SOLUTIONS

Solutions are homogenous mixtures of two or more components.

Solvent: component which is in larger quantity
Solute: component which is in lesser quantity than solvent

Concentration of solution
1. Mass percentage (w/w) :

2. Mass by Volume percentage (v/v):

3. Mass by volume percentage (w/v):

4. Parts per million:

5. Mole fraction: if no. of moles of A is nA and no. of moles of B is nB, then

Mole fraction of A and B will be,
𝒏𝑨 𝒏𝑩
𝑿𝑨 = 𝑿𝑩 =
𝒏𝑨 + 𝒏𝑩 𝒏𝑨 + 𝒏𝑩

6. Molarity: It is the number of moles of solute per litre of solution. It is represented by ‘M’.
7. Molality: It is the number of moles of solute dissolved per 1 kg of solvent. It is represented by ‘m’.

8. Normality: It is the number of grams equivalents of solute dissolved per litre of solution.

Mass %, ppm, mole fraction and molality are independent of temperature whereas molarity is a
function of temperature. This is because volume depends on temperature and mass does not.
Solubility: It is the maximum amount of substance that can be dissolved in a specified amount of solvent
at a specified temperature. Solubility depends upon:
1. Nature of solute and solvent 2. Temperature 3. Pressure
Solubility of solid in a liquid: solute dissolves in a solvent if the intermolecular interactions are similar
in solute and solvent. Like dissolves like, polar solutes dissolve in polar solvents and non-polar solutes
dissolve in non-polar solvent. Ex. NaCl (polar) and sugar(polar) dissolves in water (polar) but anthracene
(non-polar) and naphthalene (non-polar) do not dissolve in water but dissolves in benzene (non-polar).

Saturated solution: solution in which no more solute can be dissolved at same temperature and pressure.
Unsaturated solution: solution in which more solute can be dissolved at same temperature and pressure.
Effect of Temperature
Endothermic process: solubility increases with increase in temperature
Exothermic process: solubility decreases with increase in temperature
Effect of Pressure
Pressure does not have any significant effect on solubility because solids are highly incompressible.
Solubility of Gases in Liquids
Gases dissolve in liquids to form a homogenous solution. The solubility of gases in liquids generally
decrease with increase in temperature and increases with increase in pressure over the solution at a given
temperature.
Henry’s law: Solubility of a gas in a liquid is directly proportional to the partial pressure of the gas
present above the surface of the solution.
If we use mole fraction of a gas in the solution as a measure of solubility, then it can be stated that mole
fraction of the solution in a solution is directly proportional to the partial pressure of the gas
present above the surface of the solution.
Most commonly used form of Henry’s law
The partial pressure of gas in vapour phase is proportional to the mole fraction of gas in solution.
pαx
p = KHx KH = Henry’s constant
Different gases have different KH values at the same temperature. KH value increases with increases in
temperature. Higher the value of KH at a given pressure, lower is the solubility of the gas in the liquid.
➔ ⸫ Aquatic species are more comfortable in cold water rather than warm water.
Applications of Henry’s law
➔ To increase the solubility of CO2 in soft drinks and soda water, bottle is sealed under high pressure.
➔ Scuba divers have to cope up with high concentration of dissolved gases while breathing air at high
pressure under water. Increased pressure increases solubility of atmospheric gases in blood. When
these divers come to surface, pressure gradually decreases which results into release of dissolved
gases and thus bubbles of nitrogen are formed in blood which block capillaries and create medical
condition known as bend which is painful and dangerous to life.
To avoid bend and toxic effect of high concentration of nitrogen in blood, the tanks used by scuba
divers are filled with air diluted with helium (11.7% He, 56.2% N2 and 32.1% O2).
➔ At high altitudes partial pressure of oxygen is less than that of the ground level. This leads to low
concentration of oxygen in blood which causes climbers to become weak and unable to think clearly,
symptoms of condition called anoxia.
Vapour pressure of liquid solutions
Raoult’s law: For a solution of volatile liquids the partial vapour pressure of each component of the
solution is directly proportional to its mole fraction.
Thus, for component 1 and 2, partial pressures will be,
p1 = p1° x1 and p2 = p2° x2
ptotal = p1° + (p2° - p1°)x2
Composition in vapour phase
If y1 and y2 are mole fraction of components 1 and 2 respectively in the vapour phase, then by using
Dalton’s law of partial pressures;
p1 α y1 p2 α y2
p1 = y1 ptotal p2 = y2 ptotal
Vapour pressure of solutions of solids in liquids
Liquids at given temperature vaporises and under equilibrium conditions, the pressure exerted by the
vapour of the liquid over the liquid phase is called vapour pressure.
In a pure liquid, the entire surface is occupied by molecules of volatile liquid. If non-volatile solute is
added to a solvent, then vapour pressure of the solution is only from volatile solvent. These 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, because in the solution the surface has both non-volatile solute and
volatile solvent molecules and thus surface covered by the solvent molecules is lesser. Hence no. of
solvent molecules escaping from the surface is reduced and vapour pressure is also reduced. Decrease in
v.p of solvent depends on the quantity of non-volatile solute present in the solution and not on its nature.

