UNIT – III

PHASE RULE
INTRODUCTION
Phase rule is stated by William Gibbs in 1874. It is very important and versatile tool for
the study of heterogeneous equilibria. It is necessary to know about the terms like phase,
component and degree of freedom to understand the phase rule.
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) by the following
phase rule equation.
F=C-P+2
Definition of Terms

1. Phase:
‘A Phase is defined as any homogeneous, physically distinct and mechanically separable
portion of a system, which is separated from other parts of the system by definite boundaries’

Number of possible phases of a system: (a) ice, water and water vapour,
(b) water and alcohol, (c)water and excess salt and (d) oil and water

i) Liquid phase: The number of liquid phase depends on the number of liquids present and
their miscibility.
 If two liquids are immiscible, they will form two separate phases.
E.g., benzene and water
  If two liquids are miscible they will form one liquid phase only.
E.g., alcohol and water.
ii) Solid phase: Each solid forms a separate phase. The number of solid phase depends on
the number of solids present in it.
E.g., sulphur can exist two solid forms, but these are all separate phases.

iii) Gaseous phase: A gaseous mixture are miscible in all proportions, will constitute a single
phase.
E.g., a mixture of N2 and H2 forms one phase only.
iv) A solution of a substance in a solvent consists of one phase only,
E.g., glucose solution.
v) A heterogeneous mixture like:

Consists of three phases (i.e., two solids and one gaseous).

In the equilibrium reaction,

There are two solid phases, Fe and FeO and one gaseous phase consisting of H2O(g)
and H2(g). Thus three phases exists in equilibrium

2. Component(C):
The component of a system is defined as ‘the smallest number of independently variable
constituents that are in equilibrium, by means of which the composition of each phase can be
expressed in the form of chemical equations’.
E.g.,
 In the water system, the chemical composition of all the three phases can be
represented in terms of only H2O. Hence the number of component is one.

 Dissociation of ammonium chloride in a closed vessel is a two-phase one component

system.

The composition of both NH3 and HCl can be expressed in terms of NH4Cl vapour.
 Thermal decomposition of calcium carbonate

The composition of each of the three phases can be expressed in terms of atleast any
two of the independently variable constituents CaCO3 (s), CaO(s) & CO2(g). So it is a
two component system.
E.g., Solid phase: CaCO3 = CaCO3 + 0 CaO
Solid phase: CaO = 0 CaCO3 + CaO
 Solid phase: CO2 = CaCO3 – CaO
 In the equilibrium reaction,

The minimum components required to express the composition of each phase is

three.
 In the dissociation reaction,

The composition of each phase can be represented by the simplest components CuSO4 and
H2O. Hence it is a two component system.

3. Degree of Freedom/ Variance (F):

Degree of freedom is defined as, “the minimum number of independent variable
factors such as temperature, pressure and composition, which must be specified in order to
define the system completely”.
If F = 1, system is univariant or mono variant.
If F = 2, system is bivariant.
If F = 3, system is trivariant, etc.
E.g.,
 Ice, liquid water and water vapour coexist at the freezing point of water.

F= 1-3+2 =0
All the three phases are in equilibrium only at a particular temperature and pressure,
hence no condition need be specified. The system is zero variant or non-variant or invariant or
has no degrees of freedom. As soon as the temperature or pressure is altered, three phases will
not remain in equilibrium and one of the phases disappears.
 For a system consisting of water in contact with its vapour,

F= 1-2+2 =1
In this case only temperature is sufficient to specify the state of the system, since once
temperature is fixed, vapour pressure of the system is automatically fixed. Hence, degree of
freedom is one and the system is univariant.
 For a system consisting of water vapour phase only, need both the temperature and
pressure to define the system completely. Hence, degree of freedom is two and the
system is bivariant.
F= 1-1+2 =2
Advantages of Phase Rule
 It is applicable to both chemical and physical equilibria.
  It is applicable to macroscopic systems and hence no information is required
regarding molecular and micro structure.
 A convenient method to classify the equilibrium systems in terms of phases,
components and degree of freedom.
 The behaviour of system can be predicted under different conditions.
 According to phase rule, different systems having the same degrees of freedom
behave similarly.
 Phase rule helps in deciding under a given set of conditions:
(a) Existence of equilibrium among various substances.
(b) Interconvergence of substances.
(c) Disappearance of some of the substances.

