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NCERT Exemplar · Q20

Q.Although Zirconium belongs to 4d transition series and Hafnium to 5d transition series even then they show similar physical and chemical properties because ___________.

(i) both belong to d-block.
(ii) both have same number of electrons.
(iii) both have similar atomic radius.
(iv) both belong to the same group of the periodic table.
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The key idea is lanthanoid contraction — the steady decrease in atomic radius across the lanthanide series causes Zr and Hf to have nearly identical atomic radii, leading to their strikingly similar properties. The correct answer is (iii).

This is a classic question from the periodic properties chapter, and it tests a subtle but important consequence of the f-block elements. Let’s unpack why the answer isn’t the obvious one.

Why the obvious answers are wrong

You might think “both belong to d-block” or “both are in the same group” explains their similarity. After all, elements in the same group often behave alike. But that’s too vague — many d-block elements in the same group (like Cr and Mo, or Fe and Ru) show significant differences. So option (i) and (iv) are true but not the specific reason for the exceptional similarity between Zr and Hf.

Option (ii) — “both have same number of electrons” — is simply false. Zirconium (atomic number 40) has 40 electrons; Hafnium (atomic number 72) has 72. So that’s out.

The real reason is far more interesting.

The role of lanthanoid contraction

Here’s the chain of reasoning:

  1. Zirconium is in the 4d series (Period 5, Group 4). Hafnium is in the 5d series (Period 6, Group 4). Normally, moving down a group in the d-block increases atomic size because a new electron shell is added. For example, from Ti (Period 4) to Zr (Period 5), the atomic radius jumps from about 147 pm to 160 pm.

  2. But between Zr and Hf, something unusual happens. Hafnium comes after the lanthanide series (elements 57 to 71). The 14 lanthanide elements fill the 4f orbitals. As you move across the lanthanides, the nuclear charge increases by 14, but the 4f electrons are poor at shielding the outer electrons from this increased pull.

  3. This lanthanoid contraction — the steady decrease in atomic radius across the lanthanide series — means that by the time you reach Hf, its atomic radius has been “pulled in” so much that it is almost identical to Zr’s radius. Zr’s atomic radius is about 160 pm; Hf’s is about 159 pm. They differ by less than 1%.

r(Zr)≈160 pm,r(Hf)≈159 pmr(\text{Zr}) \approx 160\ \text{pm}, \quad r(\text{Hf}) \approx 159\ \text{pm} …

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