Neptunium(VI) fluoride

Neptunium(VI) fluoride[1]

Names
IUPAC name

Neptunium(VI) fluoride

Other names

Neptunium hexafluoride

Identifiers

CAS Number

* 14521-05-2 Y

3D model (JSmol)

* Interactive image

PubChem CID

* 19695135

InChI

* InChI=1S/6FH.Np/h6*1H;/q;;;;;;+6/p-6 N

SMILES

* F[Np](F)(F)(F)(F)F

Properties

Chemical formula

| F6Np
Molar mass | 351 g·mol−1
Appearance  | orange crystals
Melting point |  54.4 °C (129.9 °F; 327.5 K)
Boiling point |  55.18 °C (131.32 °F; 328.33 K)
Structure

Crystal structure

| Orthorhombic, oP28

Space group

| Pnma, No. 62

Coordination geometry

| octahedral (Oh)

Dipole moment

| 0 D
Thermochemistry[2]: 736

Std molar
entropy (S ~~o~~ 298)

| 229.1 ± 0.5 J·K−1·mol−1
Related compounds

Related fluoroNeptuniums

| Neptunium trifluoride

Neptunium tetrafluoride

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

N (what is YN ?)
Infobox references

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Neptunium(VI) fluoride (NpF6) is the highest fluoride of neptunium, it is also one of seventeen known binary hexafluorides. It is an orange volatile crystalline solid.[1] It is relatively hard to handle, being very corrosive, volatile and radioactive. Neptunium hexafluoride is stable in dry air but reacts vigorously with water.

At normal pressure, it melts at 54.4 °C and boils at 55.18 °C. It is the only neptunium compound that boils at a low temperature. Due to these properties, it is possible to easily separate neptunium from spent fuel.

## Contents

* 1 Preparation
* 1.1 Standard method
* 1.2 Other methods
* 1.2.1 Using a different starting material
* 1.2.2 Using a different fluorine source
* 2 Properties
* 2.1 Physical properties
* 2.2 Chemical properties
* 3 Uses
* 4 References

## Preparation

Neptunium hexafluoride was first prepared in 1943 by American chemist Alan E. Florin, who heated a sample of neptunium(III) fluoride on a nickel filament in a stream of fluorine and condensed the product in a glass capillary tube.[3][4] Methods of preparation from both neptunium(III) fluoride and neptunium(IV) fluoride were later patented by Glenn T. Seaborg and Harrison S. Brown.[5]

### Standard method

The usual method of preparation is by fluorination of neptunium(IV) fluoride (NpF4) by elemental fluorine (F2) at 500 °C.[6]

NpF4 \+ F2 → NpF6

In comparison, uranium hexafluoride (UF6) is formed relatively rapidly from uranium tetrafluoride (UF4) and F2 at 300 °C, while plutonium hexafluoride (PuF6) only begins forming from plutonium tetrafluoride (PuF4) and F2 at 750 °C.[6] This difference allows uranium, neptunium and plutonium to be effectively separated.

### Other methods

#### Using a different starting material

Neptunium hexafluoride can also be obtained by fluorination of neptunium(III) fluoride or neptunium(IV) oxide.[7]

2 NpF3 \+ 3 F2 → 2 NpF6
NpO2 \+ 3 F2 → NpF6 \+ O2

#### Using a different fluorine source

The preparation can also be done with the help of stronger fluorinating reagents like bromine trifluoride (BrF3) or bromine pentafluoride (BrF5). These reactions can be used to separate plutonium, since PuF4 does not undergo a similar reaction.[8][9]

Neptunium dioxide and neptunium tetrafluoride are practically completely converted to volatile neptunium hexafluoride by dioxygen difluoride (O2F2). This works as a gas-solid reaction at moderate temperatures, as well as in anhydrous liquid hydrogen fluoride at −78 °C.[10]

NpO2 \+ 3 O2F2 → NpF6 \+ 4 O2
NpF4 \+ O2F2 → NpF6 \+ O2

These reaction temperatures are markedly different from the high temperatures of over 200 °C previously required to synthesize neptunium hexafluoride with elemental fluorine or halogen fluorides.[10] Neptunyl fluoride (NpO2F2) has been detected by Raman spectroscopy as a dominant intermediate in the reaction with NpO2. Direct reaction of NpF4 with liquid O2F2 led instead to vigorous decomposition of the O2F2 with no NpF6 generation.