Limitations of Phase Rule

 It is applicable only for the systems which are in equilibrium.
 Only three degrees of freedom viz., temperature, pressure and composition are
allowed to influence the equilibrium systems.
 Under the same conditions of temperature and pressure, all the phases of the system
must be present.
 It considers only the number of phases, rather than their amounts.
PHASE DIAGRAM
Phase diagram is a graph obtained by plotting one degree of freedom against the other.
Types of Phase Diagrams
(i) P-T Diagram
If the phase diagram is plotted between temperature and pressure, the diagram is
called P -T diagram. P -T diagram is used for one component system.
(ii) T-C Diagram
If the phase diagram is plotted between temperature and composition, the
diagram is called T-C diagram T- C diagram is used for two component system
Uses of Phase Diagram
It helps in,
 Predicting whether an eutectic alloy (or) a solid solution is formed on cooling a
homogeneous liquid containing mixture of two metals.
 Understanding the properties of materials in the heterogeneous equilibrium system.
 Studying of low melting eutectic alloys, used in soldering.
APPLICATION OF PHASE RULE TO ONE COMPONENT SYSTEM
The water system is a one component system

Water system has three phases ice, water and water vapor which show the following
different equilibria
 Each equilibrium involves two phases. The nature of these phases which exist in
equilibrium at any time depends on the conditions of temperature and pressure.
The phase diagram consists of
a. Curves - OA, OB and OC.
b. Triple point -O
c. Metastable equilibrium
d. Areas AOB, AOC and BOC.

Phase diagram of water system

(a) Curves:
Curve OA is the vaporization curve of water, it represents the vapour pressure of liquid
water at different temperatures. At any point on the curve the following equilibrium will exist.

This equilibrium (i.e, line OA) will extend upto the critical temperature (374ᵒC), beyond
on which the equilibrium will disappear only vapour phase will exist
Curve OB is the sublimation curve of ice. It shows the vapour pressure of solid ice at different
temperatures. At any point on the curve the following equilibrium will exist.

This equilibrium line will extend upto the absolute zero (– 273ᵒC) where no vapour can be
present and only ice will exist
Curve OC is called melting point curve of ice, it represents the equilibrium between ice and
water. At any point on the curve the following equilibrium will exist.

The curve OC is slightly inclined towards pressure axis. This shows that melting point of ice
decreases with increase of pressure.
Along the curves P = 2, C=1
Thus applying phase rule equation,
F = C-P+2
= 1-2+2 =1
The system is univariant. (i.e.) Only one variable (either T or P) is enough to define the system
completely.

(b) Triple point:

The three curves OA, OB and OC meet at a point ‘O’, where all the three phases namely
solid, liquid and vapour are at equilibrium.

At this point the no. of phases (P) is 3, component(C) is 1 and the degree of freedom of
the system is zero
F = C − P + 2;
F=1−3+2=0
The system is invariant or nonvariant. It means that three phases can coexist only at a
definite temperature (0.0075°C) and pressure (4.58 mm of Hg). If either pressure or temperature
is changed, one of the phases will disappear.
(c) Curve OB’ (Metastable equilibrium)
The curve OB′ is called vapour pressure curve of the super-cooled water (or) metastable
equilibrium where the following equilibrium will exist.

Sometimes water can be cooled below its freezing point (0°C) without the formation of
ice, this water is called super-cooled water. Super cooled water is unstable and it can be
converted into solid ice by “seeding” (or) by slight disturbance.
(d) Areas
Areas AOC, BOC, AOB represents liquid water, solid ice and water-vapour respectively
where the no. of phases (P) and component (C) are one. Hence the degree of freedom of the
system is two i.e., bivariant. This is predicted by the phase rule:
F = C − P + 2; F = 1 − 1 + 2; F = 2
Therefore, both temperature and pressure must be fixed to define the system at any point
in the areas.
REDUCED PHASE RULE (OR) CONDENSED PHASE RULE
The maximum number of degree of freedom for a two component system will be three,
when the system exists as a single phase.
F = C − P + 2; F = 2 − 1 + 2; F = 3
In order to represent the conditions of equilibrium graphically, it requires three co-
ordinates, namely P, T and C. This requires three dimensional graph, which cannot be
conveniently represented on paper. Therefore, any two of the three variables must be chosen
for graphical representation.
A solid-liquid equilibrium of an alloy has practically no gaseous phase and the effect of
pressure is negligible. Therefore, experiments are conducted under atmospheric pressure. Thus,
the system in which only the solid and liquid phases are considered and the gas phase is ignored
is called a condensed system. Since the pressure is kept constant, the phase rule becomes
F′ = C − P + 1
This equation is called reduced phase rule (or) condensed phase rule.

COOLING CURVES / THERMAL ANALYSIS

Thermal analysis is the study of the cooling curves of various compositions of a system
during solidification. It is used for finding the shape of the freezing – point curves of any system
especially those involving metals. For any mixture of a definite composition, it is possible to
find out freezing point and eutectic point from the cooling curves.

