Block 1 Solutions and Phase Equilibrium

UNIT 3
Phase Equilibrium-I

Structure
3.1 Introduction  versus T curves

Expected Learning Outcomes Pressure dependence of  versus

3.2 Basic Terminology T curves

True, Metastable and Unstable

3.6 Clapeyron and Clausius-
Equilibrium
Clapeyron Equations
Clapeyron Equation
Phases
Clausius-Clapeyron Equation
Components
Degrees of Freedom What is a phase diagram?

3.3 Criterion for Phase Equilibrium 3.7 Summary

3.4 Gibbs Phase Rule 3.8 Terminal Questions

Deducing Gibbs Phase Rule

3.9 Answer

3.5 Stability of The Phases of a

Pure Substance

3.1 INTRODUCTION
In the Course BCHCT-133 you have learnt in detail about energetics; chemical
equilibrium and ionic equilibrium and are familiar with the meaning and
importance of equilibrium studies. Further, in the first two units of this block
you have learnt about solutions. In all these, you have learnt primarily about
the characteristics of the systems that are homogeneous, that is, the systems
in which the properties of the system are uniform throughout. You have also
come across cases of heterogeneous equilibrium like vapourisation,
sublimation, fusion, phase transformation, distribution of solutes between
phases etc. In these cases, we used different rules (laws) suitable for the
systems to understand them.

In this and the next unit we would take up equilibrium in heterogeneous

systems in a unified manner by using phase rule that applies to all kinds of
heterogeneous equilibria. The phase rule serves to identify and fix the number
of variables for a heterogeneous system. A study of phase equilibrium is
important in various domains like, chemistry, physics, metallurgy, chemical
56 engineering, material science and geology etc.
Unit 3 Phase Equilibrium-I
We will begin the unit by defining and explaining the terms such as true,
metastable, and unstable equilibrium; phase, component, degrees of freedom;
and phase transition. Thereafter, we would take up the criterion for phase
equilibrium followed by the deduction of Gibbs phase rule. Then, we would
discuss about the stability of different phases of a pure substance in terms of
chemical potential (  ). In this context we would explain the nature of  versus
T curves and their pressure dependence. This will be followed by the
derivation of Clapeyron and Clausius-Clapeyron equations and a discussion
on their importance in phase equilibria. In the next unit, we would take up the
applications of phase rule to one and two component systems.

Expected Learning Outcomes

After studying this unit, you should be able to:

❖ define and differentiate between true and metastable equilibrium;

❖ define and explain the terms like, phase, component, and degrees of
freedom in the context of phase equilibrium using suitable examples;

❖ calculate the number of phases, components and degrees of freedom

for a given heterogeneous system;

❖ state and explain the criterion for phase equilibrium in a heterogenous

system;

❖ define phase transition and describe the changes occurring during

different phase transitions;

❖ state phase rule; deduce the same and outline its significance;

❖ explain the stability of different phases of a pure substance in terms of

 versus T curves;

❖ explain the effect of pressure on the  versus T curves for a pure

substance; and

❖ derive Clapeyron and Clausius-Clapeyron equations and apply them to

heterogeneous systems in equilibrium.

3.2 BASIC TERMINOLOGY

You have learnt about the nature and characteristics of chemical and ionic
equilibria in the course BCHCT-133. However, in case of phase equilibrium
there are certain new terms, which need to be understood before taking up A true equilibrium is
phase rule and its application to phase equilibrium. achieved when the
Gibbs energy of the
3.2.1 True, Metastable and Unstable Equilibrium system is at a
minimum for the
In your earlier studies in the context of chemical equilibrium you have learnt given set of variables
equilibrium to be a state of apparent no change in the concentration of operating on the
system.
different species as a function of time. If the state of equilibrium can be
achieved from either direction, i.e., from the reactants or from the products
then, it is referred to as true equilibrium. For example, we can have a 57
Block 1 Solutions and Phase Equilibrium

system containing ice and water to be at equilibrium at 0oC and 1 atm. This
equilibrium can be achieved either by heating a sample of ice to partially melt
it to give some water or by cooling a sample of water to partially freeze it to
give some ice. Similarly, we can establish equilibrium between a liquid and its
vapours in a closed system either by heating the liquid or by partially
condensing the vapours by cooling. Thermodynamically speaking, in such
cases the Gibbs energy of the system is at its minimum when the system is at
the equilibrium.

Let’s take another example say we take a sample of clean water that is free of
dust in a smooth container and cool it slowly without any disturbance. What do
we expect? We expect that as the temperature approaches 0°C, the freezing
point of water then water would freeze. However, it is possible that the water
does not freeze, and the temperature continues to decrease and goes below
0°C and the water stays to be in the liquid state even at - 5  C . Now, if we
leave the water at - 5  C undisturbed then it can continue to stay to be in liquid
state at - 5  C . Now, since we do not observe any change can we say that we
have got the system at equilibrium. The answer is no; let us see why?

If we disturb the water at - 5  C by shaking it a bit or by stirring it or by adding a

small crystal of ice to it (i.e., we do seeding), we observe that the water at
- 5  C immediately freezes and the temperature increases to 0°C. Now, if we
take a sample of ice at say - 20 C and warm it gradually, we find that we do
not get water when the temperature becomes - 5  C ; the ice melts only when
the temperature becomes 0°C. What do we conclude from this example? We
conclude that water at - 5  C is not in a state of true equilibrium because we
could obtain it only in one direction by gradually cooling water but not by
warming ice at a lower temperature. The liquid water at - 5  C is called super
cooled water and such equilibrium that can be obtained only from one
direction is called metastable equilibrium.

Let us take another system in which we dissolve just sufficient amount of

sodium chloride in water to prepare a nearly saturated solution such that there
are a few crystals of sodium chloride along with the solution. If we observe the
system for some time, we find no change-the crystals stay along with the
A state of unstable
solution. Since we do not observe any change, can we say that the system in
equilibrium exists
when the approach to
state of equilibrium? To find answer to this, we need to leave such a system
equilibrium in a for long time, say overnight. We may be surprised to note that the crystals of
system is so slow that sodium chloride have disappeared (dissolved). In such a case since initially we
the system appears observed the system for an insufficient time it appeared to be in equilibrium
to undergo no change (apparent no change) however, the process of dissolution of salt to achieve
over a short period of true saturation was slow and was still continuing. Such a system may be
time. termed as unstable equilibrium or non-equilibrium. In fact, it does not
involve any equilibrium at all, it is just a case of very slow process.

3.2.2 Phases (P)

The word phase is derived from the Greek meaning "appearance”. Gibbs
defined a phase as a homogenous system that is "uniform throughout, not only
in chemical composition, but also in physical state". Alternatively, a phase may
be seen as “a homogeneous, physically distinct, and mechanically separable
58 portion of a system”. Mechanically separable here means that each phase can
Unit 3 Phase Equilibrium-I

be separated from every other phase of the system by mechanical means of

separation like, filtration, sedimentation, decantation etc. Further, a phase is
separated from other homogeneous parts of the system by boundary surfaces.
In phase rule, which we would take up a little later a phase, is denoted as P.
Let us take some examples to understand the term, phase.

