Phase Rule
No exceptions if perfectly applied
can calculate effect of temperature, Pressure, and concentration quantitatively on
a heterogenous system
equilibrium influenced by Temperature, Pressure and concentration but not
influenced by electrical, magnetic forces, gravity or by surface action follow the
phase rule
F + P = C + 2
where f = degree of freedom, P= number of phase, C = number of components
A phase is a homogeneous, physically distinct and mechanically separable portion
of the system, which is separated from other parts of the system
A solution of a substance in a solvent consists of one phase only eg- glucose
in water
Each solid makes up a separate phase, except in case of solid solutions
Component
The smallest number of independent variable constituents, taking part in the state
of equilibrium.
Degree of freedom
degree of freedom or variance of system is defined as minimum number of
variables such as temperature , pressure, concentration which must be fixed in
Phase Rule 1
order to describe the system
A pure gas has 2 degree of freedom as we need P, V or T to find the rest
Along any three of the curves where two phases exist in equilibrium F = 1
Phase Rule 2
Areas
1. The areas give the conditions of temp and pressure under which single phase
of water such as solid, liquid and vapour can exist
2. Necessary to specify both temperature and pressure to define a system within
area.
The point O where three curves meet is called the “triple point” and at the point all
3 phases exist so degree of freedom = 0, which means theres only one set of P
and T at which all three phases exist
if P or T is changed the number of phases decrease
Melting Curve or Fusion Curve (OC)
the curve of ice/water is special. It has negative slope and is tilted towards
pressure axis due to the fact that when ice melts, molar value decreases, ICE
melts at lower temperatures at high pressure
Phase diagram of sulpher
Phase Rule 3
At any curve phase rule finds degree of freedom to be 1
In an area F = 2 (bi varent)
Reduced Phase Rule
in two component system, when P = 1 degree of freedom has highest value of 3,
so phase diagram may be represented by a three dimensional diagram of
pressure, temperature and composition.
A solid-liquid equilibrium of an alloy has no gas phase and the effect of pressure
is small on this type of equilibrium. Therefore, experiments are conducted under
Phase Rule 4
atmospheric pressur, keeping it constant in the system in which vapour pressure
isnt considered, it is known as condensed system
. It will reduce degree of freedom by one so phase rule becomes F = C - P +1
Eutectic system
mixture of chemical compounds/ elements that have single chemical composition
that solidifies at lower temp.
2 component system in liquid state, they are miscible minimum F = 1,
Maximum = 2 after using condensed phase rule (but Pressure is constant)
For pure substance A, freezing point is higher and upon increasing conc. of B
freezing point decreases to lowest value. this is called eutectic temperature
Eutectic Point: defined as lowest melting point attained by mixture
Ag-Pb system
silver and lead are completely soluble in liquid state, dont react to form a
compound but on solidification they form an easy melting mixture (eutectic
system)
Different phases taking part in equlibrium
1. solid lead
2. solid silver
3. Solution of lead and silver
4. vapor
Boiling point/freezing point of Ag and Pb is high, so gas phase is absent and
pressure is constant
Solid-liquid eqm without gas phase is known as condensed system
Phase Rule 5
Ag-Pb system
Congruent melting
occurs during melting of compound when composition of liquid forms is the same
as composition of solid
generally happens in two component systems
Limitations of Phase rule
can be applied only on a system in equilibrium. except very slow equilibrium
system
applies to a single equilibrium system, and provides no info regarding any other
possible equilibria in the system
requires care in deciding number of phases existing in eqm state, even if a trace
of phase is present it counts
Conditions that all phases of system must be present simultaneously in identical
conditions of T and P
Euctectic System
2 component system A and B, which are miscible in liquid state (in 2 component
systems reduced phase rule is used) F = 3 - P = 2. ( 2 degree of freedom which
will be T and concentration, P is constant)
Phase Rule 6
