Introduction to Chemical

Bonding
By
Dr. Joseph Adeyemi Adekoya
Chemistry Department
CST,
Covenant University, Ota.
Office: P54, Petroleum Eng.
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 Bond Parameters
• Bond length
bond length is defined as the equilibrium distance between
the nuclei of two bonded atoms in a molecule.
• Bond lengths are measured by spectroscopic, Xray
diffraction techniques etc.
• Each atom of the bonded pair contribute to the bond
length.
• In case of a covalent bond, the contribution from each
atom is called the covalent radius of that atom.
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 Bond Parameters Contd.
• The covalent radius is measured approximately as the
radius of an atom’s core which is in contact with the core
of an adjacent atom in a bonded situation.
• The van der Waals radius represents the overall size of
the atom which includes its valence shell in a non
bonded situation.

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Quizzes

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 Quiz

• Bond angle It is defined as the angle between the orbitals

containing bonding electron pairs around the central atom in a
molecule or complex ion.
Bond angle is expressed in degree.
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 Covalent Bond Strength.
• Bond enthalpy
It is defined as the amount of energy required to break
one mole of bonds of a particular type between two atoms
in a gaseous state.
The unit of bond enthalpy is kJ per mol. Example-
The H-H bond enthalpy in hydrogen molecule is 435.8
kJ/mol.

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Covalent Bond Strength contd.

• Most simply, the strength of a bond is measured

by determining how much energy is required to
break the bond.
• This is the bond enthalpy.
• The bond enthalpy for a Cl—Cl bond,
D(Cl—Cl), is measured to be 242 kJ/mol.
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 Average Bond Enthalpies

• This table lists the

average bond
enthalpies for many
different types of
bonds.
• Average bond
enthalpies are
positive, because
bond breaking is an
endothermic process.
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 Average Bond Enthalpies Contd.
NOTE: These are
average bond
enthalpies, not
absolute bond
enthalpies; the C—H
bonds in methane,
CH4, will be a bit
different than the
C—H bond in
chloroform, CHCl3.
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Enthalpies of Reaction
• Yet another way to
estimate H for a
reaction is to compare
the bond enthalpies of
bonds broken to the
bond enthalpies of the
new bonds formed.

• In other words,
Hrxn = (bond enthalpies of bonds broken) −
(bond enthalpies of bonds formed) 11
 Enthalpies of Reaction

CH4(g) + Cl2(g) ⎯⎯→

CH3Cl(g) + HCl(g)

In this example, one

C—H bond and one
Cl—Cl bond are broken;
one C—Cl and one H—Cl
bond are formed.

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Enthalpies of Reaction

So,
Hrxn = [D(C—H) + D(Cl—Cl) − [D(C—Cl) + D(H—Cl)
= [(413 kJ) + (242 kJ)] − [(328 kJ) + (431 kJ)]
= (655 kJ) − (759 kJ)
= −104 kJ

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Bond Enthalpy and Bond Length

• We can also measure an average bond length for

different bond types.
• As the number of bonds between two atoms
increases, the bond length decreases.
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 Bond Parameters Contd.
• The larger the bond dissociation enthalpy, stronger will be
the bond in the molecule.
HCl---H + Cl
• In case of polyatomic molecules, the measurement of
bond strength is in the following way let us take the example
of H2O molecule.
H2O---H+OH; ΔaH1=502 kJ/mol
OH---H+O; ΔaH2=427 kJ/mol
In this case, the average bond enthalpy is taken.
average bond enthalpy=(502+427)/2=464.5 kJ/mol
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 Bond Order
• In Lewis description of covalent bond, the bond order is
given by the number of bonds between the two atoms in a
molecule.
• For example, the bond order of H2 which has a single
shared pair of electrons is 1.
• The bond order of O2 with 2 shared pairs of electrons is 2.
• The bond order of N2 with 3 shared pairs of electron is 3.

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 Bond Order Contd.
• For N2, the bond order is 3 and its bond enthalpy is 946
kJ/mol and it is one of the highest for diatomic molecule.
• Isoelectronic molecules and ions have identical bond
orders.
example- N2 and CO have bond order 3.
• A general correlation useful for understanding the
stabilities of molecules is that: with increase in bond order,
bond enthalpy increases and bond length decreases.

