Copper(II) fluoride

Copper(II) fluoride
Unit cell of the anhydrous form
Ball-and-stick model of crystal packing in the anhydrous form
Dihydrate
Names
IUPAC name
Copper difluoride
Other names
Cupric fluoride; Copper fluoride; Copper (2+) Difluoride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.225
EC Number
  • 232-147-3
UNII
  • InChI=1S/Cu.2FH/h;2*1H/q+2;;/p-2 Y
    Key: GWFAVIIMQDUCRA-UHFFFAOYSA-L Y
  • InChI=1/Cu.2FH/h;2*1H/q+2;;/p-2
    Key: GWFAVIIMQDUCRA-NUQVWONBAF
  • [Cu+2].[F-].[F-]
Properties
CuF2
Molar mass 101.543 g/mol (anhydrous)
137.573 g/mol (dihydrate)
Appearance White crystalline powder
When hydrated: Blue
Density 4.23 g/cm3 (anhydrous)
2.934 g/cm3 (dihydrate)[1]
Melting point 836 °C (1,537 °F; 1,109 K) (anhydrous)
130 °C (dihydrate, decomposes)
Boiling point 1,676 °C (3,049 °F; 1,949 K) (anhydrous)
+1050.0·10−6 cm3/mol
Thermochemistry
-63.8 kcal/mol (gas)[2]
Enthalpy of fusion fHfus)
13 kcal/mol[2]
63.9 kcal/mol[3]
Hazards
GHS labelling:[5]
Danger
H302, H314, H332
P260, P264, P270, P271, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P363, P405, P501
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 1 mg/m3 (as Cu)[4]
REL (Recommended)
TWA 1 mg/m3 (as Cu)[4]
IDLH (Immediate danger)
TWA 100 mg/m3 (as Cu)[4]
Related compounds
Other anions
Copper(II) bromide
Copper(II) chloride
Other cations
Silver(II) fluoride
Cobalt(II) fluoride
Related compounds
Copper(I) fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Copper(II) fluoride or cupric fluoride is an inorganic compound with the chemical formula CuF2. The anhydrous form is a white, ionic, crystalline, hygroscopic salt with a distorted rutile-type crystal structure, similar to other fluorides of chemical formulae MF2 (where M is a metal). The dihydrate, CuF2·2H2O, is blue in colour.[6]

Properties

Copper(II) fluoride is slightly soluble in water, but starts to decompose in hot water, producing basic F and Cu(OH)+ ions.

Structure

Copper(II) fluoride has a monoclinic crystal structure[7] and cannot achieve a higher-symmetry structure. It forms rectangular prisms with a parallelogram base.[8] Each copper ion has four neighbouring fluoride ions at 1.93 Å separation and two further away at 2.27 Å.[6] This distorted octahedral [4+2] coordination is a consequence of the Jahn–Teller effect in d9 copper(II),[9] and leads to a distorted rutile structure similar to that of chromium(II) fluoride, CrF2, which is a d4 compound.[6]

Coordination in copper(II) fluoride[6][7]
Copper coordination Fluorine coordination

Synthesis

Copper(II) fluoride can be synthesized from copper and fluorine at elevated temperatures. At 500 °C (932 °F) a 53% conversion is achieved.[10]

Cu + F2 → CuF2

Uses

Cupric fluoride catalyzes the decomposition of nitric oxides in emission control systems.[11]

Copper(II) fluoride can be used to make fluorinated aromatic hydrocarbons by reacting with aromatic hydrocarbons in an oxygen-containing atmosphere at temperatures above 450 °C (842 °F). This reaction is simpler than the Sandmeyer reaction, but is only effective in making compounds that can survive at the temperature used. A coupled reaction using oxygen and 2 HF regenerates the copper(II) fluoride, producing water.[12] This method has been proposed as a "greener" method of producing fluoroaromatics since it avoids producing toxic waste products such as ammonium fluoride.

Reactions

It loses fluorine in the molten stage at temperatures above 950 °C (1742 °F).

2 CuF2 → 2 CuF + F2
2 CuF → CuF2 + Cu

The complex anions CuF3, CuF42− and CuF64− are formed if CuF2 is exposed to substances containing fluoride ions F.

References

  1. ^ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  2. ^ a b T. C. Ehlert; J. S. Wang (1977). "Thermochemistry of the copper fluorides". Journal of Physical Chemistry. 81 (22): 2069–2073. doi:10.1021/j100537a005.
  3. ^ Kent, R. A.; Mcdonald, J. D.; Margrave, J. L. (1966). "Mass Spectrometric Studies at High Temperatures. IX. The Sublimation Pressure of Copper(II) Fluoride". Journal of Physical Chemistry. 70 (3): 874–877. doi:10.1021/j100875a042.
  4. ^ a b c NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  5. ^ "Copper Fluoride - ESPI Metals". www.espimetals.com. Retrieved 2026-02-19.
  6. ^ a b c d Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 1184–1185. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
  7. ^ a b Fischer, P.; Hälg, W.; Schwarzenbach, D.; Gamsjäger, H. (1974). "Magnetic and crystal structure of copper(II) fluoride". J. Phys. Chem. Solids. 35 (12): 1683–1689. doi:10.1016/S0022-3697(74)80182-4.
  8. ^ C. Billy; H. M. Haendler (1957). "The Crystal Structure of Copper(II) Fluoride". Journal of the American Chemical Society. 79 (5): 1049–51. doi:10.1021/ja01562a011.
  9. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 1190–1191. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
  10. ^ H. M. Haendler; L. H. Towle; E. F. Bennett; W. L. Patterson (1954). "The Reaction of Fluorine with Copper and Some of its Compounds. Some Properties of Copper(II) Fluoride". Journal of the American Chemical Society. 76 (8): 2178–2179. doi:10.1021/ja01637a039.
  11. ^ Meshri, Dayal T. (2000), "Fluorine compounds, inorganic, copper", Kirk-Othmer Encyclopedia of Chemical Technology, New York: John Wiley, doi:10.1002/0471238961.0315161613051908.a01, ISBN 9780471238966
  12. ^ M. A. Subramanian; L. E. Manzer (2002). "A "Greener" Synthetic Route for Fluoroaromatics via Copper (II) Fluoride". Science. 297 (5587): 1665. doi:10.1126/science.1076397. PMID 12215637. S2CID 32697750.

Further reading

  • Shashkin, S. Y.; Goddard III, W. A. (1986). "Electron Correlation effects in ligand field parameters and other properties of copper II fluoride". Journal of Physical Chemistry. 90 (2): 250–255. doi:10.1021/j100274a010.
  • P. C. de Mello; M. Hehenberg; S. Larson; M. Zerner (1980). "Studies of the electronic structure of copper fluorides and copper chlorides". Journal of the American Chemical Society. 102 (4): 1278–1288. doi:10.1021/ja00524a010.