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Zirconium(IV) fluoride describes members of a family
inorganic compounds An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemistry''. Inorg ...
with the formula Zr F4(H2O)x. All are colorless, diamagnetic solids. Anhydrous Zirconium(IV) fluoride is a component of
ZBLAN ZBLAN is the most stable, and consequently the most used, fluoride glass, a subcategory of the heavy metal fluoride glass (HMFG) group. Typically its composition is 53% Zirconium tetrafluoride, ZrF4, 20% Barium fluoride, BaF2, 4% Lanthanum triflu ...
fluoride glass Fluoride glass is a class of non-oxide optical glasses composed of fluorides of various metals. They can contain heavy metals such as zirconium, or be combined with lighter elements like aluminium and beryllium. These heavier elements cause the g ...
.


Structure

Three crystalline phases of ZrF4 have been reported, α (
monoclinic In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three Vector (geometric), vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in t ...
), β (
tetragonal In crystallography, the tetragonal crystal system is one of the 7 crystal systems. Tetragonal crystal lattices result from stretching a cubic lattice along one of its lattice vectors, so that the Cube (geometry), cube becomes a rectangular Pri ...
,
Pearson symbol The Pearson symbol, or Pearson notation, is used in crystallography as a means of describing a crystal structure. It was originated by William Burton Pearson and is used extensively in Pearson's handbook of crystallographic data for intermetallic p ...
tP40,
space group In mathematics, physics and chemistry, a space group is the symmetry group of a repeating pattern in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of the pattern that ...
P42/m, No 84) and γ (unknown structure). β and γ phases are unstable and irreversibly transform into the α phase at 400 °C. Zirconium(IV) fluoride forms several hydrates. The trihydrate has the structure .


Preparation and reactions

Zirconium fluoride can be produced by several methods.
Zirconium dioxide Zirconium dioxide (), sometimes known as zirconia (not to be confused with zirconium silicate or zircon), is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral bad ...
reacts with hydrogen fluoride and hydrofluoric acid to afford the anhydrous and monohydrates: : The reaction of Zr metal reacts at high temperatures with HF as well: : Zirconium dioxide reacts at 200 °C with solid
ammonium bifluoride Ammonium bifluoride is an inorganic compound with the formula or . It is produced from ammonia and hydrogen fluoride. This colourless salt is a glass-industrial etching, etchant and an intermediate in a once-contemplated route to hydrofluoric acid ...
to give the heptafluorozirconate salt, which can be converted to the tetrafluoride at 500 °C: : : 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 Distillation, also classical distillation, is the process of separating the component substances of a liquid mixture of two or more chemically discrete substances; the separation process is realized by way of the selective boiling of the mixt ...
or sublimation. Zirconium fluoride forms double salts with other
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
s. The most prominent is potassium hexafluorozirconate, formed by fusion of potassium fluoride and zirconium tetrafluoride: :


Applications

The major and perhaps only commercial application of zirconium fluoride is as a precursor to ZBLAN glasses. Mixture of sodium fluoride, zirconium fluoride, and
uranium tetrafluoride 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 process ...
(53-41-6 mol.%) was used as a coolant in the Aircraft Reactor Experiment. A mixture of
lithium fluoride Lithium fluoride is an inorganic compound with the chemical formula LiF. It is a colorless solid that transitions to white with decreasing crystal size. Its structure is analogous to that of sodium chloride, but it is much less soluble in water. ...
,
beryllium fluoride Beryllium fluoride is the inorganic compound with the formula Be F2. 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. Properties Ber ...
, zirconium fluoride, and uranium-233 tetrafluoride was used in the
Molten-Salt Reactor Experiment The Molten-Salt Reactor Experiment (MSRE) was an experimental molten-salt reactor research reactor at the Oak Ridge National Laboratory (ORNL) in Oak Ridge, Tennessee. This technology was researched through the 1960s, the reactor was constructed ...
. (
Uranium-233 Uranium-233 ( or U-233) is a fissile isotope of uranium that is bred from thorium-232 as part of the thorium fuel cycle. Uranium-233 was investigated for use in nuclear weapons and as a Nuclear fuel, reactor fuel. It has been used successfully ...
is used in the
thorium fuel cycle The thorium fuel cycle is a nuclear fuel cycle that uses an isotope of thorium, , as the fertile material. In the reactor, is transmuted into the fissile artificial uranium isotope which is the nuclear fuel. Unlike natural uranium, natural ...
reactors.)


References

* ORNL/TM-2006/12 Assessment of Candidate Molten Salt Coolants for the Advanced High-Temperature Reactor (AHTR), March 2006 (Accessed 2008/9/18) {{fluorine compounds Fluorides Zirconium(IV) compounds Metal halides