THE PHASE RULE 1

THE STATEMENT
The phase Rule is an important generalization dealing with the behaviour of heterogeneous
systems. In general it may be said that with the application of phase rule it is possible to predict
qualitatively by means of a diagram the effect of changingpressure, temperature and concentration on
a heterogeneous system in equilibrium. This relationship governing all heterogeneous equilibria
was first discovered as early as 1874 by an American physicist Willard Gibbs. Gibb’s Phase Rule is
free from flaws and limitations which are a common feature of all other generalizations of Physical
Chemistry based on hypothetical assumptions as to the nature of the constitution of matter. It maybe
stated mathematically as follows :
F = C–P+2

where F is the number of degrees of freedom, C is the number ofcomponents and P is the number of
phases of the system. The terms ‘phase’, ‘component’, and ‘degree of freedom’ involved in the
statement of the Phase Rule have a special significance and aclear understanding of these terms is
essential before we proceedfurther with the subject.
WHAT IS MEANT BY A ‘PHASE’ ?
A phase may be defined as : any homogeneous part of a system having all physical and chemical
properties the same throughout. A system may consist of one phase or more than one phases.

(1) A system containing only liquid water is one-phase or 1-phase system (P = 1)

(2) A system containing liquid water and water vapour (a gas) is a two-phase or 2-phase system
(P = 2).

(3) A system containing liquid water, water vapour and solid ice is a three-phase or 3-phase
system.
A system consisting of one phase only is called a homogeneous system.

A system consisting of two or more phases is called a heterogeneous system.

Explanation of the Term ‘Phase’

Ordinarily three states of matter-gas, liquid, and solid are known as phases. However in phase
rule, a uniform part of a system in equilibrium is termed a ‘phase’. Thus a liquid or a solid mixture
could have two or more phases.

Let us consider a few examples to understand the meaning of the term phase as encountered in
phase rule.
(1) Pure substances. A pure substance (solid, liquid, or gas) made of one chemical species
only, is considered as one phase. Thus oxygen (O2), benzene (C6H6), and ice (H2O) are all 1-phase
systems. It must be remembered that a phase may or may not be continuous. Thus, whether ice is
present in one block or many pieces, it is considered one phase.
(2) Mixtures of gases. All gases mix freely to form homogeneous mixtures. Therefore any
mixture of gases, say O2 and N2, is a 1-phase system.
(3) Miscible liquids. Two completely miscible liquids yield a uniform solution. Thus a solution
of ethanol and water is a 1-phase system.
(4) Non-miscible liquids. A mixture of two non-miscible liquids on standing forms two separate
layers. Hence a mixture of chloroform (CHCl3) and water constitutes a 2-phase system.
(5) Aqueous solutions. An aqueous solution of a solid substance such as sodium chloride
(orsugar) is uniform throughout. Therefore it is a 1-phase system.
However, a saturated solution of sodium chloride in contact with excess solid sodium chloride is
a 2-phase system.
(6) Mixtures of solids. (i) By definition, a phase must have throughout the same physical and
 THE PHASE RULE 2
chemical properties. Ordinary sulphur as it occurs in nature is a mixture of monoclinic and rhombic
sulphur. These allotropes of sulphur consist of the same chemical species but differ in physical
properties. Thus mixture of two allotropes is a 2-phase system.
(ii) A mixture of two or more chemical substances contains as many phases. Each of these
substances having different physical and chemical properties makes a separate phase. Thus a mixture
of calcium carbonate (CaCO3) and calcium oxide (CaO) constitutes two phases.

Let us consider the equilibrium system : the Decomposition of Calcium carbonate. When calcium
carbonate is heated in a closed vessel, we have
— —~
CaCO3 v — CaO + CO2

(solid) (solid) (gas)

There are two solid phases and one gas phase. Hence it is a 3-phase system.

WHAT IS MEANT BY ‘COMPONENTS’?

A system ‘C’ in the Phase Rule equation stands for the number of components of a system in
equilibrium. The term component may be defined as : the least number of independent chemical
constituents in terms of which the composition of every phase can be expressed by means of a
chemical equation.

