Chapter 9: Molecular Geometry

and Bonding Theories

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9.1 Molecular Shapes
Lewis structures show the compositions of molecules
and their bonds, but they do not show the shapes of
the molecules.

The molecular shape of a compound is important

because it determines many of the chemical and
physical properties of the compound.
Bond
bond
length
length
The shapes and sizes are defined
by the bond angles and distances
between the nuclei of the
component atoms.
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 Example: methane, CH4

Lewis dot Actual shape is a

appears tetrahedral.
flat
(all hydrogen atoms are same
distance from each other)
All C-H bonds are the same length.

All H-C-H bond angles are the same.

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Here are some of the shapes we will be discussing:
(get ready to memorize)

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To begin, we start with a single central atom bonded to
two or more atoms of the same type.

These have the general formula ABn where the shape

depends on the value of n.
AB2
For example: CO 2 and SO2

shape: linear bent

bond angle: 180o ≠ 180o 6

 AB3
SO3 NF3 ClF3

trigonal trigonal T-shaped

planar pyramidal
More
All atoms on A (central unusual
same plane atom) lies shape
above B
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The shape of any ABn molecule can usually be
derived from one of these five basic structures:

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 Reference Geometries
(Memorize)

# of Formula Electron Bond example

electron domain angles
domains geometry
1 A1B1 linear 180o HF
2 A1B2 linear 180o CO2
3 A1B3 trigonal planar 120o BF3
4 A1B4 tetrahedral 109.5o CH4
5 A1B5 trigonal 120o, 90o PCl5
bipyramidal
6 A1B6 octahedral 90o SF6

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9.2: VSEPR Model

The VSEPR theory stands for Valence Shell Electron

Pair Repulsion theory.

This theory explains the shape of molecules based on

the idea that electron pairs repel each other so that
the electrons involved in bonds try to get as far
apart as possible.

MIT: detecting explosives

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The VSEPR model is built on the assumption that
molecular geometry is largely determined by the
electron zones (electron domains) around the central
atom of any molecule. The electron’s repulsions
position bonds in such a way that gives us the geometry.

Electron zones repel each other in this order:

lone pair-lone pair > lone pair-shared pair > shared pair-shared pair

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In attempting to minimize electron pair repulsions,
two types of electron sets must be considered:
Electrons in bonding pairs, or nonbonding pairs.
nonbonding or
involved in lone pair
creating a single - pairs of electrons
or multiple that are not
covalent bond involved in a bond,
but are localized to
bonding pairs a single atom

Whether a bonding pair (single or multiple bonds), or

a nonbonding pair, these are all considered electron
domains.
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 #2

Examples: How many electron #3

domains around each of the central
atom(s)?
#1 #4 3

#5

2
5
5
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The best arrangement of a given number of
electron domains is the one that minimizes
the repulsions among them. (Similar to
how balloons tied together will spread
apart)

This is called electron-domain geometry.

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For example: CO2 has two oxygen atoms double
bonded to the central carbon. The two pairs of
electrons involved in the bond all have the same
charge (negative) and so try to move as far apart as
possible, making it a linear molecule. It would be
wrong to draw the bonds closer together.

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Lone pairs have a greater effect on the shape of a
molecule.

Their charge is not diluted between the attraction for

opposite nuclei and so repel bonded pairs to a
greater extent.

The unshared pair of electrons at

the top of the molecule repels
the electrons in the bonds forcing
NH3 them downward into a bent
triatomic shape.
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 4 e-
domains

Lewis electron-domain molecular

structure geometry geometry
tetrahedral trigonal pyramidal

Electron domain geometry shows the space of electrons in

the model, whereas molecular geometry only shows the
arrangement of the atoms in the structure and the bonding
domains.

*The two are the same if there are no lone-pairs in the

structure. 17
To predict the shapes of
molecules or ions:
• draw the Lewis structure and count
the number of electron domains
around the central atom.

• determine the electron domain

geometry by arranging the electrons
around the central atom so that
repulsions between domains are
minimized.

•use arrangement of bonded atoms to

determine molecular geometry
memorize
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 What would be the
shape of SnCl3-?
Valence shell Sn:
5s24d105p2
Valence e-:
Sn + 3 Cl
(4) + 3(7) + 1 = 26 e-

4 electron tetrahedral
domains

1 lone pair trigonal

(3 bonding) pyramidal
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 The effect of Nonbonding Electrons and
Multiple Bonds on bond angles:

CH4 NH3 H2O

Bond angles
decrease as the
number of lone
pairs increase.

