PHASE RULE

Vaporization, sublimation, fusion, transition of one solid phase to another, solubility of solids, liquids and gases in each other, chemical reactions between solids and liquids or gases, distribution of solutes between phases, etc are examples of heterogeneous equilibria. They can be studied by methods suitable for each particular type of equilibrium. But all of them can be treated from unified standpoint by means of a general principle called PHASE RULE.

With the help of this principle, it is possible to define the no. of variables controlling a given heterogeneous equilibrium under various experimental conditions. It is an invaluable principle applied extensively in the study and development of materials needed for various applications. It does not establish a quantitative relation among those variables.

From the thermodynamic considerations, J.W.Gibbs derived an equation that predicts the number of phases that can coexist in a given system selected for the purpose of investigation. This equation is called Gibbs Phase Rule which is P+F=C+2 P is the no. of phases coexisting in a given system. C is the no. of components in the system. F is the degree of freedom.

Statement of Phase rule:- The sum of no. of phases and degrees of freedom in a heterogeneous equilibrium exceeds the no. of components present in it by two. Explanation of terms of the Gibbs phase rule:1. No. of phases,P: A homogeneous, physically distinct and mechanically separable portion of a system is called a phase. The phase present in a system may be pure substances or homogeneous mixtures of more than two substances.

Air which is a mixture of Nitrogen, oxygen, carbondioxide,water vapours etc. constitutes a single phase. Two or more liquids completely miscible with one another also constitute a single phase. But as there will be vapours in contact with it,there will be two distinct phases. Every solid constitutes a separate phase. CaCO3(s) CaO (s) + CO2(g) There are three phases.

2. No. of Components, C :- Smallest no. of independently variable constituents, in terms of whose formulae equations may be written to express the composition of each phase of a system is called no. of components. Consider a system in which ice, water and water vapour coexist. Composition of each phase can be expressed with the single constituent,H2O.Hence this is a single component system.

In the system Na2SO4 and water,the various phases that may exist are: phase Components Na2SO4 Na2SO4 + 0 H2O Na2SO4.7 H2O Na2SO4 + 7 H2O Na2SO4.10 H2O Na2SO4 +10 H2O Na2SO4 solution Na2SO4 + x H2O Ice 0 Na2SO4 + H2O Vapour 0Na2SO4 + H2O Thus two components is the smallest no.by means of which the composition of each phase can be expressed.

3.Degree of freedom, F:- The no. of variables such as, pressure, temperature and composition that can be changed independently without changing the no. of phases in equilibrium in a given system is called degree of freedom. Eg. Ice, water and water vapour can coexist at one definite temp. and one definite pressure. One of the phases disappear if temp. or pressure is changed from that value. So it is called a nonvariant system.

If only one variant can be changed without changing the no.of phases coexisting, the system is said to be monovariant. Water in equilibrium with its vapour. At a given temp. the equilibrium vapour pressure of water can have only one fixed value.We have to specify only one variable either T or P. If no. of phases coexisting does not change, even on changing two variables, the system is said to be bivariant. Ex. A system consisting of a pure gas. Both T and P need to be specified.

True equilibrium: Is said to exist in a system undera given set of conditions when the same state can be realised from either direction by following any procedure. Ice(s) Water(l). At a pressure of 1atm.,the temp. of the system will be 0oC irrespective of the fact whether the eqbm. Is attained by partial melting of ice or by freezing of water.

Meta stable equilibrium.

It is possible to cool water slowly and carefully to a temp. of -1oC without appearance of ice. Thus water is not in stable eqbm. With ice.It is said to be in metastable equilibrium.

Phase Diagrams:Graphical representation of what phases are present in materials systems at various temperatures, pressures and compositions are called phase diagrams. The phase diagrams are used to understand and predict many aspects of the behaviour of materials. A phase diagram indicates the following.

1. Various phases coexisting at different compositions and temperatures, under equilibrium conditions. 2. Solid solubility of one material in another, under equilibrium conditions. 3. Temperature at which a material cooling under equilibrium conditions starts to solidify and the temperature range over which solidification occurs. 4. Temperatures at which different phases start to melt under equilibrium heating conditions.