Cooling curve of a. Pure solid b. Mixture of two solids

Construction of phase diagram by thermal analysis:
When a graph is plotted between temperature and time it is called as cooling curve. The
thermal analysis involves the study of cooling curve of various compositions of a two
component system during solidification.
Fig : (a). When a pure substance in the fused state is allowed to cool slowly and the
temperature is noted at definite intervals. Initially the rate of cooling curve is continuous. At
the point ‘b’ freezing starts. After this point, the temperature will remain constant until the
liquid melt is completely solidified. This is because the liquid melt and solid crystals are of the
same composition. At the horizontal section ‘bc’ the solid crystals and liquid melt are in
equilibrium. Thereafter, the temperature of solid will again decrease along the curve ‘cd’.
Fig (b). When a mixture of two solids A and B in the fused state is allowed to cool slowly.
Initially the rate of cooling curve will be continuous (ab), when the crystals of either A or B is
formed from the liquid melt, which is indicated by break in continuity of the cooling curve.
Now the temperature again decreases with time but at a different rate, because the solid crystal
and liquid melt are not of the same composition. The slope ‘bc’ of the curve represents a
continuous and progressive change in composition of liquid melt. Finally the liquid melt reaches
the point ‘c’ at which it separates as solid A and solid B. Now the temperature will remain
constant until the liquid melt is completely solidified. Point ‘c’ called eutectic point a minimum
freezing point corresponding to eutectic mixture. Thereafter temperature remain constant till
solidification up to ‘d’.
Applications:
 The melting point and eutectic temperature of various solids can be obtained.
 The percentage of the compounds can be found out.
 The behaviour of the compound can be understood from the cooling curve.
 The procedure of thermal analysis can be used to derive the phase diagram of any
two component system.
THE LEAD – SILVER SYSTEM
The Lead-Silver system is studied at constant pressure and the vapour phase is ignored.
Hence the condensed phase rule is used.
F′ = C − P + 1
The phase diagram of lead-silver system is shown as follows. It contains curves, areas
and eutectic point.

Phase diagram of Lead-Silver system

(i) Curve AO
The curve AO is known as freezing point curve of silver. Point A is the melting
point of pure Ag (961°C). The curve AO shows the melting point depression of Ag by
the successive addition of Pb. Along this curve AO, solid Ag and the melt are in
equilibrium. The melting point of silver falls gradually by addition of lead till the silver
melt gets saturated with lead.

(ii) Curve BO
The curve BO is known as freezing point curve of lead. Point B is the melting
point of pure lead (327°C). The curve BO shows the melting point depression of Pb by
the successive addition of Ag. Along this curve BO, solid Pb and the melt are in
equilibrium.

Along the curves AO and BO the number of phases (P=2) and components (C=2) are two.
The degree of freedom is F′ = C − P + 1;
F′ = 2 − 2 + 1 = 1
The system is univariant which means either temperature (or) composition must
be fixed to define the system completely.

(iii) Point ‘O’ (Eutectic point)

The curves AO and BO meet at point ‘O’ At this point silver solution becomes saturated
with lead and lead solution is saturated with silver. On further addition of silver or lead solid
will get separated. This saturation limit is represented by‘O’ called eutectic point, where three
phases coexist. The temperature at which this equilibrium exist is known as eutectic temperature
(303ᵒC) and the corresponding composition is known as eutectic composition (2.4 % Ag + 97.6
% Pb).

At this point the no. of phases (P) is 3, component (C) is 2 and the degree of freedom of
the system is zero
F′ = C − P + 1
F′ = 2 − 3 + 1 = 0
The system is invariant.
It means that this equilibrium will exist only at a definite temperature (303°C) and
composition (2.4 % Ag + 97.6 % Pb). If either temperature or composition is changed one of
the phases will disappear.
(iv) Area
The area above the line AOB has a single phase (molten Pb+Ag) or liquid melt.
According to reduced phase rule the degree of freedom.
F′ = C − P + 1; F′ = 2 − 1 + 1; F′ = 2
 The system is bivariant which means both the temperature and composition have to be
fixed to define the system completely. The area below the line AO (solid Ag + liquid melt),
below the line BO (solid Pb + liquid melt) and below the point ‘O’ (Eutectic compound + solid
Ag or solid Pb) have two phases and hence the system is univariant.
F′ = C − P + 1; F′ = 2 − 2 + 1; F′ = 1.
Application of Pattinson’s process for the desilverisation of Argentiferrous lead
The recovery of Ag from argentiferrous lead is explained in the process with the help of
phase diagram. The argentiferrous lead, having a very small amount of silver (say 0.1%), is
heated to a temperature above its melting point, so that the system has only the liquid phase
represented by the point ‘p’ in the phase diagram.
It is then allowed to cool where the temperature decreases along the line ‘pq’. As soon
as the point ‘q’ is reached, Pb is crystallised out and the solution will contain relatively
increasing amounts of Ag. On further cooling, more and more of Pb is separated along the line
‘BO’. The melt continues to be richer and richer in Ag until the point O is reached, where the
percentage of Ag rises to 2.6%.Thus, the process of raising the relative proportions of Ag in the
alloy is known as Pattinson’s process.

