02 .

Solutions

2 . SOLUTIONS Marks : 5 or 7

 Defination :
1) Solution :-
A homogeneous mixture of two or more substances is called as solution.
Eg. Solution of salt in water.
2) Binary Solution :-
When a solution is composed of two chemical substances then it is called as
binary solution.
Eg. Alcohol and Water
3) Solute :-
The substance which is present in smaller amount is called as solute.
Eg. Salt.
4) Solvent :-
The substance which is present in larger amount is called as solvent.
Eg. water

5) Dilute solution :-
A solution containing low concentration of solute are called as Dilute solution.
6) Concentrated solution :-
A solution containing high concentration of solute is called as concentrated solution.
7) Volatile subatance :-
The substance which evoporate easily is called as volatile substance.
Eg. Petrol, Ethers, camphor etc
 Types of Solution :-
There are nine types of solution whose example are given below in table.

Solute Solvent Example

Solid Liquid Sea water, sugar in water
Solid Solid Metal alloys eg.brass,bronze
Solid Gas Iodine in air

Liquid Liquid Ethanol in water, gasoline

Liquid Solid Amalgams eg. Hg in Silver
Liquid Gas Chloroform in nitrogen

Gas Liquid Oxygen in water, areated drinks

Gas Solid H2 in palladium
Gas Gas Air ( O2 , N2 Ar )

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 02 . Solutions
SOLUBILITY OF SOLUTE IN SOLVENT
(a) Saturated solution : A solution which contains the maximum amount of dissolved solute and
further the solute cannot be dissolved is called saturated solution.
(b) Supersaturated solution: A solution containing a solute more than that required to form a saturated
solution at equilibrium is called supersaturated solution.

Solubility :- The amount of solute present per unit volume of saturated solution at a specific temperature
is called as solubility. The unit of solubility is mol L-1 or mol dm-3.

 Factors affecting solubility :-

(1) Nature of solute :
A solute may be crystalline, amorphous, ionic or covalent. Hence its tendency to
dissolve changes.

(2) Nature of solvent :-

Solvent are classified as polar and nonpolar. Polar solutes dissolve in polar
solvents. For example, NaCl dissolves in water. While non polar solute disolves in nonpolar
solvent.For example, cholestrol dissolves in benzene.

(3) Temperature :-
Depending on enthalpy of solution, solubility of substance changes with
temperature. For endothermic reaction, as temperature increases solubility of substance
increases.e.g. KCl dissolve in water. For exothermic reaction, as temperature increases
solubility of substance decreases.e.g. CaCl2 dissolve in water.

(4) Pressure :- Henry’s law :

The solubility of gas in liquid is directly proportional to pressure of the gas above
the solution.

If S is the solubility of a gas in mol L-1, P is the pressure of the gas above the solution
then by Henry’s law,

S  P or S = K x P
H

Where KH is called Henry’s law constant.

UNIT OF KH :-
K = S/P = mol L-1 / bar = mol L-1 bar-1
H

Demonstration of Henry’s law :-

In case of carbonated drink beverage, the bottle is filled by dissolving CO2 gas
at high pressure and then sealed. Above the liquid sufrace there is air and undissolved CO2.
Due to high pressure the amount of dissolved CO2 is large. When the cap of the areated bottle
is removed, the pressure on the solution is lowered, hence excess of CO2 escape out in the
form of effervescence. Thus by decreasing the pressure, solubility of CO2 is decreased.

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 02 . Solutions

 RAOULT’S LAW :
The partial vapour pressure of any volatile component of a
solution is the product of vapour pressure of that pure component and the mole fraction of the
component in the solution.
Consider a solution containing two volatile components A1 and A2 with mole fractions
x and x respt. Let P O and P O be the vapour pressure of pure component A and A respt.
1 2 1 2 1 2
Then according to Raoult’s Law ,partial vapour pressures P and P are given by :
1 2
o o
P1 = x1 P1 and P2= x2 P2
According to Daltons law of partial pressure, the total pressure P is
P=P+P
1 2
o o
= x1 P1 + x2 P2
o o
= (1- x2 ) P1 + x2 P2
o o o
= P1 - P1 x2 + x2 P2
o o o
P = P1 + ( P2 - P1 ) x2
o o
Because P1 and P2 are constants, a plot of P versus x2 is a straight line . The figure also shows
the plots of P1 versus x1 and P2 versus x2 .These are straight line passing through origin.

