Uranium hexafluoride

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Uranium hexafluoride
Uranium-hexafluoride-2D-V2.svg
Uranium-hexafluoride-3D-vdW.png
Uranium-hexafluoride-crystal-3D-vdW.png
Names
IUPAC names
Uranium hexafluoride
Uranium(VI) fluoride
Identifiers
3D model (JSmol)
Abbreviationshex
ChEBI
ChemSpider
ECHA InfoCard 100.029.116 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 232-028-6
2923
PubChem CID
RTECS number
  • YR4720000
UNII
UN number 2978 (<1% 235U)
2977 (>1% 235U)
  • InChI=1S/6FH.U/h6*1H;/q;;;;;;+6/p-6 Yes check.svgY
    Key: SANRKQGLYCLAFE-UHFFFAOYSA-H Yes check.svgY
  • InChI=1/6FH.U/h6*1H;/q;;;;;;+6/p-6/rF6U/c1-7(2,3,4,5)6
    Key: SANRKQGLYCLAFE-IIYYNVFAAT
  • F[U](F)(F)(F)(F)F
Properties
UF6
Molar mass 352.02 g/mol
AppearanceColorless solid
Density 5.09 g/cm3, solid
Boiling point 56.5 °C (133.7 °F; 329.6 K) (sublimes, at atmospheric pressure)
Hydrolyzes
Solubility
Structure
Orthorhombic, oP28
Pnma, No. 62
Octahedral (Oh)
0
Thermochemistry
Std molar
entropy
(S298)
  • Solid, 227.8±1.3 J·K−1·mol−1 [2]
  • Gaseous, 377.8±1.3 J·K−1·mol−1 [2]
  • Solid, −2197.7±1.8  kJ·mol−1 [2]
  • Gaseous, −2148.1±1.8 kJ·mol−1 [2]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Toxic, corrosive, radioactive [3]
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H300, H330, H373, H411
NFPA 704 (fire diamond)
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W+OX: Reacts with water in an unusual or dangerous manner AND is oxidizer
4
0
2
W
OX
Flash point Non-flammable
Safety data sheet (SDS) ICSC 1250
Related compounds
Other anions
Uranium hexachloride
Other cations
Related uranium fluorides
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Uranium hexafluoride, sometimes called hex, is an inorganic compound with the formula U F 6. 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. [4]

Contents

Preparation

Uranium dioxide is converted with hydrofluoric acid (HF) to uranium tetrafluoride: [4]

UO2 + 4 HF → UF4 + 2 H2O

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

UO3 + HF → UF2O2 + H2O

The resulting UF4 is subsequently oxidized with fluorine to give the hexafluoride:

UF4 + F2 → UF6

Properties

Physical properties

At atmospheric pressure, UF6 sublimes at 56.5 °C. [5]

UF6 in a glass ampoule Uranium hexafluoride crystals sealed in an ampoule.jpg
UF6 in a glass ampoule

The solid-state structure was determined by neutron diffraction at 77 K and 293 K. [6] [7]

Chemical properties

UF6 reacts with water, releasing hydrofluoric acid. The compound reacts with aluminium, forming a surface layer of AlF3 that resists any further reaction from the compound.

Uranium hexafluoride is a mild oxidant. [10] It is a Lewis acid as evidenced by its binding to form heptafluorouranate(VI), [UF7]. [11]

Polymeric uranium(VI) fluorides containing organic cations have been isolated and characterized by X-ray diffraction. [12]

Application in the fuel cycle

Phase diagram of
UF6 Uranium hexafluoride phase diagram.gif
Phase diagram of UF6

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 UF6; 64 °C(147 °F; 337 K) and 152 kPa (22 psi; 1.5 atm); [13] 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 UF6 differ in their molecular weight based solely on the uranium isotope present. [14] 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 238U isotopologue of UF6 ("hex") to "U mass" is 0.676. [15]

