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
Theories of chemical bonding 1
 Energy of Interaction Between
Two H Atoms
Energies of Potent
attraction and ial
repulsion as energ
functions of y
+346 kJ
distance between mol –1
two H atoms are antibondin
shown here. g

The minimum of the

distan
attraction force ce
occur at
–346 kJ
H–H bond length of mol –1
74 pm, at which, the H – H bond
antibonding orbital
How does energy
is +346 kJ mole –1 affect the two-
Theories of chemical bonding 2
 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
How does – hybridization.
valence-bond
approach explain theTheoriesformation
of chemical bonding 3
of chemical bonds?
 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
Provide
orbital a descriptionTheories
for ofhybrid orbitals sp, sp2,
chemical bonding 4
33 3 3 2
 The sp Hybrid Orbitals
The sp hybrid orbitals: formation of two sp hybrid
orbitals
+ ++ - = + -

+ – + - = - +

hybridization of s and p orbitals = 2 sp hybrid

orbitals

↑_ ↑_ __ __
↑↓ __ __ __ Two sp hybrid orbitlas =>
Theories of chemical bonding 5
Two states of Be
 Bonds with sp Hybrid
Orbitals
Formations of bonds in these molecules are
discussed during the lecture. Be prepared to do the
same by yourself.
Cl–Be–Cl H–C≡C–H H–C≡N : O=C=O

Double and triple bonds involve pi π bonding, and

the the application of valence bond method to π
bonds will be discussed.

You are expected to be able to draw pictures to

show the π bonding.

Theories of chemical bonding 6

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

Bonding of
C2H4 Theories of chemical bonding 7
How are pi bonds
 Triple Bonds in H-C≡
C-H
H-C-C-H: three σ bonds due to overlapping of 1sH
– spC; spC – spC; and spC – 1sH.
Two π bonds in HC≡CH and HC≡N triple bonds are
due to overlapping of p orbitals results.
sp hybrid
py over orbitals
C
lap
in π bond
2s 2p 2p 2p
H H sp sp 2p 2p
px over
lap Two nodal planes
in π of π bonds are
bond perpendicular to
Draw and describe how atomic
Theories of chemical bondingeach other. 8
orbitals overlap to form all bonds
Two π Bonds in H–C≡C–H

A triple bond consists of a sigma and two pi

bonds. Overlaps of two sets of p orbitals form
of two π bonds.
Theories of chemical bonding 9
 Bonding of CO2
For CO2, the C atom forms a σ bond and a π bond
with each of two O atoms. The two nodal planes of
the two π bonds are also perpendicular.
During the lecture, I draw diagrams and explain the
two σ two π bonds in CO2. You are expected to be
able to do the same, in a test.
Resonance py over lap in π
structures bond

:O–C≡O:
px over lap in π
:O≡C–O: bond

..
Overlap p–p in σ
Discuss the bonding of allene bonds
H2C=C=CH2 O=C=O
Theories of chemical bonding or 10
 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
Theories of chemical bonding 11
(b)
 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, Theories of chemical bonding 12
Nov.
H2C=CH2, NO3–, etc
 An example of using sp2
hybrid orbitals

__ orbitals for
bonding?
Dipole moment =
Theories of chemical bonding 13
____?
 Bonding of H2C=CH2 molecules
Utilizing the sp2 hybrid orbitals, each
C atom form two H–C σ bonds for a
total of 4 σ H–C bonds. The C–C σ
bond is common to both C atoms.
A C–C π bond is formed due to C
overlap of p orbitals from each of 2s 2p 2p 2p
the C atoms. sp2 sp2 sp2
2p
Hybrid orbitals
(sp2) for H–C and
C–C σ bond
Overlap of p
orbital for C–C
π bondTheories of chemical bonding 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::, SiO 4 ,of chemical bonding
4–
Theories 15
SO 2–, ClO –, etc
 C
2s 2p 2p 2p
sp3 sp3 sp3
sp3

Theories of chemical bonding 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?

Theories of chemical bonding What are their 17

shapes?
 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
AX6, of
type   AX E,   AXare
orbitals
5
E   AX3E3  
4 2
shown
and   AXhere.
E
2 4
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.
Theories of chemical bonding 18
 Molecules with more than one
central atom
Describe the structure of CH3NCO. Take a new look at
slide 22 in
Draw the skeleton and add all valence
Bonding Basics
electrons
H3C – N – C – O
Which Lewis dot structure
18 is the most
N≡C–
important (stable)? 0o N–C≡ Which
O 10 O structure
H– 12
9o is more
H–C 0o
H C N = C = OH–C
H stable,
H
H H and why?
H
What hybridized orbitals are used for bonding in N
and C? Why are the bond angles as indicated? No of
σ and π bonds = __,Theories
__?of chemical bonding 19

Give formal charges to all atoms in all structures.

