Ionic Solid

In chemistry, an ionic compound is a chemical compound composed of ions held together by electrostatic forces termed ionic bonding. The compound is neutral overall, but consists of positively charged ions called cations and negatively charged ions called anions. These can be simple ions such as the sodium (Na⁺) and chloride (Cl⁻) in sodium chloride, or polyatomic species such as the ammonium () and carbonate () ions in ammonium carbonate. Individual ions within an ionic compound usually have multiple nearest neighbours, so are not considered to be part of molecules, but instead part of a continuous three-dimensional network. Ionic compounds usually form crystalline structures when solid.

Ionic compounds containing basic ions hydroxide (OH⁻) or oxide (O²⁻) are classified as bases. Ionic compounds without these ions are also known as salts and can be formed by acid–base reactions. Ionic compounds can also be produced from their constituent ions by evaporation of their solvent, precipitation, freezing, a solid-state reaction, or the electron transfer reaction of reactive metals with reactive non-metals, such as halogen gases.

Ionic compounds typically have high melting and boiling points, and are hard and brittle. As solids they are almost always electrically insulating, but when melted or dissolved they become highly conductive, because the ions are mobilized.

History of discovery

The word ''ion'' is the Greek , ''ion'', "going", the present participle of , ''ienai'', "to go". This term was introduced by physicist and chemist Michael Faraday in 1834 for the then-unknown species that ''goes'' from one electrode to the other through an aqueous medium.

In 1913 the crystal structure of sodium chloride was determined by William Henry Bragg and William Lawrence Bragg. This revealed that there were six equidistant nearest-neighbours for each atom, demonstrating that the constituents were not arranged in molecules or finite aggregates, but instead as a network with long-range crystalline order. Many other inorganic compounds were also found to have similar structural features. These compounds were soon described as being constituted of ions rather than neutral atoms, but proof of this hypothesis was not found until the mid-1920s, when X-ray reflection experiments (which detect the density of electrons), were performed.

Principal contributors to the development of a theoretical treatment of ionic crystal structures were Max Born, Fritz Haber, Alfred Landé, Erwin Madelung, Paul Peter Ewald, and Kazimierz Fajans. Born predicted crystal energies based on the assumption of ionic constituents, which showed good correspondence to thermochemical measurements, further supporting the assumption.

Formation

Ionic compounds can be produced from their constituent ions by evaporation, precipitation, or freezing. Reactive metals such as the alkali metals can react directly with the highly electronegative halogen gases to form an ionic product. They can also be synthesized as the product of a high temperature reaction between solids.

If the ionic compound is soluble in a solvent, it can be obtained as a solid compound by evaporating the solvent from this electrolyte solution. As the solvent is evaporated, the ions do not go into the vapor, but stay in the remaining solution, and when they become sufficiently concentrated, nucleation occurs, and they crystallize into an ionic compound. This process occurs widely in nature and is the means of formation of the evaporite minerals. Another method of recovering the compound from solution involves saturating a solution at high temperature and then reducing the solubility by reducing the temperature until the solution is supersaturated and the solid compound nucleates.

Insoluble ionic compounds can be precipitated by mixing two solutions, one with the cation and one with the anion in it. Because all solutions are electrically neutral, the two solutions mixed must also contain counterions of the opposite charges. To ensure that these do not contaminate the precipitated ionic compound, it is important to ensure they do not also precipitate. If the two solutions have hydrogen ions and hydroxide ions as the counterions, they will react with one another in what is called an acid–base reaction or a neutralization reaction to form water. Alternately the counterions can be chosen to ensure that even when combined into a single solution they will remain soluble as spectator ions.

If the solvent is water in either the evaporation or precipitation method of formation, in many cases the ionic crystal formed also includes water of crystallization, so the product is known as a hydrate, and can have very different chemical properties.

Molten salts will solidify on cooling to below their freezing point. This is sometimes used for the solid-state synthesis of complex ionic compounds from solid reactants, which are first melted together. In other cases, the solid reactants do not need to be melted, but instead can react through a solid-state reaction route. In this method, the reactants are repeatedly finely ground into a paste and then heated to a temperature where the ions in neighboring reactants can diffuse together during the time the reactant mixture remains in the oven. Other synthetic routes use a solid precursor with the correct stoichiometric ratio of non-volatile ions, which is heated to drive off other species.

In some reactions between highly reactive metals (usually from Group 1 or Group 2) and highly electronegative halogen gases, or water, the atoms can be ionized by electron transfer, a process thermodynamically understood using the Born–Haber cycle.

Bonding

Ions in ionic compounds are primarily held together by the electrostatic forces between the charge distribution of these bodies, and in particular, the ionic bond resulting from the long-ranged Coulomb attraction between the net negative charge of the anions and net positive charge of the cations. There is also a small additional attractive force from van der Waals interactions which contributes only around 1–2% of the cohesive energy for small ions. When a pair of ions comes close enough for their outer