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Engg.

Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

UNIT-VI PASE RULE


Introduction
Phase diagrams provide a graphical means of presenting the results of
experimental studies of complex natural processes, such that at a given temperature and
pressure for a specific system at equilibrium the phase or phases present can be
determined. A system and surrounding are separated by a real or an imaginary surface
called the boundary. If the system has two or more parts it is called as heterogeneous
system. If there is equilibrium between these parts it is called heterogeneous equilibria.
Phase Rule:
Gibbs predicted qualitatively the effect of pressure, temperature, concentration and
explained the equilibrium existing in heterogeneous. It stated as “provided the equilibrium
between any no. of phases is not influenced by gravity/electrical/magnetic forces/ surface
action and only by temperature, pressure and concentration, then the no. of degree of
freedom (F) of the system is related to the no. of components (c) and of phases (P) by the
phase rule equation,

F=C–P+2

for any system at equilibrium at a definite temperature and pressure.

Explanation of the terms involved :


PHASE:

Phase may be defined as “any homogeneous part of a system, which is having


physical, chemical properties same through out”

A system may consist of one phase or more than one phase

1.system containing only liquid water is one-phase system

2.system containing liquid water and water vapour is two-phase system

3.system containing liquid water, water vapour and solid ice is three –phase system

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

4mmiscible liquids form two separate phases (eg., water and chloroform).
5.Miscible liquids form only one liquid phase (Eg., water and alcohol).
6.The mixture : CaCO3 ↔ CaO + CO2 consists of 3-phases (two solid and one gas phase)
A system consisting of one phase only is homogeneous system
A system consisting of two or more phases is heterogeneous system
Component :
A component is the minimum number of independent variable chemical constituents
necessary to define any phase in the system by means of a chemical equation.

components may be oxides, elements or minerals, dependant on the system being


examined.

For example, experiments carried out in the H2O system, show that the phases which
appear over a wide temperature and pressure range are ice, liquid water and water vapour.
The composition of each phase is H2O and only one chemical parameter or component is
required to describe the composition of each phase.
ice(s) ↔ water(l) ↔ water vapour(g)
(b) A saturated solution of NaCl consists of the solid NaCl, NaCl solution and water
vapour. The chemical composition of all the three phases are NaCl and water. Hence it is
two component system.
Degree of freedom:
Degrees of Freedom (or Variance of a System): The least number of independent
variables (concentration, pressure and temperature) which must be arbitrarily fixed in
order to define a system completely.

(i) For system consisting of water in contact with vapour


Water (l) ↔ water vapour (g)
Either temperature or pressure should be stated for defining it completely. Hence, the
degree of freedom is one or system is univariant (or) mono variant
(ii) For considering a system consisting of water vapour phase only both temperature &
pressure should be stated in order to define the system. Then the system is bivariant (or) 2
degree of freedom.
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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

Phase Diagram
Phase diagram is a graph obtained by plotting one degree of freedom against
another. A plot of temperature (T) against pressure (P) it is called P-T diagram. Similarly
a plot of temperature against composition known as T-C diagram. From the diagram we
can understand the behaviour of system stability and equilibrium between phases.
Depending on the no. of components systems are classified as one component, two
component and three component.

One-component system – Water system


The system water is a three-phase, one-component system. The salient features
of the phase diagram:
(a) The curves OA, OB, OC (b) the Triple Point O (c) The areas AOC, AOB, BOC

218 atm
Critical C A
Pressure

Pressure solid (Ice) Liquid (Water)


(not scaled)
critical temperature

1.0 atm

4.58 mm O Triple point


A’ Vapour
B
- 273 0.0098˚C 100˚C (B.P) 374˚C
(not scaled) Temp. ˚C

Explanation for the curves OA, OB, OC


Curve OA (equilibrium: water ↔ water vapour): Vapour pressure curve of water. It
represents the vapour pressure of liquid water at different temperatures. The two phases

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

water and water vapour coexist in equilibrium along this curve. The curve OA terminates
at A, the critical point (218 atm, temp 374˚C) when the liquid and vapour are
indistinguishable from each other and there is only one phase. When the vapour pressure
is equal to one-atmosphere, the corresponding temperature is the boiling point (100˚C) of
water.

Curve OB (equilibrium: ice ↔ water vapour): Sublimation curve of ice. It shows the
vapour pressure of solid ice at different temperatures. The two phases solid ice and vapour
coexist in equilibrium along this curve. At the lower limit, the curve OB terminates at
absolute zero where no vapour exists.

