hemistry

le and

ple.
UNIT 12
SOLUTIONS

Aliquid may or may not be soluble in another

on the relative solubility of a liquid in
liquid. Depending
another, three cases are
DOssible. () Completely soluble, where the two liquids are soluble
in-each other in all proportions. e.g., benzene and toluene.
(i) Partially miscible in which aliquid is soluble in another to
some extent only e.g., phenol and water (ii) Immiscible in which
a liquid is practically insoluble in another one, e.g., CCl, and
water.

Completely miscible systems

Liquids like benzene and toluene mix in all proportions and in
this respect they could be compared to gases.
Vapour pressure of Liquids
When a liquid is placed in a closed vessel, part of the liquid
eVaporates and fills the available space with the vapours. As the
evaporation proceeds the number of molecules in the vapour
phase increases. These molecules move above at random and
during the random movement some of them strike the liquid
SUriace and get condensed. Thus evaporation and condensation
 Chemistn
12/2 Principles of Organic and PhySical
condition is reached when
proceed simultaneously. Eventually a
rate oI evaporation,
the rate of condensation becomes equal to the
between the liquid and the
1.e., an equilibrium is established
vapours of the liquid in
vapour phases. The pressure exerted by the vapourpressure
equilibrum with it at a given temperature iscalled the
of the liquid.
liquids
Raoult's law for Binary solutions of volatile
components
In binary solutions of volatile liquids, both the
As a result,
have appreciable tendencies to undergo evaporation.
the components, and
the vapour will contain molecules of both
will be the sum of the partial
the vap0ur pressure of the solution
pressure of
pressures exerted by each component. The partial
liquids is given by Raoult's
any component in a solution of volatile
law. It states:
liquids,
"at a given temperature, for a solution of volatile
equal
the partial vapour pressureof each component is
to the product of the vapour pressure of the
pure
component and its mole fraction in the solution"
and
Let us consider a binary solution of two volatile liquids A
liquids
B. If P, and P, are the partial vapour pressures of the two
and X, and X, are their mole fractions in solution, then
P,- PX and P,= P
Where Pº, and P are the vapour pressures of the two liquids
Aand B respectively.
Ideal solutions
An ideal solution may be defined as the solution which obeys
Raoult's lawexactly at all concentrations and at all temperatures.
Such solutions are formed by the mixing of two components which
are identical in structure. For example, if two liquids A and B
form an ideal solution, then the A-A and B-B molecular
interactions will be the same and there will be no change in
molecular interactions when the solution is formed. In other
words, the force of attraction between A and B molecules, i.e.,
 Sovtions

12/3
A-B molecular
interactions
B molecules, As there is no
will be the same a for
the A-A andB-
attractive forces in
the two change in the magnitude of the
mixing will be Components,
mixing, i.e., AH the heat change on
zero.
..volume, i.e., AV mixing will be zero.Also, there will be no change
eolutions are benzene-toluene, Common examples of ideal
chlorobenzene--bromobenzene, etc.
n-hexane-n-heptane,
Vapour
pressure-Composition
Let us consider an ideal
curve of an ideal solution
t.
o the partial solution of Aand B. According to Raoult's
vapour pressures of AandB are
and P=Po p given as, P,=P"X,
al Therefore the plots of P,A or P,B against their mole
of ractions Xor Ag Should give a straight line passing through the
pointsP A or Po
When X=1,
he variation of partial P=Px1=P, and when X=0, P x0=0.
mole fraction () is, pressure by the component Awith its
(P) of
represented the plot from X=1 (i.e., P)
Vapour
pressure
--’ 50
(ii)
nd + P,

ds

P
ids
XA =1
Mole fraction X =1
Xp =0
Fig. 1Vapour pressure compositiorn curve of an ideal solution
eys
res.