109.5o 107.3o 104.5o

Similarly, multiple bonds also occupy larger electron

domains, due to the higher electron density.

Remember: Electron zones repel each other in this order:

lone pair-lone pair > lone pair-shared pair > shared pair-shared pair
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Molecules with Expanded Valence Shells:

Recall that a central atom from the 3rd period and

beyond can have more than 4e- pairs around it.
Molecules with 5 or 6 electron domains will tend to have
shapes based on the following electron domain geometries:

trigonal-bipyramidal (5) or octahedral (6)

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 Note – the lone
Structures with 5 electron domains: pairs will occupy
equatorial positions
before axial.
PCl5
equatorial

SF4
axial

ClF3

XeF2

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Structures with 6 electron domains:

SF6

IF5

XeF4

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 Examples
octahedral

81.9o

90.o
:

XeF5 XeF4
trigonal bipyramidal

87o
87o

102o

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# of electron Electron Bonding Nonbonding Molecular
domains geometry domains domains geometry
(unpaired) (lone pairs)
2 linear 2 0 linear
3 trigonal 3 0 trigonal planar
planar 2 1 bent
4 tetrahedral 4 0 tetrahedral
3 1 trigonal pyramidal
2 2 bent
5 trigonal 5 0 trigonal
bipyramidal bipyramidal
4 1 seesaw
3 2 t-shaped
2 3 linear
6 octahedral 6 0 octahedral
5 1 square pyramidal
4 2 square planar

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What shape would the following display?

a) BrF3 b) BrF5 c) SbF6- d) TeCl4

-

T-shaped square see-saw

octahedral
pyramidal

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Molecules with More than One Central Atom:

The VSEPR theory not only applies to one central atom,

but it applies to molecules with more than one central
atom. We take in account the geometric distribution of
the terminal atoms around each central atom. For the
final description, we combine the separate description
of each atom.

In other words, we take long chain molecules and break

it down into pieces. Each piece will form a particular
shape.

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 What shapes would be around each of the central atoms?

bent
tetrahedral

trigonal planar

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What about CH2CHCOH?

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The AXE system: AXmEn:

A is the central atom, m the number of atoms X bonded

to A, and n the number of nonbonded lone-pairs of
electrons, E, about the central atom.

In this system:
methane, CH4, is AX4 ammonia, NH3, is AX3E1
water, H2O, is AX2E2
Note that different AXmEn designations can give rise to
the same overall geometry or shape:
For example:
AX2E1 and AX2E2 both give rise to bent or angular
geometries
AX2 and AX2E3 both give rise to linear geometries
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 Now that you better understand the shapes of molecules,
it’s important to revisit polarity.

9.3: Polarities (again)

Two key ideas:
1. Bond Dipoles
Differences in electronegativies between the atoms
bonded together may result in a bond dipole (polar
bond).
eg. S - F

The extent of polarity is described by the term dipole moment (µ) .

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 2. Bond (dipole) Moment – The net effect of all bond
dipoles within a given molecule. The bond moment is the
vector sum of all the bond dipoles in the molecule.

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Two outcomes: vector sum = 0 (molecule is nonpolar)
vector sum ≠ 0 (molecule is polar)

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Two requirements for a nonpolar molecule:

•All bonds involve identical atoms

•Molecular geometry must be symmetrical

Versus:

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9.4: Covalent Bonding and Orbital Overlap

Lewis structures and the V.S.E.P.R. model allows us to

hypothesize the correct geometry of thousands of
molecules. Formal charges, the concept of exceptions to the rule of
octet and resonance each play a role in helping us find reasonable
bonding arrangements. Furthermore, bond polarity measurements
can often confirm the likelihood of a specific molecular geometry.

The overall structural picture is still rather incomplete.

When we consider the pairing and sharing of electrons, we
have no real idea of how the particles are behaving or
where they may end up. Quantum theory is required to
really sort out the entire ‘package”.

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A quick review of bond orbitals from last year.

Energy level → sublevel → orbital

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s-sublevel p-sublevel
(1 orbital) (3 orbitals)

dxy dxz dyz dx2-y2 dz2

d-sublevel (5 orbitals) 42
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The Valence Bond Theory brings together Lewis’ notation
of electron-pair bonds, and the idea of atomic orbitals.

