第7章化学結合と分子の形

When forming a cation, an atom of a main group element tends to lose all of its valence electrons, thus assuming the electronic structure of the noble gas that precedes it in the periodic table. For groups 1 (the alkali metals) and 2 (the alkaline earth metals), the group numbers are equal to the numbers of valence shell electrons and, consequently, to the charges of the cations formed from atoms of these elements when all valence shell electrons are removed. For example, calcium is a group 2 element whose neutral atoms have 20 electrons and a ground state electron configuration of 1s²2s²2p⁶3s²3p⁶4s². When a Ca atom loses both of its valence electrons, the result is a cation with 18 electrons, a 2+ charge, and an electron configuration of 1s²2s²2p⁶3s²3p⁶. The Ca²⁺ ion is therefore isoelectronic with the noble gas Ar.

For groups 13–17, the group numbers exceed the number of valence electrons by 10 (accounting for the possibility of full d subshells in atoms of elements in the fourth and greater periods). Thus, the charge of a cation formed by the loss of all valence electrons is equal to the group number minus 10. For example, aluminum (in group 13) forms 3+ ions (Al³⁺).

Exceptions to the expected behavior involve elements toward the bottom of the groups. In addition to the expected ions Tl³⁺, Sn⁴⁺, Pb⁴⁺, and Bi⁵⁺, a partial loss of these atoms’ valence shell electrons can also lead to the formation of Tl⁺, Sn²⁺, Pb²⁺, and Bi³⁺ ions. The formation of these 1+, 2+, and 3+ cations is ascribed to the inert pair effect, which reflects the relatively low energy of the valence s-electron pair for atoms of the heavy elements of groups 13, 14, and 15. Mercury (group 12) also exhibits an unexpected behavior: it forms a diatomic ion, ${\text{Hg}}_2{}^{\text{2+}}$ (an ion formed from two mercury atoms, with an Hg-Hg bond), in addition to the expected monatomic ion Hg²⁺ (formed from only one mercury atom).

Transition and inner transition metal elements behave differently than main group elements. Most transition metal cations have 2+ or 3+ charges that result from the loss of their outermost s electron(s) first, sometimes followed by the loss of one or two d electrons from the next-to-outermost shell. For example, iron (1s²2s²2p⁶3s²3p⁶3d⁶4s²) forms the ion Fe²⁺ (1s²2s²2p⁶3s²3p⁶3d⁶) by the loss of the 4s electrons and the ion Fe³⁺ (1s²2s²2p⁶3s²3p⁶3d⁵) by the loss of the 4s electrons and one of the 3d electrons. Although the d orbitals of the transition elements are—according to the Aufbau principle—the last to fill when building up electron configurations, the outermost s electrons are the first to be lost when these atoms ionize. When the inner transition metals form ions, they usually have a 3+ charge, resulting from the loss of their outermost s electrons and a d or f electron.