ORGANIC

CHEMISTRY (F016)
Period 6
Introduction to Organic Chemistry, Bonding and Isomerism

Djamin Zayentha
Topics
• Introduction to Organic Chemistry
• The Structure of an Atom
• The Distribution of Electrons in an Atom
• Covalent Bonds
• Molecular Structure Representations
• Classification of Organic Compounds
• Structure Isomerism
• Single, Double, and Triple Bonds

Literature: ORGANIC CHEMISTRY 8TH EDITION – PAULA YURKANIS

BRUICE; Chapter 1
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Introduction to Organic Chemistry
Organic chemistry is the study of the structure, properties, composition, reactions,
and preparation of carbon-containing compounds.
Most organic compounds contain carbon and hydrogen, but they may also include
any number of other elements (e.g., nitrogen, oxygen, halogens, phosphorus,
silicon, sulfur)
When an organic compound reacts, some old bonds break and some new bonds
form. Bonds form when two atoms share electrons, and bonds break when two
atoms no longer share electrons.
How readily a bond forms and how easily it breaks depend on the particular
electrons that are shared, which, in turn, depend on the atoms to which the
electrons belong.

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The Structure of an Atom
• The nucleus contains positively charged
protons and uncharged neutrons.
• The electrons are negatively charged.
Atomic number of an atom equals the number of protons in its nucleus. The
atomic number is also the number of electrons that surround the nucleus of a
neutral atom

Mass number of an atom is the sum of its protons and neutrons.

(Although all carbon atoms have the same atomic number, they do not Fig 1. An atom

all have the same mass number)

Carbon can have varying numbers of neutrons.
• 98.89% of all carbon atoms have six neutrons—mass number of 12
• 1.11% have seven neutrons—mass number of 13.
These two different kinds of carbon atoms 12C and 13C) are called
isotopes.
Fig 2. Isotopes of Carbon

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The Structure of an Atom
• Atomic weight of a naturally occurring element is the average weighted mass of
its atoms
• Atomic mass is the weighted average of the isotopes in the element.
• Molecular weight is the sum of the atomic weights of all the atoms in the
molecule
• Molecular mass is the sum of the atomic masses of all the atoms in the molecule.

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The Distribution of Electrons in an Atom
The electrons in an atom can be thought of as occupying a set of concentric shells
that surround the nucleus. The first shell is closest to the nucleus. The second shell
lies farther from the nucleus, and even farther out lie the third and higher numbered
shells.
Each shell contains subshells known as atomic orbitals. The closer the atomic orbital
is to the nucleus, the lower is its energy.
Degenerate orbitals are orbitals that have the same energy
Table 1. Distribution of Electrons in the First Four Shells

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The Distribution of Electrons in an Atom
Valence and Core Electrons
The major factor that determines the chemical behavior of an element is the
number of valence electrons it has.
• Valence electrons are electrons in an atom’s outermost shell
• Core electrons are electrons in inner shells (below the outermost shell)
Valence electrons participate in chemical bonding; core electrons do not.
Elements in the same column of the periodic table have similar chemical properties
because they have the same number of valence electrons
• The chemical behavior of an element depends on its electronic configuration.

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Covalent Bonds
In explaining why atoms form bonds, G. N. Lewis proposed that an atom is most
stable if its outer shell is either filled or contains eight electrons, and it has no
electrons of higher energy
According to Lewis’s theory: an atom will give up, accept, or share electrons to
achieve a filled outer shell or an outer shell that contains eight electrons.
This theory has come to be called the octet rule

Each of the elements in the first column of the

periodic table readily loses an electron because
each has a single electron in its outermost shell

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Covalent Bonds

Fluorine has seven valence electrons. Therefore, it

readily acquires an electron to fill its outer shell.
Gaining the electron forms F-, a fluoride ion.

Elements in the same column of the periodic table

as fluorine (chlorine, bromine, and iodine) also
need one electron to have an outer shell of eight.

Elements (such as fluorine and chlorine) that

readily acquire an electron are said to be
electronegative.

