Unit-3

Phase Equilibria
 INTRODUCTION
All the chemical reactions can be
broadly classified into two types.
(i) Irreversible reaction
Zn + H2SO4 −−−−−>ZnSO4 + H2↑
(ii) Reversible reaction
(a) Homogeneous reversible reaction
N2(g) + 3H2(g) ⇄2NH3(g)
(b) Heterogeneous reversible reaction
CaCO3(s) ⇄ CaO(s) + CO2(g)
 INTRODUCTION
• The reversible reactions are represented by
two arrows in opposite directions.
• The homogeneous reversible reactions can
be studied using the law of mass action.
• But the heterogeneous systems require
different methods.
• The phase rule, given by Willard Gibbs
(1874), is used to study the behaviour of
heterogeneous reversible reactions.
 PHASE RULE
If the equilibrium between any number of phases
is not influenced by gravity, or electrical or
Magnetic forces but is influenced only by pressure,
temperature and concentration, then the number
of degree of freedom (F) of the system is related to
the number of components (C) and number of
phases (P) by the following phase rule equation.
F=C−P+2 Where,
F = degrees of freedom
C = number of components
P = number of phases
 Explanation (or) meanings of terms

Phase (P)
Phase is defined as, “any homogeneous physically
distinct and mechanically separable portion of a
system which is separated from other parts of
the system by definite boundaries” (phase).
a) Gaseous phase
b) Liquid phase
c) Solid phase
 (a) Gaseous phase

All gases are completely miscible and there is

no boundary between one gas and the other.
Examples:
Air, which is a mixture of O2, H2, N2, CO2 and
water vapour, etc., constitutes a single phase.
 (b) Liquid Phase

The number of liquid phases depends on the

number of liquids present and their miscibilities.
(i) If two liquids are immiscible, they will form two
separate liquid phase.
Example: Benzene - Water.
(ii) If two liquids are completely miscible, they will
form one liquid phase system.
Example: Alcohol-Water
 (c) Solid Phase
Every solid constitutes a separate phase.
• Decomposition of CaCO3
CaCO3(s) ⇄ CaO(s) + CO2(g)
It involves three phases, solid CaCO3, solid CaO
and gaseous CO2.
Hence this is a three phase system
 (d) Consider water system
Water system consisting of three phases.
Ice(s) ⇄ Water(l) ⇄ Vapour(g)
Each phase is physically distinct and homogeneous
and there are definite boundaries between phases.
So this forms three phase system
 Few more examples
(e) A solution of a substance in a solvent consists of one
phase only.
Example: Sugar solution in water.
(f) An emulsion of oil in water forms two phases
(g) MgCO3 (s) −−−−−> MgO(s) + CO2 (g)
It involves three phases, solid MgCO3, solid MgO and
gaseous CO2.
(h) Rhombic sulphur (s) −−−−> Monoclinic sulphur(s)
It forms two phases.
(i) Consider the following heterogeneous system.
CuSO4(s) + 5H2O(l) −−−−> CuSO4,5H2O(s)
Number of phase = 3
 Component (C)
Component is defined as, “the smallest number of
independently variable constituents, by means of
which the composition of each phase can be
expressed in the form of a chemical equation”.
 Water system
Water system consisting of three phases.
Ice(s) ⇄ Water(l) ⇄ Vapour(g)

The chemical composition of all the three phases is

H2O, but are in different physical form. Hence the
number of component is one.
 Sulphur system
(b) Sulphur exists in 4 phases namely rhombic, monoclinic,
liquid and vapour, but the chemical composition is only
sulphur.
Hence it is a one component system.
(c) Thermal decomposition of CaCO3
CaCO3(s) ⇄ CaO(s) + CO2(g)
The system consists of three phases namely, solid CaCO3,
solid CaO and gaseous CO2.
But it is a two component system, because the composition
of each of the above phases can be expressed in terms of
any two of the three components present.
• Phase Components
CaCO3 CaCO3 + 0CaO
CaO 0CaCO3 + CaO
CO2 CaCO3 − CaO
 More Examples
(d) PCl5(s) −−−−−> PCl3(l) + Cl2(g)
This system has three phases, but the number of
component is only two.
(e) An aqueous solution of NaCl is a two component
system. The constituents are NaCl and H2O.
(f) CuSO4. 5H2O(s) + CuSO4 .3H2O(s) + 2H2O(g)
It is also a three component system.
 More Examples
(g) In the dissociation of NH4Cl, the following
equilibrium occurs.
NH4Cl(s) ⇄ NH3(g) + HCl(g)
The system consists of two phases namely solid NH4Cl
and the gaseous mixture containing NH3 + HCl. When
NH3 and HCl are present in equivalent quantities the
composition of both the phases can be represented
by the same chemical compound NH4Cl and hence
the system will be a one component system.
 CHEMICALLY REACTIVE SYSTEMS
IN CASE OF CHEMICALLY REACTIVE SYSTEMS NUMBER OF COMPONENTS ARE DETERMINED
BY USING THE RELATION C = S – R
WHERE
C = NUMBER OF COMPONENTS
S = NUMBER OF CHEMICAL SPECIES PRESENT IN THE SYSTEM.
R = NUMBER OF INDEPENDENT CHEMICAL RELATIONS WHICH THE VARIOUS SPECIES
UNDERGO.

