GRADE 12

SOLUTIONS

Solutions are homogeneous mixtures of two or more than two components and its composition and
properties are uniform throughout the mixture. The component that is present in the largest quantity
is known as solvent.

Type of Solution Solute Solvent Common Examples

Gaseous Solutions Gas Gas Mixture of oxygen and nitrogen gases

Liquid Gas Chloroform mixed with nitrogen gas

Solid Gas Camphor in nitrogen gas

Liquid Solutions Gas Liquid Oxygen dissolved in water

Liquid Liquid Ethanol dissolved in water

Solid Liquid Glucose dissolved in water

Solid Solutions Gas Solid Solution of hydrogen in palladium

Liquid Solid Amalgam of mercury with sodium

Solid Solid Copper dissolved in gold

Concentration of Solutions:
(i) Mass percentage (w/w):
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Mass % of a component = 𝑋 100
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
(ii) Volume percentage (v/v):
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
Volume % of a component =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑋 100

(iii) Parts per million: It is used when solute is present in trace quantities.
𝑁𝑢𝑚𝑏𝑒𝑟𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
Parts per million =
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑋 106

(iv) Mole fraction (χ):

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
Mole fraction of a component =
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠
𝑛𝐴
χA =
𝑛𝐴+𝑛𝐵
χA = χA + χB
(v) Molarity (M): It is defined as number of moles of solute dissolved in one litre of solution.
 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑛2
Molarity = =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒 𝑉(𝑙)

𝑛2 X 1000
=
𝑉(𝑚𝑙)
(vi) Molality (m): It is defined as the number of moles of the solute per kilogram (kg) of the
solvent.
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑛2
Molality = =
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑘𝑖𝑙𝑜𝑔𝑟𝑎𝑚 𝑊1 (𝐾𝑔)
𝑛2 X 1000
=
𝑊1

Solubility
Solubility of a substance is its maximum amount that can be dissolved in a specified amount
of solvent. It depends upon the nature of solute and solvent as well as temperature and pressure.
It is observed that polar solutes dissolve in polar solvents and non-polar solutes in nonpolar
solvents. In general, a solute dissolve in a solvent if the intermolecular interactions are similar
in the two (like dissolves like).
When a solid solute is added to the solvent, some solute dissolves and its concentration
increases in solution. This process is known as dissolution. Some solute particles in solution
collide with the solid solute particles and get separated out of solution. This process is known
as crystallisation. A solution in which no more solute can be dissolved at the same temperature and
pressure is called a saturated solution.
Solubility of one substance into another depends on the nature of the substances, temperature
and pressure.
Solubility of a Solid in a Liquid:
i) Effect of temperature - In a nearly saturated solution, the dissolution process is endothermic
(Δsol H > 0), the solubility should increase with rise in temperature and if it is exothermic
(Δsol H ˂ 0) the solubility should decrease.
ii) Effect of pressure - Pressure does not have any significant effect on solubility of solids in
liquids. It is so because solids and liquids are highly incompressible.
Solubility of a Gas in a Liquid:
Solubility of gases in liquids is greatly affected by pressure and temperature.
i) Effect of temperature - The solubility of gases increases with decrease of temperature. It is
due to this reason that aquatic species are more comfortable in cold waters rather than
in warm waters.
ii) Effect of pressure – If we increase the pressure over the solution phase by compressing the
gas to a smaller volume there will be an increase in the number of gaseous particles per unit
volume over the solution and the rate at which the gaseous particles are striking the surface of
solution to enter it increases. Thus, its solubility increases.
Henry’s law
i) At a constant temperature, the solubility of a gas in a liquid is directly proportional to the
pressure of the gas.
ii) The mole fraction of gas in the solution is proportional to the partial pressure of the gas over
the solution.
iii) The partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of
the gas (x) in the solution. (the most commonly used law)
p = KH χ
KH is the Henry’s law constant
Higher the value of KH at a given pressure, the lower is the solubility of the gas in the
liquid.
Applications of Henry’s Law:
1. To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under
high pressure.
2. [Scuba divers must cope with high concentrations of dissolved gases while breathing air at
high pressure underwater. Increased pressure increases the solubility of atmospheric gases in
blood. When the divers come towards surface, the pressure gradually decreases. This releases
the dissolved gases and leads to the formation of bubbles of nitrogen in the blood. This blocks
capillaries and creates a medical condition known as bends, which are painful and dangerous
to life.] To avoid bends, as well as, the toxic effects of high concentrations of nitrogen in the
blood, the tanks used by scuba divers are filled with air diluted with helium because it is less
soluble in blood than nitrogen.
3. At high altitudes the partial pressure of oxygen is less than that at the ground level. This
leads to low concentrations of oxygen in the blood and tissues of people living at high altitudes
or climbers. Low blood oxygen causes climbers to become weak and unable to think clearly,
symptoms of a condition known as anoxia.
Vapour Pressure of Liquid-Liquid Solutions:
A binary solution of two volatile liquids, when taken in a closed vessel, both the components
would evaporate and eventually an equilibrium would be established between vapour phase
and the liquid phase.
Raoult’s law – It states that for a solution of volatile liquids, the partial vapour pressure of
each component in the solution is directly proportional to its mole fraction.
For component 1 p1 = p10 χ1
For component 2 p2 = p20 χ2
According to Dalton’s law of partial pressures, the total pressure (P total) over the solution phase
in the container will be the sum of the partial pressures of the components of the solution.
ptotal = p1 + p2
ptotal = p100 χ1 + p20 χ2 0
= p (1-χ ) + p χ
1 2 2 2
= p 0 + (p 0 – p 0) χ
1 2 1 2
i) Total vapour pressure over the solution can be related to the mole fraction of any one
component.
ii) Total vapour pressure over the solution varies linearly with the mole fraction of
component 2.

