Solutions

Introduction

The mixture is a combination of two or more substances.

Mixtures

Homogeneous which Heterogeneous mixture

mixing of components which mixing of
uniform. components nonuniform.
Example: true solution Example: collides

Here we will be studied the properties of homogeneous mixture that is true solution.

Solution:

Solution is a homogeneous mixture of two or more substances solution consist of solvent and solutes

Solvent : a large amount of solution.

Solute : small amount of solution.

Here, we studies by binary solution.

Types of solution:
Based on physical states of solvent and solute

No. Solute Solvent Example Memory Hint

1 Solid Liquid Sugar in water, sea water S → L (common)

2 Solid Solid Alloys (brass, bronze) Metal mix

3 Solid Gas Iodine in air Rare

4 Liquid Liquid Ethanol in water Miscible liquids

5 Liquid Solid Amalgam (Hg + metal) Mercury case

6 Liquid Gas Chloroform in N₂ Rare

7 Gas Liquid CO₂ in water (soda) Cold drink!

8 Gas Solid H₂ in palladium Absorption

9 Gas Gas Air (O₂ + N₂ etc.) Most common

 Capacity of solution to dissolve solute:
Capacity of solution to dissolve solutes called solubility.

What happens when solute adds to solvent?

• At first, solute dissolves quickly.

• After some time, dissolving becomes slower.

• Finally, dissolving stops completely.

At this stage, the solution becomes saturated.

Saturated Solution:-
A saturated solution contains the maximum amount of solute that can dissolve in a given amount of solvent at a

given temperature.

OR

A solution in which no more solute can dissolve in a given amount of solvent at a given temperature.

At saturation:
Some solute particles dissolve into solution (dissolution)

Some particles come back and form solid (crystallization)

Crystallisation is the process of forming

pure solid crystals of a substance from its

supersaturated solution.

Both processes occur at the same rate.

Dissolution rate = Crystallization rate

Unsaturated Solution:-

A solution in which more solute can still dissolve in a given amount of solvent
at a given temperature.

Supersaturated Solution:-

A solution that contains more solute than the saturated solution at the same temperature.

Factors Affecting Solubility

1. Nature of Solute and Solvent

Golden Rule: “Like dissolves like”

• Polar solute dissolves in

polar solvent.

Example: Salt in water

• Non-polar solute dissolves

in non-polar solvent.

Example: Oil in benzene

• If nature is different → solubility is low.

2. Effect of Temperature on Solubility

The change in solubility with temperature depends on the enthalpy of solution (heat absorbed or released during
dissolution).

Endothermic Dissolution:- Heat is absorbed during dissolution.

Example: KCl, NH₄NO₃

Effect: Solubility increases with increase in temperature.

Reason: According to Le-Chatelier's Principle, addition of heat favours the endothermic process.

Exothermic Dissolution:- Heat is released during dissolution

Examples: CaCl₂, Li₂SO₄·H₂O

Effect: Generally, solubility decreases with increase in temperature.

There is no strict rule that:

Endothermic → always increases

Exothermic → always decreases

Example: CaCl₂ (exothermic) → solubility increases

NH₄NO₃ (endothermic) → solubility increases

So, behaviour depends on overall thermodynamics, not only heat.

Observations of Different Substances

NaCl, NaBr, KCl → slight change with temperature

KNO₃, NaNO₃, KBr → solubility increases greatly

Na₂SO₄ → solubility decreases with temperature.

Solubility of Gases in Water

Gas dissolution is exothermic (condensation process)

Effect: Solubility of gases decreases with increase in temperature

Example: Cold drinks lose gas when heated.

Final Conclusion (Write This ✍️)

Solubility depends on enthalpy of solution

Endothermic processes generally increase solubility with temperature

Exothermic processes generally decrease solubility

However, no strict correlation always exists

Solubility of gases decreases with increase in temperature.

