Uranium hexafluoride explained

Uranium hexafluoride, sometimes called hex, is an inorganic compound with the formula . Uranium hexafluoride is a volatile, toxic white solid that is used in the process of enriching uranium, which produces fuel for nuclear reactors and nuclear weapons.

Preparation

Uranium dioxide is converted with hydrofluoric acid (HF) to uranium tetrafluoride:^[1]

In samples contaminated with uranium trioxide, the oxyfluoride is produced in the HF step:

The resulting is subsequently oxidized with fluorine to give the hexafluoride:

Properties

Physical properties

At atmospheric pressure, sublimes at 56.5 °C.^[2]

The solid-state structure was determined by neutron diffraction at 77 K and 293 K.^{[3] [4]}

Chemical properties

UF₆ reacts with water, releasing hydrofluoric acid. The compound reacts with aluminium, forming a surface layer of that resists any further reaction from the compound.

Uranium hexafluoride is a mild oxidant.^[5] It is a Lewis acid as evidenced by its binding to form heptafluorouranate(VI), .^[6]

Polymeric uranium(VI) fluorides containing organic cations have been isolated and characterized by X-ray diffraction.^[7]

Application in the fuel cycle

As one of the most volatile compounds of uranium, uranium hexafluoride is relatively convenient to process and is used in both of the main uranium enrichment methods, namely gaseous diffusion and the gas centrifuge method. Since the triple point of ; 64 °C(147 °F; 337 K) and 152 kPa (22 psi; 1.5 atm);^[8] is close to ambient conditions, phase transitions can be achieved with little thermodynamic work.

Fluorine has only a single naturally occurring stable isotope, so isotopologues of differ in their molecular weight based solely on the uranium isotope present.^[9] This difference is the basis for the physical separation of isotopes in enrichment.

All the other uranium fluorides are nonvolatile solids that are coordination polymers.

The conversion factor for the isotopologue of ("hex") to "U mass" is 0.676.^[10]

Gaseous diffusion requires about 60 times as much energy as the gas centrifuge process: gaseous diffusion-produced nuclear fuel produces 25 times more energy than is used in the diffusion process, while centrifuge-produced fuel produces 1,500 times more energy than is used in the centrifuge process.

In addition to its use in enrichment, uranium hexafluoride has been used in an advanced reprocessing method (fluoride volatility), which was developed in the Czech Republic. In this process, spent nuclear fuel is treated with fluorine gas to transform the oxides or elemental metals into a mixture of fluorides. This mixture is then distilled to separate the different classes of material. Some fission products form nonvolatile fluorides which remain as solids and can then either be prepared for storage as nuclear waste or further processed either by solvation-based methods or electrochemically.

Uranium enrichment produces large quantities of depleted uranium hexafluoride (D or D-) as a waste product. The long-term storage of D- presents environmental, health, and safety risks because of its chemical instability. When is exposed to moist air, it reacts with the water in the air to produce (uranyl fluoride) and HF (hydrogen fluoride) both of which are highly corrosive and toxic. In 2005, 686,500 tonnes of D- was housed in 57,122 storage cylinders located near Portsmouth, Ohio; Oak Ridge, Tennessee; and Paducah, Kentucky.^{[11] [12]} Storage cylinders must be regularly inspected for signs of corrosion and leaks. The estimated lifetime of the steel cylinders is measured in decades.^[13]

Accidents and disposal

There have been several accidents involving uranium hexafluoride in the US, including a cylinder-filling accident and material release at the Sequoyah Fuels Corporation in 1986 where an estimated 29 500 pounds of gaseous escaped.^{[14] [15]} The U.S. government has been converting D to solid uranium oxides for disposal.^[16] Such disposal of the entire D stockpile could cost anywhere from $15 million to $450 million.^[17]

Further reading

• Gmelins Handbuch der anorganischen Chemie, System Nr. 55, Uran, Teil A, p. 121–123.
• Gmelins Handbuch der anorganischen Chemie, System Nr. 55, Uran, Teil C 8, p. 71–163.
• R. DeWitt: Uranium hexafluoride: A survey of the physico-chemical properties, Technical report, GAT-280; Goodyear Atomic Corp., Portsmouth, Ohio; 12. August 1960; .
• Ingmar Grenthe, Janusz Drożdżynński, Takeo Fujino, Edgar C. Buck, Thomas E. Albrecht-Schmitt, Stephen F. Wolf: Uranium, in: Lester R. Morss, Norman M. Edelstein, Jean Fuger (Hrsg.): The Chemistry of the Actinide and Transactinide Elements, Springer, Dordrecht 2006;, p. 253–698; (p. 530–531, 557–564).
• US-Patent 2535572: Preparation of UF₆; 26. December 1950.
• US-Patent 5723837: Uranium Hexafluoride Purification; 3. March 1998.

