CHM361

INORGANIC CHEMISTRY

Chapter 1
Valence Bond Theory

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Topic content
► 2.1 Lewis Structures
► 2.2 Valence Shell Electron Pair Repulsion
Theory (VSEPR)
► 2.3 Valence Bond Theory
► 2.4 Orbital Hybridization: sp3, sp2 sp, sp3 d
and sp3d2

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At the end of lesson student should be
able apply and solve the problems
regarding on:
► Orbital hybridization
► Valence Bond Theory (VBT)
► Hybridization Of Atomic Orbital (sp3, sp2
sp, sp3 d and sp3d2)
► The Mode of Orbital Overlap
► Types of Covalent Bonds.
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 LEWIS STRUCTURE

► Visualizing what molecule look

like-convert molecular formula to Lewis
structure
► Only valence electrons are important in
bonding.
► Lewis dot structures show valence
electrons surrounding atom.

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► We visualize the four valence orbitals of an atom as the sides of a box.
Electrons are put into orbitals according to Hund’s rule.
► Examples Be has 2 valence electrons. Therefore Lewis structure is

► N has 5 valence electrons. Therefore Lewis structure is

► Br has 7 valence electrons. Therefore Lewis structure is

► C has 4 valence electrons. Therefore Lewis structure is

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# Rules for writing Lewis symbol for covalent
bonding

1. Choose the most symmetry structure

2. Calculate N value. N is the number of
needed electrons for the entire atom to
achieve octet structure.
3. Calculate the A value. A is the number
of available electrons of each atom in
the compound.
4. Calculate S. S is the number of shared
electrons between the atoms by using
the following formula:
S=N-A
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Example : Lewis structure for CO2

1. Choose the most symmetry structure.

2. N= 8+ 8(2)=24 electrons needed
3. A=4 +6(2)=16 electrons available
4. S= 24-16= 8 electrons shared

.. ..
: O::C: :O: 7
How does bond form?
► The valence bond model or atomic orbital model was
developed by Linus Pauling in order to explain how
atoms come together and form molecules.
► The model theorizes state that
❑ a covalent bond forms when two orbitals overlap
to produce a new combined orbital containing two
electrons of opposite spin.
► This overlapping results in a decrease in the
energy of the atoms forming the bond.
► The shared electron pair is most likely to be found in
the space between the two nuclei of the atoms
forming the bonds.

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► This theory can also be applied to
molecules with more than two atoms such
as water.
► Each covalent bond results in a new
combined orbital with two oppositely
spinning electrons.
► In order for atoms to bond according to
the valence bond model, the orbitals must
have an unpaired electron.
► Strength of bonding depends on the
amount of overlap : the greater the
overlap, the stronger the bond
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 VSEPR

► The familiar VSEPR (Valence Shell

Electron Pair Repulsion) approach
to molecular structure was
developed by Ronald Gillespie.

► The basic idea is that lone pairs of

electrons occupy space around a
central atom in much the same way
as do atoms that are bonded to the
central atom. Ronald
Gillespie.
► The lone pairs and bonded atoms then assume
that geometry that minimizes electrostatic
repulsion between them.

► The main principle in VSEPR is to arrange atom as

far as possible to minimize electron-pair repulsion
in the following order

► Lone pair-Lone pair > Lone pair-bond pair > bond pair-bond pair

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Electron domains and molecular geometry

observed geometry is
each lone pair of electrons that where the electron
plus each atom bonded to the domains are as far apart
central atom constitute an as possible
electron ‘domain’
lone pair
of
electron
N s
H
H
H

Lewis dot diagram Ammonia

of ammonia trigonal pyramidal
(derived from tetrahedral geometry)
 Using VSEPR
In order to use VSEPR to predict molecular structure:

1) Draw up Lewis dot diagram for the molecule or ion. The first atom (e.g. Br in
BrF5) is always the central atom. Place the other atoms around the central atom.

place 5 F
red = 7
atoms
valence
around
electrons
central Br
for Br
If these are single bonds, contribute one electron per attached atom. Then add the
valence electrons for the central atom = 7 for Br.

