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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

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

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 1. The process of fractional distillation is used
volatile liquid. to separate components from a liquid
3. The composition of the vapour phase mixture based on the differences of their
can be determined using Dalton's law. boiling points.
Mole fraction of A in the vapour phase


Mole fraction of B in the vapour phase


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.
vapour has more A
B P 5. Principle of fractional distillation

0.0 Mole fraction of A Boiling Point


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
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 liquid phase of the mixture?
cold surface of the glass beads into c) Is the vapour phase richer in benzene or
liquid with the composition of C2. methylbenzene? Give evidence.
b) The liquid composition C2 will boil at T2
heat supplied by hot vapour going up
the column.
The vapour given off again ascends a) Vapour pressure of pure benzene is 1120
the column where it condenses to a mm Hg. This is because methylbenzene is
liquid of composition C3. a more polar hydrocarbon with bigger
molecular size compared to benzene.
c) The process is repeated and the Hence, its intermolecular VDW forces are
percentage of liquid A in the vapour as it expected to be stronger. Consequently, it is
ascends the column gradually less volatile than benzene. As a result of
increases. this, its vapour pressure in the pure state

Eventually, pure A will distill over and should be lower.

is collected.
d) As more and more A is distilled over, the b) Let the partial pressure of benzene PB and

percentage of B in the liquid remaining methylbenzene P MB be.

in the flask increases. PB = X benzene Pbenzene

PB = X benzene (1120).(1)
Eventually, only B is left in the flask
and will then be distilled over.
PMB = (1 X benzene ) Pmetthylbenzene
PMB = (1 X benzene ) (405)(2)
Question 1 If the mole fraction of the two compound in
the vapour state are the same, the partial
Benzene and methylbenzene form an ideal pressure should also be the same.
mixture. In pure liquid, the saturated vapour Thus (1) = (2)
pressures at 80C are 405 mm Hg and 1120 X benzene (1120) = (1 X benzene ) (405)
mm Hg. 1525 X benzene = 405

a) What is the vapour pressure of pure X benzene = 0.27

benzene? Explain your answer. Hence, mole fraction of benzene is 0.27

b) If the mole fraction of benzene equals that and that of methylbenzene is 0.73 in the

of methylbenzene in the vapour state, what liquid phase of the mixture.

are their respective mole fractions in the

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
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
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
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
Negative Deviation from Raoult's
Positive Deviation from Raoult's Law
1. A non-ideal mixture exhibits negative

1. A non-ideal mixture is said to exhibit deviation if its vapour pressure is lower

positive deviation from Raoult's law if its than the predicted vapour pressure by

total vapour pressure is higher than Raoult's law.

the predicted vapour pressure / 2. This occurs because

calculated value by Raoult's law. the strength of the intermolecular

forces in the mixture are significantly
2. This happens because higher than the intermolecular forces

the intermolecular forces in the in the pure components.

mixture are weaker than the

intermolecular forces of the pure 3. This results in lower vapour pressure
components. 4. Hence, the mixture registers a negative
3. Due to these weakening of intermolecular deviation from Raoult's law.
forces, the mixture is more volatile. 5. The vapour pressure-composition and
4. This results in a higher vapour pressure boiling point-composition graphs of a
of the non-ideal mixture. negatively deviated non-ideal mixture of A
5. Hence, the mixture gives a positive and B are shown below;
deviation from Raoult's law.
6. The graphs below illustrate this for a
positively deviated non-ideal mixture of
A and B.
7. This is because the vapour pressure of the
mixture is able to attain the external
atmospheric pressure at a much lower
STEAM DISTILLATION 8. The vapour pressure of the mixture is
contributed by the vapour pressures of
1. It is a technique that is used to separate both the liquids rather than just one liquid
two immiscible liquids, for example, water in their pure state.
from an insoluble or almost insoluble 9. Consequently, steam distillation will cause
organic compound such as phenylamine or boiling of liquid organic compounds at
nitrobenzene. temperatures very much lower than their
2. A mixture of water-phenylamine and water- normal boiling temperatures.
nitrobenzene form immiscible liquid 10. This is a very important characteristic of
mixtures. steam distillation.
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 At room pressure (1 atm), liquid A and B

saturated vapour pressure (Dalton's law). boils at T2 and T3 respectively because at

that temperature, the saturated vapour
Ptotal = P component 1 + P component 2
pressures of A and B are equal to the
5. Consequently, the mixture boils at a very external atmospheric pressure of 1 atm.
much lower temperature than the boiling At T1, the mixture is able to achieve a
points of the individual pure components of combined saturated vapour pressure (P1
the mixture. + P2) of 1 atm.
6. If the boiling points of immiscible Hence, the mixture boils at T1 much lower
component liquids A and B are 100C and than the boiling points of the pure
70C respectively, the mixture of any components of the mixture. T1 < T2 < T3.
proportion comprising of A and B will boil
at a temperature lower than 70C.
12. Based on these characteristics, this
technique is usually employed; and water which is contaminated
When there is a need to separate an with nonvolatile impurities.
organic compound from water but
the organic compound decomposes
easily on heating or nearing its
How is Steam Distillation
boiling point. Carried Out?
Hence, it cannot be distilled at
1. Steam distillation is used to separate an
room conditions.
organic compound from water without
Since, a mixture comprising of undergoing decomposition and in its
the organic compound and water pure state.
boils at a temperature very much 2. Since, water is one of the components
lower than its boiling point, the and the boiling point of water is 100C,
organic compound can be the mixture which is steam distillated
collected before it decomposes boils below 100C.
by using steam distillation. 3. So, steam which has a temperature of

The organic compound is 100C is passed into this mixture

prevented from being subjected directly or indirectly.

to extreme heat. 4. The steam gives up its latent heat of

vaporisation/condensation to the
When there is a need to separate an
organic compound with a very high
5. The components of the mixture absorbs
boiling point (due to large relative
this heat energy and increases its rate
molecular mass) from its mixture
of vaporisation, hence, increasing their
with water.
individual vapour pressures.
Since, the mixture boils at a
6. When the combined vapour pressure of
very much lower temperature,
the mixture is equal to 1 atm, the
the organic compound
mixture boils. By this way, steam is able
vaporises at a much lower
to boil the mixture.
temperature, enabling it to be
7. Besides this, the bubbles of steam, if it
collected at a lower temperature
is directly passed on to the mixture,
than its boiling point.
agitates the mixture and causes more of
When there is a need to purify a the molecules of the mixture to
mixture of an organic compound 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
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
m H2O = 100

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

= (101 103 ) (3.01 104 )

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

156.9 3.01 104 Answer

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

100% 27 %

3.70 +
Let A = organic compound and B =

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


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


25 3.3 103
75 18 98 103

Thus = 178.2

Test Power 5