2.

Solutions


Solutions:
Solutions are homogeneous mixtures of two or more than two components.
Binary solution consists of two components

Types of solutions:
Gaseous solution solvent is gas, e.g., mixture of oxygen and nitrogen gases
Liquid solution solvent is liquid, e.g., oxygen dissolved in water
Solid solution solvent is solid, e.g., solution of hydrogen in palladium

Expressing concentration of solutions:
Mass percentage (w/w) of a component
Mass of the component in the solution
100
Total mass of the solution

Volume percentage ( v/v) of a component
Volume of the component
100
Total volume of the solution

Mass by volume percentage (w/v)
Mass of the solute
100
Total volume of the solution in mL

Parts per million
6
Number of parts of the component
Total number of parts of all the components of the solution

Mole fraction of a component
Number of moles of the component
Total number of moles of all the components

i
i
i
n
x
n

Molarity (M)
Moles of the solute
Volume of the solution in litre

Molality (m)
Moles of the solute
Mass of the solvent in kg


Solubility:
Solubility of a substance is the maximum amount of the substance that can be dissolved in a
specified amount of a solvent at a specified temperature.

Solubility of a solid in a liquid:
Effect of temperature (Le Chateliers principle)
When the dissolution process is endothermic, the solubility will increase
with increase in temperature.


When the dissolution process is exothermic, the solubility will decrease
with increase in temperature.
Effect of pressure: Pressure does not affect solubility.

Solubility of a gas in a liquid:
Henrys law The solubility of a gas in a liquid is directly proportional to the pressure of
the gas.
Or

The partial pressure of a gas in vapour phase (p) is proportional to the mole fraction of the
gas (x) in the solution.
H
p K x
Where, K
H
Henrys law constant
Some applications of Henrys law
The solubility of CO
2
in soft drinks and soda water is increased by sealing
the bottles under high pressure.
At high pressure underwater, scuba divers have to cope with high
concentrations of dissolved gases while breathing air.
At high altitudes, climbers become weak and are unable to think clearly,
which are symptoms of a condition called anoxia
Effect of temperature
With increase in temperature, the solubility of gases in liquids decreases.

Vapour pressure of liquid solutions:
Vapour pressure of liquidliquid solutions:
Raoults law For a solution of volatile liquids, the partial vapour pressure of each
component in the solution is directly proportional to its mole fraction.
o
1 1
o o o
total 1 2 1 2
p p x
p p p p x


(For an ideal solution at constant temperature)



Vapour pressure of solutions of solids in liquids:
1 1 1
p x p

Ideal and non-ideal solutions:
Ideal solutions
Solutions which obey Raoults law over the entire range of concentrations
mix
mix
H 0
V 0

In an ideal solution, the solutesolute and solventsolvent interactions are nearly
equal to the solutesolvent interactions.
Non-ideal solutions
Solutions which do not obey Raoults law over the entire range of concentrations
Positive deviation from Raoults law
Vapour pressure of the solution is higher than that predicted by Raoults
law.
Solutesolvent interactions are weaker than solutesolute and solvent
solvent interactions.
Negative deviation from Raoults law
Vapour pressure of the solution is lower than that predicted by Raoults law.
Solutesolute and solventsolvent interactions are weaker than solute
solvent interactions.


(For a two-component solution showing positive deviation from Raoults
law)




(For a two-component solution showing negative deviation from Raoults
law)

Colligative properties and determination of molar mass:
Relative lowering of vapour pressure:
o
1 1 1 2
2 o o
1 1 1 2
p p p n
x
p p n n

For dilute solutions,
2 1
n n
o
1 1 2
o
1 1
o
1 1 2 1
o
1 2 1
Or,
p p n
p n
p p w M
p M w

o
1 1
o
1
p p
p
Relative lowering of vapour pressure
Elevation of boiling point:
o
b b b
T T T = Elevation of boiling point

Where, K
b
= Boiling-point elevation constant
Or, Molal elevation constant
Or, Ebullioscopic constant
2
2 1
2
2
1
1000
1000
Or,
b b
b
b
b
b
T K m
K w
T
M w
w K
M
T w

Depression of freezing point:
o

f f f
T T T = Depression of freezing point
f f
T K m
Where,
f
K = Freezing point depression constant


Or, Molal depression constant
Or, Cryoscopic constant

2
2 1
2
2
1
1000
1000
Or,
f
f
f
f
K w
T
M w
K w
M
T w


Values of K
f
and K
b
:
2
1
fus
2
1
vap
1000
1000
f
f
b
b
R M T
K
H
R M T
K
H

Osmosis and osmotic pressure:
2
2 2
2 2
2

Or,
Or,

CRT
n
RT
V
w RT w
M n
V M

If two solutions have the same osmotic pressure at a given temperature, then the
solutions are called isotonic solutions.
Abnormal molar masses: Molar mass lower or higher than expected or normal value
Vant Hoff factor, i: Expresses the quantitative extent to which a solute is dissociated or
associated
Normal molar mass
Abnormal molar mass
Observed colligative property
Calculated colligative property
Number moles of particles after association/dissociation
Number of moles of particles before associat
i
ion/dissoication

Modification of the equations for colligative properties:
o
1 1 2
o
1 1
2

b b
f f
p p n
i
n p
T iK m
T iK m
n
i RT
V