UNIT ONE: INTRODUCTION TO ORGANIC CHEMISTRY

UNIT ONE: INTRODUCTION TO ORGANIC CHEMISTRY

UNIT ONE
INTRODUCTION TO ORGANIC CHEMISTRY
Unit Outcomes
After completing this unit, you will be able to:
➢ grasp knowledge on the historical development of organic chemistry and the classification
of organic compounds;
➢ draw the general formulas of alkanes, alkenes, alkynes, alcohols, aldehydes, ketones,
carboxylic acids and esters;
➢ develop skills in naming and writing the molecular and structural formulas of simple
alkanes, alkenes, alkynes, alcohols, aldehydes, ketones, carboxylic acids and esters;
➢ explain isomerism and name the possible isomers of simple alkanes, alkenes and alkynes;
➢ become familiar with the major natural sources of hydrocarbons;
➢ explain the major physical and chemical properties and the general methods of preparing
alkanes, alkenes, alkynes, benzene and alcohols;
➢ describe the uses of organic compounds in the manufacture of plastics, beverages,
pharmaceuticals, soaps and detergents, dry cleaning chemicals, fuels, pesticides, and
herbicides; and
➢ demonstrate scientific inquiry skills: classifying, asking and answering questions,
interpreting information, drawing and predicting conclusions.
MAIN CONTENTS
1.1 Introduction
1.2 Saturated hydrocarbons (alkanes)
1.3 Unsaturated hydrocarbons (alkenes and alkynes)
1.4 Aromatic hydrocarbons
1.5 Natural sources of hydrocarbons
1.6 Alcohols
1.7 Industrial and agricultural applications of organic compounds
Unit Summary
Review Exercise
1
1.1 INTRODUCTION
Competencies
By the end of this section, you will be able to:
• elaborate the historical development of organic compounds;

