PHASE RULE
Dr.S.Ignatius Arockiam,
Assistant Professor,
Dept of chemistry,
SJC.
PHASE RULE
Gibbs phase rule
“ In a heterogeneous system in equilibrium is not affected by
gravity or by electrical and magnetic forces, the number of
degrees of freedom(F) of the system is related to the number
of component(C) and the number of phases(P) existing at
equilibrium”.
It is expressed by mathematically,
F=C–P+2
where,
F - number of degrees of freedom
C - number of components
P - number of phases
2 - additional variables of temperature and pressure
PHASE RULE
Phase
It is defined as “ Physically distinct, homogenous and mechanically separable
part of a system ”.
(i) A gaseous mixture constitutes a single phase since gases are completely
miscible.
example : Air
(ii) Two or more liquids which are miscible with one another constitute a single phase
as there is no bounding surfaces separating the different liquids.
example : water and alcohol, chloroform and benzene constitute one
phase system.
(iii) A system consisting of a liquid in equilibrium with its vapour constitute a two
phase system
example : H2O(l) H2O(g)
PHASE RULE
Component
It is defined as “Minimum number of independent variable constituents
which are required to express the composition of each phase in the system”.
In a chemically reactive system, the number of components is given by
C=N-E
Where, C - components.
N - Number of chemical species
E - Number of independent equations relating to the
concentrations of the species.
Each independent chemical equilibrium involving the constituents count as one
equation.
The condition that a solution be electrically neutral also counts as one equation if
ions are considered as constituents.
PHASE RULE
Examples
(i)Sulphur system
(a)monoclinic sulphur, (b)rhombic sulphur (c)liquid sulphur
(d) sulphur vapour. (C = 1; P=4)
(ii) Water system
solid,liquid and vapour
(C=1 ; P = 3)
.
(iii) Salt + water system
Certain salts are capable of existing as hydrates with different
number of water molecules of crystallization.
The system is a two component.(C=2 , P = 1)
The composition of each phase of the hydrates is completely
described in terms of the anhydrous salt and water alone. e.g.,
Na2SO4 + water
PHASE RULE
Degrees of Freedom
“It is defined as the minimum number of independent variables
such as temperature, pressure and concentration which should
be specified in order to define the system completely”.
Examples
(i) H2O(l) H2O(g) (F = 1) Monovariant
(ii) A gaseous mixture say N2 and O2 gases is completely defined when three
variables(T,P and C).
(F=3) Trivariant.
PHASE RULE
Advantages
(i) It provides a simple method of classifying equilibrium states of
systems.
(ii) The phase rule confirms that the different systems having the
same number of degrees of freedom behave in same
manner.
(iii) It is applicable only to macroscopic systems and not concerned
with molecular structure.
(iv) It predicts the behaviour of the systems with changes in the
variables that govern the system in equilibrium.
(v) It predicts that, under a given conditions whether a number of
substances taken together would remain in equilibrium or it
involves in some interconversion or elimination.
.
PHASE RULE
Phase diagrams
“A phase diagram is the sum of the description of the
behaviour of the phases present in equilibrium”
The number of phases that exist in equilibrium depends upon the conditions of
temperature and pressure or temperature and composition, pressure being
constant.
These conditions are determined experimentally and the values of the
variables can be exposed graphically by using appropriates coordinates.
These diagrams are called phase diagram.
It is very easy to describe the phase behaviour of a system by such
diagrams and to investigate the conditions in which various
phases will constitute the system .
PHASE RULE
Application of Gibbs Phase Rule
One Component System
From the mathematical expression of phase rule,
F=C–P+2
When C = 1, P = 1
F = 1-1+2
=2
All one component systems can be completely described graphically by
stating only two variables such as pressure
and temperature on appropriate axis.
PHASE RULE
Water System
It is a one component system.
Water exists in three possible phases viz. ice (solid) , water (liquid), and
vapour (gas). These three single phases may form four possible equilibria.
(i) Solid Liquid
(ii) Liquid Vapour
(iii) Solid Vapour
(iv) Solid Liquid Vapour
PHASE RULE
Phase Diagram of water system
PHASE RULE
The phase diagram consists of the following important
aspects
(i) Stable curves: three OB, OA and OC
(ii) Metastable curve: one OA'
(iii) Areas: three AOB, COB and AOC
(iv) Triple point: One O
Thank you
