Chemical Bonding: Conceptual Doubts Cleared (2)

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Question

Why does NH3\text{NH}_3 have a smaller bond angle (107°107°) than CH4\text{CH}_4 (109.5°109.5°), even though both have sp3sp^3 hybridization on the central atom?

Solution — Step by Step

Both N (in NH3_3) and C (in CH4_4) are sp3sp^3 hybridized. Each has four electron pairs around the central atom, giving an idealized tetrahedral arrangement with 109.5°109.5° angles.

In CH4_4: all four pairs are bond pairs (with H atoms). In NH3_3: three are bond pairs (with H atoms) and one is a lone pair on N.

The order of electron-pair repulsion strength is:

lone pair–lone pair>lone pair–bond pair>bond pair–bond pair\text{lone pair--lone pair} > \text{lone pair--bond pair} > \text{bond pair--bond pair}

A lone pair occupies more space than a bond pair because it’s held by only one nucleus, not two.

The lone pair on N pushes the three N–H bond pairs closer together, compressing the H–N–H angle from the ideal 109.5°109.5° down to 107°107°. CH4_4 has no lone pairs, so all repulsions are equal and the angle stays at 109.5°109.5°.

Final Answer: Lone-pair repulsion in NH3_3 compresses bond angles below the tetrahedral value. CH4_4, with no lone pairs, retains the ideal 109.5°109.5° angle.

Why This Works

VSEPR theory says molecular shape is determined by minimizing repulsion among all electron pairs (bonding + lone). A lone pair “occupies more angular space” because its electron density is concentrated near one atom, so it bullies the bond pairs into a tighter arrangement.

Continuing the trend: H2_2O has two lone pairs on O, and the H–O–H angle drops further to 104.5°104.5°. The pattern is consistent — each additional lone pair compresses the bond angle by roughly 2°3°2°-3°.

Alternative Method

Argue from electron-density orientation: lone pair density is mostly close to N, while bond pair density extends out toward the H. So the lone pair “pushes” each H closer to its neighbours. Same conclusion, more visual.

“Both NH3_3 and CH4_4 are tetrahedral, so they must have the same bond angle.” This conflates electron geometry (tetrahedral in both) with molecular geometry (tetrahedral CH4_4 vs trigonal pyramidal NH3_3). Always distinguish the two.

Quick angle-prediction recipe: count lone pairs on the central atom. Subtract roughly 2.5°2.5° per lone pair from 109.5°109.5°. NH3_3107°107°, H2_2O → 104.5°104.5°. NEET often asks “rank H2_2O, NH3_3, CH4_4 by bond angle” — answer: CH4_4 > NH3_3 > H2_2O.

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