Nitryl fluoride
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ECHA InfoCard | 100.030.007 | ||
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InChI
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Properties | |||
Chemical formula | FNO2 | ||
Molar mass | 65.003 g·mol−1 | ||
Melting point | −166 °C (−267 °F; 107 K) | ||
Boiling point | −72 °C (−98 °F; 201 K) | ||
Related compounds | |||
Other anions | nitryl chloride, nitryl bromide | ||
Other cations | nitrosyl fluoride, sulfuryl fluoride | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is YN ?) Infobox references |
Nitryl fluoride, NO2F, is a colourless gas and strong oxidizing agent, which is used as a fluorinating agent[1] and has been proposed as an oxidiser in rocket propellants (though never flown).
It is a molecular species, not ionic, consistent with its low boiling point. The structure features planar nitrogen with a short N-F bond length of 135 pm.[2]
Preparation
Henri Moissan and Paul Lebeau recorded the preparation of nitryl fluoride in 1905 by the fluorination of nitrogen dioxide. This reaction is highly exothermic, which leads to contaminated products. The simplest method avoids fluorine gas but uses cobalt(III) fluoride:[3]
- NO2 + CoF3 → NO2F + CoF2
The CoF2 can be regenerated to CoF3. Other methods have been described.[4]
Thermodynamic properties
The thermodynamic properties of this gas were determined by IR and Raman spectroscopy[5] The standard heat of formation of FNO2 is -19 ± 2 kcal/mol.3
- The equilibrium of the unimolecular decomposition of FNO2 lies on the side of the reactants by at least six orders of magnitude at 500 kelvin, and two orders of magnitude at 1000 kelvin.[5]
- The homogeneous thermal decomposition cannot be studied at temperatures below 1200 kelvin.[5]
- The equilibrium shifts towards the reactants with increasing temperature.[5]
- The dissociation energy of 46.0 kcal of the N-F bond in nitryl fluoride is about 18 kcal less than the normal N-F single bond energy. This can be attributed to the “reorganization energy” of the NO2 radical; that is, the NO2 radical in FNO2 is less stable than the free NO2 molecule. Qualitatively speaking, the odd electron “used up” in the N-F bond forms a resonating three-electron bond in free NO2, thus stabilizing the molecule with a gain of 18 kcal.[5]
Reactions
Nitryl fluoride can be used to prepare organic nitro compounds and nitrate esters.
See also
References
- ^ Merck Index, 13th edition (2001), p.1193
- ^ F. A. Cotton and G.Wilkinson, Advanced Inorganic Chemistry, 5th edition (1988), Wiley, p.333.
- ^ Davis, Ralph A.; Rausch, Douglas A. (1963). "Preparation of Nitryl Fluoride". Inorganic Chemistry. 2 (6): 1300–1301. doi:10.1021/ic50010a048.
- ^ Faloon, Albert V.; Kenna, William B. (1951). "The Preparation of Nitrosyl Fluoride and Nitryl Fluoride1". Journal of the American Chemical Society. 73 (6): 2937–2938. doi:10.1021/ja01150a505. hdl:2027/mdp.39015095101013. ISSN 0002-7863.
- ^ a b c d e Tschuikow-Roux, E. (1962). "Thermodynamic Properties of Nitryl Fluoride". Journal of Physical Chemistry. 66 (9): 1636–1639. doi:10.1021/j100815a017.
External links
- WebBook page for NO2F
- National Pollutant Inventory - Ionic Fluoride and related compounds fact sheet
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HF | He | |||||||||||||||||
LiF | BeF2 | BF BF3 B2F4 | CF4 CxFy | NF3 N2F4 | OF OF2 O2F2 O2F | F− | Ne | |||||||||||
NaF | MgF2 | AlF AlF3 | SiF4 | P2F4 PF3 PF5 | S2F2 SF2 S2F4 SF4 S2F10 SF6 | ClF ClF3 ClF5 | HArF ArF2 | |||||||||||
KF | CaF2 | ScF3 | TiF3 TiF4 | VF2 VF3 VF4 VF5 | CrF2 CrF3 CrF4 CrF5 CrF6 | MnF2 MnF3 MnF4 | FeF2 FeF3 | CoF2 CoF3 | NiF2 NiF3 | CuF CuF2 | ZnF2 | GaF3 | GeF4 | AsF3 AsF5 | SeF4 SeF6 | BrF BrF3 BrF5 | KrF2 KrF4 KrF6 | |
RbF | SrF2 | YF3 | ZrF4 | NbF4 NbF5 | MoF4 MoF5 MoF6 | TcF6 | RuF3 RuF4 RuF5 RuF6 | RhF3 RhF5 RhF6 | PdF2 Pd[PdF6] PdF4 PdF6 | AgF AgF2 AgF3 Ag2F | CdF2 | InF3 | SnF2 SnF4 | SbF3 SbF5 | TeF4 TeF6 | IF IF3 IF5 IF7 | XeF2 XeF4 XeF6 XeF8 | |
CsF | BaF2 | * | LuF3 | HfF4 | TaF5 | WF4 WF6 | ReF6 ReF7 | OsF4 OsF5 OsF6 OsF 7 OsF8 | IrF3 IrF5 IrF6 | PtF2 Pt[PtF6] PtF4 PtF5 PtF6 | AuF AuF3 Au2F10 AuF5·F2 | HgF2 Hg2F2 HgF4 | TlF TlF3 | PbF2 PbF4 | BiF3 BiF5 | PoF4 PoF6 | At | RnF2 RnF6 |
Fr | RaF2 | ** | Lr | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og |
↓ | ||||||||||||||||||
* | LaF3 | CeF3 CeF4 | PrF3 PrF4 | NdF3 | PmF3 | SmF2 SmF3 | EuF2 EuF3 | GdF3 | TbF3 TbF4 | DyF3 | HoF3 | ErF3 | TmF2 TmF3 | YbF2 YbF3 | ||||
** | AcF3 | ThF4 | PaF4 PaF5 | UF3 UF4 UF5 UF6 | NpF3 NpF4 NpF5 NpF6 | PuF3 PuF4 PuF5 PuF6 | AmF3 AmF4 AmF6 | CmF3 | Bk | Cf | Es | Fm | Md | No |
- AgPF6
- KAsF6
- LiAsF6
- NaAsF6
- HPF6
- HSbF6
- NH4PF6
- KPF6
- KSbF6
- LiPF6
- NaPF6
- NaSbF6
- TlPF6
- Cs2AlF5
- K3AlF6
- Na3AlF6
and pseudohalogenides
- BaSiF6
- BaGeF6
- (NH4)2SiF6
- Na2[SiF6]
- K2[SiF6]
- CBrF3
- CBr2F2
- CBr3F
- CClF3
- CCl2F2
- CCl3F
- CF2O
- CF3I
- CHF3
- CH2F2
- CH3F
- C2Cl3F3
- C2H3F
- C6H5F
- C7H5F3
- C15F33N
- C3H5F
- C6H11F
lanthanide, actinide, ammonium
- VOF3
- CrOF4
- CrF2O2
- NH4F
- (NH4)2ZrF6
- CsXeF7
- Li2TiF6
- Li2ZrF6
- K2TiF6
- Rb2TiF6
- Na2TiF6
- Na2ZrF6
- K2NbF7
- K2TaF7
- K2ZrF6
- UO2F2
- FNO
- FNO2
- FNO3
- KHF2
- NaHF2
- NH4HF2
and iodosyl
- F2OS
- F3OP
- PSF3
- IOF3
- IO3F
- IOF5
- IO2F
- IO2F3