Phase Rule and Equilibria

C.U.
SHAH COLLEGE OF PHARMACY

S.N.D.T. WOMEN’S UNIVERSITY
PHASE RULE AND

EQUILIBRIA
Presented by:- Submitted to:-

Ruchika Rajani Dr. Aparna Palshetkar
(ASSISTANT PROFESSOR)
Introduction
Phase rule is law relating variables of a
system in thermodynamic equilibrium,
deduced by the American physicist J.
Willard Gibbs in his papers on
thermodynamics (1875–78).
The phase rule is able to predict the
conditions necessary to be specified for a
heterogeneous system to exhibit
equilibrium.
In practice we encounter states of matter in
coexistence. During the study of chemical systems, we
usually deal with the system containing two or more
phases in equilibrium, which are called heterogeneous
or polyphase system.
The position of the equilibrium between these
states is affected by the environment (temperature,
pressure) and composition.
Phase Rule
Phase rule states that “ If the equilibrium between
any number of phases is not influenced by gravity,
or electrical, or magnetic forces, or by surface
action but are influenced only by temperature,
pressure and concentration , then the number of
degrees of freedom (F) of the system is related to
the number of components (C ) and number of
phases (P) by the following phase rule equation :
F=C –P+2
 Phase :- A homogeneous, physically distinct and mechanically
separable portion of system, which is separated from other such
parts of the system by definite boundary surfaces. Eg:-
 one phase system – N₂ and H₂ ; Mohr’s salt solution [ FeSO4.
(NH4)2SO4.6H2O] solution.
 two phase system :- benzene and water
 three phase system :-
CaCO3 (s) CaO (s) + CO2 (g)
 Component :- The smallest number of independent variable
constituents, by means of which the composition of each phase
can be expressed in the form of chemical equations.
eg:- i) Sulphur exists in four phases namely rhombic, monoclinic,
liquid and vapour, but the chemical composition of all
phases is S. Thus is an one component system.
ii) NaCl + H₂O → NaCl solution. Therefore it is a two component
system.
 Degree of freedom :- The minimum number of
independent variable factors such as temperature,
pressure and concentration of the phases, which
must be fixed in order to define the condition of a
system completely.
Phase Diagram
The graphical presentation giving the conditions
of temperature and pressure under which the
various phases are existing and transform from
one phase to another is known as phase diagram
of the system. A phase diagram consist of areas,
curves or lines and points.
One Component System
We consider a system containing one component, namely, that
for water which is illustrated in figure below:-
Curve
OB
OA
OC
Two Component System
A two component system is usually studied in
the form of condensed system. A condensed
system can be studied by reducing a
comparatively less important variable.
This reduces the degree of freedom of the
system by 1 and the system can easily be
studied with the help of a two dimensional
phase diagram.
1. Pb-Ag System (Eutectic Mixture)
2. Zn- Mg System
3. Na-k System
Ternary Phase System
• As one proceeds from binary systems to systems with three
or more components, the phase diagrams become more
complex.
• Each component adds another dimension to the

representation of the phase equilibrium.
• Thus, for three components, two dimensions are required

to represent the phase diagrams for a single temperature
and pressure; these are conveniently depicted by a
triangular diagram in which each vertex represents a pure
component.
• This system is considered non-condensed. If we hold the
temperature constant and the system is condensed where
pressure is held at 1atm then the degrees of freedom of the
system are only 2.
Phase equilibrium in three component
systems
Ternary Systems with one pair
of partially miscible liquids
• An example of this is benzene and water which
are partially miscible. Alcohol is completely
miscible with both benzene and water. The
addition of sufficient alcohol to a two-phase
system of benzene and water would produce a
single liquid phase in which all three components
are miscible.
• The curve afdeic, frequently termed the binodal
curve, marks the extent of the two-phase region.
• F=2 in a single-phase region, so two concentrations
must be defined to fix the particular region. Within
the binodal curve, afdeic, F=1 so we need to know
one concentration term, since this will allow the
composition of one phase to be fixed on the binodal
curve. From the tie line, we can then obtain the
composition of the conjugate phase.
• The tie lines in this case are not parallel to the base
of the triangle. It depends on the relative solubility of
the third component (alcohol) in the other two
components (water,benzene).
References
 Jensen W.B. ; “Generalising the Phase Rule” ;
Department of Chemistry, University of Cincinnati.
 P.S. Sayed S. (2010); “ Chapter 6:- Phase Rule”;
www.research gate.in
 Gibbs J. W. Scientific Papers: Thermodynamics Vol. 1,
Dover Publications (1961).
 Bahl A., Bahl B.S., Tuli G.D. () ; “Essentials of
Physicaol Pharmacy”; edition; S. Chand Publications

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C.U.

SHAH COLLEGE OF PHARMACY

PHASE RULE AND

Presented by:- Submitted to:-

• Each component adds another dimension to the

• Thus, for three components, two dimensions are required

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