InformationToKnowledge (talk | contribs) Copying the contents of Ice XII sub-article, in preparation for a merge. (Includes Ice XIV in it already.) |
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[[File:Phase diagram of water.svg|thumb|[[Semi-log plot|Log-lin]] pressure-temperature [[phase diagram]] of water. The [[Roman numeral]]s correspond to some ice phases listed below.]] |
[[File:Phase diagram of water.svg|thumb|[[Semi-log plot|Log-lin]] pressure-temperature [[phase diagram]] of water. The [[Roman numeral]]s correspond to some ice phases listed below.]] |
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[[File:3D representation of several phases of water.jpg|thumb|An alternative formulation of the phase diagram for certain ices and other phases of water<ref>{{cite journal |last1=David |first1=Carl |title=Verwiebe's '3-D' Ice phase diagram reworked |journal=Chemistry Education Materials |date=8 August 2016 |url=https://opencommons.uconn.edu/chem_educ/94/ }}</ref>]] |
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The '''phases of ice''' are all possible [[states of matter]] for [[Properties of water|water]] as a solid. Currently, 19 phases, including both crystalline and [[Amorphous solid|amorphous]] ice, have been observed at various densities. |
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[[Image:Melting curve of water.svg|thumb|Pressure dependence of ice melting]] |
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Currently, 19 solid phases of [[Properties of water|water]] (both crystalline and [[Amorphous solid|amorphous]]) have been observed at various densities, along with hypothetical proposed '''phases of ice''' that have not been observed.<ref name="Metcalfe-2021">{{cite news|last1=Metcalfe|first1=Tom|date=9 March 2021|title=Exotic crystals of 'ice 19' discovered|language=en|work=Live Science|url=https://www.livescience.com/exotic-ice-19-discovered.html}}</ref> |
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== Theory == |
== Theory == |
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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: for some pressures higher than {{convert|1|atm|MPa|abbr=on}}, water freezes at a temperature ''below'' 0 °C, |
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: for some pressures higher than {{convert|1|atm|MPa|abbr=on}}, water freezes at a temperature ''below'' 0 °C. Subjected to higher pressures and varying temperatures, ice can form in nineteen separate known crystalline phases. With care, at least fifteen of these phases (one of the known exceptions being ice X) can be recovered at ambient pressure and low temperature in [[metastable]] form.<ref>{{cite journal|last=La Placa|first=S. J.|author2=Hamilton, W. C.|author3=Kamb, B.|author4=Prakash, A.|year=1972|title=On a nearly proton ordered structure for ice IX|journal=Journal of Chemical Physics|volume=58|issue=2|pages=567–580|doi=10.1063/1.1679238|bibcode = 1973JChPh..58..567L }}</ref><ref>{{cite journal|last=Klotz|first=S.|author2=Besson, J. M.|author3=Hamel, G.|author4=Nelmes, R. J.|author5=Loveday, J. S.|author6=Marshall, W. G.|year=1999|title=Metastable ice VII at low temperature and ambient pressure|journal=Nature|volume=398|issue=6729|pages=681–684|doi=10.1038/19480|bibcode = 1999Natur.398..681K |s2cid=4382067}}</ref> The types are differentiated by their crystalline structure, proton ordering,<ref>{{cite web|url=https://www.uwgb.edu/dutchs/Petrology/Ice%20Structure.HTM|title=Ice Structure|last=Dutch|first=Stephen|publisher=University of Wisconsin Green Bay|access-date=12 July 2017|url-status=dead|archive-url=https://web.archive.org/web/20161016143124/http://www.uwgb.edu/dutchs/petrology/Ice%20Structure.HTM|archive-date=16 October 2016}}</ref> and density. There are also two [[metastable]] phases of ice under pressure, both fully hydrogen-disordered; these are Ice IV and Ice XII. |
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== Crystal structure == |
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[[Image:cryst struct ice.png|thumb|250px|Crystal structure of ice I<sub>h</sub>. Dashed lines represent hydrogen bonds]] |
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[[File:Icexii-ru.jpg|thumb|250px|The crystal structure of ice XII]] |
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The accepted [[crystal structure]] of ordinary ice was first proposed by [[Linus Pauling]] in 1935. The structure of ice I<sub>h</sub> is the [[Wurtzite (crystal structure)|wurtzite lattice]], roughly one of crinkled planes composed of [[tessellation|tessellating]] hexagonal rings, with an [[oxygen]] atom on each vertex, and the edges of the rings formed by [[hydrogen bond]]s. The planes alternate in an ABAB pattern, with B planes being reflections of the A planes along the same axes as the planes themselves.<ref name=bjerrum>{{cite journal|last=Bjerrum|first=N|title=Structure and Properties of Ice|journal=Science|date=11 April 1952|volume=115|issue=2989|pages=385–390|doi=10.1126/science.115.2989.385|pmid=17741864|bibcode = 1952Sci...115..385B }}</ref> The distance between oxygen atoms along each bond is about 275 [[picometre|pm]] and is the same between any two bonded oxygen atoms in the lattice. The angle between bonds in the crystal lattice is very close to the [[tetrahedral angle]] of 109.5°, which is also quite close to the angle between hydrogen atoms in the water molecule (in the gas phase), which is 105°. |
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This tetrahedral bonding angle of the water molecule essentially accounts for the unusually low density of the crystal lattice – it is beneficial for the lattice to be arranged with tetrahedral angles even though there is an energy penalty in the increased volume of the crystal lattice. As a result, the large hexagonal rings leave almost enough room for another water molecule to exist inside. This gives naturally occurring ice its rare property of being less dense than its liquid form. The tetrahedral-angled hydrogen-bonded hexagonal rings are also the mechanism that causes liquid water to be densest at 4 °C. Close to 0 °C, tiny hexagonal ice I<sub>h</sub>-like lattices form in liquid water, with greater frequency closer to 0 °C. This effect decreases the density of the water, causing it to be densest at 4 °C when the structures form infrequently. |
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In the most common form of ice, ice I<sub>h</sub>, the crystal structure is characterized by the oxygen atoms forming [[Hexagonal crystal family|hexagonal symmetry]] with near [[tetrahedral]] bonding angles. This structure is stable down to {{convert|-268|C|K F|0}}, as evidenced by x-ray diffraction<ref name=Rottger>{{cite journal|first1=K. |last1=Rottger |first2=A. |last2=Endriss |first3=J. |last3=Ihringer |first4=S. |last4=Doyle |first5=W. F. |last5=Kuhs|title=Lattice Constants and Thermal Expansion of H<sub>2</sub>O and D<sub>2</sub>O Ice I<sub>h</sub> Between 10 and 265 K |journal=Acta Crystallogr. |year=1994 |volume= B50 |issue=6 |pages=644–648 |doi=10.1107/S0108768194004933}}</ref> and extremely high resolution thermal expansion measurements.<ref name=Buckingham>{{cite journal|author=David T. W. Buckingham, J. J. Neumeier, S. H. Masunaga, and Yi-Kuo Yu|title=Thermal Expansion of Single-Crystal H<sub>2</sub>O and D<sub>2</sub>O Ice Ih|journal=Physical Review Letters |year=2018 |volume=121 |issue=18|pages=185505 |doi=10.1103/PhysRevLett.121.185505 |pmid=30444387|bibcode=2018PhRvL.121r5505B|doi-access=free}}</ref> Ice I<sub>h</sub> is also stable under applied pressures of up to about {{convert|210|MPa|atm}} where it transitions into ice III or ice II.<ref>{{cite journal|author=P. W. Bridgman|title=Water, in the Liquid and Five Solid Forms, under Pressure |journal=Proceedings of the American Academy of Arts and Sciences |year=1912 |volume=47 |issue=13 |pages=441–558 |doi=10.2307/20022754 |jstor=20022754 }}</ref> |
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=== Amorphous ice === |
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While most forms of ice are crystalline, several amorphous (or "vitreous") forms of ice also exist. Such ice is an [[amorphous solid]] form of water, which lacks long-range order in its molecular arrangement. Amorphous ice is produced either by [[supercooling|rapid cooling]] of liquid water to its [[glass transition temperature]] (about 136 K or −137 °C) in milliseconds (so the molecules do not have enough time to form a [[Crystal structure|crystal lattice]]), or by compressing ordinary ice at low temperatures. The most common form on Earth, low-density ice, is usually formed in the laboratory by a slow accumulation of water vapor molecules ([[physical vapor deposition]]) onto a very smooth [[metal]] crystal surface under 120 K. In [[outer space]] it is expected to be formed in a similar manner on a variety of cold substrates, such as dust particles.<ref>{{cite journal|doi=10.1126/science.1061757|pmid=11743196|title=Estimation of water-glass transition temperature based on hyperquenched glassy water experiments|first3=C. A.|last3=Angell|first2=S|year=2001|last2=Borick|last1=Velikov|first1=V.|journal=Science|volume=294|issue=5550|pages=2335–8|bibcode = 2001Sci...294.2335V |s2cid=43859537 }}</ref> By contrast, '''hyperquenched glassy water''' (HGW) is formed by spraying a fine mist of water droplets into a liquid such as propane around 80 K, or by hyperquenching fine [[micrometer (unit)|micrometer]]-sized droplets on a sample-holder kept at [[liquid nitrogen]] temperature, 77 K, in a vacuum. Cooling rates above 10<sup>4</sup> K/s are required to prevent crystallization of the droplets. At liquid nitrogen temperature, 77 K, HGW is kinetically stable and can be stored for many years. |
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Amorphous ices have the property of suppressing long-range density fluctuations and are, therefore, nearly [[Hyperuniformity|hyperuniform]].<ref>{{Cite journal |last1=Martelli |first1=Fausto |last2=Torquato |first2=Salvatore |last3=Giovambattista |first3=Nicolas |last4=Car |first4=Roberto |date=2017-09-29 |title=Large-Scale Structure and Hyperuniformity of Amorphous Ices |url=https://link.aps.org/doi/10.1103/PhysRevLett.119.136002 |journal=Physical Review Letters |volume=119 |issue=13 |pages=136002 |doi=10.1103/PhysRevLett.119.136002|pmid=29341697 |s2cid=44864111 |arxiv=1705.09961 |bibcode=2017PhRvL.119m6002M }}</ref> Despite the epithet "ice", [[Statistical_classification|classification]] analysis utilizing [[Neural network (machine learning)|neural networks]] has shown that amorphous ices are [[glass]]es.<ref>{{Cite journal |last1=Martelli |first1=Fausto |last2=Leoni |first2=Fabio |last3=Sciortino |first3=Francesco |last4=Russo |first4=John |date=2020-09-14 |title=Connection between liquid and non-crystalline solid phases in water |url=https://aip.scitation.org/doi/10.1063/5.0018923 |journal=The Journal of Chemical Physics |volume=153 |issue=10 |pages=104503 |doi=10.1063/5.0018923 |pmid=32933306 |bibcode=2020JChPh.153j4503M |hdl=11573/1440448 |s2cid=221746507 |issn=0021-9606|hdl-access=free }}</ref> |
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== Pressure-dependent states == |
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[[File:Water phase diagram extended to negative pressurs.png|thumb|Water phase diagram extended to negative pressures calculated with TIP4P/2005 model.<ref name="conde2009"/>]] |
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Ice from a theorized superionic water may possess two crystalline structures. At pressures in excess of {{convert|50|GPa|psi|abbr=on}} such ''superionic ice'' would take on a [[body-centered cubic]] structure. However, at pressures in excess of {{convert|100|GPa|psi|abbr=on}} the structure may shift to a more stable [[face-centered cubic]] lattice. Some estimates suggest that at an extremely high pressure of around {{convert|1.55|TPa|psi|abbr=on}}, ice would develop [[metal]]ic properties.<ref>{{cite journal |last1=Militzer |first1=Burkhard |last2=Wilson |first2=Hugh F. |title=New Phases of Water Ice Predicted at Megabar Pressures |journal=Physical Review Letters |date=2 November 2010 |volume=105 |issue=19 |page=195701 |doi=10.1103/PhysRevLett.105.195701 |pmid=21231184 |arxiv=1009.4722 |bibcode=2010PhRvL.105s5701M |s2cid=15761164 }}</ref> |
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== Heat and entropy == |
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[[File:3D representation of several phases of water.jpg|thumb|An alternative formulation of the phase diagram for certain ices and other phases of water<ref>{{cite journal |last1=David |first1=Carl |title=Verwiebe's '3-D' Ice phase diagram reworked |journal=Chemistry Education Materials |date=8 August 2016 |url=https://opencommons.uconn.edu/chem_educ/94/ }}</ref>]] |
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Ice, water, and [[water vapour]] can coexist at the [[triple point]], which is exactly {{cvt|273.16|K|C}} at a pressure of 611.657 [[Pascal (unit)|Pa]].<ref>{{cite journal |last1=Wagner |first1=Wolfgang |last2=Saul |first2=A. |last3=Pruss |first3=A. |title=International Equations for the Pressure Along the Melting and Along the Sublimation Curve of Ordinary Water Substance |journal=Journal of Physical and Chemical Reference Data |date=May 1994 |volume=23 |issue=3 |pages=515–527 |doi=10.1063/1.555947 |bibcode=1994JPCRD..23..515W }}</ref><ref>{{cite journal|doi=10.1256/qj.04.94 | volume=131 | issue=608 | title=Review of the vapour pressures of ice and supercooled water for atmospheric applications | year=2005 | journal=Quarterly Journal of the Royal Meteorological Society | pages=1539–1565 | last1 = Murphy | first1 = D. M.| bibcode=2005QJRMS.131.1539M | s2cid=122365938 | url=https://zenodo.org/record/1236243 | doi-access=free }}</ref> The [[kelvin]] was defined as {{sfrac|1|273.16}} of the difference between this triple point and [[absolute zero]],<ref>{{cite web|url=http://www1.bipm.org/en/si/base_units/|title=SI base units|publisher=Bureau International des Poids et Mesures|access-date=31 August 2012|url-status=live|archive-url=https://web.archive.org/web/20120716202131/http://www.bipm.org/en/si/base_units/|archive-date=16 July 2012}}</ref> though this definition [[2019 redefinition of SI base units|changed]] in May 2019.<ref>{{cite web |url=https://www.bipm.org/utils/common/pdf/SI-statement.pdf |title=Information for users about the proposed revision of the SI |publisher=Bureau International des Poids et Mesures |access-date=6 January 2019 |archive-date=21 January 2018 |archive-url=https://web.archive.org/web/20180121160000/https://www.bipm.org/utils/common/pdf/SI-statement.pdf |url-status=dead }}</ref> Unlike most other solids, ice is difficult to [[Superheating|superheat]]. In an experiment, ice at −3 °C was superheated to about 17 °C for about 250 [[picosecond]]s.<ref>{{cite journal|journal=Nature|volume=439|pages=183–186|year=2006| doi=10.1038/nature04415|pmid=16407948|title=Ultrafast superheating and melting of bulk ice|bibcode=2006Natur.439..183I|last1=Iglev|first1=H.|last2=Schmeisser|first2=M.|last3=Simeonidis|first3=K.|last4=Thaller|first4=A.|last5=Laubereau|first5=A.|issue=7073|s2cid=4404036}}</ref> |
Ice, water, and [[water vapour]] can coexist at the [[triple point]], which is exactly {{cvt|273.16|K|C}} at a pressure of 611.657 [[Pascal (unit)|Pa]].<ref>{{cite journal |last1=Wagner |first1=Wolfgang |last2=Saul |first2=A. |last3=Pruss |first3=A. |title=International Equations for the Pressure Along the Melting and Along the Sublimation Curve of Ordinary Water Substance |journal=Journal of Physical and Chemical Reference Data |date=May 1994 |volume=23 |issue=3 |pages=515–527 |doi=10.1063/1.555947 |bibcode=1994JPCRD..23..515W }}</ref><ref>{{cite journal|doi=10.1256/qj.04.94 | volume=131 | issue=608 | title=Review of the vapour pressures of ice and supercooled water for atmospheric applications | year=2005 | journal=Quarterly Journal of the Royal Meteorological Society | pages=1539–1565 | last1 = Murphy | first1 = D. M.| bibcode=2005QJRMS.131.1539M | s2cid=122365938 | url=https://zenodo.org/record/1236243 | doi-access=free }}</ref> The [[kelvin]] was defined as {{sfrac|1|273.16}} of the difference between this triple point and [[absolute zero]],<ref>{{cite web|url=http://www1.bipm.org/en/si/base_units/|title=SI base units|publisher=Bureau International des Poids et Mesures|access-date=31 August 2012|url-status=live|archive-url=https://web.archive.org/web/20120716202131/http://www.bipm.org/en/si/base_units/|archive-date=16 July 2012}}</ref> though this definition [[2019 redefinition of SI base units|changed]] in May 2019.<ref>{{cite web |url=https://www.bipm.org/utils/common/pdf/SI-statement.pdf |title=Information for users about the proposed revision of the SI |publisher=Bureau International des Poids et Mesures |access-date=6 January 2019 |archive-date=21 January 2018 |archive-url=https://web.archive.org/web/20180121160000/https://www.bipm.org/utils/common/pdf/SI-statement.pdf |url-status=dead }}</ref> Unlike most other solids, ice is difficult to [[Superheating|superheat]]. In an experiment, ice at −3 °C was superheated to about 17 °C for about 250 [[picosecond]]s.<ref>{{cite journal|journal=Nature|volume=439|pages=183–186|year=2006| doi=10.1038/nature04415|pmid=16407948|title=Ultrafast superheating and melting of bulk ice|bibcode=2006Natur.439..183I|last1=Iglev|first1=H.|last2=Schmeisser|first2=M.|last3=Simeonidis|first3=K.|last4=Thaller|first4=A.|last5=Laubereau|first5=A.|issue=7073|s2cid=4404036}}</ref> |
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[[Image:Melting curve of water.svg|thumb|Pressure dependence of ice melting]] |
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The latent [[heat of melting]] is {{val|5987|u=J|up=mol}}, and its latent [[heat of sublimation]] is {{val|50911|u=J|up=mol}}. The high latent heat of sublimation is principally indicative of the strength of the [[hydrogen bond]]s in the crystal lattice. The latent heat of melting is much smaller, partly because liquid water near 0 °C also contains a significant number of hydrogen bonds. By contrast, the structure of ice II is hydrogen-ordered, which helps to explain the entropy change of 3.22 J/mol when the crystal structure changes to that of ice I. Also, ice XI, an orthorhombic, hydrogen-ordered form of ice I<sub>h</sub>, is considered the most stable form at low temperatures. |
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The transition entropy from ice XIV to ice XII is estimated to be 60% of Pauling entropy based on DSC measurements.<ref name="pmid29923547">{{cite journal| author=Köster KW, Fuentes-Landete V, Raidt A, Seidl M, Gainaru C, Loerting T | display-authors=etal| title=Author Correction: Dynamics enhanced by HCl doping triggers 60% Pauling entropy release at the ice XII-XIV transition. | journal=Nat Commun | year= 2018 | volume= 9 | issue= | pages= 16189 | pmid=29923547 | doi=10.1038/ncomms16189 | pmc=6026910 | bibcode=2018NatCo...916189K}}</ref> The formation of ice XIV from ice XII is more favoured at high pressure.<ref name="pmid30101255">{{cite journal| author1=Fuentes-Landete V|author2= Köster KW|author3= Böhmer R|author4=Loerting T|author4-link=Thomas Loerting| title=Thermodynamic and kinetic isotope effects on the order-disorder transition of ice XIV to ice XII. | journal=Phys Chem Chem Phys | year= 2018 | volume= 20 | issue= 33 | pages= 21607–21616 | pmid=30101255 | doi=10.1039/c8cp03786h | pmc= |bibcode= 2018PCCP...2021607F|s2cid= 51969440| doi-access=free}}</ref> |
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Subjected to higher pressures and varying temperatures, ice can form in nineteen separate known crystalline phases. With care, at least fifteen of these phases (one of the known exceptions being ice X) can be recovered at ambient pressure and low temperature in [[metastable]] form.<ref>{{cite journal|last=La Placa|first=S. J.|author2=Hamilton, W. C.|author3=Kamb, B.|author4=Prakash, A.|year=1972|title=On a nearly proton ordered structure for ice IX|journal=Journal of Chemical Physics|volume=58|issue=2|pages=567–580|doi=10.1063/1.1679238|bibcode = 1973JChPh..58..567L }}</ref><ref>{{cite journal|last=Klotz|first=S.|author2=Besson, J. M.|author3=Hamel, G.|author4=Nelmes, R. J.|author5=Loveday, J. S.|author6=Marshall, W. G.|year=1999|title=Metastable ice VII at low temperature and ambient pressure|journal=Nature|volume=398|issue=6729|pages=681–684|doi=10.1038/19480|bibcode = 1999Natur.398..681K |s2cid=4382067}}</ref> The types are differentiated by their crystalline structure, proton ordering,<ref>{{cite web|url=https://www.uwgb.edu/dutchs/Petrology/Ice%20Structure.HTM|title=Ice Structure|last=Dutch|first=Stephen|publisher=University of Wisconsin Green Bay|access-date=12 July 2017|url-status=dead|archive-url=https://web.archive.org/web/20161016143124/http://www.uwgb.edu/dutchs/petrology/Ice%20Structure.HTM|archive-date=16 October 2016}}</ref> and density. There are also two [[metastable]] phases of ice under pressure, both fully hydrogen-disordered; these are [[Ice IV|IV]] and [[Ice XII|XII]]. Ice XII was discovered in 1996. In 2006, [[Ice XIII|XIII]] and [[Ice XIV|XIV]] were discovered.<ref>{{cite journal |last1=Salzmann |first1=Christoph G. |last2=Radaelli |first2=Paolo G. |last3=Hallbrucker |first3=Andreas |last4=Mayer |first4=Erwin |last5=Finney |first5=John L. |title=The Preparation and Structures of Hydrogen Ordered Phases of Ice |journal=Science |date=24 March 2006 |volume=311 |issue=5768 |pages=1758–1761 |doi=10.1126/science.1123896 |pmid=16556840 |bibcode=2006Sci...311.1758S |s2cid=44522271 }}</ref> Ices [[Ice XI|XI]], XIII, and XIV are hydrogen-ordered forms of ices I{{sub|h}}, V, and XII respectively. In 2009, ice XV was found at extremely high pressures and −143 °C.<ref>{{cite magazine|url=http://www.sciencenews.org/view/generic/id/47258/title/A_very_special_snowball|title=A Very Special Snowball|author=Sanders, Laura|magazine=Science News|date=11 September 2009|access-date=11 September 2009|url-status=live|archive-url=https://web.archive.org/web/20090914174027/http://www.sciencenews.org/view/generic/id/47258/title/A_very_special_snowball|archive-date=14 September 2009}}</ref> At even higher pressures, ice is predicted to become a [[metal]]; this has been variously estimated to occur at 1.55 TPa<ref>{{cite journal |last1=Militzer |first1=Burkhard |last2=Wilson |first2=Hugh F. |title=New Phases of Water Ice Predicted at Megabar Pressures |journal=Physical Review Letters |date=2 November 2010 |volume=105 |issue=19 |page=195701 |doi=10.1103/PhysRevLett.105.195701 |pmid=21231184 |arxiv=1009.4722 |bibcode=2010PhRvL.105s5701M |s2cid=15761164 }}</ref> or 5.62 TPa.<ref>{{cite journal|author=MacMahon, J. M.|title=Ground-State Structures of Ice at High-Pressures|doi=10.1103/PhysRevB.84.220104|arxiv=1106.1941|bibcode=2011PhRvB..84v0104M|year=1970|journal=Physical Review B|volume=84|issue=22|pages=220104|s2cid=117870442}}</ref> |
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When medium-density amorphous ice is compressed, released and then heated, it releases a large amount of heat energy, unlike other water ices which return to their normal form after getting similar treatment.<ref name="Nature2023" /> |
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=== Non-crystalline ice === |
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===Hydrogen disorder=== |
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As well as crystalline forms, solid water can exist in amorphous states as [[amorphous solid water]] (ASW) of varying densities. Water in the [[interstellar medium]] is dominated by amorphous ice, making it likely the most common form of water in the universe. Low-density ASW (LDA), also known as hyperquenched glassy water, may be responsible for [[noctilucent clouds]] on Earth and is usually formed by [[vapor deposition|deposition]] of water vapor in cold or vacuum conditions. High-density ASW (HDA) is formed by compression of ordinary ice I{{sub|h}} or LDA at GPa pressures. Very-high-density ASW (VHDA) is HDA slightly warmed to 160 K under 1–2 GPa pressures. |
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{{see also|Ice rules|Geometrical frustration#Water ice}}{{anchor|proton disorder}} |
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[[File:Wurtzite-boat-chair.png|thumb|The Wurtzite structure. In Ice I<sub>h</sub>, the oxygen atoms are arranged on the lattice points, and the hydrogen atoms are on the bonds between lattice points. Each oxygen atom has 4 neighboring ones. Note that the lattice bipartites into two subsets, here colored black and white.]] |
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The [[hydrogen]] atoms in the crystal lattice lie very nearly along the hydrogen bonds, and in such a way that each water molecule is preserved. This means that each oxygen atom in the lattice has two hydrogens adjacent to it: at about 101 pm along the 275 pm length of the bond for ice Ih. The crystal lattice allows a substantial amount of disorder in the positions of the hydrogen atoms frozen into the structure as it cools to absolute zero. As a result, the crystal structure contains some [[residual entropy]] inherent to the lattice and determined by the number of possible configurations of hydrogen positions that can be formed while still maintaining the requirement for each oxygen atom to have only two hydrogens in closest proximity, and each H-bond joining two oxygen atoms having only one hydrogen atom.<ref name=bernal>{{cite journal|last1=Bernal|first1=J. D.|last2=Fowler |first2=R. H.|title=A Theory of Water and Ionic Solution, with Particular Reference to Hydrogen and Hydroxyl Ions|journal=The Journal of Chemical Physics|date=1 January 1933|volume=1|issue=8|pages=515|doi=10.1063/1.1749327|bibcode=1933JChPh...1..515B}}</ref> This residual entropy {{math|{{var|S}}{{sub|0}}}} is equal to 3.4±0.1 J mol<sup>−1</sup> K<sup>−1</sup> <math>=R\ln(1.50 \pm 0.02)</math>.<ref>{{Cite journal |last=Berg |first=Bernd A. |last2=Muguruma |first2=Chizuru |last3=Okamoto |first3=Yuko |date=2007-03-21 |title=Residual entropy of ordinary ice from multicanonical simulations |url=https://link.aps.org/doi/10.1103/PhysRevB.75.092202 |journal=Physical Review B |language=en |volume=75 |issue=9 |doi=10.1103/PhysRevB.75.092202 |issn=1098-0121|arxiv=cond-mat/0609211 }}</ref> |
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=== Calculations === |
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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 by volcanic action.<ref>{{cite news|url=https://www.nytimes.com/2004/12/09/science/09ice.html|title=Astronomers Contemplate Icy Volcanoes in Far Places|author=Chang, Kenneth|work=The New York Times|date=9 December 2004|access-date=30 July 2012|url-status=live|archive-url=https://web.archive.org/web/20150509123243/http://www.nytimes.com/2004/12/09/science/09ice.html|archive-date=9 May 2015}}</ref> |
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There are various ways of approximating this number from first principles. The following is the one used by [[Linus Pauling]].<ref>{{cite journal |last=Pauling |first=Linus |author-link=Linus Pauling |date=1 December 1935 |title=The Structure and Entropy of Ice and of Other Crystals with Some Randomness of Atomic Arrangement |journal=Journal of the American Chemical Society |volume=57 |issue=12 |pages=2680–2684 |doi=10.1021/ja01315a102}}</ref><ref>{{Cite book |last=Petrenko |first=Victor F. |url=http://www.oxfordscholarship.com/view/10.1093/acprof:oso/9780198518945.001.0001/acprof-9780198518945 |title=Physics of Ice |last2=Whitworth |first2=Robert W. |date=2002-01-17 |publisher=Oxford University Press |isbn=978-0-19-851894-5 |chapter=2. Ice Ih |doi=10.1093/acprof:oso/9780198518945.003.0002}}</ref> |
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Ice from a theorized [[superionic water]] may possess two crystalline structures. At pressures in excess of {{convert|500000|bar|psi}} such ''superionic ice'' would take on a [[body-centered cubic]] structure. However, at pressures in excess of {{convert|1000000|bar|psi}} the structure may shift to a more stable [[face-centered cubic]] lattice. It is speculated that superionic ice could compose the interior of ice giants such as Uranus and Neptune.<ref name=Phys.org-2013-04-25>{{cite news |website=Phys.org |url=http://phys.org/news/2013-04-phase-dominate-interiors-uranus-neptune.html |title=New phase of water could dominate the interiors of Uranus and Neptune |first=Lisa |last=Zyga |date=25 April 2013}}</ref> |
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Suppose there are a given number {{mvar|N}} of water molecules in an ice lattice. To compute its residual entropy, we need to count the number of configurations that the lattice can assume. The oxygen atoms are fixed at the lattice points, but the hydrogen atoms are located on the lattice edges. The problem is to pick one end of each lattice edge for the hydrogen to bond to, in a way that still makes sure each oxygen atom is bond to two hydrogen atoms. |
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The oxygen atoms can be divided into two sets in a checkerboard pattern, shown in the picture as black and white balls. Focus attention on the oxygen atoms in one set: there are {{math|{{var|N}}/2}} of them. Each has four hydrogen bonds, with two hydrogens close to it and two far away. This means there are <math display="inline">\tbinom 4 2 = 6</math> allowed configurations of hydrogens for this oxygen atom (see [[Binomial coefficient]]). Thus, there are {{math|6{{sup|{{var|N}}/2}}}} configurations that satisfy these {{math|{{var|N}}/2}} atoms. But now, consider the remaining {{math|{{var|N}}/2}} oxygen atoms: in general they won't be satisfied (i.e., they will not have precisely two hydrogen atoms near them). For each of those, there are {{math|2{{sup|4}} {{=}} 16}} possible placements of the hydrogen atoms along their hydrogen bonds, of which 6 are allowed. So, naively, we would expect the total number of configurations to be |
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<math display="block">6^{N/2} (6/16)^{N/2} = (3/2)^N .</math> |
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Using [[Boltzmann's entropy formula]], we conclude that |
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<math display="block">S_0 = k\ln(3/2)^N = n R \ln(3/2),</math>where {{mvar|k}} is the [[Boltzmann constant]] and R is the [[molar gas constant]]. So, the molar residual entropy is <math>R \ln(3/2) = 3.37 \mathrm{J}\cdot\mathrm{mol}^{-1}\mathrm{K}^{-1}</math>. |
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The same answer can be found in another way. First orient each water molecule randomly in each of the 6 possible configurations, then check that each lattice edge contains exactly one hydrogen atom. Assuming that the lattice edges are independent, then the probability that a single edge contains exactly one hydrogen atom is 1/2, and since there are 2N edges in total, we obtain a total configuration count <math>6^N \times (1/2)^{2N} = (3/2)^N </math>, as before. |
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=== Refinements === |
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[[File:Iceviiistructure-ru.gif|thumb|The crystal structure of ice VIII]] |
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This estimate is 'naive', as it assumes the six out of 16 hydrogen configurations for oxygen atoms in the second set can be independently chosen, which is false. More complex methods can be employed to better approximate the exact number of possible configurations, and achieve results closer to measured values. Nagle (1966) used a series summation to obtain <math>R\ln(1.50685 \pm 0.00015)</math>.<ref>{{Cite journal |last=Nagle |first=J. F. |date=1966-08-01 |title=Lattice Statistics of Hydrogen Bonded Crystals. I. The Residual Entropy of Ice |url=https://pubs.aip.org/jmp/article/7/8/1484/382171/Lattice-Statistics-of-Hydrogen-Bonded-Crystals-I |journal=Journal of Mathematical Physics |language=en |volume=7 |issue=8 |pages=1484–1491 |doi=10.1063/1.1705058 |issn=0022-2488}}</ref> |
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As an illustrative example of refinement, consider the following way to refine the second estimation method given above. According to it, six water molecules in a hexagonal ring would allow <math>6^6 \times (1/2)^6 = 729</math> configurations. However, by explicit enumeration, there are actually 730 configurations. Now in the lattice, each oxygen atom participates in 12 hexagonal rings, so there are 2N rings in total for N oxygen atoms, or 2 rings for each oxygen atom, giving a refined result of <math>R\ln(1.5\times (730/729)^2) = R\ln(1.504)</math>.<ref>{{Cite journal |last=Hollins |first=G. T. |date=December 1964 |title=Configurational statistics and the dielectric constant of ice |url=https://dx.doi.org/10.1088/0370-1328/84/6/318 |journal=Proceedings of the Physical Society |language=en |volume=84 |issue=6 |pages=1001 |doi=10.1088/0370-1328/84/6/318 |issn=0370-1328}}</ref> |
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== Known phases == |
== Known phases == |
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<!-- Other articles link here. --> |
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These phases are named according to the [[Percy Williams Bridgman|Bridgman]] nomenclature. The majority have only been created in the laboratory at different temperatures and pressures.<ref>{{Cite web|last1=Flatz|first1=Christian|last2=Hohenwarter|first2=Stefan|title=Neue kristalline Eisform aus Innsbruck|url=https://www.uibk.ac.at/newsroom/neue-kristalline-eisform-aus-innsbruck.html.de|access-date=2021-02-18|website=Universität Innsbruck|language=de}}</ref> |
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{| class="wikitable" |
{| class="wikitable" |
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|- |
|- |
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! Phase |
! Phase |
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! Year of discovery |
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! Characteristics |
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! Temperature thresholds |
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! Pressure thresholds |
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! Density |
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! Crystal form |
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! Other characteristics |
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|- |
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| Ice I{{sub|h}} |
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| [[Amorphous ice]] |
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| NA (always known) |
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| [[Amorphous ice]] is ice lacking crystal structure. Amorphous ice exists in four forms: low-density (LDA) formed at atmospheric pressure, or below, medium-density (MDA), 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"). Recently, a medium-density amorphous form ("MDA") has been shown to exist, created by ball-milling ice I{{sub|h}} at low temperatures.<ref>{{Cite journal |last1=Rosu-Finsen |first1=Alexander |last2=Davies |first2=Michael B. |last3=Amon |first3=Alfred |last4=Wu |first4=Han |last5=Sella |first5=Andrea |last6=Michaelides |first6=Angelos |last7=Salzmann |first7=Christoph G. |date=2023-02-03 |title=Medium-density amorphous ice |url=https://www.science.org/doi/10.1126/science.abq2105 |journal=Science |language=en |volume=379 |issue=6631 |pages=474–478 |doi=10.1126/science.abq2105 |pmid=36730416 |bibcode=2023Sci...379..474R |s2cid=256504172 |issn=0036-8075}}</ref> |
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| {{cvt|0|C|F}} (freezing) |
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| NA (atmospheric) |
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| 0.917 g/cm<sup>3</sup> |
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| Hexagonal |
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| Virtually all ice in the [[biosphere]] is ice I{{sub|h}}, with the exception only of a small amount of ice I{{sub|c}}. Has a [[refractive index]] of 1.31. |
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|- |
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| |
| Ice I{{sub|c}} |
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| 1943 |
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| Normal hexagonal crystalline ice. Virtually all ice in the [[biosphere]] is ice I{{sub|h}}, with the exception only of a small amount of ice I{{sub|c}}. |
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| {{convert|130|and|220|K|C}} (formation)/{{convert|240|K|C}} (conversion to Ice I{{sub|h}})<ref>{{Cite journal |last1=Murray |first1=B.J. |last2=Bertram |first2=A. K. |year=2006 |title=Formation and stability of cubic ice in water droplets |url=https://open.library.ubc.ca/media/download/pdf/52383/1.0041852/3 |journal=Phys. Chem. Chem. Phys. |volume=8 |issue=1 |pages=186–192 |bibcode=2006PCCP....8..186M |doi=10.1039/b513480c |pmid=16482260 |hdl-access=free |hdl=2429/33770}}</ref><ref>{{cite journal |last=Murray |first=B.J. |year=2008 |title=The Enhanced formation of cubic ice in aqueous organic acid droplets |pages=025008 |journal=Env. Res. Lett. |volume=3 |doi=10.1088/1748-9326/3/2/025008|bibcode = 2008ERL.....3b5008M |issue=2 |doi-access=free }}</ref> |
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| NA (atmospheric) |
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| Similar to Ice Ih |
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| Diamond<ref name="DowellRinfret1960">{{Cite journal |last1=Dowell |first1=L. G. |last2=Rinfret |first2=A. P. |date=December 1960 |title=Low-Temperature Forms of Ice as Studied by X-Ray Diffraction |journal=Nature |language=en |volume=188 |issue=4757 |pages=1144–1148 |bibcode=1960Natur.188.1144D |doi=10.1038/1881144a0 |issn=0028-0836 |s2cid=4180631}}</ref> |
