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Unit 7 Phaserule

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TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL


PHASE RULE (UNIT – VII)
The Phase rule is given by Willard Gibbs. It is defined as, In heterogeneous systems, if
equilibrium between phases are not influenced by gravity, magnetic & electrical forces, but are
influenced only by pressure, temperature and concentration, then the number of degree of freedom (F) of
the system is related to number of components (C) and number of phases(P) by the following phase rule
equation F=C-P+2

Q.NO.1 Define phase, component, degree of freedom, phase rule equation & Merits – demerits of
phase rule.
1. Phase: It is defined as, “any homogenous, physically distinct and mechanically separable portion of
the system, which is separated from other such parts of the system by definite boundary surfaces”.
Examples:
 Water consists of three phases
Ice (S) ↔ Water (L) ↔ Water vapour (g)
 A gaseous mixture, miscible in all proportions, will constitute only one phase.
 The two immiscible liquids (benzene and water) will form two liquid phases.
 The two miscible liquids (i.e. alcohol and water) will form one separate phase.
 A solution of a substance in a solvent consists of one phase only e.g.: Sugar solution in water.
 A heterogeneous mixture like
CaCO3 (S)  CaO(S) + CO2 (g)
Consists of three phases (i.e. two solids and one gaseous)
2. Component: It is defined as, “the smallest number of independent variable constituents, by the
means of which the composition of each phase can be expressed in the form of chemical equation”.
Examples:
In the water system, the chemical composition of all the three phases is H2O. Hence, it is one
component system.
Ice (S) ↔ Water (l) ↔ vapour (g)
 The sulphur system consists of four phases, rhombic, monoclinic, liquid and vapour, the
chemical composition of all the phases is ‘S’. Hence, it is also one component system.
 A saturated solution of NaCl consists of solid NaCl, NaCl solution, and water vapour. The
chemical composition of all the three phases is NaCl & H2O. Hence, it is a two component
system.
3. Degree of freedom: It is defined as, “the minimum number of independently variable factors,
such as pressure temperature and composition, which must be specified to represent the condition of a
system”.
Examples:
a. In the water system
Ice (S) ↔ Water (l) ↔ Vapour (g)
Three phases will be in equilibrium only at particular temperature and pressure. The system is,
zero variant, or non-variant or invariant and has no degree of freedom.

b. For a system consisting of water in contact with its vapour.


Water (l) ↔ Vapour (g)
We must state either temperature or pressure to define the system completely. Hence; the degree of
freedom is one (or) the system is invariant.

c. For a system consisting of


NaCl (S) ↔ NaCl – Water (aq) ↔ Water vapour (g)
We must state either temperature or pressure. Hence the system is univariant (degree of
freedom is one).
For a gaseous mixture of N2 and H2, we must state both the temperature and pressure. Hence, the system
is bivariant (degree of freedom is two).
_________________________________________________________________________________ 1
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
Phase rule: is defined as, In heterogeneous systems, if equilibrium between phases are not influenced
by gravity, magnetic & electrical forces, but are influenced only by pressure, temperature and
concentration, then the number of degree of freedom (F) of the system is related to number of
components (C) and number of phases (P) by the following phase rule equation F=C-P+2
Merits of phase rule
1. It is applicable to both physical and chemical equilibria.
2. It is a convenient method of classifying the equilibrium states in terms of phases, components
and degree of freedom.
3. It indicates different system with same degree of freedom behave similarly.
4. It helps us to predict the behaviours of a system, under different sets of variables.
5. It helps in deciding whether the number of substances remains in equilibrium or not.
Limitations of phase rule
1. It can be applied only for the system in equilibrium.
2. Only three variables like P, T, & C are considered, but not electrical, magnetic and
gravitational forces.
3. It is applied only to a single equilibrium system.
4. It requires utmost care in deciding the number of phases existing in equilibrium.
5. Solid and liquid phases must not be in finely – divided state; otherwise deviations occur.

