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 Component
Component: The least number of independently variable
constituents by means of which the composition of each phase
can be expressed either directly or in terms of chemical
equations
Examples (non reactive system)

Minimum no. of constituents sufficient5 for determining the composition

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of all phases of system

Reactive system)

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Component for chemical reactive system
Determine the number of components
C = N – E or C = S- R

C = No. of Components
N/S = No. of species
E/R = No. of independent equations relating their
concentrations
Non reacting system → No. of components = No. of chemical constituents
Reacting system → No. of components = or ≠ No. of chemical constituents

Electrical neutrality C = S-(E+R)

R = No. of restrictions for
charge neutrality

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Examples (reactive system)

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Examples

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 Degree of freedom
The degree of freedom (F) of a system is defined as the number of
independent variable factors (pressure, temperature and concentration)
which must be specified so that the remaining variables are fixed
automatically and the system is completely defined.

A system with F = 0 is known as nonvariant 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 degrees of freedom.

Examples
For a pure gas
For a given sample of any pure gas PV = RT. If the values of pressure (P) and
temperature (T) be specified, volume (V) can have only one definite value,
or that the volume (the third variable) is fixed automatically. Hence a
system containing a pure gas has two degrees of freedom (F = 2).

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 Degree of freedom
For a mixture of gases
A system containing a mixture of two or more gases is completely defined
when its composition, temperature and pressure are specified. If pressure
and temperature only are specified, the third variable i.e., composition
could be varied. Since it is necessary to specify three variables to define the
system completely, a mixture of gases has three degrees of freedom (F = 3).
For water & water vapour
Such system can be completely defined by specifying either temperature
or pressure. This is because on fixing one variable, the other becomes fixed
automatically. Hence, either temperature or pressure is required to specify
the system. Therefore, F = 1.
P = 2, C = 1

For ice-water-vapour system

If all the three phases are present in equilibrium. Then no condition has to
be specifies. This is because the three phases of water can exist together in
equilibrium at a particular temperature and pressure (Freezing point of
water) and no condition is necessary to be specified to define the system.
Thus, it is a non-variant/invariant system
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P = 3, C = 1
 Degree of freedom
For saturated NaCl solution

The saturated solution of sodium chloride in equilibrium with solid sodium

chloride and water vapour.

Thus the system is completely defined if we specify temperature only. The

other two variables i.e,. the composition of NaCl-solution (solubility) and
vapour pressure have a definite value at a fixed temperature. Hence the
system has one degree of freedom. Therefore, F = 1.

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 Gibb’s Phase Rule

If a heterogeneous system at equilibrium is influenced by

temperature, pressure and composition (concentration)
and not by other actions like electrical, magnetic and
gravitational forces or by surface action, then the number
of phases (P) and degrees of freedom (F) is greater than
the number of components (C) by two. Mathematiaally

P+F = C+2 or
F = C-P+2

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 Derivation of the phase rule
Consider a system consisting of ‘C’ components distributed in
‘P’ phases as shown in figure.

C distributes in equilibrium itself among the phase

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 Derivation of the phase rule
To calculate the no. degrees of freedom of the system:

• First add up the total no. of variables required to describe

separately each phase
• Then subtract the no. of those variables whose values are
fixed by free energy equilibrium relations among the
different phases
Hence,
F=(total no. of variables)-(no. of variables already fixed)

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 Derivation of the phase rule
This system will remain in equilibrium as
long as the temperature and pressure is fixed
• The state of the system will depend upon the variables-
pressure and temperature
• Again, in order to define the composition of each phase, it is
necessary to specify the concentration term
If mole fractions are used to measure the concentrations we
need to specify the mole fraction of all but one of the
components, the remaining one can be easily found out.
 Because, the sum of the mole fractions of all the components
must be unity
For a system having ‘C’ components, there are (C-1)
concentration terms in each phase
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A) Total no. of variables: For any system, there is only one
pressure and one temperature
Hence these are 2 variables.

For a system having ‘C’ components, there are (C-1)

concentration terms in each phase

Number of concentration terms in ‘P’ phases = P(C-1)

So, total no. of variables = P(C-1)+2

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 Derivation of the phase rule
B) No. of fixed variables:
For a system having three phases α, β and γ in equilibrium and μα, μβ and μγ
are the chemical potentials of each component in the three phases, there are
two equations known μα = μβ and μβ = μγ.

Similarly, for P phases, (P-1) equations are known for each component
Total no. of known variables for C components = C(P-1)
F=(total no. of variables)-(no. of variables already fixed)
Therefore, degrees of freedom is given by,
F= [P(C-1)+2]-[C(P-1)]
F= PC-P+2-CP+C
F= C-P+2
This is phase rule
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Application of Phase Rule to a one-component system

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Application of Phase Rule to a one-component system

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Phase diagrams
A phase diagram is a plot showing the conditions of pressure and
temperature under which two or more physical states can exist
together in a state of dynamic equilibrium.

Phase diagram of one

component system
The diagram consists of
(a) Regions or Areas
(b) Lines or Curves and
(c) Triple point.

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Application of Phase Rule to a one-component
Water system

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 Application of Phase Rule to a one-component
Water system

The phase diagram water consists

of:
(1) Three stable curves OA, OB, OC
(2) One triple point O
(3) Three areas AOC, AOB, BOC
(4) One metastable curve (OA/)

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 Curve OA (Vaporization curve)

F = C-P+2 = 1-2+2 = 1 29 11/10/2020

 Curve OB (Sublimation curve)

F = C-P+2 = 1-2+2 = 1 30 11/10/2020

 Curve OC ( Melting or Fusion curve )

Curve OC represents the equilibrium

between Ice and Water.
Ice ↔ water
• Along this curve two phase co-exist in
equilibrium
• The very little slop of the curve as well as
its inclination towards pressure axis due
to the abnormal behavior of water and
ice (Density of ice is less than of water)
• The curve OC starts from point O but
there is no limit for this curve. It goes
upto a point corresponding to 2000 atm
and -200c.
• Along curve OC P=2, C=1 and F=1

F = C-P+2 = 1-2+2 = 1 31 11/10/2020

 Triple point (O)

The point O, where all the three

curves OA, OB and OC meet is
known as triple point. At this point
all he three phase co-exist.
• The equilibrium in three phases
is attained at 0.0076ºC and 4.68
mm Hg.
• At this point P=3
• if any of the variable either
pressure or temperature or both
are changed, the three phases
would not exist and one of the
phases would disappear.

F = C-P+2 = 1-3+2 = 0
The system at the triple point is32 nonvariant. 11/10/2020
Metastable system : Supercooled Water/Vapour System

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 Areas AOC, AOB and BOC

The areas or regions between the curves show the

conditions of temperature and pressure under which a
single phase–ice, water or vapour is capable of stable
existence.

Thus,
Area AOC represents conditions for the one-phase system water.
Area AOB represents conditions for the one-phase system vapour.
Area BOC represents conditions for the one-phase system ice.
In all the three areas there being one-phase and one-component,
we have
F=C–P+2=1–1+2=2

Thus each system water, water vapour, or ice has 2 degrees of

freedom i.e., the system is bivariant. 34 11/10/2020
Question

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