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Methane

Methane (US: /ˈmɛθn/ METH-ayn, UK: /ˈmθn/ MEE-thayn) is a chemical compound with the chemical formula CH4 (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Earth makes it an economically attractive fuel, although capturing and storing it poses technical challenges due to its gaseous state under normal conditions for temperature and pressure.

Methane
Ball and stick model of methane
Spacefill model of methane
  Carbon, C
  Hydrogen, H
Names
Preferred IUPAC name
Methane[1]
Systematic IUPAC name
Carbane (never recommended[1])
Other names
  • Carbon tetrahydride
  • Carburetted hydrogen
  • Hydrogen carbide
  • Marsh gas
  • Methyl hydride
  • Natural gas
Identifiers
  • 74-82-8 Y
3D model (JSmol)
  • Interactive image
3DMet
  • B01453
1718732
ChEBI
  • CHEBI:16183 Y
ChEMBL
  • ChEMBL17564 Y
ChemSpider
  • 291 Y
ECHA InfoCard 100.000.739
EC Number
  • 200-812-7
59
KEGG
  • C01438 N
MeSH Methane
  • 297
RTECS number
  • PA1490000
UNII
  • OP0UW79H66 Y
UN number 1971
  • DTXSID8025545
  • InChI=1S/CH4/h1H4 Y
    Key: VNWKTOKETHGBQD-UHFFFAOYSA-N Y
Properties
CH4
Molar mass 16.043 g·mol−1
Appearance Colorless gas
Odor Odorless
Density
  • 0.657 kg/m3 (gas, 25 °C, 1 atm)
  • 0.717 kg/m3 (gas, 0 °C, 1 atm)[2]
  • 422.8 g/L (liquid, −162 °C)[3]
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
14 nmol/(Pa·kg)
Conjugate acid Methanium
Conjugate base Methyl anion
−17.4×10−6 cm3/mol[5]
Structure
Td
Tetrahedral at carbon atom
0 D
Thermochemistry[6]
35.7 J/(K·mol)
186.3 J/(K·mol)
−74.6 kJ/mol
−50.5 kJ/mol
−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 4.4–17%
Related compounds
Related alkanes
Related compounds
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).
N verify (what is YN ?)

Naturally occurring methane is found both below ground and under the seafloor and is formed by both geological and biological processes. The largest reservoir of methane is under the seafloor in the form of methane clathrates. When methane reaches the surface and the atmosphere, it is known as atmospheric methane.[9]

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 edit

 
Covalently bonded hydrogen and carbon in a molecule of methane.

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. The lowest-energy MO is the result of the overlap of the 2s orbital on carbon with the in-phase combination of the 1s orbitals on the four hydrogen atoms. Above this energy level is a triply degenerate set of MOs that involve overlap of the 2p orbitals on carbon with various linear combinations of the 1s orbitals on hydrogen. The resulting "three-over-one" bonding scheme is consistent with photoelectron spectroscopic measurements.

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 odorant, usually blends containing tert-butylthiol, as a safety measure. Methane has a boiling point of −161.5 °C at a pressure of one atmosphere.[3] As a gas, it is flammable over a range of concentrations (5.4%–17%) in air at standard pressure.

Solid methane exists in several modifications. Presently nine are known.[16] Cooling methane at normal pressure results in the formation of methane I. This substance crystallizes in the cubic system (space group Fm3m). The positions of the hydrogen atoms are not fixed in methane I, i.e. methane molecules may rotate freely. Therefore, it is a plastic crystal.[17]

Chemical reactions edit

The primary chemical reactions of methane are combustion, steam reforming to syngas, and halogenation. In general, methane reactions are difficult to control.

Selective oxidation edit

Partial oxidation of methane to methanol (CH3OH), a more convenient, liquid fuel, is challenging because the reaction typically progresses all the way to carbon dioxide and water even with an insufficient supply of oxygen. The enzyme methane monooxygenase produces methanol from methane, but cannot be used for industrial-scale reactions.[18] Some homogeneously catalyzed systems and heterogeneous systems have been developed, but all have significant drawbacks. These generally operate by generating protected products which are shielded from overoxidation. Examples include the Catalytica system, copper zeolites, and iron zeolites stabilizing the alpha-oxygen active site.[19]

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 edit

Like other hydrocarbons, methane is an extremely weak acid. Its pKa in DMSO is estimated to be 56.[21] It cannot be deprotonated in solution, but the conjugate base is known in forms such as methyllithium.

A variety of positive ions derived from methane have been observed, mostly as unstable species in low-pressure gas mixtures. These include methenium or methyl cation CH+3, methane cation CH+4, and methanium or protonated methane CH+5. Some of these have been detected in outer space. Methanium can also be produced as diluted solutions from methane with superacids. Cations with higher charge, such as CH2+6 and CH3+7, have been studied theoretically and conjectured to be stable.[22]

Despite the strength of its C–H bonds, there is intense interest in catalysts that facilitate C–H bond activation in methane (and other lower numbered alkanes).[23]

Combustion edit

 
Methane bubbles can be burned on a wet hand without injury.

