Chapter 2: Structure of Atom
1. Dalton’s Atomic Theory & Limitations
Dalton proposed that matter consists of indivisible atoms. His theory
explained laws of chemical combination but failed to explain existence of
subatomic particles and isotopes.
2. Discovery of Subatomic Particles
ὒ Discovery of Electron – Cathode Ray Tube Experiment (J.J.
Thomson, 1897)
Setup: A discharge tube with two electrodes, evacuated at low pressure
(~10⁻⁴ atm), high voltage applied.
Observations:
1. Rays originated from cathode and moved towards anode → called cathode
rays. 2. Travel in straight lines and cast shadows. 3. Can rotate a paddle
wheel → show particles with mass. 4. Deflected by electric & magnetic fields
→ negatively charged.
Conclusion: Fundamental constituents of atoms, called electrons.
ὒ Discovery of Charge on Electron – Millikan’s Oil Drop Experiment
(1909)
Setup: Tiny oil drops sprayed between two charged plates. With X-rays, drops
became charged.
Observation: By balancing gravitational pull with electric force, Millikan
measured the smallest charge carried by a drop.
Result: Determined electronic charge:
e = 1.602 × 10⁻¹⁹ C
ὒ Discovery of Proton – Canal Ray Experiment (E. Goldstein, 1886)
Setup: Discharge tube with perforated cathode. Rays observed traveling
opposite to cathode rays.
Observations:
1. Rays were positively charged. 2. Heavier than electrons. 3. Nature
depended on gas used (H⁺ being lightest).
Conclusion: Existence of positively charged particles, called protons.
ὒ Discovery of Neutron (James Chadwick, 1932)
Setup: Bombarded thin beryllium sheet with α-particles → emitted neutral
radiation.
Observations: Neutral rays ejected protons from paraffin wax.
Conclusion: Rays consisted of uncharged particles with mass similar to
protons → neutrons.
ὒ Rutherford’s Gold Foil Experiment (1911)
Setup: Directed α-particles on thin gold foil, with fluorescent screen (ZnS)
detector.
Observations:
1. Most α-particles passed through → atom is mostly empty. 2. A few
deflected at small angles → positive charge concentrated. 3. Very few
bounced back → dense core exists.
Conclusion: Proposed nuclear model of atom → tiny, dense, positively charged
nucleus surrounded by electrons.
ὒ Photoelectric Effect (Einstein, 1905)
Setup: Light of sufficient frequency falls on a metal surface → electrons
emitted.
Observations:
1. No electrons emitted below threshold frequency (regardless of intensity). 2.
Above threshold, intensity ∝ number of electrons, frequency ∝ kinetic energy.
Equation:
hν = hν₀ + ½ mv²
Conclusion: Light shows particle nature (photons).
3. Thomson’s Model of Atom
Atom as a positively charged sphere with electrons embedded like seeds in
watermelon. Disproved later.
4. Rutherford’s Nuclear Model
Gold foil experiment (already described above). Observations: Most passed
undeflected, few deflected at large angles. Conclusion: Nucleus is small,
dense, and positively charged.
5. Bohr’s Atomic Model
Bohr postulated quantized orbits for electrons. Angular momentum quantized:
mvr = nh/2π
Energy difference between levels corresponds to radiation:
ΔE = hν
6. Hydrogen Spectrum
Spectral lines due to electron transitions. Series:
• Lyman (UV) • Balmer (Visible) • Paschen (IR) • Brackett (IR) • Pfund (IR)
Rydberg Formula:
1/λ = R (1/n₁² – 1/n₂²)
7. Dual Nature of Matter
De Broglie: λ = h/mv
Heisenberg Uncertainty: Δx·Δp ≥ h/4π
8. Quantum Mechanical Model
Developed by Schrödinger. Describes electrons as wave functions. Orbitals
are regions with high probability of finding electrons.
Quantum Numbers:
n → principal (size) l → azimuthal (shape) m → magnetic (orientation) s → spin
(±1/2)
9. Shapes of Orbitals
s → spherical p → dumbbell d → clover-leaf
10. Rules for Filling Orbitals
• Aufbau Principle: Fill lowest energy first. • Pauli Exclusion: No two electrons
can have same 4 quantum numbers. • Hund’s Rule: Maximum multiplicity.
n + l Rule Order:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p
< 7s < 5f < 6d < 7p
11. Electronic Configurations
Examples: H: 1s¹ O: 1s² 2s² 2p⁴ Na: 1s² 2s² 2p⁶ 3s¹
