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Physical Chemistry

Atomic Structure — Bohr Model, Quantum Numbers & Orbitals

2 November 202617 pages
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Atomic structure moves from particles to waves. The numericals use a short list of formulas — E = hν, the Bohr energy and radius, the Rydberg equation, λ = h/mv and Δx·Δp ≥ h/4π — and the theory questions come down to quantum numbers and how electrons fill orbitals.

What you will be able to do

The big picture

From particles to waves.

In one line: Electrons are both particles and waves: Bohr’s fixed orbits explain the hydrogen spectrum, but only the quantum-mechanical model of orbitals and quantum numbers explains configurations and the periodic table.
Question typeFormula
Lightc = νλ; ν̄ = 1/λ; E = hν = hc/λ
Photoelectric effecthν = hν₀ + ½mv²
Bohr (H-like)rₙ = 52.9 n²/Z pm; Eₙ = −13.6 Z²/n² eV; vₙ = 2.18 × 10⁶ Z/n m s⁻¹
Spectral line1/λ = Rₕ Z² (1/n₁² − 1/n₂²); Rₕ = 109 677 cm⁻¹
Matter wavesλ = h/mv = h/p
UncertaintyΔx · Δp ≥ h/4π
Think of it like this: Think of an electron in an atom as a guitar string fixed at both ends. Only certain wavelengths fit — those are the allowed energy levels. Pluck it harder and it jumps to a higher “note”; when it falls back, it gives out light of exactly the energy difference. That is why each element has its own line spectrum, like a fingerprint.

Subatomic particles and early models

What the atom is made of.

ParticleCharge / CMass / kgDiscovered by
Electron−1.602 × 10⁻¹⁹9.109 × 10⁻³¹J. J. Thomson (cathode rays, e/m = 1.758820 × 10¹¹ C kg⁻¹)
Proton+1.602 × 10⁻¹⁹1.673 × 10⁻²⁷Goldstein (canal rays)
Neutron01.675 × 10⁻²⁷Chadwick (1932)

Electromagnetic radiation and quanta

Light as a wave and as a stream of photons.

c = ν λ ν̄ = 1/λ E = hν = hc/λ

c = 3.0 × 10⁸ m s⁻¹; h = 6.626 × 10⁻³⁴ J s

Photoelectric effect

hν = hν₀ + ½ m v²

hν₀ = work function (threshold energy); no electrons are emitted below ν₀, however intense the light

Solved example 01 — Photons in a beam

How many photons of wavelength 500 nm carry 1.0 J of energy?

  1. E per photon = hc/λ = (6.626 × 10⁻³⁴ × 3.0 × 10⁸) / (5.00 × 10⁻⁷) = 3.98 × 10⁻¹⁹ J.
  2. N = 1.0 / 3.98 × 10⁻¹⁹.

Answer: About 2.5 × 10¹⁸ photons.

Solved example 02 — Photoelectron energy

The threshold frequency of a metal is 7.0 × 10¹⁴ s⁻¹. Find the kinetic energy of electrons emitted by light of frequency 1.0 × 10¹⁵ s⁻¹.

  1. KE = h(ν − ν₀) = 6.626 × 10⁻³⁴ × (10.0 − 7.0) × 10¹⁴.

Answer: KE ≈ 1.99 × 10⁻¹⁹ J.

The Bohr model

Fixed orbits with quantised angular momentum.

rₙ = 52.9 n²/Z pm
Eₙ = −2.18 × 10⁻¹⁸ Z²/n² J = −13.6 Z²/n² eV
vₙ = 2.18 × 10⁶ Z/n m s⁻¹

Radius ∝ n²/Z; energy ∝ −Z²/n²; velocity ∝ Z/n

Key idea: Energy is negative because the electron is bound: zero energy means a free electron at infinity. Ionisation energy of H = +13.6 eV = 2.18 × 10⁻¹⁸ J per atom = 1312 kJ mol⁻¹. Kinetic energy = −E; potential energy = 2E.

Solved example 03 — Bohr radius and energy of He⁺

Find the radius and energy of the first orbit of He⁺.

  1. Z = 2, n = 1.
  2. r = 52.9 × 1²/2 = 26.45 pm.
  3. E = −13.6 × 2²/1² = −54.4 eV.

Answer: r = 26.45 pm; E = −54.4 eV.

