Chapter 10 Notes

CHEM 1411 General Chemistry Chemistry: A Molecular Approach by Nivaldo J. Tro

Chemical Bonding II:

10 Molecular Shapes,
VB and MO Theory
Chapter Objectives:
• Learn how to use VSEPR Theory to predict
the shapes of molecules.
• Learn the basics of Valence Bond Theory and
Molecular Orbital Theory and how they are
used to model covalent bonding.

Mr. Kevin A. Boudreaux

Angelo State University 1
www.angelo.edu/faculty/kboudrea

VSEPR Theory
Getting in Shape

2
Chapter 10 Notes

Molecular Shapes
• The approximate shape of a molecule can be
predicted from the Lewis dot structure using the
Valence-Shell Electron-Pair Repulsion (VSEPR)
model, which depicts electrons in bonds and lone
pairs as “electron groups” or “charge clouds” that
repel one another and stay as far apart as possible.
– Every group of electrons, whether in a bond or a
lone pair, counts as a charge cloud. (Multiple
bonds count as one charge cloud.
– There are five basic shapes in the VSEPR model,
with some variations depending on how many
charge clouds are in lone pairs vs. covalent bonds.
• The three-dimensional shape of a molecule is often
important in determining its chemical behavior,
particular for biologically important molecules. 3

The Basic VSEPR Shapes

A Balloon Analogy for VSEPR Theory

4
MOV: VSEPRmovie
Chapter 10 Notes

Shapes: Two Charge Clouds

• 2 bonds, 0 lone pairs (LP): linear, 180°
Cl Be Cl

O C O

Shapes: Three Charge Clouds

• 3 bonds, 0 LP: trigonal planar, 120°
• 2 bonds, 1 LP: bent, < 120°
(Electron clouds in lone pairs take up more room than those in covalent
bonds; this causes the other atoms to be more squashed together.)

H C H

F
O S O
F B F
6
Chapter 10 Notes

Shapes: Four Charge Clouds

• 4 bonds, 0 LP: tetrahedral, 109.5°
• 3 bonds, 1 LP: trigonal pyramidal, <109.5°
• 2 bonds, 2 LP: bent, <109.5°

H C H

Shapes: Four Charge Clouds

H N H

H O H

8
Chapter 10 Notes

Shapes: Five Charge Clouds

• 5 bonds, 0 LP: trigonal bipyramidal,
120° (equatorial), 90° (axial)
• 4 bonds, 1 LP: seesaw (unsymmetrical tetrahedron),
<120° (equatorial), <90° (axial)
• 3 bonds, 2 LP: T-shaped, <90°
• 2 bonds, 3 LP: linear, 180°

Shapes: Five Charge Clouds

Cl

Cl P Cl

Cl Cl

10
Chapter 10 Notes

Shapes: Five Charge Clouds

F

F S F

11

Shapes: Five Charge Clouds

F Br F

F Xe F

12
Chapter 10 Notes

Shapes: Six Charge Clouds

• 6 bonds, 0 LP: octahedral, 90°
• 5 bonds, 1 LP: square pyramidal, <90°
• 4 bonds, 2 LP: square planar, 90°
F
F F
S
F F
F

13

Shapes: Six Charge Clouds

F

F Br F

F F

F Xe F

F
14
Chapter 10 Notes

Shapes of Larger Molecules

• The shapes of larger molecules are a composite of
the shapes of the atoms within the molecule, each of
which can be predicted using VSEPR theory.

15

Summary of VSEPR Shapes

16
Chapter 10 Notes

Summary of VSEPR Shapes

17

Summary of VSEPR Shapes

18
Chapter 10 Notes

Molecular Shape and Polarity

• For diatomic molecule, the polarity of the molecule
depends on the polarity of the only covalent bond: if
the bond is polar the molecule must be polar.

19

Molecular Shape and Polarity

• In molecules with more than one bond, the shape
and the polarity of the bonds determine whether the
molecule is polar.

20
Chapter 10 Notes

Determining Molecular Polarity

• To determine whether a molecule is polar:
– Draw a Lewis structure for the molecule and
predict its shape using VSEPR theory.
– Determine whether the molecule contains polar
bonds. If the molecule contains polar bonds,
superimpose a vector ( ), pointing towards
the more electronegative atom of each bond.
– Determine whether the polar bonds add together
to form a net dipole moment by adding the
vectors corresponding to the polar bonds together.
If the vectors sum to zero, the molecule is
nonpolar, but if there is a net vector, the molecule
is polar.

