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Exercise · Q27

Q.What is the cause of lanthanoid contraction, and how does the ionic radius of Lu3+\text{Lu}^{3+} compare with that of La3+\text{La}^{3+}?

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As one moves across the lanthanoid series from lanthanum to lutetium, one additional proton is added to the nucleus at each step, and (for most members) one additional electron is added to the 4f subshell. The 4f orbitals are unusually diffuse and radially poorly defined, so a 4f electron shields another electron in the same 4f subshell only weakly -- this is the poor 4f-4f shielding that is the root cause of the whole phenomenon.

Because each new 4f electron fails to fully compensate for the added proton, the effective nuclear charge felt by the atom's outer electrons (6s26s^2, and the 5d5d/5p5p/5s5s core beneath them) rises steadily at every step across the series. This rising effective nuclear charge pulls the outer electron cloud in a little more tightly at each element, so both the atomic radius and the ionic radius of Ln3+\text{Ln}^{3+} decrease steadily -- essentially without reversal -- from La to Lu. …

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