• A mixture of gases say air is a single phase as all gases mix in all
proportions and are not separable by mechanical means as given above.
However, one must remember that the gases in the mixture should not
react with one another for it to be a one-phase system. For example, if
we mix unequal amounts of NH 3 and HCl gas then the two would react
to form solid ammonium chloride that would settle down and some of the
gas (in excess) would also remain. Thus, there would be two phases;
solid phase (ammonium chloride) and gaseous phase (the gas in
excess).

• Any true solution by definition is a homogeneous mixture of two or more

substances irrespective of their physical state (solid/liquid/gas) or their
relative amounts in the mixture. A dilute solution of sodium chloride in
water or a mixture of alcohol and water that form true solutions are
examples of one-phase systems. We cannot separate the constituents of
a true solution by mechanical means. Thus, a true solution is a single
phase.

• Just breaking the system into smaller parts does not form new phases. A
large block of ice or crushed ice; both are examples of one phase
systems.

• A system may consist of a number of solid or liquid phases but can have
only one gaseous phase. For example, two or more miscible liquids
constitute a single phase. However, if one or more of these liquids are
volatile then their vapours in equilibrium also constitute a phase. For
example, a system containing a mixture of alcohol and water in
equilibrium with their vapours will be a two-phase system; one liquid
phase and one vapour (or gas phase). Thus, two miscible liquids in
equilibrium with their vapours constitute a two-phase system.

• An aqueous solution of sodium chloride (or any other soluble substance)

is a one-phase system as it is a true solution. However, a saturated
solution of sodium chloride in contact with excess solid sodium chloride
forms two-phase system.

• Mixtures of two allotropes say monoclinic and rhombic sulphur

constitutes two phases because a phase must have the same physical
and chemical properties. Two allotropes are chemically identical but
differ in their physical properties.

• A heterogeneous mixture of different solid substances would have as

many phases as there are substances present in the system. However, if
we have a mixture of two solids and a solid solution is formed between
them then it becomes a one-phase system, as a solid solution is
homogeneous. 59
Block 1 Solutions and Phase Equilibrium

3.2.3 Components (C)

The concept of phases in a system is relatively straightforward but the idea of
components in the context of phase equilibrium (also phase rule) is a little
involved. The number of components of a system can be defined as, “the
It is immaterial which
smallest number of independently variable chemical constituents of the system
of the constituents
are chosen as in terms of which composition of each phase in equilibrium can be completely
components; it is their defined either directly or in the form of an equation”. It is important to note the
number that is distinction between the components and constituents. The components are
important. not same as constituents of the system i.e., the elements or compounds
present in the system. Alternatively, we can say components are those
chemically distinct constituents whose concentrations may be independently
varied in the various phases of the system.

The requirement of smallest number is crucial in this definition. If the

concentrations of the chosen components are stated for each phase, then the
concentrations of any and all substances present in each phase of the system
are uniquely fixed. Let us understand it with the help of some examples of
different types of systems. We begin with systems where constituents do not
All the constituents
react.
need not be
components, but all
a) Systems in which the constituents do not react
the components must
be the constituents in • Let’s take one of very simple systems in which ice, water and water
the system.
vapours are in equilibrium. In this case there are three phases viz., solid,
liquid and gas however, the composition of each phase can be expressed
in terms of only one component viz., water. You may note here that in this
system there is only one constituent so the components have to be one; it
can’t be lesser (you cannot have zero components) or greater (a
component has to be a constituent of the system and we have only one
constituent here). You may note here that hydrogen and oxygen, the
constituents of water, are not to be regarded as components. It is so
because, they are not present in the system as such, but they are
combined in definite proportions to form water, and their amounts cannot
be varied independently.

• In a system containing sugar and water there are two possibilities. First, if
the solution is unsaturated it will be a homogeneous system i.e., it will have
only one phase. It has two constituents, sugar and water and we need to
specify both of them to express the composition of the solution as

x Sugar + y H2O

i.e., the number of components is two. Secondly, if the amount of sugar in

the system is more than its solubility in given amount of water then the
system would become a heterogeneous system having two phases:
homogeneous sugar solution and undissolved sugar. Here again, we
would need two components to specify the composition of each phase as

Aqueous phase: x Sugar + y H2O

Solid phase: Sugar + 0 H2O
60
Unit 3 Phase Equilibrium-I
Thus, it is a two-component system. In general, we can say that in systems
where the constituents do not react, the number of components is equal to the
number of constituents.

b) Systems in which constituents undergo chemical reaction

In such cases the number of components, C is given as C = C − R ; where C 

is the number of constituents in the system and R is the number of reactions
actually taking place in the system or the restrictions (or constraints) on
independent variability of the concentration of the constituents. Let’s take
some examples to understand it.

• Thermal decomposition of calcium carbonate as given below

CaCO 3 ⇌ CaO + CO 2

In this case there are three distinct constituents viz., calcium carbonate,
calcium oxide and carbon dioxide between which the equilibrium exists. An aqueous solution
However, all of these are not to be taken as the components, as they are of sodium chloride
not mutually independent, there is one restriction on their concentration to contains three
be varied independently. This restriction happens to be the equilibrium species (constituents)
constant because of which if we specify the concentrations of any two of i.e., water,
Na+ ions, and
the constituents, that of the third automatically gets fixed. Therefore, the
Cl− ions. Now since
number of components in this case would be; C = 3 − 1 = 2 . That is, it is a
the number of Na+
two-component system. Now, the question comes up is that which of the ions, and Cl− ions
three constituents of the system are the components? In principle, the must be equal (it is a
choice of components of the system out of the constituents is arbitrary i.e., constraint) the
we can choose any two constituents. However, in this particular case the number of
choice makes a difference let’s see how? components would be
C = 3 −1= 2
If we choose CaCO3 and CaO as the components; then the composition of
each phase can be expressed by the following equations:

Phase Composition in terms of

components
CaCO3 = CaCO3 + 0 CaO
CaO = 0 CaCO3 + CaO
CO 2 = CaCO3 − CaO

You may note here that we have used both zero and negative quantities
of the components to express the composition of different phases as
equations. We will get similar equations if we choose CaCO3 and CO2 as
the components.
Phase Composition in terms
of components
CaCO3 = CaCO3 + 0 CO 2
CaO = CaCO3 − CO 2
CO 2 = 0 CaCO3 + CO 2

However, if we choose CaO and CO2 as the components then the use of
negative quantities can be avoided as shown below.
61
Block 1 Solutions and Phase Equilibrium

Phase Composition in terms of

components
CaCO3 = CaO + CO 2

CaO = CaO + 0 CO 2

CO 2 = 0 CaO + CO 2

Therefore, as a matter of convention, in this case we use CaO and CO 2 as

the components for the system though other two choices are also correct.

