UNIT 13 PHASE EQUILIBRIA

Structure
13.1 Introduction
Objectives
13.2 Definition of the Terms
13.3 Criteria for Equilibrium
13.4 Phase Rule
13.5 Stability of the Phases of a Pure Substance
13.6 Phase Transitions and Heat Capacity Anomalies
13.7 Application of Phase Rule to One Component Systems
13.8 Application of Phase Rule to Two Component Systems
13.9 Application of Phase Rule to Solid-Gas Equilibria
13.10 Summary
13.1 1 Terminal Questions
13.12 Answers

13.1 INTRODUCTION

The study of the effect of various parameters such as pressure, temperature or

composition on the physical state of chemical substances is the subject matter of
phase equilibria. In Unit 9, you have studied the criteria for equilibrium. In unit 14,
we shall consider the various aspects of chemical equilibria. In this unit, we shall
discuss physical equilibria. This means :
focussing our attention on the equilibria regarding physital state and
relating physical equilibria to various parameters such as pressure, temperature
and composition using phase rule.

We shall define the terms such as phase, component, degrees of freedom and phase
transition. We will deduce phase rule. One component system will be studied in the
light of phase rule. Among the two component systems, only solid-liquid and solid-
gas systems will be discussed. We have discussed liquid-liquid systems in Units 10 and
11 of this block. Applications of phase equilibria study will also be included in our
discussion.

Objectives
After studying this unit, you should be able to:
define the terms, phase, component and degrees of freedom,

calculate the number of phases, components and degrees of freedom in a system,

state and deduce the phase rule,

comment on the stability of the phases of subliming and non-subliming

substances,

explain the two types of phase transitions, and

apply the phase rule to the study'of one component and two componept systems.
 Phase Equilibria
13.2 DEFINITION OF THE TERMS

In 1876, Gibbs deduced a simple relationship among the number of phases in

equilibrium, the number of components and the number of intensive variables known
as degrees of freedom. Let us first define the terms phase, component and degrees of
freedom.

Phase
Phase (PJ is defined as a physically distinct and homogeneous part of the system that
is mechanically separable from other parts of the system. The definition as suggested
by Gibbs is that a phase is a state of matter that is uniform throughout, not only in
chemical composition but also in physical state.

Let us discuss some examples for counting the number of phases in a system.
A gas or a gaseous mixture is a single phase since there cannot be an interface
between one gas and another. Air, for example, is one phase system, although it is
a mixture of many gases.

A system of totally miscible liquids will exist in one phase only as far as the liquid
phase is concerned. But since each liquid has its vapour above, the total number
of phases in a system of miscible liquids is two, one for the liquid and the other
for vapour. These two phases are separated by the surface of the solution in the
liquid phase.

A system of two immiscible liquids has a total of three phases, two fot the
substances in the liquid state and another for the vapour phase containing
vapours of both the liquids.

A crystal is a single phase. Different solids having different crystal structures

constitute different phases, irrespective of the fact whether they have same
chemical composition or not. A mixture of graphite and diamond constitutes two
phases although both are only allotropic modifications of carbon.

Next we take up the definition of the word, component.

Components
The number of components ( C ) in a system is the smallest number of substances in
terms of which the composition of all the phases in the system can be described
separately. The number of components may be smaller. than the qumber of chemical
substances that are present in the system.

The definition is easy to apply when the species do not react, for then we simply count
their number. For example, phase equilibria containing ice, water and its vapour is a
one component system since the composition of each phase can be expressed in terms
of the component, H20, only. A mixture of ethanol and water is a two component
system.
If the species react chemically and are at equilibrium, we have t o take into account the
significance of the phrase' all the phases' in the above definition. Dissociation of
calcium carbonate in a closed vessel is a two component system although at first it
may appear to be a three component system, namely, CaCO3, CaO and C02.

You can see that the composition of any one species is related to the other two and
the dissociation of calcium carbonate is, therefore, a two component system.

In the case of solid ammonium chloride being heated in a closed vessel, there is an
equilibrium between the solid ammonium chloride and its vapour (which consists of
ammonia and hydrogen chloride molecules). Since both the phases have the formal
composition 'NH,Cl', it is a one component system. However, if ammonia or
hydrogen chloride is added to the system, the system has two components because
now the relative amounts of hydrogen chloride and ammonia are not the s h e .
 m ~ b R&
~ d u t ~ o.ad w If there arc 'S'substances (may be chemical compounds or ionic species) and 'R'
relations (which include equations representing chemical equilibria or charge
neutrality) among them, then the number of components ( C ) can be calculated using
the equation,

T o illustrate this, we can consider two examples. If you consider a solution of glucose
in water, there are two substances and hence's = 2. But there is n u relation between
them and so R = 0; therefore, C= 2 and this is a two component system.

