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Exercise · Q23

Q.Explain why the H-P-H\text{H-P-H} bond angle in phosphine (≈93.6∘\approx 93.6^\circ) is considerably smaller than the H-N-H\text{H-N-H} bond angle in ammonia (≈107.8∘\approx 107.8^\circ).

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Both NH3\text{NH}_3 and PH3\text{PH}_3 are trigonal pyramidal, sp3sp^3-type molecules with one lone pair, so at first glance both might be expected to show a similar, near-tetrahedral bond angle. However, nitrogen is considerably smaller and more electronegative than phosphorus. In NH3\text{NH}_3, nitrogen holds its three N-H bonding electron pairs relatively close and tightly, so these bonding pairs strongly repel one another (and the lone pair repels them even more strongly), pushing the molecule's hybridisation close to a genuine, near-ideal sp3sp^3 description and giving a bond angle (107.8 degrees) reasonably close to the tetrahedral 109.5∘109.5^\circ. In PH3\text{PH}_3, phosphorus is larger and less electronegative, so its P-H bonding pairs are held less tightly and sit farther from the central atom, reducing the mutual bond pair-bond pair (and lone pair-bond pair) repulsion considerably. With weaker inter-pair repulsion to overcome, phosphorus's bonding orbitals need less s-character mixed in to spread the bonds apart, and the P-H bonds end up using orbitals with much grea …

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