NATIONAL INSTITUTE OF TECHNOLOGY

RAIPUR, CHHATTISGARH

TERM PAPER
On

PHASE RULE

Guided by: Submitted by:

Dr. Kafeel Ahmed P. Bindu Prasad Reddy
Faculty : Applied Chemistry Roll.No:21117074

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 ACKNOWLEDGEMENT

I would like to express my special thanks of gratitude to

my teacher “Dr. Kafeel Ahmed” who gave me the
golden opportunity to do this wonderful term project on
PHASE RULE., Who also helped me in completing my
project. I came to know about so many things. I am really
thankful to them. Secondly I would like to thank my
parents and friends who helped me a lot in finalizing this
project within the limited time frame..

I would also like to extend my gratitude to the

dean “Dr. A.M. Rawani” for providing me with with all
the wonderful faculty that was required.

P. Bindu Prasad Reddy

21117074
SEM-1

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 ABSTRACT
The Gibbs Phase Rule relates the number of degrees of
freedom to the number of components and number of phases
in a system at thermodynamic equilibrium. In determining the
number of components, one must determine the number of
independent reactions and the number of stoichiometric
constraints.
A phase is defined as any homogeneous and physically distinct
part of a system bounded by a surface and is mechanically
separable from other parts of the system. A phase may be
gaseous , liquid or solid. It is perfectly homogeneous and
distinct from every other phase that is present in the system.
There must be a definite boundary between any two phases.
This boundary is known as the interface. Air constitutes a single
phase only as it contains a mixture of nitrogen, oxygen, carbon
dioxide, water vapour etc.,. A system consisting of only one
phase is said to be homogeneous. A mixture of two immiscible
liquids such as water and benzene, will exist in two distinct
liquid phases and in addition there will be a vapour phase. Thus
there will be three phases each separated from the other by a
well-defined bounding surface. A system consisting of more
than one phase is said to be heterogeneous

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 CONTENTS

S.No Chapter Page.No

1. INTRODUCTION 5
2. DEGREES OF FREEDOM 6-9
3. METHODOLOGY 10
4. RESULT 11
5. CONCLUSION 12
6. REFERENCES 13

INTRODUCTION
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 I. Two or difference phase present in equation with one another
constitutes a heterogeneous system such heterogeneous system
can be conveniently studied with help of generalization called
Gibb’s phase rule.
II. It is applicable to all heterogeneous system and also free from
exceptions.
III. This rule predicts qualitatively the effect of temperature, pressure
and concentration heterogeneous equation.

PHASE:
The physically distinct homogeneous and mechanical operable parts of
a heterogeneous system are called phases.

Example:

A system consisting of liquid in equation with vapor constitutes 2

phases.

Ice, Liquid water, Water vapour constitutes three phase system

COMPONENT:
The number of components of system at equation is defined as
minimum number of independently variable constitutes which are
required to express composition of each phase in system.

In chemically reactive system, number of components is given by

C=N–E Where ,

C Component N Number of chemical species

E Number of independent equation relating the concentration

of N species

Example :

Sulphur consists of 4 phases namely monoclinic, rhombic, liquid sulphur

and vapour sulphur.The composition of each phase of a system can be
expressed only in terms of sulphur. So it is one component system….

Degrees of freedom
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Degree of freedom in variance of system can be defined as a maximum
number of variable factors such as Temperature, pressure and
concentration which should be arbitarily fixed in order to defined the
system the system completely.

Degree of freedom System

F=0 Invariant
F=1 Mono variant
F=2 Bi variant
F=3 Tri variant
For Example :
For a given sample of any gas PV = Nrt

Any of two variable ( P , V , T ) define the system completely. Hence the

system is bivariant or it has 2 degree of freedom.

It is a one component system water in 3 +ve phase ice (solid) , water

(liquid), vapour (gas).

These 3 phases may form 4 possible equilibria.

Solid Liquid

Liquid Vapour

Solid Vapour

Phase diagram of water system consists of

 Stable curves : Three OB, OC, OA
 Metastable curves : One OA
 Areas : 3 AOB, COB, AOC
 Triple Point : 1