Let us reexamine the equilibrium of solid ammonium chloride with its vapour. Here
S = 3 since there are three substances, NH4C1, NH3 and HCl. But R = 2 since these
are two relations as shown below :
(1) NH4Cl(s) +INH,(g) + HCl (g)
(2) Concentration of NHs = Concentration of HCl (and both of them are in
gaseous phase).

- -
Therefore C = S R = 3 2 = 1. This is a one component system. If extra HCl (g)
is added, then the second relation given above no more holds. That is, R = 1
although S = 3. This is therefore a two component system, as
C = S - R = 3 - 1=2.

Degrees of Freedom
The number of degrees of freedom (F) or variance of a system is the smallest number
of intensive variables such as pressure, temperature and composition which are to be
specified to describe the state of the system completely.
If F = 0, the system is invariant and this means none of the intensive variables
can be changed.
In case F = 1, the system is univariant and one of the intensive variables can be
changed. .
For a bivariant system, F is equal to 2, and two of the intensive variables can be
changed.

The phase rule relates the degrees of freedom to the number of phases and the
components. Before studying phase rule, let us recapitulate the criteria for
equilibrium.

SAQ 1
Calculate the number of phases in the following cases :
a) A closed beaker-partially filled with toluene and water;
b) A closed beaker partially filled with acetone and water.

......................................................................
......................................................................
.J

SAQ 2
Calculate the number of components in the following cases :
a) Dissociation of ammonia in a closed vessel;
b) Dissociation of ammonia in a closed vessel containing nitrogen.
 Phase Equilibria
13.3 CRITERIA FOR EQUILIBRIUM 1

In unit 9, we have discussed the conditions for equilibrium; the changes in Helmholtz
free energy function (at constant volume and temperature) and Gibbs free energy
function (at constant pressure and temperature) are zero for a system under
equilibrium.
That is, dA = 0 and d G = 0 . . .(13.2)
'
Apart from this, the chemical potential of a component must be the same in all the
phases at equilibrium. If there are three phases a,/3 and y for the component i, then
we can write

The conclusion given in Eq. 13.3 comes from the fact that a substance will tend t o
pass spontaneously from the phase where it has higher chemical potential to the phase
of lower chemical potential. The phase change of a substance would continue till the
chemical potentials become equal in all the phases (in which case the resulting system
is said to have attained equilibrium). For example, if at any temperature and pressure,
ice, water and its vapour are in equilibrium then,

Normally, a system can attain equilibrium conditions from either direction. For
example, the equilibrium between ice and water; at 273.15 K and 1.013 x lo5 Pa
(1 atm) pressure can be attained either by partial melting of ice or partial freezing of
water. This is a stable equilibrium. But yet another variety, called metastable
equilibrium, also exists which certainly does not represent a condition of stability. To
illustrate this, you can consider the case of cooling water slowly and carefully to a
temperature of 272 K (or even lower) without the appearance of ice. But starting from
ice at a lower temperature, and heating it, it is not possible td have water at 272 K.
Thus a metastable,equilibrium can be attained from one way only and not by both the
ways. A system under metastable equilibrium reverts to stable equilibrium if disturbed
even slightly by stirring or by the addition of a phase which is stable under the
experimental conditions. Thus water at 272 K on slight stirring or on the addition of a
small quantity of ice, begins to solidify and, as temperature rises to 273 K, the
conditions of stable equilibrium are established.

13.4 PHASE RULE

In a heterogeneous equilibrium, not influenced by gravitational or electrical or

magnetic forces, the number of degrees of freedom ( F ) of the system is defined by the
number of components ( C ) and the number of phases ( P ) according to the equation,

Once the values of C and P are known, F can be calculated.

Let us take up some examples to understand Eq. 13.4. In the vaporization equilibrium
of water (C = l), there are two phases (liquid and vapour) and hence, F = C P + 2-
-
=1 2 + 2 = 1. That is, specifying pressure or temperature fixes the other. This is all
the more understandable from the general statement that at a particular temperature,
vapour pressure of a liquid is constant. If all the three phases, ice, water and its
vapour, are t o be in equilibrium, then F = 1 - 3 + 2 = 0; that is, the system is
invariant. This means all the three phases of water are in equilibrium only at a fixed
temperature and pressure. Any effoit to change pressure or temperature results in the
disappearance of one of the phases.

Deduction of Phase Rule

Having stated the phase rule, we shall now deduce the same. Consider a system of C
componeiits existing in P phases. We want to calculate the number of independent
variables or degrees of freedom 'F' in order to define the state of the system
Solutions and Phase Rule completely. The value of F can be given by the following equation also:

F = (Total number of variables) - (number of relations) . . . (13.5)

First let'us calculate the total number of variables. T o define the composition of each
phase, it is necessary t o define the concentration of ( C - 1) constituents of that phase.
For P phases, the total number of concentration variables is P (C- 1) and these, along
with two variables, pressure and temperature, constitute the total number of variables.
Total number of variables = P (C- I) + 2 . . . (13.6)
Regarding the number of relations, we know that for one component existing in three
phases a,/3 and y, there are two relatibns,

Pa = P g and jig = ji,

The relation ji, = p, need not be specified but is understood. As two relations are
required for three phases of a component, (P- 1) relations are there for P phases of a
component. Hence, a total number of C ( P - 1) relations exist for P phases of C
components.
Number of relations = C (P- 1) . . . (13.7)
Using Eqs. 13.6 and 13.7 in Eq. 13.5,
F = P(C-1) + 2 - C(P-1)

Having derived phase rule, we will apply it to various systems. Its application can be
seen in the study of phase diagrams. A phase diagram speaks about the stability of
various phases at various temperatures, pressures and compositions.

