Methane
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Names | |||
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Preferred IUPAC name
Methane[1] | |||
Systematic IUPAC name
Carbane (never recommended[1]) | |||
Other names
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Identifiers | |||
3D model (
JSmol ) |
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3DMet | |||
1718732 | |||
ChEBI | |||
ChEMBL | |||
ChemSpider | |||
ECHA InfoCard
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100.000.739 | ||
EC Number |
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59 | |||
KEGG | |||
MeSH | Methane | ||
PubChem CID
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RTECS number
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UNII | |||
UN number | 1971 | ||
CompTox Dashboard (EPA)
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Properties | |||
CH4 | |||
Molar mass | 16.043 g·mol−1 | ||
Appearance | Colorless gas | ||
Odor | Odorless | ||
Density | |||
Melting point | −182.456 °C (−296.421 °F; 90.694 K)[3] | ||
Boiling point | −161.5 °C (−258.7 °F; 111.6 K)[3] | ||
Critical point (T, P) | 190.56 K (−82.59 °C; −116.66 °F), 4.5992 MPa (45.391 atm) | ||
22.7 mg/L[4] | |||
Solubility | Soluble in ethanol, diethyl ether, benzene, toluene, methanol, acetone and insoluble in water | ||
log P | 1.09 | ||
Henry's law
constant (kH) |
14 nmol/(Pa·kg) | ||
Conjugate acid
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Methanium | ||
Conjugate base
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Methyl anion
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−17.4×10−6 cm3/mol[5] | |||
Structure | |||
Td | |||
Tetrahedral at carbon atom | |||
0 D | |||
Thermochemistry[6] | |||
Heat capacity (C)
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35.7 J/(K·mol) | ||
Std molar
entropy (S⦵298) |
186.3 J/(K·mol) | ||
Std enthalpy of (ΔfH⦵298)formation |
−74.6 kJ/mol | ||
Gibbs free energy (ΔfG⦵)
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−50.5 kJ/mol | ||
Std enthalpy of (ΔcH⦵298)combustion |
−891 kJ/mol | ||
Hazards[7] | |||
GHS labelling: | |||
Danger | |||
H220 | |||
P210 | |||
NFPA 704 (fire diamond) | |||
Flash point | −188 °C (−306.4 °F; 85.1 K) | ||
537 °C (999 °F; 810 K) | |||
Explosive limits
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4.4–17% | ||
Related compounds | |||
Related alkanes
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Related compounds
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Supplementary data page | |||
Methane (data page) | |||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Methane (
Naturally occurring methane is found both below ground and under the
The Earth's atmospheric methane concentration has increased by about 160% since 1750, with the overwhelming percentage caused by human activity.[10] It accounted for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases, according to the 2021 Intergovernmental Panel on Climate Change report.[11] Strong, rapid and sustained reductions in methane emissions could limit near-term warming and improve air quality by reducing global surface ozone.[12]
Methane has also been detected on other planets, including Mars, which has implications for astrobiology research.[13]
Properties and bonding
Methane is a tetrahedral molecule with four equivalent C–H bonds. Its electronic structure is described by four bonding molecular orbitals (MOs) resulting from the overlap of the valence orbitals on C and H
Methane is an odorless, colourless and transparent gas.[14] It does absorb visible light, especially at the red end of the spectrum, due to overtone bands, but the effect is only noticeable if the light path is very long. This is what gives Uranus and Neptune their blue or bluish-green colors, as light passes through their atmospheres containing methane and is then scattered back out.[15]
The familiar smell of natural gas as used in homes is achieved by the addition of an
Solid methane exists in several
Chemical reactions
The primary chemical reactions of methane are combustion, steam reforming to syngas, and halogenation. In general, methane reactions are difficult to control.
Selective oxidation
Partial
One group of bacteria catalyze methane oxidation with nitrite as the oxidant in the absence of oxygen, giving rise to the so-called anaerobic oxidation of methane.[20]
Acid–base reactions
Like other
A variety of
Despite the
Combustion
Methane's heat of combustion is 55.5 MJ/kg.[24] Combustion of methane is a multiple step reaction summarized as follows:
- CH4 + 2 O2 → CO2 + 2 H2O
- (ΔH = −891 kJ/mol, at standard conditions)
Peters four-step chemistry is a systematically reduced four-step chemistry that explains the burning of methane.
