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
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| Names |
| IUPAC name
Methanedithione
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| Other names
Carbon bisulfide
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| Identifiers |
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CAS Number
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75-15-0 Y |
| ChEBI |
CHEBI:23012 Y |
| ChemSpider |
6108 Y |
| EC Number |
200-843-6 |
| Jmol 3D model |
Interactive image |
| KEGG |
C19033 N |
| PubChem |
6348 |
| RTECS number |
FF6650000 |
| UNII |
S54S8B99E8 Y |
| UN number |
1131 |
InChI
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InChI=1S/CS2/c2-1-3 Y
Key: QGJOPFRUJISHPQ-UHFFFAOYSA-N Y
-
InChI=1/CS2/c2-1-3
Key: QGJOPFRUJISHPQ-UHFFFAOYAS
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| Properties |
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Chemical formula
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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) |
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Solubility in water
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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] |
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Refractive index (nD)
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1.627[4] |
| Viscosity |
0.436 cP (0 °C)
0.363 cP (20 °C) |
| Structure |
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Molecular shape
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Linear |
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Dipole moment
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0 D (20 °C)[1] |
| Thermochemistry |
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Specific
heat capacity (C)
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75.73 J/mol·K[1] |
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Std molar
entropy (So298)
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151 J/mol·K[1] |
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Std enthalpy of
formation (ΔfHo298)
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88.7 kJ/mol[1] |
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Gibbs free energy (ΔfG˚)
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64.4 kJ/mol[1] |
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Std enthalpy of
combustion (ΔcHo298)
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1687.2 kJ/mol[3] |
| Hazards |
| Safety data sheet |
See: data page |
| GHS pictograms |
[4] |
| GHS signal word |
Danger |
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GHS hazard statements
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H225, H315, H319, H361, H372[4] |
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GHS precautionary statements
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P210, P281, P305+351+338, P314[4]
ICSC 0022 |
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EU classification (DSD)
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F T 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 |
|
| Flash point |
−43 °C (−45 °F; 230 K)[1] |
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Autoignition
temperature
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102 °C (216 °F; 375 K)[1] |
| Explosive limits |
1.3%-50%[5] |
| Lethal dose or concentration (LD, LC): |
|
LD50 (median dose)
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3188 mg/kg (rat, oral) |
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LC50 (median concentration)
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>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] |
|
LCLo (lowest published)
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4000 ppm (human, 30 min)[6] |
| US health exposure limits (NIOSH): |
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PEL (Permissible)
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TWA 20 ppm C 30 ppm 100 ppm (30-minute maximum peak)[5] |
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REL (Recommended)
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TWA 1 ppm (3 mg/m3) ST 10 ppm (30 mg/m3) [skin][5] |
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IDLH (Immediate danger)
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500 ppm[5] |
| Related compounds |
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Related compounds
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Carbon dioxide
Carbonyl sulfide
Carbon diselenide |
| Supplementary data page |
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Structure and
properties
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Refractive index (n),
Dielectric constant (εr), etc. |
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Thermodynamic
data
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Phase behaviour
solid–liquid–gas |
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Spectral data
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UV, IR, NMR, MS |
| N verify (what is YN ?) |
| Infobox references |
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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]
Contents
- 1 Occurrence and manufacture
- 2 Reactions
- 2.1 Addition of nucleophiles
- 2.2 Chlorination
- 2.3 Coordination chemistry
- 2.4 Carbon disulfide hydrolase
- 3 Polymerization
- 4 Uses
- 4.1 Fumigation
- 4.2 Insecticide
- 4.3 Solvent
- 4.4 Manufacturing
- 4.5 Working Fluid
- 4.6 Spectroscope prisms
- 5 Health effects
- 6 See also
- 7 References
- 8 External links
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] United States production in 2007 was 56,000 tonnes.[9]
Reactions
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 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 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.[11]
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]
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]
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 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
The mechanism by which this hydrolase converts CS2 into H2S is similar to that of how carbonic anhydrase hydrates CO2 to HCO3−.[citation needed] 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.[citation needed] The water is deprotonated to give a zinc hydroxide that adds the substrate to give a Zn-O-C(S)SH intermediate.[citation needed] A similar process is proposed[by whom?] to convert COS into CO2.[citation needed]
- CS2 + H2O → COS + H2S
- COS + H2O → CO2 + H2S
Polymerization
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
Fumigation
It can be used in fumigation of airtight storage warehouses, airtight flat storages, bins, grain elevators, railroad box cars, shipholds, barges and cereal mills.[14]
Insecticide
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]
Solvent
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]
Manufacturing
The principal industrial uses of carbon disulfide are the manufacture of viscose rayon, cellophane film, carbon tetrachloride and xanthogenates and electronic vacuum tubes.
