Chapter 10

Chemical Bonding II: Molecular

Geometry and Hybridization of
Atomic Orbitals

Chemistry 101
Chemistry Department
Lecturer: Dr. Adeeb Al-Sheikh
Valence shell electron pair repulsion
(VSEPR) model:

Predict the geometry of the molecule from the

electrostatic repulsions between the electron (bonding
and nonbonding) pairs.
# of atoms # lone
Arrangement of Molecular
Class bonded to pairs on
electron pairs Geometry
central atom central atom
AB2 2 0 linear linear

© McGraw-Hill Education. 10-2

Beryllium Chloride

© McGraw-Hill Education. 10-3

 VSEPR (1 of 4)

# of atoms # lone Arrangement

Molecular
Class bonded to pairs on of electron
Geometry
central atom central atom pairs
AB2 2 0 linear Linear
trigonal trigonal
AB3 3 0
Planar Planar

© McGraw-Hill Education. 10-4

Boron Trifluoride

© McGraw-Hill Education. 10-5

 VSEPR (2 of 4)

# of atoms # lone
Arrangement of Molecular
Class bonded to pairs on
electron pairs Geometry
central atom central atom

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral

© McGraw-Hill Education. 10-6

Methane

© McGraw-Hill Education. 10-7

 VSEPR (3 of 4)
# of atoms # lone Arrangement
Molecular
Class bonded to pairs on of electron
Geometry
central atom central atom pairs
AB2 2 0 linear linear
trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal

Jump to long Jump to long

description description
© McGraw-Hill Education. 10-8
Phosphorus Pentachloride

© McGraw-Hill Education. 10-9

 VSEPR (4 of 4)
# lone
# of atoms
pairs on Arrangement of Molecular
Class bonded to
central electron pairs Geometry
central atom
atom
AB2 2 0 linear linear
AB3 3 0 trigonal planar trigonal planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral

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Sulfur Hexafluoride

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Summary of VSEPR

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 Tetrahedral Bond Angles

lone - pair vs. lone - pair lone - pair vs. bonding- bonding - pair vs. bonding -
 
repulsion pair repulsion pair repulsion

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 VSEPR: 3 Electron Groups

# of atoms # lone
Arrangement of Molecular
Class bonded to pairs on
electron pairs Geometry
central atom central atom
trigonal trigonal
AB3 3 0
planar planar
trigonal
AB2E 2 1 bent
planar

© McGraw-Hill Education. 10-14

 VSEPR: 4 Electron Groups (1 of 2)

# of atoms # lone
Arrangement of Molecular
Class bonded to pairs on
electron pairs Geometry
central atom central atom

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

© McGraw-Hill Education. 10-15

VSEPR: 4 Electron Groups (2 of 2)

# of atoms # lone Arrangement

Molecular
Class bonded to pairs on central of electron
Geometry
central atom atom pairs

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal
AB2E2 2 2 tetrahedral bent

© McGraw-Hill Education. 10-16

 VSEPR: 5 Electron Groups (1 of 3)

# of atoms # lone
Arrangement of Molecular
Class bonded to central pairs on central
electron pairs Geometry
atom atom
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron

© McGraw-Hill Education. 10-17

 VSEPR: 5 Electron Groups (2 of 3)

# of atoms # lone
Arrangement of Molecular
Class bonded to central pairs on central
electron pairs Geometry
atom atom
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T- shaped
bipyramidal

© McGraw-Hill Education. 10-18

VSEPR: 5 Electron Groups (3 of 3)
# of atoms # lone
Arrangement of Molecular
Class bonded to pairs on central
electron pairs Geometry
central atom atom
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal

© McGraw-Hill Education. 10-19

VSEPR: 6 Electron Groups (1 of 2)

# of atoms # lone Arrangement

Molecular
Class bonded to pairs on of electron
Geometry
central atom central atom pairs

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal

© McGraw-Hill Education. 10-20

VSEPR: 6 Electron Groups (2 of 2)

# of atoms # lone Arrangement

Molecular
Class bonded to pairs on of electron
Geometry
central atom central atom pairs

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
square
AB4E2 4 2 octahedral
planar

© McGraw-Hill Education. 10-21

Summary of Molecular Shapes

© McGraw-Hill Education. 10-22

 Predicting Molecular Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the central atom and
number of atoms bonded to the central atom.
3. Use VSEPR to predict the geometry of the molecule.

