Фазовые диаграммы: условия и состояния вещества

Chart used to show conditions at which physical phases of a substance occur

A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions (pressure, temperature, volume, etc.) at which thermodynamically distinct phases (such as solid, liquid or gaseous states) occur and coexist at equilibrium.

Common components of a phase diagram are lines of equilibrium or phase boundaries, which refer to lines that mark conditions under which multiple phases can coexist at equilibrium. Phase transitions occur along lines of equilibrium. Metastable phases are not shown in phase diagrams as, despite their common occurrence, they are not equilibrium phases. Triple points are points on phase diagrams where lines of equilibrium intersect. Triple points mark conditions at which three different phases can coexist. For example, the water phase diagram has a triple point corresponding to the single temperature and pressure at which solid, liquid, and gaseous water can coexist in a stable equilibrium (273.16 and a partial vapor pressure of 611.657). The pressure on a pressure temperature diagram (such as the water phase diagram shown) is the partial pressure of the substance in question. The solidus is the temperature below which the substance is stable in the solid state. The liquidus is the temperature 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 consists of a mixture of crystals and liquid (like a "slurry"). Working fluids are often categorized on the basis of the shape of their phase diagram.

In addition to temperature and pressure, other thermodynamic properties may be graphed in phase diagrams. Examples of such thermodynamic properties include specific volume, specific enthalpy, or specific entropy. For example, single component graphs of temperature vs. specific entropy (T vs. s) for water/steam or for a refrigerant are commonly used to illustrate thermodynamic cycles such as a Carnot cycle, Rankine cycle, or vapor compression refrigeration cycle. Any two thermodynamic quantities may be shown on the horizontal and vertical axes of a two dimensional diagram. Additional thermodynamic quantities may each be illustrated in increments as a series of lines—curved, straight, or a combination of curved and straight. Each of these iso lines represents the thermodynamic quantity at a certain constant value.

It is possible to envision three dimensional (3D) graphs showing three thermodynamic quantities. For example, for a single component, a 3D Cartesian coordinate type graph can show temperature (T) on one axis, pressure (p) on a second axis, and specific volume (v) on a third. Such a 3D graph is sometimes called a p–v–T diagram. The equilibrium conditions are shown as curves on a curved surface in 3D with areas for solid, liquid, and vapor phases and areas where solid and liquid, solid and vapor, or liquid and vapor coexist in equilibrium. A line on the surface called a triple line is where solid, liquid and vapor can all coexist in equilibrium. The critical point remains a point on the surface even on a 3D phase diagram. An orthographic projection of the 3D p–v–T graph showing pressure and temperature as the vertical and horizontal axes collapses the 3D plot into the standard 2D pressure–temperature diagram. When this is done, the solid–vapor, solid–liquid, and liquid–vapor surfaces collapse into three corresponding curved lines meeting at the triple point, which is the collapsed orthographic projection of the triple line.

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, 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, as shown at right. Such a mixture can be either a solid solution, eutectic or peritectic, among others. These two types of mixtures result in very different graphs. 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 two component diagram with components A and B in an "ideal" solution is shown. The construction of a liquid vapor phase diagram assumes an ideal liquid solution obeying Raoult's law and an ideal gas mixture obeying Dalton's law of partial pressure. A tie line from the liquid to the gas at constant pressure would indicate the two compositions of the liquid and gas respectively. 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 more information. In addition to the above mentioned types of phase diagrams, there are many 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 cooling. The inverse of this, when one solid phase transforms into two solid phases during cooling, 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 is usually unknown, the preferred concentration measure is mole fraction. A volume based measure like molarity would be inadvisable.

Polymorphic and polyamorphic substances have multiple crystal or amorphous phases, which can be graphed in a similar fashion to solid, liquid, and gas phases.

Some organic materials pass through intermediate states between solid and liquid; these states are called mesophases. Attention has been directed to mesophases because they enable display devices and have become commercially important through the so called liquid crystal technology. Phase diagrams are used to describe the occurrence of mesophases.