Phase Equilibria

Phase. A phase is defined as any homogeneous and physically distinct part of a system, which
is bounded by .a surface and is mechanically separable from other parts of the system.

Examples of various types of phases are

(i) A gas mixture constitutes a single phase since gases are completely miscible.
(ii) Immiscible liquids constitute different phases. Thus, carbon tetrachloride (CC14)
and water (H20), which do not mix with each other, form two phases,
(iii) Completely miscible liquids such as water and alcohol and benzene and chloroform
constitute one-phase systems.
(iv) Consider the decomposition of calcium carbonate into C02 and CaO.

Here there are two solid ·phases and one gaseous phase. So it is a three-phase system.

Components. The number of component of a system at equilibrium is defined as the smallest

number of independently variable constituents by means of which the composition of each
phase can be expressed either directly or in terms of chemical equations.

For examples:

(i) Water exists in three phases, viz.

However, the composition of each phase can be expressed In terms of H20. Hence,
it is a one-component system.
(ii) Sulphur exists in four phases, viz., rhombic sulphur, monoclinic sulphur, liquid and
vapour. However, since the composition of each phase can be expressed in terms of
sulphur only, it is a one component system.
(iii) Consider an aqueous sucrose solution. The composition of the solution phase can
be expressed by specifying the amounts of sugar and water. Hence, it is a two
component" system.

Q-1. How to calculate the number of components for chemically reactive system?

In a chemically reactive system, the number of components is given by

C=N–E
Where N is the number of chemical species and E is the number of independent equations
relating the concentrations of the N species. Each independent chemical equilibrium involving
the constituents counts as one equation. The condition that a solution be electrically neutral
also counts as one equation if ions are considered as constituents.

Example l. Explain why KCI-NaCI-H20 system should.be regarded as a 3-component system

whereas KCI-NaBr-H20 system should be regarded as a 4-component system.

We know that the number of components is given by C = N - E where N is the number of

species (constituents) and E is the number of independent equations relating their
concentrations. For the KCl - NaCl - H20 system, N=3 (viz., KCl, NaCl, H20). Since then: is no
independent equation relating their concentrations, E=0. Hence,

C=3–0=3

For the KCl~NaBr-H20 system,

; Here number of chemical equation, E = 1 and number of

chemical species, N = 5 (viz., KCI, NaBr, NaCl, KBr, H20)

C=N–E=5–1=4

Degree of Freedom (F): The degree of freedom of a system is defined as the number of
independent variables such as temperature, pressure and concentration (or composition) which
must be specified in order to define the system completely. Thus, the state of a pure gas can be
specified by two variables P and T or P and V, since the third variable can be calculated from
the equation of state (i.e., PV = nRT). This means that a pure gas has two degrees of freedom.
Gibbs Phase Rule

The celebrated phase rule, enunciated by J. Willard Gibbs, states that if the equilibrium in a
heterogeneous system is not affected by gravity or by electrical and magnetic forces, the
number ·of degrees of freedom, F, of the system is related to the number of components, C and
the number of phases, P, existing at equilibrium with one another by the equation

F=C–P+2

If F = 0, the system is called invariant; If F = l, Univariant (Monovariant), if F = 2, bivariant

and if F = 3, trivariant, etc.
 1. The greater the number of phases, the smaller is the number of degrees of freedom,
such as T, P and composition, required to specify the system completely.
2. For a given number of components, the number of phases is maximum when the number
of degrees of freedom is zero. Thus, for a one-component system, the maximum number
of phases is three and for-a two-component-system, the maximum number of phases is
four.

Example: Determine the number· of degrees of freedom in each of the following systems.
Suggest the variables that could correspond to these degrees of freedom. ·

(a) Liquid water and water vapour in equililJrium.

(b) Liquid water and water vapour in equilibrium at a pressure of 1 atm.

Solution: From the Gibbs Phase rule, F = C - P + 2

(a) ln this case, C = l, Hence. F = 1 - 2 + 2 = 1.

That is, only one variable T or P need to be specified.

(b) Since the pressure is held constant, the degree of freedom reduces by one. Hence, the phase
rule equation becomes F = C – P + I.

In this case, C = l and P = 2.

F=1-2+1=0

The system under the given 'conditions is thus invariant.

The Phase Diagram

What is Phase Diagram?

