Methanol

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Methanol
Methanol
Methanol
Methanol
Methanol
IUPAC name methanol
Other names hydroxymethane
methyl alcohol
methyl hydrate
wood alcohol
carbinol
Identifiers
InChI InChI=1/CH4O/c1-2/h2H,1H3
InChIKey OKKJLVBELUTLKV-UHFFFAOYAX
Standard InChI InChI=1S/CH4O/c1-2/h2H,1H3
Standard InChIKey OKKJLVBELUTLKV-UHFFFAOYSA-N
CAS number [67-56-1]
EC number 200-659-6
RTECS PC1400000
ChemSpider 864
SMILES
Properties[1][2][3]
Chemical formula CH3OH
Molar mass 32.042 kJ mol−1
Appearance colorless liquid
Density 0.7914 g cm−3
Melting point

–97 °C (176 K)

Boiling point

64.7 °C (337.8 K)

Triple point –97.7 ºC (175.5 K)
Critical point 513 K, 81 bar
Solubility in water miscible
log P –0.82
Vapor pressure 12.3 kPa at 20 ºC
Acidity (pKa) approx. 15.5
Refractive index (nD) 1.3288 at 20 ºC
Viscosity 0.59 mPa s at 20 °C
Dipole moment 1.69 D (gas)
Thermochemistry[1][4]
Std enthalpy of formation ΔfHo298 –239.5 kJ mol−1
Std enthalpy of combustion ΔcHo298 –725.7 kJ mol−1
Standard molar entropy So298 127.2 J K–1 mol–1
Std enthalpy of vaporization ΔvapHo298 37 kJ mol−1
Hazards[2][5][6]
Material safety data sheet (MSDS) ICSC 0057
EU index number 603-001-00-X
GHS pictograms Flam. Liq. 2Acute Tox. 3STOT SE 1
GHS signal word DANGER
GHS hazard statements H225, H331, H311, H301, H370
Flash point 12 °C (54 ºF)
Autoignition temp. 464 ºC (867 ºF)
Explosive limits 5.5–44%
PEL (U.S.) 200 ppm TWA
IDLH level 6000 ppm
Related compounds
Other alcohols Ethanol
Propanol
Butanol
Other compounds Chloromethane
Methoxymethane
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)

Methanol, also known as methyl alcohol, carbinol, wood alcohol, wood naphtha or wood spirits, is a toxic chemical with formula CH3OH (often abbreviated MeOH). Drinking 10 ml will cause blindness, and as little as 100 ml will cause death, as many unfortunate individuals found out during the Prohibition. It is the simplest alcohol, and is a light, volatile, colourless, flammable, toxic liquid with a distinctive odor that is very similar to but slightly sweeter than ethanol (drinking alcohol).[7] At room temperature it is a polar liquid and is used as an antifreeze, solvent, fuel, and as a denaturant for ethanol. It is also used for producing biodiesel via transesterification reaction.

Methanol is produced naturally in the anaerobic metabolism of many varieties of bacteria, and is ubiquitous in the environment. As a result, there is a small fraction of methanol vapor in the atmosphere. Over the course of several days, atmospheric methanol is oxidized by oxygen with the help of sunlight to carbon dioxide and water.

Methanol burns in air forming carbon dioxide and water:

2CH3OH + 3O2 → 2CO2 + 4H2O

A methanol flame is almost colorless in bright sunlight conditions, causing an additional safety hazard around open methanol flames.[2]

Because of its toxic properties, methanol is frequently used as a denaturant additive for ethanol manufactured for industrial uses — this addition of methanol economically exempts industrial ethanol from the rather significant 'liquor' taxes that would otherwise be levied as it is the essence of all potable alcoholic beverages. Methanol is often called wood alcohol because it was once produced chiefly as a byproduct of the destructive distillation of wood. It is now produced synthetically by a multi-step process: natural gas or coal gas and steam are reformed in a furnace to produce hydrogen and carbon monoxide; then, hydrogen and carbon monoxide gases react under pressure in the presence of a catalyst. Methanol is also produced from the gasification of a range of renewable biomass materials, such as wood and black liquor from pulp and paper mills.