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
H = −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 edit

Given appropriate conditions, methane reacts with halogen radicals as follows:

•X + CH4 → HX + •CH3
•CH3 + X2 → CH3X + •X

where X is a halogen: fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). This mechanism for this process is called free radical halogenation. It is initiated when UV light or some other radical initiator (like peroxides) produces a halogen atom. A two-step chain reaction ensues in which the halogen atom abstracts a hydrogen atom from a methane molecule, resulting in the formation of a hydrogen halide molecule and a methyl radical (•CH3). The methyl radical then reacts with a molecule of the halogen to form a molecule of the halomethane, with a new halogen atom as byproduct.[25] Similar reactions can occur on the halogenated product, leading to replacement of additional hydrogen atoms by halogen atoms with dihalomethane, trihalomethane, and ultimately, tetrahalomethane structures, depending upon reaction conditions and the halogen-to-methane ratio.

This reaction is commonly used with chlorine to produce dichloromethane and chloroform via chloromethane. Carbon tetrachloride can be made with excess chlorine.

Uses edit

Methane 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.

Fuel edit

Methane is used as a fuel for ovens, homes, water heaters, kilns, automobiles,[26][27] turbines, etc.

As the major constituent of natural gas, methane is important for electricity generation by burning it as a fuel in a gas turbine or steam generator. Compared to other hydrocarbon fuels, methane produces less carbon dioxide for each unit of heat released. At about 891 kJ/mol, methane's heat of combustion is lower than that of any other hydrocarbon, but the ratio of the heat of combustion (891 kJ/mol) to the molecular mass (16.0 g/mol, of which 12.0 g/mol is carbon) shows that methane, being the simplest hydrocarbon, produces more heat per mass unit (55.7 kJ/g) than other complex hydrocarbons. In many cities, methane is piped into homes for domestic heating and cooking. In this context it is usually known as natural gas, which is considered to have an energy content of 39 megajoules per cubic meter, or 1,000 BTU per standard cubic foot. Liquefied natural gas (LNG) is predominantly methane (CH4) converted into liquid form for ease of storage or transport.

Rocket propellant edit

Refined liquid methane as well as LNG is used as a rocket fuel,[28] when combined with liquid oxygen, as in the TQ-12, BE-4 and Raptor engines.[29] Due to the similarities between methane and LNG such engines are commonly grouped together under the term methalox.

As a liquid rocket propellant, a methane/liquid oxygen combination offers the advantage over kerosene/liquid oxygen combination, or kerolox, of producing small exhaust molecules, reducing coking or deposition of soot on engine components. Methane is easier to store than hydrogen due to its higher boiling point and density, as well as its lack of hydrogen embrittlement.[30][31] The lower molecular weight of the exhaust also increases the fraction of the heat energy which is in the form of kinetic energy available for propulsion, increasing the specific impulse of the rocket. Compared to liquid hydrogen, the specific energy of methane is lower but this disadvantage is offset by methane's greater density and temperature range, allowing for smaller and lighter tankage for a given fuel mass. Liquid methane has a temperature range (91–112 K) nearly compatible with liquid oxygen (54–90 K). The fuel currently sees use in operational launch vehicles such as Zhuque-2 and Vulcan as well as in-development launchers such as Starship, Neutron, and Terran R.[32]

Chemical feedstock edit

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 metal-based catalyst (nickel), steam reacts with methane to yield a mixture of CO and H2, known as "water gas" or "syngas":

CH4 + H2O ⇌ CO + 3 H2

This reaction is strongly endothermic (consumes heat, ΔHr = 206 kJ/mol). Additional hydrogen is obtained by the reaction of CO with water via the water-gas shift reaction:

CO + H2O ⇌ CO2 + H2

This reaction is mildly exothermic (produces heat, ΔHr = −41 kJ/mol).

Methane is also subjected to free-radical chlorination in the production of chloromethanes, although methanol is a more typical precursor.[34]

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)

Generation edit

 
Global methane budget (2017). Shows natural sources and sinks (green), anthropogenic sources (orange), and mixed natural and anthropogenic sources (hatched orange-green for 'biomass and biofuel burning').

Methane can be generated through geological, biological or industrial routes.

Geological routes edit

 
Abiotic sources of methane have been found in more than 20 countries and in several deep ocean regions so far.

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 edit

Most of Earth's methane is biogenic and is produced by methanogenesis,[39][40] a form of anaerobic respiration only known to be conducted by some members of the domain Archaea.[41] Methanogens occur in landfills and soils,[42] ruminants (for example, cattle),[43] the guts of termites, and the anoxic 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]

 
Testing Australian sheep for exhaled methane production (2001), CSIRO
 
This image represents a ruminant, specifically a sheep, producing methane in the four stages of hydrolysis, acidogenesis, acetogenesis, and methanogenesis.