ich OX=0 (i.e., 0). It is shown by the line (/) in Fig. 1. Similarly, the
d B anation of partial pressure (P) of the component Bwith itsmole
ilar action (X) isrepresented by the plot from X-1(i.e., P) to X=0
e in e, 0). It is shown by the line (ii) in Fig. 1. The total vapour
ther ESSure P, exerted by the solution at any composition is given
i.e., the Sum of the partial vapour pressures according to Dalton's
12/4
Principles of Organic and Physical Chemistry
law of partialpressures. Thus,
P= P,+P,- PX,+P
From the figure it is evident
This is shown in line (iiil in Fig. 1.
of different compositions
that the vapour pressure of solutions
of ideal solution, are intermediate between the values
in case
P, and Po.B
Solutions
Deviation from Ideal Behaviour-Non-ideal
deviations from ideal
Most of the solutions show appreciable
solutions
behaviour, i.e., they deviate from Raoult's law. Thesebehaviour
non-ideal
are called non-ideal solutions. The origin of
between the
lies in the relative strengths of the interactions
molecules of A and B. Depending on the relative attractive forces
ideal
between A-A, B-B and A-B molecules, the deviation from the
behaviou° may be positive or negative.
(i) Non-idealsolutions showing positive deviations
Consider a binary solution of two liquids A and B. If the A-B
interactions in the solution are weaker than the A-A and B-B
interactions in the two liquids, the escaping tendency of the
molecules of A and B from the solution becomes more than that
from the pure liquids. As a result, each component of the solution
has a partial vapour pressure greater than that expected from

VapourP=P,+P .
pressure pressure
Vapour
P PB

B Mole fraction B
Mole fraction
X=1 X,=0 X,-1 X-0
X-0 X-1 X=0 X=1
Fig.2 Vapour pressure - composition curve for
non-ideal solutions (a) with positive deviation
(b) with negative deviation
 12/5
Solutions

Raoult'slaw and hence the total vapour pressure of the solution

will be greater than that of an ideal solution of sarne composition.
Thus, P>P" P,>P°X, and P>P,X, +P"gg The positive
deviation is shown in Fig. 2(a) in which dotted lines show ideal
behaviour while the solid lines show positive deviation S.
Acetaldehyde - carbon disulphide, ethanol-chloroform, acetone
carbon disulphide, etc., are examples of this type.
i) Non-ideal solution with negative deviation
Consider a binary solution of two liguids A and B in which the
A -B interactions are stronger than the A-A and B-B interactions
in the two liquids. Due to stronger A-B interactions, the escaping
tendency of the molecules of A and B from the solution becomes
less than that from the pure liguids. As a result, each component
of the solution has a partial vapour pressure less than th£t
expected from Raoult's law. Due tothis the total vapour pressure
the
of the solution will be less than that of an ideal solution of
same composition. Thus,
P<A) P<P, and P<P,X, +PXp. Thenegative deviation
behaviour
isshown in Fig.3.8. (b) in which dotted lines show ideal
Chloroform
while the solid lines show negative deviations.
acetone, chloroform nitric acid, water-sulphuric acid, etc., are
examples of this type.
Fractional Distillation
which its
Boiling point of a solution is the temperature at
atmospheric pressure.
vapour pressure becomes equal to the
attain the
Thus, a solution having a high vapour pressure can
hence
atmospheric pressure at a relatively low temperature and
solution of
will have a low boiling point. When we heat a binary
the more volatile
two volatile liquids, the vapour will be richer in
component, i.e., the component having greater vapour pressure.
condensation will give a
As a consequence of this, thevapour on
on further
liquid richer in the more volatile component. This liquid
richer in
vaporisation and condensation will yield a liquid still
is
the more volatile component. By repeating ths process, it
 12/6
Principles of Organic and Physical
possible to separate the more volatile component from the Chemistry
volatile one and the process is known as fractional less
In order to
distillation.
understand the process of fractional
temperature comnposition graph is used. Since the composition
of the liquid and vapour are different, temperature composition
distil ation,
graph will give two curves namely vapour compositi0n curve and
liquid composition curve. Since the vapour state eXists at higher
temperatures, vapour composition curve will be above the liquid
Composition curve. The temperature-composition curve for an
ideal solution is as shown in Fig.3.

