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PHASE RULE

ENROLLMENT NO. NAME ROLL NO.


140280105002 BAROT JAY 405002
140280105004 CHAUDHARI JAYDEEP 405003
140280105006 CHAUDHARY YATIN 405005
140280105038 PRAJAPATI MEET 405037
140280105052 SOLANKI PRADIP 405051

CHEMICAL ENGG.
SEM-4
PHASE RULE

Any homogeneous part of a system having all


physical and chemical properties the same
throughout.

A system may consists of one or more than one


phases.
Gibbs Phase Rule : -
F=CP+2
Where,
F = Number of degree of freedom
C = Number of components
P = Number of phases of system
COMPONENTS
MEANING OF COMPONENTS

The least number of independent chemical constituents in terms of which the


composition of every phase can be expressed by means of a chemical
equation.
EXPLANATION OF THE TERM COMPONENT
(A)The chemical formula representing the composition of a phase is written on
LHS.
(B)The rest of the chemical constituents existing independently in the system as
represented by chemical formulas are placed on RHS.
(C)The quantities of constituents on RHS can be made minus(-) or zero(0) to get
at the composition of the phase on LHS.
EXAMPLES OF COMPONENTS

(1)Water and sulphur systems are 1-component systems


Water system has three phases : ice, water and water vapour. The
composition of all three phases is expressed in terms of one chemical
individual H2O.Thus water system has one component only.
(2)Mixture of gases.
A mixture of gases say O2 and N2 constitutes one phase only. It composition
can be expressed by two chemical substances O2 and N2. Hence a mixture of
O2 and N2 has two components.
PHASE COMPONENTS
Gaseous Mixture = x O2 + y N2
(3)An aqueous solution of sodium chloride or any other solute is a two-component
or 2-component system.
DEGREES OF FREEDOM
MEANING

The term degree of freedom represented by F in the phase rule equation(F=C-


P+2) is defined as follows: The least number of variable factors
(concentrations, pressure, temperature) which must be specified so that the
remaining variables are fixed automatically and the system is completely
defined.
A system with F=0 is known as nonvariant or having no degree of freedom.
A system with F=1 is known as univariant or having one degree of freedom.
A system with F=2 is known as bivariant or having two degrees of freedom.
EXPLANATION

A system is defined completely when it retains the same state of


equilibrium(or can be reproduced exactly) with the specified variables. Let us
consider some examples.
(1) For a pure gas, F=2. For a given sample of any gas PV=RT. If the values of P
and T be specified, V can have only one definite value, or that the V is fixed
automatically. Any other sample of the gas under the same P and T as
specified above, will be identical with the first one. Hence a system
containing a pure gas has two degrees of freedom(F=2).
(2) For a mixture of gases, F=3. A system containing a mixture of two or more
gases is completely defind when its composition, T and P are specified. If P
and T only are specified, the third variable i.e. composition could be varied.
Since it is necessary to specify three variables to define the system
completely.
OTHER EXAMPLES

(3) For water to water vapour, F=1.The system water in equilibrium with water
vapour, has two variables T and P. at a definite T the vapour P of water can have
only one fixed value. Thus if one variable is specified, the other is fixed
automatically.
(4) For saturated NACL solution, F=1.
(5) For ice-water-vapour system, F=0.
Derivation of Gibbs phase rule eqation
The Gibbs phase rule describes the degrees of freedom available to describe a
particular system with various phases and substances.

To derive the phase rule, let us begin with a system that has c independent
chemical species.

Factors in to account for any restrictions due to stoichiometry, equilibrium or


mass or charge constraint
Thus for a system with acetic acid, H+ and C2H3O2- are not independent of
HC2H3O2 (because [H+] = [C2H3O2-] and [C2H3O2-] is related to [HC2H3O2] via
Ka.

We will assume no chemical reactions (which reduces the number of independent


chemical species).

Now let each chemical component exist in the maximum number of phases, p.
When we include the two quantities, temperature and pressure, as degrees of freedom
that can describe our system, the total degrees of freedom of the system (before considering
thermodynamic constraints) is

f=PxC+2

However, the number of chemical components in each phase is not truly independent since
the total of the each mole fraction must equal one . X + X +X + ....Xc = 1

This yields one constraint for each phase; therefore, the total degrees of freedom becomes
F = p x c + 2 p = p( c- 1) + 2

