SEd Sci 221- ORGANIC CHEMISTRY

Chapter 1- Introduction to Organic Chemistry

Introduction
This chapter is focused on the meaning and importance of organic chemistry,
the structure and properties of organic compounds and the classification of organic
compounds and their functional groups.
Learning Outcomes:
In this chapter, you are expected to:
1. State the meaning and importance of Organic Chemistry
2. Explain and illustrate the structure and properties of organic compounds
3. Classify and distinguish organic compounds through their functional groups

Learning Contents:
This chapter contains the following lessons for you to be able to meet the
expected learning outcomes:
Introduction to Organic Chemistry
1. Definition and Importance of Organic Chemistry
2. Structure and Importance of Organic Compounds
3. Review of Atomic Structure
a. Ionic and Covalent Bonding
b. Character of Covalent Compound
c. Bonding in Carbon
4 Molecular Orbital Theory
a. Atomic Orbitals
b. Sigma Bonding
c. Pi Bonding
Definition and Importance of Organic Chemistry

Organic chemistry is the study of the chemistry of carbon compounds. Carbon

is singled out because it has a chemical diversity unrivaled by any other chemical
element. Its diversity is based on the following:

 Carbon atoms bond reasonably strongly with other carbon atoms.

 Carbon atoms bond reasonably strongly with atoms of other elements.

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  Carbon atoms make a large number of covalent bonds (four).

Most organic chemicals are covalent compounds, which is why we

introduce organic chemistry here. By convention, compounds containing
carbonate ions and bicarbonate ions, as well as carbon dioxide and carbon
monoxide, are not considered part of organic chemistry, even though they
contain carbon.
The simplest organic compounds are the hydrocarbons, compounds
composed of carbon and hydrogen atoms only. Some hydrocarbons have
only single bonds and appear as a chain (which can be a straight chain or can
have branches) of carbon atoms also bonded to hydrogen atoms. These
hydrocarbons are called alkanes (saturated hydrocarbons). Each alkane has
a characteristic, systematic name depending on the number of carbon atoms
in the molecule.

Although originally defined as the chemistry of biological molecules,

organic chemistry has since been redefined to refer specifically to carbon
compounds — even those with non-biological origin. Some carbon molecules
are not considered organic, with carbon dioxide being the most well known
and most common inorganic carbon compound, but such molecules are the
exception and not the rule.

Organic chemistry focuses on carbon and following movement of the

electrons in carbon chains and rings, and also how electrons are shared with
other carbon atoms and heteroatoms. Organic chemistry is primarily
concerned with the properties of covalent bonds and non-metallic elements,
though ions and metals do play critical roles in some reactions.

The applications of organic chemistry are myriad, and include all sorts
of plastics, dyes, flavorings, scents, detergents, explosives, fuels and many,
many other products. Read the ingredient list for almost any kind of food that
you eat — or even your shampoo bottle — and you will see the handiwork of
organic chemists listed there.

Importance of Organic Chemistry

Human life has become very simple by using organic chemicals.

The importance of organic chemicals in the daily life and industrial area can be
explained as follows.

1. Food Vitamins, proteins, sugar, flour, fats etc. are all organic compounds.
Organic chemicals are also used to meet their requirement. Important
contribution is.
2. Agriculture is an important place for organic chemical for the growth of
agricultural production. Various types of fertilizers, chemicals used in seed

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 protection; Like - gamoxine and various insecticides are only one type of
organic compound.
3. Different types of medicines such as chloromyctin, streptomycin, aspirin,
chloroform, paracetamol, urotropin, etc. are examples of organic compounds
and their synthesis is only for organic chemicals.
4. Fabrics made from cloth silk, woolen, cotton and many types of rayon,

noyolan terrylines are the same as organic chemicals.

5. In war, many explosive-used explosives like Dynamite TNT, Ashrugas,

Mustard Gas, etc. are organic chemicals.

6. Fuel and energy except wood and coal. Many fuels have been provided by
organic chemicals; Such as diesel, petrol cooking gas, etc.
7. Rubber and Plastic various types of rubber, plastic, polyethylene, neoprene
rubber, polypropylene, etc. Organic substances are only for organic
chemicals.
8. Cosmetics cream, soap, paint, camphor, oil, perfume, etc. makeup and
decoration materials are only received by organic chemicals.
9. Other wood accessories and leather, paper, varnish, photographic developer,
resins, etc. are only for organic chemicals.

Structure and Importance of Organic Compounds

Introduction to structure drawing

Observe the following drawings of the structure of retinol, the most common
form of vitamin A. The first drawing follows a Lewis-based structure which is helpful
when you want to look at every single atom; however, showing all of the hydrogen
atoms makes it difficult to compare the overall structure with other similar molecules
and makes it difficult to focus in on the double bonds and OH group.

Retinol: Lewis-type straight-line drawing

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 The following is a skeletal (a.k.a. line-angle) formula for retinol. With this
simplified representation, one can easily see the carbon-carbon bonds, double
bonds, OH group, and CH3 groups sticking off of the main ring and chain. Also, it is
much quicker to draw this than the one above.

Retinol: Skeletal formula

Importance of structure

Learning and practicing the basics of organic chemistry will help you
immensely in the long run as you learn new concepts and reactions. Some people
say that organic chemistry is like another language, and in some aspects, it is. At
first it may seem difficult or overwhelming, but the more you practice looking at and
drawing organic molecules, the more familiar you will become with the structures and
formulae. Another good idea is to get a model kit and physically make the molecules
that you have trouble picturing in your head.