3. Effect of Pressure on Solubility

For Solids and Liquids:

Pressure has no significant effect, because solids and liquids are incompressible
For Gases in Liquids:

Solubility increases with increase in pressure.

• More pressure → more gas dissolves

• Less pressure → gas escapes

Henry's Law
At constant temperature, the solubility of a gas in a liquid is
directly proportional to the pressure of the gas above the solution.

Mathematical Expression:

SαP

S = KH P

KH = S/p

Where: KH = Henry’s constant

S = solubility of gas (mol L⁻¹)

P = pressure (bar)

Unit of KH is mol L-1 bar-1

When P = 1 bar, then

KH = S

So, Henry’s constant equal to solubility at 1 bar

Exceptions to Henry’s Law:

NH₃ and CO₂ do not obey Henry’s law

Reason:They react with water:

NH₃ + H₂O ⇌ NH₄⁺ + OH⁻

CO₂ + H₂O ⇌ H₂CO₃

✔ Due to reaction, their solubility becomes higher than expected.

Vapour Pressure of Liquid–Liquid Solutions

• Consider a binary solution of two volatile liquids A₁ and A₂ placed in a closed container.
• Both liquids evaporate.
• Equilibrium is established between liquid and vapour phases.
• Both components are present in the vapour phase.
• The partial pressures of the components are related to their mole fractions in the solution.

This relationship is given by Raoult’s law.

Raoult’s Law

The partial vapour pressure of each component is equal to the product of its mole fraction and vapour pressure in
pure state.

Consider a binary solution of two volatile liquids A1 and A2,

P1 = partial vapour pressure of A1.

P10 = vapour pressure of pure component A1.

X1 = mole fraction of A1 in solution.

P2 = partial vapour pressure of A2.

P20 = vapour pressure of pure component A2.

X2 = mole fraction of A2 in solution.

Then according to Raoult’s law

P1 = X1 P10

P2 = X2 P20

According to Dalton’s law of partial pressures, the total pressure P above the solution is,

P = P1 + P2

P = X1 P10 + X2 P20

But X1 + X2 = 1, therefore X1 = 1 - X2

P = (1 - X2) P10 + X2 P20

P = P10 - X2 P10 + X2 P20

P = (P20 - P10) X2 + P20

Graphical representation

P10 and P20 are constants

Plot a graph P vs X2 is straight line, in same graph we also plot P1 vs

X1 and P2 vs X2. These also straight lines passing through origin.

• For P vs X2 is straight line, P = P10 at X2 = 0 and P = P20 at X2 = 1

• For P1 vs X1 is straight line, P1 = 0 at X1 = 0 and P1 = P10 at X2 = 1
• For P2 vs X2 is straight line, P2 = 0 at X2 = 0 and P2 = P20 at X2 = 1

Composition of vapour phase :

The composition of vapour in equilibrium with the solution can be determined by Dalton’s law of partial
pressures.

If we take y1 and y2 as the mole fractions of two components in the vapour, then P1 = y1 P and P2 = y2 P

Where P1 and P2 are the partial pressures of two components in the vapour and P is the total vapour pressure.

Ideal and Non-Ideal Solutions (Using Raoult's Law)

1. Ideal Solutions

👉 Definition: Solutions which obey Raoult’s law over entire concentration range

👉 Characteristics:

✔ Obey Raoult’s law at all concentrations

✔ No heat change → ∆mixH = 0

✔ No volume change → ∆mixV = 0

✔ Intermolecular forces are similar: solute–solute ≈ solvent–solvent ≈ solute–solvent

✔ Vapour pressure lies between pure components

👉 Examples:

Benzene and Toluene : The most common example due to their similar structure and intermolecular interactions.

n-Hexane and n-Heptane: Similar alkanes that form an ideal solution.

Ethyl Bromide and Ethyl Iodide: Halogenated hydrocarbons with similar sizes and forces.

