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|Jmol-3D images||Image 1|
|Molar mass||16.04 g mol−1|
|Density||0.6556 g L−1|
-182 °C, 90.7 K, -296 °F
-164--160 °C, 109-113 K, -263--256 °F
|Solubility in water||22.7 mg L−1|
|kH||14 nmol Pa−1 kg−1|
|Dipole moment||0 D|
| Std enthalpy of
|−74.87 kJ mol−1|
| Std enthalpy of
|−891.1–−890.3 kJ mol−1|
| Standard molar
|186.25 J K−1 mol−1|
|Specific heat capacity, C||35.69 J K−1 mol−1|
|GHS signal word||DANGER|
|GHS hazard statements||H220|
|GHS precautionary statements||P210|
|S-phrases||(S2), S16, S33|
|Flash point||−188 °C|
|Supplementary data page|
| Structure and
|n, εr, etc.|
Solid, liquid, gas
|Spectral data||UV, IR, NMR, MS|
(what is: / ?)|
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Methane (pronounced /ˈmɛθeɪn/ or /ˈmiːθeɪn/) is a chemical compound with the chemical formula CH4. It is the simplest alkane, the main component of natural gas, and probably the most abundant organic compound on earth. The relative abundance of methane makes it an attractive fuel. However, because it is a gas at normal conditions, methane is difficult to transport from its source.
Methane is a relatively potent greenhouse gas. The concentration of methane in the Earth's atmosphere in 1998, expressed as a mole fraction, was 1745 nmol/mol (parts per billion, ppb), up from 700 nmol/mol in 1750. By 2008, however, global methane levels, which had stayed mostly flat since 1998, had risen to 1800 nmol/mol.
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 level in energy 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 a safety measure achieved by the addition of an odorant, usually blends containing tert-butylthiol. Methane has a boiling point of −161 °C (−257.8 ° F) at a pressure of one atmosphere. As a gas it is flammable only over a narrow range of concentrations (5–15%) in air. Liquid methane does not burn unless subjected to high pressure (normally 4–5 atmospheres).
Main reactions with 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 incomplete amounts of oxygen. The enzymes methane monooxygenase can produce methanol from methane, but they 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 CH3+, methane cation CH4+, and methanium or protonated methane CH5+. Some of these have been detected in outer space. Methanium can also be produced as diluted solutions from methane with super acids. Cations with higher charge, such as CH6++ and CH7+++, have been studied theoretically and conjectured to be stable.
In the combustion of methane, multiple steps are involved. The following equations are part of the process, with the net result being:
CH4 + 2 O2 → CO2 + 2 H2O (ΔH = −891 k J/ mol (at standard conditions))
- CH4+ M* → CH3 + H + M
- CH4 + O2 → CH3 + HO2
- CH4 + HO2 → CH3 + 2 OH
- CH4 + OH → CH3 + H2O
- O2 + H → O + OH
- CH4 + O → CH3 + OH
- CH3 + O2 → CH2O + OH
- CH2O + O → CHO + OH
- CH2O + OH → CHO + H2O
- CH2O + H → CHO + H2
- CHO + O → CO + OH
- CHO + OH → CO + H2O
- CHO + H → CO + H2
- H2 + O → H + OH
- H2 + OH → H + H2O
- CO + OH → CO2 + H
- H + OH + M → H2O + M*
- H + H + M → H2 + M*
- H + O2 + M → HO2 + M*
The species M* signifies an energetic third body, from which energy is transferred during a molecular collision. Formaldehyde (HCHO or H2CO) is an early intermediate (reaction 7). Oxidation of formaldehyde gives the formyl radical (HCO) (reactions 8, 9 & 10), which then give carbon monoxide (CO) (reactions 11, 12 & 13). Any resulting H2 oxidizes to H2O or other intermediates (reaction 14 & 15). Finally, the CO oxidizes, forming CO2 (reaction 16). In the final stages (reactions 17, 18 & 19), energy is transferred back to other third bodies. The overall speed of reaction is a function of the concentration of the various entities during the combustion process. The higher the temperature, the greater the concentration of radical species and the more rapid the combustion process.
Reactions with halogens
Methane reacts with halogens given appropriate conditions 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 new chlorine atom. 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 component.
Methane is important for electrical generation by burning it as a fuel in a gas turbine or steam boiler. Compared to other hydrocarbon fuels, burning methane produces less carbon dioxide for each unit of heat released. 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 purposes. 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.
Liquefied natural gas
Liquefied natural gas or LNG is natural gas (predominantly methane, CH4) that has been converted to liquid form for ease of storage or transport.
