Block 1 Solutions and Phase Equilibrium

UNIT 2
SOLUTIONS-II

Structure
2.1 Introduction Nernst Distribution Law

Expected Learning Outcomes Dissociation of a Solute in one of

the Solvents
2.2 Partially Miscible Liquid
Systems Association of a Solute in one of
the Solvents
Critical Solution Temperatures
Applications of Distribution Law:
Effect of Impurity on Partial
Solvent Extraction
Miscibility of Liquids
2.5 Summary
2.3 Immiscible Liquid Pairs
2.6 Terminal Questions
Principle of Steam Distillation
2.7 Answers
2.4 Nernst Distribution Law and
its Applications

2.1 INTRODUCTION
In Unit 1, we have discussed the completely miscible liquid systems. In this
unit, we shall study the partially miscible and completely immiscible liquid
systems.

Under partially miscible liquid systems, we will describe the variation of their
miscibility with temperature and explain critical solution temperature. In
completely immiscible systems, we will discuss about the vapour pressure of
such systems as well as steam distillation and its principle.

We shall then explain Nernst distribution law and illustrate the calculation of
distribution constant. We will also consider the situations where the solute
dissociates or associates in one or both the liquids.

Finally, we will highlight the applications of the distribution law and illustrate its
use in calculating the amount of the substances left un-extracted after a given
number of extractions. This will help us in understanding the principle of
extraction by the solvents.

In the next two units of this Block, you shall study important aspects of phase
equilibrium.
36
Unit 2 Solutions-II

Expected Learning Outcomes

After studying this unit, you should be able to:

 describe the effect of temperature on the miscibility of partially miscible

liquid pairs;

 define critical solution temperature or consolute temperature;

 explain the effect of impurities on the consolute temperature;

 discuss the principle of steam distillation;

 state distribution law and write the expression for distribution coefficient;

 arrive at the expression of distribution coefficient when the solute

dissociates or associates in one/both the liquids;

 discuss the applications of distribution law; and

 explain the principle of solvent extraction.

2.2 PARTIALLY MISCIBLELIQUID SYSTEMS

Some liquid pairs do not form solutions in all compositions. Such liquid pairs
are said to be partially miscible liquids. However, due to increased solubility
with increase or decrease of temperature, these may become completely
miscible.

We can understand such a system by using the example of a system

containing phenol and water. When a very small amount of phenol is added to
water at room temperature, it dissolves completely to give a single liquid
phase. However, when the addition of phenol is continued, a point is reached
when phenol does not dissolve anymore. At this point, two phases, i.e., two
liquid layers are formed–one consisting of water saturated with phenol and the
other containing phenol saturated with water. Further addition of phenol
causes water to shift from water–rich layer to phenol–rich layer.

If the addition of phenol is continued, a point is reached when phenol acts as a

solvent for all the water present and the two phases merge with each other to
form a single phase, i.e., solution of water in phenol. Thus, on shaking equal
volumes of phenol and water, two layers are formed–one of saturated solution
phenol in water and the other of saturated solution water in phenol.

2.2.1 Critical Solution Temperatures

It has been experimentally found that at a constant temperature, the
composition of the two layers, although different from each other, remains
constant as long as the two phases are present. Such solutions of different
compositions coexisting with each other are termed as conjugate solutions.

The addition of small amounts of phenol or water changes the volumes of the
two layers and not their compositions. As the temperature is increased, the
behaviour remains the same except that the mutual solubility of the two
increases. When the temperature reaches 338.8 K, the composition of the two
37
Block 1 Solutions and Phase Equilibrium

layers becomes identical and thereafter, the two liquids are completely
miscible; i.e., at and above 338.8K, phenol and water dissolve in each other in
all proportions and yield only a single liquid layer on mixing. The variation of
mutual solubility of water and phenol with temperature is shown in Fig. 2.1

Fig. 2.1: Phenol-water system; cPh stands for composition of phenol and cw for
composition of water.

At a particular temperature, say 325 K point A represents the composition of

water-rich layer and point A1, represents the composition of phenol-rich layer
in equilibrium with the first layer. Between these two compositions, all mixtures
will yield two layers of compositions A and A1. Outside these compositions, the
two liquids are soluble mutually at 325 K. Similar behaviour is seen at other
temperatures below 338.8 K. We can conclude that the dome-shaped area
represents the range of existence of two liquid phases and the area outside
the dome represents a single liquid phase. The temperature corresponding to
the point B, i.e., the temperature at which the solubility becomes complete is
called the critical solution temperature or the consolute temperature.

