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Exercises · 7.11

Q.Explain why NH3 is basic while BiH3 is only feebly basic.

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Step 1: Basicity depends on lone-pair availability.

The basic character of EH3EH_3 hydrides (E = N, P, As, Sb, Bi) depends on how readily the lone pair on the central atom E can be donated to an acceptor (e.g. H+H^+).

Step 2: Nitrogen.

Nitrogen is small, and its lone pair, held in a compact sp3sp^3 hybrid orbital, is close to the nucleus but still spatially accessible and has considerable p-character, making it strongly available for donation. This makes NH3NH_3 a good Lewis/Bronsted base (readily accepts H+H^+ to form NH4+NH_4^+).

Step 3: Bismuth.

Bismuth is a much larger atom. Down the group, due to the inert pair effect, the ns² lone pair increasingly resists participating in bonding/donation — it becomes more tightly held close to the (large, poorly-shielding) nucleus in an orbital with greater s-character, and is spatially far less accessible to an incoming acceptor. This makes the lone pair on Bi a poor donor.

Step 4: Trend across the group. …

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