• Let us consider sublimation of ammonium chloride as the next example of

the type of systems where the constituents can react. We know that on
sublimation, ammonium chloride decomposes into ammonia gas and HCl
gas and an equilibrium exists as given below.
NH 4 Cl(s ) ⇌ NH 3 (g) + HCl (g)

In this case there are three constituents in the system viz., solid
ammonium chloride, ammonia gas and HCl gas. Further, there are two
restrictions also; first of these restrictions is the equilibrium constant (as in
case of decomposition of calcium carbonate) and the second restriction
being the requirement that the concentrations of ammonia gas and HCl
gas must be equal. This is so because the decomposition of NH 4 Cl(s )
gives a molecule each of NH 3 (g) and HCl (g) .

[NH3(g)] = [HCl(g)]
therefore, the number of components in this case would C = 3 − 2 = 1That
is, it is a one-component system.
If at equilibrium, ‘a’ moles of NH 4 Cl(s ) has decomposed then the amounts
of NH 3 (g) and HCl (g) in the gas phase would be ‘a’ moles each. The
composition of the two phases can be expressed in terms of NH 4 Cl(s ) as
follows

Phase Constituents Composition in terms

of components
Gas NH a (g) + HCl (g) = a NH 4 Cl

Solid NH 4 Cl = NH 4 Cl
* in equal amounts (‘a’ moles each)

However, you should remember that this is true only if NH 3 (g) and HCl (g)
are produced from the sublimation of NH 4 Cl(s ) only. In case we add some
NH 3 (g) (or HCl (g) ) from outside, the equilibrium gets disturbed; the
amounts of NH 3 (g) and HCl (g) are no more equal (i.e., the second
restriction is lifted) and it becomes a two-component system

C = 3 −1= 2

To understand it, let us say we begin with solid NH 4 Cl(s ) , on sublimation a

part of it gets decomposed to give equal amounts of NH 3 (g) and HCl (g)
62
Unit 3 Phase Equilibrium-I
and an equilibrium is established. Now, if we add some HCl (g) from
outside to this system at equilibrium, this will suppress the equilibrium.
Some HCl (g) molecules will combine with NH 3 (g) molecules to give back
some solid NH 4 Cl(s ) and a new equilibrium would set up. If we assume
that at this stage effectively ‘a’ moles of NH 4 Cl(s ) have decomposed, then
in the gas phase the amounts of NH 3 (g) and HCl (g) would be ‘a’ moles
and ‘(a+b)’ moles respectively, where ‘b’ is the number of moles of HCl (g)
added from outside. The equilibrium and equilibrium concentrations of
different species can be represented as

Components NH 4 Cl(s ) + HCl (g) ⇌ NH 3 (g) + HCl (g)

Conc. (in moles) a (a+ b)

The composition of the two phases now would be expressed as follows

Phase Constituents Composition in terms of

components

Gas NH 3 (g) + HCl (g) = a NH 4 Cl + b HCl

Solid NH 4 Cl(s ) = NH 4 Cl + 0 HCl

* in unequal amounts (‘a’ moles and (a+b) moles respectively)

In case we had added ammonia instead of HCl (g) to the system then
again it would have been a two-component system and the components
would be NH 4 Cl(s ) and NH 3 (g) .

• Let us take a system obtained by mixing ethanol and acetic acid and
allowing it to react. How many components are there in the system? Let’s
analyse. You know from your earlier studies that ethanol and acetic acid
would react to give ethyl acetate and water. The following equilibrium
would exist.
CH3 COOH + C 2H5 OH ⇌ CH3 COOC 2H5 + H2 O

We see that the system would have four constituents and there is one
restriction due to equilibrium. We may promptly say that the number of
components to be C = 4 − 1 = 3. However, there is one more restriction i.e.,
the amounts of ethyl acetate and water formed in the reaction would be Degrees of freedom
equal and the number of components would be C = 4 − 2 = 2. “the smallest number
of independent
3.2.4 Degrees of Freedom (F) variables such as
temperature, pressure,
A system is said to be defined completely if we specify different variables of
composition etc. which
the system such that the system retains the same state of equilibrium.
must be fixed in order
Alternatively, we can say that same state of equilibrium in the given system
to completely define
can be reproduced using the specified variables. The variables used to define
the state of the system
the system are chosen from the state functions of the system, such as
at equilibrium”.
pressure, temperature, volume, energy, entropy, and the concentrations of the
various components in different phases. However, we do not need to specify
all of these variables as specifying some of these variables, automatically
determines the values of the other variables. However, there is a minimum
number of variables that need to be specified and this number is called the 63
Block 1 Solutions and Phase Equilibrium

degrees of freedom or variance of the system and is denoted as F. So, we

can define the number of degrees of freedom as, “the smallest number of
independent variables such as temperature, pressure, composition etc. which
must be specified (fixed) in order to completely define the state of the system
at equilibrium”. In the context of phase equilibrium, we consider only three
variables viz., pressure, temperature and the concentration.

In an alternative definition the number of degrees of freedom can be defined

as, “the number of intensive variables that can be varied independently without
changing the number of phases present in the system”. Let’s take some
examples to understand the meaning of degrees of freedom.

• If the system consists of a certain amount of a pure gas, its state can be
specified completely by using any two of the variables viz., pressure,
temperature, and the volume. This is so because if any two of these are
known, the third can be calculated from gas equation. We say that the
system has two degrees of freedom, or the system is bivariant.
Degrees of freedom
• In the system having equilibrium between water and water vapor, at any
“the number of given temperature, the pressure of vapor in equilibrium with liquid water
intensive variables that i.e., its vapour pressure is fixed in value. So, we need to specify only one
can be varied variable say temperature to determine the state of the system. Thus, the
independently without system has only one degree of freedom, or is said to be univariant.
changing the number
• Going further, if we take a system in which ice, water and water vapour
of phases present in
are in equilibrium. It happens precisely at a temperature of 0.0075oC and
the system”
pressure of 4 mm of Hg. Any change in pressure, temperature or
concentration will destroy the equilibrium and generally two of the
phases will be lost. This implies that we cannot change any of the
variables i.e., the degree of freedom (F) is zero i.e., the system is
invariant.

Having learnt about the basic terminology for studying phase equilibrium why
don’t you solve the following simple questions to assess your understanding.

SAQ 1
Calcium carbonate on heating in a closed vessel decomposes as per the
following equation. How many phases are there in the system?

CaCO3 (s ) ⇌ CaO(s) + CO 2 (g )

SAQ 2
Calculate the number of components in a system containing a mixture of
PCl 5 (s ) , PCl 3 (g) and Cl 2 (g) . Consider that the following equilibrium exists in
the system
PCl 5 (s ) ⇌ PCl 3 (g) + Cl 2 (g)
64
Unit 3 Phase Equilibrium-I

SAQ 3
A certain amount of solid ammonium chloride was heated in a closed
container where it undergoes sublimation. In the vapour phase ammonium
chloride decomposes to give NH 3 (g) and HCl(g) .The following equilibrium is
established.
NH 4Cl(s ) ⇌ NH 3 (g) + HCl(g)

To this system at equilibrium, ‘b’ moles of ammonia was added. Once the
equilibrium was reestablished, ‘a’ moles of ammonium chloride had sublimed.
Express the system in the form of equation and express the composition of the
phases in terms of the components.

