Chapter 9

Chapter 9
Covalent Bonding:
Orbitals
Section 9.1
Hybridization and the Localized Electron Model
EXERCISE!
Draw the Lewis structure for methane, CH4.

 What is the shape of a methane molecule?
tetrahedral
 What are the bond angles?
109.5o H
H C H
H
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Section 9.1
CONCEPT CHECK!
What is the valence electron configuration of a

carbon atom?
s2p2
Why can’t the bonding orbitals for methane be
formed by an overlap of atomic orbitals?

Section 9.1
Bonding in Methane
 Assume that the carbon atom has four equivalent
atomic orbitals, arranged tetrahedrally.

Section 9.1
Hybridization
 Mixing of the native atomic orbitals to form special
orbitals for bonding.

Section 9.1
sp3 Hybridization
 Combination of one s and three p orbitals.
 Whenever a set of equivalent tetrahedral atomic
orbitals is required by an atom, the localized electron
model assumes that the atom adopts a set of sp3
orbitals; the atom becomes sp3 hybridized.
 The four orbitals are identical in shape.

Section 9.1
An Energy-Level Diagram Showing the Formation of
Four sp3 Orbitals

Section 9.1
The Formation of sp3 Hybrid Orbitals

Section 9.1
Tetrahedral Set of Four sp3 Orbitals

Section 9.1
EXERCISE!
Draw the Lewis structure for C2H4 (ethylene)?

 What is the shape of an ethylene molecule?
trigonal planar around each carbon atom
 What are the approximate bond angles around the
carbon atoms?
120o
H H
C C
H H
Section 9.1
CONCEPT CHECK!
Why can’t sp3 hybridization account for the

ethylene molecule?

Section 9.1
sp2 Hybridization
 Combination of one s and two p orbitals.
 Gives a trigonal planar arrangement of atomic
orbitals.
 One p orbital is not used.
 Oriented perpendicular to the plane of the sp2
orbitals.

Section 9.1
Sigma (Σ) Bond

 Electron pair is shared in an area centered on a line
running between the atoms.

Section 9.1
Pi (Π) Bond
 Forms double and triple bonds by sharing electron
pair(s) in the space above and below the σ bond.
 Uses the unhybridized p orbitals.

Section 9.1
An Orbital Energy-Level Diagram for sp2 Hybridization

Section 9.1
The Hybridization of the s, px, and py Atomic Orbitals

Section 9.1
Formation of C=C Double Bond in Ethylene
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Section 9.1
EXERCISE!
Draw the Lewis structure for CO2.

 What is the shape of a carbon dioxide molecule?
linear
180o
O C O

Section 9.1
sp Hybridization
 Combination of one s and one p orbital.
 Gives a linear arrangement of atomic orbitals.
 Two p orbitals are not used.
 Needed to form the π bonds.

Section 9.1
The Orbital Energy-Level Diagram for the Formation of sp

Hybrid Orbitals on Carbon

Section 9.1
When One s Orbital and One p Orbital are Hybridized, a Set of Two sp
Orbitals Oriented at 180 Degrees Results

Section 9.1
The Orbitals for CO2

Section 9.1
EXERCISE!
Draw the Lewis structure for PCl5.

 What is the shape of a phosphorus pentachloride
molecule?
trigonal bipyramidal
90 and 120
o o
Cl Cl
Cl P Cl
Cl
Section 9.1
dsp3 Hybridization
 Combination of one d, one s, and three p orbitals.
 Gives a trigonal bipyramidal arrangement of five
equivalent hybrid orbitals.

Section 9.1
The Orbitals Used to Form the Bonds in PCl5

Section 9.1
EXERCISE!
Draw the Lewis structure for XeF4.

 What is the shape of a xenon tetrafluoride
molecule?
octahedral
F
90o and 180o
F Xe F
F
Section 9.1
d2sp3 Hybridization
 Combination of two d, one s, and three p orbitals.
 Gives an octahedral arrangement of six equivalent
hybrid orbitals.

Section 9.1
How is the Xenon Atom in XeF4 Hybridized?

Section 9.1
CONCEPT CHECK!
Draw the Lewis structure for HCN.

Which hybrid orbitals are used?
Draw HCN:
 Showing all bonds between atoms.
 Labeling each bond as σ or π.

Section 9.1
CONCEPT CHECK!
Determine the bond angle and expected

hybridization of the central atom for each of the
following molecules:
NH3 SO2 KrF2
CO2 ICl5
NH3 – 109.5o, sp3
SO2 – 120o, sp2
KrF2 – 90o, 120o, dsp3
CO2 – 180o, sp
ICl5 – 90o, 180o, d2sp3
Section 9.1
Using the Localized Electron Model

 Draw the Lewis structure(s).
 Determine the arrangement of electron pairs using
the VSEPR model.
 Specify the hybrid orbitals needed to accommodate
the electron pairs.

Section 9.2
The Molecular Orbital Model
 Regards a molecule as a collection of nuclei and

electrons, where the electrons are assumed to occupy
orbitals much as they do in atoms, but having the orbitals
extend over the entire molecule.
 The electrons are assumed to be delocalized rather than
always located between a given pair of atoms.

Section 9.2
 The electron probability of both molecular orbitals is

centered along the line passing through the two nuclei.
 Sigma (σ) molecular orbitals (MOs)
 In the molecule only the molecular orbitals are available
for occupation by electrons.

