CHAPTER 6

CHEMICAL BONDING II

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 6.1 A Magnetic Liquid: O2

Oxygen is paramagnetic.
Paramagnetic material has unpaired electrons.
Neither Lewis theory nor valence bond theory
predicts this result.

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 According to Lewis model, a chemical bond is a
shared electron pair.
According to Valence bond theory, a chemical
bond is the overlap between two half filled
atomic orbitals(AOs).
When two atoms approach each other, the
elecrons and nucleus of one interacts with the
nucleus nd electrons of the other.
We calculate the effect of these interactons on
the valence electrons.
If the energy of the system is lowered with these
interactions, a chemical bond is formed.

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 Problems with Lewis Theory
Lewis theory generally predicts trends in properties, but it
does not give good numerical predictions.
Example: bond strength and bond length

Lewis theory gives good first approximations of the bond

angles in molecules, but it usually cannot be used to get
the actual angle.

Lewis theory cannot write one correct structure for many

molecules where resonance is important.

Lewis theory often does not predict the correct magnetic

behavior of molecules.
For example, O2 is paramagnetic, although the Lewis
structure predicts it is diamagnetic.
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 6.2 Valence Bond Theory: Orbital Overlap
and the Chemical Bond

The potential energy of

the two H atoms is lowest
when they are separated
by a distance that allows
their 1s orbitals to
overlap without too much
repulsion between their
nuclei.

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 Summarizing Valence Bond Theory

The valence electrons of the atoms in a molecule reside in

quantum-mechanical atomic orbitals.

The orbitals can be the standard s, p, d, and f orbitals, or

they may be hybrid combinations of these.

A chemical bond results from the overlap of two half-filled

orbitals and spin-pairing of the two valence electrons (or
less commonly the overlap of a completely filled orbital with
an empty orbital).

The geometry of the overlapping orbitals determines the

shape of the molecule.
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 Orbital Diagram for the Formation of H2S

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 Valence Bond Theory: Main Concepts

1. The valence electrons of the atoms in a molecule reside

in quantum-mechanical atomic orbitals. The orbitals can
be the standard s, p, d, and f orbitals, or they may be
hybrid combinations of these.

2. A chemical bond results when these atomic orbitals

interact and there is a total of two electrons in the new
molecular orbital.
The electrons must be spin-paired.

3. The shape of the molecule is determined by the geometry

of the interacting orbitals.

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 Bonding with Valence Bond Theory

According to valence bond theory, bonding takes

place between atoms when their atomic or hybrid
orbitals interact.
Overlap

To interact, the orbitals must do either of the

following:
Be aligned along the axis between the atoms
Be parallel to each other and perpendicular to the
interatomic axis

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 6.3 Valence Bond Theory and Hybridization

One of the issues that arises is that the number of partially

filled or empty atomic orbitals did not predict the number of
bonds or orientation of bonds.
C = 2s22px12py12pz0 would predict two or three bonds that
are 90 apart, rather than four bonds that are 109.5 apart.

To adjust for these inconsistencies, it was postulated that

the valence atomic orbitals could hybridize before
bonding took place.
One hybridization of C is to mix all the 2s and 2p orbitals to
get four orbitals that point at the corners of a tetrahedron.

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 Unhybridized Carbon Orbitals in CH4:
Predict the Wrong Bonding and Geometry

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 Hybridization
Some atoms hybridize their orbitals to
maximize bonding.
More bonds = more full orbitals = more
stability

Hybridizing is mixing different types of

orbitals in the valence shell to make a
new set of degenerate orbitals.
sp, sp2, sp3, sp3d, sp3d2

The same type of atom can have different

types of hybridization.
C = sp, sp2, sp3

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 Hybrid Orbitals
The number of standard atomic orbitals combined = the number of
hybrid orbitals formed.
Example for carbon:
Combining one 2s atomic orbital with three 2p atomic orbitals gives
four sp3 hybrid orbitals.
H cannot hybridize.
Its valence shell only has one orbital.

The number and type of standard atomic orbitals combined

determines the shape of the hybrid orbitals.

