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Chemical Bonding and Orbitals

Sep 11, 2025

Overview

This lecture covers polar covalent bonds, atomic orbitals and electron configurations, valence bond theory, orbital hybridization, and the relationship between bond strength and bond length.

Polar Covalent Bonds

  • Nonpolar covalent bonds form when the electronegativity difference (ΔEN) is less than 0.5.
  • Bonds with ΔEN between 0.5 and 1.7 are polar covalent, showing unequal electron sharing.
  • Bonds with ΔEN greater than 1.7 are generally ionic, representing electron transfer.
  • Arrow notation (→) or δ+ / δ– symbols indicate bond polarity, pointing toward the more electronegative atom.
  • In methanol and similar molecules, C–O and O–H bonds are polar; C–C and C–H are nonpolar.

Atomic Orbitals & Electron Configuration

  • Atomic orbitals include s (spherical), p (hourglass), d, and f shapes.
  • Three p orbitals (px, py, pz) are degenerate (equal energy).
  • Aufbau principle: lowest energy orbitals fill first; Pauli exclusion: max two electrons per orbital with opposite spins; Hund’s rule: fill degenerate orbitals singly before pairing.
  • Example: Carbon (atomic #6) has configuration 1s² 2s² 2p².
  • Negative charge means adding electrons; positive charge means subtracting electrons.
  • Isoelectronic species have the same number of electrons.

Valence Bond Theory & Bond Types

  • Covalent bonds form via overlap of atomic orbitals, with maximum electron density along the bond axis.
  • Sigma (σ) bonds form from direct overlap on the internuclear axis (all single bonds are σ).
  • Pi (π) bonds form from parallel overlap above and below the axis (found in double and triple bonds as second/third bonds).
  • In multiple bonds, first bond is σ; additional bonds are π.

Hybridization & Molecular Geometry

  • sp³ hybridization: 4 domains, tetrahedral geometry, 109.5° bond angle (e.g., methane).
  • sp² hybridization: 3 domains, trigonal planar geometry, 120° bond angle (e.g., ethylene).
  • sp hybridization: 2 domains, linear geometry, 180° bond angle (e.g., acetylene).
  • Domains = bonds (single, double, triple) or lone pairs; double/triple counts as one domain.

Bond Strength and Length

  • Single bonds are longest and weakest; triple bonds are shortest and strongest.
  • Energy to break C–C bonds: single = 368 kJ/mol, double = 632 kJ/mol, triple = 820 kJ/mol.
  • Rank bond length: triple < double < single.

Key Terms & Definitions

  • Electronegativity (EN) — the ability of an atom to attract electrons in a bond.
  • Polar Covalent Bond — a bond with unequal sharing of electrons (ΔEN = 0.5–1.7).
  • Nonpolar Covalent Bond — a bond with equal electron sharing (ΔEN < 0.5).
  • Ionic Bond — bond formed by electron transfer (ΔEN > 1.7).
  • Sigma (σ) Bond — a bond formed by head-on orbital overlap.
  • Pi (π) Bond — a bond formed by side-on orbital overlap (above/below axis).
  • Hybridization — mixing of atomic orbitals to form new, degenerate orbitals.
  • Degenerate Orbitals — orbitals of equal energy.
  • Domain — a bond or lone pair around a central atom.

Action Items / Next Steps

  • Practice identifying bond polarity and placing partial charges in molecules.
  • Practice writing electron configurations and orbital diagrams.
  • Complete homework problems on hybridization and molecular geometry.
  • Read next section on VSEPR theory and intermolecular forces.