Through general chemistry, you may have already experienced looking at

molecular structure. The different ways to draw organic molecules include Lewis-
type, condensed formulae, and skeletal formulae. It will be more helpful if you
become comfortable going from one style of drawing to another, and look at
drawings and understanding what they mean, than knowing which kind of drawing is
named what.

An example of a drawing that incorporates all three ways to draw organic

molecules would be the following additional drawing of retinol. The majority of the
drawing uses the skeletal formula, but the -CH 3 are written as condensed formulae,
and the -OH group is written in Lewis-type form.

Drawing the structure of organic molecules

Although larger molecules may look complicated, they can be easily

understood by breaking them down and looking at their smaller components.

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 All atoms want to have their valence shell full, a “closed shell.” Hydrogen has
a full shell with only 2 e – whereas carbon, oxygen, and nitrogen want to have 8 e –(an
“octet”). When looking at the different representations of molecules, keep in mind
the Octet Rule. Also remember that hydrogen can bond one time, oxygen can bond
up to two times, nitrogen can bond up to three times, and carbon can bond up to four
times.

Lewis-type

Lewis-type structures are similar to traditional Lewis structures, but instead

of covalent bonds being represented by electron dots, the two shared electrons are
shown by a line.

(A) 

(B)

(C)

Lone pairs remain as two electron dots, but they are usually left out even
though they are still there. Notice how the three lone pairs of electrons were not draw
in around chlorine in example B.

Condensed formulae

A condensed formula is made up of the elemental symbols. The order of the

atoms suggests the connectivity. Condensed formulas can be read from either

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direction and H3C is the same as CH3, although the latter is more common because
Look at the examples below and match them with their identical molecule under
Kekulé structures and bond-line formulas.

(A)  CH3CH2OH     (B)  ClCH2CH2CH(OCH3)CH3       (C) H3CNHCH2COOH

Let’s look closely at example B. As you go through a condensed formula, you

want to focus on the carbons and other elements that aren’t hydrogen. The
hydrogens are important, but are usually there to complete octets. Also, notice the -
OCH3 is in written in parentheses which tell you that it not part of the main chain of
carbons. As you read through a a condensed formula, if you reach an atom that
doesn’t have a complete octet by the time you reach the next hydrogen, then it’s
possible that there are double or triple bonds. In example C, the carbon is double
bonded to oxygen and single bonded to another oxygen. Notice how COOH means
C(=O)-O-H instead of CH3-C-O-O-H because in the latter structure carbon does not
have a complete octet and oxygens.

Skeletal formulae

Because of the typical (more stable) bonds that atoms tend to make in
molecules, skeletal chains often end up looking like zig-zag lines. If you work with a
molecular model kit you will find it difficult to make stick straight molecules (unless
they contain sp triple bonds), whereas zig-zag molecules and bonds are much more
feasible.

(A) 

(B)

(C)

These molecules correspond to the exact same molecules depicted for Lewis-
type structures and condensed formulae. Notice how the carbons are no longer
drawn in and are replaced by the ends and bends of a lines. In addition, the
hydrogens have been omitted, but could be easily drawn in (see practice problems).
Although we do not usually draw in the H’s that are bonded to carbon, we do draw
them in if they are connected to other atoms besides carbon (example is the OH
group above in example A) . This is done because it is not always clear if the non-
carbon atom is surrounded by lone pairs or hydrogens. Also in example A, notice

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how the OH is drawn with a bond to the second carbon, but it does not mean that
there is a third carbon at the end of that bond/ line.

PROBLEMS

1. (6) How many carbons are in the following drawing? How many

hydrogens?

2.  (5 C) How many carbons are in the following drawing? How many
hydrogens?

3.  How many carbons are in the following drawing? How many

hydrogens?

4. Look at the following molecule of vitamin A and draw in the hidden

hydrogens and electron pairs.

 (Hint: Do all of the carbons have 4

bonds? Do all the oxygens have a full octet?)
5. How many bonds can hydrogen make?

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 6. How many bonds can chlorine make?
7. Dashed lines means the atomic bond goes ___________(away/toward)
you.
8. Draw ClCH2CH2CH(OCH3)CH3 in Lewis and skeletal form.

Review of Atomic Structure

a. Ionic and Covalent Bonding
b. Character of Covalent Compound
c. Bonding in Carbon

Chemical Bonds

Introduction to Chemical Bonding

Chemical bonding describes a variety of interactions that hold atoms together in

chemical compounds.

Chemical bonds

Chemical bonds are the connections between atoms in a molecule. These bonds
include both strong intramolecular interactions, such as covalent and ionic bonds.
They are related to weaker intermolecular forces, such as dipole-dipole interactions,
the London dispersion forces, and hydrogen bonding. The weaker forces will be
discussed in a later concept.

Covalent Bonds

Chemical bonds are the forces of attraction that tie atoms together. Bonds are
formed when valence electrons, the electrons in the outermost electronic “shell” of
an atom, interact. The nature of the interaction between the atoms depends on their
relative electronegativity. Atoms with equal or similar electronegativity form covalent
bonds, in which the valence electron density is shared between the two atoms. The
electron density resides between the atoms and is attracted to both nuclei. This type
of bond forms most frequently between two non- metals.

When there is a greater electronegativity difference than between covalently bonded

atoms, the pair of atoms usually forms a polar covalent bond. The electrons are still
shared between the atoms, but the electrons are not equally attracted to both
elements. As a result, the electrons tend to be found near one particular atom most
of the time. Again, polar covalent bonds tend to occur between non-metals.