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| A metastable [[cubic crystal|cubic]] crystalline variant of ice. |
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|- |
|- |
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| Low-density amorphous ice (LDA) |
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| [[Ice Ic|Ice I{{sub|c}}]] |
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| |
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| A metastable [[cubic crystal|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,<ref>{{cite journal |last1=Murray |first1=Benjamin J. |last2=Bertram |first2=Allan K. |title=Formation and stability of cubic ice in water droplets |journal=Physical Chemistry Chemical Physics |date=2006 |volume=8 |issue=1 |pages=186–192 |doi=10.1039/b513480c |pmid=16482260 |bibcode=2006PCCP....8..186M |hdl=2429/33770 |hdl-access=free }}</ref><ref>{{cite journal|last=Murray |first=Benjamin J. |year=2008 |title=The Enhanced formation of cubic ice in aqueous organic acid droplets |journal=Environmental Research Letters |volume=3 |doi=10.1088/1748-9326/3/2/025008 |page=025008 |bibcode=2008ERL.....3b5008M |issue=2 |doi-access=free }}</ref> when it transforms into ice I{{sub|h}}. It may occasionally be present in the upper atmosphere.<ref>{{cite journal |last=Murray |first=Benjamin J.|author2=Knopf, Daniel A. |author3=Bertram, Allan K. |year=2005|title=The formation of cubic ice under conditions relevant to Earth's atmosphere|journal=Nature|volume=434|pages=202–205|doi=10.1038/nature03403|pmid=15758996|issue=7030|bibcode=2005Natur.434..202M|s2cid=4427815}}</ref> More recently, it has been shown that many samples which were described as cubic ice were actually stacking disordered ice with trigonal symmetry.<ref>{{cite journal |last1=Malkin |first1=Tamsin L. |last2=Murray |first2=Benjamin J. |last3=Salzmann |first3=Christoph G. |last4=Molinero |first4=Valeria |last5=Pickering |first5=Steven J. |last6=Whale |first6=Thomas F. |title=Stacking disorder in ice I |journal=Physical Chemistry Chemical Physics |date=2015 |volume=17 |issue=1 |pages=60–76 |doi=10.1039/c4cp02893g|pmid=25380218 |doi-access=free }}</ref> The first samples of ice I with cubic symmetry (i.e. cubic ice) were only reported in 2020.<ref>{{cite journal |last1=Salzmann |first1=Christoph G. |last2=Murray |first2=Benjamin J. |title=Ice goes fully cubic |journal=Nature Materials |date=June 2020 |volume=19 |issue=6 |pages=586–587 |doi=10.1038/s41563-020-0696-6|pmid=32461682 |bibcode=2020NatMa..19..586S |s2cid=218913209 }}</ref> |
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| |
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| NA (atmospheric or lower) |
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| 0.94 g/cm<sup>3</sup> <ref name="adsabs.harvard.edu" /> |
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| NA (amorphous) |
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| More [[viscous]] than normal water.<ref name="adsabs.harvard.edu">{{Cite journal|last1=Jenniskens |first1=Peter |last2=Blake |first2=David F. |year=1994 |title= Structural transitions in amorphous water ice and astrophysical implications |journal=Science |volume=265 |pages=753–6 | pmid = 11539186|issue=5173 |bibcode = 1994Sci...265..753J |doi=10.1126/science.11539186 |url= https://zenodo.org/record/1230888}}</ref><ref>{{cite journal|doi= 10.1086/178220|title= Crystallization of amorphous water ice in the solar system|author1=Jenniskens P. |author2=Blake D. F. |journal=Astrophysical Journal |volume=473|pages=1104–13|year= 1996 | pmid = 11539415 |bibcode=1996ApJ...473.1104J|issue= 2|s2cid= 33622340|doi-access=free}}</ref><ref>{{cite journal|pmid=11542399 | volume=107 | issue=4 |date=July 1997 | pages=1232–41 |author1=Jenniskens P. |author2=Banham S. F. |author3=Blake D. F. |author4=McCoustra M. R. |title=Liquid water in the domain of cubic crystalline ice Ic|journal=Journal of Chemical Physics|bibcode = 1997JChPh.107.1232J |doi = 10.1063/1.474468 }}</ref> |
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|- |
|- |
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| Medium-density amorphous ice (MDA) |
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| [[Ice II]] |
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| 2023<ref name="Nature2023">{{Cite journal |last1=Rosu-Finsen |first1=Alexander |last2=Davies |first2=Michael B. |last3=Amon |first3=Alfred |last4=Wu |first4=Han |last5=Sella |first5=Andrea |last6=Michaelides |first6=Angelos |last7=Salzmann |first7=Christoph G. |date=3 February 2023 |title=Medium-density amorphous ice |journal=Science |language=en |volume=379 |issue=6631 |pages=474–478 |doi=10.1126/science.abq2105 |pmid=36730416 |bibcode=2023Sci...379..474R |s2cid=256504172 |issn=0036-8075}}</ref><ref>{{cite news|author=|newspaper=Nature|title=Scientists made a new kind of ice that might exist on distant moons|url=https://www.nature.com/articles/d41586-023-00293-w |date=4 February 2023}}</ref> |
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| A [[rhombohedral]] crystalline form with highly ordered structure. Formed from ice I{{sub|h}} by compressing it at temperature of 190–210 K. When heated, it undergoes transformation to ice III. |
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| {{cvt|-200|C|F}} (freezing) |
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| NA (requires [[shear force]]) |
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| 1.06±0.06 g cm<sup>3</sup><ref name="SM-20230203">{{cite news |last=Sullivan |first=Will |title=Scientists Have Created a New Type of Ice - It looks like a white powder and has nearly the same density as liquid water |url=https://www.smithsonianmag.com/smart-news/scientists-have-created-a-new-type-of-ice-180981579/ |date=3 February 2023 |work=[[Smithsonian (magazine)|Smithsonian Magazine]] |accessdate=4 February 2023 }}</ref> |
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| NA (amorphous) |
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| Experimental procedure generates shear force by crushing ice into powder with centimeter-wide stainless-steel balls added to its container. |
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|- |
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| High-density amorphous ice (HDA) |
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| [[Ice III]] |
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| 1984<ref name="Nature 310, 393 1984" /> |
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| 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. |
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| <{{convert|140|K|C}} (normal formation); <{{convert|30|K|C}} (vapor deposition)<ref name="adsabs.harvard.edu"/><ref name="auto1">{{cite journal|doi=10.1086/176585|title= High-density amorphous ice, the frost on insterstellar grains|author1=Jenniskens P. |author2=Blake D. F. |author3=Wilson M. A. |author4=Pohorille A. |journal=Astrophysical Journal |volume=455|page=389|year=1995|bibcode=1995ApJ...455..389J|hdl= 2060/19980018148|s2cid= 122950585|hdl-access=free}}</ref> {{convert|77|K|C}} (stability point)<ref name="Nature 310, 393 1984">{{cite journal|author1=Mishima O. |author2=Calvert L. D. |author3=Whalley E. |journal= Nature |volume=310|pages=393–395 |year=1984|bibcode = 1984Natur.310..393M |doi = 10.1038/310393a0 |issue=5976|title='Melting ice' I at 77 K and 10 kbar: a new method of making amorphous solids|s2cid=4265281 }}</ref> |
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| At {{convert|77|K|C}}: 1.6 GPa (formation from Ih);<ref name="Nature 310, 393 1984" /> 0.5nbsp;GPa (formation from LDA)<ref>{{cite journal |last1=Mishima |first1=O. |title=An apparently 1st-order transition between two amorphous phases of ice induced by pressure|doi=10.1038/314076a0|journal=Nature |volume=314 |issue= 6006|year=1985 |pages=76–78 |last2=Calvert |first2=L. D. |last3=Whalley |first3=E.|bibcode = 1985Natur.314...76M |s2cid=4241205 }}</ref> |
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| 1.17 g/cm<sup>3</sup> (ambient pressure)<ref name="Nature 310, 393 1984" /> |
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| NA (amorphous) |
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| |
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| Very high-density amorphous ice (VHDA) |
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| [[Ice IV]] |
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| 1996<ref>{{cite journal|author=O.Mishima|journal=Nature |volume=384 |pages=546–549 |year=1996|doi=10.1038/384546a0|title=Relationship between melting and amorphization of ice|issue=6609|bibcode = 1996Natur.384..546M |s2cid=4274283 }}</ref> |
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| A metastable rhombohedral phase. It can be formed by heating [[high-density amorphous ice]] slowly at a pressure of 810 MPa. It does not form easily without a nucleating agent.<ref>{{cite web|url=https://water.lsbu.ac.uk/water/ice_iv.html|title=Ice-four (Ice IV)|access-date=27 May 2022|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=http://archive.wikiwix.com/cache/20110812002214/http://www.lsbu.ac.uk/water/ice_iv.html|archive-date=12 August 2011}}</ref> |
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| {{convert|160|K|C}} (formation from HDA); {{convert|77|K|C}} (stability point) |
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| 1 and 2 GPa (formation at {{convert|160|K|C}}); ambient (at {{convert|77|K|C}}) |
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| 1.26 g/cm<sup>3</sup> ({{convert|77|K|C}}; ambient pressure)<ref>{{cite journal|doi=10.1039/b108676f|title=A second distinct structural "state" of high-density amorphous ice at 77 K and 1 bar|year=2001|author1-link=Thomas Loerting|last1=Loerting|first1=Thomas|last2=Salzmann|first2=Christoph|last3=Kohl|first3=Ingrid|last4=Mayer|first4=Erwin|last5=Hallbrucker|first5=Andreas|s2cid=59485355|journal=Physical Chemistry Chemical Physics |volume=3 |pages=5355–5357 |issue=24 |bibcode=2001PCCP....3.5355L }}</ref> |
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| NA (amorphous) |
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| |
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|- |
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| |
| Ice II |
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| 1900<ref name="Hobbs">{{cite book |last=Hobbs |first=Peter V. |date=May 6, 2010 |title=Ice Physics |url=https://books.google.com/books?id=7Is6AwAAQBAJ&pg=PA61 |publisher=[[Oxford University Press]] |pages=61–70 |isbn=9780199587711 |access-date=December 6, 2014}}</ref> |
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| A [[monoclinic]] crystalline phase. Formed by cooling water to 253 K at 500 MPa. Most complicated structure of all the phases.<ref>{{cite web|url=http://www.lsbu.ac.uk/water/ice_v.html|title=Ice-five (Ice V)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=https://web.archive.org/web/20031012054327/http://www.lsbu.ac.uk/water/ice_v.html|archive-date=12 October 2003}}</ref> |
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| {{convert|190|K|C}}-{{convert|210|K|C}} (formation from ice I{{sub|h}}); {{convert|77|K|C}} (stability point)<ref name="Hobbs" /> |
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| 300 [[MPa]]<ref name="auto">{{cite web |url=http://www.lsbu.ac.uk/water/ice_ii.html |title=Ice-two structure |author=Chaplin, Martin |date=October 18, 2014 |work=Water Structure and Science |publisher=[[London South Bank University]] |access-date=December 6, 2014}}</ref> |
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| |
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| [[Rhombohedral]] |
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| |
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|- |
|- |
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| |
| Ice III |
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| 1900<ref name="Hobbs" /> |
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| A tetragonal crystalline phase. Formed by cooling water to 270 K at 1.1 GPa. Exhibits [[Debye relaxation]].<ref>{{cite web|url=http://www.lsbu.ac.uk/water/ice_vi.html|title=Ice-six (Ice VI)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=https://web.archive.org/web/20120923113355/http://www.lsbu.ac.uk/water/ice_vi.html|archive-date=23 September 2012}}</ref> |
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| {{cvt|250|K|C}} (formation from liquid water); {{convert|77|K|C}} (stability point)<ref name="Hobbs" /> |
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| 300 MPa (formation from liquid water)<ref name="auto"/> |
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| {{nowrap|1160 kg/m<sup>3</sup>}} (at 350 MPa)<ref>{{Cite web |date=2012-02-04 |title=Ice III (ice-three) structure |url=http://www.lsbu.ac.uk/water/ice_iii.html |access-date=2023-06-06 |archive-url=https://web.archive.org/web/20120204094529/http://www.lsbu.ac.uk/water/ice_iii.html |archive-date=2012-02-04 }}</ref> |
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| [[Tetragonal]] |
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| Very high relative [[permittivity]] at 117. A [[specific gravity]] of 1.16 with respect to water. |
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|- |
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| |
| Ice IV |
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| 1900<ref name="Hobbs"/> |
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| A cubic phase. The hydrogen atoms' positions are disordered. Exhibits Debye relaxation. The hydrogen bonds form two interpenetrating lattices. |
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| {{convert|190|K|C}}-{{convert|210|K|C}} (formation from HDA); {{convert|77|K|C}} (stability point) |
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| 810 MPa (formation from HDA) |
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| |
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| Rhombohedral |
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| Typically requires a nucleating agent to form.<ref>{{cite web|url=https://water.lsbu.ac.uk/water/ice_iv.html|title=Ice-four (Ice IV)|access-date=27 May 2022|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=http://archive.wikiwix.com/cache/20110812002214/http://www.lsbu.ac.uk/water/ice_iv.html|archive-date=12 August 2011}}</ref> |
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|- |
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|Ice |
| Ice V |
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| |
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|Forms at around 5 GPa, when Ice VII becomes tetragonal.<ref name="viit">{{cite journal |last1=Grande |first1=Zachary M. |display-authors=etal |title=Pressure-driven symmetry transitions in dense H2O ice |journal=APS Physics |year=2022 |volume=105 |issue=10 |page=104109 |doi=10.1103/PhysRevB.105.104109|bibcode=2022PhRvB.105j4109G |s2cid=247530544 }}</ref> |
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| {{convert|253|K|C}} (formation from liquid water) |
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| 500 MPa (formation from liquid water) <ref name="auto2">{{cite web|url=http://www.lsbu.ac.uk/water/ice_v.html|title=Ice-five (Ice V)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=https://web.archive.org/web/20031012054327/http://www.lsbu.ac.uk/water/ice_v.html|archive-date=12 October 2003}}</ref> |
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| 1.24 g cm<sup>3</sup> (at 350 MPa).<ref>{{Cite journal|last=Drost-Hansen|first=W.|date=1969-11-14|title=The Structure and Properties of Water. D. Eisenberg and W. Kauzmann. Oxford University Press, New York, 1969. xiv + 300 pp., illus. Cloth, $10; paper, $4.50|journal=Science|volume=166|issue=3907|pages=861|doi=10.1126/science.166.3907.861|issn=0036-8075}}</ref> |
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| [[Monoclinic]] |
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| Most complicated structure of all the phases. Includes 4-membered, 5-membered, 6-membered, and 8-membered rings and a total of 28 [[Molecule|molecules]] in the unit cell.<ref name=chaplin>{{cite web|title=Ice-five (Ice V)|url=http://www.lsbu.ac.uk/water/ice_v.html|last=Chaplin|first=Martin|date=20 December 2019|access-date=5 June 2021|archiveurl=https://web.archive.org/web/20200813070858/http://www1.lsbu.ac.uk/water/ice_v.html|archivedate=2020-08-13}}</ref><ref name=kamb1967>{{Cite journal | doi = 10.1107/S0365110X67001409| title = Structure of ice. V| journal = Acta Crystallographica| volume = 22| issue = 5| pages = 706| year = 1967| last1 = Kamb | first1 = B.| last2 = Prakash | first2 = A.| last3 = Knobler | first3 = C.| url = https://resolver.caltech.edu/CaltechAUTHORS:20160913-124848654}}</ref> |
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| Ice VI |
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| 1912<ref>[https://www.jstor.org/stable/20022754 ''Water, in the Liquid and Five Solid Forms, under Pressure''] P.W. Bridgman (1912), www.jstor.org, retrieved 3 October 2019</ref> |
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| A more ordered version of ice VII, where the hydrogen atoms assume fixed positions. It is formed from ice VII, by cooling it below {{convert|5|°C|K|abbr=on}} at 2.1 GPa. |
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| {{convert|270|K|C}} (formation from liquid water); {{convert|130|K|C}} - {{convert|355|K|C}} (stability range) |
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| 1.1 GPa (formation from liquid water) <ref name="auto2"/> |
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| 1.31 g/cm<sup>3</sup><ref>[https://www.science.org/doi/10.1126/science.150.3693.205 ''Reports: Structure of Ice VI''] science.sciencemag.org, B. Kamb, 8 October 1965.</ref> |
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| Tetragonal |
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| Exhibits [[Debye relaxation]].<ref>{{cite web|url=http://www.lsbu.ac.uk/water/ice_vi.html|title=Ice-six (Ice VI)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=https://web.archive.org/web/20120923113355/http://www.lsbu.ac.uk/water/ice_vi.html|archive-date=23 September 2012}}</ref> |
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| Ice VII |
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| 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/cm{{sup|3}}, slightly higher than ordinary ice. |
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| {{convert|270|K|C}} (formation from ice I{{sub|h}}) |
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| 1.1 GPa (formation from ice I{{sub|h}}); 5 GPa (formation of tetragonal structure)<ref name="viit">{{cite journal |last1=Grande |first1=Zachary M. |display-authors=etal |title=Pressure-driven symmetry transitions in dense H2O ice |journal=APS Physics |year=2022 |volume=105 |issue=10 |page=104109 |doi=10.1103/PhysRevB.105.104109|bibcode=2022PhRvB.105j4109G |s2cid=247530544 }}</ref> |
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| |
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| Cubic/tetragonal |
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| The hydrogen atoms' positions are disordered. Exhibits Debye relaxation. The hydrogen bonds form two interpenetrating lattices. Tetragonal form known as Ice VII{{sub|t}}. |
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| Ice VIII |
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| |
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| Proton-ordered symmetric ice. Forms at pressures around 70 GPa,<ref>{{cite web|url=http://www.lsbu.ac.uk/water/ice_vii.html|title=Ice-seven (Ice VII)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=http://archive.wikiwix.com/cache/20111102114345/http://www.lsbu.ac.uk/water/ice_vii.html|archive-date=2 November 2011}}</ref> or perhaps as low as 30 GPa.<ref name="viit"/> |
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| <{{convert|5|°C|K|abbr=on}} (formation from ice VII) |
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| 2.1 GPa (formation from ice VII) |
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| |
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| Cubic |
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| Hydrogen atoms assume fixed positions.<ref>{{cite web |url=http://www.lsbu.ac.uk/water/ice_viii.html |title=Ice-eight structure |access-date=January 2, 2008 |author=Chaplin, Martin |date=July 1, 2007 |work=Water Structure and Science}}</ref> |
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| Ice IX |
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| |
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| An [[orthorhombic]], low-temperature equilibrium form of hexagonal ice. It is [[ferroelectric]]. Ice XI is considered the most stable configuration of ice I{{sub|h}}.<ref>{{cite web|url=http://www.lsbu.ac.uk/water/ice_xi.html|title=Ice-eleven (ice XI)|access-date=11 March 2017|author=Chaplin, Martin|date=17 February 2017|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=https://web.archive.org/web/20170323123657/http://www1.lsbu.ac.uk/water/ice_xi.html|archive-date=23 March 2017}}</ref> |
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| {{convert|165|K|C}} (formation from ice III); <{{convert|140|K|C}} (stability point) |
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| 200 MPa-400 MPa (stability range) |
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| 1.16 g/cm{{sup|3}} |
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| Tetragonal |
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| Proton-ordered equivalent to Ice III.<ref>{{Cite journal |last=La Placa |first=Sam J. |last2=Hamilton |first2=Walter C. |last3=Kamb |first3=Barclay |last4=Prakash |first4=Anand |date=1973-01-15 |title=On a nearly proton‐ordered structure for ice IX |url=https://doi.org/10.1063/1.1679238 |journal=The Journal of Chemical Physics |volume=58 |issue=2 |pages=567–580 |doi=10.1063/1.1679238 |issn=0021-9606}}</ref> |
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| Ice X |
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| |
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| 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{{sup|−3}} at 127 K (i.e., approximately 1.3 times denser than water). |
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| {{convert|165|K|C}} (formation from ice III); <{{convert|140|K|C}} (stability point) |
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| 30-70 GPa (from ice VII)<ref name="auto4">{{cite web|url=http://www.lsbu.ac.uk/water/ice_vii.html|title=Ice-seven (Ice VII)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=http://archive.wikiwix.com/cache/20111102114345/http://www.lsbu.ac.uk/water/ice_vii.html|archive-date=2 November 2011}}</ref><ref name="viit"/> |
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| |
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| Cubic |
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| Has symmetrized hydrogen bonds - a hydrogen atom is found at the center of two oxygen atoms. |
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| |
| Ice XI |
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| |
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| A monoclinic crystalline phase. Formed by cooling water to below 130 K at 500 MPa. The proton-ordered form of ice V.<ref name="Ice XII">{{cite web|url=http://www.lsbu.ac.uk/water/ice_xii.html|title=Ice-twelve (Ice XII)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=http://archive.wikiwix.com/cache/20111102114347/http://www.lsbu.ac.uk/water/ice_xii.html|archive-date=2 November 2011}}</ref> |
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| {{convert|72|K|C}} (formation from ice I<sub>c</sub>) |
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| |
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| |
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| [[Orthorhombic]] |
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| [[Ferroelectric]]. The most stable configuration of ice I{{sub|h}}.<ref>{{cite web|url=http://www.lsbu.ac.uk/water/ice_xi.html|title=Ice-eleven (ice XI)|access-date=11 March 2017|author=Chaplin, Martin|date=17 February 2017|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=https://web.archive.org/web/20170323123657/http://www1.lsbu.ac.uk/water/ice_xi.html|archive-date=23 March 2017}}</ref> |
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| Ice XII |
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| 1996<ref>C. Lobban, J.L. Finney and W.F. Kuhs, The structure of a new phase of ice, Nature 391, 268–270, 1998</ref> |
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| An orthorhombic crystalline phase. Formed below 118 K at 1.2 GPa. The proton-ordered form of ice XII.<ref name="Ice XII"/> |
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| {{convert|260|K|°C °F|lk=in}} (formation from liquid water); {{convert|77|K}} (formation from ice I<sub>h</sub>); {{convert|183|K|C}} (formation from HDA ice) |
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| {{convert|0.55|GPa|lk=in|atm}} (formation from liquid water); 0.81-1.00 GPa/min (from ice I<sub>h</sub>); 810 MPa (formation from HDA ice) |
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| 1.3 g·cm{{sup|−3}} (at {{convert|127|K|C}}) |
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| Tetragonal |
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| Metastable. Observed in the phase space of ice V and ice VI. A topological mix of seven- and eight-membered rings, a 4-connected net (4-coordinate [[sphere]] packing)—the densest possible arrangement without [[hydrogen bond interpenetration]]. |
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| Ice XIII |
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| 2006<ref name="Salzmann2006">{{cite journal |last1=Salzmann |first1=Christoph G. |last2=Radaelli |first2=Paolo G. |last3=Hallbrucker |first3=Andreas |last4=Mayer |first4=Erwin |last5=Finney |first5=John L. |title=The Preparation and Structures of Hydrogen Ordered Phases of Ice |journal=Science |date=24 March 2006 |volume=311 |issue=5768 |pages=1758–1761 |doi=10.1126/science.1123896 |pmid=16556840 |bibcode=2006Sci...311.1758S |s2cid=44522271 }}</ref> |
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| {{convert|130|K|C}} (formation from liquid water) <ref name="Ice XII" /> |
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| 500 MPa (formation from liquid water)<ref name="Ice XII" /> |
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| |
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| Monoclinic |
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| The proton-ordered form of ice V.<ref name="Ice XII">{{cite web|url=http://www.lsbu.ac.uk/water/ice_xii.html|title=Ice-twelve (Ice XII)|access-date=30 July 2012|author=Chaplin, Martin|date=10 April 2012|work=Water Structure and Science|publisher=London South Bank University|url-status=live|archive-url=http://archive.wikiwix.com/cache/20111102114347/http://www.lsbu.ac.uk/water/ice_xii.html|archive-date=2 November 2011}}</ref> |
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|- |
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| Ice XIV |
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| 2006<ref name="Salzmann2006" /> |
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| <{{convert|118|K|C}} (formation from ice XII); <{{convert|140|K|C}} (stability point) |
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| 1.2GPa (formation from ice XII)<ref name="Ice XII"/> |
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| |
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| Orthorhombic |
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| The proton-ordered form of ice XII.<ref name="Ice XII"/> Formation requires [[HCl]] doping.<ref name="pmid16556840">{{cite journal| author=Salzmann CG, Radaelli PG, Hallbrucker A, Mayer E, Finney JL| title=The preparation and structures of hydrogen ordered phases of ice. | journal=Science | year= 2006 | volume= 311 | issue= 5768 | pages= 1758–61 | pmid=16556840 | doi=10.1126/science.1123896 | pmc= | bibcode=2006Sci...311.1758S | s2cid=44522271 | url=https://pubmed.ncbi.nlm.nih.gov/16556840 }}</ref> |
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|- |
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| Ice XV |
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| 2009<ref>{{cite magazine|url=http://www.sciencenews.org/view/generic/id/47258/title/A_very_special_snowball|title=A Very Special Snowball|author=Sanders, Laura|magazine=Science News|date=11 September 2009|access-date=11 September 2009|url-status=live|archive-url=https://web.archive.org/web/20090914174027/http://www.sciencenews.org/view/generic/id/47258/title/A_very_special_snowball|archive-date=14 September 2009}}</ref> |
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| {{convert|80|K|C}}- {{convert|108|K|C|abbr=off}} (formation from liquid water) |
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| 1.1GPa (formation from liquid water) |
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| |
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| |
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| A proton-ordered form of ice VI formed by cooling water to around 80–108 K at 1.1 GPa. |
| A proton-ordered form of ice VI formed by cooling water to around 80–108 K at 1.1 GPa. |
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| Ice XVI |
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| 2016{{r|cnr|discovery|lsbu|porousice|xvi}} |
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| The least dense crystalline form of water, topologically equivalent to the empty structure of sII [[clathrate hydrates]]. |
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| <{{convert|118|K|C}} (formation from ice III); <{{convert|140|K|C}} (stability point) |
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| 1.2GPa (from ice VII)<ref name="Ice XII"/> |
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| 0.81 g/cm{{sup|3}})<ref name="falenty2014">{{Cite journal | doi = 10.1038/nature14014| pmid = 25503235| title = Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate| journal = Nature| volume = 516| issue = 7530| pages = 231–233| year = 2014| last1 = Falenty | first1 = A. | last2 = Hansen | first2 = T. C. | last3 = Kuhs | first3 = W. F. | bibcode = 2014Natur.516..231F| s2cid = 4464711}}{{closed access}}</ref> |
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| |
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| The least dense crystalline form of water, topologically equivalent to the empty structure of sII [[clathrate hydrates]]. Transforms into the stacking-faulty ice I<sub>c</sub> and further into ordinary ice I<sub>h</sub> when above 145–147 K at positive pressures. Theoretical studies predict ice XVI to be thermodynamically stable at negative pressures (that is under [[tension (physics)|tension]]).<ref name="conde2009">{{cite journal|last1=Conde|first1=M.M.|last2=Vega|first2=C.|last3=Tribello|first3=G.A.|last4=Slater|first4=B.|title=The phase diagram of water at negative pressures: Virtual ices|journal=[[J. Chem. Phys.|The Journal of Chemical Physics]]|date=2009|volume=131|issue=34510|pages=034510|doi=10.1063/1.3182727|bibcode=2009JChPh.131c4510C|pmid=19624212}}{{closed access}}</ref><ref name="jacobson2009">{{cite journal|last1=Jacobson|first1=Liam C.|last2=Hujo|first2=Waldemar|last3=Molinero|first3=Valeria|title=Thermodynamic Stability and Growth of Guest-Free Clathrate Hydrates: A Low-Density Crystal Phase of Water|journal=[[J. Phys. Chem. B|Journal of Physical Chemistry B]]|date=2009|volume=113|issue=30|pages=10298–10307|doi=10.1021/jp903439a|pmid=19585976|doi-access=free}}{{closed access}}</ref> |
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|- |
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| Square ice |
| Square ice |
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| |
| 2014<ref name=Algara-Siller2015>{{cite journal |title=Square ice in graphene nanocapillaries |first1=G. |last1=Algara-Siller |first2=O. |last2=Lehtinen |first3=F. C. |last3=Wang |first4=R. R. |last4=Nair |first5= U. |last5=Kaiser |first6=H. A. |last6=Wu |first7=A. K. |last7=Geim |first8=I. V. |last8=Grigorieva |journal=Nature |volume=519 |issue=7544 |pages=443–445 |date=2015-03-26 |doi=10.1038/nature14295|pmid=25810206 |arxiv=1412.7498 |bibcode=2015Natur.519..443A |s2cid=4462633 }}</ref> |
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| Room temperature (in the presence of [[graphene]]) |
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| 10GPa <ref name=graphene>{{cite web |url=http://www.zmescience.com/science/chemistry/graphene-square-ice-0534534 |title=Sandwiching water between graphene makes square ice crystals at room temperature |date=2015-03-27 |work=ZME Science |access-date=2018-05-02}}</ref> |
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| |
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| Square |
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| Formation likely driven by the [[van der Waals force]], which allows [[water vapor]] and liquid water to pass through laminated sheets of [[graphene oxide]], unlike smaller molecules such as [[helium]].<ref name=graphene /> |
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| Ice XVII |
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| |
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| A porous hexagonal crystalline phase with helical channels, with density near that of ice XVI.{{r|xvii.discovery|xvii.lsbu|porousice}} Formed by placing hydrogen-filled ice in a vacuum and increasing the temperature until the hydrogen molecules escape.{{r|xvii.discovery}} |
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| <{{convert|118|K|C}} (formation from ice III); <{{convert|140|K|C}} (stability point) |
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| 1.2GPa (from ice III) |
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| Near that of ice XVI.{{r|xvii.discovery|xvii.lsbu|porousice}} |
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| Hexagonal |
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| A porous crystalline phase with helical channels, with density Formed by placing hydrogen-filled ice in a vacuum and increasing the temperature until the hydrogen molecules escape.{{r|xvii.discovery}} |
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| Ice XVIII |
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| |
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| <{{convert|118|K|C}} (formation from ice III); <{{convert|140|K|C}} (stability point) |
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| 1.2GPa (from ice VII)<ref name="Ice XII"/> |
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| |
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| A form of water also known as superionic water or superionic ice in which oxygen ions develop a crystalline structure while hydrogen ions move freely. |
| A form of water also known as superionic water or superionic ice in which oxygen ions develop a crystalline structure while hydrogen ions move freely. |
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| Ice XIX |
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| 2018<ref name="pmid29780552">{{cite journal |last1=Gasser|first1=TM|last2=Thoeny|first2=AV|last3= Plaga|first3= LJ|last4= Köster|first4= KW|last5= Etter|first5= M|last6= Böhmer|first6= R |display-authors=etal |year=2018 |title=Experiments indicating a second hydrogen ordered phase of ice VI. |journal=Chem Sci |volume=9 |issue=18 |pages=4224–4234 |doi=10.1039/c8sc00135a |pmc=5942039 |pmid=29780552}} </ref> |
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| Another phase related to ice VI formed by cooling water to around 100 K at approximately 2 GPa.<ref name="Metcalfe-2021" /> |
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| <{{convert|100|K|C}} (formation from ice VI{{sub|h}}); <ref name="Metcalfe-2021">{{cite news|last1=Metcalfe|first1=Tom|date=9 March 2021|title=Exotic crystals of 'ice 19' discovered|language=en|work=Live Science|url=https://www.livescience.com/exotic-ice-19-discovered.html}}</ref> |
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| 2GPa (formation from ice VI{{sub|h}})<ref name="Metcalfe-2021" /> |
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| |
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| |
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| Formation requires HCl doping.<ref name="pmid29780552" /><ref name="Metcalfe-2021" /><ref name="pmid33602936">{{cite journal |author=Yamane R, Komatsu K, Gouchi J, Uwatoko Y, Machida S, Hattori T, Kagi H |display-authors=etal |year=2021 |title=Experimental evidence for the existence of a second partially-ordered phase of ice VI. |journal=Nat Commun |volume=12 |issue=1 |pages=1129 |doi=10.1038/s41467-021-21351-9 |pmc=7893076 |pmid=33602936|bibcode=2021NatCo..12.1129Y }}</ref> |
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|} |
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== |
== History of research == |
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[[File:Ice III phase diagram.svg|thumb|Phase diagram of water, showing the region where ice III is stable.]] |
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[[image:Icecube-detail.jpg|thumb|Photograph showing details of an ice cube under magnification. Ice I<sub>h</sub> is the form of ice commonly seen on Earth.]] |
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=== Ice II === |
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[[image:Phase Space of Ice Ih.png|thumb|Phase space of ice I<sub>h</sub> with respect to other ice phases.]] |