The Phase diagram shows at a glance the properties of the substance; melting point, boiling
point, transition points, triple points. Every point on the phase diagram represents a state of the
system, since it describes values of T and P.

From figure 1. At temperature Tm, the solid is stable; at the point between Tm and Tb, the liquid
is stable, while above Tb the gas is stable. (Tm = melting temperature and Tb = boiling
temperature)

The Clapeyron Equation

 ONE-COMPONENT SYSTEMS

Since the minimum number of phases in any system is 1, it is evident that

F=C–P+2=1–1+ 2=2

The one-component system is, thus, Bivariant. It can be completely defined by specifying two
variables. The two variables are temperature and pressure. The composition or concentration
remains invariably 100 per cent because there is only one component.

If a one-component system has two phases in contact with each other,

F=C–P+2=1–2+2=1

The system is then said to be monovariant. It can be completely defined by specifying only one
variable, viz., either temperature or pressure. If temperature is · fixed, pressure of the system
is fixed automatically and vice-versa. Thus, the system consisting of a liquid in contact with its
vapour, e.g.

H2O (l) ⇌ H2O (g)

Is monovariant. If temperature is fixed, the pressure of the vapour is fixed automatically. This
is because at each temperature, there can be one and only one vapour pressure.

Phase Diagram of Water System

Water can exist in three phases, namely, solid, liquid and vapour. Hence, there can be three
forms of equilibria, viz.,

l. Liquid ⇌ Vapour

2. Solid ⇌ Vapour

3. Solid ⇌ Liquid.

Each equilibrium involves two phases. The phase diagram for the water system is shown in
Fig. 2.

The curve OA represents the equilibrium between liquid water and vapour at different
temperature. It is called the vapour pressure curve of water as it gives the vapour pressure of
water at different temperatures. It can be seen that, for any given temperature, there exists one
and only one vapour pressure. Similarly, for each vapour pressure, only one temperature can
be maintained. Thus, the degree of freedom of the system is one, i.e., the system is Univariant:

F=C -P+2=1–2+2=1

At 100°C, the vapour pressure of water equals the pressure of the atmosphere (I atm = 760 ~
Hg). This is, therefore, the boiling point of water. The curve OA extends as far as the 'critical
temperature of water (374 °C) since above this temperature liquid water cannot exist.

The variation of vapour pressure with temperature is quantitatively given by Clapeyron

equation or Clapeyron-Clausius equation, viz.,

     

= or the integrated form of this equation is:   =     
(  )    

The curve OB represents the equilibrium between ice and vapour. It is called the vapour
pressure curve of ice or sublimation curve of ice. Its lower end B extends to absolute zero.
Again, as can be seen, for each temperature, there can be one and only one pressure and
similarly for each pressure, one and only one temperature can be maintained. In other words,
the degree of freedom is I.

The variation of vapour pressure of ice with temperature, is quantitatively given by Clapeyron
or Clapeyron-Clausius equation, viz.,

     

= or   =  
 (  )    
Since, along OA, the two phases are liquid and vapour and along OB, the two phases are solid
and vapour, at the point O, where the two curves meet, three phases, namely, solid, liquid and
vapour will coexist. Such a point is known as the triple point; ·Tue temperature and pressure
at the triple point of water are 0·0075oC and 4·58 mm of Hg, respectively. According to the
phase .rule, O is an invariant point :

F=C–P+2=l–3+2=0

The curve OC represents the equilibrium between ice and water liquid. It is called the fusion
curve of ice as it indicates the temperatures and pressures at which the solid (ice) and liquid
(water) can coexist in equilibrium. In other words, this curve shows the effect of pressure on
the melting point of ice. As can be seen, the line OC is inclined towards the pressure axis,
which indicates that the melting point of ice is lowered by increase of pressure. This follows
from Clapeyron equation, viz.

     

= or   =  
 (  )    

Since density of ice is less than that of water, Vs is greater than Vl. In other words, the
expression on the right hand side of the above equation is negative. Hence, dT/dP should also
have a negative sign. This means that the increase of pressure must lower and decrease of
pressure must raise the freezing point of water. It can be easily shown with the help of the
above equation that freezing point of water is lowered by 0·0075°C by I atm increase in
pressure. Thus, while the freezing point of water at a pressure of 4·58 mm is +0·0075°C, at a
higher pressure of 760 mm (i.e., l atm) it is reduced to 0°C.

