Carbonyl sulfide

Last updated
Carbonyl sulfide
Carbonyl-sulfide-2D-dimensions.png
Carbonyl-sulfide-3D-vdW.png
Names
IUPAC names
Carbonyl sulfide [1]
Oxidosulfidocarbon [1]
Systematic IUPAC name
Thioxomethanone
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.006.674 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 207-340-0
KEGG
PubChem CID
UNII
UN number 2204
  • InChI=1S/COS/c2-1-3 Yes check.svgY
    Key: JJWKPURADFRFRB-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/COS/c2-1-3
    Key: JJWKPURADFRFRB-UHFFFAOYAF
  • O=C=S
Properties
COS
Molar mass 60.075 g/mol
Appearancecolorless 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)
Critical point (T, P)101.85 °C (215.3 °F; 375.0 K), 58.03 standard atmospheres (5,879.9 kPa; 852.8 psi) [2]
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)
Std molar
entropy (S⦵298)
231.5 J/(mol⋅K)
−141.8 kJ/mol
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger
H220, H315, H319, H331, H335
P210, P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P311, P312, P321, P332+P313, P337+P313, P362, P377, P381, P403, P403+P233, P405, P410+P403, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 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. propaneInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
4
1
Explosive limits 12–29%
Safety data sheet (SDS) Carbonyl sulfide MSDS
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).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Carbonyl sulfide is the chemical compound with the linear formula O=C=S . 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.

Contents

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. [3] Some carbonyl sulfide that is transported into the stratospheric sulfate layer is oxidized to sulfuric acid. [4] Sulfuric acid forms particulate which affects energy balance due to light scattering. [5] The long atmospheric lifetime of COS makes it the major source of stratospheric sulfate, though sulfur dioxide from volcanic activity can be significant too. [5] 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. [6] [7] [8] 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, [9] 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. [10] The average total worldwide release of carbonyl sulfide to the atmosphere has been estimated[ when? ] at about 3 million tons per year, of which less than one third was related to human activity. [10] It is also a significant sulfur-containing impurity in many fuel gases such as synthesis gas, which are produced from sulfur-containing feedstocks. [11]

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.

Carbonyl sulfide has been observed in the interstellar medium (see also List of molecules in interstellar space), in comet 67P [12] and in the atmosphere of Venus, where, because of the difficulty of producing COS inorganically, it is considered a possible indicator of life. [13]

Reactions and applications

Carbonyl sulfide is used as an intermediate in the production of thiocarbamate herbicides. [14]

The hydrolysis of carbonyl sulfide is promoted by chromium-based catalysts: [11]

COS + H2O → CO2 + H2S

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. [15] [16]

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. [17]

In ecosystem science, [18] are increasingly being used to describe the rate of photosynthesis. [19] [20]

Synthesis

Carbonyl sulfide was first described in 1841, [21] 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 +⁠1/8⁠S8 → COS

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

A laboratory synthesis entails the reaction potassium thiocyanate and sulfuric acid:

KSCN + 2 H2SO4 + H2O → KHSO4 + NH4HSO4 + COS

The resulting gas contains significant amounts of byproducts and requires purification. [22]

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. [14] High concentrations (above 1000 ppm) can cause sudden collapse, convulsions, and death from respiratory paralysis. [10] [14] Occasional fatalities have been reported, practically without local irritation or olfactory warning. [14] In tests with rats, 50% animals died when exposed to 1400 ppm of COS for 90 minutes, or at 3000 ppm for 9 minutes. [14] 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. [14]

Carbonyl sulfide is a potential alternative fumigant [23] 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.

Related Research Articles

<span class="mw-page-title-main">Carbon dioxide</span> Chemical compound with formula CO₂

Carbon dioxide is a chemical compound with the chemical formula CO2. It is made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. As the source of carbon in the carbon cycle, atmospheric CO2 is the primary carbon source for life on Earth. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, and seawater. When carbon dioxide dissolves in water, it forms carbonate and mainly bicarbonate, which causes ocean acidification as atmospheric CO2 levels increase.

<span class="mw-page-title-main">Carbon monoxide</span> Colourless, odourless, tasteless and toxic gas

Carbon monoxide is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simplest carbon oxide. In coordination complexes, the carbon monoxide ligand is called carbonyl. It is a key ingredient in many processes in industrial chemistry.

