LESSON 4 CHEMICAL BONDING

4.0 Introduction

We know a lot about chemical compound. We can determine their compositions and formulas. We
can represent reactions of compounds by chemical equations. We can do all that without really having
to consider the ultimate structure of atoms and molecules. We know the shape of molecules that is
arrangements of atoms in space define the chemistry of molecules. In this lecture we will learn about
the interaction between atoms called chemical bonds. Most of our discussion will centre on Lewis
theory, valence bond theory and hybridization.

4.0.0 Learning Outcomes

By the end of this lesson, you will be able to:

a) describe bonding in terms of Lewis structures
b) use VSEPR to explain shapes of simple molecules
c) use valence bond theory and hybridization to describe the chemical bond

4.0 Electronic Structure and Chemical Bonding

There are four different but related approaches to explain how atoms combine to form covalent bond:
1) Lewis dot structure.
2) Valence Shell Electron Pair Repulsion theory (VSEPR).
3) Valence bond theory (VBT) and hybridization of atomic orbital.
4) Molecular Orbital (MOT) Theory.

In this Lecture we will describe the interactions between atoms called chemical bonds. Most of our
discussion will centre on the simplest method of representing chemical bonding, known as the Lewis
theory. We will explore, however, another relatively simple theory, one for prediction probable shape-
Valence – Shell Electron – Pair Repulsion (VSEPR) theory. The subject of chemical bonding in more
depth will be examined in SCH 200-(Atomic Structure and Chemical Bonding), especially molecular
orbital theory.

4.1 Lewis Theory

Some fundamental ideas in Lewis theory are:

1. Electrons, especially those of the outermost (valence) electronic shell, play a fundamental role
in chemical bonding.
2. In some cases electrons are transferred from one atom to another. Positive and negative ions
are formed and attract each other through electrostatic forces called ionic bonds.
3. In other cases one or more pairs of electrons are shared between atoms; this sharing of electrons
is called a covalent bond.
4. Electrons are transferred, or shared, in such a way that each atom acquires an especially stable
electron configuration. Usually this is a noble gas configuration, one with eight outer shell
electrons, or an octect.
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 4.1.1 Lewis Symbols and Lewis Structures

A Lewis symbol consists of a chemical symbol to represent the nucleus and core (inner shell) electrons
of an atom, together with dots placed around the symbol to represent the valence (outer shell) electrons.

Examples.
Lewis structure for: Na electron configuration [Ne]3s1 is
Na
N electron configuration [He]2s22p3 is

N
O electron configuration [He]2s22p4 is

SELF-TEST QUESTIONS
1 Write the Lewis symbols for the following elements: H, He, Li, C, N, O, F, Ne, Cl,
Na, Mg, Al, K and Ca

A Lewis structure is a combination of Lewis symbols that represent either the transfer or sharing of
electrons in a chemical bond.

4.1.2 Ionic Bonding (Transfer of Electrons)

+ -
Na + Cl Na Cl

-
Cl
2+
Mg + 2 Cl Mg -
Cl

E-tivity -2.5.2 Lewis structure of NaCl.

Numbering, pacing and 1.2.4

sequencing

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 Title Lewis structure of NaCl.
Purpose The purpose of this e-tivity is to enable you to describe Lewis
structure of NaCl
Brief summary of overall task Read the materials on these links
[Link]
FuE&ab_channel=Schoenherr%26DiamantopoulosChemistry
Videos

Spark

Individua task a) Draw Lewis structure of MgO.

b) .

Interaction begins 1. Draw Lewis structure of CaCl2

2. Provide positive and constructive feedback on the team
learners ‘views and ideas. Do this on the discussion
forum 1.2.4
E-moderator interventions 1. Ensure that learners are focused on the contents and
context of discussion.
2. Stimulate further learning and generation of new ideas.
3. Provide feedback on the learning progress.
4. Round-up the e-tivity
Schedule and time This task should take two hours
Next Resonance structures

4.1.3 Covalent Bonding (Sharing of Electrons

Hydrogen molecule is written showing a pair of dots between hydrogen atoms, indicating that the
hydrogen share the pair of electrons in covalent bond

H + H H H

Two hydrogen A hydrogen

atom molecule
The shared pair is usually represented by a line. E.g.