Solved example 04 — Ionisation energy of Li²⁺

Find the energy needed to remove the electron from Li²⁺ in its ground state.

  1. Z = 3, n = 1: E₁ = −13.6 × 9 = −122.4 eV.
  2. Ionisation energy = 0 − E₁.

Answer: 122.4 eV per ion.

Limitations

The hydrogen spectrum

Each line is one jump between two levels.

ν̄ = 1/λ = Rₕ Z² (1/n₁² − 1/n₂²)

Rₕ = 109 677 cm⁻¹ (Rydberg constant); n₂ > n₁

Seriesn₁ (lower level)n₂Region
Lyman12, 3, 4…Ultraviolet
Balmer23, 4, 5…Visible
Paschen34, 5, 6…Infrared
Brackett45, 6…Infrared
Pfund56, 7…Infrared

Solved example 05 — The red Balmer line

Find the wavelength of the line for n = 3 → n = 2 in hydrogen.

  1. ν̄ = 109 677 × (1/4 − 1/9) = 109 677 × 5/36 = 15 233 cm⁻¹.
  2. λ = 1 / 15 233 cm = 6.565 × 10⁻⁵ cm.

Answer: λ ≈ 656.5 nm (red, the Hα line).

Solved example 06 — Counting lines

Electrons in a sample of hydrogen atoms are excited to n = 5. How many lines can appear in the emission spectrum, and how many are in the Balmer series?

  1. Total = 5 × 4 / 2 = 10.
  2. Balmer lines end on n = 2: from 5, 4 and 3 → 3 lines.

Answer: 10 lines; 3 in the Balmer series.

Solved example 07 — Same line from He⁺

Which transition in He⁺ has the same wavelength as the n = 2 → 1 transition in hydrogen?

  1. For H: Z² (1/1 − 1/4) = 3/4.
  2. For He⁺ (Z² = 4): 4 (1/n₁² − 1/n₂²) = 3/4 → 1/n₁² − 1/n₂² = 3/16.
  3. n₁ = 2, n₂ = 4 gives 1/4 − 1/16 = 3/16.

Answer: n = 4 → n = 2 in He⁺.

Check yourself

Answers at the end.

Dual nature and uncertainty

Electrons behave as waves too.

λ = h / mv = h / p

de Broglie relation; significant only for very small masses

Δx · Δp ≥ h / 4π (Δx · m Δv ≥ h / 4π)

Heisenberg’s uncertainty principle: position and momentum cannot both be known exactly

Solved example 08 — de Broglie wavelength

Compare the de Broglie wavelengths of (a) an electron moving at 1.0 × 10⁶ m s⁻¹ and (b) a 0.10 kg ball at 10 m s⁻¹.

  1. (a) λ = 6.626 × 10⁻³⁴ / (9.109 × 10⁻³¹ × 1.0 × 10⁶) = 7.27 × 10⁻¹⁰ m.
  2. (b) λ = 6.626 × 10⁻³⁴ / (0.10 × 10) = 6.6 × 10⁻³⁴ m.

Answer: (a) 727 pm — comparable to atomic sizes, so it matters. (b) 6.6 × 10⁻³⁴ m — undetectable.

Solved example 09 — Uncertainty in velocity

The position of an electron is known to within 0.1 nm. Find the minimum uncertainty in its velocity.

  1. Δv ≥ h / (4π m Δx) = 6.626 × 10⁻³⁴ / (4 × 3.142 × 9.109 × 10⁻³¹ × 1.0 × 10⁻¹⁰).
  2. = 6.626 × 10⁻³⁴ / 1.145 × 10⁻³⁹.

Answer: Δv ≥ 5.8 × 10⁵ m s⁻¹ — huge, so an exact orbit is meaningless.

Quantum numbers and orbitals

Four numbers describe each electron.

Quantum numberSymbolValuesDescribes
Principaln1, 2, 3…Shell: size and energy
Azimuthall0 to n − 1 (s, p, d, f = 0, 1, 2, 3)Subshell: shape; orbital angular momentum √[l(l+1)] h/2π
Magneticmₗ−l to +l (2l + 1 values)Orientation of the orbital
Spinmₛ+½, −½Spin of the electron
OrbitalnlRadial nodesAngular nodes
1s1000
2s2010
2p2101
3s3020
3p3111
3d3202
4f4303

Solved example 10 — Valid quantum numbers

Which set is not possible: (a) n = 3, l = 2, mₗ = −2; (b) n = 2, l = 2, mₗ = 0; (c) n = 4, l = 0, mₗ = 0?