Thus for c components, the number of additional constraints is c(p 1)

f = p ( c - 1 ) + 2 c ( p 1 ) = pc - p + 2 pc + c = c p + 2

Thus we have derived the Gibbs phase rule: f = c p + 2


ONE COMPONENT SYSTEM
For a one-component system we can write the phase rule equation as :
F=CP+2=1P+2=3P
Three cases may arise :
Case 1: When only one phase is present,
F=31=2
Thus the system is bivariant. It can be completely defined by specifying the two
variables,temperature and pressure. Or that, both the temperature and pressure
can be varied independently.Therefore a single phase is represented by an area
on P, T-graph.
Case 2: When two phases are in equilibrium,
F=32=1
The system then has one degree of freedom and is termed monovariant. This means
that the
pressure cannot be changed independently if we change the temperature. The
pressure is fixed
automatically for a given temperature. A two-phase system is depicted by a line on
a P, T-graph.
Case 3: When three phases are in equilibrium,
F=3P=33=0
F=0
The system has zero degree of freedom and is termed nonvariant or invariant. This special condition can be
attained at a definite temperature and pressure. The system is, therefore, defined completely and no further
statement of external conditions is necessary. A three-phase system is depicted by a point on the P, T-graph.
At this point the three phases (solid, liquid, vapour) are in equilibrium and, therefore, it is referred to as the
Triple point.
Under normal conditions the system water is a three-phase, one-component system. The
three phases involved are liquid water, ice, water vapour. All these phases can be represented by
one chemical entity H2O and hence one component of the system. The number of phases which
can exist in equilibrium any time depends on the conditions of temperature and pressure. The
phase diagram of the system/ water/ice/vapour is shown in Fig.The salient features of the
phase diagram are listed below.
(1) The Curves OA, OB, OC
These three curves meet at the point O and divide the diagram into three regions or areas.
Curve OA, the Vapour Pressure curve of Water. It represents the vapour pressure of liquid
water at different temperatures. The two phases water and water vapour coexist in equilibrium
along this curve.
Curve OB, the Sublimation curve of Ice. It shows the vapour pressure of solid ice at different
temperatures. The two phases solid ice and vapour coexist in equilibrium along this curve. At the
lower limit the curve OB terminates at absolute zero ( 273C) where no vapour exists.
Curve OC, the Fusion curve of Ice. It depicts the effect of pressure on the melting point of
ice. Here ice and water coexist in equilibrium.. Since ice melts with decrease in volume by Le
Chateliers principle the melting point is lowered by an increase of pressure. It may be noted that
the 1.0 atmosphere line meets the fusion curve at 0C which is the normal melting point of ice.
Therefore,
F = C P + 2 = 1 2 + 2 = 1
(2) The Triple point O
The curves OA, OB and OC meet at the triple point O where all the three phases liquid
water/ice/vapour are in equilibrium. This occurs at 0.0076C and vapour pressure 4.58 mm Hg.
Since there are three phases and one component, we have
F = C P + 2 = 1 3 + 2 = 0
i.e., the system at the triple point is nonvariant. Thus if either pressure or temperature is
changed, the three phases would not exist and one of the phases would disappear.
3) Area AOC, AOB, BOC
The areas or regions between the curves show the conditions of temperature and
pressure under which a single phaseice, water or vapour is capable of stable
existence. Thus,
Area AOC represents conditions for the one-phase system water.
Area AOB represents conditions for the one-phase system water vapour.
Area BOC represents conditions for the one-phase system ice.
In all the three areas there being one-phase and one-component, we have
F = C P + 2 = 1 1 + 2 = 2
Thus each system water, water vapour, or ice has 2 degrees of freedom i.e., the
system is bivariant.

(4) Metastable system : Supercooled Water/Vapour System


The vapour pressure curve of water AO can be continued past the triple point as
shown by the dashed line OA'. That is, water can be supercooled by carefully
eliminating solid particles. The supercooled water/vapour system is metastable
(unstable). It at once reverts to the stable system ice/vapour on the slightest
disturbance or introducing a crystal of ice.
It is a one-component, four-phase system. The four phases are :
(a) Two solid polymorphic forms :
(i) Rhombic Sulphur (SR) (ii) Monoclinic Sulphur (SM)
(b) Sulphur Liquid (SL)
(c) Sulphur Vapour (SV)
All the four phase can be represented by the only chemical individual
sulphur itself and hence one component of the system.
The two crystalline forms of sulphur SR and SM exhibit
enantiotropy with a transition point at 95.6C. Below this
temperature SR is stable, while above it SM is the stable variety. At
95.6C each form can be gradually transformed to the other and the
two are in equilibrium. At 120C, SM melts.
The salient features of the phase
diagram are described below.
(i) The six curves AB, BC, CD, BE, CE, EG
(ii) The three Triple points B, C, E
(iii) The four areas :
ABG marked solid Rhombic
BEC marked solid Monoclinic
GECD marked liquid Sulphur
ABCD marked Sulphur vapour
TWO COMPONENT SYSTEMS:
When a single phase is present in a two-component system, the degree of
freedom is three, F = 2 1 + 2 = 3
This means that three variables must be specified in order to describe the
condition of the phase.
Thus in such a system, in addition to pressure and temperature the
concentration of one of the components has also to be given. For graphic
representation of these variables, three coordinate axes at right angles to
each other would be required. Therefore the phase diagram obtained would
be a solid model.For the sake of having simple plane diagrams we generally
consider only two variables, the third one being a constant.
For example, for a solid/liquid equilibrium, the gas phase in usually absent
and the effect of pressure on the equilibrium is very small. Thus when a two-
component system consists of solid and liquid phases only, the effect of
pressure may be disregarded. Then it is necessary to take into account the
remaining variables viz., temperature and concentration. Such a solid/liquid
system with the gas phase absent is called a condensed system.
THE ZINCCADMIUM SYSTEM
This is another example of a metal/metal system with a eutectic. The phase
diagram is shown in Fig which is similar to the one for silver/lead system. It
consists of :
Curve AO; the Freezing point curve of Zinc. A represents the freezing point
(or melting point) of zinc (419C). The curve AO shows that the melting point
of zinc is lowered by the addition of cadmium. The phases in equilibrium
along AO are solid zinc and liquid solution of zinc and cadmium. Applying the
reduced phase rule equation.
F' = C P + 1 = 2 2 + 1 = 1
Thus the system solid zinc/solution is monovariant
. Curve BO; the Freezing point curve of Cadmium. The point B represents
the melting point of cadmium (321C). The curve BO shows the fall of melting
point of cadmium on the addition of zinc. Along this curve, solid cadmium is in
equilibrium with the liquid solution of zinc and cadmium.
Applying the reduced phase rule equation to the equilibrium cadmium/solution,

