Uranium trioxide

Uranium trioxide
	solid γ-UO3 (gamma polymorph) oxygen diameters sharply reduced for visibility
General
Systematic name	Uranium trioxide Uranium(VI) oxide
Other names	Uranyl oxide Uranic oxide
Molecular formula	UO3
CAS number	[1344-58-7]
Properties
Molar mass	286.2873 g/mol Commercial samples may have undergone isotope fractionation, and their molecular mass may be significantly different
Density and phase	5.5 – 8.7 g/cm3
Solubility (water)	Partially soluble
Solubility (dog lung fluid)	< 5 days (Morrow, 1972)
Melting point	~ 200 – 650 °C decomp. (s)
Structure
Coordination geometry	γ-UO3: [UO2]2+[UO4]2-
Crystal structure	Space group I41/amd (γ-UO3)
Hazards
MSDS	UO3-MSDS
Main hazards	highly toxic: teratogen, immunotoxin, neurotoxin, genotoxin, nephrotoxin
Related compounds
Other uranyl compounds	Uranyl nitrate Uranyl hydroxide Uranyl acetate
Related trioxides	Tungsten trioxide Molybdenum trioxide Chromium trioxide
Other uranium oxides	Uranium dioxide Triuranium octaoxide
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references

Uranium trioxide (UO₃), also called uranyl oxide, uranium(VI) oxide, and uranic oxide, is the hexavalent oxide of uranium. The solid may be obtained by heating uranyl nitrate to 400 °C. Its most commonly encountered polymorph, γ-UO₃, is a yellow-orange powder.

Production and use

There are three methods to generate uranium trioxide. As noted below, two are used industrially in the reprocessing of nuclear fuel and uranium enrichment.

1. U₃O₈ can be oxidized at 500°C with oxygen.^[1] Note that above 750°C even in 5 Atm O_{2 UO3 decomposes into U3O8.^[2]}
2. Uranyl nitrate, (UO₂(NO₃)₂·6H₂O) can be heated to yield UO₃. This occurs during the reprocessing of nuclear fuel. Fuel rods are dissolved in HNO₃ to separate uranyl nitrate from plutonium and the fission products (the PUREX method). The pure uranyl nitrate is converted to solid UO₃ by heating at 400 °C. After reduction with hydrogen (with other inert gas present) to uranium dioxide, the uranium can be used in new MOX fuel rods.
3. Ammonium diuranate or sodium diuranate (Na₂U₂O₇·6H₂O) may be decomposed. Sodium diuranate, also known as yellowcake, is converted to uranium trioxide in the enrichment of uranium. Uranium dioxide and uranium tetrafluoride are intermediates in the process which ends in uranium hexafluoride. ^[3]

Uranium trioxide is shipped between processing facilities in the form of a gel.

Cameco Corporation, which operates at the world's largest uranium refinery at Blind River, Ontario, produces high-purity uranium trioxide.

Health and safety hazards

Like all hexavalent uranium compounds, UO₃ is hazardous by inhalation, ingestion, and through skin contact. It is a poisonous, radioactive substance, which may cause shortness of breath, coughing, acute arterial lesions, and changes in the chromosomes of white blood cells and gonads leading to severe birth defects if inhaled. ^[4][5]

Chemistry and structure

Solid state structure

The only well characterized binary trioxide of any actinide is UO₃, of which several polymorphs are known. Solid UO₃ loses O₂ on heating to give green-colored U₃O₈: reports of the decomposition temperature in air vary from 200–650 °C. Heating at 700 °C under H₂ gives dark brown uranium dioxide (UO₂), which is used in MOX nuclear fuel rods.

Alpha

The α (alpha) form: a layered solid where the 2D layers are linked by oxygen atoms (shown in red)

Hydrated uranyl peroxide formed by the addition of hydrogen peroxide to an aqueous solution of uranyl nitrate when heated to 200-225 °C forms an amorphous uranium trioxide which on heating to 400-450 °C will form alpha-uranium trioxide.[6] It has been stated that the presence of nitrate will lower the temperature at which the exothermic change from the amorphous form to the alpha form occurs.[7]

Beta

β (beta) UO3. This solid has a structure which defeats most attempts to describe it.

