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Shapes of molecules

1.3.3 Shapes of Molecules

Electron-pair repulsion theory predicts the three-dimensional shape of a covalent molecule or polyatomic ion.

Electron pairs around a central atom repel each other and arrange themselves as far apart as possible to minimise repulsion.

A multiple bond (double or triple) counts as one region of electron density, because its bonding pairs all lie in the same direction in space.

This is why CO₂ is linear and each carbon in C₂H₄ is trigonal planar.

Lone pairs repel more strongly than bonding pairs, because they are held closer to the central atom.

The repulsion order is lone pair–lone pair > lone pair–bond pair > bond pair–bond pair, and each lone pair compresses the bond angle by approximately 2.5°.

Key Definition Bond length is the distance between the nuclei of two bonded atoms.

Key Definition Bond angle is the angle between two covalent bonds that share a common atom.

Both bond length and bond angle depend on the arrangement of electron pairs around the central atom.

The ten specified species span the major geometries:

  • Linear — BeCl₂ and CO₂; bond angle 180°
  • Trigonal planar — BCl₃ and C₂H₄; bond angle 120°
  • Tetrahedral — CH₄ and NH₄⁺; bond angle 109.5°
  • Trigonal pyramidal — NH₃; bond angle 107°
  • Bent (non-linear) — H₂O; bond angle 104.5°
  • Trigonal bipyramidal — PCl₅; bond angles 90° and 120°
  • Octahedral — SF₆; bond angle 90°

Exam questions frequently ask for the shapes of analogous species, and the method is always the same:

  1. Count the bonding regions, treating each multiple bond as a single region.
  2. Count the lone pairs on the central atom.
  3. Match the totals to the corresponding standard geometry.
  4. Adjust the predicted bond angle for lone-pair compression (about 2.5° per lone pair).

Precision matters in marking: exact bond angles must be stated, and shape names must use the full standard term, especially "trigonal pyramidal" rather than just "pyramidal".