F' = C P + 1 = 2 2 + 1 = 1
Thus the degree of freedom is one and the equilibrium is monovariant. The
Eutectic point O. The curves AO and BO meet at O. Here, solid zinc, solid
cadmium and solution are in equilibrium. The number of phases is, therefore,
three.
F=CP+1=23+1=0
Thus the system at point O is nonvariant. The point O is called the eutecic point.
Both the temperature and composition being fixed, the system has no degree of freedom.
The eutectic temperature is 270 and the eutectic composition is 83% cadmium 17% zinc.
The Area above AO. In this area, both the components zinc and cadmium are present as
liquid solution of varying composition. The solution of the two metals being homogeneous,
constitutes one phase only. Thus the system represented by the area above AO is
bivariant.
F=CP+1=21+1=2
The Area above BO. In this area, zinc and cadmium exist as liquid solution. The
composition of the solution is indicated on the composition axis. The liquid solution,
regardless of its composition, represents one phase only. Thus the system in the area above
BO is bivariant.
F=CP+1=21+1=2
The effect of cooling. If the solution in the area above AO is cooled, zinc separates as the
curve itself is reached. This continues till the point O when the solid eutectic mixture (83%
Cd + 17% Zn) separates. Similarly, the solution above BO on cooling allows the separation
of cadmium. This continues till the point O is reached at 270C and eutectic mixture
separates. As clear from the diagram, the area below the curve AO represents zinc and
solution; the area below BO shows cadmium and solution. The area below the eutectic
temperature represents the system solid zinc/ solid cadmium.
THE SILVERLEAD SYSTEM

This system has two components and four phases. The


phases are : (i) solid silver; (ii) solid lead; (iii) solution of
molten silver and lead; and (iv) vapour.
The boiling points of silver and lead being considerably
high, the vapour phase is practically absent. Thus Ag/Pb
is a condensed system with three phases. In such a case,
pressure can have no effect on the system. Therefore we
need consider only the two remaining variables, namely
the temperature (T) and concentration (C). The complete
TC diagram of the system Ag/Pb is shown in Fig.
The salient features of the diagram are : (a) Two curves, AC and BC (b) Eutectic
point, C Solution (Ag/Pb) 100 Pb 0 Ag (c) Three areas : (i) above ACB; (ii) below
AC; (iii) below BC Curve AC; the Freezing point curve of Ag. A represents the
freezing point or melting point of solid silver (961C) and the curve AC shows that
the addition of lead lowers the melting point along it. The phases in equilibrium
along AC are solid silver and solution of silver and lead. Applying the reduced
phase rule equation:
F' = C P + 1 = 2 2 + 1 = 1
Thus the system Ag/solution is monovariant.
Curve B; the Freezing point curve of Pb. B represents the melting point of solid
lead (327C) and the curve BC shows that the melting point is lowered by addition
of silver. The phases in equilibrium along BC are solid lead and solution. The
system is monovariant.
The Eutectic point C. The curves AC and BC intersect at C, which is called the
eutectic point. Here three phases solid Ag, solid Pb, and solution are in equilibrium.
Applying the reduced phase rule equation
F' = C P + 1 = 2 3 + 1 = 0
Thus the system Ag/Pb/solution at C is nonvariant. Both the variables,
temperature (303C) and composition (97.5% Pb, 2.5% Ag) are fixed. If you raise the
temperature above the eutectic temperature, the solid phases Ag and Pb disappear
and if you cool below it, you will land in the solid Ag/Pb area where solution phase
is nonexistent.