Lecture 1.

2
Phase Transitions
of Pure Substances
CH117 Physical Chemistry 2
Contents
• Phase Stability
• terminology
• phase transitions
• thermodynamic criteria of phase stability
• Phase Boundaries
• the phase rule
• Thermodynamics of Phase Transitions
• dependence of stability on T and p
• location of phase boundaries

2
Phase Stability

3
Terminology in Phase Equilibria
A phase is a form of matter that is uniform throughout in chemical composition and physical
state.
e.g. solid, liquid, and gas phases, as well as various solid phases like allotropes or polymorphs of
the same substance.
The number of phases in a system is denoted P.
a gas or a gaseous mixture: P = 1
a crystal of a substance: P = 1
two fully mixed miscible liquids: P = 1
a dilute aqueous solution of sodium chloride: P = 1
pure ice: P = 1
a slurry of ice and water: P = 2
the system 𝐶𝑎𝐶𝑂3 𝑠 ⇌ 𝐶𝑎𝑂 𝑠 + 𝐶𝑂2 𝑔 at equilibrium: P = 3
Two metals form a two-phase system (P = 2) if they are immiscible, but a single-phase system
(P = 1) if they are miscible and actually mixed (forming an alloy).

4
Terminology in Phase Equilibria
In a solution (a), atoms of A are surrounded by atoms of A and B, and any sample cut from the
sample, even microscopically small, is representative of the composition of the whole.
A solution represents a single phase.
A dispersion (b) is uniform on a macroscopic scale but not on a microscopic scale, because it
consists of grains or droplets of one substance in a matrix of the other.
A dispersion consists of two phases.

5
Phase Transitions
A phase transition is a spontaneous conversion of one phase into another phase, occurring at a
characteristic transition temperature, Ttrs, for a given pressure.
At the transition temperature, the two phases are at equilibrium and the Gibbs energy of the
system is a minimum at the prevailing pressure.

6
Phase Transitions
The detection of a phase transition is not always straightforward, as there may be nothing to see,
especially if the two phases are both solids.
Thermal analysis takes advantage of the heat that is either evolved or absorbed during a transition
and can therefore be used to detect phase transitions.

7
Phase Transitions

DSC

8
Phase Transitions

XRD (X-ray diffraction)

9
Phase Transitions
A phase transition that is predicted
by thermodynamics to be
spontaneous might occur too slowly
to be significant in practice.
The discussion of the rate of
attainment of equilibrium is a
kinetic problem and is outside the
range of thermodynamics.
Thermodynamically unstable phases
that persist because the transition is
kinetically hindered are called
metastable phases.

10
Thermodynamic Criteria of Phase Stability
We focus on the molar Gibbs energy, Gm, which is a quantity
that plays such an important role that it is given a special
name and symbol: the chemical potential, μ. It is a measure
of the “potential” that a substance has for undergoing
change—physical or chemical.
For a system that consists of a single substance, Gm = μ.

The following discussions are based on the following

consequence of the Second Law:

11
Phase Boundaries

12
Phase Boundaries
The phase diagram of a pure substance shows the regions of pressure and temperature at which
its various phases are thermodynamically stable. Any two intensive variables may be used.
Lines separating the regions are called
phase boundaries (or coexistence
curves). They show the values of p and
T at which two phases exist in
equilibrium and their chemical
potentials are equal.
A single phase is represented by an
area on a phase diagram.

13
Phase Boundaries
Consider a liquid sample of a pure substance in a closed vessel.
The pressure of the vapor in equilibrium with the liquid is its
vapor pressure.
In a phase diagram, the liquid-vapor phase boundary shows how
the vapor pressure of the liquid varies with temperature.
Similarly, the solid-vapor phase boundary shows the temperature
variation of the sublimation vapor pressure, the vapor pressure
of the solid phase.
Vapor pressure increases with temperature because at higher
temperature, more molecules have sufficient energy to escape from
their neighbors in the condensed state.

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Phase Boundaries
When a liquid is in an open vessel and is subject to an external
pressure, it is possible for the liquid to vaporize from its surface.
Only when the temperature is such that pvap = pext will it be
possible for vaporization to occur throughout the bulk of the
liquid and for the vapor to expand freely into the surroundings.
This condition of free vaporization throughout the liquid is called
boiling.
The temperature at which pvap = pext is called the boiling
temperature at that pressure.
when pext = 1 atm: “normal boiling point,” Tb
when pext = 1 bar: “standard boiling point”

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Phase Boundaries
When a liquid is heated in a rigid, closed
vessel (a), boiling does not occur.
Instead, the vapor pressure (and hence,
the vapor density) rises as the
temperature is raised (b).
At the same time, the density of the liquid
decreases as it expands.
There comes a stage at which the density
of the vapor is equal to the density of the
liquid, and the surface between the two
phases disappears (c).
This is called the critical point of the
substance.