Curve OC (equilibrium: water ↔ water): Fusion curve of ice. It depicts the effect of
pressure on the melting point of ice. Here ice and water coexist in equilibrium. The fact
that OC slopes to the left indicates that the melting point of ice decreases with increase of
pressure.
Since ice melts with decrease in volume, by Le Chatelier’s principle the melting point is
lowered by an increase of pressure. It may be noted that the 1 atm. line meets the fusion
curve at 0˚C which is the normal melting point of ice.
Along the curves OA, OB, OC there are two phases in equilibrium and one component.
Apply the phase rule;

F = C- P +2 ; 1 – 2 + 2 = 1 (monovariant)

The Triple point ‘O’: The curves OA, OB, and OC meet at the triple point ‘O’ where all
the three phases liquid water/ice/vapour are in equilibrium. This occurs at 0.0098˚C and
vapour pressure 4.58 mm Hg. Since there are three phases and one component,
F = C- P +2 ; 1 – 3 + 2 = 0 ( non variant).

If either pressure or temp. is changed, the three phases would not exist and one of the
phases would disappear.

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

Area AOC, AOB, BOC:


Area AOC represents conditions for the one-phase system water.
Area AO B represents conditions for the one-phase system water vapour.
Area BOC represents conditions for the one-phase system ice.
In all the three areas there being one-phase and one-component,
F = C- P +2 ; 1 – 1 + 2 = 2 ( Bi variant)
Metastable system: supercooled water / vapour
The vapour pressure curve of water AO continued as dashed line OA’. That is, water can
be super-cooled by carefully below its freezing temperature without the separation of Ice.
The super-cooled water/vapour system is metastable (unstable), because as soon as small
particle of ice is brought in contact with the super-cooled liquid, the entire liquid
solidifies.
Salient features of the water system:
(i) The curve OA is the vapour pressure curve of water, Hence, water and its vapor
co-exist in equilibrium. No. of phases 2, the degree of freedom 1. The system is
monovariant.
(ii) The curve OB is the vapour pressure curve of Ice. It is called sublimation curve.
Solid is in equilibrium with vapour. The system is monovariant.
(iii) The curve OC is the fusion curve of ice. Ice and water co-exist in equilibrium.
The system is monovariant.
(iv) The curve OA’ is vapour pressure curve of the metastable water.
(v) The point O where the three curve OA,OB,OC meet, called as Triple point.

Condensed Phase Rule


If we consider the two component system of solid ↔ liquid equilibrium it is
generally characterized by the absence of the vapour phase and are relatively unaffected
by changes in pressure. If we keep the pressure constant of a system it will constitute a
condensed system. The degree of freedom get reduced by one and for such a system the
phase rule becomes
F= C – P + 1 known as condensed (reduced) phase rule.

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

Two variables to be considered Viz. temp and conc. Solid-liquid equilibriums are
represented on T-C diagrams.
Cooling curves / Thermal Analysis
The shape of the freezing point curves for any system, especially those involving
metals, can be determined by thermal analysis - a method involving a study of the cooling
curves of various compositions of a system during solidification.
Construction of phase diagram by thermal analysis:
When a graph is plot 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.
(1): Considering a pure solid substance is in fused state is cooled slowly. The
temperature is noted at different time interval. Initially the rate of cooling curve is
continuous. At the point ‘b’ freezing starts. After this pt. 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’.

Temp.
Beginning of freezing
c
End of freezing
b
Freezing point
d

Time

(2) Considering a mixture of two solids A and B is in fused state. Allow 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.

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR
a
Freezing point

Temp.
Beginning of freezing
b
d
c End of freezing
Eutectic temperature
e

Time
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 upto ‘d’.
Eutectic System :
A binary system consisting of two components, which are completely miscible
with one another in liquid state but they do not form any compound and on solidification
they give rise merely to an intimate mixture known as eutectic system (easy melting)
(Pb-Ag, Pb-Sb, KI-H2O)
Eutectic point: Two solid substances capable of forming solid solutions having the
properties of lowering each others freezing point. The minimum freezing point
corresponding to eutectic mixture is eutectic point.
Eutectic mixture: It is a solid solution of two or more substances having the lowest
freezing point of all the possible mix of components.

