Copper(I) chloride

Last updated
Copper(I) chloride
Nantokite-unit-cell-3D-balls.png
Copper(I) chloride purified.jpg
Names
IUPAC name
Copper(I) chloride
Other names
Cuprous chloride
Identifiers
3D model (JSmol)
8127933
ChEBI
ChemSpider
DrugBank
ECHA InfoCard 100.028.948 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 231-842-9
13676
PubChem CID
RTECS number
  • GL6990000
UNII
  • InChI=1S/ClH.Cu/h1H;/q;+1/p-1 Yes check.svgY
    Key: OXBLHERUFWYNTN-UHFFFAOYSA-M Yes check.svgY
  • InChI=1/ClH.Cu/h1H;/q;+1/p-1
    Key: OXBLHERUFWYNTN-REWHXWOFAC
  • Cl[Cu]
Properties
CuCl
Molar mass 98.999 g/mol [1]
Appearancewhite powder, slightly green from oxidized impurities
Density 4.14 g/cm3 [1]
Melting point 423 °C (793 °F; 696 K) [1]
Boiling point 1,490 °C (2,710 °F; 1,760 K) (decomposes) [1]
0.047 g/L (20 °C) [1]
1.72×10−7
Solubility insoluble in ethanol,
acetone; [1] soluble in concentrated HCl, NH4OH
Band gap 3.25 eV (300 K, direct) [2]
-40.0·10−6 cm3/mol [3]
1.930 [4]
Structure
Zincblende, cF20
F43m, No. 216 [5]
a = 0.54202 nm
0.1592 nm3
4
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Warning
H302, H410
P264, P270, P273, P301+P312, P330, P391, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
140 mg/kg
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 1 mg/m3 (as Cu) [6]
REL (Recommended)
TWA 1 mg/m3 (as Cu) [6]
IDLH (Immediate danger)
TWA 100 mg/m3 (as Cu) [6]
Safety data sheet (SDS) JT Baker
Related compounds
Other anions
Copper(I) fluoride
Copper(I) bromide
Copper(I) iodide
Other cations
Silver(I) chloride
Gold(I) chloride
Related compounds
 Copper(II) chloride
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 ?)
IR absorption spectrum of copper(I) chloride IR Spectrum of Copper(I) chloride.png
IR absorption spectrum of copper(I) chloride

Copper(I) chloride, commonly called cuprous chloride, is the lower chloride of copper, with the formula CuCl. The substance is a white solid sparingly soluble in water, but very soluble in concentrated hydrochloric acid. Impure samples appear green due to the presence of copper(II) chloride (CuCl2).

Contents

History

Copper(I) chloride was first prepared by Robert Boyle in the mid-seventeenth century from mercury(II) chloride ("Venetian sublimate") and copper metal: [7]

HgCl2 + 2 Cu → 2 CuCl + Hg

In 1799, J.L. Proust characterized the two different chlorides of copper. He prepared CuCl by heating CuCl2 at red heat in the absence of air, causing it to lose half of its combined chlorine followed by removing residual CuCl2 by washing with water. [8]

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. [9] This application was significant during the nineteenth and early twentieth centuries when coal gas was widely used for heating and lighting. [10]

Synthesis

Copper(I) chloride is produced industrially by the direct combination of copper metal and chlorine at 450–900 °C: [11] [12]

2 Cu + Cl2 → 2 CuCl

Copper(I) chloride can also be prepared by reducing copper(II) chloride with sulfur dioxide, or with ascorbic acid (vitamin C) that acts as a reducing sugar: [13] [14]

2 CuCl2 + SO2 + 2 H2O → 2 CuCl + H2SO4 + 2 HCl
2 CuCl2 + C6H8O6 → 2CuCl + 2HCl + C6H6O6

Many other reducing agents can be used. [12]

Properties

Copper(I) chloride has the cubic zincblende 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). [5]

Copper(I) chloride is a Lewis acid. It is classified as soft according to the hard-soft acid-base concept. Thus, it forms a series of complexes with soft Lewis bases such as triphenylphosphine:

CuCl + 1 P(C6H5)3 → 1/4 {CuCl[P(C6H5)3]}4
CuCl + 2 P(C6H5)3 → CuCl[P(C6H5)3)]2
CuCl + 3 P(C6H5)3 → CuCl[P(C6H5)3)]3

CuCl also forms complexes with halides. For example H3O+ CuCl2− forms in concentrated hydrochloric acid. [15] Chloride is displaced by CN− and S2O32−. [12]