Since the mutual solubility of phenol and water increases with rise in
temperature, the critical solution temperature (CST) lies on top of the dome.
Hence, such liquid systems are said to possess an upper critical solution
temperature or upper consolute temperature. Thus, the critical solution
temperature, for phenol-water system is 338.8 K. At and above 338.8K, phenol
and water are completely miscible with each other in all proportions. At this
temperature, the composition of the solution is 36.1% phenol and 63.9%
water.

Here, you can consider the line formed by joining the points A and A1 as the tie
line and consider a point C on it. Similar to the interpretation of lever rule for
liquid–vapour equilibrium studied in Unit 1, here also we can use lever rule as
the two layers are in equilibrium. Thus, at any point C, the relative amounts of
the two separate layers are given by the relationship,
Mass of the layer A A 1C …(2.1)

Mass of the layer A 1 AC
38
Unit 2 Solutions-II

There are some liquid pairs (e.g., triethylamine-water) for which mutual
solubilities decrease with rise in temperature. As the temperature is
decreased, the mutual solubilities increase and below the consolute
temperature, the two liquids become miscible in all proportions. Such systems
possess lower consolute temperature. The variation of mutual solubility of
triethylamine and water with temperature is shown in Fig. 2.2.

Fig. 2.2: Triethylamine-water system; cTA stands for the composition of

triethylamine.

Above 291.5 K, on shaking triethylamine and water two layers are formed; but
below 291.5 K, triethylamine and water are completely miscible with each
other in all proportions.

There are a few liquids pairs, e.g., nicotine and water which show both the
upper and lower consolute temperatures. These liquid pairs are completely
miscible above a certain temperature (upper consolute temperature) and also
below a certain temperature (lower consolute temperature). The variation of
mutual solubilities of nicotine and water with temperature is shown in Fig. 2.3.

Fig. 2.3: Nicotine-water system; cNt stands for the composition of nicotine.

Within the enclosed area, the two liquids are only partially miscible, while
outside the enclosed area, they are completely miscible. The composition
39
Block 1 Solutions and Phase Equilibrium

corresponding to both the upper and the lower consolute temperatures is the
same, viz., 34% nicotine.

Table 2.1 lists the consolute temperatures of some liquid pairs. The two liquid
components are denoted as A and B.

Table 2.1: Consolute Temperatures of Some Liquid Pairs

Components Consolute temperature / K

A B Upper Lower

Water Phenol 338.8 __

Aniline Hexane 333.6 __

Methanol Carbon 323.5 __

disulphide

Water Diethylamine __ 316

Water Triethylamine __ 291.5

Water Nicotine 483 334

Water m-Toluidine 393 280

2.2.2 Effect of Impurities on CST Values

The presence of an impurity, dissolved in one or both of the phases, changes
the CST values as well as the liquid composition at CST. Substance soluble in
only one of the liquids raises the upper CST and lowers the lower CST. For
example, one percent solution of sodium chloride raises the upper CST of
phenol-water system by 120 . About 0.12 molar solution of naphthalene
(insoluble in water) in phenol raises the upper CST of phenol-water system by
about 300. Substances which are soluble in both the liquids tend to lower the
upper CST and raise the lower CST. For example, sodium oleate is soluble in
both water and phenol. Addition of 1% solution of sodium oleate to phenol-
water system lowers the CST value by 450.

As seen above, the presence of small amounts of impurities produces a very

large change in the CST value. The change in CST values is usually a linear
function of concentration of impurities. Traces of water present in alcohol are
estimated by measuring their CST values with cyclohexane.

As mentioned above a very small amount of sodium oleate lowers the CST
value of phenol-water system considerably. Thus, by making phenol
completely miscible with water (adding appropriate amounts of sodium oleate),
lysol-like disinfectants are made.

SAQ 1
Give one example each for liquid pairs with
a) lower critical solution temperature.
40
Unit 2 Solutions-II
b) upper critical solution temperature.
c) both upper and lower critical solution temperatures.

SAQ 2
What is the effect of adding 0.1 molar KCl on the CST of phenol-water
system?

SAQ 3
What would happen when potassium carbonate is added to a solution of water
and alcohol?

2.3 IMMISCIBLE LIQUID PAIRS

In Sec. 2.2, we studied properties of the partially miscible liquid pairs. In this
section, we will discuss the characteristics of the completely immiscible liquid
pairs. We should, however, understand that there is always some solubility of
a substance into the other. But this is so low that we can call it insoluble or
completely immiscible.