Explanation of the Term ‘Component’

To understand the above definition and to use it for finding the number of components of a
system, remember that :
(a) The chemical formula representing the composition of a phase is written on LHS.
(b) The rest of the chemical constituents existing independently in the system as
represented by chemical formulas are placed on RHS.
(c) The quantities of constituents on RHS can be made minus (–) or zero (0) to get at
thecomposition of the phase on LHS.
Now let us proceed to discuss the number of components of some systems.
(1) Water and sulphur systems are 1-component systems. Water system has three phases :
ice, water, and water vapour. The composition of all the three phases is expressed in terms of one
chemical individual H2O. Thus water system has one component only.
Sulphur system has four phases : rhombic sulphur, monoclinic sulphur, liquid sulphur and
sulphur vapour. The composition of all these phases can be expressed by one chemical individual
sulphur (S). Hence it is a 1-component system.
As is clear from above, when all the phases of a system can be expressed in terms of one
chemical individual, it is designated as a one-component or 1-component system.
(2) Mixture of gases. A mixture of gases, say O2 and N2, constitutes one phase only. Its
composition can be expressed by two chemical substances O2 and N2.
Phase Components
Gaseous Mixture = x O2 + y N2
Hence a mixture of O2 and N2 has two components. In general the number of components of a
gaseous mixture is given by the number of individual gases present.
(3) Sodium chloride solution. A solution of sodium chloride in water is a 1-phase system. Its
composition (xNaCl.yH2O) can be expressed in terms of two chemical individuals, sodium chloride
and water.
Phase Components
Aq. solution of = NaCl + y H2O
sodium chloride
 THE PHASE RULE 3
Therefore an aqueous solution of sodium chloride or any other solute is a two-component or 2-
component system.
A saturated solution of sodium chloride, in contact with excess solid sodium chloride has two
phase, namely aqueous solution and solid sodium chloride. The composition of both phase can be
expressed in terms of two chemical individuals NaCl and H2O.
Phase Components
Aq. solution of = x NaCl + y H2O
sodium chloride
Solid sodium chloride = NaCl + 0 H2O
Hence a saturated solution of sodium chloride or any other solute in contact with solid solute,
is 2-component system.

(4) Decomposition of Calcium carbonate. When calcium carbonate is heated in a closed vessel,
the following equilibrium system results.
CaCO3 — —~
v — CaO + CO 2

(solid) (solid) (gas)

It has three phase : calcium carbonate, calcium oxide, and carbon dioxide. The composition of all
the phase can be expressed in terms of any two of the three chemical substances in equilibrium.
Let us select calcium oxide (CaO) and carbon dioxide (CO2) as the components. Then we can
write,
Phase Components
CaCO3 = CaO + CO2
CaO = CaCO3 – CO2
CO2 = CaCO3 – CaO
Again, selecting calcium carbonate (CaCO3) and calcium oxide (CaO) as the components, we
have
Phase Components
CaCO3 = CaCO3 + 0 CaO
CaO = 0 CaCO3 + CaO
CO2 = CaCO3 – CaO
Thus decomposition of calcium carbonate is a 2-components system.
Furthermore, as is clear from the above examples, by the components of a system is meant the
number of chemical individuals and not any particular chemical substances by name.

(5) Dissociation of Ammonium chloride. Ammonium chloride when heated in a closed vessel
exists in equilibrium with the products of dissociation, ammonia (NH3) and hydrogen chloride gas
(HCl).
NH4Cl — —~
v — NH3 + HCl
 THE PHASE RULE 4
(solid) (gas) (gas)
The system consists of two phase, namely, solid NH4Cl and the gaseous mixture containing NH3
and HCl. The constituents of the mixture are present in the same proportion in which they are
combined in solid NH4Cl. The composition of both the phase can, therefore, be expressed in terms of
the same chemical individual NH4Cl.
Phase Components
Solid = NH4Cl
Gaseous = x NH3 + x HCl or x NH4Cl

Thus dissociation of ammonium chloride is a one-component system.

DEGREES OF FREEDOM
The term Degree of Freedom represented by F in the phase Rule equation (F = C – P + 2) is
defined as follows : the least number of variable factors (concentration, pressure and temperature)
which must be specified so that the remaining variables are fixed automatically and the system is
completely defined

A system with F = 0 is known as nonvariant or having no degree of freedom.

A system with F = 1 is known as univariant or having one degree of freedom.
A system with F = 2 is known as bivariant or having two degrees of freedom.
Explanation of the Term Degree of Freedom
A system is defined completely when it retains the same state of equilibrium (or can be reproduced
exactly) with the specified variables. Let us consider some examples.

