Uranyl hydroxide

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Uranyl hydroxide
Kristallstruktur Uranylhydroxid.png
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
UN number 2909
  • InChI=1S/2H2O.2O.U/h2*1H2;;;/q;;;;+2/p-2 X mark.svgN
    Key: VWIQIIGYDAPONF-UHFFFAOYSA-L X mark.svgN
  • O=[U+2]=O.[OH-].[OH-]
Properties
UH
2
O
4
Molar mass 304.0424 g mol−1
Related compounds
Related compounds
Sulfuric acid
Chromic acid
Uranium trioxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Uranyl hydroxide is a hydroxide of uranium with the chemical formula UO2(OH)2 in the monomeric form and [(UO2)2(OH)4]2- in the dimeric; both forms may exist in normal aqueous media. In aerobic conditions, up to 5 hydroxides can bind to Uranyl {[(UO2)2(OH)5]3-}. Uranyl hydroxide hydrate is precipitated as a colloidal yellowcake from oxidized uranium liquors near neutral pH.

Contents

Uranyl hydroxide was once used in glassmaking and ceramics in the colouring of the vitreous phases and the preparation of pigments for high temperature firing. The introduction of alkaline diuranates (like sodium diuranate) into glasses leads to yellow by transmission, green by reflection; moreover these glasses become dichroic and fluorescent under ultraviolet rays.

Uranyl hydroxide is teratogenic and radioactive.

Formation

The formation of uranyl hydroxide hydrate can occur via hydrated uranyl fluoride [(UO2F2)(H2O)]7·4H2O which is not stable at an elevated water vapor pressure. A complete loss of fluorine is undergone and the formation of uranyl hydroxide hydrate ([(UO2)4O(OH)6]·5H2O) occurs. This uranyl hydroxide species is structurally similar to the uranyl hydroxide hydrate minerals schoepite and metaschoepite. X-ray diffraction data was gathered and found that this species has expanded interlayer spacing suggesting there may be additional water molecules in between uranyl layers. Unlike metaschoepite, however, this species does not form UO2(OH)2 upon dehydration. [1]

Reactions

1) (UO2(OH)+ + H2O → [(UO2(OH)(H2O)]+

2) [(UO2(OH)(H2O)]+ + H2O → [(UO2(OH)(H2O)2]+

UO2(OH)2 reacts with water in a hydration reaction to form [(UO2(OH)2)(H2O)]+ and the monohydrate form also reacted with water to form dihydrates [(UO2OH)(H2O)2]+ and trihydrates [(UO2OH)(H2O)3]+. The hydration reaction to form the monohydrate was significantly slower than if the hydroxide were replaced with acetate or nitrate. This could be due to the strongly basic (OH)- reducing the Lewis acidity of U or because the more complex acetate and nitrate anions provide more degrees of freedom. However, it was found that the formation of the dihydrate uranyl hydroxide hydrate (2) was nearly three times faster than the monohydrate (1). [2]

Mechanisms

A mechanism for oxygen exchange between the UO22+ cations in a highly alkaline solution was proposed and investigated by Shamov et al. in the Journal of the American Chemical Society. [3] An equilibrium between [UO2(OH)4]2-] and [UO2(OH)5]3-] was observed followed by the formation of the stable [UO3(OH)3·H2O]3−] intermediate that formed from [UO2(OH)5]3-] via intramolecular water elimination.

Related Research Articles

The actinide or actinoid series encompasses at least the 14 metallic chemical elements in the 5f series, with atomic numbers from 89 to 102, actinium through nobelium. Number 103, lawrencium, is also generally included despite being part of the 6d transition series. The actinide series derives its name from the first element in the series, actinium. The informal chemical symbol An is used in general discussions of actinide chemistry to refer to any actinide.

<span class="mw-page-title-main">Sodium hydroxide</span> Chemical compound with formula NaOH

Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations Na+ and hydroxide anions OH.

<span class="mw-page-title-main">Uranyl nitrate</span> Chemical compound

Uranyl nitrate is a water-soluble yellow uranium salt with the formula UO2(NO3)2 · n H2O. The hexa-, tri-, and dihydrates are known. The compound is mainly of interest because it is an intermediate in the preparation of nuclear fuels. In the nuclear industry, it is commonly referred to as yellow salt.

