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Phase Rule6.1

homogeneous. A mixture of two immiscible liquids such as water and

CHAPTER-6

PHASE RULE

6.1 Introduction

Engineering Chemistry6.2

Statement

If F = C

A is defined as an homogeneous, physically

Example :

1. The number of liquid phase depends on the number of

6.2 Phase Rule

6.3 Explanation of terms

Phase Rule6.3

i) If two liquids are immiscible, they will form two separate miscible one liquid phase

2. Solid phase

3. Gaseous phase

Since a gaseous mixture are thoroughly miscible in all 2 2

3 (s) (s) 2 (g)

(s) 2O(g) (s) 2(g)

2O(g) 2(g). Thus three phases

Engineering Chemistry6.4

6. (s) (l) (g) homogeneous solid solution single phase.

Example : 4. (NH4)2SO4.6H2O] solution has a

si II) the smallest number of independently

Example :

(s) (l) (g)

2O and

one component system. 2O. two component

Phase Rule6.5

iv) In the thermal decomposition of CaCO3,

3 (s) (s) 2 (g)

3, CaO and CO2. Suppose CaCO3

3 = CaCO3

3 2 3 (s) 2O(g) (s) 2 (g), the three component

4Cl, the following equilibrium

4Cl ( 3 (g) (

4Cl and the

3+HCl.

3

4Cl and hence the system will be a

Engineering Chemistry6.6

III

Degree of freedom as the minimum number of

A system having 1,2,3 or 0 degrees of freedom is called (s) (l) (g) (l) (g)

Phase Rule6.7

define the system completely. Hence the system

2 2, we must state both the

(aq) (g)

Merits of the Phase rule:

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

It requires no information regard

It is a convenient method of classifying equilibrium states It helps us to predict the behaviour of a system, under It indicates that different systems with same degree of It helps in deciding whether under a given set of

Engineering Chemistry6.8

b) some of the substa

Limitations of Phase rule:

1. It can be applied only for system in equilibrium.

It applies only to a single equilibrium system; and provide It requires at most care in deciding the number of phases It conditions that all phases of the system must be present It conditions that solid and liquid phases must not be in

6.4 Applications of Phase rule to one

component system (water system)

Phase Rule6.9

Since water exists in three possible phases such as solid, liquid

1.Curves

2.Areas

3.Triple point

4.Metastable equilibrium

1) Curve OA

The curve OA is called it re

Engineering Chemistry6.10

The degree of freedom of the system is one, i.e, univariant. Thus

0C). Beyond the critical temperature the

2)Curve OB

The curve OB sublimation curve

0C )

3) Curve OC

The curve O

Phase Rule6.11

The curve OC is slightly inclined towards pressu At triple point all the three phases namely ice, water and

0C and 4.58 mm

0d due

0C is the melting point of ice at 760mm of

0C. 0

Fig 6.1 Water System

Engineering Chemistry6.12

v)Curve OB ( Metastable equilibrium) The curve OB is called vapour pressure curve of the

0C without the

vi) Areas Area AOC, BOC , AOB represents water ice and vapour

6.5 Phase Diagram

Phase Rule6.13

Uses of Phase diagram

1. From the phase diagram, it is possible to predict whether

The phase diagrams are usefu

The study of low melting eutectic alloys, used in

Reduced phase rule or condensed phase rule.

We know the phase

6.5 Two component system

Engineering Chemistry6.14

In solid

condense This reduces the degree of freedom of the system by one. reduced phase rule or condensed pha For a two component system the phase rule equation is written as reduced ( condensed) form

There are various types of solid

lead Lead Zinc

Potassium iodide

Phase Rule6.15

2. Those equilibria in which the compo

Zinc

Calcium chloride

Gold

Classification of two component system

The two compone

i) Simple eutectic formation : A system with two substances which are completely

In this system the

Engineering Chemistry6.16

ii) a)Formation of compound with congruent melting point : In this type of binary alloy system the two substances b) Formation of compound with incongruent melting point : Of the above compounds, a compound is said to poss with a composition different from that of the original. iii) Formation of solid solution :

In this type

C

6.6 Simple eutectic systems

Phase Rule6.17

eutectic point.

1, the solid A will separate out. The

Solid A

(Eutectic )

Solid A + solid B

(Eutectic )

Solid B

(Eutectic )

Solid A + solution Solid B + solution

Fig 6.2 The simple Eutectic system

Engineering Chemistry6.18

temperature t1, solid A is in equilibrium with solution of

2, it is in equilibrium with

similar series of changes will be obtained on cooling.

Construction of Phase diagram by Thermal analysis

Thermal analysis is a method involving a study of the The shape of the freezing point curves for any thermodynamic properties. Le

Phase Rule6.19

Example 1 :

If a pure substance say x , in molten state is cooled slowly the temperature of the solid begins to decrease along the curve Exam When a molten liquid containing two components ( say A Time

Temperature

b c d Time

Temperature

b c e a d

Engineering Chemistry6.20

compound also begins to solidify. Now the temperature cooling of solid mass begins. The temperature of horizontal line

Time Composition

Temperature

a b c d e f g h i

Solid A + solid B

Pure A

10% B 20% B 40% B
50% B
70% B
80% B
90% B

100% B

Temperature

Fig 6.4 Cooling curve of various compositions

of two solids

Phase Rule6.21

Uses of Cooling curves

1. Cooling curves are used to find the percentage purity of

It is used to find the melting point of the compounds

Thermal analysis is useful in derivat

U

Used to analyse the behaviour of the compounds.

The curve AC:

solid lead and

6.7 Lead Silver system

Engineering Chemistry6.22

Curve BC is the freezing point curv

solid silver and liquid Point C is the eutectic point where solid silver, solid lead and

100% Pb 100% Ag

1234 K

C

Liquid melt

Liquid

Solid Lead

Liquid + solid silver

Solid silver + Eutectic

A B

Composition

600 K

Solid A

(Eutectic ) D 2 2.6% Ag

Fig 6.5 Lead-Silver System

576 K

Phase Rule6.23

iv) Areas have two phases and the system is univariant.

The phase diagram of lead

Engineering Chemistry6.24

without change in concentration till any point y on the curve AC g of lead.

1. Eutectic systems are useful in predicting the suitable alloy

It is u

1. State the phase rule and what ar

State the condensed phase rule

Explain Phase, component and degree of freedom.

Describe the water system

Briefly describe the construction of phase diagram using

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