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
Molecular formula	UO3
CAS number	[1344-58-7]
Properties
Molar mass	286.2873 g/mol Commercial samples may have undergone isotope fractionation, and their formula mass may be significantly different
Density and phase	5.5 – 8.7 g/cm3
Solubility (water)	Partially soluble
Biological half-life	< 5 days (dog lung fluid)[1]
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)

'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.

Contents

Production and use

Health and safety hazards

Structure

Solid state structure

Alpha

Beta

Gamma

Delta

High pressure form

Hydrates

Bond valence parameters

Molecular forms

Gas phase

Matrix isolation

Computational study

Reactivity

Electrochemical modification

Amphoterism/Reactivity to form related uranium(VI) anions and cations

Uranium oxides in ceramics

References

External links

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.

# U₃O₈ can be oxidized at 500°C with oxygen.^[2] Note that above 750°C even in 5 atm O₂ UO₃ decomposes into U₃O₈.^[3]
# 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.
# 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.^[4]
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.
It has been reported that the corrosion of uranium in a silica rich aqueous solution forms both uranium dioxide and uranium trioxide.^[5] In pure water, schoepite {(UO₂)₈O₂(OH)₁₂.12(H₂O)} is formed ^[6] in the first week and then after four months studtite {(UO₂)O₂·4(H₂O)} was formed. Reports on the corrosion of uranium metal have been published by the Royal Society.^[7][8]

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 congenital malformations if inhaled.^1[9]

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.3 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.[10]

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 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.[11][12] 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.3

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.[13]

''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 an octahedral environment which are distorted towards square planar by an elongation of the axial oxygen-uranium bonds.''

Delta

''The delta (δ) form is a cubic solid where the oxygen atoms are arranged between the uranium atoms.''[14]

High pressure form

There is a high-pressure solid form with U₂O₂ and U₃O₃ rings in it.^[15]
[16]

Hydrates

Several hydrates of uranium trioxide are known, e.g., UO₃•6H₂O.³

Bond valence parameters

It is possible by bond valence calculations^[17] 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 structures 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 structure.
The formula to use is

$$
s = e^{-rac{R-R_O}{B}}


The sum of the ''s'' values is equal to the oxidation state of the metal centre.
For uranium binding to oxygen the constants R_O 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.^{[18] [19]}

Molecular forms

While uranium trioxide is encountered as a polymeric solid under ambient conditions, some work has been done on the molecular form in the gas phase, in matrix isolations studies, and computationally.

Gas phase

At elevated temperatures gaseous UO₃ is in equilibrium with solid U₃O₈ and molecular oxygen.
::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 °C and 2500 °C. The vapor pressure of monomeric UO₃ in equilibrium with air and solid U₃O₈ at ambient pressure, about 10⁻⁵ mbar (1 mPa) at 980 °C, rising to 0.1 mbar (10 Pa) at 1400 °C, 0.34 mbar (34 Pa) at 2100 °C, 1.9 mbar (193 Pa) at 2300 °C, and 8.1 mbar (809 Pa) at 2500 °C. ^[20][21]

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'' molecular 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 Å (176 to 179 pm).^[22]

Computational study

Calculations predict that the point group of molecular 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]

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.^[24]
2 CF₂Cl₂ + UO₃ → UF₄ + CO₂ + COCl₂ + Cl₂
4 CF₂Cl₂ + 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.^[25]

Electrochemical modification

The reversible insertion of magnesium cations into the lattice of uranium trioxide by cyclic voltammetry using a graphite electrode modified 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 modified 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.^[26]
It has been the case that it is possible to insert lithium ^[27][28][29] 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.

Amphoterism/Reactivity to form related uranium(VI) 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,
U₂O₇²⁻, or other poly-uranates.
Important diuranates include ammonium diuranate ((NH₄)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.^[30]
;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.

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.

