Phase diagram

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In physical chemistry, mineralogy, and materials science, a phase diagram is a type of graph used to show the equilibrium conditions between the thermodynamically-distinct phases. In mathematics and physics, a phase diagram also has an alternative meaning, as a synonym for a phase space.

[edit] Pressure-temperature 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 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 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. 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 fluid. 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, the liquid and gaseous phases can blend continuously into each other. However, 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^{[citation needed]}.

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, that is the temperature at which metal melts. 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.

[edit] Binary phase diagrams

Other much more complex types of phase diagrams can be constructed, particularly when more than one pure component is present. In that case concentration becomes an important variable. Phase diagrams with more than two dimensions can be constructed that show the effect of more than two variables on the phase of a substance. Phase diagrams can use other variables in addition to or in place of temperature and pressure and composition, for example the strength of an applied electrical or magnetic field and they can also involve substances that take on more than just three states of matter.

One type of phase diagram plots temperature against the relative concentrations of two substances in a binary mixture called a binary phase diagram. Such a mixture can be either a solid solution, eutectic or peritectic, among others. These two types of mixtures result in very different graphs. A textbook example of a eutectic phase diagram is that of the olivine (forsterite and fayalite) system.

Another type of binary phase diagram is a boiling point diagram for a mixture of two components, i. e. chemical compounds. For two particular volatile components at a certain pressure such as atmospheric pressure, a boiling point diagram shows what vapor (gas) compositions are in equilibrium with given liquid compositions depending on temperature. In a typical binary boiling point diagram, temperature is plotted on a vertical axis and mixture composition on a horizontal axis. A simple example diagram with hypothetical components 1 and 2 in a non-azeotropic mixture is shown at right. The fact that there are two separate curved lines joining the boiling points of the pure components means that the vapor composition is usually not the same as the liquid composition the vapor is in equilibrium with. See Vapor-Liquid Equilibrium for a fuller discussion.

In addition to the above mentioned types of phase diagrams, there are thousands of other possible combinations. Some of the major features of phase diagrams include congruent points, where a solid phase transforms directly into a liquid. There is also the peritectoid, a point where two solid phases combine into one solid phase during heating. The inverse of this, when one solid phase transforms into two solid phases during heating, is called the eutectoid.

A complex phase diagram of great technological importance is that of the iron-carbon system for less than 7% carbon (see steel).

The x-axis of such a diagram represents the concentration variable of the mixture. As the mixtures are typically far from dilute and their density as a function of temperature usually unknown the preferred concentration measure is mole fraction. A volume based measure like molarity would be unadvisable.

[edit] Common components of a phase diagram

Lines of equilibrium or phase boundaries refer to the lines that demarcate where phase transitions occur.

A triple point is, in a pressure-temperature phase diagram, the unique intersection of the lines of equilibrium between three states of matter, usually solid, liquid, and gas.

For a phase diagram with temperature on the vertical axis, a solidus is a line below which the substance is stable in the solid state. A liquidus is a line above which the substance is stable in a liquid state. There may be a gap between the solidus and liquidus; within the gap, the substance is replaced by a mixture of solid crystals and liquid.

[edit] Liquid crystal phase diagrams

In liquid crystal physics, phase diagrams are used in the case of mixing of nematogenic compounds to distinguish between the isotropic liquid phase, the nematic liquid phase.