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

Simple eutectic systems (Pb-Ag system) or Two Component System

961˚ C
A X
Liquid

Solid Ag +
Temperature ˚ C. liquid 327˚ C
B

Solid Pb +
303˚ C liquid
C
Eutectic +
Solid Ag Eutectic +
Solid Pb

100 % Ag 97.4 % Pb 100 % Pb


0% Pb 2.6 % Ag 0% Ag
Composition
This system has two components and four phases. The phases are (a) solid Ag (b)
solid Pb (c) solution of molten Ag and Pb and (d) vapour. The boiling points of silver and
lead being considerably high, the vapour phase is practically absent.
The salient features of the diagram are:
(a) Two curves, AC and BC
(b) Eutectic point C
(c) Three areas (i) above ACB (ii) below AC (iii) below BC

Curve AC (the freezing point curve of Ag.) shows the effect on freezing point of Ag on
addition of lead in small quantities. The curve starts A (961˚C), the melting point of Ag,
where pure Ag co-exists as solid and liquid (vapour being neglected). This curve indicates
that the melting point of Ag falls gradually on adding Pb, along AC, till the lowest point
C (303˚C) is reached, where the solution gets saturated with respect to lead. At C, no more
lead can go in solution and consequently, melting point of Ag does not fall any further;
and if any lead is added, it separates as the solid phase. Along this curve, solid Ag and
solution co-exist and hence, according to reduced phase rule equation: F = 3-P = 3-2 = 1,
i.e., the system is univariant. The point C (303˚C) corresponds to a fixed composition of

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

2.6% Ag and 97.4% Pb and is known as eutectic composition. On cooling, the whole mass
crystallizes out as such.

Curve BC (freezing point curve of Pb) represents the effect on freezing point of Pb on
gradual addition of small amounts of Ag to it. Point B is the melting point of pure lead
(327˚C). Along BC, the melting point gradually falls on the addition of Ag, till lowest
point O is reached, where the solution gets saturated with respect to Ag and the melting
point of lead does not fall any more. On cooling, the whole mass (having eutectic
composition) crystallizes out. The system is monovariant.

Eutectic point C: The curve AC and BC intersect at C, which is called the eutectic point.
Here three phases solid Ag, solid Pb, and solution are in equilibrium. Applying the
reduced phase rule;
F = C - P + 1 = 2 - 3+1 = 0 (nonvariant)
Both variables temperature (303˚C) and composition (97.4 % Pb, 2.6% Ag: eutectic
composition) are fixed. If the temperature is raised above the eutectic temperature, the
solid phases Ag and Pb disappear. No mixture of lead and silver has a melting point lower
than the eutectic temperature.

Below the temperature line of eutectic, there are two regions viz.,
(i) the region marked eutectic + solid Ag, in which crystalline silver and solid
eutectic are stable, and
(ii) the region marked eutectic + solid Pb, in which crystalline lead and solid
eutectic are stable.

Area ACB: This region represents the single phase system, the solution of molten Ag and
Pb. Applying the reduced phase rule;
F = C - P + 1 = 2 - 1+1 = 2 (Bivariant)
Alloys – importance
An alloy is a metallic, intimately mixed solid mix of tow or more different elements, one
of which at least is essentially a metal.

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Engg. Chemistry SIDDARTHA INSTITUTE OF SCIENCE & TECHNOLOGY PUTTUR

Advantages of alloys over metals:


(a) To enhance the harness of metal: Pure metal are in general soft. An alloy is
harder than its component elements.
i. Addition of 0.5 % arsenic to lead makes it so hard that it can be used for
making bullets.
ii. Addition of 0.15 – 1.5% carbon to pure iron which is very soft will result in
the formation of steel alloy, which is hard.
(b) Lowering of melting point: The melting point of an alloy is lower than of its
constituents elements – alloying can enhance the fusibility of metals.
(c) Enhancement of tensile strength: Tensile strength of a metal can be increased.
(d) Enhancement of corrosion resistance: Alloys are more resistant to corrosion than
metal.
(e) Color modification: Alloying can alter the color and brightness. Brass-yellow;
Copper-red; Zinc-Silver white.
(f) Enhancement of cast-ability: Alloys expand on solidification this expansion is one
of the essential requirement to good castings.

Iron-Carbon Alloy System

Iron-carbon phase diagram describes the iron-carbon system of alloys containing up to


6.67% of carbon, discloses the phases compositions and their transformations occurring
with the alloys during their cooling or heating.

Carbon content 6.67% corresponds to the fixed composition of the iron carbide Fe 3C.

The diagram is presented in the picture:

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The following phases are involved in the transformation, occurring with iron-carbon
alloys:

L - Liquid solution of carbon in iron;

δ-ferrite – Solid solution of carbon in iron.