Uses of Eutectic system

 Suitable alloy composition can be predicted.
 Making solders, used for joining two metal pieces together.
Differences between Melting point, Eutectic point and Triple point
1. Melting Point: It is the temperature at which the solid and liquid phases, having
the same composition, are in equilibrium.

2. Eutectic Point: It is the temperature at which two solids and a liquid phase are
In equilibrium

3. Triple Point: It is the temperature at which three phases are in equilibrium.

 All the eutectic points are melting points

 All the melting points need not be eutectic points.
 Similarly all the eutectic points are triple points, but all the triple points need not be
eutectic points.

SAFETY FUSES AND SOLDERS

A fuse that burns slowly for communicating fire to a detonator or blasting cap and that
consists usually of a train of fine black powder surrounded by a tight wrapping.
 Safety fuse consisted of a tube of gunpowder surrounded by a waterproofed varnished
jute rope. It replaced earlier and less reliable methods of igniting gunpowder blasting charges
which had caused many injuries and deaths in the mining industry. The safety fuse burns at a
rate of typically about 30 seconds per foot (1 second per cm).
Impact of Safety fuse
Given the unreliability of fuses and means of detonation prior to Bickford’s fuse, this new
technology changed the safety and conditions of mining. Due to poor record keeping or lack
thereof, it is relatively difficult to determine the exact number of mining accidents and related
statistics prior to the invention of the safety fuse. However "this fuse soon replaced the less reliable
fuses which were made of straws or quills filled with black powder, thus greatly reducing the
hazard of accidental explosions in mining or construction." Word of the reliability of Bickford's
safety fuse spread, and was soon in large demand across world markets.
Bickford’s fuse not only dramatically improved the safety conditions of mines around the
world, but also contributed to the development of dynamite. Alfred Nobel created dynamite in
1867, by moulding nitroglycerine and a mud-like compound found near his laboratories
called kieselguhr into individual cylinders. At the end of each cylinder Nobel inserted a blast cap
which could be ignited in one of two ways. First, by inserting a safety fuse into the blast cap and
igniting the fuse, it will set the blast cap off and produce enough energy to detonate the dynamite.
Second, it is possible to detonate dynamite by inserting a blast cap into the end of the cylinder and
then by attaching an electrical wire into the blast cap and producing a current which will travel
from the source to the blast cap will also set off the dynamite.

ALLOYS
Most of the metals have good physical and mechanical properties such as ductility,
malleability, luster, electrical and thermal conductivities etc., but are soft, chemically reactive
and susceptible for corrosion.
The physical and mechanical properties can be modified by alloying them with metals
or non-metals so that they can be made suitable for engineering applications.
Alloys are mostly prepared by fusion of metals. Metals (or) metals and non-metals are
fused separately by heating to a high temperature. The molten mass is stirred thoroughly to
ensure proper mixing and achieve uniform composition. It is then cooled slowly.
Definition
Alloys are homogeneous mixture of two or more elements out of which at least one is
metal. When one of them is mercury it is called amalgam.
Example: Brass (Cu & Zn); steel (Fe, Ni, Cr, C….); Bronze (Cu & Sn)
Properties of alloys:
 Alloys are harder, less malleable and lower melting point than their component metals
  Possess low electrical conductivity
 Resist against corrosion and action of acids
 Possess more tensile strength and better casting characteristics.
Importance or Purpose of Alloys
Alloys are prepared to bring about certain special properties.
 To increase hardness: Soft gold is hardened when alloyed with copper. Iron is
hardened by Ni, Cr, and carbon (called steel); soft Pb is hardened by0.5 % As (bullet
metal).
 To increase workability: Pure gold is soft and non-workable; when alloyed with
copper, it becomes suitable for making ornaments.
 To modify colour and brightness: Copper when alloyed with zinc, becomes bright;
similarly when Al is alloyed with Cu.
 To make resistant to corrosion: Steel is corrosion resistant because of alloying of Fe
with Ni, Cr, and carbon.
 To lower the melting point: When Pb is alloyed with tin (Sn) the melting point of the
resulting alloy is lower than the individual constituent metals-used as solder.
 To change the chemical reactivity: The high reactivity of sodium is decreased when
alloyed with Hg; but reactivity of Al is increased when alloyed with Hg.
Functions and effect of Alloying Elements
Addition of small amounts of metals like Ni, Cr, Mo, Mn, Si impart some special
properties of steel. Such alloys are known as special steels or alloy steels
Alloying elements influence the composition and stability of the different phases of Fe-
C system.
S.No Element Effect on properties Uses of alloys
1 Nickel a) Fine grains are produced For making balance
b) Coefficient of expansion and wheels
corrosion resistance increases
2 Chromium Tensile strength, depth hardening and For making surgical
resistance to corrosion are increased instruments, cutlery etc.
3 Manganese a) Hot shortness is removed For making grinding
b) Abrasion resistance is increased wheels, steering spindles
and rails
4 Vanadium a) Reversible stresses are produced For making axles, pins,
b) Tensile strength and resistance to heavy locomotive
abrasion are increased. forgings, piston rods, etc.
5 Molybdenum Cutting hardness at high temperature is For making high speed
increased, because phases are stabilized tools
6 Tungsten a) Grain structure is refined. For making cutting tools,
b) Magnetic retentivity as well as cutting permanent magnets, etc.
hardness are increased.
 7 Nickel and Corrosion resistance and tensile strength For making stainless steel
Chromium are increased.

