Module 3

Phase Rule - Alloys

 Phase
• A form of matter that is uniform throughout in chemical
composition and physical state.

• Solid, liquid and gas phase of a substance.

• Various solid phases such as the white and black allotropes of

phosphorous.

• The number of phases in system is denoted as P.

• A gas, or a mixture of gases is P = 1.

• Two fully miscible liquids also form a single phase.

 Phase
• If you look at a mixture and can see a boundary between two of
the components, those substances are in different phases.
• A mixture containing a solid and a liquid consists of two phases.
• A mixture of various chemicals in a single solution consists of
only one phase, because you can't see any boundary between
them.
• 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.
Examples of Phases

CaCO3 CaO + CO2

 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
Thermal Analysis
 Thermodynamics of Phase Stability

• When two or more phases are in equilibrium, the chemical potential (𝛍) of a
substance is the same in each phase and is the same at all points in each phase.

• 𝛍 is a measure of the potential that a

substance has for undergoing a change in the
system.

• is the rate of change of a free energy of a

system with respect to the change in the
number of atoms or molecules of the species
that are added to the system.
 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 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 and
component pressure)
COMPONENTS PHASE

DEFINITION

DEGREE OF FREEDOM
 1) The mixture of ice and water = have two •A chemically and
phase which is solid and liquid structurally homogeneous
portion of material
2) The mixture of oxygen gas and nitrogen gas •Separated with other parts
= have one phase which is gas phase (the of the system
system is homogeneous)

3) The mixture of oil and water = have 2 same

phase(liquid). Oil and water are not
homogeneous and have the boundaries to
separate both phase

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

= 3 phase (2 solid,1 gas)

PHASE
 The least number of
different substances
required to describe the
OR composition of all phases in
the system
The number of chemical
species that can explain the
composition of all phase in a 1) water, CO2 = one
system component
2) Aqueous solution of
potassium nitrate = 2
component system because
have potassium nitrate salt
and water.

COMPONENT
 DEGREE OF FREEDOM (F)

The number of variables that may UNIVARIANT

be changed independently without
causing the appearance of a new
phase or disappearance of an TYPES
existing phase BIVARIANT

EXAMPLES

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

F = C – P +2 Means: only one The number of components is not

=2–3+2 variable, either always easy to determine at first
= 1 (univariant) temperature or pressure glance, and it may require careful
can be changed examination of the pyhsical
independently conditions of the system at
equilibrium
 Derivation from Phase Rule
Balancing of FIXED PARAMETERS and SYSTEM VARIABLES

HOW MANY VARIABLES ARE THERE IN A CHEMICAL SYSTEM?

• Simplistically, “3”,
Pressure, Temperature, Composition,

• BUT, for more than one phase, what is the TOTAL number of
variables?
 Assign C components between P phases

• For each Phase, composition is defined by (C-1) concentration terms.

• For ALL Phases in the system, P(C-1) = the number of concentration terms.

• Can also vary Pressure & Temperature, or P + T, which = 2 more variables.

• TOTAL NUMBER OF VARIABLES =

P(C-1) +2
• Since the system is in equilibrium, BY DEFINITION, we have already implicitly
defined some of the variables.

• So, if system is “in equilibrium”, and if there is NO NET CHANGE in the net
“amounts” of chemicals moving between phases that are in dynamic equilibrium,
• Aµα = Aµβ = Aµγ….. = Aµ∞

• Bµα = Bµβ = Bµγ….. = Bµ ∞

• Bµα = Bµβ = Bµγ….. = Bµ ∞

• The chemical potential or the chemical flux of a given chemical must be the same
in all phases coexisting at equilibrium-No NET Change!

For EACH Component, there are (P-1) independent equations relating the
chemical potential, µ, of that component in ALL of the Phases. There are C(P-1)
independent equations.
 For EACH Component, there are (P-1) independent equations relating the
chemical potential, µ, of that component in ALL of the Phases.

There are C(P-1) independent equations.

Thus, we “FIX” C(P-1) variables when we stipulate that the system is in

equilibrium.

F = number of “Freedom” factors

F = [P(C-1) +2] – [C(P-1)] =C–P+2

TOTAL AUTOMATICALLY FIXED
Standard phase diagram for water (H2O)

ONE COMPONENT
SYSTEM

Standard phase diagram for carbon dioxide

(CO2)
 TA curve = known as melting point or
Standard phase diagram for water (H2O) freezing point

Represent the equilibrium between ice

and liquid
Special case
!!!!!
Has a negative slope

Water as the liquid is denser than the solid

(ice floats on water).