Examples :
1. Consider a system consisting of following species PCl5, PCl3, Cl2
following equilibrium exists between these species.
PCl5 ⇄ PCl3 + Cl2
thus here S = 3 & R = 1 Hence, C = S – R = 3 – 1 = 2

2. Consider thermal decomposition of CaCO3 in a sealed tube.

CaCO3(s) ⇄ CaO (s) + CO2(g)
C=S-R=3–1=2
Number of Components in Ionic System:
• Ionic System:
• NaCl-KBr-H2O
• NaCl ⇄ Na+ + Cl-
• KBr ⇄ K+ + Br-
• Na+ + Br- ⇄ NaBr
• K+ + Cl - ⇄ KCl
• NaCl + KBr ⇄ NaBr + KCl
• Therefore there are nine species in the above system
• undergoing five reactions as given above.
• Species present : NaCl, KCL, NaBr, KBr, Na+ , Cl- K+ , Br- and H2O
• C = S – (R + 1)
• C = 9 –(4+1) = 4
 Degree of Freedom (F)
Degree of freedom is defined as, “the minimum number
of independent variable factors such as temperature,
pressure and concentration, which must be fixed in
order to define the system completely”.

A system having F=1, is called univariant,

A system having F=2, is called bivariant,
A system having F=3, is called trivariant
A system having F=0, is called nonvariant.
 Example
(a) Consider the following equilibrium
Ice(s) ⇄ Water(l) ⇄ Vapour(g)
These three phases will be in equilibrium only at a
particular temperature and pressure. Hence, this system
does not have any degree of freedom, so it is non variant
or zero variant.

(b) For Water ⇄ Water Vapour system, F=1, The system has
two variables, P and T. At definite T, the vapour pressure of
water can have only one fixed value. Thus if one variable is
specified , the other is fixed automatically. Hence this
system has one degree of freedom, it is MONOVARIANT or
UNIVARIANT.
 Example
(c) For a pure gas, PV=RT, if P and T values are
specified there can have be only one definite value
of V or that the volume is fixed automatically.
Thus it has two degrees of freedom, the system is
BIVARIANT.
For a gaseous mixture of N2 and H2, we must state
the pressure and temperature and composition.
Hence, the system is trivariant.
TRIVARIANT SYSTEM
A mixture of two or more gases is completely defined only
when P, T and Composition are specified. If P and T be
specified the third variable i.e. composition may be varied.
Since it is necessary to specify three variables to define the
system completely, it has three degrees. Thus it is
TRIVARIANT.
NONVARIANT SYSTEM
For ice, water, water vapour system, F=0, In this system, the
three phases coexist at the tripple point of water. Since the
tripple point temperature of water has a definite value, the
vapour pressure of water has also a fixed value. Since both
the variables are already fixed, the system is defined
automatically and there being no need to specify any variable.
Hence this system has no degree of freedom.
 Phase Rule Derivation
• Consider a heterogeneous system containing C
components (C1, C2, C3…………….CC) distributed
among P phases (P1, P2,P3…………….PP).
• Number of degree of freedom (F) =Total number of
Variables – Number of variable Defined by the
System because of its being in equilibrium.
Calculations of total number of variables:-
• Suppose a phase has two components then if the molar
concentration of one of the components known then that of other
can be calculated automatically since sum total of mole fraction of all
the components is one. Therefore for C components if we know
molar concentrations of (C-1) components then molar concentration
of remaining one can be determined easily.
• For system consisting of P phases if concentrations P(C-1)
components is known than that of other can be easily determined.
Beside concentration variable other variables like temperature and
pressure are same for all the phases in equilibrium.
• So total number of variable required to know properties of all the
components are:
• Total Number of Variable = P (C-1)+2
• Here factor two is added for temperature and pressure.
Calculations of number of variables defined by the
system because of its being in equilibrium:-
• Contribution of any component in a mixture towards the total free
energy of the system of a constant composition at constant temperature
and pressure is termed chemical potential and it is denoted by μ.
• Further chemical potential of any component is same in all the phases if
there is a multiphase equilibrium.
• Thus for a system consisting of three phases in equilibrium the chemical
potential of a component can be represented as:
• (μ1)P1 = (μ1)P2 = (μ1)P3
• Now if we know (μ1)P1 = (μ1)P2 and (μ1)P2 = (μ1)P3
• Then (μ1)P1 = (μ1)P3 need not to be specified so for one component
system in three phases two relations or variables are required so for P
number of phases (P-1) relations or variables are required and for C
components in P phases C(P-1) relations are required. Thus total
number of degree of freedom can be calculated easily
 Phase rule
• Number of degree of freedom (F) =
• Total number of Variables – Number of variable
Defined by the System because of its being in
equilibrium.
• F = P(C-1) + 2 – C(P-1)
• F = C-P + 2
 Phase rule at constant pressure
• Condensed systems have no gas phase. When their
properties are insensitive to the (small) changes in pressure
which occur, one fewer variable needs to be specified, which
results in the phase rule at constant pressure
F=C−P+1
• This is sometimes misleadingly called the "condensed phase
rule", but it is not applicable to condensed systems which
are subject to high pressures (for example in geology), since
the effects of these pressures can be important. The rule is
useful for some applications in materials science.
 Advantages of Phase rule
• Phase rule is applicable to both Chemical and Physical equilibria.
• Phase rule is applicable to macroscopic systems and hence no information is
required regarding molecular or micro structure.
• We can conveniently classify equilibrium states in terms of phases,
components and degrees of freedom.
• The behaviour of system can be predicted under diff. conditions.
• According to phase rule, diff. systems behave similarly if they have
same degrees of freedom.
• Phase rule helps in deciding under a giving set of conditions:
1) Existence of equilibrium among various substances.
2) Inter convergence of substance or
3) Disappearance of some of the substances.
 Limitations of Phase rule
• Phase rule is applicable only for those systems which are in
equilibrium. It is not much use for those systems which attain
the equilibrium state very slowly.
• Only three degrees of freedom viz, temperature, pressure
and components are allowed to influence the equilibrium
systems.
• Under the same conditions of temperature and pressure, all
the phases of the system must be present.
• It considers only the number of phases, rather than their
amounts.
 Applying the phase rule to:

