Class 11.

Chapter: Structure of the atom

1. Planck’s Quantum Theory

 Energy is emitted or absorbed in discrete packets called quanta (singular:

quantum).
 The energy of each quantum is directly proportional to its frequency:
E = hν,
where E = energy, ν = frequency, h = Planck’s constant (6.626 × 10⁻³⁴ Js).
 Matter can emit or absorb energy only in whole number multiples of hν.
 This theory explained the black body radiation spectrum and introduced the
concept of quantization of energy.

2. Photoelectric Effect

 Discovered by Heinrich Hertz, explained by Albert Einstein using Planck’s

Quantum Theory.
 When light of sufficient frequency falls on a metal surface, it emits electrons.
 The emitted electrons are called photoelectrons.
 Key points:
o Threshold frequency (ν₀): Minimum frequency needed to eject electrons.
o No electrons are emitted if ν < ν₀, irrespective of light intensity.
o Kinetic energy of electrons increases with frequency, not intensity.
o Einstein’s equation:
K.E. = hν – φ,
where φ = work function of the metal.

3. Black Body Radiation

 A black body is an ideal object that absorbs all radiation falling on it.
 When heated, it emits radiation called black body radiation.
 Classical theory failed to explain the intensity distribution (UV catastrophe).
 Planck’s Quantum Theory successfully explained the observed spectrum.
 Intensity vs. wavelength graph shows a peak that shifts with temperature.

4. Absorption and Emission Spectra

 Emission Spectrum: Formed when atoms release energy (excited to ground

state).
o Discrete lines represent specific wavelengths emitted.
o Each element has a unique emission spectrum (like a fingerprint).
 Absorption Spectrum: Formed when atoms absorb energy (ground to excited
state).
o Dark lines on a continuous spectrum at specific wavelengths.
o These lines correspond to wavelengths absorbed by the substance.
⚛️Bohr’s Atomic Model (1913)
Niels Bohr modified Rutherford’s atomic model to explain the stability of atoms and the line spectrum of
hydrogen.

Postulates of Bohr's Model

1. Electrons revolve in fixed orbits (energy levels):

Electrons move around the nucleus in circular paths called orbits or shells (designated as K, L, M,
etc.) without radiating energy.
2. Quantization of angular momentum:
Only those orbits are allowed in which the angular momentum of the electron is an integral multiple of
h/2π, i.e.,

mvr = nh /2π

 m = mass of electron
 v = velocity of electron
 r = radius of orbit
 n = orbit number (1, 2, 3...)
 h = Planck’s constant

3. Energy emission or absorption:

Electrons absorb or emit energy only when they jump from one orbit to
another:
o Jump to a higher level: absorb energy
o Jump to a lower level: release energy
The energy difference is given by:

∆E = E2 - E1 = hv(nu)

4. Energy of an orbit is fixed:

The energy of an electron in a particular orbit is constant and negative,
indicating a bound system.
5. Radius of nth orbital

. rn =n2h2/4π2me2Z

rn =52.9n2/Z

6. Energy of nth orbital

En= -Rh(1/n2)

Successes of Bohr’s Model

 Explained the stability of atoms.

 Successfully explained the hydrogen spectrum and one-electron systems like
He⁺, Li²⁺.
 Introduced the idea of quantized energy levels.
Limitations of Bohr’s Model

1. Only valid for hydrogen-like atoms:

Couldn’t explain the spectra of multi-electron atoms.
2. No explanation for fine structure:
Could not explain the splitting of spectral lines in high-resolution spectra.
3. Zeeman and Stark effects:
Failed to explain the effect of magnetic field (Zeeman effect) and electric field (Stark effect) on
spectral lines.
4. No wave-particle duality:
Didn’t consider the wave nature of electrons (as later proposed by de Broglie).
5. Contradicts Heisenberg Uncertainty Principle:
Bohr’s idea of definite electron orbits violates the uncertainty principle.

Quantum Mechanical Model of the Atom

Developed mainly by Erwin Schrödinger (1926), this model is based on quantum theory and wave
mechanics.