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Covalent Bonds
A covalent bond is formed when two atoms share a pair of electrons
A covalent bond is commonly shown by a solid line rather than by a pair of dots

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Nonpolar and Polar Covalent Bonds
A nonpolar covalent bond is a
Fig 3. The Electronegativities of Selected Elements a
covalent bond between atoms with
essentially the same
electronegativity. (electronegativity
difference between the bonded
atoms is less than 0.5)
A polar covalent bond is a covalent
bond between atoms with different
electronegativities.
(electronegativity difference
between the bonded atoms is
between 0.5 and about 1.9)

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Molecular Structure Representations
Lewis Structure
The chemical symbols we have been using, in which the valence electrons are
represented as dots or solid lines, are called Lewis structures
The atoms in Lewis structures are always lined up linearly or at
right angles. Therefore, they do not tell us anything about the
bond angles in the actual molecule.

When drawing a Lewis structure, make sure hydrogen atoms are surrounded by two electrons and C,
O, N, and halogen (F, Cl, Br, I) atoms are surrounded by eight electrons, in accordance with the octet
rule.
Once the atoms and the electrons are in place, you must examine each atom to see whether a
formal charge should be assigned to it.

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Molecular Structure Representations
Lewis Structure

Kekulé Structure
These are like Lewis structures except that lone pairs are normally omitted

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Molecular Structure Representations
Condensed Structures
Condensed structures omit some (or all) of the covalent bonds and list atoms bonded to a
particular carbon (or nitrogen or oxygen) next to it (with a subscript if there is more than one
of a particular atom)

Skeletal Structures
Skeletal structures show the carbon–carbon bonds as lines, but do not show the carbons or the
hydrogens that are bonded to the carbons.

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Classification of Organic Molecules
Organic compounds are classified based on bonding patterns.
Organic Compounds can be classified on two bases.
1.Structure 2. Functional Groups
• Acyclic or open chain compounds
• Cyclic or closed chain compounds

Hydrocarbon: An organic molecule containing only carbon and hydrogen

Hydrocarbon Category Type of bonds
Alkane All single bonds
Alkene At least one double bond
Alkyne At least one triple bond
Aromatic Contains alternating single and double bonds
Alkanes are saturated hydrocarbons( maximum number of hydrogen atoms).
Alkenes and alkynes are unsaturated hydrocarbons (they have at least one double or triple bond)
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 Classification of Organic Molecules
Classification Based on the Structure
ACYCLIC OR ALICYCLIC HETEROCYCLIC
COMPOUNDS
OPEN-CHAIN
COMPOUNDS
AROMATIC HETEROCYCLIC
COMPOUNDS
STRUCTURE HETEROCYCLIC
COMPOUNDS
BENZENOID AROMATIC
COMPOUNDS

CYCLIC OR CLOSED- AROMATIC

CHAIN COMPOUNDS COMPOUNDS
NON-BENZENOID
AROMATIC COMPOUNDS
HOMOCYCLIC
COMPOUNDS ALICYCLIC
COMPOUNDS
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Classification of Organic Molecules
Acyclic or Open-chain Compounds
Acyclic compounds opposite to cyclic compounds because their molecules don’t
form any ring. It is called open-chain compounds because they have a linear
structure. The best examples of these compounds are acyclic aliphatic compounds
and alkanes. Open-chain compounds can be understood by straight-chain
compounds and branched-chain compounds.

Cyclic or Closed-chain Compounds

Cyclic compounds are also known as “ring compounds”, and as its second name
suggests, these are compounds where one or more than one number of atoms
get connected to form a closed ring.
Cyclic compounds are also categorized into two divisions. The first division is about
“Heterocyclic,” and the second division is about “Homocyclic.”
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Classification of Organic Molecules
Cyclic or Closed-chain Compounds: Heterocyclic
By simple definition heterocyclic compounds are like any other dominant branch of
organic compounds in which two or more two atoms join in the ring shape in their
molecules. Although they have atoms of carbon, it must be noticed that at least
one atom of another element also exists. Heterocyclics are divided into two broad
categories: alicyclic heterocyclic compounds and aromatic heterocyclic
compounds.
Alicyclic Heterocyclic Compounds Aromatic Heterocyclic Compounds
Alicyclic compounds, containing one or more Aromatic cyclic compounds containing one or
heteroatoms in their rings are called alicyclic more heteroatoms in their molecules are
heterocyclic compounds. called aromatic heterocyclic compounds.

