Chapter 11

Theories of Covalent Bonding

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VALENCE BOND THEORY:

 DEVELOPED BY LINUS PAULING, who

received the Nobel Prize in 1954 for his
work
 A view of chemical bonding in which bonds
arise from the overlap of atomic orbitals on
two atoms to give a bonding orbital of
electrons localized between the bonded
atoms
 RULE: Realize that Valence Bond Theory
and all the others don't explain everything
 The Central Themes of VB Theory

Basic Principle

A covalent bond forms when the orbitals of two atoms overlap

and the overlap region, which is between the nuclei, is
occupied by a pair of electrons.

(The two wave functions are in phase so the amplitude increases

between the nuclei.)
 The Central Themes of VB Theory

Themes

A set of overlapping orbitals has a maximum of two electrons

that must have opposite spins.
The greater the orbital overlap, the stronger (more stable) the
bond.
The valence atomic orbitals in a molecule are different from
those in isolated atoms.
There is a hybridization of atomic orbitals to form molecular
orbitals.
 Figure 11.1 Orbital overlap and spin pairing in three
diatomic molecules.

Hydrogen, H2

Hydrogen fluoride, HF
Regular atomic orbital
overlap can explain these
bonds.

Fluorine, F2
VALENCE BOND THEORY:
Ha to Hb: 1sa to 1sb overlap radius = 74 pm

As overlap increases, strength of bond increases -

both electrons are mutually attracted to both
atomic nuclei.
At optimum distance between nuclei with
maximum overlap, a sigma s bond (strong
primary bond) forms. Max electron density is
along the axis of the bond

Ha to Fb: 1sa to 2pb direct overlap or s bond

VALENCE BOND THEORY:

F to F: the picture looks like a 2p orbital

on one F is overlapping with a 2p
orbital on the other F atom, but actually
each F is sp3 hybridized & electrons are
localized between two atomic nuclei
VALENCE BOND THEORY:

We cannot use this direct overlap picture

for CH4’s bonding. The 2s and the three
2p orbitals on each C do not fit into the
CH4 molecule's 109o bond angles, since
the 2p orbitals are at 90° to each other

Valence Bond Theory states that HYBRID

orbitals of the outermost orbitals on an
atom are formed from the atoms’ atomic
orbitals
 Hybrid Orbitals

Key Points

The number of hybrid orbitals obtained equals the number of

atomic orbitals mixed.
The type of hybrid orbitals obtained varies with the types of
atomic orbitals mixed.

Types of Hybrid Orbitals

sp sp2 sp3 sp3d sp3d2

 Figure 11.2 The sp hybrid orbitals in gaseous BeCl2.

atomic
orbitals
on Be
hybrid
orbitals

You have to
know how to
draw this
energy hybrid
formation.

orbital box diagrams

Figure 11.2 The sp hybrid orbitals in gaseous BeCl2(continued).

orbital box diagrams with orbital contours

Figure 11.3 The sp2 hybrid orbitals in BF3.

You have to know

how to draw this
energy hybrid
formation.

Note the three sigma

bonds formed between B
and each F.
 Figure 11.4 The sp3 hybrid orbitals in CH4.

You have to know how to draw

this energy hybrid formation.
Figure 11.5 The sp3 hybrid orbitals in NH3.

You have to know how to draw

this energy hybrid formation.
 Figure 11.5 continued The sp3 hybrid orbitals in H2O.

You have to know how to

draw this energy hybrid
formation.
VALENCE BOND THEORY

Expanded Valence Shells have hybrid

orbitals using s, p & d atomic orbitals.
Example: PCl5 P: [Ne]3s23p3

dsp3 hybridization results in 5 s bonds

and trigonal bipyramidal geometry

(You can write these as dsp3 or sp3d)

Figure 11.6 The sp3d hybrid orbitals in PCl5.

You have to know

how to draw this
energy hybrid
formation.
 Figure 11.7 The sp3d2 hybrid orbitals in SF6.

You have to know how to draw this

energy hybrid formation.
Figure 11.8
The conceptual steps from molecular formula to the
hybrid orbitals used in bonding.

Step 1 Step 2 Step 3

Molecular
shape and e-
Molecular Lewis Hybrid
formula structure group
orbitals
arrangement
Figure 10.1 Figure 10.12 Table 11.1
SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

PROBLEM: Use partial orbital diagrams to describe mixing of the atomic

orbitals of the central atom leads to hybrid orbitals in each of
the following:
(a) Methanol, CH3OH (b) Sulfur tetrafluoride, SF4

SOLUTION: The groups around C are

(a) CH3OH arranged as a tetrahedron.

