110 Chemistry in Quantitative Language

Each has a tetrahedral geometry. CF2 Cl2 has two polar C–F bonds (χ = 1.5) and
two C–Cl bonds (χ = 0.5). Therefore, the C–F bonds are more polar than the C–Cl
bonds. The vector components do not cancel; hence, the molecule is polar. Although
CCl4 contains four polar C–Cl bonds, the molecule is symmetrical and the bond vectors
cancel, making CCl4 nonpolar.
(b) SO2 and SO3
The Lewis structures and vector diagrams of SO2 and SO3 are

O O
S S
O O O O and S S
O O O O

Both contain polar S–O bonds (χ = 1.0). The molecular geometry of SO2 is bent and
is asymmetrical hence SO2 is polar. The molecular shape for SO3 is trigonal planar. All
groups attached to the central S atom are the same, and are symmetrical, so the bond
vectors cancel, making SO3 nonpolar.

10.4 Valence Bond Theory

Valence Bond Theory (VBT), originally proposed by Heitler and London, uses quantum
mechanics to explain how valence electrons of different atoms combine to form a molecule.
The primary focus of this theory is on the formation of individual bonds from the atomic orbitals
of the participating atoms composing the molecule.

10.4.1 Postulates of valence bond theory

The basic assumptions of this theory are:

• A covalent bond is formed by the overlap of two atomic orbitals.

• Only atomic orbitals with unpaired electrons are involved in covalent bond formation.
• If the electrons present in the atomic orbitals have parallel spins, no bond will result, and
no molecule will be formed.
• If the atomic orbitals have more than one unpaired electron, more than one bond can be
formed.
• A covalent bond is formed by the overlap of half-filled valence atomic orbitals. The inner
electrons do not play any role in the bond formation.
• During the formation of a covalent bond, only the valence electrons from each bonded atom
participate. The other electrons remain unaffected.
• The strength of a covalent bond depends upon the degree of orbital overlap—the greater
the overlap, the greater the strength of the resulting covalent bond.
• A covalent bond is directional. The bond will lie along the direction of orbital overlap.
• Based on the nature of the overlap, two types of covalent bonds are possible: sigma (σ )
bonds and pi (π ) bonds. A σ -bond results from the end-to-end or axial overlap of atomic
orbitals, while a π -bond arises from parallel or sideways overlap.
 Chemical Bonding 2: Modern Theories of Chemical Bonding 111

10.5 Valence Bond Theory: Types of Overlap

10.5.1 Sigma (σ ) bond

A σ -bond is a molecular orbital formed by the end-to-end overlap of atomic orbitals. It is
cylindrically symmetrical and is the strongest type of bond. All single bonds are σ -bonds. A
σ -bond can occur between two s-orbitals, s and p orbitals, or two p orbitals. These bonds are
then termed σ S–S overlapping, σ S–P overlapping, and σ P–P overlapping, as illustrated below.

s - orbital s - orbital s - s overlapping

s - orbital p - orbital sp - overlapping

+
p - orbital p - orbital p - p overlapping

10.5.2 Pi (π ) bond
A π -bond results from the sidewise or parallel overlap of p orbitals on adjacent atoms. The
electron density in a π -bond is distributed above and below the inter-nuclear axis.

+
or

p - orbital p - orbital p - p overlapping

10.5.3 The strength of sigma and pi bonds

A σ -bond is stronger than a π -bond, because the axial or head-on overlap which occurs in a
σ -bond is more complete than the sideways overlap in a π -bond.

• A single bond contains one σ -bond.

• A double bond contains one σ -bond and one π -bond.
• A triple bond contains one σ -bond and two π -bonds.

Since a multiple bond contains both σ -bonds and π -bonds, it is stronger than either alone.
112 Chemistry in Quantitative Language

10.6 Hybridization

The atomic overlap model proposed in the 1930s worked well to explain covalent bonding and
geometry in small molecules like H2 and HF, but it needed modification as it could not adequately
explain the geometrical shapes of polyatomic molecules such as CH4 , NH3 , and H2 O. To resolve
the discrepancy between the predicted and observed bond angles in polyatomic molecules, in
1931 Pauling introduced the concept of hybridization. Hybridization is defined as the intermixing
of two or more pure atomic orbitals with somewhat different energies (e.g. s and p orbitals)
to form new orbitals, known as hybrid orbitals, that have equal energies, identical shapes, and
symmetrical orientations in space. These new hybrid orbitals can then overlap with those in other
atoms to form σ -bonds.
To form hybrid atomic orbitals, an electron is promoted from a filled ns2 subshell to an
empty np or (n − 1)d valence orbital, followed by mixing or hybridization, to give a new set
of energetically equivalent orbitals with the proper orientation to form bonds.

