Chemistry:Carbonyl sulfide

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Carbonyl sulfide
Carbonyl sulfide
Space-filling 3D model of carbonyl sulfide
Names
IUPAC names
Carbonyl sulfide[1]
Oxidosulfidocarbon[1]
Systematic IUPAC name
Thioxomethanone
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
EC Number
  • 207-340-0
KEGG
UNII
UN number 2204
Properties
COS
Molar mass 60.075 g/mol
Appearance colorless gas
Odor sulfide-like
Density 2.51 g/L
Melting point −138.8 °C (−217.8 °F; 134.3 K)
Boiling point −50.2 °C (−58.4 °F; 223.0 K)
0.376 g/100 mL (0 °C)
0.125 g/100 mL (25 °C)
Solubility very soluble in KOH, CS2
soluble in alcohol, toluene
−32.4×10−6 cm3/mol
0.65 D
Thermochemistry
41.5 J/mol K
231.5 J/mol K
-141.8 kJ/mol
Hazards
Safety data sheet Carbonyl sulfide MSDS
GHS pictograms GHS02: FlammableGHS04: Compressed GasGHS06: ToxicGHS07: Harmful
GHS Signal word Danger
H220, H280, H315, H319, H331, H335
P210, P261, P264, P271, P280, P302+352, P304+340, P305+351+338, P311, P312, P321, P332+313, P337+313, P362, P377, P381, P403, P403+233, P405, P410+403, P501
NFPA 704 (fire diamond)
Flammability code 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no codeNFPA 704 four-colored diamond
4
3
1
Explosive limits 12-29%
Related compounds
Related compounds
 Carbon dioxide
Carbon disulfide
Carbonyl selenide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is ☑Y☒N ?)
Infobox references

Carbonyl sulfide is the chemical compound with the linear formula OCS. It is a colorless flammable gas with an unpleasant odor.[not verified in body] It is a linear molecule consisting of a carbonyl double bonded to a sulfur atom. Carbonyl sulfide can be considered to be intermediate between carbon dioxide and carbon disulfide, both of which are valence isoelectronic with it.

Occurrence

Carbonyl sulfide is the most abundant sulfur compound naturally present in the atmosphere, at 0.5±0.05 ppb, because it is emitted from oceans, volcanoes and deep sea vents. As such, it is a significant compound in the global sulfur cycle. Measurements on the Antarctica ice cores and from air trapped in snow above glaciers (firn air) have provided a detailed picture of OCS concentrations from 1640 to the present day and allow an understanding of the relative importance of anthropogenic and non-anthropogenic sources of this gas to the atmosphere.[2] Some carbonyl sulfide that is transported into the stratospheric sulfate layer is oxidized to sulfuric acid.[3] Sulfuric acid forms particulate which affects energy balance due to light scattering.[4] The long atmospheric lifetime of COS makes it the major source of stratospheric sulfate, though sulfur dioxide from volcanic activity can be significant too.[4] Carbonyl sulfide is also removed from the atmosphere by terrestrial vegetation by enzymes associated with the uptake of carbon dioxide during photosynthesis, and by hydrolysis in ocean waters.[5][6][7] Loss processes, such as these, limit the persistence (or lifetime) of a molecule of COS in the atmosphere to a few years.

The largest man-made sources of carbonyl sulfide release include its primary use as a chemical intermediate and as a byproduct of carbon disulfide production; however, it is also released from automobiles and their tire wear,[8] coal-fired power plants, coking ovens, biomass combustion, fish processing, combustion of refuse and plastics, petroleum manufacture, and manufacture of synthetic fibers, starch, and rubber.[9] The average total worldwide release of carbonyl sulfide to the atmosphere has been estimated[when?] at about 3 million tons/year, of which less than one third was related to human activity.[9] It is also a significant sulfur-containing impurity in many fuel gases such as synthesis gas, which are produced from sulfur-containing feedstocks.[10]

Carbonyl sulfide is present in foodstuffs, such as cheese and prepared vegetables of the cabbage family. Traces of COS are naturally present in grains and seeds in the range of 0.05–0.1 mg·kg−1.

Carbonyl sulfide has been observed in the interstellar medium (see also List of molecules in interstellar space), in comet 67P[11] and in the atmosphere of Venus, where, because of the difficulty of producing COS inorganically, it is considered a possible indicator of life.[12]

Reactions and applications

Carbonyl sulfide is used as an intermediate in the production of thiocarbamate herbicides.[13]

The hydrolysis of carbonyl sulfide is promoted by chromium-based catalysts:[10]

COS + H
2O → CO
2 + H
2S

This conversion is catalyzed in solution by carbonic anhydrase enzymes in plants and mammals. Because of this chemistry, the release of carbonyl sulfide from small organic molecules has been identified as a strategy for delivering hydrogen sulfide, which is gaseous signaling molecule.[14][15]

This compound is found to catalyze the formation of peptides from amino acids. This finding is an extension of the Miller–Urey experiment and it is suggested that carbonyl sulfide played a significant role in the origin of life.[16]

In ecosystem science, atmospheric studies of carbonyl sulfide are increasingly being used to describe the rate of photosynthesis.[17][18]

Synthesis

Carbonyl sulfide was first described in 1841,[19] but was apparently mischaracterized as a mixture of carbon dioxide and hydrogen sulfide. Carl von Than first characterized the substance in 1867. It forms when carbon monoxide reacts with molten sulfur.

