Limitations of the Octet Rule

Limitations of the Octet Rule

The octet rule, though useful, is not universal. It is quite useful for understanding the structures of most of the organic compounds and it applies mainly to the second period elements of the periodic table. There are three types of exceptions to the octet rule.

The incomplete octet of the central atom

In some compounds, the number of electrons surrounding the central atom is less than eight. This is especially the case with elements having less than four valence electrons. Examples are LiCl, BeH₂ and BCl₃.

Li, Be and B have 1,2 and 3 valence electrons only. Some other such compounds are AlCl₃ and BF₃.

Odd-electron molecules

In molecules with an odd number of electrons like nitric oxide, No and nitrogen dioxide, NO₂, the octet rule is not satisfied for all the atoms

The expanded octet

Elements in and beyond the third period of the periodic table have, apart from 3s and 3p orbitals, 3d orbitals also available for bonding. In a number of compounds of these elements there are more than eight valence electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not apply in such cases.

Some of the examples of such compounds are: PF₅, SF₆, H₂SO₄, and a number of coordination compounds.

Interestingly, sulphur also forms many compounds in which the octet rule is obeyed. In sulphur dichloride, the S atom has an octet of electrons around it.

Other drawbacks of the octet theory

• It is clear that octet rule is based upon the chemical inertness of noble gases. However, some noble gases (for example xenon and krypton) also combine with oxygen and fluorine to form a number of compounds like XeF₂, KrF₂, XeOF₂ etc.,
• This theory does not account for the shape of molecules.
• It does not explain the relative stability of the molecules being totally silent about the energy of a molecule.