Copper(I) chloride

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Copper(I) chloride
Sample of copper(I) chloride
Unit cell of nantokite
Names
IUPAC name
Copper(I) chloride
Other names
Cuprous chloride
Identifiers
3D model (
JSmol
)
8127933
ChEBI
ChemSpider
DrugBank
ECHA InfoCard
 100.028.948 Edit this at Wikidata
EC Number
  • 231-842-9
13676
RTECS number
  • GL6990000
UNII
  • InChI=1S/ClH.Cu/h1H;/q;+1/p-1 checkY
    Key: OXBLHERUFWYNTN-UHFFFAOYSA-M checkY
  • InChI=1/ClH.Cu/h1H;/q;+1/p-1
    Key: OXBLHERUFWYNTN-REWHXWOFAC
  • Cl[Cu]
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
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:
GHS07: Exclamation markGHS09: Environmental hazard
Warning
H302, H410
P264, P270, P273, P301+P312, P330, P391, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 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).
checkY verify (what is checkY☒N ?)
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).

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]

  • White copper(I) chloride crystals on copper wire
    White copper(I) chloride crystals on copper wire
  • Copper(I) chloride partially oxidized in air
    Copper(I) chloride partially oxidized in air

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 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

1,5-cyclooctadiene are particularly stable:[16]

Structure of COD complex of CuCl

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

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

Gatterman-Koch reaction to form benzaldehydes.[20]

In the

arenediazonium salt with CuCl leads to an aryl chloride. For example:[21][22]

(Example Sandmeyer reaction using CuCl)

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

Early investigators observed that copper(I) halides catalyse 1,4-addition of

organocuprate reagents that are widely used today in organic synthesis:[24]

(Addition of RMgX to C=C-C=O mediated by CuCl)

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]

(Alkylation of sorbate ester at 4-position mediated by CuCl)

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

References

  1. ^
    ISBN 1-4398-5511-0
    .
  2. doi:10.1016/0038-1098(96)00020-8
    .
  3. ISBN 1-4398-5511-0
    .
  4. ISBN 0-07-049439-8
  5. ^
    PMID 9976955
    .
  6. ^ a b c 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. ISBN 0471238961
    .
  12. ^
    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. S2CID 85408826
    .
  15. doi:10.1021/j100455a006
    .
  16. ^ Nicholls, D. (1973) Complexes and First-Row Transition Elements, Macmillan Press, London.
  17. 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. PMID 37083229
    .
  20. ISSN 0368-1769
    .
  21. ISBN 013033832X
    .
  22. ^
    ISBN 978-0-470-46259-1
  23. doi:10.1021/ja01854a005
    .
  24. ISBN 9783527600083
    .
  25. ISBN 978-0-471-97924-1
    .
  26. ISSN 0370-1301
    .
  27. ^ "Nantokite".
  28. ^ "List of Minerals". 21 March 2011.

External links

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