CHE1014

Physical Chemistry
Lecture 8
01 July 2025
Equilibrium in Pure
Systems
(Chapter 5)
 Phase Equilibria

Phase Rule

What we going to learn

today? One-component
Phase Diagrams

Thermodynamic
aspects of phase
transitions
Phase Equilibria
Introduction
Phase diagram is a graphical
representation of the physical
states of a substance under
different conditions of
temperature and pressure.

A typical phase diagram has

pressure on the y-axis and
temperature on the x-axis

As we cross the lines or curves

on the phase diagram, a phase
change occurs.
The Number of Phases

Phase is defined as a homogeneous part of the

heterogeneous system

The number of phases in a system is denoted P

Examples:
Ice : 1 single phase
Ice and water : 2-phase system
Alloy of 2 metals: 2-phase (if immiscible), but 1-phase system if miscible.
The Number of Phases

A solution of B in A

 a homogeneous mixture of the two miscible

substances— is uniform on a molecular scale.
 In a solution, 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.
 It is therefore a single phase. (a)
The Number of Phases

A dispersion of B in A

 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 small sample could come entirely from one of the
minute grains of pure A and would not be
representative of the whole. A dispersion therefore
consists of two phases. (b)
Example

 A solution of sodium chloride in water is a single phase (P = 1).

 Ice is a single phase even though it might be chipped into small

fragments.

 A slurry of ice and water is a two-phase system (P = 2) even

though it is difficult to map the physical boundaries between
the phases.

 A system in which calcium carbonate undergoes the thermal

decomposition CaCO3(s) → CaO(s) + CO2(g) consists of two solid
phases (one consisting of calcium carbonate and the other of
calcium oxide) and one gaseous phase (consisting of carbon
dioxide), so P = 3.
Phase Transitions

 A phase transition, the spontaneous

conversion of one phase into another
phase, occurs at a characteristic
transition temperature, Ttrs, for a given
pressure.

 At the transition temperature the two

phases are in equilibrium
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, which takes advantage of the heat

that is evolved or absorbed during a transition, can be
used.
 Thus, if the phase transition is exothermic and the
temperature of a sample is monitored as it cools, the
presence of the transition can be recognized by a pause
in the otherwise steady fall of the temperature A cooling curve at constant pressure. The flat
section corresponds to the pause in the fall of
temperature while an exothermic transition
 Similarly, if a sample is heated steadily and the (freezing) occurs. This pause enables Tf to be
transition is endothermic, there will be a pause in the located even if the transition cannot be
temperature rise at the transition temperature. observed visually.
Phase Transitions
 Differential scanning calorimetry is also
used to detect phase transitions
Phase boundaries

 The phase diagram of a pure substance

shows the regions of pressure and
temperature at which its various phases are
thermodynamically stable.

 The lines separating the regions, which are

called phase boundaries (or coexistence
curves), show the values of p and T at which
two phases coexist in equilibrium and their
chemical potentials are equal.

 A single phase is represented by an area on a

phase diagram.
Characteristic properties related to
phase transitions
 Vapour pressure
 The pressure of a vapour in equilibrium
with the liquid
 the liquid–vapour phase boundary in a
phase diagram shows how the vapour
pressure of the liquid varies with
temperature

 Sublimation vapour pressure

 the vapour pressure of the solid phase
 solid–vapour phase boundary in a phase
diagram shows how the vapour pressure
of the solid varies with temperature.
Characteristic properties related to
phase transitions
 Boiling
 free vaporization throughout the liquid
when the temperature is such that the
vapour pressure is equal to the external
pressure will it be possible for
vaporization to occur throughout the bulk
of the liquid and for the vapour to
expand freely into the surroundings

 Boiling temperature
 The temperature at which the vapour
pressure of a liquid is equal to the
external pressure
Characteristic properties related to
phase transitions
 Boiling does not occur when a liquid is heated in a
rigid, closed vessel. Instead, the vapour pressure,
and hence the density of the vapour, rises as the
temperature is raised.

