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Acetylene
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Acetylene (IUPAC name: ethyne) is the chemical compound with the symbol C2H2. It is the simplest alkyne.
As an alkyne, acetylene is unsaturated because its two carbon atoms are bonded together in a triple bond. The carbon-carbon triple bond leaves the carbon atoms with two sp hybrid orbitals for sigma bonding, placing all four atoms in the same straight line, with CCH bond angles of 180°.
Acetylene was discovered in 1836 by Edmund Davy who identified it as a "new carburet of hydrogen." It was rediscovered in 1860 by French chemist Marcellin Berthelot, who coined the name "acetylene." The Nobel Laureate Gustaf Dalén was blinded by an acetylene explosion.
Preparation
The principal raw materials for acetylene manufacture are calcium carbonate (limestone) and coal.
Discussion
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Encyclopedia
Acetylene (IUPAC name: ethyne) is the chemical compound with the symbol C2H2. It is the simplest alkyne.
As an alkyne, acetylene is unsaturated because its two carbon atoms are bonded together in a triple bond. The carbon-carbon triple bond leaves the carbon atoms with two sp hybrid orbitals for sigma bonding, placing all four atoms in the same straight line, with CCH bond angles of 180°.
Acetylene was discovered in 1836 by Edmund Davy who identified it as a "new carburet of hydrogen." It was rediscovered in 1860 by French chemist Marcellin Berthelot, who coined the name "acetylene." The Nobel Laureate Gustaf Dalén was blinded by an acetylene explosion.
Preparation
The principal raw materials for acetylene manufacture are calcium carbonate (limestone) and coal. The calcium carbonate is first converted into calcium oxide and the coal into coke, then the two are reacted with each other to form calcium carbide and carbon monoxide:
- CaO + 3C ? CaC2 + CO
Calcium carbide (or calcium acetylide) and water are then reacted by any of several methods to produce acetylene and calcium hydroxide. This reaction was discovered by Friedrich Wohler in 1862.
- CaC2 + 2H2O ? Ca(OH)2 + C2H2
Calcium carbide synthesis requires an extremely high temperature, ~2000 degrees Celsius, so the reaction is performed in an electric arc furnace. This reaction was an important part of the late-1800s revolution in chemistry enabled by the massive hydroelectric power project at Niagara Falls.
Acetylene can also be manufactured by the partial combustion of methane with oxygen, or by the cracking of hydrocarbons.
Berthelot was able to prepare acetylene from methyl alcohol, ethyl alcohol, ethylene, or ether, when he passed any one of these as a gas or vapour through a red-hot tube. Berthelot also found acetylene was formed by sparking electricity through mixed cyanogen and hydrogen gases. He was also able to form acetylene directly by combining pure hydrogen with carbon using electrical discharge of a carbon arc.
Reactions
- Above 400 °C (673 K) the pyrolysis of acetylene will start, which is relatively low for a hydrocarbon. The main products are the dimer vinylacetylene (C4H4) and benzene. At temperatures above 900 °C (1173 K), the main product will be soot.
- Using acetylene, Berthelot was the first to show that an aliphatic compound could form an aromatic compound when he heated acetylene in a glass tube to produce benzene with some toluene. Berthelot oxidized acetylene to yield acetic acid and oxalic acid. He found acetylene could be reduced to form ethylene and ethane.
- Polymerization of acetylene with Ziegler-Natta catalysts produces polyacetylene films. Polyacetylene, a chain of carbon molecules with alternating single and double bonds, was the first organic semiconductor to be discovered; reaction with iodine produces an extremely conductive material.
- In the Kucherov reaction (invented in 1881 by the Russian chemist Mikhail Kucherov) acetylene is hydrated to acetaldehyde with a mercury salt such as mercury(II) bromide. Before the advent of the Wacker process this reaction was conducted on an industrial scale.
- Formation of acetylides with many metal ions, when bubbled through the solutions of their salts. Several, e.g. silver acetylide and copper acetylide, are powerful explosives. Copper acetylide is also formed by reacting acetylene with metallic copper or its alloys; these materials are therefore unsuitable for installations for handling acetylene.
Reppe chemistry
Walter Reppe discovered that acetylene can react at high pressures with heavy metal catalysts to give industrially significant chemicals:
- With aldehydes to give ethynyl diols.
This is industrially used to produce 1,4-butynediol from formaldehyde and acetylene:
- HCCH + CH2O ? CH2(OH)CCCH2OH
Uses
with water.]]
Approximately 80 percent of the acetylene produced annually in the United States is used in chemical synthesis. The remaining 20 percent is used primarily for oxyacetylene gas welding and cutting due to the high temperature of the flame; combustion of acetylene with oxygen produces a flame of over 3300 °C (6000 °F), releasing 11.8 kJ/g. Oxyacetylene is the hottest burning common fuel gas.
