PHASE RULE

Gibb’s Phase Rule-Statement of Gibb’s Phase Rule,Terms

involved with examples, Application of Phase rule to one
component water system . Reduced Phase Rule, Application of
Phase rule to Two Component System (Pb- Ag), Advantages and
Limitations of Phase Rule. Numerical problems on Phase Rule.
 Gibb’s Phase Rule
• The 'phase rule' was given by J.W. Gibbs in 1874 and further studied by H.W.B. Roozeboom in
1884.
• The phase rule is able to predict the conditions necessary to be specified for a heterogeneous
system to exhibit equilibrium.
• Phase rule was based on the basis of the principles of thermodynamics. The phase rule is able
to predict qualitatively, by means of diagram, the effect of changing temperature, pressure, or
concentration on a heterogeneous system in equilibrium.

Statement-
In heterogeneous system in equilibrium, the sum of the number of phases and degree of freedom is
greater than the number of components by two provided the equilibrium between any number of
phases is not influenced by gravity, electric/magnetic forces or by surface action, and is only influenced
by temperature, pressure and concentration. It is expressed as

It is applicable for all the universally present heterogeneous systems.

 GIBB'S PHASE RULE

Mathematically, the rule is written as

F=C-P+2

• Where F = Number of degrees of freedom,

• C = Number of components

• P = Number of phases of the system

For understanding the various applications of phase rule a clear understanding of the various
terms, phases (P), components (C) and degrees of freedom (F) present in the phase rule, is
essential which have their specific meaning.
 Phase(P)
• A phase is defined as “ an homogeneous, physically distinct and
mechanically separable portion of system, which is separated from other
such parts of the system by definite boundary surfaces”.
• 1. Liquid phase : The number of liquid phase depends on the number of
liquids present and their miscibility.
• i) If two liquids are immiscible, they will form two separate liquid phases.
Example : benzene and water
• ii) If two liquids are miscible they will form one liquid phase only.
Example : alcohol and water
• 2. Solid phase Each solid forms a separate phase. The number of solid
phase depends on the number of solids present in it. Example : Many
forms of sulphur can exist together, but these are all separate phases.
 Phase(P)
• 3. Gaseous phase Since a gaseous mixture are thoroughly miscible in all
proportions, it will form one phase only. Example : a mixture of N2 and H2
forms one phse only.
• 4. A solution of a substance in a solvent consists of one phase only, e.g.
glucose solution.
• A heterogeneous mixture like:
CaCO3 (s)→ CaO (s) + CO2 (g) consists of three phases ( i.e., two solids and
one gaseous).
In the equilibrium reaction,
Fe(s) + H2O(g) →FeO(s) + H2(g) There are two solid phases, Fe and FeO
and one gaseous phase consisting of H2O(g) and H2(g). Thus three phases
exists in equilibrium
 Components (C)
• The minimum number of independently variable constituents in terms of which the
composition of each phase of a heterogeneous system can be expressed directly or
in the form of a chemical equation are called the components of system (C)
1. A system consisting of a solution of sugar in water (P = 1 i.e. solution phase) is a
two-component system because the solution phase present in the system consists
of two constituents-water and sugar.

2. Consider the following system consisting of ice, water and vapour in equilibrium.

– Ice (s) ,.,Water (l) ,., vapour (g)

The system consists of three phases ice, water and vapour phase. The chemical
substance present in each phase is H20. Therefore, the composition of each phase
is expressed in terms of H20. Hence, it is called one-component system
 Component(C)

• 3. The saturated solution of sodium chloride consists of three phases-solid

sodium chloride, salt solution and water vapour in equilibrium.
NaCI (s)↔ NaCI (aq)↔ Water vapour (g)

• 4.The chemical composition of each phase of the system can be expressed if

we consider two chemical constituents NaCI and water as shown below.
Phase Components
(i) NaCI (s) = NaCI + OH20
(ii) NaCI(aq) = yNaCI + xH20
(iii) H20(g) = ONaCI + H20

• Hence, it is a two-component system.

 Component ( c)
• 5.The system, CuS04.5H20 (s)↔ CuS04.3H20 (s) + 2H20 (g)
is a three- phase and two component system. It requires two constituents CuS04 and
H20 to express the composition of each phase of the system.

