Ice - Phases

Phases

Ice may be any one of the 15 known solid phases of water.

Most liquids under increased pressure freeze at higher temperatures because the pressure helps to hold the molecules together. However, the strong hydrogen bonds in water make it different: water, under a pressure higher than 1 atm (0.10 MPa), freezes at a temperature below 0 °C. The melting of ice under high pressures is thought to contribute to the movement of glaciers.

Ice, water, and water vapour can coexist at the triple point, which is exactly 0.01 °C (273.16 K) at a pressure of 611.73 Pa (the Kelvin is in fact defined as 1/273.16 of the difference between this triple point and absolute zero). Unlike most other solids, ice is difficult to superheat. In an experiment, ice at −3 °C was superheated to about 17 °C for about 250 picoseconds.

Subjected to higher pressures and varying temperatures, ice can form in fifteen separate known phases. With care all these phases except ice X can be recovered at ambient pressure and low temperature. The types are differentiated by their crystalline structure, ordering and density. There are also two metastable phases of ice under pressure, both fully hydrogen-disordered; these are IV and XII. Ice XII was discovered in 1996. In 2006, XIII and XIV were discovered. Ices XI, XIII, and XIV are hydrogen-ordered forms of ices Ih, V, and XII respectively. In 2009, ice XV was found at extremely high pressures and −143 °C. At even higher pressures, ice is predicted to become a metal; this has been variously estimated to occur at 1.55 TPa or 5.62 TPa.

As well as crystalline forms, solid water can exist in amorphous states as amorphous solid water (ASW), low-density amorphous ice (LDA), high-density amorphous ice (HDA), very high-density amorphous ice (VHDA) and hyperquenched glassy water (HGW).

In outer space, hexagonal crystalline ice (the predominant form found on Earth) is extremely rare. Amorphous ice is more common; however, hexagonal crystalline ice can be formed via volcanic action.

Phase Characteristics
Amorphous ice Amorphous ice is an ice lacking crystal structure. Amorphous ice exists in three forms: low-density (LDA) formed at atmospheric pressure, or below, high density (HDA) and very high density amorphous ice (VHDA), forming at higher pressures. LDA forms by extremely quick cooling of liquid water ("hyperquenched glassy water", HGW), by depositing water vapour on very cold substrates ("amorphous solid water", ASW) or by heating high density forms of ice at ambient pressure ("LDA").
Ice Ih Normal hexagonal crystalline ice. Virtually all ice in the biosphere is ice Ih, with the exception only of a small amount of ice Ic.
Ice Ic A metastable cubic crystalline variant of ice. The oxygen atoms are arranged in a diamond structure. It is produced at temperatures between 130 and 220 K, and can exist up to 240 K, when it transforms into ice Ih. It may occasionally be present in the upper atmosphere.
Ice II A rhombohedral crystalline form with highly ordered structure. Formed from ice Ih by compressing it at temperature of 190–210 K. When heated, it undergoes transformation to ice III.
Ice III A tetragonal crystalline ice, formed by cooling water down to 250 K at 300 MPa. Least dense of the high-pressure phases. Denser than water.
Ice IV A metastable rhombohedral phase. It can be formed by heating high-density amorphous ice slowly at a pressure of 810 MPa. It doesn't form easily without a nucleating agent.
Ice V A monoclinic crystalline phase. Formed by cooling water to 253 K at 500 MPa. Most complicated structure of all the phases.
Ice VI A tetragonal crystalline phase. Formed by cooling water to 270 K at 1.1 GPa. Exhibits Debye relaxation.
Ice VII A cubic phase. The hydrogen atoms' positions are disordered. Exhibits Debye relaxation. The hydrogen bonds form two interpenetrating lattices.
Ice VIII A more ordered version of ice VII, where the hydrogen atoms assume fixed positions. Formed from ice VII, by cooling it below 5 °C (278 K).
Ice IX A tetragonal phase. Formed gradually from ice III by cooling it from 208 K to 165 K, stable below 140 K and pressures between 200 MPa and 400 MPa. It has density of 1.16 g/cm3, slightly higher than ordinary ice.
Ice X Proton-ordered symmetric ice. Forms at about 70 GPa.
Ice XI An orthorhombic, low-temperature equilibrium form of hexagonal ice. It is ferroelectric. Ice XI is considered the most stable configuration of ice Ih. The natural transformation process is very slow and ice XI has been found in Antarctic ice 100 to 10,000 years old. That study indicated that the temperature below which ice XI forms is −36 °C (240 K).
Ice XII A tetragonal, metastable, dense crystalline phase. It is observed in the phase space of ice V and ice VI. It can be prepared by heating high-density amorphous ice from 77 K to about 183 K at 810 MPa. It has a density of 1.3 g cm−3 at 127 K (i.e., approximately 1.3 times more dense than water).
Ice XIII A monoclinic crystalline phase. Formed by cooling water to below 130 K at 500 MPa. The proton-ordered form of ice V.
Ice XIV An orthorhombic crystalline phase. Formed below 118 K at 1.2 GPa. The proton-ordered form of ice XII.
Ice XV The proton-ordered form of ice VI formed by cooling water to around 80–108 K at 1.1 GPa.

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