The density
of ice increases on heating (up to 70 K)
Water shrinks on melting
Pressure reduces ice's melting point
Liquid water has a high density
that increases on heating (up to 3.984°C)
The surface of water is more dense than the bulk
Pressure reduces the temperature of maximum
density
There is a minimum in the density
of supercooled water
Water has a low coefficient of expansion
(thermal expansivity)
Water's thermal expansivity reduces increasingly
(becoming negative) at low temperatures
Water's
thermal expansivity increases with increased pressure
The number of nearest neighbors increases
on melting
The number of nearest neighbors increases
with temperature
Water has unusually low compressibility
The compressibility drops as temperature
increases up to 46.5°C
There is a maximum in the compressibility-temperature relationship
The speed of sound increases with temperature
up to 74°C
The speed of
sound may show a minimum
'Fast sound' is found at high frequencies and shows an discontinuity at higher pressure
NMR spin-lattice relaxation time is very
small at low temperatures
The NMR shift increases to a maximum at low (supercool) temperatures
The refractive index of water has a maximum
value at just below 0°C
The change in volume as liquid changes to gas is very large
Most solids expand and become less dense when heated. Hexagonal, cubic and amorphous ices all become denser at low temperatures. All
expand slightly with cooling at all temperatures below about 70 K with a minimum
thermal expansivity at about 33 K (expansion
coefficient (α) ~ -0.000003 K-1). This appears to be due
to alteration in the net bending motion of three tetrahedral hydrogen bonded molecules with temperature,
as higher frequency modes are reduced [209]. This is a similar but unrelated phenomenon to the maximum density anomaly that occurs in liquid water. Interestingly, the density maximum for hexagonal ice is at about 72 K at ambient pressure and this is the maximum temperature for its catalyzed phase transition to ice XI. [
Anomalies page : Back to Top 
]
It is usual for liquids to contract on freezing and expand on melting. This is because the molecules are in fixed positions within the solid but require more space to move around within the liquid.
When water freezes at 0°C its volume increases by about 9% under atmospheric pressure. If the melting point is lowered by increased pressure, the increase in volume on freezing is even greater (for example, 16.8% at -20°C [561]). Opposite is shown the molar volumes of ice and water along the melting point curve [561].
The structure of ice (Ih) is open with a low packing efficiency where all the water molecules are involved in four straight tetrahedrally-oriented hydrogen bonds; for comparison, solid hydrogen sulfide has a face centered cubic closed packed structure with each molecule having twelve nearest neighbors [119]. On melting, some of these ice (Ih) bonds break, others bend and the structure undergoes a partial collapse, like other tetrahedrally arranged solids such as the silica responsible for the Earth's crust floating on the outside of our planet. This is different from what happens with most solids, where the extra movement available in the liquid phase requires more space and therefore melting is accompanied by expansion.
In contrast, it should be noted that the high-pressure ices (ice III, ice V, ice VI and ice VII) all expand on melting to form liquid water (under high pressure). It is the expansion in volume when going from liquid to solid, under ambient pressure, that causes much of the tissue damage in biological organisms on freezing. In contrast, freezing under high pressure directly to the more dense ice VI may cause little structural damage [535].
An interesting phenomenon, due to the expansion on freezing, is
the formation of thin
ice spikes that occasionally grow out of (pure water) ice cubes
on freezing [564a]. This phenomenon appears to be a general property of any material that expands on freezing [564b]. [ Anomalies page : Back to Top ]
Increasing pressure normally promotes liquid freezing, shifting the melting point to higher temperatures. This is shown by a forward sloping liquid/solid line in the phase diagram. In water, this line is backward sloping with slope 13.46 MPa K-1 at 0°C, 101.325 kPa. As the pressure increases, the liquid water equilibrium shifts towards a collapsed structure (for example, CS ) with higher entropy. This lowers the melting free energy change (ΔG=ΔH-TΔS) such that it will be zero (that is, at the melting point) at a lower temperature.
The minimum temperature that liquid water can exist without ever freezing is -21.985°C at 209.9 MPa; at higher pressures water freezes to ice-three, ice-five, ice-six or ice-seven at increasing temperatures. Stretching ice has the reverse effect; ice melting at +6.5°C at about -95 MPa negative pressure within stretched microscopic aqueous pockets in mineral fluorite [243].a
It should be noted that ice skating (or skiing) does not produce sufficient pressure to lower the melting point significantly, except at very sharp edges, or involving powdered ice on the ice surface. The increase in slipperiness is normally generated by frictional heating, perhaps initially involving the ultra-thin surface layer of disorganized and weakly held frozen water (see [1238] for a review).