Ideal solutions
Solution which obeys Raoult’s law over the entire range of concentration are known as ideal solution.
 Δ mix H = 0 (no heat is absorbed or evolved when two components are mixed)
 Δ mix V = 0 ( volume of solution is equal to the volume of two components)
In pure components, intermolecular interactions will be of the type A—A and B—B.
Whereas in binary solutions i.e when two components are
mixed, along with A—A and B—B there will be also A—B type
of interactions.
If the intermolecular attractive forces between A—A and
B—B are nearly equal to those between A—B, then it will
lead to ideal solution.
Ex. Benzene and Toulene
n-hexane and n-heptane
Bromoethane and Iodoethane
Chlorobenzene and Bromobenzene
Non-ideal solution
Solution which does not obey Raoult’s law over the entire range of concentration are known as non-ideal
solution.
Vapour pressure of such solution is either lower or higher than that predicted by Raoult’s law.
If it is higher → positive deviation
If it is lower → negative deviation

Positive Deviation
A—B interactions are weaker than those between A—A or B—B interaction i.e intermolecular attractive
forces between solute—solvent molecules are weaker than
those between solute—solute or solvent—solvent molecules.
This increases vapour pressure than what was expected from
Raoult’s law.
➢ ΔmixH = positive (because its endothermic process)
➢ ΔmixV = positive (newly formed intermolecular
interactions are loosely held & thus volume increases)
Ex. Ethyl alcohol and Cyclohexane
Carbon tetrachloride and Chloroform
Acetone and Carbon disulphide
Benzene and Acetone
Acetone and Ethyl alcohol
Ethyl alcohol and Water

Negative deviation
A—B interactions are stronger than those between A—A or B—B interaction i.e intermolecular
attractive forces between solute—solvent molecules are
stronger than those between solute—solute or solvent—solvent
molecules. This decreases vapour pressure than what was
expected from Raoult’s law.
➢ ΔmixH = negative (because its exothermic process)
➢ ΔmixV = negative (newly formed intermolecular
interactions are tightly held & thus volume decreases)
Ex. Acetone and chloroform
Water and Nitric acid
Acetone and Aniline
Phenol and Aniline
Diethyl ether and Chloroform
Chloroform and Diethyl ether

Azeotropes
These are the solutions (liquid mixtures) which boil at constant temperature having same composition in
liquid and vapor phase and the two components cannot be separated by fractional distillation.
Minimum boiling azeotrope Maximum boiling azeotrope
These are the solutions which show large These are the solutions which show large
positive deviation from Raoult’s law negative deviation from Raoult’s law

Ex. Ethanol-water mixture Ex. Nitric acid-water mixture

Colligative properties
These properties depend on number of solute particles irrespective of their nature relative to the total
number of particles present in the solution.

1. Relative Lowering of Vapour Pressure

Vapour pressure of the solvent in solution is less than that of pure solvent. According to Raoult, lowering
of vapour pressure only depends on concentration of the solute and is independent of their identity.
𝑃1 α 𝑥1
𝑃1 = 𝑃10 𝑥1
Reduction of the vapor pressure of the solvent is given as
𝛥𝑃1 = 𝑃10 − 𝑃1
𝛥𝑃1 = 𝑃10 − 𝑃10 𝑥1
𝛥𝑃1 = 𝑃10 (1 − 𝑥1 )
𝛥𝑃1 = 𝑃10 𝑥2 ⸪𝑥1 + 𝑥2 = 1
𝛥𝑃1
= 𝑥2
𝑃10
𝑃10 − 𝑃1
= 𝑥2
𝑃10
𝑃10 − 𝑃1 𝑛2
0 =
𝑃1 𝑛1 + 𝑛2
Where n1 and n2 are number of moles of solvent and solute.
For dilute solution, n2 is too small than n1, hence;
𝑃10 − 𝑃1 𝑛2
0 =
𝑃1 𝑛1 + 𝑛2
0
𝑃1 − 𝑃1 𝑛2
=
𝑃10 𝑛1
0
𝑃1 − 𝑃1 𝑤2 ⁄𝑀2
=
𝑃10 𝑤1⁄𝑀1

