19 types of ice

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Ice explodes, sinks in water, conducts current, generates a powerful magnetic field.

As a child, my friend glued a cockroach to the bottom of an ice mold on a drop of plasticine, poured it with water and froze it. Then he threw filled ice cubes at the wall and shouted “I am Sabziro!” And I always chose Glacius in Killer Instinct because he was graceful. In “Semievia” a jet engine was built from ice on an asteroid and it was drowned with ice. And, of course, “Cat’s Cradle”. Meanwhile, in reality …

Argonne National Laboratory invented the technology in 1980 ice slurry (ice slurry), which does not form ice build-ups, does not stick together, flows through pipes and is 5-7 times more effective than plain water for cooling.

Ice microcrystals “Ice blood” well penetrate into small blood vessels without harm to cells. In cardiac arrest, the time to rescue the victim could theoretically increase from 10 to 45 minutes.

D. Pike suggested adding sawdust to the ice and from this composite (pykerite) make … an aircraft carrier.

With a little digging, I learned how deep the icy rabbit hole is.

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A pioneer in exploring different types of ice – Percy Williams Bridgeman, Nobel laureate in physics in 1946, he worked with high pressures (up to 10 GPa), discovered / described in 1912 5-6 types of ice per year.

“Ice Rules”

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Bernal-Fowler rules:

  • a) the oxygen atom of each molecule H2О is bonded to four neighboring hydrogen atoms: with two hydrogen atoms by a covalent bond, with two neighboring ones – through hydrogen bonds (as is the case in the crystal structure of ice);
  • b) only one proton H can be located on the oxygen – oxygen line+;
  • c) a proton participating in the formation of a hydrogen bond and located between oxygen atoms has two equilibrium positions and can be located both near its oxygen atom at a distance of approximately 1 A, and near a neighboring oxygen atom at a distance of 1.7 A, i.e. along with the usual HO-H … OH dimer2 the ion pair HO … H-OH is also stable2… The state “proton near neighboring oxygen” is characteristic of the phase boundary, i.e. near the surface water-solid or water-gas;
  • d) the spatial bond of the O-H … O triple, where the bar denotes the covalent bond, and the dots – the hydrogen bond, cannot be arbitrary, but has a clear spatial orientation.
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Six possible molecular orientations of the central water molecule in the Walrafen pentamer.

Experiments with the magnitude and rate of change in temperature and pressure, as well as tricks with graphene, allow you to play with the structure and orientation of protons, which gives rise to 19 experimentally obtained and several theoretical types of ice.

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Phase diagram and structures of ice.

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Summary table of 15 types of ice.

Ice 0

Theoretical structure. Ice-0 can be obtained when ice crystallizes I

with

and ice I

h

from supercooled water.

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Amorphous ice

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Phase diagram of amorphous ices and liquid water.

Ice-Iaor LDA (Low-density amorphous ice)

If liquid water is cooled at a rate of about 1,000,000 K per second, then the molecules do not have time to form a crystal lattice and an amorphous ice of no density is obtained (“supercooled glassy water”, HGW). The second way is to condense water vapor on a highly cooled substrate (“amorphous solid water”, ASW).

Ice-Ia or HDA (High-density amorphous ice)

High density amorphous ice can be obtained by squeezing “regular” ice I

h

at temperatures below 140 K.

VHDA (Very-high density amorphous ice)

Very high density amorphous ice (2001) is obtained by heating HDA to 160 K at a pressure of 1-2 GPa.

An interesting video how ice melts from one phase to another:

Ice Ih

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Regular hexagonal (hexagon, so Ih) crystalline ice. Almost all ice on Earth belongs to ice Ih, and only a small part – to ice Iwith (withubic).

Ice Iwith (1987)

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Diamond-shaped arrangement of water in ice Iwith

Ice-Isd

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Stacking disordered ice

By the way, ice Isd was “discovered” when observing the solar halo:

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triangular snowflakes

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Triangular snowflake from Isd

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Phase structure Ih(a) and Iwith(b).

Ice 2 (1900)

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Get ice-II by squeezing ice Ih at temperatures from -83 ° C to -63 ° C (190-210 K) and a pressure of 300 MPa, or by decompression of ice V at a temperature of -35 ° C (238 K). When heated, ice-II is converted to ice-III.

It is believed that “ice moons” such as Ganymede may be made of ice-II.

Ice 3

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Can be obtained by cooling water to −23 ° C (250 K) and a pressure of 300 MPa.