Q. NO.2 Define phase diagram & classify systems. To explain one component system phase
diagram with using one suitable example.
Phase diagram: Phase diagram is a graph obtained by plotting one degree of freedom against
another. If temperature is plotted against pressure, the diagram is called P-T diagram.
Similarly, a plot of temperature against composition is known as T-C diagram. By the phase diagram,
we may understand the behaviour of the system, stability and equilibrium between phases.
Classification of system:
Systems are classified, on the basis of number of components, into three types.
1. One component systems.
2. Two component systems.
3. Three component systems.
One-component systems:
In any system, the minimum number of phases is one. It is evident from the phase rule equation
F=C-P+2
=1-1+2=2
For one component system the maximum number of degree of freedom is two.
The maximum number of phases in any system is three, from the phase rule equation
F=C-P+2
=1-3+2=0
The minimum number of degree of freedom is zero for one component system.
From the above calculations, it is clear that for any one-component system the maximum number
of degree of freedom is two. Therefore, such a system can be presented completely by a two
dimensional diagram. Hence, we may draw the phase diagram by taking pressure and temperature as the
two axes. These are known as pressure-temperature (P-T) diagrams, concentration (or) composition
remains constant.
The Water system:
Water can exist in three possible phases, namely, solid, liquid and vapour. Hence, there can be
three equilibriums:
1. Liquid ↔ vapour
2. Solid ↔ Vapour
3. Solid ↔ Liquid
Each equilibrium involves two phases.

_________________________________________________________________________________ 2
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL

The curve OA
It is called the vapourization curve of water; it represents the equilibrium between liquid water
and vapour. At any point on the curve the following equilibrium will exist.
Liquid water ↔ vapour

The degree of freedom of the system is one, i.e., univariant. This is predicted by the phase rule.
F=1-2+2; F=1

This equilibrium will extend up to the critical temperature (3740C). Beyond the critical
temperature, the equilibrium will disappear only water vapour will exist.

The curve OB
It is called the sublimation curve of ice; it represents the equilibrium between ice and vapour. At
any point on the curve the following equilibrium will exist.
Ice ↔ Vapour.
The degree of freedom of the system is one i.e., univariant. This is predicted by the phase rule.
F=C-P+2; F=1-2+2; F=1
This equilibrium will extend up to the absolute zero.

Triple point
The vaporization curve (OA) and the sublimation curve (OB) meet at point O, where three
phases, namely solid, liquid and vapour will coexist. Such a point is known as the “triple point”.
Temperature and pressure at the triple point of water are 0.0098 and 4.58mm respectively, according to
phase rule, the degree of freedom is zero i.e., invariant.
F=C-P+2; F=1-3+2; F=0

The curve OC
It is called the fusion curve of ice; it represents the equilibrium between ice and water.
At any point, on the curve the following equilibrium will exist.

Ice ↔ water
The curve OC shows how is the melting point of ice increased by increasing pressure. The
degree of freedom of the system is one, i.e., univariant.
_________________________________________________________________________________ 3
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
The curve OA’
It is called vapour pressure curve of the super-cool water (or) metastable equilibrium. Some
times water can be cooled below 00C without the formation of ice; this water is known as super-cool
water. The super-cool water can be preserved if the system is not subjected to stirring (or) “Seeding” by
solid. At any point on the curve the following equilibrium will exist.
Super-cool water ↔ vapour
The degree of freedom of the system is one i.e., univariant.
Area
AOB, AOC and BOC contain vapour, liquid and ice phases respectively, with in these single-
phase areas, the system is bivariant. This is predicted by the phase rule.
F=C-P+2; F=1-1+2; F=2
To locate any point in an area, temperature and pressure needs to be known.

Q. NO.3. Define phase. To explain two component system phase diagram with using one suitable
example. (OR) State phase rule & explain the terms involved. Apply the phase rule to silver-lead
system.
Answer: Phase: It is defined as, “any homogenous, physically distinct and mechanically separable
portion of the system, which is separated from other such parts of the system by definite boundary
surfaces”.
TWO COMPONENT SYSTEMS: In a two – component system, minimum number of phases is one,
i.e., P = 1, according to the phase rule equation, the maximum degree of freedom is three
F = C – P + 2; F = 2 – 1; F=3
So, the phase diagram of a binary system should be represented by a three dimensional diagram of
temperatures, pressure and composition, which can not be drawn on paper.
Generally solid-liquid equilibrium of an alloy has “no gas phase” and the effect of pressure is
small. Therefore, experiments are conducted under atmospheric pressure. Thus, the system in which
the pressure is constant (vapour phase is not considered) is known as condensed system. The phase rule
becomes.
F’=C-P+1
This is known as reduced phase rule (or) condensed phase rule. The phase diagram can be drawn
by taking temperature and composition as the two axis. This is known as (T-C) diagram.
The reduced phase rule is used only when atmospheric pressure is larger than actual vapour
pressure of the component.
Depending upon the solubility of the two components and their reactive ability, two component
systems are classified into three types
1. Simple Eutectic formation
2. Solid solution formation.
3. Compound formation.