SAQ 4
What is the number of degrees of freedom of the system containing a solid
substance and its vapour in equilibrium?

3.3 CRITERION FOR PHASE EQUILIBRIUM

In order to have different phases in a heterogenous system to be in equilibrium
they must meet the requirements of thermal, mechanical and chemical
equilibrium. Let’s outline the requirements for these equilibria so as to
establish criterion for phase equilibrium. You are aware that two systems are
said to be in thermal equilibrium if they are at same temperature. If different
phases are not in thermal equilibrium, then there will be heat flow from one
phase to another. Further, for mechanical equilibrium the pressure of all the
phases should be the same else one phase would increase in volume at the
expense of the other.

The criterion of chemical equilibrium can be expressed in terms of equality of

chemical potential of various components in different phases. In order to
establish this criterion, let us recall that for a process to be spontaneous it
must be accompanied by a decrease in Gibbs energy and for any infinitesimal
change at equilibrium, the Gibbs energy change, dG should be zero. You
would also recall from Unit 4 of BCHCT-133 course that Chemical potential of
species i in a system, is the rate of change of Gibbs energy of the system with
the number of moles of the component i when the temperature, pressure and
the number of moles of all other components is kept constant i.e.,

 G 
μ i =   …(3.1)
  ni T,P,n j

Further, the molecules of a component spontaneously move from regions of

high chemical potential to the regions of low chemical potential in a mixture.
This continues till the chemical potential of the component becomes same
throughout the system. In other words, the chemical potential of the
component should be the same in and throughout every phase present in the
system for them to be in equilibrium. Thus, we can summarise the 65
Block 1 Solutions and Phase Equilibrium

requirements for equilibrium for say component 1 between two phases (say
phase  and ) in a system as

Equilibrium Criterion
Thermal equilibrium T = T

Mechanical equilibrium p = p

Chemical equilibrium 1( ) = 1(  )

Thus, we can conclude that for a heterogeneous system at constant pressure

and temperature the criterion for phase equilibrium is that “chemical potential
of all the components is same in and throughout every phase present in the
system”.

3.4 GIBBS PHASE RULE

Josiah Willard Gibbs established in 1876 that there is a definite relationship
between the number of degrees of freedom, the number of components, and the
number of phases present in a heterogeneous system at equilibrium. This
relationship is known as the Gibbs phase rule or just as the Phase rule and
states that, “if the equilibrium of a heterogeneous system is not affected by
electrical or magnetic forces or by gravity then the degrees of freedom (F),
Josiah Willard Gibbs
number of components (C) and number of phases (P) are connected by means of
the equation,

F =C −P + 2 …(3.2)

Later, Ostwald, Roozeboom, van't Hoff, and others worked extensively and
demonstrated how this highly generalised rule could be utilized in the study of
problems in heterogeneous equilibrium. Further, it is important to note that the
validity of phase rule is not dependent on any model of atomic or molecular
structure. Our understanding of atomic and molecular structure has changed
drastically in the twentieth century, but the phase rule has withstood the test of
time. There has not been any exception or modification to the rule. However,
there is one disadvantage with the phase rule that it does not give quantitative
information about the equilibrium. It just fixes the number of variables involved
in the equilibrium. The quantitative relationships between the variables are
established through equations like Clausius - Clapeyron equation about which
you would learn in the next section. For now, let’s deduce Gibbs phase rule by
calculating the degrees of freedom of a heterogeneous system consisting of C
components present in P phases.

3.4.1 Deducing Gibbs Phase Rule

Let’s take a heterogeneous system in which C components exist in P phases.
We need to calculate the degrees of freedom for such a system to deduce
Gibbs phase rule.

As discussed above, the degrees of freedom of a heterogeneous system in

66 equilibrium refers to the number of independent variables that are required to
Unit 3 Phase Equilibrium-I
completely define the state of the system. This number equals the total
number of variables for the system minus the number of variables that are
fixed by virtue of the system being in equilibrium. That is,

F = (Total number of variables)−(Number of variables fixed due to equilibrium)

Let’s first calculate the total number of variables of the system.

As the state of all the systems depend on the temperature and the pressure,
so every system would have p and T as variables.

Next, we need to calculate the concentration variable for all the phases. For
this we assume that each phase has all the C components.

Now, for a given phase the composition can be defined by specifying the Sum of mole fractions
concentrations (mole fractions) of C − 1components; the concentration of the of all the components
remaining component would be known by difference. Thus, for one phase is equal to 1.
there will be C − 1concentration variables.

For P phases the number of concentration variables would be P (C − 1)

The total number of variables for the system would be P (C − 1) + 2 …(3.3)

Now, let us calculate the number of restrictions on the system. As discussed

above, condition of equilibrium requires that the chemical potentials of each
component should be the same in every phase. For a given component 1 to
be in equilibrium in two phases ( and ) the following must be true (i.e., a
restriction)

1( ) = 1(  ) …(3.4)

Similarly, for component 1 to be in equilibrium in three phases (  and ) the

requirement is
1( ) = 1(  ) and 1( ) = 1( ) …(3.5)

Thus, we see that the equilibrium of a given component between two phases
puts one restriction and for three phases we have two restrictions. Therefore,
for P phases we would have P − 1 restrictions. This is for one component. For
C components the number of restrictions would become C(P − 1) .

=> Total number of restrictions imposed by equilibrium= C(P − 1) …(3.6)

Thus, the degrees of freedom for the system would be:

F = (Total number of variables) – (number of variables fixed due to equilibria)

Substituting from Eq. (3.3) and Eq. (3.6)

F = [P (C − 1) + 2] − [C (P − 1)] …(3.7)

Simplifying, we get
F = [PC − P + 2] − [CP − C ] = C − P + 2

F = C −P +2 or P + F =C + 2 …(3.8)

This is the desired expression for the Gibbs phase rule. 67

Block 1 Solutions and Phase Equilibrium

In our arguments we have assumed that each component is present in all the
phases. However, if some component is missing from a given phase, then
what will happen? Will the equation change? The answer is NO. In such a
case the number of concentration variables would decrease by one. At the
same time, the number of restrictions would also decrease by one and our
phase rule equation would remain the same. This means that the phase rule is
generally valid under all conditions of distribution of components provided that
equilibrium exists in the system. Having learnt about the meaning of
equilibrium in heterogeneous systems and the Gibbs phase rule answer the
following simple question to assess your understanding.

SAQ 5
Give the criteria for phase equilibrium in a one-component system containing
three phases in equilibrium at constant temperature and pressure.

