SOLUTION

1. Definition of Solution : When two or more chemically non-reacting substances are mixed and form homo-
geneous mixture is called solution.
When the solution is composed of only two chemical substances, it is termed a binary solution, similarly, it is
called ternary and quaternary if it is composed of three and four components respectively.
Solution = solute + solvent
 Solute : Generally the component present in lesser amount than other component in solution is called solute.
 Solvent : Generally, the component present in greater amount than any or all other components is called the
solvent.
* Physical state of solvent and solution is same.
Ex. In a syrup (liquid solution) containing 60% sugar (a solid) and 40% water (a liquid - same aggregation as
solution), water is termed as the solvent.
2. Dilute Solution : A solution in which relatively a small amount of solute is dissolved in large amount of
solvent is called a dilute solution.
3. Concentrated solution : A solution in which relatively a large amount of the solute is present is called a
concentrated solution.
4. Saturated solution : The maximum amount of solute in grams, that can be dissolved in 100 g of a solvent at
a particular temperature is called solubility of the solute and such a solution is called saturated solution.
5. Super saturated solution : A solution containing more amount of solute than that required for saturation of
a given amount of solvent at a particular temperature, is called a supersaturated solution.
* It is unstable system.
6. Type s of Solut ion :

Solvent Solute Examples

1. Gas Gas Mixture of gases, air.
2. Gas Liquid Water vapour in air, mist.
3. Gas Solid Sublimation of a solid into a gas, smoke, storms.
4. Lquid Gas CO2 gas dissolve in water (aerated drink), soda water.
5. Lquid Liquid Mixture of miscible liquids e.g. alcohol in water.
6. Lquid Solid Salt in water, sugar in water.
7. Solid Gas Adsorption of gases over metals, hydrogen over palladium.
8. Solid Liquid Mercury in zinc, mercury in gold i.e. all amalgams.
9. Solid Solid Homogeneous mixture of two or more metals
(i.e. alloys) e.g. copper in gold. zinc in copper.
 Sp. Note : The solution of liquid in gas or solid in gas is not possible because the constituents can not
form a homogeneous mixture.
7. Proper t ie s of a solut ion :
(i) A solution consists of a single phase i.e. it is a monophasic system.
(ii) A solution is uniform throughout, so it has uniform properties such as density refractive index, etc.
(iii) Size of solute particles in a solution is of the order 107  108 cm.
(iv) The components of a solution can not be easily separated by physical methods.
(v) The properties of a solution are the properties of its components. i.e. the components do not lose their
properties when they form a solution.
(vi) The composition of a solution is not definite but can vary within certain limits.
(vii) Certain properties of solution such as density, viscosity, surface tension, boiling point, freezing point etc.
vary with the composition of the solution.
8. Percentage by weight :
The number of grams of solute is dissolved in one gram of solution is called weight fraction of the solute. Thus,

w
weight fraction 
w W

Where 'w' grams of solute is dissolved in W grams of solvent.

weight of solute in grams  100

weight percent 
weight of solution in grams.

w 100
w 
w W

9. Percent by volume (Volume fract ion) :

This method is used for solutions of liquid in a liquid. The volume of liquid (solute) in mL dissolved in one mL
of solution is called volume fraction.

Volume of liquid solute in mL

Volume fraction 
volume of solution in mL

Volume of solute  100

Volume percent =
Volume of solution

10. Mole fraction : The ratio of the number of moles of one component to the total number of all the compo-
nents present in the solution, is called the mole fraction of that component.
nA
Mole fraction of solute XA is given by XA 
nA  nB

nB
Mole fraction of solvent XB is given by XB 
nA  nB

Where nA is moles of solute of A & nB is moles of solvent of B.

11. Molarity (Molar concentration) :
It is defined as the number of moles of the solute dissolved in per litre or per dm3 of the solution, i.e.,

Number of moles of solute

Molarity (M) =
Number of litres of solution

or Molarity × Number of litres of solution = Number of moles of solute

Let wA g of the solute of molecular mass mA be dissolved in V litre of solution.

wA
Molarity of solution =
mA  V

wA
or Molarity × mA = = Strength of the solution
V

If V is taken in mL (cm3), then

wA
Molarity of the solution =  1000
mA  V

The unit of molarity is mol L–1 or mol dm–3.

 Molarity (second method) :
Let d = density of solution in g/mL and let it contains x% solute by mass.
Then, mass of 1 litre solution = (1000 × d)g
x
Mass of solute in 1 litre =  (1000  d)g
100
= (x × d × 10)g
Number of moles of solute in 1 litre

Mass of solute in gram x  d  10

= 
Gram molecular mass of solute mA
where mA = molecular mass of solute
x  d  10
 M mA
 Molarity of dilute solution :
Before dilution After dilution
M1V1 = M2V2
 Molarity of mixing :
Let there be three samples of solution (containing same solvent and solute) with their molarity M1, M2, M3 and
volumes V1, V2, V3 respectively. These solutions are mixed; molarity of mixed solution may be given as :
M1V1 + M2V2 + M3V3 = MR(V1 + V2 + V3)
where, MR = Resultant molarity
V1 + V2 + V3 = Resultant volume after mixing
[Note : Molarity is dependent on volume, therefore, it depends on temperature.]
1M Molar solution, i.e., molarity is 1
0.5 M or M/2 Semimolar
0.1 M or M/10 Decimolar
0.01 M or M/100 Centimolar
0.001 M or M/1000 Millimolar
12. Relation between molarity 'M' and mole fraction :
Let M be the molarity of solution, and xA, xB be mole fractions of solvent and solute, respectively.
Suppose nA and nB moles of solvent and solute are mixed to form solution.
Mass of solution = nAmA + nBm B ......(i)
where mA and mB are molar masses of solvent and solute, respectively.
Mass (n m  n B m B )
Volume of solution =  A A
Density d
1000
Molarity = Number of moles of solute ×
Volume of solution
1000  d
M = nB ×
(n A m A  n B m B )
Dividing both numerator and denominator by (nA + nB),
 nB  1000  d
M  
nA  nB  nA nB
 mA   mB
nA  nB nA  nB
x B  1000  d
M
xA m A  xBm B
13. Normalit y (N) :
The number of equivalents or gram equivalents of solute dissolved in one litre of the solution is known as
normality (N) of the solution.

Number of gram equivalents of solute

Normality(N ) 
volume of solution in litre

weight of solute in gram

=
equivalent weight  volume of solution (litre)

strength of solution in gram / litre

=
Equivalent weight of solute

Equivalent weight of a substance is that weight which reacts with or displaces one gram of hydrogen, 8 grams
of oxygen or 35.5 grams of chlorine.