If the increase in volume on freezing is prevented, an increased pressure of up to 25 MPa may be generated in water pipes; easily capable of bursting them in Winterb. An interesting question concerns what would happen to water cooled below 0°C within a vessel that cannot change its volume (isochoric cooling). Clearly if ice forms, its increased volume causes an increase in pressure which would lower the freezing point at least until the lowest melting point (-21.985°C) is reached at 209.9 MPa.e A recent thermodynamic analysis concludes that ice nucleation cannot arise above -109°C during isochoric cooling [1053], which is close to the upper bound of the realm of deeply supercooled water (-113°C), so it is unclear if ice would ever freeze in such a (unreal) system.
Melting ice, within a filled and sealed
fixed volume, may result in an apparently superheated state
where the metastable iso-dense liquid water is stretched,
relative to its equilibrium state at the (effectively) negative
pressure, due to its cohesiveness. Consequently, the ES
CS equilibrium is shifted towards the more-open ES structure.
[ Anomalies page : Back to Top ]
The high density of liquid water is due mainly to the cohesive nature of the hydrogen-bonded network, with each water molecule capable of forming four hydrogen bonds.g This reduces the free volume and ensures a relatively high-density, partially compensating for the open nature of the hydrogen-bonded network. Its density, however, is not as great as that of closely packed, isoelectronic, liquid neon (1207 kg m-3 at 27 K, with molar volume 92.8% of water). It is usual for liquids to expand when heated, at all temperatures. The anomalous temperature-density behavior of water can be explained as previously [13, 14, 1354] utilizing the range of environments within whole or partially formed clusters with differing degrees of dodecahedral puckering.c The density maximum (and molar volume minimum) is brought about by the opposing effects of increasing temperature, causing both structural collapse that increases density and thermal expansion that lowers density. Counter-intuitively, the distance between the water molecules decreases [1489] as the density decreases as the supercooling temperature is lowered, the decrease in density being primarily due to the reduction in nearest neighbors. At lower temperatures there is a higher concentration of ES whereas at higher temperatures there is more CS and fragments, but the volume they occupy expands with temperature. The change from ES to CS as the temperature rises is accompanied by positive changes in both entropy and enthalpy due to the less ordered structure and greater hydrogen bond bending respectively.
The density maximum ensures that the bottoms of freezing freshwater lakes generally remain at about 4°C and unfrozen. The change in density with temperature causes an inversion in cold water systems as the temperature is raised above about 4°C. Thus in water below about 4°C, warmer water sinks whereas when above about 4°C, warmer water rises. As water warms up or cools down through 4°C, this process causes considerable mixing with useful consequences such as increased gas exchange.
Shown below is the variation of the density of ice, liquid water, supercooled water and water vapor, in equilibrium with the liquid, with temperature (the orthobaric density).
The diagram helps explain why liquid water cannot exist above the critical point (C.Pt.). Also shown (inset) is the variation of the molar volume of liquid water with temperature about the density maximum (at 3.984°C). Note the unusual and rapid approach of the densities of supercooled water and ice (estimated at -50°C, 100 kPa [580]) at about the homogeneous nucleation temperature (~-45°C, 101 kPa). This approach moves to lower temperatures at higher pressures, seemingly absent at ~200 MPa [561] (see below, D5).
The occurrence of a density maximum, as in water, is sometimes if only rarely found (or predicted) in other liquids , such as He, Te, Si and SiO2 for a variety of reasons. The effect in liquid He4 is thought due to zero point energy and a similar reason has been put forward for water [1301] although, in practical terms, this presents a related if alternative approach to that above.