That means that an increase of pressure

favors the formation of liquid and that the
melting point of water falls with increasing
pressure.

This unique properties of water is due to the

network of hydrogen bonding in ice is more
extensive than in liquid
 The point O is the triple point for
Standard phase diagram for carbon dioxide CO2 (at 5.1 atm, -57o C). So,
(CO2) CO2 solid can’t changed to liquid
form at 1 atm.
Critical point

Has a positive slope

So, its shows that the increases

of pressure, will increased the
melting point for CO2 solid

sublimation
1 - C Systems
The system SiO2
Two environmental
variables: P and T
One component = SiO2
7 different phases
Point A:
F=C–P+2
F=1–1+2 A
F=2 C
B
Divariant area
= two variables to
define a position in
the coesite stability field
1 - C Systems
1. The system SiO2
Two environmental
variables: P and T
One component = SiO2

7 different phases
Point B:
F=C–P+2 A
F=1–2+2 C
F=1 B
Univariant area =
one variable to
define a position on the
the coesite - α-quartz
phase boundary
1 - C Systems
1. The system SiO2
Two environmental
variables: P and T
One component = SiO2
7 different phases
Point C:
F=C–P+2 A
F=1–3+2 C
F=0 B
invariant = Triple point
do not need any variable
to define equilibrium
between coesite,
a- and b-quartz
Phase Rule

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

• Application:
• A gas, e.g. water vapour 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.
• Such a system is usually described as bivariant.
 Phase Rule
• Application:
• 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.

• Application:
• When we have a liquid water, vapor and ice
• 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 invariant.
 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 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.

A cup of warm water is suspended in a large pot of water held at a steady
boil at atmospheric pressure. Will the water in the cup ever boil?
 Study of Curves:
Curve OA
❑ Vapour pressure curve of water
❑ Divides liquid and vapour
❑ Represent the equilibrium between liquid
water and vapour.
❑ It starts from the point ‘O’
❑ Ends at critical temperature (374°C)
❑ Beyond A the two phases merge into each
other.
Along the Curve OA:
No. of Component = 1, No. of Phases = 2
Degree of Freedom (F) = 3– P = 3– 2 = 1
Hence the system is univariant.
Curve OB
✔ Sublimation curve of ice.
✔ Divides Ice and Vapour
✔ Represent the equilibrium between Ice
and vapour
✔ This curve starts from point ‘O’
✔ Extend upto absolute zero (-273°C).

Along the Curve OB:

No. of Component = 1, No. of Phases = 2
Degree of Freedom (F) = 3– P = 3– 2 = 1
Hence the system is univariant.
Curve OC
✔ Freezing/melting curve.
✔ Divides Ice and water
✔ Represent equilibrium between Ice and Water
✔ This curve starts from point ‘O’
✔ ends upto point ‘C’ (2000 atmospheres and
-20°C).
✔ The Curve OC is inclined towards pressure axis.
melting point of Ice is lowered with the increase in pressure.

Along the Curve OC:

No. of Component = 1, No. of Phases = 2
Degree of Freedom (F) = 3– P = 3– 2 = 1
Hence the system is univariant.
Study of Area:
The areas represents Three phases of
Water.

BOC (Solid),
COA (Liquid) and
AOB (Vapour) Three phases of Water.

No. of Component (C ) = 1
No. of Phases (P) = 1
Degree of Freedom (F) = 3– P = 3– 1 = 2
Hence the system is bivariant.
 Study of Point ‘O’ [Triple Point]:

✔ At triple point all the three phases co-exist

in equilibrium.
✔ curve OA, OB and OC meet.
✔ 0.0098°C and 0.006 atm. or 4.58 mm Hg

No. of Component = 1
Degree of Freedom (F) = 3– P = 3 – 3 = 0

Hence the system is invariant at the triple point ‘O’

(0.0098°C and 0.006 atm. or 4.58 mm Hg)
 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.)
• Condensed System do not have gas phase and the effect of
pressure is negligible.

• Only one variable is required to define the system completely

then phase rule at constant pressure is defined as
F=C–P+1
• It is also known as Condensed or Reduced Phase Rule.
Application of
Water phase
diagram
 Application of Water phase diagram

Water can exist on Mars as only a solid or a gas.

