University Chemistry

Chapter 4: Molecular Structure

and Interaction

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 Valence Shell Electron Pair Repulsion Model
(VSEPR)
Molecular geometry is the three-dimensional arrangement of
atoms in a molecule

Valence shell
outermost electron-occupied shell of an atom
holds the electrons that are usually involved in chemical
bonding

VSEPR Model
accounts for the geometric arrangement of electron
pairs around the central atom

in terms of electrostatic repulsion between electron

pairs 2
Molecular geometry is uniquely determined from two numbers:

1. Steric Number (Ns): total number of electron pairs

around the central atom.

2. Number of lone pairs (nonbonding valence

electrons pairs) on the central atom

3
Valence shell electron pair repulsion (VSEPR) model:
# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry

AB2 2 0 linear linear

B B

4
Linear

0 lone pairs on central atom

Cl Be Cl

5
2 atoms bonded to central atom
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry
AB2 2 0 linear linear
trigonal trigonal
AB3 3 0
planar planar

6
3 atoms bonded to 0 lone pairs on central atom
central atom
7
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry
AB2 2 0 linear linear
trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral

8
4 atoms bonded to 0 lone pairs on central
central atom atom 9
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn 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
4 atoms bonded to 0 lone pairs on central
central atom atom
11
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn 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

12
6 atoms bonded to 0 lone pairs on central
central atom atom
13
14
 VSEPR – Effect of lone pairs

# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry
trigonal trigonal
AB3 3 0
planar planar
trigonal
AB2E 2 1 bent
planar

15
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

16
lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding
repulsion
> pair repulsion
> pair repulsion17
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent

O
H H

18
 VSEPR

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

19
10.1
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn 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
F

F Cl

F
20
10.1
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn 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
I

I
21
I
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

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

22
 VSEPR

# lone
pairs on Arrangement of Molecular
Class Sn central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

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

23
24
Guidelines for Applying the VSEPR Model
1. Draw Lewis structure for molecule.
2. Determine the steric number. Electrons in double
and triple bonds are treated as single bonding pair.
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
25
 4. When predicting bond angles, remember
lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding
repulsion
> pair repulsion
> pair repulsion

5. If a molecule has two or more resonance structures,

apply the VSEPR model to any one of them.

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28
29
30
31
Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

 

=qxr
q is the charge
r is the distance between charges
1 D = 3.336 x 10-30 C m 32
33
34
35
36
37
38
39
Infrared Spectroscopy, the study of the infrared
frequencies that are absorbed by a particular material.

It provides information about molecular structure and

identity.

40
41
 CO2

IR inactive – no change in dipole 42

fingerprinting – definitive method of identification

CH2 CHC N

43
 Valence Bond Theory and Hybridization
Application of VB theory to polyatomic molecules must account
for molecular geometry. Be – 1s22s2
BeCl2 Cl – 1s22s22p33s23p5

Be – to form 2 bonds, need 2 unpaired electrons

Cl – could overlap 3s or 3p orbitals to form the bonds

to form 2 equivalent bonds requires 2 equivalent orbitals
44
Hybridization: the mixing of nonequivalent atomic orbitals in
an atom (usually a central atom) to generate a set of
hypothetical equivalent bonding orbitals, called hybrid
orbitals,
+
-

45
 Cl Be Cl

promotion energy < energy released during bond formation

46
 sp2 Hybridization

BF3 B – 1s22s22p1

47
48
F F
B
F 49
 sp3 Hybridization

CH4 C – 1s22s22p2

50
51
 H

C
H H
H 52
 Hybridization – theoretical model to explain
bonding in polyatomic molecules
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 53
 Procedure for Hybridizing Atomic Orbitals

1. Draw the Lewis structure for the molecule.

2. Predict the overall arrangement of the electron
pairs (both bonding pairs and lone pairs) using the
VSEPR model (see Tables 4.1 and 4.2).

3. Predict the overall arrangement of the electron

pairs (both bonding pairs and lone pairs) using the
VSEPR model (see Tables 4.1 and 4.2).

54
55
56
57
58
Hybridization Using d Atomic Orbitals
SF6 S – [Ne]3s23p4

59
60
61
Hybridization in Double and Triple Bonds
Double Bonds: C2H4
H H
C C
H H

unhybridized

hybridzied

62
63
Another View:

64
Triple Bonds: H C C H C2H2

65
Another View:

66
67
68
 Isomers
Structural Isomers: Same molecular formula but
different bond connectivity

C4H10

69
70
Stersoisomers: Same molecular formula, identical
bond connectivity but different three-dimensional
structures
Geometric isomers: stereisomers that differ in the
spatial arrangement of the atoms relative to one
another

71
Optical isomers or enantiomers: nonsuperimposable
mirror images

CHFBr chiral molecule

chiral center

72
achiral chiral
73
24.2
Cis-Trans Isomerization in the Vision Process

74
24.2
Operation of a Polarimeter

75
Molecular Orbital Theory and Polyatomic Molecules
O3

LCAO

76
77
 Delocalized Molecular Orbitals
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.

lowest unoccupied molecular orbital - LUMO

highest occupied molecular orbital - HOMO 78

79
80
81
82
C6H6 - Benzene

83
84
 Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)

“Measure” of intermolecular force

boiling point
Generally, intermolecular
forces are much weaker melting point
than intramolecular forces. Hvap
Hfus
85
Hsub
 Types of Intermolecular Forces
Ion-ion interactions – between ions

Ion-dipole interactions – between ions and polar

molecules

For a positive ion

86
Attractive forces between an ion and a polar molecule

Ion-Dipole Interaction

87
88
89
Dipole - Dipole interactions – between polar molecules

90
91
Using statistical mechanics

kB is Boltzmann’s constant T is the absolute temperature (in Kelvin)

van der Waals interaction

92
Induced dipole – induced dipole interactions-

Attractive forces that arise as a result of temporary dipoles

induced in atoms or molecules
magnitude of the induced dipole moment, mind

the proportionality constant, , is called the polarizability

ion-induced dipole interaction

dipole-induced dipole interaction

93
94
Dispersion (or London) interactions

two identical atoms or nonpolar molecules

two nonidentical atoms or nonpolar molecules, A and B

instantaneous dipole moment.

95
Induced Dipoles Interacting With Each Other

96
Dispersion forces increase with:
• greater number of electrons
• more diffuse electron cloud
• molar mass

97
98
Decreasing molar mass
Decreasing boiling point

99
11.2
Hydrogen Bond

The hydrogen bond is a special dipole-dipole interaction

between the hydrogen atom in a polar N-H, O-H, or F-H bond
and an electronegative O, N, or F atom.
A H…B or A H…A
A & B are N, O, or F

100
 hydrogen bonds. covalent bonds.

HF(l)

101
102
Effect of Repulsive Forces

Leonard-Jones potential – model both attractive and repulsive

forces in nonionic systems

very short ranged, repulsion attraction between

between the particles. particles

103
104
Chemistry In Action

105