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 (DUF6 or D-UF6) as a waste product. The long-term storage of D-UF6 presents environmental, health, and safety risks because of its chemical instability. When UF6 is exposed to moist air, it reacts with the water in the air to produce UO2F2 (uranyl fluoride) and HF (hydrogen fluoride) both of which are highly corrosive and toxic. In 2005, 686,500 tonnes of D-UF6 was housed in 57,122 storage cylinders located near Portsmouth, Ohio; Oak Ridge, Tennessee; and Paducah, Kentucky. [16] [17] Storage cylinders must be regularly inspected for signs of corrosion and leaks. The estimated lifetime of the steel cylinders is measured in decades. [18]

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 UF6 escaped. [19] [20] The U.S. government has been converting DUF6 to solid uranium oxides for disposal. [21] Such disposal of the entire DUF6 stockpile could cost anywhere from $15 million to $450 million. [22]

Related Research Articles

Isotope separation is the process of concentrating specific isotopes of a chemical element by removing other isotopes. The use of the nuclides produced is varied. The largest variety is used in research. By tonnage, separating natural uranium into enriched uranium and depleted uranium is the largest application. In the following text, mainly uranium enrichment is considered. This process is crucial in the manufacture of uranium fuel for nuclear power plants and is also required for the creation of uranium-based nuclear weapons. Plutonium-based weapons use plutonium produced in a nuclear reactor, which must be operated in such a way as to produce plutonium already of suitable isotopic mix or grade.

Enriched uranium is a type of uranium in which the percent composition of uranium-235 has been increased through the process of isotope separation. Naturally occurring uranium is composed of three major isotopes: uranium-238, uranium-235, and uranium-234. 235U is the only nuclide existing in nature that is fissile with thermal neutrons.

<span class="mw-page-title-main">Yellowcake</span> Uranium concentrate powder

Yellowcake is a type of powdered uranium concentrate obtained from leach solutions, in an intermediate step in the processing of uranium ores. It is a step in the processing of uranium after it has been mined but before fuel fabrication or uranium enrichment. Yellowcake concentrates are prepared by various extraction and refining methods, depending on the types of ores. Typically, yellowcakes are obtained through the milling and chemical processing of uranium ore, forming a coarse powder that has a pungent odor, is insoluble in water, and contains about 80% uranium oxide, which melts at approximately 2880 °C.

<span class="mw-page-title-main">Gas centrifuge</span> Device that performs isotope separation of gases

A gas centrifuge is a device that performs isotope separation of gases. A centrifuge relies on the principles of centrifugal force accelerating molecules so that particles of different masses are physically separated in a gradient along the radius of a rotating container. A prominent use of gas centrifuges is for the separation of uranium-235 (235U) from uranium-238 (238U). The gas centrifuge was developed to replace the gaseous diffusion method of 235U extraction. High degrees of separation of these isotopes relies on using many individual centrifuges arranged in series that achieve successively higher concentrations. This process yields higher concentrations of 235U while using significantly less energy compared to the gaseous diffusion process.

<span class="mw-page-title-main">Gaseous diffusion</span> Old method of enriching uranium

Gaseous diffusion is a technology that was used to produce enriched uranium by forcing gaseous uranium hexafluoride (UF6) through microporous membranes. This produces a slight separation (enrichment factor 1.0043) between the molecules containing uranium-235 (235U) and uranium-238 (238U). By use of a large cascade of many stages, high separations can be achieved. It was the first process to be developed that was capable of producing enriched uranium in industrially useful quantities, but is nowadays considered obsolete, having been superseded by the more-efficient gas centrifuge process (enrichment factor 1.05 to 1.2).

<span class="mw-page-title-main">K-25</span> Manhattan Project codename for a program to produce enriched uranium

K-25 was the codename given by the Manhattan Project to the program to produce enriched uranium for atomic bombs using the gaseous diffusion method. Originally the codename for the product, over time it came to refer to the project, the production facility located at the Clinton Engineer Works in Oak Ridge, Tennessee, the main gaseous diffusion building, and ultimately the site. When it was built in 1944, the four-story K-25 gaseous diffusion plant was the world's largest building, comprising over 5,264,000 square feet (489,000 m2) of floor space and a volume of 97,500,000 cubic feet (2,760,000 m3).

<span class="mw-page-title-main">Honeywell Uranium Hexafluoride Processing Facility</span> Uranium conversion facility in Illinois, United States.

