Valence Bond Theory

Hybridization Theory
VSEPR

1st Theory: Valence Bond Theory

H2 bonds form because atomic valence orbitals
overlap
1s

1s

HF involves overlaps between the s orbital on H

and the 2p orbital of F

1s

2s

2p

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals

VB Theory And H2S

Assume that the
unpaired e- in S and H
are free to form a
paired bond
We may assume that
the H-S bond forms
between an s and a p
orbital

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals

Your turn!
According to VB Theory:
Which type of overlap does not occur in BH3?
A.
B.
C.
D.

s-s
s-p
p-p
none of these

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals

Your turn!
According to VB Theory:
Which orbitals overlap in the formation of NH3?
A.
B.
C.
D.

s-s
s-p
p-p
none of these

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals

Difficulties With VB Theory So Far:

Most experimental bond angles do not support
those predicted by mere atomic orbital overlap
For example: C 1s22s22p2 and H 1s1
Experimental bond angles in methane are 109.5
and all are the same
p orbitals are 90 apart, and not all valence e- in C
are in the p orbitals
How can multiple bonds form?

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals

2nd Theory: Hybridization

The mixing of atomic orbitals to allow formation
of bonds that have realistic bond angles
The new shapes that result are called hybrid
orbitals
The number of hybrid orbitals required = the
number of bonding domains + the number of
non-bonding domains on the atom

9.5 Hybrid orbitals are used to explain experimental molecular geometries

What Shall We Call These New Orbitals?

Since we have annexed the spaces previously
defined by atomic orbitals, we name the hybrid as
a combination of the orbitals used to form the new
hybrid
One atomic orbital is used for every hybrid formed
(orbitals are conserved)

9.5 Hybrid orbitals are used to explain experimental molecular geometries

Hybrids From s & p Atomic Orbitals take

VSEPR Geometry
Hybrid

Atomic
Orbitals
Used

Electron
Geometry

sp3

s + p x + py
+ pz

Tetrahedral,
bond angles
109.5

sp2

s + p x + py

Trigonal
planar, bond
angles 120

sp

s + px

Linear,
bond angles
180

9.5 Hybrid orbitals are used to explain experimental molecular geometries

Learning Check:
Identify The Hybrid Orbitals In The Following, Based
On Their VSEPR Geometry

9.5 Hybrid orbitals are used to explain experimental molecular geometries

10

Determining hybridization:
1. expand all valence electrons within the valence
energy level. For C, for example this means:
2s 2p _ ___ [He]2s2 2p1
Becomes:
2s 2p _ _ __

9.5 Hybrid orbitals are used to explain experimental molecular geometries

11

Hybridization
2. Now analyze the bonding and lone pair needs.
You will need to use one hybrid orbital for every
bonding domain and one for every non-bonding
domain.
For C in CH4 we see that there are 4 attached
atoms and no lone pairs on C. Thus we will need 4
hybrid orbitals.
H
H

C
H
9.5 Hybrid orbitals are used to explain experimental molecular geometries

12

Hybridization (sp3)
3. Now analyze the atomic orbital needs. You will need
to use one atomic orbital for every hybrid orbital .
For C in CH4 we will need 4 hybrid orbitals.
2s 2p _ _
Thus, we will need to use all valence level atomic
orbitals available to us.
(2s 2p _ _ )
S + p + p + p 4 new equivalent sp3 orbitals.
H
H

C
H
9.5 Hybrid orbitals are used to explain experimental molecular geometries

13

Bonding in CH4
The 4 hybrid orbitals are
evenly distributed around
the C
The H s-orbitals overlap
the sp3 hybrid orbitals to
form the bonds.

9.5 Hybrid orbitals are used to explain experimental molecular geometries

H
H
H

14

s & p hybrid shapes

9.5 Hybrid orbitals are used to explain experimental molecular geometries

15

Your Turn!
In the compound CH3OH, what is the expected
hybridization on O?
A. sp
B. sp2
C. sp3
D. O does not hybridize

9.5 Hybrid orbitals are used to explain experimental molecular geometries

16

Expanded Octet Hybridization

Can be predicted from the geometry as well
In these situations, d orbitals are be needed to
provide room for the extra electrons
One d orbital is added for each pair of electrons in
excess of the standard octet

9.5 Hybrid orbitals are used to explain experimental molecular geometries

17

Expanded Octet hybridization

9.5 Hybrid orbitals are used to explain experimental molecular geometries

18

Bonding Types
Two types of bonds result from
orbital overlap:
sigma bonds
from head-on overlap
lie along the bond axis
account for the first bond

pi bonds
from lateral overlap by adjacent p or
d orbitals
pi bonds are perpendicular to bond
axis
account for the second and third
bonds in a multiple bond
9.6 Hybrid orbitals can be used to describe multiple bonds

19

Hybridization of C in CH2O

O
H

1. Expand all valence electrons within the same energy

level. For C, for example this means:
2s 2p _ ___ [He]2s2 2p1
Becomes:
2s 2p _ _ __

9.6 Hybrid orbitals can be used to describe multiple bonds

20

Hybridization of C in CH2O

O
H

2. Now analyze the bonding and lone pair needs.

You will need to use one hybrid orbital for every
attached atom and one for every lone pair.
For C in CH2O we see that there are 3 attached atoms
and no lone pairs on C. Thus we will need 3 hybrid
orbitals.