H H

Atoms other than hydrogen also form covalent bonds

H + Cl H Cl

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 Cl + Cl Cl Cl

SELF-TEST QUESTIONS
1 Write Lewis structures of the following ionic compounds:
a) BaO; b) MgCl2; c) Aluminium oxide
2 Write Lewis structures of the following covalent compounds:
a) F2; b) H2O; c) NH3 d) CH4 e) O2 f)
N2

E-tivity -2.5.2 Lewis structure of water.

Numbering, pacing and 1.2.4

sequencing
Title Lewis structure of water.
Purpose The purpose of this e-tivity is to enable you to describe Lewis
structure of water
Brief summary of overall task Read the materials on these links
[Link]
=ProfessorHeath%27sChemistryChannel

Spark

Individua task c) Draw Lewis structure of CO2.

d) .

Interaction begins 3. Draw Lewis structure of H2S

4. Provide positive and constructive feedback on the team
learners ‘views and ideas. Do this on the discussion
forum 1.2.4
E-moderator interventions 5. Ensure that learners are focused on the contents and
context of discussion.
6. Stimulate further learning and generation of new ideas.
7. Provide feedback on the learning progress.
8. Round-up the e-tivity
Schedule and time This task should take two hours
Next Resonance structures
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 4.1.4 Lewis Structures and Resonance

The Lewis structure of ozone O3 are:

O O O or O O O
Which of the two Lewis structure for O3 is correct?

In fact, neither is correct by itself. Whenever it is possible to write more than one Lewis structure for a
molecule the actual electronic structure is an average of the various possibilities called a resonance
hybrid.

Ozone does not have:

• One O=O double bond and
• One O-O single bond as individual structure imply, rather ozone has two equivalent O-O bonds
that one can think of as having a bond order of 1.5 midway between pure single bond and pure
double bond. Both have an identical length of 1.28 Å.

The idea of resonance between two or more Lewis structure is indicated by drawing the individual
Lewis structure and using double headed “resonance arrow” to show that both contribute to the
resonance hybrid.

O O O O O O

SELF-TEST QUESTIONS
Draw the resonance structure of carbonate ion, CO32-.

4.2 Molecular Geometry and Bonding Theories

(Molecular geometry or shape of molecules)

Lewis structures say nothing about bond angles.

4.2.1 Valence Shell Electron Pair Repulsion Theory (VSEPR)

❖ A structure should be considered which let all the electron pairs of the valence shell of central
atom try to get further away from each other. Repulsion between lone pairs is greater than
those between bonding electrons.

The order of repulsive energy is:

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Lp-Lp>Lp-Bp>Bp-Bp

O C O Linear

H Cl Linear

O
H H V-shaped

Cl

B Trigonal planar
Cl Cl

N
H H Triangular pyramidal
H

C H Tetrahedral
H H

4.2.3 Covalent Bonding and Orbital Overlap

The VSEPR model is a simple method which allows us to predict molecular geometry BUT it does
NOT explain why bond exist between atoms.

➢ How can we explain molecular geometry and basis of bonding at the same time?
o Quantum mechanism and molecular orbitals are used.

4.3 Valence Bond Theory (VBT)

• Combine Lewis idea of electron pair bonds with electron orbitals (quantum mechanic).
• Covalent bond occurs when atom shares electrons.
• Concentrate electron density between nuclei.
• The build up of electrons density between two nuclei occurs when a valence atomic orbital of
one atom overlap with one of another.
• The orbital share a region of space i.e. they overlap.
• The overlap of orbital allows two electron of opposite spin to share the common space
between the nuclei forming a covalent bond.

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 • In the hydrogen m molecule for instance the H-H bond results from overlap of two singly
occupied H 1s orbitals.