H
C O
H H H
O also has a tetrahedral
arrangement with 2 nonbonding
e- pairs.
SAMPLE PROBLEM 11.1 Postulating Hybrid Orbitals in a Molecule

continued

2p 2p
sp3 sp3
hybridized hybridized
2s single C atom 2s single O atom
C atom O atom

(b) SF4 has a seesaw shape with 4 bonding and 1 nonbonding e- pairs.
F
F S
F 3d 3d
F

3p
sp3d
hybridized
S atom
3s S atom
VALENCE BOND THEORY

There can be more than one central

atom, and each has its own
hybridization and geometry
C2H6 and H2O2 and CH3COOH
C2H6: both C's are sp3 hybridized and
can rotate around axis of bond.
H2O2: both O's are sp3 , etc.
 Figure 11.9 The s bonds in ethane(C2H6).
both C are sp3 hybridized s-sp3 overlaps to s bonds

sp3-sp3 overlap to form a s bond

relatively even
distribution of electron
density over all s
bonds
VALENCE BOND THEORY:
Multiple Bonds
H2CO: the Lewis structures shows a double bond
between C and O, but we know it does not have
twice the bond dissociation energy of a single
C-O bond
Pauling proposed that there was only one sigma s
bond between any two atoms, and the other
multiples were weaker pi p bonds
If there are only 3 s bonds around this carbon, it
can't be sp3 hybridized - instead we have sp2
hybrid orbitals
sp2 hybridization results in only 3 s bonds, and trig
planar geometry, with 120° angles
p bond is a sideways or parallel overlap of the p
atomic orbitals rather than the direct overlap of
s bonds
Figure 11.10 The s and p bonds in ethylene (C2H4).

overlap in one position - s

p overlap - p

electron density
Proper name is ethene.
VALENCE BOND THEORY

Look at acetylene: its geometry is

linear. C is forming a triple bond to
another C and a single bond to H, so
that's only two s bonds
Therefore sp hybridization results in
only 2 s bonds, and linear geometry
There are 2 p bonds from the parallel
overlap of the 2p orbitals remaining on
both C's
Figure 11.11 The s and p bonds in acetylene (C2H2).

overlap in one position - s

p overlap - p
 SAMPLE PROBLEM 11.2 Describing the Bond in Molecules

PROBLEM: Describe the types of bonds and orbitals in acetone, (CH3)2CO.

PLAN: Use the Lewis structures to ascertain the arrangement of groups and
shape at each central atom. Postulate the hybrid orbitals taking note of
the multiple bonds and their orbital overlaps.

SOLUTION: sp2 sp2

sp3 hybridized
O
O
O sp2
H H
sp3 hybridized H C H sp 2
sp3
C C
H sp3 2
H H
H sp2 C sp C sp3 C
C H
sp2 hybridized 3 sp3 H3 C CH3
3
sp H sp 3H
H sp3 sp

pbond
sbonds
 H2CO hybrid orbitals and sigma and pi bond formation

Remember the C=C

double bond has
sigman and pi bonds.

The C has sigma bonds from its hybrid orbitals to the two H’s and the O.
The leftover p orbitals will form the pi bond.
 Figure 11.13 from 4th ed.

Restricted rotation of p-bonded molecules in C2H2Cl2.

CIS TRANS

This cis/trans arrangement will be important in chem 2, organic chem and

biology!
VALENCE BOND THEORY:
RESONANCE
Resonance Structures and p Bonding:
p resonance structures involve an
electron pair used alternately as a p
bond or a LP
Ozone: O3 O==O--O or O--O==O
All are sp2, trig planar, each has 3 sp2
orbitals and a p orbital remaining.
VALENCE BOND THEORY

Benzene: C6H6 has carbons with sp2 hybrids

and 120o angles, each C has 2 s bonds to
other C's, 1 s bond to H, and 1 p bond
electron available
Get "ring" of delocalized p e-s

SUMMARY: draw the Lewis structure;

determine arrangement of electron pairs
using VSEPR, specify the hybrid orbitals to
accommodate the e- pairs
Benzene sigma bond formation between C’s and C-Hs

The leftover p orbitals will form

alternating pi bonds as shown in
sketch.
MOLECULAR ORBITAL
THEORY:

- explains why H2 forms easily and He2 does not

- is an alternate way of viewing e- orbitals in molecules
where pure s and pure p orbitals combine to produce
orbitals that are delocalized over the molecule
- they can have different energies and are assigned
electrons just like we do in an atom - Pauli exclusion
principle and Hund's rule included
Pauling's Valence Bond Theory does not explain
everything
MO Theory doesn't either, but it does correctly predict the
electronic structure of certain molecules that do not
follow Lewis's approach, including the paramagnetism
of certain molecules, like O2
 The Central Themes of MO Theory

A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular orbitals.
Atomic wave functions are summed to obtain molecular wave
functions. The number of molecular orbitals produced is always = #
of atomic orbitals brought by the combining atoms (only orbitals on
different atoms are combined).
If wave functions reinforce each other, a bonding MO is formed
(region of high electron density exists between the nuclei).
If wave functions cancel each other, an antibonding MO is formed
(a node of zero electron density occurs between the nuclei).

