PHASE RULE

With the help of phase principle, it is possible to define the no. of variables controlling
a given heterogeneous equilibrium under various experimental conditions. It is an invaluable
principle applied extensively in the study and development of materials needed for various
applications. It does not establish a quantitative relation among those variables.
From thermodynamic considerations, [Link] derived an equation that predicts the
number of phases that can coexist in a given system selected for the purpose of investigation.
This equation is called “Gibbs Phase Rule” which is
P+F=C+2
P is the no. of phases coexisting in a given system.
C is the no. of components in the system.
F is the degree of freedom.
Statement of Phase rule:
The sum of no. of phases and degrees of freedom in a heterogeneous equilibrium
exceeds the no. of components present in it by two.
P+F=C+2
Explanation of terms of the Gibbs phase rule:
No. of phases,P:
A homogeneous, physically distinct and mechanically separable portion of a system is
called a phase. The phase present in a system may be pure substances or homogeneous
mixtures of more than two substances.
Air which is a mixture of Nitrogen, oxygen, carbon dioxide, water vapours etc.
constitutes a single phase. Two or more liquids completely miscible with one another also
constitute a single phase. Two immiscible liquids form 2 phases. But considering the vapor
phase which are in equilibrium with them, actual number of phases will be considered as 2 and
3 respectively. in contact with it, there will be two distinct phases.
Every solid constitutes a separate phase.
CaCO3(s) -----→ CaO (s) + CO2(g) (heated in a closed vessel)
There are three phases.
No. of Components, C:-
Smallest no. of independently variable constituents, in terms of whose formulae
equations may be written to express the composition of each phase of a system is called no. of
components.
 Consider a system in which ice, water and water vapour coexist. Composition of each
phase can be expressed with the single constituent, H2O. Hence this is a single component
system.
In the system Na2SO4 and water, the various phases that may exist are:
phase Components
Na2SO4 Na2SO4 + 0 H2O
Na2SO4.7 H2O Na2SO4 + 7 H2O
Na2SO4.10 H2O Na2SO4 +10 H2O
Na2SO4 solution Na2SO4 + x H2O
Ice 0 Na2SO4 + H2O
Vapour 0Na2SO4 + H2O
Thus, two components are the smallest [Link] means of which the composition of each phase
can be expressed.
Degree of freedom, F:
The no. of variables such as, pressure, temperature and composition that can be changed
independently without changing the no. of phases in equilibrium in a given system is called
degree of freedom.
Eg. Ice, water and water vapour can coexist at one definite temp. and one definite
pressure. One of the phases disappear if temp. or pressure is changed from that value. So it is
called a nonvariant system.
If only one variant can be changed without changing the [Link] phases coexisting, the
system is said to be “monovariant”.
Water in equilibrium with its vapour. At a given temp. the equilibrium vapour pressure
of water can have only one fixed [Link] have to specify only one variable, either T or P.
If no. of phases coexisting does not change, even on changing two variables, the system
is said to be “bivariant”.
Ex. A system consisting of a pure gas. Both T and P need to be specified.
True equilibrium:
Is said to exist in a system under a given set of conditions when the same state can be realised
from either direction by following any procedure.
Ice(s) ⇄ Water(l).
At a pressure of 1atm., the temp. of the system will be 0 oC irrespective of the fact whether the
is equilibrium is attained by partial melting of ice or by freezing of water.
Phase Diagram
Graphical representation of what phases are present in materials systems at various
temperatures, pressures and compositions are called phase diagrams. Phase diagrams are used
to understand and predict many aspects of the behavior of materials.
A phase diagram indicates the following.
• Various phases coexisting at different compositions and temperatures, under
equilibrium conditions.
• Solid solubility of one material in another, under equilibrium conditions.
• Temperature at which a material cooling under equilibrium conditions starts to solidify
and the temperature range over which solidification occurs.
• Temperatures at which different phases start to melt under equilibrium heating
conditions.
Classification of Systems: On the basis of no. of components present, systems can be
classified into different types as shown below.
[Link] Component Systems.
(Water, sulphur)
[Link] Component Systems.
(Pb-Ag,)-Simple eutectic
Formation of compounds with congruent melting point (Zn-Mg system),
Formation of compounds with incongruent melting point (Na-K system).
Two Component System
F = C –P + 2
= 2–P+2=4–P
Since P=1(min.); F= 3.
Ex. Mixture of 2 gases.( C=2; P =1;F=3)
( Temp., Pressure, Composition)
Choose any 2 of 3 for graphic representation assuming third to remain constant.
These systems are studied at one atm. Pressure, by varying the temperature and
composition of the system.
For such systems the Gibbs phase rule takes the form: F’ = C-P+1
This is called “condensed phase rule” or reduced phase rule.

Lead Silver System

 The temperature composition phase diagram of Pb-Ag system shown is the graphical
representation of phases of this system existing under different conditions of temperature &
composition.

A indicates the melting pt.(961oC) of silver. B indicates the melting pt.(327oC) of lead.
Only one phase, liquid phase above ACB.
Here p=1, F =2 i.e it is bivariant.
Two solid phases exist below DCE. Melt and a solid phase exist between ACB and DCE. Melt
and solid Ag exist within the area ACD. Melt and solid Pb exist within the area BCE.
AC (freezing point curve of Ag)
As increasing quantities of Pb are added to Ag, the freezing point of silver falls along
the curve AC. Solid Ag is in eqm. With solution (Pb in Ag)
Here P=2 hence F = 1
BC (freezing point curve of Pb)
If increasing quantities of Ag are added to Pb, the freezing point of Pb falls along the curve
BC. Solid Pb is in eqm. With solution (Ag in Pb)
Here P=2 hence F = 1
Composition varies with temperature along AC or BC as the case may be.
The two curves intersect at some point “C”
Where both the solids Ag and Pb must be in eqbm. With the liquid solution of the two
components.
Here C, P = 3, F= 0. It is invariant.
Under a given pressure, the system consisting of two solids and their liquid solution can exist
only at a definite temperature and the composition of the liquid phase also is definite.
The point C is the lowest temperature at which liquid can exist in eqbm. With the solids Ag and
Pb.
Point C is known as the eutectic point.

Desilverisation of lead
Pattinson’s Process: This process of de-silverization of lead is based upon the Pb – Ag phase
diagram.
Pb extracted from its ores always contains small amounts of Ag and it is known as
“argentiferous lead”.
The argentiferous lead is allowed to cool from molten state. Pure Pb solidifies.
The melt gets enriched with silver.
Solidification of pure Pb continues, until the melt is cooled to 303oC. Solid Pb formed at every
stage is removed. At 303oC, the melt is an eutectic mixture of 97.4% Pb and 2.6% Ag. Pure
lead does not solidify from it. The eutectic mixture itself solidifies, when cooled. The solid
contains 2.6% Ag. This is Pattinson’s process.
The eutectic solid is melted and heated in air, when lead is oxidized to PbO. PbO floats over
the melt as a solid scum.
It is skimmed [Link] Pb is removed like this completely, the melt left behind is Ag. It is cast
into bars.