## Properties

### Physical properties

Neptunium hexafluoride forms orange orthorhombic crystals that melt at 54.4 °C and boil at 55.18 °C under standard pressure. The triple point is 55.10 °C and 1010 hPa (758 Torr).[11]

The volatility of NpF6 is similar to those of UF6 and PuF6, all three being actinide hexafluorides. The standard molar entropy is 229.1 ± 0.5 J·K−1·mol−1. Solid NpF6 is paramagnetic, with a magnetic susceptibility of 165·10−6 cm3·mol−1.[12][13]

### Chemical properties

Neptunium hexafluoride is stable in dry air. However, it reacts vigorously with water, including atmospheric moisture, to form the water-soluble neptunyl fluoride (NpO2F2) and hydrofluoric acid (HF).

NpF6 \+ 2 H2O → NpO2F2 \+ 4 HF

It can be stored at room temperature in a quartz or pyrex glass ampoule, provided that there are no traces of moisture or gas inclusions in the glass and any remaining HF has been removed.[6] NpF6 is light-sensitive, decomposing to NpF4 and fluorine.[6]

NpF6 forms complexes with alkali metal fluorides: with caesium fluoride (CsF) it forms CsNpF6 at 25 °C,[14] and with sodium fluoride it reacts reversibly to form Na3NpF8.[15] In either case, the neptunium is reduced to Np(V).

NpF6 \+ CsF → CsNpF6 \+ 1/2 F2
NpF6 \+ 3 NaF → Na3NpF8 \+ 1/2 F2

In the presence of chlorine trifluoride (ClF3) as solvent and at low temperatures, there is some evidence of the formation of an unstable Np(IV) complex.[14]

Neptunium hexafluoride reacts with carbon monoxide (CO) and light to form a white powder, presumably containing neptunium pentafluoride (NpF5) and an unidentified substance.[2]: 732

## Uses

The irradiation of nuclear fuel inside nuclear reactors generates both fission products and transuranic elements, including neptunium and plutonium. The separation of these three elements is an essential component of nuclear reprocessing. Neptunium hexafluoride plays a role in the separation of neptunium from both uranium and plutonium.

In order to separate the uranium (95% of the mass) from spent nuclear fuel, it is first powdered and reacted with elemental fluorine ("direct fluorination"). The resulting volatile fluorides (mainly UF6, small amounts of NpF6) are easily extracted from the non-volatile fluorides of other actinides, like plutonium(IV) fluoride (PuF4), americium(III) fluoride (AmF3), and curium(III) fluoride (CmF3).[16]

The mixture of UF6 and NpF6 is then selectively reduced by pelleted cobalt(II) fluoride, which converts the neptunium hexafluoride to the tetrafluoride but does not react with the uranium hexafluoride, using temperatures in the range of 93 to 204 °C.[17] Another method is using magnesium fluoride, on which the neptunium fluoride is sorbed at 60-70% but not the uranium fluoride.[18]

