MODULE 2

Phase Equilibria
Gibbs phase rule, definition of terms with
examples, One Component Systems-
water and carbon dioxide systems –
Reduced phase rule. Two Component
eutectic Systemlead-silver systems. Alloys:
Introduction- Definition- Properties of
alloys- Significance of alloying- Ferrous
alloys- Nichrome and Stainless steel –
 Phase (P): A phase is a homogenous, physically distinct
and mechanically separable portion of a system which is
separated from other parts of the system by a definite
boundary.
Number of phase (P)

Liq. in liq. Solid in liq. Gas in liq. Solid in Solid. Gas in gas
P=1

(O2+ N2 )

Miscible Immiscible Soluble Insoluble Dissolve Insoluble Alloy No alloy

P=1 P=1 P=1 P=1 P=1 P=1 P=1 P=1
(Oil + water) (Sugar + water) (Sand + water)
(Ethanol + H2O) (O + water)
2 (H2+ water) (Steel) (Sugar + Salt)
Note: If you look at a mixture and can see a boundary between two of
the components, those substances are in different phases.
 Examples of Phases
System No. of phase

3
Fe (s), H2O(l), FeO (s), H2(g) 4

Ag+, Cl-, H2O 1

Ag+, Cl-, AgCl (s), H2O 2

Mohr’s salt [FeSO4 .(NH4 )2 SO4 .6H2O]

1
Glucose in water or Salt in water 1

Air 1
 No. of Constituents (N): Total no. of species that are present in a system

Total no. of constituents (N) = 3

Total no. of phase (P) = 3
No. of Components (C): The number of components of a system at
equilibrium is the smallest number of independently variable
constituents by means of which the composition of each phase present
can be expressed either directly or in the form of a chemical equation.

Phase 1 Phase 2 Phase 3

CaCO3 CaO CO2
Minimum no. of

CaO & CO2 CaO + CO2 1CaO + 0CO2 0CaO + 1CO2

constituents

CaCO3 & 1CaCO3 + 0CaCO3 1CaCO3 –CaO

CaO 0CaO +1CaO
CaCO3 & 1CaCO3 + 1CaCO3 – 0CaCO3 +
CO2
No. 0CO2
of Components =2 CO2 1CO2
 No. of components (C)

For non reacting species For reacting species

=
No. of species C=N E R
Where, N = No. of species
Ex: Sugar + Salt E = No. of equilibrium
N=2 R = Restricted conditions
C=2 Ex: NH4Cl(s) ⇌ NH3(g) + HCl(g)
P =1
If (a) PNH3 = PHCl
(b) PNH3 = PHCl
(b) C = N E R
Ex: (a) C = N E R
N=3
C=N E R N=3
E=1
E=1
N=3 R=0
R=1
E=1 C = 3-1 = 2
C = 3-1-1 = 1
R=0
C = 3-1 = 2
 DEGREE OF FREEDOM (F) / Variance
The number of degrees of freedom Temperature &
of a system is the minimum Pressure are
number of independent variables needed to define
of a system, such as temperature, the water.
pressure and concentration which F = 2 (Bivariant)
can define a system in equilibrium H2O (l)
completely
Here, T & P are
Note: The phase should not be change independent variables
upon variation of variables

H2O (g) Boiling point

Triple point of water T = 100 oC

⇌
H2O (l) P = 1 atm
F = 1 (Univariant)
T = 0.0075 oC
P = 4.588 mm Hg
F = 0 (Non variant) Here, T or P is independent variable
 PHASE Also known as Gibbs phase rule
RULES

F = C – P +2
Degree of
freedom or the
number of
independent The number
variables of phase
2 variables
Number of (temperature
component and pressure)
 EXAMPLES

CaCO3(s) CaO(s) + CO2(g) Calculate the degree of freedom (F)

The number of components is not
F = C–P+2 Means: only one always easy to determine at first
=2–3+2 variable, either glance, and it may require careful
= 1 (univariant) temperature or pressure examination of the pyhsical
can be changed conditions of the system at
independently equilibrium
 Phase Equilibrium
Thermal Mechanical
Equilibrium Equilibrium
(All phases should ( All phases should
be at const. T ) be at constant P)
Chemical potential (µ) : Skipping tendency from one
phase to other. One component want to be in a phase
whose µ is minimum.
Chemical
Equilibrium
(Chemical potential should be same
for a component in different phases)

