2D phase diagrams

A typical phase diagram. The dotted line gives
the anomalous behavior of water.
The green lines mark the freezing point and the blue line
the boilling point, showing how they vary with pressure.

2D phase diagrams

The simplest phase diagrams are pressure-temperature diagrams of a single simple substance, such as water. The axes correspond to the pressure and temperature. The phase diagram shows, in pressure-temperature space, the lines of equilibrium or phase boundaries between the three phases of solid, liquid and gas.

The curves on the phase diagram show the points where the free energy (and other derived properties) becomes non-analytic: their derivatives with respect to the coordinates (temperature and pressure in this example) change discontinuously (abruptly). For example, the heat capacity of a container filled with ice will change abruptly as the container is heated past the melting point. The open spaces, where the free energy is analytic, correspond to single phase regions. Single phase regions are separated by lines of non-analytical, where phase transitions occur, which are called phase boundaries.

In the diagram on the left, the phase boundary between liquid and gas does not continue indefinitely. Instead, it terminates at a point on the phase diagram called the crtical point. This reflects the fact that, at extremely high temperatures and pressures, the liquid and gaseous phases become indistinguishable, in what is known as a supercritical Fluids In water, the critical point occurs at around T_c=647.096 K (1,164.773 °R), p_c=22.064 MPa (3,200.1 psi) and ρ_c=356 kg/m³.

The existence of the liquid-gas critical point reveals a slight ambiguity in labelling the single phase regions. 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, the liquid and gaseous phases can blend continuously into each other. The solid-liquid phase boundary can only end in a critical point if the solid and liquid phases have the same symmetry group.

The solid-liquid phase boundary in the phase diagram of most substances has a positive slope ; the greater the pressure on a given substance, the closer together the molecules of the substance are brought to each other, which increases the effect of the substance's intermocular forces. Thus, the substance requires a higher temperature for its molecules to have enough energy to break out the fixed pattern of the solid phase and enter the liquid phase. A similar concept applies to liquid-gas phase changes. Water, because of its particular properties, is one of the several exceptions to the rule.