<span class="mw-page-title-main">Sulfur dioxide</span> Chemical compound of sulfur and oxygen

Sulfur dioxide or sulphur dioxide is the chemical compound with the formula SO
2. It is a colorless gas with a pungent smell that is responsible for the odor of burnt matches. It is released naturally by volcanic activity and is produced as a by-product of copper extraction and the burning of sulfur-bearing fossil fuels.

Chloromethane, also called methyl chloride, Refrigerant-40, R-40 or HCC 40, is an organic compound with the chemical formula CH3Cl. One of the haloalkanes, it is a colorless, sweet-smelling, flammable gas. Methyl chloride is a crucial reagent in industrial chemistry, although it is rarely present in consumer products, and was formerly utilized as a refrigerant. Most chloromethane is biogenic.

<span class="mw-page-title-main">Cloud condensation nuclei</span> Small particles on which water vapor condenses

Cloud condensation nuclei (CCNs), also known as cloud seeds, are small particles typically 0.2 μm, or one hundredth the size of a cloud droplet. CCNs are a unique subset of aerosols in the atmosphere on which water vapour condenses. This can affect the radiative properties of clouds and the overall atmosphere. Water vapour requires a non-gaseous surface to make the transition to a liquid; this process is called condensation.

<span class="mw-page-title-main">Dinitrogen pentoxide</span> Chemical compound

Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that contain only nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.

<span class="mw-page-title-main">Sulfur monoxide</span> Chemical compound

Sulfur monoxide is an inorganic compound with formula SO. It is only found as a dilute gas phase. When concentrated or condensed, it converts to S2O2 (disulfur dioxide). It has been detected in space but is rarely encountered intact otherwise.

<span class="mw-page-title-main">Infrared window</span> Atmospheric window

The infrared atmospheric window is an atmospheric window in the infrared spectrum where there is relatively little absorption of terrestrial thermal radiation by atmospheric gases. The window plays an important role in the atmospheric greenhouse effect by maintaining the balance between incoming solar radiation and outgoing IR to space. In the Earth's atmosphere this window is roughly the region between 8 and 14 μm although it can be narrowed or closed at times and places of high humidity because of the strong absorption in the water vapor continuum or because of blocking by clouds. It covers a substantial part of the spectrum from surface thermal emission which starts at roughly 5 μm. Principally it is a large gap in the absorption spectrum of water vapor. Carbon dioxide plays an important role in setting the boundary at the long wavelength end. Ozone partly blocks transmission in the middle of the window.

Mass-independent isotope fractionation or Non-mass-dependent fractionation (NMD), refers to any chemical or physical process that acts to separate isotopes, where the amount of separation does not scale in proportion with the difference in the masses of the isotopes. Most isotopic fractionations are caused by the effects of the mass of an isotope on atomic or molecular velocities, diffusivities or bond strengths. Mass-independent fractionation processes are less common, occurring mainly in photochemical and spin-forbidden reactions. Observation of mass-independently fractionated materials can therefore be used to trace these types of reactions in nature and in laboratory experiments.

<span class="mw-page-title-main">Dimethyl sulfide</span> Chemical compound

Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. It is the simplest thioether and has a characteristic disagreeable odor. It is a flammable liquid that boils at 37 °C (99 °F). It is a component of the smell produced from cooking of certain vegetables and seafoods. It is also an indication of bacterial contamination in malt production and brewing. It is a breakdown product of dimethylsulfoniopropionate (DMSP), and is also produced by the bacterial metabolism of methanethiol.

<span class="mw-page-title-main">Carbon tetrafluoride</span> Chemical compound

Tetrafluoromethane, also known as carbon tetrafluoride or R-14, is the simplest perfluorocarbon (CF4). As its IUPAC name indicates, tetrafluoromethane is the perfluorinated counterpart to the hydrocarbon methane. It can also be classified as a haloalkane or halomethane. Tetrafluoromethane is a useful refrigerant but also a potent greenhouse gas. It has a very high bond strength due to the nature of the carbon–fluorine bond.

Fluoroform, or trifluoromethane, is the chemical compound with the formula CHF3. It is a hydrofluorocarbon as well as being a part of the haloforms, a class of compounds with the formula CHX3 with C3v symmetry. Fluoroform is used in diverse applications in organic synthesis. It is not an ozone depleter but is a greenhouse gas.