History

In their embalming process, the ancient Egyptians used a mixture of substances, including methanol, which they obtained from the pyrolysis of wood. Pure methanol, however, was first isolated in 1661 by Robert Boyle, when he produced it via the distillation of boxwood. It later became known as pyroxylic spirit. In 1834, the French chemists Jean-Baptiste Dumas and Eugene Peligot determined its elemental composition.

They also introduced the word methylene to organic chemistry, forming it from Greek methy = "wine" + hȳlē = wood (patch of trees). Its intended origin was "alcohol made from wood (substance)", but it has Greek language errors. The term "methyl" was derived in about 1840 by back-formation from methylene, and was then applied to describe "methyl alcohol." This was shortened to "methanol" in 1892 by the International Conference on Chemical Nomenclature. The suffix -yl used in organic chemistry to form names of carbon groups, was extracted from the word "methyl."

In 1923, the German chemists Alwin Mittasch and Mathias Pier, working for BASF developed a means to convert synthesis gas (a mixture of carbon monoxide, carbon dioxide, and hydrogen) into methanol. This process used a chromium and manganese oxide catalyst, and required extremely vigorous conditions—pressures ranging from 50–220 atm, and temperatures up to 450 °C.[8] Modern methanol production has been made more efficient through use of catalysts (commonly copper) capable of operating at lower pressures, the modern low pressure methanol (LPM) was developed by ICI in the late 1960s with the technology now owned[ref. needed] by Johnson Matthey who is a leading licensor of methanol technology.

The use of methanol as a motor fuel received attention during the oil crises of the 1970s due to its availability, low cost, and environmental benefits. By the mid-1990s, over 20,000 methanol "flexible fuel vehices" capable of operating on methanol or gasoline were introduced in the U.S. In addition, low levels of methanol were blending in gasoline fuels sold in Europe during much of the 1980s and early-1990s. Automakers stopped building methanol FFVs by the late-1990s, switching their attention to ethanol fueled vehicles. While the Methanol FFV program was a technical success, rising methanol pricing in the mid- to late-1990s during a period of slumping gasoline pump prices diminished the interest in methanol fuels.

In 2006 astronomers using the MERLIN array of radio telescopes at Jodrell Bank Observatory discovered a large cloud of methanol in space, 300 billion miles across.

Production

Today, synthesis gas is most commonly produced from the methane component in natural gas rather than from coal. Three processes are commercially practiced. At moderate pressures of 4 MPa (40 atm) and high temperatures (around 850 °C), methane reacts with steam on a nickel catalyst to produce syngas according to the chemical equation:

CH4 + H2O → CO + 3H2

This reaction, commonly called steam-methane reforming or SMR, is endothermic and the heat transfer limitations place limits on the size of and pressure in the catalytic reactors used. Methane can also undergo partial oxidation with molecular oxygen to produce syngas, as the following equation shows:

2CH4 + O2 → 2CO + 4 H2

This reaction is exothermic and the heat given off can be used in-situ to drive the steam-methane reforming reaction. When the two processes are combined, it is referred to as autothermal reforming. The ratio of CO and H2 can be adjusted to some extent by the water-gas shift reaction,

CO + H2O → CO2 + H2,

to provide the appropriate stoichiometry for methanol synthesis.

The carbon monoxide and hydrogen then react on a second catalyst to produce methanol. Today, the most widely used catalyst is a mixture of copper, zinc oxide, and alumina first used by ICI in 1966. At 5–10 MPa (50–100 atm) and 250 °C, it can catalyze the production of methanol from carbon monoxide and hydrogen with high selectivity:

CO + 2H2 → CH3OH

It is worth noting that the production of synthesis gas from methane produces 3 moles of hydrogen for every mole of carbon monoxide, while the methanol synthesis consumes only 2 moles of hydrogen for every mole of carbon monoxide. One way of dealing with the excess hydrogen is to inject carbon dioxide into the methanol synthesis reactor, where it, too, reacts to form methanol according to the equation:

CO2 + 3 H2 → CH3OH + H2O

Although natural gas is the most economical and widely used feedstock for methanol production, other feedstocks can be used. Coal is increasingly being used as a feedstock for methanol production, particularly in China. In addition, mature technologies available for biomass gasification are being utilized for methanol production.

