Phase Rule

• Dr. Ashima Srivastava

• Dept of Chemistry
• JSSATE, NOIDA
INT RODUCT ION

This rule was given by an American physicist Willard Gibbs in 1874.

The Phase rule is an important generalization dealing with the behaviour of heterogenous systems.
With the help of phase rule it is possible to predict qualitatively, the effect of changing pressure,
temperature and concentration on a heterogenous system in equilibrium by means of a phase
diagram.
Statement of Phase Rule
Gibbs phase rule states that if a heterogeneous system is influenced by temperature, pressure and
concentration and not by any other action like gravity, electrical, magnetic forces or by surface
action, then the sum of number of phases (P) and degree of freedom (F) is greater than the number
of components by two.
It is expressed mathematically as follows:
P + F = C + 2 or F = C – P + 2
The terms ‘phase’, ‘component’ and ‘degree of freedom’ involved in the statement have a special
significance and clear understanding of these terms is essential.
EXPLANAT ION OF T HE T ERMS
INVOLVED IN PHASE RULE
PHASE (P)
A phase is a
• homogeneous,
• physically distinct and
• mechanically separable part of the system which is separated from other parts of the system by
definite boundaries.
• In other words, phase is any homogeneous part of the system having all physical and chemical
properties the same throughout.
Examples of Phases
• A pure substance (a solid, liquid or gas) made up of one chemical species only, is considered as one
phase. Thus oxygen (O 2 ), benzene (C 6 H 6 ) and ice (H 2 O) are all one phase systems.
• Air, which is a mixture of number of gases, is a one phase since there is no demarcation between
one gas and the other.
• An aqueous solution of a solid substance such as sodium chloride or sugar is uniform throughout.
Therefore, it is a one-phase system.
• Saturated solution of sugar in water has two phases (solution of water and sugar and solid sugar
settled at the bottom.
Examples of Phases
• Two completely miscible liquids give a uniform solution. Thus a mixture of water and ethanol is
one-phase system.
• Two immiscible liquids on standing form two separate layers. Thus, a mixture of kerosene and
water constitute two-phase system.
• When CaCO 3 is heated in a closed vessel, it decomposes to CaO and CO 2 . At equilibrium, there are
two solid and one gaseous phase, therefore a three phase system.
• CaCO 3 ⇋ CaO + CO 2
(solid) (solid) (gas)
COMPONENTS (C)
The number of components of a system is the minimum number of independent chemical
constituents by means of which the composition of each phase present can be expressed either
directly or in the form of a chemical equation.
• Zero and negative quantities of the components are also acceptable when composition of a phase
is expressed in terms of the components.
Examples of Components
1. Consider a water system consisting of three phases:
Ice (solid) ⇋Water (liquid) ⇋ Vapour (gas).
It is a one component system as each phase is a different physical form of the same
chemical compound represented by H 2 O.
2. Gaseous mixture of O 2 and N 2
constitute one phase but two-component system because the composition of the gaseous phase can
be expressed by two chemical entities O 2 and N 2 .
Phase Components
Gaseous mixture of O2 & N2 x O2 + y N 2
Examples of Components
The aqueous solution of NaCl constitutes one phase but Phase Components
to determine the composition of this homogeneous Aqueous solution of x NaCl + y H2O
phase, two chemical entities water and NaCl are NaCl
required. Therefore it is a two component system.
Examples of Components
The saturated solution of NaCl constitutes two Phase Components
phases, namely aqueous solution and solid NaCl. Aqueous solution of NaCl x NaCl + y H2O
The composition of two phases can be expressed
in terms of two chemical entities water and Solid NaCl x NaCl + 0 H2O
NaCl. Therefore it is also a two component
system.
Examples of Components
Decomposition of calcium carbonate in a closed vessel has the following equilibrium
CaCO 3 ⇋ CaO + CO 2
(solid) (solid) (gas)
This system has three phases viz. CaCO 3, CaO and CO 2 . The composition of all the three phase can be
expressed by taking minimum of any two chemical constituents in the equilibrium. Thus, it is a two
component system.
By taking CaCO 3 and CaO as constituents

Phase Components
CaCO3 (s) CaCO3+ 0 CaO
CaO (s) 0 CaCO3+ CaO
CO2 (g) CaCO3 − CaO
By taking CaCO 3 and CO 2 as constituents

Phase Components
CaCO3 (s) CaCO3 + 0 CO2
CaO (s) 0 CaCO3 − CO2
CO2 (g) 0 CaCO3 + CO2
By taking CaO and CO 2 as constituents

Phase Components
CaCO3 (s) CaO + CO2
CaO (s) CaO + 0 CO2
CO2 (g) 0 CaO + CO2
 Examples of Components
Dissociation of Ammonium chloride in a closed vessel has the following equilibrium
NH 4 Cl ⇋ NH 3 + HCl
(solid) (gas) (gas)
The system consists of two phases, namely, solid NH 4 Cl and the gaseous mixture containing NH 3 and HCl. The
constituents of the mixture are present in same proportion in which they are combined in solid NH 4 Cl.
The composition of both the phases can therefore be expressed in terms of the single chemical constituent NH 4 Cl.
Examples of Components

