CHAPTER 8

 Molecular
Structure &
Covalent Bonding
Theories
Chapter Goals

Molecular Shapes and Bonding

 Chapter Goals



 Stereochemistry


 Two Simple Theories of
Covalent Bonding



Overview of Chapter
 Overview of Chapter
electronic

molecular
 Overview of Chapter

 hybrid orbitals

 molecular polarity
 VSEPR Theory



VSEPR Theory
VSEPR Theory
VSEPR Theory
VSEPR Theory
VSEPR Theory
 VSEPR Theory
 Frequently, we will describe two geometries 
for each molecule. 
 Electronic  geometry is determined by the 
Electronic  geometry
locations of regions of high electron density 
around the central atom(s).
 Molecular geometry
Electron pairs are not used in the
molecular geometry determination just the
positions of the atoms in the molecule are
used.
 VSEPR Theory


 VSEPR Theory



 VSEPR Theory



 VSEPR Theory


 Polar Molecules: The Influence
of Molecular Geometry


A B A A B
A
linear molecule angular molecule
nonpolar
polar
 Polar Molecules: The Influence
of Molecular Geometry

or
 Valence Bond (VB) Theory
 overlap

hybridization



 Valence Bond (VB) Theory
Regions of Electronic Hybridization
High Electron Geometry
Density
2 Linear sp
3 Trigonal sp2
planar
4 Tetrahedral sp3
5 Trigonal sp3d
bipyramidal
6 Octahedral sp3d2
 Molecular Shapes and Bonding



Linear Electronic Geometry:AB2
Species (No Lone Pairs of
Electrons on A)




Linear Electronic Geometry:AB2
Species (No Lone Pairs of
Electrons on A)

Be
↑↓ ↑↓

↑↓ ↑↓↑↓↑
Linear Electronic Geometry:AB2
Species (No Lone Pairs of
Electrons on A)

Cl Be Cl

Cl Be Cl
Linear Electronic Geometry:AB2
Species (No Lone Pairs of
Electrons on A)
Cl - -- - Be
Cl Be - --- Cl
Cl
← 1.5→ 3.5
Cl Be Cl   
Electronegativities 3.5
bond dipoles
2.0 are symmetric
2.0

very polar
nonpolar bonds
molecule
Linear Electronic Geometry:AB2
Species (No Lone Pairs of
Electrons on A)

↑↓ ↑↓
⇒ ↑↓↑↑

↑↓ ↑↓ ↑↓ ↑
Linear Electronic Geometry:AB2
Species (No Lone Pairs of
Electrons on A)
 Trigonal Planar Electronic
Geometry: AB3 Species (No
Lone Pairs of Electrons on A)




 Trigonal Planar Electronic
Geometry: AB3 Species (No
Lone Pairs of Electrons on A)

B
↑↓ ↑↓ ↑

↑↓ ↑↓ ↑↓ ↑ Cl
 Trigonal Planar Electronic
Geometry: AB3 Species (No
Lone Pairs of Electrons on A)

Cl

B
Cl
B
Cl
 Trigonal Planar Electronic
Geometry: AB3 Species (No
Lone Pairs of Electrons on A)

Cl Cl B - Cl
B
Cl Cl 
Electronegativities 1.5
Cl   
3.0
B 1.5

Cl very polar bonds

 Trigonal Planar Electronic
Geometry: AB3 Species (No
Lone Pairs of Electrons on A)

↑↓ ↑↓ ↑ ⇒ ↑↓ ↑ ↑ ↑

↑↓ ↑↓ ↑↓ ↑
 Trigonal Planar Electronic
Geometry: AB3 Species (No Lone
Pairs of Electrons on A)
 Trigonal Planar Electronic
Geometry: AB3 Species (No Lone
Pairs of Electrons on A)
Tetrahedral Electronic Geometry:
AB4 Species (No Lone Pairs of
Electrons on A)




Tetrahedral Electronic Geometry:
AB4 Species (No Lone Pairs of
Electrons on A)

↑↓ ↑ ↑

↑
Tetrahedral Electronic Geometry:
AB4 Species (No Lone Pairs of
Electrons on A)
Tetrahedral Electronic Geometry:
AB4 Species (No Lone Pairs of
Electrons on A)

C - H
   2.1
Electronegativities 2.5 
0.4

slightly polar bonds

Tetrahedral Electronic Geometry:
AB4 Species (No Lone Pairs of
Electrons on A)

↑↓ ↑ ↑ ⇒ ↑ ↑ ↑ ↑

↑
Tetrahedral Electronic Geometry:
AB4 Species (No Lone Pairs of
Electrons on A)
Tetrahedral Electronic Geometry:
AB4 Species (No Lone Pairs of
Electrons on A)
Example of Molecules with More
Than One Central Atom
Alkanes CnH2n+2





Example of Molecules with More
Than One Central Atom
Alkanes CnH2n+2
Tetrahedral Electronic Geometry:
AB3U Species (One Lone Pair of
Electrons on A)


polar

Tetrahedral Electronic Geometry:
AB3U Species (One Lone Pair of
Electrons on A)

