Chemical Bonding II:

Molecular Geometry and

Hybridization of Atomic Orbitals
Chapter 10

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Valence shell electron pair repulsion (VSEPR) model:

Predict the geometry of the molecule from the electrostatic

repulsions between the electron (bonding and nonbonding) pairs.

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

B B

2
 0 lone pairs on central atom

Cl Be Cl

3
2 atoms bonded to central atom
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar

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5
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral

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7
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral

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11
12
lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding
repulsion
> pair repulsion
> 13
pair repulsion
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

trigonal trigonal
AB3 3 0
planar planar
trigonal
AB2E 2 1 bent
planar

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal

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 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
square
AB4E2 4 2 octahedral
planar

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 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?

O S O F
AB4E
AB2E F S F
distorted
bent tetrahedron
F
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Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

d+ d-

m=Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m 24
 Behavior of Polar Molecules

field off field on 25

Bond moments and resultant dipole moments in NH3 and NF3.

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Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CF4

O S

dipole moment dipole moment

polar molecule polar molecule

C
O C O
F F
no dipole moment F
nonpolar molecule no dipole moment
nonpolar molecule
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Does BF3 have a dipole
moment?

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Does CH2Cl2 have a
dipole moment?

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Chemistry In Action: Microwave Ovens

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How does Lewis theory explain the bonds in H2 and F2?

Sharing of two electrons between the two atoms.

Bond Enthalpy Bond Length Overlap Of

H2 436.4 kJ/mol 74 pm 2 1s

F2 150.6 kJ/mol 142 pm 2 2p

Valence bond theory – bonds are formed by sharing

of e- from overlapping atomic orbitals.

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Change in Potential Energy of Two Hydrogen Atoms
as a Function of Their Distance of Separation

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Change in electron density as two hydrogen atoms
approach each other.

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 Valence Bond Theory and NH3

N – 1s22s22p3

3 H – 1s1
If the bonds form from overlap of 3 2p orbitals on nitrogen with
the 1s orbital on each hydrogen atom, what would the molecular
geometry of NH3 be?
If use the
3 2p orbitals
predict 90o

Actual H-N-H
bond angle is
107.3o
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 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 36
Formation of sp3 Hybrid Orbitals

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Formation of Covalent Bonds in CH4

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sp3-Hybridized N Atom in NH3

Predict correct
bond angle

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Formation of sp Hybrid Orbitals

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Formation of sp2 Hybrid Orbitals

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How do I predict the hybridization of the central atom?
1. Draw the Lewis structure of the molecule.
2. 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 42
43
sp2 Hybridization of Carbon

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Unhybridized 2pz orbital (gray), which is perpendicular
to the plane of the hybrid (green) orbitals.

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 Bonding in Ethylene, C2H4

Sigma bond (s) – electron density between the 2 atoms

Pi bond (p) – electron density above and below plane of nuclei
of the bonding atoms 46
Another View of p Bonding in Ethylene, C2H4

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sp Hybridization of Carbon

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Bonding in Acetylene, C2H2

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Another View of the Bonding in Ethylene, C2H4

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Describe the bonding in CH2O.

H
C O
H
C – 3 bonded atoms, 0 lone pairs
C – sp2

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 Sigma (s) and Pi Bonds (p)

Single bond 1 sigma 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?
O

H
s bonds = 6 + 1 = 7
H C C O H
p bonds = 1
H
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 Experiments show O2 is paramagnetic

O
O
No unpaired e-
Should be diamagnetic

Molecular orbital theory – bonds are formed from

interaction of atomic orbitals to form molecular
orbitals.
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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
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formed.
Constructive and Destructive Interference

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Two Possible Interactions Between Two Equivalent p Orbitals

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General molecular orbital energy level diagram for the
second-period homonuclear diatomic molecules Li2, Be2, B2,
C2, and N2.

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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.

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 Number of Number of
bond order =
1
2 ( electrons in
bonding
MOs
- electrons in
antibonding
MOs
)

bond
½ 1 ½ 0
order 59
60
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.

Example: Benzene, C6H6

Delocalized p orbitals

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Electron density above and below the plane of the
benzene molecule.

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Bonding in the Carbonate Ion, CO32-

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Chemistry In Action: Buckyball Anyone?

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