Applications

Methanol is a common laboratory solvent. It is especially useful for HPLC and UV/VIS spectroscopy due to its low UV cutoff.

Feedstock

The largest use of methanol by far is in making other chemicals. About 40% of methanol is converted to formaldehyde, and from there into products as diverse as plastics, plywood, paints, explosives, and permanent press textiles.

Also in the early 1970s, a Methanol to gasoline process was developed by Mobil for producing gasoline ready for use in vehicles. One such industrial facility was built at Motunui in New Zealand in the 1980s. In the 1990s, large amounts of methanol were used in the United States to produce the gasoline additive methyl tert-butyl ether (MTBE). While MTBE is no longer marketed in the U.S., it is still widely used in other parts of the world. In addition to direct use as a fuel, methanol (or less commonly, ethanol) is used as a component in the transesterification of triglycerides to yield a form of biodiesel.

Other chemical derivatives of methanol include dimethyl ether, which has replaced chlorofluorocarbons as an aerosol spray propellant, and acetic acid. Dimethyl ether, or "DME" also can be blended with liquified petroleum gas (LPG) for home heating and cooking, and can be used as a diesel replacement transportation fuel.

Fuel for vehicles

Main article: Methanol fuel

Methanol is used on a limited basis to fuel internal combustion engines, mainly by virtue of the fact that it is not nearly as flammable as gasoline. Methanol is harder to ignite than gasoline and produces just one-eighth of the heat upon burning. Pure methanol is required by rule to be used in Champcars, Monster Trucks, USAC sprint cars (as well as midgets, modifieds, etc.), and other dirt track series such as World of Outlaws, and Motorcycle Speedway. Methanol is also used in radio control, control line and free flight airplanes (as methanol is required in the "glow-plug" engines that primarily power them), cars and trucks, from such an engine's use of a platinum filament glow plug being able to ignite the methanol vapor through a catalytic reaction. Drag racers and mud racers also use methanol as their primary fuel source. Methanol is required with a supercharged engine in a Top Alcohol Dragster and, until the end of the 2006 season, all vehicles in the Indianapolis 500 had to run methanol. Mud racers have mixed methanol with gasoline and nitrous oxide to produce more power than gasoline and nitrous oxide alone.

One of the drawbacks of methanol as a fuel is its corrosivity to some metals, including aluminium. Methanol, although a weak acid, attacks the oxide coating that normally protects the aluminium from corrosion:

6 CH3OH + Al2O3 → 2 Al(OCH3)3 + 3 H2O

The resulting methoxide salts are soluble in methanol, resulting in clean aluminium surface, which is readily oxidized by some dissolved oxygen. Also the methanol can act as an oxidizer:

6 CH3OH + 2 Al → 2 Al(OCH3)3 + 3 H2

This reciprocal process effectively fuels corrosion until either the metal is eaten away or the concentration of CH3OH is negligible. Concerns with methanol's corrosivity have been addressed by using methanol compatible materials, and fuel additives that serve as corrosion inhibitors.

When produced from wood or other organic materials, the resulting organic methanol (bioalcohol) has been suggested as renewable alternative to petroleum-based hydrocarbons. Low levels of methanol can be used in existing vehicles, with the use of proper cosolvents and corrosion inhibitors. The European Fuel Quality Directive allows up to 3% methanol with an equal amount of cosolvent to be blending in gasoline sold in Europe. Today, China uses more than one billion gallons of methanol per year as a transportation fuel in both low level blends used in existing vehicles, and as high level blends in vehicles designed to accommodate the use of methanol fuels.

Other applications

Methanol is a traditional denaturant for ethanol, thus giving the term methylated spirit.

Methanol is also used as a solvent, and as an antifreeze in pipelines and windshield washer fluid.

In some wastewater treatment plants, a small amount of methanol is added to wastewater to provide a food source of carbon for the denitrifying bacteria, which convert nitrates to nitrogen to reduce the denitrification of sensitive aquifers.

During World War II, methanol was used as a fuel in several German military rocket designs, under name M-Stoff, and in a mixture as C-Stoff.

