ELECTRONIC THEORY IN ORGANIC CHEMISTRY: BONDING, LEWIS

STRUCTURES, VSEPR THEORY,VALENCE BOND THEORY AND SHAPES OF

MOLECULES.

BONDING
Bonding is the joining of two atoms in a stable arrangement. It involves a force of attraction
which holds together two or more atoms, ions and molecules.
A. .A A A
The distances between bonded atoms are less than those between non-bonded atoms
The forces between bonded atoms are greater than those between non-bonded atoms.
Bonding is a favourable process because it leads to lowered energy and increased stability. It
may occur between atoms of the same or different elements. In an atom, valence electrons
(outermost electrons) participate in bonding, leading to a stable configuration of electrons
(octet rule). For instance, the First-row element hydrogen (1s 1) will attain the electronic
configuration of a noble gas He (1S2 ) after bonding.
Types of Bonding
There are 2 main types of bonding: ionic and covalent.
1. Ionic bonding is the complete transfer of an electron from an atom (a metal) to another atom
(a non-metal) to give ions. So, ionic bond is an electrostatic attraction between oppositely
charge ions. For example, the ionic bonding in sodium chloride is formed by the transfer of
an electron from a sodium atom to a chlorine atom. Na+ + Cl-  NaCl (s)

Typical ionic compounds consist of metallic cations from group 1 and 2 and non- metals
anions from groups 6 &7.
The formation of an ionic compound is favoured when one element has a low ionization
energy (metal) and the other a high electron affinity ( non-metal).
The driving force for the formation of ionic bonds is the considerable lowering of energy that
takes place when ions pack together closely as a solid and their opposite charges attract each
other strongly
Lattice Energy and Enthalpy
• Lattice energy is the energy needed to bring gaseous cations and gaseous anions to
form a solid lattice. For example:

• Na+ (s) + Cl- (g)  NaCl (s) lattice energy = -787kjmol-1

• Lattice enthalpy is the heat required for vaporization of the solid to a gas of ions.
Lattice enthalpy or lattice energy can be measured by combining other measurements
or applying Born-Haber cycle
 2. Covalent bonding
This bonding involves sharing of valence electrons between 2 participating atoms.
Compounds that result from covalent bonding are called molecules. E.g CH 4, H2,
NH3, O2, N2 e.t.c. the major type of bonding that exists between organic molecules is a
covalent bond. There are two types of covalent bonding: ordinary and coordinate
covalent bonding.
Covalent bond could be single bond, double bond or triple bond. i.e: C-C, C=O, C=
C etc.

Molecular Orbitals

The electrons in covalent compounds exist in molecular orbitals. Each orbital can take
one or two electrons of opposite spin.
There are three types of molecular orbitals:
 Bonding orbitals
 Non-orbitals
 Antibonding orbitals

Bonding Orbitals
Bonding orbitals are formed by two atomic orbitals merging or overlapping.
Bonding orbitals consist of the electrons from the overlapping atomic orbitals
•• ••

H Cl H Cl
• •
+ • •
•• ••

Overlap of H (1s) and Cl (2p)

This type of overlap places bonding electrons in a MOLECULAR ORBITAL along the
line ( horizontal) between the two atoms in the formation

Types of bonding orbitals

Two types of bonding orbitals can result from overlapping of orbitals:

• Sigma () molecular orbital .

 Single overlap of two s–atomic orbital, two P( horizontal) orbitals, and s and p
atomic orbitals.

H H  
• + • •  •
sigma bond ( ) 
e.g

• Pi (p) Orbital.
Double overlap of two p-orbitals. This type of bond only occurs where the two atoms
are already bonded by a sigma bond.

 All single bonds are sigma (σ) bonds.: sigma (σ) bond is formed by end-to-
end overlap of orbitals.
 A pi ( ꙥ ) bond is formed by sideways overlap of orbitals.
A pi bond is weaker than a σ ond because sideways overlap is less effective
than end-to-end overlap.
A double bond consists of one σ bond and one p bond

Non-Bonding Molecular Orbitals (NBMOs)

• These are orbitals that do not have any other orbitals to combine with during bond
formation, therefore they become NBMOs.
• Example of this can be found in Nitrogen molecule (N2).
• Each nitrogen atom in the molecule has five outer –shell electrons: 1s22s22p3 .
• Two of these outer electrons (2) exist as lone pair of electrons and they will reside in a
non-bonding orbital, since they are not unpaired. The other three electrons (3)
participate in bonding because they are unpaired.
• In a non-bonding orbital addition or removal of an electron does not change the
energy of the molecule.
 Anti-bonding Orbitals
• Electrons in sigma and Pi bonding orbitals bond the molecule together.
• Electrons can also exist in orbital which pulls the molecules apart. These orbitals are
called anti bonding orbitals.
• They have higher energies than their corresponding bonding orbitals and can thus
only be occupied by electrons which have been excited .

• These orbitals are designated by * notation , i.e * and p*

Electron Distribution in Molecules

• Electrons are distributed in molecules as:
• shared or BOND PAIRS
• unshared or LONE PAIRS or NON- BONDING PAIR
• Electron distribution is depicted with Lewis electron dot structures

Molecular Shapes
There are several theories which explain the electronic structure and shapes of molecules.
These theories include:
• Lewis Theory ( Octet Rule)
• Sidgwick-Powell theory
• Valence shell Electron Pair Repulsion ( VSEPR) theory
• Valence Bond theory
Tutorial 1
• Use Lewis theory to show the bonds formed in the following molecules: NH 3, H2, H2O,
CO2, HF, N2, HCHO, H3O +, CH3NO, BF3, SF4
• Which of these molecules does /do not obey octet rule.
Limitations of the Lewis structure
This model could not give the bond angles and shapes of molecules.

