Copper(I) chloride

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Copper(I) chloride
Copper(I) chloride pure.jpg
Copper(I)-chloride-from-xtal-unit-cell-3D-bs-17.png
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

Cuprous chloride also catalyzes the dimerization of acetylene to vinylacetylene, once used as a precursor to various polymers such a neoprene. [26]

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. [27]

Natural occurrence

Natural form of CuCl is the rare mineral nantokite. [28] [29]

See also

Copper(II) chloride

Related Research Articles

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

A Gilman reagent is a diorganocopper compound with the formula Li[CuR2], where R is an alkyl or aryl. They are colorless solids.

In chemistry, halogenation is a chemical reaction which introduces of one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

<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">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 versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. 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 Corey–House synthesis (also called the Corey–Posner–Whitesides–House reaction and other permutations) 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.

The Ullmann reaction or Ullmann coupling, named after Fritz Ullmann, couples two aryl or alkyl groups with the help of copper. The reaction was first reported by Ullmann and his student Bielecki in 1901. It has been later shown that palladium and nickel can also be effectively used.

The Ullmann condensation or Ullmann-type reaction is the copper-promoted conversion of aryl halides to aryl ethers, aryl thioethers, aryl nitriles, and aryl amines. These reactions are examples of cross-coupling reactions.

<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.

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

Copper(I) cyanide is an inorganic compound with the formula CuCN. This off-white solid occurs in two polymorphs; impure samples can be green due to the presence of Cu(II) impurities. The compound is useful as a catalyst, in electroplating copper, and as a reagent in the preparation of nitriles.

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

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

Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for esterification. It is a hygroscopic, colorless, slightly viscous liquid and is soluble in polar solvents.

Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents.

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

Grignard reagents or Grignard compounds are chemical compounds 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.

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.

In organometallic chemistry, a transition metal alkyne complex is a coordination compound containing one or more alkyne ligands. Such compounds are intermediates in many catalytic reactions that convert alkynes to other organic products, e.g. hydrogenation and trimerization.

<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. ↑ Trotuş, Ioan-Teodor; Zimmermann, Tobias; Schüth, Ferdi (2014). "Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited". Chemical Reviews. 114 (3): 1761–1782. doi:10.1021/cr400357r. PMID   24228942.
  27. ↑ 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.
  28. ↑ "Nantokite".
  29. ↑ "List of Minerals". 21 March 2011.

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