2) Work out number of electron domains = valence electron pairs (‘n’) plus attached
atoms on central atom. For BrF5 n = 6.

3) Relate n to the type of structure predicted for that value of n. n = 6 = octahedral.

4) Place lone pairs in expected positions, maximizing separation of lone pairs. For
BrF5, there is one lone pair, so mol. structure = square pyramidal.
 The structure of BrF5 from VSEPR:

Lewis dot parent molecular structure

diagram structure =
square pyramidal

lone
pair
n = 6 from five n = 6, parent structure molecular or final
attached atoms = octahedral, but one structure –
plus one site disregard
electron occupied by a lone pair the lone pair
pair
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What does hybridization mean?
‘Hybridization’ means ‘mixing’

Hybrid orbitals are generated by mixing

the characters of atomic orbitals.

A set of hybrid orbitals provides a

bonding picture for a molecule in terms
of localised σ-bonds

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 The Central Themes of VB Theory

Basic Principle

A covalent bond forms when the orbitals of two atoms

overlap and the overlap region, which is between the
nuclei, is occupied by a pair of electrons.

The two wave functions are in phase so the amplitude

increases
between the nuclei.

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 The Central Themes of VB Theory

Themes

A set of overlapping orbitals has a maximum of two

electrons that must have opposite spins.
The greater the orbital overlap, the stronger (more stable)
the bond.
The valence atomic orbitals in a molecule are different
from those in isolated atoms.
There is a hybridization of atomic orbitals to form
molecular
orbitals.

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Orbital shapes, Individual (“isolated”) Atoms

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 Rules for Predicting Molecular Geometry

1.  Sketch the Lewis structure of the molecule or

ion

2.  Count the electron pairs and arrange them in

the way that  minimizes electron-pair repulsion.

3.  Determine the position of the atoms from the

way the electron pairs are shared.

4.  Determine the name of the molecular structure

from the position of the atoms.

5.  Double or triple bonds are counted as one

bonding pair when predicting geometry.
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 To rationalize how the shapes of atomic orbitals
are transformed into the orbitals occupied in
covalently bonded species, we need the help of
two bonding theories:

Valence Bond (VB) Theory, the theory we will explore,

describes the placement of electrons into bonding
orbitals located around the individual atoms from
which they originated.

Molecular Orbital (MO) Theory places all electrons from

atoms involved into molecular orbitals spread out over
the entire species. This theory works well for excited
species, and molecules like O2. You will meet this theory
in advanced classes!

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 COVALENT BOND FORMATION (VB THEORY)

•In order for a covalent bond to form between

two atoms, overlap must occur between the orbitals
containing the valence electrons.

•The best overlap occurs when two orbitals are allowed

to meet “head on” in a straight line. When this occurs,
the atomic orbitals merge to form a single bonding
orbital and a “single bond” is formed, called a
sigma (σ) bond.

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Covalent bonds are formed when atomic orbitals
overlap.
There are two types of orbital overlap:
Sigma, s, overlap occurs when there is one bonding
interaction that results from the overlap of two orbitals.
Pi, p, overlap occurs when two bonding interactions
result from the overlap of orbitals.
single bond sigma overlap
double bond sigma and pi overlaps
triple bond sigma and two pi overlaps

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Representation of singly-occupied and doubly-occupied
s and p atomic orbitals. Singly-occupied orbitals appear
light; doubly-occupied orbitals appear darker.
Orbital overlap and spin pairing in H2.

Example: H(1s1) + H(1s1) → H2

 Orbital overlap and spin pairing in F2.

Example: F(1s22s22p5) + F(1s22s22p5) → F2

 Orbital overlap and spin pairing in HF.

Example: H(1s1) + F(1s22s22p5) → HF

 MAXIMIZING BOND
FORMATION

❖ In order for “best overlap” to occur, valence electrons

need to be re-oriented and electron clouds reshaped
to allow optimum contact.

