L.S.T. Leung Chik Wai Memorial School F.

6 Chemistry Chapter 22: Phase Equilibrium II

Chpt.22: p.1

Two Component Systems (A) Ideal Systems System which obey Raoults Law (1) Ideal solution There are 3 categories of twocomponent liquid mixtures: Completely miscible liquids : e.g. water and ethanol partially miscible liquids : e.g. water and butanoic acid immiscible liquids : e.g. water + oil / benzene / organic solvent

The completely miscible liquids are homogeneous mixture or solutions. A model of ideal solution can be developed and then the deviations of real and non-real solutions can also be shown. A solution is said to be ideal if the intermolecular forces between its molecules were just the same as those existing in the separate components of the solution, before these component are mixed together into solution. Note : An ideal solution has the following properties:

(1) Intermolecular attractions between like molecules (A-A and B-B) and unlike molecules (AB) are equal . There is thus little or no tendency for molecules to hinder or help the escape into the vapour phase of molecules of the other component. (2) There is no enthctlpy change on mixing of the two components. (3) There is no volume change on mixing of the two components. Ideal solutions obey Raoults Law. Raoults Law states that the partial pressure PA of component A in a solution equals the vapour pressure of pure component (PA0) multiplied by the mole fraction (XA) of the component in the solution. For an ideal solution consisting of two components A and B. Raoults Law maybe expressed as PA = XA PA0 and PB = XB PB0

The vapour of an ideal solution ma be considered to be an ideal gas, and Daltons law therefore applies. Thus the total vapour pressure (PT) of the solution is given by PT = PA + PB , hence PT = XA PA0 + XB PB0

Assumption of Raoults Law : the escaping tendency into vapour is proportional to the vapour pressure. Note : The vapour above a mixture of liquids does not have the same composition as the liquid. If XA(V) and XB(V) are the mole fractions of A and B in the vapour phase.

L.S.T. Leung Chik Wai Memorial School F.6 Chemistry Chapter 22: Phase Equilibrium II

Chpt.22: p.2

X A(V ) X B (V ) If A is more volatile than B PA0 > PB0 and X A(V ) X B (V ) > X A(l ) X B (l )

X A( l ) PA P = A = PB X B ( l ) PB 0

The vapour is richer than the liquid in A, the more volatile component. Example : At 80C, the vapour pressure of benzene is 10.0x104 Nm-2 and that of methylbenzene is 4.0xl04 Nm-2 . Estimate the mole fraction of methylbenzene in the vapour in equilibrium with a liquid mixture of benzene and methylbenzene at 80 0C in which the mole fraction of methylbenzene is 0.60. SOLUTION

<2> Graphical Representation of Raoults Law The following figure illustrates graphically the vapour pressure of an ideal solution which obeys Raoults law at all concentrations. -

(1) A plot of PA. and PB against XA and XB gives a straight line because the partial pressure of A and B are ____________________________________________________________ (2) The total pressure PA+PB also gives a straight line when plotted against mole fraction of the liquid. (3) Few liquids show this kind of ideal behaviuor. However, the solution would exhibit ideal behaviour nearly if the components are chemically alike.

L.S.T. Leung Chik Wai Memorial School F.6 Chemistry Chapter 22: Phase Equilibrium II

Chpt.22: p.3

(4) Most mixtures (solution) contain one component which is more volatile (i.e. higher vapour pressure) than the other. e.g. X = a more volatile liquid, has higher escaping tendency Y = a less volatile liquid, has lower escaping tendency For the plot of vapour pressure- vapour composition, when a liquid of composition a is boiled, the vapour in equilibrium with it. has a composition b - richer in the more volatile component X

For the plot of Boiling point-vapour composition, the vapour which is in equilibrium with the liquid mixture at a particular temperature always has a higher proportion of the more volatile component

Example (i) A mixture of 70% Y is distilled. The temperature of the liquid rises until it boils at T1. (ii) At T1 the boiling liquid has a composition of 70% Y whereas the vapour in equilibrium has a composition of 46% Y. At the same time, the more volatile component has 54% in vapour, which is richer than that in the liquid (30%). (iii) When the vapour cools down, it forms a distillate with the same composition as vapour (46%Y). It this liquid is distilled again the new distillate boiling at T2 contains 20% of the less volatile component Y only. The more volatile component becomes further enriched to 80%.

L.S.T. Leung Chik Wai Memorial School F.6 Chemistry Chapter 22: Phase Equilibrium II

Chpt.22: p.4

L.S.T. Leung Chik Wai Memorial School F.6 Chemistry Chapter 22: Phase Equilibrium II

Chpt.22: p.5

(B) Non-ideal System Two component systems Raoults law is an idealization which best holds for very dilute solutions. A high dilution reduces the differences in molecular structure of the components which give rise to either attractive or repulsive interaction between them. Non-ideal solutions are those solutions with strong deviation from the ideal solutions ( either positive or negative) because of the strong interaction between the solute and solvent molecules.

