Solutions

Methods of Expressing Concentrations

Mixture
A mixture is formed by mixing two or more chemically non-reacting substances.
A mixture may be either heterogeneous that consists of distinct phases or homogeneous that consists of
single phase.

Solution
Solution is a homogeneous mixture i.e., one phase system of two or more than two components. Its
constituents cannot be separated by filtration, sedimentation or centrifugation.
There are two components of a solution. Generally, the component that is present in the largest quantity is
known as solvent. One or more components present in the solution other than solvent are called solutes.
A solution in which water is solvent is called as an aqueous solution. A solution in which solvent is other
than water is called as non-aqueous solution.

Types of Solutions
Nature of solution Solute Solvent Examples
Solid solutions Gas Solid Gases adsorbed over metal surface,
Gases dissolved in minerals.
Liquid Solid Mercury in an amalgam,
Hydrated salts.
Solid Solid Alloys of metals, e.g., Interstitial solid solutions.
Liquid solutions Gas Liquid Aerated drinks
Liquid Liquid Mixture of miscible liquids, e.g., alcohol in water.
Solid Liquid Salts dissolved in water, e.g., NaCl in water.
Gaseous solutions Gas Gas Air (Mixture of many gases)
Liquid Gas Humidity in air.
Solid Gas Iodine vapours in air.

Expressing Concentration of Solutions

(a) Mass percentage (w/w):

Mass of the component

Mass % of a component = x 100%
Mass of the solution

(b) Volume percentage (v/v):

Volume of the component
Volume % of a component = x 100%
Volume of the solution
Mass of the solute
(c) Mass by volume percentage (w/v) = x 100%
Volume of the solution

Number of parts of the component

(d) Parts per million (ppm) = x 106
Total number of parts in the solution
(e) Mole Fraction (x):
Number of moles of the component
Mole fraction of a component (x) =
Total number of moles of all the components
Mass
Number of moles of the component (n) =
Molar mass
(f) Molarity (M): It is the number of moles of solute per litre of solution. Its unit is mol L -1 or M (molar)
Number of moles of solute
Molarity =
Volume of solution in L
Number of moles of solute
Molarity = x 1000
Volume of solution in mL or cc
Or,
Molarity Equations
➢ For dilution of a solution : M₁V₁= M₂V₂
➢ For mixing two non-reacting solutions : M₁V₁ + M₂V₂ = M3(V₁ + V₂)
𝑀₁𝑉₁ + 𝑀₂𝑉₂
or M3 =
(𝑉₁ + 𝑉₂)

(g) Molality (m): It is the number of moles of solute per kg of solvent. Its unit is mol kg -1 or m (molal)
Number of moles of solute
Molality =
Weight of solvent in kg
Number of moles of solute
Molality = x 1000
Weight of solvent in g

Relationship between Molarity and Molality

1000 𝑀
m=
1000 𝑑−𝑀 . 𝑀𝐵
Relationship between Molality (m) and Mole fraction of Solute (xB)
𝑥𝐵 x 1000 𝑥𝐵 x 1000
m= or m=
𝑥A x 𝑀𝐴 (1−𝑥𝐵) x 𝑀𝐴

Effect of temperature: Mass %, mole fraction and molality do not change with temperature whereas
molarity changes with temperature because volume of solution (liquid) changes with temperature.
Thus, molality is considered better for expressing concentration as compared to molarity.

Solubility and Henry’s Law

Solubility
Solubility of a substance is defined as the maximum amount of substance that can be dissolved in a
specified amount of solvent at a given temperature.
Solubility of a substance may also be defined as the maximum amount of substance (solute) in grams that
can be dissolved in 100g of solvent to form saturated solution at a given temperature.
Mass of solute (g)
Solubility = x 100
Mass of solvent
Solubility of a Solid in Liquid
Effect of temperature: The solubility of a solid in a liquid changes with temperature.
dissolution
Solute + Solvent → Solution
According to Le Chatelier’s principle, if the dissolution process is endothermic, the solubility should
increase with the rise is temperature and if it is exothermic the solubility should decrease with rise in
temperature.
Effect of pressure: Solubility of a solid in a liquid does not change with pressure as solids and liquids are
highly incompressible.
Like dissolves like: Polar solutes dissolve in polar solvents and non-polar solutes dissolves in non-polar
solvents. In general, a solute dissolves in a solvent, if the intermolecular attractions are similar in both.

Solubility of a Gas in Liquid

(a) Increases with increase of pressure at a constant temperature.
(b) Decreases with increase of temperature.
As dissolution of gas in liquid is an exothermic process, the solubility should decrease with increase in
temperature.