The particular kind of hybridization that occurs is the one that yields
the lowest overall energy for the molecule.
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 sp3 Hybridization
Atom with four electron groups around it:
Tetrahedral geometry
109.5 angles between hybrid orbitals
Atom uses hybrid orbitals for all bonds and
lone pairs

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 sp2 Hybridization
Atom with three electron groups around it:
Trigonal planar system
C = trigonal planar
N = trigonal bent
120 bond angles
Flat
Atom uses hybrid orbitals for bonds and lone pairs and uses
nonhybridized p orbital for bond

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 Types of Bonds
A sigma () bond results when the interacting atomic
orbitals point along the axis connecting the two
bonding nuclei.
Either standard atomic orbitals or hybrids
s to s, p to p, hybrid to hybrid, s to hybrid, etc.

A pi () bond results when the bonding atomic orbitals

are parallel to each other and perpendicular to the axis
connecting the two bonding nuclei.
Between unhybridized parallel p orbitals

The interaction between parallel orbitals is not as

strong as between orbitals that point at each other;
therefore, bonds are stronger than bonds.
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 Sigma and Pi Bonding

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 Orbital Diagrams of Bonding
Overlap between a hybrid orbital on one atom with a hybrid or
nonhybridized orbital on another atom results in a bond.
Overlap between unhybridized p orbitals on bonded atoms
results in a bond.
Hybrid orbitals overlap to form a bond. Unhybridized p orbitals
overlap to form a bond.

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 Bond Rotation
Because the orbitals that form the bond point along the
internuclear axis, rotation around that bond does not require
breaking the interaction between the orbitals.

But the orbitals that form the bond interact above and
below the internuclear axis, so rotation around the axis
requires the breaking of the interaction between the orbitals

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 Cis & Trans Isomers of 1,2-Dichloroethane

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 sp Hybridization
Atom with two electron groups:
Linear shape
180 bond angle
Atom uses hybrid orbitals for bonds or lone pairs and uses
nonhybridized p orbitals for bonds.

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 Formation of sp Hybrid Orbital

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 Formation of sp Hybrid Orbital in Ethyne

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 sp3d Hybridized Orbital
Atom with five electron
groups around it:
Trigonal bipyramidal
electron geometry
Seesaw, T-shaped,
linear
120 and 90 bond
angles

Use empty d orbitals from

valence shell.

d orbitalsused to make
bonds

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 sp3d Hybridized Orbital

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 sp3d2 Hybridization
Atom with six electron
groups around it:
Octahedral electron
geometry
Square pyramidal,
square planar
90 bond angles
Use empty d orbitals
from valence shell to
form hybrid
d orbitalsused to
make bonds
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 sp3d2 Hybridized Orbital

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 Predicting Hybridization and Bonding
Scheme
1. Start by drawing the Lewis structure.
2. Use VSEPR theory to predict the electron group
geometry around each central atom.
3. Use Table 6.1 to select the hybridization scheme
that matches the electron group geometry.
4. Sketch the atomic and hybrid orbitals on the atoms
in the molecule, showing overlap of the
appropriate orbitals.
5. Label the bonds as or .

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 Practice Problem on Hybridization
Example 6.1 Hybridization and Bonding Scheme
Write a hybridization and bonding scheme for bromine trifluoride, BrF3.

Procedure For
Hybridization and Bonding Scheme

Solution
Step 1 Draw the Lewis structure for the molecule. BrF3 has 28 valence electrons and the following
Lewis structure:

Step 2 Apply VSEPR theory to predict the electron The bromine atom has five electron groups and
geometry about the central atom (or interior therefore has a trigonal bipyramidal electron
atoms). geometry.

Step 3 Select the correct hybridization for the central A trigonal bipyramidal electron geometry
atom (or interior atoms) based on the electron corresponds to sp3d hybridization.
geometry (refer to Table 6.1).

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 Practice Problem on Hybridization
Example 6.1 Hybridization and Bonding Scheme
Continued

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 Practice Problem on Hybridization
Example 6.1 Hybridization and Bonding Scheme
Continued

Step 4 Sketch the molecule, beginning with the central

atom and its orbitals. Show overlap with the
appropriate orbitals on the terminal atoms.

Step 5 Label all bonds using the or notation followed

by the type of overlapping orbitals.

