1,1,1-Trichloroethane

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1,1,1-Trichloroethane
Skeletal formula of 1,1,1-trichloroethane 1,1,1-trichloroethane-2D-skeletal.png
Skeletal formula of 1,1,1-trichloroethane
Space-filling model of 1,1,1-trichloroethane 1,1,1-trichloroethane-3D-vdW.png
Space-filling model of 1,1,1-trichloroethane
1,1,1-Trichlorethan.svg
1,1,1-trichloroethane-3D-balls.png
Names
Preferred IUPAC name
1,1,1-Trichloroethane
Other names
1,1,1-TCA, Methyl chloroform, Chlorothene, Solvent 111, R-140a, Genklene, monochlorethylidene chloride (archaic)
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.688 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 200-756-3
82076
KEGG
PubChem CID
RTECS number
  • KJ2975000
UNII
UN number 2831
  • InChI=1S/C2H3Cl3/c1-2(3,4)5/h1H3 Yes check.svgY
    Key: UOCLXMDMGBRAIB-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C2H3Cl3/c1-2(3,4)5/h1H3
    Key: UOCLXMDMGBRAIB-UHFFFAOYAP
  • ClC(Cl)(Cl)C
Properties
C2H3Cl3 or CH3CCl3
Molar mass 133.40 g/mol
AppearanceColourless liquid
Odor mild, chloroform-like [1]
Density 1.32 g/cm3
Melting point −33 °C (−27 °F; 240 K)
Boiling point 74 °C (165 °F; 347 K)
0.4% (20°C) [1]
0.480 g/litre at 20 °C [2]
Vapor pressure 100 mmHg (20°C) [1]
1.437 [3]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Ozone layer impact. Irritant to the upper respiratory tract. Causes severe irritation and swelling to eyes.
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H332, H420
P261, P271, P304+P312, P304+P340, P312, P502
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
1
0
Explosive limits 7.5%-12.5% [1]
Lethal dose or concentration (LD, LC):
9600 mg/kg (oral, rat)
6000 mg/kg (oral, mouse)
5660 mg/kg (oral, rabbit) [4]
3911 ppm (mouse, 2 hr)
18000 ppm (rat, 4 hr) [4]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 350 ppm (1900 mg/m3) [1]
REL (Recommended)
C 350 ppm (1900 mg/m3) [15-minute] [1]
IDLH (Immediate danger)
700 ppm [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

The organic compound 1,1,1-trichloroethane, also known as methyl chloroform and chlorothene, is a chloroalkane with the chemical formula CH3CCl3. It is an isomer of 1,1,2-trichloroethane. A colourless and sweet-smelling liquid, it was once produced industrially in large quantities for use as a solvent. [5] It is regulated by the Montreal Protocol as an ozone-depleting substance and as such use has declined since 1996. Trichloroethane should not be confused with the similar-sounding trichloroethene which is also commonly used as a solvent.

Production

1,1,1-Trichloroethane was first reported by Henri Victor Regnault in 1840. Industrially, it is usually produced in a two-step process from vinyl chloride. In the first step, vinyl chloride reacts with hydrogen chloride at 20-50 °C to produce 1,1-dichloroethane:

CH2=CHCl + HCl → CH3CHCl2

This reaction is catalyzed by a variety of Lewis acids, mainly aluminium chloride, iron(III) chloride, or zinc chloride. The 1,1-dichloroethane is then converted to 1,1,1-trichloroethane by reaction with chlorine under ultraviolet irradiation:

CH3CHCl2 + Cl2 → CH3CCl3 + HCl

This reaction proceeds at 80-90% yield, and the hydrogen chloride byproduct can be recycled to the first step in the process. The major side-product is the related compound 1,1,2-trichloroethane, from which the 1,1,1-trichloroethane can be separated by distillation.

A somewhat smaller amount of 1,1,1-trichloroethane is produced from the reaction of 1,1-dichloroethene and hydrogen chloride in the presence of an iron(III) chloride catalyst:

CH2=CCl2 + HCl → CH3CCl3

1,1,1-Trichloroethane is sold with stabilizers because it is unstable with respect to dehydrochlorination and attacks some metals. Stabilizers comprise up to 8% of the formulation, including acid scavengers (epoxides, amines) and complexants.

