INTRODUCTION OF PHASE RULE

The phase rule is a generalization given by Willard Gibbs (1874), which seeks to explain the
equilibria existing in heterogeneous system. It may be stated as: “provided the equilibrium
between any number of phases is not influenced by gravity, or electrical, or magnetic forces or
by surface action and only by temperature, pressure and concentration, then the number of
degrees of freedom (F) of the system is related to number of components (C) and of phases (P)
by the phase rule equation for any system at equilibrium at a definite temperature and pressure.

F=C–P+2

F= degrees of freedom ,C= no of components, P= no of Phases

Explanation of terms:

Phase: A phase is defined as “an homogeneous, physically distinct and mechanically separable
portion of system, which is separated from other such parts of the system by definite
boundary surface”. For Example:

• At freezing point, water consists of three phase :

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

• A gaseous mixture, being thoroughly miscible in all proportion, will constitute one phase
only. Thus, a mixture of N2and H2 forms phase only.
• If two liquids are immiscible (i.e., benzene and water), they will form two separate phase
only.
• If two liquids are miscible (i.e., alcohol and water), they will form one liquid phase only.
• A solution of a substance in a solvent consists of phase only, e. g, glucose solution in
water.
• Each solid mark up a separate phase, except in the case of solid solution, e. g, many
forms of sulphur can exist together, but these are all separate phases.
• A heterogeneous mixture like :
 CaCO3 (s) CaO(s) + CO2 (g)

Consists of three phases (i.e., two solids and one gasous). Similarly, in the equilibrium reaction,

Fe(s) + H2O FeO(s) + H2(g)

There are two solid phases, Fe and FeO and one gaseous phase consisting of H2O(g) and H2(g).
Thus, three phases exists in equilibrium.

• A homogeneous solid solution of a salt constitutes a single phase. Thus, Mohr’s [ FeSO 4
(NH4)2SO46H2O] solution constitutes a single phase, although it consists of FeSO4 (NH4)
SO4, and H2O.

Component: by the term component is meant “the smallest number of independent variable
constituents, taking part in state of equilibrium, by mean of which the composition of each phase
can be expressed in the form of chemical equation”. For example:

i. In the water system,

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

The chemical composition of all the three phases is H2O. Hence, it is one component system.

ii. 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.

iii. In the dissociation of NH4CI in a closed vessel,

NH4CI(g) NH4CI(g) NH3(g)+HCI(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 NH4CI alone. Hence, the number of component is one.
However, if NH3 or HCl is in excess, the system become a two component system .

iv. A system of saturated solution of NaCI consists of solid salt, salt solution and water
vapour. The chemical composition of all the three phases can be expressed in terms of NaCI and
H2O. Hence, it is a two component system.

v. In 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, the composition of different phases is represented as follows:

Phase: CaCO3 = CaCO3 + 0 CaO

Phase: CaO = 0 CaCO3 + CaO

Phase: CO2 = CaCO3 – CaO

Thus, it is two component systems.

vi. In the dissociation reaction,

CuSO45H2O(s) CuSO4.3H2O(s) +2H2O(g)

The composition of each phase can be represented by the simplest component, CuSO4 and H2O

Hence, it is two component systems.

 vii. In the equilibrium, Fe(s) + H2O(g) FeO(s) + H2(g), the minimum components
required the composition phase is three. Evidently, it is a three component system.

Number of component of a system may alternatively be defined as the number of chemical

constituents of the system minus the number of equations relating to these constituents in an
equilibrium state. For example

1.Dissociation of KClO3 in a closed vessel: following equilibrium exists :

KClO3(s) 2KCl(s) + 3O2(g)

No. of constituents = 3

Now

No. of equations relating the concentration of constituents =1.

Hence, number of components = 3-1 = 2 i.e., it is a two component system.

2. Dissociation of NH4Cl:

i. Only NH4Cl is heated in a closed vessel. The equilibrium existing is:

NH4Cl(s) NH3(g) +HCl(g)

[NH3] = [HCl]

Also Keq = = [NH3][HCl]

Because the active mass of NH4Cl(s) is constant.

