CHEMISTRY FORM 6

PHYSICAL CHEMISTRY
CHAPTER 8
PHASE EQUILIBRIA

12.1 Introduction to Ideal solution

Miscible liquids
-

Formed when 2 solution

can dissolve completely
with each other and
formed a homogeneous
solution
Example : ethanol and
water

Immiscible liquids

Partially miscible liquid

- When 2 solutions are
Formed 2 separate layers
mixed, only a little
of solution when 2
amount of the solution
immiscible solutions are
can mixed with each
added together.
other. There are still 2
Example : Benzene and
visible layers observed
water
- Example : ether and
water

An ideal solution formed when 2 solutions are mixed together,

Intermolecular forces formed between A---A = B---B =A---B.
Theres no change of volume on mixing
No enthalpy change occur on mixing the solutions

As a result, the partial pressure exerted by each individual

solution of an ideal solution will be lesser than the pressure
exerted by its pure liquid, as the volume of the mixing
solution increased.

 Since it is a mixing solution, the vapour pressure exerted by each

individual solution depends on the composition of A and B. The
relationship between the vapour pressure and the composition of
liquid mixture is given by Raoults Law which state that the
partial pressure of A in a solution at a given temperature is equal
to the vapour pressure of pure A multiplied with the mole fraction
of A in the solution (or equation, PA = xA . P0A )
From the pressure exerted through vaporisation, using Daltons
Law Partial pressure of gas.
Total vapour pressure, Ptot = PA + PB
Partial pressure of A = mol fraction of A x Vapour pressure of
PA = xA PoA
Partial pressure of B = mol fraction of B x Vapour pressure of B
PB = xB PoB
From the pressure exerted through vaporisation, using Daltons
Law Partial pressure of gas.
Total vapour pressure, Ptot = PA + PB

Vapour Pressure / kPa

P0B

Po A

1
mol fraction of B

 Example : Given the vapour pressure of hexane and heptane are

10 kPa and 3 kPa respectively. If the mole fraction of hexane in
liquid mixture of hexane and heptane is 0.4, calculate the mole
fraction of heptane in the vapour that is in equilibrium with liquid
mixture
Solution : mol fraction of heptane in liquid mixture = 1 0.4 = 0.6
Phex = xhex Phex = 0.4 (10 kPa) = 4.0 kPa
Phep = xhep Phep = 0.6 (3 kPa) = 1.8 kPa
Ptotal = Phex + Phep = ( 4.0 + 1.8 ) kPa = 5.8 kPa
Mol fraction of heptane in vapour = PB / Ptot
= 1.8 kPa / 5.8 kPa = 0.31

 Example : Mixing benzene with methylbenzene gives an ideal

solution. If the vapour pressure of benzene and methylbenzene are
90 kPa and 78 kPa respectively. Calculate the mole fraction of
benzene in the vapour at a mixture composition of
a) mole fraction of benzene = 0.20
PB = xB . P0B
PMB = xMB . P0MB
PB = 0.20 x 90 kPa PMB = 0.80 x 78 kPa
PB = 18 kPa
PMB = 62.4 kPa
Ptot = 18 + 62.4 = 80.4 kPa
In vapour
Mol fraction, xB = PB / Ptot
xB = 18 / 80.4
= 0.224

b) mole fraction of methylbenzene = 0.35

PB = xB . P0B
PMB = xMB . P0MB
PB = 0.65 x 90 kPa PMB = 0.35 x 78 kPa
PB = 58.5 kPa
PMB = 27.3 kPa
Ptot = 58.5 + 27.3 = 85.8 kPa
In vapour
Mol fraction, xB = PB / Ptot
xB = 58.5 / 85.8
= 0.682

 For an ideal solution, the boiling point composition graph is the

inverse of vapour pressure composition graph
If solution A is more volatile than solution B, the vapour pressure of A
HIGHER than in B.
is ..
In the vapour pressure composition graph, the straight line Ptot also
represent the composition of the liquid phase, whereas the curve
represent the composition of the vapour phase

kPa

0
Vapour pressure composition graph

oC

10

1
Boiling point composition graph

12.2
Fractional Distillation
The most efficient method for separating an ideal solution is by
using fractional distillation. The typical apparatus for carry out
fractional distillation is shown in figure below
i. The distillation column is a long
tube filled with glass beads or short
pieces of glass tubing. The
distillation column provides a large
surface area where condensed liquid
and ascending vapour can have
maximum contact.
ii. The length of the distillation
column is largely determined by the
difference in boiling point of the
components to be separated, the
smaller the difference ; the longer
the distillation column needed to
achieve good separation.