3.5 STABILITY OF THE PHASES OF A PURE

SUBSTANCE
As discussed above, for a heterogeneous system in equilibrium the chemical
potential (  ) of each component must be the same in every phase in which
that component appears. For one component system we can say that Gibbs
𝐺
energy per mole or molar Gibbs energy, 𝐺𝑚 = 𝑛 . Further, you would recall
As the entropy
from thermodynamics that for small change in Gibbs energy we could write
increases with
increasing dG = − S dT + V dp …(3.9)
temperature, the 
versus T curves Dividing throughout by n (number of moles) we get
should be slightly
concave downwards. dGm = dμ = - S m dT + Vm dp …(3.10)
However, these are
approximated as where, Sm and Vm are the molar entropy and molar volume, respectively. We
straight lines for
can write
simplicity.
     
  = −Sm and   = Vm …(3.11)
 T  p  p T

The derivatives in Eq. (3.11) give the slopes of the  versus T and  versus
p curves, respectively. Let us take up the  versus T curves first.

3.5.1  versus T curves

You would recall from the third law of thermodynamics, that the entropy of a
substance is always positive which means that the slope of  versus T curve
will be negative. For the three phases of a single substance we can write

 solid 
  = −Sm (solid) …(3.12)
 T  p

  liquid 
  = −Sm (liquid) …(3.13)
68  T p
Unit 3 Phase Equilibrium-I
  gas 
  = −Sm (gas) …(3.14)
 T p

Further, you know that

Sm (gas)  Sm (gas)  Sm (gas) …(3.13)

(a) (b)
Fig. 3.1: Chemical potential versus temperature curves for a substance in
different phases and (b) overall nature of the curve

This means that the slope of  versus T curve for gas phase would be more
negative (i.e., the chemical potential will fall more sharply with increase in
temperature) than that for liquid phase, which in turn would be more negative
than that for the solid phase as shown in Fig. 3.1.

You would once again recall from thermodynamics that any system At a given
spontaneously goes from higher chemical potential to a lower chemical temperature the
potential where it is more stable. In other words, at a given temperature that phase with the lowest
phase of the substance would be stable which has lower chemical potential. If value of the chemical
we see the  versus T curve at temperature T1 marked on Fig 3.1 (a) we find potential is the stable
that here solid phase would be more stable. Similarly, at temperature T 2 liquid phase.

phase would be more stable. Suppose we take a liquid at a temperature T1 it

would spontaneously freeze as it is accompanied by a decrease in Gibbs
energy. Similarly, a solid at temperature T 2 would spontaneously melt.

Now if we take the system at temperature T1 i.e., in solid phase and increase
its temperature we can see from the figure that its chemical potential would
decrease. You can note that for liquid phase (if it could exist at this
temperature) the decrease in chemical potential is steeper. At a certain
temperature the  versus T curves for solid phase and liquid phase would
intersect. At this temperature the chemical potentials of the solid phase and
the liquid phase would be equal i.e., they will be in equilibrium. In other words,
the solid and liquid phase can coexist. This temperature is called the melting
point of the solid. Similarly, if we increase the temperature of the system
initially at temperature T 2 (i.e., in liquid phase) at a certain temperature, the
liquid and gas phase can coexist in equilibrium, as their chemical potentials
are equal. This is the boiling point of the substance.
The overall nature of the  versus T curve for a pure substance is shown in
Fig. (3.1 (b)). There are two transitions, from solid to liquid and from liquid to 69
Block 1 Solutions and Phase Equilibrium

vapour. These are called phase transitions because the phase of the
substance gets changed here. You may observe that these phase transitions
at Tm and T b are accompanied by a change in slope of the curve. Such
transitions are called first order phase transitions. The phases on the two
sides of the transition temperature have different entropies. Such phase
transitions e.g., conversion of ice into water require latent heat for the
transition. This means that when these transitions occur, the heat is absorbed
but there is no observable temperature change. You would recall from your
earlier studies that the ratio of heat absorbed and the corresponding change in
temperature is called heat capacity. Since here the heat is being absorbed
but the temperature does not change, we can say that in a first order phase
transitions the heat capacity is infinitely large.

In some cases, for example in sudden appearance of superconductivity in

certain metals on cooling them to very low temperatures. The phase transition
(conducting to superconducting) does not require any latent heat. Such
transitions are called second order phase transitions and such transitions
are accompanied by finite heat capacity changes. Let us now take up the
pressure dependence of  versus T curves

3.5.2 Pressure Dependence of  Versus T Curves

We have discussed about the  versus T curves at constant pressure and
have observed phase transition at characteristic temperatures. Let’s now take
up pressure dependence of these curves and see how pressure change
affects these phase transitions. We can see from Eq. (3.11) that,
  
  = Vm …(3.14)
 p T

As the molar volume is always positive this means that at a given temperature
the chemical potential of the system would vary directly with pressure i.e., it
will decrease with a decrease in p . Further, the molar volume of a gas is much
more than that of the liquid, which is roughly equal or slightly more than that of
the solid. As a result, on decreasing the pressure on the system the value of
 for gas would decrease much more than that for the liquid whereas for solid
the value will decrease slightly. Schematic  versus T curves for the solid,
liquid and gaseous state of a substance at two different pressures are given in
the Fig. 3.2; the ones at lower pressure are indicated by the dotted lines.

On reducing the
pressure the range of
temperature over
which the liquid is the
stable phase gets
reduced.

Fig. 3.2: Chemical potential versus temperature curves for a substance in

70 different phases at pressure p1 (bold line) and p2 (p2 <p1) (dotted line).
Unit 3 Phase Equilibrium-I
You may note that at lower pressure the solid and liquid curves intersect at a
lower temperature i.e., the melting point decreases. Similarly, the curves for
gaseous state and the liquid state also intersect at lower temperature
indicating the decrease in the boiling point. We are familiar with this
observation that the boiling point decreases on decreasing the pressure. You
may note here, that the effect of pressure on the boiling point is much greater
than that on the melting point because the molar volume of gas is much more
than that of the liquid.

Now if we decrease the pressure sufficiently then it may so happen that at a

certain pressure the  versus T curves for the solid phase meets that of the
gas phase at a temperature lower than that at which it meets the liquid phase
curve; Fig 3.3 (a). This means that there will be equilibrium between solid and
the gas phase i.e., the solid would undergo sublimation.

Similarly, we may have a combination of temperature and pressure at which

the solid, liquid, and vapour curves intersect at a point i.e., the solid, liquid and
vapour phase coexist and are in equilibrium; Fig 3.3 (b). Such a combination
of temperature and pressure is called the triple point for the system. This
combination of p and T for a given system is unique; if any of these
parameters were changed some of the phases would disappear.

(a) (b)
Fig. 3.3: Schematic representation of chemical potential versus temperature
curves for a substance in different phases indicating a) sublimation
and b) triple point.

The phase rule that we deduced in section 3.4 gives qualitative information about
the relationship between the numbers of phases, components and degrees of
freedom for a system. We would elaborate more on it in the next unit when we
will discuss about the phase diagrams of different one and two component
systems. For now, we need to discuss about another important equation called
Clapeyron equation that provides information on the quantitative understanding
of phase equilibria. However, before that answer the following simple question to
assess your understanding of stability of different phases of a pure substance
and the factors involved.