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Phase Boundaries
The critical temperature, Tc, is the
temperature at which the surface
disappears.
The vapor pressure at the critical
temperature is called the critical
pressure, pc.
At and above Tc, a single uniform phase
called a supercritical fluid fills the
container and an interface no longer
exists.

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Phase Boundaries
The temperature at which, under a specified pressure,
the liquid and solid phases of a substance coexist in
equilibrium is called the melting temperature. It is
the same as the freezing temperature of the
substance.
when pext = 1 atm: “normal freezing point,” Tf
when pext = 1 bar: “standard freezing point”
The normal freezing point is also called the normal
melting point.

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Phase Boundaries
There is a set of conditions under which three different phases of a substance (typically solid, liquid,
and vapor) all simultaneously coexist in equilibrium. These conditions are represented by the
triple point, a point at which the three phase boundaries meet.
The triple point temperature is denoted T3.
The triple point of a substance cannot be changed; it is invariant and occurs at a single definite
pressure and temperature characteristic of the substance.

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Phase Boundaries
recap:

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The Phase Rule
The phase rule gives the number of parameters that can be varied independently, at least to a small
extent, without affecting the number of phases in equilibrium.
The phase rule is a general relation between the variance, F, the number of components, C, and the
number of phases at equilibrium, P.
• variance (F) - also known as the number of degrees of freedom; the number of intensive
variables that can be changed independently without disturbing the number of phases at
equilibrium
• number of components (C) – the minimum number of types of independent species (ions or
molecules) necessary to define the composition of all the phases present in the system
• constituent – any chemical species that is present
• component – a chemically independent constituent of a system
e.g. a solution of ethanol in water: two constituents, two components
a solution of sodium chloride in water: three constituents, two components (CNa = CCl)

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The Phase Rule
The phase rule relates these quantities by considering the conditions for equilibrium to exist
between the phases in terms of the chemical potentials of all the constituents.
J.W. Gibbs derived this phase rule and showed it to be:

THE PHASE RULE

For a single-phase, single-component system, F = 2 (bivariant): it is represented by an area on a
phase diagram.
For a two-phase, single-component system, F = 1 (univariant/monovariant): it is represented by a
line on a phase diagram.
For a three-phase, single-component system, F = 0 (invariant): it is represented by a point on a
phase diagram.
For a four-phase, single-component system, F < 0 (equilibrium is impossible).

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The Phase Rule

23
Thermodynamics of Phase Transitions

24
Variation of μ with T and p
The fundamental equation of thermodynamics in molar form is:

For a single-component system, Gm = μ, so the same equation holds for the chemical potential as
that for the molar Gibbs energy:

Hence,

By combining the equality of chemical potentials of a substance in each phase with these
expressions for the variation of μ with T and p, it is possible to deduce how phase equilibria
respond to changes in the conditions.

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Temperature Dependence of Stability
Recall the temperature dependence of the chemical potential:

Because for all substances, Sm > 0 above T = 0, the chemical potential of a pure substance decreases
as the temperature is raised.
Also, because Sm(g) > Sm(l), the slope is steeper for gases than for liquids. Because it is almost
always the case that Sm(l) > Sm(s), the slope is also steeper for a liquid than the corresponding solid.

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Temperature Dependence of Stability

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Pressure Dependence of Stability: Melting
Recall the pressure dependence of the chemical potential:

Because for all substances, Vm > 0, an increase in pressure raises the chemical potential of any pure
substance.

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Pressure Dependence of Stability: Melting
(a)
In most cases, Vm(l) > Vm(s), so
an increase in pressure
increases the chemical
potential of the liquid phase of
a substance more than that of
its solid phase.
The effect of pressure in such
a case is to raise the freezing
temperature slightly.

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Pressure Dependence of Stability: Melting
(b)
For substances where Vm(s) >
Vm(l) (such as water), an
increase in pressure increases
the chemical potential of the
solid phase more than that of
the liquid phase.
The effect of pressure in such
a case is to lower the freezing
temperature slightly.

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Pressure Dependence of Stability: Melting
Exercise 2.1.1
Calculate the effect on the chemical potentials of ice and water of increasing the pressure from 1.00
bar to 2.00 bar at 0oC. The mass density of ice is 0.917 g cm-3 and that of liquid water is 0.999 g cm-3
under these conditions.

