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

• Two key concepts are:

− Electrons repel each other
− Electron groups assume orientations to minimize
repulsion

• Electron groups can be chemical bonds or lone pairs

• This is the Valence Shell Electron Pair Repulsion Theory (VSEPR)
• Usually we find geometry around the central atom
2
Two Electron Groups: Linear Geometry
• Two electron groups achieve maximum separation by assuming a
180° bond angle (linear geometry)
Example: BeCl2

Example: CO2

Example: acetylene (C2H2)

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

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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

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Six Electron Groups: Octahedral Geometry
• Six electron groups achieve maximum separation by assuming
the shape of an octahedron

Example: SF6

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Let’s work a problem
Determine the geometry of the NO3- anion.

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Effect of Lone Pairs on Geometry
• Lone pairs of electrons on central atoms count as electron groups

• Electron geometry = geometric arrangement of the electron

groups (the five examples given earlier)

• Molecular geometry = geometric arrangement of the atoms only,

may be different from electron geometry

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Four Electron Groups, One Lone Pair
• Consider ammonia (NH3)

• Electron geometry is tetrahedral

• Molecular geometry is trigonal pyramidal

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Four Electron Groups, Two Lone Pairs
• Consider water (H2O)

• Electron geometry is tetrahedral

• Molecular geometry is bent (or angular)

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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

Electron group repulsions:

lone pair/lone pair > lone pair/bonded pair > bonded pair/bonded pair

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Effects of Lone Pairs on Bond Angles
• Exact bond angles in NH3 and H2O not critical but understand the
trends that are being shown:

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Five Electron Groups, One Lone Pair
• Consider SF4

• Electron geometry is trigonal

bipyramidal, lone pair occupies
one of the five positions

• Does the lone pair occupy an

axial or equatorial position?

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Five Electron Groups, One Lone Pair
• Lone pair occupies the equatorial position to minimize repulsive effects with
the other groups

• Molecular geometry is “seesaw”

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Five Electron Groups, Two Lone Pairs
• Consider BrF3

• Lone pairs both occupy equatorial positions to minimize repulsions

• Molecular geometry is “T-shaped”

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Five Electron Groups, Three Lone Pairs
• Consider XeF2

• Lone pairs occupy all equatorial positions to minimize repulsions

• Molecular geometry is linear

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Six Electron Groups, One Lone Pairs
• Consider BrF5

• Lone pair occupies any one of the positions

• Molecular geometry is square pyramidal

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Six Electron Groups, Two Lone Pairs
• Consider XeF4

• Lone pairs occupy positions 180°apart to minimize repulsions

• Molecular geometry is square planar

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Summarizing VSEPR
• Table 10.1 summarizes all the geometries covered along with
ideal bond angles

• Don’t memorize – understand!

• Best way to study: practice, practice, practice

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Predicting Shapes of Larger Molecules
• Larger molecules (typically organic) contain multiple interior atoms
instead of one central atom

Lewis structure of glycine:

• VSEPR can be used to determine

molecular geometries around each interior
atom

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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
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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

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Molecular Shape and Polarity
• Understanding molecular geometries is important in determining
molecular polarities

Ex: H2O

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Polling Question
Is CCl4 a polar or non-polar molecule?

A) Polar molecule
B) Non-polar molecule

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Molecular Shape and Polarity
• Molecular polarity important for determining its physical properties
(melting point, boiling point, water solubility, etc.)

• Molecular polarities give rise to intermolecular forces between

molecules, explored in chapter 11

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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

• CH4 known to be tetrahedral, 109.5°bond angles

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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)

• Hybridization: a mathematical combination of a certain number of

atomic orbitals to form new hybrid orbitals that are used for bonding

• Different mathematical combinations are possible to explain different

molecular geometries and bonding patterns

• # of atomic orbitals mathematically combined = # of hybrid orbitals

generated
28
sp3 Hybridization
• Mathematically combining 2s and all three 2p orbitals generates four
sp3 orbitals that are all the same energy

• Each orbital (for carbon) is occupied by 1 electron, hence four bonds

are possible (great so far for explaining CH4)

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Polling Question
If an O atom was sp3 hybridized, what would its orbital diagram be?