21

Determining Molecular Polarity

22
Chapter 10 Notes

Determining Molecular Polarity

23

Physical Properties of Polar Molecules

• The polarity of molecules has a large effect on their
chemical and physical properties:
– Polar molecules attract one another more strongly
than nonpolar molecules do, and generally have
higher boiling points.
– Polar molecules interact with each other more
than they interact with nonpolar molecules, which
is why a mixture of oil (nonpolar) and water
(polar) separates into two layers.

24
Chapter 10 Notes

25

26
Chapter 10 Notes

Examples: Shape and Polarity

1. Write Lewis structures for the following molecules
and determine their shape. State whether or not the
molecules will be polar. (sim. to Ex. 10.1-10.5)
a. BF3

b. NH3

c. SF2

d. CF4

e. NO3-
27

Examples: Shape and Polarity

1. Write Lewis structures for the following molecules
and determine their shape. State whether or not the
molecules will be polar. (sim. to Ex. 10.1-10.5)
f. PF3

g. HCN

h. SbF5

i. XeF2

j. XeF4
28
Chapter 10 Notes

Valence Bond
Theory

29

Models of Bonding
• VSEPR theory accounts for the shapes of molecules,
but does not tell us how those shapes come about.
• More advanced models of chemical bonding extend
the concepts of quantum mechanics and wave
functions/orbitals to describe molecules, and allow
very precise calculations to be made about the
properties of molecules.
– Valence Bond (VB) theory is a relatively simple
model which pictures covalent bonds as arising
from the overlap of orbitals on adjacent atoms.
– Molecular Orbital (MO) theory is a more
sophisticated model which pictures covalent
bonds forming from molecular orbitals
delocalized over the entire molecule.
30
Chapter 10 Notes

Valence Bond Theory

• In valence bond theory, the orbitals which overlap
on adjacent atoms are either the standard atomic
orbitals (s, p, d, f), or hybridized atomic orbitals
made by combining individual atomic orbitals.
– The interaction energy of a pair of atoms is a function of
the distance between them. If the energy of the system is
lowered as a result of the interaction, a bond forms,
otherwise, it is not.
– As two H atoms approach each other (Figure 10.6), the
interaction energy lowers as more of the 1s orbitals
overlap each other, until a minimum energy is reached
when the atoms are 74 pm apart.
– If the atoms are pushed any closer together, the repulsions
between their nuclei begin to become more important, and
the interaction energy rises.

31

Interaction Energy Diagram for H2

32
Figure 10.6
Chapter 10 Notes

Valence Bond Theory

• Covalent bonds result from the overlap of two half-
filled orbitals in which the spins of the electrons are
paired
• Each of the bonded atoms maintains its own atomic
orbitals, but the electron pair in the overlapping
orbitals is shared by both atoms.
• The shape of the molecule is determined by the
geometry of the overlapping orbitals.
• The greater the amount of orbital overlap, the
stronger the bond. This leads to a directional
character to the bond when orbitals other than s
orbitals are involved.

33

Valence Bond Theory; σ Bonds

• Bonds resulting from end-to-end overlap of orbitals

are called sigma (σ) bonds.

34
Chapter 10 Notes

Hybrid Orbitals
• The shapes of s, p, and d orbitals do not account for
the shapes of molecules, so we must use different
orbitals in a molecule from those in isolated atoms.
– [For instance, carbon’s electron configuration has
2 half-filled p orbitals 90° from each other, yet
carbon forms four bonds to hydrogen atoms to
form CH4, with bond angles of 109.5 °.]
• The wave functions for the atomic orbitals derived
from the Schrödinger equation are mathematically
combined to form new wave functions called hybrid
atomic orbitals.
• The number of hybrid orbitals equals the number of
atomic orbitals which combine; we need one hybrid
orbital for each electron pair (bond or lone pair).
35

Hybrid Orbitals
2 charge → 2 sp orbitals → linear (180°)
clouds
3 charge → trigonal planar
clouds 3 sp2 orbitals → (120°)
4 charge → 4 sp3 orbitals → tetrahedral (109.5°)
clouds
5 charge → 5 sp3d orbitals → trigonal bipyramidal
clouds (90°, 120°)
6 charge → 6 sp3d2 orbitals → octahedral (90°)
clouds

• Multiple bonds once again count as one entity when

deciding which hybridization to use.
36
Chapter 10 Notes

sp3 Hybridization
• When the s and all three p orbitals combine, the
resulting hybrid orbitals are sp3 hybrid orbitals.

• These 4 orbitals point to the corners of a tetrahedron

(109.5°).
• sp3 orbitals are used to describe the C atoms in CH4
and C2H6, the N in NH3, and the O in H2O. 37

sp3 Hybridization

38
Figure 10.7 MOV: Hybridization
Chapter 10 Notes

sp3 Orbitals in Methane

39

sp3 Orbitals in Ammonia

40
Chapter 10 Notes

sp3 Orbitals in Ethane, C2H6

H H H

C C
H
H H

41

sp2 Hybridization
• When the s and two of the three p orbitals combine,
the resulting hybrid orbitals are sp2 hybrid orbitals.