For Practice 6.1

Write a hybridization and bonding scheme for XeF4.

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 Practice Problem on Hybridization
Example 6.2 Hybridization and Bonding Scheme
Write a hybridization and bonding scheme for acetaldehyde.

Procedure For
Hybridization and Bonding Scheme

Solution
Step 1 Draw the Lewis structure for the molecule. Acetaldehyde has 18 valence electrons and the
following Lewis structure:

Step 2 Apply VSEPR theory to predict the electron The leftmost carbon atom has four electron groups
geometry about the central atom (or interior and a tetrahedral electron geometry. The rightmost
atoms). carbon atom has three electron groups and a trigonal
planar geometry.

Step 3 Select the correct hybridization for the central The leftmost carbon atom is sp3 hybridized, and the
atom (or interior atoms) based on the electron rightmost carbon atom is sp2 hybridized.
geometry (refer to Table 6.1).

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 Practice Problem on Hybridization
Example 6.2 Hybridization and Bonding Scheme
Continued

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 Practice Problem on Hybridization
Example 6.2 Hybridization and Bonding Scheme
Continued

Step 4 Sketch the molecule, beginning with the central

atom and its orbitals. Show overlap with the
appropriate orbitals on the terminal atoms.

Step 5 Label all bonds using the or notation followed

by the type of overlapping orbitals.

For Practice 6.2

Write a hybridization and bonding scheme for HCN.

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 Practice Problem on Hybridization
Example 6.3 Hybridization and Bonding Scheme
Apply valence bond theory to write a hybridization and bonding scheme for ethene, H2C CH2.

Solution
Step 1 Draw the Lewis structure for the molecule.

Step 2 Apply VSEPR theory to predict the electron The molecule has two interior atoms. Since each
geometry about the central atom (or interior atom has three electron groups (one double bond
atoms). and two single bonds), the electron geometry about
each atom is trigonal planar.

Step 3 Select the correct hybridization for the central A trigonal planar geometry corresponds to sp2
atom (or interior atoms) based on the electron hybridization.
geometry (refer to Table 6.1).

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 Practice Problem on Hybridization
Example 6.3 Hybridization and Bonding Scheme
Continued

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 Practice Problem on Hybridization
Example 6.3 Hybridization and Bonding Scheme
Continued

Step 4 Sketch the molecule, beginning with the central

atom and its orbitals. Show overlap with the
appropriate orbitals on the terminal atoms.

Step 5 Label all bonds using the or notation followed

by the type of overlapping orbitals.

For Practice 6.3

Apply valence bond theory to write a hybridization and bonding scheme for CO 2.

For More Practice 6.3

What is the hybridization of the central iodine atom in I3?

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 Problems with Valence Bond (VB) Theory

VB theory predicts many properties better than

Lewis theory.
Bonding schemes, bond strengths, bond lengths, bond
rigidity

However, there are still many properties of

molecules it doesnt predict perfectly.
Magnetic behavior of O2

In addition, VB theory presumes the electrons are

localized in orbitals on the atoms in the molecule
it doesnt account for delocalization.
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 6.4 Molecular Orbital (MO) Theory: Electron
Delocalization
In MO theory:
Applies Schrdingers wave equation to the molecule to
calculate a set of molecular orbitals
The equation solution is estimated.
The estimated solution is evaluated and adjusted until the
energy of the orbital is minimized.

In this treatment, the electrons belong to the whole

molecule, so the orbitals belong to the whole
molecule.
Delocalization

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 LCAO: Linear Combination of Atomic
Orbitals
The simplest guess starts
with the atomic orbitals of
the atoms adding together
to make molecular orbitals;
this is called the linear
combination of atomic
orbitals (LCAO) method.
Weighted sum

Because the orbitals are

wave functions, the waves
can combine either
constructively or
destructively.

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 Molecular Orbitals

When the wave functions combine constructively, the

resulting molecular orbital has less energy than the
original atomic orbitals
Called a bonding molecular orbital
Designated: ,
Most of the electron density between the nuclei

When the wave functions combine destructively, the

resulting molecular orbital has more energy than the
original atomic orbital.
Called an antibonding molecular orbital
Designated: *, *
Most of the electron density outside the internuclear axis
Nodes between nuclei
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 Interaction of 1s Orbitals

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 Molecular Orbital Theory

Electrons in bonding MOs are stabilizing.

