Zirconium tetrafluoride explained

Zirconium(IV) fluoride describes members of a family inorganic compounds with the formula (ZrF4(H2O)x. All are colorless, diamagnetic solids. Anhydrous Zirconium(IV) fluoride' is a component of ZBLAN fluoride glass.[1]

Structure

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.[2]

Zirconium(IV) fluoride forms several hydrates. The trihydrate has the structure .

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:

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

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:

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.[1]

Zirconium fluoride forms double salts with other fluorides. The most prominent is potassium hexafluorozironate, 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.[1]

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.)

References

Notes and References

  1. Book: 10.1002/14356007.a28_543 . Zirconium and Zirconium Compounds . Ullmann's Encyclopedia of Industrial Chemistry . 2000 . Nielsen . Ralph . 3527306730 .
  2. Book: 144. Chemical thermodynamics of zirconium. Paul L. Brown . Federico J. Mompean . Jane Perrone . Myriam Illemassène . Gulf Professional Publishing. 2005. 0-444-51803-7.