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Carbon disulfide

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Carbon disulfide (also spelled as carbon disulphide) is an inorganic compound with the chemical formula CS2 and structure S=C=S. It is also considered as the anhydride of thiocarbonic acid.[8] It is a colorless, flammable, neurotoxic liquid that is used as a building block in organic synthesis. Pure carbon disulfide has a pleasant, ether- or chloroform-like odor, but commercial samples are usually yellowish and are typically contaminated with foul-smelling impurities.[9]

Carbon disulfide
Carbon disulfide
Names
IUPAC name
Carbon disulfide
Systematic IUPAC name
Methanedithione
Other names
Carbon bisulfide
Dithiocarbonic anhydride[1]
Identifiers
3D model (JSmol)
1098293
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.767 Edit this at Wikidata
EC Number
  • 200-843-6
KEGG
RTECS number
  • FF6650000
UNII
UN number 1131
  • InChI=1S/CS2/c2-1-3 checkY
    Key: QGJOPFRUJISHPQ-UHFFFAOYSA-N checkY
  • InChI=1/CS2/c2-1-3
    Key: QGJOPFRUJISHPQ-UHFFFAOYAS
  • S=C=S
Properties
CS2
Molar mass 76.13 g·mol−1
Appearance Colorless liquid
Impure: light-yellow
Odor Pleasant, ether- or chloroform-like
Commercial: Foul, like rotten radish
Density 1.539 g/cm3 (−186°C)
1.2927 g/cm3 (0 °C)
1.266 g/cm3 (25 °C)[2]
Melting point −111.61 °C (−168.90 °F; 161.54 K)
Boiling point 46.24 °C (115.23 °F; 319.39 K)
2.58 g/L (0 °C)
2.39 g/L (10 °C)
2.17 g/L (20 °C)[3]
0.14 g/L (50 °C)[2]
Solubility Soluble in alcohol, ether, benzene, oil, CHCl3, CCl4
Solubility in formic acid 4.66 g/100 g[2]
Solubility in dimethyl sulfoxide 45 g/100 g (20.3 °C)[2]
Vapor pressure 48.1 kPa (25 °C)
82.4 kPa (40 °C)[4]
−42.2·10−6 cm3/mol
1.627[5]
Viscosity 0.436 cP (0 °C)
0.363 cP (20 °C)
Structure
Linear
0 D (20 °C)[2]
Thermochemistry
75.73 J/(mol·K)[2]
151 J/(mol·K)[2]
88.7 kJ/mol[2]
64.4 kJ/mol[2]
1687.2 kJ/mol[4]
Hazards
Occupational safety and health (OHS/OSH):
Inhalation hazards
 Irritant; neurotoxic
Eye hazards
 Irritant
Skin hazards
 Irritant
GHS labelling:[5]
GHS02: Flammable GHS07: Exclamation mark GHS08: Health hazard
Danger
H225, H315, H319, H332, H361fd, H372
P202, P210, P281, P303 P361 P353, P304 P340 P312, P305 P351 P338, P308 P313
ICSC 0022
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 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 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
4
0
Flash point −43 °C (−45 °F; 230 K)[2]
102 °C (216 °F; 375 K)[2]
Explosive limits 1.3–50%[6]
Lethal dose or concentration (LD, LC):
3188 mg/kg (rat, oral)
>1670 ppm (rat, 1 h)
15500 ppm (rat, 1 h)
3000 ppm (rat, 4 h)
3500 ppm (rat, 4 h)
7911 ppm (rat, 2 h)
3165 ppm (mouse, 2 h)[7]
4000 ppm (human, 30 min)[7]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 20 ppm C 30 ppm 100 ppm (30-minute maximum peak)[6]
REL (Recommended)
 TWA 1 ppm (3 mg/m3) ST 10 ppm (30 mg/m3) [skin][6]
IDLH (Immediate danger)
 500 ppm[6]
Related compounds
Related compounds
 Carbon dioxide
Carbonyl sulfide
Carbon diselenide
Supplementary data page
Carbon disulfide (data page)
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 ?)

