MOLECULAR STRUCTURE

AND COVALENT BONDING
GENERAL CHEMISTRY
LECTURE
10
1. Valence Shell Electron Pair Repulsion (VSEPR)
Theory
– Determine the shape (electronic and molecular
geometry) of the molecule
2. Polar Molecules: The Influence of Molecular
Geometry
– Determine the polarity of the molecule
3. Valence Bond (VB) Theory
– Determine the hybrid orbitals used for bonding

SCOPE
• Electron group domains around the central atom
are arranged as far apart as possible to minimize
repulsions.
• There are five basic molecular shapes based on
the number of regions of high electron density
around the central atom.

VSPER Theory
1. Two electron group domains around the central
atom.


2. Three electron group domains around the
central atom.

VSPER Theory
3. Four electron group domains around the central
atom.



4. Five electron group domains around the central
atom.

VSPER Theory
5. Six electron group domain around the central
atom.

VSPER Theory
MOLECULAR STRUCTURE
AND COVALENT BONDING
GENERAL CHEMISTRY
LECTURE
10
Electron-group repulsions and the five
basic molecular shapes.

• Electronic geometry
– based on the number of electron domains around
the central atom
• Molecular geometry
– accounts the number of nonbonding
electrons/lone pairs

• The same electron-group arrangement can give rise
to different molecular shapes.


VSPER Theory
• Lone pairs of electrons require more volume than
shared electrons.

• Criteria for the ordering of the repulsions:
a) Lone pair to lone pair is the strongest repulsion.
b) Lone pair to bonding pair is intermediate
repulsion.
c) Bonding pair to bonding pair is weakest repulsion.
lp/lp > lp/bp > bp/bp

VSPER Theory
The Different Types of Shapes
according to Electron Domains
Examples

CO
2


BF
3


NO
2
-


Total Electron Domains: 4 pairs
Examples

CCl
4



NH
3


H
2
O



Total Electron Domains: 5 pairs
Examples

PCl
5



SF
4


ClF
3


XeF
2



Total Electron Domains: 6 pairs
Examples

SF
6



BrF
5



XeF
5



The Steps in Determining
a Molecular Shape.

Example: Methane, CH
4

Electronic and molecular geometries are the
same: tetrahedral.
VSPER Theory
Exercise No. 1
Predicting Molecular Shapes
Give the molecular shape and predict the bond angles (relative
to the ideal angles) of (a) PF
3
(b)

COCl
2
and (c) BrF
5
.
SOLUTION:
(a) For PF
3
N = 8 x 4 = 32
A = 5 + 7 x 3 = 26
S = 6 -> 3 bonds
A-S = 20



P F F
F
4 electron group domain
The electronic geometry is tetrahedral arrangement.
The F-P-F bond is <109.5
o

The final shape (molecular geometry) is
trigonal pyramidal.
P
F
F
F
(b) For COCl
2
, C has the lowest EN and will be the center atom.
N = 8 x 4 = 32
A = 4 + 6 + (7 x 2) = 24
S = 8 -> 4 bonds
A-S = 16
C
Cl
O
Cl
The Cl-C-Cl bond angle is < 120
o

due to the electron density of
the C=O.
C
Cl
O
Cl
Predicting Molecular Shapes
SOLUTION:
3 electron group domain
The electronic geometry is trigonal planar
The final shape (molecular geometry) is trigonal planar
Exercise No. 1
111
o

124.5
o

Predicting Molecular Shapes
(b) For BrF
5
,
N = 8 x 6 = 48
A = 7 x 6 = 42
S = 6 e -> 10 e -> 5 bonds
A-S = 42-10 = 32
SOLUTION:
Br
F
F F
F
F
6 electron group domain
The electronic geometry is octahedral arrangement.
The final shape (molecular geometry) is
square pyramidal.
Exercise No. 1
Predicting Molecular Shapes with More Than
One Central Atom
SOLUTION:
Determine the shape around each of the central atoms in acetone,
(CH
3
)
2
C=O.
C C C
O
H
H
H
H H
H
tetrahedral
tetrahedral
trigonal planar
C
O
H
C
HH
H
C
H
H
Exercise No. 2
3. What is the shape of each of the indicated atoms in the
molecule below?
1. Trigonal planar

