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UNIT IV

PHASE RULE AND ALLOYS


Chemical reactions are of two types
1. Irreversible reaction homogeneous
2. Reversible reaction its of two types
A. homogeneous reversible reaction heterogeneous
B.heterogeneous reversible reaction --- its behaviour can be studied by PHASE RULE given
by Willard Gibbs (1874).
Phase rule
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
Explanation or meaning of terms
1. Phase (P)
Any homogeneous physically distinct and mechanically separable portion of a system which is
separated from other parts of the system by definite boundaries.
a. Gaseous phase
All gases are completely miscible and there is no boundary between one gas and the
other. For example: air single phase
b.Liquid phase
It depends on the number of liquids present and their miscibilities.
i. If two liquids are immiscible, they will form three separate phases two liquid phase
and one vapour phase. For example: benzene-water.
ii. If tow liquids are miscible, they will form one liquid phase and one vapour phase.
For example: alcohol water.
C .Solid phase
Every solid constitutes a separate phase
For example:
(i) Water system ------- three phases
(ii) Rhombic sulphur (s) monoclinic sulphur (s) ----- two phase
iii) Sugar solution in water ----- one phase
iv) CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g) ---- three phases.
2. Component (C)
The smallest number of independently variable constituents, by means of which the
composition of each phase can be expressed in the form of a chemical equation.
For example:
i) Water system ---- one component ( H2O )
ii) An aqueous system of NaCl --- two component ( NaCl , H2O )
iii) PCl5(s) PCl3 (l) + Cl2 (g) --- two component ,three phases
iv) CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g) ---- three phases,two
component
3. Degree of freedom(F)
The minimum number of independent variable factors such as temperature, pressure and
concentration, which much be fixed in order to define the system completely.
i) Water system
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Ice (s) water (l) vapour (g)
F = Non variant (or) zero variant
ii) Ice (s) water (l)
F = univariant (one)
iii) For a gaseous mixture of N2 and H2, we must state both the pressure and temperature.
Hence,the system is bivariant.
PHASE DIAGRAM:
Phase diagram is a graph obtained by plotting one degree of freedom against another.
Types of phase diagrams
(i)P-T Diagram : used for one component system
(ii) T-C Diagram : used for two component system
APPLICATIONS OF PHASE RULE TO ONE COMPONENT SYSTEM
The water system:
Water exists in three possible phases namely solid, liquid and vapour. Hence there
can be three forms of equilibria.
Solid Liquid
Liquid Vapour
Solid Vapour
Each of the above equilibrium involves two phases. The phase diagram for the water system is
shown in the figure.
This phase diagram contains curves, areas, and triple.

(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

CLASSIFICATION (OR) TYPES OF ALLOYS

ALLOYS

FERROUS ALLOYS NON-FERROUS ALLOYS


Example Example
(i)Nichrome
(i) Solder
(ii) Alnico
(ii) Brass
(iii)Stainless steel
(iii) Bronze
FERROUS ALLOYS OR ALLOY STEELS
Ferrous alloys are the type of steels in which the elements like Al,B,Cr,Co,Cu,Mn are
present in sufficient quantities, in addition to carbon & iron.
PROPERTIES
1. High yield point & strength
2. Sufficient formability,ductility & weldability
3. Corrosion & abrasion resistant
4. Less distortion & cracking
5. High temperature strength
IMPORTANT FERROUS ALLOYS
(i)NICHROME
Nichrome is an alloy of nickel & chromium
COMPOSITION
Nickel 60%
Chromium 12%
Iron 26%
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Manganese 2%
PROPERTIES
1. Good resistance to oxidation & heat
2. High melting point & electrical resistance
3. Withstand heat up to 1000-1100C
USES
1. Used for making resistance coils,heting elements in stoves & electric irons
2. Used in making parts of boilers,steam lines stills,gas turbines,aero engine
valves,retorts,annealing boxes.
(ii)ALNICO
Alnico is an alloy of aluminium-nickel-cobalt .
COMPOSITION
Aluminium 8-12%
Nickel 14-28%
Cobalt 5-35%
PROPERTIES
1. Excellent magnetic properties & high melting point
2. Magnetized to produce strong magnetic fields as high as 1500 gauss
TYPES OF ALNICO ALLOYS
Alnico alloys are of two types
1. ISOTROPIC ALNICO
It is effectively magnetized in any direction
2.ANISOTROPIC ALNICO
It possess preffered direction of magnetization.
Anisotropic alnico possesses greater magnetic capacity in their preffered
orientation than isotropic alnico.
USES
1. Used as permanent magnets in motors,generators,radio speakers
microphones,telephone receivers & galvanometers.
(iii)STAINLESS STEELS (or)CORROSIOPN RESISTANT STEELS
These are alloy steels containing chromium together with other elements such
as nickel,molybdenum,etc.
Chromium-16% or more
Carbon-0.3-1.5%
PROPERTIES
1. Resist corrosion by atmospheric gases & also by other chemicals.
2. Protection against corrosion is due to the formation of dense, non-
porous,tough film of chromium oxide at the metal surface. If the film cracks,
it gets automatically healed up by atmospheric oxygen