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Ionic Bonds

Finally, for atoms with the largest electronegativity differences (such as metals
bonding with nonmetals), the bonding interaction is called ionic, and the valence
electrons are typically represented as being transferred from the metal atom to the
nonmetal. Once the electrons have been transferred to the non-metal, both the metal
and the non-metal are considered to be ions. The two oppositely charged ions attract
each other to form an ionic compound.

Bonds, Stability, and Compounds

Covalent interactions are directional and depend on orbital overlap, while ionic
interactions have no particular directionality. Each of these interactions allows the
atoms involved to gain eight electrons in their valence shell, satisfying the octet rule
and making the atoms more stable.

These atomic properties help describe the macroscopic properties of compounds.

For example, smaller covalent compounds that are held together by weaker bonds
are frequently soft and malleable. On the other hand, longer-range covalent
interactions can be quite strong, making their compounds very durable. Ionic
compounds, though composed of strong bonding interactions, tend to form brittle
crystalline lattices.

Ionic Bonds

Ionic bonds are a subset of chemical bonds that result from the transfer of valence
electrons, typically between a metal and a nonmetal

Ionic Bonding
Ionic bonding is the process of not sharing electrons between two atoms. It
occurs between a nonmetal and a metal. Ionic bonding is also known as the
process in which electrons are "transferred" to one another because the two
atoms have different levels of electron affinity. In the picture below, a sodium
(Na) ion and a chlorine (Cl) ion are being combined through ionic bonding.
Na+ has less electronegativity due to a large atomic radius and essentially does
not want the electron it has. This will easily allow the more electronegative
chlorine atom to gain the electron to complete its 3rd energy level. Throughout
this process, the transfer of the electron releases energy to the atmosphere.

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Another example of ionic bonding is the crystal lattice structure shown above. The ions are
arranged in such a way that shows unifomity and stablity; a physical characteristic in crystals
and solids. Moreover, in a concept called "the sea of electrons," it is seen that the molecular
structure of metals is composed of stabilized positive ions (cations) and "free-flowing"
electrons that weave in-between the cations. This attributes to the metal property of
conductivity; the flowing electrons allow the electric current to pass through them. In
addition, this explains why strong electrolytes are good conductors. Ionic bonds are easily
broken by water because the polarity of the water molecules shield the anions from attracting
the cations. Therefore, the ionic compounds dissociate easily in water, and the metallic
properties of the compound allow conductivity of the solution.

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Forming an Ion

Ionic bonds are a class of chemical bonds that result from the exchange of one or
more valence electrons from one atom, typically a metal, to another, typically a
nonmetal. This electron exchange results in an electrostatic attraction between the
two atoms called an ionic bond. An atom that loses one or more valence electrons to
become a positively charged ion is known as a cation, while an atom that gains
electrons and becomes negatively charged is known as an anion.

This exchange of valence electrons allows ions to achieve electron configurations

that mimic those of the noble gases, satisfying the octet rule. The octet rule states
that an atom is most stable when there are eight electrons in its valence shell. Atoms
with less than eight electrons tend to satisfy the duet rule, having two electrons in
their valence shell. By satisfying the duet rule or the octet rule, ions are more stable.

A cation is indicated by a positive superscript charge (+ something) to the right of the

atom. An anion is indicated by a negative superscript charge (- something) to the
right of the atom. For example, if a sodium atom loses one electron, it will have one
more proton than electron, giving it an overall +1 charge. The chemical symbol for
the sodium ion is Na+1 or just Na+. Similarly, if a chlorine atom gains an extra
electron, it becomes the chloride ion, Cl –. Both ions form because the ion is more
stable than the atom due to the octet rule.

Forming an Ionic Bond

Once the oppositely charged ions form, they are attracted by their positive and
negative charges and form an ionic compound. Ionic bonds are also formed when
there is a large electronegativity difference between two atoms. This difference

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causes an unequal sharing of electrons such that one atom completely loses one or
more electrons and the other atom gains one or more electrons, such as in the
creation of an ionic bond between a metal atom (sodium) and a nonmetal (fluorine).

Formation of sodium fluoride: The transfer of electrons and subsequent attraction of oppositely charged
ions.

Determining the Formula of an Ionic Compound

To determine the chemical formulas of ionic compounds, the following two conditions
must be satisfied:

1. Each ion must obey the octet rule for maximum stability.
2. Ions will combine in a way that the overall ionic compound will be
neutral. In other words, the charges of the ions must balance out.

Magnesium and fluorine combine to form an ionic compound. What is the formula for
the compound?

Mg most commonly forms a 2+ ion. This is because Mg has two valence electrons
and it would like to get rid of those two ions to obey the octet rule. Fluorine has
seven valence electrons and usually forms the F – ion because it gains one electron
to satisfy the octet rule. When Mg 2+ and F – combine to form an ionic compound, their
charges must cancel out. Therefore, one Mg 2+ needs two F – ions to neutralize the
charge. The 2+ of the Mg is balanced by having two -1 charged ions. Therefore, the
formula of the compound is MgF 2. The subscript two indicates that there are two
fluorines that are ionically bonded to magnesium.

On the macroscopic scale, ionic compounds form crystalline lattice structures that
are characterized by high melting and boiling points and good electrical conductivity
when melted or solubilized.

Example

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Magnesium and fluorine combine to form an ionic compound. What is the formula for
the compound?

