Pb – Ag System (Eutectic binary system)

It is a two component system with four possible phases:

Solid Ag, Solid Pb, solution of Ag & Pb and vapor.
As the gaseous phase is practically absent, so one variable (pressure) is neglected.
Hence, the condensed phase rule is applicable:
F = C - P+ 1 = 2 - P + 1 = 3 - P
Thus, the system can be conveniently represented by a temperature – concentration
diagram at constant pressure.

Fig: Phase diagram of Pb - Ag System

Curves:
i. Curve AO: is called freezing point curve of Ag. This shows the effect
on freezing point of Ag on addition of Pb in small quantities. The curve
starts from point A (961⁰ C) the m.p. of Ag. This curve indicates that the
melting point of Ag falls gradually on addition of Pb, along AO till the
lowest point O (303⁰C) is reached. At point O no more Pb can go in
solution and consequently melting point of Ag does not fall any further,
and if Pb is added it separates as the solid phase. Along this curve solid
Ag and solution of Ag & Pb coexist. Hence according to condensed
phase rule: F = 3-P = 3-2 = 1 (the system is mono-variant).
 ii. Curve BO: This is called freezing point curve of Pb. The curve
represents the effect on freezing point of Pb on gradual addition of Ag.
The point B is the melting point of pure Pb (327⁰ C). Along curve BO
the m.p. of Pb gradually falls on the addition of Ag till lowest point O
is reached. The system is mono-variant along curve BO & the degree of
freedom is 1.
iii. Point O (Eutectic point): The two curves AO and BO meet at point O
where three phases (solid Ag, solid Pb and their solution) coexist, so
according to condensed phase rule the system becomes invariant.
F=3-P=3-3=0
The point O corresponds to a fixed composition of 2.6 % Ag and 97.4
% Pb, which is called eutectic composition. On further cooling the
whole mass crystallizes out.
iv. Area below Eutectic line : We have two regions in the diagram:
1. Eutectic and solid Ag area: In this area solid crystalline Ag and solid
eutectic are stable.
2. Eutectic and solid Pb area: In this area solid crystalline Pb and solid
eutectic are stable.
v. Area above AOB: In this area solution of Ag and Pb exist. On lowering
the temperature Pb begins to separate out. On further cooling whole mass
solidifies en-block to the eutectic composition (2.6 % Ag & 97.4 % Pb).
Application to pattinson’s process: In de-silverization of Pb it is used. If a
sample of Argentiferous lead containing less than 2.6 % Ag is allowed to cool
gradually, Pb will separate out and the solution will become progressively richer in
Ag till the % of Ag becomes 2.6% and on further cooling the whole mass will
solidify as such. On the other hand if Ag - Pb alloy containing Ag greater than
2.6% is allowed to cool, then pure Ag separates along the curve AO till the
eutectic composition O is reached.
Binary system: It consists of two substances which are miscible in all proportions
in the liquid phase but do not react chemically and each component has the
property of lowering each other’s freezing point. It is also called eutectic system
(easy to melt system).
Eutectic mixture: It is a solid solution of two or more substances having the
lowest freezing point of all the possible mixture of the components. It is useful to
get an alloy of low melting points.
Eutectic point: The lowest freezing point attainable corresponding to the
eutectic mixture is called the eutectic point (means lowest melting point).