History

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In 1796, the German chemist Wilhelm August Lampadius (1772–1842) first prepared carbon disulfide by heating pyrite with moist charcoal. He called it "liquid sulfur" (flüssig Schwefel).[10] The composition of carbon disulfide was finally determined in 1813 by the team of the Swedish chemist Jöns Jacob Berzelius (1779–1848) and the Swiss-British chemist Alexander Marcet (1770–1822).[11] Their analysis was consistent with an empirical formula of CS2.[12]

Occurrence, manufacture, properties

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Small amounts of carbon disulfide are released by volcanic eruptions and marshes. CS2 once was manufactured by combining carbon (or coke) and sulfur at 800–1000 °C.[13]

C 2S → CS2

A lower-temperature reaction, requiring only 600 °C, utilizes natural gas as the carbon source in the presence of silica gel or alumina catalysts:[9]

2 CH4 S8 → 2 CS2 4 H2S

The reaction is analogous to the combustion of methane.

Global production/consumption of carbon disulfide is approximately one million tonnes, with China consuming 49%, followed by India at 13%, mostly for the production of rayon fiber.[14] United States production in 2007 was 56,000 tonnes.[15]

Solvent

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Carbon disulfide can dissolve a variety of nonpolar chemicals including phosphorus, sulfur, selenium, bromine, iodine, fats, resins, rubber, and asphalt.[16]

Extraterrestrial

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In March 2024, traces of CS2 were likely detected in the atmosphere of the temperate mini-Neptune planet TOI-270 d by the James Webb Space Telescope.[17]

Reactions

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Combustion of CS2 affords sulfur dioxide according to this ideal stoichiometry:

CS2 3 O2 → CO2 2 SO2

With nucleophiles

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For example, amines afford dithiocarbamates:[18]

2 R2NH CS2 → [R2NH2 ][R2NCS2−]

Xanthates form similarly from alkoxides:[18]

RONa CS2 → [Na ][ROCS2−]

This reaction is the basis of the manufacture of regenerated cellulose, the main ingredient of viscose, rayon, and cellophane. Both xanthates and the related thioxanthates (derived from treatment of CS2 with sodium thiolates) are used as flotation agents in mineral processing.

Upon treatment with sodium sulfide, carbon disulfide affords trithiocarbonate:[18]

Na2S CS2 → [Na ]2[CS32−]

Carbon disulfide does not hydrolyze readily, although the process is catalyzed by an enzyme carbon disulfide hydrolase.

Compared to the isoelectronic carbon dioxide, CS2 is a weaker electrophile. While, however, reactions of nucleophiles with CO2 are highly reversible and products are only isolated with very strong nucleophiles, the reactions with CS2 are thermodynamically more favored allowing the formation of products with less reactive nucleophiles.[19]

Reduction

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Reduction of carbon disulfide with sodium affords sodium 1,3-dithiole-2-thione-4,5-dithiolate together with sodium trithiocarbonate:[20]

4 Na 4 CS2 → Na2C3S5 Na2CS3

Chlorination

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Chlorination of CS2 provides a route to carbon tetrachloride:[9]

CS2 3 Cl2 → CCl4 S2Cl2

This conversion proceeds via the intermediacy of thiophosgene, CSCl2.

Coordination chemistry

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CS2 is a ligand for many metal complexes, forming pi complexes. One example is CpCo(η2-CS2)(PMe3).[21]

Polymerization

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CS2 polymerizes upon photolysis or under high pressure to give an insoluble material called car-sul or "Bridgman's black", named after the discoverer of the polymer, Percy Williams Bridgman.[22] Trithiocarbonate (-S-C(S)-S-) linkages comprise, in part, the backbone of the polymer, which is a semiconductor.[23]

Uses

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The principal industrial uses of carbon disulfide, consuming 75% of the annual production, are the manufacture of viscose rayon and cellophane film.[24]

It is also a valued intermediate in chemical synthesis of carbon tetrachloride. It is widely used in the synthesis of organosulfur compounds such as xanthates, which are used in froth flotation, a method for extracting metals from their ores. Carbon disulfide is also a precursor to dithiocarbamates, which are used as drugs (e.g. Metam sodium) and rubber chemistry.

