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Chemical Energetics Overview

Jul 4, 2025

Overview

This lecture covers key concepts in chemical energetics, focusing on enthalpy changes, lattice energy, the Born-Haber cycle, factors affecting solubility, ion polarization, and the stability of group 2 compounds.

Enthalpy Changes

  • Enthalpy change of atomisation is the enthalpy change when 1 mole of gaseous atoms forms from its elements under standard conditions.
  • First electron affinity is exothermic; further electron affinities are endothermic due to electron-electron repulsion.

Lattice Energy

  • Lattice energy is the enthalpy change when 1 mole of an ionic solid forms from its gaseous ions under standard conditions.
  • The stronger (more negative) the lattice energy, the stronger the ionic bonding and the more stable the compound.
  • Similar theoretical and experimental lattice energies indicate pure ionic bonding.

Factors Affecting Lattice Energy

  • Lattice energy increases with greater ion charge and smaller ion radius, due to higher charge density and stronger electrostatic attraction.

Born-Haber Cycle

  • Born-Haber cycles use enthalpy changes (formation, atomisation, electron affinity, lattice) to calculate lattice energy.
  • Formation enthalpy under standard conditions for an element is zero.

Dissolving Salts

  • Enthalpy change of solution is the enthalpy change when 1 mole of an ionic solid dissolves in water to form a dilute solution.
  • Enthalpy of hydration refers to dissolving gaseous ions in water.
  • Factors affecting hydration enthalpy are similar to those affecting lattice energy.
  • More negative enthalpy of solution means higher solubility.

Ion Polarisation

  • Ion polarisation is the distortion of an anion's electron cloud by a cation.
  • Polarising power increases with higher cation charge density and decreases with larger cation size; anion polarizability increases with charge and size.

Thermal Stability of Group 2 Compounds

  • Down group 2, polarising power of cations decreases, leading to increased stability of carbonates and nitrates.
  • Order of stability: Ba²⁺ > Sr²⁺ > Ca²⁺ > Mg²⁺.

Solubility of Group 2 Hydroxides and Sulphates

  • Hydroxide solubility increases down the group due to more exothermic solution enthalpy.
  • Sulphate solubility decreases down the group as hydration enthalpy drops faster than lattice energy.

Key Terms & Definitions

  • Enthalpy Change of Atomisation — Energy change when 1 mole of gaseous atoms forms from elements.
  • Lattice Energy — Energy change when an ionic solid forms from gaseous ions.
  • Electron Affinity — Energy change when an atom gains 1 mole of electrons to become an anion.
  • Born-Haber Cycle — Thermochemical cycle for ionic lattice formation.
  • Enthalpy of Solution — Energy change when solid ionic compound dissolves in water.
  • Enthalpy of Hydration — Energy change when gaseous ions become hydrated ions.
  • Ion Polarisation — Distortion of anion by cation’s electric field.
  • Polarising Power — Cation’s capability to distort an anion.

Action Items / Next Steps

  • Review Born-Haber cycle diagrams and practice constructing them for different ionic compounds.
  • Memorize trends in stability and solubility for group 2 hydroxides and sulphates.