❖To form as many bonds as possible from the available

valence electrons, sometimes separation of electron
pairs must also occur.

❖We describe the transformation process as “orbital

hybridization” and we focus on the central atom in
the species...
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Figure 11.8
The conceptual steps from molecular formula to the hybrid orbitals
used in bonding.

Step 1 Step 2 Step 3

Molecular shape
Molecular Lewis and e- group Hybrid
formula structure arrangement orbitals

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 The sp hybrid orbitals (BeCl2)

1. BeCl2 molecule is predicted to be linear by VSEPR

VSEPR linear
C B C
l l both bonds equivalent
e

2. Orbital diagram for the valence electron in Be is:

#1 • No unpaired electrons

3. By promoting the 2s e- to the 2p orbital, we get the

excited state:
#2 • 2 types of orbital
overlap
with 2s and 2p
Hybridization of Be in BeCl2

Valence
e’s Hybrid sp orbitals:
1 part s, 1 part p
Atomic Be: 1s2 2s2

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 The sp hybrid orbitals (BeCl2)

4. Mixing the 2s and 2p orbitals generates two

equivalent sp hybrid orbitals:

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FORMATION OF BeCl2:

Each Chlorine atom, 1s22s22p63s23p5 , has one

unshared electron in a p orbital.

The half filled p orbital overlaps head-on with a half

full hybrid sp orbital of the beryllium to form a sigma
bond.

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5. Each Be sp orbital overlaps a Cl 3p orbital to yield
BeCl2.
2Cl + B BeCl2
e

All bond angles 180o.

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 Formation of sp hybrid orbitals

The combination of an s orbital and a p orbital produces 2

2s new orbitals called sp orbitals.

These new orbitals are called hybrid orbitals

The process is called hybridization
What this means is that both the s and one p orbital are involved in
bonding to the connecting atoms
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 The sp2 hybrid orbitals in BF3.

1. BF3 molecule is predicted to be trigonal planar by VSEPR

..
.. F ..
VSEPR • trigonal planar
. . B .. • all bonds equivalent
..
F F ..
.. ..

2. Orbital diagram for the valence electron in B is:

#1 • only 1 unpaired
electron

3. By promoting the 2s e- to the 2p orbital, we get the

excited state:

#2 • 2 types of overlap with 2s

and 2p
Hybridization of B in BF3

Hybrid sp2 orbitals:

Valence 1 part s, 2 parts p
e’s
Atomic B : 1s2 2s2 2p1

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4. Mixing the 2s and 2p orbitals generates two
equivalent sp2 hybrid orbitals:

5. Each B sp2 orbital overlaps a F 2p orbital to yield

BF3.

3 + B BF3
F 2s2 2p5
 FORMATION OF BF3:

Each fluorine atom, 1s22s22p5, has one unshared

electron in a p orbital.
The half filled p orbital overlaps head-on with a half full
hybrid sp2 orbital of the boron to form a sigma bond.

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Formation of sp2 hybrid orbitals

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 The sp3 hybrid orbitals in CH4.

1. CH4 molecule is predicted to be tetrahedral by VSEPR

H
VSEPR tetrahedral
H C H
all bonds equivalent
H

2. Orbital diagram for the valence electron in C is:

#1 • only 2 unpaired electrons

3. By promoting the 2s e- to the 2p orbital, we get the

excited state:
#2 • 2 types of overlap with 2s and 2p
Hybridization of C in CH4

Valence Hybrid sp3 orbitals:

e’s 1 part s, 3 parts p
Atomic C : 1s2 2s2 2p2

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4. Mixing the 2s and 2p orbitals generates four
equivalent sp3 hybrid orbitals:

5. Each C sp3 orbital overlaps a H 1s orbital to yield

CH4.