N N N N
 Solutions are expressed as : 1N, , , , , etc.
2 10 100 1000
1N = Normal
= One gram equivalent of the solute per litre of solution
= Normality is 1

N
= Seminormal
2
= 0.5 g equivalent of the solute per litre of solution
= Normality is 0.5

N
= Decinormal
10
= 0.1g equivalent of the solute per litre of solution
= Normality is 0.1
N
= Centinormal
100
= 0.01g equivalent of the solute per litre of solution
= Normality is 0.01

N
= Millinormal
1000
= 0.001g equivalent of the solute per litre of solution
= Normality is 0.001
14. Molality (m) :
The number of moles or gram molecules of solute dissolve in 1000 gram of the solvent is called molality of the
solution.

Number of moles of solute

Molality of a solution =
Amount of solvent in kg.

Number of moles of solute 1000

=
Amount of solvent in grams.
* It is independent of temperature.
15. Formality : It is the number of formula mass in grams present per litre of solution.
weight of solute in gram
formality 
formula mass of solute in grams  volume of solution in litre
 In case formula mass is equal to molecular mass, formality is equal to molarity.
 Depends on temperature.
16. Concentrat ion or strengt h of a solut ion (S) :
The numbers of grams of solute dissolved in one litre solution is known as its strength in grams per litre.
* Strength in grams per litre

wt.of solute in grams  1000

S =
volume of solution in mL

S = Molarity of solution  molecular wt. of solute.

S = Normality of solution  equivalent weight of solute.
17. Parts per million (ppm) : This method is used for expressing the concentration of very dilute solutions such
as hardness of water, air pollution etc.
Mass of solute in gms  10 6
ppm of substance =
Mass of solution
Volume of solute  10 6
=
volume of solution
18. Relat ion bet ween molarit y a nd normalit y :
S = Molarity × molecular weight of solute
and S = Normality × equivalent weight of solute
So we can write
Molarity × Molecular weight of solute = Normality × equivalent weight of solute.

molarity  molecular weight of solute

Normality 
equivalent weight of solute

molarity  molecular weight of solute


(molecular weight of solute/valency factor)
Normality = molarity × valency factor
N=M×n NM
19. Relation between molality and molarity :
Molarity Moles of solute mass of solvent
 
Molality volume of solution moles of solute
mass of solvent(kg)

volume of solution (in litre)

mass of solvent(in grams) W

 
volume of solution (in mL) V

Let the density of the solution be d g. mL–1

Mass of solution = V×d
Mass of solute = number of moles × molecular mass of solute
= n × mA
Mass of solvent(W) = mass of solution – Mass of solute
= (V × d) – (n × mA)
 Molarity (V  d)  (n  m A )
Thus 
Molality V
molarity  V
Molality (m) =
 V  d   n  m A 
molarity
m=
n 
d   mA 
V 

molarity
m=
d   molarity  m A 

 Sp. Note :
If the density of solution is approximately 1. then
Molality > Molarity
 Demal (D) :
Demal (D) is another unit for expressing the concentration of a solution. It is equal to molar concentration at
0°C i.e., 1D respresents one mole of the solute present in one litre of the solution at 0°C.
Ex. If 0.4 gm of NaOH is present in 40 ml of solution. What is the molarity and normality [M.wt. of NaOH = 40]
S o l . We know that

wt. of solute  1000 0.4

Molarity = =  1000 = 0.25 M
M.Wt. of solute  volume of solution (mL ) 40  40

wt.of solute
and normality   1000
Eq.wt. of solute  volume of solution(mL )

eq. wt. of NaOH = 40

0.4
so N  1000 = 0.25N
40  40

 Second method N = m × n
here n = 1, N = M, N = 0.25
Ex. The normality of 1.5M H3PO4 is –
S o l . Basicity of H3PO4 is 3
We know that N = M × n
N = 1.5 × 3 = 4.5
Ex. How much volume of 10M HCl should be diluted with water to prepare 2.00 L of 5M HCl ?
S o l . In dilution the following equation is applicable :
M1V1 = M 2V 2
10M HCl = 5M HCl
10 × V 1 = 5 × 2.00

5  2.00
V1 = = 1.00 L
10
 N
Ex. Find out the weight of H2SO4 in 150 mL, H2SO4.
7

Weight in gram
Sol. N
equivalent weight  volume

wt. in gram = eq. wt × N × volume

1 150 21
= 49 × × = = 1.05 g
7 1000 20
Ex. Find out the molarity of 1 litre of 93% H2SO4 and its density is 1.84.

Wt. in g  density  1000 93  1.84  1000

Sol. Molarity  = = 78.68 M
molecular wt.  100 98  100
Ex. A 100 cm3 solution is prepared by dissolving 2g of NaOH in water. Calculate the normality of the solution.

2 1
S o l . 2 g NaOH = g. eq. = g eq.
40 20

1
20 1
N =  1000 =
100 2

N
Normality of solution =
2
Ex. Find the percentage by weight and weight fraction of aspirin in the solution prepared by dissolving 3.65 g of
aspirin in 25.08 g of water.
S o l . weight of solution = 3.65 + 25.08 = 28.73 g

3.65
weight fraction = = 0.127
28.73

weight percent = 0.127 × 100 = 12.7%

Ex. A solution was prepared by adding 125 cm3 of isopropyl alcohol to water until the volume of the solution was
175 cm3. Find the volume fraction and volume percent of isopropyl alcohol in the solution.
Sol. volume of solute = 125 cm 3
volume of solution = 175 cm 3

125
 volume fraction = = 0.714
175

125
and volume percent =  100 = 71.4%
175

E x . 3 The density of a solution containing 13% by mass of sulphuric acid is 1.09 g/mL. Calculate the molarity and
normality of the solution.
S o l . Volume of 100 g of the solution
100 100
  mL
d 1.09
100
 litre
1.09  1000
1
 litre
1.09  10
 13
Number of moles of H2SO4 in 100 g of the solution =
98

No. of moles of H 2 SO 4 13 1.09  10

Molarity =   = 1.445 M
Volume of solution. in litre 98 1

N o t e : In solving such numericals, the following formula can be applied :

% strength of solution  density of solution  10
Molarity 
Mol. mass
Similarly,
% strength of solution  density of solution  10
Normality 
Eq. mass
We know that,
Normality = Molarity × n
 Mol. mass 98 
= 1.445 × 2 n  Eq. mass  49  2 
 
