Methane ( , ) is a chemical compound with the chemical formula (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 abundance of methane on Earth makes it an economically attractive fuel, although capturing and storing it is difficult because it is a gas at standard temperature and pressure. In the Earth's atmosphere methane is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. Methane is an organic Organic compound, and among the simplest of organic compounds. Methane is also a hydrocarbon.
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.
The Earth's atmospheric methane concentration has increased by about 160% since 1750, with the overwhelming percentage caused by human activity. It accounted for 20% of the total radiative forcing from all of the long-lived and globally mixed , according to the 2021 Intergovernmental Panel on Climate Change report. Strong, rapid and sustained reductions in methane emissions could limit near-term warming and improve air quality by reducing global surface ozone. IPCC, 2023: Summary for Policymakers. In: Climate Change 2023: Synthesis Report. A Report of the Intergovernmental Panel on Climate Change. Contribution of Working Groups I, II and III to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change Core. IPCC, Geneva, Switzerland, page 26, section C.2.3
Methane has also been detected on other planets, including Mars, which has implications for astrobiology research.
Methane is an odorless, colourless and transparent gas at standard temperature and pressure. It does absorb visible light, especially at the red end of the spectrum, due to , 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.
The familiar smell of natural gas as used in homes is achieved by the addition of an odorizer, usually blends containing tert-butylthiol, as a safety measure. Methane has a boiling point of −161.5 Degree Celsius 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, of which nine are known. Cooling methane at normal pressure results in the formation of methane I. This substance crystallizes in the cubic system (space group Fmm). 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.
One group of bacteria catalyze methane oxidation with nitrite as the Oxidizing agent in the absence of oxygen, giving rise to the so-called anaerobic oxidation of methane.
A variety of cation derived from methane have been observed, mostly as unstable species in low-pressure gas mixtures. These include methenium or methyl cation , methane cation , and methanium or protonated methane . Some of these have been detected in outer space. Methanium can also be produced as diluted solutions from methane with . with higher charge, such as and , have been studied theoretically and conjectured to be stable.
Despite the Bond 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).
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 (). 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. 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.
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 fossil fuel, 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 areas with a dense enough population, methane is piped into homes and businesses for heating, cooking, and industrial uses. In this context it is usually known as natural gas, which is considered to have an energy content of 39 per cubic meter, or 1,000 BTU per standard cubic foot. Liquefied natural gas (LNG) is predominantly methane () converted into liquid form for ease of storage or transport.
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. 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, Vulcan Centaur and New Glenn as well as in-development launchers such as SpaceX Starship, Neutron, Terran R, Nova, and Long March 9.
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 Carbon monoxide and Dihydrogen, known as "water gas" or "syngas":
This reaction is strongly endothermic (consumes heat, 206 kJ/mol).
Additional hydrogen is obtained by the reaction of carbon monoxide with water via the water-gas shift reaction:
This reaction is mildly exothermic (produces heat, −41 kJ/mol).
Methane is also subjected to free-radical chlorination in the production of chloromethanes, although methanol is a more typical precursor.Rossberg, M. et al. (2006) "Chlorinated Hydrocarbons" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. .
Hydrogen can also be produced via the direct decomposition of methane, also known as methane pyrolysis, which, unlike steam reforming, produces no (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 550 and 900 °C depending on the chosen catalyst. Dozens of catalysts have been tested, including unsupported and supported metal catalysts, carbonaceous and metal-carbon catalysts.
The reaction is moderately endothermic as shown in the reaction equation below.
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 Serpentinite.
This multistep process is used by these microorganisms for energy. The net reaction of methanogenesis is:
The final step in the process is catalyzed by the enzyme methyl coenzyme M reductase (MCR).]]
Rice cultivation generates as much as 12% of total global methane emissions due to the long-term flooding of rice fields.
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 fuel, or feedstock to other processes.
Power to methane is a technology that uses electricity to produce hydrogen from water by electrolysis and uses the Sabatier reaction to combine hydrogen with carbon dioxide to produce methane.
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.
