Carbon disulfide

From Wikipedia, the free encyclopedia
Jump to: navigation, search
Carbon disulfide
Carbon disulfide
Carbon-disulfide-3D-vdW.png
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)
0.258 g/100 mL (0 °C)
0.239 g/100 mL (10 °C)
0.217 g/100 mL (20 °C)[2]
0.014 g/100 mL (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 The flame pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)The exclamation-mark pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)The health hazard pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)[4]
GHS signal word Danger
H225, H315, H319, H361, H372[4]
P210, P281, P305+351+338, P314[4]
ICSC 0022
Inhalation hazard Irritant
Eye hazard Irritant
Skin hazard Irritant
NFPA 704
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., propane Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazards (white): no codeNFPA 704 four-colored diamond
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 hr)
15500 ppm (rat, 1 hr)
3000 ppm (rat, 4 hr)
3500 ppm (rat, 4 hr)
7911 ppm (rat, 2 hr)
3165 ppm (mouse, 2 hr)[6]
4000 ppm (human, 30 min)[6]
US health exposure limits (NIOSH):
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 constantr), 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 YesYN ?)
Infobox references

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]

Occurrence, manufacture, properties[edit]

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. It is isoelectronic with carbon dioxide. CS2 is highly flammable:

CS2 + 3 O2 → CO2 + 2 SO2

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[edit]

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[edit]

Compared to CO2, CS2 is more reactive toward nucleophiles and more easily reduced. 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.

Chlorination[edit]

Chlorination of CS2 is the principal route to carbon tetrachloride:[7]

CS2 + 3 Cl2 → CCl4 + S2Cl2

This conversion proceeds via the intermediacy of thiophosgene, CSCl2.

Coordination chemistry[edit]

CS2 is a ligand for many metal complexes, forming pi complexes. One example is CpCo(η2-CS2)(PMe3).[12]

Polymerization[edit]

CS2 polymerizes upon photolysis or under high pressure to give an insoluble material called "Bridgman's black", named after the discoverer of the polymer, P. W. Bridgman. Trithiocarbonate (-S-C(S)-S-) linkages comprise, in part, the backbone of the polymer, which is a semiconductor.[13]

Uses[edit]

The principal industrial uses of carbon disulfide, consuming 75% of the annual production are the manufacture of viscose rayon, cellophane film.[14]

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[edit]

It can be used in fumigation of airtight storage warehouses, airtight flat storages, bins, grain elevators, railroad box cars, shipholds, barges and cereal mills.[15] 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.[16]

Health effects[edit]

Carbon disulfide is highly toxic. Typical recommended TLV is 30 mg/m3, 10 ppm. Symptoms include tingling or numbness, "cramps, muscle weakness, pain, distal sensory loss, and neurophysiological impairment".[14]

Occupational exposure to carbon disulfide is associated with cardiovascular disease, in particular: stroke.[17]

See also[edit]

References[edit]

  1. ^ a b c d e f g h i j k 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. ^ a b Carbon disulfide in Linstrom, P. J.; Mallard, W. 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. ^ a b c d Sigma-Aldrich Co., Carbon disulfide. Retrieved on 2014-05-27.
  5. ^ a b c d "NIOSH Pocket Guide to Chemical Hazards #0104". National Institute for Occupational Safety and Health (NIOSH). 
  6. ^ a b "Carbon disulfide". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH). 
  7. ^ a b c Holleman, A. F.; Wiberg, E. (2001), Inorganic Chemistry, San Diego: Academic Press, 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, T.-J.; Banerjee, S.; Hemraj-Benny, T.; Wong, S. 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. ^ Werner, H. (1982). "Novel Coordination Compounds formed from CS2 and Heteroallenes". Coordination Chemistry Reviews. 43: 165–185. doi:10.1016/S0010-8545(00)82095-0. 
  13. ^ Bungo Ochiai; Takeshi Endo. "Carbon dioxide and carbon disulfide as resources for functional polymers". Prog. Polym. Sci. 30 (2): 183–215. doi:10.1016/j.progpolymsci.2005.01.005. 
  14. ^ a b Manchiu D. S. Lay, Mitchell W. Sauerhoff and Donald R. Saunders "Carbon Disulfide" in Ullmann's Encyclopedia of Industrial Chemistry 2000, Wiley-VCH, Weinheim. doi: 10.1002/14356007.a05_185
  15. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9. 
  16. ^ Worthing, C. R.; Hance. R. J. (1991). The Pesticide Manual, A World Compendium (9th ed.). British Crop Protection Council. ISBN 9780948404429. 
  17. ^ Services, Statens beredning för medicinsk och social utvärdering (SBU); Swedish Agency for Health Technology Assessment and Assessment of Social. "Occupational health and safety – chemical exposure". www.sbu.se. Retrieved 2017-06-07. 

External links[edit]