Solutions of CuCl in HCl absorb carbon monoxide to form colourless complexes such as the chloride-bridged dimer [CuCl(CO)]2. The same hydrochloric acid solutions also react with acetylene gas to form [CuCl(C2H2)]. Ammoniacal solutions of CuCl react with acetylenes to form the explosive copper(I) acetylide, Cu2C2. Alkene complexes of CuCl can be prepared by reduction of CuCl2 by sulfur dioxide in the presence of the alkene in alcohol solution. Complexes with dienes such as 1,5-cyclooctadiene are particularly stable: [16]

CuCl COD dimer - 2.png

Upon contact with water, copper(I) chloride slowly undergoes disproportionation: [17]

2 CuCl → Cu + CuCl2

In part for this reason, samples in air assume a green coloration. [18]

Uses

The main use of copper(I) chloride is as a precursor to the fungicide copper oxychloride. For this purpose aqueous copper(I) chloride is generated by comproportionation and then air-oxidized: [12]

Cu + CuCl2 → 2 CuCl
4 CuCl + O2 + 2 H2O → Cu3Cl2(OH)4 + CuCl2

Copper(I) chloride catalyzes a variety of organic reactions, as discussed above. Its affinity for carbon monoxide in the presence of aluminium chloride is exploited in the COPureSM process. [19]

In organic synthesis

CuCl is used as a co-catalyst with carbon monoxide, aluminium chloride, and hydrogen chloride in the Gatterman-Koch reaction to form benzaldehydes. [20]

In the Sandmeyer reaction, the treatment of an arenediazonium salt with CuCl leads to an aryl chloride. For example: [21] [22]

CuCl Sandmeyer.png

The reaction has wide scope and usually gives good yields. [22]

Early investigators observed that copper(I) halides catalyse 1,4-addition of Grignard reagents to alpha,beta-unsaturated ketones [23] led to the development of organocuprate reagents that are widely used today in organic synthesis: [24]

CuCl Kharasch reaction.png

This finding led to the development of organocopper chemistry. For example, CuCl reacts with methyllithium (CH3Li) to form "Gilman reagents" such as (CH3)2CuLi, which find use in organic synthesis. Grignard reagents form similar organocopper compounds. Although other copper(I) compounds such as copper(I) iodide are now more often used for these types of reactions, copper(I) chloride is still recommended in some cases: [25]

CuCl sorbate ester alkylation.png

Niche uses

CuCl is used as a catalyst in atom transfer radical polymerization (ATRP). It is also used in pyrotechnics as a blue/green coloring agent. In a flame test, copper chlorides, like all copper compounds, emit green-blue. [26]

Natural occurrence

Natural form of CuCl is the rare mineral nantokite. [27] [28]

See also

Copper(II) chloride

Related Research Articles

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are available both in anhydrous and hydrated forms which are both hygroscopic. They are common sources of iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while the hydrate is a mild oxidizing agent. It is used as a water cleaner and as an etchant for metals.

<span class="mw-page-title-main">Gilman reagent</span> Class of chemical compounds

A Gilman reagent is a lithium and copper (diorganocopper) reagent compound, R2CuLi, where R is an alkyl or aryl. These reagents are useful because, unlike related Grignard reagents and organolithium reagents, they react with organic halides to replace the halide group with an R group (the Corey–House reaction). Such displacement reactions allow for the synthesis of complex products from simple building blocks.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. The haloarene are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

<span class="mw-page-title-main">Zinc chloride</span> Chemical compound

Zinc chloride is the name of inorganic chemical compounds with the formula ZnCl2. It forms hydrates. Zinc chloride, anhydrous and its hydrates are colorless or white crystalline solids, and are highly soluble in water. Five hydrates of zinc chloride are known, as well as four forms of anhydrous zinc chloride. This salt is hygroscopic and even deliquescent. Zinc chloride finds wide application in textile processing, metallurgical fluxes, and chemical synthesis. No mineral with this chemical composition is known aside from the very rare mineral simonkolleite, Zn5(OH)8Cl2·H2O.

<span class="mw-page-title-main">Aluminium chloride</span> Chemical compound

Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula AlCl3. It forms a hexahydrate with the formula [Al(H2O)6]Cl3, containing six water molecules of hydration. Both the anhydrous form and the hexahydrate are colourless crystals, but samples are often contaminated with iron(III) chloride, giving them a yellow colour.

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

Copper(II) chloride, also known as cupric chloride, is an inorganic compound with the chemical formula CuCl2. The monoclinic yellowish-brown anhydrous form slowly absorbs moisture to form the orthorhombic blue-green dihydrate CuCl2·2H2O, with two water molecules of hydration. It is industrially produced for use as a co-catalyst in the Wacker process.