Maximum concentration of carbon in δ-ferrite is 0.09% at 2719 ºF (1493ºC) – temperature


of the peritectic transformation.

The crystal structure of δ-ferrite is BCC (cubic body centered).

Austenite – interstitial solid solution of carbon in γ-iron.

Austenite has FCC (cubic face centered) crystal structure, permitting high solubility of
carbon – up to 2.06% at 2097 ºF (1147 ºC).

Austenite does not exist below 1333 ºF (723ºC) and maximum carbon concentration at this
temperature is 0.83%.

α-ferrite – solid solution of carbon in α-iron.

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α-ferrite has BCC crystal structure and low solubility of carbon – up to 0.025% at 1333 ºF
(723ºC).

α-ferrite exists at room temperature.

Cementite – iron carbide, intermetallic compound, having fixed composition


Fe3C.

Cementite is a hard and brittle substance, influencing on the properties of steels and cast
irons.

The following phase transformations occur with iron-carbon alloys:

Alloys, containing up to 0.51% of carbon, start solidification with formation of crystals of


δ-ferrite. Carbon content in δ-ferrite increases up to 0.09% in course solidification, and at
2719 ºF (1493ºC) remaining liquid phase and δ-ferrite perform peritectic transformation,
resulting in formation of austenite.

Alloys, containing carbon more than 0.51%, but less than 2.06%, form primary austenite
crystals in the beginning of solidification and when the temperature reaches the curve
ACM primary cementite stars to form.

Iron-carbon alloys, containing up to 2.06% of carbon, are called steels.

Alloys, containing from 2.06 to 6.67% of carbon, experience eutectic transformation at


2097 ºF (1147 ºC). The eutectic concentration of carbon is 4.3%.

In practice only hypoeutectic alloys are used. These alloys (carbon content from 2.06% to
4.3%) are called cast irons. When temperature of an alloy from this range reaches 2097 ºF
(1147 ºC), it contains primary austenite crystals and some amount of the liquid phase. The
latter decomposes by eutectic mechanism to a fine mixture of austenite and cementite,
called ledeburite.

All iron-carbon alloys (steels and cast irons) experience eutectoid transformation at 1333
ºF (723ºC). The eutectoid concentration of carbon is 0.83%.

When the temperature of an alloy reaches 1333 ºF (733ºC), austenite transforms to pearlite
(fine ferrite-cementite structure, forming as a result of decomposition of austenite at slow
cooling conditions).

Critical temperatures

Upper critical temperature (point) A3 is the temperature, below which ferrite


starts to form as a result of ejection from austenite in the hypoeutectoid alloys.

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Upper critical temperature (point) ACM is the temperature, below which


cementite starts to form as a result of ejection from austenite in the hypereutectoid
alloys.

Lower critical temperature (point) A1 is the temperature of the austenite-to-


pearlite eutectoid transformation. Below this temperature austenite does not exist.

Magnetic transformation temperature A2 is the temperature below which α-


ferrite is ferromagnetic.

Phase compositions of the iron-carbon alloys at room temperature

Hypoeutectoid steels (carbon content from 0 to 0.83%) consist of primary


(proeutectoid) ferrite (according to the curve A3) and pearlite.

Eutectoid steel (carbon content 0.83%) entirely consists of pearlite.

Hypereutectoid steels (carbon content from 0.83 to 2.0%) consist of primary


(proeutectoid) cementite (according to the curve ACM) and pearlite.

Cast irons (carbon content from 2.0% to 4.3%) consist of proeutectoid cementite
C2 ejected from austenite according to the curve ACM , pearlite and transformed
ledeburite (ledeburite in which austenite transformed to pearlite)

Annealing

Annealing is a rather generalized term. Annealing consists of heating a metal to a specific


temperature and then cooling at a rate that will produce a refined microstructure.
Annealing is most often used to soften a metal for cold working, to improve
machinability, or to enhance properties like electrical conductivity.
In ferrous alloys, annealing is usually accomplished by heating the metal beyond the upper
critical temperature and then cooling very slowly, resulting in the formation of pearlite. In
both pure metals and many alloys that can not be heat treated, annealing is used to remove
the hardness caused by cold working. The metal is heated to a temperature
where recrystallization can occur, thereby repairing the defects caused by plastic
deformation. In these metals, the rate of cooling will usually have little effect. Most non-
ferrous alloys that are heat-treatable are also annealed to relieve the hardness of cold
working. These may be slowly cooled to allow full precipitation of the constituents and
produce a refined microstructure.

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