Lesson 14 and 15

Chapter 9

Covalent Bonding: Orbitals

 Chapter 9

Covalent Bonding: Orbitals

9.1 Hybridization and the Localized Electron Model

sp3 Hybridization
sp2 Hybridization
sp Hybridization
9.2 The Molecular Orbital Model
Bond Order
9.3 Bonding in Homonuclear Diatomic Molecules
Paramagnetism
9.4 Bonding in Heteronuclear Diatomic Molecules
9.5 Combining the Localized Electron and Molecular Orbital Models
 Learning Outcomes

After this lesson, you should be able to:

1- Explain the valence bond theory.

2- Identify the concept of hybridization.
3- Differentiate between types of orbital hybridization.
4- Know the relationship between hybridization and molecular geometry.
5- Predict the type of hybridization in given covalent compounds.
6- Know how calculate the bond order.
7- Describe the molecular orbital model.
8- Explain the Paramagnetism.
 Hybridization
Mixing of the native atomic orbitals to form special orbitals for bonding.

In this section we will describe the atomic orbitals used

to share electrons and hence to form the bonds.
9.1 Hybridization and the Localized Electron Model

The localized electron model views a molecule as a collection of atoms bound together by
sharing electrons between their atomic orbitals.
The arrangement of valence electrons is represented by the Lewis structure (or structures,
where resonance occurs), and the molecular geometry can be predicted from the VSEPR
model.
 sp3 Hybridization

Bonding involves only the valence orbitals. This means that the hydrogen atoms in methane use 1s orbitals.
The valence orbitals of a carbon atom are the 2s and 2p (2px, 2py and 2 pz) orbitals.

Figure 9.1 | (a) The Lewis structure of the

methane molecule. (b) The tetrahedral Figure 9.2 | The valence orbitals on a free
molecular geometry of the methane molecule carbon atom: 2s, 2px, 2py, and 2pz
1. Using the 2p and 2s atomic orbitals will lead to two different types of C−H bonds:
(a) those from the overlap of a 2p orbital of carbon and a 1s orbital of hydrogen (there will be three of
these) and
(b) those from the overlap of a 2s orbital of carbon and a 1s orbital of hydrogen (there will be one of
these). This is a problem because methane is known to have four identical C−H bonds.

2. Since the carbon 2p orbitals are mutually perpendicular, we might expect the three C−H bonds formed
with these orbitals to be oriented at 90-degree angles:

However, the methane molecule is known by experiment to be tetrahedral with bond angles of 109.5 degrees .
To account for the known structure of methane:
It makes sense to assume that the carbon atom has four equivalent atomic orbitals, arranged tetrahedrally. In fact,
such a set of orbitals can be obtained quite readily by combining the carbon 2s and 2p orbitals. This mixing of the
native atomic orbitals to form special orbitals for bonding is called hybridization. The four new orbitals are called
sp3 orbitals because they are formed from one 2s and three 2p orbitals. The four sp3 orbitals are identical in
shape, each one having a large lobe and a small lobe. The four orbitals are oriented in space so that the large lobes
form a tetrahedral arrangement.

Figure 9.3 | The “native” 2s and three 2p atomic orbitals characteristic of a free carbon atom are combined to form a new setof four sp3 orbitals. The small lobes
of the orbitals are usually omitted from diagrams for clarity.
 The hybridization of the carbon 2s and 2p orbitals also can be represented by an orbital energy-level diagram.
Carbon’s atomic orbitals are rearranged to accommodate the best electron arrangement for the molecule. The
new sp3 atomic orbitals on carbon are used to share electron pairs with the 1s orbitals from the four hydrogen
atoms (Fig.9.5).

An atom in a molecule might adopt a different set of atomic orbitals (called hybrid orbitals) from those it has in
the free state. It does not seem unreasonable that to achieve minimum energy, an atom uses one set of atomic
orbitals in the free state and a different set in a molecule.