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The properties of ice II were first described and recorded by [[Gustav Heinrich Johann Apollon Tammann]] in 1900 during his experiments with ice under high pressure and low temperatures. Having produced ice III, Tammann then tried condensing the ice at a temperature between {{convert|-70|and|-80|C|K F}} under {{convert|200|MPa|atm|abbr=on|comma=}} of pressure. Tammann noted that in this state ice II was denser than he had observed ice III to be. He also found that both types of ice can be kept at normal [[atmospheric pressure]] in a stable condition so long as the temperature is kept at that of [[liquid air]], which slows the change in conformation back to ice I<sub>h</sub>.<ref name="Hobbs"/> |
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Ice I<sub>h</sub> (hexagonal ice crystal) (pronounced: '''ice one h''', also known as '''ice-phase-one''') is the hexagonal crystal form of ordinary [[ice]], or frozen [[water (molecule)|water]].<ref>{{cite journal|url=http://atom.me.gatech.edu/zhut/Courses/Courses_HarvardCollection/caiwei/phasesofice.pdf|title=The Many Phases of Ice|author=Norman Anderson|publisher=Iowa State University|archive-url=https://web.archive.org/web/20091007073915/http://atom.me.gatech.edu/zhut/Courses/Courses_HarvardCollection/caiwei/phasesofice.pdf|archive-date=7 October 2009}}</ref> Virtually all ice in the [[biosphere]] is ice I<sub>h</sub>, with the exception only of a small amount of [[Ice Ic|ice I<sub>c</sub>]] that is occasionally present in the upper atmosphere. Ice I<sub>h</sub> exhibits many peculiar properties that are relevant to the existence of life and regulation of [[Climatology|global climate]]. For a description of these properties, see ''[[Ice]]'', which deals primarily with ice I<sub>h</sub>. |
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In later experiments by Bridgman in 1912, it was shown that the difference in volume between ice II and ice III was in the range of {{convert|0.0001|m3/kg|cuin/lb|abbr=on|comma=gaps}}. This difference hadn't been discovered by Tammann due to the small change and was why he had been unable to determine an [[Vapor–liquid equilibrium|equilibrium curve]] between the two. The curve showed that the structural change from ice III to ice II was more likely to happen if the medium had previously been in the structural conformation of ice II. However, if a sample of ice III that had never been in the ice II state was obtained, it could be supercooled even below −70 °C without it changing into ice II. Conversely, however, any superheating of ice II was not possible in regards to retaining the same form. Bridgman found that the equilibrium curve between ice II and ice IV was much the same as with ice III, having the same stability properties and small volume change. The curve between ice II and ice V was extremely different, however, with the curve's bubble being essentially a straight line and the volume difference being almost always {{convert|0.0000545|m3/kg|cuin/lb|abbr=on|comma=gaps}}.<ref name="Hobbs"/> |
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The crystal structure is characterized by the oxygen atoms forming [[Hexagonal crystal family|hexagonal symmetry]] with near [[tetrahedral]] bonding angles. Ice I<sub>h</sub> is stable down to {{convert|-268|C|K F|0}}, as evidenced by x-ray diffraction<ref name=Rottger>{{cite journal|first1=K. |last1=Rottger |first2=A. |last2=Endriss |first3=J. |last3=Ihringer |first4=S. |last4=Doyle |first5=W. F. |last5=Kuhs|title=Lattice Constants and Thermal Expansion of H<sub>2</sub>O and D<sub>2</sub>O Ice I<sub>h</sub> Between 10 and 265 K |journal=Acta Crystallogr. |year=1994 |volume= B50 |issue=6 |pages=644–648 |doi=10.1107/S0108768194004933}}</ref> and extremely high resolution thermal expansion measurements.<ref name=Buckingham>{{cite journal|author=David T. W. Buckingham, J. J. Neumeier, S. H. Masunaga, and Yi-Kuo Yu|title=Thermal Expansion of Single-Crystal H<sub>2</sub>O and D<sub>2</sub>O Ice Ih|journal=Physical Review Letters |year=2018 |volume=121 |issue=18|pages=185505 |doi=10.1103/PhysRevLett.121.185505 |pmid=30444387|bibcode=2018PhRvL.121r5505B|doi-access=free}}</ref> Ice I<sub>h</sub> is also stable under applied pressures of up to about {{convert|210|MPa|atm}} where it transitions into [[ice III]] or [[ice II]].<ref>{{cite journal|author=P. W. Bridgman|title=Water, in the Liquid and Five Solid Forms, under Pressure |journal=Proceedings of the American Academy of Arts and Sciences |year=1912 |volume=47 |issue=13 |pages=441–558 |doi=10.2307/20022754 |jstor=20022754 }}</ref> |
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==== Search for a hydrogen-disordered counterpart ==== |
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==Physical properties== |
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The density of ice I<sub>h</sub> is 0.917 g/cm<sup>3</sup> which is less than that of [[Properties of water|liquid water]]. This is attributed to the presence of [[hydrogen bonds]] which causes atoms to become closer in the liquid phase.<ref>{{cite book|url=https://books.google.com/books?id=BV6cAQAAQBAJ&pg=PA144 |first=Peter |last=Atkins |first2=Julio |last2=de Paula |page=144 |title=Physical chemistry.|date=2010|publisher=W. H. Freeman and Co.|location=New York|isbn=978-1429218122|edition=9th}}</ref> Because of this, ice I<sub>h</sub> floats on water, which is highly unusual when compared to other materials. The solid phase of materials is usually more closely and neatly packed and has a higher density than the liquid phase. When lakes freeze, they do so only at the surface while the bottom of the lake remains near {{convert|4|C|K F|0}} because water is densest at this temperature. No matter how cold the surface becomes, there is always a layer at the bottom of the lake that is {{convert|4|C|K F|0}}. This anomalous behavior of water and ice is what allows fish to survive harsh winters. The density of ice I<sub>h</sub> increases when cooled, down to about {{convert|-211|C|K F|0}}; below that temperature, the ice expands again ([[negative thermal expansion]]).<ref name=Rottger /><ref name=Buckingham /> |
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As ice II is completely hydrogen ordered, the presence of its disordered counterpart is a great matter of interest. Shephard et al.<ref>{{Citation | vauthors=((Shephard, J. J.)), ((Slater, B.)), ((Harvey, P.)), ((Hart, M.)), ((Bull, C. L.)), ((Bramwell, S. T.)), ((Salzmann, C. G.)) | year=2018 | title=Doping-induced disappearance of ice II from water's phase diagram | journal=Nature Physics | volume=14 | issue=6 | pages=569–572 | publisher=Springer Science and Business Media LLC | doi=10.1038/s41567-018-0094-z | bibcode=2018NatPh..14..569S | s2cid=54544973 | url=http://dx.doi.org/10.1038/s41567-018-0094-z}}</ref> investigated the phase boundaries of NH<sub>4</sub>F-doped ices because NH<sub>4</sub>F has been reported to be a hydrogen disordering reagent. However, adding 2.5 mol% of NH<sub>4</sub>F resulted in the disappearance of ice II instead of the formation of a disordered ice II. According to the DFC calculation by Nakamura et al.,<ref>{{Citation | vauthors=((Nakamura, T.)), ((Matsumoto, M.)), ((Yagasaki, T.)), ((Tanaka, H.)) | year=2015 | title=Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy | journal=The Journal of Physical Chemistry B | volume=120 | issue=8 | pages=1843–1848 | publisher=American Chemical Society (ACS) | doi=10.1021/acs.jpcb.5b09544 | pmid=26595233 | url=http://dx.doi.org/10.1021/acs.jpcb.5b09544}}</ref> the phase boundary between ice II and its disordered counterpart is estimated to be in the stability region of liquid water. |
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The latent [[heat of melting]] is {{val|5987|u=J|up=mol}}, and its latent [[heat of sublimation]] is {{val|50911|u=J|up=mol}}. The high latent heat of sublimation is principally indicative of the strength of the [[hydrogen bond]]s in the crystal lattice. The latent heat of melting is much smaller, partly because liquid water near 0 °C also contains a significant number of hydrogen bonds. The refractive index of ice I<sub>h</sub> is 1.31. |
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== |
=== Ice IV === |
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1981 research by Engelhardt and Kamb elucidated crystal structure of ice IV through a low-temperature single-crystal X-ray diffraction, describing it as a rhombohedral unit cell with a space group of R-3c.<ref>{{Citation | vauthors=((Engelhardt, H.)), ((Kamb, B.)) | year=1981 | title=Structure of ice IV, a metastable high‐pressure phase | journal=The Journal of Chemical Physics | volume=75 | issue=12 | pages=5887–5899 | publisher=AIP Publishing | doi=10.1063/1.442040 | url=http://dx.doi.org/10.1063/1.442040}}</ref> This research mentioned that the structure of ice IV could be derived from the structure of ice Ic by cutting and forming some hydrogen bondings and adding subtle structural distortions. Shephard et al.<ref>{{Citation | vauthors=((Shephard, J. J.)), ((Ling, S.)), ((Sosso, G. C.)), ((Michaelides, A.)), ((Slater, B.)), ((Salzmann, C. G.)) | year=2017 | title=Is High-Density Amorphous Ice Simply a "Derailed" State along the Ice I to Ice IV Pathway? | journal=The Journal of Physical Chemistry Letters | volume=8 | issue=7 | pages=1645–1650 | publisher=American Chemical Society (ACS) | doi=10.1021/acs.jpclett.7b00492 | pmid=28323429 | s2cid=13662778 | url=http://dx.doi.org/10.1021/acs.jpclett.7b00492| arxiv=1701.05398 }}</ref> compressed the ambient phase of NH<sub>4</sub>F, an isostructural material of ice, to obtain NH<sub>4</sub>F II, whose hydrogen-bonded network is similar to ice IV. As the compression of ice Ih results in the formation of high-density amorphous ice (HDA), not ice IV, they claimed that the compression-induced conversion of ice I into ice IV is important, naming it "Engelhardt–Kamb collapse" (EKC). They suggested that the reason why we cannot obtain ice IV directly from ice Ih is that ice Ih is hydrogen-disordered; if oxygen atoms are arranged in the ice IV structure, hydrogen bonding may not be formed due to the donor-acceptor mismatch.<ref>{{Citation | vauthors=((Engelhardt, H.)), ((Whalley, E.)) | year=1979 | title=The infrared spectrum of ice IV in the range 4000–400 cm−1 | journal=The Journal of Chemical Physics | volume=71 | issue=10 | pages=4050–4051 | publisher=AIP Publishing | doi=10.1063/1.438173 | url=http://dx.doi.org/10.1063/1.438173}}</ref> and Raman <ref>{{Citation | vauthors=((Salzmann, C. G.)), ((Kohl, I.)), ((Loerting, T.)), ((Mayer, E.)), ((Hallbrucker, A.)) | year=2003 | title=Raman Spectroscopic Study on Hydrogen Bonding in Recovered Ice IV | journal=The Journal of Physical Chemistry B | volume=107 | issue=12 | pages=2802–2807 | publisher=American Chemical Society (ACS) | doi=10.1021/jp021534k | url=http://dx.doi.org/10.1021/jp021534k}}</ref> |
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[[Image:cryst struct ice.png|thumb|250px|Crystal structure of ice I<sub>h</sub>. Dashed lines represent hydrogen bonds]] |
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The accepted [[crystal structure]] of ordinary ice was first proposed by [[Linus Pauling]] in 1935. The structure of ice I<sub>h</sub> is the [[Wurtzite (crystal structure)|wurtzite lattice]], roughly one of crinkled planes composed of [[tessellation|tessellating]] hexagonal rings, with an [[oxygen]] atom on each vertex, and the edges of the rings formed by [[hydrogen bond]]s. The planes alternate in an ABAB pattern, with B planes being reflections of the A planes along the same axes as the planes themselves.<ref name=bjerrum>{{cite journal|last=Bjerrum|first=N|title=Structure and Properties of Ice|journal=Science|date=11 April 1952|volume=115|issue=2989|pages=385–390|doi=10.1126/science.115.2989.385|pmid=17741864|bibcode = 1952Sci...115..385B }}</ref> The distance between oxygen atoms along each bond is about 275 [[picometre|pm]] and is the same between any two bonded oxygen atoms in the lattice. The angle between bonds in the crystal lattice is very close to the [[tetrahedral angle]] of 109.5°, which is also quite close to the angle between hydrogen atoms in the water molecule (in the gas phase), which is 105°. This tetrahedral bonding angle of the water molecule essentially accounts for the unusually low density of the crystal lattice – it is beneficial for the lattice to be arranged with tetrahedral angles even though there is an energy penalty in the increased volume of the crystal lattice. As a result, the large hexagonal rings leave almost enough room for another water molecule to exist inside. This gives naturally occurring ice its rare property of being less dense than its liquid form. The tetrahedral-angled hydrogen-bonded hexagonal rings are also the mechanism that causes liquid water to be densest at 4 °C. Close to 0 °C, tiny hexagonal ice I<sub>h</sub>-like lattices form in liquid water, with greater frequency closer to 0 °C. This effect decreases the density of the water, causing it to be densest at 4 °C when the structures form infrequently. |
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The disordered nature of Ice IV was confirmed by neutron powder diffraction studies by Lobban (1998) <ref>{{Citation | vauthors=((Colin Lobban)) | year=1998 | title=Neutron diffraction studies of ices | publisher=University College London | url=https://www.proquest.com/docview/1752797359| id={{ProQuest|1752797359}} }}</ref> and Klotz et al. (2003).<ref>{{Citation | vauthors=((Klotz, S.)), ((Hamel, G.)), ((Loveday, J. S.)), ((Nelmes, R. J.)), ((Guthrie, M.)) | year=2003 | title=Recrystallisation of HDA ice under pressure by in-situ neutron diffraction to 3.9 GPa | journal=Zeitschrift für Kristallographie - Crystalline Materials | volume=218 | issue=2 | pages=117–122 | publisher=Walter de Gruyter GmbH | doi=10.1524/zkri.218.2.117.20669 | s2cid=96109290 | url=http://dx.doi.org/10.1524/zkri.218.2.117.20669}}</ref> In addition, the entropy difference between ice VI (disordered phase) and ice IV is very small, according to Bridgman's measurement.<ref>{{Citation | vauthors=((Bridgman, P. W.)) | year=1935 | title=The Pressure‐Volume‐Temperature Relations of the Liquid, and the Phase Diagram of Heavy Water | journal=The Journal of Chemical Physics | volume=3 | issue=10 | pages=597–605 | publisher=AIP Publishing | doi=10.1063/1.1749561 | url=http://dx.doi.org/10.1063/1.1749561}}</ref> |
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==Hydrogen disorder== |
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{{see also|Ice rules|Geometrical frustration#Water ice}}{{anchor|proton disorder}} |
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[[File:Wurtzite-boat-chair.png|thumb|The Wurtzite structure. In Ice I<sub>h</sub>, the oxygen atoms are arranged on the lattice points, and the hydrogen atoms are on the bonds between lattice points. Each oxygen atom has 4 neighboring ones. Note that the lattice bipartites into two subsets, here colored black and white.]] |
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The [[hydrogen]] atoms in the crystal lattice lie very nearly along the hydrogen bonds, and in such a way that each water molecule is preserved. This means that each oxygen atom in the lattice has two hydrogens adjacent to it, at about 101 pm along the 275 pm length of the bond. The crystal lattice allows a substantial amount of disorder in the positions of the hydrogen atoms frozen into the structure as it cools to absolute zero. As a result, the crystal structure contains some [[residual entropy]] inherent to the lattice and determined by the number of possible configurations of hydrogen positions that can be formed while still maintaining the requirement for each oxygen atom to have only two hydrogens in closest proximity, and each H-bond joining two oxygen atoms having only one hydrogen atom.<ref name=bernal>{{cite journal|last1=Bernal|first1=J. D.|last2=Fowler |first2=R. H.|title=A Theory of Water and Ionic Solution, with Particular Reference to Hydrogen and Hydroxyl Ions|journal=The Journal of Chemical Physics|date=1 January 1933|volume=1|issue=8|pages=515|doi=10.1063/1.1749327|bibcode=1933JChPh...1..515B}}</ref> This residual entropy {{math|{{var|S}}{{sub|0}}}} is equal to 3.4±0.1 J mol<sup>−1</sup> K<sup>−1</sup> <math>=R\ln(1.50 \pm 0.02)</math>.<ref>{{Cite journal |last=Berg |first=Bernd A. |last2=Muguruma |first2=Chizuru |last3=Okamoto |first3=Yuko |date=2007-03-21 |title=Residual entropy of ordinary ice from multicanonical simulations |url=https://link.aps.org/doi/10.1103/PhysRevB.75.092202 |journal=Physical Review B |language=en |volume=75 |issue=9 |doi=10.1103/PhysRevB.75.092202 |issn=1098-0121|arxiv=cond-mat/0609211 }}</ref> |
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Several organic nucleating reagents had been proposed to selectively crystallize ice IV from liquid water,<ref>{{Citation | vauthors=((Evans, L. F.)) | year=1967 | title=Selective Nucleation of the High‐Pressure Ices | journal=Journal of Applied Physics | volume=38 | issue=12 | pages=4930–4932 | publisher=AIP Publishing | doi=10.1063/1.1709255 | url=http://dx.doi.org/10.1063/1.1709255}}</ref> but even with such reagents, the crystallization of ice IV from liquid water was very difficult and seemed to be a random event. In 2001, Salzmann and his coworkers reported a whole new method to prepare ice IV ''reproducibly'';<ref>{{Citation | vauthors=((Salzmann, C. G.)), ((Loerting, T.)), ((Kohl, I.)), ((Mayer, E.)), ((Hallbrucker, A.)) |author2-link=Thomas Loerting| year=2002 | title=Pure Ice IV from High-Density Amorphous Ice |journal=The Journal of Physical Chemistry B |volume=106 |issue=22 |pages=5587–5590 | publisher=American Chemical Society (ACS) |doi=10.1021/jp014391v | url=http://dx.doi.org/10.1021/jp014391v}}</ref> when [[High density amorphous ice|high-density amorphous ice (HDA)]] is heated at a rate of 0.4 K/min and a pressure of 0.81 GPa, ice IV is crystallized at about 165 K. What governs the crystallization products is the heating rate; fast heating (over 10 K/min) results in the formation of single-phase ice XII. |
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By contrast, the structure of [[ice II]] is hydrogen-ordered, which helps to explain the entropy change of 3.22 J/mol when the crystal structure changes to that of ice I. Also, [[ice XI]], an orthorhombic, hydrogen-ordered form of ice I<sub>h</sub>, is considered the most stable form at low temperatures. |
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==== Search for a hydrogen-ordered counterpart ==== |
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=== Theoretical calculation === |
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The ordered counterpart of ice IV has never been reported yet. 2011 research by Salzmann's group reported more detailed DSC data where the endothermic feature becomes larger as the sample is quench-recovered at higher pressure. They proposed three scenarios to explain the experimental results: weak hydrogen-ordering, orientational glass transition, and mechanical distortions.<ref name="pmid21946782">{{citation| last1=Salzmann|first1= CG|last2= Radaelli|first2= PG|last3= Slater|first3= B|last4= Finney|first4= JL| title=The polymorphism of ice: five unresolved questions. | journal=Phys Chem Chem Phys | year= 2011 | volume= 13 | issue= 41 | pages= 18468–80 | pmid=21946782 | doi=10.1039/c1cp21712g | pmc= | url=https://pubmed.ncbi.nlm.nih.gov/21946782 }}</ref> reported the DSC thermograms of HCl-doped ice IV finding an endothermic feature at about 120 K. Ten years later, Rosu-Finsen and Salzmann (2021) reported more detailed DSC data where the endothermic feature becomes larger as the sample is quench-recovered at higher pressure. They proposed three scenarios to explain the experimental results: weak hydrogen-ordering, orientational glass transition, and mechanical distortions.<ref>{{Citation | vauthors=((Rosu-Finsen, A.)), ((Salzmann, C. G.)) | year=2022 | title=Is pressure the key to hydrogen ordering ice IV? | journal=Chemical Physics Letters | volume=789 | page=139325 | publisher=Elsevier BV | doi=10.1016/j.cplett.2021.139325 | s2cid=245597764 | url=http://dx.doi.org/10.1016/j.cplett.2021.139325}} |
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There are various ways of approximating this number from first principles. The following is the one used by [[Linus Pauling]].<ref>{{cite journal |last=Pauling |first=Linus |author-link=Linus Pauling |date=1 December 1935 |title=The Structure and Entropy of Ice and of Other Crystals with Some Randomness of Atomic Arrangement |journal=Journal of the American Chemical Society |volume=57 |issue=12 |pages=2680–2684 |doi=10.1021/ja01315a102}}</ref><ref>{{Cite book |last=Petrenko |first=Victor F. |url=http://www.oxfordscholarship.com/view/10.1093/acprof:oso/9780198518945.001.0001/acprof-9780198518945 |title=Physics of Ice |last2=Whitworth |first2=Robert W. |date=2002-01-17 |publisher=Oxford University Press |isbn=978-0-19-851894-5 |chapter=2. Ice Ih |doi=10.1093/acprof:oso/9780198518945.003.0002}}</ref> |
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</ref> |
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=== Ice XI === |
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Suppose there are a given number {{mvar|N}} of water molecules in an ice lattice. To compute its residual entropy, we need to count the number of configurations that the lattice can assume. The oxygen atoms are fixed at the lattice points, but the hydrogen atoms are located on the lattice edges. The problem is to pick one end of each lattice edge for the hydrogen to bond to, in a way that still makes sure each oxygen atom is bond to two hydrogen atoms. |
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[[File:Ice XI View along c axis.png|thumb|250px|Crystal structure of Ice XI viewed along the c-axis]] |
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[[File:Ice XI side view.png|thumb|250px|Crystal structure of ice XI (c-axis in the vertical direction)]] |
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Ice XI is the hydrogen-ordered form of the ordinary form of ice. The total [[internal energy]] of ice XI is about one sixth lower than ice I<sub>h</sub>, so in principle it should naturally form when ice I<sub>h</sub> is cooled to below 72 [[Kelvin|K]]. The low temperature required to achieve this transition is correlated with the relatively low energy difference between the two structures.<ref>{{cite journal|last1=Fan|first1=Xiaofeng|last2=Bing|first2=Dan|last3=Zhang|first3=Jingyun|last4=Shen|first4=Zexiang|last5=Kuo|first5=Jer-Lai|title=Predicting the hydrogen bond ordered structures of ice I<sub>h</sub>, II, III, VI and ice VII: DFT methods with localized based set|journal=Computational Materials Science|date=1 October 2010|volume=49|issue=4|pages=S170–S175|doi=10.1016/j.commatsci.2010.04.004|url=http://jlk.iams.sinica.edu.tw/paper/2010/ComMateSci49S170.pdf|access-date=24 April 2012|archive-url=https://web.archive.org/web/20140714192340/http://jlk.iams.sinica.edu.tw/paper/2010/ComMateSci49S170.pdf|archive-date=14 July 2014|url-status=dead}}</ref> Hints of hydrogen-ordering in ice had been observed as early as 1964, when Dengel et al. attributed a peak in thermo-stimulated depolarization (TSD) current to the existence of a proton-ordered ferroelectric phase.<ref>{{cite journal|last1=Dengel|first1=O.|last2=Eckener|first2=U.|last3=Plitz |first3=H. |last4=Riehl|first4= N.|title=Ferroelectric behavior of ice|journal=Physics Letters|date=1 May 1964|volume=9|issue=4|pages=291–292|doi=10.1016/0031-9163(64)90366-X|bibcode = 1964PhL.....9..291D }}</ref> However, they could not conclusively prove that a phase transition had taken place, and Onsager pointed out that the peak could also arise from the movement of defects and lattice imperfections. Onsager suggested that experimentalists look for a dramatic change in heat capacity by performing a careful calorimetric experiment. A phase transition to ice XI was first identified experimentally in 1972 by Shuji Kawada and others.<ref>{{cite journal|last=Kawada|first=Shuji|title=Dielectric Dispersion and Phase Transition of KOH Doped Ice|journal=Journal of the Physical Society of Japan|date=1 May 1972|volume=32|issue=5|pages=1442|doi=10.1143/JPSJ.32.1442|bibcode = 1972JPSJ...32.1442K }}</ref><ref>{{cite journal|last1=Tajima|first1=Yoshimitsu|last2=Matsuo|first2= Takasuke|last3= Suga|first3= Hiroshi|title=Calorimetric study of phase transition in hexagonal ice doped with alkali hydroxides|journal=Journal of Physics and Chemistry of Solids|year=1984|volume=45|issue=11–12|pages=1135–1144|doi=10.1016/0022-3697(84)90008-8|bibcode = 1984JPCS...45.1135T }}</ref><ref>{{cite journal|last1=Matsuo|first1=Takasuke|last2=Tajima|first2= Yoshimitsu|last3=Suga|first3=Hiroshi|title=Calorimetric study of a phase transition in D<sub>2</sub>O ice I<sub>h</sub> doped with KOD: Ice XI|journal=Journal of Physics and Chemistry of Solids|year=1986|volume=47 |issue=2|pages=165–173 |doi=10.1016/0022-3697(86)90126-5|bibcode = 1986JPCS...47..165M }}</ref> |
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Water molecules in ice I<sub>h</sub> are surrounded by four semi-randomly directed [[hydrogen]] bonds. Such arrangements should change to the more ordered arrangement of hydrogen bonds found in ice XI at low temperatures, so long as localized proton hopping is sufficiently enabled; a process that becomes easier with increasing pressure.<ref>{{cite journal|last1=Castro Neto|first1=A.|last2=Pujol|first2= P. |last3=Fradkin|first3= E.|title=Ice: A strongly correlated proton system|journal=Physical Review B|year=2006|volume=74|issue=2|doi=10.1103/PhysRevB.74.024302|arxiv=cond-mat/0511092|page=024302|bibcode = 2006PhRvB..74b4302C |s2cid=102581583}}</ref> Correspondingly, ice XI is believed to have a [[triple point]] with hexagonal ice and gaseous water at (~72 K, ~0 Pa). Ice I<sub>h</sub> that has been transformed to ice XI and then back to ice I<sub>h</sub>, on raising the temperature, retains some hydrogen-ordered domains and more easily transforms back to ice XI again.<ref>{{cite journal |doi=10.1016/j.molstruc.2010.02.016 |title=Annealing effects on hydrogen ordering in KOD-doped ice observed using neutron diffraction |journal=Journal of Molecular Structure |volume=972 |issue=1–3 |pages=111–114 |year=2010 |last1=Arakawa |first1=Masashi |last2=Kagi |first2=Hiroyuki |last3=Fukazawa |first3=Hiroshi |bibcode=2010JMoSt.972..111A }}</ref> A neutron powder diffraction study found that small hydrogen-ordered domains can exist up to 111 K.<ref name=astro-ordering>{{cite journal|last=Arakawa|first=Masashi|author2=Kagi, Hiroyuki|author3=Fernandez-Baca, Jaime A.|author4=Chakoumakos, Bryan C.|author5=Fukazawa, Hiroshi|title=The existence of memory effect on hydrogen ordering in ice: The effect makes ice attractive|journal=Geophysical Research Letters|date=17 August 2011|volume=38|issue=16|pages=n/a|doi=10.1029/2011GL048217|bibcode=2011GeoRL..3816101A|doi-access=free}}</ref> |
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The oxygen atoms can be divided into two sets in a checkerboard pattern, shown in the picture as black and white balls. Focus attention on the oxygen atoms in one set: there are {{math|{{var|N}}/2}} of them. Each has four hydrogen bonds, with two hydrogens close to it and two far away. This means there are <math display="inline">\tbinom 4 2 = 6</math> allowed configurations of hydrogens for this oxygen atom (see [[Binomial coefficient]]). Thus, there are {{math|6{{sup|{{var|N}}/2}}}} configurations that satisfy these {{math|{{var|N}}/2}} atoms. But now, consider the remaining {{math|{{var|N}}/2}} oxygen atoms: in general they won't be satisfied (i.e., they will not have precisely two hydrogen atoms near them). For each of those, there are {{math|2{{sup|4}} {{=}} 16}} possible placements of the hydrogen atoms along their hydrogen bonds, of which 6 are allowed. So, naively, we would expect the total number of configurations to be |
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There are distinct differences in the Raman spectra between ices I<sub>h</sub> and XI, with ice XI showing much stronger peaks in the translational (~230 cm<sup>−1</sup>), librational (~630 cm<sup>−1</sup>) and in-phase asymmetric stretch (~3200 cm<sup>−1</sup>) regions.<ref>K. Abe, Y. Ootake and T. Shigenari, ''Raman scattering study of proton ordered ice XI single crystal'', in Physics and Chemistry of Ice, ed. W. Kuhs (Royal Society of Chemistry, Cambridge, 2007) pp 101–108</ref><ref>{{cite journal | last1 = Abe | first1 = K. | last2 = Shigenari | first2 = T. | year = 2011 | title = Raman spectra of proton ordered phase XI of ICE I. Translational vibrations below 350 cm-1, J | journal = The Journal of Chemical Physics | volume = 134 | issue = 10| page = 104506 | doi=10.1063/1.3551620| pmid = 21405174 | bibcode = 2011JChPh.134j4506A }}</ref> |
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<math display="block">6^{N/2} (6/16)^{N/2} = (3/2)^N .</math> |
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Ice I<sub>c</sub> also has a proton-ordered form. The total internal energy of ice XI<sub>c</sub> was predicted as similar as ice XI<sub>h</sub>.<ref>{{cite journal|last1=Raza|first1=Zamaan|last2=Alfè|first2=Dario|title=Proton ordering in cubic ice and hexagonal ice; a potential new ice phase--XIc.|journal=Physical Chemistry Chemical Physics|date=28 Nov 2011|volume=13|issue=44|pages=19788–95|doi=10.1039/c1cp22506e|pmid=22009223|bibcode = 2011PCCP...1319788R|s2cid=31673433}}</ref> |
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Using [[Boltzmann's entropy formula]], we conclude that |
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====Ferroelectric properties==== |
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<math display="block">S_0 = k\ln(3/2)^N = n R \ln(3/2),</math>where {{mvar|k}} is the [[Boltzmann constant]] and R is the [[molar gas constant]]. So, the molar residual entropy is <math>R \ln(3/2) = 3.37 \mathrm{J}\cdot\mathrm{mol}^{-1}\mathrm{K}^{-1}</math>. |
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Ice XI is [[ferroelectric]], meaning that it has an intrinsic polarization. To qualify as a ferroelectric it must also exhibit polarization switching under an electric field, which has not been conclusively demonstrated but which is implicitly assumed to be possible.<ref>{{cite journal|last=Bramwell|first=Steven T.|journal=Nature|date=21 January 1999|title=Ferroelectric ice|volume=397|issue=6716|pages=212–213|doi=10.1038/16594|bibcode = 1999Natur.397..212B |s2cid=204990667|doi-access=free}}</ref> [[Cubic ice]] also has a ferrolectric phase and in this case the ferroelectric properties of the ice have been experimentally demonstrated on monolayer thin films.<ref>{{cite journal|last=Iedema|first=M. J.|author2=Dresser, M. J. |author3=Doering, D. L. |author4=Rowland, J. B. |author5=Hess, W. P. |author6=Tsekouras, A. A. |author7=Cowin, J. P. |title=Ferroelectricity in Water Ice|journal=The Journal of Physical Chemistry B|date=1 November 1998|volume=102|issue=46|pages=9203–9214|doi=10.1021/jp982549e|s2cid=97894870}}</ref> In a similar experiment, ferroelectric layers of hexagonal ice were grown on a platinum (111) surface. The material had a polarization that had a decay length of 30 monolayers suggesting that thin layers of ice XI can be grown on substrates at low temperature without the use of dopants.<ref>{{cite journal|last=Su|first=Xingcai|author2=Lianos, L. |author3=Shen, Y. |author4= Somorjai, Gabor |title=Surface-Induced Ferroelectric Ice on Pt(111)|journal=Physical Review Letters|volume=80|issue=7|pages=1533–1536|doi=10.1103/PhysRevLett.80.1533|bibcode = 1998PhRvL..80.1533S |year=1998|s2cid=121266617}}</ref> One-dimensional nano-confined ferroelectric ice XI was created in 2010.<ref name=onedim1>{{cite journal|last=Zhao|first=H.-X. |author2=Kong, X.-J. |author3=Li, H. |author4=Jin, Y.-C. |author5=Long, L.-S. |author6=Zeng, X. C. |author7=Huang, R.-B. |author8=Zheng, L.-S. |title=Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture|journal=Proceedings of the National Academy of Sciences|date=14 February 2011|volume=108|issue=9|pages=3481–3486|doi=10.1073/pnas.1010310108|bibcode = 2011PNAS..108.3481Z |pmid=21321232 |pmc=3048133|doi-access=free }}</ref> |
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=== Ice XV === |
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The same answer can be found in another way. First orient each water molecule randomly in each of the 6 possible configurations, then check that each lattice edge contains exactly one hydrogen atom. Assuming that the lattice edges are independent, then the probability that a single edge contains exactly one hydrogen atom is 1/2, and since there are 2N edges in total, we obtain a total configuration count <math>6^N \times (1/2)^{2N} = (3/2)^N </math>, as before. |
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Although the parent phase ice VI was discovered in 1935, corresponding proton-ordered forms (ice XV) had not been observed until 2009. Theoretically, the proton ordering in ice VI was predicted several times; for example, [[density functional theory]] calculations predicted the phase transition temperature is 108 K and the most stable ordered structure is antiferroelectric in the space group ''Cc'', while an antiferroelectric ''P''2<sub>1</sub>2<sub>1</sub>2<sub>1</sub> structure were found 4 K per water molecule higher in energy.<ref name="Knight Singer 2005 pp. 21040–21046">{{cite journal | last=Knight | first=Chris | last2=Singer | first2=Sherwin J. | title=Prediction of a Phase Transition to a Hydrogen Bond Ordered Form of Ice VI | journal=The Journal of Physical Chemistry B | publisher=American Chemical Society (ACS) | volume=109 | issue=44 | date=2005-10-19 | issn=1520-6106 | doi=10.1021/jp0540609 | pages=21040–21046}}</ref> |
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On 14 June 2009, Christoph Salzmann and colleagues at the University of Oxford reported having experimentally reported an ordered phase of ice VI, named ice XV, and say that its properties differ significantly from those predicted. In particular, ice XV is [[Antiferroelectricity|antiferroelectric]] rather than [[Ferroelectricity|ferroelectric]] as had been predicted.<ref name="Wired">{{cite magazine |first= Laura |last= Sanders |title= Super-Dense Frozen Water Breaks Final Ice Frontier |url= https://www.wired.com/wiredscience/2009/09/sn_icexv/ |magazine= [[Wired (magazine)|Wired]] |publisher= [[Condé Nast Publications|Condé Nast]] |date= 11 September 2009 |access-date= 13 September 2009 }}</ref><ref>{{Cite journal|arxiv = 0906.2489|doi = 10.1103/PhysRevLett.103.105701|title = Ice XV: A New Thermodynamically Stable Phase of Ice|year = 2009|last1 = Salzmann|first1 = Christoph G.|last2 = Radaelli|first2 = Paolo G.|last3 = Mayer|first3 = Erwin|last4 = Finney|first4 = John L.|journal = Physical Review Letters|volume = 103|issue = 10|page = 105701|pmid = 19792330|bibcode = 2009PhRvL.103j5701S|s2cid = 13999983}}</ref> |
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=== Refinements === |
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This estimate is 'naive', as it assumes the six out of 16 hydrogen configurations for oxygen atoms in the second set can be independently chosen, which is false. More complex methods can be employed to better approximate the exact number of possible configurations, and achieve results closer to measured values. Nagle (1966) used a series summation to obtain <math>R\ln(1.50685 \pm 0.00015)</math>.<ref>{{Cite journal |last=Nagle |first=J. F. |date=1966-08-01 |title=Lattice Statistics of Hydrogen Bonded Crystals. I. The Residual Entropy of Ice |url=https://pubs.aip.org/jmp/article/7/8/1484/382171/Lattice-Statistics-of-Hydrogen-Bonded-Crystals-I |journal=Journal of Mathematical Physics |language=en |volume=7 |issue=8 |pages=1484–1491 |doi=10.1063/1.1705058 |issn=0022-2488}}</ref> |
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===Ice XVII=== |
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As an illustrative example of refinement, consider the following way to refine the second estimation method given above. According to it, six water molecules in a hexagonal ring would allow <math>6^6 \times (1/2)^6 = 729</math> configurations. However, by explicit enumeration, there are actually 730 configurations. Now in the lattice, each oxygen atom participates in 12 hexagonal rings, so there are 2N rings in total for N oxygen atoms, or 2 rings for each oxygen atom, giving a refined result of <math>R\ln(1.5\times (730/729)^2) = R\ln(1.504)</math>.<ref>{{Cite journal |last=Hollins |first=G. T. |date=December 1964 |title=Configurational statistics and the dielectric constant of ice |url=https://dx.doi.org/10.1088/0370-1328/84/6/318 |journal=Proceedings of the Physical Society |language=en |volume=84 |issue=6 |pages=1001 |doi=10.1088/0370-1328/84/6/318 |issn=0370-1328}}</ref> |
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[[File:IceXVII wiki.jpg|thumb|400px|Crystal structure of ice XVII]] |
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In 2016, the discovery of a new form of ice was announced.{{r|discovery}} Characterized as a "porous water ice metastable at atmospheric temperatures", this new form was discovered by taking a filled ice and removing the non-water components, leaving the crystal structure behind, similar to how ice XVI, another porous form of ice, was synthesized from a [[clathrate hydrate]].{{r|cnr|discovery|lsbu|porousice|xvi}} |