Niche uses

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Carbon disulfide insecticide ad from the 1896 issue of The American Elevator and Grain Trade magazine

It can be used in fumigation of airtight storage warehouses, airtight flat storage, bins, grain elevators, railroad box cars, ship holds, barges, and cereal mills.[25] Carbon disulfide is also used as an insecticide for the fumigation of grains, nursery stock, in fresh fruit conservation, and as a soil disinfectant against insects and nematodes.[26]

It can also be used for the Barking dog reaction.

Health effects

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Carbon disulfide has been linked to both acute and chronic forms of poisoning, with a diverse range of symptoms.[27]

Concentrations of 500–3000 mg/m3 cause acute and subacute poisoning. These include a set of mostly neurological and psychiatric symptoms, called encephalopathia sulfocarbonica. Symptoms include acute psychosis (manic delirium, hallucinations), paranoic ideas, loss of appetite, gastrointestinal and sexual disorders, polyneuritis, myopathy, and mood changes (including irritability and anger). Effects observed at lower concentrations include neurological problems (encephalopathy, psychomotor and psychological disturbances, polyneuritis, abnormalities in nerve conduction), hearing problems, vision problems (burning eyes, abnormal light reactions, increased ophthalmic pressure), heart problems (increased deaths for heart disease, angina pectoris, high blood pressure), reproductive problems (increased miscarriages, immobile or deformed sperm), and decreased immune response.[28][29]

Occupational exposure to carbon disulfide is also associated with cardiovascular disease, particularly stroke.[30]

In 2000, the WHO believed that health harms were unlikely at levels below 100 μg/m3, and set this as a guideline level.[needs update] Carbon disulfide can be smelled at levels above 200 μg/m3, and the WHO recommended a sensory guideline of below 20 μg/m3. Exposure to carbon disulfide is well-established to be harmful to health in concentrations at or above 30 mg/m3. Changes in the function of the central nervous system have been observed at concentrations of 20–25 mg/m3. There are also reports of harms to health at 10 mg/m3, for exposures of 10–15 years, but the lack of good data on past exposure levels make the association of these harms with concentrations of 10 mg/m3 findings uncertain. The measured concentration of 10 mg/m3 may be equivalent to a concentration in the general environment of 1 mg/m3.[28]

Environmental sources

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The primary source of carbon disulfide in the environment is rayon factories.[28] Most global carbon disulfide emissions come from rayon production, as of 2008.[31] Other sources include the production of cellophane, carbon tetrachloride,[31] carbon black, and sulfur recovery. Carbon disulfide production also emits hydrogen sulfide.[32]

As of 2004, about 250 g of carbon disulfide is emitted per kilogram of rayon produced. About 30 g of carbon disulfide is emitted per kilogram of carbon black produced. About 0.341 g of carbon disulfide is emitted per kilogram of sulfur recovered.[32]

Japan has reduced carbon disulfide emissions per kilogram of rayon produced, but in other rayon-producing countries, including China, emissions are assumed to be uncontrolled (based on global modelling and large-scale free-air concentration measurements). Rayon production is steady or decreasing except in China, where it is increasing, as of 2004.[32] Carbon black production in Japan and Korea uses incinerators to destroy about 99% of the carbon disulfide that would otherwise be emitted.[32] When used as a solvent, Japanese emissions are about 40% of the carbon disulfide used; elsewhere, the average is about 80%.[32]

Most rayon production uses carbon sulfide.[33][34] One exception is rayon made using the lyocell process, which uses a different solvent; as of 2018 the lyocell process is not widely used, because it is more expensive than the viscose process.[35][36] Cuprammonium rayon also does not use carbon disulfide.

