Chemistry:Uranium tetrafluoride

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Uranium tetrafluoride
Uranium tetrafluoride.jpg
Kristallstruktur Uran(IV)-fluorid.png
Names
IUPAC names
Uranium(IV) fluoride
Uranium tetrafluoride
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 233-170-1
UNII
Properties
UF4
Molar mass 314.02 g/mol
Appearance Green crystalline solid
Density 6.70 g/cm3, solid
Melting point 1,036 °C (1,897 °F; 1,309 K)
Boiling point 1,417 °C (2,583 °F; 1,690 K)
Insoluble
Structure
Monoclinic, mS60
C2/c, No. 15
Hazards
Safety data sheet External MSDS
GHS pictograms GHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
GHS Signal word Danger
H300, H330, H373, H411
Flash point Non-flammable
Related compounds
Other anions
Uranium(IV) chloride
Uranium(IV) bromide
Uranium(IV) iodide
Uranium dioxide
Other cations
Praseodymium(IV) fluoride
Thorium(IV) fluoride
Protactinium(IV) fluoride
Neptunium(IV) fluoride
Plutonium(IV) fluoride
Related compounds
Uranium hexafluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

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.[1]

Production

UF4 is prepared from UO2 in a fluidized bed by reaction with HF. The UO2 is derived from mining operations. Around 60,000 tonnes per year are prepared in this way annually. A common impurity is UO2F2. UF4 is susceptible to hydrolysis as well.[1]

UF4 is formed by the reaction of UF6 with hydrogen gas in a vertical tube-type reactor. UF4 is less stable than the uranium oxides and reacts slowly with moisture at ambient temperature, forming UO2 and HF, the latter of which is very corrosive and toxic; it is thus less favourable for long-term disposal. The bulk density of UF4 varies from about 2.0 g/cm3 to about 4.5 g/cm3 depending on the production process and the properties of the starting uranium compounds.

A molten salt reactor design, a type of nuclear reactor where the working fluid is a molten salt, would use UF4 as the core material. UF4 is generally chosen over other salts because of the usefulness of the elements without isotope separation, better neutron economy and moderating efficiency, lower vapor pressure and better chemical stability.

Reactions

Uranium tetrafluoride reacts with fluorine, first to give uranium pentafluoride and then volatile UF6:

2 UF4 + F2 → 2 UF5
2 UF5 + F2 → 2 UF6

UF4 is reduced by magnesium to give the metal:[2]

UF4 + 2 Mg → U + 2 MgF2

It is oxidized to UF5 at room temperature and then, at 100 °C, to the hexafluoride.

Structure

Like most metal fluorides, UF4 is a dense highly crosslinked inorganic polymer. As established by X-ray crystallography, the U centres are eight-coordinate with square antiprismatic coordination spheres. The fluoride centres are doubly bridging.[2][3]

Safety

Like all uranium salts, UF4 is toxic and thus harmful by inhalation, ingestion, and through skin contact.

See also

References of historical interest

  • Booth, H. S.; Krasny-Ergen, W.; Heath, R. E. (1946). "Uranium Tetrafluoride". Journal of the American Chemical Society 68 (10): 1969. doi:10.1021/ja01214a028. 

References

  1. 1.0 1.1 Peehs, Martin; Walter, Thomas; Walter, Sabine; Zemek, Martin (2007). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_281.pub2. 
  2. 2.0 2.1 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. 
  3. Kern, S.; Hayward, J.; Roberts, S.; Richardson, J. W.; Rotella, F. J.; Soderholm, L.; Cort, B.; Tinkle, M. et al. (1994). "Temperature Variation of the Structural Parameters in Actinide Tetrafluorides". The Journal of Chemical Physics 101 (11): 9333–9337. doi:10.1063/1.467963. Bibcode1994JChPh.101.9333K. https://zenodo.org/record/1232099. 

External links