Methane (US: /ˈmɛθeɪn/ or UK: /ˈmiːθeɪn/) is a chemical
compound with the chemical formula CH4 (one atom of carbon and four
atoms of hydrogen). It is a group-14 hydride and the simplest alkane,
and is the main constituent of natural gas. The relative abundance of
Earth makes it an attractive fuel, though capturing and
storing it poses challenges due to its gaseous state under normal
conditions for temperature and pressure.
Natural methane is found both below ground and under the sea floor.
When it reaches the surface and the atmosphere, it is known as
atmospheric methane. The Earth's atmospheric 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.[dubious – discuss]
2 Properties and bonding
3 Chemical reactions
3.1 Acid-base reactions
3.3 Reactions with halogens
4.1.1 Natural gas
4.1.2 Liquefied natural gas
4.1.3 Liquid-methane rocket fuel
4.2 Chemical feedstock
5.1 Geological routes
5.2 Biological routes
5.3 Industrial routes
5.3.1 Laboratory synthesis
6.1 Alternative sources
6.2 Atmospheric methane
7 Anaerobic oxidation of methane
9 Extraterrestrial methane
10 See also
13 External links
In November 1776, methane was first scientifically identified by
Alessandro Volta in the marshes of Lake Maggiore
Italy and Switzerland. Volta was inspired to search for the
substance after reading a paper written by
Benjamin Franklin about
"flammable air". Volta collected the gas rising from the marsh, and
by 1778 had isolated the pure gas. He also demonstrated that the
gas could be ignited with an electric spark.
The name "methane" was coined in 1866 by the German chemist August
Wilhelm von Hofmann. The name was derived from methanol.
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. 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.
At room temperature and standard pressure, methane is a colorless,
odorless gas. 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
−164 °C (−257.8 °F) at a pressure of one atmosphere. 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. 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.
The primary chemical reactions of methane are combustion, steam
reforming to syngas, and halogenation. In general, methane reactions
are difficult to control. Partial oxidation to methanol, for example,
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.
Like other hydrocarbons, methane is a very weak acid. Its pKa in DMSO
is estimated to be 56. It cannot be deprotonated in solution, but
the conjugate base with methyllithium is known.
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.
Despite the strength of its C–H bonds, there is intense interest in
catalysts that facilitate
C–H bond activation
C–H bond activation in methane (and other
lower numbered alkanes).
Methane burns easily.
Methane's heat of combustion is 55.5 MJ/kg.
Combustion of methane
is a multiple step reaction summarized as follows:
CH4 + 2 O2 → CO2 + 2 H2O (ΔH = −891 kJ/mol, at standard
Reactions with halogens
Given appropriate conditions, methane reacts with halogens as follows:
X2 + UV → 2 X•
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 with UV light or some other radical
initiator. A chlorine atom is generated from elemental chlorine, which
abstracts a hydrogen atom from methane, resulting in the formation of
hydrogen chloride. The resulting methyl radical, CH3•, can combine
with another chlorine molecule to give methyl chloride (CH3Cl) and a
chlorine atom. This chlorine atom can then react with another methane
(or methyl chloride) molecule, repeating the chlorination cycle.
Similar reactions can produce dichloromethane (CH2Cl2), chloroform
(CHCl3), and, ultimately, carbon tetrachloride (CCl4), depending upon
reaction conditions and the chlorine to methane ratio.
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
Methane is used as a fuel for ovens, homes, water heaters, kilns,
automobiles, turbines, and other things. It combusts with
oxygen to create heat, as demonstrated by a British inventor in a 1974
film of the National Film Board of Canada.
Main article: 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 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.
Methane in the form of compressed natural gas is used as a vehicle
fuel and is claimed to be more environmentally friendly than other
fossil fuels such as gasoline/petrol and diesel. Research into
adsorption methods of methane storage for use as an automotive fuel
has been conducted.
LNG tankers are required to transport methane.
Liquefied natural gas
Main article: Liquefied natural gas
Liquefied natural gas
Liquefied natural gas (LNG) is natural gas (predominantly methane,
CH4) that has been converted to liquid form for ease of storage or
Liquefied natural gas
Liquefied natural gas occupies about 1/600th the volume of natural gas
in the gaseous state. It is odorless, colorless, non-toxic and
non-corrosive. Hazards include flammability after vaporization into a
gaseous state, freezing, and asphyxia.
The liquefaction process involves removal of certain components, such
as dust, acid gases, helium, water, and heavy hydrocarbons, which
could cause difficulty downstream. The natural gas is then condensed
into a liquid at close to atmospheric pressure (maximum transport
pressure set at around 25 kPa or 3.6 psi) by cooling it to
approximately −162 °C (−260 °F).