Figure 9.6 | The tetrahedral set of four sp3 orbitals of the carbon atom
are used to share electron pairs with the four 1s orbitals of the
Figure 9.5 | An energy-level diagram showing the formation of four sp3 orbitals.
hydrogen atoms to form the four equivalent C−H bonds. This accounts
for the known tetrahedral structure of the CH 4 molecule.
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 The Localized Electron Model I

Example
Describe the bonding in the ammonia molecule using the localized electron model.

Solution
A complete description of the bonding involves three steps:
1. Writing the Lewis structure
2. Determining the arrangement of electron pairs using the VSEPR model
3. Determining the hybrid atomic orbitals needed to describe the bonding in the molecule

The Lewis structure for NH3 is

The four electron pairs around the nitrogen atom require a tetrahedral arrangement to
minimize repulsions.

A tetrahedral set of sp3 hybrid orbitals is obtained by combining the 2s and three 2p orbitals.
In the NH3 molecule, three of the sp3 orbitals are used to form bonds to the three hydrogen
atoms, and the fourth sp3 orbital holds the lone pair.
Figure 9.7 | The nitrogen atom in ammonia is sp 3 hybridized.
 Example
Describe the bonding in the water molecule using the localized electron model.

Solution

In H2O hybridization orbitals having the same energy level will combine to form hybrid orbitals.
The water molecule has two lone pairs and two bond pairs.

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Chapter_1._Electronic_Structure_and_Chemical_Bonding/1.07_Atomic_Orbitals_and_Covalent_Bonding
sp2 Hybridization
Ethylene (C2H4) is an important starting material in the manufacture of plastics. The C2H4 molecule has 12
valence electrons and the following Lewis structure:

A double bond acts as one effective pair, so in the ethylene molecule each
carbon is surrounded by three effective pairs.
This requires a trigonal planar arrangement with bond angles of 120
degrees.

What orbitals do the carbon atoms in this molecule employ?

The molecular geometry requires a set of orbitals in one plane at angles of

120 degrees. Since the 2s and 2p valence orbitals of carbon do not have
the required arrangement, we need a set of hybrid orbitals.
Figure 9.8 | The hybridization of the s,
px, and py atomic orbitals results in the
formation of three sp2 orbitals
centered in the xy plane. The large
lobes of the orbitals lie in the plane at
angles of 120 degrees and point
toward the corners of a triangle.

A set of three orbitals arranged at 120-degree angles in the same plane can be obtained by
combining one s orbital and two p orbitals. Since one 2s and two 2p orbitals are used to form
these hybrid orbitals, this is called sp2 hybridization. The plane of the sp2 hybridized orbitals
is determined by which p orbitals are used. Since in this case we have arbitrarily decided to
use the Px and Py orbitals, the hybrid orbitals are centered in the xy plane.

Figure 9.9 | An orbital energy-level

diagram for sp2 hybridization. Note
that one p orbital remains unchanged.
In forming the sp2 orbitals, one 2p orbital on carbon has not been used. This remaining P
orbital (Pz) is oriented perpendicular to the plane of the sp2 orbitals.

Figure 9.10 | When an s and

two p orbitals are mixed to form
a set of three sp2 orbitals, one
p orbital remains unchanged and
is perpendicular to the plane of
the hybrid orbitals. Note that in
this figure and those that follow,
the orbitals are drawn with
narrowed lobes to show them
orientations more clearly.

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How these orbitals can be used to account for the bonds in ethylene?

The three sp2 orbitals on each carbon can be used to share electrons.

Sigma (σ) bond: Formed by electron sharing in an area centered on a line running between the
atoms.

In the ethylene molecule, the 𝜎 bonds are formed using sp2 orbitals on each carbon atom and
the 1s orbital on each hydrogen atom.

Figure 9.11 | The s bonds in ethylene. Note that for each bond the shared electron
pair occupies the region directly between the atoms.
How can we explain the double bond between the carbon atoms?

In the 𝜎 bond the electron pair occupies the space between the carbon atoms. The second bond must
therefore result from sharing an electron pair in the space above and below the 𝜎 bond.

This type of bond can be formed using the 2p orbital perpendicular to the sp2 hybrid orbitals on each carbon
atom.