Boiling
Temperature

Vapour
Liquid
Mole fraction of B

Fig. 3 Boiling Poirnt Composition Curve for

an ideal solution of A and B.

In the curve, T, is the boiling

A
point of liquid A and T, that of
liquid B. Here liquid B is more volatile than
a liquid mixture of
liquid A. On heating
composition X, it will boil at T and the vapour
will have composition X, and the
residual liquid will have
composition Evidently, the vapour will be richer in the more
Y.
volatile component B and the residual liquid will be
richer in the
less volatile component A. The residual
liquid Ywill boil at a higher
temperature T, and thevapour coming off will have composition
X, i.e., richer in B. As a result, the
residual liquid will befurther
 liguid ill
hed in A1f the vtoreea i nmtinved the rsaidual
off
A Sinilatly, the vapr Mcompnitinn X, (rnming
cnndensed and
the otiginal sout ion of compoaitinn X ia
distilled ngain, it will boil at temperature T, and the vapur cnming
ofl ill be further ticher in Bas represented by Z If
this process
distillate will be
of condensing and distilling is continued. the isolate
pure B Thus in the case ofideal solutions, itis possible to
bothithe pure components by fractional distillation. Liquid mixtures
which distil with a change in composition are called azeotropic
mixtures.

Azeotropic Mixtures
The liquid mixtures which boilat a constant temperature and istil
Over Completely at the same temperature without any change tn

composition are called azeotropic mixtures or azeotropes.

Minimum boiling azeotropes
non-ideal solutions
The vapour pressure-composition curve of
with positive deviation shows a maximum. The boiling point
composition curve of such non-ideal solutions will show a
minimum as in Fig. 4. The two curves meet at the minimum
point C, where the liquid and vapour phase have the same
composition. Therefore, a liquid mixture of composition C, like a
pure liquid will boil at a fixed temperature, t giving a vapour of
the same composition. Thus the liquid mixture of compositionC
is a constant boiling mixture or azeotropic mixture or azeotrope. The
azeotropic mixture of composition C, has a boiling point lower
called a
than any other mixture of components A and B. So it is
minimum boiling azeotrope.
 12/8 Principles of Organic and Physical Chemistry

Boiling
Temperature

Vapour Vapour

Liqud Liqyid

L
Mole fraction of B

Fig.4 Boling Point-Composition curve of non-ideal solution

with postive deviation

If a liquid mixture of composition Xis distilled, the first fraction

of distillate will have composition X, , i.e., richer in the azeotropic
mixture. Consequently, the residual liquid will be richer in A. By
repeated fractional distillation the minimum boiling azeotrope
(C) will be obtained as the distillate and pure A as the residual
liquid. On the other hand, on distilling a liquid of composition Y,
the first fraction of distillate will have
composition Y, and will be
richer in the azeotropic mixture. Therefore, the residual liquid
willbe richer in B. By repeated fractional
distillation, we will get
the azeotrope as the distillate and pure B as the
residual liquid.
Some examples of this type are:
Component A and Component B and Boiling point of
its boiling point its boiling point Weight
azeotrope % of A
H,0 (373K) C,H,0H (351.3K) 351.13K 44
CH,OH (337.7K) CHC1, (334.2K) 326.5K 12.5
CH,COOH (391.5K) CHCH, (383.6K) 378.4K 28

Maximum boiling Azeotropes. Thevapour

composition curve for non ideal solution with negative pressure
deviation
shows a minimum. The boiling point
non ideal solutions will composition curves of such
show a maximum as in Fig. 5. The two
 Solutions 12/9

y CuIves meet at the maximum point Owhere the liquid and vapour
phase have the same composition. Therefore, aliquid mixture of
composition D, like a pure a liquid, will boil at a constant
temperature giving a vapour of same composition. Thus, the
constant boiling mixture or azeotrope (represented by point D) n
this case has the maximum boiling point and is therefore called
maximum boiling azeotrope.
Vapour D

