Phase Rule
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1 Unit: V The Phase Rule: Definition, Phase rule
equation, Phase, Component; Degree
of freedom, examples to solve number
of phase, component and degree of
2 Unit: V freedom
One component system: Water
system; Sulphur system
3 Unit: V Lead Silver system; Pattinson’s
process, Limitations of phase rule
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The phase rule is a generalization given by Willard Gibbs
(1874), which seeks to explain:
● The equilibrium existing in the heterogeneous system.
● It is useful to understand the effect of intensive variables,
such as temperature, pressure, or concentration, on the
equilibrium between phases as well as between chemical
constituents.
● It is used to deduce the number of degrees of freedom (f)
for a system.
It is stated that: “provided the equilibrium between any
number of phases is not influenced by gravity electrical or
magnetic forces or by surface action and only by
temperature, pressures and concentration, then the number
of degrees of freedom (F) of the system is related to the
number of components (C) and phases (P) by the phase rule
equation: F=C-P+2
3 For any system at equilibrium at definite temperature and
Phase
A phase is defined as “any homogenous, physically distinct
and mechanically separable portion of system having all the
physical and chemical properties the same throughout the
system. A system may consist of one phase or more than one
phase.
For example:
● At freezing point, water consists of three phases:
Ice
(2)(s)
A gaseousWater
mixture,
(l) being thoroughly
Water vapour
miscible
(g) in all
proportions, will constitute one phase only. Thus, a mixture
of N2 and H2 forms one phase only.
(3) If two liquids are immiscible (e.g. benzene and water),
they will form two separate phases.
(4) If two liquids are miscible (e.g. ethanol and water), they
will form one liquid phase only.
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(5) A solution of a substance in a solvent consists of one
phase only, e.g. glucose solution in water.
(6) Each solid makes up a separate phase, except in the case
of solid solutions, e.g. many forms of sulphur can exist
together, but these are all separate phases.
(7) A heterogeneous mixture like
CaCO3(s) CaO (s) + CO2 (g)
Consists of three phases (i.e., two solids and one gaseous)
Similarly, in the equilibrium reaction,
Fe (s) + H2O (g) FeO (s) + H2(g)
There are two sold phases, Fe and FeO and one gaseous
phase consisting H2O (g) and H2 (g). Thus three phases
exist in equilibrium.
(8) A homogenous solid solution of a salt constitutes a single
phase. Mohr’s salt [FesO4.(NH4)2SO4.6H2O] solution
5 constitutes a single phase.
A part of a system is homogeneous if it has identical
physical properties and chemical composition
throughout the part.
● A phase may be gas, liquid or solid.
● A gas or a gaseous mixture is a single phase.
● Totally miscible liquids constitute a single phase.
● In an immiscible liquid system, each layer is counted
as a separate phase.
● Every solid constitutes a single phase except when a
solid solution is formed.
● A solid solution is considered as a single phase.
● Each polymorphic form constitutes a separate phase.
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Component
The term component is defined as “ the smallest number of
independent variable constituents, taking part in the state of
equilibrium, by means of which the composition of each
phase can be expressed in the form of chemical equation”
For example”:
(1) In water system
Ice (s) Water (l) Vapour (g)
The chemical composition of all the three phases is H2O.
Hence it is one component system.
(2) The sulphur system consists of four phases, rhombic,
monoclinic, liquid and vapour, the chemical composition of
all phases is S. Hence, it is one component system.
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(3) In the dissociation of NH4Cl in a closed vessel,
NH4Cl(s) NH4Cl(g) NH3(g)+ HCl(g)
The proportions of NH3 and HCl are equivalent and hence,
the composition of both phases (solid and gaseous) can
be expressed in terms of NH4Cl alone. Hence the number
of component is one. However, if NH3 or HCl is in excess,
the system become two component system.
(4) 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
independently 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:
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CaCO3 = CaCO3+0 CaO
CaO = 0 CaCO3+ CaO
CO2 = CaCO3 - CaO
Thus it is a two component system.
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Number of components of a system may alternatively be
defined as the number of chemical constituents of the
system minus the number of equations relating to those
constituents in an equilibrium state. For example
2KClO3(s) 2KCl(s) + 3O2(g)
Number of constituents
2 3
[KCl] [O2]
3
Keq= 2
= [O2]
[KClO3]
No. of component= no. of constituents - no. of
equations
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relating the concentration of
constituents
Examples of heterogeneous equilibria:
• Liquid – vapour (vapourization)
• Solid – vapour (sublimation)
• Solid – liquid (fusion)
• Solid 1 – solid 2 (transition)
• Solubility of solids, liquids and gases in each other
• Vapour pressure of solutions
• Chemical reaction between solids or liquids and gases
• Distribution of solutes between different phases
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Degrees of freedom (or variance)
The term degrees of freedom or variance of a system
denoted by F is defined as the minimum number of
independently variables factors such as temperature,
pressure, concentration, which must be arbitrarily fixed in
order to define the system completely.