Chlorobenzene and Bromobenzene: Similar aromatic compounds.

Ethanol and Methanol: A rare example of polar compounds with similar hydrogen bonding.

2. Non-Ideal Solutions

👉 Definition: Solutions which do NOT obey Raoult’s law

👉 Characteristics:

❌ Do not follow Raoult’s law

✔ ∆mixH ≠ 0 (heat change occurs)

✔ ∆mixV ≠ 0 (volume changes)

✔ Intermolecular forces are different

Deviations from Raoult’s Law

A. Positive Deviation

Condition: Solute–solvent forces weaker

👉 Result: Vapour pressure higher than expected.

👉 Examples: Ethanol + Acetone: Acetone breaks hydrogen bonds

between ethanol molecules, allowing easier escape to the vapour
phase.

Carbon Disulphide + Acetone: Intermolecular forces are weakened.

Water + Methanol: Weaker hydrogen bonding compared to pure

water.

Ethanol + Water: Exhibits higher vapour pressure than predicted.

Benzene + Acetone: Weaker interaction between different molecule

types.

Carbon Tetrachloride + Chloroform: Similar to other mixtures, the interaction is weaker than pure components

B. Negative Deviation

👉 Condition: Solute–solvent forces stronger

👉 Result: Vapour pressure lower than expected.

 Examples:
• Acetone + Chloroform: Forms strong hydrogen bonds, restricting
evaporation.
• Nitric Acid + Water: Strong intermolecular attraction.
• Hydrochloric Acid + Water: Strong ion-dipole interactions.
• Acetic Acid + Pyridine: Intermolecular interaction between the carboxylic
acid and base
Chloroform + Benzene.
Acetone + Aniline.
Methanol + Acetic Acid.

Colligative Properties
Definition:

Properties that depend on number of solute particles, not nature

Types of colligative properties

1. Vapour pressure lowering

2. Boiling point elevation
3. Freezing point depression
4. Osmotic pressure.

1. Vapour Pressure Lowering

👉 Definition:

When a non-volatile, non-ionisable solute is dissolved in a solvent, the vapour pressure of the solvent
decreases.

Basic Idea: Vapour pressure = pressure exerted by vapours in equilibrium with liquid.

Non-volatile solute does not evaporate so only solvent contributes to vapour pressure.

If P1 0 is the vapour pressure of pure solvent and P1 is the vapour pressure of solvent above the solution, then P1
< P1 0 The vapour pressure lowering is ∆P = 0 1 - 33 P

Mathematical Expression:

Let: P10 = vapour pressure of pure solvent

P1 = vapour pressure of solution

then P1 < P10

👉 Vapour Pressure Lowering: ∆P = P10 - P1

Reason for Vapour Pressure Lowering

👉 Explanation:

Some surface solvent molecules are replaced by solute particles

Solute is non-volatile → cannot escape into vapour

Fewer solvent molecules are available at surface

👉 Result:

✔ Rate of evaporation decreases

✔ Vapour pressure decreases

📌 Key Points:

Only non-volatile solute shows this effect

Vapour pressure depends on number of solvent molecules escaping.

This is a colligative

Raoult's Law for Non-Volatile Solutes

Statement: For a solution containing a non-volatile solute, the vapour pressure of solvent is:

P1 = P10X1

Where:

P1 = vapour pressure of solution

P10 = vapour pressure of pure solvent

X1 = mole fraction of solvent

Vapour Pressure Lowering

As we know, X1 = 1 - X2

P1 = P10 (1 - X2)

P1 = P10 – P10X2

P10 – P1 = P10X2

Therefore: ∆P = P10 – P1 = P10X2

✔ Vapour pressure lowering depends on mole fraction of solute

✔ Hence, it is a Colligative Properties

Relative Lowering of Vapour Pressure

We have, ∆P = P10X2

Therefore ∆P/ P10 = X2

Meaning: Relative lowering = mole fraction of solute

To calculate molar mass of solute by lowering of vapour pressure

We know relationship between lowering of vapour pressure and mole fraction of solute as