SAQ 6
How would the increase in pressure affect the  versus T curves for a pure
substance? Draw a schematic diagram indicating the same.
71
Block 1 Solutions and Phase Equilibrium

3.6 CLAPEYRON and CLAUSIUS-CLAPEYRON

EQUATIONS
In our discussion on the variation of chemical potential with temperature
and the effect of pressure on the  versus T curves we have seen that the
chemical potential of a given system depends on temperature as well as
the pressure. The question comes up is ‘are the equilibrium temperature
and pressure of a system related?’ The answer is yes and such a
relationship was developed by French engineer Benoit-Paul-Émile
Benoit-Paul-Émile Clapeyron in 1834 and is known as Clapeyron equation. This was later
Clapeyron put on firm thermodynamic basis by Clausius therefore it is called
Clausius-Clapeyron equation. Let’s begin by deriving Clapeyron
equation.

3.6.1 Clapeyron Equation

Let us take a one-component system having two phases ( and ) in
equilibrium. As we know that for the two phases to be in equilibrium the
pressure, temperature and the chemical potential of the component in the two
phases should be equal. Under conditions of constant temperature and
pressure the chemical potential of two phases must be the same i.e.,

 (T , p) =   (T , p) …(3.15)

If we either change the temperature keeping the pressure constant, or change

the pressure keeping the temperature constant, one of the phases will
disappear. However, if we appropriately change both the pressure as well as
the temperature the two phases can be kept in equilibrium i.e., the two phases
would coexist. The Clapeyron equation essentially provides this dp dT
relationship. A pressure versus temperature plot along which the two phases
coexist is called coexistence curve as shown in Fig. (3.4)

Fig. 3.4: The simultaneous variation of pressure and temperature for one
component system gives coexistence curve. The chemical potential of
the two phases remains same along this curve.

Now, if we change the pressure from p to ( p + dp) the equilibrium temperature

72 will change from T to (T + dT ) . The corresponding chemical potentials would
Unit 3 Phase Equilibrium-I
be (  + d ) and (   + d  ) respectively. Therefore at ( p + dp) and
(T + dT ) the equilibrium condition would become

 (T , p) + d =   (T , p) + d  …(3.16)

On subtracting Eq. (3.15) from Eq. (3.16) we get the following expression,
(d = d  ) as  (T , p) =   (T , p) …(3.17)

Using Eq. (3.10) we can write

d = − Sm ( )dT + Vm ( )dp …(3.18)

d  = − Sm (  )dT + Vm (  )dp …(3.19)

Using Eq. (3.17) to Eq. (3.19) we get

− Sm( )dT + Vm( )dp = − Sm(  )dT + Vm(  )dp …(3.20)

Rearranging, we get

(Sm (  ) − Sm ( ) ) dT = (Vm(  ) − Vm( ) ) dp …(3.21)

dT Vm
SmdT = Vm dp  = …(3.22)
dp Sm

dp S m
or = …(3.23)
dT Vm

Eq. (3.22) and Eq. (3.23) are two variants of Clapeyron equation. It may be
that in these equations we have used molar quantities i.e., molar entropy and
molar volume. As these quantities are for the same substance, we can have
equivalent equations wherein these quantities are used per unit mass i.e.,
dp S dT V
= or = …(3.24)
dT V dp S

The significance of Clapeyron equation is that it

• gives the quantitative dependence of the equilibrium temperature on

pressure, and /or the variation in the equilibrium pressure with temperature.

• relates the ratio of the change in pressure to the change in temperature with
readily measurable quantities like molar volume and molar entropy change
for the process.

• can be used to generate schematic plots of the equilibrium pressure versus

temperature for different phase transformations like vaporization, fusion,
sublimation, or the transition between two allotropic forms of a pure
substance.

3.6.2 Clausius-Clapeyron Equation

German physicist Rudolf Julius Clausius simplified and expressed the
Clapeyron equation for vaporization and sublimation equilibria in a convenient
Rudolf Julius Clausius
approximate form. Let us take up the case of vapourisation equilibrium i.e.,
equilibrium between the liquid and vapour phase of substance A.
73
Block 1 Solutions and Phase Equilibrium
A (liquid) ⇌ A (vapour) …(3.25)

For such equilibrium we can write the Clapeyron equation as

dp  vapS
= …(3.26)
dT  vapV

As at the equilibrium temperature, the transformation is reversible we can

write,

 vapH
 vapS = …(3.27)
T
Where, vapH is the molar enthalpy of vaporisation and T is the equilibrium
temperature. Substituting in Eq. (3.26), the Clapeyron equation takes the form

dp  vapH
= …(3.28)
dT T vapV

Clausius made the following two assumptions

• the molar volume of the vapour is much larger than that for the liquid
phase,

• the vapour behave as ideal gas

In light of these assumptions we can write

vapVm (vap) = Vm (vap) − Vm ( l ) …(3.29)

and

RT
Vm(vap) = …(3.30)
p

Substituting these in Eq. (3. 28) we get,

dp  H pvapH m pvapH m
= vap m = = …(3.31
dT T Vm(vap) T .RT RT 2

dp pvapH m
 = …(3.32)
dT RT 2

Rearranging, we get

dp  H dT
 = d ln p = vap m2 …(3.32)
p RT

This is the Clausius-Clapeyron equation and can be rewritten as

vapHm dT
d ln p =  …(3.33)
R T2
Integrating Eq. (3.33) in the limits of p1 to p 2 and T1 to T 2 and assuming
vapHm to be constant in the range of temperature, we get
74
Unit 3 Phase Equilibrium-I
p2 vapHm T2 dT
 p1
d ln p =
R 
T1 T2
…(3.34)

Integrating
T
p  vapH m  1  2
In 2 = − T  …(3.35)
p1 R   T1

On applying limits

p2 vapH m 1 1
In =−  −  …(3.36)
p1 R T2 T1 

Simplifying

p2 vapH m 1 1
2.303 log =−  −  …(3.37)
p1 R T2 T1 

p2 vapH m T1 − T2 
2.303 log =−   …(3.38)
p1 R  T1 T2 

p2 vapH m T2 − T1 
2.303 log =   …(3.39)
p1 R  T1 T2 

This is the integrated form of the Clausius–Clapeyron equation for

vapourisation of a liquid and shows that the vapour pressure of a liquid
increases exponentially with increase in temperature. We can consider the
sublimation equilibrium also on exactly the same lines and obtain the
corresponding Clausius –Clapeyron equation for sublimation of a solid. The
equation would be as follows.

p2  subH m T2 − T1 
2.303 log =   …(3.40)
p1 R  T1 T2 

Where, 𝛥𝑠𝑢𝑏 𝐻𝑚 is the molar enthalpy of sublimation of the substance undergoing

sublimation. If we take indefinite integral of Eq. (3.33) i.e., without any limits we
get the following equation.
Δ v apH m
lnp = +C …(3.41)
RT

where C is the constant of integration. According to this equation, if we take the

molar enthalpy of vapourisation ( Δ v apHm ) to be constant then a plot between
Δ v apH m
lnp and 1/T would be a straight line with a negative slope equal to − .
R
Let us take an example to see an application of Clausius-Clapeyron equation.