•One-component systems.
• Binary systems.
• Liquid-vapor equilibrium.
• Temperature-composition diagrams.
 Phase Rule in One-Component
Systems
In one-component systems, the number of degrees
of freedom seems to be related to the number of
phases.
Phase diagram of water
 Phase diagram of water
• The previous figure (phase diagram for water at moderate
pressures), the curve OA is known as the vapor pressure curve;
its upper limit is at the critical temperature, 374ºC for water,
and its lower end terminates at 0.0075ºC, called the triple
point. Along the vapor pressure curve, vapor and liquid coexist
in equilibrium.
• Curve OB is the sublimation curve, and here vapor and solid
exist together in equilibrium.
• Curve OC is the melting point curve at which liquid and solid
are in equilibrium. The negative slope of OC shows that the
freezing point of water decreases with increasing external
pressure.
 Phase diagram of water
• If t1 is held constant, no matter how much the pressure is
raised, the system remains a gas.

• At t2 below the critical temperature and above the triple

point, water vapor is converted into liquid water by an
increase in pressure.

• At temperature below the triple point e.g. t3, an increase

in pressure on water in the vapor state converts the vapor
first to ice and then at higher pressure into liquid water.
• As mentioned in the table (phase rule with single component
systems) and the figure (phase diagram for water at
moderate pressures), in any one of the three regions in which
pure solid, liquid, or vapor exists, F=1-1+2=2, so two variables
(e.g. temperature and pressure are needed to describe the
system.
• Along any of the three lines, where two phases exist, F=1-
2+2=1, hence, only one condition (either temperature or
pressure) is needed to define the system. Finally, at the triple
point where the three phases exist, F=0.
• The triple point for air-free water is at 0.0075ºC and 4.58mm
Hg.
• At the triple point, all three phases are in equilibrium, that is,
the only equilibrium is at this pressure at this temperature of
0.0075 ºC. The triple point for air-free water is at 0.0075 ºC
and 4.58mm Hg. Whereas the freezing point (the point at
which liquid water is saturated with air is in equilibrium with
ice at a total pressure of 1 atm) is 0 ºC.

• In increasing the pressure from 4.58mm Hg to 1 atm, the

freezing point is lowered by 0.0075 °C. The freezing point is
then lowered an additional 0.0023 °C by the presence of
dissolved air in water at 1 atm.
 Condensed Systems

– These are systems in which the vapor phase is ignored and

only solid and/or liquid phases are considered.

– The vapor phase is disregarded and the pressure is

considered to be 1atm.

– The variables considered are: temperature and

concentration.