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

Iron(II) chloride, also known as ferrous chloride, is the chemical compound of formula FeCl2. It is a paramagnetic solid with a high melting point. The compound is white, but typical samples are often off-white. FeCl2 crystallizes from water as the greenish tetrahydrate, which is the form that is most commonly encountered in commerce and the laboratory. There is also a dihydrate. The compound is highly soluble in water, giving pale green solutions.

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

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic solids featuring octahedral Rh(III) centres. Depending on the value of n, the material is either a dense brown solid or a soluble reddish salt. The soluble trihydrated (n = 3) salt is widely used to prepare compounds used in homogeneous catalysis, notably for the industrial production of acetic acid and hydroformylation.

The Hiyama coupling is a palladium-catalyzed cross-coupling reaction of organosilanes with organic halides used in organic chemistry to form carbon–carbon bonds. This reaction was discovered in 1988 by Tamejiro Hiyama and Yasuo Hatanaka as a method to form carbon-carbon bonds synthetically with chemo- and regioselectivity. The Hiyama coupling has been applied to the synthesis of various natural products.

The Corey–House synthesis is an organic reaction that involves the reaction of a lithium diorganylcuprate with an organic halide or pseudohalide to form a new alkane, as well as an ill-defined organocopper species and lithium (pseudo)halide as byproducts.

<span class="mw-page-title-main">Diazonium compound</span> Group of organonitrogen compounds

Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group [R−N+≡N]X− where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halide.

Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive toward water.

<span class="mw-page-title-main">Grignard reagent</span> Organometallic compounds used in organic synthesis

A Grignard reagent or Grignard compound is a chemical compound with the general formula R−Mg−X, where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride Cl−Mg−CH3 and phenylmagnesium bromide (C6H5)−Mg−Br. They are a subclass of the organomagnesium compounds.

<span class="mw-page-title-main">Organocopper chemistry</span> Compound with carbon to copper bonds

Organocopper chemistry is the study of the physical properties, reactions, and synthesis of organocopper compounds, which are organometallic compounds containing a carbon to copper chemical bond. They are reagents in organic chemistry.

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

Copper(I) bromide is the chemical compound with the formula CuBr. This diamagnetic solid adopts a polymeric structure akin to that for zinc sulfide. The compound is widely used in the synthesis of organic compounds and as a lasing medium in copper bromide lasers.

Organomanganese chemistry is the chemistry of organometallic compounds containing a carbon to manganese chemical bond. In a 2009 review, Cahiez et al. argued that as manganese is cheap and benign, organomanganese compounds have potential as chemical reagents, although currently they are not widely used as such despite extensive research.

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

Organobismuth chemistry is the chemistry of organometallic compounds containing a carbon to bismuth chemical bond. Applications are few. The main bismuth oxidation states are Bi(III) and Bi(V) as in all higher group 15 elements. The energy of a bond to carbon in this group decreases in the order P > As > Sb > Bi. The first reported use of bismuth in organic chemistry was in oxidation of alcohols by Frederick Challenger in 1934 (using Ph3Bi(OH)2). Knowledge about methylated species of bismuth in environmental and biological media is limited.

Reactions of organocopper reagents involve species containing copper-carbon bonds acting as nucleophiles in the presence of organic electrophiles. Organocopper reagents are now commonly used in organic synthesis as mild, selective nucleophiles for substitution and conjugate addition reactions.

<span class="mw-page-title-main">Copper compounds</span> Chemical compounds containing copper

Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively. Copper compounds, whether organic complexes or organometallics, promote or catalyse numerous chemical and biological processes.

