Course: Chemistry for Remedial

Chapter
Program2: Chemical Bonding and Structure

1
 Chapter 2
Chemical Bonding and Structure
2.1. Introduction

What is chemical bonding?

 Chemical bond is a strong force of binding between two or
many atoms in compounds, molecules or ions.
Why do atoms combine?
 Everything wants to be more stable. It is easy to lie down than
stand up; bonding is natural way of allowing the elements to lie
down the energies of combining species.

 Atoms are bonded together to:

 attain noble gas electronic configuration.
 have stability.
2
 have lowest possible energy.
Figure: Potential-energy curve for H2: The stable molecule occurs at the bond distance
corresponding to the minimum in the potential-energy curve 3
2.2. Types of Chemical Bonding
• Chemical bonds are basically classified into three types
consisting of
(i) Ionic or electrovalent bond
(ii) Covalent bond and
(iii)Metallic bond.

• Mostly, valence electrons in the outer energy level of an atom

take part in the chemical bonding.
2.2.1. THE IONIC BONDING
 Electrons are completely transferred from one atom to
another. It is formed between electropositive species
(metals) and electronegative species (nonmetals).

 In the process of either losing or gaining negatively

charged electrons, the reacting atoms form ions. 4
 Cont’d…
 The electrostatic force of attraction between
oppositely charged ions results in the formation of
ionic bond or electrovalent bond.
 Example: Consider the formation of some ionic bandings b/n
Na+ and Cl- ions:

 Examples of ionic compounds include: NaCl, MgO, MgBr2, CaC2,

HCl, Li3N…
5
General Properties of Ionic Compounds

 Ionic compounds usually exist in the form of crystalline solids.

 Ionic compounds have high melting point and high boiling

point due to strong attraction of force between ions.

 Ionic compounds are generally soluble in water and other polar

solvents having high dielectric constants.

 Ionic compounds are good conductors of electricity in the

solutions or in their molten states.

 In ionic - compounds, each ion is surrounded by oppositely

charged ions uniformly distributed all around the ion. i.e., Ionic
bonding is non-directional.

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2.2.2. THE COVALENT BONDS
 Covalent bonds involve sharing of a pair of valence electrons by
two atoms
 When two atoms have a small difference in their tendencies to
lose or gain electrons, we observe electron sharing and covalent
bonding.
 This type of bonding most commonly occurs between nonmetal
atoms (although a pair of metal atoms can sometimes form a
covalent bond).

Example:

7
 Multiple covalent bonds are common for certain atoms
depending upon their valence configuration.
 For example, in ethylene (C2H4), a double covalent bond results
from the sharing of two sets of valence electrons.

 Atomic nitrogen (N2) is an example of a triple covalent bond.

 The polarity of a covalent bond is defined by any difference in

electro-negativity between the two atoms participating in the
covalent bond formation.

 Bond polarity describes the distribution of electron density

around two bonded atoms. 8
 For two bonded atoms with similar electronegativities, the
electron density of the bond is equally distributed (shared)
between the two atom, this is a non-polar covalent bond.

 The electron density of a covalent bond is shifted towards the

atom with the largest electro-negativity.

Example: HBr = H2 =

Polar covalent bond Non- polar covalent bond

Coordinate Covalent Bond
•A coordinate covalent bond (also called a dative bond) is formed
when one atom donates (contribute) both of the electrons to form
a single covalent bond.

Example: BF3+:NH3 H3N-BF3

•As boron does not have a full outer
shell, it is able to accept an electron 9
pair from ammonia.
Properties of covalent compounds

