Carbon disulfide

From Wikipedia, the free encyclopedia - View original article

Carbon disulfide
Carbon disulfide
Carbon-disulfide-3D-vdW.png
Identifiers
CAS number75-15-0 YesY
PubChem6348
ChemSpider6108 YesY
UNIIS54S8B99E8 YesY
EC number200-843-6
UN number1131
KEGGC19033 N
ChEBICHEBI:23012 YesY
RTECS numberFF6650000
Jmol-3D imagesImage 1
Properties
Molecular formulaCS2
Molar mass76.14 g mol−1
AppearanceColorless liquid
Impure: light-yellow
OdorChloroform (pure)
Foul (commercial)
Density1.539 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 point46.24 °C (115.23 °F; 319.39 K)
Solubility in water0.258 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]
SolubilitySoluble in alcohol, ether, benzene, oil, CHCl3, CCl4
Solubility in formic acid4.66 g/100 g[1]
Solubility in dimethyl sulfoxide45 g/100 g (20.3 °C)[1]
Vapor pressure48.1 kPa (25 °C)
82.4 kPa (40 °C)[3]
Refractive index (nD)1.627[4]
Viscosity0.436 cP (0 °C)
0.363 cP (20 °C)
Structure
Molecular shapeLinear
Dipole moment0 D (20 °C)[1]
Thermochemistry
Specific
heat capacity
C
75.73 J/mol·K[1]
Std molar
entropy
So298
151 J/mol·K[1]
Std enthalpy of
formation
ΔfHo298
88.7 kJ/mol[1]
Gibbs free energy ΔG64.4 kJ/mol[1]
Std enthalpy of
combustion
ΔcHo298
1687.2 kJ/mol[3]
Hazards
MSDSExternal MSDS
GHS pictogramsThe 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 wordDanger
GHS hazard statementsH225, H315, H319, H361, H372[4]
GHS precautionary statementsP210, P281, P305+351+338, P314[4]
ICSC 0022
EU Index006-003-00-3
EU classificationHighly Flammable F Toxic T Irritant Xi
R-phrasesR11, R36/38, R48/23, R62, R63
S-phrases(S1/2), S16, S33, S36/37, S45
Inhalation hazardIrritant
Eye hazardIrritant
Skin hazardIrritant
NFPA 704
Flash point−43 °C (−45 °F; 230 K) [1]
Autoignition temperature102 °C (216 °F; 375 K) [1]
Explosive limits50%[4]
LD503188 mg/kg (rat, oral)
Related compounds
Related compoundsCarbon dioxide
Carbonyl sulfide
Carbon diselenide
Supplementary data page
Structure and
properties
n, εr, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral dataUV, IR, NMR, MS
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
Infobox references
 
Jump to: navigation, search
This article is about the chemical substance CS2. For the software suite by Adobe Systems, see Adobe Creative Suite. For the cycle super-highway in London, see List of cycle routes in London.
Carbon disulfide
Carbon disulfide
Carbon-disulfide-3D-vdW.png
Identifiers
CAS number75-15-0 YesY
PubChem6348
ChemSpider6108 YesY
UNIIS54S8B99E8 YesY
EC number200-843-6
UN number1131
KEGGC19033 N
ChEBICHEBI:23012 YesY
RTECS numberFF6650000
Jmol-3D imagesImage 1
Properties
Molecular formulaCS2
Molar mass76.14 g mol−1
AppearanceColorless liquid
Impure: light-yellow
OdorChloroform (pure)
Foul (commercial)
Density1.539 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 point46.24 °C (115.23 °F; 319.39 K)
Solubility in water0.258 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]
SolubilitySoluble in alcohol, ether, benzene, oil, CHCl3, CCl4
Solubility in formic acid4.66 g/100 g[1]
Solubility in dimethyl sulfoxide45 g/100 g (20.3 °C)[1]
Vapor pressure48.1 kPa (25 °C)
82.4 kPa (40 °C)[3]
Refractive index (nD)1.627[4]
Viscosity0.436 cP (0 °C)
0.363 cP (20 °C)
Structure
Molecular shapeLinear
Dipole moment0 D (20 °C)[1]
Thermochemistry
Specific
heat capacity
C
75.73 J/mol·K[1]
Std molar
entropy
So298
151 J/mol·K[1]
Std enthalpy of
formation
ΔfHo298
88.7 kJ/mol[1]
Gibbs free energy ΔG64.4 kJ/mol[1]
Std enthalpy of
combustion
ΔcHo298
1687.2 kJ/mol[3]
Hazards
MSDSExternal MSDS
GHS pictogramsThe 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 wordDanger
GHS hazard statementsH225, H315, H319, H361, H372[4]
GHS precautionary statementsP210, P281, P305+351+338, P314[4]
ICSC 0022
EU Index006-003-00-3
EU classificationHighly Flammable F Toxic T Irritant Xi
R-phrasesR11, R36/38, R48/23, R62, R63
S-phrases(S1/2), S16, S33, S36/37, S45
Inhalation hazardIrritant
Eye hazardIrritant
Skin hazardIrritant
NFPA 704
Flash point−43 °C (−45 °F; 230 K) [1]
Autoignition temperature102 °C (216 °F; 375 K) [1]
Explosive limits50%[4]
LD503188 mg/kg (rat, oral)
Related compounds
Related compoundsCarbon dioxide
Carbonyl sulfide
Carbon diselenide
Supplementary data page
Structure and
properties
n, εr, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral dataUV, IR, NMR, MS
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
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, such as carbonyl sulfide.[5]

