Fluorine azide

Fluorine azide
Names
Other names
triazadienyl fluoride
Identifiers
CAS Number
  • 14986-60-8 checkY
3D model (JSmol)
  • Interactive image
PubChem CID
  • 23235952
CompTox Dashboard (EPA)
  • DTXSID40631418 Edit this at Wikidata
InChI
  • InChI=1S/FN3/c1-3-4-2
    Key: AJXWEJAGUZJGRI-UHFFFAOYSA-N
  • [N-]=[N+]=NF
Properties
Chemical formula
FN3
Molar mass 61.019 g/mol
Appearance Yellow-green gas
Melting point −139 °C (−218 °F; 134 K)
Boiling point −30 °C (−22 °F; 243 K)
Explosive data
Shock sensitivity Extreme
Friction sensitivity Extreme
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Extremely sensitive explosive
NFPA 704 (fire diamond)
[citation needed]
NFPA 704 four-colored diamondHealth (blue): no hazard codeFlammability 0: Will not burn. E.g. waterInstability 4: Readily capable of detonation or explosive decomposition at normal temperatures and pressures. E.g. nitroglycerinSpecial hazards (white): no code
0
4
Related compounds
Other cations
Hydrazoic acid
Chlorine azide
Bromine azide
Iodine azide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
Chemical compound

Fluorine azide or triazadienyl fluoride is a yellow green gas composed of nitrogen and fluorine with formula FN3.[1] Its properties resemble those of ClN3, BrN3, and IN3.[2] The bond between the fluorine atom and the nitrogen is very weak, leading to this substance being very unstable and prone to explosion.[3] Calculations show the F–N–N angle to be around 102° with a straight line of 3 nitrogen atoms.[4]

The gas boils at –30° and melts at –139 °C.[5]

It was first made by John F. Haller in 1942.[6]

Reactions

Fluorine azide can be made by reacting hydrazoic acid or sodium azide, with fluorine gas.[5][7]

HN3 + F2 → N3F + HF
NaN3 + F2 → N3F + NaF

Fluorine azide decomposes without explosion at normal temperatures to make dinitrogen difluoride:

2 FN3 → N2F2 + 2 N2.[1]

At higher temperatures such as 1000 °C fluorine azide breaks up into nitrogen monofluoride radical:[7]

FN3 → NF + N2

The FN itself dimerizes on cooling.

2 NF → N2F2

Solid or liquid FN3 can explode, releasing a large amount of energy. A thin film burns at the rate of 1.6 km/s.[8] Due to the explosion hazard, only very small quantities of this substance should be handled at a time.[9]

FN3 adducts can be formed with the Lewis acids boron trifluoride (BF3) and arsenic pentafluoride (AsF5) at -196 °C. These molecules bond with the first nitrogen atom from the fluorine.[10]

Properties

Spectroscopy

Parameter Value[9] Unit
A 48131.448 MHz
B 5713.266 MHz
C 5095.276 MHz
μa 1.1
μb 0.7

Shape

Distances between atoms are F–N 0.1444 nm, FN=NN 0.1253 nm and FNN=N 0.1132 nm.[9]

Physical

FN3 has a density of 1.3 g/cm3.[11]

FN3 adsorbs on to solid surfaces of potassium fluoride, but not onto lithium fluoride or sodium fluoride. This property was being investigated so that FN3 could boost the energy of solid propellants.[11]

The ultraviolet photoelectric spectrum shows ionisation peaks at 11.01, 13,72, 15.6, 15.9, 16.67, 18.2, and 19.7 eV. Respectively these are assigned to the orbitals: π, nN or nF, nF, πF, nN or σ, π and σ.[3]

