Contents

▪ Introduction
▪ Gibbs Phase Rule
• Phase
• Component
• Degree of Freedom
▪ Phase Diagram
▪ One Component System
• Water System
• Sulphur System
▪ Two Component system
• Pb-Ag,
• Zn-Mg
• Fe-C
▪ Metal and Alloys
▪ Heat Treatment of steel
Introduction
▪ Phase rule is an important tool to explain the state of
equilibrium in a heterogeneous system.
▪ The Phase rule was first presented by Willard Gibbs in
1874.
▪ It is very useful to understand the effect of intensive
variables such as temperature , pressure or concentration
on equilibrium between different phases as well as
chemical constituents.
▪ It predicts the behaviour of system with changes in the
variables that govern the system in equilibrium.
Gibbs Phase Rule
▪ If a heterogeneous system in equilibrium is influenced
by temperature, pressure & concentration , then the
number of degrees of freedom plus number of phases is
greater than the number of components by two.
Mathematically , 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 &
pressure
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 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.
(v) It takes no account of nature of the reactants or
products in phase reactions.
Limitations of Phase Rule:
(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.
(iii) In 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.
 Related Terms
PHASE , P :
Homogeneous , Physically distinct & mechanically
separable part of the system , which is separated from
other parts by definite boundaries.
Examples
(i) A gaseous mixture constitutes- a single phase since
gases are completely miscible.
(ii) Two or more liquids which are miscible with one
another constitute -a single phase. e.g., water and alcohol
constitute one phase system.
(iii) Two immiscible liquids forms- two phase system e.g.,
water and oil as there is bounding surfaces separating the
two liquids.
(iv) A system consisting of a liquid in equilibrium with
its vapour - two phase system
(v) Solution of NaCl in water – one phase system
but Saturated Solution of NaCl in water – two phase
system.
(vi) Each solid forms a separate phase.
when a crystal has one solid substance—one phase
system
but a crystal has two or more solid substance—two
or more phases.
COMPONENTS , C :
The minimum number of independent chemical
constituents by means of which the composition of
each phase can be expressed.
Examples
(i) Water system: the composition of each of the three
phases present can be expressed as H2O.Hence it is one
component system
ice(s) ⇌ water(l) ⇌ vapor(g) C=1

(ii) 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.
Sm or SR (s) ⇌ S(l) ⇌ S(g) C=1
▪ In a chemically reactive system, the number of
components is given by
C=S-R
where, C = components.
S= Number of chemical species
R = Number of independent equations
relating the S number of species
(iii) Decomposition of CaCO 3 :
CaCO3 (s) ⇌ CaO(s) + CO2(g)
In a chemically reactive system, the number of
components is given by
C=S–R
Here ,S=3 ,R=1
C= 3-1=2 (two component system)
(iv)Dissociation of NH4Cl –
In closed vessel-
NH4Cl (s) ⇌ NH3 (g) + HCl (g)

P=2 , Solid NH4Cl & gaseous mixture of NH3 and HCl

the constituents of the mixture are in the same
proportion in which they are combined in solid NH4Cl.
One more eq. i.e.[NH3 ] = [HCl]
C= S – R
= 3 - 2 = 1 (one component)
Degree of Freedom ,F :
The degree of freedom is defined as the minimum
number of variable factors such as temperature, pressure
and concentration which must be arbitrarily fixed in order
to define the system completely.

When- F=0 , nonvariant or invariant

F=1 , monovariant or univariant
F=2 , bivariant
F=3 , trivariant
.
Examples
(i) For water system – all the three phases are in
equilibrium only at fixed temperature (0.0098°C ) &
pressure(4.58mm of Hg). Therefore no variable need to
be specify. Hence F=0 ,the system is nonvariant
(F=C-P+2, F=1-3+2 =0)
ice(s) ⇌ water(l) ⇌ vapor(g)
When the temperature or pressure is changed
only two phases will remain in equilibrium , one phase will
disappears.
Hence F=1, the system will become monovariant.
(ii) For a pure gas PV = nRT.
P= nRT/V = CRT (As, n/V = C)
Any two of the three variables P, V, T can define the
system completely. Hence F=2 , the system is bivariant

