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*{{cite journal |author=Picardal FW, Arnold RG, Couch H, Little AM, Smith ME |title=Involvement of cytochromes in the anaerobic biotransformation of tetrachloromethane by ''Shewanella putrefaciens 200'' |journal=Appl. Environ. Microbiol. |volume=59 |issue=11 |pages=3763–70 |year=1993 |month=November |pmid=8285682 |pmc=182529 |url=http://aem.asm.org/cgi/pmidlookup?view=long&pmid=8285682}}
*{{cite journal |author=Picardal FW, Arnold RG, Couch H, Little AM, Smith ME |title=Involvement of cytochromes in the anaerobic biotransformation of tetrachloromethane by ''Shewanella putrefaciens 200'' |journal=Appl. Environ. Microbiol. |volume=59 |issue=11 |pages=3763–70 |year=1993 |month=November |pmid=8285682 |pmc=182529 |url=http://aem.asm.org/cgi/pmidlookup?view=long&pmid=8285682}}
*[http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s029carb.pdf Substance profile at ntp.niehs.nih.gov]
*[http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s029carb.pdf Substance profile at ntp.niehs.nih.gov]
*[http://chemsub.online.fr/name/carbon_tetrachloride.html ChemSub Online: Carbon tetrachloride.]



{{Halomethanes}}
{{Halomethanes}}

Revision as of 19:29, 21 December 2010

Carbon tetrachloride
Names
IUPAC name
Tetrachloromethane
Other names
1,1,1,1-Tetrachloromethane, Benziform, Benzinoform, Carbon chloride, Carbon tet, Freon 10, Halon 104, Methane tetrachloride, Perchloromethane, Tetraform, Tetrasol
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.000.239 Edit this at Wikidata
EC Number
  • 200-262-8
KEGG
RTECS number
  • FG4900000
UNII
UN number 1846
  • InChI=1S/CCl4/c2-1(3,4)5 checkY
    Key: VZGDMQKNWNREIO-UHFFFAOYSA-N checkY
  • InChI=1/CCl4/c2-1(3,4)5
    Key: VZGDMQKNWNREIO-UHFFFAOYAV
  • ClC(Cl)(Cl)Cl
Properties
CCl4
Molar mass 153.82 g/mol
Appearance colourless liquid
ether-like odor
Density 1.5867 g/cm3, liquid

1.831 g.cm-3 at -186 °C (solid)
1.809 g.cm-3 at -80 °C (solid)

Melting point -22.92 °C (250 K)
Boiling point 76.72 °C (350 K)
785–800 mg/L at 25 °C
Solubility soluble in alcohol, ether, chloroform, benzene
log P 2.64
Vapor pressure 11.94 kPa at 20 °C
1.4601
Structure
Monoclinic
Tetrahedral
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point Not flammable
Lethal dose or concentration (LD, LC):
2350 mg/kg
Related compounds
Other cations
 Silicon tetrachloride
Germanium tetrachloride
Tin tetrachloride
Lead tetrachloride
Supplementary data page
Carbon tetrachloride (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Carbon tetrachloride, also known by many other names (notably, carbon tet in the cleaning industry, and as a Halon or Freon in HVAC, see Table for others) is the organic compound with the formula CCl4. It was formerly widely used in fire extinguishers, as a precursor to refrigerants, and as a cleaning agent. It is a colourless liquid with a "sweet" smell that can be detected at low levels.

Both carbon tetrachloride and tetrachloromethane are acceptable names under IUPAC nomenclature.

History and synthesis

The production of carbon tetrachloride has steeply declined since the 1980s due to environmental concerns and the decreased demand for CFCs, which were derived from carbon tetrachloride. In 1992, production in the U.S.-Europe-Japan was estimated at 720,000 tonnes.[1]

Carbon tetrachloride was originally synthesised by the French chemist Henri Victor Regnault in 1839 by the reaction of chloroform with chlorine,[2] but now it is mainly produced from methane:

CH4 + 4 Cl2 → CCl4 + 4 HCl

The production often utilizes by-products of other chlorination reactions, such as from the syntheses of dichloromethane and chloroform. Higher chlorocarbons are also subjected to "chlorinolysis:"

C2Cl6 + Cl2 → 2 CCl4

Prior to the 1950s, carbon tetrachloride was manufactured by the chlorination of carbon disulfide at 105 to 130 °C:[1]

CS2 + 3Cl2 → CCl4 + S2Cl2

Properties

In the carbon tetrachloride molecule, four chlorine atoms are positioned symmetrically as corners in a tetrahedral configuration joined to a central carbon atom by single covalent bonds. Because of this symmetrical geometry, CCl4 is non-polar. Methane gas has the same structure, making carbon tetrachloride a halomethane. As a solvent, it is well suited to dissolving other non-polar compounds, fats and oils. It can also dissolve iodine. It is somewhat volatile, giving off vapors having a smell characteristic of other chlorinated solvents, somewhat similar to the tetrachloroethylene smell reminiscent of dry cleaners' shops.