Wetlands edit

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 edit

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 edit

Most of the subseafloor is anoxic because oxygen is removed by aerobic microorganisms within the first few centimeters of the sediment. Below the oxygen-replete seafloor, methanogens produce methane that is either used by other organisms or becomes trapped in gas hydrates.[41] These other organisms that utilize methane for energy are known as methanotrophs ('methane-eating'), and are the main reason why little methane generated at depth reaches the sea surface.[41] Consortia of Archaea and Bacteria have been found to oxidize methane via anaerobic oxidation of methane (AOM); the organisms responsible for this are anaerobic methanotrophic Archaea (ANME) and sulfate-reducing bacteria (SRB).[55]

Industrial routes edit

 
This diagram shows a method for producing methane sustainably. See: electrolysis, Sabatier reaction

Given its cheap abundance in natural gas, there is little incentive to produce methane industrially. Methane can be produced by hydrogenating carbon dioxide through the Sabatier process. Methane is also a side product of the hydrogenation of carbon monoxide in the Fischer–Tropsch process, which is practiced on a large scale to produce longer-chain molecules than methane.

An example of large-scale coal-to-methane gasification is the Great Plains Synfuels plant, started in 1984 in Beulah, North Dakota as a way to develop abundant local resources of low-grade lignite, a resource that is otherwise difficult to transport for its weight, ash content, low calorific value and propensity to spontaneous combustion during storage and transport. A number of similar plants exist around the world, although mostly these plants are targeted towards the production of long chain alkanes for use as gasoline, diesel, or feedstock to other processes.

Power to methane is a technology that uses electrical power to produce hydrogen from water by electrolysis and uses the Sabatier reaction to combine hydrogen with carbon dioxide to produce methane.

Laboratory synthesis edit

Methane can be produced by protonation of methyl lithium or a methyl Grignard reagent such as methylmagnesium chloride. It can also be made from anhydrous sodium acetate and dry sodium hydroxide, mixed and heated above 300 °C (with sodium carbonate as byproduct).[citation needed] In practice, a requirement for pure methane can easily be fulfilled by steel gas bottle from standard gas suppliers.

Occurrence edit

Methane was discovered and isolated by Alessandro Volta between 1776 and 1778 when studying marsh gas from Lake Maggiore. It is the major component of natural gas, about 87% by volume. The major source of methane is extraction from geological deposits known as natural gas fields, with coal seam gas extraction becoming a major source (see coal bed methane extraction, a method for extracting methane from a coal deposit, while enhanced coal bed methane recovery is a method of recovering methane from non-mineable coal seams). It is associated with other hydrocarbon fuels, and sometimes accompanied by helium and nitrogen. Methane is produced at shallow levels (low pressure) by anaerobic decay of organic matter and reworked methane from deep under the Earth's surface. In general, the sediments that generate natural gas are buried deeper and at higher temperatures than those that contain oil.

Methane is generally transported in bulk by pipeline in its natural gas form, or by LNG carriers in its liquefied form; few countries transport it by truck.

Atmospheric methane and climate change edit

 
Methane (CH4) measured by the Advanced Global Atmospheric Gases Experiment (AGAGE) in the lower atmosphere (troposphere) at stations around the world. Abundances are given as pollution free monthly mean mole fractions in parts-per-billion.

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.

 
Sources of global methane emissions

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]

Historic methane concentrations in the world's atmosphere have ranged between 300 and 400 nmol/mol during glacial periods commonly known as ice ages, and between 600 and 700 nmol/mol during the warm interglacial periods. A 2012 NASA website said the oceans were a potential important source of Arctic methane,[60] but more recent studies associate increasing methane levels as caused by human activity.[10]

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 fugitive emissions and gas venting from the fossil fuel industry may have been significantly underestimated.[65][66] The largest annual increase occurred in 2021 with the overwhelming percentage caused by human activity.[10]

Climate change can increase atmospheric methane levels by increasing methane production in natural ecosystems, forming a climate change feedback.[41][67] Another explanation for the rise in methane emissions could be a slowdown of the chemical reaction that removes methane from the atmosphere.[68]

Over 100 countries have signed the Global Methane Peldge, 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 edit

