Isocyanic acid

Isocyanic acid is a chemical compound with the structural formula HNCO, which is often written as H−N=C=O. It is a colourless, volatile and poisonous substance, with a boiling point of 23.5 °C. It is the predominant tautomer and an isomer of cyanic acid (aka. cyanol) (H−O−C≡N).

"Cyanol" redirects here. For the blue coal-tar dye, see Aniline.
Isocyanic acid
Names
IUPAC name
Isocyanic acid
Other names
Carbimide[1]
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.109.068
UNII
  • InChI=1S/CHNO/c2-1-3/h2H checkY
    Key: OWIKHYCFFJSOEH-UHFFFAOYSA-N checkY
  • InChI=1/CHNO/c2-1-3/h2H
    Key: OWIKHYCFFJSOEH-UHFFFAOYAE
  • Isocyanic acid: O=C=N
  • Cyanic acid: OC#N
Properties
HNCO
Molar mass 43.025 g·mol−1
Appearance Colorless liquid or gas (boiling point near room temperature)
Density 1.14 g/cm3 (20 °C)
Melting point −86 °C (−123 °F; 187 K)[2]
Boiling point 23.5 °C (74.3 °F; 296.6 K)
Dissolves
Solubility Soluble in benzene, toluene, diethyl ether
Conjugate acid Oxomethaniminium[3]
Conjugate base Cyanate
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Poisonous
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)
Infobox references

The derived anion of isocyanic acid is the same as the derived anion of cyanic acid, and that anion is [N=C=O]−, which is called cyanate. The related functional group −N=C=O is isocyanate; it is distinct from cyanate (−O−C≡N), fulminate (−O−N+≡C−), and nitrile oxide (−C≡N+−O−).[4]

Isocyanic acid was discovered in 1830 by Justus von Liebig and Friedrich Wöhler.[5]

Isocyanic acid is the simplest stable chemical compound that contains carbon, hydrogen, nitrogen, and oxygen, the four most commonly found elements in organic chemistry and biology. It is the only fairly stable one of the four linear isomers with molecular formula HOCN that have been synthesized, the others being cyanic acid (cyanol, H−O−C≡N) and the elusive fulminic acid (H−C≡N+−O−)[6] and isofulminic acid H−O−N+≡C−.[4][7]

Structure

Isocyanic acid (HNCO)

Although the electronic structure according to valence bond theory can be written as H−N=C=O, the vibrational spectrum has a band at 2268.8 cm−1 in the gas phase, which some say indicates a carbon–nitrogen triple bond.[8][9] If so, then the canonical form H−N+≡C−O− is the major resonance structure.

However, classic vibrational analysis would indicate that the 2268.8 cm−1 is the asymmetric N=C=O stretch, as per Colthup et al.[10], as well as the NIST Chemistry WebBook, [11] which also reports the corresponding symmetric N=C=O stretch (weak in infrared, but strong in Raman) to be 1327 cm−1. Based on these classic assignments, there is no need to invoke a full charged state for the N and O atoms, to explain the vibrational spectral data.

Cyanic acid (HOCN)

The tautomer, known as cyanic acid, HOCN, in which the oxygen atom is protonated exists in equilibrium with isocyanic acid to the extent of about 3%. The vibrational spectrum is indicative of the presence of a triple bond between the nitrogen and carbon atoms.[12]

Properties

In aqueous solution it is a weak acid, having a pKa of 3.7:[13]

HNCO ⇌ H+ + NCO−

Isocyanic acid hydrolyses to carbon dioxide and ammonia:

HNCO + H2O → CO2 + NH3

Dilute solutions of isocyanic acid are stable in inert solvents, e.g. ether and chlorinated hydrocarbons.[14]

At high concentrations, isocyanic acid oligomerizes to give the trimer cyanuric acid and cyamelide, a polymer. These species usually are easily separated from liquid- or gas-phase reaction products.

Isocyanic acid reacts with amines to give ureas (carbamides):

HNCO + RNH2 → RNHC(O)NH2

This reaction is called carbamylation.

HNCO adds across electron-rich double bonds, such as vinylethers, to give the corresponding isocyanates.

Isocyanic acid, HNCO, is a Lewis acid whose free energy, enthalpy and entropy changes for its 1:1 association with a number of bases in carbon tetrachloride solution at 25 °C have been reported.[15] The acceptor properties of HNCO are compared with other Lewis acid in the ECW model.

Low-temperature photolysis of solids containing HNCO creates the tautomer cyanic acid H−O−C≡N, also called hydrogen cyanate.[16] Pure cyanic acid has not been isolated, and isocyanic acid is the predominant form in all solvents.[14] Sometimes information presented for cyanic acid in reference books is actually for isocyanic acid.

