CHM 212 (ORGANIC CHEMISTRY II)

ELECTRONIC THEORY

Chemical reactions take place because of the behavior of electrons in atoms and
molecules. This behavior happens as a result of arrangement of electrons within
atoms. A neutral atom contains the same number of electrons and protons. Electrons
are arranged according to their energy levels around the nucleus of an atom. The
outermost shell of electrons in an atom is called its ‘valence shell’ and the electrons in
this shell is called ‘valence electrons’.

The electronic theory follows the theory of atomic structure. The noble gases
except Helium (He) has eight (8) electrons in their shell and these elements are very
stable. All other elements in the event of their bond formation get stabilized by having
electrons in their valence shell, this is called octet rule or octet theory.
According to this theory, an atomic specie tends to be stable when its valence
shell contains eight (8) electrons. The group one (1) metals attained this octet state by
losing one electron except Lithium (Li), and this tendency increases down the group.
On the other hand, the non-metals gain electrons to attain the octet state and this
tendency increases along the period and decreases down the group. Fluorine (F) in
group seven (7) gain an electron to attain the noble gas structure more easily than any
of the element in the same group. Thus the tendency to attain the noble gas structure
increases towards the right and towards the top of the periodic table.

i. Valence Bond Theory (VB) of Covalent Bonding:

Linus Pauling proposed the valence bond theory to explain how valence
electrons of different atoms combine to form a molecule. According to him, the
unpaired electron of one atom combines with unpaired electron of other atom to
form a molecule. The greater the overlapping, the stronger the covalent bond. Each
atomic orbital can accommodate two (2) electrons of opposite spin. Electrons enter
each atomic orbital of a given type singly before pairing of electrons occur within
those orbitals.
Carbon atom therefore, has only two unpaired electrons in its ground state
with electronic configuration as 1s22s22p12p1. With this structure, carbon is
expected to form only two covalent bond, as it did in some cases. It is however
known that the tetravalent carbon is more prevalent in which carbon forms
covalent bonds. The carbon atom contains four (4) unpaired electrons on
excitation. This happens when the electron in the 2s orbital gets promoted to the
third 2p orbital with the resulting configuration as 1s22s12p12p12p1.
ii. Molecular Orbital Theory:
When atoms combine into a molecule, the electrons contributed to the chemical
bond by each atom are no longer localized to individual atoms, but belong to
the entire molecule. In the act of the formation of the molecule, when the nuclei
 approach each other within bonding distance, the charge cloud containing the
valence electron overlap by what is called Linear Combination of Atomic Orbitals
(LCAO) and a bigger cloud around the molecule is formed. In so doing, the two
electrons that are of opposite spin originally associated with the two atoms lost
their individual identity and become common to both the atoms to form
molecular orbital. The molecular orbital has the characteristics separately from
the atoms. The constructive combination of atomic orbitals increases electron
probability between the nuclei and leads to an energetically favorable bonding
molecular orbital.

The following criteria are employed for molecular orbitals;

a) Molecular orbitals are filled beginning with the lowest energy levels.
b) Electrons enter degenerate orbitals singly, with the same spin quantum number
before pairing.
c) No more than two spin-paired electrons can be accommodated by a molecular
orbital.