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VBT
VBT
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
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.
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
+ + + - = + -
+ + - = - +
_ _ __ __
__ __ __ 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
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
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
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.
: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)
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
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
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.
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.
18
Molecules with more than one
central
Describe theatom
structure of CH NCO.
3
N=C=O
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.
19
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.
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+
22
Electronic configuration, 2, for H2
molecules
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
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)
28
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.
29