PHASE EQUILIBRIA

Phase:
The homogeneous part of a heterogeneous system which is physically and chemically different from
other parts of the same system and bounded by surfaces of separation and mechanically separable. It is
denoted by P.

Example: H2O has 3 phases: ice, water and vapor.

Component:
The number of component is defined as the minimum number of independently variable
chemical entities required to describe all parts of a system. It is denoted by C.

Example: The component of H2O is 1.

Gibbs Phase rule/Phase rule;
Gibbs combined phase, component and degrees of freedom in a relationship which is known as gibbs
phase rule or phase rule.
The phase rule is,

F=C–P+2
Where, F = Degrees of freedom
C = Component
P = Phase
In this system, two variables are used i.e., temperature and pressure. Thus, 2 indicate these
variables.
Degrees of Freedom:

The number of degrees of freedom may be defined as the number of independent variables i.e.,
temperature, pressure and composition, which must be fixed in order to define the system
completely. It is denoted by F.

Example: Degrees of freedom of H2O are invariant.

For H2O,

F=C–P+2

=1-3+2

=0

So, degrees of freedom of H2O are invariant. Invariant means two variables i.e., temperature
and pressure are fixed, these variables can’t be changed for this system.

Phase diagram:
Phase diagram is a single graph representation of the various phases of a substance or mixture
of substances that coexist in thermodynamic equilibrium.

Triple point:

Triple point is the temperature and pressure at which the solid, liquid, and vapor phases of a
pure substance can coexist in equilibrium.
Example:

The triple point temperature of H2O is 0.010 C and pressure is 0.006 atm.

Phase diagram of H2O:

 Criteria of H2O’s phase diagram:

1. AOC region represents liquid phase, BOC region represents solid phase and AOB
region represents vapor phase.
2. OA curve shows liquid and vapor phase coexist in equilibrium which is known as
vaporization curve, OB curve shows solid and vapor phase coexist in equilibrium
which is known as sublimation curve, OC curve shows solid and liquid phase coexist
in equilibrium which is known as melting curve.
3. O represents triple point where OA, OB and OC curves meet. The triple point
temperature of H2O is 0.010 C and pressure is 0.006 atm. In this point, solid, liquid
and vapor phases coexist in equilibrium.
 How it can be proved that pressure and temperature are fixed for phase diagram of
water?
Answer:

Decreased of melting point

Increased of boiling point

0.0080 C

If the pressure of this system is increased to 4 atm then the boiling point of water is increased to
1050 C and melting point of ice is decreased to 0.0080 C which don’t match with the boiling
point of water (1000 C) and melting point of ice (O0 C).
So, it can be said that pressure and temperature are fixed for phase diagram of water, if not
then this phase diagram doesn’t exist possible.
  Calculate the phase, component and degrees of freedom for solution of NaCl or
saturated solution of NaCl.
Answer:
NaCl (s) Na+ (aq) + Cl- (aq)

Phase:
Solid NaCl dissolves in H2O and obtain aqueous state of Na+ and Cl-. Thus, the phase of this
system is 1.
Component:
Two chemical entities are present in this system which are Na+ and Cl-. Thus, the component of
this system is 2.
Degrees of freedom:
F=C-P+2
=2–1+2
= 3, it indicates trivariant. Trivariant means three variables i.e., temperature,
pressure and composition, all variables can change possible for this system.

 Calculate the phase, component and degrees of freedom for solid CaCO3 when it is
heated in open container.

Answer: One directional reaction is occurred in open container. Thus, only product’s phase and
component are considered for this system.
CaCO3 (s) CaO (s) + CO2 (g)

Phase:
Solid CaCO3 dissociated into solid CaO and gaseous CO2. Thus, the phase of this system is 2.

Component:
Two chemical entities are present in this system which are CaO and CO2. Thus, the component
of this system is 2.

Degrees of freedom:
F=C-P+2
=2–2+2
= 2, it indicates divariant. Divariant means two variables i.e., temperature
and pressure can change possible for this system and third variable i.e., composition is fixed.
  Calculate the phase, component and degrees of freedom for solid CaCO3 when it is
heated in closed container.

Answer: Two directional reaction is occurred in closed container. Thus, both reactant and
product’s phase and component are considered for this system.

CaCO3 (s) CaO (s) + CO2 (g)

Phase:
In the first step, solid CaCO3 dissociated into solid CaO and gaseous CO2. As this system
remains in equilibrium, so in the 2nd step, solid CaO and gaseous CO2 again combined together
and forms solid CaCO3. These three create homogeneous phases which are physically and
chemically different from other parts of the same system. So, the phase of this system is 3.

Component:
Two chemical entities are present which are CaO and CO2. CaCO3 can’t consider as component
of this system because when CaO and CO2 again mixed together, these form CaCO3. According
to the definition of component, the minimum number of independently variable chemical entities is
considered. Thus, the component of this system is 2.

Degrees of freedom:

F=C-P+2
=2–3+2
= 1, it indicates univariant. Univariant means one variable i.e., temperature
or pressure can change possible for this system and other two variables are fixed.

 Calculate the phase, component and degrees of freedom for immiscible liquids of H2O
and CCl4.