 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 O2 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.
Theories of chemical bonding 20
There are other reasons, but it’s human nature to
 The Molecular Orbital (MO)
For a molecule, thereTheory
are certain orbitals each of
which accommodates two electrons of opposite
spin.
The MO theory combines atomic orbitals (AO) to
form MOs, & this method is called LCAO σ∗
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:
1s 1s
σ* = 1sA – 1sB
A B

σ = 1sA + 1sB
σ
The energy levels ofTheories
these AObonding
of chemical AO MO AO
21
MO for H2–type molecules: H2+,
H2, H2–, He2+

Generalize the technique

of LCAO
Theories of chemical bonding 22
Electronic configuration, σ2, for
H2 molecules

Generalize the technique

of LCAO
Theories of chemical bonding 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+ 1σ (1σ1) ½ 106 pm
H2, He22+ 1σ2 1 74, ~75
H2–, He2+ 1σ2 1σ∗ ½ ~106, 108
H22–Describe
, He2 1σ2 1σ∗ 0
the2relationships of not formed
bondlength & bondorder and e-
configurations; learn to reason

Theories of chemical bonding 24

 Sigma MOs Formed Using p AOs
Sigma MOs (σ2p σ2p* ) can be formed using p
AOs, similar to VB theory. The gain in bonding
orbital σ2p (lower energy) is at the expense of
the anti-bonding orbital σ2p* (higher energy)

Theories of chemical bonding 25

Generalize the technique
Pi π MOs from p AOs

Generalize the technique

Theories of chemical bonding 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
Write the
to be able to do the
electronic
same.
configurations
Theories of chemical bonding 27
for O , O –, F ,
 The O2+, O2, O2– , & F2+, F2, F2–
Molecules
For •O=O •O=O•
•
Paramagnetic
↑_ ↑_
, bond length
indicates
double bond,
electronic
configuration
agrees
F–F
Electronic
configuration
See p. 457 for
agree with
Theories of chemical bonding 28
two MO energy- single bond.
 MO Energy Level Diagram for
Be 2 – N 2 and 2p, the MO
Due to close energy levels of 2s
energy level diagram for Be2 to N2 differs from
those of O2 to F2. Reasons and explanation are
given during the lecture. Hope you can Give do the
same. electronic
configurati
ons for
Be2+,
Be2–, B2+,
B2,
B2–, C2+,
C2,
C2–, N2+,
See p. 457 for
two MO energy-
Theories of chemical bonding N 2 , 29

–
 A more realistic energy level
diagram for Be2 – N2 involving
__ σ* sp mixing, not in text
2p
__ __ π*2p
This diagram from my
___ CaCt website accounts
___
2p 2p for the sp mixing of the
AO for the bonding
consideration. This sp
__ σ 2p mixing effect is more
__ __π 2p detailed than that
required for freshman
__ σ*2s chemistry (not to be
_ _ tested).
2s 2s
The sp mixing of AO
__ σ 2s gives stronger σ 2s bond
Atom Ato
ic mic
and a weaker σ∗ 2s bond.
orbit Thus, the split from 2s is
Theories of chemical bonding
orbit 30

al Molecular
 Benzene
The benzene structure has fascinated scientists for
centuries. It’s bonding is particularly interesting. The C
atom utilizes sp2 hybrid AO in the sigma bonds, and
the remaining p AO overlap forming a ring of p bonds.
Sigma σ bonds
are represented + +
by lines, and the
+ +
p orbitals for the
π bonds are + +
shown by
balloon-shape – –
blobs. Note the – –
+ and – signs of
the p orbitals.
Thus, we Theories of chemical bonding 31
 Chem120 students
More About Benzene may ignore this slide.
The π and π* of C6H6
are shown here; the
symmetry is also
interesting.

Theories of chemical bonding 32

 Delocalized electrons in Benzene
and Ozone
When p bonds are adjacent to each other or
separated by on single C-C bonds, the p bonding
electrons are delocalized. The delocalized electron
path for benzene and ozone are shown here. These
picturesCO 3
2–
& have
represent delocalized
p electron electrons
of the the structures
formula contribute most to their structures. O
O
O

Theories of chemical bonding 33

 Joy on structure of
benzene – a story
Kathleen Londsdale (1903-1971) came from a very
poor family in Kildare who moved to Essex when she
was five. She studied physics, math and chemistry at
school and went to college in London when she was
16, where she did extremely well. She was offered a
place in the research team of William Bragg, so
starting her life's work on X-ray crystallography.
In 1929 she showed, by her analysis of hexamethyl
benzene, that the benzene ring was flat. Benzene
has fascinated scientists, and its precise structure
was a matter of controversy till then.
In 1945 she was elected the first ever woman Fellow
of the Royal Society. She was also created a Dame
Theories of chemical bonding 34
Commander of the Order of the Brittish Empire in
 MO for Heteronuclear Diatomic
Molecules
For
heteronuclear
diatomic
molecules, the
atomic orbitals
are at different
energy levels.
Thus, the MO
shifts are
different from
those of
homonuclear
diatomic
molecules. Theories of chemical bonding 35
Chem120 students may ignore
 Review
Explain the bonding and anti-bonding orbitals, with
a picture if possible
Describe a σ and a π bond, picture may be used.
Give the electronic configurations and bond orders
for N2, N2+, N22+, N2–, N22–, O2,
Draw the Lewis dot structure for ozone. Describe
the molecular shape and justify for it. Explain the
delocalized electrons of ozone.
Use the MO theory to explain the fact that O2 is
paramagnetic, and has a double bond. A diagram
of the MO energy levels will help. Give a few
compounds that have
Theoriesthe same
of chemical bondingnumber of 36
electrons as O .