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PHASE EQULIBRIA

PRESENTED BY
Dr. SANDEEP S. KAHANDAL
(M.Sc. Ph.D. NET, SET, GATE)
DEPARTMENT OF CHEMISTRY
V.P.M’s B.N. BANDODKAR COLLEGE OF
SCIENCE THANE.

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 Phase Equilibria
Phase Equilibria
Phases, Components and Degrees of Freedom of a System, Criteria of
Phase Equilibrium. Gibbs Phase Rule and its Thermodynamic
Derivation.
Derivation of Clapeyron Equation, Derivation of Clausius Clapeyron
Equation and its Importance in Phase Equilibria. (Numericals
expected).
Phase Diagrams of one-Component Systems (Water and Sulphur).
Two Component Systems Involving Eutectics (Lead-silver System).,
Congruent Melting Point Zinc Magnesium Incongruent Melting Point
System. Sodium-potassium System.

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GIBB’S PHASE RULE

Willard Gibbs, an American physicist in 1876 deduced Phase

Rule to study the effect of pressure, temperature and
composition on heterogeneous system. The Gibbs Phase Rule
states that, provided the equilibrium of heterogeneous system
is not affected by gravity or by electrical or magnetic forces,
(the number of degree of freedom (F) is related to the number
of components (C) and number of phases (P) by the relation
F= C - P+2

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Types of processes
Phase (P): A phase is defined as a homogeneous,
physically distinct and mechanically separable part
of a heterogeneous system.
To be physically distinct, a phase should have a
definite bounding surface.
The term mechanically separable means each phase
can be separated from every other phase by
filtration, decantation, hand picking of crystals by
shape and color, separation of one immiscible liquid
from other using a separating funnel etc.
This does not include methods of separation such as
evaporation, distillation, absorption or extraction.

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3. A mixture of two immiscible liquids such as water and
carbon tetrachloride will form two phases and in addition
third phase of vapors of two liquids in contact with them.
4. A liquid in equilibrium with its vapor will form two phases.
5. Mixture of two or more solids consists of as many phases
as the number of solids present in the state of equilibrium.
Thus, every solid present in the system is considered as a
separate phase.
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6. A solution containing completely dissolved solid
(common salt in water) is considered as a single
phase. But in a saturated solution if some salt
remains undissolved, then the system is of two
phases, one of saturated solution and other of
undissolved solid.

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 Degrees of freedom (F) or Variance

•e.g.
•State of a pure gas may be described by any two of the three
variables P, T and density. If any two known third can be
calculated. Hence it has two degrees of freedom called
bivariant system. F = 2
•Univariant in which water and water vapor are in one system
•If all phases of water exist in equilibrium, no condition needs
to be specified as the phases can coexist only at particular
temp and pressure. (F =1)
•This system has no degrees of freedom hence called invariant
system (F = 0)
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 Phase rule

It was first presented by Gibbs in 1875.

It is very useful to understand the effect of intensive variables, such
as temperature, pressure, or concentration, on the equilibrium
between phases as well as between chemical constituents.
It is used to deduce the number of degrees of freedom (F) for a
system. Sometimes called: “the variance of the system”.

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 Phase rule

It states that :
For every heterogeneous system in equilibrium, the sum of
number of phases and degrees of freedom is greater than the
number of components by two i.e.:

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

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 Advantages of Phase rule

1. Provides convenient method of classification of equilibrium states of

system.
2. Predict the behavior of system with changes in the intensive variables.
3. Indicate that different systems having the same number of degrees of
freedom behave in the same manner.
4. Applicable to macroscopic system
5. It takes no account of nature of reactant and products in phase
6. Applicable to physical and chemical equilibria.

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 Phase Diagram

1. It is a convenient graphical representation formed by plotting the

values of intensive variables for equilibrium conditions between
two phases.
2. It shows the properties such as mp, bp, phase transition point and
triple point.
3. The complexity of phase diagram increase with increase in number
of component in the system.
4. For a simple substance (one component system) phase diagram is
two dimensional plot where P & T are independent variables.
5. The phase diagram of a two component system is a three
dimensional plot, where third axis is for composition.