Occurrence and manufacture[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. A lower temperature reaction, requiring only 600 °C utilizes natural gas as the carbon source in the presence of silica gel or alumina catalysts:[5]

2 CH4 + S8 → 2 CS2 + 4 H2S

The reaction is analogous to the combustion of methane. Although 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.[6] USA production in 2007 was 56,000 tonnes.[7]

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. It is widely used in the synthesis of organosulfur compounds such as metham sodium, a soil fumigant and is commonly used in the production of the soft fabric viscose.

Addition of nucleophiles[edit]

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[edit]

Chlorination of CS2 is the principal route to carbon tetrachloride:[5]

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).[8]

Carbon disulfide hydrolase[edit]

Carbon disulfide is naturally formed in the mudpots of volcanic solfataras. It serves as a source of hydrogen sulfide, which is an electron donor for certain organisms that oxidize it into sulphuric acid or related sulfur oxides. The hyperthermophilic Acidianus strain was found to convert CS2 into H2S and CO2. The enzyme responsible for this conversion is termed carbon disulfide hydrolase.[9]

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.1 The enzyme is hexadecameric.

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.[10]

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.[11]

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.

Mechanism[edit]

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.

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

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.[12]

Uses[edit]

Fumigation[edit]

Used for fumigation in airtight storage warehouses, airtight flat storages, bins, grain elevators, railroad box cars, shipholds, barges and cereal mills.[13]

Insecticide[edit]

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.[14]

Solvent[edit]

Carbon disulfide is a solvent for phosphorus, sulfur, selenium, bromine, iodine, fats, resins, rubber, and asphalt.[15] It has been used in the purification of single-walled carbon nanotubes.[16]

Manufacturing[edit]

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

Health effects[edit]

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.

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 e Sigma-Aldrich Co., Carbon disulfide. Retrieved on 2014-05-27.
  5. ^ a b c Holleman, A. F.; Wiberg, E. (2001), Inorganic Chemistry, San Diego: Academic Press, ISBN 0-12-352651-5 
  6. ^ "Carbon Disulfide report from IHS Chemical". Retrieved June 15, 2013. 
  7. ^ "Chemical profile: carbon disulfide from ICIS.com". Retrieved June 15, 2013. 
  8. ^ 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. 
  9. ^ 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. “Evolution of a New Enzyme for Carbon Disulphide Conversion by an AcidothermophilicArchaeon” Nature, 2011, 487, 412-416. doi:10.1038/nature10464
  10. ^ 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, DOI:10.2210/pdb3ten/pdb
  11. ^ 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. Protein Data Bank Japan, 2012, PDB ID: 3teo, 3ten
  12. ^ Ochiai, Bungo; Endo, Takeshi "Carbon dioxide and carbon disulfide as resources for functional polymers" Progress in Polymer Science (2005), 30, 183-215. doi:10.1016/j.progpolymsci.2005.01.005
  13. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0080379419. 
  14. ^ Worthing, C. R.; Hance. R. J. (1991). The Pesticide Manual, A World Compendium (9th ed.). British Crop Protection Council. ISBN 9780948404429. 
  15. ^ "Carbon Disulfide". Akzo Nobel. 
  16. ^ 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. 

External links[edit]