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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.

# 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

10.1
Cl Be Cl

0 lone bonded
2 atoms pairs on to
central atom
central atom 10.1
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

10.1
10.1
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

10.1
10.1
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

10.1
10.1
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

10.1
10.1
10.1
lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding
repulsion
> pair repulsion
> 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

10.1
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

10.1
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


O
H H

10.1
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 See-Saw
AB4E 4 1 (distorted tetrahedron)
bipyramidal

10.1
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 See-Saw
AB4E 4 1
bipyramidal
trigonal
AB3E2 3 2 T-shaped
bipyramidal
F
F Cl

10.1
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 See-Saw
AB4E 4 1
bipyramidal
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal
I

I 10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

octahedral square
AB5E 5 1
pyramidal
F
F F
Br
F F

10.1
VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

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

10.1
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
AB4E

S S F S F
O O See-Saw
O O
F (distorted
Tetrahedron)
AB2E bent
10.1
Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

 

10.2
10.2
Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CH4

O S O
H
H O
dipole moment dipole moment
polar molecule polar molecule

H C H
O C O

no dipole moment H
nonpolar molecule 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.

Bond Dissociation Energy Bond Length Overlap Of

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 () and Pi Bonds ()

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  and  bonds are in the acetic acid


(vinegar) molecule CH3COOH?

H
O

 bonds = 6 + 1 = 7
H C C O H
 bonds = 1
H
10.5
Pi bond () – electron density above and below plane of nuclei
Sigma bond () – electron density between the 2 atoms
of the bonding atoms 10.5
10.5
10.5
Experiments show O2 is paramagnetic
O (has UNPAIRED e-)
O
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
Number of Number of
bond order =
1
2 ( electrons in
bonding
MOs
-
electrons in
antibonding
MOs
)

bond
½ 1 ½ 0
order
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

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