9/13/2018 Water phase diagram

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Water phases at Annapurna II, Nepal

Water Phase Diagram
The properties of the all the known different phases of water are described.

Water density
Supercooled water
Supercritical water
The ice phases
Phase diagrams
The phase diagram of water
Triple points
The Clausius Clapeyron equation

'Corresponding to the abnormal behavior of the liquid at low pressures, and probably
connected to it, the solid also shows abnormal behavior...'
Percy Bridgman, 1911 [2472]

Phase diagrams

Phase diagrams show the preferred physical states of matter at different Phase changes
thermodynamic variables, such as temperatures and pressure. Within each phase, the
material is uniform with respect to its chemical composition and physical state. At
typical temperatures and pressures on Earth (marked by an 'E' below) water is a liquid,
but it becomes solid (that is, ice) if its temperature is lowered below 0 °C and gaseous
(that is, water vapor) if its temperature is raised above 100 °C, at the same pressure.
Each line (phase line) d on a phase diagram represents a phase boundary and gives
the conditions when two phases may stably coexist in any relative proportions (having
the same Gibbs free energy and identical chemical potential). Here, a slight change in
temperature or pressure may cause the phases to abruptly change from one physical
state to the other. Where three phase lines join, there is a 'triple point', when three
phases stably coexist (having identical Gibbs free energies and identical chemical
potentials), d but may abruptly and totally change into each other given a slight change
in temperature or pressure. Under the singular conditions of temperature and pressure
where liquid water, gaseous water and hexagonal ice stably coexist, there is a 'triple point' where both the boiling point
of water and melting point of ice are equal. for a single component system, like pure water, four phase lines cannot
meet at a single point. A 'critical point' occurs at the end of a phase line where the properties of the two phases become
indistinguishable from each other, for example when, under singular conditions of temperature and pressure, liquid
water is hot enough and gaseous water is under sufficient pressure that their densities are identical (0.322 g cm-3 ). At
temperatures above the critical temperature a gas cannot be liquefied. Critical points are usually found at the high
temperature end of the liquid-gas phase line.

The phase diagram of water

The phase diagram of water is complex, a, b, c, e, f having a number of triple points and one, or possibly two, critical
points. Many of the crystalline forms may remain metastable in much of the low-temperature phase space at lower
pressures. A thermodynamic model of water and ices Ih, III, V and VI [1320] and thermodynamic functions of the phase
transitions [1658] have been described. The known ices can be divided, by cluster analysis of their structures [1717],
into the low-pressure ices (hexagonal ice, cubic ice and ice-eleven). the high-pressure ices (ice-seven, ice-eight and ice-
ten) and the others (found in the relatively narrow range of moderate pressures between about 200-2000 MPa). It is
noticeable that most phase boundaries between the ices that share phase boundaries, particularly with the liquid, are
parallel to the temperature axis, implying density-driven phase transformations [2465]; entropy-driven phase
transformations showing phase boundaries parallel to the pressure axis. All phases that share phase boundaries with
liquid water (ices Ih, III, V and VI and VII) have disordered hydrogen bonding. The phases with ordered hydrogen
bonding are found at lower temperatures and are indicated in light blue below. The structural transformation conditions
of some of these ices during compression have been described [1795]. As pressure increases, the ice phases become
denser. They achieve this by initially bending bonds, forming tighter ring or helical networks, and finally including greater
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amounts of network inter-penetration. This is particularly evident when comparing ice-five with the metastable ices (ice-
four and ice-twelve) that may exist in its phase space. Note that, in the phase diagram below, only the stable phases are
shown and that the vertical axis has a logarithmic scale scale for pressure, as the required pressures vary over more
than ten orders of magnitude.

The phase diagram of water

Detail of thw water phase diagram

The mean surface conditions on Earth, (also
atmospheric conditions, Mars and Venus on
mousing over Earth) are indicated. The complex
central part of the phase diagram is expanded
opposite. The critical point and the orange line
in the ice-one phase space refer to the low-
density (LDA) and high-density (HDA) forms of
amorphous water (ice) [16]. Although generally
accepted and supported by diverse experimental
evidence [754a, 861], the existence of this
second, if metastable, critical point is impossible
to prove absolutely at the present time and is
disputed by some [200, 618, 628, 754b, 1115].
The transition between LDA and HDA is due to
the increased entropy and attractive van der
Waals contacts in HDA compensating for the
reduced strength of its hydrogen bonding.
Mouse over border for D2O phase lines
The high-pressure phase line between ice-ten (X) and ice-eleven (XI) [81] is still subject to experimental verification.
The melting point line between supercritical water and high-pressure ice has been established [691, 2096]. Ice VII
possesses higher and lower pressure forms [1428]. Phase diagram of water at higher temperatures, up to 9000 K, have
been proposed [1671, 3199].

Both the critical points are shown as red circles in the phase diagram, above.

Many properties of cold liquid water change above about 200 MPa (for example, viscosity, self-diffusion, compressibility,
Raman spectra and molecular separation), which may be explained by the presence of a high-density liquid phase

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containing interpenetrating hydrogen bonds. The chemical properties of water are also greatly changed at high
temperatures and pressures due to the changes in dissociation, solubility, diffusivity and reactivity due to decreasing
hydrogen-bonding [1116].]

Triple points

Triple points occur where three phase lines join and the three (stable) phases may coexist at equilibrium. As the triple
point (gas:liquid:ice Ih) can be precisely reproduced in the laboratory, its temperature (defined to be exactly 273.16 K),
together with the absolute zero of temperature (0 K) determine the thermodynamic temperature scale and the size of
the kelvin.

