Solid substances that separate, forming oppositely charged ions in water are called ______.

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 [NH+
4
] and carbonate [CO2−
3
] 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.

The crystal structure of sodium chloride, NaCl, a typical ionic compound. The purple spheres represent sodium cations, Na+, and the green spheres represent chloride anions, Cl−. The yellow stipples show the electrostatic forces.

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.

The word ion is the Greek ἰόν, ion, "going", the present participle of ἰέναι, 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.[1][2]

 

X-ray spectrometer developed by Bragg

In 1913 the crystal structure of sodium chloride was determined by William Henry Bragg and William Lawrence Bragg.[3][4][5] 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.[5] Many other inorganic compounds were also found to have similar structural features.[5] 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.[5][6]

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.[7] Born predicted crystal energies based on the assumption of ionic constituents, which showed good correspondence to thermochemical measurements, further supporting the assumption.[5]

 

Halite, the mineral form of sodium chloride, forms when salty water evaporates leaving the ions behind.

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.[8] They can also be synthesized as the product of a high temperature reaction between solids.[9]

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.[10] 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.[11] 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.[10]

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.[12] 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.[13] Alternately the counterions can be chosen to ensure that even when combined into a single solution they will remain soluble as spectator ions.[12]

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.[14]

Molten salts will solidify on cooling to below their freezing point.[15] This is sometimes used for the solid-state synthesis of complex ionic compounds from solid reactants, which are first melted together.[16] 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.[9] Other synthetic routes use a solid precursor with the correct stoichiometric ratio of non-volatile ions, which is heated to drive off other species.[9]

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,[17] a process thermodynamically understood using the Born–Haber cycle.[18]

 

A schematic electron shell diagram of sodium and fluorine atoms undergoing a redox reaction to form sodium fluoride. Sodium loses its outer electron to give it a stable electron configuration, and this electron enters the fluorine atom exothermically. The oppositely charged ions – typically a great many of them – are then attracted to each other to form a solid.

Main article: Ionic 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.[19] 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.[20] When a pair of ions comes close enough for their outer electron shells [most simple ions have closed shells] to overlap, a short-ranged repulsive force occurs,[21] due to the Pauli exclusion principle.[22] The balance between these forces leads to a potential energy well with minimum energy when the nuclei are separated by a specific equilibrium distance.[21]

If the electronic structure of the two interacting bodies is affected by the presence of one another, covalent interactions [non-ionic] also contribute to the overall energy of the compound formed.[23] Ionic compounds are rarely purely ionic, i.e. held together only by electrostatic forces. The bonds between even the most electronegative/electropositive pairs such as those in caesium fluoride exhibit a small degree of covalency.[24][25] Conversely, covalent bonds between unlike atoms often exhibit some charge separation and can be considered to have a partial ionic character.[23] The circumstances under which a compound will have ionic or covalent character can typically be understood using Fajans' rules, which use only charges and the sizes of each ion. According to these rules, compounds with the most ionic character will have large positive ions with a low charge, bonded to a small negative ion with a high charge.[26] More generally HSAB theory can be applied, whereby the compounds with the most ionic character are those consisting of hard acids and hard bases: small, highly charged ions with a high difference in electronegativities between the anion and cation.[27][28] This difference in electronegativities means that the charge separation, and resulting dipole moment, is maintained even when the ions are in contact [the excess electrons on the anions are not transferred or polarized to neutralize the cations].[29]

 

The unit cell of the zinc blende structure

Ions typically pack into extremely regular crystalline structures, in an arrangement that minimizes the lattice energy [maximizing attractions and minimizing repulsions]. The lattice energy is the summation of the interaction of all sites with all other sites. For unpolarizable spherical ions, only the charges and distances are required to determine the electrostatic interaction energy. For any particular ideal crystal structure, all distances are geometrically related to the smallest internuclear distance. So for each possible crystal structure, the total electrostatic energy can be related to the electrostatic energy of unit charges at the nearest neighboring distance by a multiplicative constant called the Madelung constant[21] that can be efficiently computed using an Ewald sum.[30] When a reasonable form is assumed for the additional repulsive energy, the total lattice energy can be modelled using the Born–Landé equation,[31] the Born–Mayer equation, or in the absence of structural information, the Kapustinskii equation.[32]

Using an even simpler approximation of the ions as impenetrable hard spheres, the arrangement of anions in these systems are often related to close-packed arrangements of spheres, with the cations occupying tetrahedral or octahedral interstices.[33][34] Depending on the stoichiometry of the ionic compound, and the coordination [principally determined by the radius ratio] of cations and anions, a variety of structures are commonly observed,[35] and theoretically rationalized by Pauling's rules.[36]

Common ionic compound structures with close-packed anions[35] Stoichiometry Cation:anion
coordination Interstitial sites Cubic close packing of anions Hexagonal close packing of anions Occupancy Critical radius
ratio Name Madelung constant Name Madelung constant
MX 6:6 all octahedral 0.4142[33] sodium chloride 1.747565[37] nickeline

Bài Viết Liên Quan

Bài mới nhất

Chủ Đề