References

1. Inhalation studies of uranium trioxide, Morrow, PE, Gibb FR, Beiter HD, , , Health Physics, 1972 abstract
2. Preparation of Uranium Trioxide, Sheft I, Fried S, Davidson N, , , Journal of the American Chemical Society, 1950
3. Uranium trioxide and the UO₃ hydrates, Wheeler VJ, Dell RM, Wait E, , , J. Inorganic Nuclear Chemistry, 1964
4. Chemical Reactivity of Uranium Trioxide Part 1. — Conversion to U₃O₈, UO₂ and UF₄, Dell RM, Wheeler VJ, , , Transactions of the Faraday Society, 1962
5. Trueman ER, Black S, Read D, Hodson ME (2003) "Alteration of Depleted Uranium Metal" ''Goldschmidt Conference Abstracts,'' p. A493 abstract
6. Page of Webminerals for Schoepite
7. Ander L, Smith B (2002) "Annexe F: Groundwater transport modelling" ''The health hazards of depleted uranium munitions, part II'' (London: The Royal Society)
8. Smith B (2002) "Annexe G: Corrosion of DU and DU alloys: a brief discussion and review" ''The health hazards of depleted uranium munitions, part II'' (London: The Royal Society)
9. Uranium(VI) solubility and speciation in simulated elemental human biological fluids, Sutton M, Burastero SR, , , Chemical Research in Toxicology, 2004
10. , Sato T, , , Journal of Applied Chemistry, 1963
11. On the Uranates of Ammonium II: X-Ray Investigation of the Compounds in the system NH₃-UO₃-H2O, Debets PC, Loopstra BO, , , Journal of Inorganic Nuclear Chemistry, 1963
12. The Structure of β-UO3, Debets PC, , , Acta Crystallographica, 1966
13. The Crystal Structure of γ-UO₃, Engmann R, de Wolff PM, , , Acta Crystallographica, 1963
14. The structure of δ-UO_3>, M. T. Weller, P. G. Dickens, D. J. Penny, , , Polyhedron, 1988
15.
The crystal structure of high-pressure UO₃, Siegel S, Hoekstra HR, Sherry E, , , Acta Crystallographica, 1966
16. ''Gmelin Handbuch'' (1982) 'U-C1,' 129-135.
17. kristall.uni-mki.gwdg.de/softbv/references
18. www.ccp14.ac.uk/ccp/web-mirrors/i_d_brown
19. www.ccp14.ac.uk/solution/bond_valence/
20. High-Temperature Thermodynamic Properties of Uranium Dioxide, Ackermann RJ, Gilles PW, Thorn RJ, , , Journal of Chemical Physics, 1956
21. Volatilization of urania under strongly oxidizing conditions, Alexander CA, , , Journal of Nuclear Materials, 2005
22. Infrared spectra of matrix-isolated uranium oxide species. II: Spectral interpretation and structure of UO₃, Gabelnick SD, Reedy GT, Chasanov MG, , , Journal of Chemical Physics, 1973
23. Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl, Pyykkö P, Li J, , , Journal of Physical Chemistry, 1994
24. Uranium Tetrafluoride, Booth HS, Krasny-Ergen W, Heath RE, , , Journal of the American Chemical Society, 1946
25. Dissolution of uranium oxides in supercritical carbon dioxide containing tri-''n''-butyl phosphate and thenoyltrifluoroacetone, Trofimov TI, Samsonov MD, Lee SC, Myasoedov BF, Wai CM, , , Mendeleev Communications, 2001
26. Dueber RE, Bond AM, Dickens PG (1992) ''Journal of the Electrochemical Society'' '139', 2363-2371.
27. Insertion compounds of uranium oxides, Dickens PG, Lawrence SD, Penny DJ, Powell AV, , , , 1989

28. Lithium insertion into αUO₃ and U₃O₈, P.G. Dickens, S.V. Hawke, M.T. Weller, , , , 1985
29. Hydrogen insertion compounds of UO₃, P.G. Dickens, S.V. Hawke, M.T. Weller, , , , 1984
30. Lanthanides and Actinides, , Simon, Cotton, Oxford University Press, 1991,

External links