References

  1. ^ a b Gipstein, Edward; John F. Haller (1966). "Absorption Spectrum of Fluorine Azide". Applied Spectroscopy. 20 (6): 417–418. Bibcode:1966ApSpe..20..417G. doi:10.1366/000370266774386470. ISSN 0003-7028. S2CID 96337253.
  2. ^ Saxena, P. B. (2007-01-01). Chemistry of Interhalogen Compounds. Discovery Publishing House. p. 96. ISBN 9788183562430. Retrieved 16 June 2014.
  3. ^ a b Rademacher, Paul; Andreas J. Bittner; Gabriele Schatte; Helge Willner (1988). "Photoelectron Spectrum and Electronic Structure of Triazadienyl Fluoride, N3F". Chemische Berichte. 121 (3): 555–557. doi:10.1002/cber.19881210325. ISSN 0009-2940.
  4. ^ Peters, Nancy J. S.; Leland C. Allen; Raymond A. Firestone (1988). "Fluorine azide and fluorine nitrate: structure and bonding". Inorganic Chemistry. 27 (4): 755–758. doi:10.1021/ic00277a035. ISSN 0020-1669.
  5. ^ a b Gholivand, Khodayar; Gabriele Schatte; Helge Willner (1987). "Properties of triazadienyl fluoride, N3F". Inorganic Chemistry. 26 (13): 2137–2140. doi:10.1021/ic00260a025. ISSN 0020-1669.
  6. ^ Lowe, Derek (21 October 2008). "Things I Won't Work With: Triazadienyl Fluoride". In the Pipeline. Retrieved 15 June 2014.
  7. ^ a b Benard, D. J.; B. K. Winker; T. A. Seder; R. H. Cohn (1989). "Production of nitrogen monofluoride (a1Δ) by dissociation of fluorine azide". The Journal of Physical Chemistry. 93 (12): 4790–4796. doi:10.1021/j100349a022. ISSN 0022-3654.
  8. ^ Seder, T.A.; D.J. Benard (1991). "The decomposition of condensed phase fluorine azide". Combustion and Flame. 85 (3–4): 353–362. doi:10.1016/0010-2180(91)90139-3. ISSN 0010-2180.
  9. ^ a b c Christen, Dines.; H. G. Mack; G. Schatte; H. Willner (1988). "Structure of triazadienyl fluoride, FN3, by microwave, infrared, and ab initio methods". Journal of the American Chemical Society. 110 (3): 707–712. doi:10.1021/ja00211a007. ISSN 0002-7863.
  10. ^ Schatte, G.; H. Willner (1991). "Die Wechselwirkung von N3F mit Lewis-Säuren und HF. N3F als möglicher Vorläufer für die Synthese von N3+-Salzen = The interaction of N3F with Lewis acids and HF•N3F as possible precursor for the synthesis of N3+ salts". Zeitschrift für Naturforschung B (in German). 46 (4): 483–489. doi:10.1515/znb-1991-0410. ISSN 0932-0776. S2CID 97045269.
  11. ^ a b Brener, Nathan E.; Kestner, Neil R.; Callaway, Joseph (December 1990). Theoretical Studies of Highly Energetic CBES Materials: Final Report for the Period 2 March 1987 to 31 May 1987 (PDF). Louisiana State University, Department of Physics and Astronomy. pp. 21–27. Archived (PDF) from the original on March 3, 2016. Retrieved 25 June 2014.
  • Media related to Fluorine azide at Wikimedia Commons
  • v
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  • v
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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 ZrF2