This form can be formed by heating ammonium diuranate, while P.C. Debets and B.O. Loopstra, found four solid phases in the the UO3-H2O-NH3 system that they could all be considered as being UO2(OH)2.H2O where some of the water has been replaced with ammonia.[8][9] No matter what the exact stiochiometry or structure, it was found that calcination at 500°C in air forms the beta form of uranium trioxide.[10]

Gamma

The γ (gamma) form, with the different uranium environments in green and yellow

The most frequently encountered polymorph is γ-UO3, whose x-ray structure has been solved from powder diffraction data. The compound crystallizes in the space group I41/amd with two uranium atoms in the asymmetric unit. Both are surrounded by somewhat distorted octahedra of oxygen atoms. One uranium atom has two closer and four more distant oxygen atoms whereas the other has four close and two more distant oxygen atoms as neighbors. Thus it is not incorrect to describe the structure as [UO2]2+[UO4]2- , that is uranyl uranate. [11]. High presure solid forms exist. Gmelin Handbuch (1982) U-C1, 129-135.

The environment of the uranium atoms shown as yellow in the gamma form

The chains of U2O2 rings in the gamma form in layers, alternate layers running at 90 degrees to each other. These chains are shown as containing the yellow uranium atoms, in a octahedral environment which are distorted towards square planar by an elongation of the axial oxygen-uranium bonds.

Delta

The delta (δ) form was reported by Weller et al. (1988) Polyhedron, 7, 243-244. This is a cubic solid where the oxygen atoms are arranged between the uranium atoms

High preasure form

This is a solid which has U_{2O2 and U3O3 rings in it. S. Siegel, H.R. Hoekstra and E. Sherry, Acta Crystallographica, 1966, 20, 292-295.}

Hydrates

V.J. Wheeler, R.M. Dell and E. Wait, J. Inorganic Nuclear Chemistry, 1964, 26, 1829 states that hydrates of uranium trioxide are known.

Reactivity

Uranium trioxide reacts at 400 °C with freon-12 to form chlorine, phosgene, carbon dioxide and uranium(IV) fluoride. The freon-12 can be replaced with freon-11 which forms carbon tetrachloride instead of carbon dioxide. This is a case of a hard perhalogenated freon which is normally considered to be inert being converted chemically at a moderate temperature.^[12]

2 CF_{2Cl2 + UO3 → UF4 + CO2 + COCl2 + Cl2}

4 CF_{2Cl2 + UO3 → UF4 + 3COCl2 + CCl4 + Cl2}

Uranium trioxide can be dissolved in a mixture of tributyl phosphate and thenoyltrifluoroacetone in supercritical carbon dioxide, ultrasound was employed during the dissolution.^[13]

Bond valence parameters

It is possible by bond valence calculations[14] it is possible to estimate how great a contribution a given oxygen atom is making to the assumed valence of uranium. Zachariasen, J. Less Common Met., 1978, 62, 1-7. Lists the parameters to allow such calculations to be done for many of the actinides. Bond valence calculations use parameters which are estimated after examining a large number of crystal strucutres of uranium oxides (and related uranium compounds), note that the oxidation states which this method provides are only a guide which assists in the understanding of a crystal strucure.

The formula to use is

$s=e^{-(R-Ro)/B}$

The sum of the s values is equal to the oxidation state of the metal centre.

For uranium binding to oxygen the constants Ro and B are tabulated in the table below. For each oxidation state use the parameters from the table shown below.

Oxidation state	Ro	B
U(VI)	2.08Å	0.35
U(V)	2.10Å	0.35
U(IV)	2.13Å	0.35

It is possible to do these calculations on paper or software. A program which does it can be obtained free of charge.[15][16]

Corrosion of uranium metal

It has been reported that the corrosion of uranium in a silica rich aqueous solution forms both uranium dioxide and uranium trioxide. [17]

In pure water, schoepite {(UO_{2)8O2(OH)12.12(H2O)} is formed [18] in the first week and then after four months studtite {(UO2)O2·4(H2O)} was formed. A report on the corrosion of uranium metal has been published by the Royal Society. [19] [20]}

Electrochemistry

The reversible insertion of magnesium cations into the lattice of uranium trioxide by cyclic voltammetry using a graphite electrode modifed with microscopic particles of the uranium oxide has been investigated. This experiment has also been done for U₃O₈. This is an example of electrochemistry of a solid modifed electrode, the experiment which used for uranium trioxide is related to a carbon paste electrode experiment. It is also possible to reduce uranium trioxide with sodium metal to form sodium uranium oxides. (R.E. Dueber, A.M. Bond and P.G. Dickens, Journal of the Electrochemical Society, 1992, 139, 2363-2371.) The Journal of Solid State Electrochemistry has been started, devoted to this type of electrochemistry. [21]

It has been the case that it is possible to insert lithium ions and protons into the uranium trioxide lattice by electrochemical means, this is similar to the way that some rechargeable lithium ion batteries work. In these rechargeable cells one of the electrodes is a metal oxide which contains a metal such as cobalt which can be reduced, to maintain the electroneutrality for each electron which is added to the electrode material a lithium ion enters the lattice of this oxide electrode.

