Rizvi College of Engineering

Subject:- Applied Chemistry

Unit:- 3 Alloys
 Syllabus
Alloys
Purpose of making alloy
Phase rule- Statement
Explanation of the terms involved
Condensed Phase Rule
Two Component Systems:. Pb-Ag systems
Applications and Limitations of phase rule
Numerical on phase rule

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 Introduction
• Phase Rule applicable to study the heterogeneous systems in equilibrium
.it also help to study the effect of changing temp, pressure and
composition on the behaviour system in equilibrium by means of phase
diagram.
• A substance can exist in various states depending on the external
conditions.
• For eg. water can exist in the form of solid, liquid and vapour. A change in
the state of substance is called phase transition. Equilibrium in a system in
which phase transitions occur in addition to a chemical process is called
phase equilibrium.

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 Gibb’s Phase Rule
• Phase rule states that “ If the equilibrium between any number of phases is not
influenced by gravity, or electrical, or magnetic forces, or by surface action but are
influenced only by temperature, pressure and concentration , then the number of
degrees of freedom (F) of the system is related to the number of components (C ) and
number of phases (P)

• In every heterogeneous system in equilibrium ,the sum of number of phases and

degree of freedom is greater than the number of component by 2.
P+F=C+2
Or
F = C- P + 2
For an accurate and effective interpretation of the phase rule, it is important to understand the
meaning of the terms involved in the phase rule.

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 Phase (P)
Phase: Physically distinct & mechanically separable

e.g.
• A system containing only liquid water is = 1 P
• A system containing water and water vapour (gas) = 2 P system
• A system containing liquid water, water vapour and solid ice is = 3P
•Two miscible liquids = 1 P
•Two immiscible liquids = 2P
•Thermal decomposition of CaCo3= 3 P

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 Component
• It is defined as smallest number of independently variable constituents which taking
part in equilibrium to express the composition of all the phases can be expressed in the
form of chemical composition.
e.g.
i) Water system : ice(s) water(l) vapor(v) = H2O
P = 3 , C = 1 Hence water is 1 component system.

• Water system has three phases and the composition of all these phases is expressed in one
chemical formula. Hence one component only.
ii)Sulphur system has four phases: rhombic sulphur, monoclinic sulphur, liquid sulphur and
sulphur vapour and the composition of all these phases is expressed by one chemical
individual. = Hence Sulphur is 1 component system.

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 Component
.
iii) A salt solution
P=1,C=2
iv) Dissociation of NH4Cl :-
P= 2 , C = 1 or 2

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 ( F )Degrees of freedom or Variance
Minimum number of independent variables factors(such as temperature, pressure
and conc.) that must be fixed in order to understand the system fully.
•e.g. In water system
ice(s) water(l) vapor(v) = H2O
P=3, C=1
No parameters required , hence it is zero variant F = 0

water(s) water Vapour (g)

P=2, C=1
Either temp/pressure required, hence it is Mono variant F = 1
ice(s) or water(l) or vapor(v)
P=1, C=1
Both temp& pressure required, hence it is Bi variant F = 2
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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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Phase Diagram for one component system (Water)

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 Numericals on Phase rule

Determine degree of freedom in following system.

1. Liquid water and water vapour in equilibrium. Also suggest the
variables that could corresponds to this degree of freedom.
2. Calculate the number of components and degree of freedom in the
system of salt in water
3. Calculate the number of components and degree of freedom in a
mixture of H2 (g) , O2 (g) , H2O (g)
4. Calculate the degree of freedom in mixture of CaCO3 (s) , CaO (l) and
CO2 (g).

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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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 Condensed phase rule or reduced phase

• When P is kept constant, vapour phase of system is not considered. In this

case system is said to be condensed and phase rule reduced to:

F = C – P +1

• This is called condensed phase rule or reduced phase rule.

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 Eutectic System
• Eutectic System: Two component system in which both the components are
completely miscible in liquid phase but do not react chemically is called a
eutectic system e.g. Ag-Pb System

• Eutectic Temperature and composition: for a pure substance A, the freezing

point is higher and upon increasing the conc. of B freezing point decreases to
lowest value. This is called eutectic temperature and composition at this state
is called eutectic composition.