Methane radical reactions
Given appropriate conditions, methane reacts with halogen radicals as follows:
- •X + CH4 → HX + •CH3
- •CH3 + X2 → CH3X + •X
where X is a
This reaction is commonly used with chlorine to produce dichloromethane and chloroform via chloromethane. Carbon tetrachloride can be made with excess chlorine.
Uses
Methane may be transported as a refrigerated liquid (liquefied natural gas, or
Fuel
Methane is used as a fuel for ovens, homes, water heaters, kilns, automobiles,[26][27] turbines, etc.
As the major constituent of
(LNG) is predominantly methane (CH4) converted into liquid form for ease of storage or transport.Rocket propellant
Refined liquid methane as well as LNG is
As a
Chemical feedstock
Natural gas, which is mostly composed of methane, is used to produce hydrogen gas on an industrial scale. Steam methane reforming (SMR), or simply known as steam reforming, is the standard industrial method of producing commercial bulk hydrogen gas. More than 50 million metric tons are produced annually worldwide (2013), principally from the SMR of natural gas.[33] Much of this hydrogen is used in petroleum refineries, in the production of chemicals and in food processing. Very large quantities of hydrogen are used in the industrial synthesis of ammonia.
At high temperatures (700–1100 °C) and in the presence of a
- CH4 + H2O ⇌ CO + 3 H2
This reaction is strongly
- CO + H2O ⇌ CO2 + H2
This reaction is mildly
Methane is also subjected to free-radical
Hydrogen can also be produced via the direct decomposition of methane, also known as methane pyrolysis, which, unlike steam reforming, produces no greenhouse gases (GHG). The heat needed for the reaction can also be GHG emission free, e.g. from concentrated sunlight, renewable electricity, or burning some of the produced hydrogen. If the methane is from biogas then the process can be a carbon sink. Temperatures in excess of 1200 °C are required to break the bonds of methane to produce Hydrogen gas and solid carbon. However, through the use of a suitable catalyst the reaction temperature can be reduced to between 600 °C - 1000 °C depending on the chosen catalyst.[35] The reaction is moderately endothermic as shown in the reaction equation below.[36]
- CH4(g) → C(s) + 2 H2(g)
- (ΔH° = 74.8 kJ/mol)
Refrigerant
As a refrigerant, methane has the ASHRAE designation R-50.
Generation
Methane can be generated through geological, biological or industrial routes.
Geological routes
The two main routes for geological methane generation are (i) organic (thermally generated, or thermogenic) and (ii) inorganic (abiotic).[13] Thermogenic methane occurs due to the breakup of organic matter at elevated temperatures and pressures in deep sedimentary strata. Most methane in sedimentary basins is thermogenic; therefore, thermogenic methane is the most important source of natural gas. Thermogenic methane components are typically considered to be relic (from an earlier time). Generally, formation of thermogenic methane (at depth) can occur through organic matter breakup, or organic synthesis. Both ways can involve microorganisms (methanogenesis), but may also occur inorganically. The processes involved can also consume methane, with and without microorganisms.
The more important source of methane at depth (crystalline bedrock) is abiotic. Abiotic means that methane is created from inorganic compounds, without biological activity, either through magmatic processes or via water-rock reactions that occur at low temperatures and pressures, like serpentinization.[37][38]
Biological routes
Most of Earth's methane is
sediments below the seafloor and the bottom of lakes.This multistep process is used by these microorganisms for energy. The net reaction of methanogenesis is:
- CO2 + 4 H2 → CH4 + 2 H2O
The final step in the process is catalyzed by the enzyme methyl coenzyme M reductase (MCR).[44]
Wetlands
Wetlands are the largest natural sources of methane to the atmosphere,[45] accounting for approximately 20 - 30% of atmospheric methane.[46] Climate change is increasing the amount of methane released from wetlands due to increased temperatures and altered rainfall patterns. This phenomeon is called wetland methane feedback.[47]
Rice cultivation generates as much as 12% of total global methane emissions due to the long-term flooding of rice fields.[48]
Ruminants
Ruminants, such as cattle, belch methane, accounting for about 22% of the U.S. annual methane emissions to the atmosphere.[49] One study reported that the livestock sector in general (primarily cattle, chickens, and pigs) produces 37% of all human-induced methane.[50] A 2013 study estimated that livestock accounted for 44% of human-induced methane and about 15% of human-induced greenhouse gas emissions.[51] Many efforts are underway to reduce livestock methane production, such as medical treatments and dietary adjustments,[52][53] and to trap the gas to use its combustion energy.[54]
Seafloor sediments
Most of the subseafloor is
Industrial routes
Given its cheap abundance in natural gas, there is little incentive to produce methane industrially. Methane can be produced by
An example of large-scale coal-to-methane gasification is the
Laboratory synthesis
Methane can be produced by
Occurrence
Methane was discovered and isolated by
Methane is generally transported in bulk by
Atmospheric methane and climate change
Methane is an important greenhouse gas, responsible for around 30% of the rise in global temperatures since the industrial revolution.[56]
Methane has a global warming potential (GWP) of 29.8 ± 11 compared to CO2 (potential of 1) over a 100-year period, and 82.5 ± 25.8 over a 20-year period.[57] This means that, for example, a leak of one tonne of methane is equivalent to emitting 82.5 tonnes of carbon dioxide.