Vapour
ction
Liqud', B

opic YY
By 1
rope Mole of fraction ofB
dual
nY,
l be Fig. 5 Boiling Point-Composition curve of
quid non ideal solution with negative deviation
get
uid.
Ifa liquid mixture of composition Xis distilled, the first fraction
of distillate will have composition X,. It is richer in A. The residual
liquid will, therefore, be richer in the azeotrope. By repeated
fractional distillation, the distillate will be pure Aand the residual
liquid will be the azeotrope. Similarly, on distilling a liquid mixture
of composition Y, the first fraction of distillate will have a
composition Y, which will be richer in B. Consequently, the
ure
residual liquid will be richer in the azeotrope. Thus, by repeated
ion
fractional distillation, pure Bwill be obtained as the distillate
uch
two
and the azeotrope as the residual liquid. Some examples of this
type are:
 12/10
Principles of Organic and Physical
Component Aand
its boiling point
Component B and
its boiling poinf
Boiling point of
azeotrope
Chemintry
Weiogofht A
CHC), (334.2K) CH,COCH,(329 4K) 337.7K
g0
HCI (189K) H,0 (373K) 381.6K
20.22
HNO,(359K) H,0(373K) 393.5K
68
HCOOH (273.8K) H,0 (373K) 380.1 K
77.5
Partially Miscible Liquid Systems
Alargenumber of liquids are known which dissolve in
another only to a limited extent. e.g., ether and one
and water, triethyl amine and water, nicotine and water, phenol
Such liquids are known as partially miscible, liquid water, etc.
equal pairs. When
volumes of ether and water are shaken together, two layers
are fornmed, one of a saturated solution of
ether in water and the
other of a saturated solution of water in ether.
Such solutions of
different compositions co-existing with one another are
called
conjugate solutions. The composition of conjugate solutions
depends on temperature. In some cases, the mutual solubility
increases with temperature and at a certain temperature and
two conjugate solutions merge to become
The temperature at which two conjugate identical composition.
in
solutions merge into one
another to form one layer is called critical solutiorn
or consolute temperature. temperature (CST)
Depending on the critical solution
temperature, the partially miscible liquid pairs are of three
types.
F) Upper critical soution
temperature type. In this type, the mutual
solubility increases with temperature and above a certain
temperature the two liquids becomne completely miscible. The
temperature at or above which a pair of partially miscible liquids
become completely miscible in all proportions is called
solution temperature. Phenol-water, upper critical
methanol-cyclohexane,
disulphide-methanol, etc. are examples of this type. carbon
Phenol-water system
The variation of mutual solubility of
phenol and water with
temperature is shown in Fig.6. From the Fig. it is evident that
Solutions 12/ 11

the solubility of phenol in water as well as that of water in phenol

increases with temperature., The two solution curves meet at
the maximum on the temperature -composition curve of the
system. This point corresponds to the temperature 68.1°C and
the composition 36.1 per cent of phenol. Thus, the upper critical
solution temperature of phenol-water system is 68. 1°C. At any
temperature above 68.1°C, phenol and water are miscible in all
proportions. Out side the curve, the system is homogeneous, 1.e.,
only one layer xists.
temperature
68.1°C
CST

miscibility

T,
36.1%
Percentage of phenol 100%

Fig, 6 CST of phenol-water system

(ii) Lower critical solution temperature type

In this type the mutual solubility decreases with temperature,
and below a certain temperature the two liquids become
completely soluble. The temperature at or below which a pair of
partially miscible liquids become cormpletely miscible in all proportions
is called lower critical solution temperature. Triethylamine-water,
diethylamine-water, 1-methylpiperidine water, etc. are examples
of this type.
Triethylamine Water System
critical
It is a partially miscible liquid pair system with lower
solution temperature. Its behaviour with respect to temperature
solubilities
and composition is shown in Fig.7. In this, the mutual
decrease with temperature. The two liquids are completely
 12/ 12 Princjples of Organic and Physical
miscible at or below 18.5°C. Thus, the lower critical
Chemistry
temperature is 18.5°C. solution
Temperature
One
2080
phase
Temperature
Two
Phases Two
Phases

18.50
One phase
One phase
100 100
Weight percent of triethylamine Weight percent of nicotine
Fig. 7 Triethylamine-water system Fig.8 Nicotine-water system

(iii) Both upper and lower critical solution temperature type.