• These 3 orbitals point to the corners of an equilateral

triangle (120°), with the unhybridized p orbital 90°
from this plane.
• sp2 orbitals are used to describe the B atom in BF3,
and the C atoms in ethylene, C2H4.
42
Chapter 10 Notes

sp2 Hybridization

43
Figure 10.8

sp2 Orbitals in BF3

44
Chapter 10 Notes

sp2 Hybridization and π Bonds

• When two sp2-hybridized atoms are joined, a double
bond is form from two types of overlap:
– a sigma (σ) bond resulting from end-on-end
overlap of the sp2 orbitals.
– a pi (π) bond resulting from the side-to-side
overlap of the p orbitals.

45
Figure 10.9

Single Bonds and Double Bonds in VB Theory

• A sigma (σ) bond results from the end-to-end
overlap of cylindrical (p, sp, sp2, sp3, etc.) or
spherical (s) orbitals.
– σ-bonds are cylindrically symmetrical, and there
is free rotation around them.
– All single bonds are σ-bonds.
• A pi (π) bond results from the side-to-side overlap
of p orbitals on sp2- or sp- hybridized atoms.
– π-bonds have regions of electron density above
and below the σ-bond axis; free rotation is not
allowed around a π-bond.
– A double bond is a σ-bond + a π-bond.
– A triple bond is a σ-bond + 2 π-bonds. 46
Chapter 10 Notes

sp2 Orbitals in Formaldehyde, CH2O

47

sp2 Orbitals in Ethylene, C2H4

π-bond

p p
σ-bond
sp2 sp2
sp2 sp2
sp2 sp2

48
Chapter 10 Notes

Cis and Trans Isomers in sp2-Hybridization

49

sp Hybridization
• When the s and one of the three p orbitals combine,
the resulting hybrid orbitals are sp hybrid orbitals.

• These 2 orbitals point 180° from each other, with the

unhybridized p orbitals at 90° angles from this line.
• sp orbitals are used to describe the Be atom in
BeCl2, and the C atoms in acetylene, C2H2.
50
Chapter 10 Notes

sp Hybridization

51
Figure 10.10

sp Orbitals in BeCl2

sp Orbitals in Acetylene, C2H2

52
Chapter 10 Notes

sp3d and sp3d2 Hybridization

• The s and the three p orbitals can also combine with
d orbitals in molecules with expanded octets:
– s + p + p + p + d = sp3d hybrid orbitals
– s + p + p + p + d + d = sp3d2 hybrid orbitals

53

sp3d Orbitals in AsF5; sp3d2 Orbitals in SF6

sp3d hybrid orbitals in AsF5 sp3d2 hybrid orbitals in SF6

54
Chapter 10 Notes

Charge Clouds and Hybrid Orbitals

55

Molecular Orbital
Theory

56
Chapter 10 Notes

Molecular Orbital Theory

• The valence bond model is easy to visualize, and
works well for most molecules, but it does not
describe magnetic and spectral properties well.
Another model is used to explain these phenomena.
• In Molecular Orbital (MO) theory, electrons
occupy molecular orbitals that belong to the entire
molecule rather than to an individual atom.
• Atomic or hybrid orbitals overlap with each other to
form molecular orbitals. This overlap results in both
constructive and destructive interference between
the orbitals.
• The number of molecular orbitals formed is the
same as the number of atomic orbitals which are
combined.
57

Constructive and Destructive Interference

• Additive combinations (resulting from constructive
interference between atomic orbitals) form bonding
molecular orbitals (σ, π).
– These are lower in energy than the atomic orbitals.
– The electrons in these orbitals spend most of their
time in the region in between the nuclei, helping to
bond the atoms together.
• Subtractive combinations (resulting from destructive
interference between atomic orbitals) form
antibonding molecular orbitals (σ*, π*).
– These are higher in energy than the atomic orbitals.
– The electrons in these orbitals can’t occupy the
node in the central region and don’t contribute to
bonding.
58
Chapter 10 Notes

Molecular Orbitals in the H2 Molecule

• When two isolated H atoms interact with each other,
their 1s orbitals blend together, and the electrons
spread out over both atoms, in both additive and
subtractive combinations:

59

Molecular Orbitals in the H2 Molecule

• The two electrons which used to be in the separate
1s orbitals now reside in the σ bonding molecular
orbital, resulting in a molecule which is lower in
energy than the separate H atoms:

60
Chapter 10 Notes

Why Doesn’t He2 Form?

