CHEM14 - (5) The Chemical Bond 2

The Chemical Bond 2
CAMPO - CHEM 14
Theories on Covalent Bonding
1. Valence Bond Theory 

a. VSEPR Theory
2. Molecular Orbital Theory
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Valence Bond Theory
- covalent bond formation is due to overlap of atomic orbitals

- electrons reside in the region of overlap of atomic orbitals
- gives a localized electron model of bonding
How does Lewis theory explain the bonds in H2 and F2?
Sharing of two electrons between the two atoms.
Bond Enthalpy Bond Length Overlap Of
H2 436.4 kJ/mol 74 pm 2 1s
F2 150.6 kJ/mol 142 pm 2 2p

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Valence Bond Theory and CH4
CH4:
Experimentally
determined: All C-H
bonds are identical
According to VBT, a covalent bond is formed from the overlap of

the valence orbital containing one e- in one atom with another
valence orbital containing one e- from another atom.
2p
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Following VBT, Carbon should only be able to form two bonds from
the overlap of two of its valence orbital containing one e- each with
two H atoms each containing a half-filled valence orbital.
2p
Unstable due to
lack of octet
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Valence Bond Theory and NH3
N – 1s22s22p3
3 H – 1s1
If the bonds form from overlap of 3 2p orbitals on nitrogen with

the 1s orbital on each hydrogen atom, what would the molecular
geometry of NH3 be?
If we use the
3 2p orbitals, we
predict bond
angle at 90o
Actual H-N-H
bond angle is
CAMPO - CHEM 14 107.3o
Atomic Orbital Hybridization
Hybridization – mixing of two or more atomic orbitals to form a

new set of hybrid orbitals.
- VBT uses concept of hybridization to supplement it
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
4. In general, two steps:
a. Excitation
b. Hybridization
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G.S. :
CH4:
E.S. :
E.S. configuration can now allow formation of four bonds, BUT

still insufficient since it can’t explain how all the C-H bonds are
identical and methane’s tetrahedral shape
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H.S. :
In hybridization, orbitals are “mixed” to form a set of hybrid

orbitals possessing the properties of its constituents (e.g. sp3:
25% s character and 75% p character
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Formation of sp3 Hybrid Orbitals
Each hybrid orbital contains e-

which tend to stay away as far
from each other as possible to
minimize repulsion
CAMPO - CHEM 14 !10

Formation of Covalent Bonds in CH4
H-C-H bond angle: 109.5o

!11
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sp3-Hybridized N Atom in NH3
Predict correct
bond angle
H-N-H bond angle: 107.3o

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Valence Shell Electron Pair Repulsion (VSEPR) Theory
- provides a method for predicting the shape of molecules, based

on the electrostatic repulsion between electron pairs (bonding and
nonbonding).
According to the VSEPR model, due to e- pair repulsions, molecules adopt

geometries in which valence e- pairs are positioned as far from each other
as possible.
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Terms:
!
Bond length – distance between nuclei.

Bond angle – angle between adjacent bonds.
Electron group geometry – distribution of e- pairs.
Molecular geometry – distribution of nuclei.
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A molecule can be described with the generic formula:
where A is the central atom, X stands for any atom or group

connected to the central atom, and E represents a group of lone
pair e-
The steric number (SN = m + n) is the number of positions

occupied by atoms or lone pairs around the central atom
NH3
SN = 4 SN = 4
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Single Bonds
SN = 2
SN = 3
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Single Bonds
SN = 4
SN = 5
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Single Bonds
SN = 6
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Formation of sp Hybrid Orbitals
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Formation of sp2 Hybrid Orbitals
!21
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Geometries with Nonbonding e- (Lone Pairs)
- In predicting the molecular geometry, the extent of separation of

the valence e- is based on the total number of valence e- pairs and
not on the bonding pairs only
- We consider electron group geometry, which depicts distribution

of e- pairs, in determining molecular geometry
repulsion: lone e- pair-lone e- pair > lone e- pair-bonding > bonding-bonding
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Geometries with Lone Pairs
SN = 4
EGG MG
EGG MG
SN = 5
EGG MG
EGG MG
SN = 5
EGG MG
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SN = 6
EGG MG
EGG MG
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
SN = # of Lone Pairs
+
# of Bonded Atoms Hybridization Examples
2 sp BeCl2
3 sp2 BF3
4 sp3 CH4, NH3, H2O
5 sp3d PCl5
6 sp3d2 SF6
Molecular Geometry as a Function of Electron Group
Geometry : Summary
Bond angle – angle between adjacent bonds.
Electron group geometry – distribution of e- pairs.
Molecular geometry – distribution of nuclei.
Copyright © 2011 Pearson Canada Inc.