Pi () bond: Parallel p orbitals share an electron pair occupying the space above and below
the  bond

Figure 9.12 | A carbon–carbon double bond consists of a s bond and a p bond. In the s bond the
shared electrons occupy the space directly between the atoms. The p bond is formed from the
unhybridized p orbitals on the two carbon atoms. In a p bond the shared electron pair
occupies the space above and below a line joining the atoms.
𝝈 bonds are formed from orbitals whose lobes point toward each other
𝝅 bonds result from parallel orbitals.

A double bond always consists of one σ bond and one π bond.

The carbon atoms use sp2 hybrid orbitals to form the 𝝈 bonds to the hydrogen atoms and to each
other, and they use 𝝅 orbitals to form the 𝜋 bond with each other.

Figure 9.13 | (a) The orbitals used to form the bonds in ethylene. (b) The
Lewis structure for ethylene.
Example
Describe the bonding in the BF3 molecule using the localized electron model.

Solution

This requires a trigonal planar arrangement with bond angles of 120 degrees.
sp Hybridization
Another type of hybridization occurs in carbon dioxide, which has the following
Lewis structure:

In the CO2 molecule, the carbon atom has two effective pairs that will be arranged at an angle
of 180 degrees. We therefore need a pair of atomic orbitals oriented in opposite directions.
This requires a new type of hybridization, since neither sp3 nor sp2 hybrid orbitals will fit this
case. To obtain two hybrid orbitals arranged at 180 degrees requires sp hybridization,
involving one s orbital and one p orbital.

Figure 9.14 | When one s orbital and one p orbital are hybridized, a set of two sp orbitals oriented at 180 degrees results.
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 Two effective pairs around an atom will always require sp hybridization of that atom.
These sp hybrid orbitals are used to form the s bonds between the carbon and the oxygen atoms.
Two 2p orbitals remain unchanged on the sp hybridized carbon. These are used to form the p bonds with the
oxygen atoms.

Figure 9.16 | The orbital energy-level diagram for the

Figure 9.15 | The hybrid orbitals in the CO 2 molecule. formation of sp hybrid orbitals on carbon.

In the CO2 molecule, each oxygen atom* has three effective pairs around it, requiring a trigonal planar
arrangement of the pairs. Since a trigonal set of hybrid orbitals requires sp2 hybridization, each oxygen atom is
sp2 hybridized. One p orbital on each oxygen is unchanged and is used for the p bond with the carbon atom.
The sp orbitals on carbon form s bonds with the sp2 orbitals on the two oxygen atoms. The remaining sp2 orbitals
on the oxygen atoms hold lone pairs. The p bonds between the carbon atom and each oxygen atom are formed by
the overlap of parallel 2p orbitals. The sp hybridized carbon atom has two unhybridized p orbitals.

Each of these p orbitals is used to form a p bond with an oxygen atom.

Figure 9.17 | The orbitals of an

sp hybridized carbon atom.

Figure 9.18 | The orbital arrangement for an sp2

hybridized oxygen atom
Note that this picture of the bonding neatly explains the arrangement of electrons
predicted by the Lewis structure.

Figure 9.19 | (a) The orbitals used to form the bonds in carbon dioxide.
Note that the carbon–oxygen double bonds each consist of one s bond and
one p bond. (b) The Lewis structure for carbon dioxide.
Another molecule whose bonding can be described by sp hybridization is acetylene (C2H2), which has the
systematic name ethyne. The Lewis structure for acetylene is

Because the triple bond counts as one effective repulsive unit, each carbon has two effective pairs, which
requires a linear arrangement. Thus each carbon atom requires sp hybridization, leaving two unchanged p
orbitals.

One of the oppositely oriented, sp orbitals is used to form a bond to the hydrogen atom; the other sp
orbital overlaps with the similar sp orbital on the other carbon to form the sigma bond.

The two pi bonds are formed from the overlap of the two p orbitals on each carbon. This accounts for the
triple bond (one sigma and two pi bonds) in acetylene.
 The Localized Electron Model II
Example
Describe the bonding in the N2 molecule.

