Cyanogen
Skeletal formula of cyanogen
Ball and stick model of cyanogen
Ball and stick model of cyanogen
Spacefill model of cyanogen
Spacefill model of cyanogen
Names
Preferred IUPAC name
Oxalonitrile[1]
Systematic IUPAC name
Ethanedinitrile[1]
Other names
Cyanogen
Bis(nitridocarbon)(C—C)[2]
Dicyan[3][4]
Carbon nitride[3]
Oxalic acid dinitrile[4]
Dicyanogen
Nitriloacetonitrile
CY
Identifiers
3D model (JSmol)
1732464
ChEBI
ChemSpider
ECHA InfoCard 100.006.643
EC Number
  • 207-306-5
1090
MeSH cyanogen
RTECS number
  • GT1925000
UNII
UN number 1026
  • InChI=1S/C2N2/c3-1-2-4 checkY
    Key: JMANVNJQNLATNU-UHFFFAOYSA-N checkY
  • N#CC#N
Properties
C2N2
Molar mass 52.036 g·mol−1
Appearance Colourless gas
Odor pungent, almond-like
Density 950 mg mL−1 (at −21 °C)
Melting point −28 °C (−18 °F; 245 K)
Boiling point −21.1 °C; −6.1 °F; 252.0 K
45 g/100 mL (at 20 °C)
Solubility soluble in ethanol, ethyl ether
Vapor pressure 5.1 atm (21 °C)[5]
1.9 μmol Pa−1 kg−1
-21.6·10−6 cm3/mol
1.327 (18 °C)
Thermochemistry
241.57 J K−1 mol−1
309.07 kJ mol−1
−1.0978–−1.0942 MJ mol−1
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 forms cyanide in the body; flammable[5]
GHS labelling:
GHS02: FlammableGHS06: ToxicGHS09: Environmental hazard
Danger
H220, H331, H410
P210, P261, P271, P273, P304+P340, P311, P321, P377, P381, P391, P403, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
4
4
2
Explosive limits 6.6–32%[5]
NIOSH (US health exposure limits):
PEL (Permissible)
 none[5]
REL (Recommended)
 TWA 10 ppm (20 mg/m3)[5]
IDLH (Immediate danger)
 N.D.[5]
Safety data sheet (SDS) inchem.org
Related compounds
Related alkanenitriles
Related compounds
 DBNPA
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Infobox references

Cyanogen is the chemical compound with the formula (CN)2. The simplest stable carbon nitride, it is a colorless and highly toxic gas with a pungent odor. The molecule is a pseudohalogen. Cyanogen molecules consist of two CN groups – analogous to diatomic halogen molecules, such as Cl2, but far less oxidizing. The two cyano groups are bonded together at their carbon atoms: N≡C‒C≡N, although other isomers have been detected.[6] The name is also used for the CN radical,[7] and hence is used for compounds such as cyanogen bromide (NCBr)[8] (but see also Cyano radical.)

Cyanogen is the anhydride of oxamide:

H2NC(O)C(O)NH2 → NCCN + 2 H2O

although oxamide is manufactured from cyanogen by hydrolysis:[9]

NCCN + 2 H2O → H2NC(O)C(O)NH2

Preparation

Cyanogen is typically generated from cyanide compounds. One laboratory method entails thermal decomposition of mercuric cyanide:

2 Hg(CN)2 → (CN)2 + Hg2(CN)2

Alternatively, one can combine solutions of copper(II) salts (such as copper(II) sulfate) with cyanides; an unstable copper(II) cyanide is formed which rapidly decomposes into copper(I) cyanide and cyanogen.[10]

2 CuSO4 + 4 KCN → (CN)2 + 2 CuCN + 2 K2SO4

Industrially, it is created by the oxidation of hydrogen cyanide, usually using chlorine over an activated silicon dioxide catalyst or nitrogen dioxide over a copper salt. It is also formed when nitrogen and acetylene are reacted by an electrical spark or discharge.[11]

Isomers

Cyanogen is NCCN. There are less stable isomers in which the order of the atoms differs. Isocyanogen (or cyanoisocyanogen) is NCNC, diisocyanogen is CNNC, and diazodicarbon is CCNN.

Paracyanogen

Paracyanogen is a polymer of cyanogen. It can be best prepared by heating mercuric cyanide. It can also be prepared by heating silver cyanide, silver cyanate, cyanogen iodide or cyanuric iodide.[12] It can also be prepared by the polymerization of cyanogen at 300 to 500 °C (572 to 932 °F) in the presence of trace impurities. Paracyanogen can also be converted back to cyanogen by heating to 800 °C (1,470 °F).[9] Based on experimental evidence, the structure of this polymeric material is thought to be rather irregular, with most of the carbon atoms being of sp2 type and localized domains of π conjugation.[13]

History

Cyanogen was first synthesized in 1815 by Joseph Louis Gay-Lussac, who determined its empirical formula and named it. Gay-Lussac coined the word "cyanogène" from the Greek words κυανός (kyanos, blue) and γεννάω (gennao, I create), because cyanide was first isolated by the Swedish chemist Carl Wilhelm Scheele from the pigment "Prussian blue".[14] By the 1850s, cyanogen soap was used by photographers to remove silver stains from their hands.[15] It attained importance with the growth of the fertilizer industry in the late 19th century and remains an important intermediate in the production of many fertilizers. It is also used as a stabilizer in the production of nitrocellulose.