<span class="mw-page-title-main">Carl von Than</span> Hungarian chemist (1834–1908)

Károly Antal Than de Apát – also called as Carl von Than – was a Hungarian chemist who discovered carbonyl sulfide in 1867.

<span class="mw-page-title-main">Stratospheric aerosol injection</span> Putting particles in the stratosphere to reflect sunlight to limit global heating

Stratospheric aerosol injection (SAI) is a proposed method of solar geoengineering to reduce global warming. This would introduce aerosols into the stratosphere to create a cooling effect via global dimming and increased albedo, which occurs naturally from volcanic winter. It appears that stratospheric aerosol injection, at a moderate intensity, could counter most changes to temperature and precipitation, take effect rapidly, have low direct implementation costs, and be reversible in its direct climatic effects. The Intergovernmental Panel on Climate Change concludes that it "is the most-researched [solar geoengineering] method that it could limit warming to below 1.5 °C (2.7 °F)." However, like other solar geoengineering approaches, stratospheric aerosol injection would do so imperfectly and other effects are possible, particularly if used in a suboptimal manner.

Tectonic–climatic interaction is the interrelationship between tectonic processes and the climate system. The tectonic processes in question include orogenesis, volcanism, and erosion, while relevant climatic processes include atmospheric circulation, orographic lift, monsoon circulation and the rain shadow effect. As the geological record of past climate changes over millions of years is sparse and poorly resolved, many questions remain unresolved regarding the nature of tectonic-climate interaction, although it is an area of active research by geologists and palaeoclimatologists.

Sulfanyl (HS•), also known as the mercapto radical, hydrosulfide radical, or hydridosulfur, is a simple radical molecule consisting of one hydrogen and one sulfur atom. The radical appears in metabolism in organisms as H2S is detoxified. Sulfanyl is one of the top three sulfur-containing gasses in gas giants such as Jupiter and is very likely to be found in brown dwarfs and cool stars. It was originally discovered by Margaret N. Lewis and John U. White at the University of California in 1939. They observed molecular absorption bands around 325 nm belonging to the system designated by 2Σ+ ← 2Πi. They generated the radical by means of a radio frequency discharge in hydrogen sulfide. HS• is formed during the degradation of hydrogen sulfide in the atmosphere of the Earth. This may be a deliberate action to destroy odours or a natural phenomenon.

<span class="mw-page-title-main">Disulfur dioxide</span> Chemical compound

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<span class="mw-page-title-main">Chemical cycling</span>

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<span class="mw-page-title-main">Sulfoxylic acid</span> Chemical compound

Sulfoxylic acid (H2SO2) (also known as hyposulfurous acid or sulfur dihydroxide) is an unstable oxoacid of sulfur in an intermediate oxidation state between hydrogen sulfide and dithionous acid. It consists of two hydroxy groups attached to a sulfur atom. Sulfoxylic acid contains sulfur in an oxidation state of +2. Sulfur monoxide (SO) can be considered as a theoretical anhydride for sulfoxylic acid, but it is not actually known to react with water.

Carbonyl sulfide hydrolase (EC 3.13.1.7; abbreviated as COSase) is an enzyme that degrades carbonyl sulfide (COS) to hydrogen sulfide (H2S) and carbon dioxide (CO2). Isolated from Thiobacillus thioparus bacterium, the potential of COSase would reduce the high global warming effect of COS and change the ozone chemistry, because COS is the source of sulfur in the troposphere.