A) D)

B)

C)
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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)

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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

• When sketching the sp3 orbitals together, we ignore

the lobes

• In carbon, each sp3 orbital is occupied with 1

electron

• Used to explain the four covalent bonds carbon

usually forms in compounds

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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

33
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

• The C-C bond in ethane is capable of

rotating freely since σ bonds aren’t affected
by rotation about their axis

• In general, any covalent bond to a hybrid

orbital will be σ

• In general, all single bonds are σ bonds

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sp2 Hybridization
• Many compounds contain trigonal planar electron geometries

• Example: formaldehyde

• The unhybridized orbital diagrams are:

• Once again, carbon needs to be hybridized to

explain the bonding scheme
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sp2 Hybridization
• Mathematically combining 2s and two 2p orbitals generates three sp2 orbitals
that are both the same energy
• One of the 2p orbitals is “left over” , or “unhybridized”

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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)

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sp2 Hybridization
• The three hybrid orbitals are all in the same plane, and all are oriented
perpendicular to the unhybridized 2p orbital

• The sp2 hybrid orbitals will form σ bonds

(1 each) with three adjacent atoms

• The unhybridized p orbital is used to

explain the double bond in formaldehyde

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sp2 Hybridization
• Valence bond model (bonding scheme) of formaldehyde

• One C-O bond is a σ bond from sp2 orbital on C with p orbital on O

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Terminal Atoms
• Tro textbook does not hybridize non-H terminal atoms since it’s not needed to
explain the geometry of the molecule

• Terminal N, O and halogens use their atomic p orbitals to form σ bonds to the
central hybridized atoms as shown earlier

• Example: NF3

• Other sources do hybridize non-H terminal atoms so be mindful

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π Bonds
• Two unhybridized p orbitals can form π bonds caused by “side-to-side”
overlap
• The two mathematical phases of the orbital must overlap with the same sign
• Half the bond above the atoms, half the bond below

• 41 Don’t worry about whether the p orbital is px, py or pz

π Bonds
• p orbitals can also form σ bonds with hybrid orbitals (sp3, sp2, etc.)
• Hence, the C=O double bond is actually one σ bond: C(sp2) – O(p) and
one π bond: C(p) – O(p)
• Double bonds always consist of 1 σ bond and 1 π bond

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π Bonds
• π bonds are weaker than corresponding σ bonds due to less efficient orbital
overlap, increases chemical reactivity

• π bonds do not rotate freely as rotation would break the bond

43
sp2 Hybridization: Structure of C2H2Cl2
• Dichloroethylene (C2H2Cl2) has
a C=C double bond consisting
of 1 σ and 1 π bond

• Since π bonds don’t rotate,

the molecule is flat and rigid

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sp2 Hybridization
In summary….
• If a molecule is predicted to
have trigonal planar electron
geometry by VSEPR…

• …Its bonding can be explained

by sp2 hybridization

• Not all sp2 hybridized atoms

have double bonds

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sp Hybridization
• Some compounds contain linear electron geometries

• Example: acetylene (C2H2)

• The unhybridized orbital diagrams are:

• Once again, carbon needs to be hybridized to

explain the bonding scheme
46
sp Hybridization
• Mathematically combining 2s and one 2p orbital generates two sp orbitals
that are the same energy
• Two of the 2p orbitals are “left over” , or “unhybridized”

47
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)

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sp Hybridization
• The two hybrid orbitals are all in the same plane, and both are oriented
perpendicular to both unhybridized 2p orbitals

• The unhybridized 2p orbitals are perpendicular

to each other

• The sp hybrid orbitals will form σ bonds

(1 each) with two adjacent atoms

• The unhybridized p orbitals can form

two π bonds

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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

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Overall Summary

51 * Some 4 electron group atoms have sp2 hybridization: CHEM 2020!

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.

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