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2-dimensional diagrams
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Pressure vs temperature
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Other thermodynamic properties
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3-dimensional diagrams
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Binary phase diagrams
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Ternary phase diagrams
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Crystals
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Mesophases
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See also
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References
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Phase diagram
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From Wikipedia, the free encyclopedia
For the representation of orbits in dynamical systems, see Phase portrait. For the set of
physical states in mechanical systems, see Phase space.
Simplified temperature/pressure phase
change diagram for water.
A phase diagram in physical chemistry, engineering, mineralogy, and materials
science is a type of chart used to show conditions (pressure, temperature, etc.) at which
thermodynamically distinct phases (such as solid, liquid or gaseous states) occur and
coexist at equilibrium.
Overview
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 K and a partial vapor pressure of 611.657 Pa). The pressure on a pressure-
temperature diagram (such as the water phase diagram shown) is that of the substance
in question (e.g., the environmental pressure for a condensed state and the partial
pressure for the gas state).[1]
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").[2]
Working fluids are often categorized on the basis of the shape of their phase diagram.
2-dimensional diagrams
Pressure vs temperature
A typical phase diagram. The solid green
line shows the behaviour of the melting point for most substances; the dotted green line
shows the anomalous behavior of water. The red lines show the sublimation
temperature and the blue line the boiling point, showing how they vary with pressure.
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 behavior, where phase transitions occur, which
are called phase boundaries.
In the diagram on the right, 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,[3] in what is known
as a supercritical fluid. In water, the critical point occurs at around Tc = 647.096 K
(373.946 °C), pc = 22.064 MPa (217.75 atm) and ρc = 356 kg/m3.[4]
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.[5]
For most substances, the solid–liquid phase boundary (or fusion curve) in the phase
diagram has a positive slope so that the melting point increases with pressure. This is
true whenever the solid phase is denser than the liquid phase.[6] 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 intermolecular
forces. Thus, the substance requires a higher temperature for its molecules to have
enough energy to break out of the fixed pattern of the solid phase and enter the liquid
phase. A similar concept applies to liquid–gas phase changes.[7]
Water is an exception which has a solid-liquid boundary with negative slope so that the
melting point decreases with pressure. This occurs because ice (solid water) is less
dense than liquid water, as shown by the fact that ice floats on water. At a molecular
level, ice is less dense because it has a more extensive network of hydrogen
bonding which requires a greater separation of water molecules.[6] Other exceptions
include antimony and bismuth.[8][9]
At very high pressures above 50 GPa (500 000 atm), liquid nitrogen undergoes a liquid-
liquid phase transition to a polymeric form and becomes denser than solid nitrogen at
the same pressure. Under these conditions therefore, solid nitrogen also floats in its
liquid.[10]
The value of the slope dP/dT is given by the Clausius–Clapeyron equation for fusion
(melting)[11]
where ΔHfus is the heat of fusion which is always positive, and ΔVfus is the volume
change for fusion. For most substances ΔVfus is positive so that the slope is positive.
However for water and other exceptions, ΔVfus is negative so that the slope is
negative.
Other thermodynamic properties
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.
• Chart in U.S. units
•
enthalpy–entropy (h–s) diagram for steam
pressure–enthalpy (p–h) diagram for steam
•
temperature–entropy (T–s) diagram for steam
3-dimensional diagrams
p–v–T 3D diagram for fixed amount of pure
material
It is possible to envision three-dimensional (3D) graphs showing three
thermodynamic quantities.[12][13] 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.