Q.Lanthanoids predominantly show the oxidation state, but , and are also known. Explain, in terms of 4f-subshell occupancy, why these particular exceptions are comparatively stable.
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Start your 14-day free trial to unlock the full solution →The dominant oxidation state of the lanthanoids arises from loss of the outer electrons together with the single electron (or one 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 (). Cerium's ground state is . Removing all four of these outer electrons (rather than stopping at three, as for a typical ) empties the 4f subshell entirely, giving , a stable, noble-gas-configured ion. Because reaching this empty-subshell configuration is energetically favourable, cerium readily forms the state in addition to the usual , and 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 () or further.
Europium (). Europium's ground state is (no 5d electron, since the 4f subshell is already exactly half filled at ). Losing only the two electrons -- rather than the usual three -- leaves the 4f subshell completely undisturbed at the exceptionally stable, half-filled configuration, giving . Removing a third electron, to reach the "normal" (), would require breaking into this stable half-filled arrangement, which costs extra energy -- so europium shows an unusually strong preference for compared with its neighbouring lanthanoids. …
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