Phase Rule

Phase rule is an important generalization which is useful in understanding

the changes which takes place in a heterogeneous system existing in
equilibrium.
Phase rule is applicable to all heterogeneous systems and is free from
exceptions which are common features of all other generalizations of
physical chemistry.
In words it can be defined as follows: In a heterogeneous system, in
equilibrium, the sum of the number of degrees of freedom and the number
of phases are equal to the number of components plus 2
The phase rule is mathematically expressed as F+ P = C + 2
F+ P = C + 2 (when the number of components is 1)
F= C P + 2
F= C P + 1 (when the number of components is >1 and no gas phase)
The later is also called reduced or condensed phase rule

Condensed phase rule is usually employed for alloy systems only

P is the number of phases
C is the number of components
F is the degree of freedom.
Phase
A phase is defined as a homogeneous, physically distinct and mechanically
separable part of the system, which is separated from the rest of the system
by means of a definite boundary

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For example:

A gaseous mixture, being miscible in all proportions, will constitute
one phase only.
A mixture of N2 and H2 forms one phase only.

When two liquids are mixed, the system may be homogeneous or
heterogeneous depending on the extent of miscibility of the liquids
Ex.(a) Immiscible liquids gives raise to heterogeneous system
(i) Benzene & Water (ii) Water & Oil
.
(b) Miscible liquids give raise to homogeneous system
(i)
Alcohol &Water (ii) Water & Acetone
(c) Partially miscible liquids May be homogenous or heterogeneous
depending on concentration and temperature
(i) Phenol & Water (ii) Diethyl Ether & Water

Mixture of solids give raise to a heterogeneous system
Sugar and salt mixture (two phases)

A heterogeneous mixture like:
CaCO3 (s)

CaO (s) + CO2 (g)

consists of three phases (two solids and one gas)

Water consists of three phases for the following equilibrium
Ice (s)

Water (l)

Water vapour (g)

Mohrs salt FeSO4 (NH4)2SO4.6H2O is one phase only

P.S: n number of solids gives raise to n phases
n number of gases gives raise to just one phase

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Component
Component is the number of chemically independent species which is
required to define each phase of the system completely
For example:

In the water system,
Ice (s)

Water (l)

Water vapour (g)

the chemical composition of all the three phases is H2O. Hence, it is one
component system.

The sulphur system consists of four phases, rhombic, monoclinic,
liquid, and vapour, the chemical composition of all phases is S.
Hence, it is one component system.

A system of saturated solution of NaCl consists of solid salt, salt
solution and water vapour. The chemical composition of all the three
phases can be expressed in terms of NaCl and H2O. Hence, it is a two
component system.

In simple systems , number of components is equal to number of
constituents

In reactive systems the number of components is not equal to the
number of constituents; it may be less or more than the number of
constituents. For Example:

In the thermal decomposition of CaCO3,
CaCO3 (s)

CaO (s) + CO2 (g)

The composition of all the three phases can be expressed in terms of any two
as shown.
Phase: CaCO3 = CaO + CO2
Phase: CaO = CaCO3 CO2
Phase: CO2 = CaCO3 CaO
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Hence it is a two component system.

(No. of Constituents is 3 and number of components is 2)

Other example of the above case are

PCl5 (s)

PCl3(s) + Cl2 (g)

To calculate the number of components, it is essential to take into

consideration, the way in which the system comes into existence.

If the system comes into existence by way of random mixing of the
constituents then there is no relation between the various phases.

For example if CaCO3, CaO and CO2 are mixed randomly then it is a
three component system ( both constituents and components are three)

In general the number of components for any kind of system
(whether reactive or not, whether randomly mixed or not) can be
calculated using the formula
C= NE
Where C is the number of components
N is the number of chemically independent species
E is the equations representing the equilibrium existing within the system

Let us consider a system where three chemically independent species
viz NH4Cl (s) , NH3(g) and HCl (g) are co existing.

It may be a mono / di / tri component system depending on way in
which the system has come into existence.