Inversely related to changes in densities are the changes in volumes. Opposite are shown pressure-temperature curves of liquid water at constant volume; showing the change in pressure that would occur with temperature using a (theoretically ideal) constant volume container. There is a minimum in the curve only for volumes greater than 0.986 cm3 g-1. The data were obtained
from the IAPWS-95 equations [540]. [ Anomalies page : Back to Top ]
The structure of the surface of water generates much controversy and presents a confused picture. However both thermodynamics and experimental evidence suggest that, at lower temperatures and in contrast to the situation with other liquids, the surface in contact with the air is more dense than the bulk liquid. Thermodynamics (see elsewhere) can be used to derive 
; a measure of a difference in density between the surface density and bulk density. This shows that surface water density varies less with temperature than the bulk at low temperatures and equals it at 3.984°C. The refractive index of the surface of water at 22°C has been shown to be higher than that of the bulk and opposite in behavior to other liquids (for example, ethanol) [1482]. Thus this surface water appears to behave like water at a lower temperature, and hence has higher density.i [ Anomalies page : Back to Top ]
Increasing pressure shifts the water equilibrium towards a more collapsed structure (for example, CS). So, although pressure will increase the density of water at all temperatures (flattening the temperature density curve), there will be a disproportionate effect at lower temperatures. The result is a shift in the temperature of maximum density to lower temperatures. At high enough pressures the density maximum is shifted to below 0°C (at just over 18.84 MPa). Above 28.33 MPa it cannot be observed above the melting point (now at 270.97 K) and it cannot be observed at all above about 200 MPa. The stronger and more linear hydrogen bonding in D2O gives rise to a 25% smaller shift in the temperature of maximum density (from 11.185°C at 0.1 MPa) with respect to increasing pressure [726]. Under negative pressure (that is, increased stretching of liquid water) the temperature of maximum density increases. However, the temperature of maximum density shows a maximum with respect to pressure in this negative pressure region [419], as at very high negative pressures it reduces as the hydrogen bonds are stretched to breaking point.
A similar effect may be caused
by increasing salt concentration, which behaves like increased
pressure in breaking up the low-density clusters. Thus
in 0.36 molal NaCl the temperature of freezing and maximum
density coincide at -1.33°C. Higher salt concentrations
reduce the temperature of maximum density such that it is
only accessible in the supercooled liquid. Lowering the temperature of maximum density is not a colligative property as both the nature and concentration of the soluted affects the degree of lowering. [ Anomalies page : Back to Top ]
At a temperature below the maximum density anomaly there
must be a minimum density anomaly so long as no phase change
occurs, as the density increases with reducing temperature at much lower temperatures. This was first seen in simulations [498] and is expected to lie below the minimum temperature
accessible on supercooling (232 K, [215])
and close to where both maximum ES structuring and compressibility occur, with the liquid density close to that of hexagonal
ice (latterly confirmed [871]). It is evident that most
anomalous behavior must involve a quite sudden discontinuity
at about the homogeneous nucleation temperature (~228 K, where
the densities of supercooled water and ice approach) as the
tetrahedrally arranged hydrogen bonding approaches its limit
(two acceptor and two donor hydrogen bonds per water molecule)
and no further density reduction is possible without an energetically
unfavorable stretching (or breaking) of the bonds. By use of optical scattering data of confined water and a model that divides the liquid water into two forms of low and high density,
the density minimum has been proposed to lie at 203±5 K [1325]. A density minimum at 210 K has been experimentally determined in supercooled D2O contained in 1-D cylindrical pores of mesoporous silica [1195]. Although possibly related, density values obtained for confined water cannot be taken as necessarily giving the density minimum for the bulk supercooled liquid however. [ Anomalies page : Back to Top ]
The thermal expansivity is zero at 3.984°C, being negative below and positive above (see density and expansivity anomalies). As the temperature increases above 3.984°C, the cluster equilibrium shifts towards the more collapsed structure (for example, CS), which reduces any increase in volume due to the increased kinetic energy of the molecules. Normally the higher the volume a molecule occupies, the larger is the disorder (entropy).
Thermal expansivity (αP);
αP = [δV/δT]P/V 
<(ΔV)(ΔS)>TPN
depends on the product of the fluctuations in these factors.h In water, however, the more open structure (for example, ES)
is also more ordered (that is, as the volume of liquid water increases on lowering the temperature below 3.984°C, the entropy of liquid water reduces).
[ Anomalies page : Back to Top ]
It is usual for liquids to expand increasingly with increased temperature.
Supercooled and cold (< 3.984°C) liquid water both contract on heating [68]. As the temperature decreases,
the cluster equilibrium shifts towards the expanded, more open, structure (for example, ES),
which more than compensates for any decrease in volume
due to the reduction in the kinetic energy of the molecules.