Now number of components, C

 = No. of constituent –[ No, of equations relating to concentration of constituents]

= 3(NH4CL, NH3 and HCl) – 2 = I, i.e. it is a single component system :

ii. When NH4Cl is heated in a closed vessel along with NH3 or HCl, At equilibrium:

Keq = [NH3][HCl] ……………..(i)

But [NH3] ≠ [HCl] …………(ii)

Only one equation (i) relates the concentrations of constituents

No. of component, (C) = 3 -1 = 2, i.e. under the above conditions, the system has two
components

Degree of freedom or variance: By the term “degree of freedom is meant by” the minimum
number of independently variable factors, such as temperature, pressure and composition of the
phases, which must be arbitrarily specified in order to represent perfectly the condition of a
system. For example

i. In case of water system, Ice(s ) Water(l) Vapour(g), if all the

three phases are present in equilibrium, then no condition need to be specified, as the three
phases can be in equilibrium only at particular temperature and pressure. If condition (e.g.
Temperature or pressure is altered, three phases will not remain in equilibrium and one of the
phase disappears.

ii. For a system consisting of water n in contact with its vapour,

Water(l) Vapour(g)

We must state either the temperature or pressure to define it completely. Hence, degree of
freedom is one or system is univariant.
 iii. For a system consisting of water vapour phase only, we must the values of both the
temperature and pressure in order to describe the system completely. Hence, the system is
bivariant or has two degrees of freedom.

iv. For a system consisting of ,

NaCl(s) NaCl(aq) water vapour(g).

We must state either the temperature or pressure, because the saturation solubility is fixed at a
particular temperature or pressure. Hence, the system is univariant

v. For a gaseous mixture of N2 and H2, we must state both the pressure and temperature,
because if pressure and temperature are fixed, the volume automatically becomes definite.
Hence, for a gaseous system, two factors must be stated in order to define it completely and thus,
it has two degree of freedom (or bivariant system).

Merits of phases rule:

1. It is applicable to both physical and chemical equilibria.

2. It require no information regarding molecular/ micro-structure, since it is applicable to

macroscopic system.

3. It is a convenient method of classifying equilibrium states in terms of phases, components

and degrees of freedom.

4. It helps us to predict the behaviour of a system, under different sets of variables.

5. It indicates that different systems with same degree of freedom behave similarly.

6. It does not take into cognizance of either the nature or quantities of component present in

the system.
7. It helps in deciding whether under a given set of condition:

a. various substances would exist together in equilibrium or

b. some of the substances present would be interconverted or

c. some of the substances present would be eliminated .

Limitation of phase rule:

1. It can be applied only for system in equilibrium. Consequently, consequently, it is of little

value in case of very slow equilibrium state attaining system.

2. It applies only to a single equilibrium system: and provided 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 sate, since
it considers only the number of phases, rather than their amounts. Thus, even if a trace of the
phase is present, it accounts towards the total number of phases.

4. It conditions that all 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 occurs.

PHASE RULE FOR CHEMICAL REACTION EQUILIBRIUM

In a chemical reaction , various reactant with one another forming products. Consequently, the
phase equilibrium become rather complicated due to simultaneous presence of reactants and
products. Let Nebe the total number of chemical substances present in the overall system at
equilibrium and r be the number of reactants, then the component term C of the phase rule
equation is replaced by (Ne – r ), i.e,,,

C = Ne – r
Hence, phase rule equation becomes :

F = C –P + 2 =(Ne – r ) – p +2.

Illustration: let us consider the reaction oxygen with carbon producing a mixture of carbon
monoxide and carbon dioxide. Thus :

C(s) + O2(g) -----------à CO2

C (s) + ½ O2(g)------------------à CO(g)

No. of phases at equilibrium (P)

= Solid phase due to carbon + Gaseous phase due to CO2+ CO + O2

=1+1=2

No. of reactants ® = Carbon + oxygen

=1+1=2

No. of chemical substances present at equilibrium (Ne)

= Carbon + CO2+ CO + O2

= 1 + 1+ 1+ 1 = 4

1. Degree of freedom (F) = (Ne – r ) – p + 2 =(4 – 2) – 2 + 2 = 2

WATER SYSTEM

The water system consists of three phases , viz., ice, water and water vapour.

Ice(s) Water (I) Water vapour(g)

Since H2O is the only chemical compound involved, therefore, it is single or one-component
system . From the phase rule, when C =1,

F = C – P + 2 =1 – P + 2 = 3 – P

i.e, the degree of freedom depends on the number of phases present at equilibrium. Three
different case are possible :

(i) P = 1 ; F=2 (bivariant system)

(ii) P = 2 ; F=1 (univariant system)

(iii) P = 3 ; F=0 (invariant system)

From the above , it is clear that for any one-component system , the maximum number of
degrees of freedom is two. Therefore, such a system can be represented completely by a two-
dimensional

Diagram. The most convenient variable are the pressure and the temperature. The water system
is shown in Fig. 1 The diagram consists of :

1. Areas : AOB. AOC and BOC are the fields of existence of vapour, liquid and ice phase
respectively Within these single-phase areas, the system in bivariant , because to locate any point
in an area, temperature as well as pressure co-ordinates need to be know. This also following
from phase rule equation : F = 3 – P = 3 – 1 = 2 .