𝑷𝟎𝟏 − 𝑷𝟏 𝒘𝟐 𝒙 𝑴𝟏
=
𝑷𝟎𝟏 𝑴𝟐 𝒙 𝒘𝟏

Where w1 and w2 and M1 and M2 are the molar masses of solvent and solute respectively.

2. Elevation of Boiling point

Boiling point: It is the temperature at which vapour
pressure of the liquid equals to the atmospheric pressure.
Increase in boiling point ΔTb is known as Elevation in
boiling point.
ΔTb = Tb - T°b
ΔTb α m --------------(m → molality)
ΔTb = Kb m
Where Kb is boiling point elevation constant or molal
elevation constant
𝒘𝟐 ⁄𝑴𝟐
𝚫𝑻𝒃 = 𝑲𝒃
𝒘𝟏 ⁄𝟏𝟎𝟎𝟎

𝑲𝒃 𝒙 𝒘𝟐 𝒙 𝟏𝟎𝟎𝟎
𝜟𝑻𝒃 =
𝑴𝟐 𝒙 𝒘𝟏
3. Depression of Freezing point
Freezing point: It is the temperature at which vapour
pressure of the substance in its liquid phase is equal to the
vapour pressure in its solid state.
Decrease in freezing point ΔTf is known as Depression in
freezing point
ΔTf = T°f - Tf
ΔTf α m --------------(m → molality)
ΔTf = Kf m
Where Kf is freezing point depression constant or molal
depression constant
𝒘𝟐 ⁄𝑴𝟐
𝚫𝑻𝒇 = 𝑲𝒇
𝒘𝟏 ⁄𝟏𝟎𝟎𝟎

𝑲𝒇 𝒙 𝒘𝟐 𝒙 𝟏𝟎𝟎𝟎
𝜟𝑻𝒇 =
𝑴𝟐 𝒙 𝒘𝟏

4. Osmotic Pressure and Osmosis

Osmosis: It is the phenomenon of flow of solvent
molecules through semi permeable membrane from pure
solvent side to the solution side.
Osmotic pressure: It is the excess pressure that must be
applied to the solution side to stop osmosis i.e to stop the
movement of solvent molecules from solvent side to
solution side through a semipermeable membrane.
With increase in concentration of solution, osmosis
increases.

Π = CRT --------------------- (C is Concentration)

Osmotic pressure method is widely used to determine molar mass of protein, polymer and other
biomolecules.
Osmotic pressure method has advantages over other methods as:
• Pressure measurement is around room temperature and molarity of the solution is used instead of
molality.
• Compared to other colligative properties its magnitude is large even for dilute solutions.
• Technique of osmotic pressure for determination of molar mass of solutes is practically useful for
biomolecules as they are generally not stable at high temperature.
Reverse osmosis
Direction of osmosis can be reversed i.e movement of
solvent molecule from solution side to solvent side
through a semi permeable membrane, if a pressure
larger than osmotic pressure is applied to solution side.
This phenomenon is called reverse osmosis.

It is used in desalination of sea water. For desalination

of sea water, film of cellulose acetate is used as a
semipermeable membrane because it is permeable to
water but impermeable to impurities and ions present in
sea water.

Isotonic solutions
Two solutions having same osmotic pressure at a given temperature are called isotonic solutions.
When such solutions are separated by semipermeable membrane, no osmosis occur between them.
Ex. Osmotic pressure associated with the fluid inside the blood cell is equivalent to that of 0.9% NaCl
solution (normal saline solution) and hence it is safe to inject intravenously.
If we place the cells in a solution containing more than 0.9% NaCl, water will flow out of the cell and cell
would shrink. Such solution is called hypertonic solution.
If we place the cells in a solution containing less than 0.9% NaCl, water will flow into the cell and cell
would swell. Such solution is called hypotonic solution.