Liquefied natural gas takes up about 1/600th the volume of natural gas in the gaseous state. It is odorless, colorless, non-toxic and non-corrosive. Hazards include flammability, 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/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 heavier than that of CNG or 60% of that of diesel fuel. This makes LNG cost 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.
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 can be used in natural gas vehicles, although it is more common to design vehicles to use compressed natural gas. Its relatively high cost of production and the need to store it in more expensive cryogenic tanks have hindered widespread commercial use.
Liquid methane rocket fuel
In a highly refined form, liquid methane has been investigated as a rocket fuel. A number of Russian rockets have been proposed to use liquid methane since the 1990s, and US companies Orbitech and XCOR Aerospace developed a liquid oxygen/liquid methane rocket engine in 2005 and a larger 7,500 pounds-force (33,000 N)-thrust engine in 2007 for potential use as the CEV lunar return engine. More recently the American private space company SpaceX announced (in 2012) an initiative to develop liquid methane rocket engines, including initially, the Raptor second stage rocket engine.
Research has been conducted by NASA regarding methane's potential as a rocket fuel. One advantage of methane is that it is abundant in many parts of the solar system and it could potentially be harvested on the surface of another solar-system body, providing fuel for a return journey. Current methane engines in development produce a thrust of 7,500 pounds-force (33 kN), which is far from the 7,000,000 lbf (31 MN) needed to launch the Space Shuttle. Instead, such engines will most likely propel voyages from the Moon or send robotic expeditions to other planets in the solar system.
Although there is great interest in converting methane into useful or more easily liquified compounds, the only practical processes are relatively unselective. In the chemical industry, methane is converted to synthesis gas, a mixture of carbon monoxide and hydrogen, by steam reforming. This endergonic process (requiring energy) utilizes nickel catalysts and requires high temperatures, around 700–1100 °C:
- CH4 + H2O → CO + 3 H2
Methane is also subjected to free-radical chlorination in the production of chloromethanes, although methanol is a more typical precursor.
Naturally occurring methane is mainly produced by the process of 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 catalysed by the enzyme methyl-coenzyme M reductase. 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 if plants are a source of methane emissions.
Methane could also be produced by a non-biological process called serpentinization involving water, carbon dioxide, and the mineral olivine, which is known to be common on Mars.
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. This technology is practiced on a large scale to produce longer chain molecules than methane.
Natural gas is so abundant that the intentional production of methane is relatively rare. The only large scale facility of this kind 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 which is otherwise very hard to transport for its weight, ash content, low calorific value and propensity to spontaneous combustion during storage and transport.
Methane can also be produced by the destructive distillation of acetic acid in the presence of soda lime or similar. Acetic acid is decarboxylated in this process. Methane can also be prepared by reaction of aluminium carbide with water or strong acids.
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. The gas at shallow levels (low pressure) forms by anaerobic decay of organic matter and reworked methane from deep under the Earth's surface. In general, sediments buried deeper and at higher temperatures than those that contain oil generate natural gas.
It 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.
Methane is created near the Earth's surface, primarily by microorganisms by the process of methanogenesis. It is carried into the stratosphere by rising air in the tropics. Uncontrolled build-up of methane in the atmosphere is naturally checked — although human influence can upset this natural regulation — by methane's reaction with hydroxyl radicals formed from singlet oxygen atoms and with water vapor. It has a net lifetime of about 10 years, and is primarily removed by conversion to carbon dioxide and water.
Methane also affects the degradation of the ozone layer.
In addition, there is a large (but unknown) amount of methane in methane clathrates in the ocean floors as well as the Earth's crust. Most methane is the result of biological process called methanogenesis.
In 2010, methane levels in the Arctic were measured at 1850 nmol/mol, a level over twice as high as at any time in the 400,000 years prior to the industrial revolution. Historically, 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 to 700 nmol/mol during the warm interglacial periods. It has a high global warming potential: 72 times that of carbon dioxide over 20 years, and 25 times over 100 years, and the levels are rising. Recent research suggests that the Earth's oceans are a potentially important new source of Arctic methane.
A Bristol University study published in Nature claims that methane under the Antarctic Ice Sheet may yet play an important role globally. Researchers believe these sub-ice environments to be biologically active, in that microbes are converting organic carbon to carbon dioxide and methane.
Methane in the Earth's atmosphere is an important greenhouse gas with a global warming potential of 25 compared to CO2 over a 100-year period (although accepted figures probably represent an underestimate). This means that a methane emission will have 25 times the effect on temperature of a carbon dioxide emission of the same mass over the following 100 years. Methane has a large effect for a brief period (a net lifetime of 8.4 years in the atmosphere), whereas carbon dioxide has a small effect for a long period (over 100 years). Because of this difference in effect and time period, the global warming potential of methane over a 20 year time period is 72. The 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). Usually, excess methane from landfills and other natural producers of methane is burned so CO2 is released into the atmosphere instead of methane, because methane is a more effective greenhouse gas. Recently, methane emitted from coal mines has been successfully utilized to generate electricity.