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Replace this part of table 10.1 this format is not
present in the text. Parent table is on page 425
and 426

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Multiple Bonds
- Double and triple bonds have slightly greater repulsive effects

than single bonds because of the repulsive effect of π electrons.
- Multiple bonds tend to occupy the same position as lone pairs
repulsion: lone e- pair > bond pair (multiple bond) > bond pair (single bond)
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sp2 Hybridization of Carbon
C2H4 (ethylene): SN = 3
Only unhybridized p orbitals can form π bonds

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H H
Ethylene has a double bond in its Lewis structure.
C C
VSEPR says trigonal planar at carbon.
H H

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Unhybridized 2pz orbital (gray), which is perpendicular
to the plane of the sp2 hybrid (green) orbitals.
!37
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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 !38
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Another View of π Bonding in Ethylene, C2H4
trigonal planar
consequence of double bond: planar molecule
!39
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sp Hybridization of Carbon
C2H2 (ethyne): SN = 2
!40
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Bonding in Acetylene, C2H2
linear
!41
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Describe the bonding in CH2O.
H
C O
H
C – 3 bonded atoms, 0 lone pairs
C – sp2
!42
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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
How many σ and π bonds are in the acetic acid (vinegar)

molecule CH3COOH?
H
O
σ bonds = 6 + 1 = 7
H C C O H
π bonds = 1
H !43
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Molecules with More Than One Central Atom
The geometric distribution of terminal atoms around each central

atom must be determined and the results then combined into a single
description of the molecular shape.
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Applying VSEPR Theory
1. Draw a plausible Lewis structure.

2. Determine the number of e- groups and identify
them as bond or lone pairs.
3. Establish the e- group geometry.
4. Determine the molecular geometry.
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Practice
Determine the electron group geometry and molecular

geometry of :
a. ICl4-
b. H2CO
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Properties of Covalent Bonds
1. Bond polarity
- nonpolar bond: EN difference ≤ 0.4!
- polar bond: 0.4 < EN difference < 1.7!
- ionic bond: 1.7 ≤ EN diffrerence!
! ! ex: H-F> H-Cl> H-Br>HI (bond polarity)
One can determine a molecule’s polarity by looking at the presence or

absence of a dipole moment based on the magnitude and direction of the
bond dipoles.
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Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CF4
O H S O
H O
dipole moment dipole moment
polar molecule polar molecule
F
C
O C O
F F
no dipole moment F
nonpolar molecule no dipole moment
nonpolar molecule
Not all molecules with polar bonds are polar molecules.

Does BF3 have a dipole
moment?
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Does CH2Cl2 have a
dipole moment?
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2. Bond dissociation energy/ Bond enthalpy
- energy needed to destroy a covalent bond!

- is a measure of the strength of a covalent bond
In general, !
↑bond polarity ↑bond dissociation energy
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3. Bond order
- number of bonds present between two atoms
Single bond, bond order = 1
Double bond, bond order = 2
Triple bond, bond order = 3
In general, !
↑bond order ↓bond length ↑bond dissociation energy
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4. Bond length
- internuclear distance
In general, !
↑size of atom ↑bond length!
↑bond polarity ↓bond length!
↑bond order ↓bond length
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5. Bond angle
- becomes smaller due to presence of lone pairs!
! -deviation from ideal value!
- comparing different bond angles:
difference in central atoms ↑size of central atom ↓bond angle formed
e.g. H2O > H2S > H2Se > H2Te
difference in ligand atoms ↑size of ligand ↑bond angle formed
e.g. I2Se > Br2Se > Cl2Se > F2Se
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Practice
Determine the Lewis structure, molecular geometry and