Methane clathrates (also known as methane hydrates) are solid cages of water molecules that trap single molecules of methane. Significant reservoirs of methane clathrates have been found in arctic permafrost and along continental margins beneath the ocean floor within the gas clathrate stability zone, located at high pressures (1 to 100 MPa; lower end requires lower temperature) and low temperatures (< 15 °C; upper end requires higher pressure).[72] Methane clathrates can form from biogenic methane, thermogenic methane, or a mix of the two. These deposits are both a potential source of methane fuel as well as a potential contributor to global warming.[73][74] The global mass of carbon stored in gas clathrates is still uncertain and has been estimated as high as 12,500 Gt carbon and as low as 500 Gt carbon.[47] The estimate has declined over time with a most recent estimate of ~1800 Gt carbon.[75] A large part of this uncertainty is due to our knowledge gap in sources and sinks of methane and the distribution of methane clathrates at the global scale. For example, a source of methane was discovered relatively recently in an ultraslow spreading ridge in the Arctic.[46] Some climate models suggest that today's methane emission regime from the ocean floor is potentially similar to that during the period of the Paleocene–Eocene Thermal Maximum (PETM) around 55.5 million years ago, although there are no data indicating that methane from clathrate dissociation currently reaches the atmosphere.[75] Arctic methane release from permafrost and seafloor methane clathrates is a potential consequence and further cause of global warming; this is known as the clathrate gun hypothesis.[76][77][78][79] Data from 2016 indicate that Arctic permafrost thaws faster than predicted.[80]

Public safety and the environment edit

 
An International Energy Agency graphic showing the potential of various emission reduction policies for addressing global methane emissions.

Methane "degrades air quality and adversely impacts human health, agricultural yields, and ecosystem productivity".[81]

Methane is extremely flammable and may form explosive mixtures with air. Methane gas explosions are responsible for many deadly mining disasters.[82] A methane gas explosion was the cause of the Upper Big Branch coal mine disaster in West Virginia on April 5, 2010, killing 29.[83] Natural gas accidental release has also been a major focus in the field of safety engineering, due to past accidental releases that concluded in the formation of jet fire disasters.[84][85]

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 asphyxiant if the oxygen concentration is reduced to below about 16% by displacement, as most people can tolerate a reduction from 21% to 16% without ill effects. The concentration of methane at which asphyxiation risk becomes significant is much higher than the 5–15% concentration in a flammable or explosive mixture. Methane off-gas can penetrate the interiors of buildings near landfills and expose occupants to significant levels of methane. Some buildings have specially engineered recovery systems below their basements to actively capture this gas and vent it away from the building.

Extraterrestrial methane edit

Interstellar medium edit

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 edit

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]

 
Methane (CH4) on Mars – potential sources and sinks

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 rocket propellant on future Mars missions due in part to the possibility of synthesizing it on the planet by in situ resource utilization.[103] An adaptation of the Sabatier methanation reaction may be used with a mixed catalyst bed and a reverse water-gas shift in a single reactor to produce methane from the raw materials available on Mars, utilizing water from the Martian subsoil and carbon dioxide in the Martian atmosphere.[91]

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]

History edit

 
Alessandro Volta

Methane was first scientifically identified in November 1776 by Italian physicist Alessandro Volta in the marshes of Lake Maggiore straddling Italy and Switzerland. Volta was inspired to search for the substance after reading a paper written by Benjamin Franklin about "flammable air".[105] Volta collected the gas rising from the marsh, and by 1778 had isolated pure methane.[106] He also demonstrated that the gas could be ignited with an electric spark.[106]

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.[107]

The name "methane" was coined in 1866 by the German chemist August Wilhelm von Hofmann.[108][109] The name was derived from methanol.

Etymology edit

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.[110]

Abbreviations edit

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.[111][112] CH4-C can also mean the methane-carbon ratio, which is 1.33 by mass.[113] 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.[114] Other standard units are also used, such as nanomole (nmol, one billionth of a mole), mole (mol), kilogram, and gram.

See also edit

Explanatory notes edit

  1. ^ 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."
  2. ^ 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 edit

  1. ^ a b "Front Matter". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 3–4. doi:10.1039/9781849733069-FP001. 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.
  2. ^ "Gas Encyclopedia". from the original on December 26, 2018. Retrieved November 7, 2013.
  3. ^ a b c d Haynes, p. 3.344
  4. ^ Haynes, p. 5.156
  5. ^ Haynes, p. 3.578
  6. ^ Haynes, pp. 5.26, 5.67
  7. ^ (PDF). US: Metheson Tri-Gas Incorporated. December 4, 2009. Archived from the original (PDF) on June 4, 2012. Retrieved December 4, 2011.
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Cited sources edit

External links edit

  • Methane at The Periodic Table of Videos (University of Nottingham)
  • International Chemical Safety Card 0291
  • 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. doi:10.1016/S0920-5861(00)00456-9.
  • CDC – Handbook for Methane Control in Mining (PDF)