= 2.89 N
20. Vapour pre ssure :
At a constant temperature, the pressure exerted by the vapours of a liquid on its surface when they (liquid and
its vapours) are in equilibrium, is know as vapour pressure.
 Raoult's law :
According to this law, the partial pressure of any volatile constituents of a solution at a constant temperature is
equal to the vapour pressure of pure constituents multiplied by the mole fraction of that constituent in the
solution.
(i) For liquid – liquid solution :
Let a mixture (solution) be prepared by mixing nA moles of liquid A and nB moles of li quid B. Let PA' and PB' be
the partial pressures of two constituents A and B in solution and PA0 and PB0 the vapour pressures in pure state
respectivity.
Thus, according Raoult's law
nA
PA '  PA 0 ....(1)
nA  nB
Partial pressure of A = mole fraction of A × PA0 = XAPA0

nB 0
and PB'  PB ....(2)
nA  nB
Partial pressure of B = mole fraction of B × PB0 = XAPB0
If total pressure be PS, then
PS = PA' + PB'

nA 0 nB 0
 PA  PB
nA  nB nA  nB

= XAPA0 + XB PB0 ....(3)

PS = XAPA0 + (1 – XA)PB0 [ XA + XB = 1]

0 0 0
PS = XAPA – XA P B
+ P B

PS = XA [PA – PB ] + PB0
0 0
.....(4)
Equation 1, 2 and 3 are the straight line equation so we can draw it as follows.
 Vapour pressure 

0
PA
' + PB'
PS = PA
0

XAPA
PA' =
0
P B

PB' =
XBP 0
B

XA = 0 and XB = 1 Mole fraction  XA = 1 and XB = 0

Ex. 1 mole heptane (V.P. = 92 mm of Hg) is mixed with 4 mol. Octane (V.P. = 31 mm of Hg), form an ideal
solution. Find out the vapour pressure of solution.
S o l . total mole = 1 + 4 = 5
Mole fraction of heptane = XA = 1/5
Mole fraction of octane = XB = 4/5
0 0
PS = X A P A + XBPB
1 4
=  92   31
5 5
= 43.2 mm of Hg.
Ex. At 88°C benzene has a vapour pressure of 900 torr and toluene has a vapour pressure of 360 torr. What is the
mole fraction of benzene in the mixture with toluene that will be boil at 88°C at 1 atm pressure, benzene –
toluene form an ideal solution.
Sol. PS = 760 torr, because solution boils at 88°C
Now 760 = 900 × mole fraction of C6H6 + 360 × [1 – mole fraction of C6H6]
 760 = 900 a + 360 – 360 a
a = 0.74 where 'a' is mole fraction C6H6.
(ii) For Solid – liquid solution :
A = non volatile solids
B = volatile liquid
According to Raoult's law –
   Pm = XAPA0 + XBPB0
for A, PA0 = 0
 Pm = XBPB0 ....(5)
0 0
Let PB = P = Vapour pressure of pure state of solvent.
here XB is mole fraction of solvent
nB
PS  P0 ....(6)
nA  nB
nB
PS 
nA  nB
i.e. vapour pressure of solution  mole fraction of solvent
 P S = XB P B 0
 PS = (1 – XA) PB0
 PS = PB0 – XA PB0
 PB0  PS
 XA
PB0
P 0  PS
or  XA ....(7)
P0
P 0  PS nA
or  ....(8)
P0 nA  nB
P0 n  nB
or 0
 A
P  PS nA
P0 n
or 0
1 B
P  PS nA
P0 n
or 0
1  B
P  PS nA

PS n
or  B
P 0  PS n A

P 0  PS n A
 ....(9)
PS nB
P 0  PS w A .m B
or 
PS m A .w B

wM
or ....(10)
mW

Ex. The vapour pressure of benzene at 90°C is 1020 torr. A solution of 5 g of a solute in 58.5 g benzene has
vapour pressure 990 torr. The molecular weight of the solute is?

P 0  PS wM
Sol. 
PS m W

1020  990 5  78

990 m  58.5

m = 220
21. Col ligat ive proper t ie s :
Those physical properties of a solution which depend upon the number of particles in a given volume of the
solution or the mole fraction of the solute are called colligative properties.
The following four properties are colligative properties :
(i) Lowering of vapour pressure of the solvent.
(ii) Elevation in boiling point of the solvent.
(iii) Depression in freezing point of solvent.
(iv) Osmotic pressure.
Colligative properties  No. of particles.
 No. of molecules ( In the solution of non electrolyte)
 No. of ions (In the solution of electrolytes)
 No. of moles of solute
 Mole fraction of solute
 Equimetal solutions of different substances (non valatile, non electrolyte) have the same values of colligative
properties.
 Col ligat ive proper t ie s are t he proper t ie s of di lute solut ion :
(i) Loweri ng of vapour pre ssure :
When a non-volatile solute is dissolved in a pure solvent, the vapour pressure of the solvent is lowered i.e. the
vapour pressure of a solution is always lower than that of pure solvent, because the escaping tendency of
solvent molecules decreases (due to lesser surface area of solution available for evaporation).
If at a certain temperature P° is the vapour pressure of pure solvent, and Ps is the vapour pressure of solution
then
Lowering of vapour pressure = P°  Ps
P 0  Ps
Relative lowering of vapour pressure 
P0
from equation (8)
P 0  PS nA

P0 nA  nB
for a more dilute solution nA < < < nB
P 0  PS n A
so 
P0 nB
P P 0  PS n A
 
P0 P0 nB
P n A
 ....(11)
P0 nB
or relative lowering of vapour pressure

P 0  PS n A w A m B
=  = 
P0 nB m A w B
 Measurement of Relat ive Loweri ng i n Vapour Pre ssure
(Ost wald a nd Walker Met ho d)
The apparatus used is shown in Fig. It consists of two sets of bulbs. The first set of three bulbs is filled with
solution to half of their capcity and second set of another three bulbs is filled with the pure solvent.

Dry air

Air

Solution Solvent Weighed CaCl2 Tubes

Fig. Ostwald and Walker method

Each set is separately weighed accurately. Both sets are connected to each other and then with the accurately
weighed set of guard tubes filled with anhydrous calcium chloride or some other dehydrating agents like P2O5,
conc. H2SO 4 etc. The bulbs of solution and pure solvent are kept in a thermostat maintained at a constant
temperature.
A current of pure dry air is bubbled through the series of bulbs as shown in fig. The air gets saturated with the
vapour in each set of bulbs. The air takes up an amount of vapours proportional to the vapour pressure of the
solution first and then it takes up more amount of vapours from the solvent which is proportional to the
difference in the vapour pressure of the solvent and the vapour pressure of solution, i.e., p0 – ps.
 The two sets of bulbs are weighed again. The guard tubes are also weighed.

