PHASE EQUILIBIUM

• A stable configuration with lowest free-energy

• Any change in Temperature, Concentration, and Pressure causes an
increase in free energy and away from Equilibrium thus forcing a
move to another ‘state’
GIBB`S PHASE RULE
• The phase rule:
• a relationship for determining the least number of intensive variables that can be changed without
changing the equilibrium state of the system
• (The least number of intensive variables required to define the state of the system)
• F = C-P+2
 The Phase Rule

• F is the number of degrees of freedom, it is

the least number of intensive variables that must be
fixed/known to describe the system completely.
• C is the number of components and P is the number
of phases present.
• The number of components is the smallest number of
constituents by which the composition of each phase
in the system at equilibrium can be expressed in the
form of a chemical formula or equation.
SYSTEMS CONTAINING
ONE,TWO AND THREE
COMPONENTS
ONE COMPONENT SYSTEM
Example:
water vapor confined to a particular volume.

F=1-1+2=2
1-component,1 phase, 2 constant

- Using the phase rule only two independent variables are required to
define the system.
Because we need to know two of the variables to define the gaseous
system completely, we say that the system has two degrees of freedom.
- BIVARIANT
Example:
a system comprising a liquid, water, in equilibrium with
its vapor.
F = 1 - 2 + 2 = 1.
There is only one variable needed to define the system
completely either pressure or temperature.
DOF = 1 ( univariant)
Example:
we cool liquid water and its vapor until a third phase separates out.

F=1-3+2=0

Under these conditions, the state of the three-phase ice–water–vapor

system is completely defined, that`s why no intensive variable is needed
already. ; in other words, there are no degrees of freedom.
- Invariant
TWO COMPONENT SYSTEM
• Aka condensed system
• For the determination of the 'eutectic point' which is the "point at
which the liquid and solid phases have the same composition".
• That`s why, a eutectic mixture can be melted at a temperature lower
than the normal temperature used to melt other substances.
• F=C-P + 1
THREE COMPONENT SYSTEM
• applied in many areas of pharmacy like the
formulation of micro-capsules, polymer coating
methods and many other processes.
• Consists of 2 liquids that are partially miscible to each
other and a third component or co-solvent which has
affinity to both immiscible layers
• Described by: F=C-P
THREE COMPONENT SYSTEM
• The area within the triangle represents all the possible
combinations of A, B, and C to give three-component
systems.
• Water, peppermint oil and acacia gum
• If we use a curve at the base of the pyramid, this is
where the 3 phases co-exist
PHASE DIAGRAM
PHASE TRANSITION
• A. MOLAR HEAT OF FUSION
- heat that`s either lost or gained in conversion involving solid and
liquid by 1 mole of substance
• MOLAR HEAT OF VAPORIZATION
• - conversion involving liquid and gas by one mole liquid

Log P2/P1 = ∆Hr (T2-T1)

2.303 RT1T2

• MOLAR HEAT OF SUBLIMATION

• the amount of energy that must be added to a mole of solid at constant pressure to
turn it directly into a gas