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Chemical Bonding II:
Molecular Geometry and
Hybridization of Atomic
Orbitals
Chapter 10
10.1
Valence shell electron pair
repulsion (VSEPR) model:
Predict the geometry of the
molecule from the electrostatic
repulsions between the electron
(bonding and nonbonding) pairs.
This chart is
NOT provided
on the AP exam!
VSEPR
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
AB2
2
0
linear
linear
B
B
10.1
Cl
Be
Cl
lone pairs
on to
central
atom
20
atoms
bonded
central
atom
10.1
VSEPR
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
AB2
2
0
linear
linear
0
trigonal
planar
trigonal
planar
AB3
3
10.1
10.1
VSEPR – Trigonal Planar arrangement
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
AB3
3
0
AB2E
2
1
Arrangement of
electron pairs
Molecular
Geometry
trigonal
planar
trigonal
planar
trigonal
planar
bent
10.1
VSEPR
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
AB2
2
0
linear
linear
trigonal
planar
tetrahedral
AB3
3
0
trigonal
planar
AB4
4
0
tetrahedral
10.1
10.1
VSEPR – Tetrahedral Arrangement
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
AB4
4
0
AB3E
3
1
Arrangement of
electron pairs
Molecular
Geometry
tetrahedral
tetrahedral
tetrahedral
trigonal
pyramidal
10.1
VSEPR – Tetrahedral Arrangement
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
AB4
4
0
Arrangement of
electron pairs
Molecular
Geometry
tetrahedral
tetrahedral
AB3E
3
1
tetrahedral
trigonal
pyramidal
AB2E2
2
2
tetrahedral
bent
O
H
H
10.1
VSEPR
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
AB2
2
0
linear
linear
trigonal
planar
AB3
3
0
trigonal
planar
AB4
4
0
tetrahedral
tetrahedral
AB5
5
0
trigonal
bipyramidal
trigonal
bipyramidal
10.1
10.1
VSEPR – Trigonal Bipyramid Arrangement
Class
AB5
AB4E
# of atoms
bonded to
central atom
5
4
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
0
trigonal
bipyramidal
trigonal
bipyramidal
1
trigonal
bipyramidal
See-Saw
(distorted tetrahedron)
10.1
VSEPR – Trigonal Bipyramid Arrangement
Class
AB5
# of atoms
bonded to
central atom
5
# lone
pairs on
central atom
0
AB4E
4
1
AB3E2
3
2
Arrangement of
electron pairs
Molecular
Geometry
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
See-Saw
T-shaped
F
F
Cl
F
10.1
VSEPR – Trigonal Bipyramid Arrangement
Class
AB5
# of atoms
bonded to
central atom
5
# lone
pairs on
central atom
0
AB4E
4
1
AB3E2
3
2
AB2E3
2
3
Arrangement of
electron pairs
Molecular
Geometry
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal
See-Saw
trigonal
bipyramidal
T-shaped
linear
I
I
I
10.1
VSEPR
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
Arrangement of
electron pairs
Molecular
Geometry
AB2
2
0
linear
linear
trigonal
planar
AB3
3
0
trigonal
planar
AB4
4
0
tetrahedral
tetrahedral
AB5
5
0
trigonal
bipyramidal
trigonal
bipyramidal
AB6
6
0
octahedral
octahedral
10.1
10.1
VSEPR – Octahedral Arrangement
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
AB6
6
0
octahedral
octahedral
AB5E
5
1
octahedral
square
pyramidal
F
F
F
Arrangement of
electron pairs
Molecular
Geometry
Br
F
F
10.1
VSEPR – Octahedral Arrangement
Class
# of atoms
bonded to
central atom
# lone
pairs on
central atom
AB6
6
0
octahedral
octahedral
AB5E
5
1
octahedral
AB4E2
4
2
octahedral
square
pyramidal
square
planar
Arrangement of
electron pairs
Molecular
Geometry
F
F
Xe
F
F
10.1
10.1
lone-pair vs. lone pair
lone-pair vs. bonding
bonding-pair vs. bonding
>
>
repulsion
pair repulsion
pair repulsion
10.1
Predicting Molecular Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the central atom and
number of atoms bonded to the central atom.
3. Use VSEPR to predict the geometry of the molecule.
What are the molecular geometries of SO2 and SF4?
(In SF4, S uses an expanded octet of 10.)
F
S
S
F
S
F
AB2E
bent
AB4E
F
See-Saw
(distorted
Tetrahedron)
10.1
Dipole Moments and Polar Molecules
electron poor
region
electron rich
region
H
F
d+
d-
10.2
10.2
Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CH4
O
S
dipole moment
polar molecule
dipole moment
polar molecule
H
O
C
O
no dipole moment
nonpolar molecule
H
C
H
H
no dipole moment
nonpolar molecule
10.2
Chemistry In Action: Microwave Ovens
10.2
How does Lewis theory explain the bonds in H2 and F2?
Sharing of two electrons between the two atoms.
Overlap Of
Bond Dissociation Energy
Bond Length
H2
436.4 kJ/mole
74 pm
2 1s
F2
150.6 kJ/mole
142 pm
2 2p
Valence bond theory – bonds are formed by sharing
of e- from overlapping atomic orbitals.
10.3
Hybridization – mixing of two or more atomic
orbitals to form a new set of hybrid orbitals.
1. Mix at least 2 nonequivalent atomic orbitals (e.g. s
and p). Hybrid orbitals have very different shape
from original atomic orbitals.
2. Number of hybrid orbitals is equal to number of
pure atomic orbitals used in the hybridization
process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid
orbitals
10.4
10.4
Formation of sp2 Hybrid Orbitals
10.4
Formation of sp Hybrid Orbitals
10.4
How do I predict the hybridization of the central atom?
Count the number of lone pairs AND the number
of atoms bonded to the central atom
# of Lone Pairs
+
# of Bonded Atoms
Hybridization
Examples
2
sp
BeCl2
3
sp2
BF3
4
sp3
CH4, NH3, H2O
5
sp3d
PCl5
6
sp3d2
SF6
10.4
10.4
Sigma (s) and Pi Bonds (p)
1 sigma bond
Single bond
Double bond
1 sigma bond and 1 pi bond
Triple bond
1 sigma bond and 2 pi bonds
How many s and p bonds are in the acetic acid
(vinegar) molecule CH3COOH?
H
C
O
H
C
O
H
s bonds = 6 + 1 = 7
p bonds = 1
H
10.5
Pi bond (p) – electron density above and below plane of nuclei
Sigma bond (s) – electron density between the 2 atoms
of the bonding atoms
10.5
10.5
10.5
O
O
Experiments show O2 is paramagnetic
(has UNPAIRED e-)
No unpaired e-
Should be diamagnetic
MO Theory is NOT in the
AP Chemistry Curriculum
and will NOT be on the
AP exam! This is just a
quick overview!
Molecular orbital theory – bonds are formed from
interaction of atomic orbitals to form molecular
orbitals.
10.6
Energy levels of bonding and antibonding molecular
orbitals in hydrogen (H2).
A bonding molecular orbital has lower energy and greater
stability than the atomic orbitals from which it was formed.
An antibonding molecular orbital has higher energy and
lower stability than the atomic orbitals from which it was
formed.
10.6
10.6
Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.
10.7
1
bond order =
2
bond
order
½
(
Number of
electrons in
bonding
MOs
1
-
½
Number of
electrons in
antibonding
MOs
)
0
10.7
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.
10.8
10.6