03/31/2021
 The Water System
• How many components do you
have?
• We have only one component
which is H2O.
• In the one-phase regions, one can
vary either the temperature, or the
pressure, or both (within limits)
without crossing a phase line.
• We say that in these regions:
• f=c–p+2
=1–1+2
= 2 degrees of freedom.
 Phase Diagram of Water
• Along a phase line we have two
phases in equilibrium with each
other.
• so on a phase line the number of
phases is 2.
• If we want to stay on a phase line,
we can't change the temperature
and pressure independently.
• We say that along a phase line:
• f=c–p+2
=1–2+2
= 1 degree of freedom.
• At the triple point there are
three phases in equilibrium,
• but there is only one point on
the diagram where we can
have three phases in
equilibrium with each other.
• We say that at the triple point:
f=c–p+2
=1–3+2
= 0 degrees of freedom.
 The Carbon Dioxide System
The phase rule should be applicable for any single
component systems in general.
 Difference between H2O & CO2 system
• Though phase diagram of CO2 resembles to water phase
diagram but there are some point of difference.
• OC curve indicate +ve slope away from pressure axis
indicating that m.pt of dry ice increases with increase in
pressure this is because volume occupied by liquid CO2 is
greater than CO2 solid.
• Solid CO2 and liquid CO2 can exist at a very high pressure of
5.11 atm. Hence, at ordinary pressure solid ice will be dry i.e.
• If pressure is raised at 5.11 atm it will directly vaporize to
gaseous phase.
• At 1 atm CO2 gas solidifies into dry ice without appearance of
• liquid phase by merely cooling to -78 degree C.
 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.
 Phase Diagram of Sulphur
• C. Phase Diagram Of Sulphur System :
 Phase Diagram of Sulphur
• Sulphur system (one component system):
• Some Important Features:
• (i)Possible phases: Rhombic Sulphur (SR),mono clinic
• Sulphur(SR), Sulphur vapour (SV) and Sulphur liquid(SL).

• (ii) Maximum phases: If P=4, then F=C-P+2=1-4+2=-1

• Which is meaning less. Hence all the four phases cannot exist.

• (iii) Areas : Four areas containing one phase each

• (iv) Curves: There are six stable curves.

• a) Sublimation curve of SR
• b) Sublimation curve of SM
 Phase Diagram of Sulphur
• c) Vapour pressure curve of SL
• d) Transition curve of SR
• e) Melting curve of SM
• f) Melting curve of SR

• Meta stable curves: There are four metastable curves

• a) Sublimation curve of SR
• b) Sublimation curve of SM
• c) Vapour pressure curve of SL
• d) Melting curve of SR
 Phase Diagram of Sulphur
• Triple points:
• There are three stable triple points SR-SM-SV,
• SM-SL-SV, SR-SM-SL and one metastable triple point SR-SL-SV.

• Application of phase rule to two component system:

• As C =2,minimum P=1 and hence minimum F=C-P+2=3
• Thus there are three variables (pressure, temperature and
• composition) should be plotted .But for convenience, two
• dimension diagram are plotted by keeping the third variable
• constant. Hence we have p-t, c-p or t-c diagrams. Generally
• pressure kept constant at atmospheric pressure and we have
t-c diagram
 Classification of Two Component System
Based on the solubility and reactive ability, the two component systems are
classified into three types.
(i) Simple eutectic formation: System in which components do not react but
simply mix. For example
Bi-Cd, Pb-Ag and KI-H2O system.
(ii) System in which components react to form compounds
(a) Formation of compound with congruent melting point.
e.g, Mg-Zn and FeCl3-H2O systems.
(b) Formation of compound with incongruent melting point.
e.g,Na2SO4-H2O and NaCl- H2O systems.

(iii) Formation of solid solution.

 Simple Eutectic Formation
• A binary system consisting of two substances, which
are completely miscible in the liquid state, but
completely immiscible in the solid state is known as
eutectic (easy melt) system.
• They do not react chemically. Of the different
mixtures of two substances, the mixture having the
lowest melting point is known as the eutectic
mixture.
(ii)(a) Formation of compound with congruent melting point.

• In this type of binary alloy system the two

substances form one or more compounds with
definite proportions.
• Of the compounds, a compound is said to possess
congruent melting point, if it melts exactly at a
constant temperature into liquid, having the same
composition as that of the solid.
Formation of compound with incongruent
melting point

• Of the above compounds, a compound is said to

possess incongruent melting point If it decomposes
completely at a temperature below its melting point
yielding a new solid phase with a composition
different from that of the original.
 Formation of solid solution
• In this type when two substances, especially metals,
are completely miscible in both the solid and liquid
states.
• They form solid solutions where mixing takes place
in the atomic levels.
• A condition for the formation of solid solution is,
the two metals should not differ in atomic radius by
more than 15%.
 CONSTRUCTION OF A SIMPLE EUTECTIC
Thermal analysis (or) cooling curve
• Thermal analysis is a method involving a study of the
cooling curves of various compositions of a system
during solidification.
• The shapes of the freezing point curves for any system
(involving metals) can be determined by thermal analysis.
• The form of the cooling curve indicates the composition
of the solid.
 Cooling Curves for a Pure Solid
• A pure substance in the fused state is allowed to
cool slowly and the temperature is noted at
different time interval. Then graph is plotted
between temperature and time
• Initially the rate of cooling is continuous. When it
reaches the point ‘b’ solid begins to appear, 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’, temperature of the solid begins to
decrease along the curve ‘cd’.
 Cooling Curves for a mixture
• If a mixture of two substances (say A and B) in the fused state is
allowed to cool slowly, the cooling curve is obtained in a similar
manner.
• 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 cd).
• After the break point ‘d’ cooling of solid mass begins. The
temperature of horizontal line ‘cd’ gives the eutectic temperature.
• The experiment is repeated for different compositions of
A and B and the various cooling curves are recorded.
• From the cooling curves of various compositions, the main
phase diagram can be drawn by taking composition in X-
axis and the temperature in Y-axis.
 Uses of Cooling curves

