Module 0 - Review of CHEM 18

CHEM 40: Basic Organic Chemistry
Module 1: Bonding, Structure, and Reaction Mechanisms
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REVIEW: CHEM 18
Bonding and Structure
A. Electronic Structure and Bonding
The electrons in the outermost shell are the ones involved in the formation of chemical
bonds and in chemical reactions. These electrons are called valence electrons, and the energy
level in which they are found is called the valence shell. To show the outermost shell electrons
of an atom, a representation called a Lewis structure is used. In Lewis structures, the atomic
symbol represents the nucleus and all the completely inner shells. The symbol is surrounded by
a number of dots equal to the number of valence electrons.
B. The Formation of Chemical Bonds
Gilbert N. Lewis pointed out that the chemical inertness of the noble gases indicated a
high degree of stability of the electron configuration of these elements (the noble gases have
completely filled valence shells). Lewis then devised a model of bonding that unified many of the
observations about chemical reactions of the elements. According to the Lewis scheme, atoms
bond together in such a way that each atom participating in a chemical bond acquires a completed
valence shell electronic configuration resembling that of a noble gas nearest it in the periodic
table. The force that holds atoms together in a molecule or crystalline lattice is referred to as a
chemical bond.
There are two ways by which atoms acquire completely filled valence shells:
1. gaining or losing enough electrons- an atom that gains an electron becomes a

negatively charged ion; on the other hand, an atom that loses electrons becomes a
positively charged ion; the chemical bond between positively charged and negatively
charged ions is called an ionic bond.
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2. Sharing of electrons with other atoms or atoms- the chemical bond formed is called
covalent bond.
C. The Ionic Bond
An ionic bond is formed by the transfer of electrons from one atom to another. Atoms
having low ionization energy loses electrons easily. Ionization energy is the amount of energy
required to remove the most loosely held electron from an isolated atom in its ground state.
The alkali metals found at the far left of the periodic table have low ionization energy and
so give up electrons easily. Across the periodic table, from left to right, there is a general increase
in the ionization energy of the representative elements.
Atoms that have high electron affinity (EA) gain electrons easily. Electron affinity is the
amount of energy released when an electron is added in its ground state.
In general, electron affinity of representative elements increases in going from left to right
of the periodic table. The halogens which appear at the right side of the periodic table have high
electron affinity and so gain electrons easily. Ionic compounds contain charged particles held
together by extremely strong electrostatic interactions. For example, sodium chloride is formed
through ionic bonding between sodium and chlorine.
Sodium has low ionization potential and so readily loses one electron to form Na+ which
has electron configuration of the noble gas neon. Chlorine has high affinity and readily gains one
electron.
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D. The Covalent Bond
Atoms in the middle of the periodic table require too much energy to gain or lose sufficient
electrons in order to attain the electron configuration of the noble gases.
● these atoms acquire completely filled valence shells by sharing electrons

● an atom forms as many covalent compounds with other atoms as the number of
electrons to fill the valence shell.
A covalent bond is formed by sharing of electrons by two atoms. The formation of

hydrogen molecules is the simplest example of the formation of a covalent bond. When two
hydrogens combine, the electron from one atom combines with the electron of the other to form
an electron pair. The shared electrons now belong to both hydrogen atoms. Each of the two
atoms in a covalent bond used the two electrons in the bonds to acquire a noble gas electron
configuration. Thus, each hydrogen atom in the hydrogen molecule acquires the electron
configuration of the noble gas helium. Covalent compounds have structural units called molecules.
A molecule is a neutral collection of atoms held together by covalent bonds.
Examples:
In Lewis structures, a covalent bond is indicated by a pair of dots that lie between the two
bonded atoms. As a shorthand notation, a pair of electrons in a covalent bond is shown as a dash
or a short line between the bonded atoms; an unshared electron pair (lone pair) is shown as a
pair of dots. Let us now rewrite the structures of methane, ammonia and water using the line
and lone-pair notation.
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An atom can form as many covalent bonds with other atoms as the maximum number of
electrons needed to fill its valence shell.
Hydrogen with one valence electron needs one electron to fill its valence shell and
therefore can form one covalent bond. Carbon with four valence electrons, needs four more to
fill its valence shell and therefore forms four covalent bonds.
By similar reasoning, nitrogen with five valence electrons forms three covalent bonds;
oxygen with six valence electrons forms two covalent bonds; and the halogens (F, Cl, Br, I) with
seven valence electrons form one covalent bond.
Below are some examples which illustrate these different bonding capacities.
Carbon, nitrogen, and oxygen can form more than one bond between pair of atoms.
Sharing of one electron pair leads to a single bond. Sharing of two electron pairs leads to a double
bond, while sharing of three electron pairs leads to a triple bond. The sharing of four electron
pairs is not observed.
E. Writing Correct Lewis Structures
Lewis structures are used as a simple, shorthand and convenient notation for
representing the electronic structures of atoms, ions and molecules, which provide an accurate
accounting of electrons. Facility with writing correct Lewis structures is important in the study of
organic chemistry.
There are two necessary features for a correct Lewis structure:
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1) the electrons in the valence shell of each atom are assigned correctly, and
2) the formal charges are assigned correctly.
Sometimes covalently bonded atoms have a charge; this is called formal charge. The charge
of an atom depends on the number of electrons available to it and the number of protons in its
nucleus. To determine the number of electrons in the valence shell of an atom, we count all the
electrons of covalent bonds plus any shared electrons. To assign formal charge to an atom, we
count half of the shared plus any unshared electrons and subtract their number from the number
of valence electrons in the neutral, unbonded atom.
We can make certain generalizations about the structures of the uncharged molecules we
have encountered so far:
1) A carbon with four covalent bonds is neutral.

