UNIT III
Part 1. Corrosion
Part 2. PHASE RULE
PHASE RULE
Introduction : Phase rule may be stated as when the
equilibrium between any number of phases is influenced only
by temperature , pressure or concentration but not influenced
by gravity, electrical or magnetic forces or by surface tension
then F,C,P are related to each other as
F= C-P+2
This rule was deduced on the basis of thermodynamic
principles by J. Willard Gibbs in 1876 .
This rule predicts qualitatively the effect of temperature,
pressure and concentration on a heterogenous equilibrium.
Phase Rule : Mathematically, Gibbs phase rule may be
stated as follows : "In a heterogeneous system in
equilibrium, the number of degrees of freedom plus
the number of phases is equal to the number of
components plus two".
F + P = C + 2 or
F=C–P+2
where F = number of degrees of freedom
C = number of components
P = number of phases
2 = additional variables of temperature and
pressure
Phase: “ The physically distinct, homogenous and
mechanically separable part of a system are called
phases”.
Examples (i) A gaseous mixture constitutes a single phase
since gases are completely miscible. Air is a mixture of
N2, O2, CO2, water vapour etc. which constitute a single
phase.
(ii) Two or more liquids which are miscible with one
another constitute a single phase as there is no boundary
surfaces separating the different liquids. e.g., water and
alcohol, benzene & chloroform constitute one phase
system.
(iii) A system consisting of a liquid in equilibrium with its
vapour constitute a two phase system
Component : The number of component of a system at
equilibrium is defined as the minimum number of
independently variable constituents which are required
to express the composition of each phase in the system.
Examples (i) Sulphur system: Consists of four phases
namely monoclinic sulphur, rhombic sulphur, liquid
sulphur and sulphur vapour. The composition of each
phase of the system can be expressed in terms of
sulphur only, so, it is a one component system.
(ii) Water system: It is one component system because
the composition of each of the three phases present
can be expressed as H2O.
Degrees of Freedom : The degree of freedom or variance
of a system is defined as the minimum number of variable
factors such as temperature, pressure and concentration
which should be arbitrarily fixed in order to define the
system completely.
Examples (i) For a given sample of any gas PV = nRT. Any
two of the three variables P, V, T define the system
completely. Hence the system is bivariant or it has two
degrees of freedom.
(ii) A gaseous mixture say N2 and O2 gases (mixed 50%
each), is completely defined when three variables
temperature, pressure and concentration are specified. Thus,
the degrees of freedom is three or the system is trivariant.
Conclusion:
(i) The greater the number of components in a system, the
greater is the degree of freedom for a given number of
phases.
(ii) The greater the number of phases, the smaller is the
number of degrees of freedom.
(iii) The number of phases is maximum when the number of
degrees of freedom = Zero, for a given number of
components.
Thus, for one component system, P max. = 3 .
two component system, P max. = 4
three component system, P max. = 5
Advantages of Phase Rule :
(i) It provides a simple method of classifying equilibrium states of
systems.
(ii) The phase rule confirms that the different systems having the
same number of degrees of freedom behave in same manner.
(iii) It is applicable only to macroscopic systems and not concerned
with molecular structure.
(iv) It predicts the behaviour of systems with changes in the variables
that govern the system in equilibrium.
(v) It predicts under given conditions whether a number of
substances taken together would remain in equilibrium as such or
would involve interconversion or elimination of some of them.
(vi) It takes no account of nature of the reactants or products in
phase reactions.
(vii) It finds extensive use in the study of many heterogenous
systems. In particular it has been found extremely useful in the
extraction of metals.
Limitations:
i. The phase rule is applicable to heterogeneous systems in
equilibrium, so, it is therefore of no use for such systems
which are slow in attaining the equilibrium state.
ii. It is applicable to a single equilibrium state, so it never
gives information about the other possible equilibrium in
the system.