2. Boundary lines: separating the areas are lines OA, OB and OC, connecting the point at which
two phases can co-exist in equilibrium. In order to locate any point on a particular line, either
temperature or pressure co-ordinate should be known, because for fixed value of one co-ordinate,
the second is automatically fixed, In other words, any point on boundary lines has one degree of
freedom or is univariant. This also follows from phase rule equation : F = 3 – P = 3 – 2 = 1.

The curve OA, dividing the liquid from the vapour region, is called vapour pressure curve of
liquid water or vaporization curve. At any given temperature, there is one and only one pressure
at which water vapour is in equilibrium with liquid water. Similarly , at any given pressure, there
is one temperature at which water vapour is in equilibrium with liquid water. In other words, the
system is univariant. i.e,, has one degree of freedom. The curve OA has a natural upper limit at
+374oC. which is the critical-point, beyond which the phase merges into vapour phase and they
are no longer distinguishable from each other.

The curve OB is the sublimation curve of ice. It gives the conditions under which water vapour
is in equilibrium with solid ice. The point B has a natural limit at -273oC, beyond which the two
phases merge into each other.

The curve OC , which divies the solid –ice region from the liquid – water region, is called
melting curve, because it indicates how the melting temperature of ice or the freezing
tempereature of water varies with the pressure. The slope of OC towards the pressure axis shows
that the melting point of ice is decreased by increasing pressure.

3. Triple point: The three curves OA, OB, and OC meet at O, at which solid, liquid and
vapour are simultaneously at equilibrium. This point at 273.16 k is called a triple – point. Since
three phases co-exist, the system is invariant (F=3-3=0). In other words, there is no degree of
freedom at O, i.e., neither pressure nor temperature can be altered, even slightly, without causing
the disappearance of one of the phase.
4.Metastable curve OA’: As water does not always freeze at 0oC, so if the vessel containing
water and vapour is perfectly clean and free from dust, it is possible to super – cool water several
degrees below its freezing point 0. The dotted curve OA’, a continuation of vaporization curve
AO, represents the pressure curve of super cooled water. This curve represents a metastable
system. On slight disturbance, the super cooled water at once changes to solid ice. It may be
noted that metastable vapour pressure of supper cooledh water is higher than the vapour pressure
of ice.

Sulphur system

Sulphur can exists in four possible phases . These are

Two solid polymorphic phases

✓ Rhombic sulphur (Sr) (m.p. 114oC)

✓ Monoclinic sulphur (SM) (m.p. 120 oC)
• Sulphur liquid
• SulphurVapours

All the four phases can be represented by the only chemical individual sulphuritself.Hence this is
an one component system.Phase rule (F=C-P+2) becomes F=3-P .

Curves In Phase Diagram

Curve AB

Sublimation curve of rhombic sulphur, represented by AB curve. This curve AB gives the vapour
pressure of rhombic sulphur at different temperature. Here, the two phases in equilibrium are
(SR- SV) rhombic sulphur and its vapour, is monovarient.

Curve BC:

Sublimation curve of monoclinic sulphur, represented by BC curve. The curve BC is the

sublimation curve of monoclinic sulphur. It gives vapour pressure of monoclinic sulphur at
different temperatures. As the number of phase is 2, the system is monovarient.

Curve CD:
Vapour pressure curve of liquid sulphur, represented by CD curve. Here, the two phase (SL –
SV) equilibrium is also monovarient.

Curve CE:

Fusion curve of monoclinic sulphur, represented by CE curve. This gives the effect of pressure
on the melting point of monoclinic sulphur. The two – phase equilibrium (SM – SL) along the
curve CE is univarient. As the melting point of monoclinic sulphur is accompanied by a slight
increase of volume, it follows from Clausius – Clapeyron equation that the melting point will rise
slightly by the increase of pressure. The curve CE, therefore, slops slightly away from the
pressure axis. As the slop of this curve is much less than that of the curve BE. The two curves
meet at the point E.

Curve BE:

Transition curve of rhombic sulphur to monoclinic sulphur, represented by BE curve. The BE

curve gives the effect of pressure on the transition temperature of rhombic sulphur into
monoclinic sulphur. The equilibrium involved along the curve is (SR - SM). Both the phases are
solid.

