Anomalous properties of water

The range of anomalous properties of water Water phase anomalies Water density anomalies Water material anomalies Water thermodynamic anomalies Water physical anomalies

The range of anomalous properties of water

The anomalous properties of water are those where the behavior of liquid water is quite different from what is found with other liquids [1414].a Frozen water (ice) also shows anomalies when compared with other solids. Although it is an apparently simple molecule (H2O), it has a highly complex and anomalous character due to its intra-molecular hydrogen bonding (see [1530] for example). As a gas, water is one of lightest known, as a liquid it is much denser than expected and as a solid it is much lighter than expected when compared with its liquid form. An interisting history of the study of the anomalies of water has been published [1542].

As liquid water is so common-place in our everyday lives, it is often regarded as a typical liquid. In reality, water is most atypical as a liquid, behaving as a quite different material at low temperatures to that when it is hot. It has often been stated (for example, [127]) that life depends on these anomalous properties of water. In particular, the high cohesion between molecules gives it a high freezing and melting point, such that us and our planet is bathed in liquid water. The large heat capacity, high thermal conductivity and high water content in organisms contribute to thermal regulation and prevent local temperature fluctuations, thus allowing us to more easily control our body temperature. The high latent heat of evaporation gives resistance to dehydration and considerable evaporative cooling. Water is an excellent solvent due to its polarity, high dielectric constant and small size, particularly for polar and ionic compounds and salts.b It has unique hydration properties towards biological macromolecules (particularly proteins and nucleic acids) that determine their three-dimensional structures, and hence their functions, in solution. This hydration forms gels that can reversibly undergo the gel-sol phase transitions that underlie many cellular mechanisms [351]. Water ionizes and allows easy proton exchange between molecules, so contributing to the richness of the ionic interactions in biology.

At 4C water expands on heating or cooling. This density maximum together with the low ice density results in (i) the necessity that all of a body of fresh

water (not just its surface) is close to 4C before any freezing can occur, (ii) the freezing of rivers, lakes and oceans is from the top down, so permitting survival of the bottom ecology, insulating the water from further freezing, reflecting back sunlight into space and allowing rapid thawing, and (iii) density driven thermal convection causing seasonal mixing in deeper temperate waters carrying lifeproviding oxygen into the depths. The large heat capacity of the oceans and seas allows them to act as heat reservoirs such that sea temperatures vary only a third as much as land temperatures and so moderate our climate (for example, the Gulf stream carries tropical warmth to northwestern Europe). The compressibility of water reduces the sea level by about 40 m giving us 5% more land [65]. Water's high surface tension plus its expansion on freezing encourages the erosion of rocks to give soil for our agriculture. Notable amongst the anomalies of water are the opposite properties of hot and cold water, with the anomalous behavior more accentuated at low temperatures where the properties of supercooled water often diverge from those of hexagonal ice.c As (supercooled) cold liquid water is heated it shrinks, it becomes less easy to compress, its refractive index increases, the speed of sound within it increases, gases become less soluble and it is easier to heat and conducts heat better. In contrast as hot liquid water is heated it expands, it becomes easier to compress, its refractive index reduces, the speed of sound within it decreases, gases become more soluble and it is harder to heat and a poorer conductor of heat. With increasing pressure, cold water molecules move faster but hot water molecules move slower. Hot water freezes faster than cold water and ice melts when compressed except at high pressures when liquid water freezes when compressed. No other material is commonly found as solid, liquid and gas.d

The anomalies of water appear as a hierarchy of effects with different bounds [169]. These are shown indicatively opposite as derived from modeling, not experimental data. The Structural bounds indicate where water is more

disordered when compressed, the Dynamic bounds indicate where diffusion increases with density, and the Thermodynamic bounds show where there is a temperature of maximum density; with the data from [169] shifted upwards 38 K to give the correct temperature of maximum density under standard pressure. As density always increases with increasing pressure, a similar relationship holds with pressure along the horizontal axis. [Back to Top ]

Water phase anomalies e 1. Water has unusually high melting point. [Explanation] 2. Water has unusually high boiling point. [Explanation]
3. Water has unusually high critical point. [Explanation] 4. Solid water exists in a wider variety of stable (and metastable) crystal and amorphous structures than other materials. [Explanation] 5. The thermal conductivity of ice reduces with increasing pressure. [Explanation] 6. The structure of liquid water changes at high pressure. [Explanation] 7. Supercooled water has two phases and a second critical point at about -91C. [Explanation] 8. Liquid water is easily supercooled but glassified with difficulty. [Explanation] 9. Liquid water exists at very low temperatures and freezes on heating. [Explanation] 10. Liquid water may be easily superheated. [Explanation] 11. Hot water may freeze faster than cold water; the Mpemba effect. [Explanation] 12. Warm water vibrates longer than cold water. [Explanation] [Back to Top ]

Water density anomalies 1. 2. 3. 4.

