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.
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. Note that above 750 °C even in 5 atm O2 UO3 decomposes into U3O8.
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.
Uranium trioxide is shipped between processing facilities in the form of a gel, most often from mines to conversion plants. When used for conversion, all uranium oxides are often called reprocessed uranium(RepU).
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 uranium dioxide, uranium trioxide, and coffinite. In pure water, schoepite (UO2)8O2(OH)12·12(H2O) is formed in the first week and then after four months studtite (UO2)O2·4(H2O) was produced. This alteration of uranium oxide also leads to the formation of metastudtite, a more stable uranyl peroxide, often found in the surface of spent nuclear fuel exposed to water.
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The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula UO22+. It has a linear structure with short U–O bonds, indicative of the presence of multiple bonds between uranium and oxygen. Four or more ligands may be bound to the uranyl ion in an equatorial plane around the uranium atom. The uranyl ion forms many complexes, particularly with ligands that have oxygen donor atoms. Complexes of the uranyl ion are important in the extraction of uranium from its ores and in nuclear fuel reprocessing.
Uranium tetrachloride is an inorganic compound, a salt of uranium and chlorine, with the formula UCl4. It is a hygroscopic olive-green solid. It was used in the electromagnetic isotope separation (EMIS) process of uranium enrichment. It is one of the main starting materials for organouranium chemistry. Uranium tetrachloride is synthesised generally by the reaction of uranium trioxide (UO3) and hexachloropropene. Solvent UCl4 adducts can be formed by a simpler reaction of UI4 with hydrogen chloride in organic solvents.
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