Uses

1,1,1-Trichloroethane is an excellent solvent for many organic compounds and also one of the least toxic of the chlorinated hydrocarbons. It is generally considered non-polar, but owing to the good polarizability of the chlorine atoms, it is a superior solvent for organic compounds that do not dissolve well in hydrocarbons such as hexane. Prior to the Montreal Protocol, it was widely used for cleaning metal parts and circuit boards, as a photoresist solvent in the electronics industry, as an aerosol propellant, as a cutting fluid additive, and as a solvent for inks, paints, adhesives, and other coatings. 1,1,1-Trichloroethane was used to dry-clean leather and suede. [6] 1,1,1-Trichloroethane is also used as an insecticidal fumigant.

It was also the standard cleaner for photographic film (movie/slide/negatives, etc.). Other commonly available solvents damage emulsion and base (acetone will severely damage triacetate base on most films), and thus are not suitable for this application. The standard replacement, Forane 141 is much less effective, and tends to leave a residue. 1,1,1-Trichloroethane was used as a thinner in correction fluid products such as liquid paper. Many of its applications previously used carbon tetrachloride (which was banned in US consumer products in 1970). In turn, 1,1,1-trichloroethane itself is now being replaced by other solvents in the laboratory. [7]

Anaesthetic research

1,1,1-Trichloroethane was one of the volatile organochlorides that have been tried as alternatives to chloroform in anaesthesia. [8] In the 1880s, it was found to be a safe and strong substitute for chloroform [9] but its production was too expensive and difficult for the era. [10]

In 1880, 1,1,1-Trichloroethane was suggested as an anaesthetic. It was first referred to as "methyl-chloroform" in the same year. At the time, the narcotic effects of chloral hydrate were owed to a hypothetical metabolic pathway to chloroform in "alkaline blood". Trichloroethane was studied for its structural similarity to chloral and potential anaesthetic effects. However, trichloroethane did not exhibit any conversion to chloroform in laboratory experiments. The 1,1,2-trichloroethane isomer, which lacked a trichloromethyl group, exhibited anaesthetic effects even stronger than the 1,1,1 isomer. [11]

Safety

Although not as toxic as many similar compounds, inhaled or ingested 1,1,1-trichloroethane does act as a central nervous system depressant and can cause effects similar to those of ethanol intoxication, including dizziness, confusion, and, in sufficiently high concentrations, unconsciousness and death. [12] Fatal poisonings and illnesses linked to intentional inhalation of trichloroethane have been reported. [13] [14] [15] [16]

Prolonged skin contact with the liquid can result in the removal of fats from the skin, resulting in skin irritation.

The International Agency for Research on Cancer places 1,1,1-trichloroethane in Group 2A as a probable carcinogen. [17]

Atmospheric concentration

1,1,1-Trichloroethane (Methyl chloroform, CH3CCl3) measured by the Advanced Global Atmospheric Gases Experiment (AGAGE) in the lower atmosphere (troposphere) at stations around the world. Abundances are given as pollution free monthly mean mole fractions in parts-per-trillion. CH3CCl3 mm.png
1,1,1-Trichloroethane (Methyl chloroform, CH3CCl3) measured by the Advanced Global Atmospheric Gases Experiment (AGAGE) in the lower atmosphere (troposphere) at stations around the world. Abundances are given as pollution free monthly mean mole fractions in parts-per-trillion.
1,1,1-Trichloroethane timeseries at various latitudes. BK MC.jpg
1,1,1-Trichloroethane timeseries at various latitudes.

