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Part I- Fundamentals of chemical compositions Chemical Bonding II:

Chapter 3 (1) Valence bond theory
Chemical Bonding and Molecular structure (2) Hybridization of atomic
(.. cont.) orbitals and geometric
shape of molecular
(3) Molecular orbital theory

The valence bond (VB) theory describes how the bonding

takes place, in terms of overlapping atomic orbitals.
In this theory, the atomic orbitals discussed in Chapter 5 are
often “mixed,” or hybridized, to form new orbitals with

I. Valence bond (VB) different spatial orientations. Used together, these two
simple ideas enable us to understand the bonding,
molecular shapes,and properties of a wide variety of

theory polyatomic molecules and ions.

We will first discuss the basic ideas and application of these
two theories.
Then we will learn how an important molecular property,
polarity, depends on molecular shape. Most of this chapter
will then be devoted to studying how these ideas are applied
to various types of polyatomic molecules and ions.

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1. FORMATION OF COVALENT BONDS

 The simplest case of covalent bonding, the reaction of two hydrogen
atoms to form the diatomic molecule H2.
 An isolated hydrogen atom has the ground state electron configuration
1s1, with the probability density for this one electron spherically distributed
about the hydrogen nucleus (Figure a).
 As two hydrogen atoms approach each other, the electron of each
hydrogen atom is attracted by the nucleus of the other hydrogen atom as
well as by its own nucleus (Figure b).
 If these two electrons have opposite spins so that they can occupy the
 The bonded atoms are at lower energy (more stable) than the separated
same region (orbital), both electrons can now preferentially occupy the
atoms. This is shown in the plot of energy versus distance in Figure.
region between the two nuclei (Figure c), because they are attracted by
 As the two atoms get closer together, however, the two nuclei, being
both nuclei.
positively charged, exert an increasing repulsion on each other. At
some distance, a minimum energy, 435 kJ/mol, is reached; it
corresponds to the most stable arrangement and occurs at 0.74 Å, the
actual distance between two hydrogen nuclei in an H2 molecule.
 At greater internuclear separation, the repulsive forces diminish, but the
(b) As the atoms approach each other, the The two electrons can both occupy the
attractive forces decrease even faster.
(a) Two hydrogen
electron of each atom is attracted by the region where the two 1s orbitals overlap;  At smaller separations, repulsive forces increase more rapidly than
positively charged nucleus of the other atom, the electron density is highest
5 in the region 6
atoms separated by a
so the electron density begins to shift.
attractive forces. The magnitude of this stabilization
large distance. between the nuclei of the two atoms.

 Valence bond theory considers the interactions between

separate atoms as they are brought together to form
molecules.
 Considering the formation of H2 from two H atoms: the nucleus
are labelled HA and HB, and the electrons of which are 1 and 2,
respectively.
The two electrons can both occupy the  When the atoms are so far apart that there is no interaction
region where the two 1s orbitals
overlap; the electron density is highest
between them, electron 1 is exclusively associated with HA,
in the region between the nuclei of the while electron 2 resides with nucleus HB. Let this state be
two atoms.
described by a wave-function 1.
 The electrons are shared between the two hydrogen atoms, and a single  When the H atoms are close together, we cannot tell which
covalent bond is formed. electron is associated with which nucleus since, although we
 We say that the 1s orbitals overlap so that both electrons are now in the gave them labels, the two nuclei are actually indistinguishable,
orbitals of both hydrogen atoms. as are the two electrons. Thus, electron 2 could be with HA
 The closer together the atoms come, the more nearly this is true.
and electron 1 with HB. Let this be described by the wave-
 In that sense, each hydrogen atom then has the helium configuration 1s2.
function 2.
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An overall description of the

HA HB covalently bonded H2 molecule,
covalent is a linear combination of
wavefunctions 1 and 2.
1 2 The equation contains a
normalization factor, N.

covalent = c1.1 + c2.2 + c3.3.....

In terms of the spins of electrons 1 and

2, + corresponds to spin-pairing, and
- corresponds to parallel spins
(nonspin-paired).

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covalent = c1.1 + c2.2 + c3.3.....

>0
>0

> 0;
=0; <0

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Postulates of Valence Bond (VB) Theory

 Covalent bonds are formed when two valence orbitals (half-filled)
belonging to two different atoms overlap on each other. The electron
density in the area between the two bonding atoms increases as a result
of this overlapping, thereby increasing the stability of the resulting
II. Hybridization of
molecule.
 The presence of many unpaired electrons in the valence shell of an atom
enables it to form multiple bonds with other atoms. The paired electrons
present in the valence shell do not take participate in the formation of
atomic orbitals and
chemical bonds as per the valence bond theory. Covalent chemical
bonds of a atomic element is limited. Maximum covalent bonds of an
atom = valence atomic orbitals.
geometric shape of
 Covalent chemical bonds are directional and are also parallel to the
region corresponding to the atomic orbitals that are overlapping.
 Sigma bonds () and pi bonds () differ in the pattern that the atomic
orbitals overlap in, i.e.  are formed from sidewise overlapping whereas
molecular
the overlapping along the axis containing the nuclei of the two atoms
leads to the formation of sigma bonds ().
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II.1.a. Formation of sp3 Hybrid Orbitals