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 Water System

1. Water exist in three possible phases: ice, water, vapors

2. It is a one component system so maximum degrees of
freedom is two, when one phase is stable at equilibrium.
F= C-P+2 = 1-1+2=2
3. Phase diagram of water is two dimensional plot where P &
T are taken as axes.

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 Areas of Phase Diagram of Water System

Phase diagram is divided into three areas:

1. Area BOC – where ice has stable existence

2. Area COA – where water has stable existence
3. Area BOA – where water vapors has stable existence
P = 1, C = 1
Phase Rule for this system:
F = C-P+2 = 2
F = 1-1 +2 = 2
Degrees of freedom is two hence bivariant system.

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Various Curves of Phase Diagram of Water
System

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Triple point of water

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 IMP terms

1. Triple point: The temperature and pressure at which a substance

can exist in equilibrium in the liquid, solid, and gaseous states.

2. The triple point of pure water is at 0.01°C (273.0075 K, 32.01°F)

and 4.58 mm (611.2Pa) of mercury

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 Phase Diagram of Sulphur

Sulphur Exist in four forms:

1. Rhombic Sulphur (SR) (m.p.

114°C)
2. Monoclinic Sulphur (SM)
(m.p. 120°C) Monoclinic Sulphur Rhombic Sulphur
3. Liquid Sulphur (SL)
4. Vapour Sulphur (SV)

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 Polymorphism:
When a system exists in two or more forms and
has different properties, the phenomenon is
called polymorphism.
If the substance is an element, then it is called
allotropism.
Example sulphur exists as rhombic and
monoclinic. Thus, “S’ exhibits .polymorphism.
When rhombic Sulphur is heated to 368.6 K, it
changes to monoclinic. This temperature is
called transition T. When monoclinic sulphur is
cooled to 368.6 K, it changes to rhombic
sulphur.
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 Phase Diagram of Sulphur

2. Rhombic Sulphur

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(1) Four areas: ABEF (SR), BEC Curves In Phase Diagram
(SM), DCEF (SL), ABCD (SV)
(2) Six curves: AB, BC, CD, BE,
CE, EF.
(3) Four triple points: B, C, E and
O.

• Curve AB: Sublimation Curve of

Rhombic Sulphur
• Curve BC: Sublimation Curve of
Monoclinic Sulphur
• Curve CD: Vapor Pressure Curve
of Liquid Sulphur
• Curve CE: Fusion Curve of
Monoclinic Sulphur
• Curve BE: Transition Curve Solid
Sulphur
• Curve EF: Fusion Curve of
Rhombic Sulphur
 Description of Phase Diagram
(a) Areas: The areas

ABEF, BEC, DCEF and

ABCD represent

Rhombic Sulphur (SR),

Monoclinic Sulphur (SM),

Liquid Sulphur (Sl)and

Vapour Sulphur (Sv)).

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 (b) Curves:
1. Curve AB: Sublimation Curve of Rhombic Sulphur
Rhombic Sulphur Vapour Sulphur
2. Curve BC: Sublimation Curve of Monoclinic Sulphur
Monoclinic Sulphur Vapour Sulphur

3. Curve CD: Vapor Pressure Curve of Liquid Sulphur

liquid Sulphur Vapour Sulphur

4. Curve BE: Transition Curve Solid Sulphur

Rhombic Sulphur monoclinic Sulphur
5. Curve CE: Fusion Curve of Monoclinic Sulphur
monoclinic Sulphur liquid Sulphur
6. Curve EF: Fusion Curve of Rhombic Sulphur
Rhombic S Liquid S

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Triple Points

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0 = F = 4 -4

3 = F = 4 -1

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 Phase Diagram for Two component system

1. In two component system with P=1, the number of degrees of

freedom are highest order is three.
2. In two component system phase diagram may be represented by
three dimensional diagram of P, composition and T.
3. In this diagram two axes represents two variables while third
variable is held constant.
4. Phase Diagram may be constructed as :
1. P-T diagram keeping conc. Constant
2. P- Conc. Diagram T constant
3. T-C diagram keeping P constant.