Mg most commonly forms a 2+ ion. This is because Mg has two valence electrons
and it would like to get rid of those two ions to obey the octet rule. Fluorine has
seven valence electrons and as such, usually forms the F – ion because it gains one
electron to satisfy the octet rule. When Mg2+ and F– combine to form an ionic
compound, their charges must cancel out. Therefore, one Mg 2+ needs two F– ions to
balance. The 2+ of the Mg is balanced by having two -1 charged ions. Therefore, the
formula of the compound is MgF 2. The subscript two indicates that there are two
fluorines that are ionically bonded to magnesium.

Ionic Compounds v. Molecular Compounds

Unlike an ionic bond, a covalent bond is stronger between two atoms with similar
electronegativity. For atoms with equal electronegativity, the bond between them will
be a non- polar covalent interaction. In non-polar covalent bonds, the electrons are
equally shared between the two atoms. For atoms with differing electronegativity, the
bond will be a polar covalent interaction, where the electrons will not be shared
equally.

Ionic solids are generally characterized by high melting and boiling points along with
brittle, crystalline structures. Covalent compounds, on the other hand, have lower
melting and boiling points. Unlike ionic compounds, they are often not soluble in
water and do not conduct electricity when solubilized.

Covalent Bonds

Covalent bonding involves two atoms, typically nonmetals, sharing valence

electrons.

Forming Covalent Bonds

Covalent bonds are a class of chemical bonds where valence electrons are shared
between two atoms, typically two nonmetals. The formation of a covalent bond
allows the nonmetals to obey the octet rule and thus become more stable. For
example:

 A fluorine atom has seven valence electrons. If it shares one electron

with a carbon atom (which has four valence electrons), the fluorine will
have a full octet (its seven electrons plus the one it is sharing with
carbon).
 Carbon will then have five valence electrons (its four and the one its
sharing with fluorine). Covalently sharing two electrons is also known as
a “single bond.” Carbon will have to form four single bonds with four
different fluorine atoms to fill its octet. The result is CF 4 or carbon
tetrafluoride.

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Covalent bonding requires a specific orientation between atoms in order to achieve
the overlap between bonding orbitals. Covalent bonding interactions include sigma-
bonding (σ) and pi-bonding (π). Sigma bonds are the strongest type of covalent
interaction and are formed via the overlap of atomic orbitals along the orbital axis.
The overlapped orbitals allow the shared electrons to move freely between atoms. Pi
bonds are a weaker type of covalent interactions and result from the overlap of two
lobes of the interacting atomic orbitals above and below the orbital axis.

Covalent bonds can be single, double, and triple bonds.

 Single bonds occur when two electrons are shared and are composed of
one sigma bond between the two atoms.
 Double bonds occur when four electrons are shared between the two
atoms and consist of one sigma bond and one pi bond.
 Triple bonds occur when six electrons are shared between the two
atoms and consist of one sigma bond and two pi bonds (see later
concept for more info about pi and sigma bonds).

Covalent Bonding
Covalent bonding is the process of sharing of electrons between two
atoms. The bonds are typically between a nonmetal and a nonmetal. Since
their electronegativities are all within the high range, the electrons are
attracted and pulled by both atom's nuceli. In the case of two identical
atoms that are bonded to each other (also known as a nonpolar bond,
explained later below), they both emit the same force of pull on the
electrons, thus there is equal attraction between the two atoms (i.e.
oxygen gas, or O2, have an equal distribution of electron affinity. This
makes covalent bonds harder to break.

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There are three types of covalent bonds: single, double, and triple bonds. A
single bond is composed of 2 bonded electrons. Naturally, a double bond has 4
electrons, and a triple bond has 6 bonded electrons. Because a triple bond will
have more strength in electron affinity than a single bond, the attraction to the
positively charged nucleus is increased, meaning that the distance from the
nucleus to the electrons is less. Simply put, the more bonds or the greater the
bond strength, the shorter the bond length will be. In other words:

Bond length: triple bond < double bond < single bond

Characteristics of covalent bonds

Covalent bonds have certain characteristics that depend on the identities of

the atoms participating in the bond. Two characteristics are bond length and bond
polarity.

Bond length

The covalent bond in the hydrogen molecule (H 2) has a certain length (about
7.4 × 10−11 m). Other covalent bonds also have known bond lengths, which are
dependent on both the identities of the atoms in the bond and whether the bonds are
single, double, or triple bonds. Table 1.1. lists the approximate bond lengths for
some single covalent bonds. The exact bond length may vary depending on the
identity of the molecule but will be close to the value given in the table.

Table 1.1. Approximate bond lengths of some single bonds

Bond Length (× 10−12 m)

H–H 74

H–C 110

H–N 100

H–O 97

H–I 161

C–C 154

C–N 147

C–O 143

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 Bond Length (× 10−12 m)

N–N 145

O–O 145

Table 1.2. compares the lengths of single covalent bonds with those of double and
triple bonds between the same atoms. Without exception, as the number of covalent
bonds between two atoms increases, the bond length decreases. With more
electrons between the two nuclei, the nuclei can get closer together before the
internuclear repulsion is strong enough to balance the attraction.

