Alkali
In chemistry, an alkali (; from Arabic: "al-qaly" "ashes of the saltwort") is a basic, ionic salt of an alkali metal or alkaline earth metal chemical element. An alkali also can be defined as a base that dissolves in water. A solution of a soluble base has a pH greater than 7.0. The adjective alkaline is commonly, and alkalescent less often, used in English as a synonym for basic, especially for bases soluble in water. This broad use of the term is likely to have come about because alkalis were the first bases known to obey the Arrhenius definition of a base, and they are still among the most common bases.
Alkali metal
In aqueous solution, the alkali metal ions form aqua ions of the formula [M(HO)], where "n" is the solvation number. Their coordination numbers and shapes agree well with those expected from their ionic radii. In aqueous solution the water molecules directly attached to the metal ion are said to belong to the first coordination sphere, also known as the first, or primary, solvation shell. The bond between a water molecule and the metal ion is a dative covalent bond, with the oxygen atom donating both electrons to the bond. Each coordinated water molecule may be attached by hydrogen bonds to other water molecules. The latter are said to reside in the second coordination sphere. However, for the alkali metal cations, the second coordination sphere is not well-defined as the +1 charge on the cation is not high enough to polarise the water molecules in the primary solvation shell enough for them to form strong hydrogen bonds with those in the second coordination sphere, producing a more stable entity. The solvation number for Li has been experimentally determined to be 4, forming the tetrahedral [Li(HO)]: while solvation numbers of 3 to 6 have been found for lithium aqua ions, solvation numbers less than 4 may be the result of the formation of contact ion pairs, and the higher solvation numbers may be interpreted in terms of water molecules that approach [Li(HO)] through a face of the tetrahedron, though molecular dynamic simulations may indicate the existence of an octahedral hexaaqua ion. There are also probably six water molecules in the primary solvation sphere of the sodium ion, forming the octahedral [Na(HO)] ion. While it was previously thought that the heavier alkali metals also formed octahedral hexaaqua ions, it has since been found that potassium and rubidium probably form the [K(HO)] and [Rb(HO)] ions, which have the square antiprismatic structure, and that caesium forms the 12-coordinate [Cs(HO)] ion.
The chemistry of lithium shows several differences from that of the rest of the group as the small Li cation polarises anions and gives its compounds a more covalent character. Lithium and magnesium have a diagonal relationship due to their similar atomic radii, so that they show some similarities. For example, lithium forms a stable nitride, a property common among all the alkaline earth metals (magnesium's group) but unique among the alkali metals. In addition, among their respective groups, only lithium and magnesium form organometallic compounds with significant covalent character (e.g. LiMe and MgMe).