© McGraw-Hill Education. 10-23

 Example 10.1 (1 of 7)

Use the VSEPR model to predict the geometry of the following

molecules and ions:

(a) AsH 3

(b ) OF2

(c) AlCl−4

(d ) I3−

(e) C2 H 4

© McGraw-Hill Education. 10-24

 Example 10.1 (2 of 7)
Strategy
The sequence of steps in determining molecular geometry is as follows:

draw Lewis find arrangement of find arrangement determine geomentry

→ → →
structure electron pairs of bonding pairs based on bonding pairs

Solution
(a) The Lewis structure of AsH3 is

There are four electron pairs around the central atom; therefore, the
electron pair arrangement is tetrahedral (see Table 10.1).

© McGraw-Hill Education. 10-25

 Example 10.1 (3 of 7)
Recall that the geometry of a molecule is determined only by the
arrangement of atoms (in this case the As and H atoms). Thus,
removing the lone pair leaves us with three bonding pairs and a
trigonal pyramidal geometry, like NH3. We cannot predict the HAsH
angle accurately, but we know that it is less than 109.5 because the
repulsion of the bonding electron pairs in the As—H bonds by the lone
pair on As is greater than the repulsion between the bonding pairs.

(b) The Lewis structure of OF2 is

There are four electron pairs around the central atom; therefore,
the electron pair arrangement is tetrahedral.

© McGraw-Hill Education. 10-26

 Example 10.1 (4 of 7)
Recall that the geometry of a molecule is determined only by
the arrangement of atoms (in this case the O and F atoms).
Thus, removing the two lone pairs leaves us with two
bonding pairs and a bent geometry, like H2O. We cannot
predict the FOF angle accurately, but we know that it must
be less than 109.5° because the repulsion of the bonding
electron pairs in the O−F bonds by the lone pairs on O is
greater than the repulsion between the bonding pairs.

−
(c) The Lewis structure of AlCl4 is

© McGraw-Hill Education. 10-27

 Example 10.1 (5 of 7)

There are four electron pairs around the central atom; therefore,
the electron pair arrangement is tetrahedral. Because there are
no lone pairs present, the arrangement of the bonding pairs is the
same as the electron pair arrangement. Therefore, AlCl−4 has a
tetrahedral geometry and the ClAlCl angles are all 109.5

(d) The Lewis structure of I3− is

There are five electron pairs around the central I atom; therefore,
the electron pair arrangement is trigonal bipyramidal. Of the five
electron pairs, three are lone pairs and two are bonding pairs.

© McGraw-Hill Education. 10-28

 Example 10.1(6 of 7)
Recall that the lone pairs preferentially occupy the equatorial
positions in a trigonal bipyramid (see Table 10.2). Thus,
removing the lone pairs leaves us with a linear geometry for ,
that is, all three I atoms lie in a straight line.

(e) The Lewis structure of C2H4is

The C = C bond is treated as though it were a single bond in

the VSEPR model. Because there are three electron pairs
around each C atom and there are no lone pairs present,
the arrangement around each C atom has a trigonal planar
shape like BF3, discussed earlier.
© McGraw-Hill Education. 10-29
 Example 10.1(7 of 7)
Thus, the predicted bond angles in C2H4 are all 120°.

Comment
1) The I3− ion
is one of the few structures for which the bond angle (180) can be
predicted accurately even though the central atom contains lone pairs.

2) In C2H4,all six atoms lie in the same plane. The overall planar geometry
is not predicted by the VSEPR model, but we will see why the molecule
prefers to be planar later. In reality, the angles are close, but not equal, to
120 because the bonds are not all equivalent.

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Dipole Moments and Polar Molecules

µ=Q×r
Q is the charge
r is the distance between charges
1 D = 3.36  10−30 Cm

© McGraw-Hill Education. 10-31

Bond moments and resultant dipole
moments in NH3 and NF3.

