Lead Silver System

No. of Components: 2
When minimum number of phases , ie 1, is present the degree of freedom
becomes 3 as shown below
F = C P + 2
=2 1 + 2
=41
F=3
This shows that the system depends on three variables, In order to draw a
planar phase diagram; one of the variables is taken as constant. A Solid
liquid equilibrium of an alloy has practically no gaseous phase and the effect
of pressure is negligible. 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
Hence reduced phase rule is applied for lead silver system.
o

Melting point of lead is 327 C and that of silver is 961 C.

The lowest melting point (i.e ) eutectic point of lead - silver system is

303 oC

The composition corresponding to eutectic point is 2.6% Ag and the

rest lead.

The composition of the alloy at its lowest melting point is called

eutectic composition.

The phase diagram of Pb Ag system is drawn with the above data

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961O C
B
P

Liquid (Pb+Ag)

327 C
A
Liquid
+ Pb (s)

Liquid + Ag (s)
B
303O C

A
303O C
Hypo
eutectic

100 % Pb

Solid (Pb + Ag)

% Composition

Hyper
eutectic

100 % Ag

2.6 % Ag and 97.4 % Pb

eutectic composition

Area under consideration:

i. AOB
In the area AOB only a single phase exists. Both lead and silver are in
liquid state
Consider any point x, in the area, at that point , P= 1 and C =2
applying phase rule to the point
F= C P + 1
=21+1
F= 2
The system is bivariant, which means both pressure and temperature
has to be specified to define the point completely.

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Lines / Curves under consideration

OA and BO
i.

Curve OA : Freezing Curve of Lead

Along this curve lead starts crystallizing from Pb- Ag mixture.

Hence there exists two phases viz., Solid Pb and Liquid from which Pb
solidifies.
Thus P = 2 and C=2
F= C P + 1
=22+1
F= 1
The system is uni / monovariant

ii.

Curve OB : Freezing Curve of Silver

Along this curve silver starts crystallizing from Pb- Ag mixture.

Hence there exists two phases viz., Solid Ag and Liquid from which Ag
solidifies.
Thus P = 2 and C=2
F= C P + 1
=22+1
F= 1
The system is uni / monovariant

Point under consideration is O

From O along OA Pb crystallizes and along OB Ag crystallises
Hence at O maximum number of phases coexist ( three phases ).
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Thus P = 3 and C=2

F= C P + 1
=23+1
F= 0
The system is invariant
Point O is called eutectic point. It is defined as the lowest melting of a
mixture of two substances which are completely miscible in liquid state and
immiscible in solid state. The composition corresponding to the eutectic
point is called eutectic composition.
Compositions of eutectic systems that are not the eutectic composition are
commonly defined to be hypoeutectic or hypereutectic. Hypoeutectic
composition is composition to the left of the eutectic composition and
hypereutectic composition are compositions to the right

Application of Pattinsons process (Desilverisation of Argentiferous lead)

Argentiferrous lead, consisting of a very small amount of silver (say 0.1%),

is heated to a temperature above its melting point, so that the system
consisting of only the liquid phase represented by the point P in the phase
diagram. It is then allowed to cool. The temperature falls down along the
line p q. As soon as the point q is reached, Pb is crystallized out and the
solution will contain relatively increasing amount of Ag. On further
cooling, more and more Pb is separated along the line AO the melt
continues to be richer and richer in silver until the point O is reached, where
the percentage of Ag rises to 2.6%. Thus, the process of raising the relative
proportion of Ag in the alloy is known as Pattinsons process.

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