Chloryl fluoride

Chloryl fluoride
Names
	Other names Chlorine dioxide fluoride; Chlorine(V) fluoride dioxide;
Identifiers
CAS Number	13637-83-7 ;
3D model (JSmol)	Interactive image;
ChemSpider	123044 ;
PubChem CID	139523;
CompTox Dashboard (EPA)	DTXSID00159769 ;
	InChI InChI=1S/ClFO2/c2-1(3)4 Key: YVRLYFHVJLYEHM-UHFFFAOYSA-N ; InChI=1/ClFO2/c2-1(3)4 Key: YVRLYFHVJLYEHM-UHFFFAOYAO;
	SMILES FCl(=O)=O;
Properties
Chemical formula	ClO2F
Molar mass	86.45 g·mol−1
Appearance	Colorless gas
Density	3.534 g/L
Melting point	−115 °C
Boiling point	−6 °C
Related compounds
Related compounds	Bromyl fluoride; Iodyl fluoride; Perchloryl fluoride; Chloryl trifluoride;
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Chloryl fluoride is the chemical compound with the formula Cl O₂F. This compound is a gas boiling at −6 °C. It is commonly encountered as side-product in reactions of chlorine fluorides with oxygen sources.^[1] It is the acyl fluoride of chloric acid.

Preparation

ClO₂F was first reported by Schmitz and Schumacher in 1942, who prepared it by the fluorination of ClO₂.^[2] The compound is more conveniently prepared by reaction of sodium chlorate and chlorine trifluoride^[3] and purified by vacuum fractionation, i.e. selectively condensing this species separately from other products.

6 NaClO₃ + 4 ClF₃ → 6 ClO₂F + 2 Cl₂ + 3 O₂ + 6 NaF

Structure

In contrast to O₂F₂, ClO₂F is a pyramidal molecule as predicted by VSEPR. The differing structures reflects the greater tendency of chlorine to exist in positive oxidation states with oxygen and fluorine ligands. The related Cl-O-F compound perchloryl fluoride, ClO₃F, is tetrahedral. The related bromine compound bromyl fluoride (BrO₂F) adopts the same structure as ClO₂F, whereas iodyl fluoride (IO₂F) forms a polymeric substance under standard conditions.^[4]

Precautions

Rocket fuel chemist John Drury Clark reported in his book Ignition! that chloryl fluoride "is indecently reactive, and the hardest to keep of all the CI-O-F compounds, since it apparently dissolves the protective metal fluoride coatings that make the storage of ClF₃ comparatively simple."^[5]

References

^ Christe, K. O.; Wilson, R. D.; Schack, C. J. "Chloryl fluoride" Inorganic Syntheses, 1986, volume 24, pages 3–5. ISBN 0-471-83441-6 https://onlinelibrary.wiley.com/doi/10.1002/9780470132555.ch2
^ Schmitz, H.; Schumacheb, H. J. (1942-04-29). "Über eine neue Reaktion des Chlordioxyds. Die Bildung einer Verbindung der Formel ClO2F". Zeitschrift für anorganische und allgemeine Chemie (in German). 249 (3). Wiley: 238–244. doi:10.1002/zaac.19422490302. ISSN 0863-1786.
^ Wiberg, Egon; Wiberg, Nils; Holleman, A. F. (2001). Inorganic chemistry. San Diego: Academic Press. p. 1797. ISBN 0-12-352651-5. OCLC 48056955.
^ Holleman, A.F.; Wiberg, E.; Wiberg, N. (1995). Lehrbuch der anorganischen Chemie. de Gruyter. p. 501. ISBN 9783110126419. Retrieved 2015-02-20.
^ Clark, John Drury (23 May 2018). Ignition!: An Informal History of Liquid Rocket Propellants. Rutgers University Press. p. 302. ISBN 978-0-8135-9918-2. OCLC 281664.

External links

WebBook page for ClO2F

[1] Christe, K. O.; Wilson, R. D.; Schack, C. J. "Chloryl fluoride" Inorganic Syntheses, 1986, volume 24, pages 3–5. ISBN 0-471-83441-6 https://onlinelibrary.wiley.com/doi/10.1002/9780470132555.ch2

[2] Schmitz, H.; Schumacheb, H. J. (1942-04-29). "Über eine neue Reaktion des Chlordioxyds. Die Bildung einer Verbindung der Formel ClO2F". Zeitschrift für anorganische und allgemeine Chemie (in German). 249 (3). Wiley: 238–244. doi:10.1002/zaac.19422490302. ISSN 0863-1786.

[3] Wiberg, Egon; Wiberg, Nils; Holleman, A. F. (2001). Inorganic chemistry. San Diego: Academic Press. p. 1797. ISBN 0-12-352651-5. OCLC 48056955.

[google-4] Holleman, A.F.; Wiberg, E.; Wiberg, N. (1995). Lehrbuch der anorganischen Chemie. de Gruyter. p. 501. ISBN 9783110126419. Retrieved 2015-02-20.

[Clark2018-5] Clark, John Drury (23 May 2018). Ignition!: An Informal History of Liquid Rocket Propellants. Rutgers University Press. p. 302. ISBN 978-0-8135-9918-2. OCLC 281664.

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