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 Resonance Structures
• A single Lewis structure may be inadequate for
representation of a molecule.
• According to the concept of resonance, whenever a
single Lewis structure cannot describe a molecule
accurately, a number of structures with similar energy,
position of nuclei, bonding and non-bonding pairs of
electrons are taken as the canonical structures of the
hybrid which describes the molecule accurately.

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 Resonance Structures Contd.
• For example, O3 molecule can be
represented by two structures as
shown in the figure.
• For O3 these two structures
constitute the canonical structures or
resonance structures and their hybrid
shown by the third figure represents
the structure of O3
more accurately, this is called
resonance hybrid. 20
 Resonance Structures Contd.
• In general it may be stated that
– Resonance stabilizes the molecule as the energy of the
resonance hybrid is less than the energy of any single
canonical structure
– Resonance averages the bond characteristics as a
whole.
Resonance Energy
It is the difference between the actual bond energy of
the molecule and that of the most stable of the resonating
structures (having least energy).
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Resonance Structures of molecules contd.

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Resonance Structures of molecules contd.

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 Polarity of Bonds
• The existence of a hundred percent ionic or covalent
bond represents an ideal situation. In reality no bond or a
compound is either completely covalent or ionic. Even in
case of covalent bond between two hydrogen atoms, there
is some ionic character.
• When covalent bond is formed between two similar
atoms, for example in H2, O2, Cl2, N2 or F2,
the shared pair of electrons is equally attracted by the two
atoms.
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 Polarity of Bonds Contd.
• As a result electron pair is situated exactly between the
two identical nuclei. The bond so formed is called non
polar covalent bond.
• Contrary to this in case of a heteronuclear molecule like
HF, the shared electron pair between the two atoms gets
displaced more towards fluorine since the electronegativity
of fluorine (Unit 3) is far greater than that of hydrogen.
The resultant covalent bond is a polar covalent bond.

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 Polarity of Bonds Contd.
As a result of polarisation, the molecule possesses the dipole
moment (depicted below) which can be defined as the
product of the magnitude of the charge and the distance
between the centres of positive and negative charge. It is
usually designated by a Greek letter ‘μ;’. Mathematically, it is
expressed as follows :
Dipole moment (μ) = charge (Q) x distance of separation (r)
Dipole moment is usually expressed in Debye units (D). The
conversion factor is
1D = 3.33564 x 10-30 Cm, where C is coulomb, and m is
meter. 27
 Polarity of Bonds Contd.
• Further dipole moment is a vector quantity and is
depicted by a small arrow with tail on the positive centre
and head pointing towards the negative centre. For example
the dipole moment of HF may be represented as :
• The shift in electron density is symbolised by crossed
arrow ( ) above the Lewis structure to indicate the
direction of the shift.

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 Polarity of Bonds Contd.
• In case of polyatomic molecules the dipole moment not
only depends upon the individual dipole moments of bonds
known as bond dipoles but also on the spatial arrangement
of various bonds in the molecule. In such case, the dipole
moment of a molecule is the vector sum of the dipole
moments of various bonds. For example in H2O molecule,
which has a bent structure, the two O-H bonds are oriented
at an angle of 104.50. Net dipole moment of 6.17 x 10-30 C
m (1D = 3.33564 x 10-30 C m) is the resultant of the dipole
moments of two O-H bonds.
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 Polarity of Bonds Contd.
• Peter Debye, the Dutch chemist received Nobel prize in 1936
for his work on X-ray diffraction and dipole moments. The
magnitude of the dipole moment is given in Debye units in
order to honour him.
• Net Dipole moment of H2O, μ = 1.85 D = 1.85 x 3.33564 x
10-30 C m = 6.17 10-30 C m
• The dipole moment in case of BeF2 is zero. This is because
the two equal bond dipoles point in opposite directions and
cancel the effect of each other.

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 Polarity of Bonds Contd.
• In tetra-atomic molecule, for example in BF3, the
dipole moment is zero although the B – F bonds are
oriented at an angle of 120° to one another, the three
bond moments give a net sum of zero as the resultant of
any two is equal and opposite to the third.

