Engg.

Chemistry - II Pre class- Phase Rule and Alloys

PHASE RULE AND ALLOYS

Part 1

Learning Objectives

At the end of the unit student will become conversant with

Phase Rule

Definition / Statement of terms – Phase, Component & degree of freedom

Definition of Gibbs phase rule

One component system - water system

Phase rule for two component system - Condensed phase rule

Construction of phase diagram by thermal analysis

Simple eutectic systems - lead-silver system

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

PHASE RULE

Phase rule is an important generalization which is useful in understanding the changes which takes place

in a heterogeneous system existing in equilibrium.

PHASE RULE

Provided a heterogeneous system at equilibrium is not influenced by electric, magnetic or gravity forces,

the number of degrees of freedom (F) of the system at equilibrium is related to the number of

components (C) and the number of phases (P) of the system by the relationship F = C – P + 2 which is

known as phase rule equation.

The terms P, C and F are of special significance and hence require explanation.

PHASE

It is physically distinct and mechanically separable part of a system which is homogeneous throughout

and is separated from parts of the system by means of a definite boundary

Some examples are

(i)A gas mixture constitutes a single phase, since gases are completely miscible.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

(ii)Two miscible liquids (water and ethyl alcohol) constitute only one phase because it is homogeneous.

Water
Petrol

(iii)Two immiscible liquids (e.g. oil and water) constitute two phases.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

(iv) At freezing point, water consists of 3 phases solid, liquid and vapour form

(v)A saturated solution of NaCl in water consists of three phases. NaCl (s), NaCl solution and vapour.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

vi) A Heterogeneous mixture like CaCO3 (s) ↔ CaO (s) + CO2 (g)

consists of three phases (i.e., two solids and one gas).

Homogeneous phase is uniform throughout in its chemical composition and physical state. (no

distinction or boundaries)

Water, ice, water vapor, sugar dissolved in water, gases in general, etc.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

A pill dissolving in water Na2CO3 in Acid

Heterogeneous phase is composed of more than one phase These phases are distinguished from each

other by boundaries.

A cube of ice in water. (same chemical compositions but different physical states)

1 2 3 4

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

1- Light solid on Dense liquid

2- Mixture of 3 Immiscible liquids

3- Dense solid in light liquid

4- Mixture of two solids

COMPONENT

It is the minimum number of independent variable constituents by means of which the composition of

any phase of the system can be expressed either directly or in the form of a chemical equation.

Some examples are:

(i)Water exists in three phases solid, liquid and vapour, but the composition of each phase can be

expressed in terms of H2O. So it is a one component system

(ii)Sulphur exist in four phases SR, SM, SL and SV, but the composition of each phase can be expressed

in terms of sulphur only, so it is one component system.

(iii) Consider the equilibrium in thermal decomposition of calcium carbonate

CaCO3 (s) ↔ CaO (s) + CO2 (g)

consists of three phases (i.e., two solids and one gas).

The composition of all the three phases can be expressed in terms of any two as shown.

Phase: CaCO3 = CaO + CO2

Phase: CaO = CaCO3 – CO2

Phase: CO2 = CaCO3 – CaO

Hence it is a two component system.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

DEGREE OF FREEDOM

The minimum number of independent variables such as pressure, temperature and concentration which

must be specified in order to describe completely the state of system. It may be uni, bi, tri or non variant.

Examples are: for ice- water vapour system, F=0 for saturated Nacl solution, F=1 etc.

Consider a system having a single phase (e.g. O2 gas alone). Both temperature and pressure should be

mentioned to state oxygen system. Being a one component system, composition does not vary.

Therefore the degree of freedom taken is taken as two (i.e. , temperature and pressure). The system is

called bivariant system.

Consider a one component system having two phases (e.g. water in equilibrium with water vapors.

Being a one components system, composition does not vary at all. Out of the other two variable i.e.,

temperature and pressure, if we specify temperature of the water, the vapor pressure of the water gets

fixed (vapors pressure have definite value at definite temperature). Therefore if we specify vapor

pressure of water, the temperature of the water gets fixed. Hence by fixing either temperature or pressure

the conditions of the system will be defined. Hence the degree of freedom for the system is one. The

system is called univariant and monovariant.

