Dr.

Megha Arya(Assistant
professor)
Condensed (Reduced) PhaseRule Equation
➢ For a two-component system, when C = 2, substituting in Gibb’s phase rule equation
F= C – P + 2 ,F = 2 – P +2, F = 4 –P
➢ Minimum one phase is required to define the system at equilibrium when P = 1 and C =2
➢ F = 2 -1 + 2, F= 3
Thus, for the two-component system, the maximum number of degrees of freedom is three.
➢ For constructing a phase diagram of a two-component system, a 3-dimensional graph/diagram is required using
the three variables(Like, Temp, pressure, and concentration) as its coordinates. Thus, one of the three variables
is kept constant and a graph of two variables isconsidered.
➢ In the solid-liquid equilibrium of an alloy has practically no gas phase and the effect of pressure is small on this
type of equilibrium. Thus, keeping the pressure constant of a system, in which the vapour phase is not
considered is known as a condensed (reduced)system.
➢ F' = C –P + 1
where F' gives the remaining degrees of freedom of the system.
Since the only variables for two-component solid/liquid systems are temperature and composition, the phase
diagrams for such systems consist of Temperature-Concentration graphs (TC graphs).

Megha
• If the pressure is kept constant, graph/ diagram is called Isobaric.

• If the temperature is kept constant, graph /diagram is called Isothermal.

• If the composition is kept constant , graph/diagram is called Isoplethal.

Megha
• EUTECTIC SYSTEM: A binary system consisting of two substances,
which are miscible in all proportion in the liquid phase, but which do not
react chemically, is known as the eutectic (easy to melt) system, e.g. a
mixture of lead and silver comprises of such a system.

Eutectic point: Two or more solid substances capable of forming solid

Megha
THE SILVER–LEAD SYSTEM/ TWO COMPONENT SYSTEM
• This system has two components and four phases.
• The phases are : (i) solid silver(Ag) (ii) solid lead(Pb) (iii) solution of molten
silver and lead; and (iv) vapour.
• In such a case, pressure can have no effect on the system. Therefore we need
to consider only the two remaining variables, namely the temperature (T) and
composition (C) to describe the phase diagram at constant atmospheric
pressure.
• The gaseous phase is absent and one variable pressure is neglected, Apply
condensed phase rule
• F' = 3 – P will be applicable

Megha
THE SILVER–LEAD SYSTEM

Megha
THE SILVER–LEAD SYSTEM
The salient features of the diagram are :
• (a) Two curves, AC and BC
• (b) Eutectic point, C
• (c) Area ACB
• Curve AC: The Freezing point curve of Ag
▪ The curve AC is the freezing point curve of pure silver (Ag).
▪ A point represents the freezing point or melting point of solid silver (9610C).
▪ The curve AC shows that the addition of lead to silver, the melting point of silver decreases
gradually along with AC till point C(3030C) is reached.
▪ At point C, mp of Ag does not fall any further and if any Pb is added, It separates as the solid lead.
▪ The phases in equilibrium along AC are solid silver and solution of silver and lead.
▪ Applying the reduced phase rule equation
▪ F’= C – P + 1 = 2 – 2 + 1 = 1
▪ Thus the system Ag/solution(Pb+ Ag) is monovariant or univariant.
 THE SILVER–LEAD SYSTEM
• Curve BC : The Freezing point curve of Pb.:
▪ The Freezing point curve of Pb.
▪ BC represents the melting point of solid lead (3270C).
▪ The curve BC shows that the melting point is lowered by the addition of silver till the lowest
point C is reached.
▪ At point C, no more silver can go in solution, mp of Pb does not fall any further and if any
Ag is added, It separates as the solid silver.
▪ The phases in equilibrium along BC are solid lead and solution of silver and lead.
▪ Applying the reduced phase rule equation
F’ = C – P + 1 = 2 – 2 + 1 = 1
▪ Thus the system Pb/solution(Pb+ Ag) is monovariant or univariant either composition or
temperature needs to be specified in order to define the system.

Megha
 THE SILVER–LEAD SYSTEM
• The Eutectic point C.
• The curves 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 equation
F = C – P + 1 = 2 – 3 + 1 = 0 Thus the system Ag/Pb/solution at C is
nonvariant.
• Both the variables, temperature (3030C) and composition (97.5% Pb, 2.5% Ag) are fixed.
• If you raise the temperature above the eutectic temperature, the solid phases Ag and
Pb disappear and if you cool below it, you will land in the solid Ag/Pb area where
The solution phase does not exist.
• Eutectic temperature is the lowest temperature at which a liquid phase can exist in the
system.

Megha
 THE SILVER–LEAD SYSTEM
• Pattinson’s Process for the desilverization of Argentiferous Lead This process of recovery of
silver from argentiferous lead is based on the facts contained in the diagram.
• The argentiferous lead-containing small amount of silver (less than 0.1%) is melted
well above the melting temperature of pure lead (3270C).
• Let point X represent the system ‘molten lead’ on the diagram. It is then allowed to cool
when the temperature of the melt falls along the dashed line XY. As the temperature
corresponding to Y on the curve BC is reached solid lead begins to separate and the solution
would contain a relatively larger amount of silver. On further cooling, more lead separates
and we travel along the curve BC until the eutectic point C is reached. Lead is continuously
removed by means of ladles and the percentage of silver in the melt goes on increasing. At C,
an alloy containing 2.6% Ag and 97.4% Pb is obtained.

Megha