6=Casper Snoeks |author7=Freek Kapteijn |author8=Hüseyin Burak Eral |author9=David A. Vermaas |author10=Bastian Mei |author11=Sissi de Beer |author12=Monique Ann van der Veen |title=Carbon monoxide separation: past, present and future |journal=Chemical Society Reviews |date=2023 |volume=52 |issue=11 |pages=3741–3777 |doi=10.1039/D3CS00147D |pmid=37083229 |pmc=10243283 |url=https://pubs.rsc.org/en/content/articlepdf/2023/cs/d3cs00147d |language=en}}</ref> |
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===In organic synthesis=== |
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CuCl is used as a co-catalyst with ], aluminium chloride, and ] in the ] to form benzaldehydes.<ref>{{Cite journal|last1=Dilke|first1=M. H.|last2=Eley|first2=D. D.|date=1949|title=550. The Gattermann–Koch reaction. Part II. Reaction kinetics|url=http://xlink.rsc.org/?DOI=JR9490002613|journal=J. Chem. Soc.|language=en|pages=2613–2620| doi=10.1039/JR9490002613|issn=0368-1769}}</ref> |
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In the ], the treatment of an ] with CuCl leads to an aryl chloride. For example:<ref name="Sandmeyer">Wade, L. G. (2003) ''Organic Chemistry'', 5th ed., Prentice Hall, Upper Saddle River, New Jersey, p. 871. {{ISBN|013033832X}}.</ref><ref name="sand">March, J. (1992) , 4th ed., Wiley, New York. p. 723. {{ISBN|978-0-470-46259-1}}</ref> |
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] |
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The reaction has wide scope and usually gives good yields.<ref name="sand" /> |
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Early investigators observed that copper(I) halides catalyse 1,4-addition of ]s to alpha,beta-unsaturated ketones<ref name="Kharasch">{{cite journal | title = Factors Determining the Course and Mechanisms of Grignard Reactions. II. The Effect of Metallic Compounds on the Reaction between Isophorone and Methylmagnesium Bromide | journal = ] | volume = 63 | pages = 2308 | year = 1941 | doi = 10.1021/ja01854a005 | author1 = Kharasch, M. S. | author2 = Tawney, P. O. | issue = 9}}</ref> led to the development of ] reagents that are widely used today in ]:<ref name="Jasrzebski">Jasrzebski, J. T. B. H.; van Koten, G. (2002) ''Modern Organocopper Chemistry'', N. Krause (ed.). Wiley-VCH, Weinheim, Germany. p. 1. {{doi|10.1002/3527600086.ch1}} {{ISBN|9783527600083}}.</ref> |
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] |
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This finding led to the development of ]. For example, CuCl reacts with ] (CH<sub>3</sub>Li) to form "]s" such as (CH<sub>3</sub>)<sub>2</sub>CuLi, which find use in ]. ]s form similar organocopper compounds. Although other copper(I) compounds such as ] are now more often used for these types of reactions, copper(I) chloride is still recommended in some cases:<ref name="BertzAndMunchPetersen">Bertz, S. H.; Fairchild, E. H. (1999) ''Handbook of Reagents for Organic Synthesis, Volume 1: Reagents, Auxiliaries and Catalysts for C-C Bond Formation'', R. M. Coates, S. E. Denmark (eds.). Wiley, New York. pp. 220–3. {{ISBN|978-0-471-97924-1}}.</ref> |
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] |
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Cuprous chloride also catalyzes the ] of ] to ], once used as a precursor to various polymers such a ].<ref>{{cite journal |doi=10.1021/cr400357r |title=Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited |date=2014 |last1=Trotuş |first1=Ioan-Teodor |last2=Zimmermann |first2=Tobias |last3=Schüth |first3=Ferdi |journal=Chemical Reviews |volume=114 |issue=3 |pages=1761–1782 |pmid=24228942 |doi-access=free }}</ref> |
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===Niche uses=== |
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CuCl is used as a catalyst in ] (ATRP). It is also used in ] as a blue/green coloring agent. In a ], copper chlorides, like all copper compounds, emit green-blue.<ref>{{Cite journal |last1=Barrow |first1=R F |last2=Caldin |first2=E F |date=1949-01-01 |title=Some Spectroscopic Observations on Pyrotechnic Flames |url=https://iopscience.iop.org/article/10.1088/0370-1301/62/1/305 |journal=Proceedings of the Physical Society. Section B |volume=62 |issue=1 |pages=32–39 |doi=10.1088/0370-1301/62/1/305 |issn=0370-1301}}</ref> |
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==Natural occurrence== |
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Natural form of CuCl is the rare mineral ].<ref>{{Cite web|url=https://www.mindat.org/min-2840.html|title=Nantokite}}</ref><ref>{{Cite web|url=https://www.ima-mineralogy.org/Minlist.htm|title=List of Minerals|date=21 March 2011}}</ref> |
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==See also== |
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] |
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==References== |
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{{Reflist|30em}} |
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==External links== |
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{{Commons category|Copper(I) chloride}} |
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{{Copper compounds}} |
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{{Chlorides}} |
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{{good article}} |
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