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Carbon disulfide

 

Carbon disulfide

Carbon disulfide
Carbon disulfide
Names
IUPAC name
Methanedithione
Other names
Carbon bisulfide
Identifiers
 Y
ChEBI  Y
ChemSpider  Y
EC number 200-843-6
Jmol-3D images Image
KEGG  N
PubChem
RTECS number FF6650000
UNII  Y
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]
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
Highly Flammable F Toxic T Irritant Xi
R-phrases R11, R36/38, R48/23, R62, R63
S-phrases (S1/2), S16, S33, S36/37, S45
Inhalation hazard Irritant
Eye hazard Irritant
Skin hazard Irritant
NFPA 704
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):
LD50 (Median dose)
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]
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  (: Y/N?)

Carbon disulfide is a colorless solvent. It has an "ether-like" odor, but commercial samples are typically contaminated with foul-smelling impurities, such as carbonyl sulfide.[7]

Contents

  • Occurrence and manufacture 1
  • Reactions 2
    • Addition of nucleophiles 2.1
    • Chlorination 2.2
    • Coordination chemistry 2.3
    • Carbon disulfide hydrolase 2.4
    • Mechanism 2.5
  • Polymerization 3
  • Uses 4
    • Fumigation 4.1
    • Insecticide 4.2
    • Solvent 4.3
    • Manufacturing 4.4
    • Working Fluid 4.5
    • Spectroscope prisms 4.6
  • Health effects 5
  • See also 6
  • References 7
  • External links 8

Occurrence and manufacture

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. 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] USA production in 2007 was 56,000 tonnes.[9]

Reactions

Compared to CO2, CS2 is more reactive toward metam sodium, a soil fumigant and is commonly used in the production of the soft fabric viscose.

Addition of nucleophiles

Nucleophiles such as 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−]

Chlorination

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

CS2 is a ligand for many metal complexes, forming pi complexes. One example is CpCo(η2-CS2)(PMe3).[10]

Carbon disulfide hydrolase

Carbon disulfide is naturally formed in the mudpots of volcanic solfataras. It serves as a source of

  • Australian National Pollutant Inventory: Carbon disulfide
  • CDC - NIOSH Pocket Guide to Chemical Hazards - Carbon Disulfide
  • Inno Motion Engineering

External links

  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".  
  6. ^ a b "Carbon disulfide". Immediately Dangerous to Life and Health.  
  7. ^ a b c Holleman, A. F.; Wiberg, E. (2001), Inorganic Chemistry, San Diego: Academic Press,  
  8. ^ "Carbon Disulfide report from IHS Chemical". Retrieved June 15, 2013. 
  9. ^ "Chemical profile: carbon disulfide from ICIS.com". Retrieved June 15, 2013. 
  10. ^ Werner, H. (1982). "Novel Coordination Compounds formed from CS2 and Heteroallenes". Coordination Chemistry Reviews 43: 165–185.  
  11. ^ a b Smeulders MJ, Barends TR, Pol A, Scherer A, Zandvoort MH, Udvarhelyi A, Khadem AF, Menzel A, Hermans J, Shoeman RL, Wessels HJ, van den Heuvel LP, Russ L, Schlichting I, Jetten MS, Op den Camp HJ (2011). "Evolution of a new enzyme for carbon disulphide conversion by an acidothermophilic archaeon". Nature 478 (7369): 412–416.  
  12. ^ a b Smeulders, MJ.; Barends, TR.; Pol, A.; Scherer, A.; Zandvoort, MH.; Udvarhelyi, A.; Khadem, AF.; Menzel, A.; Hermans, J.; Shoeman, RL.; Wessels, HJ.; Van den Heuvel, LP.; Russ, L.; Schlichting, I.; Jetten, MS.; Op den Camp, HJ. RCSB Protein Data Bank, 2011, doi:10.2210/pdb3teo/pdb
  13. ^ Bungo Ochiai; Takeshi Endo. "Carbon dioxide and carbon disulfide as resources for functional polymers". Prog. Polym. Sci. 30 (2): 183–215.  
  14. ^  
  15. ^ Worthing, C. R.; Hance. R. J. (1991). The Pesticide Manual, A World Compendium (9th ed.). British Crop Protection Council.  
  16. ^ "Carbon Disulfide". Akzo Nobel. 
  17. ^ 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.  
  18. ^ "Carbon Disulfide Engines". Douglas Self. 
  19. ^ "How to work with the spectroscope. John Browning. 2nd Ed 1882

References

See also

At high levels, carbon disulfide may be life-threatening because it affects the nervous system. Significant safety data comes from the viscose rayon industry, where both carbon disulfide as well as small amounts of H2S may be present.