• define the term functional group;
• Classify organic compounds based on their functional groups.
HISTORY OF ORGANIC CHEMISTRY
Before the beginning of the 19th Century, chemists classified compounds into two classes depending
upon where they had come from. Inorganic compounds were those obtained from minerals; organic
compounds were those obtained from vegetable or animal sources, that is, from material produced
by living organisms. Indeed, until about 1850 many chemists believed that organic compounds must
have their origin in living organisms, and consequently could never be synthesized from inorganic
material.
Along with this distinction, a belief called “vitalism” (a special life – force) grew. According to this
idea, the intervention of a “vital force” was necessary for the synthesis of an organic compound.
Such synthesis, chemists held then, could take place only in living organisms. It could not take place
in the flasks of a chemistry laboratory.
Between 1828 and 1850 a number of compounds that were clearly “organic” were synthesized from
sources that were clearly “inorganic.” The first of these syntheses was accomplished by Friedrich
2
Wöhler in 1828. Wohler found that the organic compound urea (a constituent of urine) could be
made by evaporating an aqueous solution containing the inorganic compound ammonium cyanate.
In attempting to prepare ammonium cyanate, NH4CNO, from the reaction of silver cyanate, AgCNO,
and ammonium chloride, NH4Cl, he accidentally and surprisingly obtained urea, (NH2)2CO:
AgCNO (aq.) + NH4Cl (aq.) → AgCl (s) + NH4CNO (aq.)
Urea was the first organic compound synthesized in the laboratory. The synthesis of urea by
Friedrich Wöhler and subsequent synthesis of other organic compounds marked the downfall of
“vitalism” or the ‘life force’ theory.
How do you explain organic compounds at present and define organic chemistry?
The common feature of organic compounds is that they all contain the element carbon. Organic
compounds are either hydrocarbons or derivative of hydrocarbons. They are found in and derived
from plants and animals. They can also be synthesized in the laboratory. In addition to carbon and
hydrogen, organic compounds may contain nitrogen, oxygen, sulfur, halogens and phosphorus.
However, carbon compounds that are classified under oxides, carbonates, hydrogen carbonates,
cyanides and cyanates are not organic, i.e. these are inorganic.
The compounds in solid, liquid or gaseous state which contain carbon in its molecule are known as
organic compounds and derived from plants and animals. They also include those substances
synthesized in laboratories except the oxides of carbon, carbonates, hydrogen carbonates, cyanides
and cyanates. The branch of chemistry that studies carbon compounds is called organic chemistry.
This branch of chemistry was developed, starting from the theory of “vitalism” to the era in which
synthetic organic compounds are used in our daily lives. The number of inorganic compounds
discovered and prepared may be in the region of some hundred thousand. In contrast, millions of
organic compounds have been discovered, synthesized, and used at present.
What is so special about carbon that it should form so many compounds? Carbon atoms can attach
themselves to one another to an extent not possible for atoms of any other element. Carbon atoms
can form chains thousands of atoms long, or rings of all sizes; the chains and rings can have branches.
To the carbon atoms of these chains and rings there are attached other atoms. The ability of atoms
3
of the same element to join together forming long chains and rings is called catenation. Catenation
occurs most readily in carbon, forming covalent bonds to form longer chains and structures with
other carbon atoms. This is why the vast number (millions) of carbon compounds are found in nature.
The word “organic” is still used today by some people to mean “coming from living organisms” as
in the terms “organic vitamins” and “organic fertilizers.” To these people, an “organic vitamin”
means that the vitamin was isolated from a natural source and not synthesized by a chemist.
Provided that the plant is grown without the use of synthetic fertilizers and pesticides, it is
impossible to argue that “natural” vitamin C, for example, is healthier than the “synthetic” vitamin
C, because the two substances are identical in all aspects!
Classification of Organic Compounds
Any consideration of bonding in organic molecules must begin with the structural theory. Two
central premises are fundamental:
1. Carbon is always tetra covalent; that is, carbon atoms form four bonds. Similarly, nitrogen
atoms form three while oxygen and sulfur atoms make two bonds. Hydrogen and the halogens are
monovalent; their atoms form only one bond.
2. A carbon atom forms single, double or triple bonds with other carbon atom.
A functional group is the part of an organic molecule that determines its chemical properties. This
group also determines some of the physical properties of the compound. Based on the functional
groups they possess, the most common classification of organic compounds includes alkanes,
alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, carboxylic acids and esters. The
common functional groups of some organic compounds are given below.
Table 1.1 Common classes of organic compounds, their functional groups, general structural
formula with typical examples (R = alkyl or H).
4
EXERCISE 1. 1
