Carbon disulfide

Carbon disulfide, also spelled as carbon disulphide, is a colorless volatile liquid with the formula CS2. The compound is used frequently as a building block in organic chemistry as well as an industrial and chemical non-polar solvent. It has an "ether-like" odor, but commercial samples are typically contaminated with foul-smelling impurities.[7]

"CS2" redirects here. For other uses, see CS2 (disambiguation).
Carbon disulfide
Names
IUPAC name
Methanedithione
Other names
Carbon bisulfide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.000.767
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 Chloroform (pure)
Foul (commercial)
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
Safety data sheet See: data page
GHS pictograms [4]
GHS Signal word Danger
H225, H315, H319, H361, H372[4]
P210, P281, P305+351+338, P314[4]
ICSC 0022
Inhalation hazard Irritant; toxic
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 code
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
Supplementary data page
Refractive index (n),
Dielectric constant (εr), etc.
Thermodynamic
data
 Phase behaviour
solid–liquid–gas
UV, IR, NMR, MS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

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 high temperatures.

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.[8] United States production in 2007 was 56,000 tonnes.[9]

Solvent

Carbon disulfide is a solvent for phosphorus, sulfur, selenium, bromine, iodine, fats, resins, rubber, and asphalt.[10] It has been used in the purification of single-walled carbon nanotubes.[11]

Reactions

CS2 is highly flammable. Its combustion affords sulfur dioxide according to this ideal stoichiometry:

CS2 + 3 O2 → CO2 + 2 SO2

With nucleophiles

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.[12] For example, amines afford dithiocarbamates:

2 R2NH + CS2 → [R2NH2+][R2NCS2−]

Xanthates form similarly from alkoxides:

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.

Sodium sulfide affords trithiocarbonate:

Na2S + CS2 → [Na+]2[CS32−]

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

Reduction

Reduction of carbon disulfide with sodium affords sodium 1,3-dithiole-2-thione-4,5-dithiolate together with sodium trithiocarbonate:[13]

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).[14]

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.[15] Trithiocarbonate (-S-C(S)-S-) linkages comprise, in part, the backbone of the polymer, which is a semiconductor.[16]

Uses

The principal industrial uses of carbon disulfide, consuming 75% of the annual production, are the manufacture of viscose rayon and cellophane film.[17]

It is also a valued intermediate in chemical synthesis of carbon tetrachloride. It is widely used in the synthesis of organosulfur compounds such as metam sodium, xanthates, dithiocarbamates, which are used in extractive metallurgy 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 storages, bins, grain elevators, railroad box cars, shipholds, barges and cereal mills.[18] 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.[19]

Health effects

Carbon disulfide has been linked to both acute and chronic forms of poisoning, with a diverse range of symptoms.[20] Typical recommended TLV is 30 mg/m3, 10 ppm. Possible symptoms include, but are not limited to, tingling or numbness, loss of appetite, blurred vision, cramps, muscle weakness, pain, neurophysiological impairment, priapism, erectile dysfunction, psychosis, keratitis, and death by respiratory failure.[17][21][22]

Occupational exposure to carbon disulfide is associated with cardiovascular disease, particularly stroke.[23]

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).[24] 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).[25] Their analysis was consistent with an empirical formula of CS2.[26]

See also

References
  1. "Properties of substance: carbon disulfide". chemister.ru.
  2. Seidell, Atherton; Linke, William F. (1952). Solubilities of Inorganic and Organic Compounds. Van Nostrand.
  3. 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. Sigma-Aldrich Co., Carbon disulfide. Retrieved on 2014-05-27.
  5. NIOSH Pocket Guide to Chemical Hazards. "#0104". National Institute for Occupational Safety and Health (NIOSH).
  6. "Carbon disulfide". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  7. 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.
  8. "Carbon Disulfide report from IHS Chemical". Retrieved June 15, 2013.
  9. "Chemical profile: carbon disulfide from ICIS.com". Retrieved June 15, 2013.
  10. "Carbon Disulfide". Akzo Nobel.
  11. Park, Tae-Jin; Banerjee, Sarbajit; Hemraj-Benny, Tirandai; Wong, Stanislaus S. (2006). "Purification strategies and purity visualization techniques for single-walled carbon nanotubes". Journal of Materials Chemistry. 16 (2): 141–154. doi:10.1039/b510858f. S2CID 581451.
  12. 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.
  13. "4,5-Dibenzoyl-1,3-dithiole-1-thione". Org. Synth. 73: 270. 1996. doi:10.15227/orgsyn.073.0270.
  14. 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.
  15. Bridgman, P.W. (1941). "Explorations toward the limit of utilizable pressures". Journal of Applied Physics. 12 (6): 461–469. doi:10.1063/1.1712926.
  16. 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.
  17. 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
  18. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  19. Worthing, Charles R.; Hance, Raymond J. (1991). The Pesticide Manual, A World Compendium (9th ed.). British Crop Protection Council. ISBN 9780948404429.
  20. "ATSDR - Public Health Statement: Carbon Disulfide". www.atsdr.cdc.gov. Retrieved 2020-01-17.
  21. 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.
  22. Blanc, M.D., Paul David (15 November 2016). Fake Silk / The Lethal History of Viscose Rayon. Yale University Press. p. 79. 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...
  23. "Occupational health and safety – chemical exposure". www.sbu.se. Swedish Agency for Health Technology Assessment and Assessment of Social Services (SBU). Archived from the original on 2017-06-06. Retrieved 2017-06-07.
  24. 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.
  25. 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.
  26. (Berzelius and Marcet, 1813), p. 187.
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