• Melting point and eutectic temperature can be noted

from the cooling curve.
• Percentage purity of the compounds can be noted from
the cooling curve.
• The behaviour of the compounds can be clearly
understood from the cooling curve.
• The composition corresponding to its freezing point
yields the composition of the alloy.
• The procedure of thermal analysis can be used to derive
the phase diagram of any two component system.
 Eutectic System: Pb-Ag
System

Since the system is studied at

constant pressure, the vapour phase
is ignored and the condensed phase
rule is used. F′ = C − P + 1
(i) Curve AO
The curve AO is known as freezing point curve of silver. Point A is the
melting point of pure Ag (961°C). The curve AO shows the melting
point depression of Ag by the successive addition of Pb. Along this
curve AO, solid Ag and the melt are in equilibrium.
Solid Ag ⇄ Melt
According to reduced phase rule: F′ = C − P + 1; F′ = 2 − 2 + 1; F′ = 1
The system is univariant.
(ii) Curve BO
The curve BO is known as freezing point curve of lead. Point B is the
melting point of pure lead (327°C). The curve BO shows the melting
point depression of ‘Pb’ by the successive addition of ‘Ag’. Along this
curve ‘BO’, solid ‘Pb’ and the melt are in equilibrium.
Solid Pb ⇄ Melt
According to reduced phase rule : F′ = C − P + 1; F′ = 2 − 2 + 1; F′ = 1
The system is univariant.
(iii) Point ‘O’ (Eutectic point)
The curves AO and BO meet at point ‘O’ at a temperature of 303°C,
where three phases
(solid Ag, solid Pb and their liquid melt) are in equilibrium.
Solid Pb + Solid Ag ⇄ Melt
According to reduced phase rule : F′ = C − P + 1; F′ = 2 − 3 + 1; F′ = 0
The system is non-variant.
The point ‘O’ is called eutectic point or eutectic temperature and its
corresponding composition, 97.4%Pb + 2.6%Ag, is called eutectic
composition. Below this point the eutectic compound and the metal
solidify.
(iv) Areas
The area above the line AOB has a single phase (molten Pb +
Ag). According to reduced phase rule equation.
F′ = C − P + 1; F′ = 2 − 1 + 1; 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 point ‘O’
(Eutectic compound + solid Ag or solid Pb) have two phases
and hence the system is univariant
F′ = C − P + 1; F′ = 2 − 2 + 1; F′ = 1.
 Application of Pattinson’s process for the
desilverisation of Argentiferous lead
The argentiferous lead, consisting of a very small amount of
silver (say 0.1%), is heated to a temperature above its
melting point, so that the system consisting of only the
liquid phase represented by the point ‘p’ in the phase
diagram. It is then allowed to cool. The temperature falls
down along the line ‘pq’. As soon as the point ‘q’ is reached
Pb is crystallised out and the solution will contain relatively
increasing amount of ‘Ag’. On further cooling, more and
more ‘Pb’ is separated along the line ‘BO’ the melt continues
to be richer and richer in silver until the point O is reached,
where the percentage of Ag rises to 2.6%. Thus, the process
of raising the relative proportion of Ag in the alloy is known
as Pattinson’s process.
 Uses of Eutectic system
1. Suitable alloy composition can be predicted with
the help of eutectic systems.
2. Eutectic systems are used in preparing solders,
used for joining two metal pieces together
 Differences between Melting point,
Eutectic point and Triple point
1. Melting Point
It is the temperature at which the solid and liquid phases, having the
same composition, are in equilibrium.
Solid A ⇄ Liquid A
2.Eutectic Point
It is the temperature at which two solids and a liquid phase are in
equilibrium.
Solid A +Solid B ⇄ Liquid
3. Triple Point
It is the temperature at which three phases are in equilibrium.
Solid ⇄ Liquid ⇄ Vapour
All the eutectic points are melting points
 All the melting points need not be eutectic points.
 Similarly all the eutectic points are triple points, but all the
triple points need not be eutectic points.
 Systems in which two components form a
solid compound
The systems, in which two metals form
an intermetallic compound, or a salt and
water form a solid hydrate.
Consider a general case with two
components A and B which form a stable
compound AB.
The system will involve three solid
phases, A, B and AB. The fourth phase
will be a liquid (or
solution) containing varying
concentration of A and B. There are three
freezing point or melting point curves
It has the appearance of two simple viz., AC, CDE and EB. The various phases
eutectic diagrams joined together at the in equilibrium along these curves and in
position of arrows. The diagram to the different regions are labelled in the
left represents the eutectic system A/AB, phase diagram.
while that on the right the system AB/B.