 The covalent compounds do not exist as ions but they exist as

molecules.
 The m.pt. and b.pt. of covalent compounds are generally low.
 Covalent compounds are generally insoluble or less soluble in
water and other polar solvents. However, these are soluble in
non-polar solvents.
 They are poor conductors of electricity in the fused or dissolved
state.
 Molecular reactions are quite slow because energy is required
to break covalent bonds.
 Since the covalent bond is localized in between the nuclei of
atoms, it is directional in nature.
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The Octet Rule
 States that an atom tends to gain, lose or share electrons until
there are eight electrons in its valence shell (the nearest noble
gas configuration at its row).
 The octet rule guides us in allotting electrons to the atoms in a
Lewis structure; in a few cases, however, we set the rule aside.
Example: Na+ = 1s22s22p6 = 2:8  Configuration of Ne.
Cl- = 1s22s22p63s23p6 = 2:8:8  Configuration of Ar.
Note: - Hydrogen follows a special configuration called Duet rule (2
electrons in its outer most shell).
Exceptions to the Octet Rule
1) Electron deficient molecules
 Cpds containing either Be or B are often electron deficient, i.e.,
they have fewer than 8 electrons around Be or B atom.
Example: BH3, BeCl2, BF3, etc.
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2) Odd electron molecules
 A few molecules contain an odd number of valence electrons, so
they cannot possibly have all their electrons in pairs.
 Such species, called free radicals, contain a lone (unpaired)
electron, which makes them paramagnetic and extremely
reactive.
 Free radicals can react with each other to pair up their lone
electrons.
Example: NO, NO2, etc.
 When two NO2 molecules collide, for example they form
dinitrogen tetraoxide, N2O4, and each N attains an octet.
O O O O
N + N N N
O O O O
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3) Expanded valence shells (more than octet electron)
 Many molecules or ions have more than eight valence electrons
around the central atom from period 3 or higher, those in which
d-orbitals are available.
Example: PCl5 , SF6, I3-, etc.

Theories of Bonding

I) Lewis Theory of Covalent Bonding

 The Lewis structure (or Lewis formula)- is two-dimensional

structural formula consists of electron-dot symbols that depict
each atom and its neighbors.
 The bonding pairs that hold them together, and the lone pairs
that fill each atom's outer level (valence shell) - octet rule.
13
Steps to assign Lewi’s dot formula
1. Write the electron configuration of the combining atoms and
determine the valence shell electrons of each atom.
2. Add the valence shell electrons of all combining atoms (charge
on the molecule:
(i) if the molecule is positively charged, subtract the number
of charges from the total valence electrons;
(ii) if the molecule is negatively charged add the number of
charge to the total valence shell electrons.
3. Decide the central atom:
(iii)The atom with fewer numbers is taken as central atom.
(iv)Large sized and relatively electropositive atoms are
always selected as central atom.
(v)H, O and halogens are always selected as surrounding
atoms.
(vi)O and C have a tendency to form O-O and C-C chain
14
respectively.
4. Share a pair of electron between central atom and surrounding
atom (form a temporary single bond).
5. Complete the octet starting from the surrounding atom.
6. Put any remaining as after the surrounding atoms complete
their octet is put as lone pair on the central atom.
7. If the central atom has less than an octet, you must form
multiple bonds so that each atom has an octet

Example 1: What is the Lewis structure for CCl4?

Solution
1) We count the valence electrons
Carbon is group IVA contributes 4e-,
Chlorine Group IIIA contributes 7e each 28e-
32e-
15
 Cont’d…
2) Distributing electrons by placing pairs in each bond gives
Cl
Cl C Cl
Cl
3) This has used 8e- so there are 32 - 8 = 24e- left. Complete the
valence shells of Cl atoms.

Cl Cl
Cl C Cl or Cl C Cl
Cl Cl
4) This has used 24e-, non are left. Each atom has an octet & therefore,
this is the Lewis structure for CCl4.

16
Example 2: What is the Lewis structure for the carbonate ion, CO32-?
Solution:
1) This time we have an ion whose formula suggests the atom
arrangement
O
O C O
2) Counting valence electrons; carbon supplies 4e -, each oxygen
supplies 6e-, & the negative charge adds 2e-, the total is 4 + 18 + 2
= 24e-. Placing a pair in each bond gives.
O
O C
O
 This has used 6e-, leaving 18e-.

3) The 18 electrons are used to complete the octet around oxygen.

17
 Cont’d…

 This time we've run out of electrons, but C doesn't have an octet.