methane, confused, with, ethane, ethane, redirects, here, other, uses, disambiguation, meth, thayn, chemical, compound, with, chemical, formula, carbon, atom, bonded, four, hydrogen, atoms, group, hydride, simplest, alkane, main, constituent, natural, relative. Not to be confused with Ethane or ETHANE CH4 redirects here For other uses see CH4 disambiguation Methane US ˈ m ɛ 8 eɪ n METH ayn UK ˈ m iː 8 eɪ n MEE thayn is a chemical compound with the chemical formula CH4 one carbon atom bonded to four hydrogen atoms It is a group 14 hydride the simplest alkane and the main constituent of natural gas The relative abundance of methane on Earth makes it an economically attractive fuel although capturing and storing it poses technical challenges due to its gaseous state under normal conditions for temperature and pressure Methane Ball and stick model of methane Spacefill model of methane Carbon C Hydrogen HNamesPreferred IUPAC name Methane 1 Systematic IUPAC name Carbane never recommended 1 Other names Carbon tetrahydrideCarburetted hydrogenHydrogen carbideMarsh gasMethyl hydrideNatural gasIdentifiersCAS Number 74 82 8 Y3D model JSmol Interactive image3DMet B01453Beilstein Reference 1718732ChEBI CHEBI 16183 YChEMBL ChEMBL17564 YChemSpider 291 YECHA InfoCard 100 000 739EC Number 200 812 7Gmelin Reference 59KEGG C01438 NMeSH MethanePubChem CID 297RTECS number PA1490000UNII OP0UW79H66 YUN number 1971CompTox Dashboard EPA DTXSID8025545InChI InChI 1S CH4 h1H4 YKey VNWKTOKETHGBQD UHFFFAOYSA N YSMILES CPropertiesChemical formula C H 4Molar mass 16 043 g mol 1Appearance Colorless gasOdor OdorlessDensity 0 657 kg m3 gas 25 C 1 atm 0 717 kg m3 gas 0 C 1 atm 2 422 8 g L liquid 162 C 3 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 Solubility in water 22 7 mg L 4 Solubility Soluble in ethanol diethyl ether benzene toluene methanol acetone and insoluble in waterlog P 1 09Henry s lawconstant kH 14 nmol Pa kg Conjugate acid MethaniumConjugate base Methyl anionMagnetic susceptibility x 17 4 10 6 cm3 mol 5 StructurePoint group TdMolecular shape Tetrahedral at carbon atomDipole moment 0 DThermochemistry 6 Heat capacity C 35 7 J K mol Std molarentropy S 298 186 3 J K mol Std enthalpy offormation DfH 298 74 6 kJ molGibbs free energy DfG 50 5 kJ molStd enthalpy ofcombustion DcH 298 891 kJ molHazards 7 GHS labelling PictogramsSignal word DangerHazard statements H220Precautionary statements P210NFPA 704 fire diamond 240SAFlash point 188 C 306 4 F 85 1 K Autoignitiontemperature 537 C 999 F 810 K Explosive limits 4 4 17 Related compoundsRelated alkanes EthanePropaneButaneRelated compounds SilaneGermaneStannanePlumbaneSupplementary data pageMethane data page Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Naturally occurring methane is found both below ground and under the seafloor and is formed by both geological and biological processes The largest reservoir of methane is under the seafloor in the form of methane clathrates When methane reaches the surface and the atmosphere it is known as atmospheric methane 9 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 Contents 1 Properties and bonding 2 Chemical reactions 2 1 Selective oxidation 2 2 Acid base reactions 2 3 Combustion 2 4 Methane radical reactions 3 Uses 3 1 Fuel 3 1 1 Rocket propellant 3 2 Chemical feedstock 4 Generation 4 1 Geological routes 4 2 Biological routes 4 2 1 Wetlands 4 2 2 Ruminants 4 2 3 Seafloor sediments 4 3 Industrial routes 4 3 1 Laboratory synthesis 5 Occurrence 6 Atmospheric methane and climate change 6 1 Clathrates 7 Public safety and the environment 8 Extraterrestrial methane 8 1 Interstellar medium 8 2 Mars 9 History 10 Etymology 10 1 Abbreviations 11 See also 12 Explanatory notes 13 Citations 14 Cited sources 15 External linksProperties and bonding edit nbsp Covalently bonded hydrogen and carbon in a molecule of methane 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 The lowest energy MO is the result of the overlap of the 2s orbital on carbon with the in phase combination of the 1s orbitals on the four hydrogen atoms Above this energy level is a triply degenerate set of MOs that involve overlap of the 2p orbitals on carbon with various linear combinations of the 1s orbitals on hydrogen The resulting three over one bonding scheme is consistent with photoelectron spectroscopic measurements 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 odorant usually blends containing tert butylthiol as a safety measure Methane has a boiling point of 161 5 C at a pressure of one atmosphere 3 As a gas it is flammable over a range of concentrations 5 4 17 in air at standard pressure Solid methane exists in several modifications Presently nine are known 16 Cooling methane at normal pressure results in the formation of methane I This substance crystallizes in the cubic system space group Fm3 m The positions of the hydrogen atoms are not fixed in methane I i e methane molecules may rotate freely Therefore it is a plastic crystal 17 Chemical reactions editThe primary chemical reactions of methane are combustion steam reforming to syngas and halogenation In general methane reactions are difficult to control Selective oxidation edit Partial oxidation of methane to methanol CH3OH a more convenient liquid fuel is challenging because the reaction typically progresses all the way to carbon dioxide and water even with an insufficient supply of oxygen The enzyme methane monooxygenase produces methanol from methane but cannot be used for industrial scale reactions 18 Some homogeneously catalyzed systems and heterogeneous systems have been developed but all have significant drawbacks These generally operate by generating protected products which are shielded from overoxidation Examples include the Catalytica system copper zeolites and iron zeolites stabilizing the alpha oxygen active site 19 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 edit Like other hydrocarbons