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Case 1
Let us consider that the system has come into existence by the
decomposition of ammonium chloride. In such a case,
Number of chemically independent species = N = 3
There is equilibrium between reactants and product.
In addition to that as both the products are in the same phase, the
concentration of HCl will be equal to the concentration of NH3.
Thus the following two equations can be written
i. NH4Cl (s) NH3(g) + HCl (g)
ii. [HCl] =[NH3]
Thus E= 2
Therefore number of components in the system
C=NE
C= 3 2 =1 (ie mono )

Case 2
Let us consider the decomposition of ammonium chloride in presence of
a little amount of HCl or NH3

(NH4Cl (s)

N= 3
NH3(g) + HCl (g))

In such a case concentration of ammonia will not be equal to the

concentration of hydrogen chloride
Hence E=1
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C=N E = 3 1 =2
It becomes a two component system (ie di)
Case 3
Let us consider that the system has come into existence by randomly
mixing HCl, NH3 & NH4Cl . In such a case, there is no relation between
the various constituents. Hence
N= 3 & E=0

C=N E
= 3 0 =3
It becomes a three component system (i.e.tri)

FOR CALCULATION OF NUMBER OF COMPONENTS AND

PHASES FOR THE FOLLOWING SYSTEMS
REFER CLASS NOTES
1. NaCl in Water ( P = 1, C=2)
2. Glucose in Water(P = 1 , C=2)
3. NaCl ,KBr in water( P = 1 , C=4)
4. NaCl ,KCl in water saturated with respect to NaCl ( P = 2 , C=3)
5. Mixture of Sand , MgCl2 and H2O(P= 2 ,C = 3)

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Degree of freedom or variance

Degree of freedom is defined as the minimum number of independent
variables, such as temperature, pressure, and composition, which must be
specified in order to define a system completely.
For example:

In Water system based on pressure temperature conditions, water can
exist in the form of solid or liquid or vapour

Water exists in liquid phase at room temperature. This is true only if
the pressure is 1 atmosphere. However by applying pressure water can
be solidified at room temperature. So if we say H2O , without
specifying temperature and pressure, it is not clear whether the
physical state is solid or liquid, ie. the system is not defined
completely. So to define the system we need to say room temperature
and atmospheric pressure.
Merits / Advantages of Phase Rule

Phase rule is found extremely useful in metallurgy

It helps us to predict the behavior of a system, under different sets of
variables (when temp, Pr or concentration is changed).

It gives a simple method of classifying equilibrium states of systems

It is applicable to both physical and chemical equilibria (for example
electrical neutrality is a physical equilibrium).

It is applicable to macroscopic systems. Hence it is not necessary to
take into account their molecular structures.

It is a convenient method of classifying equilibrium states in terms of
phases, components, and degree of freedom.

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It indicates that different systems with same degree of freedom behave

similarly. And a same system with different degree of freedom
behaves differently.

Phase rule takes no account of the nature of the reactants or products
in phase reactions.
Limitations of Phase Rule

It can be applied only for heterogeneous systems in equilibrium.

It applies only to a single equilibrium system; and provides no
information regarding any other possible equilibrium in the system at
any given set of conditions.

It requires utmost care in deciding the number of phases existing in
an equilibrium state, since it considers only the number of phases,
rather than their amounts. Thus, even if a trace amount of the phase is
present, it accounts towards the total number of phases.

All the phases in the system must be present under the same pressure,
temperature and gravitational force.

Like thermodynamics, it does not give information about rate of
change
Phase reaction
The reaction which brings about a change in the phase of the system is
called phase reaction.

Ex. Physical reactions like vapourisation, freezing, condensation,

crystallization, precipitation etc. bring about a phase change.
Vapourisation
H2O(liq)

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H2O(gas)

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A chemical reaction may or may not bring about a phase change

Ex. N2(g) + 3H2(g) 2NH3 (g)
There is no phase change; hence it is not a phase reaction
NH3 (g) + HCl (g) NH4Cl(s)
Phase change occurs. Hence its a phase reaction.
Phase Diagram
The graphical representation of a phase reaction with respect to any two
variables is called a phase diagram. In other words the variables of a system
are taken as coordinates in a phase diagram
The phase diagram can be an isotherm (P Vs Conc) or Isobar (Temp Vs
Composition) or Isoplethal (Temp Vs Pressure)
A phase diagram helps in understanding the behavior of the phases at
equilibrium within a system.

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