1. Classify each of the following compounds as either organic or inorganic.
a. C3H8O b. CaCl2 c. Aspirin d. C3H4NO e. Salt f. HCN
5
2. “Organic” coffee is produced in Ethiopia. What does the word “organic” indicate?
3. What other elements have the ability of catenation (even though short size) as does carbon?
4. According to the structural theory, in which of the following compounds would there be oxygen
– hydrogen bond?
a. CH2O b. CH4O c. CH4NO d. C2H6O
5. Identify the functional group in each of the following compounds.
a. CH3CH2COCH2CH3 b. CH3CH2COOH c. CH3CH2CH2OH d. CH3COOCH3
6. According to the belief of early chemists, which class of compounds is associated with “vital”
force? What is the core idea of “vitalism?”
1.2 SATURATED HYDROCARBONS
Competencies
At the end of this topic, you will be able to:
• define saturated hydrocarbons and write their general formula;
• observe and define homologous series in alkanes;
• explain the physical properties of alkanes;
• apply IUPAC rules to name unbranched and branched – chain alkanes;
• explain isomerism and write possible structural isomers for C4H10, C5H12 and C6H14;
• describe general methods for the laboratory preparation of alkanes;
• prepare methane in a laboratory by the decarboxylation method;
• carry out a project to produce biogas from cow dung; and
• explain the chemical properties of alkanes.
What are hydrocarbons and on what basis do we categorize them?
Hydrocarbons are organic compounds composed of the elements carbon and hydrogen only. They
are subdivided into two groups, based on the type of bonding between carbon atoms, as saturated
and unsaturated hydrocarbons.
6
Saturated hydrocarbons are those compounds of carbon and hydrogen that contain only carbon –
carbon single bonds. Methane, ethane, and propane are the first three examples of this group.
Unsaturated hydrocarbons are those compounds of carbon and hydrogen possessing one or more
multiple bonds (double or triple bonds) between carbon atoms. Alkenes, alkynes and aromatic
hydrocarbons are examples of unsaturated hydrocarbons.
A formula that shows the way in which the atoms are attached to each other is called a dash formula
or detailed structure. The shorter form of this structure is called condensed structure. In condensed
formulas all of the hydrogen atoms that are attached to a particular carbon are written immediately
after the carbon. Here are some examples for a condensed form. (For a dash or detail structure, refer
the example given in section 1.2.2 for n – butane and isobutane.)
Molecular formula Condensed form Saturated Unsaturated
C3H8 CH3CH2CH3 Propane ✓
C3H6 CH2 = CHCH3 Propene ✓
C3H4 CH3C ≡ CH Propyne ✓
1.2.1 Alkanes or Paraffins
Alkanes are organic compounds that consist entirely of single – bonded carbon and hydrogen atoms
and lack any other functional group. Alkanes have the general formula CnH2n+2, where, n = 1, 2, 3 .
. . For example, the chemical formulas of alkanes containing one, two, three and four carbon atoms
are CH4, C2H6, C3H8, and C4H10, respectively.
When we compare the formulas of CH4 and C2H6, or C2H6 and C3H8, or C3H8 and C4H10, each pair
differs by one carbon and two hydrogen atoms or – CH2– skeleton called the methylene group. A
series of compounds in which each member differs from the next member by a constant amount (or
skeleton) is called a homologous series, and the members of the series are called homologs. The
family of alkanes forms such a homologous series, the constant difference between successive
members being CH2.
Table 1.2 Homologous series and physical constants of the first ten unbranched alkanes.
7
1.2.2 Physical Properties of Alkanes
At room temperature, the first four alkanes, methane (CH4) to butane (C4H10), are gases; whereas
pentane (C5H12) to heptadecane (C17H36) are liquids, and alkanes containing eighteen and more
carbon atoms are solids.
Alkanes are nonpolar organic compounds. Weak intermolecular forces called Van der Waal’s forces
hold their molecules together. The strength of these forces increases with increase in molecular mass
of the alkanes. Since these compounds are nonpolar, they are almost insoluble in polar solvents like
water, but they are soluble in nonpolar solvents like benzene, toluene, ether and carbon tetrachloride.
The density, melting and boiling points of the homologous series of alkanes increase as the carbon
number increases. For alkanes of the same carbon number, branched-chain isomers have lower
boiling points than the straight-chain (normal) alkanes. The reason is, as branching increases, there
is a decrease in surface area and the strength of the intermolecular force, which, in turn decreases
boiling point; e.g., the boiling points of n-pentane, iso-pentane and neo-pentane (all having the same
number of carbon and hydrogen atoms) are 36°C, 28°C and 9.5°C, respectively.
Alkanes containing all the carbon atoms in one continuous chain are called normal or straight-chain
alkanes and those containing chains with branches are known as branched-chain alkanes.
8
Example:
In alkanes (branched or straight-chain), each carbon atom is tetrahedrally bonded to four atoms
with a bond angle of 109.5°.
Figure 1.1 Structure of methane
In straight chain alkanes, the carbon atoms are not linked in straight line but in zigzag chains to
keep the tetrahedral distribution of atoms.
Figure 1.2 Zigzag chain and ball and stick model of butane
1.2.3 Nomenclature (naming) of Alkanes

