Copper(II) fluoride

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Copper(II) fluoride
Copper(II)-fluoride-unit-cell-3D-bs-17.png
Unit cell of the anhydrous form
Copper(II)-fluoride-xtal-packing-3D-bs-17.png
Ball-and-stick model of crystal packing in the anhydrous form
Fluorid mednaty.PNG
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 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 232-147-3
PubChem CID
UNII
  • InChI=1S/Cu.2FH/h;2*1H/q+2;;/p-2 Yes check.svgY
    Key: GWFAVIIMQDUCRA-UHFFFAOYSA-L Yes check.svgY
  • InChI=1/Cu.2FH/h;2*1H/q+2;;/p-2
    Key: GWFAVIIMQDUCRA-NUQVWONBAF
  • [Cu+2].[F-].[F-]
Properties
Cu F 2
Molar mass 101.543 g/mol (anhydrous)
137.573 g/mol (dihydrate)
AppearanceWhite 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
Hazards
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 1 mg/m3 (as Cu) [2]
REL (Recommended)
TWA 1 mg/m3 (as Cu) [2]
IDLH (Immediate danger)
TWA 100 mg/m3 (as Cu) [2]
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).
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Copper(II) 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. [3]

Contents

Structure

Copper(II) fluoride has a monoclinic crystal structure [4] and cannot achieve a higher-symmetry structure. It forms rectangular prisms with a parallelogram base. [5] Each copper ion has four neighbouring fluoride ions at 1.93 Å separation and two further away at 2.27 Å. [3] This distorted octahedral [4+2] coordination is a consequence of the Jahn–Teller effect in d9 copper(II), [6] and leads to a distorted rutile structure similar to that of chromium(II) fluoride, CrF2, which is a d4 compound. [3]

Coordination in copper(II) fluoride [3] [4]
Copper coordinationFluorine coordination
Copper(II)-fluoride-Cu-coord-3D-bs-17.png Copper(II)-fluoride-F-coord-3D-bs-17.png

Uses

Cupric fluoride catalyzes the decomposition of nitric oxides in emission control systems. [7]

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. [8] This method has been proposed as a "greener" method of producing fluoroaromatics since it avoids producing toxic waste products such as ammonium fluoride.

Fluorobenzene-copperfluoride-synthesis.png

Chemistry

Copper(II) fluoride can be synthesized from copper and fluorine at temperatures of 400 °C (752 °F). It occurs as a direct reaction.

Cu + F2 → CuF2

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

2CuF2 → 2CuF + F2
2CuF → CuF2 + Cu

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

Solubility

Copper(II) fluoride is slightly soluble in water, but starts to decompose when it is in hot water, producing basic F and Cu(OH) ions.[ citation needed ]

Toxicity

There is little specific information on the toxicity of Copper(II) fluoride.

Copper toxicity can affect the skin, eyes, and respiratory tract. Serious conditions include metal fume fever, and hemolysis of red blood cells. Copper can also cause damage to the liver and other major organs.

Metal fluorides are generally safe at low levels and are added to water in many countries to protect against tooth decay. At higher levels they can cause toxic effects ranging from nausea and vomiting to tremors, breathing problems, serious convulsions and even coma. Brain and kidney damage can result. Chronic exposure can cause losses in bone density, weight loss and anorexia.

Hazards

Experiments using copper(II) fluoride should be conducted in a fume hood because metal oxide fumes can occur. The combination of acids with copper(II) fluoride may lead to the production of hydrogen fluoride, which is highly toxic and corrosive.

Related Research Articles

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

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

Nickel(II) fluoride is the chemical compound with the formula NiF2. It is an ionic compound of nickel and fluorine and forms yellowish to green tetragonal crystals. Unlike many fluorides, NiF2 is stable in air.

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

Cobalt(II) fluoride is a chemical compound with the formula (CoF2). It is a pink crystalline solid compound which is antiferromagnetic at low temperatures (TN=37.7 K) The formula is given for both the red tetragonal crystal, (CoF2), and the tetrahydrate red orthogonal crystal, (CoF2·4H2O). CoF2 is used in oxygen-sensitive fields, namely metal production. In low concentrations, it has public health uses. CoF2 is sparingly soluble in water. The compound can be dissolved in warm mineral acid, and will decompose in boiling water. Yet the hydrate is water-soluble, especially the di-hydrate CoF2·2H2O and tri-hydrate CoF2·3H2O forms of the compound. The hydrate will also decompose with heat.

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

Silver(II) fluoride is a chemical compound with the formula AgF2. It is a rare example of a silver(II) compound - silver usually exists in its +1 oxidation state. It is used as a fluorinating agent.

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

Iron(III) fluoride, also known as ferric fluoride, are inorganic compounds with the formula FeF3(H2O)x where x = 0 or 3. They are mainly of interest by researchers, unlike the related iron(III) chloride. Anhydrous iron(III) fluoride is white, whereas the hydrated forms are light pink.

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

Cadmium fluoride (CdF2) is a mostly water-insoluble source of cadmium used in oxygen-sensitive applications, such as the production of metallic alloys. In extremely low concentrations (ppm), this and other fluoride compounds are used in limited medical treatment protocols. Fluoride compounds also have significant uses in synthetic organic chemistry. The standard enthalpy has been found to be -167.39 kcal. mole−1 and the Gibbs energy of formation has been found to be -155.4 kcal. mole−1, and the heat of sublimation was determined to be 76 kcal. mole−1.