Table 1.2. Comparison of bond lengths for single and multiple bonds

Bond Length (× 10−12 m)

C–C 154

C=C 134

C≡C 120

C–N 147

C=N 128

C≡N 116

C–O 143

C=O 120

C≡O 113

N–N 145

N=N 123

N≡N 110

O–O 145

O=O 121

Bonding in Carbon

The carbon atom is unique among elements in its tendency to form

extensive networks of covalent bonds not only with other elements but also
with itself. Because of its position midway in the second horizontal row of
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the periodic table, carbon is neither an electropositive nor an
electronegative element; it therefore is more likely to share electrons than
to gain or lose them. Moreover, of all the elements in the second row,
carbon has the maximum number of outer shell electrons (four) capable of
forming covalent bonds. (Other elements, such as phosphorus [P]
and cobalt [Co], are able to form five and six covalent bonds, respectively,
with other elements, but they lack carbon’s ability to bond indefinitely with
itself.) When fully bonded to other atoms, the four bonds of the carbon
atom are directed to the corners of a tetrahedron and make angles of about
109.5° with each other (see chemical bonding: Bonds between atoms). The
result is that not only can carbon atoms combine with one another
indefinitely to give compounds of extremely high molecular weight, but the
molecules formed can exist in an infinite variety of three-dimensional
structures. The possibilities for diversity are increased by the presence of
atoms other than carbon in organic compounds,
especially hydrogen (H), oxygen (O), nitrogen (N), halogens (fluorine [F], c
hlorine [Cl], bromine [Br], and iodine [I]), and sulfur (S). It is the
enormous potential for variation in chemical properties that has made
organic compounds essential to life on Earth.

The structures of organic compounds commonly are represented by

simplified structural formulas, which show not only the kinds and numbers
of atoms present in the molecule but also the way in which the atoms are
linked by the covalent bonds—information that is not given by simple
molecular formulas, which specify only the number and type of atoms
contained in a molecule. (With most inorganic compounds, the use of
structural formulas is not necessary, because only a few atoms are involved
and only a single arrangement of the atoms is possible.) In the structural
formulas of organic compounds, short lines are used to represent the
covalent bonds. Atoms of the individual elements are represented by their
chemical symbols, as in molecular formulas.

Structural formulas vary widely in the amount of three-dimensional

information they convey, and the type of structural formula used for any
one molecule depends on the nature of the information the formula is
meant to display. The different levels of sophistication can be illustrated by
considering some of the least complex organic compounds,
the hydrocarbons. The gas ethane, for example, has the molecular formula
C2H6. The simplest structural formula, drawn either in a condensed or in an
expanded version, reveals that ethane consists of two carbon atoms bonded
to one another, each carbon atom bearing three hydrogen atoms. Such a
two-dimensional representation correctly shows the bonding arrangement
in ethane, but it does not convey any information about its three-
dimensional architecture. A more sophisticated structural formula can be
drawn to better represent the three-dimensional structure of the molecule.

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Such a structural formula correctly shows the tetrahedral orientation of the
four atoms (one carbon and three hydrogens) bonded to each carbon, and
the specific architecture of the molecule.

Larger organic molecules are formed by the addition of more carbon

atoms. Butane, for example, is a gaseous hydrocarbon with the molecular
formula C4H10, and it exists as a chain of four carbon atoms with 10 attached
hydrogen atoms. As carbon atoms are added to a molecular framework, the
carbon chain can develop branches or form cyclic structures. A very
common ring structure contains six carbon atoms in a ring, each bonded in
a tetrahedral arrangement, as in the hydrocarbon cyclohexane, C6H12. Such
ring structures are often very simply represented as regular polygons in
which each apex represents a carbon atom, and the hydrogen atoms that
complete the bonding requirements of the carbon atoms are not shown.
The polygon convention for cyclic structures reveals concisely the bonding
arrangement of the molecule but does not explicitly convey information
about the actual three-dimensional architecture. It should be noted that the
polygon is only a two-dimensional symbol for the three-dimensional
molecule.

Under certain bonding conditions, adjacent atoms will form multiple

bonds with each other. A double bond is formed when two atoms use two
electron pairs to form two covalent bonds; a triple bond results when two
atoms share three electron pairs to form three covalent bonds. Multiple
bonds have special structural and electronic features that generate
interesting chemical properties. The six atoms involved in a double bond
(as in ethene, C2H4) lie in a single plane, with regions above and below the
plane occupied by the electrons of the second covalent bond. Atoms in a
triple bond (as in acetylene, or ethyne, C2H2) lie in a straight line, with four
regions beside the bond axis occupied by electrons of the second and third
covalent bonds.

Molecular Orbital Theory

a. Atomic Orbitals
b. Sigma Bonding
c. Pi Bonding
Molecular orbital (MO) theory uses a linear combination of atomic
orbitals (LCAO) to represent molecular orbitals resulting from bonds between atoms.
These are often divided into three types, bonding, antibonding, and non-bonding. A
bonding orbital concentrates electron density in the region between a given pair of
atoms, so that its electron density will tend to attract each of the two nuclei toward
the other and hold the two atoms together. An anti-bonding orbital concentrates
electron density "behind" each nucleus (i.e. on the side of each atom which is