TYPES OF STAINLESS STEEL


STAINLESS STEEL

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HEAT TREATABLE NON HEAT TREATABLE
STAINLESS STEEL STAINLESS STEEL

MAGNETIC TYPE NON MAGNETIC


TYPE
1. HEAT TREATABLE STAINLESS STEEL
COMPOSITION
Carbon-1.2%
Chromium-less than 12-16%
PROPERTIES
Magnetic,tough & can be worked in cold condition
USES
1. Can be used up to 800C
2. Good resistant towards weather & water
3. In making surgical instruments,scissors,blades,etc.
2.HEAT TREATABLE STAINLESS STEEL
PROPERTIES
Possess less strength at high temperature
Resistant to corrosion
TYPES OF NON HEAT TREATABLE STAINLESS STEEL
(a)MAGNETIC TYPE
COMPOSITION
Chromium-12-22%
Carbon-0.35%
PROPERTIES
1. Can be forged,rolled & machined
2. Resist corrosion
USES
Used in making chemical equipments& automobile parts.
(b)NON MAGNETIC TYPE
COMPOSITION
Chromium-18-26%
Nickel-8-21%
Carbon-0.15%
Total % of Cr & Ni is more than 23%.
EXAMPLE:18/8 STAINLESS STEEL
COMPOSITION: Chromium-18%
Nickel-8%
PROPERTIES
1. Resistance to corrosion.
2. Corrosion resistance is increased by adding molybdenum
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USES
In making household utensils,sinks,dental & surgical instruments.
NON FERROUS ALLOYS
Do not contain iron as one of the main constituent.
Main constituents are copper,aluminium,lead,tin,etc.
PROPERTIES
1. Softness & good formability
2. Attractive (or) very good colours
3. Good electrical & magnetic properties
4. Low density & coefficient of friction
5. Corrosion resistance
IMPORTANT NON FERROUS ALLOYS
1. COPPER ALLOYS (BRASS)
Brass contains mainly copper & zinc
PROPERTIES
Greater strength, durability & machinability
Lower melting points than Cu & Zn
Good corrosion resistance & water resistance property
2.BRONZE(COPPER ALLOY)
Bronze contains copper & tin
PROPERTIES
Lower melting point
Better heat & electrical conducting property
Non-oxidizing,corrosion resistance & water resistance property.
3.SOLDERS
Solders are low- melting alloys of tin & lead
PROPERTIES
Solder is melted to join metallic surfaces ,especially in the fields of electronic &
plumbing
USES
1. Used in electrical industry
2. Alloy with 50% tin is general-purpose solder
3. For sealing automotive radiator cores.
4. As fuses for fire-extinguishing equipments,boiler plugs,etc.
Heat treatment of alloys (steel)
Heat treatment is defined as the process of heating and cooling of solid steel
article under carefully controlled condition. During heat treatment certain physical
properties are altered without altering its chemical composition
Objectives (or) purpose of heat treatment
Heat treatment causes
i. Improvement in magnetic and electrical properties
ii. Refinement of grain structure
iii. Removal of the imprisoned trapped gases
iv. Removal of internal stress
v. Improves fatique and corrosion resistance
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Types of heat treatment of alloys (steel)
1. Annealing
Annealing means softening. This is done by heating the metal to high
temperature followed by slow cooling in a furnace.
Purpose of annealing
i. It increases the machinability
ii. It also removes the imprisoned gases
Types of annealing
Annealing can be done in two types
i. Low temperature annealing (or) process annealing
ii. High temperature annealing 9or) full annealing
Low temperature annealing (or)process annealing
It involves in heating steel to a temperature below the lower critical point
followed by slow cooling
Purpose
1. It improves mashinability by reliving the internal stress or internal strain
2. It increases ductility and shock resistance
3. It reduce hardness
(i) High temperature annealing (or) fault annealing
It involves in heating to a temperature about 30 to 50C 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 room
temperature
The approximate annealing temperature of various grades of carbon steel
are
1. Mild steel=840-870c
2. Medium carbon steel=780-840c
3. High carbon steel=760-780c
Purpose
1. It increases the ductility and machinability
2. It makes the steel softer, together with an appreciable increases 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.
The faster the rate of cooling harder will be the steel produced.
Medium and high carbon steel can be hardened but low carbon steel
cannot hardened
Purpose
1. It increases its resistance to wear ability ,to cut other metal and strength .
2. It increases abrasion resistance.
3. 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 & then cooling it slowly.
The reheating controls the development of the final properties
Thus,
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(a)For retaining strength & hardness, reheating temperature should
not exceed 400C.
(b) For developing better ductility & toughness, reheating
temperature should be within 400-600C.
Purpose
1. It removes stress &strains that might have developed during quenching.
2. Increased toughness & ductility.
3. Used for cutting tools like blade,cutters etc.
4. NORMALISING
It is the purpose of heating steel to a definite temperature
(above its higher critical temperature) & allowing it to cool gradually in air.
Purpose
1. Recovers homogeneity
2. Refines grains.
3. Removes internal stresses
4. Increases toughness
5. Used in engineering works
NOTE: The difference between normalised & annealed steel are
1. A normaled steel will not be as soft as annealed steel.
2. Also normalizing takes much lesser time than annealing.
5.CARBURIZING
The mild steel article is taken in a cast iron box within containing small
pieces of charcoal(carbon material).
It is heated to about 900 to 950C & allow it for sufficient time,so that the
carbon is absorbed to required depth .
The article is then allowed to cool slowly within the box itself.
The outer skin of the article is converted into high carbon steel containing
about 0.8 to 1.2% carbon.
Purpose
To produce hard surface on steel article
6.NITRIDING
Nitriding is the process of heating the metal alloy in presence
of ammonia to about 550C.
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.

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