• 6.In the thermal decomposition of CaCO3,

CaCO3 (s) CaO (s) + CO2 (g)
The composition of each of the three phases can be expressed in terms of at least any
two of the independent variable constituents, CaCO3, CaO and CO2. Suppose CaCO3 and
CaO are chosen as the two components, then the composition of different phases is
represented as follows:
Phase : CaCO3 = CaCO3 + 0CaO
Phase : CaO = 0CaCO3 + CaO
Phase : CO2 = CaCO3 – CaO
Thus, it is a two component system..
 Degree of Freedom (F)
• The smallest number of independently variable factors such as
temperature, pressure and concentration which must be
required in order to define the system completely are called
the degree of freedom. Degree of freedom of a system is also
known as variance.
• When a system having no degree of freedom
– F = O it is called non-variant system or invariant system
• When a system having only one degree of freedom
– F = 1 it is a univariant or a monovariant system.
• Similarly, a system having two degrees of freedom
• F = 2 is a bivariant system and so on.
 Degree of Freedom (F)

• 1The system ice ↔Water↔water vapour

has no degree of freedom(i.e., F = 0). The three phases of water i.e. ice,
liquid water and vapour can exist together in equilibrium only at a
particular-temperature and pressure (corresponding to the freezing point)
and no factor is necessary to be specified to define the system. Hence, a
system consisting of ice, Water and vapour in equilibrium has no degree of
freedom i.e. it is a non- variant system.
• 2.Consider a system consisting of water in contact with its vapour,
• Water (l)↔ Water vapour (g)
• To define this system completely, we must state either the temperature or
pressure Thus degree of freedom is one and the system is univariant.
 Degree of Freedom (F)
• 3. For a system consisting of water vapour phase only, we must state the
values of both the temperature and pressure in order to Phase Rule &
define the system completely. Hence the system is bivariant or has two
degrees of freedom.
• 4.For a mixture of gases, the number of degrees of freedom is three
(i.e.F=3).Such a system can be completely defined when the temperature,
pressure and composition are fixed. In this case, the remaining factor i.e.,
volume gets automatically fixed. For example, a gaseous mixture
consisting of 70% N2 and 30% 02 at 22°C and 1 atm pressure is completely
defined and does not require any other information for its description.
Hence, a system consisting of a mixture of gases has three
• degrees of freedom i.e. it is a trivariant system
 Degree of Freedom (F)

5.For a saturated LiCl solution, the number of degrees of

freedom is one (i.e., F = 1). This is because the system can
be completely defined by specifying the temperature
only. The other two factors i.e. composition and vapour
pressure get automatically fixed when the temperature is
fixed. Hence, a system consisting of a saturated LiCl
solution is a univariant system
 PHASE DIAGRAMS
• The graphical presentation giving the
conditions of pressure and temperature under
which the various phases are existing and
transform from one phase to another is
known as the phase diagram of the system. A
phase diagram consists of areas, curves or
lines and points.
 PHASE RULE FOR ONE-COMPONENT
SYSTEMS
• The least number of phases possible in any system is one. So, according to the phase
rule equation, a one-component system should have a maximum of two degrees of
freedom.
• When C = 1, P = 1
• So, F = C - P + 2 = 1 - 1 + 2 = 2
• Hence, a one-component system requires a maximum of two variables to be fixed in
order to define the system completely. The two variables are temperature and
pressure. So, phase diagrams for one component system can be obtained by plotting
PvsT.
• In case of a one-component system, phase diagram consists of areas, curves or lines
and points which provide the following information regarding the system:
• Point on a phase diagram represents a non-variant system.
• Area represents a bivariant system
• Curve or a line represents a univariant system.
• Water system is the example of one component system.
 Water System
• Water is a one component system which is chemically a single
compound involved in the system. The three possible phases
in this system are:
• ice (solid phase), water (liquid phase)and vapour (gaseous
phase).
• Hence, water constitutes a three-phase, one-component
system. Since water is a three-phase system, it can have the
following equilibrium:
• Ice↔ vapour,
• Ice↔ water;
• water ↔vapour
 Phase Diagram of Water System
• The existence of these equilibrium at a
particular stage depends upon the conditions
of temperature and pressure, which are the
variables of the system. If the values of vapour
pressures at different temperatures are
plotted against the corresponding
temperatures, the phase diagram of the
system is obtained
Phase Diagram