(iii) A gaseous mixture say N2 and O2 gases (mixed 50% each),

is completely defined when three variables temperature,
pressure and concentration are specified. Thus F=3 , the
system is trivariant
▪ The number of phases is maximum when the number of
degrees of freedom, F = 0, for a given number of
components.
▪ The greater the number of components in a system, the
greater is the degree of freedom.
▪ Degree of freedom always have a positive value. So It is
not possible for a single component system to have four
phases together at equilibrium.
F=C-P+2 , F= 1-4+2= -1 ( not possible)
(so for a one component system maximum 3 phases can
coexist at equilibrium)
Practice questions
▪ Q) Determine the no. of phases ,components and degree of freedom in
the following equilibrium system----
▪ (i) KCl - NaBr- H2O System—
KCl + NaBr ⇌ NaCl + KBr

▪ (ii) SYSTEM OF (PCl5 + PCl3 + Cl2 ) -

PCl5 ⇌ PCl3 + Cl2

▪ (iii) Na2SO4-Water System -

▪ (iv) CuSO4 .5H2O ⇌ CuSO4.3H2O + 2H2O

Phase diagrams :
▪ A diagram that shows the condition of the temperature
and pressure (P-T)or temperature and composition(T-C)
under equilibrium is called phase diagram.
▪ It is very easy to describe the phase behaviour of a
system by such diagrams and to investigate the conditions
in which various phases will constitute the system .
▪ A phase diagram is consist of –
i) Curves( lines)
ii) Areas (Regions)
iii) Points
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
The Water System
▪ It is a one component system.
▪ Water exists in three possible phases viz. ice (solid) ,
water (liquid), and vapour (gas).
The phase diagram consists of :
(i) Stable curves: Three OA, OB and OC
(ii) Meta stable curve: One OA'
(iii) Areas: Three AOB, COB and AOC
(iv) Triple point: One “O”
Phase Diagram of water system
(i) Stable curves
Curve OA : It is known as vapour pressure curve of water.
▪ The curve OA terminates at point A, called the critical
point .The temperature at critical point is 374 0C and
pressure is 218 atm.
▪ The rate of increase of its vapour pressure with
temperature is relatively higher at higher temperatures
and therefore the curve OA slants upwards and slopes
away from the temperature axis.
▪ It shows the vapour pressure of water increases with
increase in temperature.

▪ Along curve OA phases in equilibrium are

water(l) ⇌ vapor(g)
From phase rule,
F=C–P+2
= 1- 2 + 2
= 1 ( System is univariant )
OB : It is the sublimation curve of ice

▪ Curve OB starts From the point O & The curve terminates

at B (- 273°C). At this temperature, no vapour can exist
and therefore, only ice is left.

▪ Along this curve, solid ice is in equilibrium with its

vapour.
ice(s) ⇌ water(l)
Hence, According to phase rule,
F=C–P+2
=1–2+2
= 1 (Thus, the system is univariant).
 OC : This curve is the melting point curve or fusion curve
of ice.
▪ The curve OC shows the condition of pressure for melting
of ice.
▪ The inclination of OC line towards the pressure axis
indicates that the melting point of ice is slightly decrease
by increase in pressure.
▪ Along this curve two phases, ice and water are in
equilibrium.
ice(s) ⇌ water(l)
According to phase rule,
F=C–P+2
=1-2+2 = 1 ( the system is univariant)
(ii) OA' : Metastable Curve / Super cooled curve