 There comes a stage when the density of the (a) A liquid in equilibrium with its vapour.
vapour is equal to that of the remaining liquid and (b) When a liquid is heated in a sealed
the surface between the two phases disappears. container, the density of the vapour
phase increases and the density of the
liquid decreases slightly. There comes a
stage, (c), at which the two densities are
equal and the interface between the
fluids disappears. This disappearance
occurs at the critical temperature.
Characteristic properties related to
phase transitions
 Critical pressure, pc
 The vapour pressure at the critical
temperature , Tc
 Critical temperature, Tc
 The temperature at which the interfacial
surface of vapour-liquids disappears
 Supercritical fluid
 At and above the critical temperature, a
single uniform phase fills the container and an
interface no longer exists.
 That is, above the critical temperature, the
liquid phase of the substance does not exist.
Characteristic properties related to
phase transitions
 Melting temperature
 The temperature at which, under a
specified pressure, the liquid and solid
phases of a substance coexist in
equilibrium
 Because a substance melts at exactly the
same temperature as it freezes, the
melting temperature of a substance is
the same as its freezing temperature
Characteristic properties related to
phase transitions
 Triple point
 a set of conditions under which three
different phases of a substance (typically
solid, liquid, and vapour) all simultaneously
coexist in equilibrium.
 a point at which the three phase boundaries
meet.

 The triple point of a pure substance cannot be

changed: it occurs at a single definite pressure
and temperature characteristic of the
substance.
 marks the lowest pressure at which a liquid
phase of a substance can exist.
 Also marks the lowest temperature at which
the liquid can exist.
The Phase Rule
The Phase Rule
 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.
 Variance, F (or number of degrees of freedom),
 the number of intensive variables that can be changed independently without disturbing
the number of phases in equilibrium.
 Constituent
 any chemical species that is present.
 Component, C
 a chemically independent constituent of a system.
 The number of components, C, in a system is the minimum number of types of
independent species (ions or molecules) necessary to define the composition of all the
phases present in the system.
The Phase Rule
 The relation between these quantities, which is called the phase rule, is
established by considering the conditions for equilibrium to exist between the
phases in terms of the chemical potentials of all the constituents.

F= variance
F=C-P+2 C= no of component
P= no of phase

 When only one phase is present in a one-component system, F = 2 and both p

and T can be varied independently (at least over a small range) without
changing the number of phases.

 The system is said to be bivariant, meaning having two degrees of freedom.

In other words, a single phase is represented by an area on a phase diagram.
The Phase Rule
 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, the pressure could be selected, but

having done so the two phases would be in equilibrium only at a single
definite temperature.

 Therefore, freezing (or any other phase transition) occurs at a definite

temperature at a given pressure.
The Phase Rule
 When three phases are in equilibrium, F = 0 and the system is invariant,
meaning that it has no degrees of freedom.

 This special condition can be established only at a definite temperature and

pressure that is characteristic of the substance and cannot be changed.

 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.
 The Phase Rule
The typical regions of a one-component
phase diagram.

The lines represent conditions under

which the two adjoining phases are in
equilibrium.

A point represents the unique set of

conditions under which three phases
coexist in equilibrium.

Four phases cannot mutually coexist in

equilibrium when only one component is
present.
One-component
Phase Diagrams
Carbon Dioxide, CO2
Melting Curve (BD)
• Represents the transition
between solid and liquid
phases.
• Slopes towards the right

This slope indicates that the

melting temperature of solid
carbon dioxide rises as the
pressure is increased.
Vaporization Curve (BC)
• Represents the transition
between liquid and gas
phases.

Sublimation Curve (AB)

• Represents the transition
between solid and gas
phases.

Triple Point (B)

• Pressure and temperature
where solid, liquid, and
gas phases coexist.
Critical Point (C)
• Maximum pressure and
temperature where
liquid and gas phases are
indistinguishable.

• Beyond this point, the

gas cannot condense into
a liquid, even with
increased pressure.

• Substance becomes a
supercritical fluid
beyond this point.
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.
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.
 Consider the path 1-2-3-4.

At 1 the carbon dioxide is a

gas.

When the temperature and

pressure are adjusted to 2, the
3
vapour condenses directly to a
solid.

4 Increasing the pressure and

temperature to 3 results in the
formation of the liquid phase,
2 which evaporates to the
vapour when the conditions
are changed to 4.
1
Water, H2O
Melting Curve (BD)
• Represents the transition
between solid and liquid
phases.
• Slopes towards the left

Water’s solid-liquid line is

inclined toward the left,
meaning that the melting
point decreases if pressure
increases

It is because solid ice is less

dense than liquid water.
H2O
 The reason for this almost unique behaviour 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; 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.
Vaporization Curve (BC)
• Represents the transition
between liquid and gas
phases.

Sublimation Curve (AB)

• Represents the transition
between solid and gas
phases.

Triple Point (B)

• Pressure and temperature
where solid, liquid, and
gas phases coexist.
 Consider the path 1-2-3-4.