Arctic methane release from permafrost and methane clathrates is an expected consequence and further cause of global warming.
Methane is not toxic; however, it is extremely flammable and may form explosive mixtures with air. Methane is violently reactive with oxidizers, halogens, and some halogen-containing compounds. Methane is also an asphyxiant and may displace oxygen in an enclosed space. Asphyxia may result if the oxygen concentration is reduced to below 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. Possible health effects of breathing in methane at high concentrations, resulting in oxygen deficiency, are increased breathing and pulse rates, lack of muscular coordination, emotional upset, nausea and vomiting, loss of consciousness, respiratory collapse and death. 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 25.
Methane has been detected or is believed to exist in several locations of the solar system. In most cases, it is believed to have been created by abiotic processes. Possible exceptions are Mars and Titan.
- Venus – the atmosphere contains a large amount of methane from 60 km (37 mi) to the surface according to data collected by the Pioneer Venus Large Probe Neutral Mass Spectrometer
- Moon – traces are outgassed from the surface
- Mars – the Martian atmosphere contains 10 nmol/ mol methane. The source of methane on Mars has not been determined. Recent research suggests that methane may come from volcanoes, fault lines, or methanogens, or that it may be a byproduct of electrical discharges from dust devils and dust storms, or that it may be the result of UV radiation. In January 2009, NASA scientists announced that they had discovered that the planet often vents methane into the atmosphere in specific areas, leading some to speculate this may be a sign of biological activity going on below the surface. Analysis of observations made by a Weather Research and Forecasting model for Mars (MarsWRF) and related Mars general circulation model (MGCM) suggests that it is potentially possible to isolate methane plume source locations to within tens of kilometers, which is within the roving capabilities of future Mars rovers. The Curiosity rover, which landed on Mars in August 2012, is able to make measurements that distinguish between different isotopologues of methane; but even if the mission is to determine that microscopic Martian life is the source of the methane, the life forms likely reside far below the surface, outside of the rover's reach. Curiosity’s Sample Analysis at Mars (SAM) instrument is capable of tracking the presence of methane over time to determine if it is constant, variable, seasonal, or random, providing further clues about its source. The first measurements with the Tunable Laser Spectrometer (TLS) indicated that there is less than 5 ppb of methane at the landing site at the point of the measurement. The Mars Trace Gas Mission orbiter planned to launch in 2016 would further study the methane, as well as its decomposition products such as formaldehyde and methanol. Alternatively, these compounds may instead be replenished by volcanic or other geological means, such as serpentinization.
- Jupiter – the atmosphere contains about 0.3% methane
- Saturn – the atmosphere contains about 0.4% methane
- Titan — the atmosphere contains 1.6% methane and thousands of methane lakes have been detected on the surface In the upper atmosphere the methane is converted into more complex molecules including acetylene, a process that also produces molecular hydrogen. There is evidence that acetylene and hydrogen are recycled into methane near the surface. This suggests the presence either of an exotic catalyst, or an unfamiliar form of methanogenic life. An apparent lake of liquid methane has been spotted by the Cassini-Huygens probe, causing researchers to speculate about the possibility of life on Titan. Methane showers, probably prompted by changing seasons, have also been observed.
- Enceladus – the atmosphere contains 1.7% methane
- Uranus – the atmosphere contains 2.3% methane
- Ariel – methane is believed to be a constituent of Ariel's surface ice
- Oberon – about 20% of Oberon's surface ice is composed of methane-related carbon/nitrogen compounds
- Titania – about 20% of Titania's surface ice is composed of methane-related organic compounds
- Umbriel – methane is a constituent of Umbriel's surface ice
- Neptune – the atmosphere contains 1.6% methane
- Triton – Triton has a tenuous nitrogen atmosphere with small amounts of methane near the surface.
- Pluto – spectroscopic analysis of Pluto's surface reveals it to contain traces of methane
- Charon – methane is believed present on Charon, but it is not completely confirmed
- Eris – infrared light from the object revealed the presence of methane ice
- Comet Halley
- Comet Hyakutake – terrestrial observations found ethane and methane in the comet
- Extrasolar planets – methane was detected on extrasolar planet HD 189733b; this is the first detection of an organic compound on a planet outside the solar system. Its origin is unknown, since the planet's high temperature (700 °C) would normally favour the formation of carbon monoxide instead. Research indicates that meteoroids slamming against exoplanet atmospheres could add organic gases such as methane, making the exoplanets look as though they are inhabited by life, even if they are not.
- Interstellar clouds