Chapter 3: Physical Transformation of Pure Substances

Phase Diagrams
 (b) The phase rule

In one of the most elegant arguments of the whole of chemical

thermodynamics, which is presented in the following Justification, J.W.
Gibbs deduced the phase rule, which gives the number of parameters
that can be varied independently (at least to a small extent) while the
number of phases in equilibrium is preserved. The phase rule is a
general relation between the variance, F, the number of components, C,
and the number of phases at equilibrium, P, for a system of any
composition:
F=C−P+2 The phase rule (4A.1)
(b) The phase rule
By a constituent of a system we mean a chemical species that is
present. The variance (or number of degrees of freedom), F, of a
system is the number of intensive variables that can be
changed independently without disturbing the number of
phases in equilibrium.
(b) The phase rule
In a single-component, single-phase system (C = 1, P = 1), the pressure and
temperature may be changed independently without changing the number of
phases, so F = 2. We say that such a system is bivariant, or that it has two
degrees of freedom. On the other hand, if two phases are in equilibrium (a
liquid and its vapour, for instance) in a single-component system (C = 1, P =
2), the temperature (or the pressure) can be changed at will, but the change
in temperature (or pressure) demands an accompanying change in pressure
(or temperature) to preserve the number of phases in equilibrium constituent
of a system we mean a chemical species that is present. That is, the
variance of the system has fallen to 1.
(b) The phase rule
The number of components:
A mixture of ethanol and water has two constituents. A solution of
sodium chloride has three constituents: water, Na+ ions, and Cl−
ions but only two components because the numbers of Na+ and
Cl− ions are constrained to be equal by the requirement of charge
neutrality.
4A.3 Three representative phase
diagrams
For a one-component system, such as pure water, F = 3 − P. When only one
phase is present, F = 2 and both p and T can be varied independently (at least
over a small range) without changing the number of phases. In other words, a
single phase is represented by an area on a phase diagram. When two phases
are in equilibrium F = 1, which implies that pressure is not freely variable if
the temperature is set; indeed, at a given temperature, a liquid has a
characteristic vapour pressure. It follows that the equilibrium of two phases
is represented by a line in the phase diagram. Instead of selecting the
temperature, we could select the pressure, but having done so the two phases
would be in equilibrium at a single definite temperature. Therefore, freezing
(or any other phase transition) occurs at a definite temperature at a given
pressure.
4A.3 Three representative phase
diagrams
When three phases are in equilibrium, F = 0 and the system is invariant. This
special condition can be established only at a definite temperature and
pressure that is characteristic of the substance and outside our control. The
equilibrium of three phases is therefore represented by a point, the triple
point, on a phase diagram. Four phases cannot be in equilibrium in a one
component system because F cannot be negative.
4A.3 Three representative phase diagrams
 4A.3 Three representative phase diagrams:
(a) Carbon dioxide
The phase diagram for carbon dioxide
is shown in Fig. 4.4.
The features to notice include the
positive slope (up from left to right) of
the solid–liquid boundary; the
direction of this line is characteristic
of most substances. This slope
indicates that the melting temperature
of solid carbon dioxide rises as the
pressure is increased.
 4A.3 Three representative phase diagrams:
(a) Carbon dioxide
Notice also that, as the triple point lies above
1 atm, the liquid cannot exist at normal
atmospheric pressures whatever the
temperature. As a result, the solid sublimes
when left in the open (hence the name ‘dry
ice’). To obtain the liquid,
it is necessary to exert a pressure of at least
5.11 atm. Cylinders of carbon dioxide
generally contain the liquid or compressed
gas; at 25 °C that implies a vapour pressure of
67 atm if both the gas and liquid are present in
equilibrium.
 4A.3 Three representative phase diagrams:
(a) Carbon dioxide
the gas and liquid are present in equilibrium.
When the gas squirts through the throttle it
cools by the Joule–Thomson effect, so when
it emerges into a region where the pressure
is only 1 atm, it condenses into a finely
divided snow-like solid. That carbon dioxide
gas cannot be liquefied except by applying
high pressure reflects the weakness of the
intermolecular forces between the nonpolar
carbon dioxide molecules (Topic 16B).
 The phase diagram for water (BooK: Maron Lando)
The System Water. Above about -20°C and below 2000 atm pressure there is only one solid
phase in this system, namely, ordinary ice.
This solid phase, liquid water, and water vapor constitute the three possible single
phases in the system.
These phases may be involved in three possible two phase equilibria, namely, liquid-vapor,
solid-vapor, and solid-liquid, and one three-phase equilibrium, solid-liquid-vapor.
Applying the phase rule to the system when only a single phase is present, we see that F=
2, and therefore each single phase at equilibrium possesses two degrees of freedom. If
temperature and pressure are chosen as the independent variables, the phase rule predicts
that both of these must be stated in order to define the condition of the phase. Since two
independent variables are necessary to locate any point in an area,
it must follow that each phase on a P-T diagram occupies an area: and, as three single
phases are possible in this system, we may anticipate three such areas on the plot, one for
each phase.
 The phase diagram for water