Solution
The Lewis structure for the nitrogen molecule is

Each nitrogen atom is surrounded by two effective pairs.

This gives a linear arrangement (180 degrees) requiring a pair of oppositely directed orbitals.

Nitrogen's energy levels

 This situation requires sp hybridization. Each nitrogen atom in the nitrogen molecule has two sp hybrid
orbitals and two unchanged p orbitals. The sp orbitals are used to form the s bond between the nitrogen
atoms and to hold lone pairs. The p orbitals are used to form the two p bonds; each pair of overlapping parallel
p orbitals holds one electron pair. Such bonding accounts for the electron arrangement given by the Lewis
structure. The triple bond consists of a s bond (overlap of two sp orbitals) and two p bonds (each one from an
overlap of two p orbitals). In addition, a lone pair occupies a sp orbital on each nitrogen atom.

Figure 9.20 | (a) An sp hybridized nitrogen atom. There are two sp hybrid orbitals and two unhybridized p orbitals. (b) The s bond in the N2 molecule. (c) The
two p bonds in N2 are formed when electron pairs are shared between two sets of parallel p orbitals. (d) The total bonding picture for N 2.
The Localized Electron Model: A Summary

Figure 9.24 | The relationship of the number of effective pairs, them

spatial arrangement, and the hybrid orbital set required.
9.2 The Molecular Orbital Model

Like atomic orbitals, but for molecules.

Just as atomic orbitals are solutions to the quantum mechanical treatment of atoms, molecular orbitals
(MOs) are solutions to the molecular problem. Molecular orbitals have many of the same characteristics as
atomic orbitals. Two of the most important are:

1- Can hold two electrons with opposite spins.

2- The square of the molecular orbital wave function indicates electron probability.
 The first step is to obtain the hydrogen molecule’s orbitals, a process that is greatly simplified if we assume
that the molecular orbitals can be constructed from the hydrogen 1s atomic orbitals.

When the quantum mechanical equations for the hydrogen molecule are solved, two molecular orbitals
result, which can be represented as

where 1sA and 1sB represent the 1s orbitals from the two separated hydrogen atoms.

Figure 9.25 | The combination of hydrogen 1s atomic orbitals to form MOs. The phases of the orbitals are shown by signs inside the boundary surfaces. When
the orbitals are added, the matching phases produce constructive interference, which gives enhanced electron probability between the nuclei. This results in a
bonding molecular orbital. When one orbital is subtracted from the other, destructive interference occurs between the opposite phases, leading to a node
between the nuclei. This is an antibonding MO.
The orbital properties of most interest are size, shape (described by the electron probability distribution),
and energy. from the hydrogen molecular orbitals, can note several important points:

1. The electron probability of both molecular orbitals is centered along the line passing through the two nuclei.
For MO1 the greatest electron probability is between the nuclei, and for MO2 it is on either side of the nuclei.
This type of electron distribution is described as sigma (𝜎 ), as in the localized electron model. Accordingly, we
refer to MO1 and MO2 as sigma (𝜎) molecular orbitals.

2. In the molecule only the molecular orbitals are available for occupation by electrons. The 1s atomic
orbitals of the hydrogen atoms no longer exist, because the H2 molecule—a new entity—has its own set of
new orbitals.

Figure 9.26 | (a) The MO energy level diagram for the H2 molecule.(b) The shapes of the MOs are obtained by
squaring the wave functions for MO 1 and MO2. The positions of the nuclei are indicated by •
3. MO1 is lower in energy than the 1s orbitals of free hydrogen atoms, while MO2 is higher in energy than the 1s
orbitals.

If the two electrons (one from each hydrogen atom) occupy the lower-energy MO1, they will have lower energy
than they do in the two separate hydrogen atoms. This situation is favorable to bonding, or probonding.

If the two electrons were forced to occupy the higher-energy MO2, they would be antibonding. In this case, these
electrons would have lower energy in the separated atoms than in the molecule, and the separated state would
be favored.

Since the lower-energy MO1 is available, the two electrons occupy that MO and the molecule is stable.
The molecular orbitals of the hydrogen molecule fall into two classes: bonding and antibonding.