1,1,1-Trichloroethane is a fairly potent greenhouse gas with a 100-year global warming potential of 169 relative to carbon dioxide. [18] This is nonetheless less than a tenth that of carbon tetrachloride — which it replaced as a solvent — due to its relatively short atmospheric lifetime of about 5 years. [19]

The Montreal Protocol targeted 1,1,1-trichloroethane as a compound responsible for ozone depletion and banned its use beginning in 1996. Since then, its manufacture and use have been phased out throughout most of the world, and its atmospheric concentration has declined substantially. [19]

Related Research Articles

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

Chloroform, or trichloromethane, is an organochloride with the formula CHCl3 and a common solvent. It is a volatile, colorless, sweet-smelling, dense liquid produced on a large scale as a precursor to refrigerants and PTFE. Chloroform was once used as an inhalational anesthetic between the 19th century and the first half of the 20th century. It is miscible with many solvents but it is only very slightly soluble in water.

<span class="mw-page-title-main">Carbon tetrachloride</span> Carbon compound

Carbon tetrachloride, also known by many other names (such as carbon tet for short and tetrachloromethane, also recognised by the IUPAC), is a chemical compound with the chemical formula CCl4. It is a non-flammable, dense, colourless liquid with a "sweet" chloroform-like odour that can be detected at low levels. It was formerly widely used in fire extinguishers, as a precursor to refrigerants, an anthelmintic and a cleaning agent, but has since been phased out because of environmental and safety concerns. Exposure to high concentrations of carbon tetrachloride can affect the central nervous system and degenerate the liver and kidneys. Prolonged exposure can be fatal.

<span class="mw-page-title-main">Tetrachloroethylene</span> Chemical compound in very wide use

Tetrachloroethylene, also known as perchloroethylene or under the systematic name tetrachloroethene, and abbreviations such as perc, and PCE, is a chlorocarbon with the formula Cl2C=CCl2. It is a non-flammable, stable, colorless and heavy liquid widely used for dry cleaning of fabrics. It also has its uses as an effective automotive brake cleaner. It has a mild sweet, sharp odor, detectable by most people at a concentration of 50 ppm.

<span class="mw-page-title-main">Dichloromethane</span> Chemical compound

Dichloromethane is an organochlorine compound with the formula CH2Cl2. This colorless, volatile liquid with a chloroform-like, sweet odor is widely used as a solvent. Although it is not miscible with water, it is slightly polar, and miscible with many organic solvents.

Chloromethane, also called methyl chloride, Refrigerant-40, R-40 or HCC 40, is an organic compound with the chemical formula CH3Cl. One of the haloalkanes, it is a colorless, sweet-smelling, flammable gas. Methyl chloride is a crucial reagent in industrial chemistry, although it is rarely present in consumer products, and was formerly utilized as a refrigerant. Most chloromethane is biogenic.

<span class="mw-page-title-main">Trichloroethylene</span> C2HCl3, widely used industrial solvent

Trichloroethylene (TCE) is a halocarbon with the formula C2HCl3, commonly used as an industrial metal degreasing solvent. It is a clear, colourless, non-flammable, volatile liquid with a chloroform-like pleasant mild smell and sweet taste. Its IUPAC name is trichloroethene. Trichloroethylene has been sold under a variety of trade names. Industrial abbreviations include TCE, trichlor, Trike, Tricky and tri. Under the trade names Trimar and Trilene, it was used as a volatile anesthetic and as an inhaled obstetrical analgesic. It should not be confused with the similar 1,1,1-trichloroethane, which was commonly known as chlorothene.

Halocarbon compounds are chemical compounds in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms resulting in the formation of organofluorine compounds, organochlorine compounds, organobromine compounds, and organoiodine compounds. Chlorine halocarbons are the most common and are called organochlorides.

Organochlorine chemistry is concerned with the properties of organochlorine compounds, or organochlorides, organic compounds containing at least one covalently bonded atom of chlorine. The chloroalkane class includes common examples. The wide structural variety and divergent chemical properties of organochlorides lead to a broad range of names, applications, and properties. Organochlorine compounds have wide use in many applications, though some are of profound environmental concern, with TCDD being one of the most notorious.

The chemical compound 1,2-dichloroethane, commonly known as ethylene dichloride (EDC), is a chlorinated hydrocarbon. It is a colourless liquid with a chloroform-like odour. The most common use of 1,2-dichloroethane is in the production of vinyl chloride, which is used to make polyvinyl chloride (PVC) pipes, furniture and automobile upholstery, wall coverings, housewares, and automobile parts. 1,2-Dichloroethane is also used generally as an intermediate for other organic chemical compounds, and as a solvent. It forms azeotropes with many other solvents, including water and other chlorocarbons.