The composition of vapour phase in equilibrium with the solution is determined by the partial
pressures of the components. If y1 and y2 are the mole fractions of the components 1 and 2
respectively in the vapour phase then, using Dalton’s law of partial pressures:
p1 = y1 ptotal
p2 = y2 ptotal
In general
pi = yi ptotal

Raoult’s Law as a special case of Henry’s Law:

According to Raoult’s law, the vapour pressure of a volatile component in a given solution is
given by pi = pi0xi.
According to Henry’s law, in the solution of a gas in a liquid, if one of the components is so
volatile that it exists as a gas and its solubility is given by p = KH χ
If we compare the equations for Raoult’s law and Henry’s law, the partial pressure of the
volatile component or gas is directly proportional to its mole fraction in solution. Only the
proportionality constant KH differs from p10. Thus, Raoult’s law becomes a special case of
Henry’s law in which KH becomes equal to p10.
Vapour Pressure of Solutions of Solids in Liquids:
Liquids at a given temperature vapourise and under equilibrium conditions the pressure exerted by
the vapours of the liquid over the liquid phase is called vapour pressure.
In a pure liquid the entire surface is occupied by the molecules of the liquid. If a non-volatile
solute is added to a solvent to give a solution, the vapour pressure of the solution is solely from
the solvent alone because the solute is non-volatile. This vapour pressure of the solution at a
given temperature is found to be lower than the vapour pressure of the pure solvent at the same
temperature.
[In the solution, the surface has both solute and solvent molecules; thereby the fraction of the
surface covered by the solvent molecules gets reduced. Consequently, the number of solvent
molecules escaping from the surface is correspondingly reduced, thus, the vapour pressure is
also reduced.]
Ideal Solutions:
The solutions which obey Raoult’s law over the entire range of concentration are known
as ideal solutions.
Two important properties of ideal solutions are:
i) The enthalpy of mixing of the pure components to form the solution is zero
ΔmixH = 0, [no heat is absorbed or evolved when the components are
mixed.]
ii) the volume of mixing of the pure components to form the solution is zero
ΔmixV = 0, [the volume of solution would be equal to the sum of volumes
of the two components.]