Loss in mass in the solution bulbs  ps

Loss in mass in the solvent bulbs   (p0 – ps)

Total loss in both sets of bulbs  [ps + (p0 – ps)]

 p0
Total loss in mass of both sets of bulbs is equal to gain in mass of guard tubes.

p0  ps Loss in mass in solvent bulbs

Thus, 
p0 Total loss in mass in both sets of bulbs

Loss in mass in solvent bulbs


Gain in mass of guard tubes

Further, we know from Raoult's law,

p0  ps wA / mA

p0 wA / mA  wB / mB

Loss in mass of solvent bulbs wA / mA

 
Gain in mass of gaurd tubes wA / mA  wB / mB

The above relationship is used for calculation of molecular masses of non-volatile solutes.
For very dilute solutions, the following relationship can be applied :

p 0  p s Loss in mass of solvent bulbs w A m B

 
p0 Gain in mass of gaurd tubes w BmA

Ex. Calculate the vapour pressure lowering caused by addition of 50 g of sucrose (molecular mass = 342) to
500 g of water if the vapour pressure of pure water at 25°C is 23.8 mm Hg.
S o l . According to Raoult's law,
p0  ps n

p0 nN
n
or p  .p 0
nN

50 500
Given : n = = 0.146 ; N = = 27.78 and p0 = 23.8 mmHg
342 18

Substituting the values in the above equation,

0.146
p   23.8  0.124 mm Hg
0.146  27.78

(ii) Elevation in boiling point (Ebullioscopy) :

The boiling point of a liquid is that temperature at which its vapour pressure becomes equal to the atmospheric
pressure. i.e. 760 mm of Hg.
When a non-volatile solute is dissolved in a pure solvent, its vapour pressure is decreased. The difference Tb
of boiling points of the solution and pure solvent is called elevation in boiling point.
 If T0 is the boiling point of pure solvent and (Tb)s is the boiling point of the solution then,
(Tb)s > T0
and the elevation in boiling point
 Tb = (Tb)sT0
The elevation in boiling point (Tb) is directly proportional to lowering of vapour pressure of the solution i.e.
Tb  PoPs
nA
or Tb  P 
nB

nA w.M
 Tb  
n B m.W

for a solvent P0 & M = const.

w
 Tb 
m.W
Kw
Tb 
m.W

where K = elevation constant

w
If = 1 mole
m
and w = 1 g
then Tb= K
w
If = 1 and W = 100 grams
m
K
 Tb  K' = molecular elevation constant
100
 K = 100 K'

100K ' w
Tb 
mW

w
If = 1 and W = 1000 gram
m
K
 Tb   Kb (molal elevation constant or Ebulloscopic constant)
1000
 Kb is defined as the elevation in boiling point produced when 1 mole of solute is dissolved in 1000 g of the
solvent.

K b  w  1000
Tb 
mW

w 1000
Tb  Kb
m W
  Tb = molality × Kb
 Tb  molality
So we can say that elevation of boiling point = boiling point of the solution – boiling point of pure solvent
Tb = (Tb)s – T0
 The elevation in boiling point of solution of non-electrolyte is proportional to its molality and equimolal solution
of all the substances in the same solvent will show equal elevation in boiling points. These are known as
Raoult's laws of elevation of boiling point.
Molal elevation constant is characteristic of a particular solvent and can be calculated from the thermodynamical
relationship.
RTb2
Kb 
1000 L v
where, R is molar gas constant, Tb is the boiling point of the solvent on kelvin scale and Lv the latent heat of
vaporisation of solvent in calories per gram.
For water
2  (373)2
Kb =  0.515
1000  540
The molal elevation constant for some common solvents are given in the following table

Solvent B.P. (°C) Molal elevation constant

Water 100.0 0.52

Acetone 56.0 1.70
Chloroform 61.2 3.67
Carbon tetra chloride 76.8 5.02
Benzene 80.0 2.70
Ethyl alcohol 78.4 1.15

Ex. 0.15 g of a substance dissolved in 15 g of solvent boiled at a temperature higher by 0.216°C than that of the
pure solvent. What is the molecular weight of the substance. [Kb for solvent = 2.16°C]
S o l . Given K b = 2.16°C
w = 0.15 g
Tb = 0.216°C
W = 15 g
  Tb = molality × Kb
w
Tb   1000  K b
mW
0.15
0.216   1000  2.16
m  15
0.15  1000  2.16
m = 100
0.216  15
E x . The rise in boiling point of a solution containing 1.8 g glucose in 100 g of a solvent is 0.1°C. The molal
elevation constant of the liquid is –
S o l .  Tb = molality × Kb
w
Tb   1000  K b
mW
Tb  m  W
Kb 
1000  w
T b = 0.1°C
m = 180
W = 100
w = 1.8
180  0.1  100
Kb   1.0
1000  1.8
(iii) Depre ssion i n freezi ng poi nt (Cr yoscopy) :
The freezing point of a liquid is that temperature at which the liquid and its solid state exist in equilibrium with
each other.
It may be defined as the temperature at which the liquid and solid states of a substance have the same vapour
pressure.
When a non-volatile non-electrolyte is dissolved in a pure solvent the vapour pressure of the solvent is lowered
If To is the freezing point of pure solvent and (Tf)s is the freezing point of its solution then,
(Tf)s < To
The difference in the freezing point of pure solvent and solution is the depression of freezing point (Tf) Thus,
To  (Tf)s =  Tf
Depression in freezing point is directly proportional to the lowering of vapour pressure of solution.
 T f  P0  Ps
from Raoult's law for dilute solution :
P 0  PS w A m B
 .
P0 mA wB
wA mB 0
or P 0  PS  . .P
mA wB
for the pure solvent, P0 and mB are constant. therefore –
wA
P 0  PS 
mAwB
wA
or P   T
mAwB
wA
Tf  K
mAwB
Where K is a constant, called depression constant .
wA
when = 1 (one mole of solute)
mA
and wB = 1g.
then Tf = K
wA
If = 1 and wB = 100 g
mA
K
then Tf  K'
100
K' is called molecular depression constant.
It is defined as the depression of freezing point produced when 1 mole of the solute is dissolved in 100 g of the
solvent.
Thus K' = 100 K
100K ' w A
S o Tf 
mA  wB
wA
If = 1 and wB = 1000 g
mA
K
Tf   Kf
1000
Kf is called molal depression constant.
 Kf is defined as the depression of freezing point produced when 1 mole of solute is dissolved in 1000 g of the
solvent.
1000K f  w A
or Tf  or  Tf = molality × Kf
mA  wB
 Kf is characteristic of a particular solvent and can be calculated from the thermodynamical relationship

