Ice Ih

Ice Ih

Ice Ih is the hexagonal crystal form of ordinary ice, or frozen water. Virtually all ice in the biosphere is ice Ih, with the exception only of a small amount of ice Ic which is occasionally present in the upper atmosphere. Ice Ih exhibits many peculiar properties which are relevant to the existence of life and regulation of global climate. [For a description of these properties, see "Ice", which deals primarily with Ice Ih.]

Ice Ih is stable down to convert|-200|C|K F and can exist at pressures up to 0.2 GPa. The crystal structure is characterized by hexagonal symmetry and near tetrahedral bonding angles.

Physical properties

Ice Ih has a density less than liquid water, of 0.917 g/cm³, dueto the extremely low density of its crystal lattice. The density of ice Ih increases with decreasing temperature (density of ice at -180 °C is 0.9340 g/cm³).

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 ofthe hydrogen bonds in the crystal lattice. The latent heatof melting is much smaller partly because water near 0 °C is very stronglyH-bonded already.

The refractive index of ice Ih is 1.31.

Crystal structure

The accepted crystal structure of ordinary ice was first proposed by Linus Pauling in 1935. The structure of ice Ih is 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. 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 unique property of being less dense than its liquid form. The tetrahedral-angled hydrogen-bonded hexagonal rings are also the mechanism which causes liquid water to be most dense 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 most dense at 4 °C when the structures form infrequently.

Proton disorder

The protons (hydrogen atoms) in the crystal lattice lie very nearly along thehydrogen bonds, and in such a way that each water molecule is preserved. Thismeans that each oxygen atom in the lattice has two protons adjacent to it, andabout 101 pm along the 275 pm length of the bond. The crystallattice allows a substantial amount of disorder in the positions of the protonsfrozen into the structure as it cools to absolute zero. As a result,the crystal structure contains some residual entropy inherent to thelattice and determined by the number of possible configurations of protonpositions which can be formed while still maintaining the requirement for each oxygen atom to haveonly two protons in closest proximity, and each H-bond joining two oxygen atoms havingonly one proton. This residual entropy "S"0 is equal to 3.5 J mol−1 K−1. There are various ways of approximatingthis number from first principles. Assuming a given "N" watermolecules each has 6 possible arrangements this yields 6"N" possiblecombinations. Given random orientations of molecules, a given bond will haveonly a ½ chance that it has exactly one proton, or in other words, eachmolecule has a ¼ chance that its protons lie on bonds containing exactly oneproton, leaving a total number of (3/2)^N possible valid combinations.Using Boltzmann's principle, we find that S_0 = Nkln(3/2), where k is Boltzmann's Constant, which yields a value of 3.37 J mol−1 K−1, a value very close to the measured value. More complexmethods can be employed to better approximate the exact number of possibleconfigurations, and achieve results closer to measured values.

By contrast, the structure of ice II is very proton-ordered, which helps to explain the entropy change of 3.22 J/mol when the crystal structure changes to that of ice II. Also, ice XI, an orthorhombic, proton-ordered form of ice Ih, is considered the most stable form.

Notes

References

* N. H. Fletcher, The Chemical Physics of Ice, Cambridge UP (1970) ISBN 0-521-07597-1
* Victor F. Petrenko and Robert W. Whitworth, Physics of Ice, Oxford UP (1999) ISBN 0-19-851894-3
*cite web |url=http://www.lsbu.ac.uk/water/ice1h.html |title=Hexagonal ice structure |accessdate=2008-01-02 |author=Chaplin, Martin |date=2007-11-11 |work=Water Structure and Science


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