Variation in Ionic Radii

Ionic radius is the measure used to describe the size of an ion.

A cation always has fewer electrons and the same number of protons as the parent atom; it is smaller than the atom from which it is derived. For example, the covalent radius of an aluminum atom (1s²2s²2p⁶3s²3p¹) is 118 pm, whereas the ionic radius of an Al³⁺ (1s²2s²2p⁶) is 68 pm. As electrons are removed from the outer valence shell, the remaining core electrons occupying smaller shells, experience a greater effective nuclear charge Z_eff (as discussed) and are drawn even closer to the nucleus.

Cations with larger charges are smaller than cations with smaller charges (e.g., V²⁺ has an ionic radius of 79 pm, while that of V³⁺ is 64 pm). Proceeding down the groups of the periodic table, we find that cations of successive elements with the same charge generally have larger radii, corresponding to an increase in the principal quantum number, n.

An anion (negative ion) is formed by the addition of one or more electrons to the valence shell of an atom. This results in a greater repulsion among the electrons and a decrease in Z_eff per electron. Both effects (the increased number of electrons and the decreased Z_eff) cause the radius of an anion to be larger than that of the parent atom ([link]). For example, a sulfur atom ([Ne]3s²3p⁴) has a covalent radius of 104 pm, whereas the ionic radius of the sulfide anion ([Ne]3s²3p⁶) is 170 pm.

For consecutive elements proceeding down any group, anions have larger principal quantum numbers and, thus, larger radii.

Isoelectronic

Atoms and ions that have the same electron configuration are said to be isoelectronic. Examples of isoelectronic species are N^3–, O^2–, F^–, Ne, Na⁺, Mg²⁺, and Al³⁺ (1s²2s²2p⁶). Another isoelectronic series is P^3–, S^2–, Cl^–, Ar, K⁺, Ca²⁺, and Sc³⁺ ([Ne]3s²3p⁶). For atoms or ions that are isoelectronic, the number of protons determines the size. The greater the nuclear charge, the smaller the radius in a series of isoelectronic ions and atoms.