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To create ice XVII, the researchers first produced filled ice in a stable phase named C{{sub|0}} from a mixture of hydrogen (H{{sub|2}}) and water (H{{sub|2}}O), using temperatures from {{cvt|100|to|270|K|C F}} and pressures from {{cvt|360|to|700|MPa|psi atm}}.{{r|discovery}}{{efn|C{{sub|0}}, C{{sub|1}}<!-- not used elsewhere in this article as of this writing -->, and C{{sub|2}} are all stable solid phases of a mixture of H{{sub|2}} and H{{sub|2}}O molecules, formed at high pressures.{{r|discovery|lsbu}} Although sometimes referred to as [[clathrate hydrate]]s (or clathrates), they lack the cagelike structure generally found in clathrate hydrates, and are more properly referred to as filled ices.{{r|discovery|lsbu|porousice}}|name="cx.terminology"}} The filled ice is then placed in a vacuum, and the temperature gradually increased until the hydrogen frees itself from the crystal structure.{{r|discovery|lsbu}}{{efn|If kept at a temperature range between {{cvt|110|and|120|K|C F}}, after about two hours, the structure will have emptied itself of any detectable hydrogen molecules.{{r|discovery|lsbu}}}} The resulting form is [[metastable]] at room pressure while under {{cvt|120|K|C F}}, but collapses into ice I{{sub|h}} (ordinary ice) when brought above {{cvt|130|K|C F}}.{{r|discovery|lsbu}} The crystal structure is hexagonal in nature, and the pores are [[Helix|helical]] channels with a diameter of about {{cvt|6.10|Å|m in|lk=in}}.{{r|discovery|lsbu}} |
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== Ice Ic == |
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=== Cubic ice === |
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'''Ice I<sub>c</sub>''' (pronounced "ice one c" or "ice I c") is a [[metastability|metastable]] [[cubic crystal system|cubic]] [[crystalline]] variant of [[ice]]. Hans König was the first to identify and deduce the structure of ice I<sub>c</sub>.<ref>{{cite journal|last=König|first=H.|year=1943|title=Eine kubische Eismodifikation|journal=Zeitschrift für Kristallographie|language=de|volume=105|issue=1|pages=279–286|doi=10.1524/zkri.1943.105.1.279|s2cid=101738967}}</ref> The [[oxygen]] atoms in ice I<sub>c</sub> are arranged in a [[diamond]] structure and is extremely similar to ice I<sub>h</sub> having nearly identical densities and the same lattice constant along the hexagonal puckered-planes.<ref name="DowellRinfret1960">{{Cite journal |last1=Dowell |first1=L. G. |last2=Rinfret |first2=A. P. |date=December 1960 |title=Low-Temperature Forms of Ice as Studied by X-Ray Diffraction |journal=Nature |language=en |volume=188 |issue=4757 |pages=1144–1148 |bibcode=1960Natur.188.1144D |doi=10.1038/1881144a0 |issn=0028-0836 |s2cid=4180631}}</ref> It forms at temperatures between {{convert|130|and|220|K|C|abbr=off}} upon cooling, and can exist up to {{convert|240|K|C}} upon warming,<ref>{{Cite journal |last1=Murray |first1=B.J. |last2=Bertram |first2=A. K. |year=2006 |title=Formation and stability of cubic ice in water droplets |url=https://open.library.ubc.ca/media/download/pdf/52383/1.0041852/3 |journal=Phys. Chem. Chem. Phys. |volume=8 |issue=1 |pages=186–192 |bibcode=2006PCCP....8..186M |doi=10.1039/b513480c |pmid=16482260 |hdl-access=free |hdl=2429/33770}}</ref><ref>{{cite journal |last=Murray |first=B.J. |year=2008 |title=The Enhanced formation of cubic ice in aqueous organic acid droplets |pages=025008 |journal=Env. Res. Lett. |volume=3 |doi=10.1088/1748-9326/3/2/025008|bibcode = 2008ERL.....3b5008M |issue=2 |doi-access=free }}</ref> when it transforms into [[Ice Ih|ice I<sub>h</sub>]]. |
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It was reported in 2020 that [[cubic ice]] based on [[heavy water]] (D{{sub|2}}O) can be formed from ice XVII.{{r|cubic}} This was done by heating specially prepared D{{sub|2}}O ice XVII powder.{{r|cubic}} The result was free of structural deformities compared to standard cubic ice, or ice I{{sub|sd}}.{{r|cubic|lsbu.isd}} This discovery was reported around the same time another research group announced that they were able to obtain pure D{{sub|2}}O cubic ice by first synthesizing filled ice in the C{{sub|2}} phase, and then decompressing it.{{r|cubic.c2|discovery}}{{efn|name="cx.terminology"}} |
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=== Ice XVIII (superionic water) === |
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[[File:Phase_diagram_of_water.svg|thumb|Phase diagram of water]] |
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{{multiple image |
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Apart from forming from supercooled water,<ref>{{Cite journal |last1=Mayer |first1=E. |last2=Hallbrucker |first2=A. |year=1987 |title=Cubic ice from liquid water |journal=Nature |volume=325 |issue=12 |pages=601–602 |bibcode=1987Natur.325..601M |doi=10.1038/325601a0 |s2cid=4233237}}</ref> ice I<sub>c</sub> has also been reported to form from amorphous ice<ref name="DowellRinfret1960" /> as well as from the high-pressure ices [[ice II|II]], [[ice III|III]] and [[ice V|V]].<ref>{{Cite journal |last1=Bertie |first1=J. E. |last2=Calvert |first2=L. D. |last3=Whalley |first3=E. |year=1963 |title=Transformations of Ice II, Ice III, and Ice V at Atmospheric Pressure |journal=J. Chem. Phys. |volume=38 |issue=4 |pages=840–846 |bibcode=1963JChPh..38..840B |doi=10.1063/1.1733772}}</ref> It can form in and is occasionally present in the upper atmosphere<ref>{{Cite journal |last1=Murray |first1=Benjamin J. |last2=Knopf |first2=Daniel A. |last3=Bertram |first3=Allan K. |date=March 2005 |title=The formation of cubic ice under conditions relevant to Earth's atmosphere |journal=[[Nature (journal)|Nature]] |language=en |volume=434 |issue=7030 |pages=202–205 |bibcode=2005Natur.434..202M |doi=10.1038/nature03403 |issn=0028-0836 |pmid=15758996 |s2cid=4427815}}</ref> and is believed to be responsible for the observation of Scheiner's [[Halo (optical phenomenon)|halo]], a rare ring that occurs near 28 degrees from the Sun or the Moon.<ref>{{Cite journal |last=Whalley |first=E. |year=1981 |title=Scheiner's Halo: Evidence for Ice I{{sub|c}} in the Atmosphere |journal=Science |volume=211 |issue=4480 |pages=389–390 |bibcode=1981Sci...211..389W |doi=10.1126/science.211.4480.389 |pmid=17748273}}</ref> |
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| align = right |
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| total_width = 320 |
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| image1 = Superionic ice rest.svg |
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Ordinary water ice is known as ice I<sub>h</sub> (in the [[Percy Williams Bridgman|Bridgman]] nomenclature). Different types of ice, from [[ice II]] to ice XIX,<ref>{{Cite web|last1=Flatz|first1=Christian|last2=Hohenwarter|first2=Stefan|title=Neue kristalline Eisform aus Innsbruck|url=https://www.uibk.ac.at/newsroom/neue-kristalline-eisform-aus-innsbruck.html.de|access-date=2021-02-18|website=Universität Innsbruck|language=de}}</ref> have been created in the laboratory at different temperatures and pressures. |
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| alt1 = Superionic ice at rest |
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| caption1 = In the absence of an applied [[electric field]], H<sup>+</sup> ions [[Atomic diffusion|diffuse]] in the O<sup>2−</sup> lattice. |
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| image2 = Superionic ice conducting.svg |
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Some authors have expressed doubts whether ice I<sub>c</sub> really has a cubic crystal system, claiming that it is merely ''stacking-disordered ice I'' (“ice I<sub>sd</sub>”),<ref>{{Cite journal |last1=Murray |first1=Benjamin J. |last2=Salzmann |first2=Christoph G. |last3=Heymsfield |first3=Andrew J. |last4=Dobbie |first4=Steven |last5=Neely |first5=Ryan R. |last6=Cox |first6=Christopher J. |year=2015 |title=Trigonal Ice Crystals in Earth's Atmosphere |url=http://eprints.whiterose.ac.uk/86859/8/MurrayTrigonalIceCrystals.pdf |journal=Bulletin of the American Meteorological Society |volume=96 |issue=9 |pages=1519–1531 |bibcode=2015BAMS...96.1519M |doi=10.1175/BAMS-D-13-00128.1}}</ref><ref>{{Cite web |last=Chaplin |first=Martin |date=15 September 2019 |title=Stacking disordered ice; Ice I{{sub|sd}} |url=http://www1.lsbu.ac.uk/water/ice1h1c.html |archive-url=https://web.archive.org/web/20201022120831/http://www1.lsbu.ac.uk/water/ice1h1c.html |archive-date=22 Oct 2020 |access-date=3 December 2019 |website=Water Structure and Science |publisher=[[London South Bank University]]}}</ref><ref>{{Cite journal |last1=Malkin |first1=Tamsin L. |last2=Murray |first2=Benjamin J. |last3=Salzmann |first3=Christoph G. |last4=Molinero |first4=Valeria |last5=Pickering |first5=Steven J. |last6=Whale |first6=Thomas F. |year=2015 |title=Stacking disorder in ice I |journal=Physical Chemistry Chemical Physics |volume=17 |issue=1 |pages=60–76 |doi=10.1039/C4CP02893G |pmid=25380218 |doi-access=free}}</ref> and it has been dubbed the ″most faceted ice phase in a literal and a more general sense.″<ref>{{Cite journal |last1=Kuhs |first1=W. F. |last2=Sippel |first2=C. |last3=Falenty |first3=A. |last4=Hansen |first4=T. C. |year=2012 |title=Extent and relevance of stacking disorder in "ice I{{sub|c}}" |journal=Proceedings of the National Academy of Sciences of the United States of America |volume=109 |issue=52 |pages=21259–21264 |bibcode=2012PNAS..10921259K |doi=10.1073/pnas.1210331110 |pmc=3535660 |pmid=23236184 |doi-access=free }}</ref> |
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| alt2 = Superionic ice conducting protons in an electric field |
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| caption2 = When an electric field is applied, H<sup>+</sup> ions migrate towards the [[anode]]. |
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| footer = A remarkable characteristic of superionic ice is its ability to act as a [[Electrical conductor|conductor]]. |
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However, in 2020, two research groups individually prepared ice I<sub>c</sub> without stacking disorder. Komatsu et al. prepared C<sub>2</sub> hydrate at high pressure and decompressed it at 100 K to make hydrogen molecules extracted from the structure, resulting in ice I<sub>c</sub> without stacking disorder.<ref name="pmid32015342">{{cite journal |author=Komatsu K, Machida S, Noritake F, Hattori T, Sano-Furukawa A, Yamane R |display-authors=etal |title=Ice Ic without stacking disorder by evacuating hydrogen from hydrogen hydrate. |journal=Nat Commun |year=2020 |volume=11 |issue=1 |pages=464 |pmid=32015342 |doi=10.1038/s41467-020-14346-5 |pmc=6997176|arxiv=1909.03400 |bibcode=2020NatCo..11..464K }}</ref> Del Rosso et al. prepared [[ice XVII]] from C<sub>0</sub> hydrate and heated it at 0 GPa to obtain pure ice I<sub>c</sub> without stacking disorder.<ref name="pmid32015533">{{cite journal |author=Del Rosso L, Celli M, Grazzi F, Catti M, Hansen TC, Fortes AD |display-authors=etal |title=Cubic ice Ic without stacking defects obtained from ice XVII. |journal=Nat Mater |year=2020 |volume=19 |issue=6 |pages=663–668 |pmid=32015533 |doi=10.1038/s41563-020-0606-y |pmc= |arxiv=1907.02915 |bibcode=2020NatMa..19..663D |s2cid=195820566 |url=https://pubmed.ncbi.nlm.nih.gov/32015533 }}</ref> Pure ice I<sub>c</sub> prepared in the latter method transforms into ice I<sub>h</sub> at 226 K with an enthalpy change of -37.7 J/mol.<ref name="pmid37227149">{{cite journal| author=Tonauer CM, Yamashita K, Rosso LD, Celli M, Loerting T| title=Enthalpy Change from Pure Cubic Ice Ic to Hexagonal Ice Ih. | journal=J Phys Chem Lett | year= 2023 | volume= 14 | issue= 21 | pages= 5055–5060 | pmid=37227149 | doi=10.1021/acs.jpclett.3c00408 | pmc=10240532 }}</ref> |
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}} |
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In 1988, predictions of the so-called superionic water state were made.<ref name="Demontis">{{cite journal |doi=10.1103/PhysRevLett.60.2284 |pmid=10038311 |title=New high-pressure phases of ice |first1=P. |last1=Demontis |first2=R. |last2=LeSar |first3=M. L. |last3=Klein |display-authors=1 |journal=Phys. Rev. Lett. |volume=60 |issue=22 |pages=2284–2287 |year=1988 |url=http://eprints.uniss.it/377/1/Demontis_P_Articolo_1988_New.pdf }}</ref> In superionic water, water molecules break apart and the oxygen ions [[crystallization|crystallize]] into an evenly spaced lattice while the [[hydrogen ions]] float around freely within the oxygen lattice.<ref name="newscientist.com">[https://www.newscientist.com/article/mg20727764.500-weird-water-lurking-inside-giant-planets.html Weird water lurking inside giant planets], New Scientist,01 September 2010, Magazine issue 2776.</ref> The freely mobile hydrogen ions make superionic water almost as [[electrical resistivity and conductivity|conductive]] as typical metals, making it a [[Fast ion conductor|superionic conductor]].<ref name="LLNL_Nature2019">{{cite journal |last1=Millot |first1=Marius |last2=Coppari |first2=Federica |last3=Rygg |first3=J. Ryan |last4=Correa Barrios |first4=Antonio |last5=Hamel |first5=Sebastien |last6=Swift |first6=Damian C. |last7=Eggert |first7=Jon H. |title=Nanosecond X-ray diffraction of shock-compressed superionic water ice |journal=Nature |date=8 May 2019 |volume=569 |issue=7755 |pages=251–255 |doi=10.1038/s41586-019-1114-6|pmid=31068720 |osti=1568026 |s2cid=256768272 |url=https://www.osti.gov/biblio/1568026 }}</ref> The ice appears black in color.<ref name="NP-20180205"/><ref name="auto3"/> It is distinct from [[Self-ionization of water|ionic water]], which is a hypothetical liquid state characterized by a disordered soup of hydrogen and oxygen ions. |
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The initial evidence came from optical measurements of laser-heated water in a [[diamond anvil cell]],<ref name="Goncharov">{{cite journal |doi=10.1103/PhysRevLett.94.125508 |pmid=15903935 |title=Dynamic Ionization of Water under Extreme Conditions |first1=Alexander F. |last1=Goncharov |first2=Nir |last2=Goldman |first3=Laurence E. |last3=Fried |first4=Jonathan C. |last4=Crowhurst |first5=I-Feng W. |last5=Kuo |first6=Christopher J. |last6=Mundy |first7=Joseph M. |last7=Zaug |display-authors=1 |journal=Phys. Rev. Lett. |volume=94 |issue=12 |pages=125508 |year=2005 |url=https://digital.library.unt.edu/ark:/67531/metadc1417703/m2/1/high_res_d/15015926.pdf }}</ref> and from optical measurements of water shocked by extremely powerful lasers.<ref name="NP-20180205">{{cite journal |author=Millot, Marius |display-authors=etal |title=Experimental evidence for superionic water ice using shock compression |date=5 February 2018 |journal=[[Nature Physics]] |volume=14 |issue=3 |pages=297–302 |doi=10.1038/s41567-017-0017-4 |bibcode=2018NatPh..14..297M |osti=1542614 |s2cid=256703104 |url=https://www.osti.gov/biblio/1542614 }}</ref> The first definitive evidence for the crystal structure of the oxygen lattice in superionic water came from x-ray measurements on laser-shocked water which were reported in 2019.<ref name="LLNL_Nature2019"/> In 2005 Laurence Fried led a team at Lawrence Livermore National Laboratory to recreate the formative conditions of superionic water. Using a technique involving smashing water molecules between [[diamond]]s and super heating it with [[laser]]s they observed frequency shifts which indicated that a [[phase transition]] had taken place. The team also created [[computer model]]s which indicated that they had indeed created superionic water.<ref name="nature.com" /> In 2013 Hugh F. Wilson, Michael L. Wong, and Burkhard Militzer at the University of California, Berkeley published a paper predicting the [[face-centered cubic]] lattice structure that would emerge at higher pressures.<ref name=Phys.org-2013-04-25/> Additional experimental evidence was found by Marius Millot and colleagues in 2018 by inducing high pressure on water between diamonds and then shocking the water using a laser pulse.<ref name="NP-20180205"/><ref name="auto3">{{Cite magazine|url=https://www.wired.com/story/a-bizarre-form-of-water-may-exist-all-over-the-universe/|title=A Bizarre Form of Water May Exist All Over the Universe|last=Sokol|first=Joshua|date=2019-05-12|magazine=Wired|access-date=2019-05-13|issn=1059-1028}}</ref> |
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== Ice II == |
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{{As of|2013}}, it is theorized that superionic ice can possess two crystalline structures. At pressures in excess of {{convert|50|GPa|psi|lk=in|abbr=on}} it is predicted that superionic ice would take on a [[body-centered cubic]] structure. However, at pressures in excess of 100 GPa, and temperatures above 2000 K, it is predicted that the structure would shift to a more stable [[face-centered cubic]] lattice.<ref name=Phys.org-2013-04-25/> |
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Ice II is a [[rhombohedral]] crystalline form of [[ice]] with a highly ordered structure. It is formed from [[ice Ih|ice I<sub>h</sub>]] by compressing it at a temperature of 198 [[Kelvin|K]] at 300 [[MPa]] or by decompressing [[ice V]]. When heated it undergoes transformation to [[ice III]].<ref>{{cite web |url=http://www.lsbu.ac.uk/water/ice_ii.html |title=Ice-two structure |author=Chaplin, Martin |date=October 18, 2014 |work=Water Structure and Science |publisher=[[London South Bank University]] |access-date=December 6, 2014}}</ref> Ordinary [[water]] ice is known as [[Ice Ih|ice I<sub>h</sub>]], (in the [[Percy Williams Bridgman|Bridgman]] nomenclature). Different types of ice, from ice II to [[ice XIX]], have been created in the laboratory at different temperatures and pressures. It is thought that the cores of [[icy moon]]s like [[Jupiter|Jupiter's]] [[Ganymede (moon)|Ganymede]] may be made of ice II.{{citation needed|date=January 2020}} |
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In 2018, researchers at LLNL squeezed water between two pieces of diamond with a pressure of {{convert|360000|psi|MPa|order=flip|abbr=on|lk=in}}. The water was squeezed into Ice VII, which is 60 percent denser than normal water.<ref name=":0">{{Cite news|url=https://www.nytimes.com/2018/02/05/science/superionic-water-neptune-uranus.html|title=New Form of Water, Both Liquid and Solid, Is 'Really Strange'|last=Chang|first=Kenneth|date=2018-02-05|work=The New York Times|access-date=2018-02-13|language=en-US|issn=0362-4331}}</ref> The compressed ice was then transported to the [[University of Rochester]] where it was blasted by a pulse of laser light. The reaction created conditions like those inside of [[ice giant]]s such as Uranus and Neptune by heating up the ice thousands of degrees under a pressure a million times greater than the Earth's atmosphere in only 10 to 20 billionths of a second. The experiment concluded that the current in the conductive water was indeed carried by ions rather than electrons and thus pointed to the water being superionic.<ref name=":0" /> More recent experiments from the same [[Lawrence Livermore National Laboratory]] team used x-ray crystallography on laser-shocked water droplets to determine that the oxygen ions enter a face-centered-cubic phase, which was dubbed ice XVIII and reported in the journal ''Nature'' in May 2019.<ref name="LLNL_Nature2019"/> |
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===History=== |
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The properties of ice II were first described and recorded by [[Gustav Heinrich Johann Apollon Tammann]] in 1900 during his experiments with ice under high pressure and low temperatures. Having produced ice III, Tammann then tried condensing the ice at a temperature between {{convert|-70|and|-80|C|K F}} under {{convert|200|MPa|atm|abbr=on|comma=}} of pressure. Tammann noted that in this state ice II was denser than he had observed ice III to be. He also found that both types of ice can be kept at normal [[atmospheric pressure]] in a stable condition so long as the temperature is kept at that of [[liquid air]], which slows the change in conformation back to ice I<sub>h</sub>.<ref name="Hobbs">{{cite book |last=Hobbs |first=Peter V. |date=May 6, 2010 |title=Ice Physics |url=https://books.google.com/books?id=7Is6AwAAQBAJ&pg=PA61 |publisher=[[Oxford University Press]] |pages=61–70 |isbn=9780199587711 |access-date=December 6, 2014}}</ref> |
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=== Ice XIX === |
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In later experiments by Bridgman in 1912, it was shown that the difference in volume between ice II and ice III was in the range of {{convert|0.0001|m3/kg|cuin/lb|abbr=on|comma=gaps}}. This difference hadn't been discovered by Tammann due to the small change and was why he had been unable to determine an [[Vapor–liquid equilibrium|equilibrium curve]] between the two. The curve showed that the structural change from ice III to ice II was more likely to happen if the medium had previously been in the structural conformation of ice II. However, if a sample of ice III that had never been in the ice II state was obtained, it could be supercooled even below −70 °C without it changing into ice II. Conversely, however, any superheating of ice II was not possible in regards to retaining the same form. Bridgman found that the equilibrium curve between ice II and [[ice IV]] was much the same as with ice III, having the same stability properties and small volume change. The curve between ice II and [[ice V]] was extremely different, however, with the curve's bubble being essentially a straight line and the volume difference being almost always {{convert|0.0000545|m3/kg|cuin/lb|abbr=on|comma=gaps}}.<ref name="Hobbs"/> |
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The first report regarding ice XIX was published in 2018 by Thomas Loerting's group from Austria.<ref name="pmid29780552"/> They quenched HCl-doped ice VI to 77 K at different pressures between 1.0 and 1.8 GPa to collect [[differential scanning calorimetry]] (DSC) thermograms, [[Dielectric spectroscopy|dielectric spectrum]], [[Raman spectroscopy|Raman spectrum]], and [[X-ray diffraction]] patterns. In the DSC signals, there was an endothermic feature at about 110 K in addition to the endotherm corresponding to the ice XV-VI transition. Additionally, the Raman spectra, dielectric properties, and the ratio of the lattice parameters differed from those of ice XV. Based on these observations, they proposed the existence of a second hydrogen-ordered phase of ice VI, naming it ice beta-XV. |
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In 2019, Alexander Rosu-Finsen and Christoph Salzman argued that there was no need to consider this to be a new phase of ice, and proposed a "deep-glassy" state scenario.<ref name="pmid30713649">{{cite journal |last1=Rosu-Finsen |first1=A|last2= Salzmann |first2=CG |year=2019 |title=Origin of the low-temperature endotherm of acid-doped ice VI: new hydrogen-ordered phase of ice or deep glassy states? |journal=Chem Sci |volume=10 |issue=2 |pages=515–523 |doi=10.1039/c8sc03647k |pmc=6334492 |pmid=30713649}}</ref> According to their DSC data, the size of the endothermic feature depends not only on quench-recovery pressure but also on the heating rate and annealing duration at 93 K. They also collected neutron diffraction profiles of quench-recovered [[deuterium]] chloride-doped, D<sub>2</sub>O ice VI/XV prepared at different pressures of 1.0, 1.4 and 1.8 GPa, to show that there were no significant differences among them. They concluded that the low-temperature endotherm originated from kinetic features related to glass transitions of deep glassy states of ''disordered'' ice VI. |
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=== Quest for a hydrogen-disordered counterpart of ice II === |
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Distinguishing between the two scenarios (new hydrogen-ordered phase vs. deep-glassy disordered ice VI) became an open question and the debate between the two groups has continued. Thoeny et al. (Loerting's group) <ref name="pmid31257365">{{cite journal |author1=Thoeny AV|author2= Gasser TM|author3= Loerting T|author3-link=Thomas Loerting |year=2019 |title=Distinguishing ice β-XV from deep glassy ice VI: Raman spectroscopy. |journal=Phys Chem Chem Phys |volume=21 |issue=28 |pages=15452–15462 |doi=10.1039/c9cp02147g |pmc= |pmid=31257365|bibcode= 2019PCCP...2115452T|s2cid= 195764029|doi-access=free }} </ref> collected another series of Raman spectra of ice beta-XV, and reported that (i) ice XV prepared by the protocol reported previously contains both ice XV and ice beta-XV domains; (ii) upon heating, Raman spectra of ice beta-XV showed loss of H-order. In contrast, Salzmann's group again argued for the plausibility of a 'deep-glassy state' scenario based on neutron diffraction and neutron inelastic scattering experiments.<ref name="pmid31972078">{{cite journal |author=Rosu-Finsen A, Amon A, Armstrong J, Fernandez-Alonso F, Salzmann CG |year=2020 |title=Deep-Glassy Ice VI Revealed with a Combination of Neutron Spectroscopy and Diffraction. |journal=J Phys Chem Lett |volume=11 |issue=3 |pages=1106–1111 |doi=10.1021/acs.jpclett.0c00125 |pmc=7008458 |pmid=31972078}}</ref> Based on their experimental results, ice VI and deep-glassy ice VI share very similar features based on both elastic (diffraction) scattering and inelastic scattering experiments, and are different from the properties of ice XV. |
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As ice II is completely hydrogen ordered, the presence of its disordered counterpart is a great matter of interest. Shephard et al.<ref>{{Citation | vauthors=((Shephard, J. J.)), ((Slater, B.)), ((Harvey, P.)), ((Hart, M.)), ((Bull, C. L.)), ((Bramwell, S. T.)), ((Salzmann, C. G.)) | year=2018 | title=Doping-induced disappearance of ice II from water's phase diagram | journal=Nature Physics | volume=14 | issue=6 | pages=569–572 | publisher=Springer Science and Business Media LLC | doi=10.1038/s41567-018-0094-z | bibcode=2018NatPh..14..569S | s2cid=54544973 | url=http://dx.doi.org/10.1038/s41567-018-0094-z}}</ref> investigated the phase boundaries of NH<sub>4</sub>F-doped ices because NH<sub>4</sub>F has been reported to be a hydrogen disordering reagent. However, adding 2.5 mol% of NH<sub>4</sub>F resulted in the disappearance of ice II instead of the formation of a disordered ice II. According to the DFC calculation by Nakamura et al.,<ref>{{Citation | vauthors=((Nakamura, T.)), ((Matsumoto, M.)), ((Yagasaki, T.)), ((Tanaka, H.)) | year=2015 | title=Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy | journal=The Journal of Physical Chemistry B | volume=120 | issue=8 | pages=1843–1848 | publisher=American Chemical Society (ACS) | doi=10.1021/acs.jpcb.5b09544 | pmid=26595233 | url=http://dx.doi.org/10.1021/acs.jpcb.5b09544}}</ref> the phase boundary between ice II and its disordered counterpart is estimated to be in the stability region of liquid water. |
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In 2021, further crystallographic evidence for a new phase (ice XIX) was individually reported by three groups: Yamane et al. (Hiroyuki Kagi and Kazuki Komatsu's group from Japan), Gasser et al. (Loerting's group), and Salzmann's group. Yamane et al. <ref name="pmid33602936"/> collected neutron diffraction profiles ''in situ'' (''i.e.'' under high pressure) and found new Bragg features completely different from both ice VI and ice XV. They performed [[Rietveld refinement]] of the profiles based on the <math>\sqrt{2} \times \sqrt{2} \times 1</math> supercell of ice XV and proposed some leading candidates for the space group of ice XIX: P-4, Pca21, Pcc2, P21/a, and P21/c. They also measured dielectric spectra ''in situ'' and determined phase boundaries of ices VI/XV/XIX. They found that the sign of the slope of the boundary turns negative from positive at 1.6 GPa indicating the existence of two different phases by the [[Clausius–Clapeyron relation]]. |
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== Ice III == |
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Gasser et al. <ref name="pmid33602946">{{cite journal| author=Gasser TM, Thoeny AV, Fortes AD, Loerting T| title=Structural characterization of ice XIX as the second polymorph related to ice VI. | journal=Nat Commun | year= 2021 | volume= 12 | issue= 1 | pages= 1128 | pmid=33602946 | doi=10.1038/s41467-021-21161-z | pmc=7892819 | bibcode=2021NatCo..12.1128G }} </ref> also collected powder neutron diffractograms of quench-recovered ices VI, XV, and XIX and found similar crystallographic features to those reported by Yamane et al., concluding that P-4 and Pcc2 are the plausible space group candidates. Both Yamane et al.'s and Gasser et al.'s results suggested a partially hydrogen-ordered structure. Gasser et al. also found an isotope effect using DSC; the low-temperature endotherm for DCl-doped D<sub>2</sub>O ice XIX was significantly smaller than that of HCl-doped H<sub>2</sub>O ice XIX, and that doping of 0.5% of H<sub>2</sub>O into D<sub>2</sub>O is sufficient for the ordering transition. |
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{{redirect|the form of water|the German high-speed train|ICE 3}} |
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[[File:Ice III phase diagram.svg|thumb|Phase diagram of water, showing the region where ice III is stable.]] |
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Ice III is a form of solid matter that consists of [[tetragonal]] [[Crystal|crystalline]] [[ice]] formed by cooling [[water]] to {{nowrap|250 [[Kelvin|K]]}} (about {{Nowrap|-10 [[°C]]}}) at {{nowrap|300 [[Pascal (unit)|MPa]]}}. It is the least dense of the high-pressure water [[phase (matter)|phases]], with a [[density]] of {{nowrap|1160 kg/m<sup>3</sup>}} (at 350 MPa).<ref>{{Cite web |date=2012-02-04 |title=Ice III (ice-three) structure |url=http://www.lsbu.ac.uk/water/ice_iii.html |access-date=2023-06-06 |archive-url=https://web.archive.org/web/20120204094529/http://www.lsbu.ac.uk/water/ice_iii.html |archive-date=2012-02-04 }}</ref> It has a very high relative [[permittivity]] at 117 and has a [[specific gravity]] of 1.16 with respect to water. |
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Several months later, Salzmann et al. published a paper based on ''in-situ'' powder neutron diffraction experiments of ice XIX.<ref name="pmid34039987">{{cite journal| author=Salzmann CG, Loveday JS, Rosu-Finsen A, Bull CL| title=Structure and nature of ice XIX. | journal=Nat Commun | year= 2021 | volume= 12 | issue= 1 | pages= 3162 | pmid=34039987 | doi=10.1038/s41467-021-23399-z | pmc=8155070 | bibcode=2021NatCo..12.3162S }} </ref> In a change from their previous reports, they accepted the idea of the new phase (ice XIX) as they observed similar features to the previous two reports. However, they refined their diffraction profiles based on a disordered structural model (Pbcn) and argued that new Bragg reflections can be explained by distortions of ice VI, so ice XIX may still be regarded as a deep-glassy state of ice VI. The crystal structure of ice XIX including hydrogen order/disorder is still under debate as of 2022. |
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Ordinary water ice is known as {{nowrap|[[ice Ih|ice I<sub>h</sub>]]}} (in the [[Percy Williams Bridgman|Bridgman]] nomenclature). Different types of ice, from [[Ice II]] to [[Ice XIX]], have been created in the laboratory at different temperatures and pressures. |
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<!--Ice VII is the only disordered phase of ice that can be ordered by simple cooling,<ref name="Johari et al."/><ref>Note: ice I<sub>h</sub> theoretically transforms into proton-ordered ice XI on geologic timescales, but in practice it is necessary to add small amounts of KOH catalyst.</ref> and it forms (ordered) ice VIII below 273 K up to ~8 GPa. Above this pressure, the VII–VIII transition temperature drops rapidly, reaching 0 K at ~60 GPa.<ref name="pruzan">{{Citation |first1=Ph. |last1=Pruzan |first2=J. C. |last2=Chervin |first3=B. |last3=Canny |name-list-style=amp |journal=Journal of Chemical Physics |volume=99 |issue=12 |pages=9842–9846 |year=1993 |title=Stability domain of the ice VIII proton-ordered phase at very high pressure and low temperature |doi=10.1063/1.465467 |bibcode = 1993JChPh..99.9842P }}.</ref> Thus, ice VII has the largest stability field of all of the molecular phases of ice. The cubic oxygen sub-lattices that form the backbone of the ice VII structure persist to pressures of at least 128 GPa;<ref name="hemley">{{Citation |first1=R. J. |last1=Hemley |first2=A. P. |last2=Jephcoat |first3=H. K. |last3=Mao |journal=[[Nature (journal)|Nature]] |issue=6150 |volume=330 |pages=737–740 |year=1987 |title=Static compression of H<sub>2</sub>O-ice to 128 GPa (1.28 Mbar) |doi=10.1038/330737a0 |bibcode = 1987Natur.330..737H |s2cid=4265919 |url=https://zenodo.org/record/1233067 |display-authors=etal}}.</ref> this pressure is substantially higher than that at which water loses its molecular character entirely, forming ice X. In high pressure ices, protonic diffusion (movement of protons around the oxygen lattice) dominates molecular diffusion, an effect which has been measured directly.<ref>{{cite journal|last=Katoh|first=E.|s2cid=38999963|title=Protonic Diffusion in High-Pressure Ice VII|journal=Science|date=15 February 2002 |volume=29=5558|issue=5558|pages=1264–1266|doi=10.1126/science.1067746|bibcode = 2002Sci...295.1264K|pmid=11847334}}</ref>--> |
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<!--In detail, ice XV has a smaller density (larger unit-cell volume) than ice VI. This makes the VI-to-XV disorder-to-order transition much favoured at low pressures. Indeed, [[differential scanning calorimetry]] by Shephard and Salzmann revealed that reheating quench-recovered HCl-doped ice XV at ambient pressure even produces exotherms originating from transient ordering, ''i.e.'' more ordered ice XV is obtained at ambient pressure. Being consistent with this, the ice VI-XV transition is reversible at ambient pressure.<ref name="Shephard Salzmann 2015 pp. 63–66">{{cite journal | last=Shephard | first=Jacob J. | last2=Salzmann | first2=Christoph G. | title=The complex kinetics of the ice VI to ice XV hydrogen ordering phase transition | journal=Chemical Physics Letters | publisher=Elsevier BV | volume=637 | year=2015 | issn=0009-2614 | doi=10.1016/j.cplett.2015.07.064 | pages=63–66| arxiv=1507.02665 }}</ref> |
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It was also shown that HCl-doping is selectively effective in producing ice XV while other acids and bases (HF, LiOH, HClO<sub>4</sub>, HBr) do not significantly enhance ice XV formations.<ref name="Rosu-Finsen Salzmann 2018 p. 244507">{{cite journal | last=Rosu-Finsen | first=Alexander | last2=Salzmann | first2=Christoph G. | title=Benchmarking acid and base dopants with respect to enabling the ice V to XIII and ice VI to XV hydrogen-ordering phase transitions | journal=The Journal of Chemical Physics | publisher=AIP Publishing | volume=148 | issue=24 | date=2018-06-28 | issn=0021-9606 | doi=10.1063/1.5022159 | page=244507| arxiv=1801.03812 }}</ref> |
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Based on powder neutron diffraction, the crystal structure of ice XV has been investigated in detail. Komatsu et al. suggested that, in combination with density functional theory calculations, none of the possible perfectly ordered orientational configurations are energetically favoured, suggesting that there are several energetically close configurations that coexist in ice XV. They proposed 'the orthorhombic ''Pmmn'' space group as a plausible space group to describe the time-space averaged structure of ice XV.<ref name="Komatsu Noritake Machida Sano-Furukawa 2016 p. ">{{cite journal | last=Komatsu | first=K. | last2=Noritake | first2=F. | last3=Machida | first3=S. | last4=Sano-Furukawa | first4=A. | last5=Hattori | first5=T. | last6=Yamane | first6=R. | last7=Kagi | first7=H. | title=Partially ordered state of ice XV | journal=Scientific Reports | publisher=Springer Science and Business Media LLC | volume=6 | issue=1 | date=2016-07-04 | issn=2045-2322 | doi=10.1038/srep28920 | page=| pmc=4931510 }}</ref> |
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== Ice IV == |
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Salzmann et al. argued that ''P''-1 model is still the best (with the second best candidate of ''P''2<sub>1</sub>), whereas Rietveld refinement using the Pmmn space group only works well for poorly ordered samples. The lattice parameters, in particular ''b'' and ''c'', are good indicators of the ice XV formation. Combining density functional theory calculations, they successfully constructed fully ordered model in ''P''-1 and showed that experimental diffraction data should be analysed using space groups that permit full hydrogen order while the Pmmn model only accepts partially ordered structures.<ref name="Salzmann Slater Radaelli Finney 2016 p. ">{{cite journal | last=Salzmann | first=Christoph G. | last2=Slater | first2=Ben | last3=Radaelli | first3=Paolo G. | last4=Finney | first4=John L. | last5=Shephard | first5=Jacob J. | last6=Rosillo-Lopez | first6=Martin | last7=Hindley | first7=James | title=Detailed crystallographic analysis of the ice VI to ice XV hydrogen ordering phase transition | journal=The Journal of Chemical Physics | publisher=AIP Publishing | volume=145 | issue=20 | date=2016-11-22 | issn=0021-9606 | doi=10.1063/1.4967167 | page=| arxiv=1607.04794 }}</ref> --> |
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{{for|the high speed train|ICE 4}} |
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'''Ice IV''' is a metastable high-pressure phase of [[ice]]. It is formed when liquid water is compressed with an immense force. |
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==Practical implications== |
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=== Preparation === |
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=== Earth's natural environment === |
