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Exercises · 3.4

Q.On the basis of quantum numbers, justify that the sixth period of the periodic table should have 32 elements.

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The sixth period corresponds to n=6n=6 and fills the 6s6s, 4f4f, 5d5d, and 6p6p subshells. The total number of orbitals in these subshells is 1+7+5+3=161 + 7 + 5 + 3 = 16, and since each orbital holds 2 electrons, the period accommodates 16×2=3216 \times 2 = 32 elements.

Why the Aufbau Principle decides period length

The periodic table is built by filling atomic orbitals in order of increasing energy — the Aufbau Principle. Each period begins when a new principal quantum number nn starts to fill, and ends when all orbitals of that nn (and any lower-nn orbitals that lie within its energy range) are completely filled.

The sixth period is special because it includes the 4f4f subshell. Although n=4n=4 is lower than n=6n=6, the 4f4f orbitals have an energy that falls between the 6s6s and 5d5d orbitals. So when we reach n=6n=6, the filling order is:

6s→4f→5d→6p6s \rightarrow 4f \rightarrow 5d \rightarrow 6p

This is not arbitrary — it follows directly from the (n+ℓ)(n+\ell) rule: for 6s6s, n+ℓ=6+0=6n+\ell = 6+0 = 6; for 4f4f, n+ℓ=4+3=7n+\ell = 4+3 = 7; for 5d5d, n+ℓ=5+2=7n+\ell = 5+2 = 7; for 6p6p, n+ℓ=6+1=7n+\ell = 6+1 = 7. Among orbitals with the same (n+ℓ)(n+\ell), the one with lower nn fills first — hence 4f4f before 5d5d before 6p6p.

Watch out

A common mistake is to think the sixth period only fills n=6n=6 orbitals. In fact, it also fills the 4f4f subshell (14 elements, the lanthanides), which belong to n=4n=4 but are placed in the sixth period because of their energy.

Step-by-step count of orbitals and elements

  1. The 6s6s subshell has ℓ=0\ell = 0, so only one orbital (mℓ=0m_\ell = 0). It holds 2 electrons → 2 elements (Cs, Ba).

  2. The 4f4f subshell has ℓ=3\ell = 3, giving 2ℓ+1=72\ell+1 = 7 orbitals (mℓ=−3,−2,−1,0,+1,+2,+3m_\ell = -3, -2, -1, 0, +1, +2, +3). Each orbital holds 2 electrons → 14 elements (the lanthanides, La through Lu or Ce through Lu depending on convention).

  3. The 5d5d subshell has ℓ=2\ell = 2, giving 2ℓ+1=52\ell+1 = 5 orbitals. Each holds 2 electrons → 10 elements (transition metals like Hf through Hg).

  4. The 6p6p subshell has ℓ=1\ell = 1, giving 2ℓ+1=32\ell+1 = 3 orbitals. Each holds 2 electrons → 6 elements (Tl through Rn).

Tip

You can remember the orbital count for any subshell: ss has 1 orbital, pp has 3, dd has 5, ff has 7. The pattern is simply 2ℓ+12\ell+1. …

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