12.3 Non ideal solution

In a non-ideal solution :
The intermolecular forces of attraction between A---B could
be stronger or weaker than A---A and B---B
Thus, the partial vapour pressures and the total pressure
measured can be lower or higher than expected.
When this occur, we said that the mixture solution formed
deviates from Ideal Solution.
In the deviation from ideal solution, it can be categorise into 2
type of deviations
a) Positive deviation
b)
Negative deviation

Negative deviation
HCl H2O ; HNO3 H2O ; H2SO4
Example HCOOH ; phenol aniline ; acetone
(CH3COCH3) CHCl3

Positive deviation
Propanol H2O ; ethanol H2O ;
ethanol toluene ; ethanol and
benzene

Happen
when

Intermolecular forces between A---B

molecules are stronger than in
between A---A and B---B

Intermolecular forces between A---B

molecules are weaker than in
between A---A and B---B

Partial
pressure
of
mixture

Since the intermolecular forces are

stronger in A---B ; the partial vapour
pressure are lower than expected in
Raoults Law

Since the intermolecular forces are

weaker in A---B ; the partial vapour
pressure are higher than expected in
Raoults Law

Since the intermolecular forces are

Heat
stronger, meaning that A --- B are
changes more stable than their individual
forces, thus the process is exothermic

Since the intermolecular forces are

weaker, meaning that A --- B are less
stable than their individual force thus
the process is endothermic

Negative deviation

Positive deviation

HCl and H2O

Ethanol, C2H5OH and H2O

Reason

Volume
of
mixture

The forces hold between HCl HCl

are pure Van Der Waals forces
whereas the forces between H2O
H2O are pure hydrogen bonding
However, when HCl and H2O are
mixed together, it will ionised to form
HCl + H2O
H-3O+ + ClThe ionic interactions between
hydrated ions are stronger than both
Van Der Waals forces and hydrogen
bond.

The intermolecular forces between

ethanol ethanol are hydrogen
bonding and same goes to between
water water.
However, when this 2 solutions are
mixed, the hydrogen between water
are broken by ethanol and reduce the
intermolecular forces formed between
ethanol water.

Since mixing the solution causes a

stronger attraction forces formed
between A---B ; so when 50 cm3 A +
50 cm3 B < 100 cm3.

Since mixing the solution causes a

weaker attraction forces formed
between A---B ; so when 50 cm3 A +
50 cm3 B > 100 cm3.

Negative deviation

Vapour
pressure
compositi
on curve

Boiling
point
compositi
on curve

Positive deviation

Negative deviation
Mixture
Water

b.p. (oC)

Positive deviation
Azeotrope

Azeotrope
b.p. (oC)

100

Mixture

b.p.

(oC)
b.p. (oC)

composition
31.8

120.5

C2H5OH

78.5

composition
95.6

78.0

HNO3

86

68.2

Water

100

4.4

CHCl3

61.2

80

CHCl3

61.2

93

C2H5OH

78.5

64.5
CH3COCH3

56.2

20

59.4
7

Negative deviation

vapour

Boiling
point of
pure A
First distillate :
Pure A
2nd Distillate :
Azeotropic mixture
Residue
Pure B

liquid

First distillate :
Pure B
2nd Distillate :
Azeotropic mixture
Residue
Pure A

Boiling
point of
pure B

Positive deviation

Boiling
point of
pure A

First distillate
vapour:
Azeotropic mixture
2nd Distillate :
Pure A
Residue
Pure B

Boiling
point of
pure B

liquid

First distillate :
Azeotropic mixture
2nd Distillate :
Pure B
Residue
Pure A

12.4 Fractional distillation under reduced pressure

Distillation under reduced pressure is usually used to distil
out substances that have high boiling point.
A substance will only boiled when its vapour pressure
reaches the external pressure
Some organic solution decomposed at temperature below its
boiling point at atmospheric pressure. It is therefore
undesirable to distil such liquid at normal boiling point.
In such case, theres a necessity to distil at reduced pressure
To do this a vacuum pump is connected to side arm to
reduce the pressure.
So, if the external pressure is reduced, the boiling point is
also reduced (less heat is required), theres no need to
distillate at its normal boiling point and therefore, may
prevent the decomposition of the organic substance