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Classification of Organic Molecules
Cyclic or Closed-chain Compounds: Homocyclic
Homocyclic or carbocyclic compounds can be defined as molecules that are (or
are known to contain) ring structures that feature only carbon atoms within the
ring. They are divided into two compounds: alicyclic compound and aromatic
compound.
Alicyclic Compounds Aromatic Compounds
The alicyclic compound is aliphatic and cyclic. These are cyclic compounds that are
It has one or more than one all-carbon ring unsaturated. These compounds are also
that can be saturated or unsaturated. The called aromatics or arenas. These compounds
bonds which exist in pairs of atoms can be can be distinguished by one or more than one
any type of bond (single, double or triple) planar ring of atoms linked by covalent bonds
of two different types.

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Classification of Organic Molecules
Classification Based on Functional Groups
Functional groups are what we call the structural patterns that we use to classify organic
compounds. Organic compounds can contain other elements in addition to carbon and
hydrogen. Functional groups are a pattern of certain elements bonded together with
certain bonds (single, double, or triple).
Functional Group Name Functional Group
Alcohols (Alkanols) -OH (hydroxy)
Ethers (Alkoxy Alkanes)
Amines (Amino)
Aldehydes (Alkanals) -CHO (Aldehydic)
Ketones (Alkanones) (Carbonyl)
Carboxylic Acid (Alkanoic Acid) -COOH (Carboxyl)
Esters (Alkyl Alkanoates) (Ester
Amides (Alkanamides) (Amid)
Acetylenes (Alkynes)
Alkyl Halides 20
Structure Isomerism
Isomers are molecules that have the same molecular formula, but have a different
arrangement of the atoms in space. That excludes any different arrangements
which are simply due to the molecule rotating as a whole, or rotating about
particular bonds. In structural isomerism, the atoms are arranged in a completely
different order.
CHAIN ISOMERISM

STRUCTURAL ISOMERISM FUNCTIONAL GROUP ISOMERISM

POSITION ISOMERISM

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Structure Isomerism
Chain Isomerism
These isomers arise because of the possibility of branching in carbon chains
There are two isomers of butane, C4H10.
In one of them, the carbon atoms lie in a "straight
chain" whereas in the other the chain is branched.

There are three isomers of pentane, C5H12.

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Structure Isomerism
Position Isomerism
In position isomerism, the basic carbon skeleton remains unchanged, but important
groups are moved around on that skeleton.
There are two position isomers with the molecular
formula C3H7Br. In one of them the bromine atom
is on the end of the chain, whereas in the other it's
attached in the middle.

For the molecule with formula C4H9OH, there are

four isomers possible.

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Structure Isomerism
Functional Group Isomerism
In this variety of structural isomerism, the isomers contain different functional
groups - that is, they belong to different families of compounds (different
homologous series).
A molecular formula C3H6O could be either
propanal (an aldehyde) or propanone (a ketone)

Another common example is illustrated by the

molecular formula C3H6O2 . Amongst the several
structural isomers of this are propanoic acid (a
carboxylic acid) and methyl ethanoate (an ester).

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Molecular Orbital Theory
Molecular orbital (MO) theory combines the tendency of atoms to fill their octets by
sharing electrons (the Lewis model) with their wave-like properties, assigning electrons to a
volume of space called an orbital
A molecular orbital describes the volume of space around a molecule where an electron is
likely to be found. And like atomic orbitals, molecular orbitals, too, have specific sizes,
shapes, and energies
The covalent bond that is formed when two s orbitals overlap is called a sigma (σ) bond.
When two p atomic orbitals overlap, the side of one orbital overlaps the side of the other.
The side-to-side overlap of two parallel p orbitals forms a bond that is called a pi (π) bond.