Henry’s Law
At constant temperature, the solubility of a gas in a liquid is directly proportional to the pressure of gas over
the solution.
Or
The partial pressure of the gas in vapour phase (P) is directly proportional to the mole fraction of the gas (x)
in the solution.
P = kHx
Where, kH = Henry’s law constant. It depends on the nature of gas.
Greater the kH value, the lower will be the solubility and vice versa.
kH increases with increase in temperature so solubility of a gas in a liquid decreases with increase of
temperature.

Applications of Henry’s Law

1. Soft drinks and soda water bottles are sealed under high pressure to increase the solubility of CO₂.
2. In scuba diving:

To avoid bends, scuba divers use O2, diluted with less soluble Helium gas for breathing.
3. At high altitude,
Raoult’s Law, Ideal and Non-Ideal Solution
In a closed vessel,
Liquid ⇌ Vapour

At equilibrium,
Rate of evaporation = Rate of condensation
The pressure exerted by the vapours in equilibrium with liquid at a gives temperature, is called its vapour
pressure.

Raoult’s Law
It gives relationship between partial vapour pressures and mole fractions of volatile components in the
solution. It states that, “For any solution, the partial vapour pressure of each volatile component in the
solution directly proportional to its mole fraction in the solution.”
▪ Raoult’s law for a solution of two volatile liquids, A and B
PA ∝ xA and PB ∝ xB

PA = P0A xA and PB = P0B xB

⇒ Total vapour pressure of the solution, PT = PA + PB = P0A xA + P0B xB

Mole fractions in vapour phase –

𝑃𝐴 𝑃𝐵
yA = ; yB =
𝑃𝑇 𝑃𝑇

▪ Raoult’s law for a solution containing volatile solvent and non-volatile solute
Solute being non-volatile has no contribution to the vapour pressure and the vapour pressure of a
solution is due to solvent only.
Since,
Psolvent = P0solvent . xsolvent
Psolution = Psolvent
Psolution = P0solvent . xsolvent
When a non-volatile solute is dissolved in a pure solvent, the vapour pressure of the pure solvent
decreases.
Psolution < P0solvent
Because the non-volatile solute particles are present on surface of the solution so the rate of evaporation of
molecules of the volatile solvent from the surface of solution decreases.

Liquid-Liquid Volatile Solutions are Classified into Two Types

on the Basis of Racult’s Law as Follows:
▪ Ideal Solution
➢ The solution which obeys Raoult’s law at all concentration and at all
temperature, i.e.,
PA = P0A xA and PB = P0B xB
 ➢ If the intermolecular attractive forces between the solute-solvent (A-B interaction) are nearly equal to
those between the solvent-solvent (A-A) and solute-solute (B-B), it forms ideal solation.
➢ Enthalpy of mixing, ΔmixingH = 0
➢ Volume change on mixing ΔmixingV = 0
Examples: n-hexane and n -heptane, Bromoethane and chloroethane, benzene and toluene.

▪ Non-Ideal solution
➢ The solution which does not obey Raoult’s law at all concentrations and at all temperature i.e., PA ≠
P0A xA and PB ≠ P0B xB
➢ If the intermolecular attractive forces between the solute-solvent (A-8 interaction) are not equal
(ether stronger or weaker) to those between the solvent-solvent (A-A) and solute-solute (B-B), it
forms non-ideal solution.
➢ Enthalpy of mixing, ΔmixingH ≠ 0
➢ Volume change on mixing ΔmixingV ≠ 0

Examples: Ethanol and acetone, ethanol and water, chloroform and acetone, nitric acid and water.

Types of Non-Ideal Solutions

▪ Non-ideal solution showing positive deviations
➢ In this case, intermolecular attractive forces between the solute and solvent
(A-B) are weaker than those between the solvent (A-A) and the solute (B-B),
i.e., PA > P0A xA and PB > P0B xB
➢ ΔmixingH = +ve
➢ ΔmixingV = +ve
➢ Dissolution is endothermic so, heating increases solubility.
Examples: Ethanol and acetone, ethanol and water, CS2, and acetone.

• Non-Ideal solution showing negative deviations

➢ In this case, intermolecular attractive forces between the solute and solvent
(A-B) are stronger than those between the solvent (A-A) and the solute (B-B),
i.e., PA < P0A xA and PB < P0B xB
➢ ΔmixingH = -ve
➢ ΔmixingV = -ve
➢ Dissolution is exothermic so, heating decreases solubility.
Examples: Chloroform and acetone, nitric acid and water, phenol and aniline.

Azeotropes
These are binary solutions (liquid mixtures) having the same composition in liquid and vapour phase and it
is not possible to separate the components of an azeotrope by fractional distillation. These are also called
as constant boiling mixtures.