4) Now, move one of the unshared pairs on oxygen into one of the
bond. 2-
O
C
O O
 Notice that the oxygen hasn't lost the pair, but carbon completes its
octet by sharing it.

5) Finally we should be sure to indicate the charge on the ion by

enclosing the Lewis structure in brackets with the charge outside.
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RESONANCE STRUCTURES
 Some molecules have structures that are not expressed correctly
by single Lewis structure.

 For example consider the carbonate ion (CO32- ), whose Lewis

structure was indicated in example 2,

 The three Lewis structures shown in figure below differ only in the
position of the double bond.

 Such Lewis structures are said to be resonance structures.

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 Each of these structures is known as Resonance contributor.

 The most stable Lewis structures is assumed to be a hybrid of all

resonance contributors

 Thus, the resonance hybrid structure of carbonate ion is

assumed to be as follows.

Activity
Write all resonance contributors and the most probable (resonance
hybrid) strictures of each of the following structures:
O3, NO2- , SO2 and C6H6
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 II) Sidwick-powell theory (Valence Shell Electron Pair
Repulsion (VSEPR) Theory)

 This theory was proposed for the first time by Sidwick and Powell in
1940 and developed by Gillespie and Nyholm in 1957.
 This theory is very useful in predicting the geometry or shape of
polyatomic molecules or ions of non-transition elements.
 According to this theory, “the shape of a given species (molecule or
ion) depends on the number and nature of electron pairs
surrounding the central atom of the species.”
 Molecular Geometry is the general shape of a molecule as
determined by the relative position of atomic nuclei.
 The valence shell electron pairs are arranged about each atom so that
electron pairs are kept as far away from one another as possible, thus
minimizing the electron pair repulsion. 21
 The basic principles of VSEPR theory
1.Electron pairs will arrange themselves to be as far apart as possible
so that the repulsion between them is at minimum.

2.Lone pair of electrons takes more room on the surface of atom than
that of bonding pairs. According to the VSEPR theory, the repulsion
of electron pair is in the following order:
Lone pair-Lone Pair > Lone Pair- Bond Pair > Bond Pair- Bond Pair

3.The repulsive force decreases sharply with increasing bond angle

4.The geometries that minimize the repulsion between groups of

electrons have been mathematically established.

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Table 2.1: The basic sets of five geometries, general formula of
molecules, bond angles and examples.
Geometrical General Angles Examples 3-D view of 2-Dview
description formula geometry
Linear AX2 1800 BeCl2, CO2, CS2

Trigonal-
planar AX3 1200 BCl3,CO32,SO3

Tetrahedron AX4 109.5 CH4,CCl4,NH4+,

SiF4,BF4-, ClO4,
PO43-

Trigonal AX5 900,1200 PF5, PCl5,AsF5

bipyramid

Octahedron AX6 900 SF6,SeF6,PF6-,Si

F62-
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 Table 2.2: Summary of the electron pair geometry and molecular
geometry.
Electro pairs Electro pair Molecular Example Other
Total Bonding Lone geometry Geometry Examples
pair pair
2 2 0 Linear Linear BeF2, HCN, CS2,
CO2
3 3 0 Trigonal Trigonal SO3, NO3-, CO32-
planar planar

2 1 Trigonal Bent(V- SO2, PbCl2,

planar shape) SnBr2, O3,SnCl2

4 4 0 Tetrahedral Tetrahedral SiCl4, SO42-, ClO4-

3 1 Tetrahedral Trigonal PF3, ClO3-, H3O+

pyramidal 24
 Table 2.2 (Cont’d…)

4 2 2 Tetrahedral Bent OF2, SCl2

(angular)

5 0 Trigonal Trigonal PF5, AsF5,

bipyramidal bipyramid SOF4
5 al
4 1 Trigonal Distorted SF4, IF4+,
bipyramidal tetrahedral
XeO2F2,
(See Saw) IO2F2-
3 2 Trigonal T-shape ClF3,
5 bipyramidal
BrCl3

