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Department of Chemistry, Sapienza - University of Rome, p.le Aldo Moro 5 00185 Roma, Italy
Nanochemistry Research Institute, Department of Applied Chemistry, Curtin University, GPO Box U1987,
Perth, WA 6845, Australia
ABSTRACT: For most materials, the solid at and near the triple-point
temperature is denser than the liquid with which it is in equilibrium.
However, for water and certain other materials, the densities of the
phases are reversed, with the solid being less dense. The profound
consequences for the appearance of the pVT diagram of one-component
materials resulting from such anomalous volume changes in solid-
liquid transitions are discussed. We discuss and illustrate how the 3D
pVT phase diagram changes for this case. A more complex case occurs in
systems where the solid liquid eld displays continuous density
reversal at high pressure, making the phase diagrams of some elements
unexpectedly complex. The controversial case of graphite is presented as
an example of the diculties of interpretation. A current version of the
carbon pT phase diagram is provided, in a 2D pT representation as well as
in a virtual 3D version. The phase diagram of sodium, newly determined
to extremely high pressures and illustrated here, shows both melting
maxima and minima as well as a number of phase transitions as pressure
increases.
KEYWORDS: Upper-Division Undergraduate, Graduate Education/Research, Physical Chemistry, Materials Science, Phases/
Phase Transitions/Diagrams, Thermodynamics
passes through zero to negative values at some pressure. This to rise, the melting point falls further to a minimum of about
causes a smooth maximum in the pT plane, without any accom- 300 K at 118 GPa, accompanied by a series of phase changes to
panying rst-order liquid-liquid phase transition. Figure 5 illus- increasingly complex crystal structures.19a,c,d,21 The initial max-
trates how the width of the solid-liquid phase gap in the pVT imum in the melting point is not accompanied by a phase
diagram passes through zero as the Clapeyron slope goes from transition, either in the solid or liquid. The phase transition
positive to negative through the point of volume (density) equality. points are collected in Table 1.
Figure 4 displays the experimental pT phase diagram of Similarly complex is the behavior shown by cesium, where two
sodium in all its complexity,19 whereas Figure 6 shows the simple distinct maxima are reported in the T versus p melting curve.22
pV behavior of the phases at T = 298 K as determined by a rst- Much of the evidence for anomalous and unusual phase diagram
principles density functional theory study.20 In this gure, the behaviors for one-component systems at high pressures can be
bcc-fcc phase change is not distinguishible owing to the very found among the elements16,23 and in polymer materials.24
small volume change accompanying the transition, so that a
single continuous curve ts the pV data for both solid phases AUTHOR INFORMATION
rather well.
The 3D pVT diagram of sodium, liquid and solid only, is Corresponding Author
reported in Figure 7. This shows that at low pressures the less *E-mail: l.glasser@curtin.edu.au.
dense liquid is more compressible than the solid, with the two
phases reaching equality of density at a maximum melting point
ACKNOWLEDGMENT
at about 31 GPa and 990 K, whereafter the melting point
decreases to a bcc-fcc phase transition. As pressure continues We acknowledge helpful discussions with Nigel Marks
(Curtin) on the properties of carbon and the possibilities of
Table 1. pVT Data on the High-Pressure Phase Relations of liquid-liquid phase transitions. The 3D phase and other dia-
Sodium grams depicted were prepared with the aid of the free scalable
vector graphics program Inkscape.29
Crystal Structurea,b or Transition Point p/GPac T/Kc V/3 (estimated)