[Link] Gibbs phase rule, various variables are temperature,
pressure and composition. It does not take in account the
electric and magnetic influences. For consideration of
such variables, the factor 2 of the Phase rule has to be
adjusted accordingly.
[Link] the phases in the system must be present under the
same temperature, and pressure.
v. No solid or liquid phases should be finely divided,
otherwise deviation occurs.
Advantages and Limitations of the Phase Rule
Advantages of the Phase Rule
1. Universality: The phase rule is applicable to all systems-solid, liquid, or gaseous-
irrespective of their chemical nature, provided the system is at equilibrium.
2. No Need for Detailed Knowledge of Composition: It can be applied without
requiring prior knowledge of the chemical composition or molecular structure of the
substances involved.
3. Predicts the Number of Degrees of Freedom: It helps to determine the
number of variables (e.g., temperature, pressure, composition) that can be inde-
pendently altered without disturbing the equilibrium.
4. Graphical Representation of Equilibria: The phase rule forms the basis for
constructing phase diagrams, which graphically represent equilibria between dif-
ferent phases and are extremely useful in metallurgy, material science, and chem-
istry.
5. Simplifies Complex Systems: It provides a simple relationship between the
number of components, phases, and degrees of freedom, thereby simplifying the
study of complicated heterogeneous systems.
6. Useful in Industrial Applications: It aids in understanding and optimizing
industrial processes such as alloy formation, glass manufacture, crystallization, and
refining of metals.
Limitations of the Phase Rule
1. Applicable Only at Equilibrium: The phase rule is valid only for systems in
true thermodynamic equilibrium. It cannot be applied to systems in transition
or metastable states (e.g., supercooled liquids).
2. No Information About the Nature of Phases: It does not give any information
about the physical or chemical nature of the phases or the type of reactions
occurring between them.
3. Assumes Perfect Equilibrium: The rule assumes ideal conditions and neglects
kinetic factors; thus, it may not describe real systems accurately where equilibrium
is not attained quickly.
1
4. Not Suitable for Systems with Many Components: For multicomponent
systems, the graphical and analytical treatment becomes complex and often im-
practical.
5. No Information About Quantitative Composition: While it tells the number
of phases that can coexist, it does not provide their quantitative composition
or relative proportions.
6. Limited to Non-reactive Systems in Simple Form: In its simple form, the
phase rule does not directly account for chemical reactions between components
unless the system is treated as a reduced component system.
7. Neglect of Electric and Magnetic E↵ects: In the Gibbs Phase Rule, the
variables considered are temperature, pressure, and composition. It does not take
into account the influence of electric or magnetic fields.
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Phase diagrams :
• The number of phases that exist in equilibrium depends
upon the conditions of temperature and pressure or
temperature and composition, pressure being constant.
• These conditions are determined experimentally and
interdependence of values of the variables can be shown
graphically using appropriate coordinates.
• These diagrams are termed phase diagram. A phase
diagram is the sum total of the description of the behavior
of the phases under equilibrium.
• It is very easy to describe the phase behavior of a system
by such diagrams and to investigate the conditions in
which various phases will constitute in the system .
Application of Gibbs Phase Rule to
One Component System:
From the mathematical expression,
F=C –P+2
When C = 1, P = 1
F = 1-1+2 = 2
Hence, all one component systems can be completely
described graphically by stating only two variables, pressure
and temperature on appropriate axis.
The Water System : It is an one component system.
Water exists in three phases :
Ice (solid) , Water (liquid), and Vapour (gas)
These three single phases may form four possible
equilibria.