According to Raoult’s law, the vapour pressure of a liquid is lowered on the

addition of another liquid, if the latter is soluble in the former. Otherwise, the
vapour pressure of each component remains unaffected and each liquid exerts
its own vapour pressure independent of the other. Thus, when two completely
immiscible liquids A and B are mixed, the total vapour pressure (p) above the
mixture will be the sum of the vapour pressures of the pure liquids at that
temperature, i.e.,

p  pA0  pB0 …(2.2)

where p A0 and pB0 are respectively, the vapour pressures of pure A and B. You
also know that a system starts boiling when its total vapour pressure becomes
equal to the atmospheric pressure. The mixture of two immiscible liquids A
and B will thus start boiling at a temperature (T) at which,

pA0  pB0 = atmospheric pressure …(2.3)

This temperature will be lower than the normal boiling point of either A or B. Condensate or
The mixed vapours thus obtained and condensed will have a composition distillate is the liquid
dependent on the partial pressures of A and B at temperature T. Since the obtained by
number of moles of each component present in the vapour phase is condensing the
proportional to its vapour pressure, the mole ratio of A to B (nA/nB) in the vapours.
condensate is given by

nA pA0
 …(2.4)
nB pB0

41
Block 1 Solutions and Phase Equilibrium

If wA and wB are the masses of A and B in the condensate, and MA and MB

their respective molar masses, then

nA w A / MA p0
w A MB
   A …(2.5)
nB wB / MB wBMA pB0

or wA p0 M …(2.6)
 A A
wB pB0 MB

Having understood the above concepts, let us see how these are useful in the
technique of steam distillation.

2.3.1 Principle of Steam Distillation

The fact, that a system of immiscible liquids starts boiling at temperatures less
than the normal boiling points of both the liquids, is made use of in steam
distillation. The steam distillation is a process of purifying organic liquids which
have high boiling points and are immiscible with water. For purification by
steam distillation, an impure compound

i) must be immiscible in water,

ii) should not decompose at the temperature of steam,

iii) should have a fairly high vapour pressure at 373 K, and

iv) should have non-volatile impurities.

For example, chlorobenzene has a boiling point of 405 K. A mixture of water

and chlorobenzene distils at a constant temperature of 363.3 K, when the
external pressure in 9.8 × 104 Pa, by passing steam through it.

Let us explain the procedure for purifying an organic liquid using steam
distillation. The apparatus used for steam distillation is as shown in Fig. 2.4.

A water condenser
has a water inlet (D)
and an outlet (E).
This condenser is
used for cooling the
vapours (below
373 K) to get the
liquid.

Fig. 2.4: Steam Distillation.

The impure organic compound is taken in a round-bottomed flask (A) and a

small quantity of water is added. The flask must be kept in a slanting position
42
Unit 2 Solutions-II

to prevent the impure liquid from splashing up into the condenser. The flask A
is then heated gently. Now, steam from container B is bubbled through the
contents of the flask A. The vapours of the organic compound mix with steam
and escape into the water condenser C. The condensate thus obtained in the
flask F is a mixture of water and the organic compound. This mixture can then
be separated by means of a separating funnel.

Let us now understand the application of Eq. 2.6 with the help of the following
example.

Example 1

A mixture of water and an organic liquid A, which is immiscible in water, distils

at 368 K when the external pressure is 1.00 ×105 Pa. The vapour pressure of
water at 368 K is 8.35 × 104 Pa. Calculate the relative molecular mass of A if
the distillate contains40% of water by weight.

Solution

Let us represent the vapour pressures of pure water and the organic liquid A
0 0
at 368 K as p H2O and pA , respectively. At a total pressure of 1.00 × 105 Pa, the
liquid mixture boils; therefore,

pH0 O  pA = 1.00 × 105 Pa

0
2

0
At the distillation temperature, pH2o = 8.35 × 104 Pa

0
Hence, pA = (1.00 × 105 Pa - 8.35 × 104 Pa) = 1.65 ×104 Pa

Using Eq. 2.6,

wH O pH0 O  MH O
2
 2 2

wA p  MA
0
A

But water is 40% by weight; hence, we can write

40 8.35  10 4 Pa 0.018 kg mol1

 
60 1.65  10 4 Pa MA

or 8.35 104 Pa 60
MA   0.018 kg mol1 
1.65 10 Pa
4
40

= 0.137 kg mol-1

The relative molecular mass of A = 137

SAQ 4
Why does a mixture of two immiscible liquids boil at a temperature which is
lower than the boiling point of any of the pure liquids?

43
Block 1 Solutions and Phase Equilibrium

2.4 NERNST DISTRIBUTION LAW AND ITS

APPLICATIONS
In this section, we will discuss the distribution of a solute when added to a pair
of immiscible liquids. Let us take the example of distribution of iodine when
added to two immiscible liquids-water and carbon tetrachloride and
understand what is Nernst distribution law.