LNG achieves a higher reduction in volume than compressed natural gas
(CNG) so that the energy density of
LNG is 2.4 times greater than
that of CNG or 60% that of diesel fuel. This makes
efficient to transport over long distances where pipelines do not
exist. Specially designed cryogenic sea vessels (
LNG carriers) or
cryogenic road tankers are used for its transport.
Methane must be
cooled below its critical temperature of -82.3 °C in order to be
liquified under pressure.
LNG, when it is not highly refined for special uses, is principally
used for transporting natural gas to markets, where it is regasified
and distributed as pipeline natural gas. It is used in LNG-fueled road
vehicles. However, it remains more common to design vehicles to use
compressed natural gas. As of 2002[update], the relatively higher cost
LNG production and the need to store
LNG in more expensive
cryogenic tanks had slowed widespread commercial use.
Natural gas located far from its user base is often released into the
atmosphere of flared. Some is subjected to gas to liquids technologies
(GTL) to produce liquid fuels, which are more readily transported than
Liquid-methane rocket fuel
Refined liquid methane is used as a rocket fuel.
reported to offer the advantage over kerosene of depositing less
carbon on the internal parts of rocket motors, reducing the difficulty
of re-use of boosters.
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 or Titan), providing fuel for a return journey.
Methane is converted to synthesis gas, a mixture of carbon monoxide
and hydrogen, by steam reforming. This endergonic process (requiring
energy) utilizes catalysts and requires high temperatures, around
CH4 + H2O → CO + 3 H2
Methane is also subjected to free-radical chlorination in the
production of chloromethanes, although methanol is a more typical
See also: Biogeochemistry
There are two main routes for geological methane generation, organic
(thermogenic), and inorganic (abiotic, meaning non-living). Thermally
generated methane, referred to as thermogenic, originates from deeper
sedimentary strata. Thermogenic methane (CH4) formation occurs due to
the breakup of organic matter, forced by elevated temperatures and
pressures. This type of methane is considered to be the primary
methane type in sedimentary basins, and from an economical perspective
the most important source of natural gas. Thermogenic methane
components are generally 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 involved anaerobic and aerobic processes can also
consume methane, with and without microorganisms. The more important
source of methane at depth (crystalline bedrock) is abiotic. Abiotic
means that the methane formation took place involving inorganic
compounds, without biological activity, magmatic or created at low
temperatures and pressures through water-rock reactions.
Main article: methanogenesis
Naturally occurring methane is mainly produced by microbial
methanogenesis. This multistep process is used by
microorganisms as an energy source. The net reaction is
CO2 + 8 H+ + 8 e− → CH4 + 2 H2O
The final step in the process is catalyzed by the enzyme Coenzyme-B
Methanogenesis is a form of anaerobic
respiration used by organisms that occupy landfill, ruminants (e.g.,
cattle), and the guts of termites.
It is uncertain whether plants are a source of methane
There are many technological methane production methods. Methane
created from biomass in industrial plants via biological route is
called biogas. A more synthetic method to produce methane is
hydrogenating carbon dioxide through the Sabatier process.
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. 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
very hard to transport for its weight, ash content, low calorific
value and propensity to spontaneous combustion during storage and
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. As of 2016,
this is mostly under development and not in large-scale use.
Theoretically, the process could be used as a buffer for excess and
off-peak power generated by highly fluctuating wind generators and
solar arrays. The conversion efficiency of power to methane is
49–65%, and full power–methane–power cycle is 30–38%.
Although methane can in principle be produced by a variety of forcing
methods, it is conveniently generated by protonation of methyl lithium
and methylmagnesium iodide.
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
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
Methane is generally transported in bulk by pipeline in its natural
gas form, or
LNG carriers in its liquefied form; few countries
transport it by truck.
Testing Australian sheep for exhaled methane production (2001), CSIRO
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
Rice fields also generate large amounts of methane during
Methane hydrates/clathrates (ice-like combinations of
methane and water on the sea floor, found in vast quantities) are a
potential future source of methane. Cattle belch methane accounts for
16% of the world's annual methane emissions to the atmosphere. One
study reported that the livestock sector in general (primarily cattle,
chickens, and pigs) produces 37% of all human-induced methane.
Early research has found a number of medical treatments and dietary
adjustments that help slightly limit the production of methane in
ruminants. A 2009 study found that at a conservative estimate,
at least 51% of global greenhouse gas emissions were attributable to
the life cycle and supply chain of livestock products, meaning all
meat, dairy, and by-products, and their transportation. More
recently, a 2013 study estimated that livestock accounted for 44
percent of human-induced methane and 14.5 percent of human-induced
greenhouse gas emissions. Many efforts are underway to reduce
livestock methane production and trap the gas to use as energy.