SAQ 3
The four phases of sulphur are rhombic, monoclinic, liquid and vapour. Can all these
four phases exist in equilibrium at a particular temperature and pressure?

13.5 STABILITY OF THE PHASES OF A PURE

SUBSTANCE

The golden rule with reference to phase study is that the phase with the lowest
chemical potential is the stable phase. This rule can be used in making inferences from
the curves obtained by plotting chemical potential of a pure substance against
temperature for each phase. For most of the substances, ji against T plots for solid,
liquid and vapour phases are of the type shown in Fig. 13.1 (a).

At the melting poipt (TI), the solid curve (AB) and the liquid curve (CD) meet.
Similarly, at the boiling &int (Tz), the liquid curve (CD) and the vapour curve (EF)
meet.

Applying the golden rule given at the beginning of this section, we can infer that for
substances exhibiting behaviour of the type represented in Fig. 13.1 (a), solid phase is
the stable phase below the melting point. Between melting and boiling points, liquid
phase is stable and above boiling point, vapour phase is stable. Evidently this is
66 applicable for non-subliming substances.
 (8) (b)
Fik.13.1: p against Tplots at constant pressure: (a) for non-sublimlng substances; (b) lor sublimhg
substances; in both tbe plots, g, I and s refer to vapour, liquid and miid phw curvea.

In the case of subliming substances, p against T curves are of the type shown in
Fig. 13.1 (b). The sublimation temperature (T3), is the point of intersection between
the solid (AB) and the vapour (EF) curves. Hence, below T,, solid phase is stable and
above T3, the vapour phase is stable.
As per Clapeyron equation studied earlier, we are aware that a decrease in pressure
affects melting and boiling points t o different extent. If the pressure is reduced Clapeyron equation (Eq. 9.49 of
Unit 9) gives a quantitative
sufficiently, the boiling point of a liquid may even fall below the melting point of a account of the variation of
solid whereby the substance is said to sublime. Hence the type of p Vs Tcurves and equilibrium temperature with '

the type of stable phases would be decided by the experimental conditions of pressure pressun,
as well. This explains the fact that above 5.2 x lo5 Pa pressure, solid carbon dioxide
-
dp = AH- ...(9.49)
melts to give a liquid and, below 5.2 x 105 Pa pressure, solid carbon dioxide sublimes.
dT TAV
SAQ 4 This equation could be usal for
any phase equilibria.
Fig. 13.la or b gives p against T plot of a pure substance at constant pressure. For a
substance in a closed system,

What thermodynamic property of a substance is given by the slope of Fig. 13.la or b?

13.6 PHASE TRANSITIONS AND HEAT CAPACITY

ANOMALIES
The transition from one phase to another on the change of temperature or pressure or
both is generally referred to as phase transition. The phase transitions are of two
types. hose phase transitions requiring latent heat for the transition are called first
order phase transitions. Typical examples of this category are the conversion of ice to
water or water to steam or rhombic sulphur to monoclinic sulphur. During each of
these transitions, heat is absorbed but without any observable temperature change.
This means that in a first order phase transitipn, heat capacity, which is the ratio of
heat absorbed to temperature change, is infinitely large.
The other variety, second order phase transition, does not require any latent heat. As
a result, during the transition, heat capacity also changes through a finite amount
only. Typical examples for second order phase transitions are in the conducting -
superconducting transformations. During this transition, material loses electrical
Solutions and Phase RUI~ resistance. Lead, indium and titanium etc undergo transition of this type. In the
following sections, we discuss the application of the phase rule to one and two
component systems which are instances of first order phase transition.

13.7 APPLICATION OF PHASE RULE TO ONE

COMPONENT SYSTEMS
~ ~ p l i c a t i oofn phase rule (Eq. 13.8) to one co'mponent system leads to the general
expression,

Hence, a maximum of three phases can be present at a point in this case. It is called a
triple point and the system is invariant (F= 0).
For one component system, p against T plot is quite convenient. Then, dpld T gives
the slope of the plot. For each equilibrium, this is defined by Clapeyron equation
(Eq. 9.49). .If dpld T is negative, you can expect that as temperature increases
(d T = positive), pressure would decrease (dp = negative) and the curve is of the type
shown in Fig. 13.2(a). But if dp is positive, then an increase in temperature (d T =
dT
positive) causes an increase in pressure also (dp = positive), as shown in Fig. 13.2(b).