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F (degrees of freedom; variance):
number of attributes of a system (T, P, phase
composition) that can be changed independently without
creating or destroying a phase, or ...
number of parameters (T, P, system composition) that
need to be described to completely define the
composition and identity of each phase.
F=3 : trivariant
F=2 : divariant
F=1 : univariant
F=0 : invariant
if F < 0 then there must be disequilibrium.
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● If we consider the water system, at a specific
temperature and pressure, three phase of water- ice,
liquid and vapour are, in equilibrium
Ice (s) Water (l) Water vapour (g)
hence, degree of freedom = 0
● Similarly equilibrium of liquid water (l) vapour (g)
has two phase and hence F = 1
When the degree of freedom of a given system is one, it
is referred to as univariant system
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If the system containing liquid water, pieces of ice are
added and this system with 2 phases is allowed to come
to equilibrium, then it is an univariant system. Only one
variable, either temperature or pressure need to be
specified in order to define the system. If the pressure on
the system is maintained at 1 atm, then the temperature
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of the system gets automatically fixed at 0 C, the normal
melting point of ice.
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For the reduction of nickel oxide, NiO,
NiO(s) + CO(g) = Ni(s) + CO2(g)
There are four constituents. There are now two constraints on
the composition of the phases of the system, the first as a
result of the overall stoichiometry of the chemical equation,
and the second because the amount of CO and CO2 in the gas
phase are related. Therefore, only
C = N - R = 4 - 2 = 2
independent components are necessary to specify the
composition of each phase. If, however, additional CO was
artificially added to the system, the constraint imposed by the
balance of CO and CO2 in the gas phase would be lost and the
composition of each phase could instead only be specified by
C = N - R = 4 - 1 = 3
independent components.
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Limitations of Phase rule
● Phase rule is applicable for only those systems which are
in equilibrium. Consequently it not much use for those
systems which attain the equilibrium state very slowly.
● It applies only to a single equilibrium system; and provides
no information regarding any other possible equilibria in the
system.
● It requires utmost care in deciding the number of phases
existing in an equilibrium state, since it considers the
number of phases, rather than their amounts. Thus, even if a
trace of a phase is present, it accounts towards the total
number of phases.
● It conditions that all the phases of the system must be
present simultaneously, under the identical conditions of
temperature and pressure.
● It conditions that solid and liquid phases must not be in
finely-divided
18 state; otherwise deviations occur.
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Phase diagram
Phase diagram is a graphical representation of the physical
states of a substance under different conditions of
temperature and pressure. A typical phase diagram has
pressure on the y-axis and temperature on the x-axis. As we
cross the lines or curves on the phase diagram, a phase
change occurs. In addition, two states of the substance
coexist in equilibrium on the lines or curves.
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Triple point – the point on a phase diagram at which the three
states of matter: gas, liquid, and solid coexist
Critical point – the point on a phase diagram at which the
substance is indistinguishable between liquid and gaseous
states
Fusion(melting) (or freezing) curve – the curve on a phase
diagram which represents the transition between liquid and
solid states
Vaporization (or condensation) curve – the curve on a phase
diagram which represents the transition between gaseous and
liquid states
Sublimation (or deposition) curve – the curve on a phase
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diagram which represents the transition between gaseous and
How many intensive variables can be independently specified
at the triple point of water ?
At the triple point, all three phases exist in
Read :
equilibrium.
This is the unique aspect of the triple point and this
problem.
Number of chemical species
Given : C 1
present:
Number of phases present at
P 3
equilibrium:
o
Equation : Gibbs Phase Rule : Free = C - P + 2
o
Solve : Free 0
NO intensive variables can be independently
specified at the triple point !
This means that there is just one triple point and
ALL of the properties of all of the phases are fixed !
The triple point is unique.
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Phase Diagram of Water System
Water
Ice
Water Vapour
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The slope of OC towards the pressure axis shows that the
melting point of ice is decreased by increasing pressure.
The melting curve or fusion curve of ice/water is very special.
It has a negative slope (or tilted towards pressure axis) due to
the fact that when ice melts, the molar volume decreases. Ice
actually melt at lower temperature at higher pressure.
