Chlorine oxide trifluoride or chlorine trifluoride oxide is a corrosive liquid molecular compound with formula ClOF3. It was developed secretly as a rocket fuel oxidiser.
Names | |
---|---|
IUPAC name
trifluoro(oxo)-λ5-chlorane
| |
Identifiers | |
| |
3D model (JSmol)
|
|
PubChem CID
|
|
| |
| |
Properties | |
ClF3O | |
Molar mass | 108.44 g·mol−1 |
Density | 1.865 |
Melting point | −42 °C (−44 °F; 231 K) |
Boiling point | 29 °C (84 °F; 302 K) |
Structure | |
monoclinic | |
C2/m | |
a = 9.826, b = 12.295, c = 4.901 α = 90°, β = 90.338°, γ = 90°[2]
| |
Lattice volume (V)
|
592.1 |
Formula units (Z)
|
8 |
Hazards | |
GHS labelling: | |
Danger | |
Related compounds | |
Related compounds
|
BrOF3; IOF3 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
|
Chlorine oxide trifluoride was originally made at Rocketdyne[3] by treating dichlorine monoxide with fluorine. Other substances that could react with fluorine to make it includes sodium chlorite (NaClO2), and chlorine nitrate (ClONO2). The first published production method was a reaction of dichlorine monoxide with oxygen difluoride (OF2). Yet other production methods are reactions between ClO2F or ClO3F and chlorine fluorides.[4] A safer approach is the use chlorine nitrate with fluorine.
As a Lewis base it can lose a fluoride ion to Lewis acids, yielding the difluorooxychloronium(V) cation (ClOF2+).[5] Compounds with this include: ClOF2BF4, ClOF2PF6, ClOF2AsF6, ClOF2SbF6, ClOF2BiF6, ClOF2VF6, ClOF2NbF6, ClOF2TaF6, ClOF2UF6, ClOF2, (ClOF2)2SiF6, ClOF2MoOF5, ClOF2Mo2O4F9,[4] ClOF2PtF6.[6]
Functioning as a Lewis acid, it can gain a fluoride ion from a strong base to yield a tetrafluorooxychlorate(V) anion: ClOF4− ion.[7] These include KClOF4, RbClOF4, and CsClOF4.[8] This allows purification of ClOF3, as at room temperature a solid complex is formed, but this decomposes between 50 and 70 °C. Other likely impurities either will not react with alkali fluoride, or if they do will not easily decompose.[3]
Chlorine trifluoride oxide fluoridates various materials such as chlorine monoxide, chlorine, glass or quartz.[3] ClOF3 + Cl2O → 2ClF + ClO2F;[6] 2ClOF3 + 2Cl2 → 6ClF + O2 at 200 °C[6]
Chlorine trifluoride oxide adds to chlorine fluorosulfate, ClOF3 + 2ClOSO2F → S2O5F2 + FClO2 + 2ClF. The reaction also produces SO2F2.[3]
Chlorine trifluoride oxide can fluoridate and add oxygen in the same reaction, reacting with molybdenum pentafluoride, silicon tetrafluoride, tetrafluorohydrazine (over 100 °C), HNF2, and F2NCOF. From HNF2 the main result was NF3O. From MoF5, the results were MoF6 and MoOF4.[3]
It reacts explosively with hydrocarbons.[3] With small amounts of water, ClO2F is formed along with HF.[3]
Over 280 °C ClOF3 decomposes to oxygen and chlorine trifluoride.[3]
The boiling point of chlorine trifluoride oxide is 29 °C.[9]
The shape of the molecule is a trigonal bipyramid, with two fluorine atoms at the top and bottom (apex) (Fa) and an electron pair, oxygen and fluorine (Fe) on the equator.[7] The Cl=O bond length is 1.405 Å, Cl-Fe 1.603 Å, other Cl-Fa 1.713 Å, ∠FeClO=109° ∠FaClO=95°, ∠FaClFe=88°. The molecule is polarised, Cl has a +1.76 charge, O has −0.53, equatorial F has −0.31 and apex F has −0.46. The total dipole moment is 1.74 D.[10]