Solution Chemistry

Solution and Colligative Properties

Concentration Units, Raoult's Law, and Colligative Properties

High Weightage in JEE Main

Introduction

A solution is a homogeneous mixture of two or more substances where the components are uniformly distributed at the molecular level. The substance present in smaller quantity is called the solute, while the substance present in larger quantity is called the solvent.

Solubility is defined as the maximum amount of solute that can dissolve in 100g of solvent at a given temperature to form a saturated solution.

Types of Solutions

Solvent Solute Example
Gas Gas Air
Gas Liquid Humid air
Gas Solid Smoke
Liquid Gas Aerated drinks
Liquid Liquid Alcohol in water
Liquid Solid Sugar in water
Solid Gas H₂ in Pd
Solid Liquid Hg in Zn
Solid Solid Alloys

Concentration Units

Percentage
% w/w = (Wt. solute / Wt. solution) × 100
% w/v = (Wt. solute / Vol. solution) × 100
% v/v = (Vol. solute / Vol. solution) × 100
% v/w = (Vol. solute / Wt. solution) × 100
Molarity (M)
Moles of solute per liter of solution
Temperature dependent
M = n/V (in liters)
Most common concentration unit
Molality (m)
Moles of solute per kg of solvent
Temperature independent
m = (moles of solute) / (kg of solvent)
Preferred for precise work
Normality (N)
Gram equivalents per liter of solution
N = M × n-factor
Used in titrations
Temperature dependent
Mole Fraction (X)
Ratio of moles of component to total moles
Temperature independent
XA + XB = 1
Used in Raoult's Law
Parts Per Million (ppm)
For very dilute solutions
ppm = (mass of solute / total mass) × 10⁶
Temperature independent
Used for trace contaminants

Important Relationships

Normality = Molarity × n-factor (n = basicity for acids, acidity for bases)
Molarity (M) = (Molality × Density) / (1 + (Molality × Molecular Mass / 1000))
Molality (m) = Molarity / (Density - (Molarity × Molecular Mass / 1000))

Colligative Properties

Colligative properties depend only on the number of solute particles in solution, not on their identity. The four main colligative properties are:

Vapor Pressure Lowering
Due to non-volatile solute
ΔP = P⁰ - P = P⁰Xsolute
Relative lowering = (P⁰ - P)/P⁰ = Xsolute
Boiling Point Elevation
ΔTb = Kb × m
Kb = molal elevation constant
m = molality
Kb (water) = 0.52 °C kg mol⁻¹
Freezing Point Depression
ΔTf = Kf × m
Kf = molal depression constant
m = molality
Kf (water) = 1.86 °C kg mol⁻¹
Osmotic Pressure
π = CRT
π = (n/V)RT
C = molar concentration
Most sensitive colligative property

Raoult's Law

Raoult's Law states that the partial vapor pressure of each component in an ideal solution is equal to the vapor pressure of the pure component multiplied by its mole fraction in the solution: PA = P⁰A × XA

Ideal vs Non-Ideal Solutions

Property Ideal Solution Positive Deviation Negative Deviation
Raoult's Law Obeys Does not obey Does not obey
ΔHmix = 0 > 0 (Endothermic) < 0 (Exothermic)
ΔVmix = 0 > 0 < 0
Molecular Interactions A-A ≈ A-B ≈ B-B A-B < A-A, B-B A-B > A-A, B-B
Examples Benzene + Toluene Acetone + Ethanol Acetone + Chloroform

Azeotropic Mixtures

Azeotropes are constant boiling mixtures that have the same composition in liquid and vapor phases. They cannot be separated by simple distillation.

Minimum Boiling Azeotrope
Show positive deviation
Boiling point lower than components
Example: Ethanol + Water (95.6%)
Maximum Boiling Azeotrope
Show negative deviation
Boiling point higher than components
Example: HCl + Water (20.2%)

Osmosis and Osmotic Pressure

Osmosis is the spontaneous flow of solvent molecules through a semipermeable membrane from a pure solvent to a solution or from a dilute to a concentrated solution.

Types of Osmosis

Exo-Osmosis
Outward flow of solvent
Cell placed in hypertonic solution
Cell shrinks
Endo-Osmosis
Inward flow of solvent
Cell placed in hypotonic solution
Cell swells
Reverse Osmosis
Applied pressure > osmotic pressure
Solvent flows from solution to pure solvent
Used in water purification

Types of Solutions Based on Osmotic Pressure

Type Osmotic Pressure Solvent Flow Example
Isotonic π1 = π2 No net flow 0.9% NaCl (physiological saline)
Hypertonic π1 > π2 Into solution 1 Concentrated salt solution
Hypotonic π1 < π2 Out of solution 1 Distilled water
Van't Hoff Equation for Osmotic Pressure: π = CRT = (n/V)RT

Abnormal Molecular Masses

When solutes dissociate or associate in solution, the observed colligative properties differ from expected values, leading to abnormal molecular masses.

Dissociation
Increases number of particles
Observed molecular mass < Normal molecular mass
Van't Hoff factor i > 1
Example: NaCl → Na⁺ + Cl⁻
Association
Decreases number of particles
Observed molecular mass > Normal molecular mass
Van't Hoff factor i < 1
Example: 2CH₃COOH ⇌ (CH₃COOH)₂

Van't Hoff Factor (i)

i = (Normal molecular mass) / (Observed molecular mass)
i = (Observed colligative property) / (Calculated colligative property)
i = (Number of particles after dissociation/association) / (Number of particles before dissociation/association)

Degree of Dissociation/Association

For dissociation: α = (i - 1) / (n - 1) where n = number of ions
For association: α = (i - 1) / (1/n - 1) where n = number of molecules associating

Modified Colligative Properties

  • Relative lowering of vapor pressure = iXB
  • Elevation in boiling point: ΔTb = iKbm
  • Depression in freezing point: ΔTf = iKfm
  • Osmotic pressure: π = iCRT

Important Points to Remember

Key Points for JEE Main

  • Molality is temperature independent, while molarity is temperature dependent
  • Osmotic pressure is the most sensitive colligative property for determining molecular mass
  • For electrolytes, colligative properties depend on the number of ions produced
  • Raoult's law is applicable only to ideal solutions and very dilute solutions
  • Azeotropes cannot be separated by simple distillation
  • Reverse osmosis is used in water purification and desalination
  • Van't Hoff factor i > 1 for dissociation, i < 1 for association

Do's

Practice concentration unit conversions
Understand the difference between molarity and molality
Learn to calculate Van't Hoff factor
Memorize Kb and Kf values for water

Don'ts

Don't confuse molarity with molality
Don't forget to account for dissociation/association
Don't apply Raoult's law to concentrated solutions
Don't neglect temperature effects on molarity

JEE Main Weightage

This chapter typically carries 2-3 questions in JEE Main, making it a high-weightage chapter. Questions often focus on concentration calculations, colligative properties, Raoult's law, and Van't Hoff factor.

Chapter Weightage in JEE Main

Weightage High (2-3 questions)