 IDEAL AND NON IDEAL SOLUTIONS

1. Ideal solutions
The solutions which obey Raoult’s law over entire range of concentrations
are called as ideal solution. The vapour pressure of ideal solutionalways lies between vapour
pressures of pure components.
Examples: Benzene + Toluene.

2. Nonideal solutions
The solutions which does not obey Raoult’s law over entire range of
concentrations are called as ideal solution. The vapour pressure of non ideal solution
can be higher or lower than those of pure components.

3. Deviation from the Raoult’s law :

Non Ideal solution shows two types of deviation from Raoults law

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 02 . Solutions

 Positive deviation from Raoult’s law :

Solutions whose vapour pressure are higher than those of pure components exhibits positive
deviation . Exanple ethanol and acetone.
B. Negative deviation from Raoult’s law :
Solutions whose vapour pressure are lower than those of pure components exhibits negative
deviation . Exanple chloroform and acetone.

 COLLIGATIVE PROPERTIES 

 Definition :
“The properties of solution which depends upon the number of solute particles present and not
open the nature of the solute are called colligative properties.”
There are four colligative properties :-
A] Vapour pressure lowering .
B] Boiling point elevation .
C] Freezing point depression .
D] Osmotic pressure.
The colligative properties are essentially the properties of dilute solution which behave as
ideal solution. To study colligative properties, the solute should be taken as non-volatile.

A] VAPOUR PRESSURE LOWERING :

The pressure exerted by the vapour of liquid at the state of equilibrium on the surface of
liquid is called vapour pressure. When a nonvolatile solute is dissolved in volatile solvent, the vapour
pressure of solvent decreases. This is called Vapour pressure lowering .
O
If P1 is the vapour pressure of the pure solvent and P1 is the vapour pressure of solution of
nonvolatile solute. Then the vapour pressure of the solution is less then the vapour pressure of
pure solvent .i.e P1  P1
O

Therefore , the vapour pressure lowering is , P = P O - P

1 1

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 02 . Solutions
. RAOULT’S LAW FOR SOLUTIONS OF NONVOLATILE SOLUTE :
The vapour pressure of solvent over the solution is equal to the product
of vapour pressure of that pure solvent and the mole fraction of the component in the solution.
Thus
P1= P 10 x 1
For a binary solution containing one solute, x1 = 1 - x2
0
P1 = P1 x1
0
= P1 (1 - x2)
0 0
= P1 - P1 x2
0 0
P1 - P1 = P1 x2
P = P 0 x .................. (1)
1 2
Thus P depends on x 2that is on number of solute particles. Therefore P , the lowering
of vapour pressure is a colligative property.

Relative lowering of vapour pressure :-

The ratio of vapour pressure lowering of solvent divided by the vapour pressure of
pure solvent is called relative lowering of vapour pressure. Thus,
P P10 - P 1
Relative lowering of vapour pressure = 0 =
P1 P 10
From equation (1) we get, P = P 0 x .i.e P = x
1 2 2
P 10
P10 - P1
therefore, x =
2
P 10

Molar mass of solute from vapour pressure lowering :-

P
We know that, relative lowering of vapour pressure is given by P 0 = x 2
1
But n
x2 = 2
n1 + n2
n2
x2 = since n1 >> n2  n1 + n2 = n1
n1
P = n2
P 10 n1
If W2 g of solute with molar mass M2 is dissolved in W1 g of solvent
of molar mass M1, then
W1
Number of moles of solvent, n is given by1 n  and
1 M1
W2
Number of moles of solute, n is given by, n2 
2 M2
 P n2 W2/M2
=
0 = n
P 1
W /M
1 1 1
0
P P1 - P1 W /M
0= = W2 /M2
P P0
1 1 1 1

From the above relation, molar mass of solute, M2 can be determined if all other values
are known.

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 02 . Solutions

B] BOILING POINT ELEVATION :

The temperature at which vapour pressure of liquid is equal to atmospheric pressure
of liquid is called Boiling point of liquid. When sugar is added to boiling water, water stops boiling for some
time.It is because boiling point of solution is higher than that of water. Thus when a non volatile solute is
dissolved in the solvent, boiling point of solvent increases. This increase in boiling point is called
Elevation of Boiling point or boiling point Elevation.