2.4.1 Nernst Distribution Law

Water and carbon tetrachloride are practically immiscible with each other but
iodine dissolves both in water and carbon tetrachloride. When iodine is added
to a mixture of water and carbon tetrachloride at a certain temperature, iodine
distributes itself between the two immiscible layers-water and carbon
tetrachloride. Let the concentrations of iodine in water and carbon tetrachloride
be cI and cII, respectively, at a particular temperature. Then ,we have
cI
K …(2.7)
cII

where K is a constant at a constant temperature.

If more of iodine, is added to this system, it again distributes itself between the
two layers. Now, the concentration of iodine in both the layers will be more
than that in the previous case. Let the concentrations be c ' and c ' in water
l Il

and CCl4 layers, respectively. Though c '

c and c  c , the ratio c' / c' is
'
l l lI Il l lI
again equal to the constant, K, i.e.,
c c' …(2.8)
l
 I K
c'II
c
lI

It is evident that, in each case, I2 distributes itself between the two immiscible
layers in such a way that the ratio of its concentration in the two layers is a
constant at a certain temperature. It was pointed out by Nernst that the ratio,
cl / cll is constant only when the solute exists in the same molecular form, i.e.,
the relative molecular mass of the solute is the same in two layers. The Nernst
distribution law may be stated as follows:
At a fixed temperature, a substance X distributes itself between the two
immiscible solvents A and B in equilibrium with each other in such a way that
the ratio of the concentration of X in the two solvents is constant, provided that
the solute X is in the same molecular state in both the solvents.

Mathematically,
Concentration of X in solvent A
K …(2.9)
Concentration of X in solvent B

The constant K is called the distribution coefficient or partition coefficient of the

solute between the two solvents. You can see from the data given in Table 2.2
that the value of K is fairly constant in dilute solutions. But, as the
concentration increases, there is a deviation.

44
Unit 2 Solutions-II
Table 2.2: Distribution of I2 between H2O and CCl4

C CC
4

K
CH d
1 m
0

CC d
1
0

H C
O l
C
l 3
O 3

2
4
 

2-


-
m
o
l
m
o
l
m

4
-2
3.22 2.745 1.17  10
-2
5.03 4.29 1.17  10
-2
7.63 6.54 1.17  10
-2
11.5 10.1 1.14  10
-2
13.4 11.96 1.12  10

The distribution coefficient K depends upon

 nature of the solute,

 nature of the solvents and
 temperature.

The distribution law can be derived taking into account thermodynamic

considerations.

Thermodynamic Derivation of Distribution Law

In BCHCT-133 course, Block 2, Unit 5 on Chemical Equilibrium-I, Eq. 5.4

stated the relation of the chemical potential of an ideal gas to its partial
pressure in a mixture of gases. Similar expressions can be written when the
concentration and the mole fraction are considered in a mixture of gases.
Here, we are going to use the modified form of Eq. 5.4 to denote the chemical
potentials of a solute (such as iodine) in the two immiscible liquids. Instead of
mole fraction used in a similar situation, we are going to use activity (a) which
is an ‘effective’ mole fraction. In the case of an infinitely dilute solution, activity
becomes equal to mole fraction; hence, similar to Eq. 5.4.The chemical
potentials of iodine, μ 1 and μ 2 ,respectively in water and carbon tetrachloride
are given by following equations.

μ 1  μ 10  RT lna1 …. (2.10)

μ 2  μ 20  RT lna2 …. (2.11)

where μ10 and μ20 are standard chemical potentials of iodine in water and
carbon tetrachloride at unit activity; also,a1 and a2 are the activities of iodine in
water and carbon tetrachloride, respectively.

At equilibrium, μ1 = μ2

Hence, μ 10  RT ln a1  μ 20  RT ln a2
or μ 20  μ 10  RT ln a1  RT ln a2
 RT ln a1 / a2
At constant temperature, μ 10 and μ 20 are constants.

Also, R is constant. Therefore, it follows that

45
Block 1 Solutions and Phase Equilibrium
a1 / a2 = constant …(2.12)

This is another form of the distribution law. At low concentrations, activities

can be replaced by concentration, and we get
a1 c1
 = constant
a2 c2

a1 c1
or  =K
a2 c2

Nernst first gave attention to the fact that the above statement of the
distribution law is valid only when the solute undergoes no change such as
dissociation or association in either of the solvents. If a solute dissociates into
simple molecules or ions or if it associates to form complex molecules, then
the distribution law does not apply to the total concentration of the solute in
each of the two phases. It is applicable to the concentration of a particular
species common to both the layers. Let us look at this in some detail by
considering the following cases.

