Phase Equilibria ( Total Recall )

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( A ) Raoults law & azeotropic mixture

( A ) Raoults law
( i ) Definition [ STPM 1999 ] ( ii ) Formulae / Calculations
The vapour pressure , PA of a mixture of miscible liquids is given
by the product of the vapour pressure of that pure component
P
o
A and its mole fraction .
PA = P
o
A XA
PA = P
o
A XA / PB = P
o
B XB
PT = PA + PB
XA =
()
+ ()
/ XB =
()
+ ()

XA + XB = 1
( B ) Azeotropic mixture
( i ) Definition [ STPM 2007 ]
A mixture with a constant boiling point and has a fixed composition which cannot be separated by distillation .
( ii ) Limitations on the separation of two components forming an azeotropic mixture
~ Complete separation cannot be done .

( iii ) How to obtain pure ethanol from an azeotropic mixture with 96% of ethanol ??
~ Use anhydrous calcium chloride ( CaCl2 dehydrating agent )
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( B ) Ideal mixture
( i ) Properties
Attractive forces : same strong
Vapour pressure : same as estimated by Raoults law
Volume of solution : exactly same as the total volume of liquids
Enthalpy change : zero ( thermally neutral ) [ heat released during bond formation = heat absorbed during bond breaking ]
Temperature of solution : remain unchanged

( ii ) Examples
Mixture of liquids Type of intermolecular forces
1. Benzene & methylbenzene ( toluene ) [ STPM 1999 ]

van der Waals forces
2. Heptane & octane [ STPM 2007 S ] / hexane & heptane

van der Waals forces
3. Methanol & water

Hydrogen bonds
4. Propan-1-ol & propan-2-ol / butan-1-ol & butan-2-ol

Hydrogen bonds


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( iii ) Diagram [ Benzene & methylbenzene ]
(a) Vapour pressure-composition diagram ( STPM 1999 ) (b) Boiling point-composition diagram ( Pahang 2011 )




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( C ) Negative deviation
( i ) Properties
Attractive forces : ( solution ) stronger than( pure liquids )
Vapour pressure : less than estimated by Raoults law
Volume of solution : less than the total volume of liquids
Enthalpy change : exothermic ( negative ) [ heat released during bond formation > heat absorbed during bond breaking ]
Temperature of solution : increase

( ii ) Examples
Mixture of liquids Type of intermolecular forces
1. Nitric acid and water ( STPM 2006 )

Pure liquid Solution
Nitric acid : Permanent
dipole( van der Waals forces )
Water : hydrogen bonds

Electrostatic force / Ionic
bond
2. Chloroform ( trichloromethane ) and acetone ( propanone )

Chloroform : Permanent
dipole( van der Waals forces )
Acetone : Permanent
dipole( van der Waals forces )
Hydrogen bonds
3. Acetone and tribromomethane ( bromoform )

Bromoform : Permanent
dipole( van der Waals forces )
Acetone : Permanent
dipole( van der Waals forces )
Hydrogen bonds
4. Methanoic acid ( formic acid ) and water


Methanoic acid : hydrogen
bonds
Water : hydrogen bonds
Ion-dipole attractions

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( iii ) Diagram [ Nitric (V) acid and water ]
(a) Vapour pressure-composition diagram ( STPM 2007 S ) (b) Boiling point-composition diagram ( STPM 2006 E )







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( D ) Positive deviation
( i ) Properties
Attractive forces : ( solution ) weaker than ( pure liquids )
Vapour pressure : more than estimated by Raoults law
Volume of solution : more than the total volume of liquids
Enthalpy change : endothermic ( positive ) [ heat released during bond formation < heat absorbed during bond breaking ]
Temperature of solution : decrease

( ii ) Examples
Mixture of liquids Type of intermolecular forces
1. Ethanol and water ( STPM 2009 ) Pure liquid Solution
Ethanol : hydrogen bonds
( weaker )
Water : hydrogen bonds
( strong )
Hydrogen bonds
( weakest )
2. Propan-1-ol and water

Propan-1-ol : hydrogen bonds
( weaker )
Water : hydrogen bonds
( strong )
Hydrogen bonds
3. Butan-1-ol and methylbenzene

Butan-1-ol : hydrogen bonds
Methylbenzene : van der Waals
forces
van der Waals forces
4. Chloroform ( trichloromethane ) and ethanol

Chloroform : van der Waals
forces
Ethanol : hydrogen bonds
Hydrogen bonds
( weak )

Phase Equilibria ( Total Recall )
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( iii ) Diagram [ ethanol and water ]
(a) Vapour pressure-composition diagram (b) Boiling point-composition diagram ( STPM 2004 E / 2009 S )








Phase Equilibria ( Total Recall )
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( E ) Fractional distillation
( i ) Principle ~ Answering skill * Refer full notes !!!
Mixture with C1 composition will be heated to boil at T1 temperature .
This will produces a vapour with C2 composition with more ( ) .
The vapour will be cooled in the column and forms liquid .
The liquid with C2 composition will be reheated to form a vapour at T2 temperature with C3 composition which is riched in ( ) .
Boiling , cooling and condensation process will be repeated .
( ) will be obtained as distillate and ( ) will be the residue .

( ii ) For ideal mixture

Distillate : ( pure liquid ) ~ a lower boiling point / higher vapour pressure
Residue : ( pure liquid ) ~ a higher boiling point / lower vapour pressure
( iii ) For negative deviation
Distillate : ( pure liquid ) ~ a lower boiling point / higher vapour pressure
Residue : ( azeotropic mixture ) ~ a higher boiling point / lower vapour pressure
* Must write the composition !!!
( iv ) For positive deviation
Distillate : ( azeotropic mixture ) ~ a higher boiling point / lower vapour pressure
* Must write the composition !!!
Residue : ( pure liquid ) ~ a lower boiling point / higher vapour pressure



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( F ) Fractional distillation under reduced pressure
( i ) Advantages
The fractional distillation can be carried out at lower temperature .
So that , the organic substance which are not stable at high temperature can be extracted .
*Extra !!!
At reduced pressure , the boiling point of organic substance will be lowered .
Thus , the organic substance can be extracted without any decomposition .
( ii ) Disadvantages
At reduced pressure , apparatus that are strong and can withstand low pressure have to be used .
This will increases the cost of extraction .