PHASE RULE
CHEMICAL REACTION
IRREVERSIBLE REVERSIBLE
Homogeneous Heterogeneous
Phase rule – found by williard Gibbs in 1874
homogeneous reaction can be studied by law of
mass action
Phase
Any homogeneous physically distinct and mechanically separable
portion of a system which is separated from other parts of the
system by definite boundaries.
Gaseous phase : All gases are completely miscible and there is
no boundary between one gas and the other
Liquid phase : It depends upon the number of liquids present
and their miscibilities.
2 liquids – immiscible 2 liquids – miscible
2 liquid phase + 1 vapour phase 1 liquid phase + 1 vapor phase
Solid phase: Every Solid constitutes a separate phase
Component
The smallest number of independent chemical
constituent term of which composition of every phase
can be expressed in chemical equation
Example
Composition – H2O , Component -1
Component -1
Degree of freedom
Minimum number of independent variable such as temperature,
pressure and concentration which must be fixed in order to
define system completely.
F = C-P + 2
= 1- 3 +2 = 0 ( Zero variant)
F = C-P + 2
= 1- 1 +2 = 2 (Bivariant)
Phase rule
The number of degree of freedom of the system is related to
number of component (c) and number of phase (p)
F = C-P + 2
ONE COMPONENT SYSTEM ( WATER SYSTEM)
water exist in three possible phases – solid , liquid & vapour
The possible formation are
The phase diagram consits of
1. Curves - OA, OB, OC , OB’
2. Point O
3. Areas – AOB, BOC , AOC
OA curve
The curve OA is called as vapourisation curve
At any point OA, equilibrium exist between
The degree of freedom is
F = C-P +2 , F= 1-2+2 , F =1 ( univariant)
OA curve extend upto 374°C
Beyond 374°C, only vapour phase exist
OB curve
The curve OB is called as sublimation curve
At any point OB, equilibrium exist between
The degree of freedom is
F= C-P+2
F= 1-2+2
F = 1 ( univariant)
OB curve extends upto absolute zero
only Ice phase present and No vapour phase
OC curve
The curve OC is called as Melting point curve
At any point OC, equilibrium exist between
The degree of freedom is
F= C-P+2
F= 1-2+2
F = 1 ( univariant)
OC slightly inclined to pressure axis (218 atm)
The melting point of ice decreases with increase in pressure.
Point O
The point O is called as Triple point
All three curves OA, OB and OC meet at point O
At any point O, equilibrium exist between
The degree of freedom is
F= C-P+2
F= 1-3+2
F = 0 ( Zero variant)
Temperature – 0.0075°C, Pressure – 4.58 mm
OB’ curve
The curve OB’ is called as meta stable equilibrium curve
At any point OB’, equilibrium exist between
water can be cooled below 0°C without formation of ice is called
as Super cooled water
super cool water is unstable , easily converted to ice by seeding
or slight disturbance.
Areas
AOC – water , AOB – vapour, BOC – Ice
The degree of freedom is
F= C-P+2
F= 1-1+2
F = 2 (Bivariant)
Reduced or condensed phase rule
Only Solid and liquid phase is considered, gas phase is ignored
The system is studied at constant pressure
F’ = C- P + 1
Two component system (Pb-Ag or Binary alloy or simple
Eutectic)
The system is studied at constant pressure, gas phase is ignored
and condensed phase rule is used
F’ = C- P + 1
AO curve
The curve AO is called as Freezing point curve of Ag
The Point A , melting point of Ag (961°C)
Along AO,
The reduced phase rule is
F’= C-P+1
F= 2-2 +1
F = 1 ( univariant)
The melting of Ag decreases with successive addition of Pb
BO curve
The curve BO is called as Freezing point curve of Pb
The Point B , melting point of Pb (327°C)
Along BO,
The reduced phase rule is
F’= C-P+1
F= 2-2 +1
F = 1 ( univariant)
The melting of Pb decreases with successive addition of Ag
Point O
The point O is called as Eutectic point
AO and BO curve meet at point O at temperature 303°C
Along point O,
The reduced phase rule is
F’= C-P+1
F= 2-3 +1
F = 0 ( Zero variant)
Below the point O, metal solidify and eutectic composition ( 97.4 %
Pb + 2.6 % Ag)
Areas
The area above the line AOB consists of single phase
The reduced phase rule is
F’= C-P+1
F= 2-1 +1
F = 2 ( bi variant)
The area below the line AO, BO &O consists of two phase
The reduced phase rule is
F’= C-P+1
F= 2-2 +1
F = 1 ( univariant)
Pattinson’s process
The process of raising the relative proportion of Ag in the alloy
Argentiferous lead Liquid Allowed to cool
(0.1 % Ag) Heat above
melting point
Temperature falls down along the line pq
As soon as point ‘q’ reached , Pb crystallizes out and Ag is
increased
On further cooling, Pb separated out along BO and the solution
become richer in Ag until point O reached.
percentage of Ag is 2.6 %
Uses
Suitable alloy composition can be predicted
For making Solders (joining two metals)
Uses Limitations
Applicable to both physical and only applied for system in
chemical equilibrium equilibrium
Indicate that different system Only three variable P, T and C is
having same degree of freedom considered
behave similarly
It helps to decide whether All phases of system must be in
system in equilibrium or not same condition