Chemistry:Carbon disulfide

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Short description: Neurotoxic compound with formula S=C=S
Carbon disulfide
Carbon disulfide
Carbon-disulfide-3D-vdW.png
Names
IUPAC name
Carbon disulfide
Systematic IUPAC name
Methanedithione
Other names
Carbon bisulfide
Identifiers
3D model (JSmol)
1098293
ChEBI
ChEMBL
ChemSpider
EC Number
  • 200-843-6
KEGG
RTECS number
  • FF6650000
UNII
UN number 1131
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)[1]
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)[2]
0.14 g/L (50 °C)[1]
Solubility Soluble in alcohol, ether, benzene, oil, CHCl3, CCl4
Solubility in formic acid 4.66 g/100 g[1]
Solubility in dimethyl sulfoxide 45 g/100 g (20.3 °C)[1]
Vapor pressure 48.1 kPa (25 °C)
82.4 kPa (40 °C)[3]
−42.2·10−6 cm3/mol
1.627[4]
Viscosity 0.436 cP (0 °C)
0.363 cP (20 °C)
Structure
Linear
0 D (20 °C)[1]
Thermochemistry
75.73 J/(mol·K)[1]
151 J/(mol·K)[1]
88.7 kJ/mol[1]
64.4 kJ/mol[1]
1687.2 kJ/mol[3]
Hazards
GHS pictograms GHS02: Flammable GHS06: Toxic GHS08: Health hazard
GHS Signal word Danger
H225, H315, H319, H361, H372
P210, P281, P305+351+338, P314
ICSC 0022
Inhalation hazard Irritant; neurotoxic
Eye hazard Irritant
Skin hazard Irritant
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 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
4
3
0
Flash point −43 °C (−45 °F; 230 K)[1]
102 °C (216 °F; 375 K)[1]
Explosive limits 1.3–50%[5]
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)[6]
4000 ppm (human, 30 min)[6]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 20 ppm C 30 ppm 100 ppm (30-minute maximum peak)[5]
REL (Recommended)
 TWA 1 ppm (3 mg/m3) ST 10 ppm (30 mg/m3) [skin][5]
IDLH (Immediate danger)
 500 ppm[5]
Related compounds
Related compounds
 Carbon dioxide
Carbonyl sulfide
Carbon diselenide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Tracking categories (test):

Carbon disulfide (also spelled as carbon disulphide) is an inorganic compound with the chemical formula CS
2 and structure S=C=S. 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.[7]

History

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).[8] 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).[9] Their analysis was consistent with an empirical formula of CS2.[10]

Occurrence, manufacture, properties

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.[11]

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:[7]

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.[12] United States production in 2007 was 56,000 tonnes.[13]

Solvent

Carbon disulfide is a solvent for phosphorus, sulfur, selenium, bromine, iodine, fats, resins, rubber, and asphalt.[14]

Reactions

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

CS2 + 3 O2 → CO2 + 2 SO2

With nucleophiles

For example, amines afford dithiocarbamates:[15]

2 R2NH + CS2 → [R2NH2+][R2NCS2−]

Xanthates form similarly from alkoxides:[15]

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:[15]

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.[16]

Reduction

Reduction of carbon disulfide with sodium affords sodium 1,3-dithiole-2-thione-4,5-dithiolate together with sodium trithiocarbonate:[17]

4 Na + 4 CS2 → Na2C3S5 + Na2CS3

Chlorination

Chlorination of CS2 provides a route to carbon tetrachloride:[7]

CS2 + 3 Cl2 → CCl4 + S2Cl2

This conversion proceeds via the intermediacy of thiophosgene, CSCl2.