Historic and current exposure

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Industrial workers working with carbon disulfide are at high risk. Emissions may also harm the health of people living near rayon plants.[28]

Concerns about carbon disulfide exposure have a long history.[24][37][38]: 79  Around 1900, carbon disulfide came to be widely used in the production of vulcanized rubber. The psychosis produced by high exposures was immediately apparent (it has been reported with 6 months of exposure[28]). Sir Thomas Oliver told a story about a rubber factory that put bars on its windows so that the workers would not jump out to their deaths.[38]: 17  Carbon disulfide's use in the US as a heavier-than-air burrow poison for Richardson's ground squirrel also led to reports of psychosis. No systematic medical study of the issue was published, and knowledge was not transferred to the rayon industry.[33]

The first large epidemiological study of rayon workers was done in the US in the late 1930s, and found fairly severe effects in 30% of the workers. Data on increased risks of heart attacks and strokes came out in the 1960s. Courtaulds, a major rayon manufacturer, worked hard to prevent publication of this data in the UK.[33] Average concentrations in sampled rayon plants were reduced from about 250 mg/m3 in 1955–1965 to about 20–30 mg/m3 in the 1980s (US figures only?[United States-centric]).[28] Rayon production has since largely moved to the developing world, especially China, Indonesia and India.[34][33]

Rates of disability in modern factories are unknown, as of 2016.[34][39] Current manufacturers using the viscose process do not provide any information on harm to their workers.[33][34]