This theory postulates that e- within a molecule occupy

the atomic orbitals of the original atoms, and that the e-
of one atom are attracted to the nucleus of another atom,
and a bond forms when the orbitals overlap.
For example:

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Attraction between atoms increases as atoms approach one
another until they reach a minimum distance (lowest PE) where
the e- density begins to cause repulsion between the two atoms.

* Each bond represents that overlap of orbitals

between two bonded atoms.
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 The Lewis structure treats all covalent bonds as identical
and would therefore predict, for example, that all single
bonds would have the same properties.

The VSEPR theory helps predict molecular shape, although

there’s no obvious relationship to the filling and shapes of
atomic orbitals.

However, the examples of H2, HF, and F2

Provides us with reasons why bond lengths
and strengths are so variable – there are
different types of orbitals involved in
bonding.

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However, the valence bond theory must do some “fancy
footwork” to harmonize orbital theory with known
molecular geometry.

For example – Let’s look at methane (CH4)

The geometry is predicted to be tetrahedral with

109.5o bond angles.

Average bond energy is 414 kJ/mol.

Methane is known to have 4 identical C-H bonds.

What’s the problem?

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 Carbon has 4 valence electrons (1s22s22p2).
Hydrogen has 1 valence electron (1s1)

C
1s 2s 2p

2 in the s orbital, and 2 in the

p orbitals (px and py)
It would seem that the 2s electrons become unpaired and
one of them enters the otherwise empty 2pz orbital.

C
2s 2p

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From this:
1. Two different bond types would form:

C H
2s 2p 1s

1 would involve the overlap of H 1s orbital

with the 2s orbital of C.

3 would involve the overlap of the H

1s orbital with the 2p orbitals of C.

So why does experimental evidence point to 4

identical C-H bonds?

2. Since the 2p orbitals are mutually perpendicular, we

would expect the three bonds formed to have 90o angles.
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 Valence Bond Theory addresses these issues by suggesting
that during the bonding process the original atomic orbitals
hybridize. Therefore, in methane, the s and p orbitals for
carbon become hybrids.

Instead of distinct s and p orbitals, we now have combined

1 s with 3 p orbitals to form 4 sp3 hybrids. (new shape)

In methane, all four bonds are now going to be the same.

Orbitals – crash course (10 min) 50
9.5: Hybrid Orbitals
Hybridization is the concept of mixing different atomic
orbitals to form new hybrid (bonding) orbitals suitable
for the qualitative description of atomic bonding
properties. Hybridized orbitals are very useful in the
explanation of the shape of molecular shapes for
molecules.

Recall from 32S: atomic orbitals are standing waves associated with the
electrons bound to a nucleus. When you bring atoms together the boundary
conditions for these standing waves change and so the standing waves
which were the atomic orbitals change. That is all hybridization is. It's
analogous to holding down and releasing a violin string while you're playing. There's
one standing wave (one frequency) while you're holding down the string, and
another standing wave (another frequency) when you release the string.
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There exist 5 types of hybridization:
1. sp hybridization: e- promotion

Example: BeH2 Be
1s 2sH H 2p
Turns to:

1s 2-2sp 2p
orbitals
The promotion of a Be 2s electron to a 2p orbital requires energy.

Note the energy

change for the
hybrid orbitals.
The elongated sp hybrid orbitals have one large lobe
which can overlap (bond) with another atom more
effectively. This produces a stronger bond (higher bond
energy) which offsets the energy required to promote the
2s electron.

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Note:

The Be 2sp orbitals are identical

(50% s and 50%p character) and
oriented 180° from one another
(i.e. bond lengths will be
identical and the molecule
linear)

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Another example of sp hybridization:

magnesium hydride

3s

Mg 1s
3sp 3p
3s 3p
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2. sp2 hybridization

Example: BF3
e- promotion

B F F F 2p
2p

2s 3- sp2 orbitals
33% s 66% p
1s 1s

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3. sp3 hybridization

Example: CH4

e- promotion

4- 2sp3
orbitals

25% s, 75%p character

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Lone pair electrons in hybrid obitals
If lone pair electrons are present on the central atom, these
can occupy one or more of the sp3 orbitals.
No promotion of electrons is required here for the excited
state as the existing arrangement is just what we need.