Main Features

1. Electron as a wave:
Electrons exhibit wave-like properties (as per de Broglie), and their behaviour is described by a wave
function (Ψ).
2. Schrödinger’s Equation:
Describes how the wave function of a quantum system evolves:

. Hψ=Eψ

 Ψ = wave function
 E = energy of the system
 Ĥ = Hamiltonian operator (total energy operator)

3. Probability of finding an electron:

The square of the wave function, , gives the probability density of finding an electron in a particular
region in space.
4. No definite path:
Unlike Bohr’s model, electrons do not move in definite circular orbits. Their position and momentum
cannot be known simultaneously (Heisenberg Uncertainty Principle).
5. Atomic Orbitals:
The space around the nucleus where the probability of finding an electron is high is called an orbital (s,
p, d, f types).
6. Quantum Numbers:
Describe the size, shape, orientation, and spin of orbitals:
o n (Principal Quantum Number): energy level
o l (Azimuthal Quantum Number): shape of orbital
o m (Magnetic Quantum Number): orientation
o s (Spin Quantum Number): spin of electron (+½ or –½)
Comparison of Bohr Model and Quantum Mechanical Model
Feature Bohr Model Quantum Mechanical Model
Electron Definite circular orbit No definite path, only probability
path
Basis Classical + quantum Purely quantum theory
theory
Applicable Hydrogen-like atoms All atoms
to
Considers Particle nature of Wave-particle duality
electron
Explains Line spectrum of Line spectrum of multi-electron
hydrogen atoms

🌈 1. Line Spectrum of Hydrogen Atom

Definition:

The spectrum of light emitted by hydrogen when electrons transition between energy levels is called line
emission spectrum.

It consists of discrete lines due to quantized energy levels in atoms.

Hydrogen Spectrum Series:

Series Transition (n₂ → n₁) Region

Lyman n₂ → 1 Ultraviolet
Balmer n₂ → 2 Visible
Paschen n₂ → 3 Infrared
Brackett n₂ → 4 Infrared
Pfund. n₂ → 5. Infrared
Formula for wave number (ν̄):

R= Rydberg constant = 1.097×10-7 m-1

n2 > n1

⚖️3. Dual Behaviour of Matter (Wave-Particle Duality)

Proposed by de Broglie.

Matter like electrons exhibits both particle and wave nature.

Important Concept:

Macroscopic objects have negligible wave properties.

Microscopic particles (like electrons) show significant wave behaviour.

📏 4. De Broglie’s Relationship

λ =h/mv. =h/p

Where

Λ = 3.2 Å. = wavelength (m),

h = Planck’s constant ,

m= mass of the particle,

V = velocity of the particle.

 It shows that a moving particle has an associated wavelength.

🔍 5. Heisenberg’s Uncertainty Principle

Statement:

It is impossible to simultaneously determine the exact position and momentum of a particle.

Formula:

Δx Δp ≥ h/4π

Δ x Δ (mv) ≥ h /4 π ,

Δ x Δ v ≥ h /4 π m

Where:

Δ x = uncertainty in position,

Δp = uncertainty in momentum,

h= Planck’s constant. =6.626 ×10-34 js

🌀 6. Difference Between Orbit and Orbital

🔢 7. Quantum Numbers

Quantum numbers describe the location and properties of electrons.

a) Principal Quantum Number (n)

 Principal quantum numbers are denoted by the symbol ‘n’. They designate the
principal electron shell of the atom
 The value of the principal quantum number can be any integer with a positive value that is
equal to or greater than one. The value n=1 denotes the innermost electron shell of an atom.
 principal quantum number, n, cannot have a negative value or be equal to zero because it is
not possible for an atom to have a negative value or no value for a principal shell.
 Formula: Maximum electrons = 2n2
 Indicates: Size and energy of orbital
 b) Azimuthal Quantum Number (l)
 The azimuthal (or orbital angular momentum) quantum number describes the shape of a given
orbital. It is denoted by the symbol ‘l’ and its value is equal to the total number of angular
nodes in the orbital.

 value of the azimuthal quantum number can indicate either an s, p, d, or f subshell which vary
in shape
 the value of the azimuthal quantum number ranges between 0 and (n-1).
 For example , if n =3, then l= 0,1, and 2
 Orbitals:

l=0: s-orbital (spherical)

l=1: p-orbital (dumbbell)

l=2: d-orbital (cloverleaf)

l=3: f-orbital (complex)

Max electrons in a subshell = 2(2l+1)

c) Magnetic Quantum Number (m or )

 The total number of orbitals in a subshell and the orientation of these orbitals are determined
by the magnetic quantum number.
 It is denoted by the symbol ‘ml’.
 The value of the magnetic quantum number is dependent on the value of the azimuthal .
 the value of ml ranges between the interval -l to +l. Therefore, it indirectly depends on the
value of n.
 Number of orbitals in a subshell = (2l+1)

d) Spin Quantum Number (s or )

 The electron spin quantum number is independent of the values of n, l, and m l.