CO + 1/8 S
8 → COS

This reaction reverses above 1200 K (930 °C; 1700 °F).

A laboratory synthesis entails the reaction potassium thiocyanate and sulfuric acid. The resulting gas contains significant amounts of byproducts and requires purification.[20]

KSCN + 2 H
2SO
4 + H
2O → KHSO
4 + NH
4HSO
4 + COS

Hydrolysis of isothiocyanates in hydrochloric acid solution also affords COS.

Toxicity

As of 1994, limited information existed on the acute toxicity of carbonyl sulfide in humans and in animals.[13] High concentrations (above 1000 ppm) can cause sudden collapse, convulsions, and death from respiratory paralysis.[9][13] Occasional fatalities have been reported, practically without local irritation or olfactory warning.[13] In tests with rats, 50% animals died when exposed to 1400 ppm of COS for 90 minutes, or at 3000 ppm for 9 minutes.[13] Limited studies with laboratory animals also suggest that continued inhalation of low concentrations (around 50 ppm for up to 12 weeks) does not affect the lungs or the heart.[13]

Carbonyl sulfide is a potential alternative fumigant[21] to methyl bromide and phosphine. In some cases, however, residues on the grain result in flavours that are unacceptable to consumers, such as in barley used for brewing.

References

  1. ↑ 1.0 1.1 International Union of Pure and Applied Chemistry (2005). Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005). Cambridge (UK): RSC–IUPAC. ISBN:0-85404-438-8. p. 292. Electronic version.
  2. ↑ Montzka, S. A.; Aydin, M.; Battle, M.; Butler, J. H.; Saltzman, E. S.; Hall, B. D.; Clarke, A. D.; Mondeel, D. et al. (2004). "A 350-year atmospheric history for carbonyl sulfide inferred from Antarctic firn air and air trapped in ice". Journal of Geophysical Research 109 (D18): 22302. doi:10.1029/2004JD004686. eid D22302. Bibcode: 2004JGRD..10922302M. https://escholarship.org/content/qt17j6m436/qt17j6m436.pdf?t=n6lm7g. 
  3. ↑ Crutzen, P. (1976). "The possible importance of COS for the sulfate layer of the stratosphere". Geophysical Research Letters 3 (2): 73–76. doi:10.1029/GL003i002p00073. Bibcode: 1976GeoRL...3...73C. 
  4. ↑ 4.0 4.1 Seinfeld, J. (2006). Atmospheric Chemistry and Physics. London: J. Wiley. ISBN 978-1-60119-595-1. 
  5. ↑ Campbell, J. E.; Carmichael, G. R.; Chai, T.; Mena-Carrasco, M.; Tang, Y.; Blake, D. R.; Blake, N. J.; Vay, S. A. et al. (2008). "Photosynthetic Control of Atmospheric Carbonyl Sulfide During the Growing Season". Science 322 (5904): 1085–1088. doi:10.1126/science.1164015. PMID 19008442. Bibcode: 2008Sci...322.1085C. http://www.escholarship.org/uc/item/82r9s2x3. 
  6. ↑ Kettle, A. J.; Kuhn, U.; von Hobe, M.; Kesselmeier, J.; Andreae, M. O. (2002). "Global budget of atmospheric carbonyl sulfide: Temporal and spatial variations of the dominant sources and sinks". Journal of Geophysical Research 107 (D22): 4658. doi:10.1029/2002JD002187. Bibcode: 2002JGRD..107.4658K. 
  7. ↑ Montzka, S. A.; Calvert, P.; Hall, B. D.; Elkins, J. W.; Conway, T. J.; Tans, P. P.; Sweeney, C. (2007). "On the global distribution, seasonality, and budget of atmospheric carbonyl sulfide (COS) and some similarities to CO2". Journal of Geophysical Research 112 (D9): 9302. doi:10.1029/2006JD007665. eid D09302. Bibcode: 2007JGRD..112.9302M. 
  8. ↑ "Automotive tire wear as a source for atmospheric OCS and CS2". Geophysical Research Letters 1 (9): 815–818. 1993. doi:10.1029/93GL00972. Bibcode: 1993GeoRL..20..815P. 
  9. ↑ 9.0 9.1 9.2 "Carbonyl Sulfide CASRN: 463-58-1". Hazardous Substances Data Bank. National Library of Medicine. http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@DOCNO+6127. 