## References

1. ↑ 1.0 1.1 Gmelins Handbuch der anorganischen Chemie, System Nr. 71, Transurane, Teil C, p. 108–114.
2. ↑ 2.0 2.1 Yoshida, Zenko; Johnson, Stephen G.; Kimura, Takaumi; Krsul, John R.. Neptunium.
3. ↑ Florin, Alan E. (1943) Report MUC-GTS-2165
4. ↑ Fried, Sherman; Davidson, Norman (1948). "The Preparation of Solid Neptunium Compounds". J. Am. Chem. Soc. 70 (11): 3539–3547. doi:10.1021/ja01191a003. PMID 18102891. https://pubs.acs.org/doi/abs/10.1021/ja01191a003.
5. ↑ , Glenn T. & Harrison S. Brown"Preparation of Neptunium Hexafluoride" US patent 2982604, published 1961-05-02, issued 1961-04-25
6. ↑ 6.0 6.1 6.2 6.3 Malm, John G.; Weinstock, Bernard; Weaver, E. Eugene (1958). "The Preparation and Properties of NpF6; a Comparison with PuF6". J. Phys. Chem. 62 (12): 1506–1508. doi:10.1021/j150570a009. .
7. ↑ Fried, Sherman; Davidson, Norman (1948). "The Preparation of Solid Neptunium Compounds". J. Am. Chem. Soc. 70 (11): 3539–3547. doi:10.1021/ja01191a003. PMID 18102891.
8. ↑ Trevorrow, L. E.; Gerding, T. J.; Steindler, M. J. (1968) Laboratory Investigations in Support of Fluid-bed Fluoride Volatility Processes, Part XVII, The Fluorination of Neptunium(IV) fluoride and Neptunium(IV) oxide (Argonne National Laboratory Report ANL-7385) 1 January 1968. doi:10.2172/4492135
9. ↑ Trevorrow, L. E.; Gerding, T. J.; Steindler, M. J. (1968). "The Fluorination of Neptunium(IV) Fluoride and Neptunium(IV) Oxide". J. Inorg. Nucl. Chem. 30 (10): 2671–2677. doi:10.1016/0022-1902(68)80394-X. https://www.sciencedirect.com/science/article/abs/pii/002219026880394X.
10. ↑ 10.0 10.1 Eller, P. Gary; Asprey, Larned B.; Kinkead, Scott A.; Swanson, Basil I.; Kissane, Richard J. (1998). "Reactions of Dioxygen Difluoride with Neptunium Oxides and Fluorides". J. Alloys Compd. 269 (1–2): 63–66. doi:10.1016/S0925-8388(98)00005-X. https://www.sciencedirect.com/science/article/abs/pii/S092583889800005X.
11. ↑ Keller C. (1969) Die Chemie des Neptuniums. In: Anorganische Chemie. Fortschritte der Chemischen Forschung, vol 13/1. Springer, Berlin, Heidelberg. doi:10.1007/BFb0051170
12. ↑ Hutchison, Clyde A.; Weinstock, Bernard (1960). "Paramagnetic Resonance Absorption in Neptunium Hexafluoride". J. Chem. Phys. 32 (1): 56. doi:10.1063/1.1700947. Bibcode: 1960JChPh..32...56H. https://aip.scitation.org/doi/10.1063/1.1700947.
13. ↑ Hutchison, Clyde A.; Tsang, Tung; Weinstock, Bernard (1962). "Magnetic Susceptibility of Neptunium Hexafluoride in Uranium Hexafluoride". J. Chem. Phys. 37 (3): 555. doi:10.1063/1.1701373. Bibcode: 1962JChPh..37..555H. https://aip.scitation.org/doi/10.1063/1.1701373.
14. ↑ 14.0 14.1 Peacock, R. D. (1976). "Some Reactions of Neptunium Hexafluoride". J. Inorg. Nucl. Chem. 38 (4): 771–773. doi:10.1016/0022-1902(76)80353-3. https://www.sciencedirect.com/science/article/abs/pii/002219027680353.
15. ↑ Trevorrow, LeVerne E.; T. J., Gerding; Steindler, Martin J. (1968). "Reaction of Neptunium Hexafluoride". Inorg. Chem. 7 (11): 2226–2229. doi:10.1021/ic50069a010. https://pubs.acs.org/doi/abs/10.1021/ic50069a010.
16. ↑ Uhlíř, Jan; Mareček, Martin (2009). "Fluoride Volatility Method for Reprocessing of LWR and FR Fuels". Journal of Fluorine Chemistry 130 (1): 89–93. doi:10.1016/j.jfluchem.2008.07.002.
17. ↑ , Waldo R.; Robert L. Harris & Reynold A. Ledoux"Separation of Neptunium from Uranium Hexafluoride Containing the Same" US patent 3615267, published 1971-10-26, issued 1971-10-26
18. ↑ Nakajima, Tsuyoshi; Groult, Henri, eds (2005). Fluorinated Materials for Energy Conversion. Elsevier. p. 559. ISBN 9780080444727.