The System Water.

For two phases in equilibrium the phase rule predicts that F = 1. Since a single
variable determines a line, we may expect for each two-phase equilibrium a line on
the P-T plot.
As three such equilibria may occur in the system, the diagram will be characterized
by the existence of three lines separating the various areas from each other.
Finally, for the three-phase equilibrium F = 0: ie, no variables need be specified.
This must mean that when all three phases coexist the temperature and pressure are
fixed, and the position of this equilibrium on the diagram is characterized by the
intersection of the three lines at a common point.
 The phase diagram for water.
Although the phase rule makes it possible to
predict the general appearance of the diagram,
the exact positions of all lines and points can be
determined only by experiment.
An inspection of the possible equilibria in this
system shows that the data necessary for the
construction of a P-T plot are:
(a) the vapor pressure curve of water (liquid-
vapor equilibrium),
(b) the sublimation curve of ice (solid-vapor
equilibrium),
(c) the melting point curve of ice as a function
of pressure (solid-liquid equilibrium), and
(d) the position of the solid-liquid-vapor
equilibrium point.
These experimental data for the system water
are shown in Figure 15-1.
 The phase diagram for water.
In this phase diagram line AO gives the
sublimation curve of ice, line OB the
vapor pressure curve of liquid water, and
and OC the line along which equilibria
between ice and liquid water occur at
various pressures. O is the triple point at
which ice, water, and water vapor are in
equilibrium. This equilibrium is possible
only at 0.010°C and 4.58 mm pressure.
As predicted by the phase rule, there are
three areas on the diagram, disposed as
shown one such area corresponding to
each of the single phases.
 The phase diagram for water
The vapor pressure curve of water, line OB, extends
from the triple point O up to the critical point B,
corresponding to 3740C and 220 atm pressure.
However, under certain conditions it is possible to
supercool water below point O to yield the
metastable liquid-vapor equilibrium shown by the
dotted line OD. The fact that OD lies above AO shows
that at temperatures below that of the triple point
liquid water has a vapor pressure higher than the
sublimation pressure of ice, and hence the
supercooled liquid is unstable at these temperatures
with respect to the ice.
The sublimations curve of ice, line AO, may
extend from absolute zero up to O. No superheating
of ice beyond O has ever been realized.
 The phase diagram for water
Line OC runs from O up to a point corresponding to
2000 atm pressure and about -20°C; at this point
ordinary ice, type I, in equilibrium with water
undergoes a transformation into another solid
modification, type III, in equilibrium with the liquid.
The slope of this line indicates that the melting
point of ice is lowered by increase in pressure in
accord with the Le Châtelier principle and the fact
that ice has larger specific volume than liquid water.
The slopes of the lines OA, OB, and OC are
determined at each point by the Clapeyron
equation or one of its modifications as applicable in
each instance. From the slopes and this equation it
is possible to evaluate the heats of vaporization
from OB, the heats of sublimation from AO, and the
heats of fusion from OC.
 The phase diagram for water
Since no liquid may exist above the critical temperature,
dotted line BE has been inserted in the diagram to
separate the liquid from vapor above the critical
temperature.
Consequently, the vapor area lies below and to the
right and AOBE, the liquid area above OB and between the
lines OCBE, while the solid area extends to the left of OC
and above AO.
The manner in which a diagram such as Figure 15-1
may be used to follow the changes that occur the system
with a change in the variables may be seen from the
following example. Suppose it is desired to know the
behavior of the system on heating ice at a pressure of 760
mm and temperature T1, corresponding to point X in the
diagram, to a point corresponding to point Y at the same
pressure but temperature T2. Starting with ice at X and
heating it slowly at constant pressure, the system follows
line XN with increase in the temperature of ice.
 The phase diagram for water

