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Exercises · 7.36

Q.Arrange the following in the order of property indicated for each set:

(i) F2, Cl2, Br2, I2 - increasing bond dissociation enthalpy.
(ii) HF, HCl, HBr, HI - increasing acid strength.
(iii) NH3, PH3, AsH3, SbH3, BiH3 – increasing base strength.
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Step 1: (i) Bond dissociation enthalpy of halogens.

The approximate bond enthalpies are F–F ≈ 155, Cl–Cl ≈ 242, Br–Br ≈ 192, I–I ≈ 151 kJ/mol. Fluorine's bond is anomalously weak (not the strongest, despite F being the smallest) because of strong lone-pair–lone-pair repulsion between the closely-spaced small F atoms; overall the order of increasing bond dissociation enthalpy is:

I2<F2<Br2<Cl2I_2 < F_2 < Br_2 < Cl_2

Step 2: (ii) Acid strength of hydrogen halides.

Down the group, the H–X bond becomes progressively weaker (longer, more diffuse orbital overlap) as X becomes larger, so the acid ionises more readily in water; acid strength therefore increases down the group:

HF<HCl<HBr<HIHF < HCl < HBr < HI

(HF is a comparatively weak acid in water partly also due to strong hydrogen bonding/ion-pairing effects, reinforcing this trend.)

Step 3: (iii) Base strength of Group 15 hydrides. …

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