VAPOUR-PRESSURE

COMPOSITION GRAPH

1. A solution that obey Raoults law is

known as ideal solution
2. Examples of ideal solution, a mixture of Mole fraction of liquid B

Heptane and octane When we combine both the graphs above

Propan 1 ol and Propan 2 ol
Benzene and methylbenzene
3. In order to plot a vapour-pressure
composition graph for liquid A and B, we 205

need
a) Vapour pressure of A in pure state
b) Vapour pressure of B in pure state
4. Example, let Mole fraction of A
Pure vapour pressure

A 250 mm Hg

B 205 mm Hg
205

5. The vapour pressure-composition

graphs of A and B are shown below

Mole fraction of A

Composition of Vapour

Mole fraction of liquid A 1. The composition of the ideal liquid

mixture and the composition of its
vapour phase will not be the same.
2. The vapour phase will always have a
 higher composition of the more
volatile liquid.
3. The composition of the vapour phase
can be determined using Dalton's law.
Mole fraction of A in the vapour phase
1. The process of fractional distillation is used
to separate components from a liquid
mixture based on the differences of their
boiling points.

=
+

Mole fraction of B in the vapour phase

=
+

Vapour
pressure 2. The more volatile components will distill
Pure A over first.
3. The liquid left in the flask gets richer in the
less volatile component.
Composition of the 4. Finally, it too is distilled over.
Pure
vapour has more A
B P 5. Principle of fractional distillation

0.0 Mole fraction of A Boiling Point

1.0

Vapour pressure of pure A is higher than

Pure B
pure B
A is more volatile than B T1

When a ratio of P is heated, the vapour

phase will have a higher mole fraction of A. T2

[The vapour composition curve for the liquid

mixture lies to the right of the liquid
composition curve. C1 C2
0.0
Boiling Point
mole fraction of A 1.0

1.0 mole fraction of B 0.0

8.3 Fractional distillation of ideal a) A liquid mixture of composition C1 boils
solution at T1.
The vapour given off will ascend the
 column where it condenses on the
cold surface of the glass beads into
liquid with the composition of C2.
b) The liquid composition C2 will boil at T2
heat supplied by hot vapour going up
the column.
The vapour given off again ascends
the column where it condenses to a
liquid of composition C3.
c) The process is repeated and the
percentage of liquid A in the vapour as it
ascends the column gradually
increases.
Eventually, pure A will distill over and
is collected.
d) As more and more A is distilled over, the
percentage of B in the liquid remaining
in the flask increases.
Eventually, only B is left in the flask
and will then be distilled over.
Question 1
Benzene and methylbenzene form an ideal
mixture. In pure liquid, the saturated vapour
pressures at 80C are 405 mm Hg and 1120
mm Hg.
a) What is the vapour pressure of pure
benzene? Explain your answer.
b) If the mole fraction of benzene equals that
of methylbenzene in the vapour state, what
are their respective mole fractions in the
liquid phase of the mixture?
c) Is the vapour phase richer in benzene or
methylbenzene? Give evidence.
Answer
a) Vapour pressure of pure benzene is 1120
mm Hg. This is because methylbenzene is
a more polar hydrocarbon with bigger
molecular size compared to benzene.
Hence, its intermolecular VDW forces are
expected to be stronger. Consequently, it is
less volatile than benzene. As a result of
this, its vapour pressure in the pure state
should be lower.
b) Let the partial pressure of benzene PB and
methylbenzene P MB be.
PB = X benzene Pbenzene
PB = X benzene (1120).(1)
Similarly
PMB = (1 X benzene ) Pmetthylbenzene
PMB = (1 X benzene ) (405)(2)
If the mole fraction of the two compound in
the vapour state are the same, the partial
pressure should also be the same.
Thus (1) = (2)
X benzene (1120) = (1 X benzene ) (405)
1525 X benzene = 405
X benzene = 0.27
Hence, mole fraction of benzene is 0.27
and that of methylbenzene is 0.73 in the
liquid phase of the mixture.
 Using Daltons law
c) The vapour phase is richer in more volatile
Vapour pressure of the mixture
benzene. In the liquid phase of (b), the
mole fraction of benzene is 0.27 while in the = Pheptane + Phexane
vapour phase it has increased to 0.50.
= 64 + 168