Organic chemistry uses a simplified and systematic way of naming organic compounds. The
names of alkanes and most of the organic compounds are derived from:
9
i. a prefix: indicating the number of carbon atoms

ii. a suffix: indicating the type of the functional group present in the molecule.
The following table introduces the prefixes that are used to indicate the presence of one to ten
carbon atoms in the longest continuous carbon chain.
Table 1.3 Prefixes commonly used to indicate one to ten carbon atoms.
Prefix Number of carbon atoms Prefix Number of carbon atoms
Meth- One Hex- Six
Eth- Two Hept- Seven
Prop- Three Oct- Eight
But- Four Non- Nine
Pent- Five Dec- Ten
From Table 1.2, you can note that the names of all alkanes contain the suffix ‘-ane’, which
indicates that their functional group is a carbon — carbon single bond. Except for the first four
members of the family, the name is simply derived from the Greek (or Latin) prefix for the particular
number of carbons in the alkane; thus, pentane for five, hexane for six, heptane for seven, and so
on.
Common Names of Alkanes
Lower members of the alkane homologous series have common names. The prefixes used in the
common names are n- (normal), ‘iso-’ and ‘neo-’. The prefix n- is used when all the carbon atoms
form a continuous chain.
Example:
a. H3C — CH2 — CH2 — CH2 — CH2—CH2—CH3 n- Heptane

b. H3C — CH2 — CH2 — CH3 n- butane
c. H3C — CH2 — CH2 — CH2 — CH2—CH3 n-Hexane
10
Iso- is used when all the carbon atoms form a continuous chain, except for the one next to the last
carbon. Example:
Neo- is used when there is a central carbon that is bonded to four other carbon atoms. Example:
IUPAC System Nomenclature of Alkanes
It is difficult to have common names for the more branched and complex alkanes. In naming such
alkanes, the more systematic, convenient and appropriate one is the International Union of Pure
and Applied Chemistry (IUPAC) system. According to IUPAC rule, each different compound
should have a different name. In order to apply this system, it is very important to know the rules
to be followed, what alkyl groups are, and how they are named.
Alkyl groups are obtained by removing one hydrogen atom from the corresponding alkanes. Their
general formula is CnH2n+1, where n = 1, 2, 3 . . .. The names of alkyl radicals are derived from the
names of the corresponding parent alkanes by changing the suffix -ane to -yl.
11
Table 1.4 Formulas, names and structures of some alkyl groups.
The system of naming organic compounds is based on the recommendations of IUPAC.

The following are the rules established by IUPAC to name branched-chain hydrocarbons.
1. Select the longest continuous chain of carbon atoms in the molecule as the parent
structure. The name of the straight-chain alkane possessing the same number of carbon
atoms is used as the name of this longest chain. The groups attached to the parent structure
are called side chains or substituents. Example:
12
There are seven carbon atoms in the longest chain (the parent structure). Therefore, it gets the
name “heptane”.
2.Assign numbers to the carbon atoms of the longest chain starting from one end to the other so
that the carbon atoms to which substituents are attached get the lowest possible number.
Example:
To check which direction of numbering is correct; add the locants (numbers assigned to the carbon
atoms to which substituents are attached).
The sum of locants in the first case is 3 + 4 = 7 and in the second case, 4 + 5 = 9. So, numbering
should be from left to right in this case. Thus, the first option is correct.
3. Indicate the position of the side chain by using the number assigned to the carbon atom to
which it is attached. If the same substituent appears more than once, use the prefix di-, tri-,
tetra- etc. before the name of the substituent to show two, three, four, etc. substituents,
respectively.
4. Numbers are separated from each other by commas while they are separated
from substituent names by hyphens.
13
5. Arrange the names of the side chains before the parent name in alphabetical order. The
complete name of the alkane given in the above example will then be 4-ethyl-3-methyl
heptane (substituents in alphabetical order). Example:
The longest chain has six carbon atoms thus the parent name is hexane. There are two methyl groups
at carbon-2 and another two methyl groups on carbon-4 and one chlorine atom at carbon-3.
Therefore, the correct name of the compound is 3-chloro -2, 2, 4, 4-tetramethylhexane. In deciding
on alphabetical order, disregard multiplying prefixes such as di-, tri-, tetra-, etc.
Note:
When F, Cl, Br and I appear as substituents, change the names fluorine, chlorine, bromine and iodine
to fluoro, chloro, bromo and iodo, respectively. Example:
There are seven carbon atoms in the parent structure, so it takes the name heptane. There are two
methyl groups at carbon-2 and two methyl groups at carbon-4 and carbon-5 and one fluorine at
carbon-3. So, the name of the compound is 3-fluoro-2, 2, 4, 5-tetramethyl heptane.
The following additional examples illustrate IUPAC rules of naming and writing branched – chain
alkanes.
a. IUPAC names from given structures
14
b. Structural formulas from given IUPAC names
15
1.2.4 Isomerism
The word “isomer” is derived from the Greek words “isos” and “meros”, which mean “equal parts”.
Isomerism is the phenomenon in which more than one compounds have the same chemical formula
but different chemical structures. Compounds that have identical chemical formula but differ in
properties and the arrangement of atoms in the molecule are called isomers. Alkanes exhibit a type
of structural isomerism called chain or skeletal isomerism. These structures differ in the
arrangement of carbon and hydrogen atoms.
There is only one possible structure for each of the first three alkanes, namely, methane (CH4), ethane
(C2H6) and propane (C3H8). Those alkanes containing four or more carbon atoms can exhibit more
than one structure or isomers.
Isomers of butane (C4H10)