2 3 Trigonal Linear XeF2, IF2-

bipyramidal 25
 Table 2.2 (Cont’d…)
6 0 Octahedral Octahedral IOF5,
SCl6

5 1 Octahedral Square TeF5-,

6
pyramidal BeF5,
XeF5+
4 2 Octahedral Square planar ICl4-

 Generally the electron pair geometry depends on the number of

electron pairs around central atom.
 Where as, the Molecular geometry depends on both the number of
electron pairs and the nature (bonding and lone pair) of electron
pairs around central atom.
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Merits of Knowing Shape of Covalent Compounds

 Knowing the shape (geometry) of covalent molecules is a key to

understand its physical and chemical behavior.
 One of the most important and far-reaching effects of molecular
shape is molecular polarity, which can influence melting and
boiling points, solubility, chemical reactivity, and even biological
function.

Bond Polarity

In general, a covalent bond is:

 polar if it occurs between two different atoms.
 nonpolar if it occurs between two identical atoms.
 Dipole Moments
- It is a measure of the polarity of a bond.
- Is often represented by a special arrow. 27
 Arrow points toward more EN atom.
H F

Polarity of Diatomic Molecules

 Diatomic Molecules - molecules made of only two atoms.
 If atoms are the same, molecule is nonpolar.
 If atoms are diff., molecule is polar.
NOTE: Polar does not mean charged.
 Is Cl2 polar or nonpolar?
 Is CO polar or nonpolar?

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Molecules With 3 or More Atoms

• A molecule with 3 or more atoms is:

– Polar if its central atom has lone pairs OR
• If the outer atoms are not all the same.
– Nonpolar if its central atom has no lone pairs AND
• All the outer atoms are identical.

Example: CO2 vs. H2O

i) Consider the Lewis structure of CO2:

 This molecule is nonpolar.

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ii) Consider the Lewis structure of H2O:
 This molecule is polar.

Exercise: CH4 vs. CH3Cl

 Neither CH4 nor CH3Cl has any lone pairs on the central carbon
atom.
 Is CH4 polar or nonpolar?
 Is CH3Cl polar or nonpolar?
H H
H C H H C Cl
H H
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Properties of Polar Molecules
Polar molecules tend to align when placed in an electric field with
the positive end of the molecule oriented toward the negative plate
and the negative end toward the positive plate.
We can use an electrically charged object to attract polar molecules,
but nonpolar molecules are not attracted.
Polar solvents are better at dissolving polar substances, and nonpolar
solvents are better at dissolving nonpolar substances.

Molecules are always randomly distributed in the liquid state in the

absence of an electric field. When an electric field is applied, polar
molecules like HF will align to the dipoles with the field direction.

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III)The Valence Bond Theory (VBT)
 The VBT was proposed by Heitler and London to explain the
formation of covalent bond quantitatively using quantum
mechanics.
 Later on, Linus Pauling improved this theory by introducing the
concept of hybridization.
 The main postulates of this theory are as follows:
i) A covalent bond is formed by the overlapping of two half filled
valence atomic orbitals of two different atoms.
ii)The electrons in the overlapping orbitals get paired and
confined between the nuclei of two atoms.
iii)The electron density between two bonded atoms increases due
to overlapping. This confers stability to the molecule.
iv)Greater the extent of overlapping, the stronger is the bond
formed.
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 VBT…
 As the two atoms are brought more closely
together, however, the repulsion of the atomic nuclei becomes
more important than the electron-nucleus attraction and the
bond become unstable.
 For each bond, then, there is a condition of optimal orbital
overlap that leads to a maximum bond strength (bond energy) at
a particular internuclear distance (bond length).

Figure: Atomic orbital overlap and bonding in H2

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 VBT…
• The s orbital is spherical, but p and d orbitals have particular
orientations.
• Thus, in p & d orbitals, more electron density is in one direction
than in another.
• The bond involving p or d orbitals will tend to be oriented in the
direction that maximizes overlap.

Figure: s-s, s-p and p-p oribital overlapping and spin pairing in 3-D
molecules 34
Sigma(σ-) and Pi (π-) Bonds
 Based on the pattern of overlapping, covalent bonds are classified as
sigma- and pi- bonds.
i) σ-bond
 The covalent bond formed due to overlapping of atomic orbital along
the inter-nucleus axis (head on overlapping) is called σ-bond
(sigma bond)
 It is a stronger bond and cylindrically symmetrical.
 The σ-bond (overlapping) is further classified as σs-s overlapping, σs-p
overlapping and σp-p overlapping (See the following figure).