This type of system gives a closed solubility curve and therefore.
possesses both an upper and a lower critical solution temperature.
Nicotine water, glycerol-m-toluidine,
etc. are examples of this type. water-2-methylpiperidine,
Nicotine-water system
It is system with upper and lower critical
solution
temperature.
In other words, these liquids are
completely miscible above
critical solution temperature (208°C) and below the lower upper
critical
solution temperature (61°C). Between 208C and 61°C
are and water only partially miscible and nicotine
separate into two layers.
The behaviour of this system with
respect to temperature and
composition is shown in Fig.8.
Effect of Impurity on Miscibility
temperature
The critical solution
temperature is characteristic of a
particular system and is very much influenced by the presence
of impurities. If the impurity is soluble in only one of
the liquids,
Solutions 12/ 13

the mutual solubilities are decreased and the upper CST is raised
while the lower CST is lowered. For example, one percent Na
raises the CST of phenol-water system by about 12°C. Ab0ut 1.3
percent ofwater insoluble naphthalene in phenol raises the C$T
by 30°. If the impurity is soluble in both the liquids in the same
order, the mutual solubility of the liquids is increased and the
upper CST is lowered while the lower CST is raised. For example,
0.98% sodium oleate lowers the CST of phenol water system by
43.7°C.

Completely immiscible liquid pairs

When two liquids are immiscible, the addition of one liquid to
theother will not affect the properties of the other. Each wilexert
of
its own vapour pressure (P, or P)independent of the presence
the other and the total vapour pressure (P) will be equal to the
sum of the individual vapour pressures, ie., P=P,+P:

If the mixture of two immiscible liquids be distilled, theboiling

point will be the temperature at which the sum of the vapour
this
pressures is equal to that of the atmospheric pressure. From
it is obvious that the liquid mixture will boil at a temperature
In
lower than that at which either of the components will boil.
liquids will
other words, the boiling point of a miture of immiscible
be lower than the boiling point of any one of the pure constituents.
Steam distillation

Distillation carried in a curent of steamis called steam distillation.

of organic
This technique is commonly used for the purification
with uwater. The
liquids which are steam volatile but immiscible
intoit (Fig.9).
impure organic liquid is heated and steam is passed
steam are condensed and
The vapour of the organic liquid and
consists
collected in the receiver. The distillate in the receiver
other of water. The
of two layers, one of pure organic liquid and
pure liquid is separated by means of a separating funnel.
12/ 14
Principles of Organic and Physical
Chermistry
safety tube
steam
to sink

Subst -receiver
ande

distillate of water and

pure organic liquid
Fig. 9. Steam distillation

Theory of steam distillation

As already mentioned, the boiling of a mixture of two immiscible
liquids will be the temperature at which the sum of the vapour
pressures of the constituent liquids is equal to the atmospheric
pressure and hence willbe lower than the boiling points of either
of the components. In steam distillation, the organic liquid is
mixed with water (b.p.100°C). Therefore, the organic liquid wil
boil at a temperature lower than 100°C. For example, the boiling
point of aniline is 184°C, but the steam distillation temperature
is 98°C.

Calculation of Molar mass

Steam distillation of immiscible liquids may be utilised to
determine the molecular weight of one of the liquids. The relative
amounts of the two liquids in the distillate can be calculated by
knowing that the number of moles of each component present in
the vapour phase is proportional to its vapour pressure. If P, and
P, are the vapour pressures of the two liquids 1 (water) and 2
(organic liquid) and n, and n, are their respective number of moles,
n,aP, and n,aP
Solutions 12/ 15

.(i)
P,

But n,=
W and W where w, and w,are the actual m
M, n,= M,
of the liquids 1 and 2 in the distillate and M, and M, are their
respective molar masses.