© McGraw-Hill Education. 10-32

 Example 10.2 (1 of 6)
Predict whether each of the following molecules has a
dipole moment:

(a) BrCl

(b ) BF3 (trigonal planar)

(c ) CH 2 Cl2 (tetrahedral)

© McGraw-Hill Education. 10-33

 Example 10.2 (2 of 6)

Strategy
Keep in mind that the dipole moment of a molecule
depends on both the difference in electronegativities of
the elements present and its geometry.

A molecule can have polar bonds (if the bonded atoms

have different electronegativities), but it may not possess
a dipole moment if it has a highly symmetrical geometry.

© McGraw-Hill Education. 10-34

 Example 10.2 (3 of 6)
Solution
a) Because bromine chloride is diatomic, it has a linear geometry.
Chlorine is more electronegative than bromine (see Figure 9.5),
so BrCl is polar with chlorine at the negative end

Thus, the molecule does have a dipole moment. In fact, all

diatomic molecules containing different elements possess
a dipole moment.
© McGraw-Hill Education. 10-35
 Example 10.2 (4 of 6)
b) Because fluorine is more electronegative than boron, each
B−F bond in BF3 (boron trifluoride) is polar and the three
bond moments are equal. However, the symmetry of a
trigonal planar shape means that the three bond moments
exactly cancel one another:

An analogy is an object that is pulled in the directions shown

by the three bond moments. If the forces are equal, the object
will not move. Consequently,BF3 has no dipole moment; it is a
nonpolar molecule.
© McGraw-Hill Education. 10-36
 Example 10.2 (5 of 6)

c) The Lewis structure of CH2Cl2 (methylene chloride) is

This molecule is similar to CH4 in that it has an overall

tetrahedral shape. However, because not all the bonds are
identical, there are three different bond angles: HCH, HCCl,
and ClCCl. These bond angles are close to, but not equal to,
109.5° .

© McGraw-Hill Education. 10-37

 Example 10.2 (6 of 6)

Because chlorine is more electronegative than carbon, which

is more electronegative than hydrogen, the bond moments do
not cancel and the molecule possesses a dipole moment:

Thus, CH2Cl2 is a polar molecule.

© McGraw-Hill Education. 10-38

 Hybridization
Hybridization – mixing of two or more atomic orbitals to
form a new set of hybrid orbitals

1. Mix at least 2 nonequivalent atomic orbitals (e.g. s and

p). Hybrid orbitals have very different shape from
original atomic orbitals.
2. Number of hybrid orbitals is equal to number of pure
atomic orbitals used in the hybridization process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid orbitals
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Formation of sp3 Hybrid Orbitals

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Formation of Covalent Bonds in CH4

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sp3 -Hybridized N Atom in NH3

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Formation of sp Hybrid Orbitals

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Formation of sp2 Hybrid Orbitals

© McGraw-Hill Education. 10-44

How do I predict the hybridization of the
central atom?
1. Draw the Lewis structure of the molecule.
2. Count the number of lone pairs AND the number of atoms
bonded to the central atom

# of Lone Pairs
+
# of Bonded Atoms Hybridization Examples

2 sp BeCl2

3 sp 2 BF3

4 sp 3 CH 4 , NH 3 , H 2 O

5 sp 3 d PCl5

6 sp 3d 2 SF6

© McGraw-Hill Education. 10-45

Important Hybrid Orbitals

© McGraw-Hill Education. 10-46

 Example 10.3 (1 of 8)
Determine the hybridization state of the central (underlined)
atom in each of the following molecules:

(a) BeH 2

(b ) AlI3

(c) PF3
Describe the hybridization process and determine the
molecular geometry in each case.

