Why can elements in the 3rd period exceed 8 valence electrons?

Sulfur can have 12 valence electrons in #SO_4^(2-)# and Chlorine has 10 in #[ClO_4]^-# Why?

1 Answer
Jul 25, 2018

What's new in #n = 3#?


Recall that the angular momentum quantum number #l# tells you what orbital subshell you have, #s,p,d,f,...# Well, you should take note that

#" "color(white)(/)s, p, d, f, . . .#
#l = 0, 1, 2, 3, . . . , n-1#,

i.e. that the maximum #l# is one less than #n#, the principal quantum number (which indicates the energy level), where:

#n = 1, 2, 3, . . . #

Hence, if we are on the third period, we introduce #n = 3#, and so, #n - 1 = 2# and orbitals with UP TO #l = 2#, #d# orbitals, are possible. That is, #3s#, #3p#, AND #3d# orbitals are usable.

This is especially notable in silicon, phosphorus, sulfur, and chlorine if we consider the third period.

Usage of those #3d# orbitals allows for extra space to hold electrons, and as a result, hypervalency is possible.

https://www.sciencedirect.com/science/article/pii/S0010854507002470

This expansion of "orbital space" is known in, for example:

  • #"PF"_5#, where phosphorus has #10# valence electrons around it arranged in a trigonal bipyramidal geometry.

https://upload.wikimedia.org/

  • #"SF"_6#, where sulfur has #12# valence electrons around it arranged in an octahedral geometry.

https://upload.wikimedia.org/

  • #"ClF"_5#, where chlorine has #12# valence electrons around it arranged in a square pyramidal geometry (two of which are in one lone pair).

https://upload.wikimedia.org/