See also

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References

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  1. ^ "Carbon disulfide chemistry". PubChem. Retrieved August 24, 2022.
  2. ^ a b c d e f g h i j k "Properties of substance: carbon disulfide". chemister.ru.
  3. ^ Seidell, Atherton; Linke, William F. (1952). Solubilities of Inorganic and Organic Compounds. Van Nostrand.
  4. ^ a b Carbon disulfide in Linstrom, Peter J.; Mallard, William G. (eds.); NIST Chemistry WebBook, NIST Standard Reference Database Number 69, National Institute of Standards and Technology, Gaithersburg (MD) (retrieved 2014-05-27).
  5. ^ a b Sigma-Aldrich Co., [www.sigmaaldrich.com/product/sigald/180173 Carbon disulfide]. Retrieved on 2024-10-23.
  6. ^ a b c d NIOSH Pocket Guide to Chemical Hazards. "#0104". National Institute for Occupational Safety and Health (NIOSH).
  7. ^ a b "Carbon disulfide". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  8. ^ Informatics, NIST Office of Data and. "Carbon disulfide". webbook.nist.gov. Retrieved 2024-05-07.
  9. ^ a b c Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN 0-12-352651-5.
  10. ^ Lampadius (1796). "Etwas über flüssigen Schwefel, und Schwefel-Leberluft" [Something about liquid sulfur and liver-of-sulfur gas (i.e., hydrogen sulfide)]. Chemische Annalen für die Freunde der Naturlehre, Arzneygelährtheit, Haushaltungskunst und Manufacturen (Chemical Annals for the Friends of Science, Medicine, Economics, and Manufactures) (in German) (2): 136–137.
  11. ^ Berzelius, J.; Marcet, Alexander (1813). "Experiments on the alcohol of sulphur, or sulphuret of carbon". Philosophical Transactions of the Royal Society of London. 103: 171–199. doi:10.1098/rstl.1813.0026. S2CID 94745906.
  12. ^ (Berzelius and Marcet, 1813), p. 187.
  13. ^ Warnecke, Friedrich (1941). "Die gewerbliche Schwefelkohlenstoffvergiftung". Archiv für Gewerbepathologie und Gewerbehygiene (in German). 11 (2). Springer Science and Business Media LLC: 198–248. Bibcode:1941IAOEH..11..198W. doi:10.1007/bf02122927. ISSN 0340-0131. S2CID 72106188.
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  16. ^ "Carbon Disulfide". Akzo Nobel. Archived from the original on 2017-09-03. Retrieved 2010-12-16.
  17. ^ Benneke, Björn; Roy, Pierre-Alexis; Coulombe, Louis-Philippe; Radica, Michael; Piaulet, Caroline; Ahrer, Eva-Maria; Pierrehumbert, Raymond; Krissansen-Totton, Joshua; Schlichting, Hilke E. (2024-03-05), JWST Reveals CH$_4$, CO$_2$, and H$_2$O in a Metal-rich Miscible Atmosphere on a Two-Earth-Radius Exoplanet, arXiv:2403.03325
  18. ^ a b c Yokoyama, Masataka; Imamoto, Tsuneo (1984). "Organic Reactions of Carbon Disulfide". Synthesis. 1984 (10). Georg Thieme Verlag KG: 797–824. doi:10.1055/s-1984-30978. ISSN 0039-7881.
  19. ^ Li, Zhen; Mayer, Robert J.; Ofial, Armin R.; Mayr, Herbert (2020-04-27). "From Carbodiimides to Carbon Dioxide: Quantification of the Electrophilic Reactivities of Heteroallenes". Journal of the American Chemical Society. 142 (18): 8383–8402. doi:10.1021/jacs.0c01960. PMID 32338511. S2CID 216557447.
  20. ^ "4,5-Dibenzoyl-1,3-dithiole-1-thione". Org. Synth. 73: 270. 1996. doi:10.15227/orgsyn.073.0270.
  21. ^ Werner, Helmut (1982). "Novel Coordination Compounds formed from CS2 and Heteroallenes". Coordination Chemistry Reviews. 43: 165–185. doi:10.1016/S0010-8545(00)82095-0.
  22. ^ Bridgman, P.W. (1941). "Explorations toward the limit of utilizable pressures". Journal of Applied Physics. 12 (6): 461–469. Bibcode:1941JAP....12..461B. doi:10.1063/1.1712926.
  23. ^ Ochiai, Bungo; Endo, Takeshi (2005). "Carbon dioxide and carbon disulfide as resources for functional polymers". Progress in Polymer Science. 30 (2): 183–215. doi:10.1016/j.progpolymsci.2005.01.005.
  24. ^ a b Lay, Manchiu D. S.; Sauerhoff, Mitchell W.; Saunders, Donald R.; "Carbon Disulfide", in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000 doi:10.1002/14356007.a05_185
  25. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
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  29. ^ Preventing hearing loss caused by chemical (ototoxicity) and noise exposure (Report). U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health. 2018-03-01. doi:10.26616/nioshpub2018124.
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  31. ^ a b "Carbon Disulfide Health Effects Assessment for HEAC Discussion April 2008". Division of Occupational Safety and Health (DOC). State of California Department of Industrial Relations. April 2008. Retrieved 24 March 2023.
  32. ^ a b c d e Blake, Nicola J. (2004). "Carbonyl sulfide and carbon disulfide: Large-scale distributions over the western Pacific and emissions from Asia during TRACE-P". Journal of Geophysical Research. 109 (D15): D15S05. Bibcode:2004JGRD..10915S05B. doi:10.1029/2003JD004259. S2CID 43793469.
  33. ^ a b c d e Swan, Norman; Blanc, Paul (20 February 2017). "The health burden of viscose rayon". ABC Radio National. Retrieved 24 March 2023.
  34. ^ a b c d Nijhuis, Michelle (2009). "Bamboo Boom: Is This Material for You?". Scientific American Special Editions. Vol. 19, no. 2. pp. 60–65. Bibcode:2009SciAm..19f..60N. Retrieved 24 March 2023.
  35. ^ "Regenerated cellulose by the Lyocell process, a brief review of the process and properties :: BioResources". BioRes. 2018.
  36. ^ Tierney, John William (2005). Kinetics of Cellulose Dissolution in N-MethylMorpholine-N-Oxide and Evaporative Processes of Similar Solutions (Thesis).
  37. ^ St. Clair, Kassia (2018). The Golden Thread: How Fabric Changed History. London: John Murray. pp. 213–215. ISBN 978-1-4736-5903-2. OCLC 1057250632.
  38. ^ a b Blanc, M.D., Paul David (15 November 2016). Fake Silk / The Lethal History of Viscose Rayon. Yale University Press. ISBN 9780300204667. Retrieved 17 December 2020. in 1915,...[of 16] carbon disulfide poisoning cases....one worker had been briefly committed to an asylum and several others had experienced nervous system complaints...
  39. ^ Monosson, Emily (2016). "Toxic textiles". Science. 354 (6315): 977. Bibcode:2016Sci...354..977M. doi:10.1126/science.aak9834. PMID 27884997. S2CID 45869497.
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