Phase Components
NH4Cl (s) NH4Cl
Gaseous mixture of NH3 & HCl x NH3+ x HCl or x NH4Cl
DEGREE OF FREEDOM (F)
Degree of freedom is the minimum number of independently variable factors, such as temperature,
pressure and composition of the phases, which must be specified in order to define the system.
A system with F=0 is known as Invariant or having no degree of freedom.
A system with F=1 is known as Univariant or having one degree of freedom.
A system with F=2 is known as Bivariant or having two degree of freedom.
Example of Degree of Freedom
• If all the three phases of water system are present in equilibrium, there is no need of any variable
to be specified as the three phases can exist in equilibrium only at fixed temperature and pressure.
• Ice (s) ⇋Water (l) ⇋ Vapour (g), since the number of phases and components is three and one
respectively, the degree of freedom F= C−P+2 = 1−3+2= 0.
PHASE DIAGRAMS
• A phase diagram is a plot showing the conditions of pressure and temperature under which two or more
phases can exist together in a state of dynamic equilibrium. It is the graphical representation obtained by
plotting one degree of freedom against the other.
• If temperature is plotted against pressure the diagram is called P -T diagram. If temperature is plotted
against composition, the diagram is called T-C diagram.
• The study of phase diagram is important for proper understanding of the relative stability of equilibrium
between phases. From the knowledge of number of phases and components of the system, phase rule
enables to predict the conditions under which the system can remain in equilibrium.
ONE COMPONENT SYST EM: WAT ER SYST EM

Water can exist in three possible phases namely solid, liquid and vapour. All
the three phases can be represented by only one chemical entity H 2O;
therefore, it is a one component system On the basis of experimental data
obtained for the water system a plot of relationships between the three
phases under different conditions of temperature and pressure is shown by
phase diagram in Fig
Phase Diagram of Water System

The diagram consists of areas, lines or curves and a triple point.

(i) Areas
The diagram is divided into three areas:
Area AOB represents the conditions for solid (ice) in the system.
Area AOC represents the conditions for liquid (water) in the system.
Area BOC represents the conditions for gas (vapour) in the system.
In order to define the system completely at any point in the area, it is essential to specify both the
temperature and pressure. Therefore areas have two degrees of freedom and are called bivariant systems. It
can also be concluded from the phase rule equation.
F= C−P+2 = 1−1+2= 2.
Lines or Curves
(ii) Lines or Curves
There are three lines or curves separating the areas.
Curve OA (Melting or Fusion Curve) represents the equilibrium between ice and water :
ice (solid) ⇋ water (liquid)
Curve OC (Vapour Pressure Curve) represents the equilibrium between water and vapour :
water (liquid) ⇋ vapour (gas)
Curve OB (Sublimation Curve) represents the equilibrium between ice and vapour :
ice (solid) ⇋ vapour (gas)
Lines or Curves
To define the system completely only one of the variables viz. temperature or pressure has to be
specified since the other variable can be read from the graph (Univariant).
It can also be concluded from the phase rule equation, F= C−P+2 = 1−2+2= 1.
Triple Point
(iii) Triple Point
The three curves OA, OB and OC meet at point O which is known as triple point. At this point all the
three phases namely, ice, water and vapour are in equilibrium with one another.
Applying the phase rule to this point, F= C−P+2 = 1−3+2= 0.
Thus the degree of freedom at triple point is zero. It means that the phases can co -exist in
equilibrium only at definite temperature and pressure. The values of temperature and pressure at O
are 0.0078C and 4.58 mm of Hg respectively.
Metastable state
Normally liquid water solidifies at 0C at one atmospheric pressure. However, it is possible to super -cool
water several degrees below its freezing point ( if the vessel is thoroughly clean and dust free). Super -
cooled water is a metastable state (unstable state). On slight disturbance, the super -cooled water at one
changes into ice.
The dotted curve OC’ represents the metastable equilibrium
between super-cooled water and vapour,
super-cooled water ⇋ vapour,
which on slight disturbance or by adding stable ice crystal (stable)
reverts to true stable equilibrium, solid ⇋ vapour.
Inclinatio n of melting point curve towards pressure axis

Curve OB and OC indicate that the vapour pressures of ice and water increases with temperature while OA
curve indicates that the melting point of ice is lowered by the increase of the pressure. Freezing of water is
a process during which specific volume increases.
ice ⇋ Water
sp. vol. ice > sp. vol. water
• The effect of pressure on this equilibrium can be understood by Le Chatelier’s Principle . The increase in
pressure would make the change go in the direction in which the specific volume decreases, i.e. some ice
melts and in doing so, the system will require latent heat of fusion which is derived from the system
itself. Thus the temperature of the system decreases with increase in pressure and OA curve is slightly
inclined towards the pressure axis.
SULPHUR SYST EM
• The sulphur system is another one component system and the only chemical individual representing the different phases is sulphur itself. It
is a classical example of one component system where polymorphism and solid -solid transformation are exhibited. (Polymorphism is the
phenomenon in which the same chemical substance exists in more than one different crystalline forms and in the case of elemen ts, it is
called allotropy).
• In the sulphur system, the four different are: Rhombic sulphur (S R ), monoclinic sulphur (S M ), liquid sulphur (S L ) and vapour sulphur (S V ). All
the four phases can be represented by a single chemical entity ‘Sulphur’ (S).
•
• Since C=1, all the four phases cannot be present at a time because F cannot have the negative value ( -1). Maximum number of phases that
can be present simultaneously is three.
• F= C−P+2
• = 1−P+2
• = 3−P
Merits of Phase Rule
Limitations of Phase Rule