Methane

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 methane on Earth makes it an attractive fuel, although capturing and storing it poses challenges due to its gaseous state under normal conditions for temperature and pressure. Natural occurring methane is found both below ground and under the sea floor, 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 150% since 1750, and it accounts for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases. Methane has also been detected on other planets, including Mars, which has implications for astrobiology research. 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 of methane to methanol is challenging because the reaction typically progresses all the way to carbon dioxide and water even with an insufficient supply of oxygen. The enzymes methane monooxygenase produces methanol from methane, but cannot be used for industrial-scale reactions. 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. One group of bacteria drive methane oxidation with nitrite as the oxidant in the absence of oxygen, giving rise to the so-called anaerobic oxidation of methane.