P.G. Dickens, S.D Lawrence, D.J. Penny and A.V. Powell, Solid State Ionics, 1989, 32/33, 77-83. (Li+) P.G. Dickens, S.D Lawrence and M.T. Weller, Mat. Res. Bull., 1985, 20, 635. (Li+) P.G. Dickens, S.V. Hawke and M.T. Weller, Mat. Res. Bull., 1984, 19, 543. (H+)

Molecular forms

While uranium trioxide is mostly encountered as a polymeric solid some work has been done on molecular forms in inert gas matrices and in the vapor phase, too.

Matrix isolation

Infrared spectroscopy of molecular UO₃ isolated in an argon matrix indicates a T-shaped structure (point group C_2v) for the molecule. This is in contrast to the commonly encountered D_3h symmetry exhibited by most trioxides. From the force constants the authors deduct the U-O bond lengths to be between 1.76 and 1.79 angstroms (176 to 179 picometers). ^[22]

Calculations indicate that the point group of gaseous UO₃ is C_2v, with an axial bond length of 1.75 Å, an equatorial bond length of 1.83 Å and an angle of 161 ° between the axial oxygens. The more symmetrical D_3h species is a saddle point, 49 kJ/mol above the C_2v minimum. The authors invoke a second-order Jahn-Teller effect as explanation. ^[23]

Gas phase

At elevated temperatures gaseous UO₃ and O₂ are in equilibrium with solid U₃O₈. ^[24]

¹/₃ U₃O₈(s) + ¹/₆ O₂(g) ${\overrightarrow {\gets }}$ UO₃(g)

With increasing temperature the equilibrium is shifted to the right. This system has been studied at temperatures between 900 and 1500 °C. The vapor pressure of monomeric UO₃ is low but appreciable, about 10⁻⁵ mbar (1 mPa) at 980 °C, rising to 10⁻¹ mbar (10 Pa) at 1400 °C, 0.34 mbar (34 Pa) at 1800 K, 19 mbar (1.9 kPa) at 2000 K, and 81 mbar (8.1 kPa) at 2200 K. ^{[25] [26]}

Uranium oxides in ceramics

UO₃-based ceramics become green or black when fired in a reducing atmosphere and yellow to orange when fired with oxygen. Orange-coloured Fiestaware is a well-known example of a product with a uranium-based glaze. UO₃-has also been used in formulations of enamel, uranium glass, and porcelain.

Prior to 1960, UO₃ was used as an agent of crystallization in crystalline coloured glazes. It is possible to determine with a Geiger counter if a glaze or glass was made from UO₃.

Related anions and cations

Uranium oxide is amphoteric and reacts as acid and as a base, depending on the conditions.

As an acid:

UO₃ + H₂O → UO₄²⁻ + H⁺

Dissolving uranium oxide in a strong base like sodium hydroxide forms the doubly negatively charged uranate anion (UO₄²⁻). Uranates tend to agglomerate, forming diuranate, U₂O₇^{2−</sup,> or other poly-uranates. Important diuranates include ammonium diuranate ((NH_{4)2U2O7), sodium diuranate (Na2U2O7) and magnesium diuranate (MgU2O7), which forms part of some yellowcakes. It is worth noting that uranates of the form M2UO4 do not contain UO42− ions, but rather flattened UO6 octahedra, containing a uranyl group and bridging oxygens[27].}}

As a base:

UO₃ + H₂O → UO₂²⁺ + OH⁻

Dissolving uranium oxide in a strong acid like sulfuric or nitric acid forms the double positive charged uranyl cation. The uranyl nitrate formed (UO₂(NO₃)₂ˑ6H₂O) is soluble in ethers, alcohols, ketones and esters; for example, tributylphosphate. This solubilty is used to separate uranium from other elements in nuclear reprocessing, which begins with the dissolution of nuclear fuel rods in nitric acid. The uranyl nitrate is then converted to uranium trioxide by heating.

From nitric acid one obtains uranyl nitrate, trans-UO₂(NO₃)₂·2H₂O, consisting of eight-coordinated uranium with two bidentate nitrato ligands and two water ligands as well as the familiar O=U=O core.

