Zirconium tetrafluoride

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Zirconium(IV) fluoride
Kristallstruktur Uran(IV)-fluorid.png
Names
IUPAC names
Zirconium(IV) fluoride
Zirconium tetrafluoride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.107 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 232-018-1
PubChem CID
UNII
  • InChI=1S/4FH.Zr/h4*1H;/q;;;;+4/p-4 Yes check.svgY
    Key: OMQSJNWFFJOIMO-UHFFFAOYSA-J Yes check.svgY
  • InChI=1/4FH.Zr/h4*1H;/q;;;;+4/p-4
    Key: OMQSJNWFFJOIMO-XBHQNQODAN
  • F[Zr](F)(F)F
Properties
ZrF4
Molar mass 167.21 g/mol
Appearancewhite crystalline powder
Density 4.43 g/cm3 (20 °C)
Melting point 910 °C (1,670 °F; 1,180 K)
1.32 g/100mL (20 °C)
1.388 g/100mL (25 °C)
Structure
Monoclinic, mS60
C12/c1, No. 15
Hazards
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
98 mg/kg (oral, mouse)
98 mg/kg (oral, rat) [1]
Related compounds
Other anions
Zirconium(IV) chloride
Zirconium(IV) bromide
Zirconium(IV) iodide
Other cations
Titanium(IV) fluoride
Hafnium(IV) 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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Zirconium(IV) fluoride describes members of a family inorganic compounds with the formula (Zr F4(H2O)x. All are colorless, diamagnetic solids. Anhydrous Zirconium(IV) fluoride' is a component of ZBLAN fluoride glass. [2]

Contents

Structure

Tetragonal ZrF4 ZrF4tetragonal.jpg
Tetragonal ZrF4

Three crystalline phases of ZrF4 have been reported, α (monoclinic), β (tetragonal, Pearson symbol tP40, space group P42/m, No 84) and γ (unknown structure). β and γ phases are unstable and irreversibly transform into the α phase at 400 °C. [3]

Zirconium(IV) fluoride forms several hydrates. The trihydrate has the structure (μ−F)2[ZrF3(H20)3]2. [4]

Preparation and reactions

Zirconium fluoride can be produced by several methods. Zirconium dioxide reacts with hydrogen fluoride and hydrofluoric acid to afford the anhydrous and monohydrates:

ZrO2 + 4 HF → ZrF4 + 2 H2O

The reaction of Zr metal reacts at high temperatures with HF as well:

Zr + 4 HF → ZrF4 + 2 H2

Zirconium dioxide reacts at 200 °C with solid ammonium bifluoride to give the heptafluorozirconate salt, which can be converted to the tetrafluoride at 500 °C:

2ZrO2 + 7 (NH4)HF2 → 2 (NH4)3ZrF7 + 4 H2O + NH3
(NH4)3ZrF7 → ZrF4 + 3 HF + 3 NH3

Addition of hydrofluoric acid to solutions of zirconium nitrate precipitates solid monohydrate. Hydrates of zirconium tetrafluoride can be dehydrated by heating under a stream of hydrogen fluoride.

Zirconium fluoride can be purified by distillation or sublimation. [2]

Zirconium fluoride forms double salts with other fluorides. The most prominent is potassium hexafluorozironate, formed by fusion of potassium fluoride and zirconium tetrafluoride: [5]

ZrF4 + 2 KF → K2ZrF6

Applications

The major and perhaps only commercial application of zirconium fluoride is as a precursor to ZBLAN glasses. [2]

Mixture of sodium fluoride, zirconium fluoride, and uranium tetrafluoride (53-41-6 mol.%) was used as a coolant in the Aircraft Reactor Experiment. A mixture of lithium fluoride, beryllium fluoride, zirconium fluoride, and uranium-233 tetrafluoride was used in the Molten-Salt Reactor Experiment. (Uranium-233 is used in the thorium fuel cycle reactors.)[ citation needed ]

Related Research Articles

<span class="mw-page-title-main">Hydrofluoric acid</span> Solution of hydrogen fluoride in water

Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. It is used to make most fluorine-containing compounds; examples include the commonly used pharmaceutical antidepressant medication fluoxetine (Prozac) and the material PTFE (Teflon). Elemental fluorine is produced from it. It is commonly used to etch glass and silicon wafers.

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

Beryllium fluoride is the inorganic compound with the formula BeF2. This white solid is the principal precursor for the manufacture of beryllium metal. Its structure resembles that of quartz, but BeF2 is highly soluble in water.