H + H H H

1s 1s H2
molecule

• In the valence bond model, the strength of covalent bond depends on amount of overlap. The
greater the overlap, the stronger the bond. This in turn, means that bond formed by overlap
other than s- orbitals have directionalities to them.

In the fluorine molecule, F2, for instance each atom has electron configuration:
[He]2s22pz22py22px1
Meaning that the fluorine bond results from overlap of two singly occupied two 2p orbitals. The 2p
orbitals must point directly to one another for optimum overlap to occur, and the F-F form bond along
the orbitals.

F F
F + F

2p 2p F2
molecule
F F
atom atom

In HCl, the covalent bond involves overlap of 1s orbital (non-directional) with chlorine 3p orbital and
formed along p-axis.

1s 3p HCl molecule
The key ideas of valence bond theory can be summarized by few statements:
i. Covalent bonds are formed by overlap of atomic orbitals, each of which contains 1 electron of
opposite spin.
ii. Each of the bonded atoms maintains its own atomic orbitals, but the electron pair in the
overlapping pair is shared by both atoms.
iii. The greater the amount of orbital overlap the stronger the bond. This leads to a directional
character to the bond when other than s – orbitals are formed.

4.4 Molecular Geometry and Hybrid Orbitals

Hybrid Orbitals
For polyatomic molecules we would like to be able to explain:
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The number of bonds formed
Their geometries
sp Hybrid Orbitals
Consider the Lewis structure of gaseous molecules of BeF2:

• The VSEPR model predicts this structure will be linear

• What would valence bond theory predict about the structure?
The fluorine atom electron configuration:
• 1s22s22p5

• There is an unpaired electron in a 2p orbital

• This unpaired 2p electron can be paired with an unpaired electron in the Be atom to form a
covalent bond
The Be atom electron configuration:
• 1s22s2

• In the ground state, there are no unpaired electrons (the Be atom is incapable of forming a
covalent bond with a fluorine atom
• However, the Be atom could obtain an unpaired electron by promoting an electron from the
2s orbital to the 2p orbital:

This would actually result in two unpaired electrons, one in a 2s orbital and another in a 2p
orbital
• The Be atom can now form two covalent bonds with fluorine atoms
• We would not expect these bonds to be identical (one is with a 2s electron orbital, the other is
with a 2p electron orbital)
However, the structure of BeF2 is linear and the bond lengths are identical
• We can combine wavefunctions for the 2s and 2p electrons to produce a "hybrid" orbital for
both electrons
• This hybrid orbital is an "sp" hybrid orbital

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 • The orbital diagram for this hybridization would be represented as:

Note:
• The Be 2sp orbitals are identical and oriented 180° from one another (i.e. bond lengths will be
identical and the molecule linear)
• The promotion of a Be 2s electron to a 2p orbital to allow sp hybrid orbital formation requires
energy.
o The elongated sp hybrid orbitals have one large lobe which can overlap (bond) with
another atom more effectively
o This produces a stronger bond (higher bond energy) which offsets the energy required
to promote the 2s electron
sp2 and sp3 Hybrid Orbitals
Whenever orbitals are mixed (hybridized):
• The number of hybrid orbitals produced is equal to the sum of the orbitals being hybridized
• Each hybrid orbital is identical except that they are oriented in different directions
BF3
Boron electron configuration:

• The three sp2 hybrid orbitals have a trigonal planar arrangement to minimize electron
repulsion

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NOTE: sp2 refers to a hybrid orbital being constructed from one s orbital and two p orbitals.
Although it looks like an electron configuration notation, the superscript '2' DOES NOT refer to the
number of electrons in an orbital.
• An s orbital can also mix with all 3 p orbitals in the same subshell
CH4

Thus, using valence bond theory, we would describe the bonds in methane as follows: each of the
carbon sp3 hybrid orbitals can overlap with the 1s orbitals of a hydrogen atom to form a bonding pair
of electrons

NOTE: sp3 refers to a hybrid orbital being constructed from one s orbital and three p orbitals.
Although it looks like an electron configuration notation, the superscript '3' DOES NOT refer to the
number of electrons in an orbital.