Simple Eutectic: If two substances are completely miscible in the liquid state, but completely
immiscible in the solid state, form a simple eutectic. Of the various mixture, one mixture has the lowest
melting point such a mixture is known as a eutectic mixture (eutectic means easy melting).
Solid Solution: When two substances, especially metals, are completely miscible in both the solid and
liquid states, they form solid solutions, where mixing takes place in the atomic levels. A condition for
the formation of solid solution is, the two metals should not differ in atomic radius by more than 15%.
Compound formation: Under some conditions, two metals chemically react to give one or more
compounds with definite proportions. Of the compounds, a compound is said to possess congruent
(constant) melting point, if it melts exactly at a constant temperature into liquid, having the same
composition as that of solid.
A compound is said to possess incongruent melting point, if it decomposes completely at a
temperature below its melting point yielding a new solid phase with a composition different from that of
the original.

_________________________________________________________________________________ 4
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
Thermal Analysis or Cooling Curves: The shape of the cooling curves can be determined by thermal
analysis. Thermal analysis is a method involving a study of cooling curves of various compositions of a
system during solidification. The cooling curve is obtained by plotting fall of temperature with time.
The principle of the method can be understood from the following examples.

1. When a pure substance in the liquid state is allowed to cool slowly and the temperature is
noted at definite times. The cooling curve (fig) shows the rate of cooling is continuous up to
the point ‘b’ the solid begins to separate, and the temperature will remain constant, until the
liquid is completely solidified (indicated by the line ‘b’). Thereafter, the fall in temperature
will again become continuous (indicated by the line ‘cd’).
2. If a mixture of two solids in the liquid state is cooled slowly and the cooling curve is
obtained in a similar manner (fig). The cooling curve shows the rate of cooling is continuous
up to the point ‘b’. At the point ‘b’ one of the solids begins to separate, this separation will
extent up to the point ‘c’. At the point ‘c’ the eutectic compound begins to separate. The
temperature remains constant along cd until the solidification completes. Thereafter the fall
of temperature becomes uniform, but the rate of fall is quite different from the previous one.
Uses
1. Melting point and eutectic temperature can be noted from the cooling curve.
2. Percentage purity of the compounds can be known.
3. The behaviour of the compounds can be clearly understood from the cooling curves.
4. The procedure of thermal analysis can also be used to derive the phase diagram of any two
component system.

Simple Eutectic (Pb-Ag system)


It is a two-component system. The phase diagram of the Pb-Ag system is shown in the fig
Curve AO
Point A is the melting point of pure Silver. Curve AO shows melting point depression of silver
by the addition of lead. At any point in this curve there is equilibrium between solid Ag and liquids part.
According to reduced phase rule equation. The system is univarient.
F’=C-P+1; F’=2-2+1; F’=1
Curve BO
Point B is the melting point of pure lead, (327oC), curve BO shows the melting point depression
of lead on gradual addition of silver to it. Along this curve solid lead and solution co – exist and hence
the system is univariant.

_________________________________________________________________________________ 5
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL

Point O: The two curves AO & BO meet at point O, where three phases solid pb, solid Ag and their
solution co-exist, according to condensed phase rule the system is invariant.
F’=C-P+1; F’=2-1+1; F’=2
The point ‘O’ is known as eutectic point, its composition (Ag=2.6%; Pb=97.4%) and
temperature (3030C) is known as eutectic composition and eutectic temperature respectively. Further
cooling below the eutectic temperature respectively. Further cooling below the eutectic temperature will
cause simultaneous crystallization of a mixture of lead and silver.

Area AOB: Consists of only one phases namely pb-Ag solution. According to reduced phase rule
equation.
F’=C-P+1; F’=2-1+1; F’=2
The system is bivarient i.e., both T & composition has to be specified to define the system.
Let us consider a point p, which represents a sample of lead containing less than 2.6% silver. On
cooling the temperature falls gradually till point p’. On further cooling lead begins to separate and the
concentration of Ag increase in the solution till the point O is reached, after that whole mass solidifies
(2.6% Ag; 97.4% pb). This process is utilized in the pattinson’s process of desilverization of lead.
Below the eutectic point (O), area COEF consists of solid and eutectic compound, where
crystalline silver and eutectic compounds are stable. Similarly the area ODFG consists of solid Pb and
eutectic compound, where crystalline lead eutectic compounds are stable.
Applications to pattinson’s process: If a sample of argentiferrous lead, containing less than 2.6% Ag is
allowed to cool gradually, lead will separate out and the solution will become progressively richer in Ag,
till the percentage 2.6 of Ag is reached; and on further cooling, the whole mass will solidify as such. On
the other hand, if lead-silver allow containing Ag greater than 2.6% is allowed to cool, and then pure
silver separates along the curve AO, till the eutectic composition at O is reached.

