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Strength of
Strength of
Strength of Intermolecular
Intermolecular Intermolecular attraction between
attraction in pure A attraction in pure B particle A and
particle B in mixture
• the escape tendency of molecule A or B in
mixture equals to their respective escape
tendency in pure A and pure B
• ===> no enthalpy change upon mixing
• ===> no volume change upon mixing
• Reasons: interaction doesn’t change upon
mixing
• more nearly alike the two substances are
chemically, the more nearly they exhibit ideal
behaviour
Actually, ideal solutions are seldom found and their existence only
holds for very dilute solutions.
Ex. 21.3
• Which of the following solution mixtures
are ideal solutions?
• a) benzene and methylbenzene
• b) cyclohexane and ethanol
• c) bromomethane and iodomethane
• d) propanone and trichloromethane
• e) propan-1-ol and propan-2-ol
• f) n-hexane and n-heptane
Composition of vapour?
Average
Strength of
Strength of
+ Strength of > Intermolecular
Intermolecular Intermolecular attraction between
attraction in pure A attraction in pure B particle A and
particle B in mixture
• The vapour pressure would be higher and the boiling
point would be lower compared with ideal behaviour
Example: Binary mixture of cyclohexane and ethanol
CH3CH2 O
H H
O
CH3CH2
CH3CH2 O
H
CH3CH2 O
H
CH3CH2 O
H
Average
Strength of
Strength of
+ Strength of < Intermolecular
Intermolecular Intermolecular attraction between
attraction in pure A attraction in pure B particle A and
particle B in mixture
• The vapour pressure would be lower and the boiling
point would be higher compared with ideal behaviour
Example: mixture of ethyl ethanoate & trichloromethane
CH3 CH3 Cl
Cl
O C O C H C Cl H C Cl
OC2H5 OC2H5 Cl Cl
Weak Van der Waal’s force
in pure ethyl ethanoate Weak Van der Waal’s force
in pure trichloromethane
Cl CH3
Cl C H O C
Cl OC2H5
B.p.(A)
PBo
y(g) z(g)
x(l) y(l)
y(l) z(l)
Repeating boiling and condensation
Tedious!!!
Tz
z(l)
Fractional distillation
fractionating tower for petroleum refining
21.5 Azeotropic Mixtures
Liquid mixtures which deviate negatively from Raoult's law
show a maximum in the boiling point-composition curve
Start from x
==> distillate = pure B
Start from w
==> distillate = pure A
Start from M
==> distillate = remain M
M is azeotropic mixture/
constant boiling mixture
(vapour composition =
liquid composition upon
boiling)
• Start from x, residue?
• Azeotropic mixture M
• Start from w, residue?
• Azeotropic mixture M
• start from M, residue?
• Azeotropic mixture M
• What to do for M?
Discard?? Think about
it !!!
Positive Deviation from Raoult’s Law
Liquid mixtures which deviate positively from Raoult's law
show a minimum in the boiling point-composition curve
• Start from X, distillate and
residue?
• Distillate =
Azeotropic mixture M
Residue = pure B
• Start from Y, distillate and
residue?
• Distillate =
Azeotropic mixture M
Residue = pure A
• start from M, distillate and X Y
residue?
• Azeotropic mixture M
• impossible to separate a non-ideal solution into
pure components by fractional distillation!
What should we do with azeotropic mixture??
Discard???
Solve the problem???
• Add a little amount of one of the component
and fractional distillation can be continued!!!
Ex 21.8
a) A constant boiling mixture (azeotropic mixture) is a
mixture of liquids with a fixed composition and it cannot
be separated by fractional distillation since the vapour
composition is the same as the liquid composition.