(1) (b)
Fig. 13.2: Types of p against T plots: (a) dp is negative; b) dp is positive.
dT dT

You can calculate dpld T using Clapeyron equation once A H and A V are known.
Normally to calculate the change in molar volume of a substance between two phases
a, and p, densities of the phases (do and ds) and the molar mass (M) of the substance
are used.

The p against T plots for various phases are made by measuring the equilibrium
temperatures corresponding to various pressures. Let us now study the phase diagram
of water.

Phase Diagram of Water

The phase diagram for water is given in Fig. 13.3. It would be interesting to apply
Clapeyron equation (Eq. 9.49) and phase rule (Eq; 13.8) to this phase equilibria.
Let us first apply Clapeyron equation to the following three equilibria:
i) Fusion (ice --,water)
ii) Vaporization (water
iii) Sublimation (ice -- 2vapour)
vapour)
For all the above transitions, A H is positive. Ice floats on water and this means,
density of water is more than that of ice and the molar volume of ice is more than that
of water. Again, when a small quantity of water is heated, steam comes out in large
- volume. Thus the molar volume of steam is more than that of liquid water. Similarly,
molar volume of steam is larger than that of ice. We use V to represent the molar
volume of a particular phase.
 FIE.13.3: Phase d hy m of water; s, I and g s t u ~ dfor solid, liquid and vapour p h m .

Using the above ideas, *values for the three equilibria can be calculated. Note
dT
that the temperatures are an positive.

Vaporization: *=
dT
-AH
- (+ve)
TA V - (+ve) (+ve) = (+ve)
AVfUion=Vwatcr- Via:. = negative
..
A vvaporizntion=Vvapour- V w . t s ~ ~ 0 ~ l t l \
dp
, Sublimation: -- A H .- (+ve) A V,ublimarion=
Vvspoir- Ycc=positive
d T - TA V - (+ve) (+ve) = (+ve)
The decrease of melting point of
ice with increase of pressure has
Eq. 13.1 1 shows a negative slope for the p against T plot for fusion, and the curve OB, an interesting application in
the fusion curve of ice, illustrates this. Eqs. 13.12 and 13.13 indicate positive slopes. winter sports. In ice-skating.for
The vaporization curve of water (OC) and the sublimation curve of ice (AO) bear example, there is a bladelike metal
frame attached to the shoes of the
testimony to this. In short, the'increase of pressure depresses the melting point of ice,
skater. This arrangement ensures
whereas the boiling point of water and sublimation temperature of ice are increased. minimum area of contact between
Also the sublimation curve (AO) has a steeper slope than the vaporization curve (OC) the skater and ice surface. Because
since near the point 0, of this, there is a high pressure
exerted on the ice surface on
which the skater stands and
moves. At this increased pressure,
Although ice exists in various crystalline modifications at high pressures, they have the melting point of ice is much
low. Hence ice melts and provides
not been shown in Fig. 13.3 for simplicity.
a lubricating layer of water which
speeds up the skater's movement.
Application. of Phase Rule t o Curves
-
Let us now apply phase rule, F = 3 P to these three curves. Since along each curve,
there are two phases in equilibrium, P = 2 and F = 3 - 2 =l. That is, the mention of
temperature or pressure automatically fixes the value of the other parameter when
two phases are in equilibrium. The curve O D is the vapour pressure curve of
metastable water. You may be interested to know that water, if cooled very carefully,
may exist in the liquid state even below freezing temperature. Water is then said to be
supercooled. It is in a metastable equilibrium with its vapour under these conditions.
The p against Trelationship of this metastable equilibrium is given by the dotted
curve OD. The curve OD is above OA signifying that the metastable system has a
higher vapour pressure than the stable one at the same temperature. Slight stirring or
addition of ice to water in metastable equilibrium results in the commencement of
solidification of water and return to stable equilibrium. The curve OC terminates at
C, the critical temperature, above which a substance exists only as a gas.
Solutior and Phase Rule Application of Phase Rule to Areas in the Diagram
Inside the area AOB, ice is the stable phase, whereas in'the regions BOC and AOC,
the stable phases are water and vapour, respectively. Application of rule
-
requires ( F = 3 I = 2) two degrees of freedom, namely, precise specification of
both temperature and pressure to specify a point.

Triple Point
The point 0 is called the triple point and all the three phases coexist at this pressure
and temperature (273.16 K and 610 Pa). This is an invariant point, since
-
F = 3 3 = 0 and the change of temperature o r pressure causes the disappearance of
one of the phases.
Let us utilise the phase diagram in understanding the changes taking place when ice at
atmospheric pressure (approximately 103 Pa) and below 273.15 K, as represented by
the point x, is heated. At 273.15 K, ice begins t o melt and this is indicated by the
pointy. The temperature remains constant till fusion is complete. Again the
temperature increases and at a point z (373.15 K), there is equilibrium between water
and vapour. Once again temperature remains constant till vaporization is complete.
After this, again the temperature increases, and at a point z', it is in the form of steam
completely. So far, we studied the phase diagram of water. Let us now study the
phase diagram of sulphur.
The Phase Diagram of Sulphur
The phase diagram of (sulphbr (Fig. 13.4) is interesting due t o the phase transition
curves of the two allotropic modifications, and the dresence of a metastable triple point.