▪ Sometimes, it is possible to cool down water, below its

freezing point without separation of ice. this water is said
to be super cooled water.
▪ The vapour pressure curve of liquid water AO extends
below O as shown by the dotted curve OA‘.
▪ This equilibrium is called metastable (highly unstable)
equilibrium as slight disturbance brings it to the stable
region OB of the phase diagram.
(iii) Areas
▪ The areas between the curves shows the conditions of
temperature and pressure under which a single phase 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.
Hence, According to phase rule,
F=C–P+2
= 1 - 1 +2 = 2 ( the system is Bivariant)
(iv) The Triple point O
The point O at which the curves AO, BO and CO meet
together is called the triple point.(temperature ,0.0098°C
& pressure, 4.58mm of Hg)
At this point all the three phases viz , ice, water and
vapour co-exist.
ice(s) ⇌ water(l) ⇌ vapor(g)
According to phase rule, at triple point O,
F = C –P + 2,
=1-3+2 ,
F = 0 ( nonvariant)
The Sulphur
System
The Sulphur System:
▪ It is a one component system.
▪ Having four phases …
Rhombic Sulphur, SR
Monoclinic Sulphur, SM
Liquid Sulphur, SL
Vapour Sulphur, SV
From the phase rule when C=1
F= C-P+2
= 1-P+2 = 3 - P
As degree of freedom can not have a minus value,
therefore out of 4 phases only three are present at a time.
Phase Diagram of Sulphur system
▪ In the Sulphur system, one solid allotropic form transforms into
the other , SR⇌ SM
▪ Below 95.60C SR is stable and above 95.60C SM is stable.
▪ Such a system in which two or more solid states exist in
equilibrium is called a polymorphic system.
▪ The phase diagram consists of the following:
1. Curves: Six Curves
(i) Curve AB, It is the vapour pressure curve of rhombic
sulphur. Along this curve, two phases SR and SV exist in
equilibrium. SR⇌ SV
(ii) Curve BC, It is the vapour pressure curve of monoclinic
sulphur. Two phases SM⇌ SV
(iii) Curve CD, the vapour pressure curve of liquid sulphur.
Here, SL⇌ SV
 (iv) Curve BE, transition curve of SR to SM.
SR⇌ SM
The line BE slopes away from the pressure axis showing that the
transition temperature can be raised with increase in pressure.
(v) Curve CE, the fusion curve of SM.
SM ⇌ SL
The curve ends at point E because monoclinic sulphur does not
exist beyond this point.
(vi) Curve EG, It is the fusion curve of SR.
SR⇌ SL
▪ Along all the six curves, two phases are in equilibrium. Hence the
degree of freedom, F = C – P + 2 = 1 – 2 + 2 = 1 (univariant).
▪ Hence only one variable (either pressure or temperature) is
required to explain the system completely.
2. Areas :The phase diagram has four areas.
Each area consists of a single phase
(i) ABG, (rhombic sulphur)
(ii) BECB, (monoclinic sulphur)
(iii) GECD (liquid sulphur)
(iv) ABCD, (vapour sulphur)
For each area, C =1; P =1,
hence the degree of freedom will be
F=3–1
= 2 (bivariant system).
3. Triple Points: There are three stable triple points .
(i) B (95.6 °C, 0.006 mm),
SR ⇌ SM ⇌ SV
(ii) C (120 °C, 0.04 mm)
SM ⇌ SL ⇌ SV
(iii) E (151 °C, 1290 atm).
SR ⇌ SM ⇌ SL
Three phases exist in equilibrium at all the points. Therefore
,the degree of freedom along these triple points is
F=C–P+2
= 1 – 3 + 2 = 0 (invariant or non-variant)
Metastable equilibria : Three Metastable curves
(i) Dashed Curve BF It is the vapour pressure curve of metastable
SR. If rhombic sulphur is heated rapidly, it will bypass the transition
point B without changing to monoclinic sulphur and will melt at F.
metastable SR ⇌ metastable SV (monovariant)
(ii) Dashed curve CF It is the vapour pressure curve of
supercooled liquid sulphur. When the liquid sulphur is cooled
rapidly, it does not change to monoclinic sulphur at point C and
continues to exist as supercooled liquid.
metastable SL ⇌ metastable SV (monovariant)
(iii) Dashed curve FE This is the fusion curve of metastable SR.
metastable SR ⇌metastable SL (monovariant)