Coordination chemistry

CS2 is a ligand for many metal complexes, forming pi complexes. One example is CpCo(η2-CS2)(PMe3).[18]

Polymerization

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.[19] Trithiocarbonate (-S-C(S)-S-) linkages comprise, in part, the backbone of the polymer, which is a semiconductor.[20]

Uses

The principal industrial uses of carbon disulfide, consuming 75% of the annual production, are the manufacture of viscose rayon and cellophane film.[21]

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

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.[22] 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.[23]

Health effects

Carbon disulfide has been linked to both acute and chronic forms of poisoning, with a diverse range of symptoms.[24]

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), and reproductive problems (increased miscarriages, immobile or deformed sperm), and decreased immune response.[25][26]

Occupational exposure to carbon disulfide is also associated with cardiovascular disease, particularly stroke.[27]

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 sulfide 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.[25]

Environmental sources

The primary source of carbon disulfide in the environment is rayon factories.[25] Most global carbon disulfide emissions come from rayon production, as of 2008.[28] Other sources include the production of cellophane, carbon tetrachloride,[28] carbon black, and sulfur recovery. Carbon disulfide production also emits carbon disulfide.[29]

(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.[29]

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).[29] Carbon black production in Japan and Korea uses incinerators to destroy about 99% of the carbon disulfide that would otherwise be emitted.[29] When used as a solvent, Japanese emissions are about 40% of the carbon disulfide used; elsewhere, the average is about 80%.[29]

Most rayon production uses carbon sulfide.[30][31] 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.[32][33] Cuprammonium rayon also does not use carbon disulfide.

Historic and current exposure

Industrial workers working with carbon disulfide are at high risk. Emissions may also harm the health of people living near rayon plants.[25]

Concerns about carbon disulfide exposure have a long history.[21][34][35]: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[25]). 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 (suicide).[35]: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.[30]

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.[30] 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?Template:Globalize inline).[25] Rayon production has since largely moved to the developing world, especially China, Indonesia and India.[31][30]

Rates of disability in modern factories are unknown, (As of 2016).[31][36] Current manufacturers using the viscose process do not provide any information on harm to their workers.[30][31]