Fluoride volatility is the tendency of highly fluorinated molecules to vaporize at comparatively low temperatures. Heptafluorides, hexafluorides and pentafluorides have much lower boiling points than the lower-valence fluorides. Most difluorides and trifluorides have high boiling points, while most tetrafluorides and monofluorides fall in between. The term "fluoride volatility" is jargon used particularly in the context of separation of radionuclides.

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

Chromium(III) fluoride is an inorganic compound with the chemical formula CrF3. It forms several hydrates. The compound CrF3 is a green crystalline solid that is insoluble in common solvents, but the hydrates [Cr(H2O)6]F3 (violet) and [Cr(H2O)6]F3·3H2O (green) are soluble in water. The anhydrous form sublimes at 1100–1200 °C.

<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">Uranium tetrafluoride</span> Chemical compound

Uranium tetrafluoride is the inorganic compound with the formula UF4. It is a green solid with an insignificant vapor pressure and low solubility in water. Uranium in its tetravalent (uranous) state is important in various technological processes. In the uranium refining industry it is known as green salt.

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

Rubidium fluoride (RbF) is the fluoride salt of rubidium. It is a cubic crystal with rock-salt structure.

<span class="mw-page-title-main">Hexafluorosilicic acid</span> Octahedric silicon compound

Hexafluorosilicic acid is an inorganic compound with the chemical formula H
2SiF
6. Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless.

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

Ammonium bifluoride is the inorganic compound with the formula [NH4][HF2] or [NH4]F·HF. It is produced from ammonia and hydrogen fluoride. This colourless salt is a glass-etchant and an intermediate in a once-contemplated route to hydrofluoric acid.

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

Manganese tetrafluoride, MnF4, is the highest fluoride of manganese. It is a powerful oxidizing agent and is used as a means of purifying elemental fluorine.

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

FLiBe is the name of a molten salt made from a mixture of lithium fluoride (LiF) and beryllium fluoride. It is both a nuclear reactor coolant and solvent for fertile or fissile material. It served both purposes in the Molten-Salt Reactor Experiment (MSRE) at the Oak Ridge National Laboratory.

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

Potassium heptafluorotantalate is an inorganic compound with the formula K2[TaF7]. It is the potassium salt of the heptafluorotantalate anion [TaF7]2−. This white, water-soluble solid is an intermediate in the purification of tantalum from its ores and is the precursor to the metal.

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

Germanium tetrafluoride (GeF4) is a chemical compound of germanium and fluorine. It is a colorless gas.

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

Neptunium(VI) fluoride (NpF6) is the highest fluoride of neptunium, it is also one of seventeen known binary hexafluorides. It is an orange volatile crystalline solid. It is relatively hard to handle, being very corrosive, volatile and radioactive. Neptunium hexafluoride is stable in dry air but reacts vigorously with water.

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

Hafnium tetrafluoride is the inorganic compound with the formula HfF4. It is a white solid. It adopts the same structure as zirconium tetrafluoride, with 8-coordinate Hf(IV) centers.

<span class="mw-page-title-main">Tetrafluoroberyllate</span> Anion

Tetrafluoroberyllate or orthofluoroberyllate is an anion with the chemical formula [BeF4]2−. It contains beryllium and fluorine. This fluoroanion has a tetrahedral shape, with the four fluorine atoms surrounding a central beryllium atom. It has the same size, charge, and outer electron structure as sulfate SO2−4. Therefore, many compounds that contain sulfate have equivalents with tetrafluoroberyllate. Examples of these are the langbeinites, and Tutton's salts.

Gadolinium(III) fluoride is an inorganic compound with a chemical formula GdF3.

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

Cerium(IV) fluoride is an inorganic compound with a chemical formula CeF4. It is a strong oxidant that appears as a white crystalline material. Cerium(IV) fluoride has an anhydrous form and a monohydrate form.

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

Protactinium(V) fluoride is a fluoride of protactinium with the chemical formula PaF5.

References

  1. ↑ "Zirconium compounds (as Zr)". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 3 Nielsen, Ralph (2000). "Zirconium and Zirconium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a28_543. ISBN   3527306730.
  3. ↑ Paul L. Brown; Federico J. Mompean; Jane Perrone; Myriam Illemassène (2005). Chemical thermodynamics of zirconium. Gulf Professional Publishing. p. 144. ISBN   0-444-51803-7.
  4. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 965. ISBN   978-0-08-037941-8.
  5. ↑ Meshri, Dayal T. (2000), "Fluorine compounds, inorganic, titanium", Kirk-Othmer Encyclopedia of Chemical Technology, New York: John Wiley, doi:10.1002/0471238961.2009200113051908.a01, ISBN   9780471238966
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