Curve EG:

Fusion curve of rhombic sulphur, represented by EG curve. Here, the two phase (SR – SL)
equilibrium is also monovarient as the number of phases is 2.

For any curve,

phase rule becomes, F= 3-P = 3-2 = 1 (Monovarient).

Triple Points

Triple Points B:

Point B is the transition temperature (95.6oC) at which rhombic sulphur changes into monoclinic
sulphur. B is thus a triple point at which three phase, two solids and the vapour (SR – SM – SV)
coexist in equilibrium.
Triple Points C

The point C is the melting point (120oC) of monoclinic sulphur. This is another triple point at
which three phases, viz., monoclinic sulphur, liquid and vapour (SM – SL – SV) are in
equilibrium. This is a non – variant point.

Triple Points E

E is another triple point where three phases, viz., rhombic sulphur monoclinic sulphur and liquid
sulphur (SR – SM – SL) are in equilibrium and the system is non – variant. At E, the temperature
is 151oC and the pressure is 1290 atm.

At any Triple Point, phase rule becomes: F = 3-P = 3-3 = 0 (nonvarient)

Areas in Phase Diagram

Area ABEG (Rhombic Sulphur)

Area BCEB (Monoclinic Sulphur)

Area DCEG (Sulphur Liquid)

Area ABCD (SulphurVapours)

In an area, Phase Rule becomes: F = 3-P= 3-1 = 2 (bivariant). It means two variables must be
defined to describe any point in these areas.

Metastable Equilibrium

Metastable equilibria indicated by solid line BF, EF, CF are metastable curve thus, here F
represents melting point of the metastable rhombic sulphur. F, is the another triple point where
the three phases viz. SR – SL – SV, coexist in metastable equilibrium with liquid. It should be
noted that the variation of vapour pressure of all phases of sulphur with temperature always can
be studied with the help of Clausius – Clapeyron equation. The BE curve, slops away from the
pressure axis because, dp/dt have positive sign in Clausius – Clapeyron equation due to lesser
density (1.95 g/cm3) of monoclinic sulphur than rhombic sulphur (2.05 g/cm3) and VB is larger
than VA.
Bi – Cd Phase diagram
This is an example of a two component system which forms a simple eutectic. The various
phases that may be present are (I) solid bismuth (ii) solid cadmium (iii) solution of bismuth in
cadmium or vice versa in the molten stale (iv) vapour.
Curve AO. It represents the freezing point curve of bismuth to which different amounts of
cadmium are added. The point A represents the melting point, or freezing point of pure bismuth
(2710C). We find that the melting point of bismuth is lowered gradually by addition of cadmium
into it. The added cadmium goes into the solution and the separation of bismuth occurs till the
point is reach. At this point, no more cadmium goes into the solution as the solution becomes
saturated with cadmium and hence the melting point of bismuth does not fall further. Thus the
point O represents the composition with lowest melting (point 1440C). Point O represents the
eutectic point. Along the curve AO, two phases in equilibrium are solid bismuth and liquid melt
(neglecting the vapour phase). Therefore the system is univariant as shown below.

Curve BO. This is the freezing point curve of cadmium to which different amounts of bismuth
are added. The point B represent the melting point or freezing point of pure cadmium (32 1 V)
We find that melting point of cadmium decreases as more and more of bismuth is added into it
the added bismuth goes into the solution and the separation of solid cadmium takes place.
Thiscontinues till the point O is reached. At this point no more bismuth goes into the solution
and the solution is said to have become saturated with bismuth.
Hence, the melting point does not fall any longer.

Along the curve two Phases solid cadmium and liquid melt are in equilibrium
Therefore, F=C-P+1=2+1=1 i.e., the system is univariant.
it may be noted that the point -, on me curves AO and BO represent the initial freezing points
while the points on the line CD represent the final freezing points. It may also be noted that the
curve AO is not only freezing point curve of bismuth but may also be considered as solubility
curve of bismuth because the points on this curve represent the solubilities of bismuth in the
molten cadmium at various temperatures Similarly, the curve BO may also be considered as the
solubility curve of cadmium.