10.6.1 Characteristics of hybrid orbitals

• Hybridization takes place only in orbitals of almost similar energies and belonging to the
same atom or ion. For example, a 2s orbital cannot hybridize with a 3s orbital since they
have very different energy levels.
• The number of hybrid orbitals formed is equal to the number of pure atomic orbitals used
in the hybridization process.
• The hybrid orbitals are degenerate: that is, they are always equivalent in energy and shape.
• Hybridization can take place between filled, half-filled, or empty orbitals.
• The hybrid orbitals are oriented to have the maximum space and minimum repulsion
between them, thus defining their geometry.
• The shapes and orientations of hybrid orbitals are very different from the shape of the
original atomic orbitals.
• Generally, the d orbitals are unlikely to participate in hybridization because of their large
size and high energy compared to the s and p orbitals. However, mixing of d orbitals
can take place when highly electronegative atoms are bonded to a central atom causing
a contraction in the size of the d orbitals.
• Hybridized orbitals provide more efficient overlap than pure s, p, and d orbitals due to their
fixed orientation. Therefore, they form stronger directional bonds than the pure s, p, or d
atomic orbitals.
• Hybrid orbitals overlap to form σ -bonds. Unhybridized orbitals overlap to form π -bonds.

10.6.2 Types of hybrid orbitals

Hybridization can be classified as sp3 , sp2 , sp, sp3 d, or sp3 d2 , depending on the orbitals involved
in the mixing.

10.6.2.1 sp3 hybridization—tetrahedral structure

Here, an s orbital and all three of the p orbitals mix to form four new sp3 orbitals with identical
shapes and energies, which are therefore said to be degenerate. Each sp3 hybrid orbital is used
to form a sigma bond and has 25% s and 75% p character. An sp3 hybridized atom has four
 Chemical Bonding 2: Modern Theories of Chemical Bonding 113

regions of electron density, whose mutual electron repulsion favors a tetrahedral geometry with
109.5◦ bond angles. Note that hybrid orbitals can overlap with any atomic orbital of a different
atom to form a bond. For example, in the CH4 molecule, the 2s and 2p atomic orbitals of carbon
hybridize to form four sp3 hybrid orbitals with a tetrahedral orientation. These four orbitals on
the C overlap with the 1s atomic orbitals of the hydrogen to form four CH σ -bonds as illustrated
below.

H H H H
Hybridization
Bonding

2s 2p sp3 sp3 sp3 sp3

Four sp3 hybrid
Promote orbitals on C in CH4
H
σ
σ σ
H C H
σ
109°
2s 2p
H
Unhybridized C atom
[He]2s22p2 Tetrahedron

10.6.2.2 sp2 hybridization—trigonal planar structure

In sp2 hybridization, one s and two p orbitals combine to form three new hybrid orbitals that can
each overlap with another atom’s orbitals to form σ -bonds. The new orbitals formed are called
sp2 hybrids, and the unhybridized p-orbital is used for π -bonding. The three hybrid orbitals are
directed toward the corners of an equilateral triangle and make an angle of 120◦ with one another.
Each of the hybrid orbitals formed has 33.33% s character and 66.66% p character. Molecules in
which the central atom is linked to three atoms through sp2 hybrid orbitals usually have a trigonal
planar shape. We can use BF3 as an example.
Boron has five electrons and the electronic configuration1s2 2s2 2p1 .Three of these electrons
are in the valence shell. To form bonds with three fluorine atoms, one electron in the 2s orbital
of B is excited or promoted to its 2p orbital. One 2s orbital mixes with two 2p orbitals to give
three new sp2 hybrid orbitals. One of the 2p orbitals of the boron is empty and unhybridized. The
three sp2 hybrid orbitals point to the corners of a triangle. The angle between any two of them
is 120o . Each of the three B sp2 hybrids orbital overlaps with a 2p atomic orbital of a fluorine to
form three B-F sigma bonds in BF3 .

Unhybridized
and vacant 2p
orbital F F F
Hybridization
Bonding

2s 2p sp2 sp2 sp2

Three sp2 hybrid
Promote orbitals on B in BF3
F

B
F F
2s 2p
Trigonal planar
Unhybridized B atom
[He]2s22p1
114 Chemistry in Quantitative Language

10.6.2.3 sp hybridization

In a system involving sp hybridization, the central atom’s s orbital and one of its p orbitals have
mixed to form two new sp hybrids, leaving two unhybridized p orbitals, which are used for
π -bond formation as needed. The two sp hybrid orbitals arranged linearly with a bond angle
of 180o . The unhybridized p orbitals are oriented in a plane perpendicular to the hybridized sp
orbitals. To illustrate sp hybridization, consider BeF2 . In the ground state, Be cannot form any
bonds. With appropriate energy it promotes an electron from the 2s to the 2p orbital. One s orbital
and one p orbital combine to form two sp hybrid orbitals. The two valence electrons distribute
themselves among the two sp hybrid orbitals, making it possible to form two identical Be–F
bonds. The hybridization process is illustrated below.

