Uranate

A uranate is a ternary oxide involving the element uranium in one of the oxidation states 4, 5 or 6. A typical chemical formula is M_xU_yO_z, where M represents a cation. The uranium atom in uranates(VI) has two short collinear U–O bonds and either four or six more next nearest oxygen atoms.^[1] The structures are infinite lattice structures with the uranium atoms linked by bridging oxygen atoms.

Uranium oxides are the foundation of the nuclear fuel cycle ("ammonium diuranate" and "sodium diuranate" are intermediates in the production of uranium oxide nuclear fuels) and their long-term geological disposal requires a thorough understanding of their chemical reactivity, phase transitions, and physical and chemical properties.^[2]

Synthesis

A method of general applicability involves combining two oxides in a high temperature reaction.^[3] For example,

Na₂O + UO₃ → Na₂UO₄

Another method is the thermal decomposition of a complex, such as an acetate complex. For example, microcrystalline barium diuranate, BaU₂O₇, was made by thermal decomposition of barium uranyl acetate at 900 °C.^[4]

Ba[UO₂(ac)₃]₂ → BaU₂O₇ ... (ac=CH₃CO₂⁻)

Uranates can be prepared by adding alkali to an aqueous solution of a uranyl salt. However, the composition of the precipitate that forms is variable and depends on the chemical and physical conditions used.^[3]

Uranates are insoluble in water and other solvents, so pure samples can only be obtained by careful control of reaction conditions.^{[citation needed]}


Formula	U-ox. state	Space group	Symmetry	Formula	U-ox. state	Space group	Symmetry	Formula	U-ox. state	Space group	Symmetry
Li₂UO₄	VI	α: Fmmm, Pnma β:	orthorhombic hexagonal	BaU₂O₇	VI	I4₁/amd	tetragonal	Sr₂UO₅	VI	P2₁/c	monoclinic
Na₂UO₄	VI	α: Cmmm β: Pnma	orthorhombic orthorhombic	SrU₂O₇	VI			Li₆UO₆	VI		hexagonal
K₂UO₄	VI	α: I4/mmm β:	tetragonal orthorhombic	CaU₂O₇	VI			Ca₃UO₆	VI	P2₁	monoclinic
Cs₂UO₄	VI	I4/mmm	tetragonal	MgU₃O₁₀	VI		hexagonal	Sr₃UO₆	VI	P2₁	monoclinic
MgUO₄	VI	Imma	orthorhombic	Li₂U₃O₁₀	VI	α: P2₁/c β: P2	monoclinic monoclinic	Ba₃UO₆	VI	Fm-3m	cubic
CaUO₄	VI	R-3m	rhombohedral	SrU₄O₁₃	VI		monoclinic	NaUO₃	V	Pbnm	orthorhombic
SrUO₄	VI	α: R-3m β: Pbcm	rhombohedral orthorhombic	Li₂U₆O₁₉	VI		orthorhombic	KUO₃	V	Pm3m	cubic
BaUO₄	VI	Pbcm	orthorhombic	K₂U₇O₂₂	VI	Pbam	orthorhombic	RbUO₃	V	Pm3m	cubic
Li₂U₂O₇	VI		orthorhombic	Rb₂U₇O₂₂	VI	Pbam	orthorhombic	CaUO₃	IV		cubic
Na₂U₂O₇	VI	C2/m	monoclinic	Cs₂U₇O₂₂	VI	Pbam	orthorhombic	SrUO₃	IV		orthorhombic
K₂U₂O₇	VI	R-3m	hexagonal	Li₄UO₅	VI	I4/m	tetragonal	BaUO₃	IV	Pm3m	cubic
Rb₂U₂O₇	VI	R-3m	hexagonal	Na₄UO₅	VI	I4/m	tetragonal	Li₃UO₄	V		tetragonal
Cs₂U₂O₇	VI	α: C2/m β: C2/m γ: P6/mmc	monoclinic monoclinic hexagonal	Ca₂UO₅	VI	P2₁/c	monoclinic	Na₃UO₄	V	Fm-3m	cubic

Uranium(VI)

Structures

CaUO₄ structure^[5]

BaUO₄ structure^[5]

All uranates(VI) are mixed oxides, that is, compounds made up of metal(s), uranium and oxygen atoms. No uranium oxyanion, such as [UO₄]²⁻ or [U₂O₇]²⁻, is known. Instead, all uranate structures are based on UO_n polyhedra sharing oxygen atoms in an infinite lattice.^[1] The structures of uranates(VI) are unlike the structure of any mixed oxide of elements other than actinide elements. A particular feature is the presence of linear O-U-O moieties, which resemble the uranyl ion, UO₂²⁺. However, the U-O bond length varies from 167 pm, which is similar to the bond length of the uranyl ion, up to about 208 pm in the related compound α-UO₃, so it is debatable as to whether these compounds all contain the uranyl ion. There are two principal types of uranate which are defined by the number of nearest-neighbour oxygen atoms in addition to the "uranyl" oxygens.^[1]

