Unit- Phase Rule

The ‘phase rule’ generalization was given by J.W. Gibbs in 1874 and further studied by
H.W.B. Roozeboom 1884. The phase rule is able to predict the conditions necessary to be
specified for a heterogeneous system to exhibit equilibrium. During the study of chemical
systems, we usually deal with the systems containing two or more phases in equilibrium,
which are called heterogeneous or polyphase systems. Phase rule was based on the basis
of the principles of thermodynamics. The phase rule is able to predict qualitatively, by
means of diagram, the effect of changing temperature, pressure, or concentration on a
heterogeneous system in equilibrium. In this chapter we will study the phase rule and its
various applications in the daily life.

1 GIBB’S PHASE RULE

Phase rule may be defined as:

When a heterogeneous system in equilibrium at a definite temperature and

pressure, the number of degrees of freedom is equal to by 2 the difference in the
number of components and the number of phases provided the equilibrium is not
influenced by external factors such as gravity, electrical or magnetic forces,
surface tension etc.
It is applicable for all the universally present heterogeneous systems.
Mathematically, the rule is written as
F=C–P+2

Where F = Number of degrees of freedom, C =

Number of components
P = Number of phases of the system
For understanding the various applications of phase rule a clear understanding of the
various terms, phases (P), components (C) and degrees of freedom (F) present in the phase
rule, is essential which have their specific meanings.
 Phase Rule !%

[2] Components (C)

The minimum number of independently variable constituents in terms of which the
composition of each phase of a heterogeneous system can be expressed directly or in the form
of a chemical equation are called the components of system (C).

For example, a system consisting of a solution of sugar in water (P = 1 i.e.

solution phase) is a two-component system because the solution phase present in the
system consists of two constituents—water and sugar.
Some common examples related to the components are as follows:
(a) Consider the following system consisting of ice, water and vapour in
equilibrium.

Ice (s) º Water (l) º Vapour (g)

The system consists of three phases ice, water and vapour phase. The
chemical substance present in each phase is H 2O. Therefore, the
composition of each phase is expressed in terms of H 2O. Hence, it is called
one-component system.
(b) The saturated solution of sodium chloride consists of three phases—solid
sodium chloride, salt solution and water vapour in equilibrium.

NaCI (s) º NaCI (aq) º Water Vapour (g)

Ca CO3(s) º CaO(s) + CO2(g)

The chemical composition of each phase of the system can be expressed

if we consider two chemical constituents NaCI and water as shown
below.
Phase Components
(i) NaCI (s) = NaCI + 0H2O
(ii) NaCI(aq) = yNaCI + xH2O
(iii) H2O(g) = 0NaCI + H2O
Hence, it is a two-component system.

(c) The system, CuSO4.5H2O (s) º CuSO4.3H2O (s) + 2H2O (g) is a three-
phase and two component system. It requires two constituents CuSO 4 and H2O
to express the composition of each phase of the system.

[3] Degree of Freedom (F)

The smallest number of independently variable factors such as temperature,
pressure and concentration which must be required in order to define the system
completely are called the degree of freedom. Degree of freedom of a system is
also known as variance.
When a system having no degree of freedom
F = 0 it is called non-variant system or invariant system.
 When a system having only one degree of freedom
F = 1 it is a univariant or a monovariant system.
Similarly, a system having two degrees of freedom
F = 2 is a bivariant system and so on.
The term degree of freedom can be understood with the help of following examples:

º º
(a) The system ice water vapour has no degree of freedom (i.e., F = 0).
The three phases of water i.e. ice, liquid water and vapour can exist
together in equilibrium only at a particular-temperature and pressure
(corresponding to the freezing point) and no factor is necessary to be
specified to define the system. Hence, a system consisting of ice, water
and vapour in equilibrium has no degree of freedom i.e. it is a non-
variant system.
(b) For a mixture of gases, the number of degrees of freedom is three (i.e., F = 3). Such
a system can be completely defined when the temperature, pressure and composition
are fixed. In this case, the remaining factor i.e.,
volume gets automatically fixed. For example, a gaseous mixture consisting of 70%
N2 and 30% O2 at 22°C and 1 atm pressure is
completely defined and does not require any other information for its
description. Hence, a system consisting of a mixture of gases has three
degrees of freedom i.e. it is a trivariant system.

(c) For a saturated LiCl solution, the number of degrees of freedom is one
(i.e., F = 1). This is because the system can be completely defined by
specifying the temperature only. The other two factors i.e. composition
and vapour pressure get automatically fixed when the temperature is
fixed. Hence, a system consisting of a saturated LiCl solution is a
univariant system.