AOC = Water
BOC= ice
AOB = Water vapour
 Phase Diagram &Curves
• The phase diagram consists of
• 1.Curves : There are three curves OA, OB and OC.
• 2.Areas : Three curves OA , OB and OC divide the diagram into three areas
AOB, AOC and BOC.
• 3.Triple point : The above three curves meet at the point O and is known as
triple point.
• 4.Metastable equilibrium : The curve OA represents the metastable
equilibrium
• Applying the phase rule on this curve,
• C = 1 and P = 2
• F=C-P+2=1-2+2=1
• Hence, the curve represents a univariant system.This explains that only one
factor(either temperature or pressure)is sufficient to be fixed in order to define
the system.
 Curve OA
• The curve OA is called vaporisation curve, it represents the
equilibrium between water and vapour.
• At any point on the curve the following equilibrium will exist.
• Water ↔Water vapour .
• The degree of freedom of the system is one, i.e, univariant.
Thus applying phase rule equation,
• F = C – P + 2 = 1 – 2 + 2 ; F = 1 This equilibrium (i.e, line OA )
will extend upto the critical temperature ( 3740C). Beyond the
critical temperature the equilibrium will disappear only water
vapour will exist.
 Curve OB
• The curve OB is called sublimation curve of ice, it represents
the equilibrium between ice and vapour.
• At any point on the curve the following equilibrium will exist.
Ice↔ Vapour .
• The degree of freedom of the system is one, i.e., univariant.
This is predicted by the phase rule.
• F = C – P + 2 ; F = 1 – 2 + 2 ; F = 1 This equilibrium line will
extend up to the absolute zero(– 2730C ) where no vapour
can be present and only ice will exist.
 Curve OC
• The curve OC is called melting point curve of ice, it represents
the equilibrium between ice and water.
• At any point on the curve the following equilibrium will exist.
Ice↔ Water.
• The degree of freedom of the system is one, i.e., univariant.
This is predicted by the phase rule.
• F = C – P + 2 ; F = 1 – 2 + 2 ; F = 1.
• The curve OC is slightly inclined towards pressure axis. This
shows that melting point of ice decreases with increase of
pressure. The degree of freedom of the system is one. i.e.,
univariant.
 Triple point O
• Triple point (Point ‘O’) At triple point all the three phases namely ice, water and
vapour coexist. Thus the value of P is 3.
• Ice↔ water↔ water vapour
• F=C-P+2, F=1-3+2, F=0
• Applying phase rule equation, the degree of freedom at this point is zero. It means
that three phases can coexist in equilibrium only at a definite temperature and
pressure.
• The values are 0.00750C and 4.58 mm respectively. At this triple point, neither
pressure nor temperature can be altered even slightly without causing the
disappearance of one of the phases.
• The triple point is not the same as the ordinary melting point of ice ( i.e, 00C). It’s
value has been increased due to the fact that 00C is the melting point of ice at
760mm of mercury and a decrease of 4.58 mm will rise the melting point to
0.00750
 Curve OA’ ( Metastable equilibrium)
• The curve OB is called vapour pressure curve of the
super-cool water or metastable equilibrium. Where
the following equilibrium will exist.
• Super-cool water↔ Vapour.
• Sometimes water can be cooled below 00C without
the formation of ice, this water is called super-cooled
water.
• Super-cooled water is unstable and it can be
converted into solid by ‘seeding’ or by slight
disturbance.
 Areas
• Area AOC, BOC , AOB represents water, ice
and vapour respectively. In order to define the
system at any point in the areas, it is essential
to specify both temperature and pressure. The
degree of freedom of the system is two. i.e.,
Bivariant. This is predicted by the phase rule
• F = C – P + 2; F = 1 – 1 +2 ; F = 2
 Areas
• Area Phase exits Component
• (i) Area BOC Ice H20
• (ii Area AOC Water H20
• (iii)Area AOB Vapour H20
• Thus, for every area contains
• C = I and P = I Therefore, applying phase rule on areas
• F=C-P+2=I-I+2=2
• Hence, each area is a bivariant system. So, it becomes
necessary to specify both the temperature and the
pressure to define a one phase-system
 Cooling Curve of a single metal

If a pure substance , in molten state is cooled slowly and the temperature is noted
at different time interval. The graph is plotted between temperature and time (the
cooling curve). In this diagram AB denotes the rate of cooling of molten liquid and
the liquid starts solidifying at the freezing point B. Now the temperature remains
constant until the liquid melt is completely solidified. Solidification completes at
the point ‘C’. The horizontal line ‘BC’ represents the equilibrium between the solid
and liquid melt. After the point ‘C’, the temperature of the solid begins to decrease
along the curve ‘CD’
 Cooling Curve of a two metals