Butane has two isomers namely n – butane and 2 - methylpropane
Isomers of pentane (C5H12)
Pentane has three isomers:
16
EXERCISE 1. 2
1. Write the dash and condensed formulas of 3 – ethyl – 2, 2 – dimethyl pentane. What is its
molecular formula?
2. The following names are given wrongly. Give the correct (IUPAC) name in each case.
a. 2 – ethyl butane b. 1,3,3-trimethyl pentane c. 2, 2-diethyl propane
d. 2 – chloro – 3 – bromo pentane e. 2, 4, 5- tri methyl hexane
3. Arrange the following six alkanes in decreasing order of boiling point by comparing their
masses and effect of branching.
a. n – pentane b. 2 – methyl pentane c. 2, 2 – dimethyl butane
d. 2 – methyl butane e. 2, 2 – dimethyl propane f. n – hexane
4. Liquid alkanes are insoluble in water but float on water. Give reason for this property.
5. Which of the following statements is / are true about isomers?
a. They have the same molecular formula.
b. They are homologs.
c. They have the same boiling and melting points.
d. They are different compounds.
6. Draw and name all possible structural isomers of hexane.
1.2.5 Preparation of Alkanes
17
The primary natural source of alkanes is petroleum. Petroleum is a complex mixture of organic
compounds, most of which are alkanes and aromatic hydrocarbons. Natural gas, bottled gas and
petrochemicals (CH4 up to C4H10) are obtained from fractional distillation of petroleum. Alkanes
can also be prepared in the laboratory. Some methods of their preparation are as follows:
1. Hydrogenation of alkenes with a metal catalyst.
Example
2. Reduction of alkyl halides using zinc in aqueous acid or sodium. Reduction using sodium is
called Wűrtz synthesis which is somewhat exothermic.
2R – X + Zn → R–R + ZnX2 (Zinc halide)
Example
2CH3CH2 – Br + Zn → CH3CH2CH2CH3 + ZnBr2

Ethyl bromide Butane Zinc bromide
3. Heating sodium salt of an organic acid with soda lime (mixture of sodium hydroxide and
calcium oxide); the reaction brings about the removal of the carboxylate group from the sodium
salt of the carboxylic acid. This type of reaction is called decarboxylation.
General Reaction:
18
Example
Methane (CH4)
Methane is the main constituent (about 90%) of natural gas. It is obtained during fractional
distillation of petroleum. Methane is also formed by the decay and decomposition of animal
and plant remains in swampy or marshy lands.
EXPERIMENT 1. 1
Laboratory Preparation of Methane

