The Shapes of Molecules: VSEPR Theory

  • The shape (geometry) of a molecule influences physical and chemical properties, including melting point, boiling point, and reactivity
  • Valence Shell Electron Pair Repulsion (VSEPR) Theory: based on Lewis structures and the principles that:
    • Valence electron pairs repel each other
    • The geometry around the central atom will minimize the repulsion
  • VSEPR Nomenclature
    • A = central atom
    • X = bonding atom
    • E = lone pair
  • If a molecule has 2 or more resonance structures, the VSEPR model can be applied to any one of them
  • If there’s more than one central atom in a molecule, consider the bonding about each atom independently
  • Steric number = number of atoms bonded to central atom + number of lone pairs
    • Used to predict geometries

Molecules Without Lone Pairs

Formula TypeSNGeometryBond angle
AX₂2Linear180°
AX₃3Trigonal planar120°
AX₄4Tetrahedral109.5°
AX₅5Trigonal bipyramidal120° (equatorial)90° (axial)
AX₆6Octahedral90°

Molecules With Lone Pairs

  • Electrons in bonds have less “spatial distribution that lone pairs, meaning:

    • Electrons in bonds take up less space

    • Lone-pair electrons can be anywhere

    • Lone pair electrons take up more space and therefore experience more repulsion

    • Repulsive forces for molecules with lone pairs

    • Lone pair/lone pair repulsion (most repulsion) -> lone pair/bonding pair repulsion -> bonding pair/bonding pair repulsion (least repulsion)

    • In molecules with lone-pair electrons, angles between bonded atoms tend to be smaller

    • When atomic size increases, lone pairs occupy larger spatial volumes, so angles between bonded atoms tend to be even smaller

Formula TypeSNGeometryBond angle
AX₂E3BentLess than 120°
AX₃E4Trigonal pyramidalLess than 109.5°
AX₂E₂4BentLess than 109.5°
AX₄E5See-sawLess than 120° (equatorial)Less than 90° (axial)
AX₃E₂5T-shapedLess than 90°
AX₂E₃5Linear180° - not less than because there’s no other way to minimize repulsion
AX₅E6Square pyramidalLess than 90°
AX₄E₂6Square planar90°
AX₃E₃6T-shapedLess than 90°
AX₂E₄6Linear180°

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