The Honeywell Uranium Hexafluoride Processing Facility, a uranium conversion facility, is located 1.9 miles (3 km) northwest of Metropolis, Illinois, United States. The plant, Honeywell Specialty Chemicals in Metropolis, Illinois, has a nominal capacity of 15,000 tU as uranium hexafluoride per year. ConverDyn, a general partnership between affiliates of Honeywell and General Atomics, is the exclusive agent for conversion sales from the Honeywell Uranium Hexafluoride Processing Facility.

<span class="mw-page-title-main">Eurodif</span> Nuclear enrichment company in France

Eurodif, which means European Gaseous Diffusion Uranium Enrichment Consortium, is a subsidiary of the French company Orano, which operates a uranium enrichment plant, called the Georges-Besse plant, established at the Tricastin Nuclear Power Center in Pierrelatte in Drôme. The nuclear site of Pierrelatte includes many nuclear installations, of which the largest are the Eurodif fuel factory and the Tricastin nuclear power station.

Fluoride volatility is the tendency of highly fluorinated molecules to vaporize at comparatively low temperatures. Heptafluorides, hexafluorides and pentafluorides have much lower boiling points than the lower-valence fluorides. Most difluorides and trifluorides have high boiling points, while most tetrafluorides and monofluorides fall in between. The term "fluoride volatility" is jargon used particularly in the context of separation of radionuclides.

Molecular laser isotope separation (MLIS) is a method of isotope separation, where specially tuned lasers are used to separate isotopes of uranium using selective ionization of hyperfine transitions of uranium hexafluoride molecules. It is similar to AVLIS. Its main advantage over AVLIS is low energy consumption and use of uranium hexafluoride instead of vaporized uranium. MLIS was conceived in 1971 at the Los Alamos National Laboratory.

<span class="mw-page-title-main">Uranium tetrafluoride</span> Chemical compound

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.

<span class="mw-page-title-main">Uranium pentafluoride</span> Chemical compound

Uranium pentafluoride is the inorganic compound with the chemical formula UF5. It is a pale yellow paramagnetic solid. The compound has attracted interest because it is related to uranium hexafluoride, which is widely used to produce uranium fuel. It crystallizes in two polymorphs, called α- and β-UF5.

The Fowler process is an industry and laboratory route to fluorocarbons, by fluorinating hydrocarbons or their partially fluorinated derivatives in the vapor phase over cobalt(III) fluoride.

<span class="mw-page-title-main">Plutonium hexafluoride</span> Chemical compound

Plutonium hexafluoride is the highest fluoride of plutonium, and is of interest for laser enrichment of plutonium, in particular for the production of pure plutonium-239 from irradiated uranium. This isotope of plutonium is needed to avoid premature ignition of low-mass nuclear weapon designs by neutrons produced by spontaneous fission of plutonium-240.

A hexafluoride is a chemical compound with the general formula QXnF6, QXnF6m−, or QXnF6m+. Many molecules fit this formula. An important hexafluoride is hexafluorosilicic acid (H2SiF6), which is a byproduct of the mining of phosphate rock. In the nuclear industry, uranium hexafluoride (UF6) is an important intermediate in the purification of this element.

The Zippe-type centrifuge is a gas centrifuge designed to enrich the rare fissile isotope uranium-235 (235U) from the mixture of isotopes found in naturally occurring uranium compounds. The isotopic separation is based on the slight difference in mass of the isotopes. The Zippe design was originally developed in the Soviet Union by a team led by 60 Austrian and German scientists and engineers captured after World War II, working in detention. In the West the type is known by the name of the man who recreated the technology after his return to the West in 1956, based on his recollection of his work in the Soviet program, Gernot Zippe. To the extent that it might be referred to in Soviet/Russian usage by any one person's name, it was known as a Kamenev centrifuge.

<span class="mw-page-title-main">Neptunium(VI) fluoride</span> Chemical compound

Neptunium(VI) fluoride (NpF6) is the highest fluoride of neptunium, it is also one of seventeen known binary hexafluorides. It is a volatile orange crystalline solid. It is relatively hard to handle, being very corrosive, volatile and radioactive. Neptunium hexafluoride is stable in dry air but reacts vigorously with water.