polarity:
a. SNF3
b. XeOF4
Arrange accdg to increasing bond angle:

a. PH3, NH3, AsH3
b. OSF2, OSCl2, OSBr2
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How can VBT explain this observation?
Experiments show O2 is paramagnetic
O
O
No unpaired e-
Should be diamagnetic
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Molecular Orbital Theory (MOT)
- although VBT provides a simple description of bonding and structures, it fails to

describe some observed properties of some molecules!
! e.g. paramagnetism of O2; existence of the stable species H2+
Molecular orbital theory – bonds are formed from

interaction of atomic orbitals to form molecular
orbitals.
- The theory assigns the e- in a molecule to a series of orbitals that belong to the
molecule as a whole.
- MO are spread over the entire molecule as opposed to in VBT where e- from !
atomic overlap are localized in the region of overlap
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Constructive and Destructive Interference
Formation of bonding and antibonding  
molecular orbitals in hydrogen (H2)
The interaction of two hydrogen atoms according to molecular theory

a.) The addition of two 1s orbitals in phase to form a σ1s molecular orbital. This
orbital produces electron density between the nuclei, leading to a chemical bond.
b.) The addition of two orbitals 1s out of phase to produce a σ*1s antibonding orbital.
This orbital has a nodal plane where there is zero e- density.
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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.
H2 Overlap of two 1s orbitals leads to
formation of two molecular orbitals:
destructive interference forms

antibonding molecular orbital (σ*1s)
- higher in energy than the two
atomic orbitals due to repulsion of
exposed (+) charged nucleus
constructive interference forms

bonding molecular orbital (σ1s)
-lower in energy than the two
atomic orbitals
Because the σ1s MO is lower in energy than the 1s AO, H2 is more stable
than its separate H atoms.
H2
VBT: 1s AO of two H atoms overlap

to form a chemical bond, that these
AO do not change but only simply
overlap
MOT: 1s AO of two H atoms not only

overlap, but also simultaneously
transformed into two MO with new
energies and e- distributions
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Molecular Orbital (MO) Configurations
!
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
(Aufbau Process).
4. Each MO can accommodate up to two electrons (Pauli
Exclusion Principle).
5. Use Hund’s rule when adding electrons to MOs of the same
energy (degenerate orbitals).
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.
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Bond Order
Stable species have more electrons in

bonding orbitals than antibonding.
Bond Order = 1/2 (No. e- in bonding MOs - No. e- in antibonding MOs)
So long as BO > 0, a bond would still exist

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He2
BO = 0, meaning no bond is formed
Effect of bonding e- is cancelled by

antibonding e-
He2 is not expected to exist.
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Bond Order = 1/2 (No. e- in bonding MOs - No. e- in antibonding MOs)
bond
½ 1 ½ 0
order
MOT is able to predict and explain the existence of H2+ and He2+. A
BO = 1/2 would still indicate that a bond exists, although it would be
less than that of a single bond. VBT is not able to explain this.
CAMPO - CHEM 14
Orbital energy-level diagrams for Second Period elements
Li2
BO = 1
CAMPO - CHEM 14 Li2 can exist!
Be2
Be Be
Be-Be
BO = O
Be2 can’t exist!
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Two Possible Interactions Between Two Equivalent p Orbitals
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σ MOs are expected to have lower energy than π MOs due to more extensive/more
efficient overlap in head-to-head 2p overlap than side-to-side 2p overlap .
Possible molecular orbital energy-level schemes for diatomic molecules of the second-period elements
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Experiment shows C2 to be diamagnetic, supporting a
modified energy-level diagram
Expected MO Diagram for C2
Modified MO Diagram for C2

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modified order
expected order of σ and π MO
of σ and π MO due to 2s-2p
mixing
O2,F2,Ne2 and all other Z≥8 will follow B2, C2, N2 and all other Z ≤ 7 will follow the modified
the expected energy diagram energy diagram as a result of 2s-2p mixing
The modified energy diagram for the elements below
Oxygen is a result of 2s-2p mixing.
2s-2p mixing is due to the interaction of σ1s and σ2p