2 DERIVATION OF PHASE RULE EQUATION

The Gibb’s phase rule can be derived on the basis of thermodynamic principle as
follows.
Let us consider a heterogeneous system consisting of P(P 1, P2, P3 ...P)
number of phases and C(C1, C2, C3 ... C) number of components in equilibrium.
Let us assume that the system is non-reacting i.e. the passage of a component
from one phase to another does not involve any chemical reaction. When the
system is in equilibrium state it can be explained completely by specifying the
following variables:
(i) Pressure (ii) Temperature (iii) Composition of each phase.
 Phase Rule !'

(a) Total number of variables required specifying the state of system:

(i) Temperature: same for all phases
(ii) Pressure: same for all phases
(iii) Concentration
Independent concentration variables for one phase with respect to the C
components = C – 1 [3 Conc. of last component is independent]
\ Independent concentration variables for P phases with respect to the C
components = P(C – 1)
Total number of variables = P(C – 1) + 2 ...(1)
(b) The total number of equilibria:
The various phases present in the system can remain in equilibrium only when the
chemical potential (m) of each component is the same in each phases, i.e.
m1, P1 = m1, P2 = m1 , P 3 = ... = m1, P Component 1
m2, P1 = m2, P2 = m2, P3 = ... = m2, P Component 2
: : : :
: : : :
: : : :
mC, P1 = mC, P2 = m C, P 1 = ... = mC, P Component C
(a) For each component the no of equilibria for P phases = (P – 1)
(b) For C component the no of equilibria for P phases = C(P – 1)
Total no. of equilibria involved (E) = C(P – 1) ...(2)
From eq. 1 & 2 we get
F=[P(C–1)+2]–[C(P–1)]
F=[CP–P+2–CP+C]
F=C–P+2
This above equation is Gibb’s phase rule equation.
Some conclusions from the phase rule equation:
(a) For a system having a specified number of components, the greater the
number of phases, the lesser is the number of degrees of freedom. For
example,
(i) When the system consists of only one phase, we have
C = 1 and P = 1
So, according to the phase rule,
F = C – P + 2 = 1 – 1 + 2 = 2. The system has two degrees of freedom. (ii) When
the system consists of two phases in equilibrium, we have
C = 1 and P=2
F = C – P + 2 = 1 – 2 + 2 = 1. The system is monovariant.
Engineering Chemistry

(b) A system having a given number of components and the maximum possible
number of phases in equilibrium is non-variant.

For a one component system, the maximum possible number of phases is

three. When a one-component system has three phases in equilibrium, it has
no degree of freedom or non-variant system.
(c) For a system having a given number of phases, the larger the number of
components, the greater will be the number of the degrees of freedom of
the system.
For example,
For one-component system: C=1, P=2

\ F=C–P+2=1–2+2=1
For two-component system: C=2, P=2

\ F=C–P+2=2–2+2=2
The two-component system has a higher number of degrees of freedom.

3 PHASE DIAGRAMS

The graphical presentation giving the conditions of pressure and temperature

under which the various phases are existing and transform from one phase to
another is known as the phase diagram of the system. A phase diagram consists
of areas, curves or lines and points.

Phase Diagram

Depending upon the

component present in system
For one For two
component system component system
[Water system]

Component which react to Components which are

form compounds completely miscible but do
not react (Eutectic mixture)
[Pb-Ag system]

System having System having

congruent melting point Incongruent melting
[Zn – Mg system] point [Na-K System]
 Phase Rule "

4 PHASE RULE FOR ONE-COMPONENT SYSTEMS

The least number of phases possible in any system is one. So, according to the
phase rule equation, a one-component system should have a maximum of two
degrees of freedom.
When C=1, P=1

So, F=C–P+2=1–1+2=2

Hence, a one-component system requires a maximum of two variables to be

fixed in order to define the system completely. The two variables are temperature
and pressure. So, phase diagrams for one component system can be obtained by
plotting P vs T.
In case of a one-component system, phase diagram consists of areas, curves
or lines and points which provide the following informations regarding the
system:
Point on a phase diagram represents a non-variant system.
Area represents a bivariant system
Curve or a line represents a univariant system.
Water system and the sulphur system are the example of one component systems.