A bonding molecular orbital is lower in energy than the atomic orbitals of which it is composed. Electrons in
this type of orbital will favor the molecule; that is, they will favor bonding.

An antibonding molecular orbital is higher in energy than the atomic orbitals of which it is composed.
Electrons in this type of orbital will favor the separated atoms (they are antibonding).

Figure 9.27 | Bonding and antibonding molecular

orbitals (MOs).
4. The bonding molecular orbital in the H2 molecule shows the electrons have the greatest probability of being
between the nuclei.

On the other hand, the electron distribution for the antibonding molecular orbital is such that the electrons are
mainly outside the space between the nuclei. This type of distribution is not expected to provide any bonding
force.

Figure 9.26 | (a) The MO energy level diagram for the H2 molecule.(b) The shapes of the MOs are obtained by
squaring the wave functions for MO 1 and MO2. The positions of the nuclei are indicated by •
5. The labels on molecular orbitals indicate their symmetry (shape), the parent atomic orbitals, and
whether they are bonding or antibonding. Antibonding character is indicated by an asterisk. For the H2
molecule, both MOs have s symmetry, and both are constructed from hydrogen 1s atomic orbitals.
The molecular orbitals for H2 are therefore labeled as follows:

6. Molecular electron configurations can be written in much the same way as atomic (electron)
configurations. Since the H2 molecule has two electrons in the 𝜎1s molecular orbital, the electron
configuration is 𝜎 1s2.

7. Each molecular orbital can hold two electrons, but the spins must be opposite.

8. Orbitals are conserved. The number of molecular orbitals will always be the same as the number of
atomic orbitals used to construct them.
 Bond Order
To indicate bond strength, we use the concept of bond order.

Bond order is the difference between the number of bonding electrons and the number of antibonding
electrons divided by 2.

We divide by 2 because, from the localized electron model, we are used to thinking of bonds in terms
of pairs of electrons.

Since the H2 molecule has two bonding electrons and no antibonding electrons, the bond order is:
Larger bond order means greater bond strength.

Helium molecule (He2).

Does this model predict that this molecule will be stable?

Since the He atom has a 1s2 configuration, 1s orbitals are used to construct the molecular orbitals, and the
molecule will have four electrons. It is apparent that two electrons are raised in energy and two are lowered in
energy. Thus the bond order is zero:

This implies that the He2 molecule is not stable with respect to the two free He atoms, which agrees with the
observation that helium gas consists of individual He atoms.
9.3 Bonding in Homonuclear Diatomic Molecules

Homonuclear diatomic molecules: (those composed of two identical atoms) of elements in Period 2 of the
periodic table.
Since the lithium atom has a 1s22s1 electron configuration, we should use the Li 1s and 2s orbitals to form the
molecular orbitals of the Li2 molecule. However, the 1s orbitals on the lithium atoms are much smaller than the
2s orbitals and therefore do not overlap in space to any appreciable extent.

Thus the two electrons in each 1s orbital can be assumed to be localized and not to participate in the bonding.
To participate in molecular orbitals, atomic orbitals must overlap in space. This means that only the valence
orbitals of the atoms contribute significantly to the molecular orbitals of a molecule.

Figure 9.31 | The relative sizes of the lithium 1s and 2s atomic orbitals in Li2.
The electron configuration for Li2 (valence electrons only) is 𝜎 2s2 and the bond order is

Li2 is a stable molecule (has lower energy than two separated lithium atoms). However, this does not mean
that Li2 is the most stable form of elemental lithium. In fact, at normal temperature and pressure, lithium
exists as a solid containing many lithium atoms bound to each other.

Figure 9.32 | The molecular orbital energy-level diagram for the Li2 molecule.
 Paramagnetism
Most materials have no magnetism until they are placed in a magnetic field. However, in the presence of such a
field, magnetism of two types can be induced.

1- Paramagnetism
Causes the substance to be attracted into the inducing magnetic field.

2-Diamagnetism
Causes the substance to be repelled from the inducing magnetic field.