0.002 Tf2
Kf 
Lf

Where, Tf is the freezing point of solvent in absolute scale and Lf the the latent heat of fusion in calories per
gram of the solvent. For water,

0.002  (273)2
Kf  = 1.86
80
the molal depression constant for some common solvents are given in the following table

Solvent F. P. ( ° C ) Molal depre ssion solvent s

Water 0.0 1.86

Ethyl alcohol – 114.6 1.99

Chloroform – 63.5 4.70

Carbon tetra chloride – 22.8 29.80

Benzene 5.5 5.12

Camphor 179.0 39.70

Ex. If freezing point of a solution prepared from 1.25 g of a non electrolyte and 20 g of water is 271.9 K, the
molar mas of the solute will be –

S o l . Given = (Tf)s = 271.9 K

w = 1.25 g W = 20 g Kf = 1.86

Tf = T0 – (Tf)s

= 273 – 271.9

Tf = 1.1

Tf = molality × Kf

w
Tf   1000  K f
mW
w  1000  K f
m
Tf  W

1.25  1000  1.86

m
1.1  20

m = 105.68
Ex. Molal depression constant for water is 1.86°C. The freezing point of a 0.05 molal solution of a non electrolyte
in water is :
Sol. Tf = molality × Kf
= 0.05 × 1.86 = 0.093°C
(Tf)S = T0 – 0.093 = 0 – 0.093
(Tf)S = – 0.093
(iv) Osmosis a nd osmot ic pre ssure : Maximum level


 Osmosis : Hydrostatic pressure
Osmosis is defined as the spontaneous flow of solvent initial level
molecules through semipermeable membrane from a Sugar solution
dilute solvent to a solution or from a dilute to a
Semi perme-
concentrated solution. able membrane
 Osmot ic pre sssure ( ) :
Water
The hydrostatic pressure developed as a result of
osmosis is a measure of osmotic pressure of the
solution.
or
The hydrostatic pressure built up on the solution which
just stops the osmosis.
osmotic pressure = hydrostatic pressure

 = hdg External pressure

h = increase in level in the tube
of unit cross section. Piston

d = density of solution,
g = acceleration due to gravity
Solution Solvent (water)
or
The external pressure which must be applied on the
solution in order to stop the flow of the solvent into
the solution through semipermeable membrane is
Semipermeable membrane
equal to osmotic pressure.
22. Va n't Hoff law for di lute solut ion :
The osmotic pressure (P or  ) of a solution is directly proportional to its concentration(C) when the tempera-
ture is kept constant. The concentration of the solution containg in one gram mole in V litres is equal to 1/V.
thus P  C (when temperature is constant)

1
or P 
V
PV = constant or V = constant
23. Gay – Lussac – Va n't Hoff law (Pre ssure - Temperature law) :
Concentration remaining same, the osmotic pressure of a dilute solution directly proportional to its absolute
temperature (T), i.e.,
P  T

P
or  consant
T


or  consant
T

Combining the two laws, i.e., when concentration and temperature both are changing, the osmotic pressure
will be given by :
 P  CT
or P = kCT
1  1
or P = k. .T  since, C  
V  V
or PV = ST or V = ST
S is called molar solution constant.
Here, V is the volume solution containing one gram mole of the solute. The value of S comes out to 0.082
litre atm K –1 mol –1 which is in agreement with the value of R, the molar gas constant. In case, the solution
contains n gram moles in V litre, the general equation would become :
PV = nST
or  V = nST
E x . A cane sugar solution has an osmotic pressure of 2.46 atm at 300 K. What is the strength of the solution.
Sol.  V = nST
n
or   ST  = CST
V
 2.46
or C    0.1 M
ST 300  0.0821
 Isotonic or iso-osmotic solution :
Solutions which have the same osmotic pressure are termed isotonic or iso-osmotic solutions

i.e. C1ST = C2ST
C1 = C2
 Hypertonic solution
A solution having higher osmotic pressure than some other solution is said to be called hypertonic solution.
 Hypotonic solution
A solution having a lower osmotic pressure relative to some other solution is called hypotonic solution.
 Semipermeable Membra ne
A membrane which allows the passage of solvent molecules but not that of solute. when a solution is
separated from the solvent by it is known as semipermeable membrane.
Some example of it are as follows
(a) Copper ferrocyanide Cu 2[Fe(CN) 6] ;
(b) Calcium phosphate membrane; and
(c) Phenol saturated with water.
E x . A solution containing 8.6 g urea in one litre was found to be isotonic with 0.5% (wt./vol.) solution of an
organic, non-volatile solution. The molecular weight of latter is
S o l . Solutions are isotonic
so 

n1 n
ST  2 ST {S & T are constant}
V1 V2
n n
so, 1  2
V1 V2
 w1   w2 
or    
 m 1  v 1  urea  m 2  v 2 organic
8.6 0.5
or 60  1000  m  100
2

m2 = 34.89
 Reverse Osmosis :
If external pressure greater than osmotic pressure is applied, the flow of solvent molecules can be made to
proceed from solution towards pure solvent, i.e., in reverse direction of the ordinary osmosis.
* Reverse osmosis is used for the desalination of sea water for getting fresh drinking water.
24. Ideal Solutions :
A solution which obeys Rault's law exactly at all concentrations and at all temperatures is called an ideal
solution.
An ideal solution possesses the following characteristics :
(i) Volume change of mixing shoule be zero.
 Vmix = 0 ; Vsolvent + Vsolute = Vsolution
(ii) Heat change on mixing should be zero.
 Hmix = 0 (Heat is neither absorbed nor evolved)
(iii) There should be no chemical reaction between solvent and solute.
(iv) Solute molecules should not dissociate in the ideal solution.
(v) Solute molecules should not associate in ideal solution.
(vi) Ideal solution must obey Raoult's law at all concentrations.
Ex : (i) Benzene and toluene
(ii) Carbon tetrachloride and silicon tetra chloride.
(iii) n - Hexane and n - heptane
(iv) Ethylene dibromide and ethylene dichloride.
25. Non Ideal solutions :
Those solutions which do not obey Rault's law are called non-ideal solutions.
For such solutions PA  PAo  X A
PB  PBo  X B
Non ideal solutions are formed when the components differ much in their structures and polarities.
Hmixing  zero
Vmixing  zero
Non ideal solutions show either positive or negative deviations from Rault's law.
Ex. Two liquids A and B form an ideal solution. At 300 K, the vapour pressure of a solution containing 1 mole of
A and 3 mole of B is 550 mm of Hg. At the same temperature, if one more mole of B is added to this solution,
the vapour pressure of the solution increases by 10 mm of Hg. Determine the vapour pressure of A and B in
their pure states.
0
S o l . Let the vapour pressure of pure A be = p 0A ; and the vapour pressure of pure B be = p B .
Total vapour pressure of solution (1 mole A + 3 mole B)