The density of ice increases on heating (up to 70 K). [Explanation] Water shrinks on melting. [Explanation] Pressure reduces ice's melting point. [Explanation] Liquid water has a high density that increases on heating (up to 3.984C). [Explanation] 5. The surface of water is more dense than the bulk. [Explanation] 6. Pressure reduces the temperature of maximum density. [Explanation] 7. There is a minimum in the density of supercooled water. [Explanation] 8. Water has a low coefficient of expansion (thermal expansivity). [Explanation] 9. Water's thermal expansivity reduces increasingly (becoming negative) at low temperatures. [Explanation] 10. Water's thermal expansivity increases with increased pressure. [Explanation] 11. The number of nearest neighbors increases on melting. [Explanation] 12. The number of nearest neighbors increases with temperature. [Explanation]

13. Water has unusually low compressibility. [Explanation] 14. The compressibility drops as temperature increases up to 46.5C.
[Explanation]

15. There is a maximum in the compressibility-temperature relationship.

[Explanation] 16. The speed of sound increases with temperature up to 74C. [Explanation] 17. The speed of sound may show a minimum. [Explanation] 18. 'Fast sound' is found at high frequencies and shows an discontinuity at higher pressure. [Explanation] 19. NMR spin-lattice relaxation time is very small at low temperatures. [Explanation] 20. The NMR shift increases to a maximum at low (supercool) temperatures [Explanation] 21. The refractive index of water has a maximum value at just below 0C. [Explanation] 22. The change in volume as liquid changes to gas is very large. [Explanation] [Back to Top ]

Water material anomalies 1. No aqueous solution is ideal. [Explanation] 2. D2O and T2O differ significantly from H2O in their physical properties.
[Explanation]

3. Liquid H2O and D2O differ significantly in their phase behavior.

[Explanation] 4. Solutes have varying effects on properties such as density and viscosity. [Explanation] 5. The solubilities of non-polar gases in water decrease with temperature to a minimum and then rise. [Explanation] 6. The dielectric constant of water is high. [Explanation] 7. The dielectric constant shows a temperature maximum. [Explanation] 8. Proton and hydroxide ion mobilities are anomalously fast in an electric field. [Explanation] 9. The electrical conductivity of water rises to a maximum at about 230C. [Explanation] 10. Acidity constants of weak acids show temperature minima. [Explanation] 11. X-ray diffraction shows an unusually detailed structure. [Explanation] 12. Under high pressure water molecules move further away from each other with increasing pressure. [Explanation] [Back to Top ]

Water thermodynamic anomalies 1. The heat of fusion of water with temperature exhibits a maximum at
-17C. [Explanation]

2. Water has over twice the specific heat capacity of ice or steam.
[Explanation] 3. The specific heat capacity (CP and CV) is unusually high. [Explanation] 4. The specific heat capacity CP has a minimum at 36C. [Explanation] 5. The specific heat capacity (CP) has a maximum at about -45C. [Explanation] 6. The specific heat capacity (CP) has a minimum with respect to pressure. [Explanation] 7. The heat capacity (CV) has a maximum. [Explanation] 8. High heat of vaporization. [Explanation] 9. High heat of sublimation. [Explanation] 10. High entropy of vaporization. [Explanation] 11. The thermal conductivity of water is high and rises to a maximum at about 130C. [Explanation] [Back to Top ]

Water physical anomalies 1. 2. 3. 4. 5. 6. 7. 8. 9.

Water has unusually high viscosity. [Explanation] Large viscosity increase as the temperature is lowered. [Explanation] Water's viscosity decreases with pressure below 33C. [Explanation] Large diffusion decrease as the temperature is lowered. [Explanation] At low temperatures, the self-diffusion of water increases as the density and pressure increase. [Explanation] The thermal diffusivity rises to a maximum at about 0.8 GPa. [Explanation] Water has unusually high surface tension. [Explanation] Some salts give a surface tension-concentration minimum; the Jones-Ray effect. [Explanation] Some salts prevent the coalescence of small bubbles. [Explanation] [Back to Top ]

The figure left shows some of the anomalous properties of liquid water that are related to temperature. The graph uses data that have been scaled between their maximum and minimum values (see original data).

Footnotes
Whether or not the properties of water are seen to be anomalous depends upon the materials used in the comparison and the interpretation of the term 'anomalous'. For example, it could well be argued that water possesses exactly those properties that one might deduce from its structure (see for example, [402]). Other tetrahedrally interacting liquids, such as liquid Si, SiO 2 and BeF2 have many similar 'anomalies', as do other materials where mixed phases may arise, such as liquid Te [1538]. Comparisons between water, liquid sodium, argon and benzene appear to Franks [112] to indicate several of the properties given above as not being anomalous. However, these materials are perhaps not the most typical of liquids. My list gives the unusual properties generally understood to make liquid water (and ice) stand out from 'typical' liquids (or solids). See [242] for a review concentrating on the non-anomalous properties of water; that is, those that are the 'same' as for other liquids. [Back]
a

It is therefore very difficult to obtain really pure water (for example, < 5 ng g). For a review of aqueous solubility prediction, see [744]. Note that ice, in contrast, is a very poor solvent and this may be made use of when purifying water (for example, degassing) using successive freeze-thaw cycles. [Back]
b 1

Some scientists attribute the low temperature anomalous nature of water to the presence of a second critical point; an interesting if somewhat unproductive hypothesis as a sole explanation (as the attribution mixes cause with effect). Water's anomalies do not require this as an explanation.[Back]
c

The temperature range of 'hot' and 'cold' water varies in these examples; see the individual entries for details. [Back]
d

The anomalies of water are divided into groups but, clearly, some anomalies may be included under more than one topic and there may not be universal agreement for the groupings shown. [Back]
e