1,1-Dichloroethane is a chlorinated hydrocarbon. It is a colorless oily liquid with a chloroform-like odor. It is not easily soluble in water, but miscible with most organic solvents.

1,2-Dichloroethylene or 1,2-DCE is the name for a pair of organochlorine compounds with the molecular formula C2H2Cl2. The two compounds are isomers, each being colorless liquids with a sweet odor. It can exist as either of two geometric isomers, cis-1,2-dichloroethene or trans-1,2-dichloroethene, but is often used as a mixture of the two. They have modest solubility in water. These compounds have some applications as a degreasing solvent. In contrast to most cis-trans compounds, the Z isomer (cis) is more stable than the E isomer (trans) by 0.4 kcal/mol.

1,1-Dichloroethylene, commonly called vinylidene chloride or 1,1-DCE, is an organochloride with the molecular formula CCl2CH2. It is a colorless liquid with a sharp odor. Like most chlorocarbons, it is poorly soluble in water but soluble in organic solvents. 1,1-DCE was the precursor to the original clingwrap, Saran, for food, but this application has been phased out.

1,1,2-Trichloroethane, vinyl trichloride or 1,1,2-TCA, is an organochloride solvent with the molecular formula C2H3Cl3 and the structural formula CH2Cl—CHCl2. It is a colourless, sweet-smelling liquid that does not dissolve in water, but is soluble in most organic solvents. It is an isomer of 1,1,1-trichloroethane, and a byproduct of its manufacture.

<span class="mw-page-title-main">1,1,1,2-Tetrachloroethane</span> Chemical compound

1,1,1,2-Tetrachloroethane is a chlorinated hydrocarbon. It is a colorless liquid with a sweet chloroform-like odor. It is used as a solvent and in the production of wood stains and varnishes. It is an isomer of 1,1,2,2-tetrachloroethane.

<span class="mw-page-title-main">Hexachlorobutadiene</span> Chemical compound

Hexachlorobutadiene, (often abbreviated as "HCBD") Cl2C=C(Cl)C(Cl)=CCl2, is a colorless liquid at room temperature that has an odor similar to that of turpentine. It is a chlorinated aliphatic diene with niche applications but is most commonly used as a solvent for other chlorine-containing compounds. Structurally, it has a 1,3-butadiene core, but fully substituted with chlorine atoms.

1,1,2-Trichloro-1,2,2-trifluoroethane, also called trichlorotrifluoroethane or CFC-113, is a chlorofluorocarbon. It has the formula Cl2FC−CClF2. This colorless, volatile liquid is a versatile solvent.

<span class="mw-page-title-main">Chloroacetaldehyde</span> Chemical compound

Chloroacetaldehyde is an organic compound with the formula ClCH2CHO. Like some related compounds, it is highly electrophilic reagent and a potentially dangerous alkylating agent. The compound is not normally encountered in the anhydrous form, but rather as the hemiacetal (ClCH2CH(OH))2O.

<span class="mw-page-title-main">Perchloromethyl mercaptan</span> Chemical compound

Perchloromethyl mercaptan is the organosulfur compound with the formula CCl3SCl. It is mainly used as an intermediate for the synthesis of dyes and fungicides (captan, folpet). It is a colorless oil, although commercial samples are yellowish. It is insoluble in water but soluble in organic solvents. It has a foul, unbearable, acrid odor. Perchloromethyl mercaptan is the original name. The systematic name is trichloromethanesulfenyl chloride, because the compound is a sulfenyl chloride, not a mercaptan.

Thermo-Chem, Inc., also referred to as Thermo-Chem, is a 50-acre Superfund site located in Egelston Township near Muskegon, Michigan.

