Methane

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Methane
File:Methane-2D-stereo.svg Methane
General
Other names Marsh gas
Firedamp
Molecular formula CH4
SMILES C
Molar mass 16.0425 g/mol
Appearance colorless gas
CAS number [74-82-8]
InChI InChI=1/CH4/h1H4
Properties
Density and phase 0.717 kg/m³, gas
Solubility in water 3.5 mg/100 ml (17 °C)
Melting point −182.5 °C (90.6 K, -296.5 °F)
Boiling point −161.6 °C (111.55 K, -258.88 °F)
Triple point 90.1 K, 0.117 bar
Critical point 190.5 K (−82.6 °C)
at 4.6 MPa (45 atm)
Structure
Molecular shape Tetrahedral
Symmetry group Td
Dipole moment Zero
Hazards
MSDS External MSDS
EU classification Highly flammable (F+)
R-phrases R12
S-phrases (S2), S9, S16, S33
Flash point −188 °C
Autoignition temperature 537 °C
Maximum burning
temperature:
2148 °C
Explosive limits 5–15%
Supplementary data page
Spectral data UV, IR, NMR, MS
Related compounds
Related alkanes Ethane
Propane
Related compounds Methanol
Chloromethane
Formic acid
Formaldehyde
Related hydrides Silane
Except where noted otherwise, data are given for
materials in their standard state (at 25 °C, 100 kPa)
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Overview

Methane is a chemical compound with the molecular formula CH4. It is the simplest alkane, and the principal component of natural gas. Methane's bond angles are 109.5 degrees. Burning one molecule of methane in the presence of oxygen releases one molecule of CO2 (carbon dioxide) and two molecules of H2O:

CH4 + 2O2 → CO2 + 2H2O

Methane's relative abundance and clean burning process makes it a very attractive fuel. However, because it is a gas (at normal temperature and pressure - see, STP) and not a liquid or solid, methane is difficult to transport from the areas that produce it to the areas that consume it. Converting methane to derivatives that are more easily transported, such as methanol, is an active area of research. Certain microorganisms can effect this selective oxidation using enzymes called methane monooxygenases.

Methane is a relatively potent greenhouse gas with a high global warming potential (i.e., warming effect compared to carbon dioxide).[1] When averaged over 100 years each kg of CH4 warms the Earth 25[2] times as much as the same mass of CO2. The total warming effect of CH4 is smaller than that of CO2, since there is approximately 220 times as much CO2 in the Earth's atmosphere as methane.[3] However, methane in the atmosphere is eventually oxidised, producing carbon dioxide and water. Methane in the atmosphere has a half life of seven years, meaning that every seven years, half of the methane present is converted to carbon dioxide and water.

The Earth's crust contains huge amounts of methane. Large amounts of methane are produced anaerobically by methanogenesis. Other sources include mud volcanoes which are connected with deep geological faults.

Properties

Methane is the major component of a natural gas, about 97% by volume. At room temperature and standard pressure, methane is a colorless, odorless gas; the smell characteristic of natural gas is an artificial safety measure caused by the addition of an odorant, often methanethiol or ethanethiol. Methane has a boiling point of −161°C at a pressure of one atmosphere. As a gas it is flammable only over a narrow range of concentrations (5–15%) in air. Liquid methane does not burn unless subjected to high pressure (normally 4–5 atmospheres.)

Potential health effects

Methane is not toxic; however, it is highly flammable and may form explosive mixtures with air. Methane is violently reactive with oxidizers, halogens, and some halogen-containing compounds. Methane is also an asphyxiant and may displace oxygen in an enclosed space. Asphyxia may result if the oxygen concentration is reduced to below 19.5% by displacement. The concentrations at which flammable or explosive mixtures form are much lower than the concentration at which asphyxiation risk is significant. When structures are built on or near landfills, methane off-gas can penetrate the buildings' interiors and expose occupants to significant levels of methane. Some buildings have specially engineered recovery systems below their basements to actively capture such fugitive off-gas and vent it away from the building. An example of this type of system is in the Dakin Building, Brisbane, California.

Reactions of methane

Main reactions with methane are: combustion, steam reforming to syngas, and halogenation. In general, methane reactions are hard to control. Partial oxidation to methanol, for example, is difficult to achieve; the reaction typically progresses all the way to carbon dioxide and water.