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 Polarity of Bonds Contd.
• In case of NH3 and NF3 molecule. Both the
molecules have pyramidal shape with a lone pair of
electrons on nitrogen atom. Although fluorine is more
electronegative than nitrogen, the resultant dipole
moment of NH3 (1.46 D), the orbital dipole due to
lone pair is in the same direction as the resultant dipole
moment of the N – H bonds, whereas in NF3 the
orbital dipole is in the direction opposite to the
resultant dipole moment of the three N – F bonds. The
orbital dipole because of lone pair decreases the effect
of the resultant N – F bond moments, which results in
the lower dipole moment of NF3. 32
Polarity of Bonds Contd.

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Polarity of
Bonds Contd.

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Polarity of Bonds Contd.

Example Dipole moment

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 Polarity of Bonds Contd.
The partial covalent character of ionic bonds was discussed by
Fajan’s in terms of the following rules:
• The smaller the size of the cation and the larger the size of the
anion, the greater the covalent character of an ionic bond.
• The greater the charge on the cation, the greater the covalent
character of the ionic bond.
• For cations of the same size and charge, the one, with
electronic configuration (n-1)dnnso, typical of transition
metals, is more polarising than the one with a noble gas
configuration, ns2 np6, typical of alkali and alkaline earth metal
cations. 36
 Polarity of Bonds Contd.
The cation polarises the anion, pulling the electronic
charge toward itself and thereby increasing the electronic
charge between the two. This is precisely what happens in
a covalent bond, i.e., build-up of electron charge density
between the nuclei.
The polarising power of the cation, the polarisability of
the anion and the extent of distortion (polarisation) of
anion are the factors, which determine the per cent
covalent character of the ionic bond.
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Valence Shell • A multiple bond is treated as if it is a single
electron pair and the two or three electron
Electron Pair
pairs of a multiple bond are treated as a single
Repulsion super pair.
Theory • Where two or more resonance structures can
represent a molecule, the VSEPR model is
applicable to any such structure.
• The repulsive interaction of electron pairs
decrease in the order:
• Lone pair (lp) – Lone pair (lp) > Lone pair
(lp) – Bond pair (bp) > Bond pair (bp) – Bond
pair (bp)
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 • Nyholm and Gillespie (1957) refined the VSEPR
Valence Shell model by explaining the important difference
Electron Pair between the lone pairs and bonding pairs of
Repulsion electrons. While the lone pairs are localised on the
Theory central atom, each bonded pair is shared between
two atoms. As a result, the lone pair electrons in a
molecule occupy more space as compared to the
bonding pairs of electrons. This results in greater
repulsion between lone pairs of electrons as
compared to the lone pair – bond pair and bond
pair – bond pair repulsions. These repulsion effects
result in deviations from idealised shapes and
alterations in bond angles in molecules. 40
 • For the prediction of geometrical shapes of molecules
Valence Shell with the help of VSEPR theory, it is convenient to
Electron Pair divide molecules into two categories as (i) molecules in
which the central atom has no lone pair and (ii)
Repulsion
molecules in which the central atom has one or more
Theory lone pairs.
• The VSEPR Theory is able to predict geometry of a
large number of molecules, especially the compounds
of p-block elements accurately. It is also quite
successful in determining the geometry quite
accurately even when the energy difference between
possible structures is very small. The theoretical basis of
the VSEPR theory regarding the effects of electron pair
repulsions on molecular shapes is not clear and
continues to be a subject of doubt and discussion. 41
Shapes of molecules

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Shapes of
molecules
contd.

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Shapes of molecules contd.

X
X X
X

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Shapes of
molecules
contd.

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Shapes of BeCl2, HgCl2
molecules
contd. BF3

CH4, NH4+

PCl5

SF5

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Shapes of
molecules
contd.

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Shapes of
molecules
containing
Bond Pair
and
Lone Pair

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Shapes of molecules contd.

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Shapes of Molecules
containing Bond Pair
and Lone Pair

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Shapes of Molecules
containing Bond Pair
and Lone Pair

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