(1) For a pure gas, F = 2. For a given sample of any pure gas PV = RT. If the values of pressure
(P) and temperature (T) be specified, volume (V) can have only one definite value, or that the volume
(the third variable) is fixed automatically. Any other sample of the gas under the same pressure and
temperature as specified above, will be identical with the first one. Hence a system containing a pure
gas has two degrees of freedom (F = 2).
(2) For a mixture of gases, F = 3. A system containing a mixture of two or more gases is
completely defined when its composition, temperature and pressure are specified. If pressure and
temperature only are specified, the third variable i.e., composition could be varied. Since it is necessary
to specify three variables to define the system completely, a mixture of gases has three degrees of
freedom (F = 3).
(3) For water : water vapour, F = 1. The system water in equilibrium with water vapour, has
two variables temperature and pressure. At a definite temperature the vapour pressure of water
canhave only one fixed value. Thus if one variable (temperature or pressure) is specified, the other
is fixed automatically. Hence the system water has one degree of freedom (F = 1).
(4) For saturated NaCl solution, F = 1. The saturated solution of sodium chloride in equilibrium
with solid sodium chloride and water vapour.

NaCl — —~
v — NaCl-solution — —~
v — water vapour
(solid)
 Thus the system is completely defined if we specify temperature only. The other two variables
i.e,. the composition of NaCl-solution (solubility) and vapour pressure have a definite value at a
fixed temperature. Hence the system has one degree of freedom.
(5) For ice-water-vapour system, F = 0. In the system ice : water : vapour, the three phases
coexist at the freezing point of water. Since the freezing temperature of water has a fixed value,
thevapour pressure of water has also a definite value. The system has two variables (temperature
and pressure) and both these are already fixed. Thus the system is completely defined
automatically, there being no need to specify any variable. Hence it has no degree of freedom (F =
0).

PHASE DIAGRAMS
A phase diagram is a plot showing the conditions of pressure and temperature under which two or
more physical states can exist together in a state of dynamic equilibrium. Fig. 19.1 is a typical phase
diagram for a one-component system. The diagram consists of : (a) the Regions or Areas;

(b) the Lines or Curves; and (c) the Triple point.

The significance of the characteristic features (Areas, Curves, Triple point) of a phase diagram
are discussed below.

(1) Regions or Areas

The diagram is divided into three regions or areas which are labelled as ‘solid’, ‘liquid’, and
‘vapour’. These areas in Fig. 19.1 are COB, COA and AOB. Each of the three areas shows the
conditions of temperature and pressure under which the respective phase can exist. Applying the
phase rule to the system when only one phase is present, we have

F = 1–1+2=2
i.e., each single phase has two degrees of freedom

C A

Liquid

Solid
Pressure

O
Vapour
A

Triple point

Temperature
Figure 19.1
 Thus each area of phase diagram represents a bivariant system. At conditions wholly within
one of the three areas, both the variables (pressure and temperature) can be varied independently
without causing a change in the state of equilibrium. Therefore in order to define the condition of the
phase both pressure and temperature must be stated.
(2) Lines or Curves
There are three lines or curves separating the regions or areas. These curves show the conditions
of equilibrium between any two of the three phases i.e., solid/liquid, liquid/vapour, solid/vapour.

(a) Solid/liquid line (OC) which represents the equilibrium Solid : Liquid, is referred to as the
Melting curve or Fusion curve.
(b) Liquid/vapour line (OA) which represents the equilibrium Liquid : Vapour, is referred to as
the Vapour Pressure curve or Vaporisation curve for the liquid.
(c) Solid/vapour line (OB), which represents the equilibrium Solid : Vapour, is referred to as
the Sublimation curve.
Applying phase rule to a one-component two-phase system.
F = C–P+2=1–2 +2=1

Thus phase rule predicts that the two phase equilibria stated above will have one degree of
freedom. Along any of three lines on the phase diagram when one variable (pressure or temperature)
is specified, the other is fixed automatically.

3) Triple Point
The three boundary lines enclosing the three areas on the phase diagram intersect at a common
point called the Triple point. A triple point shows the conditions under which all the three phases
(solid, liquid, vapour) can coexist in equilibrium. Thus the system at the triple point may be represented
as :
Solid             Liquid             Vapour
Applying the phase rule equation, we have
F=C–P+2=1–3+2=0
which predicts that the system has no degree of freedom.
At the triple point both pressure and temperature on the diagram are fixed and, therefore, the
system is nonvariant. This implies that if we try to change temperature or pressure, the equilibrium
will be disturbed. For example, if we lower the pressure on the system, all the liquid will vaporise,
leaving only two phases.
In case of water system, the temperature and pressure for the triple point are 0.0076º and 4.58 mm
Hg respectively.