Plutonium tetrafluoride

Plutonium tetrafluoride[1]

A sample of plutonium tetrafluoride produced at the Hanford Site during the Cold War[2][3]
Names
IUPAC name
Plutonium(IV) fluoride
Other names
Plutonium tetrafluoride
Identifiers
CAS Number
  • 13709-56-3 ☒N
3D model (JSmol)
  • Interactive image
ChemSpider
  • 123078
PubChem CID
  • 139558
CompTox Dashboard (EPA)
  • DTXSID90160061 Edit this at Wikidata
InChI
  • InChI=1S/4FH.Pu/h4*1H;/q;;;;+4/p-4
    Key: USCBBUFEOOSGAJ-UHFFFAOYSA-J
  • F[Pu](F)(F)F
Properties
Chemical formula
PuF4
Molar mass 320 g/mol
Appearance reddish-brown monoclinic crystals
Density 7.1 g/cm3
Melting point 1,027 °C (1,881 °F; 1,300 K)
Structure
Crystal structure
Monoclinic, mS60
Space group
C12/c1, No. 15
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Chemical compound

Plutonium(IV) fluoride is a chemical compound with the formula (PuF4). This salt is generally a brown solid but can appear a variety of colors depending on the grain size, purity, moisture content, lighting, and presence of contaminants.[4][5] Its primary use in the United States has been as an intermediary product in the production of plutonium metal for nuclear weapons usage.[3]

Formation

Plutonium(IV) fluoride is produced in the reaction between plutonium dioxide (PuO2) or plutonium(III) fluoride (PuF3) with hydrofluoric acid (HF) in a stream of oxygen (O2) at 450 to 600 °C. The main purpose of the oxygen stream is to avoid reduction of the product by hydrogen gas, small amounts of which are often found in HF.[6]

PuO2 + O2 + 4 HF → PuF4 + O2 + 2 H2O
4 PuF3 + O2 + 4 HF → 4 PuF4 + 2 H2O

Laser irradiation of plutonium hexafluoride (PuF6) at wavelengths under 520 nm causes it to decompose into plutonium pentafluoride (PuF5) and fluorine; if this is continued, plutonium(IV) fluoride is obtained.[7]

Properties

In terms of its structure, solid plutonium(IV) fluoride features 8-coordinate Pu centers interconnected by doubly bridging fluoride ligands.[8]

Reaction of plutonium tetrafluoride with barium, calcium, or lithium at 1200 °C give Pu metal:[4][5][3]

PuF4 + 2 Ba → 2 BaF2 + Pu
PuF4 + 2 Ca → 2 CaF2 + Pu
PuF4 + 4 Li → 4 LiF + Pu
Plutonium tetrafluoride sample with example of one color illustrated through reference to a color standard[9]

References

  1. ^ Lide, David R. (1998), Handbook of Chemistry and Physics (87 ed.), Boca Raton, Florida: CRC Press, pp. 4–76, ISBN 0-8493-0594-2
  2. ^ Pfeiffer, Martin (March 3, 2019). "FOI 2019-00371.Loaded powder pan at RMC line". Pfeiffer Nuclear Weapon and National Security Archive. Retrieved May 23, 2019.
  3. ^ a b c United States Department of Energy (1997). Linking Legacies: Connecting the Cold War Nuclear Weapons Production Processes to Their Environmental Consequences (PDF). Washington D.C.: United States Department of Energy. pp. 184, passim.
  4. ^ a b Baldwin, Charles E.; Navratil, James D. (1983-05-19). "Plutonium Process Chemistry at Rocky Flats". In Carnall, William T.; Choppin, Gregory R. (eds.). Plutonium Chemistry. ACS Symposium Series. Vol. 216. AMERICAN CHEMICAL SOCIETY. pp. 369–380. doi:10.1021/bk-1983-0216.ch024. ISBN 9780841207721.
  5. ^ a b Christensen, Eldon L.; Grey, Leonard W.; Navratil, James D.; Schulz, Wallace W. (1983-05-19). "Present Status and Future Directions of Plutonium Process Chemistry". In Carnall, William T.; Choppin, Gregory R. (eds.). Plutonium Chemistry. ACS Symposium Series. Vol. 216. AMERICAN CHEMICAL SOCIETY. pp. 349–368. doi:10.1021/bk-1983-0216.ch023. ISBN 9780841207721. OSTI 6781635.
  6. ^ Gmelins Handbuch der anorganischen Chemie, System Nr. 71, Transurane, Teil C, pp. 104–107.
  7. ^ 4670239, Rabideau, Sherman W. & Campbell, George M., "Photochemical preparation of plutonium pentafluoride", issued 1987-06-02 
  8. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  9. ^ Pfeiffer, Martin (March 3, 2019). "PuF4 Pics ORO 2019 00475-FN Final Response 20190312_Page_07_Image_0001". Pfeiffer Nuclear Weapon and National Security Archive. Retrieved May 23, 2019.
  • v
  • t
  • e
Plutonium(II)
Plutonium(III)
  • PuAs
  • PuH3
  • PuP
  • PuB
  • PuF3
  • PuCl3
  • PuBr3
  • PuI3
  • PuN
Plutonium(IV)
  • PuC
  • Pu(NO3)4
  • PuF4
  • PuO2
  • Pu(IO3)4
  • Pu(C8H8)2
Plutonium(V)
  • PuF5
  • XePuF6
Plutonium(VI)
  • PuF6
Plutonium(VIII)
  • PuO4
  • v
  • t
  • e
Salts and covalent derivatives of the fluoride ion
HF ?HeF2
LiF BeF2 BF
BF3
B2F4
+BO3
CF4
CxFy
+CO3
NF3
FN3
N2F2
NF
N2F4
NF2
?NF5
OF2
O2F2
OF
O3F2
O4F2
?OF4
F2 Ne
NaF MgF2 AlF
AlF3
SiF4 P2F4
PF3
PF5
S2F2
SF2
S2F4
SF3
SF4
S2F10
SF6
+SO4
ClF
ClF3
ClF5
?ArF2
?ArF4
KF CaF
CaF2
ScF3 TiF2
TiF3
TiF4
VF2
VF3
VF4
VF5
CrF2
CrF3
CrF4
CrF5
?CrF6
MnF2
MnF3
MnF4
?MnF5
FeF2
FeF3
FeF4
CoF2
CoF3
CoF4
NiF2
NiF3
NiF4
CuF
CuF2
?CuF3
ZnF2 GaF2
GaF3
GeF2
GeF4
AsF3
AsF5
Se2F2
SeF4
SeF6
+SeO3
BrF
BrF3
BrF5
KrF2
?KrF4
?KrF6
RbF SrF
SrF2
YF3 ZrF3
ZrF4
NbF4
NbF5
MoF4
MoF5
MoF6
TcF4
TcF
5