[1] Water System

Water is a one component system which is chemically a single compound
involved in the system. The three possible phases in this system are: ice (solid
phase), water (liquid phase) and vapour (gaseous phase).
Hence, water constitutes a three-phase, one-component system. Since water is a
three-phase system, it can have the following equilibria:

iceº vapour,
ice º water;

water º vapour

The existence of these equilibria at a particular stage depends upon the conditions of
temperature and pressure, which are the variables of the system. If the values of vapour
pressures at different temperatures are plotted against the corresponding temperatures, the
phase diagram of the system is obtained.
The phase diagram of the water system is shown in Fig. 2.1. The explanation of the
phase diagram of water system is as follows:
" Comprehensive Engineering Chemistry

C
Critical point
B
218 atm
Water
Vapour
Pressure (atm)

Ice pressure
curve
1.0 atm E D

O Water
vapour
4.58 Triple
mm A¢ point
Metastable
curve A
F. P B. P
0 0.0098 100 374
Sublimation
curve Temperature °C

Fig. 2.1 Phase diagram of water system

= +KHLAI
The phase diagram of the water system consists of three stable curves and one
metastable curve, which are explained as follows:

(i) Curve OB: The curve OB is known as vapour pressure curve of water and tells
about the vapour pressure of water at different temperatures. Along this curve, the
two phases—water and vapour exist together in equilibrium.

At point D, the vapour pressure of water become equal to the atmospheric

pressure (100°C), which represents the boiling point of water. The curve OB
finishes at point B (temp. 374°C and pressure 218 atm) where the liquid water
and vapour are indistinguishable and the system has only one phase. This point is
called the critical point.
Applying the phase rule on this curve,
C = 1 and P=2
F=C–P+2=1–2+2=1

Hence, the curve represents a univariant system. This explains that only one
factor (either temperature or pressure) is sufficient to be fixed in order to define
the system.

(ii) Curve OA: It is known as sublimation curve of ice and gives the vapour pressure
of solid ice at different temperatures. Along sublimation curve, the two phases ice
and vapour exist together in equilibrium. The lower end of the curve OA extends to
absolute zero (–273°C) where no vapour exists.
44 Comprehensive Engineering Chemistry

Area Phase exits Component

(i) Area AOC ice H2O
(ii) Area COB water H2O
(iii) Area below BOA vapour H2O
Thus, for every area contains
C=1 and P = 1
Therefore, applying phase rule on areas
F=C–P+2=1–1+2=2

Hence, each area is a bivariant system. So, it becomes necessary to specify both the
temperature and the pressure to define a one phase-system.
Table 2.1: Some salient features of the water system

Curve/ area/ Name of Phases in No. of Degree of the

point the system equilibrium phase (P) freedom (F)
Curve OB Vapourisation curve Liquid & vapour 02 01(Univariant)
Curve OA Sublimation curve Solid & vapour 02 01(Univariant)
Curve OC Fusion curve Solid & liquid 02 01(Univariant)
Curve OA¢ Metastable Liquid & vapour 02 01(Univariant)
vaporization curve
Area AOC Ice 01 02(Bivariant)
Area BOC Water 01 02(Bivariant)
Area AOB Vapour 01 02(Bivariant)
Point O Ice & water 03 0(Invariant)
& vapour

5 TWO-COMPONENT SYSTEMS

When the two independent components are present in a heterogeneous system, the
system is referred to as a two-component system. Hence, according to the phase rule,
for a two-component system having one phase,
F=C–P+2=2–1+2=3

Therefore, the two component system having one phase will have three degrees of
freedom or three variables would be required to define the system. The three variables are
pressure (P), temperature (T) and concentration (C). This will require a three-dimensional
phase diagram for the study of a two-component system. However, in order to simplify
the study, a two-component system is usually studied in the form of a condensed system.
A condensed system can be studied by reducing a comparatively less important variable.
This reduces the degree of freedom of the system by 1 and the system can easily be
studied with the help of a two-dimensional phase diagram.
 "$ Comprehensive Engineering Chemistry

It can have a maximum of following four phases:

Solid lead, Solid silver, Solution of molten silver & lead and Vapours

The boiling points of silver and lead are considerably high and the vapour
pressure of the system is very low. So, the vapour phase can be ignored and the
system can be studied as a condensed system. This system thus can be easily studied
with the help of a two dimensional T – C diagram and the reduced phase rule
equation, F ¢ = C – P + 1, can be used. This system is generally studied at constant
pressure (atmospheric). The phase diagram of Lead-Silver system is shown in Fig.
2.2.