However, once N is reached the ice begins to melt, the

temperature remains constant until the fusion is
complete and only then does the temperature begin to
rise again along NM. Between N and M the only change
is an increase in the temperature of the liquid. But at M
vaporization sets in, and the temperature again is
constant until all the liquid is converted to vapor. On
complete transformation of liquid to vapor, any further
addition of heat results merely in an increase of the
temperature of the vapor along MY until the latter point
is reached.
In the same way it is possible with the aid of Figure
15-1 to predict and outline any changes that may take
place in this system with a variation of temperature,
pressure, or both.
 Book: Atkins
At high pressures a number of other solid
modifications besides the ordinary form have
been observed.
The phase diagram for water.
The liquid–vapour boundary in the phase diagram
summarizes how the vapour pressure of liquid water varies
with temperature. It also summarizes how the boiling
temperature varies with pressure: we simply read off the
temperature at which the vapour pressure is equal to the
prevailing atmospheric pressure. The solid–liquid boundary
shows how the melting temperature varies with the
pressure; its very steep slope indicates that enormous
pressures are needed to bring about significant changes.
Notice that the line has a negative slope (down from left to
right) up to 2 kbar, which means that the melting
temperature falls as the pressure is raised.
The reason for this almost unique behavior can be
traced to the decrease in volume that occurs on
melting: it is more favourable for the solid to
transform into the liquid as the pressure is raised.
The decrease in volume is a result of the very open
structure of ice: as shown in Fig. 4A.10, the water
molecules are held apart, as well as together, by the
hydrogen bonds between them but the hydrogen-
bonded structure partially collapses on melting and
the liquid is denser than the solid. Other
consequences of its extensive hydrogen bonding are
the anomalously high boiling point of water for a
molecule of its molar mass and its high critical
temperature and pressure.
The Figure 4.5 shows that water has one liquid
phase but many different solid phases other than
ordinary ice (‘ice I’).
Some of these phases melt at high
temperatures. Ice VII, for instance, melts at 100
°C but exists only above 25 kbar.
Two further phases, Ice XIII and XIV, were
identified in 2006 at –160 °C but have not yet
been allocated regions in the phase diagram.
Note that five more triple points occur in
the diagram other than the one where vapour,
liquid, and ice I coexist. Each one occurs at a
definite pressure and temperature that cannot be
changed.
The solid phases of ice differ in the
arrangement of the water molecules:
under the influence of very high pressures,
hydrogen bonds buckle and the H2O
molecules adopt different arrangements.

These polymorphs of ice may

contribute to the advance of glaciers, for
ice at the bottom of glaciers experiences
very high pressures where it rests on
jagged rocks.
(c) Helium
When considering helium at low temperatures it is necessary
to distinguish between the isotopes 3He and 4He.
Figure 4A.11 shows the phase diagram of helium-4. Helium
behaves unusually at low temperatures because the mass of its
atoms is so low and their small number of electrons results in
them interacting only very weakly with their neighbours. For
instance, the solid and gas phases of helium are never in
equilibrium however low the temperature: the atoms are so
light that they vibrate with a large-amplitude motion even at
very low temperatures and the solid simply shakes itself apart.
Solid helium can be obtained, but only by holding the atoms
together by applying pressure.
(c) Helium
The isotopes of helium behave differently
for quantum mechanical reasons.
Pure helium-4 has two liquid phases.
(c) Helium
Pure helium-4 has two liquid phases. The
phase marked He-I in the diagram behaves
like a normal liquid;
the other phase, He-II, is a superfluid; it is
so called because it flows without viscosity.
Provided we discount the liquid crystalline
substances.
Helium is the only known substance with a
liquid–liquid boundary, shown as the λ-line
(lambda line) in Fig. 4.7.
(c) Helium