Fig. 13.4: P h w -&gram of sulphur; S, S,IS,and S, refer to rhombic, monoclinic, Uquid and vapour
phucs of sulphur.
The stable form of sulphur at ordinary temperatures and under one atmosphere
pressure is rhombic sulphur. If rhombic sulphur is heated, it slowly transforms to
solid monoclin~csulphur at 368.6 K. Above 368.6 K, monoclinic sulphur is stable and
it melts at 392.2 K to give liquid sulphur which is stable upto its boiling point (717.8
K). The transformation of one crystalline modification)to another is often very s l o ~ ~ a n d ,
if rhombic sulphur is heated quickly to 387.2 K, it melts.- he curve BO represents the
metastable equilibrium, between rhombic sulphur.and sulphur vapour. !ikewise, if
liquid sulphur is allowed to cool quickly, monoclinic sulphur may not
separate out at C, and CO represents metastable equilibrium between liquid and r a w Equlllki.
vapour forms of sulphur. The curve OE is the fusion curve of rhombic sulphur and it
asain represents metastable equilibrium.
The curves AB and BC are the sublimation curves of rhombic and monoclinic forms.
BE represents the transition from rhombic to monoclinic form. CE and EF are the
fusion curves of monoclinic and rhombic forms. CD is the vapour pressure curve of
liquid sulphur.
Application of Clapeyron equation to various equilibria mentioned above indicates
that for all these changes (from left to right in evely case in Fig. 13.4), the change in
enthalpy and molar volume are positive although the magnitudes are different. Hence
the slopesdp(as given b yA-H4 are positive fot all the curves. This indicates
dT TA V
that for all the transitions (from left to right in Fig. 13.4). the equilibrium
temperatures increase with pressute. Application of phase rule to these curves gives
-
F = 3 P = 3- 2 = 1, which means that specification of temperature or pressure is
sufficient to define the equilibrium along each of the curves.
In the regions ABE, BEC, ECD and below ABCD, only one phase is stable and hence
-
F = 3 1 = 2. That is, within the above regions, both pressure and temperature are
to be specified to define any point'.
There are four triple points corresponding to three stable equilibria and one
metastable equilibria. The phases under equilibrium in each of these triple points is
given in Table 13.1. In this table, B, C, E and 0 stand for the points specified in Fig.
13.4. Also S,, S, SI and S , stand for rhombic, monoclinic, liquid and vapour forms of
sulphur.
Table 13.1: Trlple polnb In the Phw D i . m of Sulphur

A1 Phaaa under qulllbrlum

B S,. S m ~d SR

C , S I and S,
S
E S,, S, and S I
0 S,, S,and S, (metastable)

The application of p h k e rule to these triple points indicates that the system is
invariant (P= 3 and F = 3 - 3 = 0). In this section, we applied the phase rule to one
component systems. In the next section, we shall take up the study of two component
systems.

SAQ 5
The phase diagram of carbon dioxide is given in Fig. 13.5.

T/K
FIB. 13.5: Phuc d(.lt.m d carbon dloxk, ;ql and 8 rt.nd for mlld, Uquid an& ".pour ph-.
Solutions and Phase Rule : Using this phase diagram,. answer the following:
a) suggest a name for the curve YO.
b) identify the triple point.
c) carbon dioxide gas cylinders are filled at 6.7 x lo6 P a and 298 K. What are the
phases in equilibrium inside the cylinder?

13.8 APPLICATION OF PHASE RULE TO TWO

COMPONENT SYSTEMS

Two component systems are also known as binary systems. When a single phase is
present in a two component system, phase rule states that F = 2 - 1 + 2 = 3. This
requires three variables in order to specify a system. We must have a phase diagram in
three coordinate axes to understand such a system. Since it is quite difficult to
understand such a diagram, it is simplified as a two dimensional plot, keeping one of
the three variables constant. In this case, each type of equilibria is studied separately.
Thus the usual practice is to study liquid-gas, liquid-liquid, solid-liquid and solid-gas
equilibria individually. We concentrate our attentionon the solid-liquid equilibria in
this section. The solid-gas equilibria will be studied in Section 13.9.

Phase Rule for the Condensed Systems

Solid-liquid equilibria are characterised generally by the absence of gas phase and are
not much affected by small changes in pressure. Systems in which the gas phase is
absent are called condensed systems. Measurements on solid-liquid equilibria in
condensed systems are usually carried out at atmospheric pressure. Because of the
relative insensitivity of such systems to small variations in pressure, the pressure may
be considered constant. For such a system, the phase rule takes the form,

Eq. 13.14 is known as phase rule for condensed systems. For two component systems,
Eq. 13.14 becomes.