It should be noted that this behavior requires that
the thermodynamic work (dW) equals -pΔV rather than
the usual +pΔV (pressure times change in volume) [404]. The behavior expected, if water acted as most other
liquids at lower temperatures, is shown as the dashed
line opposite. The blue line shows the expansivity of
ice. Also, for water and other materials with negative thermal expansivity, both 
and 
are negative [1147] whereas normally both are positive. [ Anomalies page : Back to Top ]
The thermal expansion of water increases with increased pressure up to about 44°C in contrast to most other liquids where thermal expansion decreases with increased pressure. This is due to the collapsed structure of water having a greater thermal expansivity than the expanded structure and the increasing pressure shifting the equilibrium towards a more collapsed structure.
Opposite is shown (blue area) the range of temperatures
and pressures where the thermal expansion increases
with increased pressure.
[ Anomalies page : Back to Top ]
Each water molecule in hexagonal ice has
four nearest neighbors. On melting, the partial collapse of the
open hydrogen bonded network allows nonbonded molecules to approach
more closely so increasing this number. Normally in a liquid the
movement of molecules, and the extra space they find themselves
in, means that it becomes less likely that they will be found close
to each other; for example, argon has exactly twelve nearest neighbors
in the solid state but only an average of about ten on melting.
[ Anomalies page : Back to Top ]
If a water molecule is in a fully hydrogen-bonded structure with
strong and straight hydrogen bonds (such as hexagonal
ice) then it will only have four nearest neighbors. In the liquid
phase, molecules approach more closely due to the partial collapse
of the open hydrogen bonded network. As the temperature of liquid
water increases, the continuing collapse of the hydrogen bonded
network allows nonbonded molecules to approach more closely so increasing
the number of nearest neighbors. This is in contrast to normal liquids
where the increasing kinetic energy of molecules and space available
due to expansion, as the temperature is raised, means that it becomes
less likely that molecules will be found close to each other.
[ Anomalies page : Back to Top ]
It may be thought that water should have a high compressibility
(κT = -[δV/δP]T/V)
as the large cavities in
liquid water allows plenty of scope for the water structure
to collapse under pressure without water molecules approaching
close enough to repel each other. The deformation causes the
growth in the radial distribution function peak at about 3.5
Å with increasing or pressure [51]
(and temperature [50]),
due to the collapsing structure. The low compressibility of
water is due to water's high-density, again due to the cohesive
nature of the extensive hydrogen bonding. This reduces the
free space (compared with other liquids) to a greater extent
than the contained cavities increase it. At low temperatures
D2O has a higher compressibility than H2O
(for example, 4% higher at 10°C but only 2% higher at
40°C [188]) due
its stronger hydrogen bonding producing
an ESCS equilibrium shifted towards the more-open ES structure. Also noteworthy is that solutions of highly compressible
liquids, such as diethyl ether (1.88 GPa-1) in
water, reduce the compressibility of the water, as they occupy
its clathrate cavities.
[ Anomalies page : Back to Top ]
In a typical liquid the compressibility decreases as the structure
becomes more compact due to lowered temperature. In water,
the cluster equilibrium shifts
towards the more open structure (for example, ES ) as the temperature is reduced due to it favoring the more
ordered structure (that is, ΔG for ESCS becomes more
positive). As the water structure is more open at these lower
temperatures, the capacity for it to be compressed increases
[68].
The effect is not a simple dependency on density, however, or else the minimum at 46.5°C for isothermal (that is, without change in temperature) compressibilityh
κT = -[δV/δP]T/V
κT = [δρ/δP]T/ρ <(ΔV)2>TPN
and the minimum at 64°C for adiabatic (that is, without loss or gain of heat energy, also called isentropic)
compressibility (κS = -[δV/δP]S/V
[112]) would
both be at the density minimum (4°C). Relationships
between κT and κS are given
elsewhere.
Compressibility depends on fluctuations in the specific volume and these will be large where water molecules fluctuate between being associated with a more open structure, or not, and between the different environments within the water clusters. At high pressures (for example, ~200 MPa) this compressibility anomaly, although still present, is far less apparent [706].