Consider a one component system having three phases ( eg. Ice (s) ↔ Water (l) ↔ Water vapour

(g)). All the three phases of water will exist only at particular temperature and particular vapor pressure

and being a one component system, the composition does not vary. When all the three phases are in

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

equilibrium, both temperature and pressure get fixed. Therefore the degree of freedom is zero. The

system is called in-variant and non-variant.

Merits of Phase Rule

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

(2) It requires no information regarding molecular/micro-structure, since it is applicable to macroscopic

systems.

(3) It is a convenient method of classifying equilibrium states in terms of phases, components, and

degree of freedom.

(4) It helps us to predict the behaviour of a system, under different sets of variables.

(5) It indicates that different systems with same degree of freedom behave similarly..

(6) It helps in deciding whether under a given set of conditions: (a) various substances would exist

together in equilibrium or (b) some of the substances present would be interconverted or (c) some of the

substances present would be eliminated.

Limitations of Phase Rule

(1) It can be applied only for system in equilibrium. Consequently, it is of little value in case of very

slow equilibrium state attaining system.

(2) It applies only to a single equilibrium system; and provides no information regarding any other

possible equilibria in the system.

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(3) It requires utmost care in deciding the number of phases existing in an equilibrium state, since it

considers only the number of phases, rather than their amounts. Thus, even if a trace of the phase is

present, it accounts towards the total number of phases.

Phase reaction

The reaction which brings about a change in the phase of the system is called phase reaction.

Ex. Physical reactions like vapourisation, freezing, condensation, crystallization, precipitation etc. bring

about a phase change.

Vapourisation

H2O(liq) H2O(gas)

A chemical reaction may or may not bring about a phase change

Ex. N2(g) + 3H2(g) ▬▬► 2NH3 (g)

There is no phase change; hence it is not a phase reaction

NH3 (g) + HCl (g) ▬▬► NH4Cl(s)

Phase change occurs. Hence it’s a phase reaction.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

Phase Diagram

The graphical representation of a phase reaction with respect to any two variables is called a phase

diagram. In other words the variables of a system are taken as coordinates in a phase diagram

The phase diagram can be an isotherm (P Vs Conc) or Isobar (Temp Vs Composition) or Isoplethal

(Temp Vs Pressure)

A phase diagram helps in understanding the behavior of the phases at equilibrium within a system.

Phase diagram of one component water system

Phase Rule for Two-component Alloy Systems (Condensed Phase Rule)

● In a two-component system, when P = 1, degree of freedom (F) has the highest value

F = C-P+2 = 2-1+2 = 3.

● Since the maximum number of degrees of freedom in a two-component system is three, so the phase

behaviour of a binary system may be represented by a three-dimensional diagram of pressure,

temperature, and composition, which cannot be conveniently shown on paper.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

● A solid-liquid equilibrium of any alloy has practically no gas phase and the effect of pressure is small

in this type of equilibrium.

● Therefore, experiments are, conducted under atmospheric pressure. Thus, keeping the pressure

constant for a system, in which vapour phase is not considered, is known as condensed system.

● It will reduce the degrees of freedom of the system by one and for such a system, the phase rule

becomes: F = C-P+1

● This is known as the reduced (or condensed) phase rule, having two variables, namely, temperature

and concentration (or composition) of the constituents.

● Therefore, solid-liquid equilibria are represented on temperature-composition diagrams.

Thermal Analysis-Cooling Curves

The shape of the freezing point curves for any system, especially those involving metals, can be

determined by thermal analysis- “ a method involving a study of the cooling curves of various

compositions of a system during solidification”.

The form of the cooling curve indicates the composition of the solid.

“The graph plotted between the fall of temperature with time is known as a cooling curve”.

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Engg.Chemistry - II Pre class- Phase Rule and Alloys

Eutectic System

A binary system consisting of two substances, which are miscible in all proportions in the liquid phase,

but which do not react chemically, is known as the “eutectic (easy to melt) system”.

e.g., a mixture of lead and silver, Bi-Cd system, Sn-Pb system

Application of eutectics:

● Low-melting alloys are used in safety devices (e.g., as plugs in automobiles), fire-sprinklers, and as

‘fail safe’ device in boilers.

● By suitable choice of metals, very low melting alloys can be obtained, e.g., wood’s metal (alloy

containing 50% Bi, 25% Pb, 12.5% Cd, and 12.5% Sn) melts at 65º C only.

SIMPLE EUTECTIC SYSTEM

For Alloys Pre Class Notes Refer Part 2

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