Chapter 12

Ideal Solution

Phase Equilibrium

1) Two miscible liquids , A and B, form an ideal solution when mixed if intermolecular attraction forces between A and A(AA), between B and B(B..B),and between A and B(AB) are equal. 2) Examples of ideal solution : (a) benzene and toluene (b) hexane and heptane (c) propan-1-ol and propan-2-ol (d) chlorobenzene and bromobenzene (e) tetrachloromethane and tetrafluoromethane 3 During mixing, there (a)no change in temperature (b)no change in total volume 4) The vapour pressure of a liquid is the pressure exerted by molecules of the liquid when a equilibrium is established between the vapour and the liquid at constant temperature.

Raoults Law
1) At a given temperature, if two liquid A and B form an ideal solutionof A is thevapour pressure directly proportional to mole fraction of A in the solution, and the proportional constant is the vapour pressure of pure A at the given temperature. 2) In mathematical terms,

xA + xB = 1
3) Total vapour pressure, P T :

PT = P A +PB =XA . P
A

+ XB . P
A

=(1- XB) P =XB (P

B

+ XB . P
A

-P

)+P

4) Graph of vapour pressure against XB :

5) Composition of vapour phase :

Using Daltons law of partial pressure, Partial pressure of a gas= Mole fraction . Total pressure Mole fraction of A, YA = PA / PT = PA /PA +PB Similarity, mole fraction of B , YB = PB /PT = PB /PA+PB And YA + YB = 1

Deviation from Raoults Law 1) Positive deviation: The vapour pressure of the solution is higher than that predicted by Raoults ,aw, that is the case where it behaves ideally. a) Without maximum point

b) With maximum point

Characteristics : a)Attractive forces between molecules of A and B are weaker than those between A-A and B-B. b)The molecules of A and B in the solution have greater tendency to escape into the vapour phase compared to those in pure liquids. 2)Effects of positive deviation : a) Increase in volume/the system expands b)Absorption of heat during mixing 3)Examples : a) Carbon disulphide and propanone b) Water and ethanol 4)Explanations : The molecule of carbon disulphide is linear, S=C=S, which is non -polar. The Molecule of propanone is polar. This is because O atom is more electronegative than carbon. Intermolecular forces between propanone-carbon disulphite are weaker than those that exist between propanone -propanone and between carbon disulphide-carbon disulphite. 6) Negative deviation : The vapour pressure of solution is less than that predicted by Raoults law. a) Without minimum point

b)With minimum point

characteristics : a) Attractive forces between molecules of A and B are stronger than those between A-A and B-B. b) The molecules of A and B have lesser tendency to escape compared to those in pure liquids. 7) Effects of negative deviation : a) Decrease in volume b) Heat is evolved 8) Examples : a) Trichloromethane and propanone b) Water and hydrogen fluoride c) Phenol and phenylamine 9) Explanation : ~Trichloromethane and propanone both are polar molecules. This is because trichloromethane has three chlorine atoms that attract electrons from their covalent bonds and due to inductive effect, the single hydrogen atom is very electron deficient and carries a partial positive charge. In the presence of propanone molecule, there is an attraction known as the H atom of trichloromethane. Boiling Point Composition Diagrams 1) Fractional distillation is a technique used in the laboratory to separate a mixture or two liquids of different boiling points into pure components. 2) For a mixture that consists of two component while the residue is the less volatile component. 3) Boiling point-composition diagram :

4) If you boil a liquid mixture C 1, it will boil at a temperature T 1 and the vapour over the

top of the boiling liquid will have the composition C 2. The vapour is much richer in the more volatile component B than the original liquid mixture was.

4) Uses : a) Manufacture of oxygen, nitrogen and noble gases from liquefied air. b) Purification of petrol c) Manufacture of whisky and other alcoholic drinks

Azeotropic Mixture: 1) Boiling point-composition diagram with maximum boiling point :

2) The solution with composition C is known as azeotropic mixture. 3) Two properties of azeotropic mixture : a) Constant boiling point

b) The equilibrium vapour has the same composition as the liquid. 4) The left hand side which has a bigger leaf shape will produce pure A as distillate and azeotropic mixture as residue. 5) While the right hand side which has smaller leaf wi ll produce pure B as distillate and azeotropic mixture as residue. 6) Boiling point-composition diagram with minimum boiling point :

7) The solution with composition Z 2 is the azeotropic mixture having its boiling point. 8) The fractional distillation on solution of right side(small leaf shape) will give azeotropic mixture as distillate pure B as residue. While the left side(big leaf shape) will also give azeotropic mixture as distillate and pue A. 9) An azeotropic mixture cannot be separated into pure components by fractional distillate. 10) An azeotropic is a mixture of two liquids of certain composition having a constant boiling point and the vapour given off during boiling has the same

composition as that of the mixture. It is n ot a compound as there is no chemical reaction involved. 11) Fractional distillation on an azeotrop would give the same azeotrop as distillate.