© McGraw-Hill Education. 10-47

 Example 10.3 (2 of 8)

Strategy
The steps for determining the hybridization of the central atom in a
molecule are:

use VSEPR to determine the use Table 10.4 to

draw Lewis structure electron pair arrangement determine the
→ →
of the molecule surrounding the central atom hybridization state of
(Table 10.1) the central atom

Solution
2 2
a) The ground-state electron configuration of Be is 1s 2s and the
Be atom has two valence electrons. The Lewis structure of BeH2
is
H—Be—H

© McGraw-Hill Education. 10-48

 Example 10.3 (3 of 8)
There are two bonding pairs around Be; therefore, the electron
pair arrangement is linear. We conclude that Be uses sp hybrid
orbitals in bonding with H, because sp orbitals have a linear
arrangement (see Table 10.4). The hybridization process can be
imagined as follows. First, we draw the orbital diagram for the
ground state of Be:

By promoting a 2s electron to the 2p orbital, we get the excited

state:
 
2s 2p
© McGraw-Hill Education. 10-49
 Example 10.3 (4 of 8)

The 2s and 2p orbitals then mix to form two hybrid orbitals:

The two Be−H bonds are formed by the overlap of the Be

sp orbitals with the 1s orbitals of the H atoms. Thus, BeH2 is
a linear molecule.

© McGraw-Hill Education. 10-50

 Example 10.3 (5 of 8)

b) The ground-state electron configuration of  Ne  3s 2 3p1. Therefore,

the Al atom has three valence electrons. The Lewis structure of
AlI3 is

There are three pairs of electrons around Al; therefore, the electron
2
pair arrangement is trigonal planar. We conclude that Al uses sp
2
hybrid orbitals in bonding with I because sp orbitals have a trigonal
planar arrangement. The orbital diagram of the ground-state Al atom
is

© McGraw-Hill Education. 10-51

 Example 10.3 (6 of 8)

By promoting a 3s electron into the 3p orbital we obtain the

following excited state:
  
3s 3p
The 3s and two 3p orbitals then mix to form three sp 2 hybrid
orbitals:

The sp 2 hybrid orbitals overlap with the 5p orbitals of I to form

three covalent Al−I bonds. We predict that the AlI3 molecule is
trigonal planar and all the lAll angles are 120°.
© McGraw-Hill Education. 10-52
 Example 10.3 (7 of 8)

c) The ground-state electron configuration of P is  Ne  3s 2 3p3 .

Therefore, P atom has five valence electrons. The Lewis structure
of PF3 is

There are four pairs of electrons around P; therefore, the electron pair
arrangement is tetrahedral. We conclude that P uses sp3 hybrid
orbitals in bonding to F, because sp3 orbitals have a tetrahedral
arrangement. The hybridization process can be imagined to take
place as follows. The orbital diagram of the ground-state P atom is

© McGraw-Hill Education. 10-53

 Example 10.3 (8 of 8)
By mixing the 3s and 3p orbitals, we obtain four sp 3 hybrid
orbitals.

3
As in the case of NH3 , one of the sp hybrid orbitals is
used to accommodate the lone pair on P. The other three
sp 3 hybrid orbitals form covalent P−F bonds with the 2p
orbitals of F. We predict the geometry of the molecule to
be trigonal pyramidal; the F−F angle should be somewhat
less than 109.5°.

© McGraw-Hill Education. 10-54

 Example10.4 (1 of 4)
Describe the hybridization state of phosphorus in phosphorus
pentabromide (PBr5).

PBr5

© McGraw-Hill Education. 10-55

sp2 Hybridization of Carbon (1 of 2)

© McGraw-Hill Education. 10-56

sp2 Hybridization of Carbon (2 of 2)

Unhybridized 2pz orbital (gray), which is perpendicular to the

plane of the hybrid (green) orbitals.

© McGraw-Hill Education. 10-57

 Bonding in Ethylene, C2H4

Sigma bond (σ) – electron density between the 2 atoms

Pi bond (π) – electron density above and below plane of nuclei of the
bonding atoms

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Sigma (σ) and Pi Bonds (π)

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

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sp Hybridization of Carbon

© McGraw-Hill Education. 10-60

Bonding in Acetylene, C2H2

© McGraw-Hill Education. 10-61

 Example 10.5 (1 of 3)

Describe the bonding in the formaldehyde molecule whose

Lewis structure is

Assume that the O atom is sp 2 −hybridized.

© McGraw-Hill Education. 10-62

 Example 10.5 (2 of 3)
Strategy
Follow the procedure shown in Example 10.3.