When a molten liquid containing two components ( say A and B) is cooled slowly
then the cooling curve is different . As before, initially the rate of cooling is
continuous. When it reaches the point ‘b’ one substance ( either A or B) begins to
solidify out of the melt, which is indicated by a break and the rate of cooling is
different. On further cooling at the break point ‘c’ the second compound also begins
to solidify. Now the temperature remains constant until the liquid melt is
completely solidified, which forms the eutectic mixture (line cc’) . After the break
point ‘d’ cooling of solid mass begins. The temperature of horizontal line ‘cd’ gives
the eutectic temperature.
 Two-Component System & Condensed or
Reduced Phase Rule
• When the two independent components are present in a heterogeneous
system, the system is referred to as a two-component system. Hence,
according to the phase rule, for a two-component system having one phase,
• F=C-P+2=2-I+2=3
• Therefore, the two component system having one phase will have three
degrees of freedom or three variables would be required to define the
system. The three variables are pressure (P), temperature (T) and
concentration (C). This will require a three-dimensional phase diagram for
the study of a two-component system.
• However, in order to simplify the study, a two-component system is usually
studied in the form of a 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 I and the system can easily best studied
with the help of a two-dimensional phase diagram.
 Two-Component System Pb & Ag &
Condensed or Reduced Phase Rule
• It can have a maximum of following four phases:
• Solid lead, Solid silver, Solution of molten silver & lead and
Vapours .P=C-F+2, P=2-0+2, P=4
• The boiling points of silver and lead are considerably high
and the vapour pressure of the system is very low. So, the
vapour phase can be ignored and the system can be
studied as a condensed system. This system thus can be
easily studied with the help of a two dimensional T - C
diagram and the reduced phase rule equation, F' = C - P +
1, can be used. This system is generally studied at constant
pressure (atmospheric).
 Two-Component System Pb & Ag
• It is a two component system . The two metals
are completely miscible in liquid state and do
not form any compound . There is almost no
effect of pressure on this system. The
temperature- composition phase diagram
contains two curves ” AO” &” BO “ one area
” AOB” and the eutectic point “O”.
 Two Component System Pb-Ag
•
 Curve AO
• i)The Curve AO is the freezing point curve of
pure silver and represents the effect of
addition of pure lead on the melting point of
pure silver. All along the curve AO two phases
–solid silver and liquid are in equilibrium.
According to reduced phase rule equation.
• F’ = C – P + 1 = 2 – 2 + 1 = 1, i.e. F’ = 1 ( The
system is univariant )
 Curve BO
• ii) Curve BO (Freezing point curve of lead): The BO curve shows the
variation of the melting point of lead on addition of silver. The pure
lead melts at 327°C (point B). Addition of silver lowers its melting
point along curve BO. The added silver dissolves in molten lead to
form Ag-Pb solution with the separation of some part of solid lead.
Therefore, the two phases, solid lead and Ag-Pb solution remain
together in equilibrium along the curve BO.
• Hence, P = 2, (solid Pb and melt of Ag-Pb)
– C = 2(Pb and Ag)
– So, C = 2 and P = 2,
– On applying the reduced phase rule
• F ' = C - P + 1 = 2 - 2 + 1 = 1 The system is univariant.
 Area (AOB)
• The area above the line AOB has a single phase (molten
Pb+Ag). According to reduced phase rule equation, F’ = C
– P + 1 ; = 2 – 1 + 1 = 2 ; i.e., F’ = 2 The system is
bivariant. Both the temperature and composition have to
be specified to define the system completely. The area
below the line AO( solid Ag + liquid melt), below the line
BO ( solid Pb +liquid melt) and below the eutectic point
‘O’ have two phases and the system is univariant.
According to reduced phase rule equation, F’ = C – P + 1 ;
= 2 – 2 + 1 = 1 i.e., F’ = 1
.
 Eutactic Point (O)
• Point O ( Eutectic point) is the point where
solid silver, solid lead and their solution
coexist. The curves AO and BO meet at point
O. Since the experiment is carried out at
constant pressure, the number of degree of
freedom for the system at the eutectic point O
is zero on the basis of reduced phase rule.
• F=C-P+1, F=2-3+1, F=0
 Desilverisation of Argentiferrous Lead
(Pattinson's Process)
• The process, which is used for the recovery of silver from
argentiferrous lead is called Pattinson's process and involves the
desilverisation of lead in accordance to the phase diagram of lead-
silver system.
• The argentiferrous lead contains a small percentage of silver (less
than 0.1%). For its recovery, the argentiferrous lead is heated above
its melting point when a liquid melt consisting of silver-lead solution
is obtained. Now if the silver lead solution is cooled, then Pb
continues to separate out and is regularly removed. In the end, a
eutectic solution containing 2.6% Ag (corresponding to point O ) is
obtained. Thus, the above process increases the percentage of silver
in the argentiferrous lead. Therefore, the eutectic mixture containing
2.6% silver can be treated for the recovery of silver profitably.
 Uses of Eutectic system