II.1. Hybridization – mixing of two or more
atomic orbitals to form a new set of hybrid
atmoic orbitals.
1. Mix at least 2 nonequivalent atomic orbitals (e.g. s and p).
Hybrid orbitals have very different shape from original
atomic orbitals.
2. Number of hybrid orbitals is equal to number of pure atomic
orbitals used in the hybridization process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid orbitals

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sp3 Hybridization of Carbon

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II.1.b. Formation of sp2 Hybrid Orbitals

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Bonding in Ethylene, C2H4

sp2 Hybridization of Carbon

Sigma bond () – electron density between the 2 atoms

Pi bond () – electron density above and below plane of nuclei

21 of the bonding atoms 22

II.1.c. Formation of sp Hybrid Orbitals

sp Hybridization of Carbon

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Bonding in Acetylene, C2H2 Valence shell electron pair repulsion (VSEPR) model:

Predict the geometry of the molecule from the electrostatic

repulsions between the electron (bonding and nonbonding) pairs.

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

B B

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VSEPR VSEPR
# of atoms # lone # of atoms # lone
bonded to pairs on Arrangement of Molecular bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear AB2 2 0 linear linear

trigonal trigonal trigonal trigonal
AB3 3 0 AB3 3 0
planar planar planar planar
AB4 4 0 tetrahedral tetrahedral

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VSEPR VSEPR
# of atoms # lone # of atoms # lone
bonded to pairs on Arrangement of Molecular bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear AB2 2 0 linear linear

trigonal trigonal trigonal trigonal
AB3 3 0 AB3 3 0
planar planar planar planar
AB4 4 0 tetrahedral tetrahedral AB4 4 0 tetrahedral tetrahedral
trigonal trigonal trigonal trigonal
AB5 5 0 AB5 5 0
bipyramidal bipyramidal bipyramidal bipyramidal
AB6 6 0 octahedral octahedral

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VSEPR VSEPR
# of atoms # lone # of atoms # lone
bonded to pairs on Arrangement of Molecular bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry Class central atom central atom electron pairs Geometry

trigonal trigonal
AB3 3 0 AB4 4 0 tetrahedral tetrahedral
planar planar
trigonal trigonal
AB2E 2 1 bent AB3E 3 1 tetrahedral
planar pyramidal

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VSEPR VSEPR
# of atoms # lone # of atoms # lone
bonded to pairs on Arrangement of Molecular bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry Class central atom central atom electron pairs Geometry
trigonal trigonal
AB4 4 0 tetrahedral tetrahedral AB5 5 0
bipyramidal bipyramidal
trigonal trigonal distorted
AB3E 3 1 tetrahedral AB4E 4 1
pyramidal bipyramidal tetrahedron
AB2E2 2 2 tetrahedral bent

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VSEPR VSEPR
# of atoms # lone
# of atoms # lone bonded to pairs on Arrangement of Molecular
bonded to pairs on Arrangement of Molecular Class central atom central atom electron pairs Geometry
Class central atom central atom electron pairs Geometry
trigonal trigonal
trigonal trigonal AB5 5 0
AB5 5 0 bipyramidal bipyramidal
bipyramidal bipyramidal trigonal distorted
AB4E 4 1
trigonal distorted bipyramidal tetrahedron
AB4E 4 1
bipyramidal tetrahedron trigonal
AB3E2 3 2 T-shaped
trigonal bipyramidal
AB3E2 3 2 T-shaped
bipyramidal trigonal
AB2E3 2 3 linear
bipyramidal

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Predicting Molecular Geometry Dipole Moments and Polar Molecules

1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the central atom and electron rich
electron poor
region
number of atoms bonded to the central atom. region

3. Use VSEPR to predict the geometry of the molecule. H F

What are the molecular geometries of SO2 and SF4?

d+ d-
O S O F
AB4E
AB2E F S F
distorted
m=Qxr
bent tetrahedron Q is the charge
F
r is the distance between charges
37 1 D = 3.36 x 10-30 C m 38

Behavior of Polar Molecules Bond moments and resultant dipole moments in NH3 and NF3.

field off field on 39 40

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Sigma () and Pi Bonds ()

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

How many  and  bonds are in the acetic acid (vinegar)

molecule CH3COOH?

O
H
 bonds = 6 + 1 = 7
H C C O H
 bonds = 1
H
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Energy levels of bonding and antibonding molecular

orbitals in hydrogen (H2).

III. Molecular orbital

(MO) theory
A bonding molecular orbital has lower energy and greater
stability than the atomic orbitals from which it was formed.

An antibonding molecular orbital has higher energy and

lower stability than the atomic orbitals from which it was
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formed.

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Constructive and Destructive Interference Two Possible Interactions Between Two Equivalent p Orbitals

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General molecular orbital energy level diagram for the
second-period homonuclear diatomic molecules Li2, Be2, B2,
C2, and N2.
Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.

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Number of Number of
bond order =
1
2 ( electrons in
bonding
MOs
- electrons in
antibonding
MOs
)

bond
½ 1 ½ 0
order 49 50

Delocalized molecular orbitals are not confined between

Electron density above and below the plane of the
two adjacent bonding atoms, but actually extend over three
benzene molecule.
or more atoms.

Example: Benzene, C6H6

Delocalized  orbitals

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Bonding in the Carbonate Ion, CO32-

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