Preparation

Isocyanic acid can be made by protonation of the cyanate anion, such as from salts like potassium cyanate, by either gaseous hydrogen chloride or acids such as oxalic acid.[17]

HNCO also can be made by the high-temperature thermal decomposition of the trimer cyanuric acid:

In the reverse of the famous synthesis of urea by Friedrich Wöhler,

isocyanic acid is produced and rapidly trimerizes to cyanuric acid.

Occurrence

Isocyanic acid has been detected in many kinds of interstellar environments.[7]

Isocyanic acid is also present in various forms of smoke, including smog and cigarette smoke. It was detected using mass spectrometry, and easily dissolves in water, posing a health risk to the lungs.[18]

See also

References
  1. Cyanamide also has this name, and for which it is more systematically correct
  2. Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  3. "Oxomethaniminium | CH2NO | ChemSpider". www.chemspider.com. Retrieved 27 January 2019.
  4. William R. Martin and David W. Ball (2019): "Small organic fulminates as high energy materials. Fulminates of acetylene, ethylene, and allene". Journal of Energetic Materials, volume 31, issue 7, pages 70-79. doi:10.1080/07370652.2018.1531089
  5. Liebig, J.; Wöhler, F. (1830). "Untersuchungen über die Cyansäuren". Ann. Phys. 20 (11): 394. Bibcode:1830AnP....96..369L. doi:10.1002/andp.18300961102.
  6. Kurzer, Frederick (2000). "Fulminic Acid in the History of Organic Chemistry". Journal of Chemical Education. 77 (7): 851–857. Bibcode:2000JChEd..77..851K. doi:10.1021/ed077p851.
  7. Donghui Quan, Eric Herbst, Yoshihiro Osamura, and Evelyne Roueff (2010): "Gas-grain modeling of isocyanic acid (HNCO), cyanic acid (HOCN), fulminic acid (HCNO), and isofulminic acid (HONC) in assorted interstellar environments" The Astrophysical Journal, volume 725, issue 2, pages doi:10.1088/0004-637X/725/2/2101
  8. Nakamoto, part A, p 190
  9. Teles, Joaquim Henrique; Maier, Günther; Andes Hess, B.; Schaad, Lawrence J.; Winnewisser, Manfred; Winnewisser, Brenda P. (1989). "The CHNO Isomers". Chemische Berichte. 122 (4): 753–766. doi:10.1002/cber.19891220425.
  10. Colthup, Norman B.; Daly, Lawrence H.; Wiberley, Stephen E. (1990). Introduction to Infrared and Raman Spectroscopy. Academic Press (Elsevier). ISBN 978-0-12-182554-6.
  11. "Isocyanic acid". National Institute of Standards and Technology (U.S. Department of Commerce). Retrieved 2023-04-20.
  12. Teles, Joaquim Henrique; Maier, Günther; Andes Hess, B.; Schaad, Lawrence J.; Winnewisser, Manfred; Winnewisser, Brenda P. (1989). "The CHNO Isomers". Chem. Ber. 122 (4): 1099–0682. doi:10.1002/cber.19891220425.
  13. IUPAC SC-Database Archived 2017-06-19 at the Wayback Machine A comprehensive database of published data on equilibrium constants of metal complexes and ligands
  14. A. S. Narula, K. Ramachandran “Isocyanic Acid” in Encyclopedia of Reagents for Organic Synthesis, 2001, John Wiley & Sons, New York. doi:10.1002/047084289X.ri072m Article Online Posting Date: April 15, 2001.
  15. Nelson, J. (1970) Hydrogen-bonded complexes of isocyanic acid: Infrared spectra and thermodynamic measurements. Spectrochimica Acta Part A: Molecular Spectroscopy 26,109-120.
  16. Jacox, M.E.; Milligan, D.E. (1964). "Low-Temperature Infrared Study of Intermediates in the Photolysis of HNCO and DNCO". Journal of Chemical Physics. 40 (9): 2457–2460. Bibcode:1964JChPh..40.2457J. doi:10.1063/1.1725546.
  17. Fischer, G.; Geith, J.; Klapötke, T. M.; Krumm B. (2002). "Synthesis, Properties and Dimerization Study of Isocyanic Acid" (PDF). Z. Naturforsch. 57b (1): 19–25. doi:10.1515/znb-2002-0103. S2CID 37461221.
  18. Preidt, Robert. "Chemical in Smoke May Pose Health Risk". MyOptumHealth. AccuWeather. Retrieved 14 September 2011.
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