Chloryl fluoride

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Chloryl fluoride
Chloryl fluoride.svg
Chloryl-fluoride-3D-vdW.png
Names
Other names
chlorine dioxide fluoride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/ClFO2/c2-1(3)4 X mark.svgN
    Key: YVRLYFHVJLYEHM-UHFFFAOYSA-N X mark.svgN
  • InChI=1/ClFO2/c2-1(3)4
    Key: YVRLYFHVJLYEHM-UHFFFAOYAO
  • FCl(=O)=O
Properties
ClFO2
Molar mass 86.45 g·mol−1
Density 3.534 g/L
Melting point −115 °C
Boiling point −6 °C
Related compounds
Related compounds
 Perchloryl fluoride
Chloryl trifluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Chloryl fluoride is the chemical compound with the formula ClO2F. It is commonly encountered as side-product in reactions of chlorine fluorides with oxygen sources. [1] It is the acyl fluoride of chloric acid.

Contents

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. This species is a gas boiling at −6 °C:

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

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