 What is Congruent Melting Point?
• Along the freezing point curve CDE of the compound AB, solid AB is in
equilibrium with the solution phase. At the maximum point D of this
curve, the composition of the solid compound and the liquid phase in
contact is the same, which is indicated by X on the composition axis.
• The corresponding temperature T, therefore, coincides with the
melting point of the compound AB.
• When the solid compound AB and the liquid phase have identical
composition at the maximum point on the freezing point curve, the
corresponding temperature is said to be the Congruent Melting
Point of the compound.
• At point D since both the phases have the same composition, the
system has one component only. Hence it is nonvariant.
• F=C–P+1=1–2+1=0
 THE FERRIC CHLORIDE–WATER SYSTEM
• This provides an example of a 2-component system in which many
compounds (hydrates) are formed. It is a composite system made of several
simple eutectic systems.
• Seven-phase condensed system. Ferric chloride (Fe2Cl6) forms four stable
crystalline hydrates :
• Fe2Cl6.12H2O Dodecahydrate
• Fe2Cl6.7H2O Heptahydrate
• Fe2Cl6.5H2O Pentahydrate
• Fe2Cl6.4H2O Tetrahydrate
• The other three phases involved are ice, anhydrous ferric chloride and
solution. Since all measurements of temperature and concentration are
made at atmospheric pressure, the vapour phase is ignored and the system
Fe2Cl6/H2O is considered a condensed system.
• Two components. As the composition of all the seven phases can be
represented by the constituents Fe2Cl6 and H2O, it is a two-component
system.
Phase Diagram of Fe2Cl6/H2O System
 Phase Diagram of Fe2Cl6/H2O System
In this system four congruently melting compounds are formed which are,
• dodecahydrate(Fe2Cl6.12H2O)
• heptahydrate(Fe2Cl6.7H2O)
• pentahydrate (Fe2Cl6.5H2O)
• tetrahydrate(Fe2Cl6.4H2O).
The phase diagram consists of four maxima corresponding to the
formation of these hydrates.
• Points C,E,G,I represents the congruent melting points of dodeca, hepta,
penta and tetra hydrates respectively.
• The congruent melting point of a salt hydrate is also known as the
dystectic point.
 Phase Diagram of Fe2Cl6/H2O System
There are five cryohydric points at B,D,F,H and G.
• L is the melting point of ice.
• Addition of Fe2Cl6 lowers the melting point along AB.
• At the cryohydric point B the solution becomes saturated w.r.t
dodecahydrate and represents the lowest temperature that can be
attained with this system.
• Curves BCD,DEF,FGH and HIJ represents the solubilities of dodeca,
hepta, penta and tetra respectively while JK represents the solubility
characteristic of the anhydrous salt.
• In the diagram the solubility of each hydrate increases with the rise
of temperature.
 Phase Diagram of Fe2Cl6/H2O System
The Curves:
• The point A represents the normal freezing point of water. The curve AB
shows the lowering of freezing point on the addition of ferric chloride and
hence is named as the freezing point curve of water. The freezing point
falls till the point B is reached where a new phase Fe2Cl6.12H2O separates.
Now as the temperature is raised and more of Fe2Cl6 is added, we travel
along the curve BCD. Fe2Cl6.12H2O and saturated solution are in
equilibrium along this curve which is, therefore, called the solubility curve
of dodecahydrate.
• It will be noted that both the increase and the decrease in the proportion
of Fe2Cl6 in the solution at C will cause a lowering of solubility. Thus at a
temperature such as tº, the 12H2O has two distinct solubilities in water, X1
and X2. This phenomenon of having two solubilities at the same
temperature, characteristic of systems producing solid compounds, is
called retroflex solubility.
 Phase Diagram of Fe2Cl6/H2O System
• The solubility curve BCD of 12H2O terminates at D where another
hydrate 7H2O separates. The curve DEF is the solubility curve of the
heptahydrate. At F, the 5H2O appears and FGH is its solubility curve.
AT H, 4H2O separates and HIJ is its solubility curve. At J, solid ferric
chloride (Fe2Cl6) appears and JK is the solubility curve of the
anhydrous salt.
• Along the curves AB, BCD, DEF, FGH, HIJ and JK, one solid phase and
one liquid (solution) phase are in equilibrium. Therefore applying the
reduced phase rule equation we have
• F=C–P+1=2–2+1=1
• Hence the systems ice/solution, 12H2O/solution, 7H2O/solution,
5H2O/solution, 4H2O/solution, and Fe2Cl6/solution represented by
the various curves are monovariant.
C. Phase Diagram of Mg –Zn system:
Mg and Zn reacts to form
stable compound MgZn2 with congruent melting point.

i)Possible phases: Mg(s), Zn(s), MgZn2 (s), liquid/melt and vapour .

ii)Melting points: Mg=650oC and Zn=420oC.

