Nitrosyl perchlorate
Structure of nitrosyl perchlorate
Names
IUPAC name
Perchloryl nitrite
Other names
Nitrosyl perchlorate
Perchloric nitrous anhydride
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/ClNO5/c3-1(4,5)7-2-6
    Key: ONKVXKHGDFDPFZ-UHFFFAOYSA-N
  • N(=O)OCl(=O)(=O)=O
Properties
NOClO4
Molar mass 129.46 g/mol
Appearance white solid
Density 2.169 g/cm3[1]
Melting point 100 °C (212 °F; 373 K) (decomposes)
Reacts
Structure
Rhombic[1]
Thermochemistry
-154.0 kJ/mol[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Nitrosyl perchlorate is the inorganic compound with the formula NO(ClO4). A hygroscopic white solid, it is the salt of the nitrosonium cation with the perchlorate anion. It is an oxidant and strong electrophile, but has fallen out of use with the availability of the closely related salt nitrosonium tetrafluoroborate NO(BF4).

Preparation

Nitrosyl perchlorate was first produced in 1909 by passing dinitrogen trioxide gas into concentrated perchloric acid:[1][2]

N2O3 + 2 HClO4 → 2 NOClO4 + H2O

It can also be prepared by passing dinitrogen trioxide gas into a mixture of sodium perchlorate and sulfuric acid. A much purer product can be produced by reacting dichlorine heptoxide with anhydrous nitric acid.[1]

Structure

The structure of NOClO4 has not been elucidated by X-ray crystallography. However, the Raman spectroscopy of NOClO4 suggests that nitrosyl perchlorate consists of distinct NO+ and ClO4– ions.[3]

Properties

Nitrosyl perchlorate decomposes at 100 °C to nitronium perchlorate, which then subsequently decomposes into chlorine and nitrogen oxides.[4][5]

This compound hydrolyzes in water to form nitrous acid and perchloric acid:[4]

NOClO4 + H2O → HNO2 + HClO4

With a strong base, such as sodium hydroxide, it produces perchlorate, nitrite, nitrate, nitric oxide, and water. This reaction was used to calculate the heat of formation of nitrosyl perchlorate. As a strong oxidizer, nitrosyl perchlorate reacts explosively with various organic compounds, such as ethanol, acetone, ether, and aniline.[2][4]

Uses

Nitrosyl perchlorate is used in the laboratory as a perchlorating agent.[6][7] Although it has been investigated as a potential rocket propellant, it has not been commercialized.[1]

References

  1. 1 2 3 4 5 6 "Perchlorates: A Review of their Thermal Decomposition and Combustion, with an Appendix on Perchloric Acid" (PDF). R.P.E. Technical Report. 68 (11). 1968. Retrieved 28 December 2023.
  2. 1 2 K. A. Hofmann; Graf Armin Zedtwitz (1909). "Nitrosyl-perchlorat: das Anhydrid der salpetrigen Säure mit der Überchlorsäure" [Nitrosyl perchlorate: the anhydride of nitrous acid with perchloric acid]. Berichte der deutschen chemischen Gesellschaft (in German). 42 (2): 2031–2034. doi:10.1002/cber.19090420285.
  3. ↑ William Rogie Angus; Alan H. Leckie (1935). "Investigations of raman spectra II—The raman spectra of perchloric acid and nitrosyl perchlorate". Proceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences. 150 (871): 615–618. doi:10.1098/rspa.1935.0125.
  4. 1 2 3 Markowitz, Meyer M.; Ricci, John E.; Goldman, Richard J.; Winternitz, Paul F. (1 July 1957). "The Chemical Properties of Nitrosyl Perchlorate: The Neutralization Equivalent". J. Am. Chem. Soc. 79 (14): 3659–3661. doi:10.1021/ja01571a013. Retrieved 31 October 2023.
  5. ↑ Glasner, A.; Pelly, I.; Steinberg, M. (4 February 1969). "Thermal decomposition of nitrosyl perchlorate and nitryl perchlorate—I: Mechanism of decomposition". J. Inorg. Nucl. Chem. 31: 3395–3404. doi:10.1016/0022-1902(69)80322-2. Retrieved 31 October 2023.
  6. ↑ Thomas J. Wierenga; J. Ivan Legg (1982). "Synthesis and characterization of cobalt(III) nicotinic acid complexes". Inorganic Chemistry. 21 (7): 2881–2885. doi:10.1021/ic00137a071.
  7. ↑ M.M. Markowitz; J.E. Ricci; R.J. Goldman; P.F. Winternitz (1960). "A new method for the conversion of inorganic salts to the corresponding perchlorates". Journal of Inorganic and Nuclear Chemistry. 16 (1–2): 159–161. doi:10.1016/0022-1902(60)80104-2.
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