Along the curve OC, there are two phases, namely, ice and water. Therefore, according to the
Phase rule, the system should be univariant, i.e., the degree of freedom should be one. This is
seen to be actually the case as, for any given pressure, melting point will ‘have one definite
value (i. e., solid and liquid phases will coexist in equilibrium at one particular temperature
only). The ·curve OC must meet the other two curves at the triple point O.

Metastable equilibrium. Sometimes it is possible with due care to cool water (or, as a matter
of fact, any liquid) below its freezing temperature without the separation of ice. The water is
then said “to be supercoiled' and can be kept as such almost indefinitely if the presence of ice
or any other solid phase is ·carefully avoided. The vapour pressure curve of liquid water AO
can, therefore, continue below the point O; as shown by the dotted curve OA'. The (Liquid ⇌
vapour) system along,the curve OA' is said to be in metastable equilibrium because as soon as
a small particle of ice is brought in contact with the supercooled liquid, the entire liquid
solidifies. It will be seen from the phase diagram that the curve OA' lies above the curve OB.
Thus, the metastable system has a higher vapour pressure than the stable one at the same
temperature.

Triple Point. It will be interesting to note the effect of heating and applying pressure on the
system when all the three phases coexist as at the triple point' O. The effect of heat will be
simply to cause more and more of the ice to melt but there will be no rise in temperature or
pressure until the whole of the ice has completely changed into liquid". When this happens, the
system has only two phases (liquid and vapour). The system changes from non-variant to
univariant. Therefore, further addition of heat will cause a rise of temperature. The equilibrium
will shift along the 'curve OA.

Now, suppose, pressure is applied to the system at the triple point. There can be no change in
pressure or temperature as long as all the three phases are present. The only effect of applying
pressure will be to cause condensation of vapour to liquid or solid phase. Ultimately, the vapour
phase will disappear, only two phases, solid and liquid, will stay, and further application of
pressure will cause increase of pressure with change of temperature along the curve OC.

SULPHUR SYSTEM

Sulphur exists in two crystalline forms, rhombic and monoclinic, with 95·6°C as the transition
temperature at one atm pressure at which they can be transformed into one another. Below
95·6°C, rhombic is the stable form while above it, monoclinic is the stable variety. At 95·6°C,
both forms are in equilibrium with each other. Each point has its own characteristic melting
point. Thus, under a pressure of one atm, melting point of rhombic sulphµr (SR) is l14oC while
that of monoclinic sulphur (SM) is 120°C. The liquid form of sulphur (SL) undergoes notable
changes in colour and viscosity when heated .and ultimately boils at 444·7°C. Thus, sulphur
can exist in four possible phases, two solids (SR and SM), one liquid (SL) and one vapour (Sv)
phase. However, not all the four phases can coexist at the same time since the number of phases
coexisting in a one-component system cannot exceed three, as already shown.
 Fig 3. The Phase diagram for the Sulphur System.

The phase diagram of sulphur system is represented in .Fig; 3.

The curve AO is the sublimation curve of rhombic sulphur and gives the vapour pressure of
rhombic sulphur at different temperatures. The two phases in equilibrium are rhombic sulphur
and the vapour. The equilibrium (SR ⇌ SV) is monovariant. Therefore, at ·one temperature,
there can be one vapour pressure only.

The point O is the transition temperature (95·6°C) at which rhombic sulphur changes into
monoclinic sulphur. O is thus a triple point at which three phases, two solids and the vapour
(SR ⇌ SM ⇌ SV) coexist in equilibrium. This is a non-variant point.

The curve OB is the sublimation curve of monoclinic sulphur. It gives vapour pressure of
monoclinic sulphur at different temperatures. As the number of phases is 2, the system is
monovariant.

The Clapeyron-Clausius equation can be used to study quantitatively the variation of vapour
pressure of solid sulphur (SR or SM) with temperature.
The point B is the melting point (120°C) of monoclinic sulphur. This is another triple point at
which three phases, viz., sulphur monoclinic, liquid and vapour (SM ⇌ SL ⇌ SV) are in
equilibrium. This is a non-variant point.

The curve BE is the vapour pressure curve for liquid sulphur. The two-phase equilibrium
(SL⇌SV) is monovariant.

The variation of vapour-pressure of liquid sulphur with temperature can be studied, again, with
the help of the Clapeyron-Clausius equation. . .

