Uranium(IV) sulfate

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Uranium(IV) sulfate
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/H2O4S.U/c1-5(2,3)4;/h(H2,1,2,3,4);/q;+2/p-2 Yes check.svgY
    Key: SMWCBVIJCHHBAU-UHFFFAOYSA-L Yes check.svgY
  • InChI=1/H2O4S.U/c1-5(2,3)4;/h(H2,1,2,3,4);/q;+2/p-2
    Key: SMWCBVIJCHHBAU-NUQVWONBAD
  • [U+2].[O-]S([O-])(=O)=O
Properties
U(SO4)2
Molar mass 430.15 g/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Uranium(IV) sulfate (U(SO4)2) is a water-soluble salt of uranium. It is a very toxic compound. Uranium sulfate minerals commonly are widespread around uranium bearing mine sites, where they usually form during the evaporation of acid sulfate-rich mine tailings which have been leached by oxygen-bearing waters. Uranium sulfate is a transitional compound in the production of uranium hexafluoride. It was also used to fuel aqueous homogeneous reactors.

Contents

Preparation

Uranyl sulfate in solution is readily photochemically reduced to uranium(IV) sulfate. The photoreduction is carried out in the sun and requires the addition of ethanol as a reducing agent. Uranium(IV) crystallizes or is precipitated by ethanol in excess. It can be obtained with different degrees of hydration. U(SO4)2 can also be prepared through electrochemical reduction of U(VI) and the addition of sulfates. Reduction of U(VI) to U(IV) occurs naturally through a variety of means, including through the actions of microorganisms. Formation of U(SO4)2 is an entropically and thermodynamically favorable reaction.

Mining and presence in the environment

In-situ leaching (ISL), a widespread technique used to mine uranium, is implicated in the artificial increase of uranium sulfate compounds. ISL was the most widely used method to mine uranium in the United States during the 1990s. The method involves pumping an extraction liquid (either sulfuric acid or an alkaline carbonate solution) into an ore deposit, where it complexes with the uranium, removing the liquid and purifying the uranium. This synthetic addition of sulfuric acid unnaturally raises the abundance of uranium sulfate complexes at the site. The lower pH caused by the introduction of acid increases the solubility of U(IV), which is typically relatively insoluble and precipitates out of solution at neutral pH. Oxidation states for uranium range from U3+ to U6+, U(III) and U(V) are rarely found, while U(VI) and U(IV) predominate. U(VI) forms stable aqueous complexes and is thus fairly mobile. Preventing the spread of toxic uranium compounds from mining sites often involves reduction of U(VI) to the far less soluble U(IV). The presence of sulfuric acid and sulfates prevents this sequestration, however, by both lowering the pH and through the formation of uranium salts. U(SO4)2 is soluble in water, and thus far more mobile. Uranium sulfate complexes also form quite readily.

Environmental and health effects

U(IV) is much less soluble, and thus less environmentally mobile, than U(VI), which also forms sulfate compounds such as UO2(SO4). Bacteria which are able to reduce uranium have been proposed as a means of eliminating U(VI) from contaminated areas, such as mine tailings and nuclear weapons manufacture sites. Contamination of groundwater by uranium is considered a serious health risk, and can be damaging to the environment as well. Several species of sulfate reducing bacteria also have the ability to reduce uranium. The ability to clear the environment of both sulfate (which solubilizes reduced uranium) and mobile U(VI) makes bioremediation of ISL mining sites a possibility.

U(SO4)2 is a semi-soluble compound and exists in a variety of hydration states, with up to nine coordinating waters. U(IV) can have up to five coordinating sulfates, although nothing above U(SO4)2 has been significantly described. Kinetics data for U(SO4)2+ and U(SO4)2 reveal that the bidentate complex is strongly favored thermodynamically, with a reported K0 of 10.51, as compared to K0=6.58 for the monodentate complex. U(IV) is much more stable as a sulfate compound, particularly as U(SO4)2. Běhounekite is a recently (2011) described U(IV) mineral with the chemical composition U(SO4)2 (H2O)4. The uranium center has eight oxygen ligands, four provided by the sulfate groups and four from the water ligands. U(SO4)2 (H2O)4 forms short, green crystals. Běhounekite is the first naturally occurring U(IV) sulfate to be described.

