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).[7]

Copper(I) chloride
Names
IUPAC name
Copper(I) chloride
Other names
Cuprous chloride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.028.948
EC Number
  • 231-842-9
RTECS number
  • GL6990000
UNII
Properties
CuCl
Molar mass 98.999 g/mol[1]
Appearance white 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
Safety data sheet JT Baker
Very toxic (T+)
Harmful (Xn)
Dangerous for the environment (N)
R-phrases (outdated) R22, R50/53
S-phrases (outdated) (S2), S22, S60, S61
NFPA 704 (fire diamond)
Flammability code 0: Will not burn. E.g. waterHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
0
3
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]
Related compounds
Other anions
 Copper(I) bromide
Copper(I) iodide
Other cations
 Copper(II) chloride
Silver(I) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references
A white precipitate of Copper(I) Chloride suspended in a solution of Ascorbic Acid in a 2 dram vial.
IR absorption spectrum of copper(I) chloride

History

Copper(I) chloride was first prepared by Robert Boyle in the mid-seventeenth century[8] from mercury(II) chloride ("Venetian sublimate") and copper metal:

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.[9]

An acidic solution of CuCl was formerly used for analysis of carbon monoxide content in gases, for example in Hempel's gas apparatus.[10] This application was significant[11] during the nineteenth and early twentieth centuries when coal gas was widely used for heating and lighting.

Synthesis

Copper(I) chloride is produced industrially by the direct combination of copper metal and chlorine at 450–900 °C:[12][13]

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:

Many other reducing agents can be used.[14]

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, which is classified as soft according to the Hard-Soft Acid-Base concept. Thus, it forms a series if 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

Although CuCl is insoluble in water, it dissolves in aqueous solutions containing suitable donor molecules. It forms complexes with halide ions, for example forming H3O+ CuCl2− in concentrated hydrochloric acid. Chloride is displaced by CN− and S2O32−.

Solutions of CuCl in HCl or NH3 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 o 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:[15]

In absence of other ligands, its aqueous solutions are unstable with respect to disproportionation:[16]

2 CuCl → Cu + CuCl2

In part for this reason samples in air assume a green coloration.

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:

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.

In organic synthesis

CuCl is used with carbon monoxide, aluminium chloride, and hydrogen chloride in the Gatterman-Koch reaction to form benzaldehydes.

In the Sandmeyer reaction.[17][18] Treatment of an arenediazonium salt with CuCl leads to an aryl chloride, for example:

The reaction has wide scope and usually gives good yields.

Early investigators observed that copper(I) halides catalyse 1,4-addition of Grignard reagents to alpha,beta-unsaturated ketones[19] led to the development of organocuprate reagents that are widely used today in organic synthesis:[20]

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 extensive 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:[21]

Here, Bu indicates an n-butyl group. Without CuCl, the Grignard reagent alone gives a mixture of 1,2- and 1,4-addition products (i.e., the butyl adds at the C closer to the C=O).

Copper(I) chloride is also an intermediate formed from copper(II) chloride in the Wacker process.

In polymer chemistry

CuCl is used as a catalyst in Atom Transfer Radical Polymerization (ATRP).

Niche Uses

Copper(I) chloride is also used in pyrotechnics as a blue/green coloring agent. In a flame test, copper chlorides, like all copper compounds, emit green-blue.