 The value of ms offers insight into the direction in which the electron is spinning.
 The possible values of the electron spin quantum number are +½ and -½.
 The positive value of ms implies an upward spin on the electron which is also called ‘spin up’
and is denoted by the symbol ↑. If ms has a negative value, the electron in question is said to
have a downward spin, or a ‘spin down’, which is given by the symbol ↓

✅ Summary of All Quantum Numbers:

📘 1. Shapes of Atomic Orbitals

📌 Orbitals are regions around the nucleus where the probability of finding an electron is maximum.

🔹 s-orbital

Shape: Spherical. , Symmetrical around the nucleus.

Number of orientations: 1

Present in every shell (1s, 2s, 3s, etc.)

🔹 p-orbital

Shape: Dumbbell. , Three orientations: pₓ, pᵧ, p𝓏 along x, y, z axes.

Present from n = 2 onwards (2p, 3p, etc.)

🔹 d-orbital

Shape: Clover leaf (except d𝓏² which is a dumbbell with a donut).

Five orientations: dₓᵧ, dᵧ𝓏, d𝓏ₓ, dₓ²–ᵧ², d𝓏²

Present from n = 3 onwards (3d, 4d, etc.)

📘 2. Energies of Atomic Orbitals

📌 In hydrogen atom:

Orbitals with same principal quantum number (n) have equal energy (degenerate)

📌 In multi-electron atoms:

 Orbitals of same shell have different energies.

 Energy depends on n + l rule (Aufbau principle):
  Lower the value of (n + l), lower the energy.
 If (n + l) is same, orbital with lower n has lower energy.

🔹 Order of increasing energy:

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s …

✅ Key point: 4s is filled before 3d due to lower (n + l).

📘 3. Filling of Electrons in Orbitals (Electronic Configuration Rules)

✅ Rules for filling:

(i) Aufbau Principle

Electrons fill orbitals in the order of increasing energy (lowest first). Use the diagonal rule:

1s → 2s → 2p → 3s →3p → 4s→ 3d → 4p → 5s …

(ii) Pauli's Exclusion Principle

No two electrons in an atom can have the same set of all four quantum numbers.

An orbital can hold maximum 2 electrons with opposite spins.

(iii) Hund's Rule of Maximum Multiplicity

In orbitals of equal energy (degenerate), electrons fill singly first before pairing.

All unpaired electrons have parallel spins.

✍️Example:

📘 4. Electronic Configuration

📌 Notation:
Written as shell with orbital and superscript for number of electrons.

Example: Oxygen (Z = 8) → 1s² 2s² 2p⁴

✅ Electronic configurations of first 20 elements:

Element Z Configuration

H 1 1s¹

He 2 1s²

Li 3 1s² 2s¹

Be 4 1s² 2s²

B 5 1s² 2s² 2p¹

C 6 1s² 2s² 2p²

N 7 1s² 2s² 2p³

O 8 1s² 2s² 2p⁴

F 9 1s² 2s² 2p⁵

Ne 10 1s² 2s² 2p⁶

Na 11 1s² 2s² 2p⁶ 3s¹

Mg 12 1s² 2s² 2p⁶ 3s²

Al 13 1s² 2s² 2p⁶ 3s² 3p¹

Si 14 1s² 2s² 2p⁶ 3s² 3p²

P 15 1s² 2s² 2p⁶ 3s² 3p³

S 16 1s² 2s² 2p⁶ 3s² 3p⁴

Cl 17 1s² 2s² 2p⁶ 3s² 3p⁵

Ar 18 1s² 2s² 2p⁶ 3s² 3p⁶

K 19 1s² 2s² 2p⁶ 3s² 3p⁶ 4s¹

Ca 20 1s² 2s² 2p⁶ 3s² 3p⁶ 4s²

📘 5. Stability of Completely Filled and Half-Filled Orbitals

✅ Why are these configurations stable?

Due to:

1. Symmetrical distribution of electrons.

2. Exchange energy: When orbitals have unpaired electrons with parallel spins, they can exchange positions →
adds extra stability.

✍️Example:

 Chromium (Z = 24)

Expected: [Ar] 3d⁴ 4s²

Actual: [Ar] 3d⁵ 4s¹

👉 3d⁵ is half-filled, so more stable.

 Copper (Z = 29)

Expected: [Ar] 3d⁹ 4s²

Actual: [Ar] 3d¹⁰ 4s¹

👉 3d¹⁰ is fully filled, so more stable.

✅ Summary Table:

Configuration Type Reason for Stability

Half-filled (p³, d⁵) Exchange energy, symmetry

Fully filled (p⁶, d¹⁰) Maximum symmetry, low energy