Phase matter: Encyclopedia II - Phase matter - Phase diagrams

Phase matter - Phase diagrams

Main article: Phase diagram

The different phases of a system may be represented using a phase diagram. The axes of the diagrams are the relevant thermodynamic variables. For simple mechanical systems, we generally use the pressure and temperature. The following figure shows a phase diagram for a typical material exhibiting solid, liquid and gaseous phases.

The markings on the phase diagram show the points where the free energy is non-analytic. The open spaces, where the free energy is analytic, correspond to the phases. The phases are separated by lines of non-analyticity, where phase transitions occur, which are called phase boundaries.

In the above diagram, the phase boundary between liquid and gas does not continue indefinitely. Instead, it terminates at a point on the phase diagram called the critical point. At temperatures and pressure above the critical point, the phyiscal property differences that differeniate the liquid phase from the gas phase become less defined. This reflects the fact that, at extremely high temperatures and pressures, the liquid and gaseous phases become indistinguishable. In water, the critical point occurs at around 647 K (374 °C or 705 °F) and 22.064 MPa.

The existence of the liquid-gas critical point reveals a slight ambiguity in our above definitions. When going from the liquid to the gaseous phase, one usually crosses the phase boundary, but it is possible to choose a path that never crosses the boundary by going to the right of the critical point. Thus, phases can sometimes blend continuously into each other. This new phase which has some properties that are similar to a liquid and some properties that are similar to a gas is call a supercritical fluid. We should note, however, that this does not always happen. For example, it is impossible for the solid-liquid phase boundary to end in a critical point in the same way as the liquid-gas boundary, because the solid and liquid phases have different symmetry.

An interesting thing to note is that the solid-liquid phase boundary in the phase diagram of most substances, such as the one shown above, has a positive slope. This is due to the solid phase having a higher density than the liquid, so that increasing the pressure increases the melting temperature. However, in the phase diagram for water the solid-liquid phase boundary has a negative slope. This reflects the fact that ice has a lower density than water, which is an unusual property for a material.

Adapted from the Wikipedia article "Phase diagrams", under the G.N U Free Docmentation License. Please also see http://en.wikipedia.org/wiki