iii)Curves and point: Freezing point curve of Zn to which increasing amount of

Mg are added .The lowest temperature reached is 380oC(eutectic point)
below which Mg Zn2 is formed.
iv)Freezing point curve of solid MgZn2 to which
increasing amount of Mg are added. The freezing
point keeps on increasing till it reaches its maximum
at 590oC which represents congruent melting point.
On further adding MgZn2 ,its freezing point decreases
and is lowest at 347oC which is the another eutectic
point.

v)Freezing point curve of Mg to which increasing

amount of Zn are added. The freezing point decreases
still the lowest freezing point of 347oC is obtained.
 Compound formation with
incongruent melting point
• NaCl-Water (NaCl.2H2O)
• Na-K System
• Na2SO4-Water
(Na2SO4.10H2O, Na2SO4.7H2O & Na2SO4.4H2O)
 Incongruent melting point system
Compounds combined together to form one or more
compounds which are unstable and do not possess congruent
melting points.
A system is said to possess incongruent melting point, if on
heating it decomposes much below its melting point and
forms a new solid phase and a solution having different
composition from the corresponding solid state. It has no
sharp melting point. The decomposition at this temperature is
known as transition or meritectic or peritectic temperature.
Original solid ⇄ New solid + solution (melt)
 NaCl-H2O system
D. Phase Diagram of NaCl-H2O system:
Sodium chloride and water react to form stable
compound NaCl.2H2O with incongruent melting
point(o.15oC)
i)Possible phases: NaCl (s), NaCl.2H2O(s),ice solid, solution and
water vapour.

ii)Curves and point: a)Freezing point curve of H2O to which

increasing amount of NaCl are added .The lowest temperature
reached is -21.2oC(23% NaCl). At this point NaCl.2H2O starts
separating . Hence it is eutectic point.
Phase Equilibrium

By B.K Choudhary 81
 NaCl-H2O system
b) Solubility curve of NaCl.2H2O (s):
It rises with increase of temperature till at 0.15oC.
It starts decomposing to give anhydrous NaCl.

c) Solubility curve of anhydrous NaCl :

Which increases with increase of temperature.
 Sodium sulphate-water system
• Sodium sulphate forms two hydrates Na2SO4.10H2O
(decahydrate) and Na2SO4.7H2O (heptahydrate). Furthermore, the
anhydrous salt can exist in two enantiotropic crystalline forms, viz.,
rhombic and monoclinic. The remaining phases are solid ice,
solution, and vapour.
• Since all determinations are made at atmospheric pressure, the
vapour phase is ignored.
• Thus the system Na2SO4-H2O is a six phase condensed system.
• The composition of all the six phases can be represented by the
constituents Na2SO4 and H2O.
• Hence the sodium sulphate-water system has two components.
Sodium sulphate-water system
 Sodium sulphate-water system
• The Curve AB, the Melting point curve of ice. The point A (0ºC) is the
melting point of ice.
• The curve AB shows the lowering of melting point of ice on the addition of
anhydrous Na2SO4.
• The two phases in equilibrium along AB are ice and solution. Applying the
reduced phase rule equation,
• F=C–P+1=2–2+1=1
• That is the system ice/solution is monovariant.

The Eutectic point B. At B, a new solid phase Na2SO4.10H2O appears.

This is the lowest temperature (– 1.3ºC) attainable or the Eutectic Point
where three phases, namely, ice, Na2SO4.10H2O, and solution can
coexist in equilibrium.
• Applying reduced phase rule equation,
• F = C – P + 1 = 2 – 3 + 1 = 0 and the system is nonvariant.
 Sodium sulphate-water system
• The Curve BF, the Solubility curve of 10H2O. If the system at B is heated and
more of anhydrous Na2SO4 added, we travel along the curve BF. Along this
curve, saturated solution of sodium sulphate and Na2SO4.10H2O is in
equilibrium. Thus the curve BF shows that the solubility of 10H2O increases with
temperature until the point F is reached. The system Na2SO4.10H2O/solution is
monovariant.
• F=C–P+1=2–2+1=1
• The Transition point F. At F, Na2SO4.10H2O loses water and changes to the
anhydrous rhombic Na2SO4. Thus, this point represents the transition
temperature (32.2ºC).
• Na2SO4. 10H2O ⇄ Na2SO4 + 10H2O
• This temperature may also be regarded as the incongruent melting point of
Na2SO4.10H2O as the composition of the liquid phase (solution) is different from
that of the solid hydrate in equilibrium.
• AT F, there are two components and three phases viz., Na2SO4.10H2O, Na2SO4
and the solution. Hence the system is nonvariant.
• F=C–P+1=2–3+1=0
 Sodium sulphate-water system