Working Fluid
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]
Spectroscope prisms
Due to its high optical dispersion it was used in some spectroscopes.[19]
Health effects
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.
Carbon disulfide has been linked to toxin-induced parkinsonism. [20]
See also
- Carbon monosulfide
- Carbon subsulfide
- Carbon diselenide
References
- ^ a b c d e f g h i j k http://chemister.ru/Database/properties-en.php?dbid=1&id=1955
- ^ Seidell, Atherton; Linke, William F. (1952). Solubilities of Inorganic and Organic Compounds. Van Nostrand.
- ^ 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)
- ^ a b c d Sigma-Aldrich Co., Carbon disulfide. Retrieved on 2014-05-27.
- ^ a b c d "NIOSH Pocket Guide to Chemical Hazards #0104". National Institute for Occupational Safety and Health (NIOSH).
- ^ a b "Carbon disulfide". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH).
- ^ a b c Holleman, A. F.; Wiberg, E. (2001), Inorganic Chemistry, San Diego: Academic Press, ISBN 0-12-352651-5
- ^ "Carbon Disulfide report from IHS Chemical". Retrieved June 15, 2013.
- ^ "Chemical profile: carbon disulfide from ICIS.com". Retrieved June 15, 2013.
- ^ 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.
- ^ 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. Bibcode:2011Natur.478..412S. doi:10.1038/nature10464.
- ^ 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
- ^ 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.
- ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
- ^ Worthing, C. R.; Hance. R. J. (1991). The Pesticide Manual, A World Compendium (9th ed.). British Crop Protection Council. ISBN 9780948404429.
- ^ "Carbon Disulfide". Akzo Nobel.
- ^ 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.
- ^ "Carbon Disulfide Engines". Douglas Self.
- ^ "How to work with the spectroscope. John Browning. 2nd Ed 1882
- ^ http://www.ninds.nih.gov/disorders/parkinsons_disease/detail_parkinsons_disease.htm
External links
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Wikimedia Commons has media related to Carbon disulfide. |
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Wikisource has the text of the 1911 Encyclopædia Britannica article Carbon Bisulphide. |
- Australian National Pollutant Inventory: Carbon disulfide
- CDC - NIOSH Pocket Guide to Chemical Hazards - Carbon Disulfide
- Inno Motion Engineering
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Inorganic compounds of carbon and related ions
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| Compounds |
- CBr4
- CCl4
- CF
- CF4
- CI4
- CO
- CO2
- CO3
- COS
- CS
- CS2
- CSe2
- C3O2
- C3S2
- CH4
- C2H6
- C3H8
- C4H10
- C5H12
- C6H14
- C7H16
- C8H18
- C6H6
- SiC
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| Carbon ions |
- Carbides [:C≡C:]2–, [::C::]4–, [:C=C=C:]4–
- Cyanides [:C≡N:]–
- Cyanates [:O-C≡N:]–
- Thiocyanates [:S-C≡N:]–
- Fulminates [:C≡N-O:]–
- Thiofulminates [:C≡N-S:]–
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| Oxides and related |
- Oxides
- Metal carbonyls
- Carbonic acid
- Bicarbonates
- Carbonates
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| Authority control |
- GND: 4131839-0
- NDL: 00568536
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