TWO COMPONENT
SYSTEM
 Binary Component 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.
 Types of Binary 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
Eutectic Mixture
Solid solution of such two component system which has
lowest melting point of all the possible mixtures of the
components is known as Eutectic mixture and the
corresponding freezing point temperature is known as
Eutectic point.
For Example: Cu – Ag, Pb-Ag, Bi - Cd
 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.
• Condensed System do not have gas phase and the effect of
pressure is negligible.

• Only one variable is required to define the system completely

then phase rule at constant pressure is defined as
F=C–P+1
• It is also known as Condensed or Reduced Phase Rule.
 General Features of Phase Diagram of Two
Component System
Consider a system of
composition represented
by line LS. “L” represent
system above melting
point & “S” represent
system in solidified state.
If “L” is cooled then no
solid will separate till point
“P” on the freezing point
curve BC is reached. At this
temperature solid B will
separate out.
The solidification result in
the evolution of heat called
heat of solidification, which
slow downs the cooling up to
point Q.
During cooling from P to Q,
the composition of liquid
phase changes from P to C
along the curve PC.
On reaching the eutectic
point “C”, the second solid A
will separate out and
temperature will remain
constant till all the liquid has
been solidified.
 Application of Phase Rule

Binary Component System – Lead-Silver System

Binary Component System-Lead-Silver

Phase Diagram of Lead – Silver System

 Various phases are
(a) Solid Lead
(b) Solid Silver
(c ) Solution of Lead & Silver in molten state
(d) Vapour

Small changes of pressure has negligible effect on the

equilibrium between lead and silver in solid state or in
molten state and hence vapour phase will not exist.
Thus Reduced Phase Rule can be applied.
F = C+1–P
= 2 + 1 -3 = 0
In Pb – Ag system, two components are present i.e. Lead
& Silver. Hence C = 2
Study of Curves:
Curve OA
This is called the freezing point curve of silver to which
successive quantities of lead are added.
Point ‘A’ indicate the melting point of Pure Silver (961°C).
Melting point of silver is lowered gradually by the addition
of lead to it.
Along the curve OA added Lead goes into solution and
separation of Silver occurs when point ‘O’ is reached.

At point ‘O’ no more Lead goes into solution as the

solution becomes saturated with respect to Lead & hence
the melting point of Silver do not fall.
Along the Curve OA two phases, Solid Silver and Liquid
(melt) are in equilibrium. So, P = 2
No. of Component (C ) = 2
By Reduced Phase Rule F = C + 1 –P
=2+ 1–2 =1
Hence the system is univariant.
Curve OA
This is called the freezing point curve of Lead to which
successive quantities of Silver are added.
Point ‘B’ indicate the melting point of Pure Lead (327°C).
Melting point of Lead is lowered gradually by the addition
of Silver to it.
Along the curve OB added Silver goes into solution and
separation of Lead occurs when point ‘O’ is reached.

At point ‘O’ no more Silver goes into solution as the

solution becomes saturated with respect to Silver & hence
the melting point of Lead do not fall.

Along the Curve OB two phases, Solid Lead and Liquid

(melt) are in equilibrium. So, P = 2
No. of Component (C ) = 2
By Reduced Phase Rule F = C + 1 –P
=2+ 1–2 =1
Hence the system is univariant.
Study of Area:
Area AOD and BOE
Each area has two phases, Solid Silver + Liquid in area
AOD and Solid Lead + Liquid in area BOE.
Number of Phases = 2
Number of Component = 2
Degree of Freedom = C + 1 –P = 2 + 1 – 2 = 1

Hence the system is univariant.

Area above AOB
In this area only liquid phase is present as the
temperature is above the melting point of any mixture i.e.
P=1
Number of Phases = 1
Number of Component = 2
Degree of Freedom = C + 1 –P = 2 + 1 – 1 = 2

Hence the system is bivariant.

Area below DOE
In this area only solid phase is present i.e. Pure Silver and
Pure Lead. So, No. of Phases (P) = 2

Number of Phases = 2
Number of Component = 2
Degree of Freedom = C + 1 –P = 2 + 1 – 2 = 1

Hence the system is univariant.

Study of Point ‘O’ [Eutectic Point]:

At point ‘O’ the curve OA and OB meets

At point ‘O’ all the three phases i.e. Solid Silver, Solid Lead
and Fuses mass (Liquid mixture) co-exist.

Number of Phases = 3
Number of Component = 2
Degree of Freedom = C + 1 –P = 2 + 1 – 3 = 0
Hence the system is invariant.
67