The sample is weighed with the electromagnet turned off and then weighed again
with the electromagnet turned on. An increase in weight when the field is turned on
indicates the sample is paramagnetic.

Studies have shown that paramagnetism is associated with unpaired electrons and
diamagnetism is associated with paired electrons. Any substance that has both paired
and unpaired electrons will exhibit a net paramagnetism, since the effect of paramagnetism
is much stronger than that of diamagnetism.

Figure 9.36 | Diagram of the kind of apparatus used to measure the paramagnetism of
a sample. A paramagnetic sample will appear heavier when the electromagnet is
turned on because the sample is attracted into the inducing magnetic field.
Figure 9.38 | The molecular orbital energy-level diagrams, bond orders, bond energies, and bond lengths
for the diatomic molecules B2 through F2. Note that for O 2 and F2 the σ2p orbital is lower in energy than the
π2p orbitals.
9.4 Bonding in Heteronuclear Diatomic Molecules
Heteronuclear (different atoms) diatomic molecules:

A special case involves molecules containing atoms adjacent to each other in the periodic table. Since the atoms
involved in such a molecule are so similar, we can use the molecular orbital diagram for homonuclear molecules.

For example, we can predict the bond order and magnetism of nitric oxide (NO) by placing its 11 valence
electrons (5 from nitrogen and 6 from oxygen) in the molecular orbital energy-level diagram.
The molecule should be paramagnetic and has a bond order of

Experimentally, nitric oxide is indeed found to be paramagnetic. Notice that this odd electron molecule is
described very naturally by the MO model. In contrast, the localized electron model, in the simple form used in
this text, cannot be used readily to treat such molecules.

Figure 9.40 | The molecular orbital energy-level diagram for the NO molecule.
We assume that orbital order is the same as that for N2. The bond order is 2.5.
 The Molecular Orbital Model I
Example
For the species O2, O2+, and O2-, give the electron configuration and the bond order for each. Which has the
strongest bond?

Solution
The O2 molecule has 12 valence electrons (6 + 6); O2+ has 11 valence electrons (6 + 6 - 1); and O2 - has 13 valence
electrons (6 + 6 + 1). We will assume that the ions can be treated using the same molecular orbital diagram as
for the neutral diatomic molecule:
The electron configuration for each species can then be taken from the diagram:

O2 = (σ2s)2 (σ2s*)2 (σ2p)2 (𝜋2p)4 (𝜋2p*)2

O2+ = (σ2s)2 (σ2s*)2 (σ2p)2 (𝜋2p)4 (𝜋2p*)1
O2- = (σ2s)2 (σ2s*)2 (σ2p)2 (𝜋2p)4 (𝜋2p*)3

The bond orders are:

Thus O2 + is expected to have the strongest bond of the three species.

 The Molecular Orbital Model III
Example
Use the molecular orbital model to predict the magnetism and bond order of the NO + and CN- ions.

Solution
The NO+ ion has 10 valence electrons (5 + 6 - 1). The CN- ion also has 10 valence electrons (4 + 5 + 1). Both
ions are therefore diamagnetic and have a bond order derived from the equation

Figure 9.41 | The molecular orbital energy-level diagram for both the NO+ and CN- ions.
9.5 Combining the Localized Electron and Molecular Orbital Models
Molecule with resonance:
It is usually a double bond that can have different positions around the molecule:
The single σ bonds remain localized.
The π bonds are said to be delocalized.
Species such as O3 and NO3- the double bond changes position in the resonance structures. Since a double
bond involves one 𝜎 and one 𝜋 bond, there is a 𝜎 bond between all bound atoms in each resonance
structure. It is really the 𝜋 bond that has different locations in the various resonance structures.

Thus for molecules that require resonance, we will use the localized electron model to describe the 𝜎 bonding
and the molecular orbital model to describe the 𝜋 bonding. This allows us to keep the bonding model as
simple as possible and yet give a more physically accurate description of such molecules.

Figure 9.44 | The resonance structures for O 3 and NO3- . Note that it is the double
bond that occupies various positions in the resonance structures.