As methane is gradually converted into carbon dioxide (and water) in the atmosphere, these values include the climate forcing from the carbon dioxide produced from methane over these timescales.
Annual global methane emissions are currently approximately 580 Mt,[58] 40% of which is from natural sources and the remaining 60% originating from human activity, known as anthropogenic emissions. The largest anthropogenic source is agriculture, responsible for around one quarter of emissions, closely followed by the energy sector, which includes emissions from coal, oil, natural gas and biofuels.[59]
Global monitoring of atmospheric methane concentrations began in the 1980s.[10] The Earth's atmospheric methane concentration has increased 160% since preindustrial levels in the mid-18th century.[10] In 2013, atmospheric methane accounted for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases.[61] Between 2011 and 2019 the annual average increase of methane in the atmosphere was 1866 ppb.[11] From 2015 to 2019 sharp rises in levels of atmospheric methane were recorded.[62][63]
In 2019, the atmospheric methane concentration was higher than at any time in the last 800,000 years. As stated in the AR6 of the IPCC, "Since 1750, increases in CO2 (47%) and CH4 (156%) concentrations far exceed, and increases in N2O (23%) are similar to, the natural multi-millennial changes between glacial and interglacial periods over at least the past 800,000 years (very high confidence)".[11][a][64]
In February 2020, it was reported that
Climate change can increase atmospheric methane levels by increasing methane production in natural ecosystems, forming a
Over 100 countries have signed the Global Methane Pledge, launched in 2021, promising to cut their methane emissions by 30% by 2030.[69] This could avoid 0.2˚C of warming globally by 2050, although there have been calls for higher commitments in order to reach this target.[70] The International Energy Agency's 2022 report states "the most cost-effective opportunities for methane abatement are in the energy sector, especially in oil and gas operations".[71]
Clathrates
Public safety and the environment
Methane "degrades air quality and adversely impacts human health, agricultural yields, and ecosystem productivity".[81]
Methane is extremely flammable and may form
The 2015–2016 methane gas leak in Aliso Canyon, California was considered to be the worst in terms of its environmental effect in American history.[86][87][88] It was also described as more damaging to the environment than Deepwater Horizon's leak in the Gulf of Mexico.[89]
In May 2023 The Guardian published a report, blaming Turkmenistan to be the worst in the world for methane super emitting. The data collected by Kayrros researchers indicate, that two large Turkmen fossil fuel fields leaked 2.6m and 1.8m tonnes of methane in 2022 alone, pumping the CO2 equivalent of 366m tonnes into the atmosphere, surpassing the annual CO2 emissions of the United Kingdom.[90]
Methane is also an
Extraterrestrial methane
Interstellar medium
Methane is abundant in many parts of the Solar System and potentially could be harvested on the surface of another Solar System body (in particular, using methane production from local materials found on Mars[91] or Titan), providing fuel for a return journey.[28][92]
Mars
Methane has been detected on all planets of the Solar System and most of the larger moons.[citation needed] With the possible exception of Mars, it is believed to have come from abiotic processes.[93][94]
The Curiosity rover has documented seasonal fluctuations of atmospheric methane levels on Mars. These fluctuations peaked at the end of the Martian summer at 0.6 parts per billion.[95][96][97][98][99][100][101][102]
Methane has been proposed as a possible
Methane could be produced by a non-biological process called serpentinization[b] involving water, carbon dioxide, and the mineral olivine, which is known to be common on Mars.[104]
Titan
Methane has been detected in vast abundance on Titan, the largest moon of Saturn, it comprises a significant portion of its atmosphere and also exists in a liquid form on its surface, where it comprises the majority of the liquid in Titan's vast lakes of hydrocarbons; the second largest of which is believed to be almost pure methane in composition.[105]
The presence of stable lakes of liquid methane on Titan, as well as the surface of Titan being highly chemically active and rich in organic compounds, has led scientists to consider the possibility of life existing within Titan's lakes, using methane as a solvent in the place of water for Earth-based life[106] and using hydrogen in the atmosphere to derive energy with acetylene, in much the same way that Earth-based life uses glucose.[107]
History
Methane was first scientifically identified in November 1776 by
Following the Felling mine disaster of 1812 in which 92 men perished, Sir Humphry Davy established that the feared firedamp was in fact largely methane.[110]
The name "methane" was coined in 1866 by the German chemist August Wilhelm von Hofmann.[111][112] The name was derived from methanol.
