Electronic Structures of Cations

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Hydrogen atom (center) contains a single proton and a single electron. Removal of the electron gives a cation (left), whereas addition of an electron gives an anion (right). The hydrogen anion, with its loosely held two-electron cloud, has a larger radius than the neutral atom, which in turn is much larger than the bare proton of the cation. Hydrogen forms the only charge-+1 cation that has no electrons, but even cations that (unlike hydrogen) still retain one or more electrons are still smaller than the neutral atoms or molecules from which they are derived. Source: By Jkwchui – Own work, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=12617370

Electronic Structures of Cations (OpenStax Chemistry 2e)

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, Hg22+ (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.

Related Research: Research Article: Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation

Source:

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019, February 14). Chemistry 2e. Houston, Texas: OpenStax. Access for free at: https://openstax.org/books/chemistry-2e

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