Steam Distillation: 1) Two immiscible liquids separate into layers when mixed together. They are independent of each other. 2) When the mixture is shaken and allowed to reach equilibrium, the vapour phase contains the molecules of both components. 3) In systems of water and organic liquids which are not miscible, the vapour pressure of each component is the same as that of pure liquids respectively. Total pressure, P T = P
1

+P

4) The mixture boils when total pressure equals to 1.0 atm. Hence, the boiling oint of the mixture is lower than that of each component. 5) The vapour composition and the boiling point of system are always constant. 6) Since the saturated vapour pressure of a liquid is directly proportional to the mole fraction in the vapour phase, P1 P2

Where n1 = number of moles of organic substance, and N2 = number of moles of water.

Where m= mass in gram, and M+ molecular mass

7) In order to obtain a high ratio of a) high molecular mass

, the organic substance should have:

b) high vapour pressure at the boiling point of the mixture 8) The distillate contains water and the organic substances in constant composition. 9) Uses : a) Purification of organic substances of high boiling points b) Purification of organic substances that decompose at boiling point. c) Determination of molecular mass of unknown substances.

Distribution of Solute between Two Phases : ~ distribution law (partition law) 1)If a solute X is dissolved in two immiscible liquids and in the state of equilibrium,
         

= K ; where K is known as partition

coefficient and value of K is constant at a given temperature. 2) The partition law is true if a) temperature remains constant b) X exists in the same molecular state in both solvents c) X does not decompose or associate in each solvent d) X does not react with solvent

3) The law is not obeyed if a) HCI is distributed between water and benzene b) ethanoic acid is distributed between water and CCl 4 4) Experiment to determine the partition coefficient of iodine between water and tetrachloromethane : a) Shake a small amount of iodine with certain vol umes of water and CCI 4 b) Allow the system to reach equilibrium c) Using a pipette, transfer a sample of bottom layer into a conical flask and titrate with standard aqueous sodium thiosulphate. d) Repeat the above process on the upper layer. e) Partition coefficient, K=
        

f) Repeat the experiment by using different volumes of water and CCI 4 . 5) If ammonia solution is shaken with trichloromethane , two layers are formed and the molecules of NH 3 are distributed between them. 6) The concentration of ammonia in each layer and titrate with standard HCI. Ammonia will be neutralized by HCI according to equation: HCI + NH3 NH4CI

7) Experiment results show that the partiti on coefficient is 23.5:

         

= 23.5

8) If a solute X associates in one layer but remains as a monomer

In another, the partition law can be modified a follow:

Solvent 1

Xn

Solvent 2

 

   

 

 

=K1

Where K1 is the partition coefficient = Log =K = log K

Log C1 n log C 2 = log K Hence, log C 1 = n log C 2 + log K 9) The advantages of ether as extracting agent: a) Inert, non-reactive, many organic subtances are very soluble in it. b) Low density and will separate as upper layer in the separating funnel. c) Very volatile and can be distilled over easily, leaving the solute as residue. d) Immiscible with water. 12) Disadvantages of ether: a) Highly flammable b) The vapour is very poisonous

13) In laboratory extraction, it is more effective if the ether provided is divided into a few equal proportions and carry out the extraction with each one of them. More solute can be extracted into the organic layer with this method.

Chromatography:

~Chromatography is a chemical technique for separating mixtures of coloured chemicals. This technique is important in biology as well as chemistry; it is also used by forensic scientists.

1) Types of chromatography : a) Thin layer chromatography b) Paper chromatography

c) Gas chromatography 2) Uses: a) To identify substances in a mixture b) To determine the purify of a substance 3) Thin layer chromatography a) Development of thin layer

b) Chromatogram

4) Determination of

values:
     

=
5) Result:

Substance

A  

B   

C   values

6) The identities of A, B, and C can be determined by comparing their with those of standard values.