References
  1. Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press. p. 4.61. ISBN 1439855110.
  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: 27. 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 1439855110.
  4. Patnaik, Pradyot (2002) Handbook of Inorganic Chemicals. McGraw-Hill, ISBN 0-07-049439-8
  5. 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. doi:10.1103/PhysRevB.50.5868.
  6. NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  7. Pastor, Antonio C. (1986) U.S. Patent 4,582,579 "Method of preparing cupric ion free cuprous chloride" Section 2, lines 4–41.
  8. Boyle, Robert (1666). Considerations and experiments about the origin of forms and qualities. Oxford. As reported in Mellor.
  9. Proust, J. L. (1799). "Recherches sur le Cuivre". Ann. Chim. Phys. 32: 26–54.
  10. Martin, Geoffrey (1917). Industrial and Manufacturing Chemistry (Part 1, Organic ed.). London: Crosby Lockwood. pp. 330–31.
  11. Lewes, Vivian H. (1891). "The Analysis of Illuminationg Gases". Journal of the Society of Chemical Industry. 10: 407–413.
  12. Richardson, H. W. (2003). "Copper Compounds". Kirk-Othmer Encyclopedia of Chemical Technology. doi:10.1002/0471238961.0315161618090308.a01.pub2.
  13. Zhang, J.; Richardson, H. W. "Copper Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a07_567.pub2. ISBN 978-3-527-30673-2.
  14. Glemser, O.; Sauer, H. (1963). "Copper(I) Chloride". In Brauer, G. (ed.). Handbook of Preparative Inorganic Chemistry. 1 (2nd ed.). New York: Academic Press. p. 1005.
  15. Nicholls, D. (1973) Complexes and First-Row Transition Elements, Macmillan Press, London.
  16. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 1185. ISBN 978-0-08-037941-8.
  17. Wade, L. G. (2003) Organic Chemistry, 5th ed., Prentice Hall, Upper Saddle River, New Jersey, p. 871. ISBN 013033832X.
  18. March, J. (1992) Advanced Organic Chemistry, 4th ed., Wiley, New York. p. 723. ISBN 978-0-470-46259-1
  19. 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.
  20. 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.
  21. 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.
Salts and covalent derivatives of the chloride ion
HCl He
LiCl BeCl2 BCl3
B2Cl4		 CCl4 NCl3
ClN3		 Cl2O
ClO2
Cl2O7		 ClF
ClF3
ClF5		 Ne
NaCl MgCl2 AlCl
AlCl3		 SiCl4 P2Cl4
PCl3
PCl5		 S2Cl2
SCl2
SCl4		 Cl2 Ar
KCl CaCl
CaCl2		 ScCl3 TiCl2
TiCl3
TiCl4		 VCl2
VCl3
VCl4
VCl5		 CrCl2
CrCl3
CrCl4		 MnCl2 FeCl2
FeCl3		 CoCl2
CoCl3		 NiCl2 CuCl
CuCl2		 ZnCl2 GaCl2
GaCl3		 GeCl2
GeCl4		 AsCl3
AsCl5		 Se2Cl2
SeCl4		 BrCl KrCl
RbCl SrCl2 YCl3 ZrCl3
ZrCl4		 NbCl4
NbCl5		 MoCl2
MoCl3
MoCl4
MoCl5
MoCl6		 TcCl4 RuCl3 RhCl3 PdCl2 AgCl CdCl2 InCl
InCl2
InCl3		 SnCl2
SnCl4		 SbCl3
SbCl5		 Te3Cl2
TeCl4		 ICl
ICl3		 XeCl
XeCl2
XeCl4
CsCl BaCl2   HfCl4 TaCl5 WCl2
WCl3
WCl4
WCl5
WCl6		 Re3Cl9
ReCl4
ReCl5
ReCl6		 OsCl4 IrCl2
IrCl3
IrCl4		 PtCl2
PtCl4		 AuCl
AuCl3		 Hg2Cl2,
HgCl2		 TlCl PbCl2,
PbCl4		 BiCl3 PoCl2,
PoCl4		 AtCl RnCl2
FrCl RaCl2   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
LaCl3 CeCl3 PrCl3 NdCl2,
NdCl3		 PmCl3 SmCl2,
SmCl3		 EuCl2,
EuCl3		 GdCl3 TbCl3 DyCl2,
DyCl3		 HoCl3 ErCl3 TmCl2
TmCl3		 YbCl2
YbCl3		 LuCl3
AcCl3 ThCl4 PaCl5 UCl3
UCl4
UCl5
UCl6		 NpCl4 PuCl3 AmCl2
AmCl3		 CmCl3 BkCl3 CfCl3 EsCl3 Fm Md No LrCl3

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