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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

physical and chemical properties the same

throughout.

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

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

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

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

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.

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.

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

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

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

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.

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