1. Dalton's Atomic Theory

John Dalton (1808) proposed the first scientific atomic theory with the following postulates:

  • Matter is made of tiny, indivisible particles called atoms.
  • Atoms of the same element are identical in mass, size, and properties.
  • Atoms of different elements have different masses and properties.
  • Atoms combine in simple whole-number ratios to form compounds.
  • Atoms can neither be created nor destroyed in a chemical reaction (conservation of mass).

Laws Explained by Dalton's Theory

Law Statement Example
Law of Conservation of Mass Mass of reactants = Mass of products in a chemical reaction 2H2+O22H2O — mass balanced
Law of Definite Proportions A compound always contains elements in a fixed mass ratio Water is always 1:8 by mass (H:O)
Law of Multiple Proportions When two elements form more than one compound, masses of one element that combine with a fixed mass of the other are in simple ratios CO and CO₂: O combining with fixed C is in ratio 1:2
Gay-Lussac's Law of Gaseous Volumes Gases combine in simple whole-number ratios by volume (at same T and P) H2:O2:H2O=2:1:2 by volume
Avogadro's Law Equal volumes of all gases at same T and P contain equal number of molecules 1 L of H₂ and 1 L of O₂ have same number of molecules

Limitations of Dalton's Theory

  • Atoms are not indivisible — they contain subatomic particles (protons, neutrons, electrons).
  • Atoms of the same element can have different masses — isotopes (e.g., 12C and 14C).
  • Does not explain the nature of chemical bonding.
  • Does not account for the existence of allotropes (e.g., diamond and graphite are both carbon).

2. Atoms and Molecules — Key Definitions

Term Definition Example
Atom Smallest particle of an element that retains its chemical identity C, Na, Fe
Molecule Smallest particle of a substance (element or compound) that can exist independently O2, H2O, CO2
Element Pure substance made of only one type of atom Gold, Oxygen, Carbon
Compound Pure substance made of two or more elements in fixed ratio Water (H2O), Salt (NaCl)
Mixture Combination of two or more substances not chemically combined Air, seawater, alloys
Ion Charged particle formed by gain or loss of electrons from an atom/molecule Na+, Cl, SO42

Atomic and Molecular Mass

Atomic masses are measured on the unified atomic mass unit (u) or Dalton (Da), defined as exactly 112 of the mass of one 12C atom:

1 u=1.66054×1027 kg

  • Atomic mass of an element = average mass of naturally occurring isotopes, weighted by their abundance.
  • Molecular mass = sum of atomic masses of all atoms in a molecule.
  • Formula mass = sum of atomic masses of all atoms in the formula unit (used for ionic compounds, e.g., NaCl).

Important Atomic Masses to Memorise

Element Symbol Atomic Mass (u) Element Symbol Atomic Mass (u)
Hydrogen H 1 Sodium Na 23
Carbon C 12 Magnesium Mg 24
Nitrogen N 14 Aluminium Al 27
Oxygen O 16 Sulphur S 32
Fluorine F 19 Chlorine Cl 35.5
Phosphorus P 31 Calcium Ca 40
Iron Fe 56 Copper Cu 63.5

3. The Mole — Definition and Avogadro's Number

The mole (mol) is the SI unit of amount of substance. One mole of any substance contains exactly:

NA=6.022×1023 entities (atoms, molecules, ions, electrons, etc.)

This number is called Avogadro's number (NA). The mole is defined such that one mole of 12C has a mass of exactly 12 grams.

Key Mole Relations

Quantity Formula Units
Number of moles n=mM m = mass (g), M = molar mass (g/mol)
Number of particles N=n×NA NA=6.022×1023 mol1
Volume at STP (gas) V=n×22.4 L At STP (0°C, 1 atm) — old definition
Volume at STP (gas) V=n×22.7 L At new STP (0°C, 1 bar) — IUPAC 1982
Molar mass of gas M=d×22.4 (at old STP) d = density in g/L at STP

Note for JEE/NEET: Most problems use the old STP (0°C, 1 atm) with molar volume = 22.4 L/mol. If the problem specifies 25°C and 1 atm (SATP), use 24.5 L/mol. Always check the conditions given.

4. Molar Mass and Percentage Composition

The molar mass (molecular weight) of a substance is the mass of one mole of that substance, numerically equal to its molecular/formula mass in grams.