The curve OC is the transition curve, which 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. The system is monovariant. Since transformation
of rhombic into monoclinic sulphur is accompanied by increase of volume, the increase of
pressure causes a rise in the transition temperature. This can be predicted with the help of
Clapeyron equation which, when applied to SR ⇌ SM equilibrium, may be put as

     


= ( ! )
or   = 
 
  

Where ∆Htrs is the molar heat of transition. Since density of monoclinic sulphur (1 ·95 g cm-3)
is less than that of rhombic sulphur (2·05 g cm-3), VB is larger than VA. The right hand side of
the above equation is, therefore, positive. Hence, dP/dT should also have a positive sign. This
means that increase of pressure raises the transition temperature. The curve OC, therefore,
slopes away from the pressure axis.

The curve BC is the fusion curve for monoclinic sulphur. This gives the effect of pressure on
the melting point of monoclinic sulphur. The two-phase equilibrium (SM ⇌ SL) along the curve
BC is univariant. As the melting of monoclinic sulphur is accompanied by a slight increase of
volume, it follows from Clapeyron-Clausius equation that the melting point will rise slightly
by the increase of pressure. The curve BC, therefore, slopes slightly away from the pressure
axis. As the slope of this curve is much less than that of the curve OC, the two curves meet at
the point C. Thus, C 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 C, the temperature is 151 °C ·and the pressure is 1290 atm.

The curve CD is the fusion curve for rhombic sulphur: The equilibrium along this curve is SR
⇌ SL. As the number of phases is 2, the-system is monovariant.
Metastable Equilibria. In addition to the stable equilibria- discussed above, there· are also
some metastable equilibria indicated by the dotted lines in Fig. 4. Since the conversion of one
solid into another solid, as that of rhombic sulphur into monoclinic sulphur, at the point O
(95·6°C) involves molecular rearrangement necessary for bringing about the change in the
crystalline form, the process is naturally slow. Therefore, unless heating is done extremely
slowly, there is a possibility that the first solid may not change into the second solid at the
normal transition point. The first solid, therefore, will exist in metastable equilibrium with its
vapour. ·

This possibility in sulphur system is represented by the dotted line OA′. If the
temperature of rhombic sulphur is allowed to rise .rather quickly at about 95·6°C, it will persist
in equilibrium with its vapour phase without changing into monoclinic sulphur for several
degrees above the normal transition temperature. Thus, along the dotted curve OA' which is
the extension of the curve AO, the metastable equilibrium, SR ⇌ SV exist. The vapour pressure
at each temperature, as can be seen, is higher than the vapour pressure of monoclinic sulphur
which is the stable phase in this range.

Similarly, if liquid sulphur is allowed to cool along the curve EB, the solid phase
(monoclinic sulphur) may not separate out at B unless cooling is extremely slow. The line BA'
in this case represents the metastable equilibrium between liquid sulphur and its vapour (i.e.,
SL ⇌ SV). The point A', therefore, represents the melting point of the metastable rhombic
sulphur. This is another 'triple point where the three phases, SR – SL - SV, coexist in metastable
equilibrium. The temperature A' has been found to be about 114°C.

The curve A'C, evidently, gives the effect of pressure on the melting point of metastable
rhombic sulphur. In other words, this is the fusion curve of metastable- rhombic sulphur along
which rhombic sulphur is in metastable equilibrium with the liquid.

Area. The curves AQ and OC both involve rhombic sulphur in equilibrium with the vapour
phase in one case and solid monoclinic sulphur in the other, it can be shown that the area
bounded by these lines towards the left represents conditions for the stable existence of rhombic
sulphur alone. Similarly, as the curves BE and BC both have liquid phase as common, in
equilibrium with vapour in the first case and with solid monoclinic sulphur in the second case,
the area bounded by these lines represents liquid sulphur as the stable phase. Similarly, as the
curves AO, OB, and BE have the vapour phase as common, the area lying below these lines
represents only vapour as the stable phase. Lastly, as the lines OC, OB and BC have monoclinic
sulphur as the common phase, the triangular area bounded by these lines represents monoclinic
sulphur as the stable phase. The existence of this form of sulphur, evidently, is limited on all
sides.