Types of Azeotropes
• Minimum Boiling Azeotrope
➢ The non-ideal solutions showing large positive deviation from Raoult’s law, form minimum boiling
azeotrope at a specific composition.
➢ Example: 95% ethanol and 5% water (by volume)
Ethanol = 351.3 K, Water = 373 K, Azeotrope = 351.1 K

• Maximum Boiling Azeotrope

 ➢ The non-ideal solutions showing large negative deviation from Raoult’s law, form maximum boiling
azeotrope at a specific composition.
➢ Example: 68% Nitric acid and 32% water (by mass)
Nitric acid = 359 K, Water = 373 K, Azeotrope = 393.5 K

Colligative Properties
Colligative Properties
Properties of solutions which depend only on the number of solute particle but not on their nature are called
Colligative Properties.
There are four Colligative Properties:
(a) Relative lowering of vapour pressure
(b) Elevation of boiling point
(c) Depression of freezing point
(d) Omotic pressure
Application: By measuring a colligative property of a solution, molar mass of the non-volatile solute can be
calculated.
Conditions for getting accurate value of molar mass:

• Solute must be non-volatile.

• Solution must be dilute.
• Solute particles must not undergo any association or dissociation in the solution.

Relative lowering of vapour pressure

When a non-volatile solute is added to a pure solvent its vapour pressure decreases.
P solution < P0A
Psolution = Psolvent (PA) (Since solute is non volatile)
PA = P0A xA (According to Raoult’s law)
PA = P0A (1 – xB)
PA = P0A – P0A xB
P0A - PA = P0A xB
𝑃0𝐴 − 𝑃𝐴
= xB
𝑃0𝐴
Where P0A is vapour pressure of pure solvent, PA is vapour of solvent in the solution, P0A - PA, is the
𝑃0𝐴 − 𝑃𝐴
lowering in vapor pressure and is the relative lowering of vapour pressure.
𝑃0𝐴
Since the relative lowering of vapour pressure depends on mole fraction of the solute (xB), it is a colligative
property.
Calculation of molar mass of salute:
According to the Raoult’s law
PA = P0A xA (where, xA = mole fraction of solvent)
⟹ PS = P0A xA (Since, xA is always <1 ⟹ PS < P0A)
⟹ PS = P0A (1 – xB) (xB = mole fraction of solute)
𝑃0𝐴 − 𝑃𝑠 𝑃0𝐴 − 𝑃𝐴
⟹ xB = =
𝑃0𝐴 𝑃0𝐴
𝑛𝐵
⟹ xB = (nA = No. of moles of solute, nB = No. of moles of solvent)
𝑛𝐴+𝑛𝐵
𝑛𝐵
≈ (nB from denominator can be neglected as law is applicable to dilute solutions)
𝑛𝐴
𝑤𝐵⁄𝑀𝐵
⟹ xB =
𝑤𝐴⁄𝑀𝐴
𝑃0𝐴 − 𝑃𝑠 𝑤𝐵 . 𝑀𝐴 𝑃0𝐴 − 𝑃𝐴 𝑤𝐵 . 𝑀𝐴
⟹ = or =
𝑃0𝐴 𝑤𝐴 . 𝑀𝐵 𝑃0𝐴 𝑤𝐴 . 𝑀𝐵
So MB, can be determined.

Elevation of Boiling Point

▪ Boiling point: The boiling point of a liquid is defined as the temperature
at which its vapour pressure becomes equal to the atmospheric pressure.
▪ The vapour pressure of the pare solvent decreases when a non volatile
solute is added to it and the boiling point is inversely proportional to
vapour pressure. Therefore, boiling point of the solvent increases when a
non volatile solute is added, i.e., Tb > T0b
▪ The difference in boiling point of solution and the pure solvent is called
elevation of boiling point (ΔTb).
▪ ΔTb = Tb (solution) - T0b (solvent) or Tb (solution) = T0b (solvent) + ΔTb
For dilute solutions, the elevation of boiling point is directly proportional to
molality (molal concentration) of the solution.
ΔTb ∝ m
ΔTb = kb . m
Where, kb = Boiling point elevation constant or molal elevation constant or ebullioscopic constant.
𝑤𝐵 . 1000
ΔTb = kb .
𝑤𝐴 . 𝑀𝐵
Using this, the molar mass of non-volatile solute (MB) can be calculated.

