( 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 ) Phase Equilibria ( Total Recall ) All prepared by alextan58@gmail.com
( 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
Phase Equilibria ( Total Recall ) All prepared by alextan58@gmail.com ( iii ) Diagram [ Benzene & methylbenzene ] (a) Vapour pressure-composition diagram ( STPM 1999 ) (b) Boiling point-composition diagram ( Pahang 2011 )
Phase Equilibria ( Total Recall ) All prepared by alextan58@gmail.com
( 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
Phase Equilibria ( Total Recall ) All prepared by alextan58@gmail.com
( iii ) Diagram [ Nitric (V) acid and water ] (a) Vapour pressure-composition diagram ( STPM 2007 S ) (b) Boiling point-composition diagram ( STPM 2006 E )
Phase Equilibria ( Total Recall ) All prepared by alextan58@gmail.com
( 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 ) All prepared by alextan58@gmail.com ( iii ) Diagram [ ethanol and water ] (a) Vapour pressure-composition diagram (b) Boiling point-composition diagram ( STPM 2004 E / 2009 S )
Phase Equilibria ( Total Recall ) All prepared by alextan58@gmail.com
( 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
Phase Equilibria ( Total Recall ) All prepared by alextan58@gmail.com
( 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 .