Merits of phase rule


1.It is applicable to both physical and chemical equilibria.
2.It is a convenient method of classifying the equilibrium states interms of phases, components and
degree of freedom.
3.It indicates different system with same degree of freedom behave similarly.
4.It helps us to predict the behaviours of a system, under different sets of variables.
5.It helps in deciding whether the number of substances remains in equilibrium or not.

_________________________________________________________________________________ 6
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
Limitations of phase rule
1.It can be applied only for the system in equilibrium.
2.Only three variables like P, T, & C are considered, but not electrical, magnetic and gravitational
forces.
3.It is applied only to a single equilibrium system.
4.It requires utmost care in deciding the number of phases existing in equilibrium.
5.Solid and liquid phases must not be in finely – divided state; otherwise deviations occur.

Q. NO. 4. Define phase. To explain two component system phase diagram with using one suitable
example (OR) To discuss Pb -Ag two component system.
Answer: Phase: It is defined as, “any homogenous, physically distinct and mechanically separable
portion of the system, which is separated from other such parts of the system by definite boundary
surfaces”.

TWO COMPONENT SYSTEMS: In a two – component system, minimum number of phases is one,
i.e., P = 1, according to the phase rule equation, the maximum degree of freedom is three
F = C – P + 2; F = 2 – 1; F=3
So, the phase diagram of a binary system should be represented by a three dimensional diagram of
temperatures, pressure and composition, which can not be drawn on paper.
Generally solid-liquid equilibrium of an alloy has “no gas phase” and the effect of pressure is
small. Therefore, experiments are conducted under atmospheric pressure. Thus, the system in which
the pressure is constant (vapour phase is not considered) is known as condensed system. The phase rule
becomes.
F’=C-P+1
This is known as reduced phase rule (or) condensed phase rule. The phase diagram can be drawn
by taking temperature and composition as the two axis. This is known as (T-C) diagram.
The reduced phase rule is used only when atmospheric pressure is larger than actual vapour
pressure of the component.

Pb-Ag system: It is a two-component system. The phase diagram of the Pb-Ag system is shown in the
fig

_________________________________________________________________________________ 7
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
Curve AO: Point A is the melting point of pure Silver. Curve AO shows melting point depression of
silver by the addition of lead. At any point in this curve there is equilibrium between solid Ag and
liquids part. According to reduced phase rule equation. The system is univarient.
F’=C-P+1; F’=2-2+1; F’=1

Curve BO: Point B is the melting point of pure lead, (327oC), curve BO shows the melting point
depression of lead on gradual addition of silver to it. Along this curve solid lead and solution co – exist
and hence the system is univariant.

Point O: The two curves AO & BO meet at point O, where three phases solid pb, solid Ag and their
solution co-exist, according to condensed phase rule the system is invariant.
F’=C-P+1; F’=2-1+1; F’=2
The point ‘O’ is known as eutectic point, its composition (Ag=2.6%; Pb=97.4%) and
temperature (303OC) is known as eutectic composition and eutectic temperature respectively. Further
cooling below the eutectic temperature respectively. Further cooling below the eutectic temperature will
cause simultaneous crystallization of a mixture of lead and silver.

Area AOB: Consists of only one phases namely pb-Ag solution. According to reduced phase rule
equation.
F’=C-P+1; F’=2-1+1; F’=2
The system is bivarient i.e., both T & composition has to be specified to define the system.
Let us consider a point p, which represents a sample of lead containing less than 2.6% silver. On
cooling the temperature falls gradually till point p’. On further cooling lead begins to separate and the
concentration of Ag increase in the solution till the point O is reached, after that whole mass solidifies
(2.6% Ag; 97.4% pb). This process is utilized in the pattinson’s process of desilverization of lead.
Below the eutectic point (O), area COEF consists of solid and eutectic compound, where
crystalline silver and eutectic compounds are stable. Similarly the area ODFG consists of solid Pb and
eutectic compound, where crystalline lead eutectic compounds are stable.