4H + C CH4
1s1
FORMATION OF CH4:

Each hydrogen atom, 1s1, has one unshared

electron in an s orbital. The half filled s orbital
overlaps head-on with a half full hybrid sp3 orbital
of the carbon to form a sigma bond.

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Formation of sp3 hybrid orbitals

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Unshared Pairs, Double or Triple
Bonds

Unshared pairs occupy a hybridized orbital the

same as bonded pairs: See the example of NH3
that follows.

Double and triple bonds are formed from electrons

left behind and unused in p orbitals. Since all
multiple bonds are formed on top of sigma bonds,
the hybridization of the single (σ) bonds determine
the hybridization and shape of the molecule...
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The sp3 hybrid orbitals in NH3.
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Hybridization of N in NH3

Valence
e’s
Atomic N: 1s2 2s2 2p3

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 FORMATION OF NH3:

Each hydrogen atom, 1s1, has one unshared

electron in an s orbital. The half filled s orbital
overlaps head-on with a half full hybrid sp3 orbital
of the nitrogen to form a sigma bond.

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Figure 11.5 The sp3 hybrid orbitals in H2O.
continued

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 The sp3d hybrid orbitals in PCl5.
1. PCl5 molecule is predicted to be trigonal bipyramidal by
VSEPR

2. Orbital diagram for the valence electron in P is

shown below.
Hybridization of P in PCl5 P: 1s2 2s2 2p6 3s2 3p3

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 The sp3d hybrid orbitals in PCl5.
3. By promoting the 3s e- to the 3d orbital, we get
the excited state. Mixing the 3s, 3p and 3d
orbitals generates five equivalent sp3d hybrid
orbitals:

4. Each P sp3d orbital overlaps a Cl 3p orbital to yield

PCl5.
FORMATION OF PCl5:

Each chlorine atom, 1s22s22p63s23p5, has one unshared

electron in a p orbital. The half filled p orbital
overlaps head-on with a half full hybrid sp3d orbital
of the phosphorus to form a sigma bond.

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Bond angles 120o and
90o

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The sp3d2 hybrid orbitals in SF6.
Hybridization of S in SF6 S: 1s2 2s2 2p6 3s2 3p4

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 FORMATION OF SF6:

Each fluorine atom, 1s22s22p5, has one unshared

electron in a p orbital. The half filled p orbital
overlaps head-on with a half full hybrid sp3d2 orbital
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of the phosphorus to form a sigma bond.
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 Figure 11.9 The σ bonds in ethane(C2H6).

both C are sp3

hybridized s-sp3 overlaps to σ
bonds

sp3-sp3 overlap to form a σ

bond relatively even
distribution of
electron density over
all σ bonds

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Figure 11.10 The σ and π bonds in ethylene (C2H4).

overlap in one position -

σ

p overlap - π

electron
density 74
Figure 11.11 The σ and π bonds in acetylene (C2H2).

overlap in one position -

σ

p overlap - π

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Summary: Regions, Shapes and Hybridization

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Overlap of Orbitals

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The degree of overlap is determined by the system’s potential energy

equilibrium bond
distance

The point at which the potential energy is78a minimum is

called the equilibrium bond distance
Hybrid orbitals can be used to explain bonding and molecular
geometry

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 Multiple Bonds
 
Everything we have talked about so far has only dealt with
what we call sigma bonds
 
Sigma bond (σ) → A bond where the line of electron
density is concentrated symmetrically along the line
connecting the two atoms.

Hybridization of atomic orbitals 80

Pi bond (π) → A bond where the overlapping regions
exist above and below the internuclear axis (with a
nodal plane along the internuclear axis).

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Example: H2C=CH2

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Example: H2C=CH2

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Example: HC≡CH

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“Conclusion ”

IF you can draw a Lewis structure for a species,

and count electronic regions around central atom,
you can immediately determine:

• the shape of the species about the central atom

• the hybridization of the species based on the

central atom

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 Determine the hybridization state of the central
atom (underlined) in each of the following
molecules?

1.BeH2
2.AlI3
3.PF3
4.SF4