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Several organic nucleating reagents had been proposed to selectively crystallize ice IV from liquid water,<ref>{{Citation | vauthors=((Evans, L. F.)) | year=1967 | title=Selective Nucleation of the High‐Pressure Ices | journal=Journal of Applied Physics | volume=38 | issue=12 | pages=4930–4932 | publisher=AIP Publishing | doi=10.1063/1.1709255 | url=http://dx.doi.org/10.1063/1.1709255}}</ref> but even with such reagents, the crystallization of ice IV from liquid water was very difficult and seemed to be a random event. |
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[[image:Icecube-detail.jpg|thumb|Photograph showing details of an ice cube under magnification. Ice I<sub>h</sub> is the form of ice commonly seen on Earth.]] |
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[[image:Phase Space of Ice Ih.png|thumb|Phase space of ice I<sub>h</sub> with respect to other ice phases.]] |
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Virtually all ice in the [[biosphere]] is ice I<sub>h</sub> (pronounced: '''ice one h''', also known as '''ice-phase-one'''). Ice I<sub>h</sub> exhibits many peculiar properties that are relevant to the existence of life and regulation of [[Climatology|global climate]]. <ref>{{cite web |type=Physics 511 paper |url=http://atom.me.gatech.edu/zhut/Courses/Courses_HarvardCollection/caiwei/phasesofice.pdf|title=The Many Phases of Ice|author=Norman Anderson|publisher=Iowa State University|archive-url=https://web.archive.org/web/20091007073915/http://atom.me.gatech.edu/zhut/Courses/Courses_HarvardCollection/caiwei/phasesofice.pdf|archive-date=7 October 2009}}</ref> For instance, its density is lower than that of [[Properties of water|liquid water]]. This is attributed to the presence of [[hydrogen bonds]] which causes atoms to become closer in the liquid phase.<ref>{{cite book|url=https://books.google.com/books?id=BV6cAQAAQBAJ&pg=PA144 |first=Peter |last=Atkins |first2=Julio |last2=de Paula |page=144 |title=Physical chemistry.|date=2010|publisher=W. H. Freeman and Co.|location=New York|isbn=978-1429218122|edition=9th}}</ref> Because of this, ice I<sub>h</sub> floats on water, which is highly unusual when compared to other materials. The solid phase of materials is usually more closely and neatly packed and has a higher density than the liquid phase. When lakes freeze, they do so only at the surface, while the bottom of the lake remains near {{convert|4|C|K F|0}} because water is densest at this temperature. This anomalous behavior of water and ice is what allows fish to survive harsh winters. The density of ice I<sub>h</sub> increases when cooled, down to about {{convert|-211|C|K F|0}}; below that temperature, the ice expands again ([[negative thermal expansion]]).<ref name=Rottger /><ref name=Buckingham /> |
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Besides ice I<sub>h</sub>, a small amount of ice I<sub>c</sub> may occasionally present in the upper atmosphere clouds.<ref>{{cite journal |last=Murray |first=Benjamin J.|author2=Knopf, Daniel A. |author3=Bertram, Allan K. |year=2005|title=The formation of cubic ice under conditions relevant to Earth's atmosphere|journal=Nature|volume=434|pages=202–205|doi=10.1038/nature03403|pmid=15758996|issue=7030|bibcode=2005Natur.434..202M|s2cid=4427815}}</ref> It is believed to be responsible for the observation of Scheiner's [[Halo (optical phenomenon)|halo]], a rare ring that occurs near 28 degrees from the Sun or the Moon.<ref>{{Cite journal |last=Whalley |first=E. |year=1981 |title=Scheiner's Halo: Evidence for Ice I{{sub|c}} in the Atmosphere |journal=Science |volume=211 |issue=4480 |pages=389–390 |bibcode=1981Sci...211..389W |doi=10.1126/science.211.4480.389 |pmid=17748273}}</ref> However, many atmospheric samples which were previously described as cubic ice were later shown to be stacking disordered ice with trigonal symmetry,<ref>{{Cite journal |last1=Murray |first1=Benjamin J. |last2=Salzmann |first2=Christoph G. |last3=Heymsfield |first3=Andrew J. |last4=Dobbie |first4=Steven |last5=Neely |first5=Ryan R. |last6=Cox |first6=Christopher J. |year=2015 |title=Trigonal Ice Crystals in Earth's Atmosphere |url=http://eprints.whiterose.ac.uk/86859/8/MurrayTrigonalIceCrystals.pdf |journal=Bulletin of the American Meteorological Society |volume=96 |issue=9 |pages=1519–1531 |bibcode=2015BAMS...96.1519M |doi=10.1175/BAMS-D-13-00128.1}}</ref><ref>{{Cite web |last=Chaplin |first=Martin |date=15 September 2019 |title=Stacking disordered ice; Ice I{{sub|sd}} |url=http://www1.lsbu.ac.uk/water/ice1h1c.html |archive-url=https://web.archive.org/web/20201022120831/http://www1.lsbu.ac.uk/water/ice1h1c.html |archive-date=22 Oct 2020 |access-date=3 December 2019 |website=Water Structure and Science |publisher=[[London South Bank University]]}}</ref><ref>{{cite journal |last1=Malkin |first1=Tamsin L. |last2=Murray |first2=Benjamin J. |last3=Salzmann |first3=Christoph G. |last4=Molinero |first4=Valeria |last5=Pickering |first5=Steven J. |last6=Whale |first6=Thomas F. |title=Stacking disorder in ice I |journal=Physical Chemistry Chemical Physics |date=2015 |volume=17 |issue=1 |pages=60–76 |doi=10.1039/c4cp02893g|pmid=25380218 |doi-access=free }}</ref> and it has been dubbed the ″most faceted ice phase in a literal and a more general sense.″<ref>{{Cite journal |last1=Kuhs |first1=W. F. |last2=Sippel |first2=C. |last3=Falenty |first3=A. |last4=Hansen |first4=T. C. |year=2012 |title=Extent and relevance of stacking disorder in "ice I{{sub|c}}" |journal=Proceedings of the National Academy of Sciences of the United States of America |volume=109 |issue=52 |pages=21259–21264 |bibcode=2012PNAS..10921259K |doi=10.1073/pnas.1210331110 |pmc=3535660 |pmid=23236184 |doi-access=free }}</ref> The first true samples of cubic ice were only reported in 2020.<ref>{{cite journal |last1=Salzmann |first1=Christoph G. |last2=Murray |first2=Benjamin J. |title=Ice goes fully cubic |journal=Nature Materials |date=June 2020 |volume=19 |issue=6 |pages=586–587 |doi=10.1038/s41563-020-0696-6|pmid=32461682 |bibcode=2020NatMa..19..586S |s2cid=218913209 }}</ref><ref name="pmid32015342">{{cite journal |author=Komatsu K, Machida S, Noritake F, Hattori T, Sano-Furukawa A, Yamane R |display-authors=etal |title=Ice Ic without stacking disorder by evacuating hydrogen from hydrogen hydrate. |journal=Nat Commun |year=2020 |volume=11 |issue=1 |pages=464 |pmid=32015342 |doi=10.1038/s41467-020-14346-5 |pmc=6997176|arxiv=1909.03400 |bibcode=2020NatCo..11..464K }}</ref><ref name="pmid32015533">{{cite journal |author=Del Rosso L, Celli M, Grazzi F, Catti M, Hansen TC, Fortes AD |display-authors=etal |title=Cubic ice Ic without stacking defects obtained from ice XVII. |journal=Nat Mater |year=2020 |volume=19 |issue=6 |pages=663–668 |pmid=32015533 |doi=10.1038/s41563-020-0606-y |pmc= |arxiv=1907.02915 |bibcode=2020NatMa..19..663D |s2cid=195820566 |url=https://pubmed.ncbi.nlm.nih.gov/32015533 }}</ref> |
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In 2001, Salzmann and his coworkers reported a whole new method to prepare ice IV ''reproducibly'';<ref>{{Citation | vauthors=((Salzmann, C. G.)), ((Loerting, T.)), ((Kohl, I.)), ((Mayer, E.)), ((Hallbrucker, A.)) |author2-link=Thomas Loerting| year=2002 | title=Pure Ice IV from High-Density Amorphous Ice |journal=The Journal of Physical Chemistry B |volume=106 |issue=22 |pages=5587–5590 | publisher=American Chemical Society (ACS) |doi=10.1021/jp014391v | url=http://dx.doi.org/10.1021/jp014391v}}</ref> when [[High density amorphous ice|high-density amorphous ice (HDA)]] is heated at a rate of 0.4 K/min and a pressure of 0.81 GPa, ice IV is crystallized at about 165 K. What governs the crystallization products is the heating rate; fast heating (over 10 K/min) results in the formation of single-phase [[ice XII]]. |
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Low-density ASW (LDA), also known as hyperquenched glassy water, may be responsible for [[noctilucent clouds]] on Earth and is usually formed by [[vapor deposition|deposition]] of water vapor in cold or vacuum conditions. Ice clouds form at and below the Earth's high latitude mesopause (~90 km) where temperatures have been observed to fall as to below 100 K.<ref>{{cite journal |last1=Lübken |first1=F.-J. |last2=Lautenbach |first2=J. |last3=Höffner |first3=J. |last4=Rapp |first4=M. |last5=Zecha |first5=M. |title=First continuous temperature measurements within polar mesosphere summer echoes |journal=Journal of Atmospheric and Solar-Terrestrial Physics |date=March 2009 |volume=71 |issue=3–4 |pages=453–463 |doi=10.1016/j.jastp.2008.06.001|bibcode=2009JASTP..71..453L }}</ref> It has been suggested that homogeneous nucleation of ice particles results in low density amorphous ice.<ref>{{cite journal |last1=Murray |first1=Benjamin J. |last2=Jensen |first2=Eric J. |title=Homogeneous nucleation of amorphous solid water particles in the upper mesosphere |journal=Journal of Atmospheric and Solar-Terrestrial Physics |date=January 2010 |volume=72 |issue=1 |pages=51–61 |doi=10.1016/j.jastp.2009.10.007|bibcode=2010JASTP..72...51M }}</ref> Amorphous ice is likely confined to the coldest parts of the clouds and stacking disordered ice I is thought to dominate elsewhere in these [[polar mesospheric clouds]].<ref>{{cite journal |last1=Murray |first1=Benjamin J. |last2=Malkin |first2=Tamsin L. |last3=Salzmann |first3=Christoph G. |title=The crystal structure of ice under mesospheric conditions |journal=Journal of Atmospheric and Solar-Terrestrial Physics |date=May 2015 |volume=127 |pages=78–82 |doi=10.1016/j.jastp.2014.12.005 |bibcode=2015JASTP.127...78M |doi-access=free }}</ref> |
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=== Crystal structure === |
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The crystal structure of ice IV was elucidated by Engelhardt and Kamb in 1981 by low-temperature single-crystal X-ray diffraction.<ref>{{Citation | vauthors=((Engelhardt, H.)), ((Kamb, B.)) | year=1981 | title=Structure of ice IV, a metastable high‐pressure phase | journal=The Journal of Chemical Physics | volume=75 | issue=12 | pages=5887–5899 | publisher=AIP Publishing | doi=10.1063/1.442040 | url=http://dx.doi.org/10.1063/1.442040}}</ref> Its structure is described by a rhombohedral unit cell with a space group of R-3c. The hydrogen geometry had been suggested to be completely disordered as IR <ref>{{Citation | vauthors=((Engelhardt, H.)), ((Whalley, E.)) | year=1979 | title=The infrared spectrum of ice IV in the range 4000–400 cm−1 | journal=The Journal of Chemical Physics | volume=71 | issue=10 | pages=4050–4051 | publisher=AIP Publishing | doi=10.1063/1.438173 | url=http://dx.doi.org/10.1063/1.438173}}</ref> and Raman <ref>{{Citation | vauthors=((Salzmann, C. G.)), ((Kohl, I.)), ((Loerting, T.)), ((Mayer, E.)), ((Hallbrucker, A.)) | year=2003 | title=Raman Spectroscopic Study on Hydrogen Bonding in Recovered Ice IV | journal=The Journal of Physical Chemistry B | volume=107 | issue=12 | pages=2802–2807 | publisher=American Chemical Society (ACS) | doi=10.1021/jp021534k | url=http://dx.doi.org/10.1021/jp021534k}}</ref> spectra consist only of broad peaks, and the disordered nature was confirmed by neutron powder diffraction studies by Lobban (1998) <ref>{{Citation | vauthors=((Colin Lobban)) | year=1998 | title=Neutron diffraction studies of ices | publisher=University College London | url=https://www.proquest.com/docview/1752797359| id={{ProQuest|1752797359}} }}</ref> and Klotz et al. (2003).<ref>{{Citation | vauthors=((Klotz, S.)), ((Hamel, G.)), ((Loveday, J. S.)), ((Nelmes, R. J.)), ((Guthrie, M.)) | year=2003 | title=Recrystallisation of HDA ice under pressure by in-situ neutron diffraction to 3.9 GPa | journal=Zeitschrift für Kristallographie - Crystalline Materials | volume=218 | issue=2 | pages=117–122 | publisher=Walter de Gruyter GmbH | doi=10.1524/zkri.218.2.117.20669 | s2cid=96109290 | url=http://dx.doi.org/10.1524/zkri.218.2.117.20669}}</ref> In addition, the entropy difference between ice VI (disordered phase) and ice IV is very small, according to Bridgman's measurement.<ref>{{Citation | vauthors=((Bridgman, P. W.)) | year=1935 | title=The Pressure‐Volume‐Temperature Relations of the Liquid, and the Phase Diagram of Heavy Water | journal=The Journal of Chemical Physics | volume=3 | issue=10 | pages=597–605 | publisher=AIP Publishing | doi=10.1063/1.1749561 | url=http://dx.doi.org/10.1063/1.1749561}}</ref> |
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==== Engelhardt–Kamb Collapse (EKC) ==== |
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Engelhardt and Kamb mentioned in the paper in 1981 that the structure of ice IV could be derived from the structure of [[ice Ic]] by cutting and forming some hydrogen bondings and adding subtle structural distortions. Shephard et al.<ref>{{Citation | vauthors=((Shephard, J. J.)), ((Ling, S.)), ((Sosso, G. C.)), ((Michaelides, A.)), ((Slater, B.)), ((Salzmann, C. G.)) | year=2017 | title=Is High-Density Amorphous Ice Simply a "Derailed" State along the Ice I to Ice IV Pathway? | journal=The Journal of Physical Chemistry Letters | volume=8 | issue=7 | pages=1645–1650 | publisher=American Chemical Society (ACS) | doi=10.1021/acs.jpclett.7b00492 | pmid=28323429 | s2cid=13662778 | url=http://dx.doi.org/10.1021/acs.jpclett.7b00492| arxiv=1701.05398 }}</ref> compressed the ambient phase of NH<sub>4</sub>F, an isostructural material of ice, to obtain NH<sub>4</sub>F II, whose hydrogen-bonded network is similar to ice IV. As the compression of [[ice Ih]] results in the formation of high-density amorphous ice (HDA), not ice IV, they claimed that the compression-induced conversion of ice I into ice IV is important, naming it "Engelhardt–Kamb collapse" (EKC). They suggested that the reason why we cannot obtain ice IV directly from ice Ih is that ice Ih is hydrogen-disordered; if oxygen atoms are arranged in the ice IV structure, hydrogen bonding may not be formed due to the donor-acceptor mismatch. |
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=== Quest for hydrogen ordering === |
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As discussed above, ice IV is a hydrogen-disordered phase. Its ordered counterpart, however, has never been reported yet. Salzmann et al. (2011) <ref name="pmid21946782">{{citation| last1=Salzmann|first1= CG|last2= Radaelli|first2= PG|last3= Slater|first3= B|last4= Finney|first4= JL| title=The polymorphism of ice: five unresolved questions. | journal=Phys Chem Chem Phys | year= 2011 | volume= 13 | issue= 41 | pages= 18468–80 | pmid=21946782 | doi=10.1039/c1cp21712g | pmc= | url=https://pubmed.ncbi.nlm.nih.gov/21946782 }}</ref> reported the DSC thermograms of HCl-doped ice IV finding an endothermic feature at about 120 K. Ten years later, Rosu-Finsen and Salzmann (2021) <ref>{{Citation | vauthors=((Rosu-Finsen, A.)), ((Salzmann, C. G.)) | year=2022 | title=Is pressure the key to hydrogen ordering ice IV? | journal=Chemical Physics Letters | volume=789 | page=139325 | publisher=Elsevier BV | doi=10.1016/j.cplett.2021.139325 | s2cid=245597764 | url=http://dx.doi.org/10.1016/j.cplett.2021.139325}} |
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</ref> reported more detailed DSC data where the endothermic feature becomes larger as the sample is quench-recovered at higher pressure. They proposed three scenarios to explain the experimental results: weak hydrogen-ordering, orientational glass transition, and mechanical distortions. |
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== Ice V == |
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{{About|the form of water ice|the high-speed train|Intercity Experimental{{!}}ICE V|internal combustion engine vehicle|Internal combustion engine#Applications{{!}}ICEV|the King Gizzard & the Lizard Wizard song|Ice V (song)}} |
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{{Redirect|Ice 5|the ice hockey series|Freeway Face-Off}} |
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Ice V, pronounced "ice five", is a [[monoclinic crystal system|monoclinic]] crystalline [[Ice#Phases|phase of water]], formed by cooling water to 253 [[kelvin|K]] at 500 [[MPa]]. It has a [[density]] of 1.24 g cm<sup>3</sup> (at 350 MPa).<ref>{{Cite journal|last=Drost-Hansen|first=W.|date=1969-11-14|title=The Structure and Properties of Water. D. Eisenberg and W. Kauzmann. Oxford University Press, New York, 1969. xiv + 300 pp., illus. Cloth, $10; paper, $4.50|journal=Science|volume=166|issue=3907|pages=861|doi=10.1126/science.166.3907.861|issn=0036-8075}}</ref> |
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Ice V has a complicated structure, including 4-membered, 5-membered, 6-membered, and 8-membered rings and a total of 28 [[Molecule|molecules]] in the unit cell.<ref name=chaplin>{{cite web|title=Ice-five (Ice V)|url=http://www.lsbu.ac.uk/water/ice_v.html|last=Chaplin|first=Martin|date=20 December 2019|access-date=5 June 2021|archiveurl=https://web.archive.org/web/20200813070858/http://www1.lsbu.ac.uk/water/ice_v.html|archivedate=2020-08-13}}</ref><ref name=kamb1967>{{Cite journal | doi = 10.1107/S0365110X67001409| title = Structure of ice. V| journal = Acta Crystallographica| volume = 22| issue = 5| pages = 706| year = 1967| last1 = Kamb | first1 = B.| last2 = Prakash | first2 = A.| last3 = Knobler | first3 = C.| url = https://resolver.caltech.edu/CaltechAUTHORS:20160913-124848654}}</ref> [[Ganymede (moon)|Ganymede]]'s interior probably includes a liquid water ocean with tens to hundreds of kilometers of ice V at its base.<ref name=showman1997>{{Cite journal | doi = 10.1006/icar.1997.5778| title = Coupled Orbital and Thermal Evolution of Ganymede| journal = Icarus| volume = 129| issue = 2| pages = 367–383| year = 1997| last1 = Showman | first1 = A. | bibcode = 1997Icar..129..367S| url = http://www.lpl.arizona.edu/~showman/publications/showman-etal-1997.pdf}}</ref> |
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== Ice VI == |
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'''Ice VI''' is a form of [[ice]] that exists at [[high pressure]] at the order of about 1 [[GPa]] (= 10 000 [[bar (unit)|bar]]) and temperatures ranging from 130 up to 355 Kelvin (−143 °C up to 82 °C); see also the phase diagram of water. Its discovery and the discovery of other high-pressure forms of water were published by [[Percy Williams Bridgman|P.W. Bridgman]] in January 1912.<ref>[https://www.jstor.org/stable/20022754 ''Water, in the Liquid and Five Solid Forms, under Pressure''] P.W. Bridgman (1912), www.jstor.org, retrieved 3 October 2019</ref> |
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It is part of one of the inner layers of [[Titan (moon)|Titan]].<ref>{{Cite web|url=https://solarsystem.nasa.gov/moons/saturn-moons/titan/in-depth/|title=Titan - in Depth}}</ref> |
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=== Properties === |
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Ice VI has a [[density]] of 1.31 g/cm<sup>3</sup> and a [[tetragonal crystal system]] with the [[List of space groups#List of Tetragonal|space group P4<sub>2</sub>/nmc]]; its [[Crystal structure#unit cell|unit cell]] contains 10 water molecules and has the dimensions a=6.27 [[Å]] and c=5.79 Å.<ref>[https://www.science.org/doi/10.1126/science.150.3693.205 ''Reports: Structure of Ice VI''] science.sciencemag.org, B. Kamb, 8 October 1965.</ref> |
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The [[triple point]] of ''ice VI'' with [[ice VII]] and liquid water is at about 82 °C and 2.22 GPa and its triple point with [[ice V]] and liquid water is at 0.16 °C and 0.6324 GPa = 6324 bar.<ref>[http://www1.lsbu.ac.uk/water/water_phase_diagram.html Water Phase Diagram] {{Webarchive|url=https://web.archive.org/web/20160314181432/http://www1.lsbu.ac.uk/water/water_phase_diagram.html |date=2016-03-14 }} www1.lsbu.ac.uk, version of 9 September 2019, retrieved 3 October 2019</ref> |
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Ice VI undergoes phase transitions into ices [[ice XV|XV]]<ref name="pmid19792330">{{cite journal| author=Salzmann CG, Radaelli PG, Mayer E, Finney JL| title=Ice XV: a new thermodynamically stable phase of ice. | journal=Phys Rev Lett | year= 2009 | volume= 103 | issue= 10 | pages= 105701 | pmid=19792330 | doi=10.1103/PhysRevLett.103.105701 | pmc= | arxiv=0906.2489 | bibcode=2009PhRvL.103j5701S | s2cid=13999983 | url=https://pubmed.ncbi.nlm.nih.gov/19792330 }}</ref> and XIX <ref name="pmid33602936">{{cite journal |author=Yamane R, Komatsu K, Gouchi J, Uwatoko Y, Machida S, Hattori T, Kagi H |display-authors=etal |year=2021 |title=Experimental evidence for the existence of a second partially-ordered phase of ice VI. |journal=Nat Commun |volume=12 |issue=1 |pages=1129 |doi=10.1038/s41467-021-21351-9 |pmc=7893076 |pmid=33602936|bibcode=2021NatCo..12.1129Y }}</ref> upon cooling depending on pressure as [[hydrochloric acid]] is doped. |
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== Ice VII == |
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[[File:Ice VII Crystal Structure.jpg|thumb|The crystal structure of Ice VII. The red atoms are oxygen while the pink atoms are hydrogen. Image generated using CrystalMaker®.]] |
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Ice VII is a [[cubic crystal system|cubic crystalline]] form of [[ice]]. It can be formed from liquid water above 3 [[Pascal (unit)|GPa]] (30,000 atmospheres) by lowering its temperature to room temperature, or by decompressing [[heavy water]] (D<sub>2</sub>O) [[Ice#Phases|ice VI]] below 95 K. (Different types of ice, from [[ice II]] to [[Superionic water|ice XVIII]], have been created in the laboratory at different temperatures and pressures. Ordinary water ice is known as [[ice Ih|ice I<sub>h</sub>]] in the [[Percy Williams Bridgman|Bridgman]] nomenclature.) Ice VII is [[metastable]] over a wide range of temperatures and pressures and transforms into low-density [[amorphous ice]] (LDA) above {{Convert|120|K|C}}.<ref>S. Klotz, J. M. Besson, G. Hamel, R. J. Nelmes, J. S. Loveday and W. G. Marshall, Metastable ice VII at low temperature and ambient pressure, Nature 398 (1999) 681–684.</ref> Ice VII has a [[triple point]] with liquid water and ice VI at 355 K and 2.216 GPa, with the melt line extending to at least {{Convert|715|K|C}} and 10 GPa.<ref name="IAPWS">{{cite web | url = http://www.iapws.org/relguide/meltsub.pdf | title = IAPWS, Release on the pressure along the melting and the sublimation curves of ordinary water substance, 1993 | access-date = 2008-02-22 | archive-url = https://web.archive.org/web/20081006141126/http://www.iapws.org/relguide/meltsub.pdf | archive-date = 2008-10-06 }}</ref> Ice VII can be formed within nanoseconds by rapid compression via shock-waves.<ref>{{cite journal | last1 = Dolan | first1 = D | last2 = Gupta | first2 = Y | title = Nanosecond freezing of water under multiple shock wave compression: Optical transmission and imaging measurements | journal = J. Chem. Phys. | volume = 121 | issue = 18 | pages = 9050–9057 | year = 2004 | doi = 10.1063/1.1805499 | pmid = 15527371 | bibcode = 2004JChPh.121.9050D }}</ref><ref>{{cite journal | last1 = Myint | first1 = P | last2 = Benedict | first2 = L | last3 = Belof | first3 = J | title = Free energy models for ice VII and liquid water derived from pressure, entropy, and heat capacity relations | journal = J. Chem. Phys. | volume = 147 | issue = 8 | page = 084505 | year = 2017 | doi = 10.1063/1.4989582 | pmid = 28863506 | bibcode = 2017JChPh.147h4505M | osti = 1377687 | doi-access = free }}</ref> It can also be created by increasing the pressure on ice VI at ambient temperature.<ref name="Johari et al.">{{Citation |first1=G. P. |last1=Johari |first2=A. |last2=Lavergne |first3=E. |last3=Whalley |name-list-style=amp |journal=Journal of Chemical Physics |volume=61 |issue=10 |page=4292 |year=1974 |title=Dielectric properties of ice VII and VIII and the phase boundary between ice VI and VII |doi=10.1063/1.1681733 |bibcode = 1974JChPh..61.4292J }}</ref> At around 5 GPa, Ice VII becomes the tetragonal Ice VII<sub>t</sub>.<ref name="viit">{{cite journal |last1=Grande |first1=Zachary M. |display-authors=etal |title=Pressure-driven symmetry transitions in dense H2O ice |journal=APS Physics |year=2022 |volume=105 |issue=10 |page=104109 |doi=10.1103/PhysRevB.105.104109|bibcode=2022PhRvB.105j4109G |s2cid=247530544 }}</ref> |
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Like the majority of ice phases (including [[ice Ih|ice I<sub>h</sub>]]), the [[hydrogen]] atom positions are disordered.<ref name="Petrenko">{{Citation |first1=V. F. |last1=Petrenko |first2=R. W. |last2=Whitworth |title=The Physics of Ice |publisher=Oxford University Press |location=New York |year=2002 }}.</ref> In addition, the [[oxygen]] atoms are disordered over multiple sites.<ref name="kuhs">{{Citation |first1=W. F. |last1=Kuhs |first2=J. L. |last2=Finney |first3=C. |last3=Vettier |first4=D. V. |last4=Bliss |name-list-style=amp |journal=Journal of Chemical Physics |volume=81 |issue=8 |pages=3612–3623 |year=1984 |title=Structure and hydrogen ordering in ices VI, VII, and VIII by neutron powder diffraction |doi=10.1063/1.448109 |bibcode = 1984JChPh..81.3612K }}.</ref><ref name="jorgensen">{{Citation |first1=J. D. |last1=Jorgensen |first2=T. G. |last2=Worlton |journal=Journal of Chemical Physics |volume=83 |issue=1 |pages=329–333 |year=1985 |title=Disordered structure of D<sub>2</sub>O ice VII from in situ neutron powder diffraction |doi=10.1063/1.449867 |bibcode = 1985JChPh..83..329J |url=https://zenodo.org/record/1232091 }}.</ref><ref name="nelmes">{{Citation |first1=R. J. |last1=Nelmes |first2=J. S. |last2=Loveday |first3=W. G. |last3=Marshall |journal=[[Physical Review Letters]] |volume=81 |issue=13 |pages=2719–2722 |year=1998 |title=Multisite Disordered Structure of Ice VII to 20 GPa |doi=10.1103/PhysRevLett.81.2719 |bibcode=1998PhRvL..81.2719N|display-authors=etal}}.</ref> The structure of ice VII comprises a [[hydrogen bond]] framework in the form of two interpenetrating (but non-bonded) sublattices.<ref name="kuhs"/> Hydrogen bonds pass through the center of the water hexamers and thus do not connect the two lattices. Ice VII has a density of about 1.65 g cm<sup>−3</sup> (at 2.5 GPa and {{Convert|25|C|F K}}),<ref>D. Eisenberg and W. Kauzmann, The structure and properties of water (Oxford University Press, London, 1969); (b) The dodecahedral interstitial model is described in L. Pauling, The structure of water, In Hydrogen bonding, Ed. D. Hadzi and H. W. Thompson ([[Pergamon Press]] Ltd, London, 1959) pp 1–6.</ref> which is less than twice the [[cubic ice]] density as the intra-network O–O distances are 8% longer (at 0.1 MPa) to allow for interpenetration. The cubic unit cell has a side length of 3.3501 Å (for D<sub>2</sub>O, at 2.6 GPa and {{Convert|22|C|F K}}) and contains two water molecules.<ref name="jorgensen"/> |
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Ice VII is the only disordered phase of ice that can be ordered by simple cooling,<ref name="Johari et al."/><ref>Note: ice I<sub>h</sub> theoretically transforms into proton-ordered [[ice XI]] on geologic timescales, but in practice it is necessary to add small amounts of KOH catalyst.</ref> and it forms (ordered) [[ice VIII]] below 273 K up to ~8 GPa. Above this pressure, the VII–VIII transition temperature drops rapidly, reaching 0 K at ~60 GPa.<ref name="pruzan">{{Citation |first1=Ph. |last1=Pruzan |first2=J. C. |last2=Chervin |first3=B. |last3=Canny |name-list-style=amp |journal=Journal of Chemical Physics |volume=99 |issue=12 |pages=9842–9846 |year=1993 |title=Stability domain of the ice VIII proton-ordered phase at very high pressure and low temperature |doi=10.1063/1.465467 |bibcode = 1993JChPh..99.9842P }}.</ref> Thus, ice VII has the largest stability field of all of the molecular phases of ice. The cubic oxygen sub-lattices that form the backbone of the ice VII structure persist to pressures of at least 128 GPa;<ref name="hemley">{{Citation |first1=R. J. |last1=Hemley |first2=A. P. |last2=Jephcoat |first3=H. K. |last3=Mao |journal=[[Nature (journal)|Nature]] |issue=6150 |volume=330 |pages=737–740 |year=1987 |title=Static compression of H<sub>2</sub>O-ice to 128 GPa (1.28 Mbar) |doi=10.1038/330737a0 |bibcode = 1987Natur.330..737H |s2cid=4265919 |url=https://zenodo.org/record/1233067 |display-authors=etal}}.</ref> this pressure is substantially higher than that at which water loses its molecular character entirely, forming [[ice X]]. In high pressure ices, protonic diffusion (movement of protons around the oxygen lattice) dominates molecular diffusion, an effect which has been measured directly.<ref>{{cite journal|last=Katoh|first=E.|s2cid=38999963|title=Protonic Diffusion in High-Pressure Ice VII|journal=Science|date=15 February 2002 |volume=29=5558|issue=5558|pages=1264–1266|doi=10.1126/science.1067746|bibcode = 2002Sci...295.1264K|pmid=11847334}}</ref> |
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==Natural occurrence== |
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Scientists hypothesize that ice VII may comprise the ocean floor of [[Europa (moon)|Europa]] as well as [[Exoplanet|extrasolar planets]] (such as [[Gliese 436 b|Awohali]], and [[Gliese 1214 b|Enaiposha]]) that are largely made of water.<ref>University of Liège (2007, May 16). Astronomers Detect Shadow Of Water World In Front Of Nearby Star. ScienceDaily. Retrieved Jan. 3, 2010, from {{cite web |url=https://www.sciencedaily.com/releases/2007/05/070516151053.htm |title=Astronomers Detect Shadow of Water World in Front of Nearby Star |access-date=2018-04-22 |url-status=live |archive-url=https://web.archive.org/web/20170821212607/https://www.sciencedaily.com/releases/2007/05/070516151053.htm |archive-date=2017-08-21 }}</ref><ref>{{cite web |url=http://www.cfa.harvard.edu/news/2009/pr200924.html |title=Astronomers Find Super-Earth Using Amateur, Off-the-Shelf Technology |author=David A. Aguilar |date=2009-12-16 |publisher=Harvard-Smithsonian Center for Astrophysics |access-date=January 23, 2010 |url-status=live |archive-url=https://web.archive.org/web/20120407045343/http://www.cfa.harvard.edu/news/2009/pr200924.html |archive-date=April 7, 2012 }}</ref> |
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In 2018, ice VII was identified among [[Inclusion (mineral)|inclusions]] found in natural [[diamonds]].<ref>{{cite journal |author=O. Tschauner |author2=S Huang |author3=E. Greenberg |author4=V.B. Prakapenka |author5=C. Ma |author6=G.R. Rossman |author7=A.H. Shen |author8=D. Zhang |author9=M. Newville |author10=A. Lanzirotti |author11=K. Tait |title = Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth's deep mantle | journal = Science |year = 2018 |volume=359 |issue = 6380 |pages=1136–1139 |doi = 10.1126/science.aao3030 |pmid = 29590042 |bibcode = 2018Sci...359.1136T |s2cid = 206662912 | url = https://www.science.org/doi/10.1126/science.aao3030|doi-access = free }}</ref> Due to this demonstration that ice VII exists in nature, the [[International Mineralogical Association]] duly classified ice VII as a distinct [[mineral]].<ref>{{cite journal|url=https://www.science.org/content/article/pockets-water-may-lay-deep-below-earth-s-surface|title=Pockets of water may lay deep below Earth's surface|author=Sid Perkins|journal=Science|date=2018-03-08|access-date=March 8, 2018|url-status=live|archive-url=https://web.archive.org/web/20180308220310/http://www.sciencemag.org/news/2018/03/pockets-water-may-lay-deep-below-earth-s-surface|archive-date=March 8, 2018}}</ref> The ice VII was presumably formed when water trapped inside the diamonds retained the high pressure of the deep [[mantle (geology)|mantle]] due to the strength and rigidity of the diamond lattice, but cooled down to surface temperatures, producing the required environment of high pressure without high temperature.<ref>{{cite news|last1=Netburn|first1=Deborah|title=What scientists found trapped in a diamond: a type of ice not known on Earth|url=http://www.latimes.com/science/sciencenow/la-sci-sn-water-in-diamonds-20180308-story.html|access-date=12 March 2018|work=Los Angeles Times|url-status=live|archive-url=https://web.archive.org/web/20180312003000/http://www.latimes.com/science/sciencenow/la-sci-sn-water-in-diamonds-20180308-story.html|archive-date=12 March 2018}}</ref> |
In 2018, ice VII was identified among [[Inclusion (mineral)|inclusions]] found in natural [[diamonds]].<ref>{{cite journal |author=O. Tschauner |author2=S Huang |author3=E. Greenberg |author4=V.B. Prakapenka |author5=C. Ma |author6=G.R. Rossman |author7=A.H. Shen |author8=D. Zhang |author9=M. Newville |author10=A. Lanzirotti |author11=K. Tait |title = Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth's deep mantle | journal = Science |year = 2018 |volume=359 |issue = 6380 |pages=1136–1139 |doi = 10.1126/science.aao3030 |pmid = 29590042 |bibcode = 2018Sci...359.1136T |s2cid = 206662912 | url = https://www.science.org/doi/10.1126/science.aao3030|doi-access = free }}</ref> Due to this demonstration that ice VII exists in nature, the [[International Mineralogical Association]] duly classified ice VII as a distinct [[mineral]].<ref>{{cite journal|url=https://www.science.org/content/article/pockets-water-may-lay-deep-below-earth-s-surface|title=Pockets of water may lay deep below Earth's surface|author=Sid Perkins|journal=Science|date=2018-03-08|access-date=March 8, 2018|url-status=live|archive-url=https://web.archive.org/web/20180308220310/http://www.sciencemag.org/news/2018/03/pockets-water-may-lay-deep-below-earth-s-surface|archive-date=March 8, 2018}}</ref> The ice VII was presumably formed when water trapped inside the diamonds retained the high pressure of the deep [[mantle (geology)|mantle]] due to the strength and rigidity of the diamond lattice, but cooled down to surface temperatures, producing the required environment of high pressure without high temperature.<ref>{{cite news|last1=Netburn|first1=Deborah|title=What scientists found trapped in a diamond: a type of ice not known on Earth|url=http://www.latimes.com/science/sciencenow/la-sci-sn-water-in-diamonds-20180308-story.html|access-date=12 March 2018|work=Los Angeles Times|url-status=live|archive-url=https://web.archive.org/web/20180312003000/http://www.latimes.com/science/sciencenow/la-sci-sn-water-in-diamonds-20180308-story.html|archive-date=12 March 2018}}</ref> |
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Ice XI is thought to be a more stable conformation than ice I<sub>h</sub>, and so it may form on Earth. However, the transformation is very slow. According to one report, in Antarctic conditions it is estimated to take at least 100,000 years to form without the assistance of catalysts.{{citation needed|date=August 2017}} Ice XI was sought and found in Antarctic ice that was about 100 years old in 1998.<ref>{{cite journal |doi=10.1016/S0009-2614(98)00908-7 |title=Proton ordering in Antarctic ice observed by Raman and neutron scattering |journal=Chemical Physics Letters |volume=294 |issue=6 |pages=554–558 |year=1998 |last1=Fukazawa |first1=Hiroshi |last2=Mae |first2=Shinji |last3=Ikeda |first3=Susumu |last4=Watanabe |first4=Okitsugu |bibcode=1998CPL...294..554F }}</ref> A further study in 2004 was not able to reproduce this finding, however, after studying Antarctic ice which was around 3000 years old.<ref>{{cite journal|last=Fortes|first=A. D.|author2=Wood, I. G.|author3=Grigoriev, D.|author4=Alfredsson, M.|author5=Kipfstuhl, S.|author6=Knight, K. S.|author7=Smith, R. I.|title=No evidence for large-scale proton ordering in Antarctic ice from powder neutron diffraction|journal=The Journal of Chemical Physics|date=1 January 2004|volume=120|issue=24|pages=11376–9|doi=10.1063/1.1765099|url=http://jcp.aip.org/resource/1/jcpsa6/v120/i24/p11376_s1?isAuthorized=no|pmid=15268170|bibcode=2004JChPh.12011376F|access-date=22 April 2012|archive-url=https://archive.today/20120729031327/http://jcp.aip.org/resource/1/jcpsa6/v120/i24/p11376_s1?isAuthorized=no|archive-date=29 July 2012|url-status=dead}}</ref> The 1998 Antarctic study also claimed that the transformation temperature (ice XI => ice I<sub>h</sub>) is {{convert|-36|°C|K}}, which is far higher than the temperature of the expected triple point mentioned above (72 K, ~0 Pa). Ice XI was also found in experiments using pure water at very low temperature (~10 K) and low pressure – conditions thought to be present in the upper atmosphere.<ref>{{cite journal | last1 = Furić | first1 = K. | last2 = Volovšek | first2 = V. | year = 2010 | title = Water ice at low temperatures and pressures; new Raman results | journal = J. Mol. Structure | volume = 976 | issue = 1–3| pages = 174–180 | doi=10.1016/j.molstruc.2010.03.024| bibcode = 2010JMoSt.976..174F }}</ref> Recently, small domains of ice XI were found to form in pure water; its phase transition back to ice I<sub>h</sub> occurred at 72 K while under hydrostatic pressure conditions of up to 70 MPa.<ref>{{cite journal|last1=Yen|first1=Fei|last2=Chi|first2=Zhenhua|title=Proton ordering dynamics of H<sub>2</sub>O ice|journal=Physical Chemistry Chemical Physics|date=16 Apr 2015|volume=17|issue=19|pages=12458–12461|doi=10.1039/C5CP01529D|pmid=25912948|arxiv = 1503.01830 |bibcode = 2015PCCP...1712458Y |s2cid=7736338}}</ref> |
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== Ice VIII == |
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[[File:Iceviiistructure-ru.gif|thumb|The crystal structure of ice VIII]] |
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=== Human industry === |
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Ice VIII is a [[tetragonal]] crystalline form of [[ice]] formed from [[ice VII]] by cooling it below 5 °C. It is more ordered than ice VII, since the [[hydrogen]] atoms assume fixed positions.<ref>{{cite web |url=http://www.lsbu.ac.uk/water/ice_viii.html |title=Ice-eight structure |access-date=January 2, 2008 |author=Chaplin, Martin |date=July 1, 2007 |work=Water Structure and Science}}</ref> |