Methane has a global warming potential (GWP) of 29.8 ± 11 compared to (potential of 1) over a 100-year period, and 82.5 ± 25.8 over a 20-year period. This means that, for example, a leak of one tonne of methane is equivalent to emitting 82.5 tonnes of carbon dioxide. Burning methane and producing carbon dioxide also reduces the greenhouse gas impact compared to simply venting methane to the atmosphere.
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, 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 industry, which includes emissions from coal, oil, natural gas and biofuels.
Keeling Curve 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, but more recent studies associate increasing methane levels as caused by human activity.
Global monitoring of atmospheric methane concentrations began in the 1980s. The Earth's atmospheric methane concentration has increased 160% since preindustrial levels in the mid-18th century. In 2013, atmospheric methane accounted for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases.IPCC. Between 2011 and 2019 the annual average increase of methane in the atmosphere was 1866 ppb. From 2015 to 2019 sharp rises in levels of atmospheric methane were recorded.
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 (47%) and (156%) concentrations far exceed, and increases in (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)".
In February 2020, it was reported that fugitive emissions and gas venting from the fossil fuel industry may have been significantly underestimated.
The largest annual increase occurred in 2021 with the overwhelming percentage caused by human activity.
Climate change can increase atmospheric methane levels by increasing methane production in natural ecosystems, forming a climate change feedback.Carrington, Damian (July 21, 2020) First active leak of sea-bed methane discovered in Antarctica , The Guardian Another explanation for the rise in methane emissions could be a slowdown of the chemical reaction that removes methane from the atmosphere.
Over 100 countries have signed the Global Methane Pledge, launched in 2021, promising to cut their methane emissions by 30% by 2030. 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. 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".
Methane is extremely flammable and may form explosive mixtures with air. 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 29. 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.
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. It was also described as more damaging to the environment than Deepwater Horizon's leak in the Gulf of Mexico.
In May 2023 The Guardian published a report blaming Turkmenistan as the worst in the world for methane super emitting. The data collected by Kayrros researchers indicate that two large Turkmen fossil fuel fields Methane leak 2.6 million and 1.8 million of methane in 2022 alone, pumping the Carbon dioxide equivalent of 366 million tonnes into the atmosphere, surpassing the annual emissions of the United Kingdom.
Methane is also an asphyxiant gas 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.
Negative methane, the Ion of methane, is also known to exist in interstellar space. Its mechanism of formation is not fully understood.
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.
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 and oxygen from the raw materials available on Mars, utilizing water from the Martian soil and carbon dioxide in the Martian atmosphere.
Methane could be produced by a non-biological process called serpentinite involving water, carbon dioxide, and the mineral olivine, which is known to be common on Mars.
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 and using hydrogen in the atmosphere to derive energy with acetylene.
Volta was initially motivated by reports of inflammable air present in marshes by his friend Father Carlo Guiseppe Campi. While on a fishing trip to Lake Maggiore straddling Italy and Switzerland in November 1776, he noticed the presence of bubbles in the nearby marshes and decided to investigate. Volta collected the gas rising from the marsh and demonstrated that the gas was inflammable.
Volta notes similar observations of inflammable air were present previously in scientific literature, including a letter written by Benjamin Franklin.
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.
The name "methane" was coined in 1866 by the German chemist August Wilhelm von Hofmann.; see footnote on pp. 57–58McBride, James Michael (1999) "Development of systematic names for the simple alkanes". Chemistry Department, Yale University (New Haven, Connecticut). The name was derived from methanol.
Chemical reactions
Selective oxidation
Acid–base reactions
Combustion
Peters four-step chemistry is a systematically reduced four-step chemistry that explains the burning of methane.
Methane radical reactions
Uses
Fuel
Rocket propellant
Chemical feedstock
Refrigerant
Generation
Geological routes
Biological routes
Wetlands
Ruminants
Seafloor sediments
Industrial routes
Laboratory synthesis
Occurrence
Atmospheric methane and climate change
Clathrates
Public safety and the environment
Extraterrestrial methane
Interstellar medium
Mars
Titan
History
Etymology
Abbreviations
See also
Explanatory notes
Citations
Cited sources
External links
target="_blank" rel="nofollow"> Gas (Methane) Hydrates – A New Frontier – United States Geological Survey (archived 6 February 2004)
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