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

Hydrogen fluoride (fluorane) is an inorganic compound with chemical formula HF. It is a very poisonous, colorless gas or liquid that dissolves in water to yield an aqueous solution termed hydrofluoric acid. It is the principal industrial source of fluorine, often in the form of hydrofluoric acid, and is an important feedstock in the preparation of many important compounds including pharmaceuticals and polymers, e.g. polytetrafluoroethylene (PTFE). HF is also widely used in the petrochemical industry as a component of superacids. Due to strong and extensive hydrogen bonding, it boils at near room temperature, much higher than other hydrogen halides.

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

Xenon difluoride is a powerful fluorinating agent with the chemical formula XeF
2
, and one of the most stable xenon compounds. Like most covalent inorganic fluorides it is moisture-sensitive. It decomposes on contact with water vapor, but is otherwise stable in storage. Xenon difluoride is a dense, colourless crystalline solid.

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

Zinc fluoride is an inorganic chemical compound with the chemical formula ZnF2. It is encountered as the anhydrous form and also as the tetrahydrate, ZnF2·4H2O (rhombohedral crystal structure). It has a high melting point and has the rutile structure containing 6 coordinate zinc, which suggests appreciable ionic character in its chemical bonding. Unlike the other zinc halides, ZnCl2, ZnBr2 and ZnI2, it is not very soluble in water.

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

Tungsten oxytetrafluoride is an inorganic compound with the formula WOF4. It is a colorless diamagnetic solid. The compound is one of many oxides of tungsten. It is usually encountered as product of the partial hydrolysis of tungsten hexafluoride.

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

Tetrafluorohydrazine or perfluorohydrazine, N2F4, is a colourless, nonflammable, reactive inorganic gas. It is a fluorinated analog of hydrazine.

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

The dioxygenyl ion, O+
2
, is a rarely-encountered oxycation in which both oxygen atoms have a formal oxidation state of +1/2. It is formally derived from oxygen by the removal of an electron:

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

Copper(I) fluoride or cuprous fluoride is an inorganic compound with the chemical formula CuF. Its existence is uncertain. It was reported in 1933 to have a sphalerite-type crystal structure. Modern textbooks state that CuF is not known, since fluorine is so electronegative that it will always oxidise copper to its +2 oxidation state. Complexes of CuF such as [(Ph3P)3CuF] are, however, known and well characterised.

<span class="mw-page-title-main">Caesium hexafluorocuprate(IV)</span> Chemical compound with +4 oxidized copper

Caesium hexafluorocuprate is the inorganic compound with the chemical formula Cs
2
CuF
6
. It is a red solid that degrades upon contact with water. It was first prepared be heating CsCuCl
3
and caesium fluoride at 410°C under 350 atmospheres of fluorine:

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

Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF3 containing phosphorus, sulfur and fluorine. It spontaneously ignites in air and burns with a cool flame. The discoverers were able to have flames around their hands without discomfort, and called it "probably one of the coldest flames known". The gas was discovered in 1888.

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

Chromium(II) fluoride is an inorganic compound with the formula CrF2. It exists as a blue-green iridescent solid. Chromium(II) fluoride is sparingly soluble in water, almost insoluble in alcohol, and is soluble in boiling hydrochloric acid, but is not attacked by hot distilled sulfuric acid or nitric acid. Like other chromous compounds, chromium(II) fluoride is oxidized to chromium(III) oxide in air.

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

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

Monofluorophosphate is an anion with the formula PO3F2−, which is a phosphate group with one oxygen atom substituted with a fluoride atom. The charge of the ion is −2. The ion resembles sulfate in size, shape and charge, and can thus form compounds with the same structure as sulfates. These include Tutton's salts and langbeinites. The most well-known compound of monofluorophosphate is sodium monofluorophosphate, commonly used in toothpaste.

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

Difluorophosphate or difluorodioxophosphate or phosphorodifluoridate is an anion with formula PO2F−2. It has a single negative charge and resembles perchlorate and monofluorosulfonate in shape and compounds. These ions are isoelectronic, along with tetrafluoroaluminate, phosphate, orthosilicate, and sulfate. It forms a series of compounds. The ion is toxic to mammals as it causes blockage to iodine uptake in the thyroid. However it is degraded in the body over several hours.

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

A carbonate fluoride, fluoride carbonate, fluorocarbonate or fluocarbonate is a double salt containing both carbonate and fluoride. The salts are usually insoluble in water, and can have more than one kind of metal cation to make more complex compounds. Rare-earth fluorocarbonates are particularly important as ore minerals for the light rare-earth elements lanthanum, cerium and neodymium. Bastnäsite is the most important source of these elements. Other artificial compounds are under investigation as non-linear optical materials and for transparency in the ultraviolet, with effects over a dozen times greater than Potassium dideuterium phosphate.

References

  1. Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN   0-07-049439-8
  2. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 3 4 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 1184–1185. ISBN   978-0-08-037941-8.
  4. 1 2 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.
  5. 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.
  6. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 1190–1191. ISBN   978-0-08-037941-8.
  7. 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
  8. 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.