TcF6
RuF3
RuF
4

RuF5
RuF6
RhF3
RhF4
RhF5
RhF6
PdF2
Pd[PdF6]
PdF4
?PdF6
Ag2F
AgF
AgF2
AgF3
CdF2 InF
InF3
SnF2
SnF4
SbF3
SbF5
TeF4
?Te2F10
TeF6
+TeO3
IF
IF3
IF5
IF7
+IO3
XeF2
XeF4
XeF6
?XeF8
CsF BaF2   LuF3 HfF4 TaF5 WF4
WF5
WF6
ReF4
ReF5
ReF6
ReF7
OsF4
OsF5
OsF6
?OsF
7

?OsF
8
IrF2
IrF3
IrF4
IrF5
IrF6
PtF2
Pt[PtF6]
PtF4
PtF5
PtF6
AuF
AuF3
Au2F10
?AuF6
AuF5•F2
Hg2F2
HgF2
?HgF4
TlF
TlF3
PbF2
PbF4
BiF3
BiF5
?PoF2
PoF4
PoF6
AtF
?AtF3
?AtF5
RnF2
?RnF
4

?RnF
6
FrF RaF2   LrF3 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
LaF3 CeF3
CeF4
PrF3
PrF4
NdF2
NdF3
NdF4
PmF3 SmF2
SmF3
EuF2
EuF3
GdF3 TbF3
TbF4
DyF2
DyF3
DyF4
HoF3 ErF3 TmF2
TmF3
YbF2
YbF3
AcF3 ThF3
ThF4
PaF4
PaF5
UF3
UF4
UF5
UF6
NpF3
NpF4
NpF5
NpF6
PuF3
PuF4
PuF5
PuF6
AmF2
AmF3
AmF4
? AmF6
CmF3
CmF4
 ?CmF6
BkF3
BkF
4
CfF3
 ?CfF4
EsF3
EsF4
?EsF6
Fm Md No
  • v
  • t
  • e
Ac Th Pa U Np Pu Am Cm Bk Cf Es
+6 UF6
UCl6
NpF6 PuF6 AmF6 EsF6
+5 PaF5
PaCl5
PaBr5
PaI5
UF5
UCl5
UBr5
NpF5 PuF5
+4 ThF4
ThCl4
ThBr4
ThI4
PaF4
PaCl4
PaBr4
PaI4
UF4
UCl4
UBr4
UI4
NpF4
NpCl4
NpBr4
PuF4 AmF4 CmF4 BkF4 CfF4 EsF4
+3 AcF3
AcCl3
AcBr3
AcI3
ThF3
ThCl3
ThI3
UF3
UCl3
UBr3
UI3
NpF3
NpCl3
NpBr3
NpI3
PuF3
PuCl3
PuBr3
PuI3
AmF3
AmCl3
AmBr3
AmI3
CmF3
CmCl3
CmBr3
CmI3
BkF3
BkCl3
BkBr3
BkI3
CfF3
CfCl3
CfBr3
CfI3
EsF3
EsCl3
EsBr3
EsI3
+2 ThI2
ThCl2
AmF2
AmCl2
AmBr2
AmI2
CfI2
CfCl2
EsCl2
EsBr2
EsI2