methane is an extremely weak acid Its pKa in DMSO is estimated to be 56 21 It cannot be deprotonated in solution but the conjugate base is known in forms such as methyllithium A variety of positive ions derived from methane have been observed mostly as unstable species in low pressure gas mixtures These include methenium or methyl cation CH 3 methane cation CH 4 and methanium or protonated methane CH 5 Some of these have been detected in outer space Methanium can also be produced as diluted solutions from methane with superacids Cations with higher charge such as CH2 6 and CH3 7 have been studied theoretically and conjectured to be stable 22 Despite the strength of its C H bonds there is intense interest in catalysts that facilitate C H bond activation in methane and other lower numbered alkanes 23 Combustion edit nbsp Methane bubbles can be burned on a wet hand without injury 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 DH 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 edit Given appropriate conditions methane reacts with halogen radicals as follows X CH4 HX CH3 CH3 X2 CH3X Xwhere X is a halogen fluorine F chlorine Cl bromine Br or iodine I This mechanism for this process is called free radical halogenation It is initiated when UV light or some other radical initiator like peroxides produces a halogen atom A two step chain reaction ensues in which the halogen atom abstracts a hydrogen atom from a methane molecule resulting in the formation of a hydrogen halide molecule and a methyl radical CH3 The methyl radical then reacts with a molecule of the halogen to form a molecule of the halomethane with a new halogen atom as byproduct 25 Similar reactions can occur on the halogenated product leading to replacement of additional hydrogen atoms by halogen atoms with dihalomethane trihalomethane and ultimately tetrahalomethane structures depending upon reaction conditions and the halogen to methane ratio This reaction is commonly used with chlorine to produce dichloromethane and chloroform via chloromethane Carbon tetrachloride can be made with excess chlorine Uses editMethane 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 Fuel edit Methane is used as a fuel for ovens homes water heaters kilns automobiles 26 27 turbines etc As the major constituent of natural gas methane is important for electricity generation by burning it as a fuel in a gas turbine or steam generator Compared to other hydrocarbon fuels methane produces less carbon dioxide for each unit of heat released At about 891 kJ mol methane s heat of combustion is lower than that of any other hydrocarbon but the ratio of the heat of combustion 891 kJ mol to the molecular mass 16 0 g mol of which 12 0 g mol is carbon shows that methane being the simplest hydrocarbon produces more heat per mass unit 55 7 kJ g than other complex hydrocarbons In many cities methane is piped into homes for domestic heating and cooking In this context it is usually known as natural gas which is considered to have an energy content of 39 megajoules per cubic meter or 1 000 BTU per standard cubic foot Liquefied natural gas LNG is predominantly methane CH4 converted into liquid form for ease of storage or transport Rocket propellant edit Refined liquid methane as well as LNG is used as a rocket fuel 28 when combined with liquid oxygen as in the TQ 12 BE 4 and Raptor engines 29 Due to the similarities between methane and LNG such engines are commonly grouped together under the term methalox As a liquid rocket propellant a methane liquid oxygen combination offers the advantage over kerosene liquid oxygen combination or kerolox of producing small exhaust molecules reducing coking or deposition of soot on engine components Methane is easier to store than hydrogen due to its higher boiling point and density as well as its lack of hydrogen embrittlement 30 31 The lower molecular weight of the exhaust also increases the fraction of the heat energy which is in the form of kinetic energy available for propulsion increasing the specific impulse of the rocket Compared to liquid hydrogen the specific energy of methane is lower but this disadvantage is offset by methane s greater density and temperature range allowing for smaller and lighter tankage for a given fuel mass Liquid methane has a temperature range 91 112 K nearly compatible with liquid oxygen 54 90 K The fuel currently sees use in operational launch vehicles such as Zhuque 2 and Vulcan as well as in development launchers such as Starship Neutron and Terran R 32 Chemical feedstock edit 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 metal based catalyst nickel steam reacts with methane to yield a mixture of CO and H2 known as water gas or syngas CH4 H2O CO 3 H2This reaction is strongly endothermic consumes heat DHr 206 kJ mol Additional hydrogen is obtained by the reaction of CO with water via the water gas shift reaction CO H2O CO2 H2This reaction is mildly exothermic produces heat DHr 41 kJ mol Methane is also subjected to free radical chlorination in the production of chloromethanes although methanol is a more typical precursor 34 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 DH 74 8 kJ mol Generation edit nbsp Global methane budget 2017 Shows natural sources and sinks green anthropogenic sources orange and mixed natural and anthropogenic sources hatched orange green for biomass and biofuel burning Methane can be generated through geological biological or industrial routes Geological routes edit See also Biogeochemistry nbsp Abiotic sources of methane have been found in more than 20 countries and in several deep ocean regions so far 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 edit Main article Methanogenesis Most of Earth s methane is biogenic and is produced by methanogenesis 39 40 a form of anaerobic respiration only known to be conducted by some members of the domain Archaea 41 Methanogens