Combustion

In the combustion of methane, several steps are involved:

Methane is believed to form a formaldehyde (HCHO or H2CO). The formaldehyde gives a formyl radical (HCO), which then forms carbon monoxide (CO). The process is called oxidative pyrolysis:

CH4 + O2 → CO + H2 + H2O

Following oxidative pyrolysis, the H2 oxidizes, forming H2O, replenishing the active species, and releasing heat. This occurs very quickly, usually in significantly less than a millisecond.

2H2 + O2 →2H2O

Finally, the CO oxidizes, forming CO2 and releasing more heat. This process is generally slower than the other chemical steps, and typically requires a few to several milliseconds to occur.

2CO + O2 →2CO2

Hydrogen activation

The strength of the carbon-hydrogen covalent bond in methane is among the strongest in all hydrocarbons, and thus its use as a chemical feedstock is limited. Despite the high activation barrier for breaking the C–H bond, CH4 is still the principal starting material for manufacture of hydrogen in steam reforming. The search for catalysts which can facilitate C–H bond activation in methane and other low alkanes is an area of research with considerable industrial significance.

Reactions with halogens

Methane reacts with all halogens given appropriate conditions, as follows:

CH4 + X2 → CH3X + HX

where X is a halogen: fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). This mechanism for this process is called free radical halogenation.

Uses

Fuel

Methane is important for electrical generation by burning it as a fuel in a gas turbine or steam boiler. Compared to other hydrocarbon fuels, burning methane produces less carbon dioxide for each unit of heat released. Also, methane's heat of combustion is about 802 kJ/mol, which is lower than any other hydrocarbon, but if a ratio is made with the molecular mass (16.0 g/mol) divided by the heat of combustion (802 kJ/mol) it is found that methane, being the simplest hydrocarbon, actually produces the most heat per unit mass than other complex hydrocarbons. In many cities, methane is piped into homes for domestic heating and cooking purposes. In this context it is usually known as natural gas, and is considered to have an energy content of 1,000 BTU/standard cubic foot.

Methane in the form of compressed natural gas is used as a fuel for vehicles, and is claimed to be more environmentally friendly than alternatives such as gasoline/petrol and diesel. Research is being conducted by NASA on methane's potential as a rocket fuel. One advantage of methane is that it is abundant in many parts of the solar system and it could potentially be harvested in situ, providing fuel for a return journey. [2]

Industrial uses

Methane is used in industrial chemical processes and may be transported as a refrigerated liquid (liquefied natural gas, or LNG). While leaks from a refrigerated liquid container are initially heavier than air due to the increased density of the cold gas, the gas at ambient temperature is lighter than air. Gas pipelines distribute large amounts of natural gas, of which methane is the principal component.

In the chemical industry, methane is the feedstock of choice for the production of hydrogen, methanol, acetic acid, and acetic anhydride. When used to produce any of these chemicals, methane is first converted to synthesis gas, a mixture of carbon monoxide and hydrogen, by steam reforming. In this process, methane and steam react on a nickel catalyst at high temperatures (700–1100 °C).

CH4 + H2O → CO + 3H2

The ratio of carbon monoxide to hydrogen in synthesis gas can then be adjusted via the water gas shift reaction to the appropriate value for the intended purpose.

CO + H2O → CO2 + H2

Less significant methane-derived chemicals include acetylene, prepared by passing methane through an electric arc, and the chloromethanes (chloromethane, dichloromethane, chloroform, and carbon tetrachloride), produced by reacting methane with chlorine gas. However, the use of these chemicals is declining, acetylene as it is replaced by less costly substitutes, and the chloromethanes due to health and environmental concerns.

Sources of methane

Natural gas fields

The major source of methane is extraction from geological deposits known as natural gas fields. It is associated with other hydrocarbon fuels and sometimes accompanied by helium and nitrogen. The gas at shallow levels (low pressure) is formed by anaerobic decay of organic matter and reworked methane from deep under the Earth's surface. In general, sediments buried deeper and at higher temperatures than those which give oil generate natural gas. Methane is also produced in considerable quantities from the decaying organic wastes of solid waste landfills.

Alternative sources

Apart from gas fields an alternative method of obtaining methane is via biogas generated by the fermentation of organic matter including manure, wastewater sludge, municipal solid waste (including landfills), or any other biodegradable feedstock, under anaerobic conditions. Methane hydrates/clathrates (icelike combinations of methane and water on the sea floor, found in vast quantities) are a potential future source of methane. Some say that significant quantities are also produced by cattle belching. This however, remains to be proven and most scientists refute this as a fact. [4][5] The livestock sector in general (primarily cattle, chickens, and pigs) produces 37% of all human-induced methane".[6] However animals "that put their energies into making gas are less efficient at producing milk and meat". Early research has found a number of medical treatments and dietary adjustments that help limit the production of methane in ruminants.[7] [8]

Industrially, methane can be created from common atmospheric gases and hydrogen (produced, perhaps, by electrolysis) through chemical reactions such as the Sabatier process, Fischer-Tropsch process. Coal bed methane extraction is a method for extracting methane from a coal deposit.

