Electrostatic model of ionic binding 2026-10-13
For two point electric charges in vacuum, Coulomb's law gives the interaction potential energywith zero at infinite separation. Here is the distance between them and is the vacuum permittivity. Opposite signs give negative potential energy and attraction; equal signs give positive potential energy and repulsion. For a finite collection of distinct point electric charges, sum over to count each pair once. A bulk ionic crystal requires the extended lattice sum, including both signs, rather than multiplying one attractive pair by the coordination number.[ref]
The Feynman Lectures on Physics, Volume II by Richard Feynman and others. §8–1, equations (8.1)–(8.3); §8–3, many-neighbour lattice sum
At short distances, overlapping electron density makes the simple point-charge picture inadequate. Quantum mechanics, including the Pauli exclusion principle, matters to the steep repulsive contribution. Pure attraction proportional to would collapse as ; it cannot set an equilibrium spacing on its own. A useful illustrative model isHere scales an assumed fixed arrangement, packages its attractive contribution, and represents short-range repulsion. The constants have units energy times length and energy times length to the power , respectively. This is a model, not a fitted description of a named salt.[ref]
The Feynman Lectures on Physics, Volume II by Richard Feynman and others. §8–3, close-distance repulsion and limits of a purely electrostatic lattice calculation
Differentiating gives and , so the stationary spacing is a stable minimum. For the diagram's stipulated , put and . ThenThe dimensionless curves show how competing interactions select a spacing. Their energy scale and exponent are synthetic; neither is a measured lattice energy or a melting prediction.
Ionic bonding 2026-10-13
Ionic bonding binds oppositely charged ions through attraction governed by electrostatics. In ordinary solid sodium chloride, each cation interacts with many anions, and also with other cations: attraction and repulsion together contribute to the binding of an extended ionic crystal. The chemical formula specifies equal numbers of the two kinds of ions; it does not divide the solid into isolated two-atom molecules.[ref]
This distinction explains a striking combination of properties: ordinary dry sodium chloride conducts electric current poorly, while its molten form or a sufficiently concentrated chemical solution in water conducts well. The ions already exist in the solid; their ability to move through the sample changes. A conductivity experiment on salt solutions tests this transport picture, rather than simply asserting that charged constituents must make every material conductive.
An isolated ion pair, a plane of an extended ionic crystal, and a synthetic potential energy model with a stable spacing
. Original schematic geometry and calculated model curves, not a measured electron density, diffraction pattern, or experimental lattice energy. Four nearest neighbours are visible in the plane of the rock salt structure; two more lie perpendicular to it. Disk sizes are arbitrary. The right-hand curves use the explicitly stipulated dimensionless model below. Details. Lattice energy 2026-10-13
A lattice energy needs a reaction, a sign convention, and a stated amount. Using the lattice-dissociation enthalpy convention for sodium chloride,The reverse lattice-formation enthalpy is negative with the same magnitude when initial and final states match. Chemistry 2e gives for this separation, per mole of sodium chloride formula units. This is about electronvolts per formula unit, not per individual ion. It concerns separated gaseous ions, rather than neutral chemical atoms, molten salt, or hydrated ions in water.[ref]
Chemistry 2e. §7.5, “Ionic Bond Strength and Lattice Energy”, positive convention, reverse convention and NaCl value
Also distinguish an internal energy change from an enthalpy change: . A static point-charge calculation omits motion and thermal contributions. Reversing a reaction reverses its energy change; replacing internal energy with enthalpy additionally changes the defined quantity. The Born-Haber cycle infers a lattice-formation enthalpy by combining other enthalpies, ionization energies, and electron affinities. These imagined stages are a thermodynamic accounting path, not a claim about the actual sequence of a chemical reaction.[ref]
Physical properties of salts 2026-10-13
Many ionic crystals have high melting temperatures compared with small molecular solids, because reorganizing their strongly interacting ions costs energy. But melting leaves a dense liquid with interactions; it does not perform the complete separation defining a lattice energy. At fixed pressure, the transition occurs when the Gibbs free energies of the solid and liquid match. The relevant enthalpy and entropy differences both matter, so lattice energy alone is not a universal ordering of melting temperatures. Strong covalent bonds in extended networks can also give high melting temperatures.[ref]
Chemistry 2e. §10.5, “Ionic Solids” and “Covalent Network Solid”; §16.4, equations defining Gibbs free energy and its change