Ideal behaviour of the solutions can be explained by considering two components A and B.
In pure components, the intermolecular attractive interactions will be of types A-A and B-B,
whereas in the binary solutions in addition to these two interactions, A-B type of interactions
will also be present. If the intermolecular attractive forces between the A-A and B-B are nearly
equal to those between A-B, this leads to the formation of ideal solution.
EG: Solution of n-hexane and n-heptane
bromoethane and chloroethane
benzene and toluene
Non-ideal Solutions:
When a solution does not obey Raoult’s law over the entire range of concentration, then
it is called non-ideal solution.
Positive Deviation:
If the vapour pressure of a solution is higher than that predicted by Raoult’s law, then it said
to show positive deviation.
In such solutions A-B interactions are weaker than those between A-A or B-B, i.e., the
intermolecular attractive forces between the solute-solvent molecules are weaker than those
between the solute-solute and solvent-solvent molecules. This means that in such solutions,
molecules of A (or B) will find it easier to escape than in pure state, increasing the vapour
pressure.
Eg: i) Mixture of ethanol and acetone [In pure ethanol, molecules are hydrogen bonded. On
adding acetone, its molecules get in between the ethanol molecules and break some of the
hydrogen bonds between them, thus weakening the interactions.]
ii) Mixture of carbon disulphide and acetone.
Negative Deviation:
If the vapour pressure of a solution is lower than that predicted by Raoult’s law, then it said to
show negative deviation.
In such solutions A-B interactions are stronger than those between A-A or B-B, i.e., the
intermolecular attractive forces between the solute-solvent molecules are stronger than
those between the solute-solute and solvent-solvent molecules. This means that in such
solutions, molecules of A (or B) will find it difficult to escape than in pure state, decreasing
the vapour pressure.

Eg: i) Mixture of phenol and aniline

ii) Mixture of chloroform and acetone
Azeotropes:
Binary mixtures having the same composition in liquid and vapour phase and boil at a constant
temperature are called azeotropes. In such cases, it is not possible to separate the components
by fractional distillation.
Types of azeotropes:
i) Minimum boiling azeotrope
The solutions which show a large positive deviation from Raoult’s law form minimum boiling
azeotrope at a specific composition.
Eg: 95% ethanol by volume in 5% water
ii) maximum boiling azeotrope
The solutions which show a large negative deviation from Raoult’s law form maximum boiling
azeotrope at a specific composition.
Eg: 68% nitric acid and 32% water by mass
Colligative Properties:
The properties that depend on the number of solute particles irrespective of their nature
relative to the total number of particles present in the solution are called colligative
properties.
Relative Lowering of Vapour Pressure:
The vapour pressure of a solvent in solution in presence of non-volatile solute is less than that
of the pure solvent.
According to Raoult’s law,
p1 = p 10 (1 – χ 1)
Δp1 = p10 – p1= p 10 - p 10 χ 1
= p10 (1 – χ1)
= p10 χ2 [since, 1 – χ1= χ 2]
The relative lowering of the vapour pressure,
Δp1 = p10 – p1 = χ2
p10 p10
The relative lowering of vapour pressure and is equal to the mole fraction of the solute.
p01 −p1 n2
0 = n1+𝑛2
p1
p01 −p1 n2
0 = [Since, for dilute solutions n2 < < n1]
p1 n1