Solid tetrachloromethane has 2 polymorphs: crystalline II below -47.5 °C (225.6 K) and crystalline I above -47.5 °C.[3]

At -47.3 °C it has monoclinic crystal structure with space group C2/c and lattice constants a = 20.3, b = 11.6, c = 19.9 (.10−1 nm), β = 111°.[4] With a specific gravity greater than 1, carbon tetrachloride will be present as a dense nonaqueous phase liquid if sufficient quantities are spilled in the environment.

Uses

A brass, Pyrene carbon-tetrachloride, fire extinguisher.

In the 20th century, carbon tetrachloride was widely used as a dry cleaning solvent, as a refrigerant, and in lava lamps.[5]

In 1910, The Pyrene Manufacturing Company of Delaware filed a patent for a device using carbon tetrachloride to extinguish fires.[6] The liquid vaporized and extinguished the flames by inhibiting the chemical chain reaction of the combustion process. It was an early 20th century presupposition that the fire suppression ability of carbon tetrachloride relied on oxygen removal. A carbon tetrachloride fire extinguisher was patented in 1911, taking the form of a brass bottle with a hand pump to expel a jet of liquid.[7] Such extinguishers were commonly used until the mid-20th century.

One specialty use of carbon tetrachloride was by stamp collectors to reveal watermarks on the backs of postage stamps without damaging the stamp. A small amount of the liquid was placed on the back of a stamp sitting in a black glass or obsidian tray. The letters or design of the watermark could then be clearly detected.

However, once it became apparent that carbon tetrachloride exposure had severe adverse health effects, safer alternatives such as tetrachloroethylene were found for these applications, and its use in these roles declined from about 1940 onward. The fact that high temperatures cause it to react to produce phosgene made it especially hazardous when used against fires. This reaction also caused a rapid depletion of oxygen. Carbon tetrachloride persisted as a pesticide to kill insects in stored grain, but in 1970, it was banned in consumer products in the United States.

Prior to the Montreal Protocol, large quantities of carbon tetrachloride were used to produce the freon refrigerants R-11 (trichlorofluoromethane) and R-12 (dichlorodifluoromethane). However, these refrigerants are now believed to play a role in ozone depletion and have been phased out. Carbon tetrachloride is still used to manufacture less destructive refrigerants. Carbon tetrachloride has also been used in the detection of neutrinos.

Carbon tetrachloride is one of the most potent hepatotoxins (toxic to the liver), and is widely used in scientific research to evaluate hepatoprotective agents.[8][9]

Reactivity

Carbon tetrachloride has practically no flammability at lower temperatures. Under high temperatures in air, it forms poisonous phosgene.

Because it has no C-H bonds, carbon tetrachloride does not easily undergo free-radical reactions. Hence, it is a useful solvent for halogenations either by the elemental halogen, or by a halogenation reagent such as N-bromosuccinimide.

In organic chemistry, carbon tetrachloride serves as a source of chlorine in the Appel reaction.

Solvent

It is used as a solvent in synthetic chemistry research, but because of its adverse health effects, it is no longer commonly used, and chemists generally try to replace it with other solvents.[citation needed] It is sometimes useful as a solvent for infrared spectroscopy, because there are no significant absorption bands > 1600 cm−1. Because carbon tetrachloride does not have any hydrogen atoms, it was historically used in proton NMR spectroscopy. However, carbon tetrachloride is toxic, and its dissolving power is low.[10] Its use has been largely superseded by deuterated solvents. Use of carbon tetrachloride in determination of oil has been replaced by various other solvents[8].

Safety

Time-series of atmospheric concentrations of CCl4 (Walker et al., 2000).

Exposure to high concentrations of carbon tetrachloride (including vapor) can affect the central nervous system, degenerate the liver[9] and kidneys[11] and may result (after prolonged exposure) in coma and even death.[12] Chronic exposure to carbon tetrachloride can cause liver[13][14] and kidney damage and could result in cancer.[15] More information can be found in Material safety data sheets.[16]

In 2008, a study of common cleaning products found the presence of carbon tetrachloride in "very high concentrations" (up to 101 mg m−3) as a result of manufacturers' mixing of surfactants or soap with sodium hypochlorite (bleach).[17]

Carbon tetrachloride is also both ozone-depleting[18] and a greenhouse gas.[19] However, since 1992[20] its atmospheric concentrations have been in decline for the reasons described above (see also the atmospheric time-series figure). CCl4 has an atmospheric lifetime of 85 years[21]