2) A nitrogen atom with three covalent bonds and one electron pair is neutral.
3) Halogens (F, Cl, Br, I) with one covalent bond and three lone pairs are neutral.
In the following exercises you will encounter examples where atoms have formal charges.
So far, we have considered the Lewis model of bonding which describes chemical bonds in terms
of the valence electrons.
SAQ_A. Lewis Structure
Write a Lewis structure for each of the following:

1. CH3F 7. NH4OH
2. CH3CH3 8. H3O+
3. H3PO4 9. NH4+
4. H2CO3 10. NaOH
5. HNO3 11. CH2O
6. H2SO4 12. CH3OCH3
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ASAQ_A. Lewis Structure
Write a Lewis structure for each of the following:
1. CH3F
2. CH3CH3
3. H3PO4
4. H2CO3
5. HNO3
6. H2SO4
7. NH4OH
8. H3O+
9. NH4+
10. NaOH
11. CH2O
12. CH3OCH3
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Resonance structures are a set of two or more Lewis Structures that collectively
describe the electronic bonding of a single polyatomic species including fractional bonds and
fractional charges. Resonance structures are capable of describing delocalized electrons that
cannot be expressed by a single Lewis formula with an integer number of covalent bonds.
Example:
Recommended Online Reading
If you would like to learn more how to draw Lewis structures properly, click the following
hyperlinked texts.
1) Lewis Symbols and Structures

2) Formal Charges: Mathematical and Intuitive Method
3) Formal Charges and Resonance
F. CHEMICAL BONDING THEORIES
How does electron sharing occur? Before we proceed in the discussion of theories that
describe bond formation, let us review the fundamental concepts of electron configuration from
your general chemistry course.
Rule 1 The lowest-energy orbitals fill up first, according to the order 1s 2s 2p 3s 3p 4s

3d, a statement called the Aufbau principle. Note that the 4s orbital lies
between the 3p and 3d orbitals in energy.
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Aufbau principle describes the rules for determining the electron

configuration of an atom.
Rule 2 Electrons act as if they were spinning around an axis, in much the same way
that the earth spins. This spin can have two orientations, denoted as up ↑ and
down ↓. Only two electrons can occupy an orbital, and they must be of opposite
spin, a statement called the Pauli exclusion principle.
Pauli exclusion principle states that no more than two electrons can occupy
the same orbital, and those two electrons must have spins of opposite sign.
Rule 3 Hund’s rule states that if two or more empty orbitals of equal energy are
available, one electron occupies each, with their spins parallel, until all are
half-full.
SAQ_B. Electron Configuration