Example:
The liquid formed between the skate and ice act as a lubricant
so that the skater moves gracefully across the ice. The skate
apply a very high pressure on to the ice.
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Liquid H2O Solid H2O
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The Sulphur System
Sulphur solid exists in two crystalline forms.
● Orthorhombic. S8 or S(rh)
● Monoclinic. S4 or S(mo)
Yellow sulphur of the orthorhombic (or rhombic)
crystalline form. It is the form that commonly
exists under normal conditions.
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Phase diagram of Sulphur
151
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The melting curve or fusion curve of ice/water is very
special. It has a negative slope (or tilted towards
pressure axis) due to the fact that when ice melts, the
molar volume decreases. Ice actually melt at lower
temperature at higher pressure.
Example:
The liquid formed between the skate and ice act as a lubricate
so that the skater moves gracefully across the ice. The skate
apply a very high pressure on to the ice.
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Reduced (or condensed) phase rule
In a two-component system, when P=1 degree of freedom
(F) has the highest value: F=C-P+2= 2-1+2=3. Since the
maximum number of degrees of freedom in a two
component system is three, so the phase behavior of any
binary system may be represented by a three dimensional
diagram of pressure, temperature and composition.
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A solid liquid equilibrium of an alloy has practically no gas
phase and the effect of pressure is small on this type of
equilibrium. Therefore, experiments are, usually, conducted
under atmospheric pressure. Thus keeping the pressure
constant of a system, in which vapour pressure is not
considered, is known as condensed system. It will reduce the
degrees of freedom of the system by one and for such a
system, the phase rule becomes: F=C-P+1
This is known as the reduced (or condensed) phase rule, having
two variables, namely, temperature and concentration (or
composition) of the constituents.
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Eutectic system
A eutectic system is a mixture of chemical compounds or
elements that have a single chemical composition that
solidifies at a lower temperature than any other
composition made up of the same ingredients. This
composition is known as the eutectic composition and the
temperature at which it solidifies is known as the eutectic
temperature. On a phase diagram the intersection of the
eutectic temperature and the eutectic composition gives
the eutectic point. Non-eutectic mixtures will display
solidification of one component of the mixture before the
other.
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Phase Diagram of lead-silver system o
961 C
o
327 C
o
303 C(2.6 mass
% Ag)
● Liquid + solid Pb and
34 ● Solid Pb + eutectic
Description of the phase diagram for lead-silver
system
A (327 C) .
o
Freezing point of lead C=1, P=2, F=0 Fixed T
o
C (961 C) Freezing point of silver C=1, P=2, F=0 Fixed T
o
B (303 C, 2.6 Eutectic point C=2, P=3, F=0 Fixed T and
mass composition
%AB
Ag) Crystallization of lead C=2, P=2, F=1 T or composition
begins
BC Crystallization of silver C=2, P=2, F=1 T or composition
begins
Area above ABC Liquid phase C=2, P=1, F=2 T and composition
Area below DBE Solid mixture C=2, P=2, F=1 T or composition
Area ADBA Solid lead in equilibrium C=2, P=2, F=1 T or composition
with liquid having
composition given by the
curve AB
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Area CEBC Solid silver in C=2, P=2, F=1 T or composition
equilibrium
with liquid having
composition given
by the
curve BC
DBE Both lead and C=2, P=3, F=0 Fixed T
silver
separate from
liquid of
composition B
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Pattinson’s process for the desilverisation of argentiferous
lead
The process of heating argentiferous lead containing a very
small quantity of silver (~0.1 mass%) and cooling to get
pure lead and liquid richer in silver is known as the
Pattinson’s process. This process can be understood by
following the phase diagram of the lead-silver system.
The argentiferous lead is melted and heated to a
temperature above the melting point of pure lead. Let the
point a'' represent this system on the diagram. This system
is then allowed to cool slowly and the temperature of the
melt decreases along a''-a'. At a', solid lead starts
separating. As the system further cools, more and more
lead separates and the liquid in equilibrium with the solid
lead gets richer in silver. The lead that separates floats and
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is continuously removed by ladles.
When the temperature of the liquid reaches ‘a’ on the
line DBE, the eutectic temperature, solid lead is in
equilibrium with the liquid having the composition B.
After removing the lead that separates, the liquid is
cooled further when it solidifies to give a mixture of
lead and silver having the eutectic composition of 2.6
mass % of silver. This solid mixture of lead and silver is
subjected to other processes for the recovery of silver
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