Now, from eg.(i), we have,

W W
M M, P

i.e.,
W, M
M, W, P,

W_ M ..(i)
W, P, M,
W
M,= P, W
*M .(ii)

i.e., Thus molar mass of organic liquid,

M, =1x 2 yi ..(iv)
P, W,
Example 1. A mixtureof water and organic liquid L distills at
95°C. The vapour pressures of water and the liquid L at this
temperature are 640 mm and 120mm respectively. The
composition of the distillate is H,0:L= 1:1.6. Calculate the molar
mass of the liquid.
Solution:Mass of water, W,=1.6; mass of liquid W,=1.6; vapour
pressure of water, P,=640 mm; vapour pressure of l:quid,
12/ 16
Principles of Organic and Physical
P=120mm molar mass of water, M,= T6; Molar mass of Chemis
liquid L=M,try
640 1.6
x18 = 153.6
We have, M, x18 ie., M, 120 1
W

SELF STUDY PROBLEMS

1, In the distillation of liquidL by steam, the mixture
99°C at a pressure of 760mm. At this temperature the boils at
pressure of water is 733 mm. The composition of vapour
H,0: L=4:1. Calculate the molar mass of liquid L difrom
stil atthisei
data.
Ans: 122.16
MODEL QUESTIONS
Section A(Each question carries 1 mark)
1.
An example of a completely miscible liquid pair is
2. n-hexane-n-heptane system is an example of .
solution.
3. Solutions which show deviations from Raoult's law are called

4. Liquid mixtures which distil without any change in

composition are called
5. An example of minimum boiling azeotrope is
6.
HCI-H,0 system is an example boiling azeotrope.
7. The temperature at which twoconjugate solutions merge
into one another to formn one layer is called
8.
Phenol-water system is an example of partially miscible
solutions with
9. 1S an
example of a solution with lower critical solution
temperature.
10. is a solution having both lower and upper
critical
solution temperature.
Solutions 12/ 17

1 Distillation carried in a current of a steam is called

12. The boiling point of a mixture of immiscible liquids will be
lower than the boiling point of any one of the pure
constituents,

13. What are ideal and non ideal solutions?

14. What is CST?

15. What are azeotropes?
16. What is the effect of impurity on miscibility of partially
miscible liquids?
17. State Raoult's law.
18. What is meant by the term ideal solution?
Section B (Each question carries 2 marks)
1. Explain critical solution temperature and fractional
distillation.
2. What are azeotropes? Explain with an example.
3 Define ideal solution. In what cases do solutions deviate from
ideal behaviour?

4. Describe the principle of fractional distillation.

5 Sketch the vapour-pressure-composition of a maximum
boiling azeotrope.
6. Sketch the boiling point - composition curves ofa maximum
boiling azeotrope.
7. Sketch the temperature-composition curve for minimum
boiling azeotrope.
8 Give the principle of steam distillation.
9. What are the conditions at which the solutions deviate from
ideal behaviour?

10. Sketch the different types of boiling point-composition curves

for a pair of completely miscible liquids.
12/ 18 Principles of Organic and Physical
11, Absolute alcohol cannot be prepared by repeated
Chemistry
of wash. Explain the reason using Boiling distil at
point-Compositionion
diagram.
12. Calculae the mole fraction of C,H,0H and water in a
made by dissolving 9.2 g alcohol in 18 g water. solution
Section C (Each question carries 4 Marks)
1 What are azeotropes? Sketch the vapour pressure.
composition and boiling point composition curves of a
maximum boiling azerotrope.
2. Define critical solution temperature. Explain systems having
upper and lower CST usingexamples.
3. Sketch the yapour pressure composition and boiling point
composition curves of a minimum boiling azeotrope.
4. State Raoult's law. Discuss the factors responsible for
deviation from Raoult's law by taking suitable examples.
SectionD (Each question carries 15 Marks)
1. (a) What are ideal solutions? Sketch the vapour-pressure
composition curves for ideal and non ideal solutions,
(b) Discuss the factors responsible for deviation from
Raoult's law by taking suitable examples.
(c) What is the principle of steam distillation?
2. (a) What is CST? Explain systems having upper and lower
CST using examples.
(b) What is the effect of impurity on the critical solution
temperature?
(c) Explain the principle of fractional distillation.