 Defination :-
“The increase in the boiling point of pure solvent when a non volatile solute is dissolved in it
is called boiling point elevation. It is denoted by  T b.
The difference between the boiling point of solution and boiling point of solvent at constant
pressure is called boiling point elevation.
If ‘ To ’ be the boiling point of solvent and ‘ T ’ be the boiling point of solution then.
b b

T = T - T o
b b b

 Determination of Molar mass of solute from boiling point elevation :-

For dilute solution, boiling point elevation is directly proportional to molality of solution ,
 T  m
b

 T = K x m............... (1)
b b

Where Kb is boiling point elevation constant or molal elevation constant or Ebbulioscopic constant .
When m = 1 molal, T = K
b b

Elevation of boiling point produced by one molal solution is called as Ebbulioscopic constant
-1
The unit of Kb is, K Kg mol .
From equation (1) ,  T = Kx m
b b

If W2 g of solute with molar mass M2 is dissolved in W1 g of solvent , then

moles of solute
m=
mass of solvent in kg
W2 / M 2
=
W / 1000kg
1

W2 x 1000
=
M xW
2 1
Substituting this value of ‘m’ in above equation we get
W2 x 1000
 Tb = Kb 
MxW
2 1

Hence,
K x W x 1000
b 2
M2 =  T xW
b 1

Knowing all other quantities, molar mass of solute M2 can be calculated.

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 02 . Solutions
B] FREEZING POINT DEPRESSION :
The temperature at which vapour pressure of liquid is equal to vapour pressure of its
solid is called Freezing point of liquid. When sugar is added to water, its freezing point decreases. Thus
when a non volatile solute is dissolved in the solvent, freezing point of solvent decreases. This
decrease in freezing point is called freezing point depression.

 Defination :-
“The decrease in the freezing point of pure solvent when a non volatile solute is dissolved in it
is called freezing point depression.It is denoted by  T f .
The difference between the freezing point of solvent and freezing point of solution at
constant pressure is called freezing point depression.
If ‘ To ’ be the freezing point of solvent and ‘ T ’ be the freezing point of solution then.
f f

T =T o
-T
f f f

 Determination of Molar mass of solute from freezing point depression :-

For dilute solution, freezing point depression is directly proportional to molality of solution ,
 T  m
f

 T = K x m .............. (1)
f f

Where Kb is freezing point depression constant or cryoscopic constant .

When m = 1 molal, T = K
f f

Depression in freezing point produced by one molal solution is called as cryoscopic constant.
-1
The unit of Kf is, K Kg mol .
From equation (1) ,  T = K xm
f f

If W2 g of solute with molar mass M2 is dissolved in W1 g of solvent , then

moles of solute
m =
mass of solvent in kg
W2 / M 2
=
W / 1000kg
1

W2 x 1000
=
MxW
2 1

Substituting this value of ‘m’ in above equation we get

W2 x 1000
 Tf = Kf 
MxW
2 1

Hence, Kf x W2 x 1000
M2 =
 Tf x W 1

Knowing all other quantities, molar mass of solute M2 can be calculated.

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 02 . Solutions

 D] OSMOSIS AND OSMOTIC PRESSURE :

1) Semipermeable membrane :-
A membrane which is permeable to solvent and not to solute is known as semipermeable
membrane.
Eg. Animal bladders, white of an egg , copper ferrocyanide, calcium phosphate etc.
2) Osmosis :-
A spontaneous flow of solvent molecule from lower concentration to higher
concentration through semipermeable membrane is called osmosis.
Eg. Plant absorb water through roots due to osmosis.
The process of osmosis can be demonstrated by following type of expt.
The mouth of thistle funnel is closed
with semipermeable membrane. This funnel is
then filled with sugar solution. The level of the
solution is marked. The thistle funnel is then
placed in water vessel.As the time passes,
it is observed that level of sugar solution
increases. This indicate that water from the
container is diffusing in the solution. This
process is called osmosis.

3) Osmotic pressure :-
The pressure applied to the solution to stop the flow of solvent into solution through
semipermeable membranes is called osmotic pressure.
It is represented by  .

