Physical Chemistry

Practical Solutions Chemistry

and Chemical Equilibrium
Second Semester
2020-2021
Department of Chemistry
Second year
Aveen AL-Saka
Phase Equilibria and the
Phase Rule
• In most systems we usually encounter phases in
coexistence.

• For example, a glass of ice water on a hot

summer day comprises three coexisting phases:
ice (solid), water (liquid), and vapor (gaseous).
 Gibb's Phase Rule

Gibb's Phase rule used to explain the equilibrium existing

between the heterogeneous systems

F: degree of freedom or variation: is the smallest number of variable

factors such as temperature, pressure or concentration which must be
.specified in order to define the system completely

C: Number of components: is the smallest number of independently

variable constituents by means of which the composition of each phase
.can be expressed either directly or in the form of a chemical equation

P: phase: is any homogeneous and physically distinct part of a system

which is separated from other parts of the system by definite boundary
.surface
The number of components in the equilibrium mixture of ice, liquid
water, and water vapor is one because the composition of all three
.phases is described by the chemical formula H2O

• Example:
• water vapor confined to a particular volume.

• F = 1 - 1 + 2 = 2
• 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.
 Application of the phase rule
Two-Component Systems
water- phenol system

binary systems are represented at constant

pressure. By fixing the(P), the degrees of
freedom is reduced by:
F  C  P 1
Reduced Gibb's Phase rule: at constant P.
• The dome shaped curve  shows the limits of
temperature and concentration within which two
liquid phases exist in equilibrium.
• The region outside this dome shaped curve
contains systems having one liquid phase.
 Application of the phase rule
Three-Component Systems
In three component system(C=3) the maximum number of
degrees of freedom is four (F=4), since the minimum number of
phases that can exist in any system is one(P=1). Hence in order to
define such a system completely, four variable are required
namely temperature, pressure and concentration of two of the
three components. This will require a three dimensional diagram

F  3 1 2  4 4
Ternary systems are represented at constant
temperature&pressure.By fixing the(T&P), the
: degrees of freedom is reduced by

Reduced Gibb's Phase rule: at constant T & P

F CP