<span class="mw-page-title-main">Fluorochemical industry</span> Industry dealing with chemicals from fluorine

The global market for chemicals from fluorine was about US$16 billion per year as of 2006. The industry was predicted to reach 2.6 million metric tons per year by 2015. The largest market is the United States. Western Europe is the second largest. Asia Pacific is the fastest growing region of production. China in particular has experienced significant growth as a fluorochemical market and is becoming a producer of them as well. Fluorite mining was estimated in 2003 to be a $550 million industry, extracting 4.5 million tons per year.

ConverDyn is a general partnership between American multinational firms General Atomics and Honeywell that provides uranium hexafluoride (UF6) conversion and related services to utilities operating nuclear power plants in North America, Europe, and Asia. The company is the sole marketing agent of UF6 produced at the Honeywell Uranium Hexafluoride Processing Facility in Metropolis, Illinois.

Depleted uranium hexafluoride (DUHF; also referred to as depleted uranium tails, depleted uranium tailings or DUF6) is a byproduct of the processing of uranium hexafluoride into enriched uranium. It is one of the chemical forms of depleted uranium (up to 73-75%), along with depleted triuranium octoxide (up to 25%) and depleted uranium metal (up to 2%). DUHF is 1.7 times less radioactive than uranium hexafluoride and natural uranium.

References

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  2. 1 2 3 4 Johnson, Gerald K. (1979). "The Enthalpy of Formation of Uranium Hexafluoride". The Journal of Chemical Thermodynamics . 11 (5): 483–490. doi:10.1016/0021-9614(79)90126-5.
  3. Uranium(VI) fluoride
  4. 1 2 Peehs, Martin; Walter, Thomas; Walter, Sabine; Zemek, Martin (2007). "Uranium, Uranium Alloys, and Uranium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a27_281.pub2. ISBN   978-3-527-30385-4.
  5. Brickwedde, Ferdinand G.; Hoge, Harold J.; Scott, Russell B. (1948). "The Low Temperature Heat Capacities, Enthalpies, and Entropies of UF4 and UF6". J. Chem. Phys. 16 (5): 429–436. Bibcode:1948JChPh..16..429B. doi: 10.1063/1.1746914 .
  6. J. H. Levy; John C. Taylor; Paul W. Wilson (1976). "Structure of Fluorides. Part XII. Single-Crystal Neutron Diffraction Study of Uranium Hexafluoride at 293 K". J. Chem. Soc., Dalton Trans. (3): 219–224. doi:10.1039/DT9760000219.
  7. J. H. Levy, J. C. Taylor and A. B. Waugh (1983). "Neutron Powder Structural Studies of UF6, MoF6 and WF6 at 77 K". Journal of Fluorine Chemistry. 23: 29–36. doi:10.1016/S0022-1139(00)81276-2.
  8. J. C. Taylor, P. W. Wilson, J. W. Kelly: „The structures of fluorides. I. Deviations from ideal symmetry in the structure of crystalline UF6: a neutron diffraction analysis", Acta Crystallogr. , 1973, B29, p. 7–12; doi : 10.1107/S0567740873001895.
  9. Kimura, Masao; Schomaker, Werner; Smith, Darwin W.; Bernard (1968). "Electron-Diffraction Investigation of the Hexafluorides of Tungsten, Osmium, Iridium, Uranium, Neptunium, and Plutonium". J. Chem. Phys. 48 (8): 4001–4012. Bibcode:1968JChPh..48.4001K. doi:10.1063/1.1669727. Archived from the original on 2023-01-11. Retrieved 2020-10-10.
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  11. J. A. Berry; R. T. Poole; A. Prescott; D. W. A. Sharp; J. M. Winfield (1976). "The oxidising and fluoride ion acceptor properties of uranium hexafluoride in acetonitrile". J. Chem. Soc., Dalton Trans. (3): 272–274. doi:10.1039/DT9760000272.
  12. S. M. Walker; P. S. Halasyamani; S. Allen; D. O'Hare (1999). "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. 121 (45): 10513–10521. doi:10.1021/ja992145f.
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  15. "Unit converter molar mass calculator". TranslatorsCafé. Mississauga, Ontario, Canada: ANVICA Software Development. 1 February 2021.
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Further reading