Give the ground-state electron configuration for each of the following elements:
(a) Oxygen
(b) Silicon
(c) Sulfur
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ASAQ_B. Electron Configuration
(a) Oxygen: 1s2 2s2 2p4
(b) Silicon: 1s2 2s2 2p6 3s2 3p4
(c) Sulfur: 1s2 2s2 2p6 3s2 3p2
G. VALENCE BOND THEORY (VBT)
According to VBT, a covalent bond results when two atoms approach each other closely
so that a singly occupied orbital on one atom overlaps a singly occupied orbital on the other atom.
The electrons are now paired in the overlapping orbitals and are attracted to the nuclei of both
atoms, thus bonding the atoms together. Here are the key ideas of VBT:
● Covalent bonds are formed by overlap of two atomic orbitals, each of which contains one
electron. The spins of the two electrons are opposite.
● Each of the bonded atoms retains its own atomic orbitals, but the electron pair in the
overlapping orbitals is shared by both atoms.
● The greater the amount of orbital overlap, the stronger the bond.
In the H2 molecule, for example, the H—H bond results from the overlap of two singly
occupied hydrogen 1s orbitals. In this figure, the overlapping orbitals of the H2 molecule form an
elongated egg shape. If we are going to pass a plane right at the middle of the bond, we’ll get
a circle, implying that the bond is cylindrically symmetrical. Such bonds are formed by a head-
on overlap of two atomic orbitals along the line drawn between the two nuclei, giving rise to a
sigma bond.
During the bond-forming reaction (see the illustration below), 436 kJ/mol of energy is
released. Because the product H2 molecule has 436 kJ/mol less energy than the starting 2 H·
atoms, we say that the product is more stable than the reactant and that the H-H bond has a
bond strength of 436 kJ/mol. In other words, we would have to put 436 kJ/mol of energy into
the H-H bond to break the H2 molecule apart into H atoms.
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How close are the two nuclei in the H2 molecule? If they are too close, they will repel each
other because both are positively charged, yet if they’re too far apart, they won’t be able to share
the bonding electrons. Thus, there is an optimum distance between nuclei that leads to maximum
stability referred to as bond length. Below is a plot of energy versus internuclear distance for two
hydrogen atoms. The distance between nuclei at the minimum energy point is the bond length.
Summary: Properties of Covalent Bond

In summary, the properties of a covalent bond are:
1. Bond strength is an alternative name for bond dissociation energy, which is the amount
of energy needed to break a bond homolytically and produce two radical fragments. It
also refers to the amount of energy consumed when a bond is broken is equal to the
amount of energy liberated when a bond is formed.
2. Bond length is the equilibrium distance between the nuclei of two atoms that are
bonded to each other.
Watch the short discussion “Bond Strength and Length” to understand the relationship
of these two properties. Click the hyperlinked text.
3. Bond angle is the angle formed between two adjacent bonds.
4. Bond polarity is a measure of the distribution of electrons between two bonded atoms.
o Polar bond- joins atoms of different electronegativity
o Nonpolar bond- joins atoms of equal electronegativity
o Electronegativity:
F > O > Cl, N > Br > C, H
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H. MOLECULAR ORBITAL THEORY (MOT)
MOT describes covalent bond formation as arising from a mathematical combination of

atomic orbitals to form molecular orbitals.
● # MOs = #AOs combining
A molecular orbital (MO) describes a region of space in a molecule where electrons are
most likely to be found. Like in an atomic orbital (AO), a molecular orbital has its own shape,
size and energy.
Here are the key ideas of MOT:

● molecular orbitals are to molecules what atomic orbitals are to atoms
● molecular orbitals are formed by combining atomic orbitals
o the number of molecular orbitals formed is equal to the number of atomic
orbitals combined
● relative energies of molecular orbitals:
o bonding MO (lower energy than AO)
o nonbonding MO (same energy as AO)
o antibonding (higher energy than AO)
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CHEM 40: Basic Organic Chemistry

Module 1: Bonding, Structure, and Reaction Mechanisms

Do not remove this notice.

Bonding and Structure

A. Electronic Structure and Bonding

B. The Formation of Chemical Bonds

1. gaining or losing enough electrons- an atom that gains an electron becomes a

C. The Ionic Bond

D. The Covalent Bond

● these atoms acquire completely filled valence shells by sharing electrons

A covalent bond is formed by sharing of electrons by two atoms. The formation of

E. Writing Correct Lewis Structures

There are two necessary features for a correct Lewis structure:

1) A carbon with four covalent bonds is neutral.

SAQ_A. Lewis Structure

Write a Lewis structure for each of the following:

4. H2CO3 10. NaOH

5. HNO3 11. CH2O

6. H2SO4 12. CH3OCH3

ASAQ_A. Lewis Structure

Write a Lewis structure for each of the following:

Recommended Online Reading

1) Lewis Symbols and Structures

F. CHEMICAL BONDING THEORIES

Rule 1 The lowest-energy orbitals fill up first, according to the order 1s 2s 2p 3s 3p 4s

Aufbau principle describes the rules for determining the electron

SAQ_B. Electron Configuration

ASAQ_B. Electron Configuration

(a) Oxygen: 1s2 2s2 2p4

(b) Silicon: 1s2 2s2 2p6 3s2 3p4

(c) Sulfur: 1s2 2s2 2p6 3s2 3p2

G. VALENCE BOND THEORY (VBT)

Summary: Properties of Covalent Bond

3. Bond angle is the angle formed between two adjacent bonds.

F > O > Cl, N > Br > C, H

H. MOLECULAR ORBITAL THEORY (MOT)

MOT describes covalent bond formation as arising from a mathematical combination of

Here are the key ideas of MOT:

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