References

  1. ^ a b Manfred Rossberg, Wilhelm Lendle, Gerhard Pfleiderer, Adolf Tögel, Eberhard-Ludwig Dreher, Ernst Langer, Heinz Jaerts, Peter Kleinschmidt, Heinz Strack, Richard Cook, Uwe Beck, Karl-August Lipper, Theodore R. Torkelson, Eckhard Löser, Klaus K. Beutel, “Chlorinated Hydrocarbons” in Ullmann's Encyclopedia of Industrial Chemistry, 2006 Wiley-VCH, Weinheim.doi:10.1002/14356007.a06_233.pub2
  2. ^ V. Regnault (1839). "Ueber die Chlorverbindungen des Kohlenstoffs, C2Cl2 und CCl2". Annalen der Pharmacie. 30 (3): 350. doi:10.1002/jlac.18390300310.
  3. ^ Carbon tetrachloride
  4. ^ F. Brezina, J. Mollin, R. Pastorek, Z. Sindelar. Chemicke tabulky anorganickych sloucenin (Chemical tables of inorganic compounds). SNTL, 1986.
  5. ^ Doherty RE (2000). "A History of the Production and Use of Carbon Tetrachloride, Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1—Historical Background; Carbon Tetrachloride and Tetrachloroethylene". Environmental Forensics. 1 (1): 69–81. doi:10.1006/enfo.2000.0010.
  6. ^ U.S. patent 1,010,870, filed April 5, 1910.
  7. ^ U.S. patent 1,105,263
  8. ^ a b Use of Ozone Depleting Substances in Laboratories. TemaNord 516/2003.
  9. ^ a b Seifert WF, Bosma A, Brouwer A; et al. (1994). "Vitamin A deficiency potentiates carbon tetrachloride-induced liver fibrosis in rats". Hepatology. 19 (1): 193–201. doi:10.1002/hep.1840190129. PMID 8276355. {{cite journal}}: Explicit use of et al. in: |author= (help); Unknown parameter |month= ignored (help)CS1 maint: multiple names: authors list (link)
  10. ^ W. Reusch. "Introduction to Nuclear Magnetic Resonance Spectroscopy". Virtual Textbook of Organic Chemistry. Michigan State University.
  11. ^ Liu KX, Kato Y, Yamazaki M, Higuchi O, Nakamura T, Sugiyama Y (1993). "Decrease in the hepatic clearance of hepatocyte growth factor in carbon tetrachloride-intoxicated rats". Hepatology. 17 (4): 651–60. doi:10.1002/hep.1840170420. PMID 8477970. {{cite journal}}: Unknown parameter |month= ignored (help)CS1 maint: multiple names: authors list (link)
  12. ^ Recknagel R.O., Glende E.A., Dolak J.A., Waller R.L. (1989). "Mechanism of Carbon-tetrachloride Toxicity". Pharmacology Therapeutics. 43 (43): 139–154. doi:10.1016/0163-7258(89)90050-8.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  13. ^ Recknagel RO (1967). "Carbon tetrachloride hepatotoxicity". Pharmacol. Rev. 19 (2): 145–208. PMID 4859860. {{cite journal}}: Unknown parameter |month= ignored (help)
  14. ^ Masuda Y (2006). "[Learning toxicology from carbon tetrachloride-induced hepatotoxicity]" ([dead link‍]). Yakugaku Zasshi (in Japanese). 126 (10): 885–99. doi:10.1248/yakushi.126.885. PMID 17016019. {{cite journal}}: Unknown parameter |month= ignored (help)
  15. ^ Rood AS, McGavran PD, Aanenson JW, Till JE (2001). "Stochastic estimates of exposure and cancer risk from carbon tetrachloride released to the air from the rocky flats plant". Risk Anal. 21 (4): 675–95. doi:10.1111/0272-4332.214143. PMID 11726020. {{cite journal}}: Unknown parameter |month= ignored (help)CS1 maint: multiple names: authors list (link)
  16. ^ Material Safety Data Sheet, Carbon tetrachloride at Fisher Scientific
  17. ^ Odabasi M (2008). "Halogenated Volatile Organic Compounds from the Use of Chlorine-Bleach-Containing Household Products". Environmental Science & Technology. 42 (5): 1445–51. doi:10.1021/es702355u.
  18. ^ Fraser P. (1997). "Chemistry of stratospheric ozone and ozone depletion". Australian Meteorological Magazine. 46 (3): 185–193.
  19. ^ Evans WFJ, Puckrin E (1996). "A measurement of the greenhouse radiation associated with carbon tetrachloride (CCl4)". Geophysical Research Letters. 23 (14): 1769–72. doi:10.1029/96GL01258.
  20. ^ Walker, S. J., R. F. Weiss & P. K. Salameh (2000). "Reconstructed histories of the annual mean atmospheric mole fractions for the halocarbons CFC-11, CFC-12, CFC-113 and carbon tetrachloride". Journal of Geophysical Research. 105: 14285–96. doi:10.1029/1999JC900273.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  21. ^ The Atlas of Climate Change (2006) by Kirstin Dow and Thomas E. Downing ISBN 978-0-520-25558-6


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