CLASSIFICATION OF ALLOYS
According to the base metals alloys are classified into two classes
(i) Ferrous alloys
(ii) Non-ferrous alloys
FERROUS ALLOYS
They contain iron as one of the major components. Common ferrous alloys are stainless steel
cast iron etc.
Properties of the iron are improved by alloying with Cr, Ni, Mn, W, V etc.

Properties
i. Possesses high yield point
ii. Sufficient formability, ductility and weldability
iii. Corrosion and abrasion resistance
iv. Greater high temperature strength
Important ferrous alloys are
a) Nichrome
b) Stainless steel
NICHROME
Nichrome is an alloy of nickel and chromium.
Composition
Metal Percentage
Nickel 60%
Chromium 12%
Iron 26%
Manganese 2%
Properties;
 Nichrome has a silvery gray coloration.
 It shows good resistance to oxidation and heat.
 Steels containing 16 to 20% chromium with low carbon content (0.06 to 0.15%) possess
oxidation resistance up to 900oC.
  It possesses high melting point & high electrical resistance..
 It can withstand heat up to 1000 to 1100oC.
Uses
 It is widely used for making resistance coils, heating elements in stoves.
 It is also used in electric irons and other household electrical appliances.
 It is used in making parts of boilers steam-lines stills, gas-turbines, aero- engine valves,
retorts, annealing boxes.
 It is also used in making other machineries or equipments exposed to very high
temperatures.
STAINLESS STEEL (corrosion resistance steel)
These are alloy steels containing Cr with other elements such as Ni and Mo. Cr is effective
if its content is 16 % or more. Carbon content ranges from 0.3 – 1.5 % stainless steel resists
corrosion by atmospheric gases and other chemicals.

Classified as
(i) Heat treatable (Martensitic) Stainless steel: Contains 12-14% Cr and 0.12-0.35% C.
Properties:
 Magnetic, tough and can be worked in old condition.

 Resistant towards weather and water
Used in making surgical instruments, scissors, blades etc.
(ii) Ferritic Stainless steel: Cr 16-18% and C-0.12%,
Properties:
Magnetic, better corrosion resistance, ductility and easily machine able.
Used to make pump shafts, valves etc.,
(iii)Austenitic Stainless steel: 18% Cr, 8% Ni and some Mo.
Properties: Maximum resistant to corrosion
Used in making household utensils, dental and surgical instruments.

STAINLESS STEEL

If steel contains18% Cr and 8% Ni, it is referred to as18/8 stainless steel. It is the most
widely used stainless steel.
Properties:
It exhibits maximum resistance to corrosion. Corrosion resistance of which can be further
increased by adding a little quantity of molybdenum
Uses:
It is used in making household utensils, sinks, dental and surgical instruments.
Advantages:
 It is tough, hard, strong and durable.
 It has good finish. It is rust proof, corrosion resistant, resistant to wear and tear.
 It can be easily cleaned with water and soap after usage; even if the film Cr2O3 is
removed carelessly by stretching, new film is developed and original appearance is
restored.
Disadvantage: No scrap value like brass and bronze.

NON-FERROUS ALLOYS
BRASS: Alloy of Cu and Zinc containing more than 5% Zinc.
i) Commercial Brass / French Gold : 90% Cu and 10% Zn; Stronger and harder; Used for
making rivets, screws, jewellery etc.
ii) Cartridge brass: 70% Cu and 30% Zn; soft alloy; Used for making cartridge cases,

household articles, condenser tubes etc.

iii) Dutch metal /low brass: 80% Cu and 20% Zn; Used for making musical instruments,
flexible hoses, name plate etc.
iv) Aluminum brass: 76% Cu, 22% Zn and 2% Al; better corrosion resistance; used for
marine works.
v) Special brasses:
a) German silver: 25-50% Cu, 10-35% Zn and 5-35% Sn; Ductile, malleable; used in making
utensils, bolts, screws etc.,
b) Admirely brass / Tobin brass: 59-62% Cu, 0.5-1.5% Sn rest Zn; high corrosion resistance;

Used in propellers and marine works

BRONZE:
i) Coinage bronze / Common bronze: 89-92% Cu and 11-8% Sn; soft, ductile and durable;
Used for making pump, valves, coins, statues etc.
ii) Gun metal: 85% Cu, 8% Sn, 4% Zn and 3% Pb; Hard, tough; Used for foundry works,
water fittings, marine pump etc.
iii) High phosphorous bronze: 10-13% Sn, 0,4% P and rest is Cu; hard and brittle; Used for
making bearings, gears, taps, springs etc.

iv) Aluminum bronze: 90-93% Cu and 7-10% Al; corrosion resistance; Used for making
bushes, bearings, utensils, etc.
v) Nickel bronze: 90% Cu, 9% Ni and 1% Fe; hard, corrosion resistance; Used for rolling
purpose.
vi) Beryllium copper: 97.4% Cu and 2.6% Be; quite hard; used for making springs.

