Q.Why do Zr and Hf exhibit similar properties?
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Lanthanoid Contraction – From Intuition to Precision
Imagine you are walking across a row of the periodic table — from lanthanum (atomic number 57) to lutetium (71). Your first instinct might be: as we add more protons and more electrons, the atom should get bigger. But the opposite happens. The atoms actually shrink, steadily and stubbornly, across these 15 elements. That is the lanthanoid contraction.
Why? The answer lies in the 4f orbitals.
The core intuition: a bad shield
Every new electron you add across the lanthanoid series goes into a 4f orbital. These 4f orbitals are shaped like cloverleaves, but they are tucked deep inside the atom — very close to the nucleus. They are also notoriously poor at shielding the outer electrons from the pull of the nucleus.
Here is the key: each step adds one proton to the nucleus. That proton yanks harder on all the electrons. Normally, the new electron you add would partly cancel that pull (shielding). But 4f electrons are so diffuse and so poorly penetrating that they do a terrible job of shielding. So the net effect is that the effective nuclear charge felt by the outer electrons increases steadily across the series. The outer electrons get pulled inward, and the whole atom shrinks.
The 4f orbitals are "inside" the atom — they lie closer to the nucleus than the 5d and 6s orbitals. So adding electrons there does not push the outer shell outward; instead, the increasing nuclear charge dominates.
The precise statement
Lanthanoid contraction is the progressive and regular decrease in atomic and ionic radii of the lanthanoid elements (Ce to Lu) as atomic number increases. The contraction is about 1 pm per element, totalling roughly 15 pm from La to Lu.
This is not a small effect. It is so consistent that the radii of the later lanthanoids are almost identical to those of the 4d transition metals directly above them in the periodic table. For example, zirconium (Zr) and hafnium (Hf) have nearly the same atomic radius — a direct consequence of the lanthanoid contraction.
Atomic radius (pm)≈187−0.9×(Z−57)(rough linear fit for trivalent ions)
Why it matters
The lanthanoid contraction explains several important patterns in chemistry:
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Similarity of 4d and 5d transition metals: Elements like Zr and Hf, Nb and Ta, Mo and W are nearly identical in size and chemical behaviour. Without the lanthanoid contraction, the 5d metals would be much larger. This is why separating Hf from Zr is famously difficult — they are chemical twins.
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Trend in basicity: Across the lanthanoid series, the ionic radius decreases. This increases the charge density on the ion, making it more polarising. As a result, the basicity of the hydroxides decreases from La(OH)₃ (strong base) to Lu(OH)₃ (weak base). …
Elements in the same group normally grow larger going down, but the lanthanide contraction cancels this expected increase for hafnium. As a result zirconium and hafnium end up almost identical in size and therefore very similar in chemistry. …
The lanthanide contraction shrinks the atomic size of Hf so much that it becomes almost equal to that of Zr, making the pair chemically very similar (a 'lanthanide contraction pair').
Zirconium (Zr, atomic number 40) is in Period 5 and Hafnium (Hf, atomic number 72) is in Period 6, directly below it in Group 4. Normally, atomic/ionic radius increases going down a group.
However, between Zr and Hf lie the 14 lanthanoid elements, in which the 4f orbitals are progressively filled. Because 4f electrons have poor shielding of the nuclear charge, the effective nuclear charge felt by the outer electrons steadily increases across the lanthanoid series, causing a steady contraction in atomic/ionic size — this is the lanthanide contraction.
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- CBSE 2026Set ANNUAL1 markQ.Fill in the blank: Due to ............... Zirconium (Zr) and Hafnium (Hf) have identical radii.
›Reveal solutionSolution
Zirconium (period 5) and hafnium (period 6) have almost identical atomic/ionic radii because of lanthanide contraction, which offsets the expected increase in size on descending a group.
Normally, atomic/ionic radius increases on going down a group as a new shell is added. But between Zr (Z=40) and Hf (Z=72), the 4f orbitals are filled across the lanthanides (Z=58–71). The 4f electrons shield the nuclear charge poorly, so the effective nuclear charge felt by the outer electrons increases steadily across the lanthanide series, causing a steady contraction in atomic/ionic size — the lanthanide contraction.
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- CBSE 2026Set ANNUAL1 markMCQQ.The reason of lanthanoid contraction is(a) negligible screening effect of f-orbital(b) increasing nuclear charge(c) decreasing nuclear charge(d) decreasing screening effect
›Reveal solutionSolution
The lanthanoid contraction is caused by the poor ability of the diffuse, deeply-buried 4f orbitals to shield one another from the increasing nuclear charge, so effective nuclear charge rises steadily and atomic/ionic radii shrink across the series.