Applications to pattinson’s process: If a sample of argent ferrous lead, containing less than 2.6% Ag is
allowed to cool gradually, lead will separate out and the solution will become progressively richer in Ag,
till the percentage 2.6 of Ag is reached; and on further cooling, the whole mass will solidify as such. On
the other hand, if lead-silver allow containing Ag greater than 2.6% is allowed to cool, and then pure
silver separates along the curve AO, till the eutectic composition at O is reached.

Merits of phase rule


1. It is applicable to both physical and chemical equilibria.
2. It is a convenient method of classifying the equilibrium states interms of phases, components
and degree of freedom.
3. It indicates different system with same degree of freedom behave similarly.
4. It helps us to predict the behaviours of a system, under different sets of variables.
5. It helps in deciding whether the number of substances remains in equilibrium or not.

Limitations of phase rule


1. It can be applied only for the system in equilibrium.
2. Only three variables like P, T, & C are considered, but not electrical, magnetic and
gravitational forces.
3. It is applied only to a single equilibrium system.
4. It requires utmost care in deciding the number of phases existing in equilibrium.
5. Solid and liquid phases must not be in finely – divided state; otherwise deviations occur.

_________________________________________________________________________________ 8
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
Q.NO.5. Write in detail an account of heat treatment based on iron-carbon phase diagram.
IRON – CARBON PHASE DIAGRAM:
Iron-carbon system represents interstitial solid solutions, which are formed when the alloying elements
differ widely in their atomic sizes.
Pure iron is not suitable for fabrication of structural components because of its weak mechanical
properties. Carbon, though a non-metallic element forms alloys with iron to give various types of steel
and improves the mechanical properties of the base metal to a large extent. The size of carbon atom is
small compared to that of iron atoms and hence occupies interstitial positions in the lattice formed by the
iron atoms. The miscibility or solubility of carbon in iron depends on the crystal structure of iron, which
in turn depends on the temperature, as pure iron exists in three allotropic forms.
The cooling curve of pure molten iron

None of the allotropic forms of pure iron are as useful as their alloys with carbon. Iron melts at 15350C
and the liquid iron boils at about 30000C. Iron – carbon alloys containing up to 1.7% of carbon are
classified as steels while those containing over 1.7% carbon are called cast irons. The solid solutions of
carbon are the various forms of iron are interstitial solutions.
The various important micro constituents are as follows:
Austenite: It is a solid solution of carbon in γ–iron. The γ–iron can dissolve carbon to an increased
extent of 1.7% w/w. austenite does not exist in equilibrium below 723 0C,as it decomposes on cooling.
Cementite: Cementite is iron carbide with a specific composition of Fe3C and a complex orthorhombic
structure. It exists at all temperatures studied from 0 to 18000C. It undergoes a magnetic change at
2000C. It is hard, brittle and wears resistance.
Ferrite: This is the solution of carbon in α–iron with a maximum carbon content of 0.035% at 7230C
and 0.007% at room temperature. Ferrite is often considered to be pure α–iron, but even by this minute
amount of dissolved carbon, some of its properties are strongly affected.
Pearlite: This is the eutectoid of ferrite and cementite formed by the decomposition of austite. It
contains 0.8% carbon. Further it is a fine grained mixture of ferrite and cementite and has a lamellar
structure. More of ferrite makes pearlite soft and more of cementite makes it hard.
Martensite: This is a transformed form of austentite. It is named so after the German metallurgist
Martens. Martensite is a supersaturated interstitial solid solution of carbon in α–ferrite with a distorted
BCC or tetragonal structure. Microscopic examination of martensite reveals a series of fine needles like
structures. Martensite is extremely hard and strong, the hardness being attributed tom o the efficient
filling up of the void space in the BCC structure with carbon atoms which prevents slippage between
planes of iron atoms.
Trootsite: This is formed when the martensite is tempered in the range of 230 to 4000C. It consists of
finely dispersed aggregate or superfine particles of cementite and ferrite. It is softer but tougher than
martensite.
_________________________________________________________________________________ 9
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
Bainite: It is the transformed form of austenite in the temperature range of 260 to 5400C. It has a ferrite
matrix in which cementite is embedded. It is magnetic, moderately ductile and harder than pearlite and
tougher than martensite.
Sorbite: It is formed when martensite is tempered at 400 to 6000C. It is an important constituent in some
special steels such as rails. It consists of ferrite and globules of iron carbide.