Related Research Articles

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Sulfate Oxyanion with a central atom of sulfur surrounded by 4 oxygen atoms

The sulfate or sulphate ion is a polyatomic anion with the empirical formula SO2−4. Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many are prepared from that acid.

Iron(II) sulfate Chemical compound

Iron(II) sulfate (British English: iron(II) sulphate) or ferrous sulfate denotes a range of salts with the formula FeSO4·xH2O. These compounds exist most commonly as the heptahydrate (x = 7) but several values for x are known. The hydrated form is used medically to treat iron deficiency, and also for industrial applications. Known since ancient times as copperas and as green vitriol (vitriol is an archaic name for sulfate), the blue-green heptahydrate (hydrate with 7 molecules of water) is the most common form of this material. All the iron(II) sulfates dissolve in water to give the same aquo complex [Fe(H2O)6]2+, which has octahedral molecular geometry and is paramagnetic. The name copperas dates from times when the copper(II) sulfate was known as blue copperas, and perhaps in analogy, iron(II) and zinc sulfate were known respectively as green and white copperas.

Zinc sulfate Chemical compound

Zinc sulfate is an inorganic compound. It is used as a dietary supplement to treat zinc deficiency and to prevent the condition in those at high risk. Side effects of excess supplementation may include abdominal pain, vomiting, headache, and tiredness.

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Acid mine drainage, acid and metalliferous drainage (AMD), or acid rock drainage (ARD) is the outflow of acidic water from metal mines or coal mines.

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Potassium sulfate (US) or potassium sulphate (UK), also called sulphate of potash (SOP), arcanite, or archaically potash of sulfur, is the inorganic compound with formula K2SO4, a white water-soluble solid. It is commonly used in fertilizers, providing both potassium and sulfur.

Cerium(IV) sulfate Chemical compound

Cerium(IV) sulfate, also called ceric sulfate, is an inorganic compound. It exists as the anhydrous salt Ce(SO4)2 as well as a few hydrated forms: Ce(SO4)2(H2O)x, with x equal to 4, 8, or 12. These salts are yellow to yellow/orange solids that are moderately soluble in water and dilute acids. Its neutral solutions slowly decompose, depositing the light yellow oxide CeO2. Solutions of ceric sulfate have a strong yellow color. The tetrahydrate loses water when heated to 180-200 °C.

Potassium dichromate Chemical compound

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Ammonium sulfate Chemical compound

Ammonium sulfate (American English and international scientific usage; ammonium sulphate in British English); (NH4)2SO4, is an inorganic salt with a number of commercial uses. The most common use is as a soil fertilizer. It contains 21% nitrogen and 24% sulfur.

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2
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Biomining is the technique of extracting metals from ores and other solid materials typically using prokaryotes, fungi or plants. These organisms secrete different organic compounds that chelate metals from the environment and bring it back to the cell where they are typically used to coordinate electrons. It was discovered in the mid 1900s that microorganisms use metals in the cell. Some microbes can use stable metals such as iron, copper, zinc, and gold as well as unstable atoms such as uranium and thorium. Companies can now grow large chemostats of microbes that are leaching metals from their media, these vats of culture can then be transformed into many marketable metal compounds. Biomining is an environmentally friendly technique compared to typical mining. Mining releases many pollutants while the only chemicals released from biomining is any metabolites or gasses that the bacteria secrete. The same concept can be used for bioremediation models. Bacteria can be inoculated into environments contaminated with metals, oils, or other toxic compounds. The bacteria can clean the environment by absorbing these toxic compounds to create energy in the cell. Microbes can achieve things at a chemical level that could never be done by humans. Bacteria can mine for metals, clean oil spills, purify gold, and use radioactive elements for energy.

In situ leach

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Uranium acid mine drainage

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.

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