Some other liquids, such as formamide (also extensively hydrogen bonded), show a compressibility minimum. [ Anomalies page : Back to Top ]
At sufficiently low temperature, there must be a maximum in
this compressibility-temperature relationship, so long as
no phase change occurs, as the compressibility decreases with reducing temperature at much lower temperatures.. This is expected to lie just below
the minimum temperature accessible on supercooling (232 K,
[215]) close
to the temperature of minimum
density.
[ Anomalies page : Back to Top ]
Sound is a longitudinal pressure wave, whereby the energy is propagated as deformations in the media but the molecules then return to their original positions and are not propagated. The propagation of a sound wave depends on the transfer of vibration from one molecule to another. In a typical liquid, the speed of sound is faster (see fast sound) and decreases as the temperature increases, at all temperatures. The speed of sound in water is almost five times greater than that in air (340 m s-1).
The speed (u) is given by u2 = 1/κSρ = [δP/δρ]S ~ 1/(<(¶V)2>) [802] where κS is the adiabatic compressibility, ρ is the density and P the pressure. The anomalous nature of both these physical properties is described above (compressibility, density).
At low temperatures both compressibility and density are high, so causing a lower speed of sound. As the temperature increases the compressibility drops and goes through a minimum whereas the density goes through a maximum and then drops [67]. Combination of these two properties leads to the maximum in the speed of sound. Increasing the pressure increases the speed of sound and shifts the maximum to higher temperatures, both in line with the effect on the density. The supercooled data has been calculated for the graph, right.
The presence of salt causes small shifts in the temperature maximum in line with the Hofmeister series; reducing the temperature at higher concentrations. Ionic kosmotropes cause a slight increase in the temperature maximum at low concentrations [921].
There is a discontinuity in the pressure response to sound velocity that occurs at 290 MPa and 293 K consistent with gradual phase transition to interpenetrating hydrogen
bonded networks at the higher pressures, as seen with other
anomalies
[1374]. [ Anomalies page : Back to Top ]
Depending on the frequency, there may be a minimum in the speed of sound at low temperatures [568]. Although this may be thought due to compensation in the changes in density decrease and compressibility increase with lowering temperature, this is not apparent in the calculated data above. It is most likely due to the increasing strength of its hydrogen bonding and consequential transition to 'fast sound' at lower frequencies (see below). The data opposite is from [1151].
The speed of sound in the oceans has
a minimum at about 1000 m where the increase in speed due
to increasing pressure balances the decreasing speed with
drop in temperature. Sound waves are trapped and propagate
horizontally in this SOFAR channel.
[ Anomalies page : Back to Top ]
Water has a second sound 'anomaly' (called 'fast sound')
concerning the speed of sound. Over a range of high frequencies
(> 4 nm-1) liquid water behaves as though
it is a glassy solid rather than a liquid and sound travels
at about twice its normal speed (~3200 m s-1; similar
to the speed of sound in ice Ih). There is little effect of temperature below 20°C [1151]. At lower temperatures the speed of sound increases from its low frequency value towards the high frequency value (i.e. 'fast sound') at lower frequencies, giving rise to a minimum in the temperature-speed of sound relationship [1151] (see above). 'Fast sound' is not a true anomaly as this behavior is
what might be expected from a typical liquid, whereas the
(hydrodynamic) lower speed of sound (~1500 m s-1)
is due to the hydrogen bonding network structure of water. However, there is a discontinuity anomaly at
a density of about 1.12 g cm-1 (~300 MPa at 273 K) that may indicate a structural rearrangement
[644, 655],
due to the gradual phase transition to interpenetrating hydrogen
bonded networks at the higher pressures, as seen with other
anomalies.
[ Anomalies page : Back to Top ]
NMR spin-lattice relaxation time depends on the degree of
structure. As the water cluster equilibrium shifts towards a stiffer, tetrahedrally organized, structure
(for example, ES)
as the temperature is lowered, the NMR spin-lattice relaxation
time reduces far more than would otherwise be expected [53a].
This effect can be partially reversed by increasing the pressure,
which reduces the degree of structure.
[ Anomalies page : Back to Top ]
The NMR shift increases to a maximum at about 214 K in confined water [1496]. It is likely that the same effect will be found in supercooled unconfined water. The variation in NMR chemical shift with temperature correlates with water's hydrogen bonding and its logarithmic temperature derivative is related to the specific heat and its anomaly [1496].