• The Curve FG, the Solubility curve of rhombic Na2SO4. When the system at F is
heated, ultimately all the 10H2O will disappear and we pass along the curve FG, the
solubility curve of anhydrous rhombic Na2SO4. The curve shows that the solubility
decreases up to 125ºC with rise of temperature and then increases till we reach the
point G. At G (234ºC), the rhombic Na2SO4 changes into the monoclinic form. Thus G
represents a transition point where enantiotropic transformation occurs. With two
components and three phases in equilibrium, the system at G is nonvariant.
• F=C–P+1=2–3+1=0
• The Curve GH, the Solubility curve of monoclinic Na2SO4. On continued heating the
system at G, ultimately the rhombic Na2SO4 completely changes into the monoclinic
Na2SO4. Then we pass along the curve GH, which is the solubility curve of the
monoclinic salt. This shows that the solubility falls gradually with rise in temperature
up to 365ºC, the critical point of the solution. The system along GH has two
components and two phases, namely, Na2SO4 monoclinic and solution. Thus,
• F = C – P + 1 = 2 – 2 + 1 = 1 the system is monovariant.
 Metastable Equilibria of Na2SO4/H2O System
The metastable equilibria of the system Na2SO4-H2O are shown by dashed lines in the phase
diagram.
1. The Curve FF'. If enough time is not allowed at F, 10H2O is not changed into anhydrous
rhombic Na2SO4. The curve FF', therefore, is the solubility curve of metastable 10H2O.
2. The Curve BC. If by careful cooling, 10H2O does not separate at B, we pass along the dashed
curve BC. This is the freezing point curve of metastable supercooled solution saturated with
respect to 10H2O.
3. The Eutectic C. At C (– 3.77º), metastable 7H2O appears. Therefore, the point C is the
eutectic point where three metastable phases viz., supercooled solution, ice, and 7H2O coexist
in equilibrium.
4. The Curve CD. By raising the temperature of the system at C, we pass along the dashed
curve CD, the solubility curve of metastable 7H2O.
5. The Curve FD. When a saturated solution with respect to rhombic Na2SO4 is cooled quickly
10H2O does not appear at F (32.2º) and we pass on to D. The dashed curve FD is, therefore, the
solubility curve of metastable 10H2O.
6. The Transition point D. The point D represents the transition point where the metastable
7H2O is changed into metastable rhombic Na2SO4.
Na-K system
 Na-K system

The melting points of sodium and potassium are 97.8 C and

63.8 C respectively. Both the elements chemically combine
together in the ratio of 2:1 ratio to form a compound Na2K.
But this compound is unstable and decomposes into solid Na
and melt at a temperature of 70 C. It is the incongruent
melting point or peritectic temperature of this system
This system consists of four phases i.e. Solid K, Solid Na, Solid
Na2K and Liquid of Na and K.
Reduced phase rule is applicable on this system as pressure
does not have any effect for this system.
 Na-K system
• Curves
• (i) Curve AC (Freezing point curve of K): This curve shows the lowering in
freezing point of K by addition of Na and continues till the point ‘C’ is
reached. Along this curve, K separates out as solid phase. A new phase Na 2K
separates out at point C. The two phase exist in equilibrium along this curve.
• P=2, [ K(solid) and liuid (Na-K melt)] and C=2
• On applying the reduced phase rule F=C-P+ 1 = 2-2+1 = 1 , The system is
univariant
• (ii)Curve CD ( Fusion curve of Na2K) : Along this curve the two phases exists in
equilibrium. The Na2K is stable along this curve. [ If further the compound
would be stable as having congruent melting point then the curve may be
plotted up to the stable melting point E of the compound.
• Na2K (s) ⇄ Liquid P=2 [Na2K (s) and Liquid] and C=2
• At point D : P=3, C=2, hence F=C-P+ 1 = 2-3+1 = 0 , The system is nonvariant
 Na-K system
• 3. Areas
• (i) Area above ACBD: contains only liquid phase i.e. Melt of Na, K and Na 2K.
• Hence, P=1, C=2
• On applying the reduced phase rule F=C-P+ 1 = 2-1+1 = 2 , The system is bivariant in
the area above ACBD
• (ii) Area ACF: It consists of two phases solid K and liquid.
• (iii) Area ECG: This area consists of two phases, which exist in equilibrium i.e. Solid
Na2K and liquid.
• (iv) Area BDH: It consists of the two phases, , which exist in equilibrium i.e. Solid Na
and liquid
• (iv) Area below FCG: It consists of solid K and solid Na2K.
• (vi) Area IHLK: This area consists of two phases solid Na and solid Na2K.
• All areas from (ii) to (vi) are having two phases and two components , Hence P=2, C=2
• Applying reduced phase rule: F=C-P+ 1 = 2-2+1 = 1 , Hence all the above areas
represent univarient system
Uses (or) merits of phase rule
1. It is applicable to both physical and chemical equilibria.
2. It is a convenient method of classifying the equilibrium
states in terms of phases, components and degree of
freedom.
3. It indicates that the different systems having the same
degrees of freedom behave similarly.
Limitations of phase rule
1. Phase rule can be applied only for the systems in
equilibrium.
2. Only three variables like P, T & C are considered, but not
electrical, magnetic and gravitational forces.
3. All the phases of the system must be present under the
same conditions of pressure and temperature.
4. Solid and liquid phases must not be in finely divided state,
otherwise deviations occur.