Unit Iv Phase Rule and Alloys: Chemical Reactions Are of Two Types
Unit Iv Phase Rule and Alloys: Chemical Reactions Are of Two Types
(i)Curve OA
The curve OA is called vaporisation curve, it represents the equilibrium between water
and vapour. At any point on the curve the following equilibrium will exist.
Water Water 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 (i.e. Line OA) will extend up to the critical temperature (347o C). Beyond the
critical temperature the equilibrium will disappear only water vapour will exist.
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(ii) Curve OB
The curve OB is called 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 (line OB) will extend up to the absolute zero (-273o C), where no vapour can be
present and only ice will exist.
iii) Curve OC
The curve OC is called melting point curve of ice, it represents the equilibrium between the ice
and water. At any point on the curve the following equilibrium will exist.
Ice water
The curve OC is slightly inclined towards pressure axis. This shows that melting point of ice
decreases with increase of pressure.
The degree of freedom of the system is one i.e., univariant.
iv) point O (triple point)
The three curves OA ,OB ,OC meet at a point O ,where three phases namely solid ,liquid and
vapour are simultaneously at equilibrium .
This point is called triple point, at this point the following equilibrium will exist.
Ice water vapour
The degree of freedom of the system is zero i.e., nonvariant.This is predicted by the phase rule.
F=C-P+2; F=1-3+2=0
Temperature and pressure at the point O are 0.0075 oC and 4.58 mm respectively.
(v) Curve OB: Metastable equilibrium
The curve OB is called vapour pressure curve of the super-cool water or metastable equilibrium
where the following equilibrium will exist.
Super-cool water vapour
Sometimes water can be cooled below OoC without the formation of ice, this water is called
super cooled water. Super cooled water is unstable and it can be converted in to solid by
seeding or by slight disturbance.
vi) Areas
Area AOC, BOC, AOB represents water, ice and vapour respectively .The degree of the 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
Two component alloy system or multi component equilibria
Reduced phase rule or condensed system
The system in which only the solid and liquid are considered and the gas phase is
ignored is called a condensed system.since pressure kept constant, the phase rule becomes
F = C P + 1
This equation is called reduced phase rule.
Classification of two component system
Based on the solubility and reactive ablity, the two component systems are classified in to three
types.
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1. Simple eutectic formation - A binary system consisting of two substances, which are
completely miscible in the liquid state, but completely immiscible in the solid state, is known as
eutectic (easy melt) system. They do not react chemically. Of the different mixtures of the two
substances, the mixture having the lowest melting point is known as the eutectic mixture.
2. a) formation of compound with congruent melting point
b) Formation of compound with incongruent melting point
3. Formation of solid solution
Thermal analysis or cooling curve
Thermal analysis is a method involving a study of the cooling curves of various
compositions of a system during solidification. The form of the cooling curve indicates the
composition of the solid.
Ex: 1. Cooling curve of a pure solid.
Ex: 2. Cooling curve of a mixture A + B.
A cooling curve is a line graph that represents the change of phase of matter, typically from a
gas to a solid or a liquid to a solid.
The independent variable (X-axis) is time and the dependent variable (Y-axis) is temperature.
Below is an example of a cooling curve.
The initial point of the graph is the starting temperature of the matter, here noted as the "pouring
temperature". When the phase change occurs there is a "thermal arrest", that is the temperature
stays constant. This is because the matter has more internal energy as a liquid or gas than in the
state that it is cooling to. The amount of energy required for a phase change is known as latent
heat. The "cooling rate" is the slope of the cooling curve at any point.
A Pure substance in the fused or liquid state is allowed to cool slowly. The
temperature is noted at different times.when represented graphically the rate of cooling will be a
continuous from a to b.
When the freezing point is reached and solid making its appearance there will be a break in the
continuity of the cooling curve.The temperature will thereafter remain constant until the liquid is
completely solidified.Thereafter the fall in temperature wil again become continuous.
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a. Cooling curve of a pure substances b. Cooling curve of a mixture
If a mixture of two solids in the fused state is cooled slowly we get a cooling curve .
Here also first a continuous coling curve will be obtained as long as the mixture is in the liquid
state .
When a solid phase begins to form there will be a break in the cooling curve .But the
temperature will not remain constant unlike in the case of cooling of a purified substance.The
temperature will decrease continuously but at a different rate.The fall of temperature will
continue till the mixture forms a eutectic and the eutectic point is reached.
The temperature will thereafter remain constant until solidification is complete . Thereafter the
fall of temperature will become uniform ,but the rate of fall will be different from that for a pure
substance.
Uses of cooling curves
i) Percentage purity of the compounds can be noted from the cooling curve.
ii) The behaviour of the compounds can be clearly understood from the cooling curve.
iii) The procedure of thermal analysis can be used to derive the phase diagram of any two
component system.
BINARY ALLOY SYSTEM OR THE SIMPLE EUTECTIC SYSTEM
The Lead Sliver system
Since the system is studied at constant pressure,the vapour phase is ignorned and the
condensed phase rule is rule is used.