∆P/ P10 = X2

The mole fraction of a component of solution is equal to its moles divided by the total moles in the solution.
𝑛2
Thus, X2 = 𝑛
1 +𝑛2

Where n1 = mole of solvent

n2 = mole of solute.
For dilute solutions n1 >> n2

Therefore n1 +n2 ≈ n1
𝑛2
Hence X2 = 𝑛1

∆𝑃
∴ = 𝑋2
𝑃10
∆𝑃 𝑛2
0 = 𝑋2 = 𝑛
𝑃1 1

✓ A solution is prepared by dissolving W2 g of a solute in W1 g of solvent.

𝑊
✓ The moles of solute 𝑛2 = 𝑀2
2
𝑊
✓ The moles of solvent 𝑛1 = 𝑀1
1
✓ Where M1= molar mass of solvent
✓ M2 = molar mass of solute
∆𝑃 𝑛2
𝑋2 = =
𝑃10 𝑛1
𝑊2
∆𝑃 𝑀2
=
𝑃10 𝑊1
𝑀1
∆𝑃 𝑊2 𝑀1
=
𝑃10 𝑊1 𝑀2

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

Boiling point elevation:

What is Boiling Point?

The boiling point of a liquid is the temperature at which its vapour pressure becomes equal to the external
(atmospheric) pressure.

For open containers → external pressure = 1 atm = 760 mm Hg

Boiling Point Elevation (Definition)

When a non-volatile solute is dissolved in a solvent, vapour pressure of the solution decreases so, the liquid
must be heated more to boil

Therefore: Tb > Tb0

Tb0 = boiling point of pure solvent

Tb = boiling point of solution

Increase in boiling point:

∆Tb = Tb - Tb0

Explanation Using the Graph

AB curve → pure solvent

CD curve → solution (lies below AB)

 👉 Why below?

Because solution has lower vapour pressure

At 760 mm line (1 atm):

Point A → boiling point of pure solvent (Tb0)

Point C → boiling point of solution (Tb)

Since point C occurs at a higher temperature: ➡ Solution boils at a higher

temperature

Reason Behind Boiling Point Elevation

At any temperature: Vapour pressure of solution < vapour pressure of solvent

So: Solution needs higher temperature to reach 1 atm. Hence, boiling point increases

Relation with Concentration

∆Tb α m

∆Tb = Kb. m

Where: m = molality (mol/kg)

Kb = boiling point elevation constant or ebullioscopic constant

Ebullioscopic Constant (Kb)

Defined as:

Increase in boiling point when the solution is 1 molal

Units: Kkgmol-1

Why Molality is Used?

Because:

➢ Molality does not change with temperature,

➢ Molarity changes (volume changes with temperature) so, molality is preferred.

Molar Mass Determination

Given solution contains

W2 = mass of solute (g)

W1= mass of solvent (g)

M2 = molar mass of solute

𝑊2 ×1000
Molality: 𝑚 = 𝑊1 𝑀2

Substitute into: ∆Tb = Kb. m

𝑊2 × 1000
∆𝑇𝑏 = 𝐾𝑏 .
𝑊1 𝑀2

👉 Final formula:
𝑊2 × 1000
∴ 𝑀2 = 𝐾𝑏 .
𝑊1 ∆𝑇𝑏
🔑 Final Quick Summary

✔ Non-volatile solute → lowers vapour pressure

✔ Lower vapour pressure → higher boiling point

✔∆Tb = Kb. m

✔ Use molality (temperature independent)

✔ Helps calculate molar mass.

Freezing Point Depression

What is freezing point?

Freezing point is the temperature at which liquid and solid phases of a substance are in equilibrium.

What is freezing point depression?

