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Intext · Q27

Q.Give two examples to show the anomalous behaviour of fluorine.

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Step 1: Recall why fluorine is "anomalous."

Fluorine is the first member of Group 17. Like other first-row p-block elements (Li, Be, B, C, N, O), it differs sharply from the rest of its group because of its very small atomic size, absence of d-orbitals in the valence shell, and highest electronegativity of all elements.

Step 2: Example 1 — abnormally high boiling point of HF.

HF  (b.p.=293 K)≫HCl (188 K), HBr (206 K), HI (238 K)HF \; (b.p. = 293\ K) \gg HCl\ (188\ K),\ HBr\ (206\ K),\ HI\ (238\ K)

Because F is small and intensely electronegative, the H–F bond is highly polar and HF molecules associate through strong intermolecular hydrogen bonding (even persisting as a zig-zag polymer, (HF)n(HF)_n, in the liquid/vapour). The other hydrogen halides, with larger and less electronegative halogens, show no such association and remain gases at room temperature.

Step 3: Example 2 — fluorine shows only one oxidation state.

Chlorine, bromine and iodine show oxidation states from −1-1 to +7+7 (e.g. Cl2O7Cl_2O_7, HClO4HClO_4) because they have vacant dd-orbitals to expand their octet. Fluorine (n = 2) has no dd-orbitals available and is more electronegative than oxygen itself, so it can never show a positive oxidation state — it is restricted to 00 and −1-1 only.

Step 4: Other accepted examples (either pair is sufficient). …

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