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Amorphous ice is used in some scientific experiments, especially in [[cryo-electron microscopy]] of biomolecules.<ref>{{cite journal|last1=Dubochet|first1=J.|last2=Adrian|first2=M.|last3=Chang|first3=J. .J|last4=Homo|first4=J. C.|last5=Lepault|first5=J-|last6=McDowall|first6=A. W.|last7=Schultz |first7=P. |year=1988 |title=Cryo-electron microscopy of vitrified specimens |journal=Quarterly Reviews of Biophysics |volume=21 |issue=2 |pages=129–228 |s2cid=2741633 |doi=10.1017/S0033583500004297 |pmid=3043536 |url=https://serval.unil.ch/resource/serval:BIB_D6E6989A1815.P001/REF.pdf }}</ref> The individual molecules can be preserved for imaging in a state close to what they are in liquid water. |
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Ice XVII can repeatedly [[adsorb]] and release hydrogen molecules without degrading its structure.{{r|discovery}} The total amount of hydrogen that ice XVII can adsorb depends on the amount of pressure applied, but hydrogen molecules can be adsorbed by ice XVII even at pressures as low as a few millibars{{efn|One millibar is equivalent to {{cvt|100|Pa|psi atm}}.<!-- 1 bar is defined as 100000 pa -->}} if the temperature is under {{cvt|40|K|C F}}.{{r|discovery|storage}} The adsorbed hydrogen molecules can then be released, or [[desorbed]], through the application of heat.{{r|storage}} This was an unexpected property of ice XVII, and could allow it to be used for [[hydrogen storage]], an issue often mentioned in [[environmental technology]].{{r|discovery|storage}} |
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{{about|a real form of solid water|the fictional material called Ice-nine that appears in the Kurt Vonnegut novel|Ice-nine}} |
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{{other uses|Ice-nine (disambiguation)}} |
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Aside from storing hydrogen via [[compressed hydrogen|compression]] or [[liquid hydrogen|liquification]], it can also be stored within a solid substance, either via a reversible chemical process ([[chemisorption]]) or by having the hydrogen molecules attach to the substance via the [[van der Waals force]] ([[physisorption]]).{{r|storage}} The storage method used by ice XVII falls in the latter category, physisorption.{{r|storage}} In physisorption, there is no chemical reaction, and the chemical bond between the two atoms within a hydrogen molecule remains intact. Because of this, the number of adsorption–desorption cycles ice XVII can withstand is "theoretically infinite".{{r|discovery|storage}} |
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== Ice IX == |
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One significant advantage of using ice XVII as a hydrogen storage medium is the low cost of the only two chemicals involved: hydrogen and water.{{r|storage}} In addition, ice XVII has shown the ability to store hydrogen at an H{{sub|2}} to H{{sub|2}}O [[molar ratio]] above 40%<!-- using '%' as this is a technical article, as per mos:% -->, higher than the theoretical maximum ratio for [[Clathrate hydrate#Structure|sII]] clathrate hydrates, another potential storage medium.{{r|discovery}} However, if ice XVII is used as a storage medium, it must be kept under a temperature of {{cvt|130|K|C F}} or risk being destabilized.{{r|storage}} |
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Ice IX is a form of solid [[water]] stable at temperatures below 140 [[Kelvin|K]] or –133.15 [[centigrade|C]] and pressures between 200 and 400 [[MPa]]. It has a [[tetragonal]] [[crystal]] [[Bravais lattice|lattice]] and a density of 1.16 g/cm<sup>3</sup>, 26% higher than ordinary ice. It is formed by cooling [[ice III]] from 208 K to 165 K (rapidly—to avoid forming [[ice II]]). Its structure is identical to ice III other than being completely proton-ordered.<ref>{{Cite journal |last=La Placa |first=Sam J. |last2=Hamilton |first2=Walter C. |last3=Kamb |first3=Barclay |last4=Prakash |first4=Anand |date=1973-01-15 |title=On a nearly proton‐ordered structure for ice IX |url=https://doi.org/10.1063/1.1679238 |journal=The Journal of Chemical Physics |volume=58 |issue=2 |pages=567–580 |doi=10.1063/1.1679238 |issn=0021-9606}}</ref> |
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== |
=== Outer space === |
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In outer space, hexagonal crystalline ice (the predominant form found on Earth) is extremely rare. Known examples are typically associated with volcanic action.<ref>{{cite news|url=https://www.nytimes.com/2004/12/09/science/09ice.html|title=Astronomers Contemplate Icy Volcanoes in Far Places|author=Chang, Kenneth|work=The New York Times|date=9 December 2004|access-date=30 July 2012|url-status=live|archive-url=https://web.archive.org/web/20150509123243/http://www.nytimes.com/2004/12/09/science/09ice.html|archive-date=9 May 2015}}</ref> Water in the [[interstellar medium]] is instead dominated by amorphous ice, making it likely the most common form of water in the universe.<ref name="stanley">{{cite journal|last1=Debennetti|first1=Pablo G. |last2=Stanley |first2=H. Eugene |year=2003 |title=Supercooled and Glassy Water |journal=Physics Today |volume=56 |issue=6 |pages=40–46 |bibcode=2003PhT....56f..40D|doi=10.1063/1.1595053 |url=http://polymer.bu.edu/hes/articles/ds03.pdf |access-date=19 September 2012 }}</ref> |
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Ice X, within [[physical chemistry]], is a [[cubic crystal system|cubic]] crystalline form of [[ice]] formed in the same manner as [[ice VII]], but at pressures as high as about 70 [[GPa]]. It has symmetrized hydrogen bonds, where a hydrogen atom is found at the center of two oxygen atoms. |
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Amorphous ice can be separated from crystalline ice based on its [[Near-infrared spectroscopy|near-infrared]] and infrared spectrum. At near-IR wavelengths, the characteristics of the 1.65, 3.1, and 4.53 [[μm]] water absorption lines are dependent on the ice temperature and crystal order.<ref name="NewmanBuratti2008">{{cite journal |title=Photometric and spectral analysis of the distribution of crystalline and amorphous ices on Enceladus as seen by Cassini |last1=Newman |first1=Sarah F. |last2=Buratti |first2=B. J. |last3=Brown |first3=R. H. |last4=Jaumann |first4=R. |last5=Bauer |first5=J. |last6=Momary |first6=T. |journal=Icarus |volume=193 |issue=2 |pages=397–406 |year=2008 |bibcode=2008Icar..193..397N |doi=10.1016/j.icarus.2007.04.019|url=https://dspace.mit.edu/bitstream/1721.1/114323/1/1028747523-MIT.pdf |hdl=1721.1/114323 |hdl-access=free }}</ref> The peak strength of the 1.65 μm band as well as the structure of the 3.1 μm band are particularly useful in identifying the crystallinity of water ice.<ref>{{cite journal|title=The temperature-dependent near-infrared absorption spectrum of hexagonal <formula>H2O ice|author1=Grundy, W. M. |author2=Schmitt, B. |journal=Journal of Geophysical Research|volume=103|issue=E11 |page=25809|year=1998|bibcode=1998JGR...10325809G|doi=10.1029/98je00738}}</ref><ref>{{cite journal|last1=Hagen |first1=W. |last2=ielens |first2=A.G.G.M. |last3=Greenberg |first3=J. M. |year=1981 |title=The Infrared Spectra of Amorphous Solid Water and Ice Between 10 and 140 K |journal=Chemical Physics |volume=56 |issue=3 |pages=367–379 |doi=10.1016/0301-0104(81)80158-9 |bibcode = 1981CP.....56..367H }}</ref> |
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== Ice XI == |
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[[File:Ice XI View along c axis.png|thumb|250px|Crystal structure of Ice XI viewed along the c-axis]] |
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Ice XI is the hydrogen-ordered form of the ordinary form of ice. The total [[internal energy]] of ice XI is about one sixth lower than ice I<sub>h</sub>, so in principle it should naturally form when ice I<sub>h</sub> is cooled to below 72 [[Kelvin|K]]. The low temperature required to achieve this transition is correlated with the relatively low energy difference between the two structures.<ref>{{cite journal|last1=Fan|first1=Xiaofeng|last2=Bing|first2=Dan|last3=Zhang|first3=Jingyun|last4=Shen|first4=Zexiang|last5=Kuo|first5=Jer-Lai|title=Predicting the hydrogen bond ordered structures of ice I<sub>h</sub>, II, III, VI and ice VII: DFT methods with localized based set|journal=Computational Materials Science|date=1 October 2010|volume=49|issue=4|pages=S170–S175|doi=10.1016/j.commatsci.2010.04.004|url=http://jlk.iams.sinica.edu.tw/paper/2010/ComMateSci49S170.pdf|access-date=24 April 2012|archive-url=https://web.archive.org/web/20140714192340/http://jlk.iams.sinica.edu.tw/paper/2010/ComMateSci49S170.pdf|archive-date=14 July 2014|url-status=dead}}</ref> Water molecules in ice I<sub>h</sub> are surrounded by four semi-randomly directed [[hydrogen]] bonds. Such arrangements should change to the more ordered arrangement of hydrogen bonds found in ice XI at low temperatures, so long as localized proton hopping is sufficiently enabled; a process that becomes easier with increasing pressure.<ref>{{cite journal|last1=Castro Neto|first1=A.|last2=Pujol|first2= P. |last3=Fradkin|first3= E.|title=Ice: A strongly correlated proton system|journal=Physical Review B|year=2006|volume=74|issue=2|doi=10.1103/PhysRevB.74.024302|arxiv=cond-mat/0511092|page=024302|bibcode = 2006PhRvB..74b4302C |s2cid=102581583}}</ref> Correspondingly, ice XI is believed to have a [[triple point]] with hexagonal ice and gaseous water at (~72 K, ~0 Pa). |
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At longer IR wavelengths, amorphous and crystalline ice have characteristically different absorption bands at 44 and 62 μm in that the crystalline ice has significant absorption at 62 μm while amorphous ice does not.<ref name="Moore, Marla H.; Hudson, Reggie L. 1992 353"/> In addition, these bands can be used as a temperature indicator at very low temperatures where other indicators (such as the 3.1 and 12 μm bands) fail.<ref>{{cite journal|title=Molecular ices as temperature indicators for interstellar dust: the 44- and 62-μm lattice features of H2O ice.|author1=Smith, R. G. |author2=Robinson, G. |author3=Hyland, A. R. |author4=Carpenter, G. L. |journal=Monthly Notices of the Royal Astronomical Society|volume=271|issue=2 |pages=481–489|year=1994|bibcode=1994MNRAS.271..481S|doi=10.1093/mnras/271.2.481|doi-access=}}</ref> This is useful studying ice in the interstellar medium and circumstellar disks. However, observing these features is difficult because the atmosphere is opaque at these wavelengths, requiring the use of space-based infrared observatories. |
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==Properties== |
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[[File:Ice XI side view.png|thumb|250px|Crystal structure of ice XI (c-axis in the vertical direction)]] |
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Ice XI has an [[orthorhombic]] structure with [[space group]] Cmc2<sub>1</sub> containing eight molecules per unit cell. Its lattice parameters are a=4.465(3) Å, b=7.859(4) Å, and c=7.292(2) Å at 5 K.<ref>{{cite journal|last1=Line|first1=Christina M. B.|last2=Whitworth|first2= R. W.|title=A high resolution neutron powder diffraction study of D<sub>2</sub>O ice XI|journal=The Journal of Chemical Physics|date=1 January 1996|volume=104|issue=24|pages=10008–10013|doi=10.1063/1.471745|bibcode = 1996JChPh.10410008L }}</ref><ref>{{cite journal | last1 = Leadbetter | first1 = A. J. | last2 = Ward | first2 = R. C. | last3 = Clark | first3 = J. W. | last4 = Tucker | first4 = P. A. | last5 = Matsuo | first5 = T. | last6 = Suga | first6 = S. | year = 1985 | title = The equilibrium low-structure of ice | journal = The Journal of Chemical Physics | volume = 82 | issue = 1| pages = 424–428 | doi=10.1063/1.448763| bibcode = 1985JChPh..82..424L }}</ref> There are actually 16 crystallographically inequivalent hydrogen-ordered configurations of ice with an orthorhombic structure of eight atoms per unit cell, but electronic structure calculations show Cmc2<sub>1</sub> to be the most stable.<ref>{{cite journal | last1 = Kuo | first1 = J. L. | last2 = Singer | first2 = S. J. | year = 2003 | title = Graph invariants for periodic systems: Towards predicting physical properties from the hydrogen bond topology of ice | journal = Physical Review E | volume = 67 | issue = 1| page = 016114 | doi=10.1103/physreve.67.016114| pmid = 12636571 |bibcode = 2003PhRvE..67a6114K }}</ref><ref>{{cite journal | last1 = Hirsch | first1 = T. K. | last2 = Ojamae | first2 = L. | year = 2004 | title = Quantum-Chemical and Force-Field Investigations of Ice Ih: Computation of Proton-Ordered Structures and Prediction of Their Lattice Energies | journal = The Journal of Physical Chemistry B | volume = 108 | issue = 40| page = 15856 | doi=10.1021/jp048434u}}</ref> Another possible configuration, with space group Pna2<sub>1</sub> is also of interest, as it is an antiferroelectric crystal, which Davidson and Morokuma incorrectly suggested as the most stable structure in 1984.<ref>{{cite journal | last1 = Davidson | first1 = E. R. | last2 = Morokuma | first2 = K. J. | year = 1984 | title = A proposed antiferroelectric structure for proton ordered ice I<sub>h</sub>. | journal = The Journal of Chemical Physics | volume = 81 | issue = 8| page = 3741 | doi=10.1063/1.448101|bibcode = 1984JChPh..81.3741D }}</ref> |
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==== Properties of the amorphous ice in the Solar System ==== |
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In practice, ice XI is most easily prepared from a dilute (10 mM) [[Potassium hydroxide|KOH]] solution kept just below 72 K for about a week (for [[Heavy water|D<sub>2</sub>O]] a temperature just below 76 K will suffice).<ref>{{cite journal|last=Kawada|first=Syuji|title=Dielectric properties of KOH-doped D<sub>2</sub>O ice.|journal=Journal of the Physical Society of Japan|date=1989|volume=58|issue=1|page=295|url=https://www.jstage.jst.go.jp/article/jpsj1946/58/1/58_1_295/_article|access-date=12 May 2014|bibcode = 1989JPSJ...58..295K |doi = 10.1143/JPSJ.58.295 }}</ref><ref>{{cite journal|last1=Fukazawa|first1=Hiroshi|last2=Ikeda|first2= Susumu|last3=Mae|first3= Shinji|title=Incoherent inelastic neutron scattering measurements on ice XI; the proton-ordered phase of ice I<sub>h</sub> doped with KOH|journal=Chemical Physics Letters|year=1998|volume=282|issue=2|pages=215–218|doi=10.1016/S0009-2614(97)01266-9|bibcode = 1998CPL...282..215F }}</ref> The hydroxide ions create defects in the hexagonal ice, allowing protons to jump more freely between the oxygen atoms (and so this structure of ice XI breaks the '[[ice rules]]'). More specifically, each hydroxide ion creates a [[Bjerrum defect|Bjerrum L defect]] and an ionized vertex. Both the defect and the ion can move throughout the lattice and 'assist' with proton reordering. The positive K<sup>+</sup> ion may also play a role because it is found that KOH works better than other [[alkali hydroxide]]s.<ref name = "suga">{{cite journal|last=Suga|first=Hiroshi|title=A facet of recent ice sciences|journal=Thermochimica Acta|date=1 October 1997|volume=300|issue=1–2|pages=117–126|doi=10.1016/S0040-6031(96)03121-8}}</ref> The exact details of these ordering mechanisms are still poorly understood and under question because experimentally the mobility of the hydroxide and K<sup>+</sup> ions appear to be very low around 72 K.<ref>Chris Knight and Sherwin J. Singer, ''Theoretical study of a hydroxide ion within the ice-Ih lattice'', Physics and Chemistry of Ice (Proceedings of the 11th International Conference on the Physics and Chemistry of Ice), ed., Werner F. Kuhs (Royal Soc. of Chemistry, 2007), p. 339.</ref><ref>{{cite book |url=https://books.google.com/books?id=anEoDwAAQBAJ&pg=PA329 |first1=Chris |last1=Knight |first2=Sherwin J. |last2=Singer |title=Tackling the problem of hydrogen bond order and disorder |work=Physics and Chemistry of Ice (Proceedings of the 11th International Conference on the Physics and Chemistry of Ice) |editor-first=Werner F. |editor-last=Kuhs |publisher=Royal Soc. of Chemistry |date=2007 |page=329 |isbn=9781847557773 }}</ref> The current belief is that KOH acts only to assist with the hydrogen reordering and is not required for the lower-energy stability of ice XI. However, calculations by Toshiaki Iitaka in 2010 call this into question.<ref name=stability>{{cite arXiv|last=Iitaka|first=Toshiaki|title=Stability of ferroelectric ice |date=13 July 2010|eprint=1007.1792|class=cond-mat.mtrl-sci}}</ref> Iitaka argues that the KOH ions compensate for the large net electric dipole moment of the crystal lattice along the c-axis. The aforementioned electronic structure calculations are done assuming an infinite lattice and ignore the effects of macroscopic electric fields created by surface charges. Because such fields are present in any finite size crystal, in non-doped ice XI, domains of alternating dipole moment should form as in conventional [[ferroelectrics]].<ref name=stability/> It has also been suggested that the ice I<sub>h</sub> => ice XI transition is enabled by the [[Proton tunneling|tunneling of protons]].<ref>{{cite journal|last1=Castro-Neto|first1=A. H.|last2=Pujol|first2=P|last3=Fradkin|first3=Eduardo|title=Ice: A strongly correlated proton system|journal=Physical Review Letters|date=21 Jul 2006|volume=74|issue=2|pages=024302–12|doi=10.1103/PhysRevB.74.024302|arxiv = cond-mat/0511092 |bibcode = 2006PhRvB..74b4302C |s2cid=102581583}}</ref> |
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In general, amorphous ice can form below ~130 K.<ref>{{cite journal|doi=10.1007/BF00651770|title=The heterogeneous condensation of interstellar ice grains|author=Seki, J. |author2=Hasegawa, H.|journal=Astrophysics and Space Science |volume=94|issue=1|pages=177–189|year=1983|bibcode=1983Ap&SS..94..177S|s2cid=121008219 }}</ref> At this temperature, water molecules are unable to form the crystalline structure commonly found on Earth. Amorphous ice may also form in the coldest region of the Earth's atmosphere, the summer polar mesosphere, where [[noctilucent clouds]] exist.<ref>{{cite journal |last=Murray |first=B. J.|author2=Jensen, E. J.|year=2010 |title=Homogeneous nucleation of amorphous solid water particles in the upper mesosphere|journal=J. Atmos. Sol.-Terr. Phys.|volume=72 |issue=1|pages=51–61 |doi=10.1016/j.jastp.2009.10.007|bibcode = 2010JASTP..72...51M }}</ref> These low temperatures are readily achieved in astrophysical environments such as molecular clouds, circumstellar disks, and the surfaces of objects in the outer Solar System. In the laboratory, amorphous ice transforms into crystalline ice if it is heated above 130 K, although the exact temperature of this conversion is dependent on the environment and ice growth conditions.<ref name="SolarSystemIces">{{cite book |last1=Jenniskens |last2=Blake |last3=Kouchi |title=Solar System Ices |year=1998 |publisher=Dordrecht Kluwer Academic Publishers |pages=139–155}}</ref> The reaction is irreversible and exothermic, releasing 1.26–1.6 kJ/mol.<ref name="SolarSystemIces" /> |
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An additional factor in determining the structure of water ice is deposition rate. Even if it is cold enough to form amorphous ice, crystalline ice will form if the flux of water vapor onto the substrate is less than a temperature-dependent critical flux.<ref name="Kouchi, A., Yamamoto, T., Kozasa, T., Kuroda, T., Greenberg, J. M. H. 1994 1009">{{cite journal|last1=Kouchi |first1=A. |last2=Yamamoto |first2=T. |last3=Kozasa |first3=T. |last4=Kuroda |first4=T. |last5=Greenberg |first5=J. M. |year=1994 |title=Conditions for condensation and preservation of amorphous ice and crystallinity of astrophysical ices |journal=Astronomy and Astrophysics |volume=290 |page=1009 |bibcode=1994A&A...290.1009K |url=https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/42838/1/59kozasa_AA290.pdf |archive-url=https://web.archive.org/web/20200322062604/https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/42838/1/59kozasa_AA290.pdf |archive-date=22 March 2020 |url-status=live }}</ref> This effect is important to consider in astrophysical environments where the water flux can be low. Conversely, amorphous ice can be formed at temperatures higher than expected if the water flux is high, such as flash-freezing events associated with [[cryovolcanism]]. |
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Although ice XI is thought to be a more stable conformation than ice I<sub>h</sub>, the transformation is very slow. According to one report, in Antarctic conditions it is estimated to take at least 100,000 years to form without the assistance of catalysts.{{citation needed|date=August 2017}} Ice XI was sought and found in Antarctic ice that was about 100 years old in 1998.<ref>{{cite journal |doi=10.1016/S0009-2614(98)00908-7 |title=Proton ordering in Antarctic ice observed by Raman and neutron scattering |journal=Chemical Physics Letters |volume=294 |issue=6 |pages=554–558 |year=1998 |last1=Fukazawa |first1=Hiroshi |last2=Mae |first2=Shinji |last3=Ikeda |first3=Susumu |last4=Watanabe |first4=Okitsugu |bibcode=1998CPL...294..554F }}</ref> A further study in 2004 was not able to reproduce this finding, however, after studying Antarctic ice which was around 3000 years old.<ref>{{cite journal|last=Fortes|first=A. D.|author2=Wood, I. G.|author3=Grigoriev, D.|author4=Alfredsson, M.|author5=Kipfstuhl, S.|author6=Knight, K. S.|author7=Smith, R. I.|title=No evidence for large-scale proton ordering in Antarctic ice from powder neutron diffraction|journal=The Journal of Chemical Physics|date=1 January 2004|volume=120|issue=24|pages=11376–9|doi=10.1063/1.1765099|url=http://jcp.aip.org/resource/1/jcpsa6/v120/i24/p11376_s1?isAuthorized=no|pmid=15268170|bibcode=2004JChPh.12011376F|access-date=22 April 2012|archive-url=https://archive.today/20120729031327/http://jcp.aip.org/resource/1/jcpsa6/v120/i24/p11376_s1?isAuthorized=no|archive-date=29 July 2012|url-status=dead}}</ref> The 1998 Antarctic study also claimed that the transformation temperature (ice XI => ice I<sub>h</sub>) is {{convert|-36|°C|K}}, which is far higher than the temperature of the expected triple point mentioned above (72 K, ~0 Pa). Ice XI was also found in experiments using pure water at very low temperature (~10 K) and low pressure – conditions thought to be present in the upper atmosphere.<ref>{{cite journal | last1 = Furić | first1 = K. | last2 = Volovšek | first2 = V. | year = 2010 | title = Water ice at low temperatures and pressures; new Raman results | journal = J. Mol. Structure | volume = 976 | issue = 1–3| pages = 174–180 | doi=10.1016/j.molstruc.2010.03.024| bibcode = 2010JMoSt.976..174F }}</ref> Recently, small domains of ice XI were found to form in pure water; its phase transition back to ice I<sub>h</sub> occurred at 72 K while under hydrostatic pressure conditions of up to 70 MPa.<ref>{{cite journal|last1=Yen|first1=Fei|last2=Chi|first2=Zhenhua|title=Proton ordering dynamics of H<sub>2</sub>O ice|journal=Physical Chemistry Chemical Physics|date=16 Apr 2015|volume=17|issue=19|pages=12458–12461|doi=10.1039/C5CP01529D|pmid=25912948|arxiv = 1503.01830 |bibcode = 2015PCCP...1712458Y |s2cid=7736338}}</ref> |
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At temperatures less than 77 K, irradiation from ultraviolet photons as well as high-energy electrons and ions can damage the structure of crystalline ice, transforming it into amorphous ice.<ref>{{cite journal|title=Amorphization of cubic ice by ultraviolet irradiation|author1=Kouchi, Akira |author2=Kuroda, Toshio |journal=Nature |volume=344|pages=134–135|year=1990|bibcode=1990Natur.344..134K|doi=10.1038/344134a0|issue=6262|s2cid=4306842 }}</ref><ref name="Moore, Marla H.; Hudson, Reggie L. 1992 353">{{cite journal|title=Far-infrared spectral studies of phase changes in water ice induced by proton irradiation|author1=Moore, Marla H. |author2=Hudson, Reggie L. |journal=Astrophysical Journal|volume=401|page=353|year=1992|bibcode=1992ApJ...401..353M|doi=10.1086/172065}}</ref> Amorphous ice does not appear to be significantly affected by radiation at temperatures less than 110 K, though some experiments suggest that radiation might lower the temperature at which amorphous ice begins to crystallize.<ref name="Moore, Marla H.; Hudson, Reggie L. 1992 353"/> |
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Ice I<sub>h</sub> that has been transformed to ice XI and then back to ice I<sub>h</sub>, on raising the temperature, retains some hydrogen-ordered domains and more easily transforms back to ice XI again.<ref>{{cite journal |doi=10.1016/j.molstruc.2010.02.016 |title=Annealing effects on hydrogen ordering in KOD-doped ice observed using neutron diffraction |journal=Journal of Molecular Structure |volume=972 |issue=1–3 |pages=111–114 |year=2010 |last1=Arakawa |first1=Masashi |last2=Kagi |first2=Hiroyuki |last3=Fukazawa |first3=Hiroshi |bibcode=2010JMoSt.972..111A }}</ref> A neutron powder diffraction study found that small hydrogen-ordered domains can exist up to 111 K.<ref name=astro-ordering>{{cite journal|last=Arakawa|first=Masashi|author2=Kagi, Hiroyuki|author3=Fernandez-Baca, Jaime A.|author4=Chakoumakos, Bryan C.|author5=Fukazawa, Hiroshi|title=The existence of memory effect on hydrogen ordering in ice: The effect makes ice attractive|journal=Geophysical Research Letters|date=17 August 2011|volume=38|issue=16|pages=n/a|doi=10.1029/2011GL048217|bibcode=2011GeoRL..3816101A|doi-access=free}}</ref> |
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[[Peter Jenniskens]] and David F. Blake demonstrated in 1994 that a form of high-density amorphous ice is also created during vapor deposition of water on low-temperature (< 30 K) surfaces such as interstellar grains. The water molecules do not fully align to create the open cage structure of low-density amorphous ice. Many water molecules end up at interstitial positions. When warmed above 30 K, the structure re-aligns and transforms into the low-density form.<ref name="adsabs.harvard.edu"/><ref name="auto1"/> |
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There are distinct differences in the Raman spectra between ices I<sub>h</sub> and XI, with ice XI showing much stronger peaks in the translational (~230 cm<sup>−1</sup>), librational (~630 cm<sup>−1</sup>) and in-phase asymmetric stretch (~3200 cm<sup>−1</sup>) regions.<ref>K. Abe, Y. Ootake and T. Shigenari, ''Raman scattering study of proton ordered ice XI single crystal'', in Physics and Chemistry of Ice, ed. W. Kuhs (Royal Society of Chemistry, Cambridge, 2007) pp 101–108</ref><ref>{{cite journal | last1 = Abe | first1 = K. | last2 = Shigenari | first2 = T. | year = 2011 | title = Raman spectra of proton ordered phase XI of ICE I. Translational vibrations below 350 cm-1, J | journal = The Journal of Chemical Physics | volume = 134 | issue = 10| page = 104506 | doi=10.1063/1.3551620| pmid = 21405174 | bibcode = 2011JChPh.134j4506A }}</ref> |
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====Molecular clouds, circumstellar disks, and the primordial solar nebula==== |
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[[Ice Ic|Ice I<sub>c</sub>]] also has a proton-ordered form. The total internal energy of ice XIc was predicted as similar as ice XIh |
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[[Molecular cloud]]s have extremely low temperatures (~10 K), falling well within the amorphous ice regime. The presence of amorphous ice in molecular clouds has been observationally confirmed.<ref>{{cite journal|title=High-Density Amorphous Ice, the Frost on Interstellar Grains|author1=Jenniskens, P. |author2=Blake, D. F. |author3=Wilson, M. A. |author4=Pohorille, A. |journal=Astrophysical Journal|volume=401|page=389|year=1995|bibcode=1995ApJ...455..389J|doi = 10.1086/176585 |hdl=2060/19980018148 |s2cid=122950585 |hdl-access=free}}</ref> When molecular clouds collapse to form stars, the temperature of the resulting [[circumstellar disk]] isn't expected to rise above 120 K, indicating that the majority of the ice should remain in an amorphous state.<ref name="Kouchi, A., Yamamoto, T., Kozasa, T., Kuroda, T., Greenberg, J. M. H. 1994 1009"/> However, if the temperature rises high enough to sublimate the ice, then it can re-condense into a crystalline form since the water flux rate is so low. This is expected to be the case in the circumstellar disk of IRAS 09371+1212, where signatures of crystallized ice were observed despite a low temperature of 30–70 K.<ref>{{Citation |
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<ref>{{cite journal|last1=Raza|first1=Zamaan|last2=Alfè|first2=Dario|title=Proton ordering in cubic ice and hexagonal ice; a potential new ice phase--XIc.|journal=Physical Chemistry Chemical Physics|date=28 Nov 2011|volume=13|issue=44|pages=19788–95|doi=10.1039/c1cp22506e|pmid=22009223|bibcode = 2011PCCP...1319788R|s2cid=31673433}}</ref> |
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|bibcode = 1990ApJ...355L..27O |
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| last1 = Omont | first1 = Alain | last2 = Forveille | first2 = Thierry |
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| last3 = Moseley | first3 = S. Harvey | last4 = Glaccum | first4 = William J. |
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| last5 = Harvey | first5 = Paul M. | last6 = Likkel | first6 = Lauren Jones |
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| last7 = Loewenstein | first7 = Robert F. | last8 = Lisse | first8 = Casey M. |
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| title = Observations of 40-70 micron bands of ice in IRAS 09371 + 1212 and other stars |
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| journal = Astrophysical Journal Letters |
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| issn=0004-637X |
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| date = May 20, 1990 | volume=355 | pages = L27–L30 |
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|doi = 10.1086/185730 | doi-access = free }}</ref> |
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For the primordial solar nebula, there is much uncertainty as to the crystallinity of water ice during the circumstellar disk and planet formation phases. If the original amorphous ice survived the molecular cloud collapse, then it should have been preserved at heliocentric distances beyond Saturn's orbit (~12 AU).<ref name="Kouchi, A., Yamamoto, T., Kozasa, T., Kuroda, T., Greenberg, J. M. H. 1994 1009"/> |
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==History== |
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Hints of hydrogen-ordering in ice had been observed as early as 1964, when Dengel et al. attributed a peak in thermo-stimulated depolarization (TSD) current to the existence of a proton-ordered ferroelectric phase.<ref>{{cite journal|last1=Dengel|first1=O.|last2=Eckener|first2=U.|last3=Plitz |first3=H. |last4=Riehl|first4= N.|title=Ferroelectric behavior of ice|journal=Physics Letters|date=1 May 1964|volume=9|issue=4|pages=291–292|doi=10.1016/0031-9163(64)90366-X|bibcode = 1964PhL.....9..291D }}</ref> However, they could not conclusively prove that a phase transition had taken place, and Onsager pointed out that the peak could also arise from the movement of defects and lattice imperfections. Onsager suggested that experimentalists look for a dramatic change in heat capacity by performing a careful calorimetric experiment. A phase transition to ice XI was first identified experimentally in 1972 by Shuji Kawada and others.<ref>{{cite journal|last=Kawada|first=Shuji|title=Dielectric Dispersion and Phase Transition of KOH Doped Ice|journal=Journal of the Physical Society of Japan|date=1 May 1972|volume=32|issue=5|pages=1442|doi=10.1143/JPSJ.32.1442|bibcode = 1972JPSJ...32.1442K }}</ref><ref>{{cite journal|last1=Tajima|first1=Yoshimitsu|last2=Matsuo|first2= Takasuke|last3= Suga|first3= Hiroshi|title=Calorimetric study of phase transition in hexagonal ice doped with alkali hydroxides|journal=Journal of Physics and Chemistry of Solids|year=1984|volume=45|issue=11–12|pages=1135–1144|doi=10.1016/0022-3697(84)90008-8|bibcode = 1984JPCS...45.1135T }}</ref><ref>{{cite journal|last1=Matsuo|first1=Takasuke|last2=Tajima|first2= Yoshimitsu|last3=Suga|first3=Hiroshi|title=Calorimetric study of a phase transition in D<sub>2</sub>O ice I<sub>h</sub> doped with KOD: Ice XI|journal=Journal of Physics and Chemistry of Solids|year=1986|volume=47 |issue=2|pages=165–173 |doi=10.1016/0022-3697(86)90126-5|bibcode = 1986JPCS...47..165M }}</ref> |
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====Comets==== |
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==Ferroelectric properties== |
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The possibility of the presence of amorphous water ice in comets and the release of energy during the phase transition to a crystalline state was first proposed as a mechanism for comet outbursts.<ref>Patashnick, et.al., Nature Vol.250, No. 5464, July 1974, pp. 313-314.</ref> Evidence of amorphous ice in comets is found in the high levels of activity observed in long-period, Centaur, and Jupiter Family comets at heliocentric distances beyond ~6 AU.<ref>{{cite journal|title=Activity of comets at large heliocentric distances pre-perihelion|author1=Meech, K. J. |author2=Pittichová, J. |author3=Bar-Nun, A. |author4=Notesco, G. |author5=Laufer, D. |author6=Hainaut, O. R. |author7=Lowry, S. C. |author8=Yeomans, D. K. |author9=Pitts, M. |journal=Icarus |volume=201|issue=2 |pages=719–739|year=2009|bibcode=2009Icar..201..719M|doi=10.1016/j.icarus.2008.12.045}}</ref> These objects are too cold for the sublimation of water ice, which drives comet activity closer to the Sun, to have much of an effect. Thermodynamic models show that the surface temperatures of those comets are near the amorphous/crystalline ice transition temperature of ~130 K, supporting this as a likely source of the activity.<ref>{{cite journal|title=Thermochemistry of cometary nuclei 1: The Jupiter family case|author1=Tancredi, G. |author2=Rickman, H. |author3=Greenberg, J. M. |journal=Astronomy and Astrophysics|volume=286|page=659|year=1994|bibcode=1994A&A...286..659T}}</ref> The runaway crystallization of amorphous ice can produce the energy needed to power outbursts such as those observed for Centaur Comet [[29P/Schwassmann–Wachmann]] 1.<ref>{{cite journal|title=The search for a cometary outbursts mechanism: a comparison of various theories|author=Gronkowski, P.|journal=Astronomische Nachrichten|volume=328|issue=2|pages=126–136|year=2007|bibcode= 2007AN....328..126G|doi=10.1002/asna.200510657|doi-access=free}}</ref><ref>{{cite journal|title=Outburst Dust Production of Comet 29P/Schwassmann-Wachmann 1|author1=Hosek, Matthew W. Jr. |author2=Blaauw, Rhiannon C. |author3=Cooke, William J. |author4=Suggs, Robert M. |journal=The Astronomical Journal|volume=145|issue=5 |page=122|year=2013|bibcode=2013AJ....145..122H|doi=10.1088/0004-6256/145/5/122|doi-access=free}}</ref> |
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Ice XI is [[ferroelectric]], meaning that it has an intrinsic polarization. To qualify as a ferroelectric it must also exhibit polarization switching under an electric field, which has not been conclusively demonstrated but which is implicitly assumed to be possible.<ref>{{cite journal|last=Bramwell|first=Steven T.|journal=Nature|date=21 January 1999|title=Ferroelectric ice|volume=397|issue=6716|pages=212–213|doi=10.1038/16594|bibcode = 1999Natur.397..212B |s2cid=204990667|doi-access=free}}</ref> [[Cubic ice]] also has a ferrolectric phase and in this case the ferroelectric properties of the ice have been experimentally demonstrated on monolayer thin films.<ref>{{cite journal|last=Iedema|first=M. J.|author2=Dresser, M. J. |author3=Doering, D. L. |author4=Rowland, J. B. |author5=Hess, W. P. |author6=Tsekouras, A. A. |author7=Cowin, J. P. |title=Ferroelectricity in Water Ice|journal=The Journal of Physical Chemistry B|date=1 November 1998|volume=102|issue=46|pages=9203–9214|doi=10.1021/jp982549e|s2cid=97894870}}</ref> In a similar experiment, ferroelectric layers of hexagonal ice were grown on a platinum (111) surface. The material had a polarization that had a decay length of 30 monolayers suggesting that thin layers of ice XI can be grown on substrates at low temperature without the use of dopants.<ref>{{cite journal|last=Su|first=Xingcai|author2=Lianos, L. |author3=Shen, Y. |author4= Somorjai, Gabor |title=Surface-Induced Ferroelectric Ice on Pt(111)|journal=Physical Review Letters|volume=80|issue=7|pages=1533–1536|doi=10.1103/PhysRevLett.80.1533|bibcode = 1998PhRvL..80.1533S |year=1998|s2cid=121266617}}</ref> One-dimensional nano-confined ferroelectric ice XI was created in 2010.<ref name=onedim1>{{cite journal|last=Zhao|first=H.-X. |author2=Kong, X.-J. |author3=Li, H. |author4=Jin, Y.-C. |author5=Long, L.-S. |author6=Zeng, X. C. |author7=Huang, R.-B. |author8=Zheng, L.-S. |title=Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture|journal=Proceedings of the National Academy of Sciences|date=14 February 2011|volume=108|issue=9|pages=3481–3486|doi=10.1073/pnas.1010310108|bibcode = 2011PNAS..108.3481Z |pmid=21321232 |pmc=3048133|doi-access=free }}</ref> |
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====Kuiper Belt objects==== |
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==Astrophysical implications== |