Classification Of Systems:- On the basis of no. of components present, systems can be classified into different types as shown below. 1.One Component Systems. (Water, sulphur) 2.Two Component Systems. (Pb-Ag, Bi-Cd,KI-water)-Simple eutectic

One Component Systems

F=CP+2 = 1- 1 + 2 ( P=minimum 1) = 2 i.e. system is bivariant.( temp.& pressure) If the system has 2 phases; F= 1-2 + 2= 1 Monovariant(either temp.or pressure) If the system has 3 phases; F= 1- 3 + 2 = 0 Invariant

Water System:-

A system consisting of ice, water and water vapour is a one component system.

Liquid Solid Solid

Vapour Vapour Liquid.

Within each area only one phase of water exists. Within the area bound COA liquid phase exists. Within the area bound by BOA vapour phase exists. Within the area bound by COB solid phase exists.

Along the curves two phases of water coexist. Under the conditions of temperature and pressure indicated by the curve OA, water and water vapour coexist. OA is the vaporization curve. It shows the effect of pressure on the boiling point of water. At 760 mm Hg pressure water boils at 100oC. OB is the sublimation curve. Along this curve ice and water vapour coexist.It indicates the effect of pressure on the sublimation temperature of ice.
Line OC is freezing line. At temperatures and pressures along this line ice and water coexist. It shows the effect of pressure on melting point of ice or freezing pt. of water. At 760 mm Hg pressure ice melts or water freezes at 0oC.

At pt. O, all the three phases coexist.It is called triple point.It occurs at 0.0075oC and 4.58 mm Hg pressure. Application Of phase rule: This is a single component system.That is C = 1 for this system. At the triple point , P = 3. From the Gibbs phase rule we have, F=CP+2 =13+2 = 0 That is, at the triple point, the system is invariant or no. of degree of freedom is zero.

Along any line, P = 2 F=C+2P = 1 + 2 2 = 1. The system is univariant along each curve. Within each area, P = 1 F=C+2P = 1 + 2 1 = 2. The system is bivariant within each area.

Effect of Change Of Temp. & Pressure on the eqbm.

The effect of heating ice when it is under a pressure of 1 atm. and at a certain temp. represented by the pt. X in the fig. Heating the ice slowly at constant pressure will shift the system along the line XY. At Y fusion takes place. Liquid phase also appears. Now system has F = 1 as P =2. The effect of continued heating will cause fusion of ice. When it is complete, the system again has one phase and becomes bivariant.

The temp. begins to rise along YZ. At Z vapour phase also appears. The no. of phases rises to 2 and system becomes monovariant. Continued heating will only result in more and more liquid into vapour. When the liquid phase disappears the system will have only one phase vapour and will become bivariant.(along ZZl).

Triple point: The effect of heat will be to cause more of solid to melt but there will not be rise in temp. or pressure until whole of solid has changed to liquid.The system now has 2 phases and hence becomes univariant. Further heating will cause rise of temp.(along curve OA). The effect of applying pressure will be to cause condensation of vapour to liquid or solid phase leading to vapour phase disappearing. Further application of pressure will cause increase of pressure with change in temp. along the curve OC.

Two component System.

F = C P + 2 = 2P+2=4P Since P=1(min.); F= 3. Ex. Mixture of 2 gases.( C=2; P =1;F=3) ( Temp., Pressure, Composition) Choose any 2 of 3 for graphic representation assuming third to remain constant.

If P = 2; F= 4 2 = 2 Unsaturated soln.of NaCl in H2O vapour. If P= 3; F =1. Saturated solnof NaCl in water vapour. If P = 4; F=0. Sat.soln.of sodium sulphate in water at 32.4oC.(s=2 l=1 g=1)

Two Component System:

These systems are studied at one atm. Pressure, by varying the temperature and composition of the system. For such systems the Gibbs phase rule takes the form P + F = C + 1. This is called condensed phase rule. The constant 2 in the Gibbs phase rule implies that both temperature and pressure are allowed to change.

The constant 2 in the Gibbs phase rule implies that both temperature and pressure are allowed to change. Since the pressure is held constant at atm. pressure, the constant is reduced from 2 to 1 in the condensed phase rule. Degree of freedom of such a system is given by, F=C+1-P F= 2 + 1 P F= 3 P This shows that the max.no.of phases coexisting in such a system is 3,with the degree of freedom becoming zero.