F I= C-P+1
The phase diagram of lead sliver system is shown in the figure
It contains lines,areas and the eutectic point.
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i) curve AO
The curve AO is known as freezing point curve of sliver.
Along the curve AO, solid Ag and the melt are in equilibrium.
Solid Ag melt
According to reduced phase rule
F=C-P+1
C=2
P=2
F=1
The system is univariant
ii) curve BO
The curve BO is known as freezing point curve of lead .
Along the curve BO, solid Pb and the melt are in equilibrium.
Solid Pb melt
According to reduced phase rule
F=C-P+1
C=2
P=2
F=1
The system is univariant.
iii) Point O (eutectic point)
The curves AO and BO meet at point O at a temperature of 303 o C ,where the
three phases are in equilibrium.
Solid Pb + soild Ag melt
According to reduced phase rule
F=C-P+1
C=2
P=3
F=1
The system is non-variant.
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The point O is called eutectic point or eutectic temperature and is
corresponding composition,97.4 % Pb and 2.6 % Ag ,is called eutectic
composition.below this point the eutectic compound and the metal solidfy.
iv) Areas
The area above the line AOB has a single phase( molten Pb + Ag ).
According to reduced phase rule
F=C-P+1
C=2
P=1
F=2
The system is bi-variant.
The area below the line AO ,OB and point O have two phases and hence the
system is univariant.
According to reduced phase rule
F=C-P+1
C=2
P=2
F=1
The system is uni-variant.
The process of raising the relative proportion of Ag in the alloy is known as pattinsons
process.
The Pattinson process was patented in 1833. It depended on well-known material
properties; essentially that lead and silver melt at different temperatures. The equipment
consisted of a row of about 8-9 iron pots, which could be heated from below. Agentiferous lead
was charged to the central pot and melted. This was then allowed to cool, as the lead solidified, it
was skimmed off and moved to the next pot in one direction, and the remaining metal was then
transferred to the next pot in the opposite direction. The process was repeated in the pots
successively, and resulted in lead accumulating in the pot at one end and silver in that at the
other. The process was economic for lead containing at least 250 grams of silver per ton.
Uses of eutectic system
1.suitable alloy composition can be predicted with the help of eutectic systems.
2.eutectic systems are used in preparing solders ,used for joining two metal
pieces together.
Melting point www.annauniversityplus.com
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It is the temperature at which the solid and liquid phases, having the same composition ,are in
equilibrium.
Solid A solid B
Eutectic point
It is the temperature at which two solids and a liquid phase are in equilibrium .
Solid A + solid B Liquid
Triple point
It is the temperature at which three phases are in equilibrium.
Solid liquid vapour
By definition ,
All the eutectic points are melting points, but all the melting points need not be eutectic points.
ll ly , all the eutectic points are triple points ,but all the triple points need not be eutectic points.
Uses (or) merits of phase rule
1. It is a convenient method of classifying the equilibrium states in terms of phases ,components
and degree of freedom.
2. It helps in deciding whether the given number of substances remain in equilibrium or not.
Limitations of phase rule
1.phase rule can be applied for the systems in equilibrium.
2.only three variables like P,T & C are considered ,but not electrical, magnetic and gravitational
forces.
ALLOYS
Definition
An alloy is defined as homogeneous solid solution of two or more different
element one of which at least is essentially a metal. Alloy containing Hg as a constituent
element are called amalgams.
Properties of alloys
1) Alloy are harder less malleable and possess lower melting point than their
component metals
2) Alloys possess low electrical conductivity
3) Alloys resist corrosion and the action of acids
Importance or need of making alloys
1. To increase the hardness of the metal
Example
Gold and silver are soft metal they are alloyed with copper to make them
hard
2. To lower the melting points of the metal
Example
Wood metal (an alloy of lead, bismuth, tin and cadmium) melts at 60.5c
which is far below the melting points of any of these constituent metals
3. To resist the corrosion of the metal
Example
Pure iron rested but when it is alloyed with carbon chromium (stainless
steel) which resists corrosion
4. To modify chemical activity of the metal
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Example
Sodium amalgam is less active than sodium but aluminium amalgam is
more active than aluminium
5. To modify the colour of the metal
Example
Brass an alloy of copper (red) and size (silver-white) is white colour.
6. To get good casting of metal
Example
An alloy of lead with 5% tin and 2% antimony is used fro casting printing
type due toits good casting property
Functions (or) effects of alloying elements
Addition of small amount of certain metals such as Ni, Cr, Mo, Mn, Si, v and Al
impart special properties like hardness, tensile strength, resistance to corrosion and
coefficient of expansion on steel. Such products are known as special steel or alloy steels
Some important alloying element and their functions are given in table
ALLOYS
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HEAT TREATABLE NON HEAT TREATABLE
STAINLESS STEEL STAINLESS STEEL
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