Theories of Chemical

Bonding
Theories of bonding: explanations for chemical bond, Lewis dot
structures and the following.
Valance-bond (VB) theory
Hybridization of atomic orbitals
Multiple covalent bonds
Molecular orbital (MO) theory
Delocalized electrons
Bonding in metals

Practice mental reasoning and verbal explanation

1
Energy of Interaction Between Two
H Atoms
Energies of attraction and
repulsion as functions of Potent
distance between two H ial
atoms are shown here. energ
The minimum of the
y
+346 kJ
attraction force occur at
mol 1
HH bond length of 74 pm,
at which, the antibonding antibondin
orbital is +346 kJ mole1 g
above 0, energy when H
atoms are far apart.
distan
ce
346 kJ
mol 1
H H bond
How does energy affect the two-atom
2
system?
The Valence-bond Method
Valence bond method considers the covalent bond as a result of
overlap of atomic orbitals. Electrons stay in regions between the two
atoms. Some bond examples
s-s s-p s-d p-p p-d d-d
H-H H-C H-Pd C-C Se-F Fe-Fe (?)
Li-H H-N in Pd P-P
H-F hydride
But overlapping of simple atomic orbitals does not explain all the
features. Thus, we have to take another look, or do something about
atomic orbitals hybridization.

How does valence-bond approach explain

the formation of chemical bonds?
3
 Hybridization of Atomic
Orbitals
The solutions of Schrodinger equation led to these atomic orbitals.
1s, 2s, 2p, 3s, 3p, 3d, 4s, 4p, 4d, 4f, etc.
However, overlap of these orbitals does not give a satisfactory
explanation. In order to explain bonding, these orbitals are combined
to form new set of orbitals this method is called hybridization.
During the lecture, these hybridized orbitals will be explained:
sp 2 sp hybrid orbitals from mixing of a s and a p orbital
sp 2 3 sp2 hybrid orbitals from mixing of a s and 2 p orbital
sp3 fill in you explanation please
sp3d 5 sp3d hybrid orbitals from mixing of a s and 3 p and a d
orbital
sp3d 2 ____________

Provide a description for hybrid orbitals sp, sp2, sp3, sp3d, and
4
sp3d2
The sp Hybrid Orbitals
The sp hybrid orbitals: formation oftwo sp hybrid orbitals
+ + + - = + -

+ + - = - +

hybridization of s and p orbitals = 2 sp hybrid orbitals

_ _ __ __
__ __ __ Two sp hybrid orbitlas =>
Two states of Be

5
Bonds with sp Hybrid
Orbitals
Formations of bonds in these molecules are discussed during the
lecture. Be prepared to do the same by yourself.
ClBeCl HCCH HCN : O=C=O

Double and triple bonds involve pi bonding, and the the

application of valence bond method to bonds will be discussed.

You are expected to be able to draw pictures to show the

bonding.

6
 A Bond
Sigma () bond is symmetric about Nodal plane
axis.
Pi () electron distribution above and
below axis with a nodal plane, on
which probability of finding electron is
zero; bond is not as strong as sigma -
less overlap. Overlap of 2 2p orbitals
for the formation of
bond
C
2s 2p 2p 2p
sp2 sp2 sp2 2p

Bonding of C2H4

How are pi bonds formed? 7

 Triple Bonds in H-
CC-H
H-C-C-H: three bonds due to overlapping of 1sH spC; spC spC;
and spC 1sH.
Two bonds in HCCH and HCN triple bonds are due to
overlapping of p orbitals results.

sp hybrid
orbitals
py over lap C
in bond 2s 2p 2p 2p
sp sp 2p 2p
H H
px over lap
Two nodal planes of
in bond bonds are
perpendicular to each
other.
Draw and describe how atomic orbitals
overlap to form all bonds in acetylene, H 8
CCH
Two Bonds in HCCH

A triple bond consists of a sigma and two pi bonds. Overlaps

of two sets of p orbitals form of two bonds.

9
 Bonding of CO2
For CO2, the C atom forms a bond and a bond with each of two O
atoms. The two nodal planes of the two bonds are also
perpendicular.
During the lecture, I draw diagrams and explain the two two
bonds in CO2. You are expected to be able to do the same, in a test.

Resonance py over lap in

structures bond

:OCO:
:OCO: px over lap in
.. bond

Overlap pp in
Discuss the bonding of allene bonds
O=C=O or H C=C=CH
2 2
10
H2C=C=CH2
 Bonding in CO2 another view
09_174 sigma bond
(1 pair of electrons) pi bond
(1 pair of
electrons)

O C O

pi bond
(1 pair of
electrons)
(a)

Compare with H2C=C=CH2

O C O

(b) 11
 The sp2 Hybrid Orbitals
Ground state and excited state
electronic configuration of B
_ _ _ __
_ __ __
The hybridization of a s and
two p orbitals led to 3 sp2
hybrid orbitals for bonding.
Compounds involving sp2
hybrid orbitals: BF3, CO32,
H2CO, H2C=CH2, NO3, etc

Nov. 25 12
An example of using sp2 hybrid
orbitals

__ orbitals for bonding?

Dipole moment = ____?