Acetylene is also used in the acetylene ('carbide') lamp, once used by miners (not to be confused with the Davy lamp), on vintage cars, and still sometimes used by cavers. In this context, the acetylene is generated by dripping water from the upper chamber of the lamp onto calcium carbide (CaC2) pellets in the base of the lamp.
In the early 20th century acetylene was widely used for illumination, including street lighting in some towns.
In modern times acetylene is sometimes used for carburization (that is, hardening) of steel when the object is too large to fit into a furnace.
Acetylene is the 3rd hottest chemical flame behind Cyanogen at 4525°C (8180°F) and Dicyanoacetylene's 5260 K (4990 °C, 9010 °F).
Acetylene has been proposed as a carbon feedstock for molecular manufacturing using nanotechnology.
Acetylene is used to volatilize carbon in radiocarbon dating. The carbonaceous material in an archeological sample is reacted with lithium metal in a small specialized research furnace to form lithium carbide (also known as lithium acetylide). The carbide can then be reacted with water, as usual, to form acetylene gas to be fed into mass spectrometer to sort out the isotopic ratio of carbon 14 to carbon 12.
The Future
The use of acetylene is expected to continue a gradual increase in the future as new applications are developed. One new application is the conversion of acetylene to ethylene for use in making a variety of polyethylene plastics. In the past, a small amount of acetylene had been generated and wasted as part of the steam cracking process used to make ethylene. A new catalyst developed by Phillips Petroleum allows most of this acetylene to be converted into ethylene for increased yields at a reduced overall cost.
Safety and handling
Compression
Due to the carbon-to-carbon triple bond, acetylene gas is fundamentally unstable, and will decompose in an exothermic reaction if compressed to any great extent. Acetylene can explode with extreme violence if the pressure of the gas exceeds about 200 kPa (˜39 psi) as a gas or when in liquid or solid form, so it is shipped and stored dissolved in acetone or dimethylformamide (DMF), contained in a metal cylinder with porous filling (Agamassan), which renders it safe to transport and use.
There are strict regulations on the shipment of dangerous gas cylinders throughout the world. Oxy-acetylene welding was a very popular welding process in previous decades, however, the development and advantages of arc-based welding processes have made oxy-fuel welding nearly extinct. Acetylene usage for welding has dropped significantly. However, oxy-fuel cutting is still very popular and oxy-acetylene cutting is present in nearly every metal fabrication shop.
At pressures above 15 PSI the gas becomes extremely unstable, and can be ignited by shock. For use in welding and cutting, the working pressures must be controlled by a regulator, or the gas will spontaneously combust.
Some people have been injured by acetylene explosions because of its unstable nature. Most often explosions are caused by unregulated transfer between two gas cylinders.
Toxicity
Inhaling acetylene may cause dizziness, headache and nausea. It may also contain toxic impurities: the has established a grading system for identifying and quantifying phosphine, arsine, and hydrogen sulfide content in commercial grades of acetylene in order to limit exposure to these impurities. The sulfur, phosphorus and arsenic are carryovers from the synthesis ingredient coke, an impure form of carbon and different, organic impurities would be expected from the thermal cracking of hydrocarbons source.
Acetylene has been infrequently abused in a manner akin to nitrous oxide abuse up through modern times, according to the literature. Such abuse can result in the death of the abuser due to toxicity of the above mentioned impurities phosphine, arsine, and hydrogen sulfide. Since the gas is charged (absorbed) into tanks soaked with acetone over a solid matrix, some acetone comes out with the gas, further contributing to the poisonings. The driver for this abusive behavior is better understood with the view of acetylene's anesthetic properties and addictive behaviors.
Impurities in acetylene are easily detectable by smell. Pure acetylene is a colorless and odorless gas. The characteristic garlic-like odor of technical grade acetylene is attributable to contamination by impurities. Impurities which may be present include: divinyl sulfide, ammonia, oxygen, nitrogen, phosphine, arsine, methane, carbon dioxide, carbon monoxide, hydrogen sulfide, vinylacetylene, divinyl acetylene, diacetylene, propadiene, hexadiene, butadienyl acetylene, and methyl acetylene.
Fire hazard
Mixtures with air containing between 3% and 82% acetylene are explosive on ignition. The minimum ignition temperature is 335 °C. The carbon-carbon triple bond of acetylene is weak compared to the carbon-oxygen double bonds that are formed in its combustion to form carbon dioxide, causing this combustion to be extremely energetic.
Incompatibilities
Other meanings
Sometimes the plural "acetylenes" may refer to the class of organic chemical compounds known as alkynes which contain the -C=C- group.
Natural occurrence
Acetylene is a moderately common chemical in the universe, often associated with the atmospheres of gas giants. One curious discovery of acetylene is on Enceladus, a moon of Saturn. Natural acetylene is believed to form from either catalytic decomposition of long chain hydrocarbons at temperatures = 1,770 kelvin. Since such temperatures are highly unlikely on such a small distant body, this discovery is potentially suggestive of catalytic reactions within the moon, making it a promising site to search for prebiotic chemistry.
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