Cyanogen is commonly found in comets.[16] In 1910 a spectroscopic analysis of Halley's Comet found cyanogen in the comet's tail, which led to public fear that the Earth would be poisoned as it passed through the tail. People in New York wore gas masks, and merchants sold quack-treatment "comet pills" claimed to neutralise poisoning.[16] Because of the extremely diffuse nature of the tail, there was no effect when the planet passed through it.[17][18]

Safety

Like other cyanides, cyanogen is very toxic, as it readily undergoes reduction to cyanide, which poisons the cytochrome c oxidase complex, thus interrupting the mitochondrial electron transfer chain. Cyanogen gas is an irritant to the eyes and respiratory system. Inhalation can lead to headache, dizziness, rapid pulse, nausea, vomiting, loss of consciousness, convulsions, and death, depending on exposure.[19] Lethal dose through inhalation typically ranges from 100 to 150 milligrams (1.5 to 2.3 grains).

Cyanogen produces the second-hottest-known natural flame (after carbon subnitride) with a temperature of over 4,525 °C (8,177 °F) when it burns in oxygen.[20][21]

In the Doctor Who serial "The Brain of Morbius" (the 5th serial of season 13), the Doctor synthesizes cyanogen using hydrogen cyanide as a starting material and vents it through a pipe to stop Solon from performing surgery on the brain of Morbius's body, however he completes it but shortly after dies of cyanogen poisoning.

In Dragnet (1987) Friday (Dan Aykroyd) and Streebek (Tom Hanks) are tracking down the villain who stole "the pseudohalogenic compound cyanogen".[22]

See also

References

  1. 1 2 "Front Matter". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 902. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. ↑ "oxalonitrile (CHEBI:29308)". Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. 27 October 2006. Main. Retrieved 6 June 2012.
  3. 1 2 NIOSH Pocket Guide to Chemical Hazards. Department of Health and Human Services, Centers for Disease Control, National Institute for Occupational Safety & Health. September 2007. p. 82.
  4. 1 2 The Merck Index (10th ed.). Rahway, NJ: Merck & Co. 1983. p. 385. ISBN 9780911910278.
  5. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0161". National Institute for Occupational Safety and Health (NIOSH).
  6. ↑ Ringer, A. L.; Sherrill, C. D.; King, R. A.; Crawford, T. D. (2008). "Low-lying singlet excited states of isocyanogen". International Journal of Quantum Chemistry. 106 (6): 1137–1140. Bibcode:2008IJQC..108.1137R. doi:10.1002/qua.21586.
  7. ↑ Irvine, William M. (2011). "Cyanogen Radical". Encyclopedia of Astrobiology. p. 402. doi:10.1007/978-3-642-11274-4_1806. ISBN 978-3-642-11271-3.
  8. ↑ Hartman, W. W.; Dreger, E. E. (1931). "Cyanogen Bromide" (PDF). Organic Syntheses. 11: 30.; Collective Volume, vol. 2, p. 150
  9. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 320–321. ISBN 978-0-08-037941-8.
  10. ↑ Brotherton, T. K.; Lynn, J. W. (1959). "The Synthesis And Chemistry Of Cyanogen". Chemical Reviews. 59 (5): 841–883. doi:10.1021/cr50029a003.
  11. ↑ Breneman, A. A. (January 1889). "The Fixation of Atmospheric Nitrogen". Journal of the American Chemical Society. 11 (1): 2–27. doi:10.1021/ja02126a001.
  12. ↑ Bircumshaw, L. L.; F. M. Tayler; D. H. Whiffen (1954). "Paracyanogen: its formation and properties. Part I". J. Chem. Soc.: 931–935. doi:10.1039/JR9540000931.
  13. ↑ Maya, Leon (1993). "Paracyanogen Reexamined". Journal of Polymer Science Part A (Submitted manuscript). 31 (10): 2595–2600. Bibcode:1993JPoSA..31.2595M. doi:10.1002/pola.1993.080311020.
  14. ↑ Gay-Lussac, J. L. (1815). "Recherches sur l'acide prussique". Annales de Chimie (in French). 95: 136–231. Gay-Lussac names cyanogen on p. 163.
  15. ↑ Crookes, William, ed. (1859). Photographic News: A Weekly Record of the Process of the Photography. p. 11.
  16. 1 2 "Cometary Poison Gas Geyser Heralds Surprises". science.nasa.gov. 2010-11-02. Archived from the original on 2010-11-06.
  17. ↑ "Comet's Poisonous Tail" (PDF). New York Times. 1910-02-08.
  18. ↑ "Halley's Comet 100 years ago". The Denver Post. 2010-05-25.
  19. ↑ Muir, G. D., ed. (1971). Hazards in the Chemical Laboratory. London: The Royal Institute of Chemistry.
  20. ↑ Thomas, N.; Gaydon, A. G.; Brewer, L. (1952). "Cyanogen Flames and the Dissociation Energy of N2". The Journal of Chemical Physics. 20 (3): 369–374. Bibcode:1952JChPh..20..369T. doi:10.1063/1.1700426.
  21. ↑ J. B. Conway; R. H. Wilson Jr.; A. V. Grosse (1953). "The Temperature of the Cyanogen-Oxygen Flame". Journal of the American Chemical Society. 75 (2): 499. doi:10.1021/ja01098a517.
  22. ↑ "The trichlornitromethane and the pseudo-halogenic compound cyanogen". Retrieved August 18, 2021.
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