Uranyl
The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula . 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 ...
peroxide or uranium peroxide hydrate (UO
4·nH
2O) is a pale-yellow, soluble
peroxide
In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable.
The most common peroxide is hydrogen ...
of
uranium
Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weakly ...
. It is found to be present at one stage of the
enriched uranium
Enriched uranium is a type of uranium in which the percent composition of uranium-235 (written 235U) has been increased through the process of isotope separation. Naturally occurring uranium is composed of three major isotopes: uranium-238 (2 ...
fuel cycle and in
yellowcake
Yellowcake (also called urania) is a type of uranium concentrate powder 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 f ...
prepared via the ''in situ'' leaching and resin
ion exchange
Ion exchange is a reversible interchange of one kind of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid with the reaction being used especially for softening or making water demineralised, ...
system. This compound, also expressed as UO
3·(H
2O
2)·(H
2O), is very similar to
uranium trioxide
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 ...
hydrate UO
3·''n''H
2O. The dissolution behaviour of both compounds are very sensitive to the hydration state (n can vary between 0 and 4). One main characteristic of uranium peroxide is that it consists of small needles with an average AMAD of about 1.1 μm.
The uranyl minerals
studtite
Studtite, chemical formula UO2)O2(H2O)2�2(H2O) or UO4·4(H2O), is a secondary uranium mineral containing peroxide formed by the alpha-radiolysis of water during formation. It occurs as pale yellow to white needle-like crystals often in acicula ...
, UO
4·4H
2O, and metastudtite, UO
4·2H
2O, are the only minerals discovered to date found to contain peroxide. The product is a light yellow powder.
Synthesis
In general, uranyl peroxide can be obtained from a solution of uranium (VI) by adding a peroxide, usually hydrogen peroxide solution. The dihydrate is obtained from a boiling solution of uranyl nitrate with the addition of hydrogen peroxide and drying of the precipitate, while the trihydrate is precipitated from a solution of ammonium uranyl oxalate.
Crystal structure
The
unit cell
In geometry, biology, mineralogy and solid state physics, a unit cell is a repeating unit formed by the vectors spanning the points of a lattice. Despite its suggestive name, the unit cell (unlike a unit vector, for example) does not necessari ...
consists of
uranyl
The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula . 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 ...
cations coordinated to two
water molecules and two
peroxide
In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable.
The most common peroxide is hydrogen ...
anions. The latter are μ
2-coordinated to the cation — that is, end-on. Additional water molecules are bound in the crystal by
hydrogen bonding
In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing ...
. Only the tetrahydrate has been characterized by
X-ray crystallography
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angle ...
, but
density functional theory
Density-functional theory (DFT) is a computational quantum mechanical modelling method used in physics, chemistry and materials science to investigate the electronic structure (or nuclear structure) (principally the ground state) of many-bo ...
offers a good approximation to the dihydrate.
Polyperoxouranylate allotrope
When
uranyl nitrate
Uranyl nitrate is a water-soluble yellow uranium salt with the formula . The hexa-, tri-, and dihydrates are known. The compound is mainly of interest because it is an intermediate in the preparation of nuclear fuels.
Uranyl nitrate can be prepa ...
is dissolved in an aqueous solution of
hydrogen peroxide
Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3% ...
and an
alkali metal hydroxide
The alkali hydroxides are a class of chemical compounds which are composed of an alkali metal cation and the hydroxide anion (OH−). The alkali hydroxides are:
*Lithium hydroxide (LiOH)
*Sodium hydroxide (NaOH)
*Potassium hydroxide (KOH)
*Rubidiu ...
, it forms cage clusters akin to
polyoxometalates or
fullerene
A fullerene is an allotrope of carbon whose molecule consists of carbon atoms connected by single and double bonds so as to form a closed or partially closed mesh, with fused rings of five to seven atoms. The molecule may be a hollow sphere, ...
s.
Syntheses also typically add organic materials, such as
amine
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent su ...
s, to serve as templates, akin to
zeolite
Zeolites are microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ･y where is either a metal ion or H+. These ...
s.
Applications
Radiolysis
Radiolysis is the dissociation of molecules by ionizing radiation. It is the cleavage of one or several chemical bonds resulting from exposure to high-energy flux. The radiation in this context is associated with ionizing radiation; radiolysis is ...
of uranium salts dissolved in water produces peroxides; uranyl peroxide has been studied as a possible end component of spent
radioactive waste
Radioactive waste is a type of hazardous waste that contains radioactive material. Radioactive waste is a result of many activities, including nuclear medicine, nuclear research, nuclear power generation, rare-earth mining, and nuclear weap ...
.
References
Some Chemistry of Uranium*
*
Uranyl compounds
Peroxides
Nuclear materials
Oxidizing agents
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