• Uses of Eutectic system :

• 1. Eutectic systems are useful in predicting the
suitable alloy composition.
• 2. It is used in the preparation of solders
which are used for joining two metal pieces
together.
 Uses of Eutectic system
• 1.Solders
Solder is an alloy, which is homogenous mixture having melting point
lower than that of the corresponding metal pieces, which have to be
joined together. Solders have compositions somewhat different from
the eutectics so that the freezing occurs over a range of temperatures.
The quality of solder depends upon the formation of a surface alloy
between the solder and parts of metals being used. The selection of
solder alloy is based upon the melting point desired and the pieces of
metals to be joined. Some essential qualities of the solder are as follows:
(1) Melting point of the solder should be less than the material to be
soldered.
(2) Solder should spread in liquid form and also form homogeneous
mixture with the metals.
 Uses of Eutectic system
• 2.Safety Plug
Safety plugs are also known as the safety fuses. It
is an alloy having low melting point, used to
ensure the safe working and avoid accidents.
Safety fuses are used in buildings to protect them
against fires. One alloy is woods metal, which is
used in the safety fuses. This alloy melts at 65°C
and consists of the composition woods metal
Bi = 50%, Pb = 25%, Sn = 12.5% and Cd = 12.5%.
 ADVANTAGES OF PHASE RULE
• 1.It applies to physical as well as chemical phase reactions.
• 2. It provides a convenient basis for classification of equilibrium states of
systems with the help of phases, components and degree of freedom.
• 3. It applies to macroscopic systems and hence information about
molecular structures is not essential.
• 4. Phase rule does not take any cognizance of the nature or the amounts
of substances present in the system.
• 5. It indicates that different systems having the same degree of freedom
behave in a similar fashion. Further, it helps in predicting the behavior of
a system under different conditions of governing variables.
• 6. It helps in deciding whether the given number of substances together
would exist in equilibrium under a given set of conditions or whether
some of them will have to be inter-converted or eliminated.
 LIMITATIONS OF PHASE RULE:

• Phase rule can be applied only for systems in equilibrium. It is not of much
help in case of systems which attain the equilibrium state very slowly.
• 2. All the phases of the system must be present under the same conditions
of temperature, pressure and gravitational force.
• 3. It applies only to a single equilibrium state. It does not indicate the other
possible equilibria in the system.
• 4. Phase rule considers only the number of phases but not their
quantities .Even a minute quantity of the phase,when present ,accounts
towards the number of phases .Hence much care has to be taken in
deciding the number of phases existing in the equilibrium state.
• 5. The solid and liquid phases should not be finely subdivided as to bring
about deviation from their normal values of vapour pressure.
 Numerical Problems
1. An alloy of Sn & Pb contain 73% Sn. Find the mass of
eutectic in 1Kg of solid alloy, if the eutectic contains 64% of
Sn.

Solution: 1 Kg of alloy contains 730 g Sn & 270 g Pb. In the

eutactic composition, Sn is 64% & Pb is 36%. Therefore,
corresponding to 270 g of Pb, the mass of Sn,
=270×64/36=480 g
Total mass of eutactic in alloy=270g+480 g=750g
 Numerical Problems
2. An alloy AB of 10 g weight contains 25% of A. The molten AB on
cooling gave out B and a eutectic alloy with A & B at equal
percentage. What is amount of B that has formed?

Solution: Weight of A in 10 g of alloy=2.5 g & weight of B in 10g of

alloy =7.5g. On cooling eutectic containing equal amount of A & B
separate i.e. 2.5 g each of A & B from eutectic.
Therefore amount of B formed= Original amount of B-Amount of
eutectic
= 7.5 -2.5
=5g
 Numerical Problems
3. 1000 g of a sample of argintiferrous Pb containing 0.1%Ag is
melted & then allowed to cool. If eutectic contains 2.6% Ag,
(i)what mass of eutectic will be formed and (ii) what mass of Pb
will separate out?

Solution: (i) Mass of Ag present in 1000 g argintiferrous Pb=1 g

Mass of Pb in eutectic=1×97.4/2.6=37.461g
Mass of eutectic=1+37.461=38.461 g

(ii) Mass of Pb separate out =1000-38.461=961.53 g