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CHAPTER 10
Chemical Bonding II:
Molecular Shapes and
Valence Bond Theory
1
Shapes of Molecules
• Lewis structures of molecules can be used to predict the three-
dimensional structures of molecules
Example: CO2
3
Three Electron Groups: Trigonal Planar Geometry
• Three electron groups achieve maximum separation by assuming
120° bond angles in a single plane (trigonal planar geometry)
Example: BF3
Example: formaldehyde
4
Four Electron Groups: Tetrahedral Geometry
• Four electron groups achieve maximum separation by assuming
109.5° bond angles in 3-D space (tetrahedral geometry)
Example: CH4
5
Five Electron Groups: Trigonal Bipyramidal Geometry
• Five electron groups achieve maximum separation by assuming
the shape of a trigonal bipyramid
• Two axial groups, three equatorial groups
Example: PCl5
6
Six Electron Groups: Octahedral Geometry
• Six electron groups achieve maximum separation by assuming
the shape of an octahedron
Example: SF6
7
Let’s work a problem
Determine the geometry of the NO3- anion.
8
Effect of Lone Pairs on Geometry
• Lone pairs of electrons on central atoms count as electron groups
9
Four Electron Groups, One Lone Pair
• Consider ammonia (NH3)
10
Four Electron Groups, Two Lone Pairs
• Consider water (H2O)
11
Effects of Lone Pairs on Bond Angles
• Bond angles in NH3 and H2O are somewhat distorted from the ideal
tetrahedral angle
• Lone pair electrons more spread out in space than bonded electron pairs,
hence they “compress” bond angles of the atoms in the molecule
12
Effects of Lone Pairs on Bond Angles
• Exact bond angles in NH3 and H2O not critical but understand the
trends that are being shown:
13
Five Electron Groups, One Lone Pair
• Consider SF4
14
Five Electron Groups, One Lone Pair
• Lone pair occupies the equatorial position to minimize repulsive effects with
the other groups
15
Five Electron Groups, Two Lone Pairs
• Consider BrF3
16
Five Electron Groups, Three Lone Pairs
• Consider XeF2
17
Six Electron Groups, One Lone Pairs
• Consider BrF5
18
Six Electron Groups, Two Lone Pairs
• Consider XeF4
19
Summarizing VSEPR
• Table 10.1 summarizes all the geometries covered along with
ideal bond angles
20
Polling Question
What is the molecular geometry of ICl4- ?
A) Tetrahedral
B) Octahedral
C) Square pyramidal
D) Square planar
E) Trigonal pyramidal
21
Predicting Shapes of Larger Molecules
• Larger molecules (typically organic) contain multiple interior atoms
instead of one central atom
22
Polling Question
What are the molecular geometries around the indicated carbon and
nitrogen atoms?
A) C = bent, N = tetrahedral
B) C = trigonal planar, N = trigonal pyramidal
C) C = trigonal planar, N = tetrahedral
D) C = tetrahedral, N = trigonal pyramidal
23
Drawing Tetrahedral Structures
• Tetrahedral geometries arise often in organic molecules (C with
four single bonds)
24
Molecular Shape and Polarity
• Polar covalent bonds within molecules can lead to the entire molecule
being polar if there is a net dipole moment overall
Ex: HCl
• If bond dipoles sum to zero (vector addition), they cancel out giving
zero dipole moment overall (non-polar molecule)
Ex: CO2
25
Molecular Shape and Polarity
• Understanding molecular geometries is important in determining
molecular polarities
Ex: H2O
26
Polling Question
Is CCl4 a polar or non-polar molecule?
A) Polar molecule
B) Non-polar molecule
27
Molecular Shape and Polarity
• Molecular polarity important for determining its physical properties
(melting point, boiling point, water solubility, etc.)