  10. ↑ 10.0 10.1 Hiller, Heinz; Reimert, Rainer; Marschner, Friedemann; Renner, Hans-Joachim; Boll, Walter; Supp, Emil; Brejc, Miron; Liebner, Waldemar et al. (2006). "Gas Production". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a12_169.pub2. ISBN 3527306730. 
  11. ↑ Rosetta Blog. "OMET'S FIREWORK DISPLAY AHEAD OF PERIHELION". European Space Agency. http://blogs.esa.int/rosetta/2015/08/11/comets-firework-display-ahead-of-perihelion/. 
  12. ↑ Landis, G. A. (2003). "Astrobiology: the Case for Venus". Journal of the British Interplanetary Society 56 (7–8): 250–254. Bibcode: 2003JBIS...56..250L. https://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/20030067857_2003079552.pdf. 
  13. ↑ 13.0 13.1 13.2 13.3 13.4 13.5 "Chemical Summary for Carbonyl Sulfide". U.S. Environmental Protection Agency. 2013-07-19. http://www.epa.gov/chemfact/s_carbns.txt. 
  14. ↑ Steiger, Andrea K.; Pardue, Sibile; Kevil, Christopher G.; Pluth, Michael D. (2016-06-15). "Self-Immolative Thiocarbamates Provide Access to Triggered H2S Donors and Analyte Replacement Fluorescent Probes". Journal of the American Chemical Society 138 (23): 7256–7259. doi:10.1021/jacs.6b03780. ISSN 0002-7863. PMID 27218691. 
  15. ↑ Protoschill-Krebs, G.; Wilhelm, C.; Kesselmeier, J. (1996). "Consumption of carbonyl sulphide (COS) by higher plant carbonic anhydrase (CA)". Atmospheric Environment 30 (18): 3151–3156. doi:10.1016/1352-2310(96)00026-X. Bibcode: 1996AtmEn..30.3151P. 
  16. ↑ "Carbonyl sulfide-mediated prebiotic formation of peptides". Science 306 (5694): 283–6. 2004. doi:10.1126/science.1102722. PMID 15472077. Bibcode: 2004Sci...306..283L. 
  17. ↑ Campbell, J. E.; Berry, J. A.; Seibt, U.; Smith, S. J.; Montzka, S. A.; Launois, T.; Belviso, S.; Bopp, L. et al. (April 2017). "Large historical growth in global terrestrial gross primary production". Nature 544 (7648): 84–87. doi:10.1038/nature22030. PMID 28382993. Bibcode: 2017Natur.544...84C. 
  18. ↑ Yakir, Dan; Montzka, Stephen A.; Uri Dicken; Tatarinov, Fyodor; Rotenberg, Eyal; Asaf, David (March 2013). "Ecosystem photosynthesis inferred from measurements of carbonyl sulphide flux". Nature Geoscience 6 (3): 186–190. doi:10.1038/ngeo1730. ISSN 1752-0908. Bibcode: 2013NatGe...6..186A. 
  19. ↑ Couërbe, J. P. (1841). "Ueber den Schwefelkohlenstoff". Journal für Praktische Chemie 23 (1): 83–124. doi:10.1002/prac.18410230105. 
  20. ↑ Ferm R. J. (1957). "The Chemistry of Carbonyl Sulfide". Chemical Reviews 57 (4): 621–640. doi:10.1021/cr50016a002. 
  21. ↑ Bartholomaeus, Andrew; Haritos, Victoria (2005). "Review of the toxicology of carbonyl sulfide, a new grain fumigant". Food and Chemical Toxicology 43 (12): 1687–1701. doi:10.1016/j.fct.2005.06.016. PMID 16139940. 

Further reading

  • Beck, M. T.; Kauffman, G. B. (1985). "COS and C3S2: The Discovery and Chemistry of Two Important Inorganic Sulfur Compounds". Polyhedron 4 (5): 775–781. doi:10.1016/S0277-5387(00)87025-4. 
  • J. Elliott Campbell; Jürgen Kesselmeier; Dan Yakir; Joe A. Berry; Philippe Peylin; Sauveur Belviso; Timo Vesala; Kadmiel Maseyk et al. (2017). "Assessing a New Clue to How Much Carbon Plants Take Up". EOS 98. doi:10.1029/2017EO075313. 
  • Svoronos P. D. N.; Bruno T. J. (2002). "Carbonyl sulfide: A review of its chemistry and properties". Industrial & Engineering Chemistry Research 41 (22): 5321–5336. doi:10.1021/ie020365n. 

External links



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