Metastable triple point F : The three metastable phases SR, SL and

SV are in equilibrium at this point.
SR ⇌ SL ⇌ SV (nonvariant)
 Two Component System
(Condensed System)
▪ For a two component system, If P= 1
Then F= 2 – 1 + 2 = 3 ( Trivariant)
▪ So three variable are required to represent phase
diagram.
▪ For making simple phase diagram consider only two
variables (T & C ) .
▪ Ex – Solid -liquid equilibrium , gas phase is absent and the
effect of pressure will be negligible . Hence pressure can
be kept constant . Such system with gas phase is absent
is known as condensed system.
▪ Reduced Phase Rule – F = C- P + 1
Classification of Two Component System
When two components are completely miscible in molten
state , then depending upon how they separate out as
solid phases during cooling, two component solid- liquid
equilibria can be classified into following types---
(i) Simple Eutectic Formation. Pb- Ag System
(ii) Formation of a compound having a congruent melting
point. Zn-Mg System
(iii) Formation of a solid compound which is unstable and
decomposes below its melting point to give a new solid
phase and a liquid . Such compounds have incongruent
melting point. eg. Na2SO4- H2O System
Eutectic Mixture & Eutectic Point
▪ A binary system of two compounds which are miscible in
all proportions in liquid phase, do not react chemically .
But on solidification the form Eutectic mixture.
▪ The two compounds lowers the melting point of each
other’s.
▪ The minimum melting point attainable corresponding to
eutectic mixture is called Eutectic Point.
At eutectic point two solids are in equilibrium with
solution phase.
F = C – P + 1 = 2- 3 + 1 = 0 (nonvariant)
Silver- Lead
System
Silver Lead System
This system has two component and four phases.
(i) Solid Ag
(ii) Solid lead
(iii) Solution of molten silver and lead
(iv) Vapor
▪ The vapor phase is completely absent. Since the
pressure has nearly no affect on equilibrium so the
system is conveniently represented by Condensed
System. Therefore, Reduced Phase Rule is applicable.
▪ The experimental measurements on condensed system
are carried out under atmosphere pressure.
Phase Diagram of Silver Lead System
The phase diagram of silver lead
system consists of :
(i) Two curves: OA and OB
(ii) One Point: Eutectic Point “ O”
(iii) Four Areas: Above AOB, Below AO, Below BO and
Below 3030C

▪ Apply , Reduced Phase Rule : F = C - P + 1

(i)CURVES-
(a) Curve OA – melting curve of silver
▪ At this curve, point A is melting point of solid silver,
9610 C . Curve shows that addition of lead lowers the
M.P. of silver.

▪ Solid Ag is in equilibrium with solution of Ag & Pb

F = C - P + 1
= 2 - 2 + 1
= 1( monovariant)
(b) Curve OB – melting curve of Lead.

