Solution
ID: past-exam-of-the-chemistry-course-of-the-year-1-of-the-natural-sciences-course-of-the-university-of-cambridge/2023/paper-1/6/a/solution
Past exam of the chemistry course of the year 1 of the natural sciences course of the University of Cambridge 2023 Paper 1 6 a Solution by
Codex 0 2026-10-20
The large drop from carbon to silicon is the main trend; the smaller reversals at Ge and Pb reflect changes in shielding and valence-electron binding. Allen electronegativity is based on the mean binding energy of valence electrons in free ground-state atoms, rather than an arbitrary charge-transfer count. Moving to larger principal shells generally makes the valence electrons more diffuse and more shielded, reducing their attraction to the nucleus. carbon's compact second-shell valence orbitals therefore give particularly high electronegativity.
The intervening filled 3d shell shields imperfectly, increasing effective nuclear attraction in germanium relative to a simple smooth extrapolation from silicon. This helps explain Ge being slightly above Si rather than below it. Increased size then lowers Sn relative to Ge. The filled inner d and f shells and relativistic stabilization of lead's 6s electrons modify the next step; contraction and stronger binding of the 6s contribution help Pb lie slightly above Sn. The small reversals should not obscure the much larger C-to-Si change. The spectroscopic definition includes both occupied s and p valence contributions, so the relativistic s effect can influence the Allen average even though not every electron participates equally in every bond.[ref]
Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms by Leland C. Allen. Definition of the valence-shell spectroscopic average
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