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Electronegativity and Bond Polarity

Jul 1, 2025

Overview

This lecture introduces electronegativity, explains how it differs from electron affinity, and discusses how differences in electronegativity determine bond polarity and influence molecular properties.

Electron Affinity vs. Electronegativity

  • Electron affinity (EA) is the energy released or required when an atom gains an electron (measured for atoms in the gas state).
  • Electronegativity is an atom’s ability to attract shared electrons in a chemical bond.

Electronegativity Trends

  • Electronegativity increases from left to right across a period on the periodic table.
  • Electronegativity decreases down a group.
  • Noble gases are not assigned electronegativity values.
  • The effective nuclear charge (Z_eff) increases across a period, pulling electrons closer and increasing electronegativity.

Bond Polarity and Electronegativity Differences

  • The difference in electronegativity (ΔEN) between two atoms determines bond type:
    • ΔEN = 0 to 0.4: Nonpolar covalent bond (equal or nearly equal sharing).
    • ΔEN = 0.5 to 1.9: Polar covalent bond (unequal sharing, partial charges).
    • ΔEN ≥ 2.0: Ionic bond (electron transfer).
  • Partial charges are denoted by lowercase delta (δ+ for slight positive, δ– for slight negative).

Examples and Calculations

  • Calculate ΔEN by subtracting smaller electronegativity from the larger: ΔEN = |EN_large – EN_small|.
  • Cl–Cl: ΔEN = 0; pure covalent, no polarity.
  • H–Cl: ΔEN = 0.9; polar covalent, Cl is δ– and H is δ+.
  • Na–Cl: ΔEN = 2.1; ionic, Na is δ+ and Cl is δ–.
  • C–O: ΔEN = 1.0; polar covalent, O is δ– and C is δ+.
  • C–H: ΔEN = 0.4; nonpolar covalent, very small dipole.

Bond Dipoles and Molecular Properties

  • Bond dipole: Arrow points towards the more electronegative atom (from δ+ to δ–).
  • Physical properties (solubility, melting point, etc.) are influenced by bond polarity and molecular interactions.
  • Polar molecules (e.g., HCl, HF) dissolve in water; nonpolar molecules (e.g., H₂, CH₄) do not.

Biological Relevance

  • C–O and N–H bonds are common in biological molecules (proteins, DNA).
  • Polar covalent bonds contribute to the structural strength of proteins (hair, nails, collagen).

Key Terms & Definitions

  • Electron Affinity (EA) — energy change when an atom gains an electron in the gas phase.
  • Electronegativity (EN) — tendency of an atom to attract bonding electrons.
  • Effective Nuclear Charge (Z_eff) — net positive charge felt by valence electrons.
  • ΔEN (Delta EN) — difference in electronegativity between two bonded atoms.
  • Bond Dipole — directional arrow showing partial charge separation in a bond.
  • Partial Charge (δ+, δ–) — slight positive or negative charge due to unequal sharing of electrons.

Action Items / Next Steps

  • Memorize electronegativity trends and key ΔEN cutoffs for bond type classification.
  • Practice calculating ΔEN and classifying bond types using a periodic table.
  • Review and be able to identify and draw bond dipoles on molecules.