35
 (a) (b) (c)

Figure: (a) σs-s , σs-p and σp-p overlapping in various kinds of molecules

ii) π-bond
 The covalent bond formed by sidewise overlapping of atomic orbitals is called π- bond.
 In π- bond, the electron density is present above and below the inter-nuclear axis.
 It is relatively a weaker bond than sigma bond since the electrons are not strongly attracted
by the nuclei of bonding atoms.

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Figure: p-p sideways overlap
 Orbital Hybridization
 The old version of valence bond theory is limited to diatomic
molecules only.
 For example, the covalent bond in H2, O2, Cl2, N2, HCl, etc.
molecule can be explained by the orbital overlapping of the two
atoms.
 However, it could not explain the structures and bond angles of
molecules with more than three atoms.
E.g. It could not explain the structures and bond angles of H2O,
NH3 etc.
 In order to explain the structures and bond angles of molecules,
Linus Pauling modified the valence bond theory using
hybridization concept.
 Definition: Orbital hybridization is the intermixing of two or more
atomic orbitals of similar energy to give identical and degenerate
new type of orbitals. 37
 Orbital hybridization…
 Only atomic orbitals of same atom with almost same energy can
participate in the hybridization.
 The completely-filled or half-filled or even empty orbitals can
undergo hybridization.
 The combination of orbitals belonging to different atoms is called
bonding.
 The new orbitals that are formed due to hybridization are known as
hybrid orbitals, which have mixed characteristics of atomic orbitals.
 The shapes of hybrid orbitals are identical. Usually they have one
big lobe associated with a small lobe on the other side.
 The hybrid orbitals are degenerate i.e., they have similar energy.
 The number of hybrid orbitals formed are exactly equal to the
number of atomic orbitals intermixed.
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 Orbital hybridization…
Example: If three atomic orbitals hybridize, the number of hybrid
orbitals formed will be equal to 3.
 The hybrid orbitals are filled with those electrons which were
present in the parent atomic orbitals.
 The filling up of electrons in them follows Pauli's exclusion
principle and Hund's rule.
 The hybrid orbitals participate in the σ bond formation with other
atoms.
 The hybrid orbitals are oriented in space so as to minimize
repulsions between them. This explains why the atomic orbitals
undergo hybridization before bond formation.
 The bond angles in the molecule are equal to or almost equal to the
angles between the hybrid orbitals forming the σ bonds.
 The shape of the molecule is determined by the type of
hybridization, number of bonds formed by them and the number of
lone pairs. 39
Types of Hybrid Orbitals
i) sp hybridization
- When two electron groups surround the central atom, we observe a
linear shape, which means that the bonding must have a linear
orientation.
- VB theory explains this by proposing that mixing two nonequivalent
sp hybrid hybrid orbitals that lie 1800 apart.
- Characterized by the central atom of linear molecules.
Example: CO2, BeCl2, etc.

hybridization

2s atomic 2p atomic sp hybrid sp hybrid

orbital orbital orbital orbital
40
Figure: The sp-hybridization scheme illustrated
ii) sp2 Hybridization
- In order to rationalize the trigonal planar electron group arrangement and the
shapes of molecules based on it.
- The mixing of one s and two p orbitals of the central atom to give three hybrid
orbitals that point toward the vertices of equilateral triangle.
- Each of sp2 hybrid orbitals are 1200 apart.
- VB theory proposes that the central B atom in the BF3 molecule is sp2 hybridized.

hy
br sp2 hybridized orbitals
id
i za
t io
n
n n n

Unhybridized atomic Orbitals

41
Figure: The sp-hybridization scheme illustrated
 Figure: The 3-D view of sp2 hybrid orbitals

- The figure above shows the three-sp2 orbitals in the trigonal plane,
with the third 2p orbital unhybridized and perpendicular to this
plane.
- Each sp2 orbital overlaps the 2p orbital of an F atom, and the six
valence electrons- three from B and one from each of the three F
atoms-form three bonding pairs.