= X A .p 0A  X B .p 0B [XA is mole fraction of A and XB is mole fraction of B]

1 0 3 0
550  pA  pB or 2200  p 0A  3p 0B .......(i)
4 4
1 0 4 0
Total vapour pressure of solution (1 mole A + 4 mole B) = pA  pB
5 5
1 0 4 0
560  pA  pB
5 5

2800  p 0A  p 0B .......(ii)

Solving eqs. (i) and (ii)

p 0B = 600 mm of Hg = vapour pressure of pure B
p 0A = 400 mm of Hg = vapour pressure of pure A
26. Posit ive de v iat ion from Rault's law :
This deviation is shown when the forces of attraction between A  B molecules are less than forces of attraction
between A  A and B  B molecules in the two liquids forming the solution.

PA  PAo  X A
PB  PBo  X B
The total vapour pressure of the solution will be greater than the corresponding vapour pressure expected in
case of ideal, an ideal solution of same composition. i.e.

Ptotal  PAo  X A  PBo  X B

  Hmix > 0 . Endothermic dissolution ; heat is absorbed.

  Vmix > 0 . volume is increased after dissolution.

 'A' and 'B' escape easily showing higher vapour pressure than the expected value.
Ex. (i) Ethanol and cyclohexane

(ii) Acetone and benzene

(iii) Water and methanol.

(iv) acetone + ethanol

(v) acetone + CS 2
(vi) water + ethanol

(vii) CCl 4 + toluene

(viii) CCl4 + CHCl3

27. Negat ive de v iat ion from Rault's law :

In these solutions the AB interaction are stronger than the AA and BB molecular interactions present in the
two liquids forming the solution. For thus solutions showing ve deviation.
o
PA  PA  X A
o o
PB  PAo  X B and Ptotal  PA  X A  PB  X B
–  Hmix < 0 ; exothermic dissolution heat is evolved.

–  Vmix < 0 ; volume is decreased during dissolution.

Escaping tendency of both components 'A' and 'B' is lowered showing lower vapour pressure than expected
ideally.
Ex. (i) Acetone and chloroform
(ii) Nitric acid and chloroform.
(iii) Water and HCl.
(iv) CH 3OH + CH 3COOH
(v) H 2O + HNO 3
(vi) Chloroform + diethyl ether
(vii) water + HCl
(viii) acetic acid + pyridine
(ix) chloroform + benezene
28. Relation between Dalton's Law and Raoult's Law :
The composition of the vapour in equilibrium with the solution can be calculated applying Dalton's law of
partial pressures. Let the mole fraction of vapours A and B be YA and YB respectively. Let pA and pB be the
partial pressure of vapours A and B respectively and total pressure P.
pA = Y A P .......(i)
pB = Y BP .......(ii)
pA = XAP A0 .......(iii)
0
p B = X BP B
.......(iv)
Equating eqs. (i) and (iii),
Y AP = X A P A 0
X A PA0 p A
or YA  
P P
Similarly, equating eqs. (ii) and (iv),
X B PB0 p B
YB  
P P
Thus, in case of ideal solution the vapour phase is richer with more volatile component, i.e., the one having
relatively greater vapour pressure.
29. Abnormal col ligat ive proper t ie s :
It has been observed that difference in the observed and calculated molecular masses of solute is due to associa-
tion or dissociation of solute molecules in solution. It results in a change in the number of particles in solution.
30. Association of solute particles :
The formation of a bigger molecule by the union of two, three or more solute molecules is called association.
Let 'n' simple molecules combine to give an associated molecule as :
non polar
n(X) (X)n
solvent
n single one bigger
molecules molecule.
As a result, the total number of particles in solution becomes less than the number of molecules initially
dissolved in the solution and hence the colligative properties will have lower value.
As the molar mass of solute is inversely proportional to the colligative properties, so the molar mass of solute
will be greater than theoretical value.
31. Dissociation of solute molecules :
Molecules of electrolytes undergo ionization or dissociation in ionizing solvents to give two or more particles in
solution.
For example, AB ionizes in solution to give two particles.

ionizing + –
AB A +B
solvent

This dissociation results in an increase in the total number of particles, and therefore the value of colligative
properties of such solutions will be higher.
As the colligative properties are inversely related to molecular weight, so the molecular weight of ionizable
solute will be less than the theoretical value.
32. Va n't Hoff factor (i) :
In order to express the extent of association or dissociation with certain solutes are expected to undergo in
solution.
Van't Hoff in 1886, introduced a factor, called Van't Hoff factor (i). The factor i is defined as

observed colligative property

i
Normal colligative property

Normal or actual molecular weight

i
observed molecular mass.

In case of association of solute particles in solution, the observed molecular weight of solute being more than
the normal, the value of factor 'i' is less than unity (i.e. i < 1), while for dissociation the value of i is greater than
unity (i.e. i > 1), because the observed molecular weight has lesser value than normal molecular weight.
33. Va n't Hoff factor a nd degree of dissociat ion :
The fraction of the total number of molecules which dissociates in the solution into simple ions or molecules is
called the degree of dissociation.
number of particles after dissociation
i
Number of particles initially taken.
Calculation of 'i' :
Let, solute be AxBy
AxBy  x Ay+ + yBx–
Initial mol 1 0 0
after dissociation 1 – xy
Total no. of solute particles
= 1 –  + x + y
= 1 –  +  (x + y)
= 1 –  + n [where x + y = n (total ions.)]
(i). observed colligative properties  observed number of solute particles
observed colligative properties  (1 –  + n)
(ii). Normal colligative properties  1
eq (i) 1    n
i 
eq (ii) 1
i – 1 =  (n – 1)

i 1

n 1
for strong electrolytes :  = 1 or 100% so i = n (total no. of ions)
Ex. NaCl  Na+ + Cl– (i = 2)
Ex. K2SO4  2K+ + SO42– (i = 3)
Ex. for complex compound
K4[Fe(CN) 6]  4K + + [Fe(CN) 6] 4–
n = 5
If  = 50% then find Van't hoff factor 'i' = ?
Sol. i = 1 –  + n
or i = 1 – 0.5 + 5 × 0.5 = 3
34. Va n't Hoff factor a nd degree of associat ion :
The fraction of the total number of molecules of the substance which is present as associated molecules is
known as the degree of association.