Although no bonds are formed by the lone pair in NH3, these

electrons do give rise to a charge cloud that takes up space
just like any other orbital.

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In the water molecule, the oxygen atom can form four sp3
orbitals. Two of these are occupied by the two lone pairs
on the oxygen atom, while the other two are used for
bonding.

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 chlorine

4. sp3d hybridization e- promotion

Example: PCl5 P
3s 3p 3d
Cl Cl Cl Cl Cl

5- sp3d orbitals

These hybrid orbitals give

the molecule a shape of
trigonal bipyramid.
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If one of the orbitals contains one, two, or three lone pairs
instead of bond pairs, the electron arrangement is still trigonal
bipyramidal, but the molecular shapes are now seesaw
(distorted tetrahedron), T-shaped and linear, respectively.

Counting electron domains, iodine

For example: ICl3 must hybridize in such a way as to
provide five hybrid orbitals (that is,
sp3d).

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 5. sp3d2 hybridization

Example: SF6 e- promotion

F F F F F F

This hybridization
gives rise to an
octahedral shape.

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Conclusion:

To determine the hybrid orbitals

used by an atom in bonding, we
must know the electron domain
geometry.

Each atom in a molecule could have

1 of the 5 types of hybridization.
(Table p. 361)

However, certain mild variation in the

shape is observed in the presence of
lone pair of electrons. For example,
SO2 which contains sp2 hybrid orbitals
is a slightly bent molecule. This is due
to presence of lone pair of electrons.
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What would be the hybridization of C1, C2, and O2 in the
following?

1 2 2

O is sp3
sp3
C1 is
hybridized
hybridized
C2 is sp2
hybridized

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9.6: Multiple Bonds

Orbitals can overlap in two different ways:

1. Sigma (σ) bond overlap: (strongest)

- This occurs when orbitals overlap end to end

- The electron density is between the atoms (nuclei).

- All single bonds are sigma bonds

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σ bond

axis between nuclei

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2. Pi (π) bond overlap: (weaker than sigma bonds)

- Occur when side-by-side p-orbitals overlap

(occurs in double and triple bonds)

- Electron density is not between the atoms, but lies

above or below the inter-nuclear axis.
(perpendicular)

- Prevents molecule from rotating

pi bond

Nuclear axis

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 The unused, or unhybridized orbitals handle any multiple bonding
that occurs, so if you draw a Lewis Structure that contains double
or triple bonds, you can be certain that there are electrons
residing in those unhybridized orbitals.
Example: formaldehyde
sp2 hybridized
1 bond to C,
2 lone pairs

No change
2 hydrogen

sp2
hybridized
hybridized – unhybridized –
single bond double bond
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 Example 1: ethene (C2H4)
e- promotion

C
1s 2s H H 2p C C 1 - 2p sp2
unhybridized hybridized
Turns to: orbital

3 – 2sp2
hybrid orbitals

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In almost all cases, a double Y σ π σ Y
bond has one σ bond and one X X
σ σ Y
π bond. Yσ

One π bond

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 Example 2: ethyne (C2H2) π
e- promotion
Yσ X σ X σ Y
π
C
In almost all cases,
1s 2s 2p a triple bond has
2 - 2p
Turns to: unhybridized one σ bond and
2 – 2sp orbitals two π bonds.
hybrid orbitals

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For the molecule AsCl5, perform the following operations.

1. Draw the correct Lewis Structure.

2. How many sigma bonds does the Arsenic form? __________

How many lone pairs does Arsenic have? __________
What type of Hybridization does Arsenic exhibit in this molecule
based on the number of hybrid orbitals required?

3. Show the Ground State distribution of the valence electrons on

Arsenic.

4. Show the Excited State distribution of valence electrons on

Arsenic.

5. Show the Hybridized State distribution of the valence electrons

on Arsenic.

6. What is the molecular shape of the molecule?

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Note: the hybrid orbitals in a molecule basically have two
responsibilities;
(1) To form the first bond between two atoms and
(2) To house lone pairs.

Note: any double or triple (Pi) bonding is handled by the

"unhybridized orbitals".

Next up: Molecular Orbital Theory

Time to work on end-of chapter questions.

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Video: Network Colvalent bonding and hybridization
(8 min)

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