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With radiation equilibrium temperatures of 40–50 K,<ref>{{cite journal|title=Colors and Spectra of Kuiper Belt Objects|author1=Jewitt, David C. |author2=Luu, Jane X. |journal=The Astronomical Journal|volume=122|issue=4 |pages=2099–2114|year=2001|bibcode=2001AJ....122.2099J|doi=10.1086/323304|arxiv = astro-ph/0107277 |s2cid=35561353 }}</ref> the objects in the Kuiper Belt are expected to have amorphous water ice. While water ice has been observed on several objects,<ref>{{cite journal|title=Water Ice on Kuiper Belt Object 1996 TO_66|author1=Brown, Robert H. |author2=Cruikshank, Dale P. |author3=Pendleton, Yvonne |journal=The Astrophysical Journal|volume=519|issue=1 |page=L101|year=1999|bibcode=1999ApJ...519L.101B|doi=10.1086/312098|doi-access=free}}</ref><ref>{{cite journal|title=Water ice on the surface of the large TNO 2004 DW|author1=Fornasier, S. |author2=Dotto, E. |author3=Barucci, M. A. |author4=Barbieri, C. |journal=Astronomy and Astrophysics|volume=422|issue=2 |page=L43|year=2004|bibcode=2004A&A...422L..43F|doi=10.1051/0004-6361:20048004|doi-access=free}}</ref> the extreme faintness of these objects makes it difficult to determine the structure of the ices. The signatures of crystalline water ice was observed on [[50000 Quaoar]], perhaps due to resurfacing events such as impacts or cryovolcanism.<ref>{{cite journal|title=Crystalline water ice on the Kuiper belt object (50000) Quaoar|author1=Jewitt, David C. |author2=Luu, Jane |journal=Nature|volume=432|pages=731–3|year=2004|bibcode=2004Natur.432..731J|doi=10.1038/nature03111|pmid=15592406|issue=7018|s2cid=4334385 }}</ref> |
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As was mentioned, ice XI can theoretically form at low pressures at temperatures between 50–70 K – temperatures present in astrophysical environments of the outer solar system and within permanently shaded polar craters on the Moon and Mercury. Ice XI forms most easily around 70 K – paradoxically, it takes longer to form at lower temperatures. Extrapolating from experimental measurements, it is estimated to take ~50 years to form at 70 K and ~300 million years at 50 K.<ref name=astroice/> It is theorized to be present in places like the upper atmospheres of [[Uranus]] and [[Neptune]]<ref name=astro-ordering /> and on [[Pluto]] and [[Charon (moon)|Charon]].<ref name=astroice>{{cite journal|title=Ice XI on Pluto and Charon?|publisher= Division for Planetary Sciences Meeting, American Astronomical Society|issue=49.02|journal= Bulletin of the American Astronomical Society|date=August 2005|volume=37|pages=732|bibcode=2005DPS....37.4902M|last1=McKinnon|first1=W. B.|last2=Hofmeister|first2=A.M.}}</ref> |
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====Icy moons==== |
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Small domains of ice XI could exist in the atmospheres of Jupiter and Saturn as well.<ref name=astro-ordering /> The fact that small domains of ice XI can exist at temperatures up to 111 K has some scientists speculating that it may be fairly common in interstellar space, with small 'nucleation seeds' spreading through space and converting regular ice, much like the fabled [[ice-nine]] mentioned in Vonnegut's ''[[Cat's Cradle]]''.<ref name=astro-ordering/><ref>{{cite web|last=Grossman|first=Lisa|title=Electric ice a shock to the solar system|url=https://www.newscientist.com/article/mg21128274.400-electric-ice-a-shock-to-the-solar-system.html|publisher=[[New Scientist]]|access-date=7 April 2012|date=25 August 2011}}</ref> The possible roles of ice XI in interstellar space<ref name=astroice/><ref>{{cite journal|last1=Fukazawa|first1=H.|last2=Hoshikawa|first2= A.|last3=Ishii|first3= Y.|last4= Chakoumakos|first4= B. C.|last5= Fernandez-Baca|first5= J. A.|title=Existence of Ferroelectric Ice in the Universe|journal=The Astrophysical Journal|date=20 November 2006|volume=652|issue=1|pages=L57–L60|doi=10.1086/510017|bibcode = 2006ApJ...652L..57F |doi-access=free}}</ref> and planet formation<ref>{{cite journal | last1=Iedema | first1=M. J. | last2=Dresser | first2=M. J. | last3=Doering | first3=D. L. | last4=Rowland | first4=J. B. | last5=Hess | first5=W. P. | last6=Tsekouras | first6=A. A. | last7=Cowin | first7=J. P. | title=Ferroelectricity in Water Ice | journal=The Journal of Physical Chemistry B | publisher=American Chemical Society (ACS) | volume=102 | issue=46 | year=1998 | issn=1520-6106 | doi=10.1021/jp982549e | pages=9203–9214}}</ref> have been the subject of several research papers. Until observational confirmation of ice XI in outer space is made, the presence of ice XI in space remains controversial owing to the aforementioned criticism raised by Iitaka.<ref name = "stability"/> The infrared absorption spectra of ice XI was studied in 2009 in preparation for searches for ice XI in space.<ref>{{cite journal|last=Arakawa|first=M.|author2=Kagi, H. |author3=Fukazawa, H. |title=Laboratory Measurements of Infrared Absorption Spectra of Hydrogen-Ordered Ice: a Step to the Exploration of Ice XI in Space|journal=The Astrophysical Journal Supplement Series|date=1 October 2009|volume=184|issue=2|pages=361–365|doi=10.1088/0067-0049/184/2/361|bibcode = 2009ApJS..184..361A |doi-access=free}}</ref> |
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The Near-Infrared Mapping Spectrometer (NIMS) on NASA's Galileo spacecraft spectroscopically mapped the surface ice of the Jovian satellites [[Europa (moon)|Europa]], [[Ganymede (moon)|Ganymede]], and [[Callisto (moon)|Callisto]]. The temperatures of these moons range from 90 to 160 K,<ref>{{cite journal|title=Temperatures on Europa from Galileo Photopolarimeter-Radiometer: Nighttime Thermal Anomalies|author1=Spencer, John R. |author2=Tamppari, Leslie K. |author3=Martin, Terry Z. |author4=Travis, Larry D. |journal=Science|volume=284|pages=1514–1516|year=1999|bibcode=1999Sci...284.1514S|doi=10.1126/science.284.5419.1514|pmid=10348736 |issue=5419}}</ref> warm enough that amorphous ice is expected to crystallize on relatively short timescales. However, it was found that Europa has primarily amorphous ice, Ganymede has both amorphous and crystalline ice, and Callisto is primarily crystalline.<ref name="Hansen, Gary B.; McCord, Thomas B. 2004">{{cite journal|title=Amorphous and crystalline ice on the Galilean satellites: A balance between thermal and radiolytic processes|author1=Hansen, Gary B. |author2=McCord, Thomas B. |s2cid=140162310 |journal=Journal of Geophysical Research|volume=109|issue=E1 |pages=E01012 |year=2004|bibcode=2004JGRE..109.1012H|doi = 10.1029/2003JE002149 |doi-access= }}</ref> This is thought to be the result of competing forces: the thermal crystallization of amorphous ice versus the conversion of crystalline to amorphous ice by the flux of charged particles from Jupiter. Closer to Jupiter than the other three moons, Europa receives the highest level of radiation and thus through irradiation has the most amorphous ice. Callisto is the farthest from Jupiter, receiving the lowest radiation flux and therefore maintaining its crystalline ice. Ganymede, which lies between the two, exhibits amorphous ice at high latitudes and crystalline ice at the lower latitudes. This is thought to be the result of the moon's intrinsic magnetic field, which would funnel the charged particles to higher latitudes and protect the lower latitudes from irradiation.<ref name="Hansen, Gary B.; McCord, Thomas B. 2004"/> Ganymede's interior probably includes a liquid water ocean with tens to hundreds of kilometers of ice V at its base.<ref name=showman1997>{{Cite journal | doi = 10.1006/icar.1997.5778| title = Coupled Orbital and Thermal Evolution of Ganymede| journal = Icarus| volume = 129| issue = 2| pages = 367–383| year = 1997| last1 = Showman | first1 = A. | bibcode = 1997Icar..129..367S| url = http://www.lpl.arizona.edu/~showman/publications/showman-etal-1997.pdf}}</ref> |
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The surface ice of Saturn's moon [[Enceladus]] was mapped by the Visual and Infrared Mapping Spectrometer (VIMS) on the NASA/ESA/ASI Cassini space probe. The probe found both crystalline and amorphous ice, with a higher degree of crystallinity at the "[[Tiger stripes (Enceladus)|tiger stripe]]" cracks on the surface and more amorphous ice between these regions.<ref name="NewmanBuratti2008" /> The crystalline ice near the tiger stripes could be explained by higher temperatures caused by geological activity that is the suspected cause of the cracks. The amorphous ice might be explained by flash freezing from cryovolcanism, rapid condensation of molecules from water geysers, or irradiation of high-energy particles from Saturn.<ref name="NewmanBuratti2008" /> Similarly, one of one of the inner layers of [[Titan (moon)|Titan]] is believed to contain ice VI.<ref>{{Cite web|url=https://science.nasa.gov/saturn/moons/titan/facts/|title=Titan: Facts - NASA Science|website=science.nasa.gov|accessdate=25 April 2024}}</ref> |
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== Ice XII == |
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Medium-density amorphous ice may be present on Europa, as the experimental conditions of its formation are expected to occur there as well. It is possible that the MDA ice's unique property of releasing a large amount of heat energy after being released from compression could be responsible for 'ice quakes' within the thick ice layers.<ref name="Nature2023" /> |
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[[File:Icexii-ru.jpg|thumb|250px|The crystal structure of ice XII]] |
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Ice XII is a [[metastable]], [[density|dense]], [[crystalline]] [[phase (matter)|phase]] of [[solid]] [[water]], a type of [[ice]]. Ice XII was first reported in 1996 by C. Lobban, J.L. Finney and W.F. Kuhs and, after initial caution, was properly identified in 1998.<ref>C. Lobban, J.L. Finney and W.F. Kuhs, The structure of a new phase of ice, Nature 391, 268–270, 1998</ref> |
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==== Planets ==== |
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It was first obtained by cooling [[liquid]] water to {{convert|260|K|°C °F|lk=in}} at a pressure of {{convert|0.55|GPa|lk=in|atm}}. Ice XII was discovered existing within the phase stability region of [[ice V]]. Later research showed that ice XII could be created outside that range. Pure ice XII can be created from [[ice Ih|ice I<sub>h</sub>]] at {{convert|77|K}} by rapid compression (0.81-1.00 GPa/min) or by warming [[high density amorphous ice]] at pressures between {{convert|0.8|to|1.6|GPa|atm}}. |
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Because ice XI can theoretically form at low pressures at temperatures between 50–70 K – temperatures present in astrophysical environments of the outer solar system and within permanently shaded polar craters on the Moon and Mercury. Ice XI forms most easily around 70 K – paradoxically, it takes longer to form at lower temperatures. Extrapolating from experimental measurements, it is estimated to take ~50 years to form at 70 K and ~300 million years at 50 K.<ref name=astroice/> It is theorized to be present in places like the upper atmospheres of [[Uranus]] and [[Neptune]]<ref name=astro-ordering /> and on [[Pluto]] and [[Charon (moon)|Charon]].<ref name=astroice>{{cite journal|title=Ice XI on Pluto and Charon?|publisher= Division for Planetary Sciences Meeting, American Astronomical Society|issue=49.02|journal= Bulletin of the American Astronomical Society|date=August 2005|volume=37|pages=732|bibcode=2005DPS....37.4902M|last1=McKinnon|first1=W. B.|last2=Hofmeister|first2=A.M.}}</ref> |
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Ice VII may comprise the ocean floor of [[Europa (moon)|Europa]] as well as [[Exoplanet|extrasolar planets]] (such as [[Gliese 436 b|Awohali]], and [[Gliese 1214 b|Enaiposha]]) that are largely made of water.<ref>University of Liège (2007, May 16). Astronomers Detect Shadow Of Water World In Front Of Nearby Star. ScienceDaily. Retrieved Jan. 3, 2010, from {{cite web |url=https://www.sciencedaily.com/releases/2007/05/070516151053.htm |title=Astronomers Detect Shadow of Water World in Front of Nearby Star |access-date=2018-04-22 |url-status=live |archive-url=https://web.archive.org/web/20170821212607/https://www.sciencedaily.com/releases/2007/05/070516151053.htm |archive-date=2017-08-21 }}</ref><ref>{{cite web |url=http://www.cfa.harvard.edu/news/2009/pr200924.html |title=Astronomers Find Super-Earth Using Amateur, Off-the-Shelf Technology |author=David A. Aguilar |date=2009-12-16 |publisher=Harvard-Smithsonian Center for Astrophysics |access-date=January 23, 2010 |url-status=live |archive-url=https://web.archive.org/web/20120407045343/http://www.cfa.harvard.edu/news/2009/pr200924.html |archive-date=April 7, 2012 }}</ref> |
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While it is similar in density (1.29 g/cm<sup><span style="font-size:87%;">3</span></sup> at {{convert|127|K}}) to [[ice IV]] (also found in the [[ice V]] space) it exists as a [[tetragonal]] [[crystal]]. [[Topology|Topologically]] it is a mix of seven- and eight-membered rings, a 4-connected net (4-coordinate [[sphere]] packing)—the densest possible arrangement without [[hydrogen bond interpenetration]]. |
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Small domains of ice XI could exist in the atmospheres of Jupiter and Saturn as well.<ref name=astro-ordering /> The fact that small domains of ice XI can exist at temperatures up to 111 K has some scientists speculating that it may be fairly common in interstellar space, with small 'nucleation seeds' spreading through space and converting regular ice, much like the fabled [[ice-nine]] mentioned in Vonnegut's ''[[Cat's Cradle]]''.<ref name=astro-ordering/><ref>{{cite web|last=Grossman|first=Lisa|title=Electric ice a shock to the solar system|url=https://www.newscientist.com/article/mg21128274.400-electric-ice-a-shock-to-the-solar-system.html|publisher=[[New Scientist]]|access-date=7 April 2012|date=25 August 2011}}</ref> The possible roles of ice XI in interstellar space<ref name=astroice/><ref>{{cite journal|last1=Fukazawa|first1=H.|last2=Hoshikawa|first2= A.|last3=Ishii|first3= Y.|last4= Chakoumakos|first4= B. C.|last5= Fernandez-Baca|first5= J. A.|title=Existence of Ferroelectric Ice in the Universe|journal=The Astrophysical Journal|date=20 November 2006|volume=652|issue=1|pages=L57–L60|doi=10.1086/510017|bibcode = 2006ApJ...652L..57F |doi-access=free}}</ref> and planet formation<ref>{{cite journal | last1=Iedema | first1=M. J. | last2=Dresser | first2=M. J. | last3=Doering | first3=D. L. | last4=Rowland | first4=J. B. | last5=Hess | first5=W. P. | last6=Tsekouras | first6=A. A. | last7=Cowin | first7=J. P. | title=Ferroelectricity in Water Ice | journal=The Journal of Physical Chemistry B | publisher=American Chemical Society (ACS) | volume=102 | issue=46 | year=1998 | issn=1520-6106 | doi=10.1021/jp982549e | pages=9203–9214}}</ref> have been the subject of several research papers. Until observational confirmation of ice XI in outer space is made, the presence of ice XI in space remains controversial owing to the aforementioned criticism raised by Iitaka.<ref name=stability>{{cite arXiv|last=Iitaka|first=Toshiaki|title=Stability of ferroelectric ice |date=13 July 2010|eprint=1007.1792|class=cond-mat.mtrl-sci}}</ref> The infrared absorption spectra of ice XI was studied in 2009 in preparation for searches for ice XI in space.<ref>{{cite journal|last=Arakawa|first=M.|author2=Kagi, H. |author3=Fukazawa, H. |title=Laboratory Measurements of Infrared Absorption Spectra of Hydrogen-Ordered Ice: a Step to the Exploration of Ice XI in Space|journal=The Astrophysical Journal Supplement Series|date=1 October 2009|volume=184|issue=2|pages=361–365|doi=10.1088/0067-0049/184/2/361|bibcode = 2009ApJS..184..361A |doi-access=free}}</ref> |
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==Ice XIV== |
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It is theorized that the [[ice giant]] planets [[Uranus]] and [[Neptune]] hold a layer of superionic water.<ref name="NYT-20180205">{{cite news |last=Chang |first=Kenneth |title=Newly Discovered Form of Water Ice Is 'Really Strange' – Long theorized to be found in the mantles of Uranus and Neptune, the confirmation of the existence of superionic ice could lead to the development of new materials. |url=https://www.nytimes.com/2018/02/05/science/superionic-water-neptune-uranus.html |date=5 February 2018 |work=[[The New York Times]] |accessdate=5 February 2018 }}</ref><ref name="nature.com">{{cite journal |title=Giant planets may host superionic water |journal=Nature |date=22 March 2005 |doi=10.1038/news050321-4 |last1=Marris |first1=Emma }}</ref> <ref name="Lawrence Livermore">{{cite web|author=Charlie Osolin |url=https://www.llnl.gov/news/newsreleases/2005/SF-05-04-01.html |title=Public Affairs Office: Recreating the Bizarre State of Water Found on Giant Planets |publisher=Llnl.gov |accessdate=24 December 2010}}</ref><ref name=Phys.org-2013-04-25>{{cite news |website=Phys.org |url=http://phys.org/news/2013-04-phase-dominate-interiors-uranus-neptune.html |title=New phase of water could dominate the interiors of Uranus and Neptune |first=Lisa |last=Zyga |date=25 April 2013}}</ref> [[Machine learning]] and free-energy methods predict [[close-packed]] superionic phases to be stable over a wide temperature and pressure range, and a [[body-centred cubic]] superionic phase to be kinetically favoured, but stable over a small window of parameters.<ref>{{cite journal | title = Phase behaviours of superionic water at planetary conditions | last1 = Cheng | first1 = Bingqing | last2 = Bethkenhagen | first2 = Mandy | last3 = Pickard | first3 = Chris J. | last4 = Hamel | first4 = Sebastien | journal = Nature Physics | volume = 17 | pages = 1228–1232 | year = 2021 | issue = 11 | doi = 10.1038/s41567-021-01334-9| arxiv = 2103.09035 | s2cid = 232240463 }}</ref> On the other hand, there are also studies that suggest that other elements present inside the interiors of these planets, particularly [[carbon]], may prevent the formation of superionic water.<ref name="Chau">{{cite journal |title=Chemical processes in the deep interior of Uranus |first1=Ricky |last1=Chau |first2=Sebastien |last2=Hamel |first3=William J. |last3=Nellis |journal=[[Nature Communications|Nat. Commun.]] |volume=2 |at=Article number: 203 |doi=10.1038/ncomms1198 |pmid=21343921 |year=2011 |doi-access=free }}</ref><ref name="wang-yanchao11-11" >{{cite journal |last1=Wang |first1=Yanchao |title=High pressure partially ionic phase of water ice |journal=Nature Communications |date=29 November 2011 |volume=2 |page=563 |doi=10.1038/ncomms1566 |pmid=22127059 |doi-access=free }}</ref> |
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When [[hydrochloric acid|hydrochloric-acid]]-doped ice XII is cooled down to about 110 K, it undergoes a phase transition into a partially hydrogen-ordered phase, namely ice XIV.<ref name="pmid16556840">{{cite journal| author=Salzmann CG, Radaelli PG, Hallbrucker A, Mayer E, Finney JL| title=The preparation and structures of hydrogen ordered phases of ice. | journal=Science | year= 2006 | volume= 311 | issue= 5768 | pages= 1758–61 | pmid=16556840 | doi=10.1126/science.1123896 | pmc= | bibcode=2006Sci...311.1758S | s2cid=44522271 | url=https://pubmed.ncbi.nlm.nih.gov/16556840 }}</ref> The transition entropy from ice XIV to ice XII is estimated to be 60% of Pauling entropy based on DSC measurements.<ref name="pmid29923547">{{cite journal| author=Köster KW, Fuentes-Landete V, Raidt A, Seidl M, Gainaru C, Loerting T | display-authors=etal| title=Author Correction: Dynamics enhanced by HCl doping triggers 60% Pauling entropy release at the ice XII-XIV transition. | journal=Nat Commun | year= 2018 | volume= 9 | issue= | pages= 16189 | pmid=29923547 | doi=10.1038/ncomms16189 | pmc=6026910 | bibcode=2018NatCo...916189K}}</ref> The formation of ice XIV from ice XII is more favoured at high pressure.<ref name="pmid30101255">{{cite journal| author1=Fuentes-Landete V|author2= Köster KW|author3= Böhmer R|author4=Loerting T|author4-link=Thomas Loerting| title=Thermodynamic and kinetic isotope effects on the order-disorder transition of ice XIV to ice XII. | journal=Phys Chem Chem Phys | year= 2018 | volume= 20 | issue= 33 | pages= 21607–21616 | pmid=30101255 | doi=10.1039/c8cp03786h | pmc= |bibcode= 2018PCCP...2021607F|s2cid= 51969440| doi-access=free}}</ref> |
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== Notes == |
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{{Notelist}} |
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== References == |
== References == |
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<ref name="porousice">{{cite journal |last1=Liu |first1=Yuan |last2=Huang |first2=Yingying |last3=Zhu |first3=Chongqin |last4=Li |first4=Hui |last5=Zhao |first5=Jijun |last6=Wang |first6=Lu |last7=Ojamäe |first7=Lars |last8=Francisco |first8=Joseph S. |last9=Zeng |first9=Xiao Cheng |title=An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram |journal=Proceedings of the National Academy of Sciences |date=25 June 2019 |volume=116 |issue=26 |pages=12684–12691 |doi=10.1073/pnas.1900739116 |pmid=31182582 |pmc=6600908 |bibcode=2019PNAS..11612684L |doi-access=free }}</ref> |
<ref name="porousice">{{cite journal |last1=Liu |first1=Yuan |last2=Huang |first2=Yingying |last3=Zhu |first3=Chongqin |last4=Li |first4=Hui |last5=Zhao |first5=Jijun |last6=Wang |first6=Lu |last7=Ojamäe |first7=Lars |last8=Francisco |first8=Joseph S. |last9=Zeng |first9=Xiao Cheng |title=An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram |journal=Proceedings of the National Academy of Sciences |date=25 June 2019 |volume=116 |issue=26 |pages=12684–12691 |doi=10.1073/pnas.1900739116 |pmid=31182582 |pmc=6600908 |bibcode=2019PNAS..11612684L |doi-access=free }}</ref> |
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<ref name=" |
<ref name="discovery">{{cite journal |last1=del Rosso |first1=Leonardo |last2=Celli |first2=Milva |last3=Ulivi |first3=Lorenzo |title=New porous water ice metastable at atmospheric pressure obtained by emptying a hydrogen-filled ice |journal=Nature Communications |date=7 November 2016 |volume=7 |issue=1 |pages=13394 |doi=10.1038/ncomms13394 |pmid=27819265 |pmc=5103070 |arxiv=1607.07617 |bibcode=2016NatCo...713394D }}</ref> |
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<ref name="xvii.lsbu">{{cite web | url=https://water.lsbu.ac.uk/water/ice_xvii.html | title=Ice-seventeen (Ice XVII) | first1=Martin | last1=Chaplin | access-date=12 September 2022 | archive-date=11 September 2022 | archive-url=https://archive.today/20220911222726/https://water.lsbu.ac.uk/water/ice_xvii.html | url-status=bot: unknown }}{{self-published inline|date=September 2022}}</ref> |
<ref name="xvii.lsbu">{{cite web | url=https://water.lsbu.ac.uk/water/ice_xvii.html | title=Ice-seventeen (Ice XVII) | first1=Martin | last1=Chaplin | access-date=12 September 2022 | archive-date=11 September 2022 | archive-url=https://archive.today/20220911222726/https://water.lsbu.ac.uk/water/ice_xvii.html | url-status=bot: unknown }}{{self-published inline|date=September 2022}}</ref> |
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<ref name="cnr">{{cite web | url=http://www.ifac.cnr.it/~ulivi/IceXVII.htm | title=Ice-seventeen (Ice XVII) | first1=Martin | last1=Chaplin | access-date=2022-09-11 | archive-date=2022-09-11 | archive-url=https://archive.today/20220911222749/http://www.ifac.cnr.it/~ulivi/IceXVII.htm | url-status=bot: unknown }}{{self-published inline|date=September 2022}}</ref> |
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<ref name="cubic">{{cite journal |last1=del Rosso |first1=Leonardo |last2=Celli |first2=Milva |last3=Grazzi |first3=Francesco |last4=Catti |first4=Michele |last5=Hansen |first5=Thomas C. |last6=Fortes |first6=A. Dominic |last7=Ulivi |first7=Lorenzo |title=Cubic ice Ic without stacking defects obtained from ice XVII |journal=Nature Materials |date=June 2020 |volume=19 |issue=6 |pages=663–668 |doi=10.1038/s41563-020-0606-y |pmid=32015533 |arxiv=1907.02915 |bibcode=2020NatMa..19..663D |s2cid=195820566 }}</ref> |
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<ref name="cubic.c2">{{cite journal |last1=Komatsu |first1=Kazuki |last2=Machida |first2=Shinichi |last3=Noritake |first3=Fumiya |last4=Hattori |first4=Takanori |last5=Sano-Furukawa |first5=Asami |last6=Yamane |first6=Ryo |last7=Yamashita |first7=Keishiro |last8=Kagi |first8=Hiroyuki |title=Ice Ic without stacking disorder by evacuating hydrogen from hydrogen hydrate |journal=Nature Communications |date=3 February 2020 |volume=11 |issue=1 |pages=464 |doi=10.1038/s41467-020-14346-5 |pmid=32015342 |pmc=6997176 |arxiv=1909.03400 |bibcode=2020NatCo..11..464K }}</ref> |
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<ref name="lsbu">{{cite web | url=https://water.lsbu.ac.uk/water/ice_xvii.html | title=Ice-seventeen (Ice XVII) | first1=Martin | last1=Chaplin | access-date=2022-09-11 | archive-date=2022-09-11 | archive-url=https://archive.today/20220911222726/https://water.lsbu.ac.uk/water/ice_xvii.html | url-status=bot: unknown }}{{self-published inline|date=September 2022}}</ref> |
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<ref name="lsbu.isd">{{cite web | url=https://water.lsbu.ac.uk/water/ice1h1c.html | title=Stacking disordered ice; Ice Isd | first1=Martin | last1=Chaplin | access-date=2022-09-11 | archive-date=2022-09-11 | archive-url=https://archive.today/20220911222718/https://water.lsbu.ac.uk/water/ice1h1c.html | url-status=bot: unknown }}{{self-published inline|date=September 2022}}</ref> |
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<ref name="storage">{{cite journal |last1=Del Rosso |first1=Leonardo |last2=Celli |first2=Milva |last3=Ulivi |first3=Lorenzo |title=Ice XVII as a Novel Material for Hydrogen Storage |journal=Challenges |date=June 2017 |volume=8 |issue=1 |pages=3 |doi=10.3390/challe8010003 |doi-access=free }}</ref> |
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<ref name="xvi">{{cite journal |last1=Falenty |first1=Andrzej |last2=Hansen |first2=Thomas C. |last3=Kuhs |first3=Werner F. |title=Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate |journal=Nature |date=December 2014 |volume=516 |issue=7530 |pages=231–233 |doi=10.1038/nature14014 |pmid=25503235 |bibcode=2014Natur.516..231F |s2cid=4464711 }}</ref> |
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}} |
}} |
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==Further reading== |
==Further reading== |
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* {{cite web |first=Maren |last=Hunsberger |title=A New State of Water Reveals a Hidden Ocean in Earth's Mantle |date=September 21, 2018 |work=[[Seeker (media company)|Seeker]] |url=https://www.youtube.com/watch?v=pgm4z8vJVVk |archive-url=https://ghostarchive.org/varchive/youtube/20211221/pgm4z8vJVVk |archive-date=2021-12-21 |url-status=live|via=[[YouTube]] }}{{cbignore}} |
* {{cite web |first=Maren |last=Hunsberger |title=A New State of Water Reveals a Hidden Ocean in Earth's Mantle |date=September 21, 2018 |work=[[Seeker (media company)|Seeker]] |url=https://www.youtube.com/watch?v=pgm4z8vJVVk |archive-url=https://ghostarchive.org/varchive/youtube/20211221/pgm4z8vJVVk |archive-date=2021-12-21 |url-status=live|via=[[YouTube]] }}{{cbignore}} |
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* {{cite web |first=Marcus |last=Woo |date=July 11, 2018 |title=The Hunt for Earth's Deep Hidden Oceans |work=[[Quanta Magazine]] |url=https://www.quantamagazine.org/the-hunt-for-earths-deep-hidden-oceans-20180711 }} |
* {{cite web |first=Marcus |last=Woo |date=July 11, 2018 |title=The Hunt for Earth's Deep Hidden Oceans |work=[[Quanta Magazine]] |url=https://www.quantamagazine.org/the-hunt-for-earths-deep-hidden-oceans-20180711 }} |
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*[http://www.lsbu.ac.uk/water/amorph.html Discussion of amorphous ice] at [[London South Bank University|LSBU]]'s website. |
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*[http://www.nature.com/nature/journal/v435/n7041/full/nature03708.html Glass transition in hyperquenched water] from [[Nature (journal)|Nature]] (requires registration) |
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*[http://www.sciencemag.org/cgi/content/summary/294/5550/2305?rbfvrToken=765f39b90461f7428be6054763df6aa5a115d711 Glassy Water] from [[Science (journal)|Science]], on [[phase diagram]]s of water (requires registration) |
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*[https://web.archive.org/web/20050904190945/http://www.aip.org/pnu/2002/split/612-3.html AIP accounting discovery of VHDA] |
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*[http://adsbit.harvard.edu/cgi-bin/nph-iarticle_query?1995ApJ%2E%2E%2E455%2E%2E389J HDA in space] |
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*[https://web.archive.org/web/20050828183818/http://exobiology.arc.nasa.gov/ice/high.html Computerized illustrations of molecular structure of HDA] |
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[[Category:Glaciology]] |
[[Category:Glaciology]] |
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[[Category:Cryosphere]] |
[[Category:Cryosphere]] |
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[[Category: |
[[Category:Hydrogen storage]] |
Revision as of 15:47, 30 April 2024
The phases of ice are all possible states of matter for water as a solid. Currently, 19 phases, including both crystalline and amorphous ice, have been observed at various densities.
Theory
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: for some pressures higher than 1 atm (0.10 MPa), water freezes at a temperature below 0 °C. Subjected to higher pressures and varying temperatures, ice can form in nineteen separate known crystalline phases. With care, at least fifteen of these phases (one of the known exceptions being ice X) can be recovered at ambient pressure and low temperature in metastable form.[1][2] The types are differentiated by their crystalline structure, proton ordering,[3] and density. There are also two metastable phases of ice under pressure, both fully hydrogen-disordered; these are Ice IV and Ice XII.
Crystal structure
The accepted crystal structure of ordinary ice was first proposed by Linus Pauling in 1935. The structure of ice Ih is the wurtzite lattice, roughly one of crinkled planes composed of tessellating hexagonal rings, with an oxygen atom on each vertex, and the edges of the rings formed by hydrogen bonds. The planes alternate in an ABAB pattern, with B planes being reflections of the A planes along the same axes as the planes themselves.[4] The distance between oxygen atoms along each bond is about 275 pm and is the same between any two bonded oxygen atoms in the lattice. The angle between bonds in the crystal lattice is very close to the tetrahedral angle of 109.5°, which is also quite close to the angle between hydrogen atoms in the water molecule (in the gas phase), which is 105°.
This tetrahedral bonding angle of the water molecule essentially accounts for the unusually low density of the crystal lattice – it is beneficial for the lattice to be arranged with tetrahedral angles even though there is an energy penalty in the increased volume of the crystal lattice. As a result, the large hexagonal rings leave almost enough room for another water molecule to exist inside. This gives naturally occurring ice its rare property of being less dense than its liquid form. The tetrahedral-angled hydrogen-bonded hexagonal rings are also the mechanism that causes liquid water to be densest at 4 °C. Close to 0 °C, tiny hexagonal ice Ih-like lattices form in liquid water, with greater frequency closer to 0 °C. This effect decreases the density of the water, causing it to be densest at 4 °C when the structures form infrequently.
In the most common form of ice, ice Ih, the crystal structure is characterized by the oxygen atoms forming hexagonal symmetry with near tetrahedral bonding angles. This structure is stable down to −268 °C (5 K; −450 °F), as evidenced by x-ray diffraction[5] and extremely high resolution thermal expansion measurements.[6] Ice Ih is also stable under applied pressures of up to about 210 megapascals (2,100 atm) where it transitions into ice III or ice II.[7]
Amorphous ice
While most forms of ice are crystalline, several amorphous (or "vitreous") forms of ice also exist. Such ice is an amorphous solid form of water, which lacks long-range order in its molecular arrangement. Amorphous ice is produced either by rapid cooling of liquid water to its glass transition temperature (about 136 K or −137 °C) in milliseconds (so the molecules do not have enough time to form a crystal lattice), or by compressing ordinary ice at low temperatures. The most common form on Earth, low-density ice, is usually formed in the laboratory by a slow accumulation of water vapor molecules (physical vapor deposition) onto a very smooth metal crystal surface under 120 K. In outer space it is expected to be formed in a similar manner on a variety of cold substrates, such as dust particles.[8] By contrast, hyperquenched glassy water (HGW) is formed by spraying a fine mist of water droplets into a liquid such as propane around 80 K, or by hyperquenching fine micrometer-sized droplets on a sample-holder kept at liquid nitrogen temperature, 77 K, in a vacuum. Cooling rates above 104 K/s are required to prevent crystallization of the droplets. At liquid nitrogen temperature, 77 K, HGW is kinetically stable and can be stored for many years.
Amorphous ices have the property of suppressing long-range density fluctuations and are, therefore, nearly hyperuniform.[9] Despite the epithet "ice", classification analysis utilizing neural networks has shown that amorphous ices are glasses.[10]
Pressure-dependent states
Ice from a theorized superionic water may possess two crystalline structures. At pressures in excess of 50 GPa (7,300,000 psi) such superionic ice would take on a body-centered cubic structure. However, at pressures in excess of 100 GPa (15,000,000 psi) the structure may shift to a more stable face-centered cubic lattice. Some estimates suggest that at an extremely high pressure of around 1.55 TPa (225,000,000 psi), ice would develop metalic properties.[12]
Heat and entropy
Ice, water, and water vapour can coexist at the triple point, which is exactly 273.16 K (0.01 °C) at a pressure of 611.657 Pa.[14][15] The kelvin was defined as 1/273.16 of the difference between this triple point and absolute zero,[16] though this definition changed in May 2019.[17] 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.[18]
The latent heat of melting is 5987 J/mol, and its latent heat of sublimation is 50911 J/mol. The high latent heat of sublimation is principally indicative of the strength of the hydrogen bonds in the crystal lattice. The latent heat of melting is much smaller, partly because liquid water near 0 °C also contains a significant number of hydrogen bonds. By contrast, the structure of ice II is hydrogen-ordered, which helps to explain the entropy change of 3.22 J/mol when the crystal structure changes to that of ice I. Also, ice XI, an orthorhombic, hydrogen-ordered form of ice Ih, is considered the most stable form at low temperatures.
The transition entropy from ice XIV to ice XII is estimated to be 60% of Pauling entropy based on DSC measurements.[19] The formation of ice XIV from ice XII is more favoured at high pressure.[20]
When medium-density amorphous ice is compressed, released and then heated, it releases a large amount of heat energy, unlike other water ices which return to their normal form after getting similar treatment.[21]
Hydrogen disorder
The hydrogen atoms in the crystal lattice lie very nearly along the hydrogen bonds, and in such a way that each water molecule is preserved. This means that each oxygen atom in the lattice has two hydrogens adjacent to it: at about 101 pm along the 275 pm length of the bond for ice Ih. The crystal lattice allows a substantial amount of disorder in the positions of the hydrogen atoms frozen into the structure as it cools to absolute zero. As a result, the crystal structure contains some residual entropy inherent to the lattice and determined by the number of possible configurations of hydrogen positions that can be formed while still maintaining the requirement for each oxygen atom to have only two hydrogens in closest proximity, and each H-bond joining two oxygen atoms having only one hydrogen atom.[22] This residual entropy S0 is equal to 3.4±0.1 J mol−1 K−1 .[23]
Calculations
There are various ways of approximating this number from first principles. The following is the one used by Linus Pauling.[24][25]
Suppose there are a given number N of water molecules in an ice lattice. To compute its residual entropy, we need to count the number of configurations that the lattice can assume. The oxygen atoms are fixed at the lattice points, but the hydrogen atoms are located on the lattice edges. The problem is to pick one end of each lattice edge for the hydrogen to bond to, in a way that still makes sure each oxygen atom is bond to two hydrogen atoms.
The oxygen atoms can be divided into two sets in a checkerboard pattern, shown in the picture as black and white balls. Focus attention on the oxygen atoms in one set: there are N/2 of them. Each has four hydrogen bonds, with two hydrogens close to it and two far away. This means there are allowed configurations of hydrogens for this oxygen atom (see Binomial coefficient). Thus, there are 6N/2 configurations that satisfy these N/2 atoms. But now, consider the remaining N/2 oxygen atoms: in general they won't be satisfied (i.e., they will not have precisely two hydrogen atoms near them). For each of those, there are 24 = 16 possible placements of the hydrogen atoms along their hydrogen bonds, of which 6 are allowed. So, naively, we would expect the total number of configurations to be
Using Boltzmann's entropy formula, we conclude that
The same answer can be found in another way. First orient each water molecule randomly in each of the 6 possible configurations, then check that each lattice edge contains exactly one hydrogen atom. Assuming that the lattice edges are independent, then the probability that a single edge contains exactly one hydrogen atom is 1/2, and since there are 2N edges in total, we obtain a total configuration count , as before.