External links

• Simon Cotton (Uppingham School, Rutland, UK): Uranium Hexafluoride.
• Uranium Hexafluoride (UF₆) – Physical and chemical properties of UF₆, and its use in uranium processing – Uranium Hexafluoride and Its Properties
• Uranium Hexafluoride at WebElements
• Import of Western depleted uranium hexafluoride (uranium tails) to Russia [dead link 30 June 2017]

Notes and References

1. Book: 10.1002/14356007.a27_281.pub2 . Uranium, Uranium Alloys, and Uranium Compounds . Ullmann's Encyclopedia of Industrial Chemistry . 2007 . Peehs . Martin . Walter . Thomas . Walter . Sabine . Zemek . Martin . 978-3-527-30385-4 .
2. Brickwedde . Ferdinand G. . Hoge . Harold J. . Scott . Russell B. . 1948 . The Low Temperature Heat Capacities, Enthalpies, and Entropies of UF₄ and UF₆ . . 16 . 5 . 429–436 . 10.1063/1.1746914 . 1948JChPh..16..429B. free.
3. J. H. Levy . John C. Taylor . Paul W. Wilson . Structure of Fluorides. Part XII. Single-Crystal Neutron Diffraction Study of Uranium Hexafluoride at 293 K . J. Chem. Soc., Dalton Trans. . 1976 . 219–224 . 10.1039/DT9760000219 . 3.
4. J. H. Levy, J. C. Taylor and A. B. Waugh . Neutron Powder Structural Studies of UF₆, MoF₆ and WF₆ at 77 K . Journal of Fluorine Chemistry . 1983 . 29–36 . 23 . 10.1016/S0022-1139(00)81276-2.
5. G. H. Olah . J. Welch . Synthetic methods and reactions. 46. Oxidation of organic compounds with uranium hexafluoride in haloalkane solutions . . 1978 . 5396–5402 . 100 . 17 . 10.1021/ja00485a024.
6. J. A. Berry . R. T. Poole . A. Prescott . D. W. A. Sharp . J. M. Winfield . The oxidising and fluoride ion acceptor properties of uranium hexafluoride in acetonitrile . J. Chem. Soc., Dalton Trans. . 1976 . 272–274 . 10.1039/DT9760000272 . 3.
7. S. M. Walker . P. S. Halasyamani . S. Allen . D. O'Hare . From Molecules to Frameworks: Variable Dimensionality in the UO₂(CH₃COO)₂·2H₂O/HF(aq)/Piperazine System. Syntheses, Structures, and Characterization of Zero-Dimensional (C₄N₂H₁₂)UO₂F₄·3H₂O, One-Dimensional (C₄N₂H₁₂)₂U₂F₁₂·H₂O, Two-Dimensional (C₄N₂H₁₂)₂(U₂O₄F₅)₄·11H₂O, and Three-Dimensional (C₄N₂H₁₂)U₂O₄F₆ . J. Am. Chem. Soc. . 1999 . 10513–10521 . 121 . 45 . 10.1021/ja992145f.
8. Web site: Uranium Hexafluoride: Source: Appendix A of the PEIS (DOE/EIS-0269): Physical Properties . 2022-08-18 . web.evs.anl.gov.
9. Web site: Uranium Enrichment and the Gaseous Diffusion Process . USEC Inc . 2007-09-24 . dead . https://web.archive.org/web/20071019081831/http://www.usec.com/v2001_02/HTML/Aboutusec_enrichment.asp . 2007-10-19.
10. Web site: TranslatorsCafé. 1 February 2021. Unit converter molar mass calculator. ANVICA Software Development. Mississauga, Ontario, Canada.
11. Web site: Depleted UF₆ FAQs . How much depleted uranium hexafluoride is stored in the United States? . Argonne National Laboratory.
12. Web site: Depleted UF₆ Management Program Documents . 2006-05-17 . live . https://web.archive.org/web/20080216013118/http://web.ead.anl.gov/uranium/documents/index.cfm . 2008-02-16.
13. Web site: Institute for Energy and Environmental Research . 2007-09-24 . What is DUF₆? Is it dangerous and what should we do with it? .
14. 1963288 . 2007 . Brugge . D. . Delemos . J. L. . Bui . C. . The Sequoyah Corporation Fuels Release and the Church Rock Spill: Unpublicized Nuclear Releases in American Indian Communities . American Journal of Public Health . 97 . 9 . 1595–1600 . 10.2105/AJPH.2006.103044 . 17666688 .
15. Web site: Depleted UF₆ FAQs . Have there been accidents involving uranium hexafluoride? . Argonne National Laboratory . https://web.archive.org/web/20170609171651/http://web.ead.anl.gov/uranium/faq/health/faq30.cfm . 2017-06-09.
16. Web site: Depleted UF₆ FAQs . What is going to happen to the uranium hexafluoride stored in the United States? . Argonne National Laboratory.
17. Web site: Depleted UF₆ FAQs . Are there any currently-operating disposal facilities that can accept all of the depleted uranium oxide that would be generated from conversion of DOE's depleted UF₆ inventory? . Argonne National Laboratory.