A simple iron-carbide phase diagram is depicted in the below figure, which tells about the formation of
different phases in the iron carbide system

Any point in the diagram represents a definite alloy at a definite temperature. The carbon content
is shown on the vertical axis perpendicular to the point while the temperature is shown on the vertical
axis perpendicular to the point. Further whenever an alloy is heated or cooled in such a way that a line
on the diagram is crossed, a phase change occurs. All alloys corresponding to any point in the region
above ACD in the diagram exist in the liquid phase only.
When any liquid alloy containing below 4.3% of carbon is cooled to temperatures on the curve
AE, solid crystals begin to form. Hence AC is called the ‘liquidus’ for these alloys, above which there is
only one liquid phase.
If the liquid alloys containing 0 to 0.55% carbon is cooled, the first crystals formed will be of the
solid solution of carbon in δ–iron. If the liquid alloys containing 0.55 to 4.3% carbon are cooled, the first
crystals formed are of “austenite” which is the solid solution of carbon in γ-iron. AEC is the region
where the liquid melt and austenite exist in equilibrium.
When an alloy containing up to 4.3% carbon is cooled to conditions represented by AE or EC, it
is completely converted into solid. These lines represent the “solidus” for alloys of this composition
range, below which various Fe-C compositions are completely solid.
When liquid alloys containing greater than 4.3% carbon are cooled to temperatures represented
on the curve CD, solid crystals of cementite (Fe3C) start separating out. When an alloy containing
greater than 4.3% of carbon is cooled the temperatures on the curve represented by CF, it is completely
solidified.
The alloy containing 4.3% carbon is the eutectic alloy and it will completely solidify at ‘C’
which corresponds to the temperature 11300C. This point represents the simultaneous formation of the
solid eutectic mixture containing austenite and cementite.
Therefore with the help of iron-carbon phase diagram, the cause of events taking place and the
various phase transformations occurring, while cooling liquid alloys having different carbon contents
can be understood clearly.

_________________________________________________________________________________ 10
PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry
I B.TECH JNTUH ENGINEERING CHEMISTRY COMPLETE QESTION WITH ANSWER MATERIAL
Q.NO. 6. Write a short note on Heat treatment of steel, hardening & Annealing.
Heat treatment of steel:
Heat treatment involves the combination of heating and cooling of a metal or alloy in one or more
temperature cycles to confer desirable physical properties to the metal or alloy. Heat treatment of steel
may be carried out under near equilibrium conditions to improve the ductility or under non equilibrium
conditions to enhance the hardness. During heat treatment the size and shape of the grains or the
composition of the phase undergoes changes with respect to the micro constituents and also in addition,
the internal stresses will be relieved.

Hardening: Hardening involves the transformation of austenite to martensite or the bainite phase,
making the steel hard. If steel is quenched by plunging into water or oil to 2040C or lower temperature
the carbon atoms do not have sufficient time to form cementite but remain trapped in the lattice. The
excess carbon precipitates out in hot metal and prevents the slipping of the planes. Thus quenched steel
is quite hard and strong but has lower ductility. This heat treatment is called transformation hardening.
Further the quenched steel is not useful for construction purposes, because of its brittleness. Therefore
quenching is always followed by another heat treatment process called tempering. The quenched steel is
tempered by reheating to below α–iron or γ–iron transition temperature. Normally on tempering, the
steel becomes tougher and ductile. Tempering is carried out at about 2000C to make hard steel resistant
to abrasion or at higher temperature (~ 5400C) to make tough steel capable of withstanding shock loads.
Case hardening: is a surface treatment by which the inside soft core of steel is hardened on the surface.
Low carbon steels are case hardened because they cannot be hardened by quenching.
Cyaniding: also produces case hardened, medium carbon steel articles. Here the article is immersed in a
molten bath of sodium or potassium cyanide at about 850 0C for some times to facilitate the adsorption of
both carbon and nitrogen and then quenched in oil or water.
Nitriding: produces a hard surface on alloy steels. The process involves heating the alloy in the
presence of ammonia to about 5500C. Ammonia decomposes and nitrogen formed combines with
alloying elements to form hard nitrides on the surface of the alloy.

Annealing: Annealing involves heating and holding the steel at a suitable temperature for some times to
facilitate the dissolution of carbon in γ–iron followed by a slow cooling in a controlled manner in a
furnace. Steel is softened and becomes ductile and machineable. However annealing decreases the
hardness and strength of steel. Annealed hypereutectoid steels contain cementite. They are not soft but
can be machined easily. In contrast annealed hypo eutectoid steels contain ferrite and are relatively soft
and malleable.

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PHASE RULE (UNIT – VII) Prepared by B.SRINIVAS, Asst.Prof of Chemistry

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