Methanol is used as a denaturing agent in polyacrylamide gel electrophoresis.

Direct-methanol fuel cells are unique in their low temperature, atmospheric pressure operation, allowing them to be miniaturized to an unprecedented degree. This, combined with the relatively easy and safe storage and handling of methanol may open the possibility of fuel cell powered consumer electronics, such as for laptop computers and mobile phones.

Methanol is also a widely used fuel in camping and boating stoves. Methanol burns well in an unpressurized burner, so alcohol stoves are often very simple, sometimes little more than a cup to hold fuel. This lack of complexity makes them a favorite of hikers who spend extended time in the wilderness.

Health and safety

Toxicity

Methanol is toxic. If ingested, as little as 10 ml can cause permanent blindness by destruction of the optic nerve.[9] The usual fatal dose is 100–125 ml (about 4 fl. oz.). Toxic effects take hours to start and effective antidotes can often prevent permanent damage.

Because of its similarities to ethanol (the alcohol in beverages), it is difficult to differentiate between the two (such is the case with denatured alcohol).

Methanol is toxic by two mechanisms. Firstly, methanol (whether it enters the body by ingestion, inhalation, or absorption through the skin) can be fatal due to its CNS depressant properties in the same manner as ethanol poisoning. Secondly, in a process of toxication, it is metabolised to formic acid (which is present as the formate ion) via formaldehyde in a process initiated by the enzyme alcohol dehydrogenase in the liver. The reaction to formate proceeds completely, with no detectable formaldehyde remaining.[10] Formate is toxic because it inhibits mitochondrial cytochrome c oxidase, causing the symptoms of hypoxia at the cellular level, and also causing metabolic acidosis among a variety of other metabolic disturbances.[11] Fetal tissue will not tolerate methanol. This is treated using ethanol or fomepizole.[12] Both of these drugs acts to slow down the action of alcohol dehydrogenase on methanol by means of competitive inhibition, so that it is excreted by the kidneys rather than being transformed into toxic metabolites.

The initial symptoms of methanol intoxication are those of central nervous system depression: headache, dizziness, nausea, lack of coordination, confusion, drowsiness, and with sufficiently large doses, unconsciousness and death. The initial symptoms of methanol exposure are usually less severe than the symptoms resulting from the ingestion of a similar quantity of ethanol.[7]

Once the initial symptoms have passed, a second set of symptoms arises, 10 to as much as 30 hours after the initial exposure to methanol, including blurring or complete loss of vision and acidosis. These symptoms result from the accumulation of toxic levels of formate in the bloodstream, and may progress to death by respiratory failure. The ester derivatives of methanol do not share this toxicity.

Ethanol is sometimes denatured (adulterated), and thus made undrinkable, by the addition of methanol. The result is known as methylated spirit or "meths" (UK use). (The latter should not be confused with meth, a common U.S. abbreviation for methamphetamine.)

Safety in automotive fuels

Pure methanol has been used in open wheel auto racing since the mid-1960s. Unlike petroleum fires, methanol fires can be extinguished with plain water. A methanol-based fire burns invisibly, unlike gasoline, which burns with a visible flame. If a fire occurs on the track, there is no flame or smoke to obstruct the view of fast approaching drivers, but this can also delay visual detection of the fire and the initiation of fire suppression actions. The decision to permanently switch to methanol in American IndyCar racing was a result of the devastating crash and explosion at the 1964 Indianapolis 500 which killed drivers Eddie Sachs and Dave MacDonald.[13] In 2007 IndyCars switched from methanol to ethanol.[14]

Methanol is readily biodegradable in both aerobic (oxygen present) and anaerobic (oxygen absent) environments. Methanol will not persist in the environment. The "half-life" for methanol in groundwater is just one to seven days, while many common gasoline components have half-lives in the hundreds of days (such as benzene at 10–730 days). Since methanol is infinitely soluble in water and biodegradable, methanol is unlikely to accumulate in groundwater, surface water, air or soil.[15]