Ice-III is the simplest high-pressure ice to be obtained and available for research. It was first obtained from ordinary ice at a temperature of −22 ° C (triple point temperature ice Ih – ice III – water) by increasing the pressure to 210 MPa

Ice 4

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Obtained by slowly heating (0.4 K / min) high-density amorphous ice from a temperature of 145 K at a constant pressure of 0.81 GPa.

Ice 5

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Ice-V is produced by cooling water to 253 K (−20 ° C) at a pressure of 500 MPa. The ice-V structure is the most complex of all ice phases. Ice V melts at 50 ° C.

Ice 6

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Obtained by cooling water to −3 ° C (270 K) and a pressure of 1.1 GPa. Debye relaxation is manifested in it. Ice VI melts at 81 ° C (355 K) at 2.216 GPa and at about 0 ° C at 0.6 GPa.

It is part of the inner layers of Titan.

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Ice crystal VI

more pictures

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Crystallization of water into tetragonal ice VI at room temperature and a pressure of 0.9 GPa.

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Crystal growth at trapezoidal pressure.

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Crystal growth at sinusoidal pressure.

Ice 7 (1969)

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The most disordered ice, in it not only hydrogen atoms, but also oxygen atoms are not ordered.

Can be obtained from water under a pressure of 3 GPa when cooled to room temperature. It is also obtained from ice VI by increasing pressure at room temperature.

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Ice 8

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An ordered version of ice VII in which hydrogen is fixed. It is made from ice-VII when it is cooled below 5 ° C.

Ice 9 (1973)

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Ice-IX is a metastable form of solid water at temperatures below 140 K and pressures of 200-400 MPa. Obtained from ice III when cooled.

Ice 10 (1984)

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Symmetrical ice with an ordered arrangement of protons. Formed at pressures of about 70 GPa.

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Ice-X structure (top left) and predicted variations in Pbcm, Pbca, Cmcm.

Ice 11 (1972)

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Ice-XI is the most stable configuration of ice Ih with ordered orientation of protons. Is an ferroelectric (spontaneous polarization, which can be changed by an external electric field).

Ice 12 (2003)

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It is obtained by cooling water to −13 ° C (260 K) at a pressure of 0.55 GPa. Ice-XII can also be obtained from ice Ih at a temperature of 77 K by rapid compression of 1 GPa / min or heat high-density amorphous ice to 183 K at a pressure of 0.8-1.6 GPa.

Ice 13

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Proton-ordered variation of ice-V. It is obtained by cooling water to 130K at a pressure of 500 MPa.

Ice 14 (2006)

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A modification of ice-XII, where the protons are arranged in an orderly manner. Formed by freezing water at a temperature of 118 K and a pressure of 1.2 GPa.

Ice 15 (2009)

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Ice-XV is a form of ice-VI with ordered protons, obtained by cooling water to 130 K at a pressure of 1 GPa.

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a) a phase diagram of ice with some routes used to study the ordered shape of ice and b) how a water molecule changes from a disordered ice to an ordered one.

Ice 16 (2014)

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Ice-XVI has the lowest density among all types of ice 0.81 g / cm3, topologically equivalent KS-II (gas hydrates). It is obtained by removing gas molecules from neon clathrate in a vacuum at temperatures below 147 K.

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Phase diagram of water expanded to negative pressures.

Ice 17 (2015)

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Square ice is obtained by squeezing water between two layers of graphene (1 nanometer) at room temperature (Andrey Geim calculated that the pressure there is about 10,000 atmospheres). Possibly occurs naturally in cracks in rocks and soil.

Pictures

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Ice 18 (2019)

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Super-ionic ice is four times as dense as regular ice and is electrically conductive.

Ice-XVIII or superionic water can exist at very high pressures of 50-100 GPa (the impact of a laser pulse in cell with diamond anvils) and temperature. Molecules break down into ions. Oxygen ions form a face-centered cubic lattice, while hydrogen ions randomly diffuse inside it.

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Super-ionic ice phase diagram: body-centered ionic ice (blue), face-centered / close-packed (green) and P2 ionic ice1/ c. Gray – crystalline ice, yellow – ionic liquid area.

Ice 19 (2021)

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Differences in diffraction patterns and structure of the crystal lattice of ice-VI and ice-XIX

If a pressure of 0.88 to 2.20 gigapascals is applied to ice-VI, then ice-XV is formed, and new ice-XIX. If we analyze the dielectric constant and neutron diffraction, then we come to the conclusion that the new phase is independent.

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Phase diagram of ice water-XIX

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