occur in landfills and soils 42 ruminants for example cattle 43 the guts of termites and the anoxic 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 H2OThe final step in the process is catalyzed by the enzyme methyl coenzyme M reductase MCR 44 nbsp Testing Australian sheep for exhaled methane production 2001 CSIRO nbsp This image represents a ruminant specifically a sheep producing methane in the four stages of hydrolysis acidogenesis acetogenesis and methanogenesis Wetlands edit See also Greenhouse gas emissions from 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 edit 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 edit Most of the subseafloor is anoxic because oxygen is removed by aerobic microorganisms within the first few centimeters of the sediment Below the oxygen replete seafloor methanogens produce methane that is either used by other organisms or becomes trapped in gas hydrates 41 These other organisms that utilize methane for energy are known as methanotrophs methane eating and are the main reason why little methane generated at depth reaches the sea surface 41 Consortia of Archaea and Bacteria have been found to oxidize methane via anaerobic oxidation of methane AOM the organisms responsible for this are anaerobic methanotrophic Archaea ANME and sulfate reducing bacteria SRB 55 Industrial routes edit nbsp This diagram shows a method for producing methane sustainably See electrolysis Sabatier reactionGiven its cheap abundance in natural gas there is little incentive to produce methane industrially Methane can be produced by hydrogenating carbon dioxide through the Sabatier process Methane is also a side product of the hydrogenation of carbon monoxide in the Fischer Tropsch process which is practiced on a large scale to produce longer chain molecules than methane An example of large scale coal to methane gasification is the Great Plains Synfuels plant started in 1984 in Beulah North Dakota as a way to develop abundant local resources of low grade lignite a resource that is otherwise difficult to transport for its weight ash content low calorific value and propensity to spontaneous combustion during storage and transport A number of similar plants exist around the world although mostly these plants are targeted towards the production of long chain alkanes for use as gasoline diesel or feedstock to other processes Power to methane is a technology that uses electrical power to produce hydrogen from water by electrolysis and uses the Sabatier reaction to combine hydrogen with carbon dioxide to produce methane Laboratory synthesis edit Methane can be produced by protonation of methyl lithium or a methyl Grignard reagent such as methylmagnesium chloride It can also be made from anhydrous sodium acetate and dry sodium hydroxide mixed and heated above 300 C with sodium carbonate as byproduct citation needed In practice a requirement for pure methane can easily be fulfilled by steel gas bottle from standard gas suppliers Occurrence editMethane was discovered and isolated by Alessandro Volta between 1776 and 1778 when studying marsh gas from Lake Maggiore It is the major component of natural gas about 87 by volume The major source of methane is extraction from geological deposits known as natural gas fields with coal seam gas extraction becoming a major source see coal bed methane extraction a method for extracting methane from a coal deposit while enhanced coal bed methane recovery is a method of recovering methane from non mineable coal seams It is associated with other hydrocarbon fuels and sometimes accompanied by helium and nitrogen Methane is produced at shallow levels low pressure by anaerobic decay of organic matter and reworked methane from deep under the Earth s surface In general the sediments that generate natural gas are buried deeper and at higher temperatures than those that contain oil Methane is generally transported in bulk by pipeline in its natural gas form or by LNG carriers in its liquefied form few countries transport it by truck Atmospheric methane and climate change editMain article Atmospheric methane nbsp Methane CH4 measured by the Advanced Global Atmospheric Gases Experiment AGAGE in the lower atmosphere troposphere at stations around the world Abundances are given as pollution free monthly mean mole fractions in parts per billion 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 nbsp Sources of global methane emissionsAs 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 Historic methane concentrations in the world s atmosphere have ranged between 300 and 400 nmol mol during glacial periods commonly known as ice ages and between 600 and 700 nmol mol during the warm interglacial periods A 2012 NASA website said the oceans were a potential important source of Arctic methane 60 but more recent studies associate increasing methane levels as caused by human activity 10 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 fugitive emissions and gas venting from the fossil fuel industry may have been significantly underestimated 65 66 The largest annual increase occurred in 2021 with the overwhelming percentage caused by human activity 10 Climate change can increase atmospheric methane levels by increasing methane production in natural ecosystems forming a climate change feedback 41 67 Another explanation for the rise in methane emissions could be a slowdown of the chemical reaction that removes methane from the atmosphere 68 Over 100 countries have signed the Global Methane Peldge 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 edit Methane clathrates also known as methane hydrates are solid cages of water molecules that trap single molecules of methane Significant reservoirs of methane clathrates have been found in arctic permafrost and along continental margins beneath the ocean floor within the gas clathrate stability zone located at high pressures 1 to 100 