<span class="mw-page-title-main">Iron(III) oxide-hydroxide</span> Hydrous ferric oxide (HFO)

Iron(III) oxide-hydroxide or ferric oxyhydroxide is the chemical compound of iron, oxygen, and hydrogen with formula FeO(OH).

The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula UO2+
2
. 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.

<span class="mw-page-title-main">Uranium trioxide</span> Chemical compound

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 is amorphous UO3.

<span class="mw-page-title-main">Uranyl acetate</span> Chemical compound

Uranyl acetate is the acetate salt of uranium oxide, a toxic yellow-green powder useful in certain laboratory tests. Structurally, it is a coordination polymer with formula UO2(CH3CO2)2(H2O)·H2O.

<span class="mw-page-title-main">Uranyl peroxide</span> Chemical compound

Uranyl peroxide or uranium peroxide hydrate (UO4·nH2O) is a pale-yellow, soluble peroxide of uranium. It is found to be present at one stage of the enriched uranium fuel cycle and in yellowcake prepared via the in situ leaching and resin ion exchange system. This compound, also expressed as UO3·(H2O2)·(H2O), is very similar to uranium trioxide hydrate UO3·nH2O. 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.

<span class="mw-page-title-main">Ammonium diuranate</span> Chemical compound

Ammonium diuranate or (ADU) ((NH4)2U2O7), is one of the intermediate chemical forms of uranium produced during yellowcake production. The name "yellowcake" originally given to this bright yellow salt, now applies to mixtures of uranium oxides which are actually hardly ever yellow. It also is an intermediate in mixed-oxide (MOX) fuel fabrication. Although it is usually called "ammonium diuranate" as though it has a "diuranate" ion U
2
O2−
7
, this is not necessarily the case. It can also be called diammonium diuranium heptaoxide. The structure was theorized to be similar to that of uranium trioxide dihydrate. Recent literature has shown that the structure more closely resembles the mineral metaschoepite, the partially dehydrated form of schoepite.

<span class="mw-page-title-main">Sodium diuranate</span> Mixed oxide of uranium and sodium

Sodium diuranate, also known as the yellow oxide of uranium, is an inorganic chemical compound with the chemical formula Na2U2O7. It is a sodium salt of a diuranate anion. It forms a hexahydrate Na2U2O7·6H2O. Sodium diuranate is commonly referred to by the initials SDU. Along with ammonium diuranate it was a component in early yellowcakes. The ratio of the two compounds is determined by process conditions; however, yellowcake is now largely a mix of uranium oxides.

<span class="mw-page-title-main">Uranyl chloride</span> Chemical compound

Uranyl chloride refers to inorganic compounds with the formula UO2Cl2(H2O)n where n = 0, 1, or 3. These are yellow-colored salts.

<span class="mw-page-title-main">Uranate</span> Uranium oxyanion associated with a monovalent or divalent cation

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 MxUyOz, 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. The structures are infinite lattice structures with the uranium atoms linked by bridging oxygen atoms.

Uranium compounds are compounds formed by the element uranium (U). Although uranium is a radioactive actinide, its compounds are well studied due to its long half-life and its applications. It usually forms in the +4 and +6 oxidation states, although it can also form in other oxidation states.

<span class="mw-page-title-main">Curite</span> Rare mineral

Curite is a rare mineral with the chemical composition Pb3[(UO2)4|O4|(OH)3]2·2 H2O. It is therefore a hydrated lead uranyl oxide, which forms red needles or orange, massive aggregates.

Paulscherrerite, UO2(OH)2, is a newly named mineral of the schoepite subgroup of hexavalent uranium hydrate/hydroxides. It is monoclinic, but no space group has been determined because no single-crystal study has been done. Paulscherrerite occurs as a canary yellow microcrystalline powdery product with a length of ~500 nm. It forms by the weathering and ultimate pseudomorphism of uranium-lead bearing minerals such as metaschoepite. The type locality for paulscherrerite is the Number 2 Workings, Radium Ridge near Mount Painter, North Flinders Ranges, South Australia, an area where radiogenic heat has driven hydrothermal activity for millions of years. It is named for Swiss physicist Paul Scherrer, co-inventor of the Debye-Scherrer X-ray powder diffraction camera. Study of paulscherrerite and related minerals is important for understanding the mobility of uranium around mining sites, as well as designing successful strategies for the storage of nuclear weapons and the containment of nuclear waste.