HEAT TREATMENT OF ALLOYS (STEEL):

Definition:
Heat treatment is defined as, “the process of heating and cooling of solid steel article under
carefully controlled conditions,” During heat treatment certain physical properties are altered
without altering its chemical composition.
All heat treating operations consists of three stages.
(a) Heating (b) Holding at temperature (soaking) (c) Cooling
Objectives (or) purpose of heat treatment:
 To relieve the internal stress induced during welding, casting etc.,
 To remove imprisoned gases.
 To improve strength and hardness.
 To improve machinability, ductility, electrical, mechanical and magnetic
properties.
 To improve fatigue and corrosion resistance.
Types of heat Treatment
The various heat-treatment processes are as follows:
1. Annealing 2. Hardening 3. Tempering
4. Normalizing 5. Case-Hardening (Carburizing &) Nitriding)
1. Annealing:
Annealing means softening. This is done by heating the metal to high temperature, followed
by very slow cooling in a furnace.
Purpose
 To increase machinability.
 To remove the imprisoned gases.
 To remove the internal stresses.
Types of Annealing
i. Low temperature annealing (or) process annealing.
 ii. High temperature annealing (or) full annealing.
i. Low temperature annealing (or) process annealing
It involves in heating steel to a temperature below the lower critical temperature followed
by slow cooling.
Purpose
 It improves machinability by relieving the internal stress (or) strain.
 It increases ductility and shock-resistance.
 It reduces hardness.
ii. High temperature annealing (or) full-annealing
It involves in heating steel to a temperature about 30 to 50° C above the higher critical
temperature and holding it at that temperature for sufficient time to allow the internal changes to
take place and then cooled to room temperature.
Purpose
 It increases the ductility and machinability.
 It makes the steel softer, together with an appreciable increase in its toughness.
2. Hardening (or) Quenching:
It is the process of heating steel beyond the critical temperature and then suddenly
cooling it either in oil (or) brine-water (or) some other fluid. Hardening increases the
hardness of steel. The faster the rate of cooling, harder will be the steel produced. Medium
and high-carbon steels can be hardened, but low-carbon steels cannot be hardened.
Purpose
 It increases wear resistance, ability to cut other metals and strength, but steel becomes extra
brittle.
 It increases abrasion-resistance, so that it can be used for making cutting tools.
3. Tempering:
It is the process of heating the already hardened steel to a temperature lower than its own
hardening temperature and then slowly cooling it in air. In tempering, the temperature to which
hardened steel is re-heated is of great significance as it controls the development of the final
properties. Thus,
 For retaining strength and hardness, reheating temperature should not exceed 400°C.
 For developing better ductility and toughness, reheating temperature should be within
400−600° C.
Purpose
 It removes any stress and strains that might have developed during quenching.
 It reduces the brittleness and also some hardness.
 It increases toughness and ductility.
 Cutting-tools like blades, cutters, tool-bites always require tempering.

4. Normalizing:
It is the process of heating steel to a definite temperature (above its higher critical
temperature) and allowing it to cool gradually in air. Normalized steel will not be soft as an
annealed steel but normalizing takes much lesser time than annealing process.
Purpose
 It recovers the homogeneity of the steel structure.
 It refines grain structure.
 It removes the internal stress and strain.
 It increases the toughness.
 Normalized steel is suitable for the use in engineering works.
5. Case- Hardening:
The process of getting a hard and wear resistant surface over a strong, tough and ductile
core are known as case–hardening. The steel best suited for this are low-carbon and low-alloy
steel. The different case-hardening processes are as follows:
a. Carburizing
The mild steel article is taken in a cast iron box containing small pieces of charcoal (carbon
material). It is then heated to about 900 to 950°C and allowed to keep it as such for sufficient time,
so that the carbon is absorbed to required depth. The article is then allowed to cool slowly within
the iron box itself. The outer surface of the article is converted into high-carbon steel containing
about 0.8 to 1.2% carbon.
Purpose: To produce hard-wearing surface on steel article.
b. Nitriding
Nitriding is the process of heating the metal alloy in presence of ammonia at a temperature
of about 550°C. The nitrogen (obtained by the dissociation of ammonia) combines with the surface
of the alloy to form hard nitride.
Purpose: To get super-hard surface
 QUESTION BANK
PART – A
1.State 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) by the
following phase rule equation.
F=C-P+2

2. Define condensed phase rule?

A solid-liquid equilibrium of an alloy has practically no gaseous phase and the effect of
pressure is negligible. Therefore, experiments are conducted under atmospheric pressure. Thus,
the system in which only the solid and liquid phases are considered and the gas phase is ignored
is called a condensed system. Since the pressure is kept constant, the phase rule becomes
F′ = C − P + 1
This equation is called reduced phase rule (or) condensed phase rule.