42
iii) sp3 Hybridization
- One s and all three p orbitals of the central atom mix and form four
sp3 hybrid orbitals, which point toward the vertices of a
tetrahedron.

Figure: The sp3 hybridization 43

- Its four valence electrons half fill the four sp3 hybrids, which overlap the half-
filled 1s orbitals of four H-atoms and form four C-H bonds.

sp3
sp3

sp3
sp3

The C atom in methane

is sp3 hybridized.

Figure: sp3 Hybrid orbitals and bonding in methane scheme illustrated.

44
iv) sp3d Hybridization
- One one s, the three p, and one of the five d orbitals of the central
atom mix and form five sp3d hybrid orbitals.
- The central atom of trigonal bipyramidal shape of molecules such
as PCl5 molecule are characterized by this type of hybridization.

Figure: The sp3d hybrid orbitals in the molecule of PCl5 45

v) Sp3d2 Hybridization
 The one s, the three p two of the five d orbitals of the central atom
mix and form six sp3d2 hybrid orbitals, which point to the
vertices of an octahedron.
 The central atom of octahedral shape of molecules such as SF6
molecule are characterized by this type of hybridization.

Figure: The sp3d2 hybridization in SF6 46

iv) The Molecular Orbital Theory (MOT)
 Atomic orbitals are capable of combining or overlapping, to
produce new electron distributions called molecular orbitals (MOs)
– one MO for every AO.
 Molecular orbital: is a region where electrons are most probably
found around the nuclei of two or more atoms.
 Molecular orbitals are formed by the overlap of atomic orbitals.
LCAO Methods
 In contrast to valance bond theory, in which one bonding orbital is
formed because of the interaction of two atomic orbital, in MOT
two molecular orbital results from the combination of two atomic
orbital.

47
a) Bonding molecular orbital (BMO):
 Is the combination of atomic orbitals is additive, it results in forms
bonding molecular orbitals
AOA + AOB = BMOAB
where: AO is atomic Orbital and BMO is a bonding molecular orbital.
-The energy of BMO is lower than the energy of atomic orbital in an
isolated atom.
-The electron density is concentrated b/n the two nuclei.
-Formation of BMO is exothermic process and stabilizes the
molecule.
b) Anti Bonding molecular orbital (ABMO)
 Is formed by subtraction of atomic orbital that overlap.
AOA - AOB = (ABMO)*AB
-This combination forms an antibonding MO, which has a node
between the nuclei, a region of zero electron density.
-The energy of ABMO is higher than the energy of isolated atomic
48
Types of Orbital Combination

i) s-s Combination
 When 1s- orbital from two different atoms A and B with the same
size approach each other, they overlap to form sigma 1s- bonding
molecular orbital (δ1sAB).

1sA + 1sB (δ 1sAB)

.+A +
.
+
+ .
+ .+B
A B
δ 1sAB
Figure: Formation of BMO from addition of two 1s atomic orbitals
 When 1s – orbital from two different atoms, A and B with opposite
symmetry approach each other, they form sigma anti bonding 1s
molecular orbital (δ*1sAB).

49
Figure: Formation of ABMO from subtraction of two 1s atomic orbitals
ii) p – p Combination
a) p-p combination of atomic orbitals along the internuclear axis
(head on overlap)
 Two px atomic orbitals from two atoms lie along the internuclear
axis of both atoms in symmetrical and anti-symetrical approach.
 They overlap head on to form ẟ- bonding molecular orbital ( ẟp x)
and ẟ*-anti bonding molecular orbitals (ẟ*px).

Figure: Head on combination of P- P atomic orbitals 50

b) Lateral (side way) overlap of p atomic orbitals
 py and pz atomic orbital from two atoms lie perpendicular to the
internuclear axis and to each other.
 They overlap laterally (side to side) to form л- bonding molecular
orbital (л2py, л2pz) and л-anti bonding molecular orbitals
(л*2py,л*2pz).