(bonding e - ' s) - (antibonding e - ' s)

Bond order =
2 61

MO Theory and Other Diatomic Molecules

• We will only look at homonuclear diatomic
molecules, which are composed of two identical
atoms (e.g., H2, N2, O2, F2).
• In the simple VB model, the electrons in the O2
molecule are all paired; experimentally, however, O2
is found to be paramagnetic.
• The more mathematically sophisticated MO model
predicts the correct electronic properties for O2.
• In the following slides, the σ2s and σ2s* orbitals are
produced from overlapping 2s orbitals; the σ2p and
σ2p* orbitals are produced from end-to-end overlap
of 2p orbitals; the π2p and π2p* orbitals are produced
from side-to-side overlap of 2p orbitals.

62
Chapter 10 Notes

σ, σ*, π, and π* MO’s from p Atomic Orbitals

63

MO Energy Diagrams for B2 through Ne2

64
Chapter 10 Notes

Combining VB and MO Theory

• Valence bond theory is conceptually simpler, and
works well for describing σ bonds; but molecular
orbital theory is more accurate, and is better at
describing π bonds. In practice, a combination of
the two theories is often used.

Lowest energy π bonding

molecular orbital:
65

Molecular Orbitals in Benzene

66
Chapter 10 Notes

Interesting Shapes,
Beautiful Molecules,
Odor, and Handedness

67

Interesting Molecules
O CH3 O
CH3 N
N
O O
OH
O N N
O
CH3
HN O
Caffeine O
OH H
O HO O
O O O
Taxol
O

H3C
CH3
H
CH3

α-Irone
O O
O
O
O
O
O
O O
O
O O
O
O
O
H H O
H O
HO O
O
Cholesterol
Olestra 68
Chapter 10 Notes

Odd Shapes and Beautiful Molecules

69

Shape and Smell

10.A Olfactory Receptors

10.B Shapes of some

olfactory receptor sites

10.C Different Molecules

with the Same Odor
70
Chapter 10 Notes

Shape and Taste

• Sucrose (table sugar) and aspartame (Nutra-Sweet)
are very different molecules, but both have a similar
enough overall shape that they interact with the
same taste receptors on the tongue, and both trigger
the sensation of sweetness.

71

Molecular “Handedness”
• A number of everyday things have a “handedness”
associated with them: hands (duh!), gloves, the
threads on screws or lightbulbs, etc.
– A right hand fits only into a right-handed glove.
– When these objects are reflected in a mirror, the
shape is inverted — i.e., a right-hand glove
reflected in a mirror looks like a left-hand glove.
• Some molecules also have a handedness which
causes them to adopt one of two or more possible
mirror image forms.
• This is most common with atoms of single-bonded,
sp3-hybridized carbon; a tetrahedral carbon with four
different things connected to it can be oriented in
one of two possible ways, and is said to be chiral.
72
Chapter 10 Notes

Left-Handed and Right-Handed Carbons

X X

C W W C
Z Z
Y mirror
Y

W W

X C Y Y C X

Z mirror Z 73

Stereoisomers & Physical/Biological Properties

• An organic molecule which contains a chiral carbon
can exist as one of two different stereoisomers.
– This slight difference can produce different
overall 3-D shapes, causing the two stereoisomers
to have different chemical properties.
– Since many biological systems use molecules
made of chiral carbons (amino acids, proteins,
fats, carbohydrates, nucleic acids, etc.), the two
different stereoisomers may have drastically
different biological properties.

74
Chapter 10 Notes

Dextromethorphan and Levomethorphan

• Dextromethorphan is a common over-the-counter
cough suppressant.
• Its mirror image, levomethorphan, is a narcotic
analgesic similar to morphine in its action.

75

Carvone
• Left-handed carvone is found in mint plants, and has
a characteristic odor or spearmint.
• Right-handed carvone occurs in several herbs, and
has the odor of caraway seeds.

76
Chapter 10 Notes

Thalidomide
• Until 1956, thalidomide was considered to be a very
safe, popular sedative; the largest market was for
pregnant women experiencing morning sickness.
However, it was found to cause massive birth
defects in women who used it in the early states of
pregnancy, and was banned in Europe; it was never
authorized for sale in the U.S. (The thalidomide tragedy was
a major rationale behind the passage of the Drug Amendments Act in
1962, which greatly expanded the amount of preclinical testing that was
required for new drugs.)
O

O
O N O
77
H

Cholesterol
• Cholesterol has 8 chiral carbons, and can exist in a
maximum of 28 = 256 different forms; there is only
one naturally-occurring form of cholesterol.

HO
78