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
PF6, AsF6, SbF6 compounds
  • AgPF6
  • KAsF6
  • LiAsF6
  • NaAsF6
  • HPF6
  • HSbF6
  • NH4PF6
  • LiSbF6
  • KPF6
  • KSbF6
  • LiPF6
  • NaPF6
  • NaSbF6
  • TlPF6
AlF6 compounds
  • (NH4)3[AlF6]
  • Cs2AlF5
  • Li3AlF6
  • K3AlF6
  • Na3AlF6
chlorides, bromides, iodides
and pseudohalogenides
SiF62-, GeF62- compounds
  • BaSiF6
  • BaGeF6
  • (NH4)2SiF6
  • Na2[SiF6]
  • K2[SiF6]
  • Li2GeF6
  • Li2SiF6
Oxyfluorides
  • BrOF3
  • BrO2F
  • BrO3F
  • LaOF
  • ThOF2
  • VOF
    3
  • TcO
    3
    F
  • WOF
    4
  • YOF
  • ClOF3
  • ClO2F3
Organofluorides
  • CBrF3
  • CBr2F2
  • CBr3F
  • CClF3
  • CCl2F2
  • CCl3F
  • CF2O
  • CF3I
  • CHF3
  • CH2F2
  • CH3F
  • C2Cl3F3
  • C2H3F
  • C6H5F
  • C7H5F3
  • C15F33N
  • C3H5F
  • C6H11F
with transition metal,
lanthanide, actinide, ammonium
  • VOF3
  • CrOF4
  • CrF2O2
  • NH4F
  • (NH4)3CrF6
  • (NH4)3GaF6
  • (NH4)2GeF6
  • (NH4)3FeF6
  • (NH4)3InF6
  • NH4NbF6
  • (NH4)2SnF6
  • NH4TaF6
  • (NH4)3VF6
  • (NH4)2ZrF6
  • CsXeF7
  • Li2SnF6
  • Li2TiF6
  • LiWF6
  • Li2ZrF6
  • K2TiF6
  • Rb2TiF6
  • Na2TiF6
  • Na2ZrF6
  • K2NbF7
  • K2TaF7
  • K2ZrF6
  • UO2F2
nitric acids
bifluorides
  • KHF2
  • NaHF2
  • NH4HF2
thionyl, phosphoryl,
and iodosyl
  • F2OS
  • F3OP
  • PSF3
  • IOF3
  • IO3F
  • IOF5
  • IO2F
  • IO2F3
  • v
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Nitrogen species
Hydrides
  • NH3
  • NH4+
  • NH2
  • N3−
  • NH2OH
  • N2H4
  • HN3
  • N3
  • NH5 (?)
Organic
Oxides
  • NO / (NO)2
  • N2O3
  • HNO2 / NO
    2
     / NO+
  • NO2 / (NO2)2
  • N2O5
  • HNO3 / NO
    3
     / NO+
    2
  • NO3
  • HNO / (HON)2 / N2O2−
    2
     / N2O
  • H2NNO2
  • HO2NO / ONOO
  • HO2NO2 / O2NOO
  • NO3−
    4
  • H4N2O4 / N2O2−
    3
Halides
  • NF
  • NF2
  • NF3
  • NF5 (?)
  • NCl3
  • NBr3
  • NI3
  • FN3
  • ClN3
  • BrN3
  • IN3
  • NH2F
  • N2F2
  • NH2Cl
  • NHF2
  • NHCl2
  • NHBr2
  • NHI2
Oxidation states
−3, −2, −1, 0, +1, +2, +3, +4, +5 (a strongly acidic oxide)
  • v
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Salts and covalent derivatives of the azide ion
HN3 He
LiN3 Be(N3)2 B(N3)3 CH3N3
C(N3)4
CO(N3)2
NH4N3
N3NO
N(N3)3
H2N–N3
O FN3 Ne
NaN3 Mg(N3)2 Al(N3)3 Si(N3)4 P SO2(N3)2 ClN3 Ar
KN3 Ca(N3)2 Sc(N3)3 Ti(N3)4 VO(N3)3 Cr(N3)3
CrO2(N3)2
Mn(N3)2 Fe(N3)2
Fe(N3)3
Co(N3)2
Co(N3)3
Ni(N3)2 CuN3
Cu(N3)2
Zn(N3)2 Ga(N3)3 Ge As(N3)5 Se(N3)4 BrN3 Kr
RbN3 Sr(N3)2 Y(N3)3 Zr(N3)4 Nb Mo Tc Ru(N3)63− Rh(N3)63− Pd(N3)2 AgN3 Cd(N3)2 In Sn Sb(N3)5 Te(N3)4 IN3 Xe(N3)2
CsN3 Ba(N3)2 * Lu(N3)3 Hf Ta W Re Os Ir(N3)63− Pt(N3)62− Au(N3)4 Hg2(N3)2
Hg(N3)2
TlN3 Pb(N3)2 Bi(N3)3 Po At Rn
Fr Ra(N3)2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* La(N3)3 Ce(N3)3
Ce(N3)4
Pr Nd Pm Sm(N3)3 Eu(N3)2
Eu(N3)3
Gd(N3)3 Tb Dy(N3)3 Ho(N3)3 Er Tm Yb(N3)3
** Ac(N3)3 Th(N3)4 Pa UO2(N3)2 Np Pu Am Cm Bk Cf Es Fm Md No