Calculating Molar Mass

Example: Molar mass of H2SO4:
=2(1)+32+4(16)=2+32+64=98 g/mol.

Percentage Composition

The percentage by mass of each element in a compound:

% of element=Mass of element in 1 mol of compoundMolar mass of compound×100

Example: % of H in H2SO4:
=2×198×100=298×1002.04%

5. Empirical and Molecular Formula

The empirical formula gives the simplest whole-number ratio of atoms of each element in a compound. The molecular formula gives the actual number of atoms of each element in one molecule.

Molecular formula =n× Empirical formula     where     n=Molecular massEmpirical formula mass

Steps to Determine Empirical Formula from % Composition

  • Step 1: Write down the percentage of each element (treat as grams if 100 g sample assumed).
  • Step 2: Divide each mass by the atomic mass of that element → gives mole ratio.
  • Step 3: Divide all mole values by the smallest value → gives simplest ratio.
  • Step 4: If ratios are not whole numbers, multiply by the appropriate integer (2, 3, etc.) to make them whole.
  • Step 5: Write the empirical formula using these whole-number ratios.
  • Step 6: Use given molecular mass to find n and hence the molecular formula.

Worked Example

A compound contains C: 40%, H: 6.67%, O: 53.33%. Molecular mass = 180 g/mol. Find the molecular formula.

Mole ratios: C =40/12=3.33; H =6.67/1=6.67; O =53.33/16=3.33.
Divide by smallest (3.33): C:H:O =1:2:1.
Empirical formula: CH2O; empirical mass =12+2+16=30.
n=180/30=6.
Molecular formula: C6H12O6 (glucose).

Compound Empirical Formula Molecular Formula n
Glucose CH2O C6H12O6 6
Benzene CH C6H6 6
Water H2O H2O 1
Hydrogen peroxide HO H2O2 2
Ethylene CH2 C2H4 2

6. Mole–Mass–Number Triangle

The three most common interconversions in mole concept problems:

  • Mass ↔ Moles: n=mM or m=n×M
  • Moles ↔ Number of particles: N=n×NA or n=NNA
  • Moles ↔ Volume (gas at STP): V=n×22.4 or n=V22.4

Number of Atoms in a Molecule

Total atoms in n moles of XaYb:

Atoms of X =n×a×NA
Atoms of Y =n×b×NA
Total atoms =n×(a+b)×NA

Example: Number of H atoms in 18 g of water (H2O):
Moles of H2O=18/18=1 mol.
Each H2O has 2 H atoms.
H atoms =1×2×6.022×1023=1.204×1024.

Important Mole Values to Remember

Substance Mass of 1 mol Particles in 1 mol Volume at STP
Water (H2O) 18 g 6.022×1023 molecules
Oxygen (O2) 32 g 6.022×1023 molecules 22.4 L
Carbon (C) 12 g 6.022×1023 atoms
NaCl 58.5 g 6.022×1023 formula units
Electron (e) 0.55 mg 6.022×1023 electrons

7. Vapour Density and Molar Mass

Vapour density (VD) is the ratio of the mass of a given volume of a gas to the mass of the same volume of hydrogen at the same temperature and pressure:

Vapour Density=Mass of V litres of gasMass of V litres of H2

The relation between vapour density and molar mass:

M=2×VD

This is because molar mass of H2=2 g/mol, so VD is defined relative to hydrogen.

Example: VD of CO2=22. Molar mass =2×22=44 g/mol ✓

8. Equivalent Concept (Normality)

The equivalent weight (gram equivalent) is the weight of a substance that reacts with or displaces 1 g of hydrogen (or 8 g of oxygen, or 35.5 g of chlorine).

Equivalent weight=Molar massn-factor

where the n-factor is:

  • For acids: number of H+ ions furnished per molecule (basicity).
  • For bases: number of OH ions furnished per molecule (acidity).
  • For salts: total charge on cation (or anion) per formula unit.
  • For oxidising/reducing agents: change in oxidation state per molecule.
Substance Molar Mass (g/mol) n-factor Equivalent Weight (g/eq)
HCl 36.5 1 36.5
H2SO4 98 2 49
NaOH 40 1 40
Ca(OH)2 74 2 37
KMnO4 (acidic) 158 5 31.6
K2Cr2O7 294 6 49

Normality (N): N=Number of equivalentsVolume in litres=Molarity×n-factor

Law of Equivalents: At equivalence point in a reaction: N1V1=N2V2