Lower energy than the atomic orbitals

Electrons in antibonding MOs are destabilizing.

Higher in energy than atomic orbitals
Electron density located outside the internuclear axis
Electrons in antibonding orbitals cancel stability gained
by electrons in bonding orbitals.

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 MO and Properties

Bond order = one-half of the difference between number of

electrons in bonding and antibonding orbitals
Only need to consider valence electrons
May be a fraction
Higher bond order = stronger and shorter bonds
If bond order = 0, then the bond is unstable compared to
individual atoms and no bond will form.

A substance will be paramagnetic if its MO diagram has

unpaired electrons.
If all electrons are paired, it is diamagnetic.

Bond order = (# Bonding Electrons # Antibonding Electrons)

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 Bond order = (# Bonding Electrons # Antibonding Electrons)

Bond Order H2 = (2 0) = 1

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 Why Doesnt the Molecule He2 Exist?

Bond order = (# Bonding Electrons # Antibonding Electrons)

Bond Order He2 = (2 2) = 0

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 Why Does the Molecule He2+ Exist?

Bond order = (# Bonding Electrons # Antibonding Electrons)

Bond Order He2+ = (2 1) =

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 Summarizing LCAOMO Theory
Molecular orbitals (MOs) are a linear combination of atomic orbitals (AOs).
The total number of MOs formed from a particular set of AOs always
equals the number of AOs in the set.

When two AOs combine to form two MOs, one MO is lower in energy (the
bonding MO) and the other is higher in energy (the antibonding MO).

When assigning the electrons of a molecule to MOs, we fill the lowest energy
MOs first with a maximum of two spin-paired electrons per orbital.

When assigning electrons to two MOs of the same energy, Hunds rule is
followed to fill the orbitals singly first, with parallel spins, before pairing.

The bond order in a diatomic molecule is the number of electrons in bonding

MOs minus the number in antibonding MOs divided by two.
Stable bonds require a positive bond order (more electrons in bonding
MOs than in antibonding MOs).

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 Practice Problem on Bond Order
Example 6.4 Bond Order
Apply molecular orbital theory to predict the bond order in H2 . Is the H2 bond a stronger or weaker bond than
the H2 bond?

Solution
The H2 ion has three electrons. Assign the three electrons to the molecular orbitals, filling lower-energy orbitals first
and proceeding to higher-energy orbitals.

Calculate the bond order by subtracting the number of electrons in antibonding orbitals from the number in bonding
orbitals and dividing the result by two.

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 Practice Problem on Bond Order
Example 6.4 Bond Order
Continued

Since the bond order is positive, H2 should be stable. However, the bond order of H2 is lower than the bond order of
H2 (which is 1); therefore, the bond in H2 is weaker than in H2.

For Practice 6.4

Apply molecular orbital theory to predict the bond order in H2+. Is the H2+ bond a stronger or weaker bond than the
H2 bond?

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 Second-Period Homonuclear Diatomic
Molecules

Li2 molecule Be2 molecule

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 Interaction of p Orbitals

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 Interaction of p Orbitals

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 Molecular Orbital Energy Ordering

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 Molecular Orbital Energy Diagrams for Second-
Period-p-Block Homonuclear Diatomic Molecules

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 Practice Problem on Molecular Orbital Theory
Example 6.5 Molecular Orbital Theory
Draw an MO energy diagram and determine the bond order for the N2 ion. Do you expect the bond in the N2 ion to be
stronger or weaker than the bond in the N2 molecule? Is N2 diamagnetic or paramagnetic?

Solution
Write an energy-level diagram for the molecular orbitals in N2 . Use the energy ordering for N2.

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 Practice Problem on Molecular Orbital Theory
Example 6.5 Molecular Orbital Theory
Continued

The N2 ion has 11 valence electrons (five for each nitrogen atom plus one for the negative charge). Assign the
electrons to the molecular orbitals beginning with the lowest energy orbitals and following Hunds rule.

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