At 1 the water is a gas

(Steam).

When the temperature and

pressure are adjusted to 2, the
vapour condenses directly to a
solid (Ice).

Increasing the pressure and

2 3 4 temperature to 3 results in the
formation of the liquid phase,
which evaporates to the
vapour when the conditions
are changed to 4.
1
Thermodynamic aspects
of phase transitions
The location of phase boundaries

 The precise locations of the phase

boundaries—the pressures and
temperatures at which two phases can
coexist—can be found by making use once
again of the fact that, when two phases
are in equilibrium, their chemical
potentials must be equal.

 Therefore, when the phases α and β are in

equilibrium,

μ(α; p,T) = μ(β; p,T)

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 any pure
substance:

𝑑𝑝 ∆𝑡𝑟𝑠 𝑆
=
𝑑𝑇 ∆𝑡𝑟𝑠 𝑉

 It implies that thermodynamic data can be used to

predict the appearance of phase diagrams and to
understand their form.

 A more practical application is to the prediction of the

response of freezing and boiling points to the application
of pressure, when it can be used in the form obtained by
inverting both sides:

𝑑𝑇 ∆𝑡𝑟𝑠 𝑉
=
𝑑𝑝 ∆𝑡𝑟𝑠 𝑆
1) The solid–liquid boundary

 Melting (fusion) is accompanied by a molar enthalpy change

ΔfusH, and if it occurs at a temperature T the molar entropy
Δ 𝐻
of melting (∆𝑓𝑢𝑠 𝑆) is 𝑓𝑢𝑠
𝑇
;

all points on the phase boundary correspond to equilibrium,

so T is in fact a transition temperature, Ttrs.

 The Clapeyron equation for this phase transition then

becomes
𝑑𝑝 ∆𝑓𝑢𝑠 𝐻
=
𝑑𝑇 𝑇∆𝑓𝑢𝑠 𝑉

where ΔfusV is the change in molar volume that accompanies

melting.
2) The liquid–vapour boundary
Δ𝑣𝑎𝑝𝐻
 The entropy of vaporization at a temperature T is equal to
𝑇
(as before, all points on the phase boundary correspond to
equilibrium, so T is a transition temperature, Ttrs),

 The Clapeyron equation for the liquid–vapour boundary can therefore

be written:

𝑑𝑝 ∆𝑣𝑎𝑝 𝐻
=
𝑑𝑇 𝑇∆𝑣𝑎𝑝 𝑉
2) The liquid–vapour boundary

 Because the molar volume of a gas is so much greater than the molar
volume of a liquid, ΔvapV ≈ Vm(g).
 Moreover, if the gas behaves perfectly, Vm(g) = RT/p
 These two approximations turn the exact Clapeyron equation into

𝑑𝑝 ∆𝑣𝑎𝑝 𝐻
= 𝑑𝑝 𝑝∆𝑣𝑎𝑝 𝐻
𝑑𝑇 𝑇 𝑅𝑇 =
𝑝 𝑑𝑇 𝑅𝑇 2

 By using dx/x = d ln x, this expression can be rearranged into the

Clausius–Clapeyron equation for the variation of vapour pressure
with temperature:
𝑑 ln 𝑝 ∆𝑣𝑎𝑝 𝐻 𝑝1 ∆𝑣𝑎𝑝 𝐻 1 1 𝑝1 ∆𝑣𝑎𝑝 𝐻 1 1
= ln = − − ln = −
𝑑𝑇 𝑅𝑇 2 𝑝2 𝑅 𝑇1 𝑇2 𝑝2 𝑅 𝑇2 𝑇1
3) The solid–vapour boundary

 The only difference between the solid−vapour and the

liquid−vapour boundary is the replacement of the enthalpy
of vaporization (ΔvapH) by the enthalpy of sublimation, ΔsubH.

𝑝2 ∆𝑠𝑢𝑏 𝐻 1 1
ln = −
𝑝1 𝑅 𝑇2 𝑇1

 Because the enthalpy of sublimation is greater than the

enthalpy of vaporization at similar temperatures
(ΔsubH > ΔvapH ) the equation predicts a steeper slope for the
sublimation curve than for the vaporization curve.
(recall that ΔsubH = ΔfusH + ΔvapH)

 These two boundaries meet at the triple point

 Phase Equilibria

Phase Rule

What we learn today?

One-component
Phase Diagrams

Thermodynamic
aspects of phase
transitions