 The disadvantage of reduced pressure distillation

The apparatus has to be strong to withstand reduced pressure
The liquid boils irregularly
Other impurities with low boiling point may also be distilled.
P/atm
1.0
0.8
0.5

< b<c

T/0C

1. The vapour pressure of water at 26C is

3 350 Pa. What is the vapour pressure of a
solution containing 72 g glucose, C6H12O6,
in 100 cm3 water? (Given density of water
= 1 g / cm3)
Mol of glucose = 72 g / 180
= 0.40 mol
Mol of water = 100 g / 18
= 5.56 mol
Xwater = 5.56 / (5.56 + 0.40)
= 0.93
Pwater = Xwater x P0w
= 0.93 x 3350
= 3120 Pa

2. The vapour pressure of pure benzene

at 30C is 0.1600 atm. When 20 g of a
non-volatile solvent, X, is dissolved in 180
g benzene, the vapour pressure of the
resulting solution is 0.1572 atm.
Determine the relative molecular mass of
the solvent X if the relative molecular
mass of benzene is 78.

PB
PB = x B . P @ x B = 0
PB
0
B

180
78
180
78

+ M20R

0.1572
=
0.1600

M R = 486.6

3. Calculate the mass of potassium

chloride, KCl, that must be added to 200
cm3 of water to lower its vapour pressure
by 350 Pa at 37C? (The vapour pressure
of water at 37C is 7 310 Pa).

xw

Pw
6960
= 0 xw =
7310
Pw

x w = 0 . 952
xw =
xw =

nw

nw
+ n KCl
200
18

200
18

m
74 . 5

Mass of KCl = 41.7 g

4. At temperature T, the vapour pressure

of pure benzene and ethanol are 120 mm
Hg and 50 mm Hg respectively. Assuming
that these liquids form an ideal solution
when mixed, plot a vapour pressurecomposition graph for the mixture. If
mole fraction of ethanol in the solution
mixture is 0.5, determine from the graph
(a) the mole fraction of benzene in the
vapour phase
(b) the partial vapour pressure of ethanol
(c) the total vapour pressure

a) 0.71
b) 25 mm Hg
c) 85 mm Hg

5. Methylbenzene and benzene forms an

ideal solution. The vapour pressure of pure
benzene and methylbenzene are 122 mm
Hg and 37 mm Hg respectively at room
temperature. A solution mixture contains
0.40 mole fraction of benzene.
(a) Determine the total vapour pressure
of the solution mixture.
(b) What is the composition of the vapour
which is in equilibrium at room
temperature with the above
methylbenzene-benzene mixture?
a)

b)

PB =
=
PMB =
=
Ptot =
XB =
=
XMB =

0.40 x 122 mm Hg
48.8 mm Hg
0.60 x 37 mm Hg
22.2 mm Hg
48.8 + 22.2 = 71.0 mm Hg
48.8 / 71.0
0.687
1.0 0.687 = 0.313

6. The vapour pressure of pure methanol,

CH3OH, at 298 K is 12.8 kPa. How many
moles of a non-volatile solute X per mole
of methanol is required to prepare a
solution of methanol having a vapour
pressure of 10.6 kPa at 323 K?
xM
nx

=
=
=
=
=

PM / P0M
10.6 / 12.8
0.828
1.00 0.828
0.172 mol

Theres 0.172 mol of solute / 0.828 mol of

benzene. Mole of solute / benzene
0.172 / 0.828 = 0.208 mol solute / benzene

7. The vapour pressure of water at 75C is

0.39 atm. What are the partial vapour
pressures of water in mixtures of
(a) 100.0 g water and 20.0 g glucose
(b) 100.0 g water and 20.0 g NaCl
(c) Comparing the same mass of glucose
and sodium chloride dissolved in water
which solution will boil at a lower
temperature?
a) nw = 100.0 g / 18 = 5.56 mol
ng = 20.0 g / 180 = 0.11 mol
Pw = xw x P0w
= 5.56 / (5.56+0.11) x 0.390
= 0.382 atm
b) nNaCl = 20.0 g/ 58.5 = 0.342 mol
Pw = xw x P0w
= 5.56 / (5.56+0.342) x 0.390
= 0.368 atm
c) Glucose solution the water vapour
pressure is only slightly lowered.