Example 3.1: The vapour pressure of water is found to be 3167 pascals at 25o C
and 101325 pascals at 100o C. Calculate the enthalpy of
vaporisation for water.
Solution: We are given the following data 75
Block 1 Solutions and Phase Equilibrium
T1 = 298 K p1 = 3167Pa

T 2= 373 K p2 = 101325 Pa

We assume that the enthalpy of vaporisation, ΔvapHm is constant in this

temperature range and write the Clausius-Clapeyron equation as

p2 ΔvapHm T2 − T1 
2.303 log =  
p1 R  T1T2 

This can be rearranged to get vapHm as follows

 TT  p
ΔvapHm = 2.303 R  1 2  log 2
T2 −T1  p1

substituting the values

 373  298  101325

Δv apHm = 2.303  8.314J K −1 mol −1   K log
 75  3167

Δv apHm = 2.303  8.314 J K −1mol −1 [1482] K log 32

Simplifying, we get

=> Δ v apH m = 42.71 kJ mol -1

In the discussion above we have shown that the boiling point of a substance
depends on the pressure. Let us take an example to learn how does the
Clapeyron equation helps us in determining the magnitude of this effect.

Example 3.2: The normal boiling point of water at a pressure of 1.013025 bar
is 373.15 K. By what value would the boiling point change on
increasing the pressure by 1 pascal?

(Given: Δ v apH m = 40.69 kJ mol -1 ; molar volumes of steam and liquid water at
this temperature and pressure respectively are 30.199  10 −3 m3mol -1 and
0.019  10 −3 m3mol -1 .)
dp ΔvapHm
Solution: From Eq. (3.28) we know that =
dT T ΔvapVm

dT T ΔvapVm
Reversing both sides of the equation we get =
dp ΔvapHm

Using the given data, we calculate the value of vapVm

Δv apVm = (30.199 − 0.019)  10 -3 m3mol −1 = 30.180  10 -3 m3mol −1

Substituting the values in the expression we get

dT 373.15 K  30.180  10-3 m3 mol -1
=
dp 40,690 J mol -1

Simplifying we get
dT
= 2.768  10-4 K Pa −1
76 dp
Unit 3 Phase Equilibrium-I
-4
This implies that the boiling point decreases by 2.768  10 K per Pa change in
the pressure.

3.6.3 What is a Phase Diagram?

You have learnt above that the stability of different phases of a given system
consisting of a pure substance depends on the physical variables of the
system. Further, you have also learnt about relationships between the
pressure and temperature for heterogeneous systems in terms of Clapeyron
and Clausius-Clapeyron equations and their significance. A phase diagram is
basically a graphical representation of the number of phases that exist at a
given set of values of pressure and temperature for a system of a pure
substance. Although we can use any two of the macroscopic variables viz.,
pressure, temperature and volume to construct a phase diagram, generally
pressure and temperature are used.

A typical phase diagram consists of regions, lines (or curves) and points. The
regions are that part of the phase diagram where the pressure as well as the
temperature can be varied. The lines in the phase diagram represent the
coexistence curves of two phases and permit variation of any one of the
physical properties ( p or T ). The points on the other hand have unique
values of p and T , and none of these can be varied. These can be explained
by applying phase rule. A schematic representation of the typical phase
diagram of one component system is given in the margin. We will take up the
application of phase rule to one and two component systems in the next unit.

For now, let us sum up what all we have discussed in this unit. However, before
that assess your learning by solving the following simple question

SAQ 7
The normal boiling temperature of ethanol is found to 78.4oC. If the molar
enthalpy of vaporization for ethanol is 40.5 kJ mol−1 calculate the vapour
pressure of ethanol at 50.0 C .

3.7 SUMMARY
In this introductory unit on phase equilibrium we have taken up the basic
aspects of equilibrium in heterogeneous systems and have laid down the
requisite foundation to take up application of phase rule in understanding
heterogeneous equilibria in different one and two-component systems. We
began the unit by discussing different types of equilibria encountered in
heterogeneous systems. In this context we defined and differentiated between
true, metastable and unstable equilibria. A true equilibrium can be achieved
either from forward or from the reverse direction whereas a metastable
equilibrium can be obtained only in one of the directions. On the other hand,
the unstable equilibrium is apparently observed due to a shorter span of
observation though the system is not at equilibrium.
77
Block 1 Solutions and Phase Equilibrium

The discussion on different types of equilibrium was followed by a detailed

account of terms like, phase, components, and degrees of freedom. These
terms have been defined explicitly and clarified using a wide range of
examples for each term. Then we laid down the criteria for the existence of
equilibrium in heterogeneous systems. A system must be in thermal,
mechanical, and chemical equilibria. For this the temperature, pressure and
the chemical potential need to be same throughout the system. Thereafter we
stated and deduced the Gibb’s phase rule by inductive reasoning. The next
issue we took up was the stability of different phases of a substance. It was
stated that at a given temperature the phase with lower value of chemical
potential is the stable phase. If a given system at a given temperature is in a
phase having higher value of chemical potential, then it would spontaneously
change over to the phase with lower chemical potential. In this context we
discussed and clarified the concepts of melting point, and boiling point in terms
of  versus T curves. A discussion on the effect of pressure on  versus T
curves provided an insight into decrease in melting point and boiling points on
decreasing the pressure and also the conditions for sublimation and
observance of triple point.

This was followed by discussion on two important equations viz., the

Clapeyron and Clausius-Clapeyron equation. In this context the equations
were derived and their application to heterogeneous systems was explained
with the help of examples.

3.8 TERMINAL QUESTIONS

1. How many phases are there in
a) a mixture of graphite and diamond?
b) A system containing five ice cubes of volume 1 cm3 each in 100 cm3
of water?
2. Calculate the number of components in an aqueous solution of sodium
acetate
3. What is the maximum number of phases possible in a two-component
system?
4. Using phase rule calculate the degree of freedom for a system
containing ice in a mixture of alcohol and water.
5. A certain amount of pure PCl5 (s) was kept in a closed vessel. Calculate
the number of components in a system containing a mixture of PCl5 (s) ,
PCl 3 (g) and Cl2 (g) obtained because of partial dissociation of PCl 5 (s) .

6. Calculate the number of components in a dilute aqueous solution

prepared by dissolving NaCl, LiCl and KBr in water.
7. Write the Clausius–Clapeyron equation for sublimation of a solid and
outline its significance.
8. The vapour pressure of a liquid at 50  C is equal to 12330 Pa. If the
average value of the enthalpy of vaporization between 50  C and the
78
Unit 3 Phase Equilibrium-I
-1
normal boiling point of the liquid is 42.74 kJ mol , estimate the boiling
point of the liquid.

3.9 ANSWERS
Self-Assessment Questions
1. In the decomposition of calcium carbonate giving solid calcium oxide and
carbon dioxide gas there are three phases. CaCO3 and CaO constitute
two distinct solid phases and carbon dioxide forms the gaseous third
phase
2. As given, the following equilibrium exists in a system containing a
mixture of PCl5 ( s ),PCl3 ( g ) and Cl2 (g) .