(i) Solid Liquid
(ii) Liquid Vapour
(iii) Solid Vapour
(iv) Solid Liquid Vapour
Phase Diagram for the Water System
Component: H2O (Only one)
Phases: Solid (Ice), Liquid and Vapour
Three curves (two phases)
OA, OC, OB
F = 1-2+2 = 1 (Uni-variant)
One meta-stable curve (two
phases) OD
F = 1-2+2 = 1 (Uni-variant)
One triple point (three phases)O (Liquid)
F = 1-3+2 = 0 (In-variant or non-
variant)
Three areas (one phase)
BOC, COA, AOB
F = 1-1+2 = 2 (Bi-variant)
0.0098
Phase diagram of water (Not to Scale)
The phase diagram consists of :
(i) Stable curves: three - OB, OA and OC
(ii) Metastable curve: one - OD
(iii) Areas: three - AOB, COB and AOC
(iv) Triple point: One - O
Curve OA :
It is known as vapor pressure curve of water. The curve OA starts
from point O i.e., freezing point of water, 0.0098°C under 4.579 mm
of Hg pressure and ends at A, the critical temperature (374 ° C at 218
atm.).
The rate of increase of its vapor pressure with temperature is
relatively higher at higher temperatures and therefore the curve OA
slants upwards and slopes away from the temperature axis. From
phase rule, F = C – P + 2
= 1- 2 + 2 = 1
The water vapor system is univariant Phase
Curve OB :
It is the sublimation curve of ice. Along this curve, solid ice
is in equilibrium with its vapor.
Curve OB starts From the temperature 0.0098°C above
which solid water i.e., ice cannot exist.
The curve terminates at B i.e., absolute zero (- 273°C). At
this temperature, no vapor can exist and, therefore, only ice
is left. But on other points of the curve OB, ice is in
equilibrium with vapor. Hence, there are two phases.
According to phase rule,
F=C–P+2
= 1 – 2 + 2 =1 Thus, the system is univariant.
This means that for each temperature; there may be one
pressure and for each pressure there may be one
temperature.
Curve OC :
This curve is the melting point curve or fusion curve of ice.
The inclination of OC line towards the pressure axis indicates
that the melting point of ice is slightly lowered by increase of
pressure. (According to Le Chatelier's principle the increase
in pressure causes the water - ice equilibrium to shift in such a
direction that there is a decrease in volume.)
As 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 upto a point corresponding to 2000 atm. and
- 20°C. According to phase rule, F = C – P + 2 =1-2+2 = 1
This means that for any given pressure, melting point must
have one fixed value.
Metastable Curve OD :
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.
Along curve OD liquid water coexists with vapour.
This equilibrium is called metastable equilibrium as slight
disturbance brings it to the stable region OB of the phase
diagram.
Areas :
The areas give the conditions of temperature and pressure
under which single phase - ice (solid), water (liquid) and
vapour (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 exists, ice (solid), water
(liquid) and vapour (gas) respectively.
In these areas, the degrees of freedom for the system is two
or they are bivariant.
According to phase rule,
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 three phases viz , ice, water and vapour co-exist.
Thus, P =3.
According to phase rule, F = C –P + 2,
=1-3+2 , F=0
Thus, the degree of freedom at triple point is zero, which indicates that
there is only one set of variables P, T at which all the three phases
coexist. If any of the variables is changed, then the number of phases
decreases.
The triple point O is a self defined point corresponding to 0.0098°C
temperature and 4.58 mm of Hg pressure (difference from the ordinary
freezing point, (0.000°C at 760 mm Hg pressure) because freezing
temperature is lower than triple point temperature due to effect of high
pressure and dissolved air).
Summary of Water System (One Component):
Degree of Freedom
Name of the system Phases in equilibrium
F = C- P +2
BOC (ice) Ice
AREA COA (water) Water P=1; F= 2 (Bivariant)
AOB (vapour) Vapour
OC (Melting point) Ice & Water
CURVES OA (Vaporisation) Water & Vapour P=2; F=1 (Univariant)
OB (Sublimation) Ice & Vapour
OD (Metastable ) Water & Vapour
POINT O (Triple point) Ice, Water & Vapour P=3; F=0 (Invariant)
Phase Diagram of water system