MPa lower end requires lower temperature and low temperatures lt 15 C upper end requires higher pressure 72 Methane clathrates can form from biogenic methane thermogenic methane or a mix of the two These deposits are both a potential source of methane fuel as well as a potential contributor to global warming 73 74 The global mass of carbon stored in gas clathrates is still uncertain and has been estimated as high as 12 500 Gt carbon and as low as 500 Gt carbon 47 The estimate has declined over time with a most recent estimate of 1800 Gt carbon 75 A large part of this uncertainty is due to our knowledge gap in sources and sinks of methane and the distribution of methane clathrates at the global scale For example a source of methane was discovered relatively recently in an ultraslow spreading ridge in the Arctic 46 Some climate models suggest that today s methane emission regime from the ocean floor is potentially similar to that during the period of the Paleocene Eocene Thermal Maximum PETM around 55 5 million years ago although there are no data indicating that methane from clathrate dissociation currently reaches the atmosphere 75 Arctic methane release from permafrost and seafloor methane clathrates is a potential consequence and further cause of global warming this is known as the clathrate gun hypothesis 76 77 78 79 Data from 2016 indicate that Arctic permafrost thaws faster than predicted 80 Public safety and the environment edit nbsp An International Energy Agency graphic showing the potential of various emission reduction policies for addressing global methane emissions Methane degrades air quality and adversely impacts human health agricultural yields and ecosystem productivity 81 Methane is extremely flammable and may form explosive mixtures with air Methane gas explosions are responsible for many deadly mining disasters 82 A methane gas explosion was the cause of the Upper Big Branch coal mine disaster in West Virginia on April 5 2010 killing 29 83 Natural gas accidental release has also been a major focus in the field of safety engineering due to past accidental releases that concluded in the formation of jet fire disasters 84 85 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 asphyxiant if the oxygen concentration is reduced to below about 16 by displacement as most people can tolerate a reduction from 21 to 16 without ill effects The concentration of methane at which asphyxiation risk becomes significant is much higher than the 5 15 concentration in a flammable or explosive mixture Methane off gas can penetrate the interiors of buildings near landfills and expose occupants to significant levels of methane Some buildings have specially engineered recovery systems below their basements to actively capture this gas and vent it away from the building Extraterrestrial methane editMain article Extraterrestrial atmosphere Interstellar medium edit 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 edit 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 nbsp Methane CH4 on Mars potential sources and sinksThe 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 rocket propellant on future Mars missions due in part to the possibility of synthesizing it on the planet by in situ resource utilization 103 An adaptation of the Sabatier methanation reaction may be used with a mixed catalyst bed and a reverse water gas shift in a single reactor to produce methane from the raw materials available on Mars utilizing water from the Martian subsoil and carbon dioxide in the Martian atmosphere 91 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 History edit nbsp Alessandro VoltaMethane was first scientifically identified in November 1776 by Italian physicist Alessandro Volta in the marshes of Lake Maggiore straddling Italy and Switzerland Volta was inspired to search for the substance after reading a paper written by Benjamin Franklin about flammable air 105 Volta collected the gas rising from the marsh and by 1778 had isolated pure methane 106 He also demonstrated that the gas could be ignited with an electric spark 106 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 107 The name methane was coined in 1866 by the German chemist August Wilhelm von Hofmann 108 109 The name was derived from methanol Etymology editEtymologically 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 methyle which is a back formation from the French methylene corresponding to English methylene the root of which was coined by Jean Baptiste Dumas and Eugene Peligot in 1834 from the Greek me8y methy wine related to English mead and ὕlh 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 110 Abbreviations edit 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 111 112 CH4 C can also mean the methane carbon ratio which is 1 33 by mass 113 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 114 Other standard units are also used such as nanomole nmol one billionth of a mole mole mol kilogram and gram See also edit2007 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 atmosphere climate Methanogen archaea that produce methane Methanogenesis microbes that produce methane Methanotroph bacteria that grow with methane Methyl group a functional group related to methane Explanatory notes edit 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 CH4Citations edit a b Front Matter Nomenclature of Organic Chemistry IUPAC Recommendations and Preferred Names 2013 Blue Book Cambridge The Royal Society of Chemistry 2014 pp 3 4 doi 10 1039 9781849733069 FP001 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 Gas Encyclopedia Archived from the original on December 26 2018 Retrieved November 7 2013 a b c d Haynes p 3 344 Haynes p 5 156 Haynes p 3 578 Haynes pp 5 26 5 67 Safety Datasheet Material Name Methane PDF US Metheson Tri Gas Incorporated December 4 2009 Archived from the 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