4) Isotonic solution :-
The solutions which have same osmotic pressure at same temperature are called isotonic
solution.
In isotonic solution solvent does not diffuse across the semipermeable membrane.
Eg. 1) 0.05M urea solution and 0.05M sucrose solution are isotonic .
2) 0.91 % solution of NaCl is isotonic with Human blood(RBC).

5) Hypotonic solution :-
A more dilute solution having lower osmotic pressure is called hypotonic solution.
If two such solution are seperated by SPM then solvent flows from solution of lower
osmotic pressure to higher osmotic pressure.
Eg. 1) 0.05M sucrose solution is hypotonic with 0.1 M urea solution.
2) When red-blood cells are placed in distilled water(hypotonic solution) then water
diffuses in the cells and they swell or burst. Because water has lower osmotic pressure than the
liquid in the cells.

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 02 . Solutions

6) Hypertonic solution :-
A more concentrated solution having higher osmotic pressure is called hypertonic
solution.
Eg. 1) 0.1M urea solution is hypertonic with 0.05M sucrose solution.
2) When red - blood cell are placed in 5 % solution of NaCl(hypertonic solution) then
water from the cells diffuses in the solution of NaCl & cell shrinks. Because 5 % solution of
NaCl has higher osmotic pressure than the liquid in the cells.

7) Reverse Osmosis :-
The phenomenon of flow of pure solvent under high pressure from concentrated solution
into pure solvent through a semipermeable membrane is called reverse osmosis.
Fresh water and salty water are seperated
by a semipermeable membrane. When the
pressure larger than the osmotic pressure
of solution is applied to solution, pure water
from salty water passes into fresh pure
water through the membrane.

# Osmotic pressure and concentration of solution :-

For very dilute solution, osmotic pressure follows the equation,
V = n RT
2
 = n RT/V ...........Eq(1)
2

The term n2/V is concentration in molarity (M), thus above equation can be written as
 = MRT..............Eq(2)
Where,  = Osmotic pressure in atm
V = Volume of solution in dm3
M = Concentration in molarity
n = Number of moles of solute
R = Gas constant = 8.314 J or 0.082L atm
T = Absolute temperature
# Molar mass of solute from Osmotic pressure :-
Consider Eq(1)  = n RT/V
2

If the mass of solute in V litres of solution is W2 and its molar mass is M2 then
n2 = W2 / M2
With this value of n2 , Eq(1) becomes
W2RT
 =
M2 V

W2RT
M2 =
 V

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 02 . Solutions
 VAN’T HOFF FACTOR (i) 
It is defined as the ratio of colligative property of a solution of electrolyte
divided by the colligative property of nonelectrolyte solution of same concentration.
colligative property of electrolyte solution
i=
colligative property of non-electrolyte solution of same concentration
P) T ) T )  )
= P ) = T b) = Tf ) =
 )
0 b 0 f 0 0

But colligative property  1 / Molar mass(M)

iM /M
(theoretical) (observed)

Thus , i is equal to 1 for nonelectrolyte, 2 for KNO3 and NaCl, 3 for Na2SO4 and
CaCl2 and so forth.

Modification of expression of colligative properties :

W2 x 1000
1. P = i P1 0 x2 = i W2/M2 2.  Tb = i K b x m = i K b
W /M M 2 x W1
1 1

3.  T = i K x m = W2 x 1000 4.   i MRT = i W2RT

i Kf 
f f
M2 x W 1 M2 V

 VANT HOFF FACTOR (i) AND DEGREE OF DISSOCIATION 

Consider one mole of electrolyte AxBy dissolved in a solvent. It dissociates into

‘x’ ions of A and ‘y’ ions of Bx-.
y+


AxBy  xAy+ + yBx-
Let ‘ ’ be the degree of dissociation of the solute.

At equilibrium out of 1 moles,  moles dissociate to give x. moles of Ay+

and y. moles of Bx-.
AxBy  xAy+ + yBx-
(1-  )mol x mol y mol

Total number of moles = (1-  x  y

  x+y-1)
= 1+n-1)
where, n = x + y
Van’t Hoff factor is given by,

Actual number of moles

i= –––––––––––––––––––––
Theoretical number of moles

i = 1+n-1) / 1

hence i = 1+n-1)

  i -1
n-1
**** THE END ****
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