Number of particles after association

i
Number of particles before association

Calculation of 'i' :
Let, solute be nA
nA  (A)n
Initial mol 1 0
after dissociation 1 – /n
Total no. of solute particles
= 1 –  + /n
(i). observed colligative properties  observed number of solute particles.
observed colligative properties  1 –  + /n
(ii). Normal colligative properties  1
eq (i)
 i = 1 – + /n
eq (ii)
1i

1 
1  
n
 = degree of assocation , n = no. of solute particles which are associated
Ex. A 5% solution of anhydrous CaCl2 at 0°C developed 15 atm. Osmotic pressure. What is the degree of dissocia-
tion of CaCl2.
S o l . 5 g. of CaCl2 are present in 100 ml, so 111 g (mol. wt. of CaCl2) will be present in
100  111
 2.22 lit.
5  1000
No w V = ST { n = 1}

0.082  273 22.47

or     10.09 atm
2.22 2.22

Van't Hoff factor

Actual no. of particles in solution

i
No. of particles taken

i 1
and  
n 1

here n = 3

15
1
10.09 4.91
 
3 1 10.09  2

    0.2433 or 24.33%
35. Distribution Law :
 Nernst distribut ion law
( a ) A solute on addition between two immiscible solvents distributes itself in such a way that the ratio of its
concentration in between two solvents remains constant at constant temperature provided the solute remains
in same molecular state in both solvent.
( b ) Let solute A be distributed in between two phases I and II, then according to the distribution law,

[A ] in phase I [C A ] I
K = 
[A ] in phase II [C A ]II
Moles of A in phase I Volume of phase II in litre
or K = ×
Volume of phase I in litre Moles of A in phase II
wt.of A in phase I Volume of phase II in litre
or K = ×
Volume of phase I in litre wt.of A in phase II
Where K is distribution coefficient or partition coefficient, a characteristic constant at the given temperature
for given solute-solvent - I - solvent - II system.
( c ) Also,

[C A ] I
K in favor of I =
[C A ]II
[C A ]II
K in favor of II =
[C A ] I
 Condition for validity of law
( a ) Temperature should remain constant .
( b ) Solution should be dilute.
( c ) System must be heterogeneous, i.e., two solvents should be immiscible.
( d ) Solute should not influence the immisicibility of two solvents.
( e ) Solute neither dissociate nor associate in either of the solvent.
( f ) Solute should be soluble in both solvents.
 Solute showing dissociation in either of the solvent
( a ) Let AB be a solute which dissolves in solvent I during its distribution between two immiscible solvents I and
II, then if C1 is concentration of solute in phase I and C2 its concentration of solute in phase II, according to
distribution law.
C 1 (1  )
K =
C2
Where  is the degree of dissociation of solute in solvent I.
 Solute showing association either of the solvent
( a ) Let AB be a solute which associates in solvent II as
nAB  
 (AB)n
during its distribution in between two solvents I and II.
( b ) Then, if C1 and C2 are concentrations of solute in phase I and II respectively then according to distribution law,
C1
K =
n C2
Where n is association number and 100% association is assumed.
 Extraction of solute in multistep operations
( a ) Let w g of a solute be present in V mL of solvent A. Now suppose V1 mL of another solvent B are used to
extract out solute from solvent A. Suppose n operations for extraction are made using V mL of solvent B, then
V1 = n × v.
 ( b ) Then the amount of solute (Wn) left unextracted in A after n operation using v mL of B in each step is given by
n
 KV 
Wn =  W
 v  KV 
It is clear from the equation of a solute from a given solution by extracting a liquid is more efficient when
small volumes of extracting liquid are used in large number of operations.
Ex. 100 mL water and 50 mL ether mixture is shaken with succinic acid. At equilibrium ether layer contains
0.127 g and water layer contains 0.127 g and water layer contains 1.843 g of succinic acid. Calculate distribution
coefficient in favour of water.
[Succinic acid] water
Sol. wKether =
[Succinic acid]ether

1.843 / 100 1.843 50

wKether = = × = 7.26
0.127 100 0.127
50
Ex. An organic substance has a normal molecular weight in water but gives a higher value in C6H6. The following
data were obtained during a distribution experiment
Conc.of subs.
0.01 0.02 0.24
in water (g L1 )
Conc.of subs.
1.848  10 5 2.661  10 3 1.089  10 2
in C 6 H 6 (g L1 )
Find the degree of complexity of the substance in C6H6
S o l . Let, n be the complexity of acid in C6H6 and C1, C2 are concentrations of acid in water C6H6.
C1
Then K
n C2
1
Taking log, log K = log C1 – log C2 .......(1)
n
using data in eq. ........... (1)
1
log K = log 0.01 – log 1.848 × 10–5 .......(2)
n
1
log K = log 0.12 – log 2.661 × 10–3 .......(3)
n
1
log K = log 0.24 – log 1.089 × 10–2 .......(4)
n
Solving equation (1) and (3) n = 1.999
Solving equation (3) and (4) n = 2.033
The value of n  2, which shows that organic substance form dimer in C6H6
36. Azeotropic mixture s :
Some liquids on mixing form azeotropes which are binary mixture having same composition in liquid and
vapour phase and boil at a constant temperature. Azeotropic mixture cannot be separated by fractional distillation.
Type s of Azeotropic mixture s
(i) Mi nimum boi li ng Azeotropic mixture s
The mixture of two liquids whose boiling point is less than either of the two pure components. They are formed by
non-ideal solutions showing positive deviation. For example (95.5%) + water (4.5%) + water boils at 351.15 K.
(ii) Ma ximum boi li ng Azeotropic mixture s
The mixture of two liquids whose boiling point are more than either of the two pure components. They are
formed by non-ideal solutions showing negative deviation. For example HNO 3 (68%) + water (32%) mixture
boils at 393.5 K.
 SOLVED EXA MPLE
E x . 1 A certain substance 'A' tetramerises in water to the extent of 80%. A solution of 2.5 g of A in 100 g of water
lowers the freezing point by 0.3°C. The molar mass of A is :
(A) 122 (B) 31 (C) 244 (D) 62
Sol. ( D )