Refinements
This estimate is 'naive', as it assumes the six out of 16 hydrogen configurations for oxygen atoms in the second set can be independently chosen, which is false. More complex methods can be employed to better approximate the exact number of possible configurations, and achieve results closer to measured values. Nagle (1966) used a series summation to obtain .[26]
As an illustrative example of refinement, consider the following way to refine the second estimation method given above. According to it, six water molecules in a hexagonal ring would allow configurations. However, by explicit enumeration, there are actually 730 configurations. Now in the lattice, each oxygen atom participates in 12 hexagonal rings, so there are 2N rings in total for N oxygen atoms, or 2 rings for each oxygen atom, giving a refined result of .[27]
Known phases
These phases are named according to the Bridgman nomenclature. The majority have only been created in the laboratory at different temperatures and pressures.[28]
Phase | Year of discovery | Temperature thresholds | Pressure thresholds | Density | Crystal form | Other characteristics |
---|---|---|---|---|---|---|
Ice Ih | NA (always known) | 0 °C (32 °F) (freezing) | NA (atmospheric) | 0.917 g/cm3 | Hexagonal | Virtually all ice in the biosphere is ice Ih, with the exception only of a small amount of ice Ic. Has a refractive index of 1.31. |
Ice Ic | 1943 | 130 and 220 K (−143 and −53 °C) (formation)/240 K (−33 °C) (conversion to Ice Ih)[29][30] | NA (atmospheric) | Similar to Ice Ih | Diamond[31] | A metastable cubic crystalline variant of ice. |
Low-density amorphous ice (LDA) | NA (atmospheric or lower) | 0.94 g/cm3 [32] | NA (amorphous) | More viscous than normal water.[32][33][34] | ||
Medium-density amorphous ice (MDA) | 2023[21][35] | −200 °C (−328.0 °F) (freezing) | NA (requires shear force) | 1.06±0.06 g cm3[36] | NA (amorphous) | Experimental procedure generates shear force by crushing ice into powder with centimeter-wide stainless-steel balls added to its container. |
High-density amorphous ice (HDA) | 1984[37] | <140 K (−133 °C) (normal formation); <30 K (−243.2 °C) (vapor deposition)[32][38] 77 K (−196.2 °C) (stability point)[37] | At 77 K (−196.2 °C): 1.6 GPa (formation from Ih);[37] 0.5nbsp;GPa (formation from LDA)[39] | 1.17 g/cm3 (ambient pressure)[37] | NA (amorphous) | |
Very high-density amorphous ice (VHDA) | 1996[40] | 160 K (−113 °C) (formation from HDA); 77 K (−196.2 °C) (stability point) | 1 and 2 GPa (formation at 160 K (−113 °C)); ambient (at 77 K (−196.2 °C)) | 1.26 g/cm3 (77 K (−196.2 °C); ambient pressure)[41] | NA (amorphous) | |
Ice II | 1900[42] | 190 K (−83 °C)-210 K (−63 °C) (formation from ice Ih); 77 K (−196.2 °C) (stability point)[42] | 300 MPa[43] | Rhombohedral | ||
Ice III | 1900[42] | 250 K (−23 °C) (formation from liquid water); 77 K (−196.2 °C) (stability point)[42] | 300 MPa (formation from liquid water)[43] | 1160 kg/m3 (at 350 MPa)[44] | Tetragonal | Very high relative permittivity at 117. A specific gravity of 1.16 with respect to water. |
Ice IV | 1900[42] | 190 K (−83 °C)-210 K (−63 °C) (formation from HDA); 77 K (−196.2 °C) (stability point) | 810 MPa (formation from HDA) | Rhombohedral | Typically requires a nucleating agent to form.[45] | |
Ice V | 253 K (−20 °C) (formation from liquid water) | 500 MPa (formation from liquid water) [46] | 1.24 g cm3 (at 350 MPa).[47] | Monoclinic | Most complicated structure of all the phases. Includes 4-membered, 5-membered, 6-membered, and 8-membered rings and a total of 28 molecules in the unit cell.[48][49] | |
Ice VI | 1912[50] | 270 K (−3 °C) (formation from liquid water); 130 K (−143 °C) - 355 K (82 °C) (stability range) | 1.1 GPa (formation from liquid water) [46] | 1.31 g/cm3[51] | Tetragonal | Exhibits Debye relaxation.[52] |
Ice VII | 270 K (−3 °C) (formation from ice Ih) | 1.1 GPa (formation from ice Ih); 5 GPa (formation of tetragonal structure)[53] | Cubic/tetragonal | The hydrogen atoms' positions are disordered. Exhibits Debye relaxation. The hydrogen bonds form two interpenetrating lattices. Tetragonal form known as Ice VIIt. | ||
Ice VIII | <5 °C (278 K) (formation from ice VII) | 2.1 GPa (formation from ice VII) | Cubic | Hydrogen atoms assume fixed positions.[54] | ||
Ice IX | 165 K (−108 °C) (formation from ice III); <140 K (−133 °C) (stability point) | 200 MPa-400 MPa (stability range) | 1.16 g/cm3 | Tetragonal | Proton-ordered equivalent to Ice III.[55] | |
Ice X | 165 K (−108 °C) (formation from ice III); <140 K (−133 °C) (stability point) | 30-70 GPa (from ice VII)[56][53] | Cubic | Has symmetrized hydrogen bonds - a hydrogen atom is found at the center of two oxygen atoms. | ||
Ice XI | 72 K (−201.2 °C) (formation from ice Ic) | Orthorhombic | Ferroelectric. The most stable configuration of ice Ih.[57] | |||
Ice XII | 1996[58] | 260 K (−13 °C; 8 °F) (formation from liquid water); 77 K (−196.2 °C; −321.1 °F) (formation from ice Ih); 183 K (−90 °C) (formation from HDA ice) | 0.55 gigapascals (5,400 atm) (formation from liquid water); 0.81-1.00 GPa/min (from ice Ih); 810 MPa (formation from HDA ice) | 1.3 g·cm−3 (at 127 K (−146 °C)) | Tetragonal | Metastable. Observed in the phase space of ice V and ice VI. A topological mix of seven- and eight-membered rings, a 4-connected net (4-coordinate sphere packing)—the densest possible arrangement without hydrogen bond interpenetration. |
Ice XIII | 2006[59] | 130 K (−143 °C) (formation from liquid water) [60] | 500 MPa (formation from liquid water)[60] | Monoclinic | The proton-ordered form of ice V.[60] | |
Ice XIV | 2006[59] | <118 K (−155 °C) (formation from ice XII); <140 K (−133 °C) (stability point) | 1.2GPa (formation from ice XII)[60] | Orthorhombic | The proton-ordered form of ice XII.[60] Formation requires HCl doping.[61] | |
Ice XV | 2009[62] | 80 K (−193.2 °C)- 108 kelvins (−165 degrees Celsius) (formation from liquid water) | 1.1GPa (formation from liquid water) | A proton-ordered form of ice VI formed by cooling water to around 80–108 K at 1.1 GPa. | ||
Ice XVI | 2016[63][64][65][66][67] | <118 K (−155 °C) (formation from ice III); <140 K (−133 °C) (stability point) | 1.2GPa (from ice VII)[60] | 0.81 g/cm3)[68] | The least dense crystalline form of water, topologically equivalent to the empty structure of sII clathrate hydrates. Transforms into the stacking-faulty ice Ic and further into ordinary ice Ih when above 145–147 K at positive pressures. Theoretical studies predict ice XVI to be thermodynamically stable at negative pressures (that is under tension).[11][69] | |
Square ice | 2014[70] | Room temperature (in the presence of graphene) | 10GPa [71] | Square | Formation likely driven by the van der Waals force, which allows water vapor and liquid water to pass through laminated sheets of graphene oxide, unlike smaller molecules such as helium.[71] | |
Ice XVII | <118 K (−155 °C) (formation from ice III); <140 K (−133 °C) (stability point) | 1.2GPa (from ice III) | Near that of ice XVI.[72][73][66] | Hexagonal | A porous crystalline phase with helical channels, with density Formed by placing hydrogen-filled ice in a vacuum and increasing the temperature until the hydrogen molecules escape.[72] | |
Ice XVIII | <118 K (−155 °C) (formation from ice III); <140 K (−133 °C) (stability point) | 1.2GPa (from ice VII)[60] | A form of water also known as superionic water or superionic ice in which oxygen ions develop a crystalline structure while hydrogen ions move freely. | |||
Ice XIX | 2018[74] | <100 K (−173 °C) (formation from ice VIh); [75] | 2GPa (formation from ice VIh)[75] | Formation requires HCl doping.[74][75][76] |
History of research
Ice II
The properties of ice II were first described and recorded by Gustav Heinrich Johann Apollon Tammann in 1900 during his experiments with ice under high pressure and low temperatures. Having produced ice III, Tammann then tried condensing the ice at a temperature between −70 and −80 °C (203 and 193 K; −94 and −112 °F) under 200 MPa (2,000 atm) of pressure. Tammann noted that in this state ice II was denser than he had observed ice III to be. He also found that both types of ice can be kept at normal atmospheric pressure in a stable condition so long as the temperature is kept at that of liquid air, which slows the change in conformation back to ice Ih.[42]
In later experiments by Bridgman in 1912, it was shown that the difference in volume between ice II and ice III was in the range of 0.0001 m3/kg (2.8 cu in/lb). This difference hadn't been discovered by Tammann due to the small change and was why he had been unable to determine an equilibrium curve between the two. The curve showed that the structural change from ice III to ice II was more likely to happen if the medium had previously been in the structural conformation of ice II. However, if a sample of ice III that had never been in the ice II state was obtained, it could be supercooled even below −70 °C without it changing into ice II. Conversely, however, any superheating of ice II was not possible in regards to retaining the same form. Bridgman found that the equilibrium curve between ice II and ice IV was much the same as with ice III, having the same stability properties and small volume change. The curve between ice II and ice V was extremely different, however, with the curve's bubble being essentially a straight line and the volume difference being almost always 0.0000545 m3/kg (1.51 cu in/lb).[42]
Search for a hydrogen-disordered counterpart
As ice II is completely hydrogen ordered, the presence of its disordered counterpart is a great matter of interest. Shephard et al.[77] investigated the phase boundaries of NH4F-doped ices because NH4F has been reported to be a hydrogen disordering reagent. However, adding 2.5 mol% of NH4F resulted in the disappearance of ice II instead of the formation of a disordered ice II. According to the DFC calculation by Nakamura et al.,[78] the phase boundary between ice II and its disordered counterpart is estimated to be in the stability region of liquid water.
Ice IV
1981 research by Engelhardt and Kamb elucidated crystal structure of ice IV through a low-temperature single-crystal X-ray diffraction, describing it as a rhombohedral unit cell with a space group of R-3c.[79] This research mentioned that the structure of ice IV could be derived from the structure of ice Ic by cutting and forming some hydrogen bondings and adding subtle structural distortions. Shephard et al.[80] compressed the ambient phase of NH4F, an isostructural material of ice, to obtain NH4F II, whose hydrogen-bonded network is similar to ice IV. As the compression of ice Ih results in the formation of high-density amorphous ice (HDA), not ice IV, they claimed that the compression-induced conversion of ice I into ice IV is important, naming it "Engelhardt–Kamb collapse" (EKC). They suggested that the reason why we cannot obtain ice IV directly from ice Ih is that ice Ih is hydrogen-disordered; if oxygen atoms are arranged in the ice IV structure, hydrogen bonding may not be formed due to the donor-acceptor mismatch.[81] and Raman [82]
The disordered nature of Ice IV was confirmed by neutron powder diffraction studies by Lobban (1998) [83] and Klotz et al. (2003).[84] In addition, the entropy difference between ice VI (disordered phase) and ice IV is very small, according to Bridgman's measurement.[85]
Several organic nucleating reagents had been proposed to selectively crystallize ice IV from liquid water,[86] but even with such reagents, the crystallization of ice IV from liquid water was very difficult and seemed to be a random event. In 2001, Salzmann and his coworkers reported a whole new method to prepare ice IV reproducibly;[87] when high-density amorphous ice (HDA) is heated at a rate of 0.4 K/min and a pressure of 0.81 GPa, ice IV is crystallized at about 165 K. What governs the crystallization products is the heating rate; fast heating (over 10 K/min) results in the formation of single-phase ice XII.
Search for a hydrogen-ordered counterpart
The ordered counterpart of ice IV has never been reported yet. 2011 research by Salzmann's group reported more detailed DSC data where the endothermic feature becomes larger as the sample is quench-recovered at higher pressure. They proposed three scenarios to explain the experimental results: weak hydrogen-ordering, orientational glass transition, and mechanical distortions.[88] reported the DSC thermograms of HCl-doped ice IV finding an endothermic feature at about 120 K. Ten years later, Rosu-Finsen and Salzmann (2021) reported more detailed DSC data where the endothermic feature becomes larger as the sample is quench-recovered at higher pressure. They proposed three scenarios to explain the experimental results: weak hydrogen-ordering, orientational glass transition, and mechanical distortions.[89]
Ice XI
Ice XI is the hydrogen-ordered form of the ordinary form of ice. The total internal energy of ice XI is about one sixth lower than ice Ih, so in principle it should naturally form when ice Ih is cooled to below 72 K. The low temperature required to achieve this transition is correlated with the relatively low energy difference between the two structures.[90] Hints of hydrogen-ordering in ice had been observed as early as 1964, when Dengel et al. attributed a peak in thermo-stimulated depolarization (TSD) current to the existence of a proton-ordered ferroelectric phase.[91] However, they could not conclusively prove that a phase transition had taken place, and Onsager pointed out that the peak could also arise from the movement of defects and lattice imperfections. Onsager suggested that experimentalists look for a dramatic change in heat capacity by performing a careful calorimetric experiment. A phase transition to ice XI was first identified experimentally in 1972 by Shuji Kawada and others.[92][93][94]
Water molecules in ice Ih are surrounded by four semi-randomly directed hydrogen bonds. Such arrangements should change to the more ordered arrangement of hydrogen bonds found in ice XI at low temperatures, so long as localized proton hopping is sufficiently enabled; a process that becomes easier with increasing pressure.[95] Correspondingly, ice XI is believed to have a triple point with hexagonal ice and gaseous water at (~72 K, ~0 Pa). Ice Ih that has been transformed to ice XI and then back to ice Ih, on raising the temperature, retains some hydrogen-ordered domains and more easily transforms back to ice XI again.[96] A neutron powder diffraction study found that small hydrogen-ordered domains can exist up to 111 K.[97]
There are distinct differences in the Raman spectra between ices Ih and XI, with ice XI showing much stronger peaks in the translational (~230 cm−1), librational (~630 cm−1) and in-phase asymmetric stretch (~3200 cm−1) regions.[98][99]
Ice Ic also has a proton-ordered form. The total internal energy of ice XIc was predicted as similar as ice XIh.[100]
Ferroelectric properties
Ice XI is ferroelectric, meaning that it has an intrinsic polarization. To qualify as a ferroelectric it must also exhibit polarization switching under an electric field, which has not been conclusively demonstrated but which is implicitly assumed to be possible.[101] Cubic ice also has a ferrolectric phase and in this case the ferroelectric properties of the ice have been experimentally demonstrated on monolayer thin films.[102] In a similar experiment, ferroelectric layers of hexagonal ice were grown on a platinum (111) surface. The material had a polarization that had a decay length of 30 monolayers suggesting that thin layers of ice XI can be grown on substrates at low temperature without the use of dopants.[103] One-dimensional nano-confined ferroelectric ice XI was created in 2010.[104]
Ice XV
Although the parent phase ice VI was discovered in 1935, corresponding proton-ordered forms (ice XV) had not been observed until 2009. Theoretically, the proton ordering in ice VI was predicted several times; for example, density functional theory calculations predicted the phase transition temperature is 108 K and the most stable ordered structure is antiferroelectric in the space group Cc, while an antiferroelectric P212121 structure were found 4 K per water molecule higher in energy.[105]
On 14 June 2009, Christoph Salzmann and colleagues at the University of Oxford reported having experimentally reported an ordered phase of ice VI, named ice XV, and say that its properties differ significantly from those predicted. In particular, ice XV is antiferroelectric rather than ferroelectric as had been predicted.[106][107]
Ice XVII
In 2016, the discovery of a new form of ice was announced.[64] Characterized as a "porous water ice metastable at atmospheric temperatures", this new form was discovered by taking a filled ice and removing the non-water components, leaving the crystal structure behind, similar to how ice XVI, another porous form of ice, was synthesized from a clathrate hydrate.[63][64][65][66][67]
To create ice XVII, the researchers first produced filled ice in a stable phase named C0 from a mixture of hydrogen (H2) and water (H2O), using temperatures from 100 to 270 K (−173 to −3 °C; −280 to 26 °F) and pressures from 360 to 700 MPa (52,000 to 102,000 psi; 3,600 to 6,900 atm).[64][a] The filled ice is then placed in a vacuum, and the temperature gradually increased until the hydrogen frees itself from the crystal structure.[64][65][b] The resulting form is metastable at room pressure while under 120 K (−153 °C; −244 °F), but collapses into ice Ih (ordinary ice) when brought above 130 K (−143 °C; −226 °F).[64][65] The crystal structure is hexagonal in nature, and the pores are helical channels with a diameter of about 6.10 Å (6.10×10−10 m; 2.40×10−8 in).[64][65]
Cubic ice
It was reported in 2020 that cubic ice based on heavy water (D2O) can be formed from ice XVII.[108] This was done by heating specially prepared D2O ice XVII powder.[108] The result was free of structural deformities compared to standard cubic ice, or ice Isd.[108][109] This discovery was reported around the same time another research group announced that they were able to obtain pure D2O cubic ice by first synthesizing filled ice in the C2 phase, and then decompressing it.[110][64][a]
Ice XVIII (superionic water)
In 1988, predictions of the so-called superionic water state were made.[111] In superionic water, water molecules break apart and the oxygen ions crystallize into an evenly spaced lattice while the hydrogen ions float around freely within the oxygen lattice.[112] The freely mobile hydrogen ions make superionic water almost as conductive as typical metals, making it a superionic conductor.[113] The ice appears black in color.[114][115] It is distinct from ionic water, which is a hypothetical liquid state characterized by a disordered soup of hydrogen and oxygen ions.
The initial evidence came from optical measurements of laser-heated water in a diamond anvil cell,[116] and from optical measurements of water shocked by extremely powerful lasers.[114] The first definitive evidence for the crystal structure of the oxygen lattice in superionic water came from x-ray measurements on laser-shocked water which were reported in 2019.[113] In 2005 Laurence Fried led a team at Lawrence Livermore National Laboratory to recreate the formative conditions of superionic water. Using a technique involving smashing water molecules between diamonds and super heating it with lasers they observed frequency shifts which indicated that a phase transition had taken place. The team also created computer models which indicated that they had indeed created superionic water.[117] In 2013 Hugh F. Wilson, Michael L. Wong, and Burkhard Militzer at the University of California, Berkeley published a paper predicting the face-centered cubic lattice structure that would emerge at higher pressures.[118] Additional experimental evidence was found by Marius Millot and colleagues in 2018 by inducing high pressure on water between diamonds and then shocking the water using a laser pulse.[114][115]
As of 2013, it is theorized that superionic ice can possess two crystalline structures. At pressures in excess of 50 GPa (7,300,000 psi) it is predicted that superionic ice would take on a body-centered cubic structure. However, at pressures in excess of 100 GPa, and temperatures above 2000 K, it is predicted that the structure would shift to a more stable face-centered cubic lattice.[118]
In 2018, researchers at LLNL squeezed water between two pieces of diamond with a pressure of 2,500 MPa (360,000 psi). The water was squeezed into Ice VII, which is 60 percent denser than normal water.[119] The compressed ice was then transported to the University of Rochester where it was blasted by a pulse of laser light. The reaction created conditions like those inside of ice giants such as Uranus and Neptune by heating up the ice thousands of degrees under a pressure a million times greater than the Earth's atmosphere in only 10 to 20 billionths of a second. The experiment concluded that the current in the conductive water was indeed carried by ions rather than electrons and thus pointed to the water being superionic.[119] More recent experiments from the same Lawrence Livermore National Laboratory team used x-ray crystallography on laser-shocked water droplets to determine that the oxygen ions enter a face-centered-cubic phase, which was dubbed ice XVIII and reported in the journal Nature in May 2019.[113]
Ice XIX
The first report regarding ice XIX was published in 2018 by Thomas Loerting's group from Austria.[74] They quenched HCl-doped ice VI to 77 K at different pressures between 1.0 and 1.8 GPa to collect differential scanning calorimetry (DSC) thermograms, dielectric spectrum, Raman spectrum, and X-ray diffraction patterns. In the DSC signals, there was an endothermic feature at about 110 K in addition to the endotherm corresponding to the ice XV-VI transition. Additionally, the Raman spectra, dielectric properties, and the ratio of the lattice parameters differed from those of ice XV. Based on these observations, they proposed the existence of a second hydrogen-ordered phase of ice VI, naming it ice beta-XV.
In 2019, Alexander Rosu-Finsen and Christoph Salzman argued that there was no need to consider this to be a new phase of ice, and proposed a "deep-glassy" state scenario.[120] According to their DSC data, the size of the endothermic feature depends not only on quench-recovery pressure but also on the heating rate and annealing duration at 93 K. They also collected neutron diffraction profiles of quench-recovered deuterium chloride-doped, D2O ice VI/XV prepared at different pressures of 1.0, 1.4 and 1.8 GPa, to show that there were no significant differences among them. They concluded that the low-temperature endotherm originated from kinetic features related to glass transitions of deep glassy states of disordered ice VI.
Distinguishing between the two scenarios (new hydrogen-ordered phase vs. deep-glassy disordered ice VI) became an open question and the debate between the two groups has continued. Thoeny et al. (Loerting's group) [121] collected another series of Raman spectra of ice beta-XV, and reported that (i) ice XV prepared by the protocol reported previously contains both ice XV and ice beta-XV domains; (ii) upon heating, Raman spectra of ice beta-XV showed loss of H-order. In contrast, Salzmann's group again argued for the plausibility of a 'deep-glassy state' scenario based on neutron diffraction and neutron inelastic scattering experiments.[122] Based on their experimental results, ice VI and deep-glassy ice VI share very similar features based on both elastic (diffraction) scattering and inelastic scattering experiments, and are different from the properties of ice XV.
In 2021, further crystallographic evidence for a new phase (ice XIX) was individually reported by three groups: Yamane et al. (Hiroyuki Kagi and Kazuki Komatsu's group from Japan), Gasser et al. (Loerting's group), and Salzmann's group. Yamane et al. [76] collected neutron diffraction profiles in situ (i.e. under high pressure) and found new Bragg features completely different from both ice VI and ice XV. They performed Rietveld refinement of the profiles based on the supercell of ice XV and proposed some leading candidates for the space group of ice XIX: P-4, Pca21, Pcc2, P21/a, and P21/c. They also measured dielectric spectra in situ and determined phase boundaries of ices VI/XV/XIX. They found that the sign of the slope of the boundary turns negative from positive at 1.6 GPa indicating the existence of two different phases by the Clausius–Clapeyron relation.
Gasser et al. [123] also collected powder neutron diffractograms of quench-recovered ices VI, XV, and XIX and found similar crystallographic features to those reported by Yamane et al., concluding that P-4 and Pcc2 are the plausible space group candidates. Both Yamane et al.'s and Gasser et al.'s results suggested a partially hydrogen-ordered structure. Gasser et al. also found an isotope effect using DSC; the low-temperature endotherm for DCl-doped D2O ice XIX was significantly smaller than that of HCl-doped H2O ice XIX, and that doping of 0.5% of H2O into D2O is sufficient for the ordering transition.
Several months later, Salzmann et al. published a paper based on in-situ powder neutron diffraction experiments of ice XIX.[124] In a change from their previous reports, they accepted the idea of the new phase (ice XIX) as they observed similar features to the previous two reports. However, they refined their diffraction profiles based on a disordered structural model (Pbcn) and argued that new Bragg reflections can be explained by distortions of ice VI, so ice XIX may still be regarded as a deep-glassy state of ice VI. The crystal structure of ice XIX including hydrogen order/disorder is still under debate as of 2022.
Practical implications
Earth's natural environment
Virtually all ice in the biosphere is ice Ih (pronounced: ice one h, also known as ice-phase-one). Ice Ih exhibits many peculiar properties that are relevant to the existence of life and regulation of global climate. [125] For instance, its density is lower than that of liquid water. This is attributed to the presence of hydrogen bonds which causes atoms to become closer in the liquid phase.[126] Because of this, ice Ih floats on water, which is highly unusual when compared to other materials. The solid phase of materials is usually more closely and neatly packed and has a higher density than the liquid phase. When lakes freeze, they do so only at the surface, while the bottom of the lake remains near 4 °C (277 K; 39 °F) because water is densest at this temperature. This anomalous behavior of water and ice is what allows fish to survive harsh winters. The density of ice Ih increases when cooled, down to about −211 °C (62 K; −348 °F); below that temperature, the ice expands again (negative thermal expansion).[5][6]
Besides ice Ih, a small amount of ice Ic may occasionally present in the upper atmosphere clouds.[127] It is believed to be responsible for the observation of Scheiner's halo, a rare ring that occurs near 28 degrees from the Sun or the Moon.[128] However, many atmospheric samples which were previously described as cubic ice were later shown to be stacking disordered ice with trigonal symmetry,[129][130][131] and it has been dubbed the ″most faceted ice phase in a literal and a more general sense.″[132] The first true samples of cubic ice were only reported in 2020.[133][134][135]
Low-density ASW (LDA), also known as hyperquenched glassy water, may be responsible for noctilucent clouds on Earth and is usually formed by deposition of water vapor in cold or vacuum conditions. Ice clouds form at and below the Earth's high latitude mesopause (~90 km) where temperatures have been observed to fall as to below 100 K.[136] It has been suggested that homogeneous nucleation of ice particles results in low density amorphous ice.[137] Amorphous ice is likely confined to the coldest parts of the clouds and stacking disordered ice I is thought to dominate elsewhere in these polar mesospheric clouds.[138]
In 2018, ice VII was identified among inclusions found in natural diamonds.[139] Due to this demonstration that ice VII exists in nature, the International Mineralogical Association duly classified ice VII as a distinct mineral.[140] The ice VII was presumably formed when water trapped inside the diamonds retained the high pressure of the deep mantle due to the strength and rigidity of the diamond lattice, but cooled down to surface temperatures, producing the required environment of high pressure without high temperature.[141]
Ice XI is thought to be a more stable conformation than ice Ih, and so it may form on Earth. However, the transformation is very slow. According to one report, in Antarctic conditions it is estimated to take at least 100,000 years to form without the assistance of catalysts.[citation needed] Ice XI was sought and found in Antarctic ice that was about 100 years old in 1998.[142] A further study in 2004 was not able to reproduce this finding, however, after studying Antarctic ice which was around 3000 years old.[143] The 1998 Antarctic study also claimed that the transformation temperature (ice XI => ice Ih) is −36 °C (237 K), which is far higher than the temperature of the expected triple point mentioned above (72 K, ~0 Pa). Ice XI was also found in experiments using pure water at very low temperature (~10 K) and low pressure – conditions thought to be present in the upper atmosphere.[144] Recently, small domains of ice XI were found to form in pure water; its phase transition back to ice Ih occurred at 72 K while under hydrostatic pressure conditions of up to 70 MPa.[145]
Human industry
Amorphous ice is used in some scientific experiments, especially in cryo-electron microscopy of biomolecules.[146] The individual molecules can be preserved for imaging in a state close to what they are in liquid water.
Ice XVII can repeatedly adsorb and release hydrogen molecules without degrading its structure.[64] The total amount of hydrogen that ice XVII can adsorb depends on the amount of pressure applied, but hydrogen molecules can be adsorbed by ice XVII even at pressures as low as a few millibars[c] if the temperature is under 40 K (−233.2 °C; −387.7 °F).[64][147] The adsorbed hydrogen molecules can then be released, or desorbed, through the application of heat.[147] This was an unexpected property of ice XVII, and could allow it to be used for hydrogen storage, an issue often mentioned in environmental technology.[64][147]
Aside from storing hydrogen via compression or liquification, it can also be stored within a solid substance, either via a reversible chemical process (chemisorption) or by having the hydrogen molecules attach to the substance via the van der Waals force (physisorption).[147] The storage method used by ice XVII falls in the latter category, physisorption.[147] In physisorption, there is no chemical reaction, and the chemical bond between the two atoms within a hydrogen molecule remains intact. Because of this, the number of adsorption–desorption cycles ice XVII can withstand is "theoretically infinite".[64][147]
One significant advantage of using ice XVII as a hydrogen storage medium is the low cost of the only two chemicals involved: hydrogen and water.[147] In addition, ice XVII has shown the ability to store hydrogen at an H2 to H2O molar ratio above 40%, higher than the theoretical maximum ratio for sII clathrate hydrates, another potential storage medium.[64] However, if ice XVII is used as a storage medium, it must be kept under a temperature of 130 K (−143 °C; −226 °F) or risk being destabilized.[147]
Outer space
In outer space, hexagonal crystalline ice (the predominant form found on Earth) is extremely rare. Known examples are typically associated with volcanic action.[148] Water in the interstellar medium is instead dominated by amorphous ice, making it likely the most common form of water in the universe.[149]
Amorphous ice can be separated from crystalline ice based on its near-infrared and infrared spectrum. At near-IR wavelengths, the characteristics of the 1.65, 3.1, and 4.53 μm water absorption lines are dependent on the ice temperature and crystal order.[150] The peak strength of the 1.65 μm band as well as the structure of the 3.1 μm band are particularly useful in identifying the crystallinity of water ice.[151][152]
At longer IR wavelengths, amorphous and crystalline ice have characteristically different absorption bands at 44 and 62 μm in that the crystalline ice has significant absorption at 62 μm while amorphous ice does not.[153] In addition, these bands can be used as a temperature indicator at very low temperatures where other indicators (such as the 3.1 and 12 μm bands) fail.[154] This is useful studying ice in the interstellar medium and circumstellar disks. However, observing these features is difficult because the atmosphere is opaque at these wavelengths, requiring the use of space-based infrared observatories.
Properties of the amorphous ice in the Solar System
In general, amorphous ice can form below ~130 K.[155] At this temperature, water molecules are unable to form the crystalline structure commonly found on Earth. Amorphous ice may also form in the coldest region of the Earth's atmosphere, the summer polar mesosphere, where noctilucent clouds exist.[156] These low temperatures are readily achieved in astrophysical environments such as molecular clouds, circumstellar disks, and the surfaces of objects in the outer Solar System. In the laboratory, amorphous ice transforms into crystalline ice if it is heated above 130 K, although the exact temperature of this conversion is dependent on the environment and ice growth conditions.[157] The reaction is irreversible and exothermic, releasing 1.26–1.6 kJ/mol.[157]
An additional factor in determining the structure of water ice is deposition rate. Even if it is cold enough to form amorphous ice, crystalline ice will form if the flux of water vapor onto the substrate is less than a temperature-dependent critical flux.[158] This effect is important to consider in astrophysical environments where the water flux can be low. Conversely, amorphous ice can be formed at temperatures higher than expected if the water flux is high, such as flash-freezing events associated with cryovolcanism.
At temperatures less than 77 K, irradiation from ultraviolet photons as well as high-energy electrons and ions can damage the structure of crystalline ice, transforming it into amorphous ice.[159][153] Amorphous ice does not appear to be significantly affected by radiation at temperatures less than 110 K, though some experiments suggest that radiation might lower the temperature at which amorphous ice begins to crystallize.[153]
Peter Jenniskens and David F. Blake demonstrated in 1994 that a form of high-density amorphous ice is also created during vapor deposition of water on low-temperature (< 30 K) surfaces such as interstellar grains. The water molecules do not fully align to create the open cage structure of low-density amorphous ice. Many water molecules end up at interstitial positions. When warmed above 30 K, the structure re-aligns and transforms into the low-density form.[32][38]
Molecular clouds, circumstellar disks, and the primordial solar nebula
Molecular clouds have extremely low temperatures (~10 K), falling well within the amorphous ice regime. The presence of amorphous ice in molecular clouds has been observationally confirmed.[160] When molecular clouds collapse to form stars, the temperature of the resulting circumstellar disk isn't expected to rise above 120 K, indicating that the majority of the ice should remain in an amorphous state.[158] However, if the temperature rises high enough to sublimate the ice, then it can re-condense into a crystalline form since the water flux rate is so low. This is expected to be the case in the circumstellar disk of IRAS 09371+1212, where signatures of crystallized ice were observed despite a low temperature of 30–70 K.[161]
For the primordial solar nebula, there is much uncertainty as to the crystallinity of water ice during the circumstellar disk and planet formation phases. If the original amorphous ice survived the molecular cloud collapse, then it should have been preserved at heliocentric distances beyond Saturn's orbit (~12 AU).[158]
Comets
The possibility of the presence of amorphous water ice in comets and the release of energy during the phase transition to a crystalline state was first proposed as a mechanism for comet outbursts.[162] Evidence of amorphous ice in comets is found in the high levels of activity observed in long-period, Centaur, and Jupiter Family comets at heliocentric distances beyond ~6 AU.[163] These objects are too cold for the sublimation of water ice, which drives comet activity closer to the Sun, to have much of an effect. Thermodynamic models show that the surface temperatures of those comets are near the amorphous/crystalline ice transition temperature of ~130 K, supporting this as a likely source of the activity.[164] The runaway crystallization of amorphous ice can produce the energy needed to power outbursts such as those observed for Centaur Comet 29P/Schwassmann–Wachmann 1.[165][166]
Kuiper Belt objects
With radiation equilibrium temperatures of 40–50 K,[167] the objects in the Kuiper Belt are expected to have amorphous water ice. While water ice has been observed on several objects,[168][169] the extreme faintness of these objects makes it difficult to determine the structure of the ices. The signatures of crystalline water ice was observed on 50000 Quaoar, perhaps due to resurfacing events such as impacts or cryovolcanism.[170]
Icy moons
The Near-Infrared Mapping Spectrometer (NIMS) on NASA's Galileo spacecraft spectroscopically mapped the surface ice of the Jovian satellites Europa, Ganymede, and Callisto. The temperatures of these moons range from 90 to 160 K,[171] warm enough that amorphous ice is expected to crystallize on relatively short timescales. However, it was found that Europa has primarily amorphous ice, Ganymede has both amorphous and crystalline ice, and Callisto is primarily crystalline.[172] This is thought to be the result of competing forces: the thermal crystallization of amorphous ice versus the conversion of crystalline to amorphous ice by the flux of charged particles from Jupiter. Closer to Jupiter than the other three moons, Europa receives the highest level of radiation and thus through irradiation has the most amorphous ice. Callisto is the farthest from Jupiter, receiving the lowest radiation flux and therefore maintaining its crystalline ice. Ganymede, which lies between the two, exhibits amorphous ice at high latitudes and crystalline ice at the lower latitudes. This is thought to be the result of the moon's intrinsic magnetic field, which would funnel the charged particles to higher latitudes and protect the lower latitudes from irradiation.[172] Ganymede's interior probably includes a liquid water ocean with tens to hundreds of kilometers of ice V at its base.[173]
The surface ice of Saturn's moon Enceladus was mapped by the Visual and Infrared Mapping Spectrometer (VIMS) on the NASA/ESA/ASI Cassini space probe. The probe found both crystalline and amorphous ice, with a higher degree of crystallinity at the "tiger stripe" cracks on the surface and more amorphous ice between these regions.[150] The crystalline ice near the tiger stripes could be explained by higher temperatures caused by geological activity that is the suspected cause of the cracks. The amorphous ice might be explained by flash freezing from cryovolcanism, rapid condensation of molecules from water geysers, or irradiation of high-energy particles from Saturn.[150] Similarly, one of one of the inner layers of Titan is believed to contain ice VI.[174]
Medium-density amorphous ice may be present on Europa, as the experimental conditions of its formation are expected to occur there as well. It is possible that the MDA ice's unique property of releasing a large amount of heat energy after being released from compression could be responsible for 'ice quakes' within the thick ice layers.[21]
Planets
Because ice XI can theoretically form at low pressures at temperatures between 50–70 K – temperatures present in astrophysical environments of the outer solar system and within permanently shaded polar craters on the Moon and Mercury. Ice XI forms most easily around 70 K – paradoxically, it takes longer to form at lower temperatures. Extrapolating from experimental measurements, it is estimated to take ~50 years to form at 70 K and ~300 million years at 50 K.[175] It is theorized to be present in places like the upper atmospheres of Uranus and Neptune[97] and on Pluto and Charon.[175]
Ice VII may comprise the ocean floor of Europa as well as extrasolar planets (such as Awohali, and Enaiposha) that are largely made of water.[176][177]
Small domains of ice XI could exist in the atmospheres of Jupiter and Saturn as well.[97] The fact that small domains of ice XI can exist at temperatures up to 111 K has some scientists speculating that it may be fairly common in interstellar space, with small 'nucleation seeds' spreading through space and converting regular ice, much like the fabled ice-nine mentioned in Vonnegut's Cat's Cradle.[97][178] The possible roles of ice XI in interstellar space[175][179] and planet formation[180] have been the subject of several research papers. Until observational confirmation of ice XI in outer space is made, the presence of ice XI in space remains controversial owing to the aforementioned criticism raised by Iitaka.[181] The infrared absorption spectra of ice XI was studied in 2009 in preparation for searches for ice XI in space.[182]
It is theorized that the ice giant planets Uranus and Neptune hold a layer of superionic water.[183][117] [184][118] Machine learning and free-energy methods predict close-packed superionic phases to be stable over a wide temperature and pressure range, and a body-centred cubic superionic phase to be kinetically favoured, but stable over a small window of parameters.[185] On the other hand, there are also studies that suggest that other elements present inside the interiors of these planets, particularly carbon, may prevent the formation of superionic water.[186][187]
Notes
- ^ a b C0, C1, and C2 are all stable solid phases of a mixture of H2 and H2O molecules, formed at high pressures.[64][65] Although sometimes referred to as clathrate hydrates (or clathrates), they lack the cagelike structure generally found in clathrate hydrates, and are more properly referred to as filled ices.[64][65][66]
- ^ If kept at a temperature range between 110 and 120 K (−163 and −153 °C; −262 and −244 °F), after about two hours, the structure will have emptied itself of any detectable hydrogen molecules.[64][65]
- ^ One millibar is equivalent to 100 Pa (0.015 psi; 0.00099 atm).
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Further reading
- Ice phases (www.idc-online.com)
- Fletcher, N. H. (2009-06-04). The Chemical Physics of Ice. ISBN 9780521112307.
- Petrenko, Victor F.; Whitworth, Robert W. (1999-08-19). Physics of Ice. ISBN 9780191581342.
- Chaplin, Martin (2007-11-11). "Hexagonal ice structure". Water Structure and Science. Retrieved 2008-01-02.
- London South Bank University Report
- Physik des Eises (PDF in German, iktp.tu-dresden.de)
External links
- Hunsberger, Maren (September 21, 2018). "A New State of Water Reveals a Hidden Ocean in Earth's Mantle". Seeker. Archived from the original on 2021-12-21 – via YouTube.
- Woo, Marcus (July 11, 2018). "The Hunt for Earth's Deep Hidden Oceans". Quanta Magazine.
- Discussion of amorphous ice at LSBU's website.
- Glass transition in hyperquenched water from Nature (requires registration)
- Glassy Water from Science, on phase diagrams of water (requires registration)
- AIP accounting discovery of VHDA
- HDA in space
- Computerized illustrations of molecular structure of HDA