Let us assume a component (M) is present in a system which has 3 phases in equilibrium
Phase 1 ⇌ Phase2 ⇌ Phase3
M M M
Then, µ(1) = µ(2) = µ(3)

Derivation of Phase Rule: Total no. of Equations

Non reactive system Phase =1, Χ1(1) + Χ2(1) + Χ3(1) Χn(1) = 1 (one eqation)
Total no. of variables
“C” Temperature = 1 P Phase “P” equations
Pressure = 1
Composition of µ(1) = µ(2) = µ(3)…. = µ(P) for one component
“P” (P-1) equations
Components in different phases = P × C
Total variables = PC + 2 For “C” components = C(P-1) equations
Total equations = P + C(P-1)

F = (No. of variables that should be specified) – (total no. of equations)

F = (PC+2) – [P + C(P-1)] = C-P + 2

 Phase Rule
• The phase rule is used to study and understand the way that temperature,
pressure, concentration, etc. effect the phase of a substance.

1. Application (Bivariant system):

Temperature &
Pressure are
needed to define
the water.
F = 2 (Bivariant)
H2O (l)

Here, T & P are

independent variables

• A liquid, e.g. Liquid water confined to a particular volume.

• Apply phase rule: F=1-1+2=2.
• This means that two intensive variables (temperature and pressure,
temperature and concentration) must be known to duplicate this system
exactly.
 H2O (g) Boiling point
2. Application (Univariant): T = 100 oC

⇌
H2O (l) P = 1 atm
F = 1 (Univariant)

Here, T or P is independent variable

• A liquid such as water in equilibrium with its vapor ( we have 2 phase

system)
• F=1-2+2=1.
• By stating temperature, the system is completely defined because the
pressure under which liquid and vapor can coexist is also fixed.
• If we decide to work under a particular pressure, then the temperature of the
system is automatically defined:
• The system is described as univariant.
3. Application (Non-variant): Triple point of water

T = 0.0075 oC
P = 4.588 mm Hg
F = 0 (Non variant)

▪When we have a liquid water, vapor and ice in equilibrium

▪ Phase rule states that the degrees of freedom = 1-3+2=0
▪ There are no degrees of freedom, if we attempt to vary the conditions
of temperature or pressure necessary to maintain the system, we will
lose a phase.
▪ The combination is fixed and unique.
▪ The system is nonvariant.
 Phase Rule
• As the number of components increases, so do the required degrees of freedom needed to define
the system. Consequently, as the system becomes more complex, it becomes necessary to fix
more variables to define the system.

• As the number of phases in equilibrium increases, the number of the required degrees of freedom
becomes less.

• Liquid water+vapor F=1-2+2=1

ethyl alcohol+vapor F=1-2+2=1

liquid water + liquid ethanol + vapor mixture, F=2-2+2=2

liquid water + liquid benzyl alcohol + vapor mixture →

F=2-3+2=1 → benzyl alcohol and water form two separate liquid phases and one vapor phase.
 TRIVARIANT SYSTEM
A mixture of two gases is completely defined only when
pressure, temperature and composition are specified. If
pressure and temperature are specified then the third
variable composition may be varied.
So it is necessary to specify all the three variables to
define the system completely.

F =C–P+2
=2–1+2=3

Hence the system is trivariant.

 Phase Transition

• The spontaneous conversion of one phase into another phase.

• Occurs at a characteristic temperature for a given pressure.

• Transition temperature, Ttrs, is the temperature at which the two phases are in
equilibrium.
• Vaporization
• Condensation
• Melting
• Freezing
• Sublimation
• Deposition
 Phase Diagram
How to construct?

Single phase Two phases in equil. Three phases in equil.

