1,1,1-Trichloroethane
Encyclopedia
The organic compound
1,1,1-trichloroethane, also known as methyl chloroform, is a chloroalkane. This colourless, sweet-smelling liquid was once produced industrially in large quantities for use as a solvent
. It is regulated by the Montreal Protocol
as an ozone-depleting substance and its use is being rapidly phased out.
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
:
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:
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 vinylidene chloride and hydrogen chloride in the presence of an iron(III) chloride catalyst:
1,1,1-Trichloroethane is marketed with stabilizers since 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. The Montreal Protocol targeted 1,1,1-trichloroethane as one of those compounds responsible for ozone depletion
and banned its use beginning in 1996. Since then, its manufacture and use has been phased out throughout most of the world.
. It is an excellent solvent for many organic
materials and also one of the least toxic of the chlorinated hydrocarbons. 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, adhesive
s and other coatings.
It was also the standard cleaner for photographic film (movie/slide/negatives, etc.). Other commonly available solvents damage emulsion, 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 applications for 1,1,1-trichloroethane (including film cleaning) were previously done with carbon tetrachloride
, which was banned in 1970. In the laboratory, 1,1,1-trichloroethane is being been replaced by other solvents.
1,1,1-Trichloroethane is used as an insecticidal
fumigant
.
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 intoxication, including dizziness
, confusion, and in sufficiently high concentrations, unconsciousness
and death. Fatal poisonings have been reported. and illness linked to trichloroethane from intentional inhalation in the 1980s. The removal of the chemical from correction fluid commenced due to Proposition 65 declaring it hazardous and toxic
Prolonged skin contact with the liquid can result in the removal of fats from the skin, resulting in chronic skin irritation. Studies on laboratory animals have shown that 1,1,1-trichloroethane is not retained in the body for long periods of time. However, chronic exposure has been linked to abnormalities in the liver, kidneys, and heart. Pregnant women should avoid exposure, as the compound has been linked to birth defects in laboratory animals (see teratogenesis).
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
1,1,1-trichloroethane, also known as methyl chloroform, is a chloroalkane. This colourless, sweet-smelling liquid was once produced industrially in large quantities for use as a solvent
Solvent
A solvent is a liquid, solid, or gas that dissolves another solid, liquid, or gaseous solute, resulting in a solution that is soluble in a certain volume of solvent at a specified temperature...
. It is regulated by the Montreal Protocol
Montreal Protocol
The Montreal Protocol on Substances That Deplete the Ozone Layer is an international treaty designed to protect the ozone layer by phasing out the production of numerous substances believed to be responsible for ozone depletion...
as an ozone-depleting substance and its use is being rapidly phased out.
Production
1,1,1-Trichloroethane was first reported by Henri Victor RegnaultHenri Victor Regnault
Henri Victor Regnault was a French chemist and physicist best known for his careful measurements of the thermal properties of gases. He was an early thermodynamicist and was mentor to William Thomson in the late 1840s....
in 1840. Industrially, it is usually produced in a two-step process from vinyl chloride
Vinyl chloride
Vinyl chloride is the organochloride with the formula H2C:CHCl. It is also called vinyl chloride monomer, VCM or chloroethene. This colorless compound is an important industrial chemical chiefly used to produce the polymer polyvinyl chloride . At ambient pressure and temperature, vinyl chloride...
. In the first step, vinyl chloride reacts with hydrogen chloride
Hydrogen chloride
The compound hydrogen chloride has the formula HCl. At room temperature, it is a colorless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric humidity. Hydrogen chloride gas and hydrochloric acid are important in technology and industry...
at 20-50 °C to produce 1,1-dichloroethane
1,1-Dichloroethane
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....
:
- CH2=CHCl + HCl → CH3CHCl2
This reaction is catalyzed by a variety of Lewis acids, mainly aluminium chloride
Aluminium chloride
Aluminium chloride is the main compound of aluminium and chlorine. It is white, but samples are often contaminated with iron trichloride, giving it a yellow colour. The solid has a low melting and boiling point. It is mainly produced and consumed in the production of aluminium metal, but large...
