valence
Practice
Bonding and molecular structureNational 2024

Which comparisons of bond angles are correct?

I. The bond angle in NHX3\ce{NH3} is greater than the bond angle in NFX3\ce{NF3}.

II. The bond angle in NHX3\ce{NH3} is greater than the bond angle in PHX3\ce{PH3}.

15% of national qualifiers got this right

Explanation

draft

Both statements are true, based on how the electronegativity and size of the atoms bonded to nitrogen or phosphorus affect the lone-pair/bonding-pair repulsions.

Statement I: NHX3\ce{NH3} vs NFX3\ce{NF3}
- Both have a central N with one lone pair and three bonding pairs, so both are trigonal pyramidal with an idealized angle near 109.5∘109.5^{\circ}.
- Fluorine is much more electronegative than hydrogen, so in NFX3\ce{NF3} the N–F bonding electrons are pulled away from N toward F. This leaves N with more electron density concentrated in the lone pair, which then exerts greater repulsion on the bonding pairs, compressing the F–N–F angle.
- Result: bond angle NHX3\ce{NH3} (≈107∘\approx 107^{\circ}) > bond angle NFX3\ce{NF3} (≈102∘\approx 102^{\circ}). Statement I is correct.

Statement II: NHX3\ce{NH3} vs PHX3\ce{PH3}
- Moving down the group from N to P, the central atom becomes larger and uses orbitals with more ss/pp character difference (less effective hybridization), so the bonding pairs sit farther from the nucleus and closer to pure pp orbital character (which prefer 90∘90^{\circ}).
- This causes the H–P–H angle to shrink more than the H–N–H angle.
- Result: bond angle NHX3\ce{NH3} (≈107∘\approx 107^{\circ}) > bond angle PHX3\ce{PH3} (≈93∘\approx 93^{\circ}). Statement II is correct.

Since both I and II are true, the answer is (C).

A

Picks only Statement I as true, incorrectly assuming that since P is a heavier atom it must give a larger bond angle than N (ignoring the poorer hybridization/more p-character trend down a group).

B

Picks only Statement II as true, mistakenly reasoning that F's high electronegativity would pull electron density away from N and increase the F–N–F angle rather than decrease it (misapplying electronegativity effects on lone pair repulsion).

C

Correctly recognizes that both electronegativity differences (N–F vs N–H) and the size/hybridization trend down a group (N vs P) each reduce the bond angle relative to NHX3\ce{NH3}, making both statements true.

D

Assumes all three central atoms (N in NHX3\ce{NH3}, NFX3\ce{NF3}, and P in PHX3\ce{PH3}) have identical bond angles because they are all AX3E VSEPR types, ignoring substituent electronegativity and central-atom size effects.

Concept · VSEPR bond angle trends: electronegativity and central atom size effects

USNCO 2024 National Part I exam, question 52. © American Chemical Society; reproduced for non-commercial practice.