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Uranyl hydroxide

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Uranyl hydroxide
Ball and stick model of crystalline uranyl hydroxide
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
PubChem CID
UN number 2909
CompTox Dashboard (EPA)
InChI
  • InChI=1S/2H2O.2O.U/h2*1H2;;;/q;;;;+2/p-2Key: VWIQIIGYDAPONF-UHFFFAOYSA-L
SMILES
  • O==O..
Properties
Chemical formula UH
2O
4
Molar mass 304.0424 g mol
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 , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

Uranyl hydroxide is a hydroxide of uranium with the chemical formula UO2(OH)2 in the monomeric form and in the dimeric; both forms may exist in normal aqueous media. In areobic conditions, up to 5 hydroxides can bind to Uranyl {}. Uranyl hydroxide hydrate is precipitated as a colloidal yellowcake from oxidized uranium liquors near neutral pH.

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 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 (·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.

Reactions

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1) (UO2(OH) + H2O →

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2) + H2O →

UO2(OH)2 reacts with water in a hydration reaction to form and the monohydrate form also reacted with water to form dihydrates and trihydrates . 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).

Mechanisms

A mechanism for oxygen exchange between the UO2 cations in a highly alkaline solution was proposed and investigated by Shamov et al. in the Journal of the American Chemical Society. An equilibrium between ] and ] was observed followed by the formation of the stable ] intermediate that formed from ] via intramolecular water elimination.

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. 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. doi:10.1021/ja804742f. ISSN 0002-7863. PMID 18808120.
Uranium compounds
U(II)
U(III)
Organouranium(III) compounds
  • U(C5H5)3
  • U(IV)
    Organouranium(IV) compounds
  • U(C8H8)2
  • U(C5H5)4
  • U(C5H5)3Cl
  • U(IV,V)
    U(IV,VI)
    U(V)
    U(VI)
    U(XII)
    • UO6 (hypothetical)
    Hydroxides
    HOH He
    LiOH Be(OH)2 B(OH)3 C(OH)4 N(OH)3
    [NH4]OH
    O(OH)2 FOH Ne
    NaOH Mg(OH)2 Al(OH)3 Si(OH)4 P(OH)3 S(OH)2 ClOH Ar
    KOH Ca(OH)2 Sc(OH)3 Ti(OH)2
    Ti(OH)3
    Ti(OH)4
    V(OH)2
    V(OH)3
    Cr(OH)2
    Cr(OH)3
    Mn(OH)2 Fe(OH)2
    Fe(OH)3
    Co(OH)2 Ni(OH)2 CuOH
    Cu(OH)2
    Zn(OH)2 Ga(OH)3 Ge(OH)2 As(OH)3 Se BrOH Kr
    RbOH Sr(OH)2 Y(OH)3 Zr(OH)4 Nb Mo Tc(OH)4 Ru Rh(OH)3 Pd AgOH Cd(OH)2 In(OH)3 Sn(OH)2
    Sn(OH)4
    Sb(OH)3 Te(OH)6 IOH Xe
    CsOH Ba(OH)2 * Lu(OH)3 Hf Ta W Re Os Ir Pt Au(OH)3 Hg(OH)2 TlOH
    Tl(OH)3
    Pb(OH)2
    Pb(OH)4
    Bi(OH)3 Po At Rn
    FrOH Ra(OH)2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
     
    * La(OH)3 Ce(OH)3
    Ce(OH)4
    Pr(OH)3 Nd(OH)3 Pm(OH)3 Sm(OH)3 Eu(OH)2
    Eu(OH)3
    Gd(OH)3 Tb(OH)3 Dy(OH)3 Ho(OH)3 Er(OH)3 Tm(OH)3 Yb(OH)3
    ** Ac(OH)3 Th(OH)4 Pa U(OH)2
    U(OH)3
    UO2(OH)2
    Np(OH)3
    Np(OH)4
    NpO2(OH)3
    Pu Am(OH)3 Cm(OH)3 Bk Cf Es Fm Md No
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