TWO-COMPONENT SYSTEMS

For a two-component system, the phase rule becomes F = 4 - P

Since the minimum number of phases, P, in any system is 'l, the maximum number of degrees
of freedom, F, is 3. Thus, three variables would be necessary to describe a system. Since three
variables are difficult to graph, it is customary to hold one of them say, the pressure, constant
on a diagram of temperature plotted versus concentration. This reduces the degree of freedom
of the system by one and the phase rule equation is then written as F' = 3 - P. ·

This is known as the reduced phase rule equation.

For the two-component solid-liquid equilibria, we come across the following cases: I. The two
components are miscible in the liquid state. 2. The two components are only partially miscible
in the liquid state. We shall restrict ourselves to the former case. Under this category, we shall
discuss the following cases:

A. The two components are not miscible in the solid state and form a· eutectic mixture.

B. The two components form a stable compound with congruent melting point.

C. The two components form a compound with incongruent melting point.

We shall discuss some of these systems in the following pages.

Type A. SIMPLE EUTECTIC SYSTEMS

The general phase diagram of such a system is depicted in Fig.4.

 Fig. 4. A simple eutectic system at constant pressure.

The points A and B represent the melting points of the components A and B. As
increasing quantities of B are added to A, the freezing point of A falls along the curve AC.
Similarly, as increasing quantities of A are added to B, the freezing point of B falls along the
curve BC. Thus, along the curve AC, the solid A is in equilibrium with the solution (liquid) of
the component B in A. This is called the freezing point curve of the component A. Similarly,
along the curve BC, the solid B is in equilibrium with the solution (liquid) of the component A
in B. This represents the freezing point curve of the component B. The number of phases along
AC, as well as along BC, is two. Since measurements are made at atmospheric pressure (i.e., at
constant pressure), we may apply the reduced phase rule equation. Thus, we have F' = C – P +
I = 2 – 2 + I = I. Hence, the system is monovariant. The composition varies with temperature
along AC or BC, as the case may be. The two curves intersect at some point C where both the
solids A and B must be in equilibrium with the liquid phase (i.e., the liquid solution of the two
components). The number of phases is 3. Applying the reduced phase rule equation, F' = 0.
Thus, the system at C has no degree of freedom. It is invariant. This means that under a given
pressure, the system consisting of two solids and their liquid solution i.e., A-B-L, can exist
only at a definite temperature and that the composition of the liquid (solution) phase also is
definite. The point C, as can be seen, is the lowest temperature at which liquid can exist in
equilibrium with the solids A and B. Since the mixture of A and B of composition
corresponding to point C, has the lowest melting point, the point C is known as the eutectic
point ( eutectic means easy melting).
 In the area above the lines AC and BC, the two components are present only as a
homogeneous liquid solution. As the system consists of only one phase in this area, it is
bivariant. Therefore, in order to define any point in this area, it is necessary to specify the
temperature as well as the composition. It is understood that the pressure has ·been kept
constant.

Suppose, a liquid mixture of composition represented by a point a is cooled at a constant

pressure. The temperature will fall without any change of composition until the point b on the
freezing point curve AC is reached. At this temperature, which corresponds to t1, the solid A
separates out. The system now consists of two phases and is, therefore, monovariant (assuming
pressure to be constant). The temperature will fall only with change in composition of the liquid
phase. Therefore, as cooling continues, the component A keeps on separating out and the
solution becomes relatively richer in B. The temperature and the solution composition both
change along the curve bC. Thus, at temperature t1, solid A is in equilibrium with solution of
composition x and at temperature t2 it is in equilibrium with solution of composition y. It is
evident, therefore, that in area ACD, solid A is in equilibrium with solutions of varying
composition given by the curve AC depending upon the temperature.

When the eutectic temperature is reached at d, the second solid B also begins to
crystallize out. The system now has 3 phases and, therefore, at constant pressure, it becomes
invariant. On further cooling the system, solid A and solid B separate out together in a fixed
ratio so that the composition of the solution remains constant as indicated by the point C. The
temperature also remains constant. When the solution phase has been completely solidified and
the system consists only of a mixture of solid A and solid B, it becomes monovariant .and
continued cooling results in fall of temperature below the line DD' into the area within which
only the two solids coexist, as shown.