(Will cover a region) (Will be represented by lines) (Will be represented by lines)

⇌ Liquid
Solid ⇌
Solid

⇌
Liquid ⇌
Gas

What Information? Triple point

(i) Stability of different phases at different T & P.
(ii) Properties of substance (mp, bp, transition temp.etc).
(iii) Effect of T & P on properties of substance
 Phase Diagram

Phase Diagram: shows the

regions of pressure and
temperature at which its various
phases are thermodynamically
stable.

Phase Boundary: a boundary

between regions, shows the
values of P and T at which two
phases coexist in equilibrium.
 Phase Diagram

Triple Point: all three phases

can exist.

Critical Temperature: maximum

temperature where a substance
can exist as a liquid.
• Phase Vs the term physical state (solid, liquid or gas).

• Phase includes solids, liquids and gases, but is a bit more general. It can also
apply to two liquids (oil and water, for example) which don't dissolve in each
other. You could see the boundary between the two liquids.
Standard phase diagram for water (H2O)

ONE COMPONENT
SYSTEM

Standard phase diagram for carbon dioxide

(CO2)
Phase diagram for water (H2O)

Super critical fluid

Has a negative slope

Water as the liquid is

denser than the solid (ice
floats on water).

-273

This unique properties of water is due to the That means that an increase of pressure
network of hydrogen bonding in ice is more favors the formation of liquid and that the
extensive than in liquid melting point of water falls with increasing
pressure.
Single Component System- Carbon Dioxide
Study of Area:

✔ ABD (Right Hand Side) consist of Vapour phase,

✔ Area CBD consist of Liquid phase and
✔ Area (Left Hand Side) ABC consist of Solid Phase
Study of Curves:
Curve AB
✔Curve AB is the sublimation curve
✔ Solid CO2 is in equilibrium with Gas CO2.
✔ Point ‘C’ is known as Sublimation point
✔ Temperature -78.5°C, Pressure 1 atm.
Curve BD
✔Curve BD is the vaporisation curve
✔ Liquid CO2 is in equilibrium with Gas CO2.
✔This curve starts from Triple Point ‘B’
✔ ends Critical point (Temperature 31.1°C, Pressure 72.8 atm.)
Curve BC
✔Curve BC is the fusion curve
✔ Solid CO2 is in equilibrium with Liquid CO2.
✔ This curve starts from Triple Point ‘B’ and ends at Point ‘C’.
Study of Point ‘O’ [Triple Point]:

✔ At triple point ‘B’ all the three phases of CO2 co-exist in

equilibrium
✔ curve AB, BD and BC meet.
✔ Solid CO2 = Liquid CO2 = Gas CO2
✔ So, No. of Phases = 3
Hence the system is invariant at the triple point ‘B’
(-56.6°C and 5.11 atm.)
Phase Diagram of Phase Diagram of
H2O CO2
 Difference in the Phase Diagram of H2O and CO2

✔ In CO2 phase diagram the melting point curve slopes

away from the pressure axis (+Ve slope).

✔ Solid CO2 can exist in equilibrium with Liquid CO2 only at

high pressure equal to 5.11 atm. While in H2O system Ice
and Water can exist in equilibrium at low pressure.
✔ Vapour pressure of Solid CO2 even at low temperature is
very high and many time higher than that of Ice.

✔ At low atmospheric pressure CO2 gas can be directly

solidify without attending the liquid phase just by cooling
to -78.5°C, this is why the Solid CO2 is known as Dry Ice.
 TWOComponent
Binary COMPONENTSystem
SYSTEM
Two component system is one in which it is possible to
express the composition of each phase in terms of two
substances.
Number of Phases (P) = 1
Number of Components(C ) = 2
Degree of Freedom (F) =C+2–P
=2+2–1 = 3
So to define the system
completely three variables
temperature, pressure and
composition are required.
It is difficult to construct a phase
diagram in two dimension.
When one variable is kept constant then we following possibilities:
i) Pressure–temperature diagram ( P–T ) when composition is
constant
ii) Temperature–composition diagram (T–C) when pressure is constant
iii) Pressure–composition diagram (P–C) when temperature is constant
❑ A solid liquid equilibrium of an alloy has practically no gas phase
and the effect of pressure on these equilibria is negligible.
Experiments are generally conducted at room temperature. Hence in
most cases, pressure is kept constant at 1 atmosphere and the phase
diagram is constructed using the variables, temperature and
concentration.
❑ Such a solid–liquid equilibrium with the gas phase absent is termed
as the condensed system. This will reduce the degree of freedom by
one and for such a system, the phase rule becomes
F=C–P+1
This is known as the reduced or condensed phase rule and is widely
applicable to solid–liquid two component systems. The solid–liquid
equilibria are represented on temperature–composition diagrams
 Types of Two Component System
Two component system is of three types involving solid-
liquid equilibria.
Type-I: Two component do not react with each other but
mix with each other in molten state or in solution.
For Example: Lead-Silver System, KI-H2O System