2.4.2 Dissociation of a Solute in One of the Solvents

Let us take a solute X which remains undissociated in phase I. We assume
that its concentration in phase I is c1. In phase II, let it undergo dissociation
Eqs. 2.13 to 2.21 are
written following the into A and B. If c2 is the total concentration in phase II beforedissociation, and
principle of chemical α is the degree of dissociation, then we can write
equilibrium.
X A + B
c2(1-  c 2 c 2
…(2.13)

Evidently, the concentration of the undissociated molecules of X in phase II is

c2(1–α). So as per distribution law, the distribution coefficient is given by

Concentration of X in phase I
K
Concentration of undissociated X in phase II

or K = c1/c2 (1–α) …(2.14)

The following example illustrates the application of Eq. 2.14

Example 2

An organic acid A, distributes between 1.0 dm3 each of an organic solvent, S,

and water. The concentration of the acid in aqueous layer is
1.20  10 kg dm3 and in the organic layer, it is 1.44  10 kg dm3. If the
2 3

distribution coefficient of the acid between the organic solvent and water is
0.16, calculate the degree of dissociation of the organic acid in water. Assume
that the acid does not undergo any change in its molecular state in the organic
solvent, S.
Solution

Let the concentration of the acid in the organic and water layer be c1 and c2,
respectively. Hence,

46
Unit 2 Solutions-II
c1 = 1.44 × 10-3 kg dm-3

and c2 = 1.20 × 10-2 kg dm-3

Using Eq. 2.14, we have

1.44  10 3 kg dm 3 0.12
0.16  
1.20  10  2 kg dm 3  (1  α ) (1  α )

Or 0.12
(1  α )   0.75
0.16
α  1  0.75  0.25

The percentage dissociation of the acid in water in 25%.

Let us next consider what will happen if the solute associates in one of the
solvents.

2.4.3 Association of the Solute in one of the Solvents

Let X be a solute that does not undergo dissociation or association in phase I.
Let its concentration be ci in phase I. And, it associates in phase II as given in
Eq. 2.15 to give the molecules, Xn.

Let us assume that c2 is the concentration of the solute in phase II, if there is
no association, Let α be the fraction of the molecules that is associated in
phase II to give the molecules Xn.
nX Xn

c2(1 &  c2 n

…(2.15)

Then, the concentration of the associated molecules can be calculated as

follows:
The concentration of the unassociated X = c 2 (1   )

The concentration of X used for forming associated molecules =c2α

Since n moles of X give one mole of the associated species, Xn

Concentration of the associated species, Xn  c 2  …(2.16)

n

Concentration of X in phase I
Then, K
Concentration of undissociated species in phase II

or c1 …(2.17)
K
c2 (1   )

Also, it is possible to calculate the equilibrium constant, Keq, for equilibrium

represented by Eq. 2.15, if α is known.

c2
K eq  n … (2.18)
[c 2 (1   )]n

47
Block 1 Solutions and Phase Equilibrium

c2
or [c 2 (1   )] n  n … (2.19)
K eq

1/ n
c  / n 
[c 2 (1   )]   2 
 K eq 

1/ n
 c  
[c 2 (1   )]   2  … (2.20)
 nK eq 

Substituting Eq. 2.20 in Eq. 2.17,

1/ n
c1 c  nK eq 
K  1  
 c  
1/ n
c 2   
1/ n
 2 
 nK eq 

At constant temperature, n, Keq and α are constants.

c1 .constant
K
c 12 / n

K c …(2.21)
K'   1
constant c / n
1
2

Hence, if c1 , c 2 and n are known, K’could be found out. The value of n could
help us in finding out whether the solute remains as a dimer, trimer etc. in a
particular solvent.

With the help of Eq. 2.21, it is possible to determine approximate values of n.

Two important methods for this purpose are illustrated below:

1) Method of Trial and Error

In Eq. 2.21, integer values starting with 1 and above are given to n. The
value for which Eq. 2.21 gives a constant value for K’is adopted.

2) Graphical Method
n is called the order
Eq. 2.21 can also be written as follows,
of association.

c1  K ' (c 2 )1/n

Taking logarithms on both sides, we get

1
log c1  log K '  log c 2
n
1 … (2.22)
log c1  log c 2  log K
n

Eq. 2.22 is of the type y = mx + c which is an equation for a straight line.

If a graph is plotted between log c1 and log c2, a straight line is obtained
as shown below in Fig. 2.5. The slope of the line gives the value of 1/n
from which n can be calculated. The intercept on the y-axis gives the
value of log K’and henceK’can be calculated.
48
Unit 2 Solutions-II

Fig. 2.5: log c1 plotted against log c2.