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farthest from the other atom), and so tends to pull each of the two nuclei away from
the other and actually weaken the bond between the two nuclei. Electrons in non-
bonding orbitals tend to be associated with atomic orbitals that do not interact
positively or negatively with one another, and electrons in these orbitals neither
contribute to nor detract from bond strength.
Molecular orbitals are further divided according to the types of atomic
orbitals they are formed from. Chemical substances will form bonding interactions if
their orbitals become lower in energy when they interact with each other. Different
bonding orbitals are distinguished that differ by electron configuration (electron cloud
shape) and by energy levels.
The molecular orbitals of a molecule can be illustrated in molecular orbital diagrams.
Common bonding orbitals are sigma (σ) orbitals which are symmetric about the bond
axis, and or pi (Π) orbitals with a nodal plane along the bond axis. Less common
are delta (δ) orbitals and phi (φ) orbitals with two and three nodal planes respectively
along the bond axis. Antibonding orbitals are signified by the addition of an asterisk.
For example, an antibonding pi orbital may be shown as π*.
MOT provides a global, delocalized perspective on chemical bonding. In MO
theory, any electron in a molecule may be found anywhere in the molecule, since
quantum conditions allow electrons to travel under the influence of an arbitrarily large
number of nuclei, as long as they are in eigenstates permitted by certain quantum
rules. Thus, when excited with the requisite amount of energy through high-
frequency light or other means, electrons can transition to higher-energy molecular
orbitals. For instance, in the simple case of a hydrogen diatomic molecule, promotion
of a single electron from a bonding orbital to an antibonding orbital can occur under
UV radiation. This promotion weakens the bond between the two hydrogen atoms
and can lead to photodissociation—the breaking of a chemical bond due to the
absorption of light.
Molecular orbital theory is used to interpret ultraviolet-visible
spectroscopy (UV-VIS). Changes to the electronic structure of molecules can be
seen by the absorbance of light at specific wavelengths. Assignments can be made
to these signals indicated by the transition of electrons moving from one orbital at a
lower energy to a higher energy orbital. The molecular orbital diagram for the final
state describes the electronic nature of the molecule in an excited state.
Although in MO theory some molecular orbitals may hold electrons that are
more localized between specific pairs of molecular atoms, other orbitals may hold
electrons that are spread more uniformly over the molecule. Thus, overall, bonding is
far more delocalized in MO theory, which makes it more applicable to resonant
molecules that have equivalent non-integer bond orders than valence bond (VB)
theory. This makes MO theory more useful for the description of extended systems.
An example is the MO description of benzene, C
6H
6, which is an aromatic hexagonal ring of six carbon atoms and three double bonds.
In this molecule, 24 of the 30 total valence bonding electrons—24 coming from
carbon atoms and 6 coming from hydrogen atoms—are located in 12 σ (sigma)
bonding orbitals, which are located mostly between pairs of atoms (C-C or C-H),
similarly to the electrons in the valence bond description. However, in benzene the
remaining six bonding electrons are located in three π (pi) molecular bonding orbitals

19
that are delocalized around the ring. Two of these electrons are in an MO that has
equal orbital contributions from all six atoms. The other four electrons are in orbitals
with vertical nodes at right angles to each other. As in the VB theory, all of these six
delocalized π electrons reside in a larger space that exists above and below the ring
plane. All carbon-carbon bonds in benzene are chemically equivalent. In MO theory
this is a direct consequence of the fact that the three molecular π orbitals combine
and evenly spread the extra six electrons over six carbon atoms.

Structure of benzene
In molecules such as methane, CH
4, the eight valence electrons are found in four MOs that are spread out over all five
atoms. It is possible to transform the MOs into four localized sp 3 orbitals. Linus
Pauling, in 1931, hybridized the carbon 2s and 2p orbitals so that they pointed
directly at the hydrogen 1s basis functions and featured maximal overlap. However,
the delocalized MO description is more appropriate for predicting ionization
energies and the positions of spectral absorption bands. When methane is ionized, a
single electron is taken from the valence MOs, which can come from the s bonding
or the triply degenerate p bonding levels, yielding two ionization energies. In
comparison, the explanation in VB theory is more complicated. When one electron is
removed from an sp3 orbital, resonance is invoked between four valence bond
structures, each of which has a single one-electron bond and three two-electron
bonds. Triply degenerate T2 and A1 ionized states (CH4+) are produced from different
linear combinations of these four structures. The difference in energy between the
ionized and ground state gives the two ionization energies.
As in benzene, in substances such as beta carotene, chlorophyll, or heme,
some electrons in the π orbitals are spread out in molecular orbitals over long
distances in a molecule, resulting in light absorption in lower energies (the visible
spectrum), which accounts for the characteristic colours of these substances. This
and other spectroscopic data for molecules are well explained in MO theory, with an
emphasis on electronic states associated with multicenter orbitals, including mixing
of orbitals premised on principles of orbital symmetry matching The same MO
principles also naturally explain some electrical phenomena, such as high electrical
conductivity in the planar direction of the hexagonal atomic sheets that exist
in graphite. This results from continuous band overlap of half-filled p orbitals and
explains electrical conduction. MO theory recognizes that some electrons in the
graphite atomic sheets are completely delocalized over arbitrary distances, and
reside in very large molecular orbitals that cover an entire graphite sheet, and some
electrons are thus as free to move and therefore conduct electricity in the sheet
plane, as if they resided in a metal.

Atomic Orbitals

Atoms can join together by forming a chemical bond, which is a very strong

attraction between two atoms. Chemical bonds are formed when electrons in
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different atoms interact with each other to make an arrangement that is more stable
than when the atoms are apart.

What causes atoms to make a chemical bond with other atoms, rather than
remaining as individual atoms? A clue comes by considering the noble gas
elements, the rightmost column of the periodic table. These elements—helium, neon,
argon, krypton, xenon, and radon—do not form compounds very easily, which
suggests that they are especially stable as lone atoms. What else do the noble gas
elements have in common? Except for helium, they all have eight valence electrons.
Chemists have concluded that atoms are especially stable if they have eight
electrons in their outermost shell. This useful rule of thumb is called the octet rule,
and it is a key to understanding why compounds form.

