PHASE RULE

INTRODUCTION

THEORY

The Phase rule is a generalization given by Willard Gibbs (1874)

Which deals with the behavior of heterogeneous system in the
rate of equilibria.

Definition of Phase Rule

Provided equilibrium between any number phases is not
influenced by gravitational, electrical & magnetic forces or surface
action but only by temp, pressure & concentration.

Then the number of degree of freedom(F) is related to

components(C) & Phase(P) by the phase rule equilibrium .

F=CP+2
For an accurate & effective interpretation of the phase rule, a
clear understanding of the terms involved is absolutely essential.

PHASE RULE

INTRODUCTION

THEORY

Terms1. Phase A phase is defined as any homogenous,

physically distinct & mechanically separable portion of a
system, which is separated from other such parts of the
system by definite boundary surfaces.

Examples:
i)

A freezing point of water system, ice, water & water

vapour are the there phases, each of which is
physically

distinct

&

mechanically

separable

&

homogenous.
Ice
(Solid)

ii)

Water
(liquid)

Water Vapour
(Gas)

All gases freely move in the form of homogenous

mixture. Therefore any mixture of gases, say 2 , 2 & 2
forms one phase only.

iii)

It two liquids are miscible (i.e. Alcohol & Water) & they
will form one liquid phase only.

PHASE RULE

iv)

INTRODUCTION

THEORY

It two liquids are immisicible ( i.e. Benzene (oil) &

water) these will form two separate phases.

v)

An aqueous solution of a solid substance like NaCl &

Sugar is uniform throughout. Therefore, it is a one
phase system.

vi)

Each solid substance makes a separate phase except

in the case of solid solutions.
E.g. Allotropic forms of Sulphur or Carbon, though all
exist together, but are all separate phases.

vii) Equilibriums given below:

i)

3 + 2 .

ii)

Fe

+ 2

PHASE RULE

INTRODUCTION

THEORY

2. Component A component is defined as the smallest

number of independently variable constituent taking part in
the state of equilibrium by means of which the composition
of each phase can be expressed directly or in the form of
chemical equation.
Example
i)

In the water system:

Each of these phases are different in physical form of
same chemical substances.
Hence it is one component system.

ii)

The Sulphur system consists of four phases i.e.

Rhombic, Monoclinic, Liquid & Vapour. The chemical
composition of all phases is S.
Hence it is one component system

iii)

When 3 is heated in a closed vessel the following

reaction takes place.
3 () + 2()
From above reaction we come to know that, these are
three phases 3 , () + 2()

PHASE RULE

INTRODUCTION

THEORY

All though this system has three different constituents, it

is considered as a two component system because, the
composition of each of the above phase can be
expressed in terms of any two of the three constituents
present as follows.
Thus it is a two component system.

iv)

In the equilibrium for iron metal + stem.

+ 2 () + 2 ()
the composition of each phase can be expressed in
terms of the components Fe, O + 2
Hence it is a three component system.

v)

In the dissociation of 4 in a closed vessel, which

can be represented as
4 () 4 () 3() + ()
if proportions of 3 & then it is one component
system. But it proportions varies, then it is two
component system.

vi)

& 2 is saturated solution.

PHASE RULE

INTRODUCTION

THEORY

Their three phases are Solid, liquid & vapour. Can be

expressed in terms of & 2
Hence, it is a two component system.

Degree of Freedom
Smallest number of independently variable factors such as
temperature pressure & composition of phases which must be
arbitrarily specified in order to represent perfectly the condition of
a system.

Example
i)

It all the three phases are in equilibrium, then no

condition need to be specified because the three
phases can be in equilibrium only at particular temp &
press.
() () ()
The system has no degree of freedom or invariant or
zero variant or non variant.

PHASE RULE

ii)

INTRODUCTION

THEORY

If condition like temp or pres is altered, three phases

will not remain in equilibrium & one of the phase
disappears.

()

we must state either the temp or press to define it

completely. Hence it is univariant system. i.e. F=1

iii)

For a system consisting of water vapour phase only.

We must state the values of both temp & press in order
to describe the system completely.
Hence it is bivariant . i.e. F=2

iv)

For a gaseous mixture of 2 & 2 . We must state both

press & temp. because if press & temp are fixed the
volume. automatically becomes definite.
Hence it is bivariant i.e. F=2

v)

For a system consisting of

() () ()
We must state either, temp, or press, because the
saturation solubility is fixed at a particular temp of
press.
Hence the system is Uni variant. i.e. F=1
7

PHASE RULE

INTRODUCTION

THEORY