, iron(III) chloride
Iron(III) chloride
Iron chloride, also called ferric chloride, is an industrial scale commodity chemical compound, with the formula FeCl3. The colour of iron chloride crystals depends on the viewing angle: by reflected light the crystals appear dark green, but by transmitted light they appear purple-red...
, or zinc chloride
Zinc chloride
Zinc chloride is the name of chemical compound with the formula ZnCl2 and its hydrates. Zinc chlorides, of which nine crystalline forms are known, are colorless or white, and are highly soluble in water. ZnCl2 itself is hygroscopic and even deliquescent. Samples should therefore be protected from...
. The 1,1-dichloroethane is then converted to 1,1,1-trichloroethane by reaction with chlorine
Chlorine
Chlorine is the chemical element with atomic number 17 and symbol Cl. It is the second lightest halogen, found in the periodic table in group 17. The element forms diatomic molecules under standard conditions, called dichlorine...
under ultraviolet
Ultraviolet
Ultraviolet light is electromagnetic radiation with a wavelength shorter than that of visible light, but longer than X-rays, in the range 10 nm to 400 nm, and energies from 3 eV to 124 eV...
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
1,1,2-Trichloroethane
1,1,2-Trichloroethane, or 1,1,2-TCA, is an organochloride solvent with the molecular formula C2H3Cl3. It is a colourless, sweet-smelling liquid that does not dissolve in water, but is soluble in most organic solvents...
, from which the 1,1,1-trichloroethane can be separated by distillation
Distillation
Distillation is a method of separating mixtures based on differences in volatilities of components in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction....
.
A somewhat smaller amount of 1,1,1-trichloroethane is produced from the reaction of vinylidene chloride and hydrogen chloride in the presence of an iron(III) chloride catalyst:
- CH2=CCl2 + HCl → CH3CCl3
1,1,1-Trichloroethane is marketed with stabilizers since 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. The Montreal Protocol targeted 1,1,1-trichloroethane as one of those compounds responsible for ozone depletion
Ozone depletion
Ozone depletion describes two distinct but related phenomena observed since the late 1970s: a steady decline of about 4% per decade in the total volume of ozone in Earth's stratosphere , and a much larger springtime decrease in stratospheric ozone over Earth's polar regions. The latter phenomenon...
and banned its use beginning in 1996. Since then, its manufacture and use has been phased out throughout most of the world.
Uses
1,1,1-Trichloroethane is generally considered as a nonpolar solvent. Owing to its unsymmetrical structure, it is a superior solvent for organic compounds that do not dissolve well in hydrocarbons such as hexaneHexane
Hexane is a hydrocarbon with the chemical formula C6H14; that is, an alkane with six carbon atoms.The term may refer to any of four other structural isomers with that formula, or to a mixture of them. In the IUPAC nomenclature, however, hexane is the unbranched isomer ; the other four structures...
. It is an excellent solvent for many organic
Organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, composition, reactions, and preparation of carbon-based compounds, hydrocarbons, and their derivatives...
materials and also one of the least toxic of the chlorinated hydrocarbons. Prior to the Montreal Protocol, it was widely used for cleaning metal parts and circuit boards, as a photoresist
Photoresist
A photoresist is a light-sensitive material used in several industrial processes, such as photolithography and photoengraving to form a patterned coating on a surface.-Tone:Photoresists are classified into two groups: positive resists and negative resists....
solvent in the electronics
Electronics
Electronics is the branch of science, engineering and technology that deals with electrical circuits involving active electrical components such as vacuum tubes, transistors, diodes and integrated circuits, and associated passive interconnection technologies...
industry, as an aerosol
Aerosol spray
Aerosol spray is a type of dispensing system which creates an aerosol mist of liquid particles. This is used with a can or bottle that contains a liquid under pressure. When the container's valve is opened, the liquid is forced out of a small hole and emerges as an aerosol or mist...
propellant, as a cutting fluid
Cutting fluid
Cutting fluid is a type of coolant and lubricant designed specifically for metalworking and machining processes. There are various kinds of cutting fluids, which include oils, oil-water emulsions, pastes, gels, aerosols , and air or other gases. They may be made from petroleum distillates, animal...
additive, and as a solvent for inks, paints, adhesive
Adhesive
An adhesive, or glue, is a mixture in a liquid or semi-liquid state that adheres or bonds items together. Adhesives may come from either natural or synthetic sources. The types of materials that can be bonded are vast but they are especially useful for bonding thin materials...
s and other coatings.
