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Plutonium(IV) sulfate

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Plutonium(IV) sulfate
Names
IUPAC name Plutonium(IV) sulfate
Identifiers
3D model (JSmol)
InChI
  • anhydrous: InChI=1S/2H2O4S.Pu/c2*1-5(2,3)4;/h2*(H2,1,2,3,4);/q;;+4/p-4Key: QRGPRHDJXDGLIN-UHFFFAOYSA-J
  • tetrahdyrate: InChI=1S/2H2O4S.4H2O.Pu/c2*1-5(2,3)4;;;;;/h2*(H2,1,2,3,4);4*1H2;/q;;;;;;+4/p-4Key: UAJVPPUGRHQMOQ-UHFFFAOYSA-J
SMILES
  • anhydrous: O=S(=O)().O=S(=O)().
  • tetrahdyrate: O=S(=O)().O=S(=O)()..O.O.O.O
Properties
Chemical formula Pu(SO4)2
Molar mass 506.18 g/mol
Appearance Red crystalline solid
Melting point ~800°C? (Decomposes)
Solubility in water Somewhat soluble
Structure
Crystal structure Orthorhombic
Space group Fddd (α-Pu(SO4)2·4H2O)
Pnma (β-Pu(SO4)2·4H2O)
Point group mmm (α-Pu(SO4)2·4H2O)
Related compounds
Other anions Plutonium(IV) oxide
Plutonium(IV) fluoride
Other cations Uranium(IV) sulfate
Uranyl sulfate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Infobox references
Chemical compound

Plutonium(IV) sulfate is a chemical compound consisting of plutonium and sulfate ions, with the chemical formula Pu(SO4)2·xH2O. It has been observed as a tetrahydrate, where x=4, as well as an anhydrous form, where x=0. The tetrahydrate has been used as a primary analytical standard for plutonium.

Formation & Reactions

Plutonium(IV) sulfate is produced when plutonium(IV) ions react with bisulfate or sulfate ions in aqueous solution:

Pu(aq) + 2 HSO−4(aq) → Pu(SO4)2(aq) + 2 H(aq)
Pu(aq) + 2 SO2−4(aq) → Pu(SO4)2(aq)

At high temperatures (~800°C), plutonium(IV) sulfate tetrahydrate decomposes. It first releases its water to form anhydrous plutonium(IV) sulfate, then releases sulfur oxides to form plutonium(IV) oxide.

At normal temperatures, however, plutonium(IV) sulfate tetrahydrate is stable in air, even at high humidity.

Structure

Plutonium(IV) sulfate tetrahydrate ligands are monodentate, with bonds between plutonium atoms and oxygen atoms in the water and sulfate molecules. Each plutonium atom has a coordination number of 8, and a coordination geometry of square antiprismatic. Plutonium(IV) sulfate tetrahydrate crystals have an orthorhombic crystal structure. Hydrogen bonds exist between hydrogen atoms in the water molecules and oxygen atoms in the sulfate ions that are not attached to the plutonium atom.

Allotropes

Plutonium(IV) sulfate tetrahydrate has two allotropes– α-Pu(SO4)2·4H2O and β-Pu(SO4)2·4H2O. The two forms share the same molecular geometry, but differ in the functional nature of the hydrogen bonds. The α-form transitions into the β-form at ~120°C.

α-Pu(SO4)2·4H2O has a unit cell with dimensions a=26.53Å, b=12.00Å, and c=5.69Å, where there are 8 formula units per unit cell.

β-Pu(SO4)2·4H2O has a unit cell with dimensions a=14.54Å, b=10.98Å, and c=5.67Å, where there are 4 formula units per unit cell.

Hazards

Plutonium(IV) sulfate is a highly dangerous compound, due to it being radioactive and carcinogenic.