Objective: To prepare methane and study its properties.
Materials required: Sodium acetate (CH3COONa) and soda lime (CaO, NaOH), test tubes,
delivery tube, stopper, gas jar and gas jar lid, pneumatic trough, stand, clamp, beehive shelf,
Bunsen burner and balance.
Procedure:
Arrange the assembly as shown in Figure below. Mix thoroughly 5 g powdered sodium acetate
with 10 g of soda lime. Place the mixture in the test tube and heat it. Collect the gas by the
downward displacement of water. Collect several jars of the gas.
19
Figure 1.3 Preparation of methane
Carry out the following activities with the collected gas:

Insert a burning splint into the jar full of the gas. Observe what happens in the jar. Add Ca (OH)2
solution to the jar and observe. Add a few drops of bromine water to any one of the gas jars filled
with the gas. Cover the gas jar and shake well.
Observation and analysis:
a. What is the color of the gas? Is it soluble in water?
b. Is the gas combustible? Write a balanced equation for the change.
c. What change did you observe upon addition of Ca (OH)2 solution?
d. Is there any change when bromine water is added?
Write a laboratory report on your observation and submit to your teacher
Methane can be produced in a biogas plant. This plant generates biogas, mainly consisting of
methane, by anaerobic fermentation of organic materials such as human excreta, animal dung
and agricultural residue.
The conversion of organic materials into biogas involves a sequence of reactions and is
20
graphically depicted in the figure below.
Figure 1.4 Reactions in the production of biogas
The materials that can be used to produce biogas include dung from cattle, pigs, chickens, chopped
green plants and plant wastes. The advantages of biogas technology include saving fuel such as
kerosene, wood and charcoal, and decrease in local deforestation. The residue obtained after
preparing the biogas can be used as fertilizer.
EXPERIMENT 1. 2
Production of Methane from Cow Dung

Objective: To prepare biogas from locally available materials.
Materials required: Conical flask, cow dung, water, delivery tube with tap and stopper with one
hole.
Procedure:
1. Mix some cow dung with water and pour it in a conical flask.
2. Fit the conical flask with a stopper in which a delivery tube with a tap is inserted.
21
3. Cover the conical flask with a cotton wool and place it near a window and leave it there for 3
to 4 days.
4. Check the formation of methane after 4 days. (Bring a lighted splint closer to the outlet of the
delivery tube and open the tap). See what happens.
Figure 1.5 Preparation of methane gas from cow dung.

a. What is the importance of covering the conical flask with a cotton wool and placing it near the
window?
b. What is your observation when you bring a burning splint close to the outlet of the tube?
c. What change do you think has occurred in the conical flask that leads to the formation of
methane?
Write a laboratory report in group and present to the class.
1.2.6 Chemical Properties of Alkanes

Alkanes as a class, are characterized by a general inertness to many chemical reagents. Carbon –
carbon and carbon – hydrogen bonds are quite strong; they do not break unless alkanes are heated
to very high temperatures. Alkanes are inert towards many reagents like acids, bases, oxidizing and
reducing agents. This low reactivity of alkanes accounts for the fact that alkanes were originally
called paraffins. (Latin: parum affinis, little affinity). However, alkanes undergo some reactions
under suitable conditions.
The major reactions of alkanes are the following:
22
1. Combustion: Alkanes burn in excess oxygen to form carbon dioxide and water, liberating a
greater amount of heat. This combustion occurs for example, in the cylinders of automobiles and
oil furnaces. The general equation for the reaction is:
CnH2n+2 + ½ (3n + 1)O2 → n CO2 + (n + 1) H2O + heat

For example: C3H8 (g) + 5 O2 (g) → 3 CO2 (g) + 4 H2O + 2220 kJ
The heat energy liberated is used to generate electricity, to move motor vehicles or to cook food.
2. Substitution reaction: This is a reaction that involves the replacement of one atom or a group of
atoms by another atom or group of atoms. Halogenation of alkanes is a very good example of
substitution reaction. This reaction involves reacting alkanes with chlorine and bromine in the
presence of heat or sunlight. This type of reaction is called photochemical reaction. The process
proceeds in a sequence of steps. For example, let us consider the photochemical reaction of methane
with chlorine (chlorination):
i. Chain initiating step: This stage involves absorption of energy to generate reactive particles
known as free radicals. A free radical is an atom or a group of atoms possessing unpaired electron.
It is electrically neutral. A chlorine molecule absorbs light and decomposes into two chlorine atoms:
ii. Chain propagating step: This is a step which consumes