It was also the standard cleaner for photographic film (movie/slide/negatives, etc.). Other commonly available solvents damage emulsion, 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
Correction fluid
A correction fluid is an opaque, white fluid applied to paper to mask errors in text. Once dried, it can be written over. It is typically packaged in small bottles, and the lid has an attached brush which dips into the bottle...
products such as Liquid paper
Liquid Paper
Liquid Paper is a brand of the Newell Rubbermaid company that sells correction fluid, correction pen and correction tape. Mainly used to correct typewriting in the past, correction products now mostly cover handwriting mistakes.- Brand history :...
. Many applications for 1,1,1-trichloroethane (including film cleaning) were previously done with carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride, also known by many other names 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...
, which was banned in 1970. In the laboratory, 1,1,1-trichloroethane is being been replaced by other solvents.
1,1,1-Trichloroethane is used as an insecticidal
Insecticide
An insecticide is a pesticide used against insects. They include ovicides and larvicides used against the eggs and larvae of insects respectively. Insecticides are used in agriculture, medicine, industry and the household. The use of insecticides is believed to be one of the major factors behind...
fumigant
Fumigation
Fumigation is a method of pest control that completely fills an area with gaseous pesticides—or fumigants—to suffocate or poison the pests within. It is utilized for control of pests in buildings , soil, grain, and produce, and is also used during processing of goods to be imported or...
.
Safety
Although not as toxicToxicity
Toxicity is the degree to which a substance can damage a living or non-living organisms. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a substructure of the organism, such as a cell or an organ , such as the liver...
as many similar compounds, inhaled or ingested 1,1,1-trichloroethane does act as a central nervous system
Central nervous system
The central nervous system is the part of the nervous system that integrates the information that it receives from, and coordinates the activity of, all parts of the bodies of bilaterian animals—that is, all multicellular animals except sponges and radially symmetric animals such as jellyfish...
depressant
Depressant
A depressant, or central depressant, is a drug or endogenous compound that depresses the function or activity of a specific part of the brain...
and can cause effects similar to those of intoxication, including dizziness
Dizziness
Dizziness refers to an impairment in spatial perception and stability. The term is somewhat imprecise. It can be used to mean vertigo, presyncope, disequilibrium, or a non-specific feeling such as giddiness or foolishness....
, confusion, and in sufficiently high concentrations, unconsciousness
Unconsciousness
Unconsciousness is the condition of being not conscious—in a mental state that involves complete or near-complete lack of responsiveness to people and other environmental stimuli. Being in a comatose state or coma is a type of unconsciousness. Fainting due to a drop in blood pressure and a...
and death. Fatal poisonings have been reported. and illness linked to trichloroethane from intentional inhalation in the 1980s. The removal of the chemical from correction fluid commenced due to Proposition 65 declaring it hazardous and toxic
Prolonged skin contact with the liquid can result in the removal of fats from the skin, resulting in chronic skin irritation. Studies on laboratory animals have shown that 1,1,1-trichloroethane is not retained in the body for long periods of time. However, chronic exposure has been linked to abnormalities in the liver, kidneys, and heart. Pregnant women should avoid exposure, as the compound has been linked to birth defects in laboratory animals (see teratogenesis).
Further reading
- Doherty, R.E. 2000. A History of the Production and Use of Carbon Tetrachloride, Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2 - Trichloroethylene and 1,1,1-Trichloroethane, Journal of Environmental Forensics (2000) 1, 83-93.