Mechanism: Going from Ce to Lu, the atomic number (and hence nuclear charge Z) increases by one unit at each step as an electron is added to the inner 4f subshell. The 4f orbitals are radially compact and have poor overlap/penetration properties, so one 4f electron shields another 4f electron (or the outer 5d16s2 electrons) from the nucleus very inefficiently — far less efficiently than, say, s or p electrons shield each other. Because this poor screening does not keep pace with the steadily rising nuclear charge, the effective nuclear charge (Zeff=Z−S) experienced by the outer electrons increases continuously across the series, pulling the electron cloud in and steadily shrinking the atomic and ionic radii. The cumulative shrinkage across all 14 lanthanoids is the lanthanoid contraction, and it is large enough that the third-row transition elements following the lanthanoids (e.g. Zr and Hf, Nb and Ta) end up with almost identical atomic radii to their second-row counterparts.
Why the other options are wrong/incomplete: …
- CBSE 2024Set ANNUAL1 markMCQQ.Lanthanoid contraction is due to increase in(a) atomic number(b) effective nuclear charge(c) atomic radius(d) valence electrons
›Reveal solutionSolution
Lanthanoid contraction is the steady decrease in atomic/ionic radii across the lanthanoid series, caused by an increase in effective nuclear charge that is imperfectly screened by the diffuse 4f electrons.
Across the lanthanoid series (Ce to Lu), each successive element adds one proton to the nucleus and one electron to the inner 4f subshell. The 4f orbitals have poor shielding ability (diffuse, non-directional shapes), so they do not effectively screen the outer electrons from the increasing nuclear charge.
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- CBSE 2023Set ANNUAL1 markMCQQ.Which of the following pair of ions have same size due to lanthanoid contraction?(a) Fe2+, Ni2+(b) Zr4+, Ti4+(c) Zr4+, Hf4+(d) Zn2+, Hf4+
›Reveal solutionSolution
Zr4+ (4d series) and Hf4+ (5d series) end up nearly identical in size because lanthanoid contraction cancels out the size increase normally expected on adding a new shell.
Going down a group, ionic radius normally increases as a new principal shell is added. But between the 4d series (e.g. Zr, Z = 40) and the 5d series (e.g. Hf, Z = 72), the 14 lanthanoid elements (57-71) intervene, each adding a poorly-shielding 4f electron. The resulting steady contraction in radius across the lanthanoids ('lanthanoid contraction') almost exactly cancels the expected size increase from Zr to Hf. The net result is that Zr4+ and Hf4+ have almost identical ionic radii (~72 pm) …
- CBSE 2022Set ANNUAL1 markQ.What is lanthanoid contraction?
›Reveal solutionSolution
Across the lanthanoid series, each added electron goes into the deeply buried, diffuse 4f subshell, which shields the increasing nuclear charge poorly — so the effective nuclear charge felt by outer electrons rises steadily, causing atomic/ionic size to shrink steadily from La to Lu.
Definition
Lanthanoid contraction refers to the steady and cumulative decrease in the atomic and ionic (especially Ln3+) radii of the lanthanoid elements as one moves from lanthanum (Z=57) to lutetium (Z=71) across the 4f series.
Cause
As atomic number increases across the lanthanoids, each successive electron is added to an inner 4f orbital. The 4f orbitals are radially very diffuse and penetrate poorly, so electrons within the same 4f subshell shield each other from the nuclear charge very inefficiently (poor mutual shielding). Consequently, as protons are added to the nucleus, the effective nuclear charge (Zeff) experienced by the outer (5s, 5p, 6s) electrons increases steadily across the series (since the extra positive charge is not being cancelled out by the added, poorly-shielding 4f electron). This progressively stronger pull draws the outer electron cloud inward, so the atomic/ionic radius contracts steadily with each additional element.
Consequences
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- CBSE 2021Set A1 markMCQQ.In which of the following elements 4f energy level is gradually filled?(a) Lanthanides(b) Actinides(c) Transition metals(d) Coinage metals
›Reveal solutionSolution
The 4f orbitals fill across the lanthanides (Ce → Lu).
The lanthanides (the first inner-transition series, elements 58 Ce to 71 Lu) are characterised by the gradual filling of the 4f energy level.
- Actinides fill the 5f orbitals. …
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