Sidgwick –Powel theory

• This theory states that “for molecules and ions that only contain single bonds, the
approximate shape can be predicted from the no of electron pairs in the outer or
valence shell of the central atom.
• Electron pair in atomic orbital can be unpaired electron, known as Bond pair or Paired
electrons known as Unshared electron or Lone pair
• Bond pairs and lone pairs were considered as equivalent.
Table 1. Molecular shapes as predicted by Sidgwick-Powel theory

Number of electron Shape of molecule Bond angle

pairs in outer shell

2 Linear 180o

3 Plane triangle 120o

4 Tetrahedron 109o 18’

5 Trigonal bipyramid 120o and 90o

6 Octahedron 90o

7 Pentagonal bipyramid 72o and 90o

Limitation of Sidgwick –Powel theory

Repulsive effect of lone pairs and electronegativity on shapes of molecules was not explained
by this theory. All electron pairs were taken as the same.

Tutorial 2.
Predict the shape of the following molecules and explain the observed bond angles of each.
i. SF6
ii. BrF5
iii. xeF4
iv. BF3
v. [BF4]-

VALENCE SHELL ELECTRON PAIR REPULSION THEORY (VSEPR)

VSEPR theory was postulated by Gillespie and Nyholm . The theory is an improvement over
Sidgwick-Powel theory since the theory predicts and explains molecular shapes and bond
angles more exactly
The theory is summarized as follows:
• The shape of the molecule is determined by repulsion between all of the electrons
pairs present in the valence shell. This statement is consistent with Sidgwick –Powel
theory
 • A lone pair of electrons takes up more space around the central atom than a bond pair,
since the lone pair is attracted to one nucleus whilst the bond pair is shared by two
nuclei.
• Repulsion between two lone pairs is greater than repulsion between lone pair and
bond pair, which in turn is greater than repulsion between two bond pairs., i.e
Repulsion between LPLP > LPBP > BPBP
• Presence of Lone pairs on the central atom causes slight distortion of the bond angle
from the ideal shape.
• The magnitude of repulsion between bonding pairs of electron depends on the
electronegativity difference between the central atoms and the other atoms.
• Double bond causes more repulsion than single bond and triple bonds cause more
repulsion than a double bond i.e, Repulsion in Triple bond > Double bond >Single
bond
Effect of Lone Pairs on Molecular Shape
• In CH4 there are four bonding pairs of electrons in the outer shell of the C atom. The
structures of CH4 is regular tetrahedron with bond angle of 109o 18’ ( H -C- H)
• Likewise, in NH3, there are four electron pairs in the outer shell of Nitrogen, which
contains three bond pairs and one lone pair.
• The structure was found to be tetrahedron with a bond angle H- N- H reduced from
109o 18’ to 107o 48’
• In the molecule of H2O, the central atom was found to contain four electron pairs,
therefore the molecule is said to be tetrahedron and bond angle of 109o 18’.
• However, the bond angle was found to be 104o 27’. The observed reduction in the
bond angle was attributed to the presence of two lone pairs of electrons in the outer
shell of Oxygen

Effect of Electronegativity
NF3 and NH3 both have structures based on a tetrahedron with one corner occupied by a lone
pair. The high electronegativity of F pulls the bonding electrons further away from N than in
NH3. Thus repulsion between bond pairs is less in NF 3 than in NH3. Hence the lone pair in
NF3 causes a greater distortion from tetrahedral and gives a F-N-F bond of 102o 30’ compared
with 107o 48’ in NH3

Tutorial 3
H2O and F2O are Octahedral molecules explain why their bond angles are 104 o 27’ and 102o
respectively?
 Valence Bond Theory
According to this theory, a covalent bond is formed by overlapping of two half-filled
atomic orbitals containing electron of opposite spins. The greater the overlapping, the
stronger the covalent bond. All atoms are made up of nucleus surrounded by electrons
in concentric shells. Each shell surrounding the nucleus corresponds to a principal
quantum no n. n=1, 2, 3 , 4, 5,6. etc. each shell has sub shells known as orbitals. An
atomic orbital is a region in space around the nucleus where there is probability of
finding an electron. Types of subshell or orbitals include: s, p, d, f..
This theory provides a basis for simple description of small inorganic molecules
• The number of bonds formed by an atom is usually the same as the number of
unpaired electrons in the ground state i.e lowest energy state
• Atom may form more bonds by excitation. When electrons which are paired in the
ground state received extra energy, they become unpaired .
• Then the unpaired electron will be promoted to suitable orbital where they can
suitably form bonds.
• Hence the aggregate number of bonds that such atom can form will be more.

Consider the formation of the following simple molecules :

• In HF, H has a singly occupied s orbital that overlaps with a singly filled 2p orbital on
F
• In H2O, The O atom has two singly filled 2p orbitals, each of which overlaps with a
singly occupied s orbital from two H atoms
• In NH3, there are three singly occupied p orbitals on N which overlap with s orbitals
from the tree H atoms.
• In CH4, the C atom in its ground state has the electronic configuration 1s 22s2
2px12py12pzo
• C has only 2 unpaired electrons and so can form only two bonds.
• If C is excited with sufficient energy, the 2s electrons will be unpaired, giving 1s 22s1
2px12py12pz1
• There are now four unpaired electrons which can overlap with the singly filled s
orbital on the four H atoms.