Clathrate hydrate

Clathrate hydrates, or gas clathrates, gas hydrates, clathrates, hydrates, etc., are crystalline water-based solids physically resembling ice, in which small non-polar molecules (typically gases) or polar molecules with large hydrophobic moieties are trapped inside 'cages' of hydrogen bonded, frozen water molecules. In other words, clathrate hydrates are clathrate compounds in which the host molecule is water and the guest molecule is typically a gas or liquid. Without the support of the trapped molecules, the lattice structure of hydrate clathrates would collapse into conventional ice crystal structure or liquid water. Most low molecular weight gases, including O2, H2, N2, CO2, CH4, H2S, Ar, Kr, and Xe, as well as some higher hydrocarbons and freons, will form hydrates at suitable temperatures and pressures. Clathrate hydrates are not officially chemical compounds, as the sequestered molecules are never bonded to the lattice. The formation and decomposition of clathrate hydrates are first order phase transitions, not chemical reactions. Their detailed formation and decomposition mechanisms on a molecular level are still not well understood.Clathrate hydrates were first documented in 1810 by Sir Humphry Davy who found that water was a primary component of what was earlier thought to be solidified chlorine. Clathrate hydrates, or gas clathrates, gas hydrates, clathrates, hydrates, etc., are crystalline water-based solids physically resembling ice, in which small non-polar molecules (typically gases) or polar molecules with large hydrophobic moieties are trapped inside 'cages' of hydrogen bonded, frozen water molecules. In other words, clathrate hydrates are clathrate compounds in which the host molecule is water and the guest molecule is typically a gas or liquid. Without the support of the trapped molecules, the lattice structure of hydrate clathrates would collapse into conventional ice crystal structure or liquid water. Most low molecular weight gases, including O2, H2, N2, CO2, CH4, H2S, Ar, Kr, and Xe, as well as some higher hydrocarbons and freons, will form hydrates at suitable temperatures and pressures. Clathrate hydrates are not officially chemical compounds, as the sequestered molecules are never bonded to the lattice. The formation and decomposition of clathrate hydrates are first order phase transitions, not chemical reactions. Their detailed formation and decomposition mechanisms on a molecular level are still not well understood.Clathrate hydrates were first documented in 1810 by Sir Humphry Davy who found that water was a primary component of what was earlier thought to be solidified chlorine. Clathrates have been found to occur naturally in large quantities. Around 6.4 trillion (6.4×1012) tonnes of methane is trapped in deposits of methane clathrate on the deep ocean floor. Such deposits can be found on the Norwegian continental shelf in the northern headwall flank of the Storegga Slide. Clathrates can also exist as permafrost, as at the Mallik gas hydrate site in the Mackenzie Delta of northwestern Canadian Arctic. These natural gas hydrates are seen as a potentially vast energy resource, but an economical extraction method has so far proven elusive. Hydrocarbon clathrates cause problems for the petroleum industry, because they can form inside gas pipelines, often resulting in obstructions. Deep sea deposition of carbon dioxide clathrate has been proposed as a method to remove this greenhouse gas from the atmosphere and control climate change. Clathrates are suspected to occur in large quantities on some outer planets, moons and trans-Neptunian objects, binding gas at fairly high temperatures. Gas hydrates usually form two crystallographic cubic structures: structure (Type) I (named sI) and structure (Type) II (named sII) of space groups P m 3 ¯ n {displaystyle Pm{overline {3}}n} and F d 3 ¯ m {displaystyle Fd{overline {3}}m} respectively. Seldom, a third hexagonal structure of space group P 6 / m m m {displaystyle P6/mmm} may be observed (Type H). The unit cell of Type I consists of 46 water molecules, forming two types of cages – small and large. The unit cell contains two small cages and six large ones. The small cage has the shape of a pentagonal dodecahedron (512) (which is not a regular dodecahedron) and the large one that of a tetradecahedron, specifically a hexagonal truncated trapezohedron (51262). Together, they form a version of the Weaire–Phelan structure. Typical guests forming Type I hydrates are CO2 in carbon dioxide clathrate and CH4 in methane clathrate. The unit cell of Type II consists of 136 water molecules, again forming two types of cages – small and large. In this case there are sixteen small cages and eight large ones in the unit cell. The small cage again has the shape of a pentagonal dodecahedron (512), but the large one is a hexadecahedron (51264). Type II hydrates are formed by gases like O2 and N2. The unit cell of Type H consists of 34 water molecules, forming three types of cages – two small ones of different types, and one 'huge'. In this case, the unit cell consists of three small cages of type 512, two small ones of type 435663 and one huge of type 51268. The formation of Type H requires the cooperation of two guest gases (large and small) to be stable. It is the large cavity that allows structure H hydrates to fit in large molecules (e.g. butane, hydrocarbons), given the presence of other smaller help gases to fill and support the remaining cavities. Structure H hydrates were suggested to exist in the Gulf of Mexico. Thermogenically-produced supplies of heavy hydrocarbons are common there. Iro et al., trying to interpret the nitrogen deficiency in comets, stated most of the conditions for hydrate formation in the protoplanetary nebulae, surrounding the pre-main and main sequence stars were fulfilled, despite the rapid grain growth to meter scale. The key was to provide enough microscopic ice particles exposed to a gaseous environment. Observations of the radiometric continuum of circumstellar discs around τ {displaystyle au } -Tauri and Herbig Ae/Be stars suggest massive dust disks consisting of millimeter-sized grains, which disappear after several million years (e.g.,). A lot of work on detecting water ices in the Universe was done on the Infrared Space Observatory (ISO). For instance, broad emission bands of water ice at 43 and 60 μm were found in the disk of the isolated Herbig Ae/Be star HD 100546 in Musca. The one at 43 μm is much weaker than the one at 60 μm, which means the water ice, is located in the outer parts of the disk at temperatures below 50 K. There is also another broad ice feature between 87 and 90 μm, which is very similar to the one in NGC 6302 (the Bug or Butterfly nebula in Scorpius). Crystalline ices were also detected in the proto-planetary disks of ε-Eridani and the isolated Fe star HD 142527 in Lupus. 90% of the ice in the latter was found crystalline at temperature around 50 K. HST demonstrated that relatively old circumstellar disks, as the one around the 5-million-year-old B9.5Ve Herbig Ae/Be star HD 141569A, are dusty. Li & Lunine found water ice there. Knowing the ices usually exist at the outer parts of the proto-planetary nebulae, Hersant et al. proposed an interpretation of the volatile enrichment, observed in the four giant planets of the Solar System, with respect to the Solar abundances. They assumed the volatiles had been trapped in the form of hydrates and incorporated in the planetesimals flying in the protoplanets’ feeding zones. Kieffer et al. (2006) hypothesized that the geyser activity in the south polar region of Saturn's moon Enceladus originates from clathrate hydrates, where carbon dioxide, methane, and nitrogen are released when exposed to the vacuum of space through the 'Tiger Stripe' fractures found in that area. However, subsequent analysis of plume material makes it more likely that the geysers on Enceladus derive from a salty subsurface ocean.