A recent scientific experiment has also yielded results pointing to the fact that all plants produce methane, and as the climate warms they produce more [9]. In fact 600 million metric tons of methane a year are produced, 225 of those produced by plants.

Methane in Earth's atmosphere

Methane in the Earth's atmosphere is an important greenhouse gas with a global warming potential of 25 over a 100 year period. This means that a 1 tonne methane emission will have 25 times the impact on temperature of a 1 tonne carbon dioxide emission during the following 100 years. Methane has a large effect for a brief period (about 10 years), whereas carbon dioxide has a small effect for a long period (over 100 years). Because of this difference in effect and time period, the global warming potential of methane over a 20 year time period is 72. The methane concentration has increased by about 150% since 1750 and it accounts for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases.[10]

The average concentration of methane at the Earth's surface in 1998 was 1,745 ppb.[11] Its concentration is higher in the northern hemisphere as most sources (both natural and human) are larger. The concentrations vary seasonally with a minimum in the late summer.

Methane is created near the surface, and it is carried into the stratosphere by rising air in the tropics. Uncontrolled build-up of methane in Earth's atmosphere is naturally checked—although human influence can upset this natural regulation—by methane's reaction with a molecule known as the hydroxyl radical, a hydrogen-oxygen molecule formed when single oxygen atoms react with water vapor.

Early in the Earth's history—about 3.5 billion years ago—there was 1,000 times as much methane in the atmosphere as there is now. The earliest methane was released into the atmosphere by volcanic activity. During this time, Earth's earliest life appeared. These first, ancient bacteria added to the methane concentration by converting hydrogen and carbon dioxide into methane and water. Oxygen did not become a major part of the atmosphere until photosynthetic organisms evolved later in Earth's history. With no oxygen, methane stayed in the atmosphere longer and at higher concentrations than it does today.

Emissions of methane

Houweling et al. (1999) give the following values for methane emissions (Tg/a=teragrams per year):[11]

Origin CH4 Emission
Mass (Tg/a]]) Type (%/a) Total (%/a)
Natural Emissions
Wetlands (incl. Rice agriculture) 225 83 37
Termites 20 7 3
Ocean 15 6 3
Hydrates 10 4 2
Natural Total 270 100 45
Anthropogenic Emissions
Energy 110 33 18
Landfills 40 12 7
Ruminants (Livestock) 115 35 19
Waste treatment 25 8 4
Biomass burning 40 12 7
Anthropogenic Total 330 100 55
Sinks
Soils -30 -5 -5
Tropospheric OH -510 -88 -85
Stratospheric loss -40 -7 -7
Sink Total -580 -100 -97
Emissions + Sinks
Imbalance (trend) +20 ~2.78 Tg/ppb +7.19 ppb/a

Slightly over half of the total emission is due to human activity.[10]

Living plants (e.g. forests) have recently been identified as a potentially important source of methane. A 2006 paper calculated emissions of 62–236 Tg a-1, and "this newly identified source may have important implications".[12][13] However the authors stress "our findings are preliminary with regard to the methane emission strength".[14] These findings have been called into question in a 2007 paper which found "there is no evidence for substantial aerobic methane emission by terrestrial plants, maximally 0.3% of the previously published values".[15]

Long term atmospheric measurements of methane by NOAA show that the build up of methane has slowed dramatically over the last decade, after nearly tripling since pre-industrial times [16]. It is thought that this reduction is due to reduced industrial emissions and drought in wetland areas.

Removal processes

The major removal mechanism of methane from the atmosphere is by reaction with the hydroxyl radical (·OH), which may be produced when a cosmic ray strikes a molecule of water vapor:

CH4 + ·OH → ·CH3 + H2O

This reaction in the troposphere gives a methane lifetime of 9.6 years. Two more minor sinks are soil sinks (160 year lifetime) and stratospheric loss by reaction with ·OH, ·Cl and ·O1D in the stratosphere (120 year lifetime), giving a net lifetime of 8.4 years.[11] Oxidation of methane is the main source of water vapor in the upper stratosphere (beginning at pressure levels around 10 kPa).