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 Solid – Liquid Equilibria or condensed
phase rule or reduced phase

When two components that are completely miscible in liquid state are allowed
to cool at low Temperature and components begin to separate out as solid
in any of following three forms:
1. Components are not miscible in solid state and form eutectic mixture.
Pb-Ag alloy, Cd- Bi alloy
2. Components form a stable solid compound which melts at constant
temperature to give a liquid with same composition. Such compounds are
said to have congruent melting points.: Zn-Mg system
3. Components form a solid compound which is unstable and decomposes
below its mp to give a new solid phase and liquid that is different in
composition from original compound. Such compounds have incongruent
mp e.g. : Na-K system

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 Freezing point curve of Ag
Freezing point curve of Pb

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4. F = C - P +1= 2 -1 +1 = 2, Bi- variant
Important
5. F = C - P +1= 2 -2 +1 = 1, mono variant 46
 F = C - P +1= 2 -3 +1 = 0, non-variant

At point C
2 phases- Solid Pb, Solid Ag similar to Eutectic mixture: Mixture of Pb
and Ag
1- phase: Liquid Melt 47
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 System with congruent melting point

• Congruent melting : occurs during melting of a compound when

the composition of the liquid that forms is the same as the
composition of the solid.
• It can be contrasted with incongruent melting.

• A binary system is said to be possess a congruent melting point

when it melts at sharp temperature to give a liquid of the same
composition as that of solid.

• This generally happens in two-component systems.

• e.g. Zn-Mg System

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 Zn-Mg System

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 Zn-Mg System

• Zn-Mg System is a two component system and having

congruent melting point.
• In this system zinc and magnesium, which melt at 420 °C and
650°C.
• Both metals enter into chemical combination and form an
intermetallic compound MgZn2 and melts at 590°C to give a
liquid of the same composition.
• Hence, 590°C is the congruent melting point of the system.
• In the reduced form, the system has the following four phases:
Solid magnesium, solid zinc,
Solid MgZn2
Liquid solution of Zn and Mg.

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At point D

Virtually one component system

P = 2, C =1

F = 1 -2 + 1 = -1 + 1= 0

At point A

Solid Zn in equilibrium with liquid Zn

P = 2, C =1

F = 1 -2 + 1 = -1 + 1= 0

At point B

Solid Mg in equilibrium with liquid Mg

P = 2, C =1

F = 1 -2 + 1 = -1 + 1= 0
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 Zn-Mg System

1. On applying the reduced phase rule

F=C–P+l=1–2+1=0
Therefore, at point D constitutes a non-variant system.

2. Point E (Eutectic point):

• Point E represents the eutectic point of the system at a temperature of

345°C which is the least melting point of Mg-MgZn2 system.
• Here, also three phases existing together in equilibrium at point E are
solid Mg,
• solid MgZn2 and
• liquid MgZn2 (melt)
• F=C–P+1=2–3+1=0
• The system is non-variant.

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 Zn-Mg System

3. Point C (Eutectic point):

• This point also represents the eutectic point (380°C) which is the least
melting point of Zn-MgZn2 system.
• At this point, the three phases—
• solid Zn,
• solid MgZn2 and
• liquid MgZn2 (melt) exist together in equilibrium.

F=C–P+l=2–3+1=0

• Hence, point C represents a non-variant system.

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 Areas of Zn-Mg System

• The area above the curve ACDEB constitutes a single phase system. i.e.
liquid melt consisting of a liquid solution of zinc and magnesium.
F=C–P+1=2–1+1=2
• The system is bivariant.

• Other areas of the Zn-Mg system consists of two phases and they are
univariant systems.

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 Curves of Zn-Mg System

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 Areas of Zn-Mg System

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At point C (-12 oC) Eutectic point
Three phases, Solid K, Solid Na2K, melt (liquid phase)
P = 3, C =2

F = 2 - 3 + 1 = 0, Invariant system

At point P – Peritectic point

The compound decomposes according to the equation,

Solid Na, Solid Na2K, melt (liquid phase)

P = 3, C =2

F = 2 - 3 + 1 = 0, Invariant system
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At point X
C = 2.
P=1
F =2-1+1 =2

At point M
C = 2.
P=2
F = 2-2+1=1

At point P
C = 2.
P=3
F = 2-3+1=0 69
C = 2.
P=3
F = 2-3+1=0

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Thank you….

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