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Location of Phase Boundaries
The precise locations of the phase boundaries can be found by making use of the fact that when
two phases are in equilibrium, their chemical potentials must be equal.
For phases 𝛼 and 𝛽
𝜇 𝛼; 𝑝, 𝑇 = 𝜇 𝛽; 𝑝, 𝑇
Solution of this equation in terms for p in terms of T gives an equation for the phase boundary (the
coexistence curve).

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Location of Phase Boundaries: The Slopes
When p and T are changed infinitesimally at
the equilibrium point, the chemical
potentials of the two phases change but
remain equal:

It follows that:

In terms of the temperature and pressure,

since 𝑑𝜇 = 𝑑𝐺𝑚 = 𝑉𝑚 𝑑𝑝 − 𝑆𝑚 𝑑𝑇 for a one-
component mixture,

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Location of Phase Boundaries: The Slopes
Rearranging the last equation gives the Clapeyron equation:

CLAPEYRON EQUATION
The Clapeyron equation is an exact expression for the slope of the tangent to the phase boundary
at any point and applies to any phase equilibrium of a pure substance.
It implies that thermodynamic data, i.e. Δ𝑡𝑟𝑠 𝑆, can be used to predict the appearance of phase
diagrams and to understand their form.

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The Solid-Liquid Boundary
Melting, or fusion, is accompanied by a molar enthalpy change Δ𝑓𝑢𝑠 𝐻, and if it occurs at a
temperature T, the molar entropy of melting is Δ𝑓𝑢𝑠 𝐻/𝑇.
All points on the phase boundary correspond to equilibrium, so T is in fact a transition temperature,
Ttrs.
The Clapeyron equation becomes:

For melting (increasing T), the enthalpy change is positive, and the change in molar volume is
usually small and positive (for water, it is negative). Consequently, the slope 𝑑𝑝/𝑑𝑇 is steep and
usually positive.

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The Solid-Liquid Boundary
The equation for the phase boundary,
p(T), is obtained by integration and
some assumptions:

The quantities Δ𝑓𝑢𝑠 𝐻 and Δ𝑓𝑢𝑠 𝑉 can

be treated as constant:

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The Solid-Liquid Boundary

When T is close to T*, the logarithm

can be approximated by using the
expansion:

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The Liquid-Vapor Boundary
A similar treatment gives the slope for the liquid-vapor boundary:

For boiling, the enthalpy change is positive, and the change in molar volume is large and positive.
Consequently, the slope 𝑑𝑝/𝑑𝑇 is also positive but not as steep as that for the solid-liquid boundary.
In addition, the change in molar volume is so great because 𝑉𝑚 𝑔 ≫ 𝑉𝑚 𝑙 . Therefore,

The Clapeyron equation becomes:

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The Liquid-Vapor Boundary
If the gas behaves perfectly,

So,

CLAUSIUS-CLAPEYRON EQUATION
The resulting equation, the Clausius-Clapeyron equation, gives the approximate variation of vapor
pressure with temperature.

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The Liquid-Vapor Boundary
The Clausius-Clapeyron equation can be used to predict how the vapor pressure varies with
temperature, can consequently, how the boiling temperature varies with pressure.
If it is also assumed that the enthalpy of vaporization is constant,

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The Solid-Vapor Boundary
For sublimation, the enthalpy of change is greater than that for either the enthalpies of fusion and
vaporization, because

Also, the change in molar volume is (assuming the vapor is perfect):

The equation for the slope is thus similar to that for the liquid-vapor boundary:

The only difference is that, since Δ𝑠𝑢𝑏 𝐻 is greater, the slope of the phase boundary is steeper at
similar temperatures compared to the liquid-vapor curve.

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The Solid-Vapor Boundary

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Lecture 1.2 Problems
1. For a one-component system, draw a schematic labelled phase diagram given the following
information:
- at low T and low p, only phase 𝛾 is present
- at low T and high p, only phase 𝛽 is present
- at high T and low p, only phase 𝛼 is present
- at high T and high p, only phase 𝛿 is present
- phases 𝛾 and 𝛿 are never in equilibrium
Comment on any special features of your diagram.
2. Water is heated at constant pressure from 25oC to 35oC. By how much does its chemical
potential change? The standard molar entropy of liquid water at 298 K (assumed constant) is
69.9 J K-1 mol-1.
3. The vapor pressure of benzene between 10oC and 30oC fits the expression
log 𝑝/torr = 7.960 − 1780 K /𝑇
Calculate the enthalpy of vaporization and the normal boiling point of benzene.

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 Lecture 1.2
Phase Transitions
of Pure Substances
CH117 Physical Chemistry 2
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