Similarly, if the composition of the original liquid is on the right side of the eutectic
point, as represented, say, by the point a', similar series of changes will be observed on cooling.
In this case, however, on reaching the point b' on the freezing point curve BC, the solid B will
separate out. As cooling continues, B keeps on separating and the solution becomes now richer
and richer in A. The temperature and the composition both, change along the curve b' C. Thus,
in the area BCD', solid B is in equilibrium with solutions of varying composition. Again, when
the eutectic temperature is reached at the point d', A also begins to separate out. The system
now becomes invariant. On withdrawing heat further from the system, the temperature remains
constant and solid A and solid B continue to separate in the same ratio so that the solution
composition also remains constant. Ultimately, the solution phase solidifies completely as
before and thereafter the temperature of the system can fall below the line DD' into the area of
coexistence of two solids A and B.

Consider a special case when the liquid has the same composition as that of the eutectic.
This is represented by the point c. On cooling, no solid will separate out until the eutectic
temperature is reached. At this temperature, both the solid A and B crystallise out
simultaneously. The temperature and composition of the solution remain constant until the
system gets completely solidified.

LEAD-SILVER SYSTEM

These metals are completely miscible in liquid state and do not give rise to any
compound formation. The equilibrium diagram, therefore, is similar to that shown in Fig. 4,
The various features are illustrated in Fig. 5.

Fig.5. The Phase diagram for lead-silver caption system.

Pure lead melts at 327°C and the addition of silver lowers its .melting point along AC. Thus,
AC is the freezing point curve .of lead containing varying amounts of silver. Pure silver melts
at 961 °C and the addition of lead lowers its melting point along BC. Thus, BC is the freezing
point curve of silver. Along AC, solid lead and solution (melt) coexist while along BC, solid
silver and solution (melt) coexist. The system, at constant pressure, is monovariant along AC
as well as along BC.

C is the eutectic point where the three phases, solid lead, solid silver and their liquid solution
(melt), coexist. It is an invariant point. The temperature of the eutectic is 303°C and the
composition of the solution phase is 2·6 per cent silver, as shown in the figure. The phases
coexisting in. the various areas or regions are also shown in the figure.

The phase diagram of lead-silver system has special significance in connection with the
desilverisation of lead. The argentiferous lead consisting of a very small percentage of silver is
first heated to a temperature well above its melting point so that the system consists only of the
liquid phase represented, say, by the point a, in the figure. It is then allowed to cool. The
temperature of the melt will fall along the line ab. As soon as the point b is reached, lead will
begin to crystallise out and the solution will contain relatively increasing amounts of silver.
Further cooling will shift the system along the line bC. Lead continues to separate out and is
constantly removed by means of ladels. The melt continues to be richer and richer in silver
until the point C is reached where the percentage of silver rises to 2.6. Thus, the original
argentiferous lead which might have contained 0· l pet cent (or even less) of silver, can now
contain up to 2.6 per cent of this metal. The process of raising the relative proportion of silver
in the alloy is known as Pattinson's process.
 BISMUTH-CADMIUM SYSTEM

The fully labelled phase diagram for the bismuth-cadmium system is shown in Fig. 6. The
characteristic features of this system are similar to those of lead-silver system described above.

Fig.6. The phase diagram for the bismuth-cadmium system

Pure bismuth melts at 317°C and the addition of cadmium to molten bismuth lowers its freezing
point along the curve AC which is the freezing point curve of bismuth containing varying
amounts of cadmium. Similarly, addition of bismuth to molten cadmium lowers the freezing:
point along the curve BC which is the freezing point curve of cadmium containing varying
amounts of bismuth. In the region above the curves AC and CB, bismuth and cadmium are
present in the form of a melt. Since in this region, P=l, F=2, i.e., the system is bivariant. The
two degrees of freedom are the temperature and the composition. Thus in this region,
temperature and composition can be varied without changing the number of phases. Along the.
Curve AC, bismuth freezes out and along the curve BC, cadmium freezes out. Thus, in the area
below AC and down to the eutectic point there are two phases, viz., bismuth and liquid whose
composition is determined by the temperature. Similarly, in the area below BC down to the
eutectic, the two phases in equilibrium are cadmium and liquid. Since in these regions, P = 2,
F = l, i.e., the, system is univariant.
 At the eutectic point C, three phases coexist; these are bismuth, cadmium and liquid.
The composition of the eutectic is 40% cadmium. At C, P = 3 so that F = 0, i.e., the system is
invariant. The eutectic temperature is 146°C. The area below the eutectic point is a two-phase
region as labelled in the phase diagram. Since in this region P = 2, F = 1. Thus, only the
temperature need be specified to describe the system completely.