The electrons of the molecule are placed in bonding or antibonding

orbitals of successively higher energy (just like Hund's rule).

Atomic orbitals combine most effectively with orbitals of the same type
and similar energy (s w/s, n=2 w/ n=2)
Figure 11.13
An analogy between light waves and atomic wave functions.

Amplitudes of wave
functions added

Amplitudes of
wave functions
subtracted.
Figure 11.14 Contours and energies of the bonding and antibonding
molecular orbitals (MOs) in H2.

The bonding MO is lower in energy and the antibonding MO is higher in

energy than the AOs that combined to form them.
MOLECULAR ORBITAL
THEORY
BOND ORDER: the number of bonding e-
pairs shared by 2 atoms in a molecule
Fractional bond orders are possible in MO
Theory!
Silberberg method:
B.O. = ½(# of e- in bonding orbitals - # of e-
in antibonding orbitals)
Figure 11.15 The MO diagram for H2.
Filling molecular orbitals with electrons follows the
same concept as filling atomic orbitals.

s*1s
Energy

1s 1s

H2 bond order
= 1/2(2-0) = 1
s1s

AO MO AO
of H of H2 of H
 Figure 11.16 MO diagram for He2+ and He2.

s*1s s*1s
Energy

Energy
1s 1s 1s 1s

s1s s1s
AO of MO of AO of AO of MO of AO of
He He+ He+ He He2 He

He2+ bond order = 1/2 He2 bond order = 0

SAMPLE PROBLEM 11.3 Predicting Stability of Species Using MO Diagrams

PROBLEM: Use MO diagrams to predict whether H2+ and H2- exist.

Determine their bond orders and electron configurations.

SOLUTION:
bond order bond order
= 1/2(1-0) = 1/2(2-1)
= 1/2 = 1/2
s s
+
H2 does exist H2- does exist

1s 1s 1s 1s

AO of H AO of H AO of H-
AO of H
s s
MO of H2+ MO of H2-
 Figure 11.17 Bonding in s-block homonuclear diatomic molecules.

s*2s
Energy

s*2s

2s 2s 2s
2s

s2s s2s

Li2 Be2
Li2 bond order = 1 Be2 bond order = 0
Figure 11.18
Contours and energies of s and p MOs through
combinations of 2p atomic orbitals.

Or the pz orbitals
 Figure 11.19 Relative MO energy levels for Period 2 homonuclear
diatomic molecules.

with 2s-2p
without 2s-2p mixing
mixing

Memorize
this!

MO energy levels
MO energy levels
for O2, F2, and Ne2
for B2, C2, and N2
 Figure 11.20

MO occupancy
and molecular
properties for B2
through Ne2
Figure 11.21

The paramagnetic
properties of O2
 SAMPLE PROBLEM 11.4 Using MO Theory to Explain Bond Properties

PROBLEM: As the following data show, removing an electron from N2 forms

an ion with a weaker, longer bond than in the parent molecules,
whereas the ion formed from O2 has a stronger, shorter bond:
N2 N2+ O2 O 2+

Bond energy (kJ/mol) 945 841 498 623

Bond length (pm) 110 112 121 112

Explain these facts with diagrams that show the sequence and occupancy of MOs.

SOLUTION:

N2 has 10 valence electrons, so N2+ has 9.

O2 has 12 valence electrons, so O2+ has 11.
SAMPLE PROBLEM 11.4 Using MO Theory to Explain Bond Properties

continued
N2 N2+ O2 O2 +

s2p s2p antibonding

e- lost
bonding e- lost p2p p2p

s2p s2p

p2p p2p

s2s s2s

s2s s2s

1/2(8-2)=3 1/2(7-2)=2.5 bond 1/2(8-4)=2 1/2(8-3)=2.5

orders
MO Theory Practice
1. Draw the bonding and antibonding
molecular orbitals for H2.
2. Do Valence Bond Theory (hybridization)
and MO Theory for both O2 and O22-.
Which theory works better to explain the
molecule and ion?
3. For N2, N2+ and N2- compare
a. Magnetic character
b. Net number of p bonds
c. Bond Order
d. Bond length
e. Bond strength
Answers

1. See picture in text.

2. VB Theory shows O2 as sp2 hybridized with
one s bond and one p bond. There are two
lone pairs on each O. O22- has one s bond,
and each O has three lone pairs. MO
Theory shows a bond order of 2 for O2 and
that it is paramagnetic. MO Theory shows a
bond order of 1 for O22- and diamagnetic.
But MO Theory fits the real data that O2 is
paramagnetic.
Answers con’t

N2 N2+ N2-

a. Diamag Paramag Paramag

b. 2 1.5 1.5

c. 3 2.5 2.5

d. Short Longer Longer

e. Strong Weaker Weaker