3. Define phase.
A Phase is defined as any homogeneous, physically distinct and mechanically separable portion
of a system, which is separated from other parts of the system by definite boundaries’

4.What is meant by the term component?

The component of a system is defined as ‘the smallest number of independently variable
constituents that are in equilibrium, by means of which the composition of each phase can be
expressed in the form of chemical equations’.
E.g.,
 In the water system, the chemical composition of all the three phases can be
represented in terms of only H2O. Hence the number of component is one.

5.Define degree of freedom.

Degree of freedom is defined as, “the minimum number of independent variable factors such
as temperature, pressure and composition, which must be specified in order to define the system
completely”.
If F = 1, system is univariant or mono variant.
If F = 2, system is bivariant.
If F = 3, system is trivariant, etc.
E.g.,
  Ice, liquid water and water vapour coexist at the freezing point of water.

F= 1-3+2 =0

6. What is triple point?

The three curves OA, OB and OC meet at a point ‘O’, where all the three phases namely
solid, liquid and vapour are at equilibrium.

7. What is Meta stable state?

The curve OB′ is called vapour pressure curve of the super-cooled water (or)
metastable equilibrium where the following equilibrium will exist.

Sometimes water can be cooled below its freezing point (0°C) without the formation
of ice, this water is called super-cooled water. Super cooled water is unstable and it
can be converted into solid ice by “seeding” (or) by slight disturbance.

8. Mention any two merits of phase rule.

 It is applicable to both chemical and physical equilibria.

 It is applicable to macroscopic systems and hence no information is required
regarding molecular and micro structure.
 A convenient method to classify the equilibrium systems in terms of phases,
components and degree of freedom.
 The behaviour of system can be predicted under different conditions.
 According to phase rule, different systems having the same degrees of freedom
behave similarly.

9. Mention any two limitations of phase rule.

 It is applicable only for the systems which are in equilibrium.
 Only three degrees of freedom viz., temperature, pressure and composition are
allowed to influence the equilibrium systems.
 Under the same conditions of temperature and pressure, all the phases of the
system must be present.
 It considers only the number of phases, rather than their amounts.
10. Differentiate Melting point, Eutectic point and Triple point
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.

11.What are the eutectic temperature and eutectic composition of Pb – Ag system?

Eutectic temperature (303°C) and composition (2.4 % Ag + 97.6 % Pb).

12.What is thermal analysis? Give its significance.

Thermal analysis is the study of the cooling curves of various compositions of a system
during solidification. It is used for finding the shape of the freezing – point curves of any system
especially those involving metals. For any mixture of a definite composition, it is possible to
find out freezing point and eutectic point from the cooling curves.
significance:
 The melting point and eutectic temperature of various solids can be obtained.
 The percentage of the compounds can be found out.
 The behaviour of the compound can be understood from the cooling curve.

13.What are alloys? Give two examples

Alloys are homogeneous mixture of two or more elements out of which at least one is
metal. When one of them is mercury it is called amalgam.
Example: Brass (Cu & Zn); steel (Fe, Ni, Cr, C….); Bronze (Cu & Sn)

14.What is meant by heat treatment of steel?

Heat treatment is defined as, “the process of heating and cooling of solid steel article under
carefully controlled conditions,” During heat treatment certain physical properties are altered
without altering its chemical composition.

15.What is 18/8 Stainless Steel?

If steel contains18% Cr and 8% Ni, it is referred to as18/8 stainless steel. It is the most widely
used stainless steel.
16.Mention some important properties of alloys.
 Alloys are harder, less malleable and lower melting point than their component metals
 Possess low electrical conductivity
 Resist against corrosion and action of acids
 Possess more tensile strength and better casting characteristics
17.Give the composition of Nichrome.

Metal Percentage
Nickel 60%
Chromium 12%
Iron 26%
Manganese 2%
18.Mention the uses of Nichrome
 It is widely used for making resistance coils, heating elements in stoves.
 It is also used in electric irons and other household electrical appliances.
 It is used in making parts of boilers steam-lines stills, gas-turbines, aero- engine valves,
retorts, annealing boxes.
 It is also used in making other machineries or equipments exposed to very high
temperatures.
19. Write note on Quenching
It is the process of heating steel beyond the critical temperature and then suddenly cooling
it either in oil (or) brine-water (or) some other fluid. Hardening increases the hardness of steel.
The faster the rate of cooling, harder will be the steel produced. Medium and high-carbon steels
can be hardened, but low-carbon steels cannot be hardened.