13
Bonding of H2C=CH2 molecules
Utilizing the sp2 hybrid orbitals, each C atom
form two HC bonds for a total of 4 HC
bonds. The CC bond is common to both C
atoms.
A CC bond is formed due to overlap of p
orbitals from each of the C atoms. C
2s 2p 2p 2p
sp2 sp2 sp2 2p

Hybrid orbitals (sp2)

for HC and CC
bond
Overlap of p orbital
for CC bond

14
 The sp3 Hybridized
Orbitals
Ground state and excited state
electronic configuration of C
_ _ _ _
_ _ __
The hybridization of a s and
three p orbitals led to 4 sp3
hybrid orbitals for bonding.
Compounds involving sp3 hybrid
orbitals: CF4, CH4, : NH3, H2O::,
SiO44, SO42, ClO4, etc

15
 C
2s 2p 2p 2p
sp3 sp3 sp3 sp3

16
The sp d Hybrid Orbitals
3
Hybridization of one s, three p, and a
d orbitals results in 5 sp3d hybrid
orbitals. The arrangement of these
orbitals is a trigonal pyramid. Some
structures due to these type of
orbitals are PClF4, TeCl4E, and BrF3E2.

How many unshared

electron pairs are
present in TeCl4 and BrF3?
What are their shapes?

17
The sp d Hybrid Orbitals
3 2
Hybridization of one s, three p,
and two d orbitals results in 6
sp3d2 hybrid orbitals. The
arrangement of these orbitals is
an octahedron. Compounds using
these type of orbitals are shown
here.

AX6, AX5E, AX4E2 AX3E3 and AX2E4

IOF5, IF5E, XeF4E2

No known compounds of AX3E3 and AX2E4 are known or recognized,

because they are predicted to have a T shape and linear shape
respectively when the lone pairs of electrons are ignored.

18
Molecules with more than one
central
Describe theatom
structure of CH NCO.
3

Draw the skeleton and add all valence electrons

H3C N C O
Which Lewis dot structure is the most important (stable)?

N=C=O

NCO 18 NCO Which

0o structure is
HC 10 HC
HC 12 more stable,
9o and why?
0o
H H H H
H H

What hybridized orbitals are used for bonding in N and C? Why are
the bond angles as indicated? No of and bonds = __, __?
Give formal charges to all atoms in all structures.
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Why Molecular Orbital (MO) Theory
Lewis dot and valence bond theories do not always give satisfactory
account for various properties of molecules.
For example, the dot and VB theory does not explain the fact that O 2
is paramagnetic and has a double bond.

Dot and VB structures :O O: O O

are unsatisfactory.
MO theory, different from VB in that MO theory considers the orbitals
of the whole molecules. However the approach of linear-
combination-of-atomic-orbitals (LCAO) is usually used.
There are other reasons, but its human nature to theorize. The
theory is beautiful, and worth learning or teaching.

20
 The Molecular Orbital (MO)
Theorytwo electrons of opposite spin.
For a molecule, there are certain orbitals each of which
accommodates
The MO theory combines atomic orbitals (AO) to form MOs, & this
method is called LCAO

The two atoms in the H2 molecule may be
represented by A and B. Their s orbitals 1sA
and 1sB respectively, are used for two MOs:
* = 1sA 1sB
= 1sA + 1sB
The energy levels of these AO and MO are 1sA 1sB
represented by the diagram here, with the
math hidden.

AO MO AO
21
MO for H2type molecules: H2+, H2, H2,
He2+

Generalize the technique of LCAO

22
Electronic configuration, 2, for H2
molecules

Generalize the technique of LCAO

23
Electronic Configuration of H2-type
Molecules
From the previous theory, we can fill the M Os with electrons for
the
H2-type molecule:
Molecule e-configuration Bond order bondlength
H2+ 1 (11) 106 pm
H2, He22+ 12 1 74, ~75
H2, He2+ 12 1 ~106, 108
H22, He2 12 12 0 not formed

Describe the relationships of bondlength &

bondorder and e-configurations; learn to reason

24
 Sigma MOs Formed Using p AOs
Sigma MOs (2p2p* ) can be formed using p AOs, similar to VB
theory. The gain in bonding orbital 2p (lower energy) is at the
expense of the anti-bonding orbital 2p* (higher energy)

Generalize the technique of LCAO 25

Pi MOs from p AOs

Generalize the technique of LCAO

26
MO Diagrams for O2
and F2
A full diagram of the energy
level of molecular orbitals of
O2 and F2 is shown here.
The relative (approximate)
height of these energies will
be explained verbally during
the lecture, and you are
suppose to be able to do the
same.

Write the electronic

configurations for O2,
O2, F2, F2 & Ne2.
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The O2+, O2, O2 , & F2+, F2, F2
Molecules
For O=O O=O
_ _ Paramagnetic ,
bond length
indicates double
bond, electronic
configuration
agrees
FF
Electronic
configuration agree
with single bond.

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MO Energy Level Diagram for Be2
N 2 to close energy levels of 2s and 2p, the MO energy level
Due
diagram for Be2 to N2 differs from those of O2 to F2. Reasons and
explanation are given during the lecture. Hope you can do the
same.
Give electronic
configurations
for Be2+,
Be2, B2+,
B2,
B2, C2+,
C2,
C2, N2+,
N2,
N2.

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