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VSEPR Theory and Molecular Shapes

Jul 15, 2025

Overview

This lecture introduces how to use VSEPR theory to predict molecular shapes and explains how molecular structure affects polarity and dipole moments.

Molecular Shapes: Basics

  • Molecular structures are three-dimensional, described by bond distances and bond angles.
  • VSEPR theory (Valence Shell Electron-Pair Repulsion) predicts molecular structure by minimizing repulsion between regions of electron density.
  • Electron regions include single, double, triple bonds, and lone pairs.

Electron-Pair Geometry & Molecular Structure

  • Electron-pair geometry considers all electron regions (bonds + lone pairs); molecular structure considers only the atoms' arrangement.
  • When there are no lone pairs on the central atom, electron-pair geometry and molecular structure are identical.
  • Lone pairs occupy more space than bonding pairs, causing bond angles to deviate from ideal values.

Common Geometries & Angles

  • Linear: 2 regions, 180°
  • Trigonal planar: 3 regions, 120°
  • Tetrahedral: 4 regions, 109.5°
  • Trigonal bipyramidal: 5 regions, 90° & 120°
  • Octahedral: 6 regions, 90°

Lone Pairs and Molecular Shape

  • Lone pairs reduce bond angles and change the molecular structure name (e.g., bent, trigonal pyramidal, seesaw, T-shaped, square planar).
  • In trigonal bipyramidal, lone pairs prefer equatorial positions; in octahedral, they are placed opposite each other.

VSEPR Prediction Steps

  • Write the Lewis structure.
  • Count regions of electron density around the central atom (including lone pairs and all bonds).
  • Assign electron-pair geometry based on the number of regions.
  • Determine molecular structure by considering the number and arrangement of lone pairs.

Example Structures

  • CO₂: linear geometry, linear structure (both 180°).
  • BCl₃: trigonal planar geometry & structure (120°).
  • NH₄⁺: tetrahedral geometry & structure (109.5°).
  • H₂O: tetrahedral geometry, bent structure (104.5°).
  • SF₄: trigonal bipyramidal geometry, seesaw structure.
  • XeF₄: octahedral geometry, square planar structure.

Polarity and Dipole Moments

  • Polar covalent bonds arise from a difference in electronegativity between atoms, resulting in partial charges and bond dipoles (measured in Debye units; μ = Q × r).
  • The overall molecular dipole is the vector sum of individual bond dipoles.
  • For a molecule to be polar, it must have polar bonds and a shape where dipole moments do not cancel.
  • Nonpolar molecules: bond dipoles cancel (e.g., CO₂, CH₄, BF₃).
  • Polar molecules: bond moments do not cancel (e.g., H₂O, NH₃, CH₃Cl).

Properties of Polar Molecules

  • Polar molecules align in an electric field.
  • Polar solvents dissolve polar substances; nonpolar solvents dissolve nonpolar substances.

Key Terms & Definitions

  • VSEPR theory — predicts molecular shapes based on electron pair repulsions.
  • Electron-pair geometry — arrangement of all electron regions around a central atom.
  • Molecular structure — arrangement of atoms (not lone pairs) in a molecule.
  • Bond angle — angle between two bonds from the same atom.
  • Bond dipole moment — measure of bond polarity due to differences in electronegativity.
  • Dipole moment (μ) — overall measure of molecular polarity.

Action Items / Next Steps

  • Practice predicting molecular structures using VSEPR for assigned molecules.
  • Use the molecular shape simulator online for additional practice.
  • Review homework problems on molecular polarity and dipole moments.