Sudden release from methane clathrates

At high pressures, such as are found on the bottom of the ocean, methane forms a solid clathrate with water, known as methane hydrate. An unknown, but possibly very large quantity of methane is trapped in this form in ocean sediments. The sudden release of large volumes of methane from such sediments into the atmosphere has been suggested as a possible cause for rapid global warming events in the Earth's distant past, such as the Paleocene–Eocene Thermal Maximum of 55 million years ago.

One source estimates the size of the methane hydrate deposits of the oceans at ten trillion tons (10 exagrams). Theories suggest that should global warming cause them to heat up sufficiently, all of this methane could again be suddenly released into the atmosphere. Since methane is twenty-three times stronger (for a given weight, averaged over 100 years) than CO2 as a greenhouse gas; this would immensely magnify the greenhouse effect, heating Earth to unprecedented levels (see Clathrate gun hypothesis).

Release of methane from bogs

Although less dramatic than release from clathrates, but already happening, is an increase in the release of methane from bogs as permafrost melts. Although records of permafrost are limited, recent years (1999 to 2007) have seen record thawing of permafrost in Alaska and Siberia.

Recent measurements in Siberia show that the methane released is five times greater than previously estimated [17].

Extraterrestrial methane

Methane has been detected or is believed to exist in several locations of the solar system. It is believed to have been created by processes, with the possible exception of Mars.

Traces of methane gas are present in the thin atmosphere of the Earth's Moon.[18]

Methane has also been detected in interstellar clouds.[19]

  • Methane is believed to be present on Charon, but it is not 100% confirmed.[20]

See also

References

  1. IPCC Third Assessment Report
  2. IPCC Fourth Assessment Report has updated this number to include indirect effects and states that the relative impact of CH4 to CO2 averaged over 20 years is 72.
  3. Source for figures: NASA. carbon dioxide (updated 2007.01). Methane updated (to 1998) by IPCC TAR table 6.1 [1]. The NASA total was 17 ppmv over 100%, and CO2 was increased here by 15 ppmv. To normalize, N2 should be reduced by about 25 ppmv and O2 by about 7 ppmv.
  4. http://www.mycattle.com/health/dsp_health_article.cfm?storyid=10045
  5. http://news.bbc.co.uk/1/hi/scotland/4582174.stm
  6. "Livestock’s Long Shadow–Environmental Issues and Options". Retrieved 2007-01-04. 
  7. http://news.nationalgeographic.com/news/2005/08/0816_050816_cowpollution_2.html
  8. http://news.nationalgeographic.com/news/2002/05/0509_020509_belch.html
  9. Methane emissions from terrestrial plants under aerobic conditions Nature, January 12, 2006
  10. 10.0 10.1 "Technical summary". Climate Change 2001. United Nations Environment Programme. 
  11. 11.0 11.1 11.2 "Trace Gases: Current Observations, Trends, and Budgets". Climate Change 2001. United Nations Environment Programme. 
  12. "Methane emissions from terrestrial plants under aerobic conditions". Nature. 2006-01-12. Retrieved 2006-09-07. 
  13. "Plants revealed as methane source". BBC. 2006-01-11. Retrieved 2006-09-07. 
  14. "Global warming - the blame is not with the plants". eurekalert.org. 2006-01-18. Retrieved 2006-09-06. 
  15. Duek, Tom A. (2007-03-30). "No evidence for substantial aerobic methane emission by terrestrial plants: a 13C-labelling approach.". New Phytologist. Blackwell. doi:10.1111/j.1469-8137.2007.02103.x. Retrieved 2007-04-23.  Unknown parameter |coauthors= ignored (help)
  16. "SCIENTISTS PINPOINT CAUSE OF SLOWING METHANE EMISSIONS". NOAA news Online. Retrieved 2007-05-23. 
  17. "Methane bubbles climate trouble". BBC. 2006-09-07. Retrieved 2006-09-07. 
  18. Stern, S.A. (1999). "The Lunar atmosphere: History, status, current problems, and context". Rev. Geophys. 37: 453–491. 
  19. J. H. Lacy, J. S. Carr, N. J. Evans, II, F. Baas, J. M. Achtermann, J. F. Arens (1991). "Discovery of interstellar methane - Observations of gaseous and solid CH4 absorption toward young stars in molecular clouds". Astrophysical Journal. 376: 556–560. 
  20. B. Sicardy; et al. (2006). "Charon’s size and an upper limit on its atmosphere from a stellar occultation". Nature. 439: 52. 

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