• Eutectic Point: (easily melted) is defined as the lowest melting point attained
by the mixture

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 Two Component (Ag-Pb) System
• It is a simple eutectic system in which silver and lead are completely soluble in
liquid state.
• They do not react to form a any compound but on solidification they form an
easy melting mixture.(eutectic system)
• Four phases that take part in equilibrium are:
1. solid silver
2. solid lead
3. solution of lead & silver
4. Vapor
• melting point of Ag(9610C) & Pb(3270C) being high, so gas phase is absent, so
pressure has negligible effect.
• So Ag-Pb equilibrium without gas phase is known as condensed system.

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 Ag-Pb System

9610C

3270C

3030C

R O’ S

In an alloy of Ag and Pb, Ag melts at 303C which is lower than melting point of
Ag and Pb called eutectic mixture 16
 Ag-Pb System
Areas (Bivariant System)
1. Area AOB: single phase of liquid of silver and lead F= 2
consider sample of liq. Ag and Pb ,corresponding to point P , having
less composition less than 2.6% Ag. On cooling the melt ,the temp.
decreases without change in composition till point P’ on curve BO.
Then cooling allows composition P’O lead start separating out.
2. Region enclosed by BOQ: composition of solid crystalline lead and liquid
melt of silver and lead.
3. Region enclosed by AOP : mixture of solid crystalline silver and liquid Pb
melt of silver and lead.
4. POO’R region shows stable composition of Ag crystals and solid eutectic
crystals
5. QOO’S region shows stable composition of lead crystals and solid eutectic
crystals

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Mina
 Ag-Pb System

• In an alloy of Ag and Pb, Ag melts at 303C which is lower than melting

point of Ag and Pb called eutectic mixture.

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 Advantages of Phase rule

1. Provides convenient basis for classification of equilibrium states of system with the
help of phases, components, and degree of freedom.
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 hence information about molecular structures is
not essential.
5. It dose not recognize nature or the amounts of substances presents in the system.
6. Applicable to physical and chemical phase reactions.

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 Limitation of Phase rule
1. Applicable only for the system in equilibrium
2. Applicable to a single equilibrium state. It dose not indicate the other possible
equilibria in the system.
3. The solid and liquid phases should not be so finely subdivided as to bring
about deviation from their normal values of vapour pressure.
4. Considers only number of phases not quantity of phases
5. It requires that all the phases to be present under the same conditions of
temperature and pressure.

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 Numericals Based on Phase Rule
1. An alloy of tin and lead contain 73 % tin. Find the mass of eutectic in 1 Kg of
solid alloy if the eutectic contains 64% of tin.

Solution:- wt. of alloy in1 Kg = 1000 gm

1 kg alloys contains 730 g tin and 270 g lead
in the eutectic composition, tin is 64% and lead is 36%
therefore, corresponding to 270 g of lead , the mass of tin in eutectic
= 270 x 64 / 36
= 480 g
Total mass of eutectic in alloy = 270 + 480 g
= 750 g

Total mass of eutectic in alloy = 750 g

2. An alloy of Cd and Bi contain 25 % Cd. Find the mass of eutectic in 1 Kg of
alloy, if the eutectic contains 40 % of Cd.

wt. of alloy in1 Kg = 1000 gm

Total mass of eutectic in alloy =

Total mass of eutectic in alloy =

3. An alloy of tin and lead contain 80% tin. Find the mass of eutectic in 1 Kg of
alloy, if the eutectic contains 60% of tin.

wt. of alloy in1 Kg = 1000 gm

Total mass of eutectic in alloy =

Total mass of eutectic in alloy =
4. An alloy AB of 10 g weight contains 25% of A. The molten AB on cooling gave out B and a
eutectic alloy with A and B at equal percentage. What is the amount of B that has formed?

Given data,
Wt of A in 10 g of alloy =2.5 g
wt. of B in 10 g of alloy = 7.5 g
on cooling containing equal amt. of A and B i.e. 2.5 g each
therefore, the amount of B formed = original amt – amt. in eutectic

7.5- 2.5 = 5 g
2. An alloy AB of 20 g weight contains 20% of A. The molten AB on cooling gave out B and a
eutectic alloy with A and B at equal percentage. What is the amount of B that has formed?

Given :-Given data,

ans = g
Thank
you