References

  1. 1 2 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. ↑ Lide, David R.; Kehiaian, Henry V. (1994). CRC Handbook of Thermophysical and Themochemical Data (PDF). CRC Press. p. 32.
  3. ↑ Montzka, S. A.; Aydin, M.; Battle, M.; Butler, J. H.; Saltzman, E. S.; Hall, B. D.; Clarke, A. D.; Mondeel, D.; Elkins, J. W. (2004). "A 350-year atmospheric history for carbonyl sulfide inferred from Antarctic firn air and air trapped in ice" (PDF). Journal of Geophysical Research. 109 (D18): 22302. Bibcode:2004JGRD..10922302M. doi:10.1029/2004JD004686. S2CID   1261238. eid D22302.
  4. ↑ Crutzen, P. (1976). "The possible importance of COS for the sulfate layer of the stratosphere". Geophysical Research Letters. 3 (2): 73–76. Bibcode:1976GeoRL...3...73C. doi:10.1029/GL003i002p00073.
  5. 1 2 Seinfeld, J. (2006). Atmospheric Chemistry and Physics. London: J. Wiley. ISBN   978-1-60119-595-1.
  6. ↑ Campbell, J. E.; Carmichael, G. R.; Chai, T.; Mena-Carrasco, M.; Tang, Y.; Blake, D. R.; Blake, N. J.; Vay, S. A.; Collatz, G. J.; Baker, I.; Berry, J. A.; Montzka, S. A.; Sweeney, C.; Schnoor, J. L.; Stanier, C. O. (2008). "Photosynthetic Control of Atmospheric Carbonyl Sulfide During the Growing Season". Science. 322 (5904): 1085–1088. Bibcode:2008Sci...322.1085C. doi:10.1126/science.1164015. PMID   19008442. S2CID   206515456.
  7. ↑ 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. Bibcode:2002JGRD..107.4658K. doi: 10.1029/2002JD002187 .
  8. ↑ 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. Bibcode:2007JGRD..112.9302M. doi:10.1029/2006JD007665. eid D09302.
  9. ↑ Pos W, Berreshein B (1993). "Automotive tire wear as a source for atmospheric OCS and CS2". Geophysical Research Letters. 1 (9): 815–818. Bibcode:1993GeoRL..20..815P. doi:10.1029/93GL00972.
  10. 1 2 3 "Carbonyl Sulfide CASRN: 463-58-1". Hazardous Substances Data Bank. National Library of Medicine.
  11. 1 2 Hiller, Heinz; Reimert, Rainer; Marschner, Friedemann; Renner, Hans-Joachim; Boll, Walter; Supp, Emil; Brejc, Miron; Liebner, Waldemar; Schaub, Georg; Hochgesand, Gerhard; Higman, Christopher; Kalteier, Peter; Müller, Wolf-Dieter; Kriebel, Manfred; Schlichting, Holger; Tanz, Heiner; Stönner, Hans-Martin; Klein, Helmut; Hilsebein, Wolfgang; Gronemann, Veronika; Zwiefelhofer, Uwe; Albrecht, Johannes; Cowper, Christopher J.; Driesen, Hans Erhard (2006). "Gas Production". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a12_169.pub2. ISBN   3527306730.
  12. ↑ Rosetta Blog. "OMET'S FIREWORK DISPLAY AHEAD OF PERIHELION". blogs.esa.int. European Space Agency. Retrieved 11 August 2015.
  13. ↑ Landis, G. A. (2003). "Astrobiology: the Case for Venus" (PDF). Journal of the British Interplanetary Society. 56 (7–8): 250–254. Bibcode:2003JBIS...56..250L.
  14. 1 2 3 4 5 6 "Chemical Summary for Carbonyl Sulfide". U.S. Environmental Protection Agency. 2013-07-19.
  15. ↑ 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. PMC   4911618 . PMID   27218691.
  16. ↑ 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. Bibcode:1996AtmEn..30.3151P. doi:10.1016/1352-2310(96)00026-X.
  17. ↑ Leman, L.; Orgel, L.; Ghadiri, M. R. (2004). "Carbonyl sulfide-mediated prebiotic formation of peptides". Science. 306 (5694): 283–6. Bibcode:2004Sci...306..283L. doi:10.1126/science.1102722. PMID   15472077. S2CID   11819295.
  18. ↑ What Carbonyl Sulfide Teaches Us About Earth's Biosphere on YouTube.
  19. ↑ Campbell, J. E.; Berry, J. A.; Seibt, U.; Smith, S. J.; Montzka, S. A.; Launois, T.; Belviso, S.; Bopp, L.; Laine, M. (April 2017). "Large historical growth in global terrestrial gross primary production". Nature. 544 (7648): 84–87. Bibcode:2017Natur.544...84C. doi:10.1038/nature22030. OSTI   1398774. PMID   28382993. S2CID   205255121.
  20. ↑ 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. Bibcode:2013NatGe...6..186A. doi:10.1038/ngeo1730. ISSN   1752-0908.
  21. ↑ Couërbe, J. P. (1841). "Ueber den Schwefelkohlenstoff". Journal für Praktische Chemie. 23 (1): 83–124. doi:10.1002/prac.18410230105.
  22. ↑ Ferm R. J. (1957). "The Chemistry of Carbonyl Sulfide". Chemical Reviews . 57 (4): 621–640. doi:10.1021/cr50016a002.
  23. ↑ 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.

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