  1. l must be less than n.
  2. (b) has l = n = 2.

Answer: (b) is impossible; (a) is a 3d orbital and (c) a 4s orbital.

Check yourself

Answers at the end.

Filling orbitals

Aufbau, Pauli and Hund.

Solved example 11 — Exchange energy

Why is 3d⁵ 4s¹ (Cr) more stable than 3d⁴ 4s²?

  1. In 3d⁵ all five electrons have parallel spins: the number of exchange pairs is 5 × 4 / 2 = 10.
  2. In 3d⁴ there are only 4 × 3 / 2 = 6 exchange pairs.
  3. More exchanges → more stabilisation; the half-filled set is also symmetrical.

Answer: 3d⁵ 4s¹ gains extra exchange energy and symmetry.

Advanced problems

Each needs two ideas from the chapter.

Solved example 12 — Energy to wavelength

How much energy is needed to excite an electron in hydrogen from n = 1 to n = 2, and what wavelength of light does this?

  1. ΔE = 2.18 × 10⁻¹⁸ (1 − 1/4) = 1.635 × 10⁻¹⁸ J.
  2. λ = hc/ΔE = (6.626 × 10⁻³⁴ × 3.0 × 10⁸) / 1.635 × 10⁻¹⁸.

Answer: ΔE = 1.64 × 10⁻¹⁸ J; λ ≈ 1.22 × 10⁻⁷ m = 122 nm (ultraviolet, first Lyman line).

Solved example 13 — Ratio of radii and energies

Find the ratio of (a) the radius of the third orbit of Li²⁺ to the first orbit of H, and (b) the energy of the second orbit of He⁺ to the first orbit of H.

  1. (a) r ∝ n²/Z: (9/3) / (1/1) = 3.
  2. (b) E ∝ Z²/n²: (4/4) / (1/1) = 1.

Answer: (a) 3 : 1. (b) 1 : 1 — the n = 2 level of He⁺ has the same energy as the n = 1 level of H.

Solved example 14 — Work function in electron-volts

The work function of sodium is 2.3 eV. Will light of wavelength 600 nm eject electrons? (1 eV = 1.602 × 10⁻¹⁹ J)

  1. Photon energy = hc/λ = (6.626 × 10⁻³⁴ × 3.0 × 10⁸) / (6.00 × 10⁻⁷) = 3.31 × 10⁻¹⁹ J.
  2. In eV: 3.31 × 10⁻¹⁹ / 1.602 × 10⁻¹⁹ = 2.07 eV.
  3. 2.07 eV < 2.3 eV.

Answer: No — 600 nm photons carry too little energy; no electrons are emitted, however bright the light.

Solved example 15 — Electrons with a given quantum number

How many electrons in an atom can have n = 4 and mₛ = −½? How many can have n = 3, l = 1?

  1. n = 4: 16 orbitals → 32 electrons, half with mₛ = −½.
  2. n = 3, l = 1: the 3p subshell, 3 orbitals.

Answer: 16 electrons; 6 electrons.

Exam trap gallery

Where marks are lost in this chapter.

#What students writeWhat is actually correctWhy
1Brighter light gives faster photoelectrons.Brighter light gives more electrons; their energy depends only on frequency.Each photon ejects one electron.
2Bohr’s model works for He.Only for one-electron species: H, He⁺, Li²⁺.Electron–electron repulsion is ignored.
3Energy levels get farther apart at higher n.They get closer together (E ∝ −1/n²).Lines crowd toward the series limit.
4Balmer series lies in the ultraviolet.Balmer is visible; Lyman is ultraviolet.n₁ = 2 for Balmer.
5The 2p orbital has one radial node.2p: 0 radial nodes, 1 angular node.Radial nodes = n − l − 1.
6l can equal n.l runs from 0 to n − 1.Hence no 1p or 2d orbital.
74s fills after 3d because 3 < 4.4s (n + l = 4) fills before 3d (n + l = 5).Use the (n + l) rule.
8Cu is [Ar] 3d⁹ 4s².Cu is [Ar] 3d¹⁰ 4s¹.A filled d subshell is extra stable.
9de Broglie waves matter for cricket balls too.λ is about 10⁻³⁴ m — undetectable.Only tiny masses show measurable λ.
10Number of lines from n = 4 to 1 is 3.Up to 6 lines in a sample (n(n − 1)/2).Every pair of levels gives one line.
11Ionisation energy of H is 13.6 J.13.6 eV per atom = 2.18 × 10⁻¹⁸ J = 1312 kJ mol⁻¹.Watch the units.
12Total energy and kinetic energy of an orbiting electron are equal.KE = −E and PE = 2E.Virial relation for a Coulomb orbit.
Memory hook: “Radius n²/Z, energy Z²/n², speed Z/n.” · “Lyman UV, Balmer visible, rest infrared.” · “Radial n − l − 1, angular l.” · “n + l small fills first.”