The solid-liquid equilibria are best represented using temperature-composition

diagram. Let us now discuss a method suitable for studying solid-liquid equilibria.

Thermal Analysis
Thermal analysis is a convenient method to study solid-liquid equilibria. In this
method, solids of different compositions are separately heated above their melting
points. The resulting liquids are cooled slowly and the cooling curves are constructed
by plotting temperature against time. A break in the cooling curve indicates the
crystallisation of a solid. But a horizontal portion ('halt') in the curve represents the
separation of a second solid and, the temperature remaills constant indicating the
presence of three phases-two solids and a liquid. At this point, F = 0. Once
solidification is complete, temperature falls gradually giving a smooth curve again. A
typical cooling curve for two component systems is shown in Fig. 13.6. The portion
ab represents the gradual cooling of a liquid. The portion bc, with a different slope
and a break at b shows the crystallisation of a solid phase. The horizontal portion cd
represents the separation of a second solid phase of certain composition and, the
temperature halt continues till d when the last drop of the liquid i~ rolidified. 'The
portion de represents the cooling of the solid mixture.
Fig. 13.6 :Cooling cqve for two component rystenu: b denotes tbe break .ad cd the halt, T and I stand for
temperature and time, reapectlvely.

Using the temperature corresponding to the breaks and the halts in the cooling curves,
the solid-liquid phase diagrams are constructed. We first take up the study of simple
eutectic systems.
Simple Eutectic Systems
Binary systems illustrating this type are completely miscible in the liquid phase but are
immiscible in the solid phase. Such systems have a phase diagram as represented in
Fig. 13.7. Bismuth-cadmium system illustrates this type.

From Bi-Cd phase equilibria

study, we understand that for
binary systems of this type,
Flg.13.1 Bl-Cd eutectlc ryrtsm: I stan& for mdt and cu a n d r for e u t d c mlxture; T and w l % refer to addition of one component to
tempmture and welgbt percentage, respectively. another brings down the melting
point. This has a practical
The melting points and Bi and Cd are represented by the points J and L. The curve J P application ip the metallurgy of
represents the concentrations ofsolutions saturated with Bi and the curve LP, the aluminium, which is obtained by
concentrations of solutions saturated with Cd at differant temperatures. Alternatively, the electrolysis of fused bauxite.
the curve J P represents the freezing points of solutions which yield solid Bi on Bauxite has a high melting point
and the addition of cryolite
cooling, whereas, the curve LP, gives the freezing points of solutions yielding solid (NaaAlFe) brings down the
Cd. Above JPL, there is only liquid phase, called melt, which is a solution of both melt~ngpo~ntof baux~te.The
the metals. Hence, representing any point in this region where only one phase exists, recognition of this aspect of phasf
both composition and temperature are to be specified. Along J P afid LP, two phases equilibria is one of the important
facton which have contributed to
(Bi and melt or Cd and melt) exist and hence F= 3-2 = 1. T o define any point along
the large scale production of
the curves JP and LP, either temperature or composition need be mentioned. aluminium and its resultant price
decrease by about i0.000 times
At P (413.2 K and 40% Cd), both the curves meet and three phases-solid Bi, solid
during the last hundred years.
Y
Cdand their quid solution-exist. H e n a P is an invariant ( F = 3-3 = 0) point.
Such a point is known as eutectic point. It is the lowest melting point for any solid
Solutions m d Phase Rule

Flg. 13.8: Cooling curves for BI-Cd system.