Example 3

The following results were obtained for the distribution of benzoic acid
between water and benzene at 298 K:

3
Concentration in H2O (c1) / (mol dm‾ ) 0.0033 0.0058 0.0075

3
Concentration in C6H6 (c2) / (mol dm‾ ) 0.0156 0.0495 0.0835

What conclusion can be drawn from these results regarding the molecular
form of benzoic acid in benzene? Assume that c1 represents the concentration
of the undissociated benzoic acid in water.

Solution

It is known that benzoic acid is dissociated in water into its ions. The
concentration c1 of the benzoic acid given above is that of the undissociated
c
acid. If benzoic acid remains as normal molecules in benzene, then 1 must
c2
be constant. Let us see whether it is so?

c1 0.0033 mol dm 3
  0.211
c 2 0.0156 mol dm 3

c1 0.0058 mol dm 3
  0.117
c 2 0.0495 mol dm 3

c1 0.0075 mol dm 3
  0.090
c 2 0.0835 mol dm 3

As c1 varies considerably, benzoic acid in benzene is not present as normal

c2
molecules. We can find the value of nusing trial and error method. Substituting
n = 2 in Eq. 2.21, let us see whether we get a constant value for c1 .
c 21 / 2

49
Block 1 Solutions and Phase Equilibrium

c1 0.0033 mol dm 3 0.0033 mol dm 3

   0.0264 (mol dm 3 )1 / 2

c 21 / 2 0.0156 mol dm 3/2 1 / 2

0.0125( mol dm 3 1 / 2
)

c1 0.0058 mol dm 3 0.0058 mol dm 3

1/ 2
 3 1 / 2
 3 1 / 2
 0.0260 (mol dm 3 )1/ 2
c2 (0.0495 mol dm ) 0.223( mol dm )

c1 0.0075 mol dm 3 0.0075 mol dm 3

   0.0260 (mol dm 3 )1 / 2
c 21 / 2 (0.0835 mol dm 3 )1 / 2 0.289( mol dm 3 )1/ 2

It is clear from the above calculations that the values of c1 are fairly constant.
c 12/ 2
Hence, benzoic acid in benzene exists as a dimer, (C6H5COOH) 2.

To understand the application of distribution law, when the solute undergoes

association in one solvent and dissociation in another, let us consider the
distribution of benzoic acid between water and chloroform as given in
Table 2.3.

Table 2.3: Distribution of Benzoic Acid between Water and Chloroform at

313 K

c
c
3

wc

3
3

wc
c m

c m
c m
1 m
0 o

1 m
0 o

1 m
0 o
1 m
0 o
w

1 1
c3

c
w

K
1
13
In Table 2.3, cw1 is    
c

c
3

3
l
d

l
d

l
d
l
d
m

the concentration of    

un-dissociated
benzoic acid in 2.11 7.21 0.293 1.78 4.04 0.441
aqueous layer and cc1
is the concentration of
2.68 10.8 0.248 2.31 5.23 0.442
unassociated benzoic
acid in chloroform
layer. 3.53 16.8 0.210 3.10 7.01 0.442

7.25 57.0 0.127 6.62 15.0 0.441

12.7 167.0 0.076 11.8 26.9 0.439

In Example 3, the concentrations of un-dissociated benzoic acid in aqueous

layer (c1) have been given. But in Table 2.3, cw gives the total concentration of
benzoic acid in the aqueous layer and it includes the dissociated and
un-dissociated forms. Also, cC is the total concentration of benzoic acid in
chloroform layer. You see that cw/cC is not constant. The observed results can
be explained on the basis that the acid is partially dissociated in water into
hydrogen ion and benzoate ion and partially associated in chloroform into
dimers.

Since, the distribution law can be applied to the common species present in
both the phases (i.e., un-dissociated or unassociated benzoic acid), correction
must be applied for association and dissociation. After applying these
corrections, you see that c W1 is constant as given in the last column.
c C1
Now, you have a good understanding of using distribution law in different

50
Unit 2 Solutions-II

situations. At this stage, it is worthwhile to discuss some applications of this

law.

2.4.4 Applications of the Distribution Law

The study of the distribution of a solute between two immiscible solvents is
quite useful in a number of ways. A few of these applications are given below:

1. By studying the distribution of acetic acid and benzoic acid between water
and benzene, it is possible to show that acetic acid and benzoic exist as
dimers in benzene.

2. If a solute dissociates in one of the solvents, then knowing the distribution

coefficient, the degree of dissociation of the solute can be calculated at a
particular temperature.