▪ At this curve point B is melting point of solid lead,

3270 C . Curve shows that addition of silver lowers
the melting point of lead.

▪ Solid Pb is in equilibrium with solution of Ag & Pb

F = C - P + 1
= 2 - 2 + 1
= 1 ( monovariant)
 (ii) Eutectic Point “ O”
▪ The curve OA and OB are intersect at point O ,
Eutectic point.
▪ All the three phases are co-exit in equilibrium.
Ag ⇌ Pb ⇌ Solution of Ag & Pb
F = C - P + 1
= 2 - 3 + 1
= 0 ( nonvariant)
Both Temp and Composition are fixed at 303 0 C and
2.6 % Ag & 97.4 % Pb respectively.
(iii) AREAS- four areas
(a) Above AOB –
Single Phase – Solution of Ag & Pb.
F = C - P +1
= 2 - 1 +1
= 2 ( bivariant)
(b) Below OA -
Solid Ag and Solution of Ag & Pb.
F = C - P +1
= 2 - 2 +1
= 1( univariant)
(c) Below OB -
Solid Pb and Solution of Ag & Pb.
F = C - P +1
= 2 - 2 +1
= 1 (univariant)
(d) Below 303 0 C -
divided in two -- a) Solid Ag and Eutectic
b) Solid Pb and Eutectic
F = C - P +1
= 2 - 2 +1
= 1 (univariant)
Application( Patterson's Process)
▪ The phase diagram of silver lead is useful in the extraction
of silver from the argentiferous lead .
▪ The argentiferous lead, having a very small amount of
silver (say 0.1%), is heated to a temperature above its
melting point, so that the system has only the liquid phase
represented by the point x in the phase diagram.
▪ It is then allowed to cool where the temperature
decreases along the line xy . As soon as the point y is
reached, Pb is crystallized out and the solution will contain
relatively increasing amounts of Ag .
▪ On further cooling, more and more of Pb is separated
along the line BO. The melt continues to be richer and
richer in Ag until the point O is reached, where the % of
Ag rises to 2.6%. Thus, the process of raising the relative
proportions of Ag in the alloy is known as Pattinson’s
process of desilvering of lead.
▪ This is treated for the recovery of silver profitably.
▪ This process is used to find the composition of alloy.
Two Component System having
Congruent Melting point.
 If the Two components of the system at a certain stage
enter into chemical combination with one another
forming a stable compound.
 The compound is said to have a congruent melting point,
if it melts sharply at constant temperature to give a liquid
of the same composition.
 Example- Zn- Mg System.
Zinc-Magnesium
System
Phase Diagram of Zn- Mg System
 The phase diagram of Zn-Mg consists of the following:
(i) Curves :
Curve AB: melting curve of zinc on gradual addition
of magnesium.
Curve ED: melting curve of magnesium on gradual
addition of zinc.
These curve represents the composition of the liquids in
equilibrium with solid Zn & Mg respectively
Curve BCD: melting curves of Mg (Zn)2
This curve represents the condition of equilibrium of liquid
with solid compound Mg (Zn)2
Curve BCD is divided in to two parts…
 Curve CB: It represents the lowering of melting point of
Mg (Zn)2 on addition of zinc
 Curve CD : It represents the lowering of melting point of
Mg (Zn)2 on addition of magnesium.
Along these curves system is univariant.
(ii) Points:
Point A : melting point of zinc (420 °C)
Point E : melting point of magnesium (651 °C)
Along these points system is univariant.

Point C : melting point of Mg (Zn)2 (590 °C), Congruent

melting point.
This point gives the condition of equilibrium of solid with the liquid
of the same composition.
The system is nonvariant at point C.

Point B : Eutectic point (380 °C)

Point D : Eutectic point (347 °C)

At B, the three phases are zinc, Mg (Zn) 2 and their melt.
The eutectic temperature at B is 380 °C and the
composition is 79% Zn and 21% Mg (Zn) 2 .

At D, the three phases are magnesium, Mg (Zn)2 and melt.

The eutectic temperature at D is 347 °C and the
composition is 61% Mg and 39% Mg (Zn) 2 .
At these points C = 2; P = 3 ;
F=C–P+1
2 – 3 + 1= 0 (Nonvariant)
(iii) Areas :
Area ABFA : The area contains solid zinc and solution
of Zn and Mg
Area CBGC : This area contains Mg (Zn)2 and solution of
Zn and Mg
Area CHDC : This area also contains Mg (Zn)2 and molten
Zn and Mg
Area EDIE : Solid magnesium and liquid of and solution
of Zn and Mg
Area below FBG: It represents a solid mixture of zinc and
Mg (Zn)2
Area below HDI : It represents a solid mixture of
magnesium and Mg (Zn)2
The system is Univariant in all these areas.
Area above ABCDE : It represents a single phase, solution
of zinc and magnesium.
The system is bivariant in this area.
 Cooling Effect:
• Consider a melt of composition represented by a point x.
Allow it to cool along the line xy. When it reaches y, the solid
Mg (Zn)2 separates out from the melt and the composition
varies along the curve yB.
At point B molar composition becomes 79% Zn and 21%
Mg(Zn)2.
 Similarly, if a melt of composition represented by a point x’,
allow to cool along x’y’. At point y’, Mg (Zn)2separates out
and the composition varies along the curve y’D.
At point D Molar composition becomes 61% Mg and
39% Mg(Zn)2 .
▪ The phase diagram of the Zn–Mg system have two simple
eutectic diagrams side by side, one on the left of CG and
the other on its right.
▪ The curves BC and CD should meet to give a sharp point
at C. This maxima point gives the condition of equilibrium
of solid with the liquid of the same composition, known
as congruent meting point.
▪ But a rounded maxima indicate that the compound
formed is not very stable and dissociates partly. The
dissociation of products in the liquid phase depresses the
actual melting point of the compound resulting in a
rounded melting point.