Thermodynamic data for the triple points of water

ΔH, ΔS, ΔV cm3 mol-
Triple points MPa °C -1 -1 -1 Ref. D2O [717]
kJ ˣ mol J mol K 1
661 Pa, 3.82 °C
0.000611657 0.010 536
[70]
gas liquid Ih gas liquid -44.9 -165 -22050
gas Ih -50.9 -186 -22048 1833
liquid Ih -5.98 -22 1.634
0 -201.0 717 0 MPa, -197 °C
gas Ih XI
Ih XI 0
220 MPa, -18.8
209.9 -21.985 537
°C
liquid Ih III liquid Ih -4.23 -16.9 2.434
liquid III -3.83 -15.3 -0.839 1833
Ih III 0.39 1.6 -3.273
80 MPa, -195 °C
Ih II XI 70 -199.8 2300
[2300]
225 MPa, -31.0
212.9 -34.7 537
°C
Ih II III Ih II -0.75 -3.2 -3.919
Ih III 0.17 0.7 -3.532 1833
II III 0.92 3.8 0.387
347 MPa, -21.5
344.3 -24.3 537
°C
II III V II III 1.27 5.1 0.261
II V 1.20 4.8 -0.721 1833
III V -0.07 -0.2 -0.982
≈ 0.8 GPa, -143
II VI XV 1582
°C
348 MPa, -14.5
350.1 -16.986 537
°C
liquid III V liquid III -4.61 -18.0 -0.434
liquid V -4.69 -18.3 -1.419 1833
III V -0.07 -0.2 -0.985
II V VI ≈ 620 ≈ -55 539
632.4 0.16 537 629 MPa, 2.4 °C
liquid V -5.27 -19.3 -0.949
liquid V VI
liquid VI -5.29 -19.4 -1.649 1833
V VI -0.02 -0.5 -0.700
≈ 1.5 GPa, -143
VI VIII XV 1582
°C
1950 MPa, ≈ 0
2,100 ≈5 8
°C
VI VII VIII VI VII -0.09 -o.3 -1.0
VI VIII -1.20 -4.2 -1.0 1833
VII VIII -1.10 -3.9 0.0
liquid VI VII 2,216 81.85 537 2060 MPa, 78 °C
liquid VI -6.36 -18.0 -0.59 1833
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liquid VII -6.36 -18.0 -1.64

VI VII 0.0 0.0 -1.05
VII VIII X 62,000 -173 538
super- 43,000 >700 612a
critical VII X
fluid 47,000 ≈ 727 612b
super-
critical VII Superionic ≈ 40,000 ≈ 1000 1572
fluid
[Back to Top ]
Putative phase diagram of a 'typical' liquid

Footnotes
a If water behaved more typically as a low relative
molecular mass (molecular weight) material, its
phase diagram may have looked rather like this
(where 'x' marks ambient conditions on earth).
[Back]

b The metastable phases (Ice Ic, ice IV, Ice IX and Ice XIII) do not belong in a phase diagram. However, Ice Ic (cubic
ice) has been found in the hexagonal ice phase space below -80 °C, ice IV has been found within the ice-three, ice-five
and ice-six phase spaces and Ice IX and Ice XIII have been found within the ice-two phase space. As with the stable ice
phases, at low enough temperatures these phases may be stable for extensive periods as there is insufficient energy
available to overcome the necessary activation barriers. [Back]

c Note that phase diagrams originating from this site have been copied by various sources including to and then from
Wikipedia without proper citation (or inherent permissions) of their source. Such poor scientific etiquette is easy for me
to detect and reflects badly on these authors. [ Back]

dThe Clausius Clapeyron equation. On a phase line the Gibbs free energies of the two phases (G1, G2) must be
equal and remain equal if conditions change causing movement along the phase line. Thus

But, where S is the entropy, and where V is the volume

Therefore

where L is the latent heat (enthalpy change) for the phase change. This is the Clausius-Clapeyron equation. It can also
be stated as
dT/dP = TΔV/ΔH = ΔV/ΔS

where P, T, H, V and S are the pressure, temperature, enthalpy, volume, and entropy. This may be extended to be

dT/dP=T(sign α2V2 - sign α1V1)ΔV/ΔH

where α represents the thermal expansion coefficients, for use with phases with negative expansion coefficients
including the ice phase changes
LDA Ic, HDA LDA, LDA HDA, III V, V VI, VI VII and VI VIII

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[1147b]

At a triple point, the Gibbs free energies of the three phases (G1, G2, G3) must be equal and the entropy and enthalpy
(latent heat) changes for all three phase changes (1 2, 2 3, 1 3) at that point may be calculated,
given the pressure, temperature ( ) and volume changes. [Back]

e The phase diagram for heavy water (D2O) differs little from the diagram for H2O given the scales used in the diagram.
A more accurate representation would be by shifting the temperature scale by about 3.6 K as most of the triple points
for D2O are 3 - 4 K warmer than those for H2O (see above). The pressure differences are positive or negative but not
significant given the logarithmic scale used. [Back]

f The phase diagram of water for negative pressure has been described [2666]. [Back]

Home | Site Index | Ices, introduction | Ice-Ih | Ice-Ic | Ice-Isd | II | III | IV | V | VI | VII | VIII | IX | X | XI | XII | XIII | XIV | XV | XVI| XVII |
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This page was established in 2000 and last updated by Martin Chaplin on 24 July, 2018

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