When a non-volatile solute is dissolved in a solvent, the freezing point of the solution becomes lower than that of
the pure solvent. This decrease is called depression in freezing point.

When you add a non-volatile solute (like salt) to a solvent (like water): Freezing point decreases

✔ So, solution freezes at lower temperature than pure solvent.

Therefore: Tf < Tf0

Tf0 = Freezing point of pure solvent

Tf = Freezing point of solution

Decrease in freezing point: ∆Tf = Tf0 – Tf

Understanding the Graph

Graph shows Vapour Pressure vs Temperature

Three curves:

AB → Solid solvent

CD → Pure liquid solvent

EF → Solution (always below CD)

🔸 Key Points:

1. Point B (Pure solvent freezing point)

Intersection of AB and CD

Solid + Liquid solvent in equilibrium

At temperature = Tf0

2. Point E (Solution freezing point)

Intersection of AB and EF

Solid solvent + Solution in equilibrium

At temperature = Tf

Important Observation:
 Curve EF is below CD

➡ Vapour pressure of solution is lower

So intersection happens at lower temperature

✔ Therefore: Tf < Tf0

Why Freezing Point Decreases?

In pure solvent: Molecules are close → strong attraction → freeze easily

In solution: Solute particles separate solvent molecules,

➡Attraction between solvent molecules decreases

➡ So more cooling is needed to freeze

➡ Hence, freezing point decreases

Relation with Concentration

∆Tf = Kf. m

Kf = Cryoscopic constant

m = Molality

More solute → more decrease in freezing point

Cryoscopic constant (Kf)

Defined as: decrease in freezing point when the solution is 1 molal

Units: Kkgmol-1

Molar Mass Determination

Given solution contains

W2 = mass of solute (g)

W1= mass of solvent (g)

M2 = molar mass of solute

𝑊2 ×1000
Molality: 𝑚 =
𝑊1 𝑀2

Substitute into: ∆Tf = Kf. m

𝑊2 × 1000
∆𝑇𝑓 = 𝐾𝑓 .
𝑊1 𝑀2

Final formula:
𝑊2 × 1000
∴ 𝑀2 = 𝐾𝑓 .
𝑊1 ∆𝑇𝑓

🔥 Final Summary (Exam Ready)

✔ Solution freezes at lower temperature than pure solvent

✔ Due to vapour pressure lowering

✔∆Tf = Kf. m
✔ Used to find molar mass of solute.

Osmotic pressure

What is a Semipermeable Membrane?

A semipermeable membrane is a special barrier that:

✅ Allows solvent molecules (like water) to pass

❌ Does NOT allow solute particles (like sugar, salt, large molecules)

Example: cellophane sheet

What is Osmosis?

Osmosis = Movement of solvent through a semipermeable membrane.

Direction of flow:

From pure solvent OR dilute solution ➡ To concentrated solution

Left: low concentration (or pure solvent)

Right: high concentration solution

Arrow shows net flow → toward concentrated side

🔷 Important Concept

Even though solvent moves in both directions:-

More solvent goes towards concentrated solution

Less comes back

So, net flow = toward higher concentration

Why does this happen?

Because: Vapour pressure of pure solvent > solution

Nature tries to balance concentration

So solvent moves to:

dilute the concentrated solution

Result of Osmosis

Volume decreases on dilute side

Volume increases on concentrated side

Concentration difference reduces.

Experimental Setup (What the diagram shows)

A thistle tube (funnel with a long narrow tube) is used

Its mouth is covered with a semipermeable membrane

Inside the tube: sugar solution

Outside (in beaker): pure water

What Happens?

Step 1: Osmosis begins

Water (solvent) moves from pure water → sugar solution

Reason:

solution is more concentrated, this is osmosis

Step 2: Liquid level rises

Water enters the tube. So, the level of liquid rises in the vertical tube

Step 3: Hydrostatic pressure develops

As the liquid rises, it creates pressure due to its height.