References

  1. 1 2 3 4 5 6 Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press. p. 4.61. ISBN   1-4398-5511-0.
  2. ↑ Garro, Núria; Cantarero, Andrés; Cardona, Manuel; Ruf, Tobias; Göbel, Andreas; Lin, Chengtian; Reimann, Klaus; Rübenacke, Stefan; Steube, Markus (1996). "Electron-phonon interaction at the direct gap of the copper halides". Solid State Communications. 98 (1): 27–30. Bibcode:1996SSCom..98...27G. doi:10.1016/0038-1098(96)00020-8.
  3. ↑ Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press. p. 4.132. ISBN   1-4398-5511-0.
  4. ↑ Patnaik, Pradyot (2002) Handbook of Inorganic Chemicals. McGraw-Hill, ISBN   0-07-049439-8
  5. 1 2 Hull, S.; Keen, D. A. (1994). "High-pressure polymorphism of the copper(I) halides: A neutron-diffraction study to ~10 GPa". Physical Review B. 50 (9): 5868–5885. Bibcode:1994PhRvB..50.5868H. doi:10.1103/PhysRevB.50.5868. PMID   9976955.
  6. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  7. ↑ Boyle, Robert (1666). Considerations and experiments about the origin of forms and qualities. Oxford. pp. 286–288.
  8. ↑ Proust, J. L. (1799). "Recherches sur le Cuivre". Ann. Chim. Phys. 32: 26–54.
  9. ↑ Martin, Geoffrey (1922). Industrial and Manufacturing Chemistry (Part 1, Organic ed.). London: Crosby Lockwood. p. 408.
  10. ↑ Lewes, Vivian H. (1891). "The Analysis of Illuminationg Gases". Journal of the Society of Chemical Industry. 10: 407–413.
  11. ↑ Richardson, H. W. (2003). "Copper Compounds". Kirk-Othmer Encyclopedia of Chemical Technology. doi:10.1002/0471238961.0315161618090308.a01.pub2. ISBN   0471238961.
  12. 1 2 3 4 Zhang, J.; Richardson, H. W. (2016). "Copper Compounds". Ullmann's Encyclopedia of Industrial Chemistry. pp. 1–31. doi:10.1002/14356007.a07_567.pub2. ISBN   978-3-527-30673-2.
  13. ↑ Glemser, O.; Sauer, H. (1963). "Copper(I) Chloride". In Brauer, G. (ed.). Handbook of Preparative Inorganic Chemistry. Vol. 1 (2nd ed.). New York: Academic Press. p. 1005.
  14. ↑ Tuğba Akbıyık; İnci Sönmezoğlu; Kubilay Güçlü; İzzet Tor; Reşat Apak (2012). "Protection of Ascorbic Acid from Copper(II)−Catalyzed Oxidative Degradation in the Presence of Fruit Acids: Citric, Oxalic, Tartaric, Malic, Malonic, and Fumaric Acids". International Journal of Food Properties. 15 (2): 398–411. doi:10.1080/10942912.2010.487630. S2CID   85408826.
  15. ↑ J. J. Fritz (1980). "Chloride complexes of copper(I) chloride in aqueous solution". J. Phys. Chem. 84 (18): 2241–2246. doi:10.1021/j100455a006.
  16. ↑ Nicholls, D. (1973) Complexes and First-Row Transition Elements, Macmillan Press, London.
  17. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 1185. ISBN   978-0-08-037941-8.
  18. ↑ Pastor, Antonio C. (1986) U.S. Patent 4,582,579 "Method of preparing cupric ion free cuprous chloride" Section 2, lines 4–41.
  19. ↑ Xiaozhou Ma; Jelco Albertsma; Dieke Gabriels; Rens Horst; Sevgi Polat; Casper Snoeks; Freek Kapteijn; Hüseyin Burak Eral; David A. Vermaas; Bastian Mei; Sissi de Beer; Monique Ann van der Veen (2023). "Carbon monoxide separation: past, present and future". Chemical Society Reviews. 52 (11): 3741–3777. doi:10.1039/D3CS00147D. PMC   10243283 . PMID   37083229.
  20. ↑ Dilke, M. H.; Eley, D. D. (1949). "550. The Gattermann–Koch reaction. Part II. Reaction kinetics". J. Chem. Soc.: 2613–2620. doi:10.1039/JR9490002613. ISSN   0368-1769.
  21. ↑ Wade, L. G. (2003) Organic Chemistry, 5th ed., Prentice Hall, Upper Saddle River, New Jersey, p. 871. ISBN   013033832X.
  22. 1 2 March, J. (1992) Advanced Organic Chemistry, 4th ed., Wiley, New York. p. 723. ISBN   978-0-470-46259-1
  23. ↑ Kharasch, M. S.; Tawney, P. O. (1941). "Factors Determining the Course and Mechanisms of Grignard Reactions. II. The Effect of Metallic Compounds on the Reaction between Isophorone and Methylmagnesium Bromide". J. Am. Chem. Soc. 63 (9): 2308. doi:10.1021/ja01854a005.
  24. ↑ 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.
  25. ↑ 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.
  26. ↑ Barrow, R F; Caldin, E F (1949-01-01). "Some Spectroscopic Observations on Pyrotechnic Flames". Proceedings of the Physical Society. Section B. 62 (1): 32–39. doi:10.1088/0370-1301/62/1/305. ISSN   0370-1301.
  27. ↑ "Nantokite".
  28. ↑ "List of Minerals". 21 March 2011.

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