See also

References

  1. ↑ 1.0 1.1 Methyl alcohol. In NIST Chemistry WebBook; National Institute for Standards and Technology, <http://webbook.nist.gov/cgi/inchi/InChI%3D1S/CH4O/c1-2/h2H,1H3>. (accessed 21 August 2009).
  2. ↑ 2.0 2.1 2.2 Methanol; International Chemical Safety Card 0057; International Labour Organization: Geneva, April 2000, <http://www.inchem.org/documents/icsc/icsc/eics0057.htm>.
  3. ↑ CRC Handbook of Chemistry and Physics, 62nd ed.; Weast, Robert C., Ed.; CRC Press: Boca Raton, FL, 1981; p C-374. ISBN 0-8493-0462-8.
  4. ↑ Maass, O.; Walbauer, L. J. The specific heats and latent heats of fusion of ice and of several organic compounds. J. Am. Chem. Soc. 1925, 47 (1), 1–9. DOI: 10.1021/ja01678a001. Chao, Jing; Rossini, F. D. Heats of combustion, formation, and isomerization of nineteen alkanols. J. Chem. Eng. Data 1965, 10 (4), 374–79. DOI: 10.1021/je60027a022. Carlson, H. G.; Westrum, Edgar F., Jr. Methanol: heat capacity, enthalpies of transition and melting, and thermodynamic properties from 5–300ºK. J. Chem. Phys. 1971, 54 (4), 1464–71. DOI: 10.1063/1.1675039.
  5. ↑ Index no. 603-001-00-X of Annex VI, Part 3, to Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006. OJEU L353, 31.12.2008, pp 1–1355 at p 476.
  6. ↑ Methyl alcohol. In Pocket Guide to Chemical Hazards; U.S. Department of Health and Human Services (NIOSH) Publication No. 2005-149; Government Printing Office: Washington, DC, 2005. ISBN 9780160727511, <http://www.cdc.gov/niosh/npg/npgd0397.html>.
  7. ↑ 7.0 7.1 Methanol; Emergency Response Safety and Health Database; National Institute for Occupational Safety and Health, August 2008, <http://www.cdc.gov/niosh/ershdb/EmergencyResponseCard_29750029.html>. (accessed 17 March 2009).
  8. ↑ Mittasch, Alwin; Pier, Mathias (Badische-Anilin- & Soda-Fabrik) Synthetic manufacture of methanol. US Patent 1569775, published 23 December.
  9. ↑ Methanol and Blindness; Ask A Scientist: Chemistry Archive; U.S. Department of Energy, May 2005, <http://www.newton.dep.anl.gov/askasci/chem03/chem03561.htm>. (accessed 22 May 2007).
  10. ↑ McMartin, Kenneth E.; Martin-Amat, Gladys; Noker, Patricia E.; Tephly, Thomas R. Lack of a role for formaldehyde in methanol poisoning in the monkey. Biochem. Pharmacol. 1979, 28 (5), 645–49. PMID 109089. DOI: 10.1016/0006-2952(79)90149-7.
  11. ↑ Liesivuori, Jyrki; Savolainen, Heikki Methanol and formic acid toxicity: biochemical mechanisms. Pharmacol. Toxicol. 1991, 69 (3), 157–63. PMID 1665561. DOI: 10.1111/j.1600-0773.1991.tb01290.x.
  12. ↑ Casavant, Marcel J. Fomepizole in the Treatment of Poisoning. Pediatrics 2001, 107 (1), <http://pediatrics.aappublications.org/cgi/content/full/107/1/170>. (accessed 22 May 2007).
  13. ↑ McDonald, Norris Green no longer bad luck at Indy. Toronto Star April 21, 2007, <http://www.thestar.com/comment/columnists/article/205088>.
  14. ↑ , <http://www.indycar.com/tech/ethanol.php>.
  15. ↑ Pirnie, Malcolm Evaluation of the Fate and Transport of Methanol in the Environment; American Methanol Institute: Washington, DC, January 1999, <http://www.methanol.org/pdf/evaluation.pdf>.

Further reading

  • Robert Boyle, The Sceptical Chymist (1661) – contains account of distillation of wood alcohol.
  • Gallucci, F.; Basile, A.; Drioli, E. Methanol as an energy source and/or energy carrier in membrane processes. Separ. Purif. Rev., 36 (2), 175–202.

External links

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