ANOTHER NOTE: the two steps often observed when constructing hybrid orbitals is to 1) promote
a valence electron from the ground state configuration to a higher energy orbital, and then 2)
hybridize the appropriate valence electron orbitals to achieve the desired valence electron geometry
(i.e. the correct number of hybrid orbitals for the appropriate valence electron geometry)
H2O
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Oxygen

4.5 Hybridization Involving d Orbitals

Atoms in the third period and higher can utilize d orbitals to form hybrid orbitals
PF5

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Similarly hybridizing one s, three p and two d orbitals yields six identical hybrid sp3d2
orbitals. These would be oriented in an octahedral geometry.
• Hybrid orbitals allows us to use valence bond theory to describe covalent bonds (sharing of
electrons in overlapping orbitals of two atoms)
• When we know the molecular geometry, we can use the concept of hybridization to describe
the electronic orbitals used by the central atom in bonding
Steps in predicting the hybrid orbitals used by an atom in bonding:
1. Draw the Lewis structure
2. Determine the electron pair geometry using the VSEPR model
3. Specify the hybrid orbitals needed to accommodate the electron pairs in the geometric
arrangement
NH3
1. Lewis structure

2. VSEPR indicates tetrahedral geometry with one non-bonding pair of electrons (structure
itself will be trigonal pyramidal)
3. Tetrahedral arrangement indicates four equivalent electron orbitals

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 Valence Electron Pair Number of Orbitals Hybrid Orbitals
Geometry

Linear 2 Sp

Trigonal Planar 3 Sp2

Tetrahedral 4 Sp3

Trigonal Bipyramidal 5 sp3d

Octahedral 6 sp3d2

4.6 Multiple Bonds and Orbital Overlaps

Two types of bond

Sigma (σ) and pi (π) bonds
The "inter-nuclear axis" is the imaginary axis that passes through the two nuclei in a bond:

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The covalent bonds we have been considering so far exhibit bonding orbitals which are
symmetrical about the inter-nuclear axis (either an s orbital - which is symmetric in all
directions, or a p orbital that is pointing along the bond towards the other atom, or a hybrid
orbital that is pointing along the axis towards the other atom)
Bonds in which the electron density is symmetrical about the inter-nuclear axis are termed
"sigma" or " σ " bonds
In multiple bonds, the bonding orbitals arise from a different type arrangement:
• Multiple bonds involve the overlap between two p orbitals
• These p orbitals are oriented perpendicular to the inter-nuclear (bond) axis

This type of overlap of two p orbitals is called a "pi" or "π" bond. Note that this is a single
π bond (which is made up of the overlap of two p orbitals)
In π bonds:
• The overlapping regions of the bonding orbitals lie above and below the inter-nuclear axis (there
is no probability of finding the electron in that region)
• The size of the overlap is smaller than a σ bond, and thus the bond strength is typically less than
that of a σ bond
Generally speaking:
• A single bond is composed of a σ bond.
• A double bond is composed of one σ bond and one π bond.
• A triple bond is composed of one σ bond and two π bonds.

C2H4 (ethylene; see structure above)

• The arrangement of bonds suggests that the geometry of the bonds around each carbon is
trigonal planar
• Trigonal planar suggests sp2 hybrid orbitals are being used (these would be σ bonds)
What about the electron configuration?
Carbon: 1s2 2s2 2p2

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 • Thus, we have an extra unpaired electron in a p orbital available for bonding
• This extra p electron orbital is oriented perpendicular to the plane of the three sp2 orbitals (to
minimize repulsion):

• The unpaired electrons in the p orbitals can overlap one another above and below the
internuclear axis to form a covalent bond

• This interaction above and below the inter-nuclear axis represents the single π bond between
the two p orbitals
Experimentally:
• we know that the 6 atoms of ethylene lie in the same plane.
• If there was a single σ bond between the two carbons, there would be nothing stopping the
atoms from rotating around the C-C bond.
• But, the atoms are held rigid in a planar orientation.
• This orientation allows the overlap of the two p orbitals, with formation of a π bond.
• In addition to this rigidity, the C-C bond length is shorter than that expected for a single bond.
• Thus, extra electrons (from the π bond) must be situated between the two C-C nuclei.
C2H2 (acetylene)

