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 processes. In the uranium refining industry it is known as green salt.[1]

Uranium tetrafluoride
Names
IUPAC names
Uranium(IV) fluoride
Uranium tetrafluoride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.142
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
Very toxic (T+)
Dangerous for the environment (N)
R-phrases (outdated) R26/28, R33, R51/53
S-phrases (outdated) (S1/2), S20/21, S45, S61
Flash point Non-flammable
Related compounds
Other anions
 Uranium(IV) chloride
Uranium(IV) bromide
Uranium(IV) iodide
Uranium dioxide
Other cations
 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).
N verify (what is YN ?)
Infobox references

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 favorable 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 centers are eight-coordinate with square antiprismatic coordination spheres. The fluoride centers are doubly bridging.[2][3]

Safety

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

Uranium tetrafluoride

References of historical interestt
  • 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. Peehs, Martin; Walter, Thomas; Walter, Sabine; Zemek, Martin (2007). "Uranium, Uranium Alloys, and Uranium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_281.pub2.
  2. 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.; West, M.; Hoisington, D.; Lander, G. A. (1994). "Temperature Variation of the Structural Parameters in Actinide Tetrafluorides". The Journal of Chemical Physics. 101 (11): 9333–9337. Bibcode:1994JChPh.101.9333K. doi:10.1063/1.467963.
  • "Uranium Tetrafluoride". Appendix A of the PEIS (DOE/EIS-0269). Argonne National Laboratory. Retrieved 22 November 2011.
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