Depression of Freezing Point

▪ Freezing Point: Temperature at which the vapour pressure of the
substance in its liquid phase is equal to its vapour pressure in its solid
phase, is known as its freezing point.
▪ Since, the vapour pressure of the solvent decreases in the presence of
non-volatile solute and freezing point is directly proportional to vapour
pressure, the freezing point of pure solvent decreases when non-volatile
solute is added to it, i.e., Tf < T0f
▪ The difference in freezing point of pure solvent and solution is called
depression of freezing point (ΔTf)
▪ ΔTf = T0f (solvent) - Tf (solution) or Tf (solution) = T0f (solvent) - ΔTf
For dilute solution, the depression of freezing point is directly proportional to molality (molal
concentration) of the solution.
ΔTf ∝ m
ΔTf = kf . m
Where, kf = freezing point depression constant or molal depression constant or cryoscopic constant.
𝑤𝐵 . 1000
ΔTf = kf .
𝑤𝐴 . 𝑀𝐵
Using this, the molar mass of non-volatile solute (MB) can be calculated.

Osmosis
It is the process of spontaneous flow of solvent molecules from a dilute solution to the concentrated
solution (or from pure solvent to solution) through a semi-permeable membrane. This process continues till
the concentration on both sides of membrane becomes equal.

Osmotic Pressure (π)

It is defined as the minimum pressure that must be applied to the solution to prevent the flow of solvent into
the semipermeable membrane.
It is a colligative property as it is directly proportional to molarity (molar concentration) of the solution at the
given temperature.
π = CRT [R = Solution constant (0.082L atm K-1 mol-1, or 0.0831 bar K-1 mol-1)]
𝑛
⟹ πV = nRT [∵ c = ]
𝑣
𝑤𝐵 𝑤𝐵
⟹ πV = 𝑀𝐵RT [∵ n = ]
𝑀𝐵
Where, wB = weight of solute, MB = molar mass of solute, n = no. of moles of solute
𝑤𝐵
⟹ MB = RT
π𝑉

Using this, the molar mass of non-volatile solute (MB) can be calculated.

Semi-Permeable Membrane
SPM allows only the solvent (not the solute) molecules to pass through it.
Example: Pig’s bladder, cellophane membrane and film of gelatinous precipitate of cupric ferrocyanide,
Cu2[Fe(CN)6].

Isotonic Solutions
Two different solutions which have same osmotic pressure at a given temperature are called isotonic
solutions. Isotonic solutions have same molar concentration.
Example: 0.9% (w/v) NaCl aqueous solution (Normal saline solution) is isotonic to the fluid present inside
the blood cells. So, it is safe to inject intravenously.

Hypertonic and Hypotonic Solutions

Solution which has more osmotic pressure than other solution is hypertonic and similarly the solution
having less osmotic pressure than the other solution is called hypotonic.

Reverse Osmosis
When a pressure larger than osmotic pressure is applied to the solution side, the pure solvent flows out of
solution to solvent side through semi-permeable membrane. This process is called reverse osmosis.
Use: Reverse osmosis is used for desalination of sea water (into drinking water).

Abnormal Molar Masses and van’t Hoff Factor

Abnormal Molar Masses
Colligative properties of solutions depend on number of solute particles present in solution.
If number of solute particles changes in solution (by dissociation or by association), colligative properties
also change accordingly the abnormal molar mass is observed.
van’t Hoff Factor (i)
It is a correction factor and is defined as
Total number of moles of particles after association or dissociation
i=
Total number of moles of particles before association or dissociation
Normal molar mass
or, i=
Abnormal molar mass
Abnormal colligative property
or, i=
Normal colligative property

Always the value of ‘i’ is less than unity (i < 1) for association and ‘i’ is greater than unity (i > 1) for
dissociation.
The modified equations for colligative properties for association or dissociation are:
𝑃0𝐴 − 𝑃𝐴
Relative lowering of vapour pressure : = i . xB
𝑃0𝐴
Elevation of boiling point : ΔTb = i . kb . m

Depression of freezing point : ΔTf = i . kf . m

Omotic pressure : π = i . CRT

van’t Hoff factor is related to the degree of dissociation/association as:
𝑖–1
For dissociation: α =
𝑛–1
Where, α = degree of dissociation and n = ions on dissociation from one unit of solute.

For 100% dissociation (𝛼 = 1), i = n

𝑖–1
For association: α = 1
–1
𝑚

Where, α = degree of association and m = molecules of solute associate to form one giant species after
association.
1
For 100% association (α = 1), i = 𝑚

Dissociation Association
An ⇌ nA mA ⇌ Am
Before dissociation 1 0 Before association 1 0
After dissociation 1-α nα α
After association 1-𝛼
𝑚
No. of particles after association
No. of particles after dissociation i=
i= No. of particles taken
No. of particles taken α
1−α+
𝑚
1 − α + nα =
= 1
1
𝑖–1 𝑖–1
⟹ 𝛼= ⟹ 𝛼= 1
𝑛–1 –1
𝑚