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Binary hexafluorides

Known binary hexafluorides|

| Chalcogen binary hexafluorides|

* SF6
* SeF6
* TeF6
* PoF6

|

Noble gas binary hexafluorides|

* XeF6

Transition metal binary hexafluorides|

* MoF6
* TcF6
* RuF6
* RhF6
* WF6
* ReF6
* OsF6
* IrF6
* PtF6

Actinide binary hexafluorides|

* UF6
* NpF6
* PuF6

Predicted binary hexafluorides|

| Noble gas binary hexafluorides|

* KrF6
* RnF6

|

Transition metal binary hexafluorides|

* CrF6
* PdF6

Actinide binary hexafluorides|

* AmF6

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* e

Neptunium compounds

Np(III)|

* NpF3
* NpCl3
* NpBr3
* NpI3

Np(IV)|

* NpF4
* NpCl4
* NpBr4
* NpO2
* Np(C8H8)2

Np(V)|

* NpF5

Np(VI)|

* NpF6

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* e

Salts and covalent derivatives of the fluoride ion

HF |  |  |  | He

|
|
|
|

LiF | BeF2 | BF
BF3
B2F4 | CF4
other compounds | NF3
FN3
N2F2
N2F4
NF5§  | F2O
F2O2
other compounds | F2 | Ne
NaF | MgF2 | AlF
AlF3 | SiF4 | P2F4
PF3
PF5 | S2F2
SF2
SF4
SF6 | ClF
ClF3
ClF5 | Ar
KF | CaF
CaF2 | ScF3 | TiF2
TiF3
TiF4 | VF2
VF3
VF4
VF5 | CrF2
CrF3
CrF4
CrF5
CrF6§  | MnF2 | FeF2
FeF3 | CoF2
CoF3 | NiF2 | CuF
CuF2 | ZnF2 | GaF2
GaF3 | GeF2
GeF4 | AsF3
AsF5 | Se2F2
SeF4
SeF6 | BrF
BrF3
BrF5 | KrF2
RbF | SrF
SrF2 | YF3 | ZrF3
ZrF4 | NbF4
NbF5 | MoF2
MoF3
MoF4
MoF5
MoF6 | TcF4
TcF6 | RuF3
RuF5
RuF6 | RhF3
RhF5
RhF6 | PdF2 | AgF | CdF2 | InF
InF2
InF3 | SnF2
SnF4 | SbF3
SbF5 | Te3F2
TeF4
TeF6 | IF
IF3</br>IF5</br>IF7 | XeF2
XeF4
XeF6
CsF | BaF2 |  | HfF4 | TaF5 | WF2
WF3
WF4
WF5
WF6 | Re3F9
ReF4
ReF5
ReF6
ReF7 | OsF4
OsF5
OsF6 | IrF2
IrF3
IrF4
IrF5
IrF6 | PtF2
PtF4
PtF5
PtF6 | AuF
AuF3
Au2F10
AuF5•F2 | Hg2F2
HgF2
HgF4 | TlF | PbF2
PbF4 | BiF3
BiF5 | PoF2
PoF4
PoF6 | AtF  | RnF2
FrF | RaF2 |  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og
| ↓  |  |
LaF3 | CeF3
CeF4 | PrF3 | NdF2,
NdF3 | PmF3 | SmF2,
SmF3 | EuF2,
EuF3 | GdF3 | TbF3 | DyF2,
DyF3 | HoF3 | ErF3 | TmF2
TmF3 | YbF2
YbF3 | LuF3
AcF3 | ThF4 | PaF5 | UF3
UF4
UF5
UF6 | NpF4
NpF6 | PuF3
PuF6 | AmF2
AmF3 | CmF3 | BkF3 | CfF3 | EsF3 | Fm  | Md  | No  | LrF3

§ means the substance has not been made.

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