= 232 mm Hg
Question 2
NON-IDEAL MIXTURES
Heptane and hexane when mixed, forms an
ideal mixture. If the vapour pressure of pure 1. A non-ideal mixture is a mixture whose
heptane and pure hexane is 365 mm Hg and strength of the intermolecular forces
118 mm Hg respectively at 40C, calculate the between the two component molecules
vapour pressure of a mixture containing 0.6 is not the same as the strength of the
moles of heptane and 0.7 moles of hexane. intermolecular forces in the respective
pure components.
2. As a result of this, the vapour pressure
Answer of the non-ideal mixture does not vary
linearly with mole fraction at a constant
Using Raoults law
temperature.
Pheptane = X heptane Pheptane 3. The vapour pressure of a non-ideal

0.6 mixture is either higher or lower than

= 0.6+0.7 365
the predicted vapour pressure

= 168.4 mm Hg 4. Hence, a non-ideal mixture does not

obey Raoult's law and is said to
= 168 mmHg
deviate from Raoult's law.
5. There are two types of deviation from
Raoult's law that non-ideal mixtures can
Phexane = X hexane Phexane
exhibit.
0.7 a) Positive Deviation from
= 0.6+0.7 118
Raoult's Law
= 63.5 mm Hg b) Negative Deviation from
Raoult's Law
= 64 mmHg

Positive Deviation from Raoult's
Law
1. A non-ideal mixture is said to exhibit
positive deviation from Raoult's law if its
total vapour pressure is higher than
the predicted vapour pressure /
calculated value by Raoult's law.
2. This happens because
the intermolecular forces in the
mixture are weaker than the
intermolecular forces of the pure
components.
3. Due to these weakening of intermolecular
forces, the mixture is more volatile.
4. This results in a higher vapour pressure
of the non-ideal mixture.
5. Hence, the mixture gives a positive
deviation from Raoult's law.
6. The graphs below illustrate this for a
positively deviated non-ideal mixture of
A and B.
Negative Deviation from Raoult's
Law
1. A non-ideal mixture exhibits negative
deviation if its vapour pressure is lower
than the predicted vapour pressure by
Raoult's law.
2. This occurs because
the strength of the intermolecular
forces in the mixture are significantly
higher than the intermolecular forces
in the pure components.
3. This results in lower vapour pressure
4. Hence, the mixture registers a negative
deviation from Raoult's law.
5. The vapour pressure-composition and
boiling point-composition graphs of a
negatively deviated non-ideal mixture of A
and B are shown below;

STEAM DISTILLATION
1. It is a technique that is used to separate
two immiscible liquids, for example, water
from an insoluble or almost insoluble
organic compound such as phenylamine or
nitrobenzene.
2. A mixture of water-phenylamine and water-
nitrobenzene form immiscible liquid
mixtures.
3. Since, both the liquids in the mixture are
immiscible, they exert vapour pressures
independently of each other.
4. Hence, the total vapour pressure of the
mixture is the sum of their individual
saturated vapour pressure (Dalton's law).
Ptotal = P component 1 + P component 2
5. Consequently, the mixture boils at a very
much lower temperature than the boiling
points of the individual pure components of
the mixture.
6. If the boiling points of immiscible
component liquids A and B are 100C and
70C respectively, the mixture of any
proportion comprising of A and B will boil
at a temperature lower than 70C.
7. This is because the vapour pressure of the
mixture is able to attain the external
atmospheric pressure at a much lower
temperature.
8. The vapour pressure of the mixture is
contributed by the vapour pressures of
both the liquids rather than just one liquid
in their pure state.
9. Consequently, steam distillation will cause
boiling of liquid organic compounds at
temperatures very much lower than their
normal boiling temperatures.
10. This is a very important characteristic of
steam distillation.
At room pressure (1 atm), liquid A and B
boils at T2 and T3 respectively because at
that temperature, the saturated vapour
pressures of A and B are equal to the
external atmospheric pressure of 1 atm.
At T1, the mixture is able to achieve a
combined saturated vapour pressure (P1
+ P2) of 1 atm.
Hence, the mixture boils at T1 much lower
than the boiling points of the pure
components of the mixture. T1 < T2 < T3.
12. Based on these characteristics, this
technique is usually employed;
When there is a need to separate an
organic compound from water but
the organic compound decomposes
easily on heating or nearing its
boiling point.
Hence, it cannot be distilled at
room conditions.
Since, a mixture comprising of
the organic compound and water
boils at a temperature very much
lower than its boiling point, the
organic compound can be
collected before it decomposes
by using steam distillation.
The organic compound is
prevented from being subjected
to extreme heat.
When there is a need to separate an
organic compound with a very high
boiling point (due to large relative
molecular mass) from its mixture
with water.
Since, the mixture boils at a
very much lower temperature,
the organic compound
vaporises at a much lower
temperature, enabling it to be
collected at a lower temperature
than its boiling point.
When there is a need to purify a
mixture of an organic compound
and water which is contaminated
with nonvolatile impurities.
How is Steam Distillation
Carried Out?
1. Steam distillation is used to separate an
organic compound from water without
undergoing decomposition and in its
pure state.
2. Since, water is one of the components
and the boiling point of water is 100C,
the mixture which is steam distillated
boils below 100C.
3. So, steam which has a temperature of
100C is passed into this mixture
directly or indirectly.
4. The steam gives up its latent heat of
vaporisation/condensation to the
mixture.
5. The components of the mixture absorbs
this heat energy and increases its rate
of vaporisation, hence, increasing their
individual vapour pressures.
6. When the combined vapour pressure of
the mixture is equal to 1 atm, the
mixture boils. By this way, steam is able
to boil the mixture.
7. Besides this, the bubbles of steam, if it
is directly passed on to the mixture,
agitates the mixture and causes more of
the molecules of the mixture to
constantly rise up to the surface.
 8. This increases the rate of vaporization water and an organic compound Y.
and hence, further reduces the boiling 2. Based on the ideal equation of gases
point of the mixture. pn ; because V, R and T are
9. The distillate collected is a mixture of constants
the two immiscible liquids but richer in Thus ,
the more volatile liquid. Since usually
the organic compound used here is of
higher boiling point than water, the
distillate is richer in water (the more
volatile liquid).
10. The composition of the distillate is the
same as the mole composition of the
vapour mixture.
11. The organic compound in the mixture is
then extracted using a suitable
extraction solvent such as ethoxyethane 3. The mole composition of the distillate
which will be discussed in the next can be calculated based on the
section of this chapter. following relationship
12. The diagram below shows how steam
distillation is carried out;