In one group, including M₂UO₄ (M=Li, Na, K) and MUO₄ (M=Ca, Sr) there are six additional oxygen atoms. Taking calcium uranate, CaUO₄, as an example, the six oxygen atoms are arranged as a flattened octahedron, flattened along the 3-fold symmetry axis of the octahedron which also runs through the O-U-O axis (local point group D_3d at the uranium atom). Each of these oxygen atoms is shared between three uranium atoms, which accounts for the stoichiometry, U 2×O 6×1/3 O = UO₄. The structure has been described as a hexagonal layer structure. It can also viewed as a distorted fluorite structure in which two U-O distances have decreased and the other six have increased.^[1]

In the other group, exemplified by barium uranate, BaUO₄, there are four additional oxygen atoms. These four oxygens lie in a plane and each is shared between two uranium atoms, which accounts for the stoichiometry, U 2×O 4×1/2 O = UO₄. The structure may called a tetragonal layer structure.^[1]

MgUO₄ structure.^[6]

Magnesium uranate, MgUO₄, has a quite different structure. Distorted UO₆ octahedra are linked into infinite chains; the "uranyl" U-O bond length is 192 pm, not much shorter than the other U-O bond length of 218 pm.^[1]

A number of so-called diuranates are known. They fall into two categories, compounds of exact composition, synthesized by combination of metal oxides or thermal decomposition of salts of uranyl complexes and substances of approximate composition, found in yellowcake. The name refers only to the empirical formula, M_xU₂O₇; the structures are completely different from ions such as the dichromate ion. For example, in barium diuranate, BaU₂O₇, UO₆ octahedral units are joined by sharing edges, forming infinite chains in the directions of the crystallographic a and b directions.^[4]

Uranates with more complicated empirical formulas are known. Essentially these arise when the cation:uranium ratio is different from 2:1 (monovalent cations) or 1:1 (divalent cations). Charge-balance constrains the number of oxygen atoms to be equal to half the sum of charges of the cations and uranyl groups. For example, with the cation K⁺, compounds with K:U ratios of 2, 1 and 0.5 were found, corresponding to empirical formulas K₂UO₄, K₂U₂O₇ and K₂U₄O₁₃.^[7] The uranate structures in these compounds differ in the way the UO_x structural units are linked together.

Properties and uses

A drum of yellowcake

Yellowcake is produced in the separation of uranium from other elements, by adding alkali to a solution containing uranyl salts.^[8]

When the alkali used is ammonia, so-called ammonium diuranate, known in the industry as ADU, is the main constituent of yellowcake. The exact composition of the precipitate depends to some extent on the conditions and anions that are present and the formula (NH₄)₂U₂O₇, is only an approximation. The precipitates obtained on addition of ammonia to uranyl nitrate solution under different conditions of temperature and final pH, when dried, were considered as loosely bound compounds with an ammonia/uranium ratio of 0.37 containing varying amounts of water and ammonium nitrate.^[9] In other studies it was found to approximate to the gross formulas 3UO₃·NH₃·5H₂O,^[10] The asymmetric stretching frequency of the uranyl ion was found to decrease with increasing NH₄⁺ content. This decrease is continuous and no band splitting was observed, indicating that the ammonium uranate system is homogeneous and continuous.^[11]

A collection of uranium glassware

ADU is an intermediate in the production of uranium oxides to be used as nuclear fuel; it is converted directly into an oxide by heating. β-UO₃ is produced at about 350 °C and U₃O₈ is obtained at higher temperatures. When the alkali used is sodium hydroxide, so-called sodium diuranate, SDU, is produced. This can also be converted into an oxide. Another choice of alkali is magnesium oxide, making magnesium diuranate, known as MDU.