Etymology
Etymologically, the word methane is coined from the chemical suffix "-ane", which denotes substances belonging to the alkane family; and the word methyl, which is derived from the German Methyl (1840) or directly from the French méthyle, which is a back-formation from the French méthylène (corresponding to English "methylene"), the root of which was coined by Jean-Baptiste Dumas and Eugène Péligot in 1834 from the Greek μέθυ methy (wine) (related to English "mead") and ὕλη hyle (meaning "wood"). The radical is named after this because it was first detected in methanol, an alcohol first isolated by distillation of wood. The chemical suffix -ane is from the coordinating chemical suffix -ine which is from Latin feminine suffix -ina which is applied to represent abstracts. The coordination of "-ane", "-ene", "-one", etc. was proposed in 1866 by German chemist August Wilhelm von Hofmann.[113]
Abbreviations
The abbreviation CH4-C can mean the mass of carbon contained in a mass of methane, and the mass of methane is always 1.33 times the mass of CH4-C.[114][115] CH4-C can also mean the methane-carbon ratio, which is 1.33 by mass.[116] Methane at scales of the atmosphere is commonly measured in teragrams (Tg CH4) or millions of metric tons (MMT CH4), which mean the same thing.[117] Other standard units are also used, such as nanomole (nmol, one billionth of a mole), mole (mol), kilogram, and gram.
See also
- 2007 Zasyadko mine disaster
- Abiogenic petroleum origin
- Aerobic methane production
- Anaerobic digestion
- Anaerobic respiration
- Arctic methane emissions
- Atmospheric methane
- Biogas
- Coal Oil Point seep field
- Energy density
- Fugitive gas emissions
- Global Methane Initiative
- Thomas Gold
- Halomethane, halogenated methane derivatives.
- Hydrogen Cycle
- Industrial gas
- Lake Kivu (more general: limnic eruption)
- List of straight-chain alkanes
- Methanation
- Methane emissions
- Methane on Mars:
- Methanogen, archaea that produce methane.
- microbesthat produce methane.
- Methanotroph, bacteria that grow with methane.
- Methyl group, a functional group related to methane.
Explanatory notes
- ^ In 2013 Intergovernmental Panel on Climate Change (IPCC) scientists warned atmospheric concentrations of methane had "exceeded the pre-industrial levels by about 150% which represented "levels unprecedented in at least the last 800,000 years."
- ^ There are many serpentinization reactions. Olivine is a solid solution between forsterite and fayalite whose general formula is (Fe,Mg)2SiO4. The reaction producing methane from olivine can be written as: Forsterite + Fayalite + Water + Carbonic acid → Serpentine + Magnetite + Methane , or (in balanced form):
- 18 Mg2SiO4 + 6 Fe2SiO4 + 26 H2O + CO2 → 12 Mg3Si2O5(OH)4 + 4 Fe3O4 + CH4
Citations
- ^ ISBN 978-0-85404-182-4.
Methane is a retained name (see P-12.3) that is preferred to the systematic name 'carbane', a name never recommended to replace methane, but used to derive the names 'carbene' and 'carbyne' for the radicals H2C2• and HC3•, respectively.
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Cited sources
- Haynes, William M., ed. (2016). ISBN 9781498754293.
External links
- Methane at The Periodic Table of Videos(University of Nottingham)
- International Chemical Safety Card 0291
- Gas (Methane) Hydrates – A New Frontier – United States Geological Survey (archived 6 February 2004)
- Lunsford, Jack H. (2000). "Catalytic conversion of methane to more useful chemicals and fuels: A challenge for the 21st century". Catalysis Today. 63 (2–4): 165–174. .
- CDC – Handbook for Methane Control in Mining (PDF)