Lead Silver System:The temperature composition phase diagram of Pb-Ag system shown is the graphical representation of phases of this system existing under different conditions of temperature & composition.

A indicates the melting pt.(961oC) of silver.B indicates the melting pt.(327oC) of lead. Only one phase,liquid phase above ACB. Two solid phases exist below DCE.Melt and a solid phase exist between ACB and DCE.Melt and solid Ag exist within the area ACD.Melt and solid Pb exist within the area BCE.

Ag and Pb mixture of composition x is a melt at F corresponding to t1oC.When this melt is cooled, solidification starts at the pt.G corresponding to t2oC.Solid phase separating out is pure Ag. More Ag separates out as the system is cooled and as a result, composition of the melt existing at equilibrium with the solid changes along GC. Thus at t3oC solid Ag is at equilibrium with a melt of composition L.

At 303oC,corresponding to the pt H, complete solidification occurs.Two separate solid phases are present at this pt. They are solid Ag and another solid containingg 97.4% Pb and 2.6% Ag called eutectic solid. Mixtures of any composition from D to C behave exactly like this. But initial solidification temperature decreases along AC,as the composition of the mixture changes along DC. However, the final solidification temperature remains constant at 303oC along DC for all these mixtures. Mixture of composition, y is a melt at M.Solidification commences at N. Pure solid Pb separates and composition of the melt existing at equilibrium changes along NC,when the system is cooled. Solidification is complete at Q,corresponding to 303oC. Two solid phases, such as solid Pb and eutectic solid exist at Q.

Mixture of any composition from C to E behave exactly like this. Initial solidification temperature rises along CB and final solidification temperature remains constant at 303oC along CE for these mixtures of composition from C to E. Behaviour of mixtures on either side of C on cooling their melt can be summerized as follows.(i) Their solidification starts at definite higher temperatures,given by the points on ACB,depending upon their composition.Their solidification completes at 303oC,irrespective of their composition.

In other words, when these solids are heated,they start melting at 303oC.They melt completely at definite higher temperatures given by the line ACB.Thus, they solidify over a temperature range on cooling their melt or they melt over a temperature range when the solids are heated.Composition of the mixture determines the temperature range.It becomes narrower, as the compositionapproaches C from either side of this point.

(ii) All of them on complete solidification at 303oC yield eutectic solid as one of the two solid phases. (iii)The other solid phase formed depends upon the composition of the mixture.It is solid Ag,if the composition of the mixture is between D and C.It is solid Pb, if the composition is between C and E. Mixture of composition C is unique.It is a melt at R. No solid separates until pt.C at 303oC is reached,on cooling the melt.

Solidification starts at this temperature. Temperature does not change, until solidification is complete. This mixture behaves like pure Ag or pure Pb in this respect. That is, it shows definite solidification temperature or melting temperature. It melts completely at 303oC. Complete melting of other mixtures occurs at higher temperatures than 303oC, depending upon their composition, even though melting commences at 303oC.

Thus mixture C has the lowest melting pt. or it is the easily melting mixture. Therefore it is called eutectic mixture. The composition: 97.4 % Pb & 2.6% Ag is eutectic composition. Either pure Pb or pure Ag does not solidify from a melt of eutectic composition.The mixture solidifies completely as eutectic solid.Separation of Ag or Pb is not possible by cooling a melt of eutectic composition.

Desilverization Of Lead:
Pattinsons Process: This process of desilverization of lead is based upon the Pb Ag phase diagram. Pb extracted from its ores always contains small amounts of Ag and it is known as argentiferous lead. The argentiferous lead is allowed to cool from molten state. Pure Pb solidifies.

The melt gets enriched with silver. Solidification of pure Pb continues, until the melt is cooled to 303oC. Solid Pb formed at every stage is removed. At 303oC, the melt is an eutectic mixture of 97.4% Pb and 2.6% Ag. Pure lead does not solidify from it. The eutectic mixture itself solidifies, when cooled. The solid contains 2.6% Ag. This is Pattinsons process. The eutectic solid is melted and heated in air, when lead is oxidized to PbO. PbO floats over the melt as a solid scum.

 It is skimmed off.When Pb is removed like this completely, the melt left behind is Ag. It is cast into bars.