(1) Positive deviation The vapour pressure of a mixture is greater than that predicted for an ideal solution. Reasons : (i) Attractions or bonding between molecules of component A and B (AB) are weak. (ii) Bonding of AA and BB types are broken on mixing the two components. These bonds are often hydrogen. bonds. As a result of these two factors, molecules of A and B have a greater tendency to escape from the liquid phase into the vapour phase. The liquid mixture thus has a higher vapour pressure. Note : When the two components of such a system is mixed, a temperature fall is usually observed. (2) Negative deviation The vapour pressure of a mixture is smaller than that predicted for an ideal solution. Reasons : AB attractions or bonds are stronger than AA and BB attractions or bonds. The molecules are consequently held back in the liquid phase and the vapour pressure is lower. When the two components of such a system is mixed, a temperature rise is usually observed.

Note :

Table Liquid mixture which deviate from Raoults Law Positive deviation Negative deviation benzene/ethanol methanol/water water/ethanol nitric acid/water ethyl ethanoate /ethanol trichloromethane/propanone ethanol/carbon disuiphide When a mixture of two liquids shows very large positive deviation from Raoults law, the vapour pressure-composition curve has minimum. A system with a very large negative deviation shows a minimum. The following figures shows the Liquid-vapour phase diagrams showing the positive and negative deviation from Raoults law and Boiling temperature-composition curve for systems. A maximum in the vapour pressure curves results in a minimum in the boiling temperature composition curve and vice versa.

L.S.T. Leung Chik Wai Memorial School F.6 Chemistry Chapter 22: Phase Equilibrium II

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Example At 50 0C, the vapour pressure of benzene (C6H6) is 273 torr and that of methylbenzene (C6H5CH3) is 95.0 torr. Assuming ideal behaviour, determine the total vapour pressure at 50C of a mixture of 15.62g of benzene and 73.70g of methylbenzene. In an actual experiment the vapour pressure observed in the above system is 148 torr. Briefly explain the origin of any difference. SOLUTION

<2> Bonding Interpretation of Non-ideal behaviour in terms of Molecular Interactions The vapour pressure of a liquid is a measure of the escaping tendency of the molecules within the solution. (a) Positive deviation The vapour pressure of a mixture is greater- than that predicted for an ideal solution and the boiling point is lower than expected. Example : The system of ethanol and methylbenzene In pure ethanol, the molecules are strongly polarized so that they are associated by hydrogen bonds.

When methylbenzene is introduced, the overall intermolecular attraction between the molecules are weakened by breaking up many hydrogen bonds. Thus, the escaping tendency of the molecules is enhanced and the vapour pressure rises and the boiling point falls. Note : A fall of temperature is observed because of the _____________________________________________________________________________ (b) Negative deviation The vapour pressure of a mixture is smaller than that predicted for an ideal solution and the boiling point is higher. than expected. Example : The system of trichloromethane and ethyl ethanoate In such system. new intermolecular attraction, the intermolecular hydrogen bonds is formed. This attraction is stronger than the van der Waals. forces existing in molecules of either pure liquids.

Note : A rise of temperature is observed because of the _____________________________________________________________________________

<3> Fractional Distillation Fractional distillation has a number of important applications (1) the manufacture of oxygen, nitrogen and the noble gases from liquid air. (2) the refining of petroleum. (3) the production of whisky and other alcoholic drinks. The process can be carried out by using a fractionating column (in laboratory) or fractionating tower (in industry).

Fractional distillation is equivualent to a series of consecutive simple distillation, where the condensed vapour from a previous distillation is used as the liquid for the next distillation. At each point in a column, or at each plate in a tower, an equilibrium between liquid and vapour is set up. The component with different boiling points in a mixture can be separated using fractional distillation.

Fractional Distillation of an ideal solution Example : mixture of benzene and methylbenzene (toluene)

(i)

A mixture with composition X boils at the temperature t1. the

(ii) The vapour that comes out has a composition Y, and is condensed at some point during its assent in fractionating column.

(iii) By the heating effect of further hot vapour rising up. it boils again at t2 to form a vapour of composition Z. (iv) The liquid condensed from the vapour becomes increasingly richer in benzene (the more volatile component) (v) Pure benzene can be obtained at the top of the column if the column is sufficiently long and the cooling surface area is sufficiently large. The distillate is collected at about 800C, the boiling point of benzene.

Fractional Distillation of solution showing a Negative deviation from the Raoults law The following figure shows the boiling point against composition diagram for a solution showing negative deviation from ideality.

(1) At the maximum point Z1 the liquid and the vapour have the same composition. For a mixture having composition P is distilled, the vapour formed at t1 has exactly the same composition as the liquid and no separation of the components is achieved. (2) For mixture having composition a is heated, the vapour initially formed at t2 has a composition y (richer in the more volatile compound A). If this vapour is then condensed and re-distilled, the vapour formed will have composition x. Carrying out this process in a fractionating column results finally in the separation of pure A in the distillate, leaving the maximum, constant boiling mixture in the flask. (3) For the solution has a composition to the right of Q, pure B would be obtained in the distillate, leaving the maximum, constant boiling mixture azeotrope . (4) System showing positive deviation from ideality are separable into the minimum, constant boiling mixture and the pure components.

Example The diagram shows the boiling point composition variation of a two component at 1 atmospheric pressure. (a) Find from the graph the initial and final compositions of the vapour above a mixture M (mole fraction XA = 0.4) when the mixture is distilled at 1 atmospheric pressure. (b) Starting with this mixture M, determine the minimum number of evaporation-condensation cycle (i.e. minimum number of distillation) required to produce a distillate in which XB is at least 0.9) (c) Can this two component system be separated completely by fract1ional distillation? Explain the answer briefly.