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Staple curves :
1. Vapor Pressure Curve (OA) :
The curve OA is known as vapor pressure curve of water
which starts from point O i.e. freezing point of water 0.0098 o C under
4.579 mm Hg pressure and ends at A critical temperature (3.74o at 280
atm). Above critical temperature only vapor phase exist whatever may
be the value of pressure. Vapor pressure of water increases, the rate
of increasing of vapor pressure with temperature is relatively higher at
higher temperature and therefore curves OA stands upwards & slope
away from temperature axis.
From phase rule
F=C–P+2 F=1–2+2 F=1
Water vapor system is monovariant.
2. Sublimation curve of Ice (OB) :
Along this curve solid ice is in equation with its vapor. This curve
is not prolongation of curve A but falls more steeply. Curve OB starts
from temperature 0.098o C above which solid water ice cannot exist.
The curve terminate at B i.e. absolute zero (-273oC). At this
temperature no vapor can exist and therefore only ice is left. But on
other points of curve OB, ice is in equation with vapor. Hence there
are 2 phases.
According to phase rule
F=C–P+2 F=1–2+2=1
System is monovariant.
3.Melting point of fusion curve of Ice (OC) :
Along this curve 2 phases, i.e. ice and liquid water are in
equation. The inclination of OC curve slightly towards the pressure
axis indicates that the slight increase of pressure will lower the melting
point of ice. (According to le – Chatlier principle the increase in the
pressure causes water ice equation to shift in such a direction that there
is decrease in volume). Since the melting point of ice is accompanied
by decrease in volume. It should be lowered by the increase of
pressure.
The curve OC starts from point O but there is no limit for this. Curve, it
goes up to a point corresponding to 2000 atm and -20o C.

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According to phase rule

F=C–P+2=1–2+2=1

System is unvariant / monovariant ]+-

This means that for only given pressure melting point must have one
fixed value Metastable curve(OA`) .It is a metastable curve shown in
continuation of AO. When water is cooled below its freezing point
(when it is not vigorously stirred without separation of ice, the water
is said to be super cooled) The vapor pressure curve of liquid water
AO extends below O as shown by the allotted curve OA .Along curve
OA` liquid water co exist with vapor pressure are difference than
over the solid. This equation is called metastable equation as slight
disturbance brings it to the stable region of the phase diagram.
AREAS:
The areas give the condition of temperature and pressure under
which single phase ice (solid), water (liquid) and vapor (gas) can
exist.

It is necessary to specify both temperature and pressure to define a

system within this area. In the area BOC, AOC and AOB represent the
ice (solid), water (liquid), vapor (gas) respectively.

In these areas, the degree of freedom for the system is

F=C–P+2=1–1+2=2

The triple point O

The point O at which the curves AO, BO and CO meet is called the
triple point. At this point all the 3 phases i.e.; ice, liquid and vapor co
exist’

Thus, P = 3 are to phase rule at triple point O,

F=C–P+2=1–3+2=0

INVARIANT….

Thus degree of freedom at triple point is O. This indicates that there

is only set of variables, i.e.; pressure and temperature at which all the
phases co-exist.
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When any of the variable is changed then the number of phases
decreases.

For example ,

If the temperature is raised, heat causes more and more solid to

melt. But no change in temperature or pressure of the system
occurs when the whole of the solid has changed completely into
liquid and the system becomes a 2 phased system. On applying
pressure to the system vapor starts condensing to liquid- solid phase
as long as there are 3 phases temperature and pressure remains
same. The triple point O is a self defined point corresponding to
point 0.0098oC temperature and 4.579 mm of Hg pressure
(difference from the ordinary freezing point 0.000o C and 760 mm of
Hg because freezing temperature is lower than triple point.

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 METHODOLOGY

We know the phase rule equation,

F=C–P+2 …………….. (1)

For a two component system, C = 2 and hence the above equation

becomes,

F=2–P+2=4–P ……………… (2)

The minimum number of phases in any system at equilibrium is one.

It is clear from the equation (2); the maximum number of degrees of
freedom is three.

Thus, three variables – pressure, temperature and composition of

one of the components must be specified to describe the system.
This will lead to three dimensional figures which cannot be
conveniently represented on a paper. To make this sample, one of
the three variables is kept constant.

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 RESULT

Degree of freedom System

F=O INVARIANT
F=1 MONOVARIANT
F=2 BI VARIANT
F=3 TRI VARIANT

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 CONCLUSION

If the pressure of the system is specified, the temperature is fixed by

the constraint of equilibrium between water and ice. The number of
degrees of freedom for equilibrium is 1 for co-existance of all three
phases

Gibbs’ PHASE RULE provides the theoritical foundation, based in

thermodynamics, for characterizing the chemical state of a geologic
system and predicting the equilibrium relations of the PHASES
(minerals, melts, liquids, vapours) present as a function of physical
conditions such as pressure and temperature.

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 REFERENCES

 Smith, Joe Mauk (2018). Introduction to chemical

engineering thermodynamics. United States of America:
McGraw-Hill Education. p. 422. ISBN 978-1-259-69652-7.

 Jump up to:a b c Atkins, Peter; Paula, Julio De; Keeler,

James (2018). Atkins' Physical chemistry (Eleventh ed.).
Oxford University Press. pp. 123–125. ISBN
9780198769866

 Gibbs, J. W. (1961), Scientific Papers, Dover, New York

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