28
Valence Bond Theory
• Lewis bonding model represents electrons as “dot-like” particles
• Valence bond theory: covalent bonds are formed from the overlap
(constructive interference) of atomic orbitals on adjacent atoms, each usually
containing one electron
30
Orbital Overlap in H2S Molecule
• Half-filled orbitals on H and S atoms overlap to form a bonded electron
pair
• Electrons spin-pair in the covalent bonds that are formed
• Experimental bond angles closely match the 90°angle between p
orbitals on S
31
Hybridization: Covalent Bonding in CH4
• Simple atomic orbital overlap approach works for H2S but fails for CH4
• Simple overlap predicts 90°bond angles about carbon, and only two
bonds can form
32
Hybridization: Covalent Bonding in CH4
• Orbital hybridization is used to explain experimental bonding evidence
in CH4 (and many more molecules, but we will limit ourselves to the
second row elements)
34
Polling Question
If an O atom was sp3 hybridized, what would its orbital diagram be?
A) D)
B)
C)
35
sp3 Hybridization
• The sp3 orbitals resemble both the 2s and 2p orbitals in general shape
• The four hybrid orbitals are oriented 109.5°apart (also great for explaining
CH4 geometry)
36
sp3 Hybridization
• The sp3 orbitals have two lobes (like p orbitals) but one is much smaller than
the other and pointing “inwards” and not significant for bonding purposes
37
sp3 Hybridization
• The full bonding picture for CH4 is the following →
• Hybridization is not utilized for H atoms
38
sp3 Hybridization
In summary….
• If a molecule is predicted to
have tetrahedral electron
geometry by VSEPR…
• Remember: hybridization is a
mathematical construct used to
39 explain bonding!
sp3 Hybridization
• Second row atoms (particularly C) form reasonably strong bonds with each
other, allowing large complex molecules to exist (organic chemistry!)
• Consider ethane (C2H6): each carbon atom is tetrahedral and sp3 hybridized
40
σ Bonds
• Every covalent bond in ethane is a σ (sigma)
bond, meaning “end-to-end” or “head-on”
overlap of the orbitals involved in the bonding
• Example: formaldehyde
43
sp2 Hybridization
• The sp2 orbitals resemble the sp3 orbitals in general shape
• The three hybrid orbitals are oriented 120°apart (great for trigonal planar
geometry)
44
sp2 Hybridization
• The three hybrid orbitals are all in the same plane, and all are oriented
perpendicular to the unhybridized 2p orbital
45
sp2 Hybridization
• Valence bond model (bonding scheme) of formaldehyde
• Terminal N, O and halogens use their atomic p orbitals to form σ bonds to the
central hybridized atoms as shown earlier
• Example: NF3
49
π Bonds
• π bonds are weaker than corresponding σ bonds due to less efficient orbital
overlap, increases chemical reactivity
50
sp2 Hybridization: Structure of C2H2Cl2
• Dichloroethylene (C2H2Cl2) has
a C=C double bond consisting
of 1 σ and 1 π bond
51
sp2 Hybridization: Structure of C2H2Cl2
• Since the double bond can’t rotate, there are two structures that can be
drawn that represent entirely different molecules!
53
sp2 Hybridization
In summary….
• If a molecule is predicted to
have trigonal planar electron
geometry by VSEPR…
54
Polling Question
Consider the BH3 trigonal planar molecule. What statement is true
regarding the electron configuration of the B atom itself?
H H
A) D)
B) H
C)
55
sp Hybridization
• Some compounds contain linear electron geometries
58
sp Hybridization
• The sp orbitals are a “50:50” mix of s and p in terms of shape
• The two hybrid orbitals are oriented 180°apart (great for linear geometry)
59
sp Hybridization
• The two hybrid orbitals are all in the same plane, and both are oriented
perpendicular to both unhybridized 2p orbitals
60
sp Hybridization
• The full valence bonding picture in acetylene
• C≡C triple bond is formed from 1 σ bond and 2 π bonds
• The π bonds are oriented 90°apart from each other
61
Polling Question
Are cis/trans isomers possible for molecules containing C≡C?
A) Yes
B) No
62
sp Hybridization
In summary….
• If a molecule is predicted to have linear electron geometry by VSEPR…
63
Polling Question
What is the hybridization of the oxygen atom in H3O+ ?
A) sp
B) sp2
C) sp3
D) It is not hybridized
64
Polling Question
What is the hybridization of the carbon atom in CO2?
A) sp
B) sp2
C) sp3
D) It is not hybridized
65
Overall Summary
67
Let’s work a problem
Draw a figure showing the geometry of the molecule, the hybridization of the
carbon atoms, the valence orbitals of each atom and label each bond as σ or π
using the notation in Tro.
68