2. Tetrahedral

3. Trigonal planar

4. Bent or angular

Predicting Molecular Shapes with More Than
One Central Atom
Exercise No. 3
• Molecular geometry affects molecular polarity.
– The bond dipoles either cancel or reinforce each
other.
linear molecule
nonpolar
A B

A B A
angular molecule
A
polar
Polarity and Molecular Geometry
• Polar molecules must meet the following
requirements:
– One polar bond or one lone pair of electrons on
central atom.
– Bonds and lone pairs are not symmetrically
arranged.
– Their polarities do NOT cancel.
– Net dipole moment is NOT equal to zero.
Polarity and Molecular Geometry
Bond Polarity, Bond Angle and
Bond Dipole Moment
1. Covalent bonds are formed by the overlap of
atomic orbitals.
Valence Bond (VB) Theory
2. Atomic orbitals on the central atom can mix and
exchange their character with other atoms in a
molecule.
- Hybridization of atomic orbitals

3. Hybrid orbitals have the same shapes as
predicted by VSEPR.

Valence Bond (VB) Theory
The number of hybrid orbitals obtained is equal to
the number of atomic orbitals mixed.
The type of hybrid orbitals obtained varies with
the types of atomic orbitals mixed.
sp
sp
2

sp
3

sp
3
d sp
3
d
2

Types of Hybrid Orbitals
Hybrid Orbitals
The sp Hybrid Orbitals in Gaseous BeCl
2
The sp Hybrid Orbitals in Gaseous BeCl
2
Shape:
Linear
sp-p
The sp
2
Hybrid Orbitals in BF
3
The sp
2
Hybridized Orbitals
Shape: Trigonal planar
sp
2
-p
The sp
3
Hybrid Orbitals in CH
4
The sp
3
Hybridized Orbitals
The sp
3
Hybridized Orbitals
Shape: Tetrahedral
sp
3
-p
sp
3
-s
The sp
3
Hybrid Orbitals in NH
3
and H
2
O
The sp
3
d Hybrid Orbitals in PCl
5
The sp
3
d Hybridized Orbitals
Shape: Trigonal
bipyramidal
sp
3
d-p
The sp
3
d
2
Hybrid Orbitals in SF
6
The sp
3
d
2
Hybridized Orbitals

Shape:
Octahedral
sp
3
d
2
-p
Summary: Hybridization
Regions of High
Electron Density
Electronic
Geometry
Hybridization
2 Linear sp
3 Trigonal planar sp
2
4 Tetrahedral sp
3
5 Trigonal
bipyramidal
sp
3
d
6 Octahedral sp
3
d
2
Summary: Hybridization
Molecule Lewis
Structure
Electron
group
domain
Electronic
geometry
Hybrid
Orbitals
CO
2
PO
4
3-
XeF
4
SbF
5
2 Linear sp
4 Tetrahedral
Octahedral 6
sp
3
sp
3
d
2
5 Trigonal
bipyramidal
sp
3
d
4. What is the hybridization of each of the indicated
atoms in the molecule below?
1. sp
2
2. sp
3
3. sp
2
4. sp
3
Exercise No. 4
Take home quiz
Consider the following ACl
n
species:
SCl
2
, OCl
2
, PCl
3
, SiCl
4
, SiCl
6
2-

1) Determine the EGG and MGG of each compound
2) Arrange the compounds in decreasing Cl-A-Cl
bond angles
3) Are all the molecules polar? Give the list of all
the polar compounds from the given
4) Identify the orbitals involved in the bond A-Cl