Phase Rule

1 Manipal University Jaipur

 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 freedom
2 Unit: V One component system: Water system; Sulphur
system
3 Unit: V Lead Silver system; Pattinson’s process,
Limitations of phase rule

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 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:
(1) At triple point, water consists of three phases:

Ice (s) Water (l) Water vapour (g)

(2) A gaseous mixture, being thoroughly miscible 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 constitutes a
4 single phase.
 Problems
(1) Calculate the number of phases present in the following systems: (i) CaCO3 (s)
CaO(s) + CO2 (g).
Three (two solid and one gaseous phase)
(ii) A system consisting of benzene and water.
As the two liquids are immiscible, there will be two phases – benzene and water.
(iii) A gaseous mixture of N2 , H2 and NH3.
One (a gaseous mixture is a homogenous mixture)
(iv) MgCO3 (s) MgO(s) + CO2 (g).
Three
(v) Rhombic sulphur(s) Monoclinic sulphur(s).
Two
(vi) I2 (s) I2 (g)
Two
(vii) NH4Cl (s) NH3 (g) + HCl (g) equimolar amount.
Two
(viii) Ice (s) Water (l) Water vapour (g)
Three
(ix) An emulsion of oil in water.
Two
(x) Closed beaker partially filled with benzene and water.
5Three (benzene, water and vapours)
(xi) Acetone and water.
Two (since acetone and water are miscible, the two phases are liquid + vapour)
(xii) A saturated solution of NaCl.
Three
(solid NaCl + solution + vapour; unsaturated solution of NaCl in water is a two phase two-
component system, whereas a saturated solution of NaCl in water is a three phase two-
component system)
(xiii) Mixture of O2 and N2.
One
(xiv) Finely ground mixture of graphite, sulphur and sodium chloride.
Three
(xv) A mixture of diamond powder and graphite.
Two
(xvi) Aqueous solution saturated with KCl and NaCl in contact with solid NaCl.
Two (solid NaCl + solution of KCl and NaCl)
(xvii) An iceberg floating on clear sea water in the presence of clean air.
Three (solid iceberg + liquid sea water + clean air)
(xviii) Fe(s) + H2O(g) FeO(s) + H2 (g) equilibria.
Three (Two solid phases, Fe(s) and FeO(s) and one gaseous phase consisting of H2O (g) and
H2 (g))
(xix) Solution of Mohr’s salt [FeSO4.(NH4 )2SO4.6H2O].
One phase (as it forms a homogenous mixture with water and the crystals of FeSO4 and
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(NH4)2SO4 are not physically distinct).
 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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 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 : 3

Number of components = no. of constituents - no. of

equations relating the concentration of constituents

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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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Calculate the number of components present in the following systems.
(i) CaCO3 (s) CaO(s) + CO2 (g).
Two
(ii) Ag(s) + Ag–Pb solution(l) + Pb(s) + Ag vapour(g).
Two ( Ag and Pb)
(iii) H2O (l) H2 (g) + 1/2 O2 (g).
One (As H2 (g) + 1/2 O2 (g) = H2O(g))
(iv) H2O(s) H2 (g) + H2O(g).
Two (H2O and H2)
(v) NH4Cl(s) NH3 (g) + HCl(g).
One (As NH3 (g) + HCl(g) = NH4Cl(g) when NH3 and HCl are in equimolar ratio)
vi) NH4Cl(s) xNH3 (g) + yHCl (g).
Two (NH4Cl(s) and either NH3 (g) or HCl(g) whichever is in excess)
(vii) NaCl(s) NaCl(aq) or a solution of common salt.
Two (NaCl and water)
(viii) When ammonia dissociates in (a) a closed vessel (b) a closed vessel containing nitrogen.
(a) One (only NH3)
(b) Two (NH3 and N2)
(ix) Water Water vapour.
One

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 (x) KCl + water KCl hydrate.
Two
(xi) MgCO3 (s) MgO (s) + CO2 (g) (in a closed vessel).
Two
(xii) NH4 Cl (s) NH3 (g) + HCl (g) (in open).
Three
(xiii) CuSO4.5H2O (s) CuSO4.3H2 O (s) + 2H2O (g).
Two (because the composition of each phase can be expressed with the help of
twocomponents CuSO4 and H2O)
(xiv) Explain why KCl –NaCl–H2O should be regarded as a three-component system,
whereas KCl –NaBr –H2O should be regarded as a four-component system.
A system of KCl, NaCl and H2O is a three-component system because the composition of all
five phases, solid NaCl, solid KCl, solid H2O, solution and vapour can be expressed in terms
of three species—NaCl, KCl and H2O. A system consisting of KCl, NaBr and H2O is a four-
component system (note the difference between the two systems—the first one has two salts
with a common chloride ion).
(xv) 2 CH3COOH (CH3COOH)2
One
(xvi) PCl5 (s) PCl3 (l) + Cl2 (g)
The number of phases is three, but the number of components is two. The above system is a
two-component system at lower temperatures but at higher temperatures, all the three
constituents, viz., PCl5 , PCl3 and Cl2 will be in gaseous state, and under these conditions, it
14will be a one-component system.
 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 variable factors such
as temperature, pressure, concentration, which must be arbitrarily fixed
in order to define the system completely.