Section 9.2
Combination of Hydrogen 1s Atomic Orbitals to form MOs

Section 9.2
 MO1 is lower in energy than the s orbitals of free atoms,

while MO2 is higher in energy than the s orbitals.
 Bonding molecular orbital – lower in energy
 Antibonding molecular orbital – higher in energy

Section 9.2
MO Energy-Level Diagram for the H2 Molecule

Section 9.2
 The molecular orbital model produces electron

distributions and energies that agree with our basic ideas
of bonding.
 The labels on molecular orbitals indicate their symmetry
(shape), the parent atomic orbitals, and whether they are
bonding or antibonding.

Section 9.2
 Molecular electron configurations can be written in much

the same way as atomic electron configurations.
 Each molecular orbital can hold 2 electrons with opposite
spins.
 The number of orbitals are conserved.

Section 9.2
Sigma Bonding and Antibonding Orbitals

Section 9.2
Bond Order
 Larger bond order means greater bond strength.
# of bonding e   # of antibonding e 
Bond order =
2

Section 9.2
Example: H2
2  0
Bond order = =1
2
Section 9.2
Example: H2–
2  1 1
Bond order = =
2 2

Section 9.3
Bonding in Homonuclear Diatomic Molecules
Homonuclear Diatomic Molecules

 Composed of 2 identical atoms.
 Only the valence orbitals of the atoms contribute
significantly to the molecular orbitals of a particular
molecule.

Section 9.3
Pi Bonding and Antibonding Orbitals

Section 9.3
Paramagnetism
 Paramagnetism – substance is attracted into the inducing
magnetic field.
 Unpaired electrons (O2)
 Diamagnetism – substance is repelled from the inducing
magnetic field.
 Paired electrons (N2)

Section 9.3
Apparatus Used to
Measure the
Paramagnetism of
a Sample

Section 9.3
Molecular Orbital Summary of Second Row Diatomic Molecules

Section 9.4
Bonding in Heteronuclear Diatomic Molecules
Heteronuclear Diatomic Molecules

 Composed of 2 different atoms.

Section 9.4
Heteronuclear Diatomic Molecule: HF

 The 2p orbital of fluorine is at a lower energy than the 1s
orbital of hydrogen because fluorine binds its valence
electrons more tightly.
 Electrons prefer to be closer to the fluorine atom.
 Thus the 2p electron on a free fluorine atom is at a lower
energy than the 1s electron on a free hydrogen atom.

Section 9.4
Orbital Energy-Level Diagram for the HF Molecule

Section 9.4

 The diagram predicts that the HF molecule should be
stable because both electrons are lowered in energy
relative to their energy in the free hydrogen and fluorine
atoms, which is the driving force for bond formation.

Section 9.4
The Electron Probability Distribution in the Bonding Molecular Orbital
of the HF Molecule

Section 9.4

 The σ molecular orbital containing the bonding electron
pair shows greater electron probability close to the
fluorine.
 The electron pair is not shared equally.
 This causes the fluorine atom to have a slight excess of
negative charge and leaves the hydrogen atom partially
positive.
 This is exactly the bond polarity observed for HF.

Section 9.5
Combining the Localized Electron
and Molecular Orbital Models
Delocalization
 Describes molecules that require resonance.
 In molecules that require resonance, it is the π bonding
that is most clearly delocalized, the σ bonds are localized.
 p orbitals perpendicular to the plane of the molecule are
used to form π molecular orbitals.
 The electrons in the π molecular orbitals are delocalized
above and below the plane of the molecule.

Section 9.5
Resonance in Benzene

Section 9.5
The Sigma System for Benzene

Section 9.5
The Pi System for Benzene

Section 9.5
Pi Bonding in the Nitrate Ion

Section 9.6
Photoelectron Spectroscopy (PES)
 Can be used to determine the relative energies of

electrons in individual atoms and molecules.
 High-energy photons are directed at the sample, and the
kinetic energies of the ejected electrons are measured.

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Draw the Lewis structure for methane, CH4.

What is the valence electron configuration of a

Copyright © Cengage Learning. All rights reserved 3

Copyright © Cengage Learning. All rights reserved 4

Copyright © Cengage Learning. All rights reserved 5

Copyright © Cengage Learning. All rights reserved 6

Copyright © Cengage Learning. All rights reserved 7

The Formation of sp3 Hybrid Orbitals

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Tetrahedral Set of Four sp3 Orbitals

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Draw the Lewis structure for C2H4 (ethylene)?

Why can’t sp3 hybridization account for the

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Sigma (Σ) Bond

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An Orbital Energy-Level Diagram for sp2 Hybridization

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The Hybridization of the s, px, and py Atomic Orbitals

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Formation of C=C Double Bond in Ethylene

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Draw the Lewis structure for CO2.

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The Orbital Energy-Level Diagram for the Formation of sp

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The Orbitals for CO2

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Draw the Lewis structure for PCl5.

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The Orbitals Used to Form the Bonds in PCl5

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Draw the Lewis structure for XeF4.

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How is the Xenon Atom in XeF4 Hybridized?

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Draw the Lewis structure for HCN.

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Determine the bond angle and expected

Using the Localized Electron Model

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 Regards a molecule as a collection of nuclei and

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 The electron probability of both molecular orbitals is

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Combination of Hydrogen 1s Atomic Orbitals to form MOs

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 MO1 is lower in energy than the s orbitals of free atoms,

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MO Energy-Level Diagram for the H2 Molecule

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 The molecular orbital model produces electron

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 Molecular electron configurations can be written in much

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