=

4. The mole composition of the vapour

mixture can be calculated using partial
pressures as shown below;
X organic compound = P organic compound

P total

X water = 1 X organic compound

Calculations Involving Steam
Where
Distillation
X organic compound = mole fraction of organic
1. Let us consider a steam distillation compound
process carried out on a mixture of
X water = mole fraction of water B = water

=

``
112.5 (3.01 104 )
=
18 (7.09 104 )

5. If m organic compound = a ,the % by mass = 2.65

of the organic compound can be
calculated % of chlorobenzene in the distillate
2.65
m H2O = 100
1+2.65

= 72.6%

Test Power 2

A mixture of bromobenzene and water boils at

80.5C at 101kPa. Given that the vapour
pressure of bromobenzene at 80.5C is 3.01
104 Pa. Calculate the percentage of
bromobenzene in the distillate.
Test power

A mixture of chlorobenzene and water boils at

90.5C at 101 kPa. Calculate the percentage Answer

of chlorobenzene in the distillate. Total pressure = 101 103 Pa

[vapour pressure of chlorobenzene at 90.5 C

Vapour pressure of water at 80.5C
4
is 3.01 10 ]
= (101 103 ) (3.01 104 )
Answer
= 7.09 104
Vapour pressure of water at 90.5C

= (101 103 ) (3.01 104 )

Let A = bromobenzene and B = water
4
= 7.09 10
Mr or bromobenzene = 112.5
Let
Mr of water =18
A = chlorobenzene
 relative molecular mass of the organic
=
compound.

156.9 3.01 104 Answer

=
18 7.09 104
The vapour pressure of liquid A at
= 3.70
90.8C
= 3.70
= (101 98.2) kPa = 2.8kPa
Thus, % of bromobenzene in the
Relative mass of water = 73 %
distillate
Relative mass of organic compound =

100% 27 %
+

3.70
100%
3.70 +
Let A = organic compound and B =
water

3.70 Using
= 100%
3.70 + 1

=
= 78.7 %

27 2.8 103
=
73 18 98.2 103
Test Power 3
Thus = 233.5
A mixture of an organic compound and
Test Power 4
steam were distillated out at 90.8C and
101 kPa. It is found that the distillate A mixture of an organic compound and steam

contain 27% of the organic compound were distillated out at 80C and 101.3 kPa. It is

by mass. If the vapour pressure of water found that the distillate contain 75 % of the
organic compound by mass. If the vapour
is 98.2 kPa at 90C, calculate the
pressure of water is 98 kPa at 80C, calculate
the relative molecular mass of the organic
compound.

Answer

The vapour pressure of liquid A at 90.8C

= (101.3 98) kPa = 3.3 kPa

Relative mass of water = 75 %

Relative mass of organic compound = 25 %

Let A = organic compound and B = water

Using

25 3.3 103
=
75 18 98 103

Thus = 178.2

Test Power 5