↑↓ ↑ ↑ ↑

↑↓ ↑↓ ↑↓ ↑

↑
Tetrahedral Electronic Geometry:
AB3U Species (One Lone Pair of
Electrons on A)
Tetrahedral Electronic Geometry:
AB3U Species (One Lone Pair of
Electrons on A)

N - H
Electronegativities 3.0 2.1

0.9

very polar bonds

µ

N - F
Electronegativities 3.0 4.0

1.0

µ
very polar bonds
Tetrahedral Electronic Geometry:
AB3U Species (One Lone Pair of
Electrons on A)

↑↓ ↑ ↑ ↑ ⇒ ↑↓ ↑ ↑ ↑
Tetrahedral Electronic Geometry:
AB2U2 Species (Two Lone Pairs of
Electrons on A)


polar

Tetrahedral Electronic Geometry:
AB2U2 Species (Two Lone Pairs of
Electrons on A)

↑↓ ↑↓ ↑ ↑

↑
Tetrahedral Electronic Geometry:
AB2U2 Species (Two Lone Pairs
of Electrons on A)

O - H
   2.1
Electronegativities 3.5 
1.4

very polar bonds

µ≈
Tetrahedral Electronic Geometry:
AB2U2 Species (Two Lone Pairs
of Electrons on A)

↑↓ ↑↓ ↑ ↑ ⇒ ↑↓ ↑↓ ↑ ↑
Tetrahedral Electronic Geometry:
ABU3 Species (Three Lone Pairs
of Electrons on A)



nonpolar
Tetrahedral Electronic Geometry:
ABU3 Species (Three Lone Pairs
of Electrons on A)
Tetrahedral Electronic Geometry:
ABU3 Species (Three Lone Pairs
of Electrons on A)
Tetrahedral Electronic Geometry:
ABU3 Species (Three Lone Pairs
of Electrons on A)

↑↓ ↑↓ ↑↓ ↑ ⇒ ↑↓ ↑↓ ↑↓ ↑
Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3



polar
Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3

↑↓ ↑ ↑ ↑

↑↓ ↑↓ ↑↓ ↑
Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3
Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3

As - F
   4.0
Electronegativities 2.1 
1.9

very polar bonds

Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3

↑↓ ↑ ↑ ↑ ___ ___ ___ ___ ___

⇓

↑ ↑ ↑ ↑ ↑ ___ ___ ___ ___ ___

Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3
 If lone pairs are incorporated into the trigonal 
bipyramidal structure, there are three possible 
new shapes. 
1. One lone pair ­ Seesaw shape
2. Two lone pairs ­ T­shape
3. Three lone pairs – linear
 The lone pairs occupy equatorial positions 
because they are 120o from two bonding pairs 
and 90o from the other two bonding pairs.
– Results in decreased repulsions compared to lone pair 
in axial position.
Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3

trigonal bipyramid electronic geometry
seesaw shaped molecular geometry
polar



Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3
Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3

trigonal bipyramid electronic geometry
T-shaped molecular geometry
polar



Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3
Molecular 
Geometry
Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3
 
trigonal bipyramid electronic geometry
linear molecular geometry
nonpolar

XeF2

Trigonal Bipyramidal Electronic
Geometry: AB5, AB4U, AB3U2,
and AB2U3
Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2



 octahedralnonpolar
polar
Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2

↑↓ ↑↓ ↑ ↑

↑↓ ↑↓ ↑↓ ↑
Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2

Se - F
   4.0
Electronegativities 2.4 
1.6

very polar bonds

Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2

↑↓ ↑↓ ↑ ↑ __ __ __ __ __
⇓

↑ ↑ ↑ ↑ ↑ ↑ __ __ __ __
Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2
 If lone pairs are incorporated into the octahedral 
structure, there are two possible new shapes. 
1. One lone pair ­ square pyramidal
2. Two lone pairs ­ square planar
 The lone pairs occupy axial positions because 
they are 90o from four bonding pairs.
– Results in decreased repulsions compared to lone 
pairs in equatorial positions.
Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2

octahedral electronic geometry
Square pyramidal molecular geometry
polar



Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2
Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2

octahedral electronic geometry
square planar molecular geometry
nonpolar



Octahedral Electronic Geometry:
AB6, AB5U, and AB4U2
 Compounds Containing
Double Bonds



Compounds Containing
Double Bonds
 Compounds Containing
Double Bonds

 Compounds Containing
Double Bonds


H H

C C

H H
Compounds Containing
Double Bonds

↑↓ ↑ ↑ ⇒ ↑↑↑ ↑
 Compounds Containing
Double Bonds

 Compounds Containing
Double Bonds

 Compounds Containing
Double Bonds

 Compounds Containing
Double Bonds
 σ
 Compounds Containing
Double Bonds
 π
 Compounds Containing
Double Bonds
 σπ
 Compounds Containing
Triple Bonds



Compounds Containing
Triple Bonds
Compounds Containing
Triple Bonds

↑↓ ↑ ↑ ⇒ ↑ ↑ ↑↑
 Compounds Containing
Triple Bonds
σ
 Compounds Containing
Triple Bonds
 π
σπ
 Compounds Containing
Triple Bonds

Summary of Electronic &
Molecular Geometries
 Synthesis Question

Synthesis Question
 Group Question

 End of Chapter 8