20. Write any four purpose of Normalizing

Purpose
 It recovers the homogeneity of the steel structure.
 It refines grain structure.
 It removes the internal stress and strain.
 It increases the toughness.
 Normalized steel is suitable for the use in engineering works.
 PART – B
1. Draw a neat labelled phase diagram of water system and explain areas, curves and
triple point in it.
2. State phase rule and explain the terms involved in it.
3. With the help of a neat phase diagram, describe lead – silver system (or) Discuss phase
rule and its applications to desilverisation of lead.
4. Write notes on :(i) Eutectic point (ii) Reduced phase rule (iii) Applications of phase
diagrams.
5. Describe thermal analysis with suitable cooling curves. Mention its significance.
6. What is heat treatment of alloys? What are the purposes of heat treatment?
7. Explain the various process of heat treatment.
8. Explain the functions and effect of alloying elements.
 MULTIPLE CHOICE QUESTIONS AND ANSWERS
1. Gibbs phase rule for general system
(a) P+F=C-1
(b) P+F=C+1
(c) P+F=C-2
(d) P+F=C+2
Answer: d
2. In a single-component condensed system, if degree of freedom is zero, maximum number of
phases that can co-exist _________.
(a) 0
(b) 1
(c) 2
(d) 3
Answer: c
3. The degree of freedom at triple point in unary diagram for water ________.
(a) 0
(b) 1
(c) 2
(d) 3
Answer: a
4. Above the following line, liquid phase exist for all compositions in a phase diagram.
(a) Tie-line
(b) Solvus
(c) Solidus
(d) Liquidus
Answer: c
5. Following is wrong about a phase diagram.
(a) It gives information on transformation rates.
(b) Relative amount of different phases can be found under given equilibrium conditions.
(c) It indicates the temperature at which different phases start to melt.
(d) Solid solubility limits are depicted by it.
Answer: a
6. An invariant reaction that produces a solid up on cooling two liquids:
(a) Eutectic
(b) Peritectic
(c) Monotectic
(d) Syntectic
Answer: d
7. An alloy is a
(a) Pure metal
(b) Mixture of metals in any proportion
(c) Mixture of metals in fixed proportion
(d) Mixture of two non metals
Answer: c

8. Bronze is an alloy of
(a) Copper and Nickel
(b) Copper and iron.
(c) Copper and Tin.
(d) Copper and Aluminium.
Answer: c

9. Brass is an alloy of
(a) Copper and tin
(b) Copper and nickel
(c) Copper and Aluminium.
(d) Copper and zinc
Answer: c

10. Which of the following is not an alloy?

(a) Steel
(b) Copper
 (c) Brass
(d) Bronze
Answer: b

11.An alloy can be one of the following types

(a) Homogenous
(b) Heterogeneous
(c) Intermetallic
(d) All of the above
Answer: d
12. By adding chromium to steel which of the following property is enhanced?
(a) Resistance to corrosion
(b) Electrical characteristics
(c) Magnetic property
(d) Ductility
Answer: a
13. Which of the following is not one component?
a) Water system
b) Calcium carbonate
c) Phosphorus pent oxide
d) Alloy system
Answer: b
14. Critical temperature of water system is
a) 330 degree C
b)374 degree C
c) 500 degree C
d) 100 degree C
Answer: b

15. Which of the following is heterogeneous system?

a) Water + ice
b) Water + salt
c) Water + sugar
d) Water + oil
Answer: d
16. Reduced phase rule is
(a) F = C − P + 2
(b) F = C − P + 1
(c) F = C − P + 3
(d) F = C + P + 1
Answer: a
17. Eutectic composition of Pb – Ag system is
(a) 2.4 % Pb + 97.6 % Ag
(b) 2.6 % Ag + 97.4 % Pb
(c) 2.2 % Pb + 97.8 % Ag
(d) 2.4 % Ag + 97.6 % Pb
Answer: d
18. Eutectic temperature and eutectic composition of Pb – Ag system
(a) 703°C
(b) 203°C
(c) 303°C
(4) 305°C
Answer: c
19. The heat treatment process used for softening hardened steel is
(a) Normalising
(b) Carburising
(c) Annealing
(d) Tempering
Answer: c
20. 18/8 stainless steel consists of
(a) 8% nickel and 8% chromium
(b) 18% chromium and 8% nickel
(c) 18% nickel and 18% chromium
(d) 18% nickel and 8% chromium
Answer: b
21. Non-ferrous alloys is
(a) Brass
(b) Stainless steel
 (c)Alnico
(d) Nichrome
Answer: a
22. Nichrome is an alloy of
(a) Nickel, Chromium, Iron and Manganese
(b) Copper, Chromium, Iron and Manganese
(c) Nickel, Chromium, Tin and Manganese
(d) Nickel, Chromium, Iron and Vanadium
Answer: a