Unhybridized
and vacant 2p
orbitals F F
Hybridization
Bonding

2s 2p sp sp
Two sp hybrid orbitals F –Be–F
Promote on Be in BeF2 Linear Geometry

Overlap region
2s 2p
Unhybridized Be atom F Be F
[He]2s2
F 2p orbital F 2p orbital
Lobe of sp hybrid orbital

10.6.3 Hybridization and multiple bonds

Hybridization may be applied to describe covalent bonding in molecules containing double
and triple bonds. When there is more than one central atom, the bonding around each atom is
considered independently. Let us consider ethene (ethylene) and ethyne (acetylene).

10.6.3.1 Ethene, C2 H4

Ethylene, which is a planar molecule, has the following Lewis structure:

H H
C C
H H
 Chemical Bonding 2: Modern Theories of Chemical Bonding 115

Each carbon is surrounded by three electron groups. Using the VSEPR model, we would predict
a trigonal planar geometry around each carbon atom in the structure, with an H–C–H bond angle
of 120o . This geometry calls for a planar set of orbitals at angles of 120o , which the 2s and 2p
valence orbitals of carbon do not have. Thus hybrid orbitals are needed.

Unhybridized 2p
orbital used for π
bonding
Hybridization

2s 2p sp2 sp2 sp2

Three sp2 hybrid

Promote orbitals used for σ
bonding.

2s 2p
Unhybridized C atom
[He]2s22p2

After hybridization, two of the three new identical sp2 orbitals on each carbon atom overlap
with the 1s orbitals of the hydrogen to form σ -bonds. The remaining sp2 hybrid orbital on each
carbon overlaps with the sp2 hybrid orbital of the adjacent C atom to form a σ -bond. The two
unhybridized 2p orbitals of the C atoms lie perpendicular to the plane of the trigonal sp2 hybrids
and overlap sideways to form a π -bond (Figure 10.1).

(a) (b)

p-orbital p-orbital C(2p) - C(2p)

C(sp2)
C(sp2)

H H
H H
sp2 sp2
C sp2 sp2 C 2 C C
sp2 sp
H H H H

bond bond C(sp2) - C(sp2)

Figure 10.1 Hybridization of carbon orbitals in ethylene. (a) Orbitals involved in bond formation (b)
Bonding framework

10.6.3.2 Ethyne (acetylene), C2 H2

The Lewis structure of ethyne is

H C C H
116 Chemistry in Quantitative Language

Each carbon atom is surrounded by two electron groups. This requires a linear arrangement with
a bond angle of 180o , which means that both carbons are sp hybridized. Two of the carbon’s four
valence orbitals hybridize to sp orbitals, which form sigma bonds.

Unhybridized 2p
orbitals used for π
bonding
Hybridization

2s 2p sp2 sp2
Two sp hybrid
Promote orbitals used for
σ-bonding formation

2s 2p
Unhybridized C atom
[He]2s22p2

The remaining unhybridized p orbitals each contain one electron, and can overlap to form
π -bonds, as seen in Figure 10.2.

p p
p

sp sp sp sp
H1s C C C H1s

Figure 10.2 Formation of two π bonds in ethyne from the overlap of two sets of unhybridized carbon 2p
orbitals.

Example 10.6

Consider the structure of cumulene:

H H
1 2 3
C C C

H H

a. What are the geometry and hybridization of carbon atoms 1, 2, and 3?

b. Determine the total number of σ -bonds and π -bonds in the molecule.
 Chemical Bonding 2: Modern Theories of Chemical Bonding 117

Table 10.3 Common hybridization schemes

Effective Hybrid Atomic Geometrical arrangement Examples
electron orbitals orbitals used and bond angle
pairs
2 sp s,p Linear (180◦ ) BeH2 , CO2 , C2 H2 , HgCl2
3 sp2 s,p,p Trigonal planar (120◦ ) BF3 , C2 H4 , NO− 3 , CO3
2−