There are two ways for an atom that does not have an octet of valence
electrons to obtain an octet in its outer shell. One way is the transfer of electrons
between two atoms until all atoms have octets. Because some atoms will lose
electrons and some atoms will gain electrons, there is no overall change in the
number of electrons, but individual atoms acquire a nonzero electric charge. Those
that lose electrons become positively charged, and those that gain electrons become
negatively charged. Charged atoms are called ions. Because opposite charges
attract (while like charges repel), these oppositely charged ions attract each other,
forming ionic bonds. The resulting compounds are called ionic compounds and
are the primary subject of this chapter.

The second way for an atom to obtain an octet of electrons is by sharing electrons
with another atom. These shared electrons simultaneously occupy the outermost
shell of more than one atom. The bond made by electron sharing is called
a covalent bond. Covalent bonding and covalent compounds will be discussed in
detail below.

NOTE: Despite our focus on the octet rule, we must remember that for small atoms, such as
hydrogen, helium, and lithium, the first shell is, or becomes, the outermost shell and hold
only two electrons. Therefore, these atoms satisfy a “duet rule” rather than the octet rule.

Atomic orbitals

Orbits and orbitals sound similar, but they have quite different meanings. It is
essential that you understand the difference between them.

What is the electron doing in the orbital? We don't know, we can't know, and so we
just ignore the problem! All you can say is that if an electron is in a particular orbital it
will have a particular definable energy.

Each orbital has a name.

21
The orbital occupied by the hydrogen electron is called a 1s
orbital. The "1" represents the fact that the orbital is in the energy level closest to
the nucleus. The "s" tells you about the shape of the orbital. s orbitals are
spherically symmetric around the nucleus - in each case, like a hollow ball made of
rather chunky material with the nucleus at its centre.

The orbital on the left is a 2s orbital. This is similar to a 1s

orbital except that the region where there is the greatest
chance of finding the electron is further from the nucleus - this
is an orbital at the second energy level.

If you look carefully, you will notice that there is another

region of slightly higher electron density (where the dots are
thicker) nearer the nucleus. ("Electron density" is another way
of talking about how likely you are to find an electron at a
particular place.)

2s (and 3s, 4s, etc) electrons spend some of their time closer to the nucleus than
you might expect. The effect of this is to slightly reduce the energy of electrons in s
orbitals. The nearer the nucleus the electrons get, the lower their energy.

3s, 4s (etc) orbitals get progressively further from the nucleus.

p orbitals

Not all electrons inhabit s orbitals (in fact, very few electrons live in s
orbitals). At the first energy level, the only orbital available to
electrons is the 1s orbital, but at the second level, as well as a 2s
orbital, there are also orbitals called 2p orbitals.

A p orbital is rather like 2 identical balloons tied together at the

nucleus. The diagram on the right is a cross-section through that 3-
dimensional region of space. Once again, the orbital shows where
there is a 95% chance of finding a particular electron.

Sigma and Pi bonds

Sigma and pi bonds are types of covalent bonds that differ in the
overlapping of atomic orbitals. Covalent bonds are formed by the overlapping
of atomic orbitals. Sigma bonds are a result of the head-to-head overlapping of
atomic orbitals whereas pi bonds are formed by the lateral overlap of two
atomic orbitals.

22
Various bond parameters such as bond length, bond angle, and bond enthalpy
depend on the way the overlapping of atomic orbital takes place. This overlap
occurs in two major ways, giving rise to two primary types of covalent bonds,
i.e. sigma and pi bonds.

The Sigma (σ) Bond
This type of covalent bond is formed by head-on positive (same phase) overlap
of atomic orbitals along the internuclear axis. Sigma bonds are the strongest
covalent bonds, owing to the direct overlapping of the participating orbitals.
The electrons participating in a σ bond are commonly referred to as σ electrons.
Generally, all single bonds are sigma bonds. They can be formed via the
following combinations of atomic orbitals.

S-S Overlapping
In this kind of overlapping, one ‘s’ orbital from each participating atom
undergoes head-on overlapping along the internuclear axis. An s orbital must be
half-filled before it overlaps with another.

23
The overlapping of two s orbitals resulting in a sigma bond is illustrated above.
This type of overlap occurs in H2 molecules, where each hydrogen atom has a
half-filled s orbital.

S-P Overlapping
Here, one half filed s orbital overlaps with one half-filled p orbital along the
internuclear axis, forming a covalent bond. This condition is illustrated below.

This type of overlapping can be observed in ammonia. An NH3 molecule

features 3 sigma bonds, formed by the overlap of the 2p x, 2py, and 2pz orbitals
belonging to the nitrogen atom and the 1s orbitals of the three hydrogen atoms.

P-P overlapping
In this condition, one half-filled p orbital from each participating atom
undergoes head-on overlapping along the internuclear axis. This type of
overlapping is illustrated below.

24
A Cl2 molecule features a p-p overlap of the 3pz orbitals of two chlorine atoms.
It is important to note that the head-to-head overlapping of two p orbitals gives
a sigma bond whereas the lateral overlap of these orbitals leads to the formation
of pi bonds.

The Pi (π) Bond

Pi bonds are formed by the sidewise positive (same phase) overlap of atomic
orbitals along a direction perpendicular to the internuclear axis. During the
formation of π bonds, the axes of the atomic orbitals are parallel to each other
whereas the overlapping is perpendicular to the internuclear axis. This type of
covalent bonding is illustrated below.