3. The distribution law has also been used in the study of many problems
e.g., solvent extraction, analysis and determination of equilibrium
constants. Let us study the principle of solvent extraction in detail.

Solvent Extraction

Solvent extraction is used both at laboratory and industrial scale in various

processes. An organic compound can often be extracted economically from an
aqueous solution or a suspension by,

 adding an organic solvent,

 shaking and separating the two layers, and

 finally, distilling off the organic solvent to recover the separated compound.

In the process of extraction, we make use of the fact that the distribution
coefficient of most of the organic compounds is very large in favour of organic If the distribution
solvents. It can be shown that with a given volume of an extracting liquid, the coefficient of a solute
organic compound extracted is more if the given volume of the extracting liquid between ether and
is used in a number of smaller lots than if the whole of it is used in one lot. Let water is 3 in favour of
us derive a general formula which enables the calculation of the amount that is the ether, it means
left unextracted after a given number of extractions. that the solute in
three times more
Let us consider an aqueous solution of volume V. Let the mass of an organic soluble in ether as
compound dissolved in it be w. Let us use volume v of the organic liquid for compared to that in
water.
each extraction and let the mass of the organic compound that remained
unextracted in water one extraction be w1.

After the First Extraction

w1
Concentration of the organic compound in the aqueous layer =
V

Mass of the organic compound in the organic layer = w  w1

w  w1
Concentration of the organic compound in the organic layer =
v

Distribution coefficient, K, is given by the following expression:

51
Block 1 Solutions and Phase Equilibrium
Concentration of the compund in the aqueouslayer
K
Concentration of the compund in the organiclayer

w1
or w1v
K V =
(w  w 1 ) (w  w1 )V
v

or K (w  w 1 )V  w 1v

or KwV  w1v  Kw 1V  w1(v  KV )

or KwV KV
w1  w
(v  KV ) v  KV

After the Second Extraction

Similarly, after the second extraction, the mass of the organic compound that
remains unextracted is,
2
KV  KV 
w 2  w1  w 
(v  KV )  v  KV 

After n Extractions

In general, the mass of the organic compound that remains unextracted after n
extractions is given by,
n
 KV 
wn  w  …(2.23)
 v  KV 

Applications of Solvent Extraction

1. Often we have to recover the organic compounds from an aqueous

solution using extraction method.
Desilverisation means
removal of silver. 2. Desilverisation of Argentiferrous Lead
Argentiferrous galena
is an ore of lead
Argentiferrous galena contains small quantities of silver which could be
containing silver.
extracted quite economically by Parkes process. In this process, molten zinc is
used for extracting silver from molten argentiferrous lead as it is immiscible
with molten lead. The distribution coefficient of silver between molten Zn and
molten Pb is 300 at 1073 K. Therefore, when molten zinc is added to molten
argentiferrous lead, practically the whole of silver present passes into the
molten zinc layer. On cooling, Zn-Ag alloy solidifies before lead. The solid
layer can be remove easily. As zinc is volatile, it can be separated from silver
by distillation.

2.5 SUMMARY
In this Unit, you have learnt the following:

 When two liquids are mixed, they may be completely miscible, partially
miscible or completely immiscible.

 The miscibility of partially miscible liquid pairs varies with temperature.

52
Unit 2 Solutions-II

 The miscibility of some partially miscible liquid pairs, e.g., phenol-water

increases with rise in temperature.

 The temperature at which a pair of partially miscible liquids becomes

completely miscible iscalled critical solution temperature or consolute
temperature. Thus, phenol-water system possesses an upper CST.

 Some liquid pairs possess lower CST, i.e., their mutual solubility
decreases with rise in temperature. Below a certain temperature, such
liquid pairs are completely miscible.

 Some liquid pairs possess both lower and upper CST.

 The presence of an impurity in one or both the phases changes the CST
values.

 Substances soluble in one of the liquids raise the upper CST and lower the
lower CST.

 Substances soluble in both the liquids tend to lower the upper CST and
raise the lower CST.

 A pair of immiscible liquids boil at a temperature lower than the boiling

points of any of the liquids. This fact is made use of in steam distillation.

 When a solute is added to a pair of immiscible liquids, it distributes itself

between the two liquids in such a way that the ratio of the concentrations
of the solute in the two phases remains constant. This is called the
distribution law.

 The distribution law can be used to study the state of association or

dissociation of the solute in one or both the phases.

 The distribution law also helps in determining the degree of dissociation of

a solute. The order of association of a solute can also be determined using
distribution law.

 The distribution law has applications in solvent extraction, analysis and

determination of equilibrium constants.