• The linear bond arrangement suggests that the carbon atoms are utilizing sp hybrid orbitals
for bonding

• This leaves two unpaired electrons in p orbitals

• To minimize electron repulsion, these p orbitals are at right angles to each other, and to the
inter-nuclear axis:

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 • These p orbitals can overlap two form two π bonds in addition to the single σ bond (forming a
triple bond)

Delocalized Bonding
localized electrons are electrons which are associated completely with the atoms forming the
bond in question
In some molecules, particularly with resonance structures, we cannot associate bonding
electrons with specific atoms
C6H6 (Benzene)

Benzene has two resonance forms

• The six carbon - carbon bonds are of equal length, intermediate between a single bond and
double bond
• The molecule is planar
• The bond angle around each carbon is approximately 120°
The apparent hybridization orbital consistent with the geometry would be sp2 (trigonal planar
arrangement)
• This would leave a single p orbital associated with each carbon (perpendicular to the plane of
the ring)

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With six p electrons we could form three discrete π bonds
• However, this would result in three double bonds in the ring, and three single bonds
• This would cause the bond lengths to be different around the ring (which they are not)
• This would also result in one resonance structure being the only possible structure
The best model is one in which the π electrons are "smeared" around the ring, and not
localized to a particular atom

• Because we cannot say that the electrons in the bonds are localized to a particular atom
they are described as being delocalized among the six carbon atoms
Benzene is typically drawn in two different ways:

• The circle indicates the delocalization of the p bonds

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 4.7 Resonance Structures and Hybrid Orbitals

Structure of NO3-

The Lewis structure of NO3- ion suggests that three resonance structures describe the
molecular structure
• For any individual Lewis resonance structure the electronic structure for the central N atom is
predicted to be sp2 hybrid orbitals participating in bonds with each of the O atoms, and an
electron in a p orbital participating in a bond with one oxygen (forming a double bond)
• Two of the O atoms are predicted to have sp3 hybrid orbitals, with one orbital participating in
a σ bond with the central N atom and the other orbitals filled with non-bonding electron pairs.
The other O atom is predicted to have sp2 hybrid orbitals, with one orbital participating in a π
bond with the central N and two orbitals filled with non-bonding pairs of electrons.
Furthermore, this last O atom is participating in a double bond with the central N atom and
therefore should have an electron in a p orbital to participate in a π bond with the central N
How will this arrangement look as far as the orbital diagrams?

• There are 24 valence electrons in the expected valence orbitals above

• Summing the valence electrons from the formula gives: (3 x 6) for O, plus 5 for N, plus 1 for
ionic charge = 24
What might we expect for the electron configuration if we just started with the N atom?

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 • We would predict that the N can only make two σ bonds, it would have one pair of non-bonding
electrons, and a p electron left over to participate in a π bond with one of the π bonds
• This is different from what the Lewis structure shows, and from our prediction of hybrid orbitals
from the expected geometry
• If we look at the sp3 O atoms above we see that they actually have 7 electrons (1 more than
expected), while the sp2 O atom has the expected 6. Furthermore, the N atom (in the correct sp2
configuration) has 4 electrons (1 less than expected)
• The "extra" electron from the ionic charge is correctly accounted for in the summation of
electrons
Thus, the correct way to determine electron configurations appears to be:
• begin by predicting the hybridization orbitals
• then determine lone pair arrangements and s and p bonding electrons for each atom
• confirm that all bonding electrons are correct and that the total of electrons is correct

SELF-TEST QUESTIONS
i) What is molecular geometry? Why is the study of molecular geometry important?
ii) Describe the state of hybridization of arsenic in arsenic pentafluoride (AsF5).
iii) What is the difference between a Lewis dot symbol and a Lewis structure
iv) Define the following terms: lone pairs, the octet rule, sigma bond, pi bond and bond
length.

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