References

  1. 1 2 3 4 5 6 7 NIOSH Pocket Guide to Chemical Hazards. "#0404". National Institute for Occupational Safety and Health (NIOSH).
  2. ↑ "International Programme On Chemical Safety, Environmental Health Criteria 136". World Health Organization, Geneva. 1990. Retrieved 25 December 2017.
  3. ↑ Timmermans, Jean, Physico-chemical constants of pure organic compounds (1950), p. 242
  4. 1 2 "Methyl chloroform". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  5. ↑ Manfred Rossberg, Wilhelm Lendle, Gerhard Pfleiderer, Adolf Tögel, Eberhard-Ludwig Dreher, Ernst Langer, Heinz Rassaerts, Peter Kleinschmidt, Heinz Strack, Richard Cook, Uwe Beck, Karl-August Lipper, Theodore R. Torkelson, Eckhard Löser, Klaus K. Beutel, Trevor Mann "Chlorinated Hydrocarbons" in Ullmann's Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a06_233.pub2.
  6. ↑ Morrison, R. D., Murphy, B. L. (2013). Chlorinated Solvents: A Forensic Evaluation. UK Royal Society of Chemistry. Page 203
  7. ↑ Use of Ozone Depleting Substances in Laboratories. TemaNord 516/2003 Archived 2008-02-27 at the Wayback Machine
  8. ↑ The American Practitioner 1881-01: Volume 23, page 28
  9. ↑ Methyl-Chloroform (1887) in Saint Louis Medical and Surgical Journal, page 121
  10. ↑ An introduction to modern therapeutics (1892), Brunton, T. Lauder, page 122
  11. ↑ On Two New Anaesthetics (1880), The American Journal of Pharmacy 1881-03: Vol 53, pages 119–120
  12. ↑ Toxicological Profile for 1,1,1-Trichloroethane Archived 2008-05-09 at the Wayback Machine , Agency for Toxic Substances and Disease Registry (ATSDR). 2006
  13. ↑ King, Gregory S.; Smialek, John E.; Troutman, William G. (15 March 1985). "Sudden Death in Adolescents Resulting From the Inhalation of Typewriter Correction Fluid". JAMA: The Journal of the American Medical Association. 253 (11): 1604–1606. doi:10.1001/jama.253.11.1604. PMID   3974043. Archived from the original on 23 February 2013. Retrieved 5 January 2010. We describe four cases of sudden death in adolescents associated with recreational sniffing of typewriter correction fluid occurring during the period 1979 through mid-1984.
  14. ↑ D'costa, DF; Gunasekera, NP (August 1990). "Fatal cerebral oedema following trichloroethane abuse". Journal of the Royal Society of Medicine. 83 (8): 533–534. doi:10.1177/014107689008300823. PMC   1292788 . PMID   2231588.
  15. ↑ Winekab, Charles L.; Wahba, Wagdy W.; Huston, Robert; Rozin, Leon (6 June 1997). "Fatal inhalation of 1,1,1-trichloroethane". Forensic Science International. 87 (2): 161–165. doi:10.1016/S0379-0738(97)00040-6. PMID   9237378. A 13-year-old male was found dead in the woods subsequent to 1,1,1-trichloroethane (TCE) inhalation.
  16. ↑ Wodka, Richard M.; Jeong, Erwin W. S. (1 January 1989). "Cardiac Effects of Inhaled Typewriter Correction Fluid". Annals of Internal Medicine. 110 (1): 91–92. doi:10.7326/0003-4819-110-1-91_2. PMID   2908837. Archived from the original on 14 April 2013. Retrieved 5 January 2010.
  17. ↑ IARC. 1,1,1-Trichloroethane and Four Other Industrial Chemicals. ISBN   978-92-832-0197-7.
  18. ↑ Hodnebrog Ø, Aamaas B, Fuglestvedt JS, Marston G, Myhre G, Nielsen CJ, Sandstad M, Shine KP, Wallington TJ (September 2020). "Updated Global Warming Potentials and Radiative Efficiencies of Halocarbons and Other Weak Atmospheric Absorbers". Reviews of Geophysics. 58 (3): e2019RG000691. Bibcode:2020RvGeo..5800691H. doi:10.1029/2019RG000691. PMC   7518032 . PMID   33015672.
  19. 1 2 "Chapter 8, Table 8.A.1". AR5 Climate Change 2013: The Physical Science Basis. p. 733.

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