mixture of Bi and Cd. The word 'eutectic' in Greek means easily melted. At
temperatures below 413.2 K, the system is completely a solld. Although eutectic
mixture contains both metals in a definite ratio, it is not a compound, as under a
microscope, the presence of two different crystals can be seen.
The significance of the phase digaram can be understood by considering the cooling
curve pattern of several mixtures of Bi and Cd (Fig. 13.8). On cooling a 20% solution
of Cd (curve I) in Bi, the temperature drops gradually and on rcaching the point A.
solid Bi begins to separate. During crystallisation, heat equivalent to the enthalpy of
fusion of bismuth, is released. Because of this, there is a break in the curve at the
point A. Along AA', more and more solid Bi separates and the remaining liquid melt
becomes richer in Cd. At A', the eutectic mixture separates, and due to the presence
of three phases, temperature remains constant. This corresponds to the horizontal
portion of the curve. Once the liquid is completely solidified into the eutectic mixture,
cooling proceeds smoothly again. The curve I1 represents a cooling of 30% Cd melt.
The only difference between I and I1 is that solid Bi appears at a still lower
temperature B. Again, at B', there is a halt signifying the separation of the eutectic
mixture. If a melt containing 40% Cd is cooled (curve III), there is no break in the
curve; but a halt is seen at 413.2 K indicating the crystallisation of the eutcctic
mixture. Curve 1V represents cooling of 80% Cd solution and the cooling curve
experiences a break at C representing the separation of solid Cd, while the remaining
melt approaches the eutectic composition. At C', the eutectic mixture solidifies which
is again marked by a halt in the cooling curve.Furve V is a cooling curve for 90% Cd
solution, having a break at D and a halt at D'. The curves VI and VII represent the
cooling curves of pure bismuth and cadmium liquids, respectively. Both the curves VI
and VII correspond to one component systems and hence there is a halt in these
curves where solid bismuth (at J) or solid cadmium (at L) begins to separate. From the
cooling curves I to VII, the temperatures at J , A, B, P, L, D and C, corresponding to
the different compositions of bismuth and cadmium, are noted and used in the plot of
temperature against composition given in Fig. 13.7.
Apart from Bi-Cd system, there are many other examples such as Al-Sn, Sn-Pb,
Ag-Pb, etc., which form eutectic mixtures. Eutectic systems have many practical
applications. .
Solder which is used for joining electrical components is an eutectic mixture
consisting of 67% by weight tin and 33% by weight lead.
74 Pattinson's process of extracting silver from a lead-silver alloy containing even a
 low percentage of silver also makes use of the eutectic formation principle. A Phase Equilibria
solid lead-silver alloy containing a low percentage (say, 1%) of silver is heated
above its melting point and slowly cooled. When the temperature reaches 600 K
lead separates out as solid which can be removed from the melt. The melt
continuously becomes richer in silver. At 576 K, eutectic mixture containing 2.6%
silver solidifies from which silver can be extracted.
The eutectics formed by salt-water system are used as freezing mixtures. We
shall shortly study this in detail.
It is worth pointing out that the formation of compounds and of solid solutions are
also known in the solid-liquid equilibria of two component systems. But the studies
are quite similar to eutectic systems, although indiv'idual phase diagrams differ
considerably.
Salt- Water System
Salt-water system can belong to one of the following types:
i) Eutectic type (Example: KI-H20)
ii) Compound formation (Example: Na2S04-Hz0)
As an illustration of salt-water system, we discuss KI-H20 system for which the
phase diagram is given in Fig. 13.9. The curve AB is the fusion curve of ice. The
addition of K1 to ice depresses the melting point of ice. BC is the solubility curve of
KI. You can see that the curve BC does not extend upto the melting point of pure KI.
since it is quite above the critical temperature of water. Both the curves meet at B, the
eutectic point (250.2 K) of this system. It is the lowest temperature that can be
attained by the addition of K1 to ice.

Fig. 13.9 : KI-Hz0 system:

I) Solution;
11) Solutlon + Ice;
111) Solution + K1;
IV) KI + Ice.

One of the applications of salt-water system is in the preparation of freezing mixtures.

When salt is added t o ice under adiabatic conditions (i.e., to ice in vacuum flask), ice
melts. In doing so, it absorbs heat from the rest of the mixture. The temperature falls
and, if enough salt is added, cooling continues down t o the eutectic temperature.
In Table 13.2, eutectic temperature and eutectic composition of various ice-salt
systems are given.
Table 13.2: Eutectic temperature of Freezlng Mlxturea

Name of the system % Salt In the eutrctlc (Eutrctlc temperaturr)/K

~ . a d W u c ~ Another
~ application of salt-ice equilibrium is in the clearance of ice blocked roads in
the cold countries. If for example, the temperature in that region is above 252 K, the
spreading of a large quantity of cornmop salt (more than corresponding to eutectic
composition) on the road covered with ice helps melting the ice. The heat for melting
the ice is readily available from the surrounding atmosphere of the icecovered road.
Hence, melting takes place without a decrease in temperature.

SAQ 6
Silver and lead form an eutectic with 2.6% by weight silver. The eutectic temperature
is 576 K. The melting points of lead and silver are 600 K and 1243 K. Draw the phase
diagram of Pb-Ag system on a rough scale and mark the stable phases in various
regions. Explain the changes that would occur if melt containing 60% silver is cooled.

13.9 APPLICATION OF PHASE RULE TO SOLID-GAS

EQUILIBRIA
A simple example'of gas-solid equilibrium which involves compound formation is the
reaction between solid calcium oxide and gaseous carbon dioiide yielding calcium
carbonate.

-
The application of phase rule to this equilibrium gives F = 2 3 + 2 = 1; this means,
fixation of temperature fixes equilibrium pressure of carbon .dioxide. In Unit 14 of
Block IV of this course,.we will arrive at the conclusion that at constant temperature,
the equilibrium pressure of carbon dioxide, also known as dissociation pressure, is
constant for the above system.

It is interesting to study using Fig. 13.10 as to what happens when carbon dioxide is
steadily admitted into a closed space containing calcium oxide at constant
temperature. No reaction will occur until the pressure of the gas has risen to the
dissociation pressure value at that temperature. At this pressure, the combination
takes place and the pressure remains'constant until all the calcium oxide has been
converted to calcium carbonate. After this, pressure will rise again.