See also

References

  1. ↑ 1.00 1.01 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10 "Properties of substance: carbon disulfide". http://chemister.ru/Database/properties-en.php?dbid=1&id=1955. 
  2. ↑ Seidell, Atherton; Linke, William F. (1952). Solubilities of Inorganic and Organic Compounds. Van Nostrand. 
  3. ↑ 3.0 3.1 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), http://webbook.nist.gov (retrieved 2014-05-27).
  4. ↑ 4.0 4.1 Sigma-Aldrich Co., Carbon disulfide. Retrieved on 2014-05-27.
  5. ↑ 5.0 5.1 5.2 5.3 NIOSH Pocket Guide to Chemical Hazards. "#0104". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0104.html. 
  6. ↑ 6.0 6.1 "Carbon disulfide". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/idlh/75150.html. 
  7. ↑ 7.0 7.1 7.2 Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils, ed., Inorganic Chemistry, San Diego/Berlin: Academic Press/De Gruyter, ISBN 0-12-352651-5 .
  8. ↑ Lampadius (1796). "Etwas über flüssigen Schwefel, und Schwefel-Leberluft" (in de). Chemische Annalen für die Freunde der Naturlehre, Arzneygelährtheit, Haushaltungskunst und Manufacturen (Chemical Annals for the Friends of Science, Medicine, Economics, and Manufactures) (2): 136–137. https://books.google.com/books?id=gqk5AAAAcAAJ&pg=PA136. 
  9. ↑ 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. 
  10. ↑ (Berzelius and Marcet, 1813), p. 187.
  11. ↑ Warnecke, Friedrich (1941). "Die gewerbliche Schwefelkohlenstoffvergiftung" (in de). Archiv für Gewerbepathologie und Gewerbehygiene (Springer Science and Business Media LLC) 11 (2): 198–248. doi:10.1007/bf02122927. ISSN 0340-0131. 
  12. ↑ "Carbon Disulfide report from IHS Chemical". http://www.ihs.com/products/chemical/planning/ceh/carbon-disulfide.aspx. 
  13. ↑ "Chemical profile: carbon disulfide from ICIS.com". http://www.icis.com/Articles/2008/09/08/9154319/chemical-profile-carbon-disulfide.html. 
  14. ↑ "Carbon Disulfide". Akzo Nobel. http://www.akzonobel.com/sulfurderivatives/products/carbon_disulfide/. 
  15. ↑ 15.0 15.1 15.2 Yokoyama, Masataka; Imamoto, Tsuneo (1984). "Organic Reactions of Carbon Disulfide". Synthesis (Georg Thieme Verlag KG) 1984 (10): 797–824. doi:10.1055/s-1984-30978. ISSN 0039-7881. 
  16. ↑ 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. 
  17. ↑ "4,5-Dibenzoyl-1,3-dithiole-1-thione". Org. Synth. 73: 270. 1996. doi:10.15227/orgsyn.073.0270. 
  18. ↑ 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. 
  19. ↑ Bridgman, P.W. (1941). "Explorations toward the limit of utilizable pressures". Journal of Applied Physics 12 (6): 461–469. doi:10.1063/1.1712926. Bibcode: 1941JAP....12..461B. 
  20. ↑ 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. 
  21. ↑ 21.0 21.1 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
  22. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. 
  23. ↑ Worthing, Charles R.; Hance, Raymond J. (1991). The Pesticide Manual, A World Compendium (9th ed.). British Crop Protection Council. ISBN 9780948404429. https://archive.org/details/pesticidemanualw0000unse. 
  24. ↑ "ATSDR - Public Health Statement: Carbon Disulfide". https://www.atsdr.cdc.gov/phs/phs.asp?id=472&tid=84#bookmark05. 
  25. ↑ 25.0 25.1 25.2 25.3 25.4 25.5 "Chapter 5.4 : Carbon disulfide". Air Quality Guidelines (2 ed.). WHO Regional Office for Europe, Copenhagen, Denmark. 2000. https://www.euro.who.int/__data/assets/pdf_file/0019/123058/AQG2ndEd_5_4carbodisulfide.PDF. Retrieved 31 July 2021. 
  26. ↑ (in en) 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. https://www.cdc.gov/niosh/docs/2018-124/. 
  27. ↑ "Occupational health and safety – chemical exposure" (in en). Swedish Agency for Health Technology Assessment and Assessment of Social Services (SBU). http://www.sbu.se/en/publications/sbu-assesses/occupational-health-and-safety--chemical-exposure/. 
  28. ↑ 28.0 28.1 "Carbon Disulfide Health Effects Assessment for HEAC Discussion April 2008". State of California Department of Industrial Relations. April 2008. https://www.dir.ca.gov/dosh/DoshReg/CarbonDisulfide5155-4-08.doc. 
  29. ↑ 29.0 29.1 29.2 29.3 29.4 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. doi:10.1029/2003JD004259. Bibcode: 2004JGRD..10915S05B. https://scholars.unh.edu/cgi/viewcontent.cgi?article=1072&context=earthsci_facpub. 
  30. ↑ 30.0 30.1 30.2 30.3 30.4 Swan, Norman; Blanc, Paul (20 February 2017). "The health burden of viscose rayon" (in en). ABC Radio National. http://www.abc.net.au/radionational/programs/healthreport/the-health-burden-of-viscose-rayon/8286870. 
  31. ↑ 31.0 31.1 31.2 31.3 Nijhuis, Michelle (2009). "Bamboo Boom: Is This Material for You?". Scientific American Special Editions 19 (2): 60–65. Bibcode: 2009SciAm..19f..60N. https://www.scientificamerican.com/article/bamboo-boom/. Retrieved 24 March 2023. 
  32. ↑ "Regenerated cellulose by the Lyocell process, a brief review of the process and properties :: BioResources". BioRes. 2018. https://bioresources.cnr.ncsu.edu/resources/regenerated-cellulose-by-the-lyocell-process-a-brief-review-of-the-process-and-properties/. 
  33. ↑ Tierney, John William (2005). Kinetics of Cellulose Dissolution in N-MethylMorpholine-N-Oxide and Evaporative Processes of Similar Solutions (Thesis).
  34. ↑ 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. 
  35. ↑ 35.0 35.1 Blanc, M.D., Paul David (15 November 2016). Fake Silk / The Lethal History of Viscose Rayon. Yale University Press. ISBN 9780300204667. https://yalebooks.yale.edu/book/9780300204667/fake-silk. 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..." 
  36. ↑ Monosson, Emily (2016). "Toxic textiles". Science 354 (6315): 977. doi:10.1126/science.aak9834. PMID 27884997. Bibcode: 2016Sci...354..977M. 

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