References

  1. ^ Richard E. Wilson (18 May 2011). "Structural Periodicity in Plutonium(IV) Sulfates". Inorganic Chemistry. 50 (12): 5663–5670. doi:10.1021/ic200384h. PMID 21591736.
  2. ^ Waterbury, Glenn R., Douglass, Robert M., Metz, Charles F. (1 July 1961). ""Thermogravimetric Behavior of Plutonium Metal, Nitrate, Sulfate, and Oxalate"". Analytical Chemistry. 33 (8): 1018–1023. doi:10.1021/ac60176a047.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  3. ^ NBL Program Office, "Safety Data Sheet: Plutonium Sulfate Tetrahydrate", https://www.energy.gov/sites/prod/files/2020/11/f80/SDS-Plutonium_Sulfate_2020.pdf
  4. ^ Jayadevan, N.C., Mudher, K.D.S., Chackraburtty, D.M. (25 Aug 2010). "The crystal structures of α- and β-forms of plutonium(IV) sulphate tetrahydrate". Zeitschrift für Kristallographie - Crystalline Materials. 161 (1–4): 7–14. doi:10.1524/zkri.1982.161.14.7.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. ^ C. E. Pietri, A. W. Wenzel (1 Nov 1962). "The stability of plutonium sulphate tetrahydrate, an analytical standard: a ten-year evaluation". Talanta. 18 (8): 849–852. doi:10.1016/0039-9140(71)80138-8. PMID 18960954.
  6. Lemire, R. J. et al., Chemical Thermodynamics of Neptunium and Plutonium, Elsevier, Amsterdam, 2001.
  7. C. E. Pietri (1 Nov 1962). "Plutonium Sulfate Tetrahydrate, a Proposed Primary Analytical Standard for Plutonium". Analytical Chemistry. 163 (12): 130–136. doi:10.1021/ac60192a027.
Plutonium compounds
Plutonium(II)
Plutonium(III)
Plutonium(IV)
Plutonium(V)
Plutonium(VI)
Plutonium(VIII)
Compounds containing the sulfate group (SO2−4)
H2SO4 He
Li2SO4 BeSO4 B2S2O9
-BO3
+BO3
esters
ROSO−3
(RO)2SO2
+CO3
+C2O4
(NH4)2SO4
[N2H5]HSO4
(NH3OH)2SO4
NOHSO4
+NO3
H2OSO4 +F Ne
Na2SO4
NaHSO4
MgSO4 Al2(SO4)3
Al2SO4(OAc)4
Si +PO4 SO2−4
HSO3HSO4
(HSO4)2
+SO3
+Cl Ar
K2SO4
KHSO4
CaSO4 Sc2(SO4)3 TiOSO4 VSO4
V2(SO4)3
VOSO4
CrSO4
Cr2(SO4)3
MnSO4 FeSO4
Fe2(SO4)3
CoSO4
Co2(SO4)3
NiSO4
Ni2(SO4)3
CuSO4
Cu2SO4
SO4
ZnSO4 Ga2(SO4)3 Ge(SO4)2 As +SeO3 +Br Kr
RbHSO4
Rb2SO4
SrSO4 Y2(SO4)3 Zr(SO4)2 Nb2O2(SO4)3 MoO(SO4)2
MoO2(SO4)
Tc Ru(SO4)2 Rh2(SO4)3 PdSO4 Ag2SO4
AgSO4
CdSO4 In2(SO4)3 SnSO4
Sn(SO4)2
Sb2(SO4)3 TeOSO4 I2(SO4)3
(IO)2SO4
+IO3
Xe
Cs2SO4
CsHSO4
BaSO4 * Lu2(SO4)3 Hf(SO4)2 Ta WO(SO4)2 Re2O5(SO4)2 OsSO4
Os2(SO4)3
Os(SO4)2
IrSO4
Ir2(SO4)3
Pt2(SO4)5 AuSO4
Au2(SO4)3
Hg2SO4
HgSO4
Tl2SO4
Tl2(SO4)3
PbSO4
Pb(SO4)2
Bi2(SO4)3 PoSO4
Po(SO4)2
At Rn
Fr RaSO4 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* La2(SO4)3 Ce2(SO4)3
Ce(SO4)2
Pr2(SO4)3 Nd2(SO4)3 Pm2(SO4)3 Sm2(SO4)3 EuSO4
Eu2(SO4)3
Gd2(SO4)3 Tb2(SO4)3 Dy2(SO4)3 Ho2(SO4)3 Er2(SO4)3 Tm2(SO4)3 Yb2(SO4)3
** Ac2(SO4)3 Th(SO4)2 Pa U2(SO4)3
U(SO4)2
UO2SO4
Np(SO4)2 Pu(SO4)2 Am2(SO4)3 Cm2(SO4)3 Bk Cf2(SO4)3 Es Fm Md No
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