The existence of electron shells was first observed experimentally in Charles Barkla's and Henry Moseley's X-ray absorption studies. Barkla labeled them with the letters K, L, M, N, O, P, and Q. The origin of this terminology was alphabetic. A J series was also suspected, though later experiments indicated that the K absorption lines are produced by the innermost electrons. These letters were later found to correspond to the n-values 1, 2, 3, etc. They are used in the spectroscopic Siegbahn notation.
The name for electron shells originates from the Bohr model, in which groups of electrons were believed to orbit the nucleus at certain distances, so that their orbits formed "shells" around the nucleus.
The physical chemist Gilbert Lewis was responsible for much of the early development of the theory of the participation of valence shell electrons in chemical bonding. Linus Pauling later generalized and extended the theory while applying insights from quantum mechanics.
|Subshell label||l||Max electrons||Shells containing it||Historical name|
|p||1||6||2nd shell and higher||principal|
|d||2||10||3rd shell and higher||diffuse|
|f||3||14||4th shell and higher||fundamental|
|g||4||18||5th shell and higher|
|h||5||22||6th shell and higher|
|i||6||26||7th shell and higher|
Although it is commonly stated that all the electrons in a shell have the same energy, this is an approximation. However, the electrons in a subshell do have exactly the same level of energy, with later subshells having more energy per electron than earlier ones. This effect is great enough that the energy ranges associated with shells can overlap (see Valence shells and Aufbau Principle).
Therefore, the K shell, which contains only an s subshell, can hold up to 2 electrons; the L shell, which contains an s and a p, can hold up to 2+6=8 electrons; and so forth. The general formula is that the nth shell can in principle hold up to 2n2 electrons.
Although that formula gives the maximum in principle, in fact that maximum can only be achieved (by known elements) for the first four shells (K,L,M,N). In fact, no known element has more than 32 electrons in any one shell. This is because the subshells are filled according to the Aufbau principle. The first elements to have more than 32 electrons in one shell would belong to the g-block of period 8 of the periodic table. These elements would have some electrons in their 5g subshell and thus have more than 32 electrons in the O shell (fifth principal shell).
The valence shell is the outermost shell of an atom. It is usually (and misleadingly) said that the electrons in this shell make up its valence electrons, that is, the electrons that determine how the atom behaves in chemical reactions. While atoms with complete valence shells are the most chemically non-reactive, those with only one electron in their valence shells (alkalis) or just missing one electron from having a complete shell (halogens) are the most reactive.
However, the truth is more complicated. The electrons that determine how an atom reacts chemically are those that travel furthest from the nucleus - i.e. those with the most energy. As stated in "Subshells", electrons in the inner subshells have less energy than those in outer subshells. This effect is great enough that the 3d electrons have more energy than 4s electrons, and are therefore more important in chemical reactions, hence making them valence electrons although they are not in the so-called valence shell.