9.6 Hybrid orbitals can be used to describe multiple bonds

21

sp2 Hybridization
3. Now analyze the atomic orbital needs. You will
need to use one atomic orbital for every hybrid
orbital.
For C in CH2O we will need 3 hybrid orbitals.
2s 2p _ _
Thus, we will need to use 3 valence level atomic
orbitals available to us, and one of the p orbitals will
remain.
(2s 2p _ ) _
s + p + p 3 new sp2 orbitals.
We are left with one unhybridized orbital.

9.6 Hybrid orbitals can be used to describe multiple bonds

22

Now analyze the O:

O
C

H
[He] 2s2 2p2 (2s 2p _ ) _ H
The O is has one bonding domain and 2 nonbonding domains, hence it will require three
hybrid orbitals.
No expansion needed, as one unpaired e- is
available to bond. Use 3 atomic orbitals to make
the new hybrids, sp2. (2s 2p _ ) _
Again we are left with one unhybridized p
orbital

9.6 Hybrid orbitals can be used to describe multiple bonds

23

Pi Bonding

9.6 Hybrid orbitals can be used to describe multiple bonds

24

HCC H
Each C has a
triple bond
and a single
bond
Requires 2
hybrid
orbitals, sp
unhybridized
p orbitals
used to form
the pi bond
9.6 Hybrid orbitals can be used to describe multiple bonds

25

Your Turn!
Consider a molecule of CH3CO2H:
How many pi bonds are there in the molecule?
A. 1
B. 2
C. 3
D. 4
E. There are none

9.6 Hybrid orbitals can be used to describe multiple bonds

26

VSEPR - The Five Basic Electron

Arrangements
Electron
Domain

Shape

Electron Pair
Geometri

linear

trigonal planar

tetrahedral

9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements

27

The Five Basic Electron Arrangements (Cont.)

Electron Domains
5

Shape

Electron Pair Geometry

Bipiramida trigonal
Memiliki posisi axial
dan equatorial

oktahedral
Memiliki posisi axial
dan equatorial

9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements

28

Learning Check:
Tentukan Geometri pasangan elektron untuk tiap
atom pusat

tetrahedral

tetrahedral

Trigonal
bipyramidal

9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements

29

Your Turn!
What is the electron pair geometry for C in CO2?
A.
B.
C.
D.
E.

linear
planar triangular
tetrahedral
trigonal bipyramidal
octahedral

9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements

30

Bonding Domains And Non-bonding Domains

Bonding domains are shared
between nuclei
Non-bonding domains are not
shared between nuclei-they exert a
greater electrical field
Repulsion leads non-bonding
domains to occupy larger space
The basic shapes are distorted by
non-bonding domains to create the
molecular geometry
9.2 Molecular shapes are predicted using the VSEPR model

31

Trigonal Planar Molecular Geometries

Bonding Domains

Non-bonding
Domains

Molecular
Geometry

trigonal planar

bent

9.2 Molecular shapes are predicted using the VSEPR model

32

Tetrahedral Molecular geometries

9.2 Molecular shapes are predicted using the VSEPR model

33

Trigonal Bipyramidal
Equatorial (e)
positions are
substituted first
This is because
the e,e bond
angles are 120,
while a,e bond
angles are only
90

9.2 Molecular shapes are predicted using the VSEPR model

34

Octahedral Geometries
All bond angles
are 90
Axial positions
are substituted
first

9.2 Molecular shapes are predicted using the VSEPR model

35

Learning Check:
Identify the molecular geometry for each center

Trigonal
pyramidal

Non-linear,
bent

Linear

9.2 Molecular shapes are predicted using the VSEPR model

36

Your Turn!
Which require more space?
A. bond pairs
B. lone pairs
C. both are the same

9.2 Molecular shapes are predicted using the VSEPR model

37

Your Turn!
Which bond angles are closer in a trigonal
bipyramidal structure (a= axial; e=equatorial)?
A. a-a
B. a-e
C. e-e
D. they are all the same

9.2 Molecular shapes are predicted using the VSEPR model

38

Your Turn!
What is the molecular geometry of C in CH4?
A.
B.
C.
D.
E.

Linear
Square planar
Square pyramidal
Tetrahedral
None of these

9.2 Molecular shapes are predicted using the VSEPR model

39

Polar Molecules Are Asymmetric

To determine the polarity, draw the structure using
the proper molecular geometry
Draw the bond dipoles
If they cancel, the molecule is non-polar
If the molecule has uneven dipole distribution, it is
polar

9.3 Molecular symmetry affects the polarity of molecules

40

Learning Check:
Polar or non-polar?

polar

polar

9.3 Molecular symmetry affects the polarity of molecules

Non-polar
41

Your Turn!
CH2ClCH2Cl (freon-150) is likely to be:
A. Polar
B. non-polar
C. cannot tell

9.3 Molecular symmetry affects the polarity of molecules

42

Your Turn!
Benzoyl peroxide (used in common acne
medications) is likely to be:
A. polar
B. non-polar
C. cannot tell

9.3 Molecular symmetry affects the polarity of molecules

43