Paleoclimatology research published in
Current Biology suggests that
flatulence from dinosaurs may have warmed the Earth.
Main article: Atmospheric methane
Methane concentrations up to March 2018 (Mauna Loa)
In 2010, methane levels in the Arctic were measured at 1850 nmol/mol.
This level is over twice as high as at any time in the 400,000 years.
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. The Earth's oceans are a potential important
source of Arctic methane.
Methane is an important greenhouse gas with a global warming potential
of 34 compared to CO2 over a 100-year period, and 72 over a 20-year
The Earth's atmospheric 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
(these gases don't include water vapor which is by far the largest
component of the greenhouse effect).
Methane is essentially insoluble in water, but significant deposits of
methane clathrate have been found under sediments on the ocean floors
Earth at large depths. Estimates consider up to 15,000 gigatonnes
of carbon may be stored in the form of clathrates (hydrates) in the
ocean floor, not accounting for abiotic methane, a relatively newly
discovered source of methane, formed below the ocean floor, in the
earth crust. It has been suggested, that today's methane emission
regime from the ocean floor, is potentially similar to that during the
Arctic methane release
Arctic methane release from permafrost and methane clathrates is an
expected consequence and further cause of global warming.
Anaerobic oxidation of methane
There is a group of bacteria that drive methane oxidation with nitrite
as the oxidant, the anaerobic oxidation of methane.
Methane is nontoxic, yet it is extremely flammable and may form
explosive mixtures with air.
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.
Methane gas explosions are responsible for many deadly mining
disasters. A methane gas explosion was the cause of the Upper Big
Branch coal mine disaster in
West Virginia on April 5, 2010, killing
Main article: extraterrestrial atmosphere
Methane has been detected or is believed to exist on all planets of
the solar system and most of the larger moons. With the possible
exception of Mars, it is believed to have come from abiotic
Methane (CH4) on
Mars – potential sources and sinks.
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. 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.
Methane could be produced by a non-biological process called
’'serpentinization[a] involving water, carbon dioxide, and the
mineral olivine, which is known to be common on Mars.
Sustainable development portal
2007 Zasyadko mine disaster
Abiogenic petroleum origin
Aerobic methane production
Arctic methane emissions
Coal Oil Point seep field
Halomethane, halogenated methane derivatives.
Lake Kivu (more general: limnic eruption)
List of straight-chain alkanes
Methane clathrate, ice that contains methane.
Methane (data page)
Methane on Mars: atmosphere
Methane on Mars: 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.
^ 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
Water + Carbonic acid →
Serpentine + Magnetite +
Methane , or (in balanced form): 18 Mg2SiO4 +
6 Fe2SiO4 + 26 H2O + CO2 → 12 Mg3Si2O5(OH)4 + 4 Fe3O4 + CH4
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Geophysical Research Letters. 32 (10): L10203.
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The Periodic Table of Videos
The Periodic Table of Videos (University of Nottingham)
International Chemical Safety Card 0291
Gas (Methane) Hydrates -- A New Frontier – United States Geological
Catalytic conversion of methane to more useful chemicals and fuels: a
challenge for the 21st century – Catalysis Today
CDC – Handbook for
Methane Control in Mining
Hexadecane / Cetane (C
List of alkanes
Manufactured fuel gas
Underground coal gasification
Blast furnace gas
Natural gas storage
Molecules detected in outer space
Magnesium monohydride cation
Hydrogen cyanide (HCN)
Hydrogen isocyanide (HNC)
Protonated molecular hydrogen
Protonated carbon dioxide
Protonated hydrogen cyanide
Buckminsterfullerene (C60 fullerene, buckyball)
Ethyl methyl ether
Atomic and molecular astrophysics
Diffuse interstellar band
Earliest known life forms
Extraterrestrial liquid water
Helium hydride ion
Iron–sulfur world theory
Molecules in stars
Nexus for Exoplanet System Science
PAH world hypothesis
Polycyclic aromatic hydrocarbon
Polycyclic aromatic hydrocarbon (PAH)
RNA world hypothesis
Binary compounds of hydrogen
Alkali metal hydrides
Lithium hydride, LiH
ionic metal hydride
Left (gas phase): BeH2
covalent metal hydride
Right: (BeH2)n (solid phase)
polymeric metal hydride
Borane and diborane
Left: BH3 (special conditions), covalent metalloid hydride
Right: B2H6 (standard conditions), dimeric metalloid hydride
covalent nonmetal hydride
covalent nonmetal hydride
covalent nonmetal hydride
Hydrogen fluoride, HF
covalent nonmetal hydride
Alkaline earth hydrides
Group 13 hydrides
Group 14 hydrides
Transition metal hydrides
PdHx (x < 1)