Fig 4. Forming a sigma

bond of atomic orbitals

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Single Bonds
Methane (CH4) has four covalent C-H bonds. All four bonds have the same length
(1.10 Å) and all the bond angles are the same (109.5°); we can conclude that the four
C-H bonds in methane are identical

The absence of partially charged atoms can be explained by the similar

electronegativities of carbon and hydrogen, which cause them to share their
bonding electrons relatively equally. Methane, therefore, is a nonpolar molecule

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Single Bonds
Carbon has to form four covalent bonds otherwise it would not complete its
octet

Hybrid orbitals are mixed

orbitals that result from
combining atomic orbitals. If
the one s and three p orbitals of
the second shell are all
combined and then apportioned
into four equal orbitals, each of
the four resulting orbitals will be
one part s and three parts p.
This type of mixed orbital is
called an sp3

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Single Bonds
Fig 5. Formation of an sp3
hybridized orbital

Fig 6. Hybridization of an s orbital

and three p orbitals hybridize to form
four sp3 orbitals
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Single Bonds
Tetrahedral Carbon
A carbon, such as the one in methane, that forms covalent bonds using four
equivalent sp3 orbitals is called a tetrahedral carbon

Fig 6.
(a) The four sp3 orbitals are directed toward the corners of a tetrahedron,
causing each bond angle to be 109.5°. This arrangement allows the four
orbitals to be as far apart as possible.
(b) An orbital picture of methane, showing the overlap of each sp3 orbital of
carbon with the s orbital of a hydrogen.

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Single Bonds
The Bonds in Ethane
One bond connecting two atoms is called a single bond.
All the bonds in ethane are single bonds. To bond to four atoms, each carbon uses
four sp3 orbitals as they do in methane.

Fig 7. An orbital picture of ethane. The C-C bond is formed by sp3–sp3 overlap, and each
C-H bond is formed by sp3–s overlap. (The smaller lobes of the sp3 orbitals are not
shown.) As a result, both carbons are tetrahedral and all bond angles are 109.5°

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Double Bonds
The carbons in ethene (also called ethylene) form two bonds with each other. Two
bonds connecting two atoms is called a double bond

To bond to three atoms, each carbon hybridizes three atomic orbitals: an s orbital
and two of the p orbitals. Because three orbitals are hybridized, three hybrid
orbitals are formed. These are called sp2 orbitals. After hybridization, each carbon
atom has three degenerate sp2 orbitals and one unhybridized p orbital

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Double Bonds
Fig 8.
(a) The three degenerate sp2 orbitals lie in a plane, oriented
120° from each other. (The smaller lobes of the sp2 orbitals
are not shown.)
(b) The unhybridized p orbital is perpendicular to this plane.

Because an sp2 hybridized carbon is bonded to three atoms and three points define a plane, it
is called a trigonal planar carbon. The unhybridized p orbital is perpendicular to the plane
defined by the axes of the sp2 orbitals (Figure 8b).

Fig 9. (a) One C-C bond in ethene is a σ bond formed by sp2–sp2

overlap, and the C-H bonds are σ bonds formed by sp2–s overlap.
(b) The second C-C bond is a π bond formed by side-to-side
overlap of a p orbital of one carbon with a p orbital of the other
carbon. The two p orbitals are parallel to each other.

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Triple Bonds
The two carbons in ethyne (also called acetylene) are held together by three bonds.
Three bonds connecting two atoms is called a triple bond

Fig 10. The two sp orbitals point

To bond to two atoms, each carbon hybridizes two atomic orbitals—an s in opposite directions. The two
and a p. Two degenerate sp orbitals result. Each carbon atom in ethyne, unhybridized p orbitals are
therefore, has two sp orbitals and two unhybridized p orbitals. To perpendicular to each other and
minimize electron repulsion, the two sp orbitals point in opposite to the sp orbitals. (The smaller
directions. The two unhybridized p orbitals are perpendicular to each lobes of the sp orbitals are not
other and are perpendicular to the sp orbitals (Fig. 10). shown.)

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 Triple Bonds

Fig 11.
(a) The C-C σ bond in ethyne is formed by sp–sp overlap, and the C-H bonds are formed by sp–s overlap.
The carbon atoms and the atoms bonded to them form a straight line.
(b) The two carbon–carbon π bonds are formed by side-to-side overlap of the two p orbitals of one
carbon with the two p orbitals of the other carbon.

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Conclusion Hybridization of Carbon
• If carbon is bonded to four groups, it is sp3 hybridized and, therefore,
tetrahedral with bond angles of 109.5°
• If carbon is bonded to three groups, it is sp2 hybridized and, therefore, trigonal
planar with bond angles of 120°
• If carbon is bonded to two groups, it is sp hybridized and, therefore, linear with
bond angles of 180°

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Exercises
Problems: 55, 58, 59, 63, and 70

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