51
Figure: Sideway combination of P-P atomic orbitals
Electronic configuration in MOT
 The electronic configuration in MOT depends on:

i) The Aufbau Principle: fill electrons in to molecular orbital starting from

lower energy molecular orbital.

ii) Pawel’s Exclusion Principle: each molecular orbital can contain a maximum of
two electrons with opposite spin.

iii) Hund’s rule: if the molecular orbitals are degenerates (molecular orbitals with
the same energy), electrons are filled in to degenerate molecular orbital singly
with the same spin before pairing.

a) Homonuclear diatomic molecules (Molecules made from atoms of atomic

number 8-10) (for O2, F2, and Ne2).

-There is no interaction between 2s and 2p orbitals and the BMO resulted from
head-on overlap of 2p atomic orbitals (δ2px) is lower in energy than that of p- Mos
resulted from sidewise overlapping (л2py & л2py). In this case, δ- overlap is
stronger than л- overlap.
δ1s, δ*1s, δ2s, δ*2s, δ2px, л2py, л* 2py , δ* 2px , δ3s , δ*3s, …
л2pz л* 2pz 52
Example: Write the molecular orbital electron configuration of O 2
molecule
O2 involves 16 electrons
δ1s2 , δ*1s2 , δ2s2 , δ*2s2, δ2p2x, л2p2y , л* 2p1y
л2p2z л* 2p1z
b) Homonuclear diatomic molecules (Molecules made from atoms of
atomic number less than 8) (for N2, C2, and B2).
 In this cases, interactions take place between the 2s and 2p atomic
orbitals that are strong enough to swap the ordering of the σ 2p and
π2p molecular orbitals.

 The MO electron configuration becomes

δ1s, δ 1s, δ2s, δ 2s, л2py, δ2px, л 2py , δ 2px , δ3s , δ*3s, …
* * * *

л2pz л* 2pz

Example: Write MO electron configuration of N2-

Solution: N2- involves 15 e-s ,  δ1s2, δ*1s2, δ2s2, δ*2s2, л2py2, δ2px2, л* 2py1
л2pz2 л* 2pz0
53
 Molecular orbital Electron Configuration Energy
Diagram
 The MO electron configurations can be indicated by the energy
diagram.
Example 1: Draw the MO electron configuration Energy diagram for
Li2 molecule

Solution: The MO electron

configuration of
Li2 molecule
(having 6) is: δ1s2,
δ*1s2, δ2s2.

54
 Example 2: Draw the MO electron configuration Energy diagram for N2- molecule
Solution:
Here, the σ2p MOs are at relatively
higher energy state than π2p
because of interactions between the
2s and 2p atomic orbitals that are
strong enough to swap the ordering
of the σ2p and π2p molecular orbitals.
Thus, the MO electron
configuration of N2- molecule
having 15 electrons is:
δ1s2, δ*1s2, δ2s2, δ*2s2, л2py2, δ2px2, л* 2py1
л2pz2 л* 2pz0

Exercise: Draw the MO electron

configuration Energy diagram
for O2- molecule

55
 Bond Order of Molecules

Bond order (B.O.): is the number of bonding electron pairs between

two atoms with in a covalent molecule.
Bond order =  electrons in BMO  electron s in ABMO 
 2 
 
 Molecules with bond order ½ or greater will be stable with respect
to their atoms.
 Molecules with bond order zero will be unstable.
 The greater the bond order the more stable the molecule is.
Example 1: Determine the bond order and stability of He2
Solution : Total electron = 2+2=4
Electronic configuration = δ1s2, δ*1s2
Bond order = ½ ( # e- in BMO – # e- in ABMO)
Bond order = 2  2 = 0
2
Stability : Unstable. Because B.O =0, Hence He2 molecule does not exist.
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Magnetic Property
 One of the advantages of molecular orbital theory over valence bond
theory is its ability to explain the magnetic properties of covalent
molecules.