1i
=
1
1
n
1i
0.8 = ; i  0.4
1
1
n

T = iKf × m
w B  1000
0.3 = 0.4 × 1.86 ×
mB  wA
2.5  1000
0.3 = 0.4 × 1.86 ×
m B  100
m B = 62
E x . 2 Which of the following solutions will exhibit highest boiling point ?
(A) 0.01 M Na2SO 4 (B) 0.01 M KNO3 (C) 0.015 M urea (D) 0.015 M glucose
Sol. (A)
T = i × Kb × m
i × m of Na2SO4 is highest, hence its boiling point will also be highest.
Na 2 SO 4 i × m = 3 × 0.01 = 0.03
KNO 3 i × m = 2 × 0.01 = 0.02
Urea i × m = 1 × 0.015 = 0.015
Glucose i × m = 1 × 0.015 = 0.015
E x . 3 What is the osmotic pressure of 12% solution of can sugar (mol. wt. 342) at 17°C.
S o l . 12 g. sugar is dissolved in 100 mL thus 342 g. sugar is dissolved in

8 litres

Now,  V = ST { n = 1}
ST 0.0821  290
   8.35 atm
V 2.85
E x . 4 Mixture of volatile components A and B has total vapour pressure (in torr) :
P = 254 – 119 xA
Where xA is mol fraction of A in mixture.
Hence PA° and PB° are (in torr)
(A) 254, 119 (B) 119, 254 (C) 135, 254 (D) 154, 119
Sol. (C )
when xA = 0, xB = 1
 P = PB°
 P B° = 254,
when xA = 1, xB = 0
 PA° = P = 254 – 119 = 135
E x . 5 When mango is placed in dilute aqueous solution of hydrochloric acid, it ?
(A) Shrinks (B) Swells (C) Brusts (D) Nothing happens
Sol. (A)
The H+ ion concentration in the medium is lower than that of H+ concentration present in the mango juice,
therefore osmotic pressure inside the mango is higher than that of aqueous hydrochloric acid. Therefore, H2O
will be passes out from the mango into aqueous hydrochloric acid. Therefore mango shrinks.
E x . 6 Heptane and octane form ideal solution. At 373 K, the vapour pressures of the two liquids are 105.2 kPa and
46.8 kPa respectively. What will be the vapour pressure, in bar, of a mixture of 25g of heptane and 35 g of
octane ?
S o l . (A) Heptane C 7H 16 m A = 100
(B) Octane C 8H 18 m B = 114

wA 25 35
nA    0.25 ; nB = = 0.3
m A 100 114
0.25 0.3
xA =  0.45 xB = = 0.55
0.25  0.30 0.25  0.30
= 0.45
p = p 0A x A  p B0 x B
= 105.2 × 0.45 + 46.8 × 0.55
= 47.34 + 25.74 = 73.08 kPa
E x . 7 The freezing point depression of 0.001 m K x[Fe(CN) 6] is 7.10 × 10–3 K. Determine the value of x. Given,
Kf = 1.86 K kg mol–1 for water.
Sol. x = i × Kf × m
7.10 × 10 –3 = i × 1.86 × 0.001
i = 3.817
i 1
 =
n 1
3.817  1
1 =
(x  1)  1
x = 2.817  3
 Molecular formula of the compound is K 3[Fe(CN)6].
E x . 8 The composition of vapour over a binary ideal solution is determined by the composition of the liquid. If xA and
yA are the mole fractions of A in the liquid and vapour, respectively find the value of xA for which (yA – xA) has
maximum. What is the value of the pressure at this composition ?
S o l . Since
x A PA
yA =
PB  (PA  PB )x A
Substracting xA from both the sides, we get
x A PA
y A – xA =  xA
P  (PA  PB )x A

B

Differentiating this with respect to xA, we get

d(y A  x A ) PA x A PA  PA  PB 

=  – 2
1
dx A PA  (PA  PB )x A P 
B
 (PA  PB )x A 
The value of xA at which yA – xA has a maximum value can be obtained by setting the above differential equal
to zero. Thus, we have

PA x A PA  PA  PB 

– 2
1 = 0
PA  (PA  PB )x A P

B
 (PA  PB )x A 
 PA PB  PB
Solving for xA, we get x A 
PA  PB
The value of P at this composition is
P = xA PA° + xB PB°
or P = PB° + (PA° – PB°) xA
 PA PB  PB 
or P = PB° + (PA° – PB°)   

 PA  PB 
or P = PA PB
E x . 9 A dilute solution contains m mol of solute A in 1 kg of a solvent with molal elevation constant Kb. The solute

dimerises in solution as 2A   A2. Show that equilibrium constant for the dimer formation is

K b (K b m  Tb )
K =
(2 Tb  K b m ) 2
where Tb is the elevation of the boiling point for the given solution. Assume molarity = molality
Sol. 2A 

 A2
m 0 initially
m
(m – m) after dimerization
2
m
m (1 – )
2
Where  is the degree of dimerization and m is molality which is also molarity (given). Hence due to dimerization,
final molality = m
m  
m(1 – ) + = m 1  
2  2
i = 1 + (n – 1)
1 
= 1 +  1
2 
 
 = 1  
 2
 
Tb = Kb × m × i = Kb × m  1  
 2
2(K b m  Tb )
  =
K bm
equilibrium constant K for the dimer formation is
m
[A 2 ] 
K = 2 = 2 2 =
[A ] m (1   ) 2 2m(1   ) 2

2
 K b m  Tb   2(K b m  Tb ) 
K = 2   2m 1  
 K bm   K bm 

K b (K b m  Tb )
K =
(K b m  2K b m  2 Tb ) 2

K b (K b m  Tb )
K = Proved
(2 Tb  K b m ) 2
E x . 1 0 Distribution coefficient of an organic acid between water and benzene is 4.1 in favour of C6H6. If 5 g of acid
is distributed in between 50 mL of benzene and 100 mL of water, calculate the concentration of acid in two
solvents.
S o l . Let the amount of organic acid in
C6H6 layer = a g
volume of C6H6 = 50 mL
a
 concentration of acid in C6H6 = g mL–1
50
since total amount of acid = 5 g
 Amount of acid in H2O layer = (5 – a) g
and volume of H2O = 100 mL
5 a  g
 Conc. of acid in H2O =  
 100  mL
Conc.of acid in C 6 H 6
Now, K =
Conc.of acid in H 2 O

a 100
= 
50 (5  a)

a 100
 4.1 = 
50 (5  a)
or a = 3.361 g.
 Amount of acid in 50 mL
C6H 6 = 3.361 g
3.361
 acid concentration in C6H6 =  1000 = 67.22 g/L
50
Also, amount of acid in 100 mL H2O = 5 – a = 5 – 3.361 = 1.639 g

1.639
 acid concentration in H2O =  1000 = 16.39 g/L
100