Bonding MOT
Bonding MOT
Bonding MOT
Chemistry
The Molecular Nature of
Matter and Change
Seventh Edition
11-1 Copyright McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior written consent of McGraw-Hill Education.
Chapter 11
11-2
Theories of Covalent Bonding
11-3
Valence Bond (VB) Theory
11-4
Figure 11.1 Orbital orientation and maximum overlap.
11-5
VB Theory and Orbital Hybridization
11-6
Features of Hybrid Orbitals
11-7
Figure 11.2 Formation and orientation of sp hybrid orbitals
and the bonding in BeCl2.
atomic
orbitals
hybrid
orbitals
One 2s and one 2p atomic orbital mix to form two sp hybrid orbitals.
11-8
Figure 11.2 continued
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11-9
Figure 11.3 The sp2 hybrid orbitals in BF3.
Mixing one s and two p orbitals gives three sp2 hybrid orbitals.
The third 2p orbital remains unhybridized.
11-10
Figure 11.3 continued
11-11
Figure 11.4 The sp3 hybrid orbitals in CH4.
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11-12
Figure 11.5 The sp3 hybrid orbitals in NH3.
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11-13
Figure 11.5 continued The sp3 hybrid orbitals in H2O.
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11-14
Figure 11.6 The sp3d hybrid orbitals in PCl5.
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Figure 11.7 The sp3d2 hybrid orbitals in SF6.
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Table 11.1 Composition and Orientation of Hybrid Orbitals
Trigonal Trigonal
Linear Planar Tetrahedral Bipyramidal Octahedral
Atomic orbitals one s one s one s one s one s
mixed one p two p three p three p three p
one d two d
Hybrid orbitals two sp three sp2 four sp3 five sp3d six sp3d2
formed
Orientation
11-17
Figure 11.8 From molecular formula to hybrid orbitals.
Molecular Step 1
Formula Figure 10.1
Lewis Step 2
structure Figure 10.10
Molecular shape
Step 3
and e- group
arrangement Table 11.1
Hybrid orbitals
11-18
Sample Problem 11.1 Postulating Hybrid Orbitals in a Molecule
PLAN: We use the molecular formula to draw the Lewis structure and
determine the electron-group arrangement around each
central atom. We then postulate the type of hybrid orbitals
required and write a partial orbital diagram.
SOLUTION:
(a) CH3OH
H The electron-group arrangement
is tetrahedral around both the C
C O and the O atoms.
H
H H
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Sample Problem 11.1
C has four half-filled sp3 orbitals.
↑ ↑
↑ ↑ ↑ ↑
2p
sp3
↑↓
isolated C atom hybridized C atom
2s
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Sample Problem 11.1
3d 3d
↑↓ ↑ ↑ ↑ ↑ ↑ ↑ ↑
3p sp3d
↑↓
isolated S atom hybridized S atom
3s
11-21
Limitations of the Hybridization Model
11-22
Types of Covalent Bonds
11-23
Figure 11.9 The bonds in ethane (C2H6).
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11-24
Figure 11.9 continued
11-25
Figure 11.10 The and bonds in ethylene (C2H4).
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unhybridized 2p orbitals
11-26
Figure 11.11 The and bonds in acetylene (C2H2).
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11-27
Figure 11.12 Electron density and bond order in
ethane, ethylene, and acetylene.
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11-28
Sample Problem 11.2 Describing the Types of Bonds in
Molecules
PROBLEM: Describe the types of bonds and orbitals in acetone,
(CH3)2CO.
PLAN: We use the Lewis structures to determine the arrangement of
groups and the shape at each central atom. We postulate the
hybrid orbitals, taking note of the multiple bonds present.
SOLUTION: sp2
sp3 sp2
O sp3
H C
H
C C
H H
H H
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Sample Problem 11.2
The sp3 hybridized C atoms form σ bonds using sp3 hybrid orbitals.
The sp2 hybridized C and O atoms form σ bonds using sp2 hybrid
orbitals, and the bond of the C=O double bond is formed using p
orbitals. Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
11-30
Figure 11.13 Restricted rotation around a bond.
cis-1,2-Dichloroethylene
trans-1,2-Dichloroethylene
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Molecular Orbital (MO) Theory
11-32
Figure 11.14
An analogy between light waves and atomic wave functions.
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Amplitudes of wave
functions added
Amplitudes of
wave functions
subtracted
11-33
Figure 11.15 Contours and energies of H2 bonding and
antibonding MOs.
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11-34
Molecular Orbital Diagrams
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Figure 11.16 MO diagram for H2.
H2 bond order = ½ (2 − 0) = 1
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Electrons in Molecular Orbitals
11-37
Figure 11.17 MO diagram for He2+ and He2.
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(σ1s)2(σ*1s )1 (σ1s)2(σ*1s )2
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Sample Problem 11.3 Predicting Stability of Species Using MO
Diagrams
PROBLEM: Use MO diagrams to find bond orders and predict
whether H2+ and H2− exist. If either exists, write its
electron configuration.
PLAN: Since the 1s AOs form the MOs, the MO diagrams are similar
to the one for H2. We find the number of electrons in each
species and distribute them one at a time to the MOs following
the rules for orbital filling. We calculate the bond order and
predict stability.
SOLUTION:
H2+ has one electron to place in its MOs while H2– has three electrons
to place.
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Sample Problem 11.3
For H2+, the bond order is For H2-, the bond order is
½(1 – 0) = ½; ½(2 – 1) = ½;
so we predict that H2+ exists. so we predict that H2- exists.
*
The configuration is (σ1s) .
1
The configuration is (σ1s) 2
(σ1s )1
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Figure 11.18 Bonding in s-block homonuclear diatomic molecules.
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Li2 Be2
Li2 bond order = 1 Be2 bond order = 0
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Figure 11.19 Shapes and energies of and MOs from
combinations of 2p atomic orbitals.
11-42
Figure 11.20 Relative MO energy levels for Period 2 homonuclear
diatomic molecules.
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MO energy MO energy
levels for O2, levels for B2,
F2, and Ne2 C2 and N2
11-43
Figure 11.21 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
MO occupancy and
molecular properties
for B2 through Ne2.
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Figure 11.22 The paramagnetic properties of O2.
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Sample Problem 11.4 Using MO Theory to Explain Bond Properties
PLAN: The data show that removing an electron from each parent
molecule has opposite effects: N2+ has a weaker longer bond
than N2, but O2+ has a stronger, shorter bond than O2. We
determine the valence electrons in each species, draw the
sequence of MO energy levels (showing orbital mixing in N2
but not in O2), and fill them with electrons. We then calculate
bond orders, which relate directly to bond energy and
inversely to bond length.
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Sample Problem 11.4 SOLUTION: showing MOs only
N2 N2+ O2 O2 +
σ *2p σ *2p
*2p ↑ ↑ *2p ↑
↑↓ σ2p ↑ ↑↓ ↑↓ 2p ↑↓ ↑↓
↑↓ ↑↓ 2p ↑↓ ↑↓ ↑↓ σ2p ↑↓
↑↓ σ *2s ↑↓ ↑↓ σ *2s ↑↓
↑↓ σ2s ↑↓ ↑↓ σ2s ↑↓
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Sample Problem 11.4
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Figure 11.23A The MO diagram for HF.
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Figure 11.23B The MO diagram for NO.
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Figure 11.24 The lowest energy -bonding MOs in benzene
and ozone.
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