Fig. 13.10: CaC0,-CaO-COl mystem; d.p. rt.adr for dlrociation prrmure; pco, for tbe prmun of
C01 and c the composition.

Similarly, starting from calcium carbonate kept in presence of carbon dioxide at a

high pressure, let us decrease the pressure gradually. Nq dissociation takes place till
the pressure reaches its dissociation pressure value at the temperature. Once this value
is reached, the dissociation of calcium carbonate starts and the pressure remains
constant. After complete dissociation of calcium carbonate to calcium oxide, pressure
of carbon dioxide can be decreased again.
 Phase Equilibria
13.10 SUMMARY
In this unit, we have explained the terms phase, component and degree of freedom
and derived the phase rule. The phase rule has then been applied to phase equilibria
of one and two component systems. This unit helps us in understanding the influence
of parameters like pressure, temperature and composition on the phase equilibria of
substances. Some of the practical applications of such studies have also been
sxplained.

13.11 TERMINAL QUESTIONS

1) Examine the following statements and write 'true' for the correct ones and 'false'
for the wrong ones :
a) The number of phases of a mixture of three gases enclosed in a container is 3.
b) The number of phases of a mixture of ethyl alcohol and water is 2.
c) The equilibrium point among ice, water and vapour is called eutectic point.
d) The number of phases present in a vessel half filled with water is 1.
e) The melting point of ice decreases with increasing pressure.
2) Fill in the blanks :
a) The equilibrium between liquid water and vapour below 273 K is an example
for a ..
...................................................................
b) In a one component system, maximum number of phases that can coexist in a
true equilibrium is..................................................
c) Boiling point of water........................ with increase in pressure.
..........
d) A phase transition requiring latent heal is called phase transition.
....
e) A melt of eutectic composition when cooled shows only a in the cooling
curve.
3) Suggest some applications of eutectic system studies.
4) Rice, dal and vegetables are cooked faster inside a prekure cooker than in an
open vessel. Explain the reabon.
5) If solid ammonium chloride is allowed to dissociate in a vessel already containing
some ammonia, calculate the value of F.
6) Using Fig. 13.9, identify the solids that will come out in sequence if, the following
solutions are cooled from 298 K to 250.2 K :
a) 20% KI solution
b) 60% KI solution
c) 52% KI solution.
7) Calculate the slope *
dT
of the fusion curve of ice near its melting point, if the
enthalpy of fusion ice 1s 6.003 x 10' J mol-', the densities of water and ice are
999.8 and 916.8 kg m-' and the normal melting point of ice is 273.15 K.
8) Calculate the number of components in the following system :
a) Sugar in water
b) Potassium chloride in water.

13.12 ANSWERS

1) a) 3 (two due to toluene and water liquids which are immiscible and, one due to
their vapoun) ,
b) 2 (since acetone and water are miscible).
Solutions and Phase Rule 3) The four phases of sulphur cannot coexist since then F = - 1.
4) ($ )p = -5 for a closed system, hence the slope o f w . 13.1. or b gives the
partial molar entropy of a substance with the sign inverted.
5) a) Sublimation curve
b) The point 0 corresponding to pressure 5.2 x 10' Pa and temperature 217 K.
c) Liquid and vapour.

Fig. 13.1 1 :Ag-Pb System; Istands for melt and cu stands for eutectic.

When a melt containing 60% Ag is cooled, first the temperature decreases gradually.
Then solid Ag starts forming and there is a break in the cooling rate. Once the
remaining melt reaches 2.6% Ag composition, the whole mass begins to solidify and
the temperature is constant till the solidification is complete. After that, the
temperature decreases again.

Terminal Questions
1) a) False b) True
c) False d) False
e) True.
2) a) metastable equilibrium
b) 3
c) increases
d) first order
e) halt.
3) SeeSec. 13.8.
4) Increase of pressure inside the closed cooker causes an increase in the boiling
point of water. Due to higher temperature thus obtained, the cooking is faster
inside the pressure cooker. In an open vessel, the boiling point of water is 373 K
and the temperature is not enough for fast cooking.
5) ' C=2, P = 2 and F = 2.
6) a) First ice separates and finally a mixture of ice and KI solidifies
b) First KI separates and finally a mixture of ice and KI solidifies
C) A mixture of KI and ice separates together at 250.2 K.
7) Using Eq. 13.10 and Eq. 9.49 we get.

-d-p- -- AH - AH
dT TAV
TM+
dwater
- - )
dice
 Where AH = 6.003 x 10' J mol-' Phase Equilibria
T = 273.15 K
M = 0.018 kg mol-'
dm,=,= 999.8 kg m-'
dh = 916.8 kg m-3
-
Slope dp/ d T = 1.34 x 10' Pa K-'
8) a) UsingEq. 1 3 . 1 , ~ = 2 ; s i n c e ~ = 2 a n d R = O
b) The solution contains three species, water molecules, K' ions and C1-ions.
Hence S = 3. But [K+] = [Cl].
R=landC=3-1=2.