Pi Bonds are generally weaker than sigma bonds, owing to the significantly
lower degree of overlapping. Generally, double bonds consist of one sigma and
one pi bond, whereas a typical triple bond is made up of two π bonds and one σ
bond. It is important to note that a combination of sigma and pi bonds is always
stronger than a single sigma bond.

25
Difference Between Sigma and Pi Bonds
The key differences between sigma and pi bonds are tabulated below.

Sigma Bond Pi Bond

The overlapping orbitals can be pure or The overlapping orbitals must

hybrid be unhybridized

These bonds are strong and have high bond These bonds are relatively
energies. weak.

Must exist along with a sigma

Can exist independently
bond.

Has no role in determining the

Has an impact on the shape of molecules
shape of molecules

Teaching and Learning Activities:

Activity 1:
Identify the following elements:
a. Na_(SODIUM )An excited state of this element has the electron configuration
1s2 2s2 2p6 3s1
b. S_(SULFUR) The ground state electron configuration is [Ne]3s23p4
c. Ag_(SILVER) An excited state of this element has the electron configuration
[Kr]5s24d65p26s1
d. Bi_(BISTMUTH)The ground state configuration contains three unpaired 6p
electrons.

Activity 2:
1. What is the main distinction between ionic and covalent bonding
2.  How many pairs of elec trons are shared in the following types of covalent
bonds?

Activity 3:
1. How Many Pi Bonds Exist in Double and Triple Bonds?
2. What are the Possible Combinations of Orbitals in Sigma Bonds?
3. What is the Number of Sigma and Pi bonds in a Benzene Molecule?

26
Recommended learning materials and resources for supplementary reading:

The recommended learning materials and resources in this chapter include the URL
of the resources from the Internet (PDF, youtube, slideshare, etc.)

Flexible Teaching Learning Modality (FTLM):

This chapter adopts the synchronous and asynchronous learning modalities for you
to have better access and learning of the lessons. This may include google classroom,
moodle, schoology, edmodo, Podcast, printed materials and other resources depending on
your needs and capacity to us e the material.

Assessment Task

1. Which among the following chemical bond were described by Kossel and Lewis?
a) Metallic bond
b) Polar covalent bond
c) Coordinate bond
d) Ionic and Covalent bond

2. Which among the following is not a property of Ionic bond?

a) Losing of electrons
b) Gain of electrons
c) Sharing of electrons
d) Transfer of electrons

3. If a bond is made up of a large number of organic compounds, then the bond is

termed as?
a) Ionic bond
b) Metallic bond
c) Covalent bond
d) Dipolar bond

4. The number of electrons lost by atoms of group IIIA equals

a.2
b.4
c.5
d.3

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 5. The interaction between highly electron-deficient hydrogen and highly
electronegative atom is called
A. Covalent bond
B. ionic bond
C. dipole-dipole interaction
D. hydrogen bond

Answer Key:
Activity 1:
a. Na
b. S
c. Ag
d.

Activity 2:
1. The main distinction between ionic and covalent bonding lies in the sharing of
electrons. Ionic bonding involves the transfer of electrons from one atom to
another, resulting in the formation of charged ions, while covalent bonding
involves the sharing of electrons between atoms to achieve a stable electron
configuration.
2. a. a single bond – one (2 electrons)

b. a double bond – two (4 electrons)

c. a triple bond – three (6 electrons)

Activity 3

1. A triple bond consists of two pi bonds and one sigma bond. A double
bond contains one sigma and one pi bond. Single bonds are always
sigma bonds.
2. The three most common overlap conditions that result in sigma bonds
are:
a. s-s overlap
b. s-p overlap
c. p-p overlap
3. The benzene ring consists of six carbon-carbon single bonds, all of
which are sigma bonds. Additionally, there exist six carbon-hydrogen
sigma bonds. Therefore, the total number of sigma bonds in a benzene
molecule is 12. The aromatic features alternating double bonds between
28
 carbon atoms. Therefore, the total number of pi bonds in a benzene
molecule is 3.

References:
Book:
Carey, Francis A. Organic Chemistry. University of Virginia 3 rd Edition ©1996, The McGraw-
Hill Companies, Inc.

[1] http://www.chemspider.com/Chemical-Structure.7711.html?rid=b8719dd4-7de2-
4140-aebf-afb809c26dab

[2] http://www.commonchemistry.org/ChemicalDetail.aspx?ref=109-65-9

3. Vollhardt, K. Peter C., and Neil E. Schore. Organic Chemistry: Structure and

Function. 5th ed. New York: W. H. Freeman Company, 2007. 38-40.

4. Klein, David R. Organic Chemistry I As a Second Language. 2nd ed. Hoboken,

NJ: John Wiley & Sons, Inc, 2007. 1-14.

[1] https://iupac.org/projects/project-details/?project_nr=2001-043-1-800 , accessed

[2] https://www.acdlabs.com/iupac/nomenclature/

[3] https://www.cas.org/about/cas-history

[4] https://www.dhs.gov/cisa/appendix-chemicals-interest

[5] Heller, Stephen R.; McNaught, Alan; Pletnev. Igor; Stein, Stephen; Tchekhovskoi,
Dmitrii. “InChI, the IUPAC International Chemical Identifier.”  Journal of
Cheminformatics, 2015, 7:23.

[6] https://en.wikipedia.org/wiki/Simplified_molecular-input_line-entry_system

[7] Warr, W.A. “Many InChIs and quite some feat” J. Comput. Aided Mol.
Des., 2015, 29: 681. https://doi.org/10.1007/s10822-015-9854-3

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