Solution
There are three pairs of electrons around the C atom; therefore, the electron
pair arrangement is trigonal planar. (Recall that a double bond is treated as a
2
single bond in the VSEPR model.) We conclude that C uses sp hybrid orbitals
in bonding, because sp 2 hybrid orbitals have a trigonal planar arrangement.
We can imagine the hybridization processes for C and O as follows:

© McGraw-Hill Education. 10-63

 Example 10.5 (3 of 3)
Carbon has one electron in each of the three sp 2 orbitals, which
are used to form sigma bonds with the H atoms and the O atom.
There is also an electron in the 2pz orbital, which forms a pi bond
with oxygen. Oxygen has two electrons in two of its sp 2 hybrid
orbitals. These are the lone pairs on oxygen. Its third sp 2 hybrid
orbital with one electron is used to form a sigma bond with
carbon. The 2pz orbital (with one electron) overlaps with the 2pz
orbital of C to form a pi bond.

Jump to long description

© McGraw-Hill Education. 10-64
Experiments Show O2 is Paramagnetic

−
No unpaired e
Should be diamagnetic

Molecular orbital theory – bonds are formed from interaction of

atomic orbitals to form molecular orbitals.

© McGraw-Hill Education. 10-65

 Energy Levels of Bonding and Antibonding
Molecular Orbitals in Hydrogen (H2 )

A bonding molecular orbital has lower energy and greater

stability than the atomic orbitals from which it was formed.
An antibonding molecular orbital has higher energy and lower
stability than the atomic orbitals from which it was formed.

© McGraw-Hill Education. 10-66

 Molecular Orbital (MO) Configurations
(1 of 4)
1. The number of molecular orbitals (MOs) formed is always
equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum
of all the electrons on the bonding atoms.

© McGraw-Hill Education. 10-67

Molecular Orbital (MO) Configurations
(2 of 4)
1
bond order = ( Number of electrons in bonding MOs − Number of electrons in antibonding MOs )
2

bond order 1 1 1 0
2 2

© McGraw-Hill Education. 10-68

Molecular Orbital (MO) Configurations
(3 of 4)
General molecular orbital energy level diagram for the
second-period homonuclear diatomic molecules
Li 2 , Be 2 , B2 ,C 2 and N 2 

© McGraw-Hill Education. 10-69

Molecular Orbital (MO) Configurations
(4 of 4)

© McGraw-Hill Education. 10-70

 Example 10.6 (1 of 4)
The N +2
ion can be prepared by bombarding the N2 molecule with fast-
moving electrons.
+
Predict the following properties of N 2

a) The electron configuration

b) bond order

c) magnetic properties

d) bond length relative to the bond length of N2 (is it longer or

shorter?)

© McGraw-Hill Education. 10-71

 Example 10.6 (2 of 4)
Strategy
From Table 10.5 we can deduce the properties of ions
generated from the homonuclear molecules.

How does the stability of a molecule depend on the number

of electrons in bonding and antibonding molecular orbitals?

From what molecular orbital is an electron removed to from

+
the N 2 ion from N 2?

What properties determine whether a species is

diamagnetic or paramagnetic?

© McGraw-Hill Education. 10-72

 Example 10.6 (3 of 4)

Solution
From Table 10.5 we can deduce the properties of ions generated from
the homonuclear diatomic molecules.

a) Because N +2

( σ1s ) (σ ) (σ ) (σ ) ( π ) ( π ) (σ )
2 2 1
2 * 2 * 2 * 2 *
1s 2s 2s 2p y 2p z 2p x

(b) The bond order of N +2 Is found by using Equation (10.2):

bond order = 1 2 ( 9 − 4 ) = 2.5

(c) N +2 has one unpaired electron, so it is paramagnetic

© McGraw-Hill Education. 10-73

 Example 10.6 (4 of 4)

d) Because the electrons in the bonding molecular orbitals are

responsible for holding the atoms together, N +2
should have a weaker and, therefore, longer bond than N2. (In
fact, the bond length of N +2
is 112 pm, compared with 110 pm for N2.)

Check
Because an electron is removed from a bonding molecular orbital, we
expect the bond order to decrease. The N +2
ion has an odd number of electrons (13), so it should be paramagnetic.

© McGraw-Hill Education. 10-74