Practice MCQs

Levels: Easy, Moderate, Tough.

Q01. The charge on an electron was measured by: (Easy)

Q02. The neutron was discovered by: (Easy)

Q03. Radius of the first Bohr orbit of hydrogen: (Easy)

Q04. The Balmer series of hydrogen lies in the: (Easy)

Q05. Number of orbitals in the n = 3 shell: (Easy)

Q06. Shape of a p orbital: (Easy)

Q07. Which set of quantum numbers is not allowed? (Easy)

Q08. Energy of the electron in the second orbit of H: (Moderate)

Q09. Number of radial nodes in 3s: (Moderate)

Q10. Electronic configuration of Cr (Z = 24): (Moderate)

Q11. Wavelength of the Hα line (n = 3 → 2): (Moderate)

Q12. In the photoelectric effect, kinetic energy of electrons depends on: (Moderate)

Q13. Maximum number of lines when electrons fall from n = 6 to n = 1: (Moderate)

Q14. The orbital with n = 4, l = 2 is: (Moderate)

Q15. Which orbital fills first? (Moderate)

Q16. de Broglie wavelength is inversely proportional to: (Moderate)

Q17. Energy of the first orbit of He⁺: (Moderate)

Q18. Number of angular nodes in a 4f orbital: (Moderate)

Q19. Total number of electrons with l = 1 in phosphorus (Z = 15): (Tough)

Q20. Which transition in He⁺ gives the same wavelength as 2 → 1 in H? (Tough)

Q21. Ionisation energy of H is 13.6 eV. That of Li²⁺ is: (Tough)

Q22. Minimum uncertainty in velocity of an electron with Δx = 0.1 nm is about: (Tough)

Q23. Orbital angular momentum of a d electron is: (Tough)

Q24. Ratio of radii of the third orbit of Li²⁺ and the first orbit of H: (Tough)

Q25. Shortest wavelength in the Lyman series of H: (Tough)

Answer key with explanations

  1. (b) Millikan — Oil-drop experiment.
  2. (b) Chadwick — 1932.
  3. (a) 52.9 pm — r₁ = 52.9 pm.
  4. (b) visible region — n₁ = 2.
  5. (c) 9 — n².
  6. (b) dumbbell — Two lobes.
  7. (c) n=2, l=2, mₗ=0 — l < n.
  8. (b) −3.4 eV — −13.6/4.
  9. (c) 2 — n − l − 1 = 2.
  10. (b) [Ar] 3d⁵ 4s¹ — Half-filled d.
  11. (b) 656 nm — Red line.
  12. (b) frequency — KE = h(ν − ν₀).
  13. (c) 15 — 6 × 5/2.
  14. (c) 4d — l = 2 → d.
  15. (b) 4s — n + l = 4 vs 5.
  16. (b) momentum — λ = h/p.
  17. (c) −54.4 eV — Z² = 4.
  18. (c) 3 — l = 3.
  19. (b) 9 — 2p⁶ + 3p³.
  20. (a) 4 → 2 — Z²(1/n₁² − 1/n₂²) equal.
  21. (b) 122.4 eV — × Z² = 9.
  22. (a) 5.8 × 10⁵ m s⁻¹ — h/(4πmΔx).
  23. (b) √6 h/2π — √[l(l+1)] with l = 2.
  24. (b) 3 : 1 — n²/Z = 9/3.
  25. (a) 91.2 nm — Series limit: 1/λ = Rₕ.

Check-yourself answers

One-page revision

Read this page the night before the exam.

Particles and models

Light

Bohr

Spectrum

Waves and uncertainty

Quantum numbers

Written by Ram Govind Yadav · Chemistry Educator