w2 X M1
=
w1 X M2
Where, w1 → the mass of solvent
w2 → the mass of solute
M1 → the molar mass of solvent
M2 → the molar mass of solute
p01 −p1 w2 X M 1
0 =i
p1 w1 X M2
Where, ‘i’ is van’t Hoff factor
Elevation of Boiling Point:
A liquid boil at the temperature at which its vapour pressure is equal to the atmospheric
pressure. We know that vapour pressure of the solvent decreases in the presence of non-volatile
solute. In order to make this solution boil, its vapour pressure must be increased by raising the
temperature above the boiling temperature of the pure solvent. Thus, the boiling point of a
solution is always higher than that of the boiling point of the pure solvent.
The increase in the boiling point, ΔTb = Tb – Tb0
Where, ΔTb → elevation of boiling point
Tb0 → the boiling point of pure solvent
Tb → the boiling point of solution
For dilute solutions the elevation of boiling point (ΔTb) is directly proportional to the molal
concentration of the solute in a solution.
ΔTb 𝖺 m
ΔTb = Kb m
Where, m → molality of the solution
Kb → {Boiling Point Elevation Constant
Molal Elevation Constant
Ebullioscopic Constant}
w2 X 1000
ΔTb = Kb
M2 X W1
w2 X 1000
ΔTb = i Kb
M 2 X W1
Depression of Freezing Point:
At the freezing point of a substance, the solid phase is in dynamic equilibrium with the liquid
phase. Thus, the freezing point of a substance may be defined as the temperature at which the
vapour pressure of the substance in its liquid phase is equal to its vapour pressure in the solid
phase.
According to Raoult’s law, when a non-volatile solid is added to the solvent its vapour pressure
decreases and now it would become equal to that of solid solvent at lower temperature. Thus,
the freezing point of the solvent decreases.
The decrease in the freezing point, ΔTf = Tf0 – Tf
Where, ΔTf → depression of freezing point
Tf0 → the freezing point of pure solvent
Tf → the freezing point of solution
For dilute solutions the depression of freezing point (ΔTf) is directly proportional to the molal
concentration of the solute in a solution.
ΔTf 𝖺 m
ΔTf = Kf m
Where, m → molality of the solution
Kf → {Freezing Point Depression Constant
Molal Depression Constant
Cryoscopic Constant}
w2 X 1000
ΔTf = Kf
M 2 X W1
w2 X 1000
ΔTf = i Kf
M2 X W1
Osmotic Pressure:
The process of flow of the solvent molecules from pure solvent to the solution through the
semipermeable membranes is called osmosis.
The flow of the solvent from its side to solution side across a semipermeable membrane can
be stopped if some extra pressure is applied on the solution.
The excess pressure that must be applied to a solution side to stop the passage of solvent
molecules through a semipermeable membrane into the solution is called osmotic pressure of
the solution.
Osmotic pressure is proportional to the molarity, C of the solution at a given temperature T.
Π = CRT, where, Π → the osmotic pressure
R → the gas constant.
Π = n2RT
V
 = i w2RT
M2V
The osmotic pressure method has the advantage over other methods:

1. Pressure measurement is around the room temperature

2. The molarity of the solution is used instead of molality
3. As compared to other colligative properties, its magnitude is large even for very dilute
solutions
4. It is particularly useful for biomolecules as they are generally unstable at higher
temperatures and polymers have poor solubility.
Two solutions having same osmotic pressure at a given temperature are called isotonic
solutions. When such solutions are separated by semipermeable membrane no osmosis occurs
between them.

If the salt concentration is less the solution is said to be hypotonic.

If the salt concentration is less the solution is said to be hypertonic.

• A raw mango placed in concentrated salt solution loses water via osmosis and shrivel.
• Wilted flowers revive when placed in fresh water.
• People taking a lot of salty food experience water retention in tissue cells and
intercellular spaces because of osmosis. The resulting puffiness or swelling is called
edema.
• The preservation of meat by salting and of fruits by adding sugar protects against
bacterial action. Through the process of osmosis, a bacterium on salted meat or candid
fruit loses water, shrivels and dies.
Reverse Osmosis:
The direction of osmosis can be reversed if a pressure larger than the osmotic pressure is
applied to the solution side. That is, now the pure solvent flows out of the solution through the
semi permeable membrane. This phenomenon is called reverse osmosis.
Practical utility - Reverse osmosis is used in desalination of sea water. When pressure more
than osmotic pressure is applied on solution side, pure water is squeezed out of the sea water
through the membrane.
van’t Hoff factor (i)
𝑁𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
i =
𝐴𝑏𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦
=
𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛/𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛/𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
i ˂ 1, Association of molecules
i > 1, Dissociation of molecules
i = 1, No association or dissociation of molecules
Degree of Dissociation (α)

𝑖−1
𝛼=
𝑛−1

Where, i = Calculated Van’t Hoff’s Factor

n = Assumed Van’t Hoff’s Factor