Eutectic Point O. This is the point where the two curves AO and BO meet. At this point solid
bismuth and solid cadmium are in equilibrium with the melt, i.e, three phases are present Degree
of freedom at the point O is zero.
F=C-P+1=2-3+1=0
The point O represents the lowest possible temperature (1440C) below a liquid phase cannot exist
and above which the liquid phase cannot be enriched in either component by treezing out the
other component. Such a liquid mixture of two components which has the lowest freezing point
compared to all other liquid mixtures is called emetic mixture. This mixture freezes out
completely at constant as solid phases in the same proportion in which they were present in the
liquid phase. The temperature corresponding point O is called I he cutectic temperature. This is
always lower than the melting points of the either component. In this system, eutectic mixture
(containing about 40% Cd and 60% Bi by mass) melts at 1440C, which is lower than the melting
point of bismuth (2710C of cadmium (3210C).
Iron-carbon phase diagram

Iron-carbon phase diagram describes the iron-carbon system of alloys containing up to 6.67%
of carbon, discloses the phases compositions and their transformations occurring with the alloys
during their cooling or heating.

Carbon content 6.67% corresponds to the fixed composition of the iron carbide Fe3C.

The diagram is presented in the picture:

The following phases are involved in the transformation, occurring with iron-carbon alloys:

• L - Liquid solution of carbon in iron;

 • δ-ferrite – Solid solution of carbon in iron.

Maximum concentration of carbon in δ-ferrite is 0.09% at 2719 ºF (1493ºC) – temperature of the

peritectic transformation.

The crystal structure of δ-ferrite is BCC (cubic body centered).

• Austenite – interstitial solid solution of carbon in γ-iron.

Austenite has FCC (cubic face centered) crystal structure, permitting high solubility of carbon –
up to 2.06% at 2097 ºF (1147 ºC).

Austenite does not exist below 1333 ºF (723ºC) and maximum carbon concentration at this
temperature is 0.83%.

• α-ferrite – solid solution of carbon in α-iron.

α-ferrite has BCC crystal structure and low solubility of carbon – up to 0.025% at 1333 ºF
(723ºC).

α-ferrite exists at room temperature.

• Cementite – iron carbide, intermetallic compound, having fixed composition Fe3C.

Cementite is a hard and brittle substance, influencing on the properties of steels and cast irons.

The following phase transformations occur with iron-carbon alloys:

Alloys, containing up to 0.51% of carbon, start solidification with formation of crystals of δ-

ferrite. Carbon content in δ-ferrite increases up to 0.09% in course solidification, and at 2719 ºF
(1493ºC) remaining liquid phase and δ-ferrite perform peritectic transformation, resulting in
formation of austenite.
Alloys, containing carbon more than 0.51%, but less than 2.06%, form primary austenite crystals
in the beginning of solidification and when the temperature reaches the curve ACM primary
cementite stars to form.

Iron-carbon alloys, containing up to 2.06% of carbon, are called steels.

Alloys, containing from 2.06 to 6.67% of carbon, experience eutectic transformation at 2097 ºF
(1147 ºC). The eutectic concentration of carbon is 4.3%.

In practice only hypoeutectic alloys are used. These alloys (carbon content from 2.06% to 4.3%)
are called cast irons. When temperature of an alloy from this range reaches 2097 ºF (1147 ºC), it
contains primary austenite crystals and some amount of the liquid phase. The latter decomposes
by eutectic mechanism to a fine mixture of austenite and cementite, called ledeburite.

All iron-carbon alloys (steels and cast irons) experience eutectoid transformation at 1333 ºF
(723ºC). The eutectoid concentration of carbon is 0.83%.

When the temperature of an alloy reaches 1333 ºF (733ºC), austenite transforms to pearlite (fine
ferrite-cementite structure, forming as a result of decomposition of austenite at slow cooling
conditions).

Critical temperatures

• Upper critical temperature (point)A3 is the temperature, below which ferrite starts to
form as a result of ejection from austenite in the hypoeutectoid alloys.

• Upper critical temperature (point)ACM is the temperature, below which cementite

starts to form as a result of ejection from austenite in the hypereutectoid alloys.

• Lower critical temperature (point) A1is the temperature of the austenite-to-pearlite

eutectoid transformation. Below this temperature austenite does not exist.

• Magnetic transformation temperature A2 is the temperature below which α-ferrite is

ferromagnetic.
Phase compositions of the iron-carbon alloys at room temperature

• Hypoeutectoid steels (carbon content from 0 to 0.83%) consist of primary (proeutectoid)

ferrite (according to the curve A3) and pearlite.

• Eutectoid steel (carbon content 0.83%) entirely consists of pearlite.

• Hypereutectoid steels (carbon content from 0.83 to 2.06%) consist of primary

(proeutectoid)cementite (according to the curve ACM) and pearlite.

• Cast irons (carbon content from 2.06% to 4.3%) consist of proeutectoid cementite C2
ejected from austenite according to the curve ACM , pearlite and transformed ledeburite
(ledeburite in which austenite transformed to pearlite).