References

• ^ Sheft I, Fried S, Davidson N (1950). "Preparation of Uranium Trioxide". Journal of the American Chemical Society. 72: 2172–2173.{{cite journal}}: CS1 maint: multiple names: authors list (link) DOI

^ Wheeler VJ, Dell RM, Wait E (1964). J. Inorganic Nuclear Chemistry. 25: 1829. {{cite journal}}: Missing or empty |title= (help)CS1 maint: multiple names: authors list (link)

• ^ Dell RM, Wheeler V J (1962). "Chemical Reactivity of Uranium Trioxide Part 1.conversion to U₃O₈, U0₂ and UF₄". Transaction Faraday Society: 1590–1607. DOI
• ^ Sato T (1963). Journal of Applied Chemistry. 13: 361. {{cite journal}}: Missing or empty |title= (help)
• ^ Debets PC, Loopstra BO (1963). Journal of Inorganic Nuclear Chemistry. 25: 945. {{cite journal}}: Missing or empty |title= (help)
• ^ Debets PC (1966). "The Structure of β-UO3". Acta Crystallographica. 21: 589.
• ^ Morrow, PE, Gibb FR, Beiter HD (1972). "Inhalation studies of uranium trioxide". Health Physics. 23: 273–280.{{cite journal}}: CS1 maint: multiple names: authors list (link) Abstract
• ^ Sutton M, Burastero SR (2004). "Uranium(VI) solubility and speciation in simulated elemental human biological fluids". Chemical Research in Toxicology. 17: 1468–1480. [28] DOI
• ^ Trofimov TI, Samsonov MD, Lee SC, Myasoedov BF, Wai CM (2001). "Dissolution of uranium oxides in supercritical carbon dioxide containing tri-n-butyl phosphate and thenoyltrifluoroacetone". Mendeleev Communications. 11: 129–130.{{cite journal}}: CS1 maint: multiple names: authors list (link) DOI
• ^ Booth HS, Krasny-Ergen W,Heath RE (1946). "Uranium Tetrafluoride". Journal of the American Chemical Society. 68: 1969–1970.{{cite journal}}: CS1 maint: multiple names: authors list (link) DOI
• ^ Engmann R, de Wolff PM (1963). "The Crystal Structure of γ-UO₃". Acta Crystallographica. 16: 993. DOI
• ^ Wilson WB (1961). "High-Pressure High-Temperature Investigation of the Uranium-Oxygen System". Journal Inorganic Nuclear Chemistry. 19: 212–222.[29] DOI
• ^ Gabelnick SD, Reedy GT, Chasanov MG (1973). "Infrared spectra of matrix-isolated uranium oxide species. II: Spectral interpretation and structure of UO₃". 59: 6397. {{cite journal}}: Cite journal requires |journal= (help)CS1 maint: multiple names: authors list (link)
• ^ Ackermann RJ, Thorn RJ, Alexander C, Tetenbaum M (1960). "Free Energies of Formation of Gaseous Uranium, Molybdenum, and Tungsten Trioxides". Journal of Physical Chemistry. 64: 350–355.{{cite journal}}: CS1 maint: multiple names: authors list (link) DOI page350 351 352 353 354 355
• ^ Ackermann RJ, Gilles PW, Thorn RJ (1956). Journal of Chemical Physics. 25: 1089. {{cite journal}}: Missing or empty |title= (help)CS1 maint: multiple names: authors list (link)
• ^ Alexander CA (2005). "Volatilization of urania under strongly oxidizing conditions". Journal of Nuclear Materials. 346: 312–318. [30] DOI
• ^ Mouradian and Baker (1963). "Burning Temperatures of Uranium and Zirconium in Air". Nuclear Science and Engineering. 15: 388–394.
• ^ Gilchrist RL, Glissmyer JA, Mishima J (1979). "Characterization of Airborne Uranium from Test Firings of XM774 Ammunition," Technical report no. PNL-2944 Richland, WA: Battelle Pacific Northwest Laboratory". {{cite journal}}: Cite journal requires |journal= (help)CS1 maint: multiple names: authors list (link)
• ^ Cotton, S (1991). Lanthanides and Actinides. New York. {{cite book}}: Text "page 128" ignored (help)CS1 maint: location missing publisher (link)
• ^ Stuart (1979). "Solubility and Hemolytic Activity of Uranium Trioxide". Environmental Research. 18: 385–396. DOI
• ^ Neumüller O-A (1988). Römpps Chemie-Lexikon (6 ed.). Stuttgart: Frankh'sche Verlagshandlung. ISBN 3-440-04516-1.
• ^ Gmelin Handbook of Inorganic Chemistry (8 ed.). 1977. {{cite book}}: Text "page 98" ignored (help)
• ^ Gmelin Handbuch der anorganischen Chemie (8 ed.). 1977. {{cite book}}: Text "page 118-120" ignored (help) DOI

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• ^ Green, DW (1980). "Relationship between spectroscopic data and thermodynamic functions; application to uranium, plutonium, and thorium oxide vapor species". Journal of Nuclear Materials. 88: 51–63. DOI
• ^ Pyykkö, P, Li J (1994). "Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl". Journal of Physical Chemistry. 98: 4809–13.{{cite journal}}: CS1 maint: multiple names: authors list (link)