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Exercises · 7.25

Q.Explain why inspite of nearly the same electronegativity, nitrogen forms hydrogen bonding while chlorine does not.

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Step 1: The apparent puzzle.

Nitrogen (electronegativity ≈ 3.0) and chlorine (electronegativity ≈ 3.0) have almost identical electronegativity values on the Pauling scale, so one might expect both to hydrogen-bond similarly — yet NH3NH_3 shows extensive hydrogen bonding while HClHCl does not.

Step 2: Hydrogen bonding depends on charge DENSITY, not just electronegativity.

The strength of a hydrogen bond depends not merely on the bond's overall polarity but on how concentrated (dense) the resulting partial negative charge is on the electronegative atom — this in turn depends strongly on atomic size.

Step 3: Nitrogen's small size.

Nitrogen is a small, second-period atom. The partial negative charge that develops on N in the N–H bond is therefore concentrated into a small atomic volume, giving a high charge density capable of strongly attracting a hydrogen atom on a neighbouring molecule — hence extensive hydrogen bonding in NH3NH_3.

Step 4: Chlorine's larger size. …

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