Π = hρg

Where:

h = height of liquid column

ρ (rho) = density of solution

g = acceleration due to gravity

Step 4: Equilibrium is reached

Initially: water enters faster than it leaves

Later: pressure pushes water back out

Finally: Rate of entry = Rate of exit

Liquid level stops rising

What is Osmotic Pressure (π)?

The pressure required to stop osmosis.

In this experiment: The hydrostatic pressure developed = osmotic pressure

🔷 Types of Solutions

1. Isotonic solutions

Two solutions which have same osmotic pressure.

❌ No net flow of solvent through semipermeable membrane.

Example: 0.1 M urea & 0.1 M sucrose, both solutions have same concentration same osmotic pressure.

2. Hypertonic solution

A solution which has higher concentration than other, hence have higher osmotic pressure is said to be
hypertonic solution.

Higher concentration

Higher osmotic pressure

Draws solvent towards itself

3. Hypotonic solution

A solution which has lower concentration than other, hence have lower osmotic pressure is said to be hyportonic
solution.

⚫ Lower concentration

⚫ Lower osmotic pressure

⚫ Loses solvent

Relation with Concentration

For dilute solutions:

π = MRT

Where:

M = molarity = n2/V

R = gas constant

T = temperature (K)

π = n2/V × RT

🔷 Finding Molar Mass

π = n2/V × RT

But n2 =W2/M2

π = W2/ M2V × RT

M2 = W2/ π V × RT

Where:

M2 = molar mass of solute

W₂ = mass of solute

V = volume

π = osmotic pressure

Very useful to find molar mass of large molecules (like proteins)

🔥 Quick Summary (Exam Ready)

⚫ Solvent flows from dilute → concentrated

⚫ Level rises → creates hydrostatic pressure

⚫ When flow stops → π = hρg

Formula: π = MRT

Reverse Osmosis (RO)

Definition

Reverse osmosis is the process in which solvent flows from solution to pure solvent through a semipermeable
membrane
 This happens when external pressure > osmotic pressure (π)
is applied

Key Idea

Normal osmosis: Dilute → Concentrated

Reverse osmosis: Concentrated → Dilute (or pure

solvent)

How it works A semipermeable membrane separates: Salty water (solution) → Pure water

Apply high pressure on the solution side, Pressure forces pure water to move out of solution salt/impurities are
left behind

Condition: applied pressure > osmotic pressure (π)

Applications

Desalination of seawater

Water purification (RO filters)

Removal of impurities in industries

Difference: Osmosis vs Reverse Osmosis

Feature Osmosis Reverse Osmosis

Direction of solvent Dilute → Concentrated Concentrated → Dilute

External pressure Not required Required

Condition Natural process Applied pressure > π

Energy No energy needed Needs energy

Example Plant water absorption RO water purifier

Colligative Properties: Electrolytes vs Nonelectrolytes

✅ Nonelectrolytes (Normal behaviour)

Examples: sugar (sucrose), urea, when dissolved in water.

They do NOT break into ions.

They remain as whole molecules.

Result:

Colligative properties (like boiling point elevation, freezing point depression, osmotic pressure) follow normal
formulas.

Molar mass calculated is correct.

✅ Electrolytes (Different behaviour)

Examples: NaCl, KCl, HCl, when dissolved in water.

They dissociate into ions.

Example: NaCl → Na⁺ + Cl⁻ (2 particles)

🔹 Key Observations for Electrolytes

1. They show colligative properties, but do not follow normal equations

2. Colligative properties are greater than expected because electrolytes produce more particles (ions) in solution.

3. Molar mass appears lower than actual

👉 Why?

Calculations assume fewer particles

But actually, there are more particles due to ion formation

🔹 Main Reason (VERY IMPORTANT)

Electrolytes dissociate into ions, so number of particles increases.

And remember: colligative properties depend only on the number of particles, not their type.