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.
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 Can vary both T and P independently of the other

Cannot change any parameter..beyond our control

16 Cannot vary T or P independently of the other

 F=3 : trivariant
F=2 : divariant
F=1 : univariant
F=0 : invariant

if F < 0 then there must be disequilibrium.

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 The phase rule is a generalization given by Josiah 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
18 For any system at equilibrium at definite temperature and pressure.”
 • 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 of the system gets automatically
fixed at 0oC, the normal melting point of ice.

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 Calculate the degree of freedom in the following systems:
(i) A gas in equilibrium with its solution in a liquid.
F=C–P+2
Components = 2 (gas + liquid); phases = 2 (gas + liquid)
F=2–2+2=2
(ii) A solution of a solid in a liquid in equilibrium with solvent vapour.
F=C–P+2
Components = 2 (solid + liquid); phases = 2 (solution of solid in liquid + vapour)
F=2–2+2=2
(iii) Two partially miscible liquids in the absence of vapour.
Phases and components = 2 (two miscible liquids)
F=C–P+2
F=2–2+2=2
iv) I2 (s) I2 (g)
C =1; P =2
F=C–P+2
F=1–2+2=1
(v) NH3 (g)
C =1; P =1
F=C–P+2
F=1–1+2=2
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 (vi) Ice and water in equilibrium
P = 2; C = 1
F=C–P+2
F=1–2+2=1
(vii) Silver and lead at the eutectic point
C = 2, P = 3
F = C – P + 1(condensed phase rule)
F=2–3+1=0
(viii) Saturated solution of NaCl
C = 2, P = 2
F=C–P+2
F=2–2+2=2
(ix) 2 KClO3 (s) → 2KCl(s) + 3O2
P = 3, C = 2
F=C–P+2
F=2–3+2=1
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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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 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 diagram

which represents the transition between gaseous and solid states
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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.
Given : Number of chemical species present: C 1
Number of phases present at equilibrium: P 3

Equation : Gibbs Phase Rule : oFree =C-P+2

Solve : oFree 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

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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 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

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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 Point/Mixture
The word “eutectic” is derived from the Greek words “eu,” which
means “good” or “well,” and “tecsis,” which means “melting.”

A eutectic system is a homogenous, solid mixture of two or more

substances that form a super-lattice that melts or solidifies at a
temperature lower than any of the individual ingredients’ melting point.

The term is most usually used to describe a mix of metals. Only when
there is a precise ratio between the components does a eutectic system
form.

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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.
Examples • A mixture of Ag and Pb of composition 97.4% Pb
and 2.6% Ag with eutectic point (freezing point) at 303 °C. • A
mixture of Bi–Cd of composition 60% Bi and 40% Cd with
eutectic point 144 °C
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 Characteristics of eutectic point
1. The system at eutectic point is invariant, the degree of freedom F
= 0. For a two-component system, at eutectic point, C = 2, P = 3
(both the solids and their solution), F = C – P + 1 = 2 – 3 + 1 = 0
2. It is the lowest freezing point of the system, that is, below this
temperature, the liquid phase does not exist.
3. If the liquid is cooled below the eutectic point, both the
components will solidify without change in composition.
4. Eutectics are mixtures and not compounds. When they were
examined under an electron microscope, both the constituents are
seen to lie as separate crystals. Moreover, physical properties such
as density and heat of solution of eutectic solids were almost equal
to the mean values of the constituents; hence, it is a mixture and
not a compound.
5. The alloys of eutectic composition have greater strength than their
individual components because of their crystal characteristics.
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 Use of eutectic system: Used for creating low melting alloys which
can be made into safety fuses. Safety fuse is a device containing a
small piece of low melting alloy that melts under excessive heat or
excessive current.

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 Phase Diagram of lead-silver system
961oC

327oC

303oC (2.6 mass % Ag)

1. Liquid + solid Pb and

41 2. Solid Pb + eutectic
 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 is continuously
removed by ladles.
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 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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 Description of the phase diagram for lead-silver system.
A (327oC) Freezing point of lead C=1, P=2, F=0 Fixed T

C (961oC) Freezing point of silver C=1, P=2, F=0 Fixed T

B (303oC, 2.6 mass Eutectic point C=2, P=3, F=0 Fixed T and
% Ag) composition
AB 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 silver C=2, P=3, F=0 Fixed T
separate from liquid
of
composition B

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Limitations of Phase rule
(1) 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.
(2) It applies only to a single equilibrium system; and provides no
information regarding any other possible equilibria in the
system.
(3) 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.
(4) It conditions that all the phases of the system must be present
simultaneously, under the identical conditions of temperature
and pressure.
(5) It conditions that solid and liquid phases must not be in finely-
divided state; otherwise deviations occur.
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