 If the electronic configuration of a molecule contains unpaired

electron(s), the molecule is said to be paramagnetic.
 If the electronic configuration of a molecule contains all electrons
paired, the molecule is said to be diamagnetic.
Example: Write the MO electron configuration of O2- molecule ion,
calculate bond order, determine stability and its magnetic property.
Solution:
i) MO electron configuration, O2- has 17 electrons.
O2- = 17 e-s = δ1s2 , δ*1s2 , δ2s2 , δ*2s2 , δ2p2x, л2p2y , л*2p2y ,

л2p2z л*2p1z
57
ii) Bond Order (BO)
BO = (#e- in BMO - e- in ABMO)
= (10-7)
= (3)
= 1.5

iii) Stability,  O2- molecule is stable because BO ≠ 0.

iv) Magnetic Nature
 Paramagnetic because there is one unpaired electron in a MO.

58
 2.2.3. Metallic bonding and bonding theories
Electron sea model and bonding in metals

Figure: Electron sea model in metallic bond

59
 Cont’d…
• The atoms in a pure metal are in tightly-packed layers, which form
a regular lattice structure.

• Electrostatic forces of attraction between the positively charged

neuclei and the negatively charged electrons hold the lattice
together.

• A metal is therefore a seen as a rigid framework of cations

immersed in a ‘sea’ of electrons that serve as the cement holding
the three-dimensional cationic network together – Metallic
bonding.

60
 Cont’d…
sea of electrons
• The outer electrons of the metal
atoms separate from the atoms and
create a ‘sea of electrons’.

• These electrons are delocalized,

and so are free to move through
the whole structure.
• The metal atoms become positively
charged ions and are attracted to the
sea of electrons. This attraction is
called metallic bonding.

metal ions
Figure: Illustration of delocalization of
valance electrons in Electron-sea model
61
Properties of metals
• The properties of metals are related to their structure.
i) Conduction of Heat and Electricity
• Delocalized electrons in metallic bonding allow metals to conduct
heat and electricity.
• For example, when a metal is heated,
the delocalized electrons gain kinetic
energy.
• These electrons then move faster, and
so transfer the gained energy
throughout the metal.
• This makes heat transfer in metals
very efficient.
• Delocalized electrons also conduct
electricity through metals in a
similar way.
heat
Figure: Illustration of electronic structure
of metal during thermal conduction 62
ii) High Melting Points of Metals
 Metals often have high melting
points and boiling points. Gold, for
example, has a melting point of 1064
°C and a boiling point of 2807 °C.

 This property is due to the strong

attraction between the positively-
charged metal ions and the sea of
electrons.

• In metal extraction and other

industrial processes, furnaces often
run continuously to maintain the
high temperatures needed to work Figure: Molten gold
with molten metals.
 The generally high melting points indicate that metallic bonding is
quite strong.

 Melting points increase with an increase in the number of valence

electrons to the sea, since there is a greater attractive force
63
between the cations and the electrons.
 iii) Strength of Metals
 Metals are usually strong, not brittle. When a metal is hit, the layers
of metal ions are able to slide over each other, and so the structure
does not shatter.
metal before it is hit metal after it is hit

force force

Figure: Sliding of metal atoms before and after being hammered

 The metallic bonds do not break because the delocalized electrons

are free to move throughout the structure.
 This also explains why metals are malleable (easy to shape) and
64
ductile (can be drawn into wires).
 iv) Malleability and Ductility of Metals

Figure: Comparison between metallic crystal and ionic crystal w.r.t

malleability and ductility
65
 Cont’d…
 Metals are malleable and ductile, rather than brittle,
as a result of the non-directional nature of metallic
bonds.

 The attractive forces exerted by the positive metal ions

for the mobile electrons occur in all directions.

 This means that layers of atoms can move past one

another without disrupting the force between the
positive ions and the negative sea of electrons.

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 Malleability and Ductility (cont’d…)

+ + + +
Force + + + +
+ + + +
 Mobile e-’s allow atoms to slide by
 like ball bearings in oil.

+ + + +
Force
+ + + +
+ + + +
67
Figure: Malleability and Ductility illustrated
 v) High Density

• Most metals have relatively high densities

because metallic lattices are close-packed.

The End of Chapter 2

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