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Zirconium tetrafluoride - Wikipedia

From Wikipedia, the free encyclopedia

Chemical compound

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.[2]

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(H2O)3]2.[4]

Preparation and reactions[edit]

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 hexafluorozirconate, formed by fusion of potassium fluoride and zirconium tetrafluoride:[5]

ZrF4 + 2 KF → K2ZrF6

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]

  1. ^ "Zirconium compounds (as Zr)". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  2. ^ a b c 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
Fluorine compounds

Salts and covalent derivatives of the

fluoride

ion

HF ?HeF2 LiF BeF2 BF
BF3
B2F4
+BO3 CF4
CxFy
+CO3 NF3
FN3
N2F2
NF
N2F4
NF2
?NF5
+N
+NO3 OF2
O2F2
OF
O3F2
O4F2
?OF4 F2 Ne NaF MgF2 AlF
AlF3 SiF4 P2F4
PF3
PF5
+PO4 S2F2
SF2
S2F4
SF3
SF4
S2F10
SF6
+SO4 ClF
ClF3
ClF5 ?ArF2
?ArF4 KF CaF
CaF2 ScF3 TiF2
TiF3
TiF4 VF2
VF3
VF4
VF5 CrF2
CrF3
CrF4
CrF5
?CrF6 MnF2
MnF3
MnF4
?MnF5 FeF2
FeF3
FeF4 CoF2
CoF3
CoF4 NiF2
NiF3
NiF4 CuF
CuF2
?CuF3 ZnF2 GaF2
GaF3 GeF2
GeF4 AsF3
AsF5 Se2F2
SeF4
SeF6
+SeO3 BrF
BrF3
BrF5 KrF2
?KrF4
?KrF6 RbF SrF
SrF2 YF3 ZrF2
ZrF3
ZrF4 NbF4
NbF5 MoF4
MoF5
MoF6 TcF4
TcF
5
TcF6 RuF3
RuF
4
RuF5
RuF6 RhF3
RhF4
RhF5
RhF6 PdF2
Pd[PdF6]
PdF4
?PdF6 Ag2F
AgF
AgF2
AgF3 CdF2 InF
InF3 SnF2
SnF4 SbF3
SbF5 TeF4
?Te2F10
TeF6
+TeO3 IF
IF3
IF5
IF7
+IO3 XeF2
XeF4
XeF6
?XeF8 CsF BaF2   LuF3 HfF4 TaF5 WF4
WF5
WF6 ReF4
ReF5
ReF6
ReF7 OsF4
OsF5
OsF6
?OsF
7
?OsF
8 IrF2
IrF3
IrF4
IrF5
IrF6 PtF2
Pt[PtF6]
PtF4
PtF5
PtF6 AuF
AuF3
Au2F10
?AuF6
AuF5•F2 Hg2F2
HgF2
?HgF4 TlF
TlF3 PbF2
PbF4 BiF3
BiF5 ?PoF2
PoF4
PoF6 AtF
?AtF3
?AtF5 RnF2
?RnF
4
?RnF
6 FrF RaF2   LrF3 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og ↓ LaF3 CeF3
CeF4 PrF3
PrF4 NdF2
NdF3
NdF4 PmF3 SmF
SmF2
SmF3 EuF2
EuF3 GdF3 TbF3
TbF4 DyF2
DyF3
DyF4 HoF3 ErF3 TmF2
TmF3 YbF2
YbF3 AcF3 ThF2
ThF3
ThF4 PaF4
PaF5 UF3
UF4
UF5
UF6 NpF3
NpF4
NpF5
NpF6 PuF3
PuF4
PuF5
PuF6 AmF2
AmF3
AmF4
?AmF6 CmF3
CmF4
 ?CmF6 BkF3
BkF
4 CfF3
CfF4 EsF3
EsF4
?EsF6 Fm Md No PF−6, AsF−6, SbF−6 compounds AlF2−5, AlF3−6 compounds chlorides, bromides, iodides
and pseudohalogenides SiF2−6, GeF2−6 compounds Oxyfluorides Organofluorides with transition metal,
lanthanide, actinide, ammonium nitric acids bifluorides thionyl, phosphoryl,
and iodosyl Chemical formulas

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