Health effects

Due to its high optical dispersion it was used in some spectroscopes.[19]

Spectroscope prisms

Various attempts were made in the 19th century to use carbon disulfide as the working fluid in steam engines and locomotive applications, due to its low boiling point; it would be either directly heated by the fuel, or would be used to recover waste heat from the combustion gases of other fuels and the condensing of steam in a traditional boiler. These experiments were never successful, both due to the low temperatures involved and the extreme risk of both poisoning and explosion.[18]

Working Fluid

The principal industrial uses of carbon disulfide are the manufacture of viscose rayon, cellophane film, carbon tetrachloride and xanthogenates and electronic vacuum tubes.

Manufacturing

Carbon disulfide is a solvent for phosphorus, sulfur, selenium, bromine, iodine, fats, resins, rubber, and asphalt.[16] It has been used in the purification of single-walled carbon nanotubes.[17]

Solvent

Carbon disulfide is used as an insecticide for the fumigation of grains, nursery stock, in fresh fruit conservation and as a soil disinfectant against insects and nematodes.[15]

Insecticide

Used for fumigation in airtight storage warehouses, airtight flat storages, bins, grain elevators, railroad box cars, shipholds, barges and cereal mills.[14]

Fumigation

Uses

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]

Polymerization

CS2 + H2O → COS + H2S
COS + H2O → CO2 + H2S

The mechanism by this hydrolase converts CS2 into H2S is similar to that of how carbonic anhydrase hydrates CO2 to HCO3. This similarity points to a likely mechanism. The zinc at the active site is tetrahedral, being coordinated by Cys 35, His 88, Cys 91 and water. The water is deprotonated to give a zinc hydroxide that adds the substrate to give a Zn-O-C(S)SH intermediate. A similar process is proposed to convert COS into CO2.

Mechanism

The enzyme is similar to that of carbonic anhydrases. The enzyme monomer of CS2 hydrolase displays a typical β-carbonic anhydrase fold and active site. Two of these monomers form a closely intertwined dimer with a central β-sheet capped by anα-helical domain. Four dimers form a square octameric ring through interactions of the long arms at the N and C termini. Similar ring structures have been seen in strains of carbonic anhydrases, however, in CS2 hydrolase, two octameric rings form a hexadecamer by interlocking at right angles to each other. This results in the blocking of the entrance to the active site and the formation of a single 15-Å-long, highly hydrophobic tunnel that functions as a specificity filter. This provides a key difference between carbonic anhydrase and CS2 hydrolase. This tunnel determines the enzyme's substrate specificity for CS2, which is hydrophobic as well.

CS2 hydrolase in its holoenzyme has a cofactor bound to it. In this form the only ligand to be found is the zinc ion and the molecular weight of the enzyme overall is 189404.8 g/mol. There are only eight polymer chains seen in this form and this may be due to the fact that the enzyme catalyzes the conversion of CS2 in this form.[12]

The apoenzyme form, lacking the zinc cofactor, has a molecular weight of 382815.4 g/mol. The chloride ion and the 3,6,9,12,15,18,21,24,27,30,33,36,39-tridecaoxahentetracontane-1,41-diol (C28H58O15) are the two main ligands seen on the enzyme in this form. There are 16 polymer chains seen in this form contributing to the heaviness of the enzyme. This form is also sometimes termed the selenomethionine form.[12]

The enzyme can be obtained in both apoenzyme and holoenzyme forms. The enzyme is predicted to have an isoelectric point of 5.92 and a molecular mass of 23,576 Da. The enzyme is hexadecameric.[11]

[11]

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