Phase:
These immiscible liquids form two separate layers. So, the
phase of this system is 2.
Component:

H2O and CCl4 are two different chemical entities. So, the
component of this system is 2.
Degrees of freedom:

F=C-P+2
=2–2+2
= 2, it indicates divariant. Divariant means two variables i.e. temperature

and pressure can change possible for this system and third variable i.e., composition is fixed.

 Calculate the phase, component and degrees of freedom for miscible liquids of H2O
and ethanol.
Phase:
These miscible liquids form one separate layer due to
formation of intermolecular H-bond. So, the phase of this
system is 1.
Component:

H2O and ethanol are two different chemical entities. So, the
component of this
component of this system
system is
is 2.
2.
Degrees of freedom:

F=C-P+2
= 2-1+ 2

= 3, it indicates trivariant. Trivariant means three variables i.e., temperature,

pressure and composition, all variables can change possible for this system.

 Calculate the phase, component and degrees of freedom for mixture of three solids.

Phase:
Mixture of three solids forms three homogeneous phases.
So, the phase of this system is 3.
Component:

Mixture of three solids are three different chemical entities.

So, the component of this system is 3.
Degrees of freedom:

F=C-P+2
= 3 – 3+ 2
= 2, divariant
Divariant means two variables i.e. temperature and pressure can change possible for this system
and third variable i.e., composition is fixed.

 Calculate the phase, component and degrees of freedom for mixture of three gases.
Phase:
Mixture of three gases forms one homogeneous phase because molecules of gases remain far apart, so
easily mixed together. Thus, the phase of this system is 1.
Component:

Mixture of three gases are three different chemical entities. So, the component of this system is 3.
Degrees of freedom:

F=C-P+2
= 3 – 1+ 2
= 4, tetravariant.

Tetravariant means four variables i.e. temperature, pressure, volume and composition can change
possible for this system and no variable is fixed.
Condensed phase rule:
When pressure variable becomes constant in the phase rule F=C-P+2, then it is termed as
condensed phase rule.
The condensed phase rule is,
F=C-P+1
Where, F = Degrees of freedom
C = Component
P = Phase
In this system, one variable is used i.e., temperature. Thus, 1 indicates this variable.
Note: Condensed state denotes solid/liquid state.

Phase diagram of CO2:

Answer:
 Criteria of CO2’s phase diagram:

1. CBD region represents liquid phase, ABD region represents solid phase and ABC region
represents gas phase.
2. BC curve shows liquid and gas phase coexist in equilibrium which is known as
vaporization curve, AB curve shows solid and gas phase coexist in equilibrium which is
known as sublimation curve, BD curve shows solid and liquid phase coexist in
equilibrium which is known as melting curve.
3. B represents triple point where BC, AB and BD curves meet. The triple point
temperature of CO2 is -56.570 C and pressure is 5.11 atm. In this point, solid, liquid and
gas phases coexist in equilibrium.
4. C represents critical point above which solid and liquid phases of CO2 don’t exist
separately, they combined together and remain as single phase. Thus CO2 behaves as
supercritical fluid (SFC). The critical temperature of CO2 is 30.980 C and critical pressure
is 72.79 atm.

Phase diagram of sulphur (S):

Criteria of S’s phase diagram:

1. Sulphur has one gas phase, one liquid phase and two solid phases i.e., rhombic and
monoclinic form.

2. ECD region represents liquid phase, ABE region represents rhombic solid phase, EBC
region represents monoclinic solid phase and ABCD region represents gas phase.

3. The most stable form of the sulphur element is the rhombic form and when it is heated
slowly the rhombic form of sulphur converts into monoclinic form at around 1140 C and
monoclinic form of sulphur converts into liquid form at around 119-120o C because the
solid melts at this temperature. As the pressure decreases the gas form dominates.

4. 1, 2 and 3 represent three triple points where AB, BC, CE and BE curves meet. The 1st
triple point temperature of S is 95.50 C and pressure is 3.2 x 10-5 atm in which rhombic
solid, monoclinic solid and gas form co-exist in equilibrium, the 2nd triple point
temperature of S is 1190 C in which monoclinic solid, liquid and gas form co-exist in
equilibruim, the third triple point temperature of S is 1510 C and pressure is 1288 atm in
which rhombic solid, monoclinic solid and liquid form co-exist in equilibrium.

Questions type:

1. Define the term with example:

Phase, Component, Degrees of freedom, Phase rule, Phase diagram, Triple point.
2. Draw the phase diagram of H2O and explain it’s criteria. Write down the triple point
temperature & pressure of H2O and the conversion of phase rule when vapor of H2O
condensed to liquid H2O?
3. Draw the phase diagram of CO2 and explain it’s criteria. Write down the temperature and
 pressure of CO2.

4. Calculate the phase, component and degrees of freedom for solution of NaCl or
saturated solution of NaCl.

5. Calculate the phase, component and degrees of freedom for solid CaCO3 when it is
heated in closed container.

6. Calculate the phase, component and degrees of freedom for immiscible liquids of H2O
and CCl4.

7. Calculate the phase, component and degrees of freedom for miscible liquids of H2O
and ethanol.
8. Calculate the phase, component and degrees of freedom for mixture of three solids.
9. Calculate the phase, component and degrees of freedom for mixture of three gases.