MOs whose energies are close enough (for Z ≤ 7) to
each other such that they are able to interact.
Consequence: Destabilization of σ2p causing it to lie

above π2p in the energy diagram.
with 2s-2p mixing
Molecular orbital occupancy diagrams for the homonuclear diatomic molecules of the second-period
elements

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with no 2s-2p mixing
Molecular orbital occupancy diagrams for the homonuclear diatomic molecules of the second-period
elements

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with 2s-2p mixing with no 2s-2p mixing
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There is no single “best” theory to explain covalent
bonding. Each has its own strengths and weaknesses. The
choice of which theory to use depends on which property
you want to explain.
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Bonding in the Benzene Molecule
Delocalized molecular orbitals are not confined between
two adjacent bonding atoms, but actually extend over three
or more atoms.
Example: Benzene, C6H6
Delocalized π orbitals
$78
FIGURE 11-29
Bonding in benzene, C6H6, by the valence-bond method

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Electron density above and below the plane of the
benzene molecule.
Polycentric molecular orbital : obtained by having pi

electrons delocalize around the molecule continuosly in
loops (continuos delocalization)

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The Chemical Bond 2

1. Valence Bond Theory

- covalent bond formation is due to overlap of atomic orbitals

Sharing of two electrons between the two atoms.

Bond Enthalpy Bond Length Overlap Of

F2 150.6 kJ/mol 142 pm 2 2p

According to VBT, a covalent bond is formed from the overlap of

If the bonds form from overlap of 3 2p orbitals on nitrogen with

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

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

E.S. configuration can now allow formation of four bonds, BUT

In hybridization, orbitals are “mixed” to form a set of hybrid

Each hybrid orbital contains e-

CAMPO - CHEM 14 !10

H-C-H bond angle: 109.5o

H-N-H bond angle: 107.3o

- provides a method for predicting the shape of molecules, based

According to the VSEPR model, due to e- pair repulsions, molecules adopt

Bond length – distance between nuclei.

A molecule can be described with the generic formula:

where A is the central atom, X stands for any atom or group

The steric number (SN = m + n) is the number of positions

- In predicting the molecular geometry, the extent of separation of

- We consider electron group geometry, which depicts distribution

repulsion: lone e- pair-lone e- pair > lone e- pair-bonding > bonding-bonding

1. Draw the Lewis structure of the molecule.

4 sp3 CH4, NH3, H2O

Copyright © 2011 Pearson Canada Inc.

Copyright © 2011 Pearson Canada Inc.

- Double and triple bonds have slightly greater repulsive effects

Only unhybridized p orbitals can form π bonds

Copyright © 2011 Pearson Canada Inc.

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

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

How many σ and π bonds are in the acetic acid (vinegar)

The geometric distribution of terminal atoms around each central

1. Draw a plausible Lewis structure.

Determine the electron group geometry and molecular

One can determine a molecule’s polarity by looking at the presence or

Not all molecules with polar bonds are polar molecules.

2. Bond dissociation energy/ Bond enthalpy

- energy needed to destroy a covalent bond!

difference in central atoms ↑size of central atom ↓bond angle formed

e.g. H2O > H2S > H2Se > H2Te

difference in ligand atoms ↑size of ligand ↑bond angle formed

e.g. I2Se > Br2Se > Cl2Se > F2Se

Determine the Lewis structure, molecular geometry and

Arrange accdg to increasing bond angle:

Experiments show O2 is paramagnetic

- although VBT provides a simple description of bonding and structures, it fails to

Molecular orbital theory – bonds are formed from

The interaction of two hydrogen atoms according to molecular theory

A bonding molecular orbital has lower energy and greater

An antibonding molecular orbital has higher energy and

destructive interference forms

constructive interference forms

VBT: 1s AO of two H atoms overlap

MOT: 1s AO of two H atoms not only

1. The number of molecular orbitals (MOs) formed is always

Stable species have more electrons in

Bond Order = 1/2 (No. e- in bonding MOs - No. e- in antibonding MOs)

1. Valence Bond Theory 