Type-II: Two pure component react to form a compound

which is stable up to its melting point. At melting point it
melts to gives a liquid of the same composition as that of
solid compound. The compound formed is then said to
have congruent melting point.
For Example: FeCl3-H2O System
Type-III: Two pure component react to form a compound
which is unstable up to its melting point. On heating it
starts decomposing before melting point to give a new
solid and a solution with composition different from that
of solid phase. The compound is said to have incongruent
melting point.
For Example: Na2SO4-H2O System
 Construction of Phase Diagrams
Thermal analysis (cooling curves):
▪The phase diagram of a two-component system is generally drawn by thermal
analysis.
▪ Thermal analysis is the study of the cooling curves of various compositions of
a system during solidification.
▪ In this method, solids of different compositions are taken at a temperature
above their melting points.
▪ The resulting mixture is cooled slowly and cooling curves are constructed by
plotting temperature against time.
▪ For a mixture of definite composition, cooling curves help us to determine
(1) Freezing point (2) Eutectic point
 Cooling curve
(a) Pure solid (a) Mixture of solids

a a

b c

d b

c d
Eutectic point
e

Eutectic system: The term eutectic means ‘easy to melt’. A eutectic system is a binary
system consisting of two substances which are miscible in all proportions in the liquid
phase and which do not react chemically.
Eutectic mixture: It is a solid solution of two or more substances having the lowest freezing
point of all possible mixtures of the components.
Eutectic point: Two or more solid substances capable of forming solid solutions with each
other have the property of lowering each other’s freezing point and the minimum melting
point attainable by the eutectic mixture is termed as the eutectic point (lowest melting
point).
 Application of Eutectic Mixture

Alloys which are known to form eutectic mixture are used

as ‘Fail Safe’ devices in boilers & domestic water geysers,
as plug in automobiles.

Eutectic mixtures has low melting point, so they are used

for joining two metal pieces together. For example Lead-
Tin solders.

Eutectic mixtures of Sodium & Potassium are liquid at

room temperature and are used as coolant in nuclear
reactors.
 Lead–Silver System
The system consists of four phases
(i) Solid silver
(ii) Solid lead
(iii) Solution of molten silver and lead
(iv) Vapour
27-09-2021 41

Difference between EP, MP & TP

• Melting Point: It is the temperature at which the solid
and liquid phases, having the same composition, are
in equilibrium.

• Eutectic Point: It is the temperature at which two

solids and a liquid phase are in equilibrium

• Triple Point: It is the temperature at which three

phases are in equilibrium.
 Alloys
❖A homogeneous mixture of two or more elements with metallic properties or a
metal and a non-metal possessing metallic properties.
❖Chemically, alloys are solid solutions and are harder, more malleable and have
lower melting points than the component elements.
❖The properties of a metal can be modified by alloying it with some other element.
❖Important elements that form alloys are copper, zinc, lead, tin, nickel, aluminium,
chromium and tungsten.
Purpose of Making Alloys
▪To increase the hardness of the metal (Ex. gold + Cu)
▪ To lower the melting point (Wood metal)
▪ To improve corrosion resistance (Stainless steel)
▪ To improve castability
▪ To modify chemical activity ( For ex. the chemical activity of sodium reduces on
alloying with mercury to form sodium amalgam
▪ To modify colour (Ex Brass)
 Ferrous alloys
These alloys contain iron as one of the major components.

Stainless steel
Nichrome