Chemical Bonding: Step-by-Step Worked Examples (6)

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Question

Predict the geometry, hybridization, and bond angle of the ammonia molecule (NH3_3) using VSEPR theory. Compare it with NH4+_4^+ and explain the difference.

Solution — Step by Step

Nitrogen (Group 15) has 5 valence electrons. In NH3_3: 3 are shared with H atoms in N-H bonds, leaving 2 as a lone pair.

Around N: 3 bond pairs + 1 lone pair = 4 electron domains.

4 electron domains → sp3sp^3 hybridization. Electron-domain geometry: tetrahedral. Molecular geometry (counting only atoms): trigonal pyramidal — because the lone pair is invisible in shape descriptions but takes up space.

Ideal tetrahedral angle is 109.5°109.5°. Lone pairs repel more than bond pairs (they’re closer to the central atom), squeezing the bond angles down. NH3_3: H-N-H angle is 107°107°.

NH4+_4^+: N has 4 bond pairs, no lone pairs. Still sp3sp^3, but now perfectly tetrahedral with 109.5°109.5° angles — no lone pair to distort.

Final answer: NH3_3 is sp3sp^3 hybridized, trigonal pyramidal, 107°107° bond angle. NH4+_4^+ is sp3sp^3 hybridized, tetrahedral, 109.5°109.5°.

Why This Works

VSEPR theory ranks electron-pair repulsions: lone pair-lone pair > lone pair-bond pair > bond pair-bond pair. A lone pair pushes bonds closer together, shrinking bond angles below the ideal hybridization angle.

In NH4+_4^+, donating the lone pair to a proton converts it into a bond pair — repulsion equalises and the molecule snaps to perfect tetrahedral.

Alternative Method

Use the steric number approach. Steric number = (bond pairs) + (lone pairs). NH3_3: SN = 4 → sp3sp^3, geometry depends on lone pair count. Same conclusion via a slightly more compact route.

For VSEPR shortcut: count σ\sigma-bonds and lone pairs around the central atom. That gives steric number. SN = 2 → spsp (linear). SN = 3 → sp2sp^2 (trigonal planar). SN = 4 → sp3sp^3 (tetrahedral). SN = 5 → sp3dsp^3 d. SN = 6 → sp3d2sp^3 d^2.

Common Mistake

Saying NH3_3 is “tetrahedral” because it is sp3sp^3. Hybridization gives the electron-domain geometry; the molecular geometry depends on how many of those domains are atoms vs lone pairs. NH3_3 molecules are pyramidal, not tetrahedral.

Forgetting that lone pairs squeeze bond angles. NH3_3 has 107°107°, not 109.5°109.5°. H2_2O has 104.5°104.5° (two lone pairs squeeze even more). Memorise: more lone pairs → smaller bond angles.

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