B
X
961 °C

Y
Melt (Pb-Ag solution)
Temperat
ure °C
A X Solid Ag
327 °C + Melt of Pb + Ag

Y
Solid Pb
+ melt of Eutectic point
Pb + Ag C
303 °C
E F
Solid Pb
+ Solid Ag + Eutectic
Eutectic

G H
D
Pb = 100% 97.4% Pb Ag = 100%
Ag = 0% 2.6% Ag Pb = 0%

Fig. 2.2 Phase diagram of Pb-Ag system

= +KHLAI

The phase diagram of the lead-silver system consists of following curves, which are
explained as follows:

(i) Curve AC (Freezing point curve of lead): The AC curve shows the variation of
the melting point of lead on addition of silver. The pure lead melts at 327°C (point
A). Addition of silver lowers its melting point along curve AC. The added silver
dissolves in molten lead to form Ag-Pb solution with the separation of some part of
solid lead. Therefore, the two phases, solid lead and Ag-Pb solution remain together
in equilibrium along the curve AC.
Hence, P = 2, (solid Pb and melt of Ag-Pb)
C = 2(Pb and Ag)
Engineering Chemistry

So, C = 2 and P = 2,
On applying the reduced phase rule
F ¢ = C – P + 1 = 2 – 2 + 1 = 1 The system is univariant.
(iii) Area BCF: The area consists of two phases—solid Ag and a solution of Pb and
Ag. Hence it is also univariant.

(iv) Area DCFH: This area also has the two phases which are solid Ag crystals and solid
eutectic crystals. Hence C = 2 and P = 2, the system is univariant.

(iv) Area CEGD: The area also has the solid Pb crystals and solid eutectic crystals
phases. The system is univariant.
Table 2.2: Some salient features of the Pb-Ag system.

Curve/ area/ Name of Phases in No. of Degree of

point the system equilibrium phase (P) freedom (F)
Curve AC Freezing curve of Pb Pb & Melt (Pb+Ag 02 01(Univariant)
Solution Pb & Ag)
Curve BC Freezing curve of Ag Ag & Melt 02 01(Univariant)
Pb & Ag)
Area ACE ..... Pb & melt 02 01(Univariant)
Area BCF ..... Ag & melt 02 01(Univariant)
Area above ..... Liquid (melt) 01 02(Bivariant)
ACB
Area ECF ..... Pb & Ag both in 02 01(Univariant)
solid
Point O Eutectic point Pb, Ag & melt 03 0(invariant)

6 APPLICATIONS OF THE PHASE RULE

Phase rule has wide applications in electronic industries, pharmaceutical science, medical
science, etc. Some major applications of phase rule are as follows:

[1] Solders
Solder is an alloy, which is homogenous mixture having melting point lower than that of the
corresponding metal pieces, which have to be joined together. Solders have compositions
somewhat different from the eutectics so that the freezing occurs over a range of temperatures.
The quality of solder depends upon the formation of a surface alloy between the solder and
parts of metals being used. The selection of solder alloy is based upon the melting point
desired and the pieces of metals to be joined. Some essential qualities of the solder are as
follows:
(1) Melting point of the solder should be less than the material to be soldered.

(2) Solder should spread in liquid form and also form homogeneous mixture with
the metals.
Some common solders which are available in the market are:
(i) ‘Soft solder’ alloy of Pb and Sn.
 (ii) ‘Plumber alloy’ contains Pb = 67% and Sn = 33%.
(iii) ‘Half-half alloy’ contains Pb = 50% and Sn = 50%
Half-half alloy is commonly used for soldering the pipes with a bright
surface finishing after soldering but very expensive. Also due to high contents of
tin, it is not widely applicable for several electric appliances. The solder which
contains about 60% Pb is used in the electrical wires.

[2] Safety Plug

Safety plugs are also known as the safety fuses. It is an alloy having low melting point,
used to ensure the safe working and avoid accidents. Safety fuses are used in buildings to
protect them against fires. One alloy is woods metal, which is used in the safety fuses.
This alloy melts at 65°C and consists of the composition woods metal Bi = 50%, Pb =
25%, Sn = 12.5% and Cd = 12.5%.
Engineering Chemistry

and the frozen liquid (ice) is directly converted into a gaseous state. The removed water is
stored again through the condensers. The material or tissue is left almost as a skeleton
and original matter can be obtained by adding water. By this process shrinkage of flowers
is eliminated or minimized.

All botanical samples, fruits and vegetables can be freeze-dried. This

technique is also used in pharmaceutical industry, museums, taxidermy, floral
industry and camping/hiking food processors.