Oxides and uranates of uranium(VI) have been used in the past as yellow ceramic glazes as in Fiesta and to make yellow-green uranium glass.^[12] Both of these applications are abandoned due to concern regarding radioactivity of the uranium. Uranates are important in radioactive waste management.^[13]

Uranium(V)

Several series of uranates(V) have been characterized. Compounds with the formula M^IUO₃ have a perovskite structure. Compounds M^I₃UO₄ have a defect rock-salt structure. M^I₇UO₆ structures are based on a hexagonally close-packed array of oxygen atoms. In all cases the uranium is at the centre of an octahedron of oxygen atoms. Also M^IIIUO₄ have been recently synthesized and characterized (M^III=Bi, Fe, Cr etc.).^[14]^[15] Few other compounds of uranium(V) are stable.^[3]

Uranium(IV)

Barium uranate, BaUO₃, is made from barium oxide and uranium dioxide in an atmosphere that contains absolutely no oxygen. It has a cubic crystal structure (space group Pm3m).^[16]

References

^ ^a ^b ^c ^d ^e ^f Wells, A. F. (1962). Structural Inorganic Chemistry (3rd ed.). Oxford: Clarendon Press. pp. 966–969. ISBN 978-0-19-855125-6.
^ T. Vogt, D.J. Butterey, Complex Oxides. An Introduction. World Scientific, 2019, https://www.worldscientific.com/doi/pdf/10.1142/9789813278585_fmatter
^ ^a ^b ^c Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 1269. ISBN 978-0-08-037941-8.
^ ^a ^b Allpress, J.G. (1965). "The Crystal Structure of Barium Diuranate". Journal of Inorganic and Nuclear Chemistry. 27 (7): 1521–1527. doi:10.1016/0022-1902(65)80013-6.
^ ^a ^b Loopstra, B. O.; Rietveld, H. M. (1969). "The structure of some alkaline-earth metal uranates". Acta Crystallographica Section B. 25 (4): 787–791. doi:10.1107/S0567740869002974.
^ Zachariasen, W. H. (1 December 1954). "Crystal chemical studies of the 5f-series of elements. XXI. The crystal structure of magnesium orthouranate". Acta Crystallographica. 7 (12): 788–791. doi:10.1107/S0365110X54002459.
^ Van Egmond, A. B.; Cordfunke, E. H. P. (1976). "Investigations on potassium and rubidium uranates". Journal of Inorganic and Nuclear Chemistry. 38 (12): 2245–2247. doi:10.1016/0022-1902(76)80203-5.
^ Hausen, D. M. (1961). "Characterizing and classifying uranium yellow cakes: A background". JOM. 50 (12): 45–47. Bibcode:1998JOM....50l..45H. doi:10.1007/s11837-998-0307-5. S2CID 97023067.
^ Ainscough, J. B.; Oldfield, B. W. (1962). "Effect of ammonium diuranate precipitation conditions on the characteristics and sintering behaviour of uranium dioxide". Journal of Applied Chemistry. 12 (9): 418–424. doi:10.1002/jctb.5010120907.
^ Cordfunke, E. H. P. (1962). "On the uranates of ammonium—I: The ternary system NH₃---UO₃---H₂O". Journal of Inorganic and Nuclear Chemistry. 24 (3): 303–307. doi:10.1016/0022-1902(62)80184-5.
^ Stuart, W. I.; Whateley, T. L. (1969). "Composition and structure of ammonium uranates". Journal of Inorganic and Nuclear Chemistry. 1 (6): 1639–1647. doi:10.1016/0022-1902(69)80378-7. hdl:10238/379.
^ Skelcher, Barrie (2002). The Big Book of Vaseline Glass. Atglen, PA: Schiffer Publishing. ISBN 978-0-7643-1474-2.
^ Saling, James H.; Fentiman, Audeen W. (2002). Radioactive Waste Management (2 ed.). New York: Taylor & Francis. p. 2. ISBN 978-1-56032-842-1. Retrieved 2011-02-12.
^ Popa, Karin; Prieur, Damien; Manara, Dario; Naji, Mohamed; Vigier, Jean-François; Martin, Philippe M.; Dieste Blanco, Oliver; Scheinost, Andreas C.; Prüβmann, Tim; Vitova, Tonya; Raison, Philippe E.; Somers, Joseph; Konings, Rudy J. M. (2016). "Further insights into the chemistry of the Bi–U–O system". Dalton Transactions. 45 (18): 7847–7855. doi:10.1039/C6DT00735J. PMID 27063438.
^ Guo, Xiaofeng; Tiferet, Eitan; Qi, Liang; Solomon, Jonathan M.; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Kukkadapu, Ravi K.; Wu, Di; Ilton, Eugene S.; Asta, Mark; Sutton, Stephen R.; Xu, Hongwu; Navrotsky, Alexandra (2016). "U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4". Dalton Transactions. 45 (11): 4622–4632. doi:10.1039/C6DT00066E. OSTI 1256103. PMID 26854913.
^ Barrett, S. A.; Jacobson, A. J.; Tofield, B. C.; Fender, B. E. F. (1982). "The preparation and structure of barium uranium oxide BaUO_3+x". Acta Crystallographica Section B. 38 (11): 2775–2781. doi:10.1107/S0567740882009935.