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Exercise · Q26

Q.Lanthanoids predominantly show the +3+3 oxidation state, but Ce4+\text{Ce}^{4+}, Eu2+\text{Eu}^{2+} and Yb2+\text{Yb}^{2+} are also known. Explain, in terms of 4f-subshell occupancy, why these particular exceptions are comparatively stable.

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The dominant +3+3 oxidation state of the lanthanoids arises from loss of the outer 6s26s^2 electrons together with the single 5d5d electron (or one 4f4f electron, for most members). The three exceptions cited here each arise because losing a different number of electrons happens, in each specific case, to reach or preserve an unusually stable 4f configuration -- exactly the same general principle (extra stability of an empty, half-filled or completely filled subshell) already used in this chapter to explain the Cr/Cu 3d anomalies and cerium's own 4f/5d ground-state configuration.

Cerium (Ce4+\text{Ce}^{4+}). Cerium's ground state is [Xe]4f15d16s2[\text{Xe}]4f^15d^16s^2. Removing all four of these outer electrons (rather than stopping at three, as for a typical Ln3+\text{Ln}^{3+}) empties the 4f subshell entirely, giving Ce4+=[Xe]\text{Ce}^{4+} = [\text{Xe}], a stable, noble-gas-configured 4f04f^0 ion. Because reaching this empty-subshell configuration is energetically favourable, cerium readily forms the +4+4 state in addition to the usual +3+3, and Ce4+\text{Ce}^{4+} is in fact a useful, moderately strong oxidizing agent in analytical chemistry (cerimetry) precisely because it is "driven" to be reduced back to the equally stable Ce3+\text{Ce}^{3+} (4f14f^1) or further.

Europium (Eu2+\text{Eu}^{2+}). Europium's ground state is [Xe]4f76s2[\text{Xe}]4f^76s^2 (no 5d electron, since the 4f subshell is already exactly half filled at Eu\text{Eu}). Losing only the two 6s6s electrons -- rather than the usual three -- leaves the 4f subshell completely undisturbed at the exceptionally stable, half-filled 4f74f^7 configuration, giving Eu2+\text{Eu}^{2+}. Removing a third electron, to reach the "normal" Eu3+\text{Eu}^{3+} (4f64f^6), would require breaking into this stable half-filled arrangement, which costs extra energy -- so europium shows an unusually strong preference for +2+2 compared with its neighbouring lanthanoids. …

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