4 sp3 s,p,p,p Tetrahedral (109.5◦ ) CH4 , NH4 , SnCl4 , BF−

+
4
5 sp3 d s,p,p,p,d Trigonal bipyramidal (120◦ , 90◦ ) SF4 , PF5 , XeF2 , I−3 , BrF3
6 sp3 d2 s,p,p,p,d,d Octahedral (90◦ ) SF6 , [CrF6 ]3− , [Co(NH3 )6 ]3+
7 sp3 d3 s,p,p,p,d,d,d Pentagonal bipyramidal IF7

Solution

Use the VSEPR model to determine the electron groups and molecular geometry around each
carbon atom. The geometry will suggest the hybrid orbitals used.
a. C1 and C3 are identical, having three electron groups around the central atom; geometry
is trigonal planar, sp2 hybridized. Geometry about C2 is linear and so sp hybridized.
b. There are six σ -bonds and two π -bonds:

H H
σ π π σ
C C C
σ σ
σ σ
H H

10.6.4 Hybridization of elements involving d-orbitals

Elements in the third period and beyond, with more than four electron pairs, require the
involvement of the d orbitals in covalent bond formation to accommodate the expanded octet.
This is possible because the energy of the 3d orbitals is comparable to the energy of the
3s, 3p, 4s, and 4p orbitals. They can form hybrid orbitals by mixing with the appropriate
s and p orbitals. The most important hybridized orbitals in this category are described in
Table 10.3.

10.6.4.1 sp3 d hybridization

In sp3 d hybridization, one s orbital, three p and one d combine to form five sp3 d hybrid
orbitals that point to the corners of a trigonal bipyramid. PCl5 offers an example of this
hybridization.
118 Chemistry in Quantitative Language

Cl Cl Cl Cl Cl
Unhybridized 3d orbitals
Hybridization Bonding

3s 3p 3d 3d
Five sp3d hybrid orbitals CI
Promote CI
P CI
CI
CI
3s 3p 3d Trigonal bipyramidal
Unhybridized P atom
[Ne]3s23p3

The covalent bond between phosphorous and each of the five chlorine atoms is formed by the
overlap between an sp3 d hybrid orbital on phosphorous and the p orbital on chlorine.

10.6.4.2 sp3 d2 hybridization

In sp3 d2 hybridization, one s, three p and two d orbitals combine to form six sp3 d2 hybrid orbitals,
which are directed toward the corners of a regular octahedron.
The bonding in SF6 is a good example. The single 3s, three 3p, and two 3d orbitals of the sulfur
combine to give six sp3 d2 hybrid orbitals with an octahedral structure in which all bond angles
are 90o . In the process, sulfur promotes one s and one p electron to its 3d orbitals resulting in
six orbitals each containing one electron available for bonding. The resulting orbitals are shown
below:

F F F F F F
Unhybridized 3d orbitals
Hybridization Bonding

3s 3p 3d 3d
Six sp3d2 hybrid orbitals F
Promote F F
S
F F
F
3s 3p 3d Trigonal bipyramidal
Unhybridized S atom
[Ne]3s23p4

10.6.5 Predicting the hybrid orbitals used by an atom in bonding

To determine the hybrid orbitals used by an atom in a molecule, follow the same procedure used
in determining electron group geometry and molecular structure:

1. Draw the Lewis structure for the molecule or ion.

2. Determine the electron group geometry using the VSEPR model.
3. Specify the hybrid orbitals corresponding to the geometry using Table 10.3 as a guide.
 Chemical Bonding 2: Modern Theories of Chemical Bonding 119

Example 10.7

Indicate the hybridization of orbitals used by the central atom in (a) NH+ −
4 (b) PF6 .

Solution

NH+
4 PF−
6
Step 1: Draw the Lewis structure
for the molecule or ion. F
F F
–
H P
+
H N H F F
F
H
Step 2: Determine the total The central N atom has four The central P atom has six
number of electron groups electron groups. electron groups.
around the central atom.
Step 3: Determine the number All four electron groups around All six electron groups around
of bonding groups and the the central N atom are P are bonding groups.
number of lone pairs around bonding groups.
the central atom.
Step 4: Determine the electron Tetrahedral Octahedral
group geometry due to
bonding groups and lone
pairs.
Step 5: Determine the correct sp3 sp3 d2
hybridization type of the
central atom based on the
electron geometry

10.7 Limitations of Valence Bond Theory

The Valence Bond Theory has its own set of limitations. For example, it:

• Fails to explain the tetravalency of carbon.

• Offers no explanation of the colors observed for complex ions.
• Does not consider the splitting of d-orbital energy levels.
• Assumes electrons are localized to specific locations (and thus understates the importance
of resonance).
• Fails to account for various magnetic, electronic, and spectroscopic properties of metal
complexes.
• Leads to erroneous ionic and covalent structure assignments based on magnetic data.
• Is not able to account for or predict even the relative energies of different structures.