PCl 5 ( s) ⇌ PCl3 (g) + Cl2 ( g )

There are three distinct constituents in the system i.e., PCl5 (s ) and
PCl 3 (g) and Cl2 ( g ) ,So C = 3 . However, there is one restriction on the
system i.e., the presence of equilibrium. Therefore, the number of
components in the system would be C = 3 − 1 = 2 Thus, it is a two-
component system.

3. If at the end ‘a’ moles of NH4Cl undergo sublimation and there is an

excess of ‘b’ moles of ammonia then we can write the equilibrium and
the concentrations of different species at equilibrium as

NH 4 Cl(s ) + NH 3 (g) ⇌ NH 3 (g) + HCl(g)

Conc. (in moles) (a+ b) a

The composition of the two phases now would be expressed as follows

Phase Constituents Composition in terms of

components

Gas NH 3 (g) + HCl (g) = a NH 4 Cl + b NH 3 (g)

Solid NH 4 Cl(s ) = NH 4 Cl + 0 NH 3 (g)

* in unequal amounts ((a+b) and ‘a’ mole respectively)

4. For such a system we need to specify only one of the variables i.e.,
ether the temperature or the pressure to describe the system. So, the
degrees of freedom would be one. We can arrive at the answer by using
phase rule also. As the system has one component and two phases, we
can write from phase rule, P + F = C + 2

 F = C + 2 − P = 1+ 2 − 2 = 1
5. If we represent the three phases in equilibrium as  ,  and  , then the
condition for phase equilibrium at constant temperature and pressure
would be
( ) = (  ) = ( )

6. At a given temperature the chemical potential of the system would

increase with an increase in pressure p . Further, the value of  for gas
79
Block 1 Solutions and Phase Equilibrium
would increase much more than that for the liquid whereas for solid the
value will increase slightly. The schematic  versus T curves for the
solid, liquid and gaseous state of a substance at two different pressures
are given below; the curves at higher pressure are indicated by the
dotted lines. You may note that the melting point and boiling point are
higher at higher pressure.

7. We are given the following data

T1 = 323 K p1 = ? Pa

T2 = 351.4 K p2 = 101325 Pa

Δv apHm = 40.5 kJ mol -1

We assume that the enthalpy of vaporisation, Δv apHm is constant in this

temperature range and write the Clausius-Clapeyron equation as

p2 vapHm T2 − T1 
2.303 log =  
p1 R  T1T2 

This can be rearranged as follows

p2 Δ v apHm T2 − T1 
log =  
p1 2.303R  T1T2 

substituting the values

p2 40500 J mol -1  28.4  −1
log = K
p1 2.303  8.314 J K -1mol −1 113502 

solving, we get
p2 p p2
log = 0.5293  2 = 3.383  p1 =
p1 p1 3.383

Substituting for p2, we get

101325 Pa
p1 = = 29951 Pa
3.383

Terminal Questions
1. a) As graphite and diamond are two distinct solids and can be physically
separated from their mixture therefore, there are two phases in the
80 system.
Unit 3 Phase Equilibrium-I
b) In this case there are two phases. One is the solid phase (ice) and
second is the liquid phase (water). The number of ice cubes and their
size is superfluous, it does not affect the number of phases. Similarly,
the volume of water also does not matter.

2. An aqueous solution of sodium acetate (a salt) will have three species or

constituents i.e., the sodium and acetate ions and water. However, there
is one restriction i.e., the concentration of sodium ions and acetate ions
must be equal as these are obtained from the dissociation of the salt.
Therefore, the number of components would be
C = C' − R = 3 −1 = 2

3. We know that according to the phase rule,

F = C −P + 2

It can be rearranged to give

P = C −P + 2

We are given number of components, C = 2. Now since the minimum

degrees of freedom can be zero, substituting in the above equation we get
P = 2−0 + 2 = 4

Thus, the number of phases would be 4.

4. We know that according to the phase rule,

F = C −P + 2
In this system there will be two phases viz., ice (solid phase) and
mixture of alcohol and water (liquid phase) i.e., P=2
The number of components would also be two because the
composition of the solid as well as the liquid phase can be
expressed in terms of alcohol and water as follows
Solid phase: water + 0 alcohol
Liquid phase: x water + y alcohol
Substituting in the phase rule expression we get,
F = 2− 2 + 2 = 2

Thus, the degrees of freedom would be 2.

5. We know that PCl 5 ( s) decomposes to give PCl 3 (g) and Cl2 ( g) , and the
following equilibrium exists in the system.
⇌ PCl3 ( g) + Cl2 (g)

There are three distinct constituents in the system i.e., PCl 5 (s ) , PCl 3 (g)
and Cl2 ( g) , So C' = 3 . However, there are two restrictions on the system.
The first one is the presence of equilibrium and the second, that the
amounts of PCl 3 (g) and Cl2 ( g) should be equal as these are formed from
the decomposition of PCl 5 (s ) only. Therefore, the number of components
in the system would be C = 3 − 2 = 1 Thus, it is a one-component system.
You should note here that this problem is different from that in SAQ 2. In
this problem we began with solid phosphorus pentachloride that 81
Block 1 Solutions and Phase Equilibrium
decomposed to give equilibrium mixture whereas in SAQ 2 the system
was prepared by mixing the three components. In this case the second
restriction does not apply, that is why the number of components was 2.
6. There is a total of six constituents in this system; five ions, and water. The
ions are Na+ , K + , Li+ , Cl− and Br −. Also, there are two restriction on the
system. The first restriction is that the system should be electrically
neutral i.e.,

[Na + ] + [K + ] + [Li+ ] = [Cl− ] + [Br - ]

And secondly, since potassium and bromide ions come from same
source, so their concentrations should also be equal, i.e.,

[K + ] = [Br - ]

We know that C =C ' − R

 C =6 −2 = 4

Thus, the number of components would be 4.

7. The Clausius –Clapeyron equation for sublimation of a solid can be
written as

p2 Δsub Hm T2 − T1 
2.303log =  
p1 R  T1T 2 

It shows that the vapour pressure of a solid undergoing sublimation

increases exponentially with increase in temperature.
8. We are given the following data
T1 = 323 K p1 = 12330 Pa
T2 = ? K p2 = 101325 Pa
Δv apHm = 42.74 kJ mol -1 = 42740 J mol −1

The enthalpy of vapourisation, Δv apHm is given to be constant from 50oC

to the boiling point. We can write the Clausius-Clapeyron equation as

p2 vapHm T2 − T1 
2.303 log =  
p1 R  T1T2 

This can be rearranged as follows

T2 − T1  2.303 R p
 = log 2
 T1T2  vapHm p1

substituting the values

T2 − 323  −1 2.303  8.314 JK −1 mol −1 101325

 K = −1
log
 323 T2  42740 J mol 12330

solving, we get

T2 − 323  −1
 K = 0.00041 T2 = 373.3K
82  323 T2 