Carbon disulfide

Carbon disulfide 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]

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
CompTox Dashboard (EPA)
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
Molecular shape
 Linear
0 D (20 °C)[1]
Thermochemistry
75.73 J/(mol·K)[1]
Std molar
entropy (So298)
 151 J/(mol·K)[1]
88.7 kJ/mol[1]
64.4 kJ/mol[1]
Std enthalpy of
combustion (ΔcH⦵298)
 1687.2 kJ/mol[3]
Hazards
Safety data sheet See: data page
GHS pictograms [4]
GHS Signal word Danger
GHS hazard statements
 H225, H315, H319, H361, H372[4]
GHS precautionary statements
 P210, P281, P305+351+338, P314[4]
ICSC 0022
Inhalation hazard Irritant; toxic
Eye hazard Irritant
Skin hazard Irritant
NFPA 704 (fire diamond)
4
3
0
Flash point −43 °C (−45 °F; 230 K)[1]
Autoignition
temperature
 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
Structure and
properties
 Refractive index (n),
Dielectric constant (εr), etc.
Thermodynamic
data
 Phase behaviour
solid–liquid–gas
Spectral data
 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

Being isoelectronic with carbon dioxide but more electrophilic, it is reactive toward nucleophiles. These differences in reactivity can be attributed to the weaker π donor-ability of the sulfido centers, which renders the carbon more electrophilic. 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:[12]

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).[13]

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. Trithiocarbonate (-S-C(S)-S-) linkages comprise, in part, the backbone of the polymer, which is a semiconductor.[14]

Uses

The principal industrial uses of carbon disulfide, consuming 75% of the annual production, are the manufacture of viscose rayon and cellophane film.[15]

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

It can be used in fumigation of airtight storage warehouses, airtight flat storages, bins, grain elevators, railroad box cars, shipholds, barges and cereal mills.[16] 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.[17]

Health effects

Carbon disulfide has been linked to both acute and chronic forms of poisoning, with a diverse range of symptoms.[18] 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.[15][19]

Occupational exposure to carbon disulfide is associated with cardiovascular disease, particularly stroke.[20]

See also
  • Carbon monosulfide
  • Carbon subsulfide
  • Carbon diselenide

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.
  12. "4,5-Dibenzoyl-1,3-dithiole-1-thione". Org. Synth. 73: 270. 1996. doi:10.15227/orgsyn.073.0270.
  13. 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.
  14. 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.
  15. 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
  16. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  17. Worthing, Charles R.; Hance, Raymond J. (1991). The Pesticide Manual, A World Compendium (9th ed.). British Crop Protection Council. ISBN 9780948404429.
  18. "ATSDR - Public Health Statement: Carbon Disulfide". www.atsdr.cdc.gov. Retrieved 2020-01-17.
  19. 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.
  20. "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.
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