<span class="mw-page-title-main">Cerium nitrates</span> Chemical compound

Cerium nitrate refers to a family of nitrates of cerium in the +3 or +4 oxidation state. Often these compounds contain water, hydroxide, or hydronium ions in addition to cerium and nitrate. Double nitrates of cerium also exist.

<span class="mw-page-title-main">Uranium acid mine drainage</span>

Uranium acid mine drainage refers to acidic water released from a uranium mining site using processes like underground mining and in-situ leaching. Underground, the ores are not as reactive due to isolation from atmospheric oxygen and water. When uranium ores are mined, the ores are crushed into a powdery substance, thus increasing surface area to easily extract uranium. The ores, along with nearby rocks, may also contain sulfides. Once exposed to the atmosphere, the powdered tailings react with atmospheric oxygen and water. After uranium extraction, sulfide minerals in uranium tailings facilitates the release of uranium radionuclides into the environment, which can undergo further radioactive decay while lowering the pH of a solution.

<span class="mw-page-title-main">Neodymium(III) acetate</span> Compound of neodymium

Neodymium(III) acetate is an inorganic salt composed of a neodymium atom trication and three acetate groups as anions where neodymium exhibits the +3 oxidation state. It has a chemical formula of Nd(CH3COO)3 although it can be informally referred to as NdAc because Ac is an informal symbol for acetate. It commonly occurs as a light purple powder.

<span class="mw-page-title-main">Technetium(IV) oxide</span> Chemical compound

Technetium(IV) oxide, also known as technetium dioxide, is a chemical compound with the formula TcO2 which forms the dihydrate, TcO2·2H2O, which is also known as technetium(IV) hydroxide. It is a radioactive black solid which slowly oxidizes in air.

<span class="mw-page-title-main">Gauthierite</span> Hydrous oxyuranyl mineral

Gauthierite is a very rare mineral with the idealised chemical sum formula KPb[(UO2)7O5(OH)7]·8H2O. It is a radioactive, hydrated orange-coloured lead potassium uranyl oxide hydroxide. It was found by analysing old mineral specimens, and is only known from one locality, the Shinkolobwe Mine in the Democratic Republic of the Congo. The mineral was named in honour of Gilbert Gauthier, a Belgian collector of uranium minerals, who provided a sample to one of the co-authors of the study that first identified it in 2017.

References

  1. Kirkegaard, Marie C.; Spano, Tyler L.; Ambrogio, Michael W.; Niedziela, J. L.; Miskowiec, Andrew; Shields, Ashley E.; Anderson, Brian B. (2019). "Formation of a uranyl hydroxide hydrate via hydration of [(UO 2 F 2 )(H 2 O)] 7 ·4H 2 O". Dalton Transactions. 48 (36): 13685–13698. doi:10.1039/C9DT02835H. ISSN   1477-9226. OSTI   1607115. PMID   31468045.
  2. Chien, Winnie; Anbalagan, Victor; Zandler, Melvin; Van Stipdonk, Michael; Hanna, Dorothy; Gresham, Garold; Groenewold, Gary (2004-06-01). "Intrinsic hydration of monopositive uranyl hydroxide, nitrate, and acetate cations". Journal of the American Society for Mass Spectrometry. 15 (6): 777–783. Bibcode:2004JASMS..15..777C. doi:10.1016/j.jasms.2004.01.013. ISSN   1044-0305. PMID   15144967.
  3. Shamov, Grigory A.; Schreckenbach, Georg (2008-10-15). "Theoretical Study of the Oxygen Exchange in Uranyl Hydroxide. An Old Riddle Solved?". Journal of the American Chemical Society. 130 (41): 13735–13744. Bibcode:2008JAChS.13013735S. doi:10.1021/ja804742f. ISSN   0002-7863. PMID   18808120.