Phase Equilibria

Introduction Gibbs Phase Rule & Its Applications Application to one component systems,
Water, Carbon dioxide, Sulphur system

Condensed phase rule, Two component systems, Eutectic mixture, Lead silver system

States of Matter
Matter can exists in 3 states i.e. Solid, Liq., Gas A change in external conditions of substance produces phase transition
For e.g. Ice is thermodynamically stable form of water below 0C and above this temp., liq phase is more stable (So 0C is the transition temp. between two phases)

Phase Changes
e.g. (i) Melting of Ice (ii)Evaporation of water (iii) Dissolving sugar in water
No change in Chemical composition

When a phase transition occurs, different phases come into contact with each other and at some instant of time, these phases may be in equilibrium A phase transition will proceed till an equilibrium is attained. The equilibrium in a phase transition is called Phase Equilibria
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In this Chapter
A systematic method is discussed for the phase changes that a mixture will undergo when it is heated or cooled and also when the composition of mixture is changed.

TYPES OF CHEMICAL REACTIONS

Irreversible
Zn + H2SO4 ZnSO4 + H2

Reversible
N2 (g) + 3H2 (g) 2NH3 (g) (Homogeneous) CaCO3 (s) CaO (s) + CO2 (g) (Heterogeneous)

Phase Rule
The phase rule given by Willard Gibbs (1874) is an important and versatile tool to study the heterogeneous equilibria Mathematically

F=CP+2

F = Degrees of freedom C = No of components P = No. of Phases Numeral 2 accounts for the effect of T & P.

o Phase rule enables us to predict the conditions that must be specified for a system to exhibit equilibrium
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TERMS INVOLVED IN PHASE RULE

F=CP+2
PHASE P COMPONENTS C DEGREES OF FREEDOM F

PHASE (P)
Any homogeneous, physically distinct and mechanically separable portion of a system which is separated from other parts of the system by definite boundary surface

P=3

P=1

P=1

P=2

P=2

Examples of Phases
A completely miscible homogeneous mixture of gases (O2 & N2) and liquids (water & alcohol) gives a single phase (P=1). Air (a mixture of O2, N2, CO2, H2 & water vapor) constitute a single phase (P=1) Any pair of immiscible liquids (water & kerosene)- 2 phases At a specified condition Ice water vapor (P=3) Every solid constitute a separate phase e.g. Decomposition of CaCO3: CaCO3 (s) CaO (s) + CO2 (g) (P=3) Structurally different solids e.g (SR & SM) give rise to multiphase system
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Component (C)
Components of the system are defined as the minimum number of independently variable constituents taking part in equilibrium by means of which the composition of each phase can be expressed either directly or in the form of chemical equations e.g. 1. One component Systems (i) At the freezing point Ice(s) water(l) vapor(g) The composition of all the three phases can be defined in terms of H2O (1 constituent), Hence C=1 (ii) Sulphur exist in 4 phases i.e. Rhombic, monoclinic, liquid & vapor but the chemical composition is only S. Hence C=1. 2. Two component systems (i)A sugar solution is two component system. (Water + Sugar) 3. Three C Systems A gaseous mixture of N, O, He (C=3) 10

When the constituents of the system undergo chemical reaction amongst themselves then the components are defined as The no. of C of a chemically reactive system is equal to the total number of constituents present minus the no. of independent chemical equations relating these constituents C=N-E N= Total number of constituents E= Number of independent chemical equations
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e.g. (i) Thermal decomposition of CaCO3 in a closed vessel at equilibrium CaCO3 (s) CaO (s) + CO2 (g)
N=3, E=1, Hence C=N-E or C= 3-1= 2

C=N-E

(ii) Fe (s) + H2O (g) FeO (g) + H2 (g)

N=4, E= 1, Hence C=4-1=3

(iii) Decomposition of NH4Cl: NH4Cl (s) NH3 (g) + HCl (g)

N=3, E=1, Hence C=3-1=2
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DEGREES OF FREEDOM (F)

The minimum number of independent variables like T, P & concentration, which must be specified in order to define the system completely It is also known as variance of the system. If F=0, System is called non-variant or invariant F=1, System is called univariant or monovariant F=3, Trivariant
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Examples (i) Consider a system containing a gas obeying ideal gas equation (PV=RT).
The state of this system can be defined completely by 2 parameters i.e. T& P because the 3rd parameter V, can be known by the equation. So degree of freedom is 2 (F=2)

(ii) Water (l)Vapor (g) F=C-P+2, =1-2+2 =1 (Monovariant system) (iii) Ice(s) water(l) vapor(g) F=C-P+2, =1-3+2 =0 (Nonvariant or invariant system)
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PHASE DIAGRAM
The no. of phases that can exist together in a system depends on the conditions of T & P. These conditions are determined experimentally and graph is plotted between T&P. The graph thus obtained represents the condition of equilibrium between different phases of the system and is called a phase diagram.
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PHASE DIAGRAM
Phase diagram is a graphical representation of P & T under which different phases of the system can coexists in a state of equilibrium
Terms in phase diagram 1. Phase BoundariesThe lines separating the regions of P and T 2. True equilibrium- The curves OA, OB, OC represents true equilibria between different phases

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PHASE DIAGRAM
Terms in phase diagram

3. Metastable equilibriumA system is said to be in metastable eqi. state under a given set of conditions, if that state can be attained only from one direction by carefully controlled conditions e.g. by carefully controlled cooling, it is possible to cool water below 0C without the formation of ice. The water thus cooled is called super cooled water. However water below 0C cant be obtained by melting of ice. So the super cooled water below 0C is said to be in a metastable equilibrium (curve OD)
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PHASE DIAGRAM
Terms in phase diagram

4. Triple PointA point in the phase diagram where three phases (solid, liq., gas) can co-exist. (Point O) 5. Critical Temperature (Tc)The minimum temp. above which gas can not be liquefied by applying P alone. Above Tc equilibrium Liq.Gas cant be obtained (temp corresponding to Point A)

Tc

6. Critical Pressure (Pc)- Pressure required to liquefy a gas at its Tc is called critical pressure (press. Corresponding to point A)
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OVERVOLTAGE or over potential

In some cases, during electrolysis, the actual electrochemical decomposition voltage required is more than the calculated value. The extra voltage needed is termed as overvoltage. Overvoltage = Electrochemical decomposition voltage - E cell This is common when gases are involved in electrode reaction. This is due to the fact that some electrodes have to be raised to a higher potential than that indicated in the electrochemical series for liberation of hydrogen. In, other words, the difference between the potential of the electrode when gas evolution is actually observed and theoretical value of electrode potential is termed as overvoltage.
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