2.6 TERMINAL QUESTIONS

1. Two liquids A and B are completely immiscible with each other. Their
normal boiling points are TA and TB, respectively, and TA is less than TB.
The two liquids taken together will boil at

i) TA

ii) TB

TA  TB
iii)
2

iv) a temperature less than TA.

v) a temperature more than TB.

53
Block 1 Solutions and Phase Equilibrium

2. An immiscible mixture of an organic liquid, Aand water on steam

distillation boils at 372 K at pressure 1.00 × 105 Pa. At this temperature,
the vapour pressure of water is 9.60 × 104 Pa. The ratio of the mass of
water to the mass of A in the distillate is 4:1. Calculate the relative
molecular mass of liquid A.

3. Explain the behaviour of partially miscible liquid systems with respect to

change of temperature.

4. Derive distribution law thermodynamically.

3 -3
5. When 1.00 dm of an aqueous solution containing 5.00  10 kg of a
-2 3 4
solute is shaken with 5.00  10 dm ether, it is found that 8.50  10- kg
of the solute passes into ether. How much of the solute will be left
unextracted, if the same aqueous solution is shaken with a second
-2 3
installment of 5.0  10 dm ether? The solute exists in the same
molecular state in both water and ether.

6. Succinic acid is associated in benzene. Find the order of association (n)

from the following data on the distribution of succinic acid between water
and benzene. Assume that c1 is the concentration of undissociated
succinic acid in water and c2 is the total concentration of succinct acid in
benzene.

103  c1 in water/ (kg dm-3) 1.10 1.95 2.90

103  c2 in benzene/ (kg dm-3) 14.2 41.2 96.5

2.7 ANSWERS
Self-Assessment Questions
1. See Table 2.1.

2. Raises the critical solution temperature of phenol-water system.

3. Since potassium carbonate is highly soluble in water but not in ethanol,

the solubility of ethanol in water decreases and two layers and formed.

4. The sum of the vapour pressures of the two liquids becomes equal to the
atmospheric pressure at a lower temperature.

Terminal Questions
1. iv)

2. Given that,
Mass of water 4

Mass of A 1

Vapour pressure of water ( p0 )  9.60  10 4 Pa

H O 2

Vapour pressure of liquid A ( pA0 )  1.00  105 Pa - 9.60  104 Pa

= 4.00  103 Pa
54
Unit 2 Solutions-II
Using Eq. 2.6,
wH O pH0 O  M H O
2
 2 2

wA pA0  M A

or pH0 O  MH O wA
MA  2
0
2

p A
wH O2

9.60  104 Pa  0.018 kg mol1 1

 
4.0  103 Pa 4

= 0.108 kg mol-1

Hence, the relative molecular of mass A = 108

3. See Sec. 2.2.

4. See Sec. 2.4.

5. Concentration of the solute in aqueous layer

(c1) = (5.00 – 0.850)  10‾3 kg /1.00 dm3

= 4.15  10‾3 kg dm‾3

Concentration of the solute in ether layer

(c 2 ) 
8.50  10 -4 kg  1.70  10 - 2 kg dm - 3
5.00  10 - 2 dm 3

Distribution coefficient between water and ether,

c 4.15  10 -3 kg dm-3
K 1   0.244
c 2 1.70  10 - 2 kg dm - 3

Using Eq. 2.23, the amount of the solute left after the second extraction is

2 2
 KV   0.244  1.00 dm- 3 
w2  w   5.00  10 3 kg  
 v  KV  - 2 - 3 3
 5.00  10 dm  (0.244  1.00 dm ) 

 3.44  10 3 kg

c1
6. By trial and error method, let us try whether is constant by keeping
c2
n = 1 in Eq. 2.21.

c1 1.10  10 -3 kg dm -3
  0.077
c 2 14.2  10 - 3 kg dm - 3

1.95  10 -3 kg dm -3
  0.047
41.2  10 - 3 kg dm - 3

2.90  10 -3 kg dm-3
  0.030
96.5  10 -3 kg dm-3

c1
As the value of is not constant, n  1.
c2
55
Block 1 Solutions and Phase Equilibrium

Let us now try for n = 2.

1
c1 1.10  10 - 3 kg dm - 3
K   9.23  10 - 3 (kg dm - 3 ) 2
c2 14.2  10 - 3 kg dm - 3

1
1.95  10 -3 kg dm- 3
  9.61 10- 3 (kg dm-3 ) 2
41.2  10- 3 kg dm-3

1
2.90  10 - 3 kg dm -3
  9.34  10 - 3 (kg dm - 3 ) 2
96.5  10 - 3 kg dm -3

As the value of c1 is constant, the order of association is 2. Hence,

1
c2 2
succinic acid exists as a dimer in benzene.

56