How the Born-Haber Cycle Works
The Born-Haber cycle breaks the formation of an ionic crystal lattice from its elements in their standard states into five measurable steps: first the metal sublimes from solid to gas (ΔHsub), then the gaseous metal atom is ionized, losing one or more electrons (IE). In parallel, the nonmetal molecule dissociates into separate atoms (D, or ½D for elements that need only one atom per formula unit), and each nonmetal atom picks up an electron to become an anion (EA, electron affinity). Finally the gaseous cations and anions come together to build the solid crystal lattice, releasing the lattice energy ΔHlattice — typically the largest-magnitude and always exothermic step of the whole cycle.
Because Hess's Law requires that the direct formation of the compound from its elements (ΔHf) release or absorb exactly the same total energy as the five-step indirect route, the lattice energy can be solved for by rearranging the closed cycle: ΔHlattice = ΔHf − (ΔHsub + IE + D + EA). On the diagram the path climbs (endothermic steps: sublimation, ionization, dissociation) and then drops sharply (electron affinity and, especially, lattice formation), always finishing at exactly the same energy level as the direct dashed ΔHf arrow on the right — a visual proof of Hess's Law.
Solve for lattice energy: ΔHlattice = ΔHf − (ΔHsub + IE + ½D + EA)
Sign convention: positive = endothermic (energy absorbed, path climbs) · negative = exothermic (energy released, path drops)
Coulombic trend: ΔHlattice ∝ −(z⁺ × z⁻) / (r⁺ + r⁻)
Frequently Asked Questions
What is the Born-Haber cycle?
The Born-Haber cycle is a thermochemical cycle, based on Hess's Law, that breaks the formation of an ionic solid from its elements into a sequence of measurable steps — sublimation of the metal, ionization of the metal atom, dissociation of the nonmetal molecule, electron affinity of the nonmetal atom, and lattice formation from the gaseous ions — so that the one step that cannot be measured directly, lattice energy, can be calculated from the others.
How does Hess's Law let you solve for lattice energy?
Hess's Law states that the total enthalpy change for a reaction is the same regardless of the path taken, as long as the start and end points match. Because the direct formation enthalpy delta-H-f and the five-step indirect route both start at the elements and end at the ionic solid, their sums must be equal: delta-H-f = delta-H-sub + IE + half-D + EA + delta-H-lattice, which rearranges to give the one unknown, delta-H-lattice.
Why is electron affinity sometimes positive, as with oxygen forming O2-?
Adding a first electron to a neutral atom like oxygen releases energy (EA1 is exothermic), but adding a second electron to the resulting O- ion means forcing a negative charge onto an already negative ion, which requires energy input and makes EA2 endothermic. For MgO, EA1 plus EA2 is net positive (unfavorable) even though the final lattice energy is hugely exothermic once the ions come together.
Why can't lattice energy be measured directly in the lab?
Lattice energy is defined as the enthalpy change when gaseous ions come together to form one mole of solid ionic crystal (or the reverse, for lattice dissociation) — a process that never happens in isolation in a real experiment, since you cannot produce a beaker of free-floating gaseous cations and anions and watch them condense. The Born-Haber cycle sidesteps this by using only steps that are experimentally measurable.
What does a more negative lattice energy mean physically?
A more negative (more exothermic) lattice energy means the ionic bonds in the crystal are stronger, which correlates with a higher melting point, greater hardness, and lower solubility. Lattice energy grows more negative with smaller ionic radii and higher ionic charges, which is why MgO (2+ and 2- ions) has a far larger lattice energy than NaCl (1+ and 1- ions).