[ Anomalies page : Back to Top ]
The refractive index of water (λ = 589.26 nm) rises from an estimated 1.33026 at -30°C to
a maximum value at just below 0°C (1.33434) before falling
ever increasingly to 1.31854 at 100°C [310].
This may be explained by the mixture model [60]
applied to the change from ES to CS as the temperature rises; ES possessing a lower refractive index than CS.
Most of the effect is due to the density
difference between ES and CS.
Higher density produces higher refractive index such that the
refractive index temperature maximum lies close to the density
maximum, with the small difference due to the slightly different
effect of temperature on the specific refractions of ES and CS. Although
not considered anomalous, it is interesting to note that ice
has the lowest refractive index (1.31, λ = 589 nm) of any known crystal.
[ Anomalies page : Back to Top ]
Water is one of the lightest gasses but forms a dense liquid. The volume change is the greatest known (except for metals) at 1603.6 fold, at the boiling point and standard atmospheric pressure. This change in volume allows water to be of great use in the steam generation of electrical power. [ Anomalies page : Back to Top ]
a There is some dispute over whether such a negative pressure can be reached [917]. [Back]
b Pipes burst due to the rapid formation of a network of feathery dendritic ice enclosing water which then expands on freezing within a now restricted volume to generate the required pressure [354]. The curious phenomenon of hot water pipes bursting more often than cold water pipes ([959, 1416]) is due to the differences in this dendritic ice formation causing blockage in the pipes at low percentage ice formation. [Back]
c The change in density is almost mirrored by the size of ortho-positronium bubbles, which are affected by the free volume available and show a minimum at 8°C [826]. ortho-Positronium consists of a positron - electron pair with parallel spins [826], created here by positron irradiation of water. [Back]
d The depression in the temperature of maximum density is linearly related to concentration for most solutes (ethanol and methanol are exceptional giving a slight increase in the temperature of maximum density at low concentrations) [1037], as discovered in 1839 by Despretz. Urea solutions behave strangly, producing a temperature of maximum density at up to ten molal concentration, with a minimum temperature of maximum temperature (258.6 K) at about six molal [1506].[Back]
e It would be impossible to reach this pressure in a container, unless pressure was also exerted from the outside, due to the pressure induced expansion of the vessel. Water sealed in a steel cylinder in 1871 by Boussingault was still liquid at -18°C. [Back]
f Others take a contrary view, stating that water's compressibility is twice that expected [53b]. This difference is down to the viewpoint and different theoretical expectations. In both cases, water's compressibility is unexpected; either being greater than expected due to water's open structure or less than expected (in spite of its open structure) due to the cohesive nature of its extensive hydrogen bonding. [Back]
g In liquid methanol (CH3OH) the oxygen atoms are 3% closer than they are in liquid water but its density is 21% less than water, due to methanol only able to form only two hydrogen bonds per molecule. [Back]
κT = -[δV/δP]T/V = [δρ/δP]T/ρ = <(ΔV)2>TPN /kBTV
αP = [δV/δT]P/V = <(ΔV)(ΔS)>TPN /kBTV = <(ΔV)(ΔH)>TPN /kBT2V
where κT, αP, kB, P, T, N, ρ, V, H and S are the isothermal compressibility, thermal expansion, Boltzmann constant, pressure, temperature, number of molecules, density, volume, enthalpy and entropy respectively; the <> brackets indicate the fluctuations in the values about their mean values.
i A higher refractive index is indicative of higher density or greater hydrogen bond strength (at equal density). Structured water has higher specific refraction and refractive index for its density [60] but the effect of density changes on the refractive index outweighs that of the specific refraction differences due to water structuring; thus, ice has a density of 91.7% of water and refractive index of 98.2% of water. The thermodynamics confuses this view as at 22°C thermodynamic arguments suggest the surface is less dense than the bulk (if rather less so than other liquids). The opposing views may be reconciled by consideration of the different depths probed by the two methods. [Back]
Phase anomalies (P1-P12) explanations
Material anomalies (M1-M12) explanations
Thermodynamic anomalies (T1-T11) explanations
Physical anomalies (F1-F9) explanations
Home | Site Index | The anomalies of water | Water: Introduction | The icosahedral water clusters | LSBU | Top
This page was last updated by Martin Chaplin on 24 October, 2008