Example NaCl vs Sucrose

0.1 m NaCl → gives 2 ions (Na⁺, Cl⁻)

0.1 m Sucrose → gives 1 molecule

So: NaCl solution has double particles

Therefore: Colligative property of NaCl ≈ 2 times that of sucrose

🔹 Final Conclusion

More particles = Stronger colligative effect

So:

Electrolytes → Higher colligative properties

Nonelectrolytes → Normal colligative properties

van’t Hoff factor (i)

What is van’t Hoff factor (i)?

The van’t Hoff factor (i) tells us: How many particles are actually present in solution compared to what we
expect.

Definition:
colligative property of electrolyte solution
𝑖=
colligative property of nonelectrolyte solution of same concentration

Why do we need it?

✓ Nonelectrolytes (like sugar) → do not break in solution → number of particles = same → i = 1

✓ Electrolytes (like NaCl, KCl) → dissociate into ions → number of particles increases → i > 1
Actual number of particles in solution after dissociation
𝑖=
number of formula units dissolved in solution
Alternative meaning of i

𝑀𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 (molar mass of solute)

Or 𝑖=
𝑀𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 (molar mass of solute)
Examples

Substance Dissociation Number of i value

particles
Glucose No dissociation 1 1
NaCl NaCl → Na⁺ + Cl⁻ 2 2
CaCl₂ CaCl₂ → Ca²⁺ + 2Cl⁻ 3 3
Na₂SO₄ Na₂SO₄ → 2Na⁺ + SO₄²⁻ 3 3

Important Note (Real Life)

In reality: van’t Hoff factor (i) is less than expected because:

✓ Ions attract each other

✓ They form ion pairs
✓ So actual particles decrease

Modified formulas using i

For electrolytes, multiply by i:

Vapour pressure lowering → ∆𝑃 = 𝑖 × 𝑃10 𝑥2

Boiling point elevation → ∆𝑇𝑏 = 𝑖 × 𝐾𝑏 . 𝑚

Freezing point depression → ∆𝑇𝑓 = 𝑖 × 𝐾𝑓 . 𝑚

Osmotic pressure → π = 𝑖 × MRT

Relation between i and degree of dissociation (α)

❖ The value of i is true for solutions of strong electrolytes and not for weak electrolytes that dissociate to a
small extent
❖ The weak electrolytes involve the concept of degree of dissociation (∝), that changes the van’t Hoff factor.

For electrolyte:

Let us consider an electrolyte Ax By dissociates in aqueous solution as

𝐴𝑥 𝐵𝑦 (𝑎𝑞) ⇌ 𝑥𝐴 𝑦+ + 𝑦𝐵 𝑥−
Initially 1 mol 0 mol 0 mol
At equilibrium (1-∝) mol x ∝ mol y ∝ mol
✓ If ∝ is the degree of dissociation of electrolyte, then the moles of cations are ∝x and anions are ∝y at
equilibrium.
✓ Dissolved 1 mol of electrolyte initially. ∝ mol of electrolyte dissociates and (1 ∝) mol remains
undissociated at equilibrium.

Total moles after dissociation total ions formed

Total moles after dissociation = (1-∝) + x∝ + y∝
= 1 - ∝ + x∝ + y∝
= 1 + x∝ + y∝ - ∝
= 1 + ∝ (x + y – 1)
= 1 + ∝ (n – 1)
✓ Where, n = x+y = moles of ions obtained from dissociation of 1 mole of electrolyte.
✓ The van’t Hoff factor given by
Actual number of particles in solution after dissociation
𝑖=
number of formula units dissolved in solution
 1+∝ (n – 1)
𝑖=
1

𝑖 = 1+∝ (n – 1)

∝ (n – 1) = 𝑖 − 1

i– 1
∝=
𝑛−1

🔹 Simple Understanding

i = 1 → no dissociation

i > 1 → dissociation (more particles)

i < expected → ion pairing happens