the reactive particle (free radical) produced in the chain initiation step and generates another free
radical.
iii. Chain terminating step: In this step reactive particles (free radicals) are consumed but not
generated.
In this step, ‘side reactions’ that do not lead to the formation of the desired products often take
place. For example,
Such a detailed step by step description of a chemical reaction is called reaction mechanism.
Chlorination of methane may produce different products depending on the relative amounts of
methane and chlorine.
23
The chlorination of methane is an example of a chain reaction that involves a series of steps.
3. Elimination reaction: This type of reaction involves the removal of smaller molecules from a
compound and leads to the formation of a compound containing a multiple bond (unsaturated
compound). It can also involve the removal of hydrogen atoms from adjacent carbon atoms at
relatively high temperatures. Example:
Cycloalkanes
Cycloalkanes are saturated hydrocarbons in which the carbon atoms are linked in such a manner as
to form closed chains or ring structures. They are represented by the general formula, CnH2n, where
n ≥3. Cycloalkanes with only one ring are named by attaching the prefix cyclo to the names of the
alkanes possessing the same number of carbon atoms. The following structures are examples of
24
cycloalkanes.
Uses of Alkanes
The applications of alkanes depend on the carbon chain.
❖ Alkanes up to 4 carbons (methane – butane) are mainly used for heating and cooking
purposes. Methane and ethane are the main components of natural gas.
❖ Propane and butane can be readily liquified at low pressure and are the chief components
of liquefied petroleum gas (LPG).
25
❖ Pentane to octane are reasonably volatile liquids that are used as fuels in internal
combustion engines. They are also good solvents for nonpolar substances.
❖ Nonane to hexadecane mainly contain kerosene, used for tractor and jet engines.
❖ Alkanes above pentadecane are liquids of high viscosity and are commonly used as
lubricating oil.
❖ Long – chain alkanes (C20 – C34) are sold as paraffin wax (for candle making) or used in
petroleum jelly (Vaseline). The non – volatile asphalt is used in road building.
❖ Gas oil (boiling point above 2750c) is used in diesel engines. Kerosene and gas oil are also
used for heating purposes, gas oil being the familiar furnace oil.
❖ Alkanes are also used as solvents, raw materials for making alkenes, alcohols, soaps,
detergents and plastics.
26
EXERCISE 1. 3
1. Give IUPAC name to each of the following alkanes.
2. How many isomeric dichloro propane (alkyl halides) are there? Write the structure and IUPAC
names of all these compounds.
3. Label each of the following processes as chain initiating, chain propagating or chain terminating
step.
a. Molecule → Radicals b. Radical + Radical c. Molecule + Radical
4. Give the products and balance the equation in each case.
a. Butane gas is burned in sufficient oxygen
b. Butane gas is burned in limited amount of oxygen
5. The heats of combustion of methane, ethane, propane and benzene, all in the gaseous state are,
890 1560, 2220 and 3300 kJ per mole, respectively. When 1.0 g of the respective hydrocarbon is
burned in excess oxygen, which one produces: (a) more heat? (b) more carbon dioxide?
6. Write the molecular formula of alkanes containing the following number of carbon atoms.
27
a. 10 b. 20 c. 17 d. 11
7. There are five cyclic isomeric alkanes of formula C5H10. Draw and name these compounds.
8. The radical reaction of propane with chlorine yields two different compounds. Write the chain-
initiating, chain – propagating and terminating steps for each reaction and name the products.
1.3 UNSATURATED HYDROCARBONS

Competencies
By the end of this section, you will be able to:
• define unsaturated hydrocarbons, alkenes and alkynes;

• derive general formulas for alkenes and alkynes;
• write the molecular formulas of alkenes and alkynes based on carbon atoms;
• describe the physical properties of alkenes and alkynes;
• apply IUPAC rules to name straight and branched – chain alkenes and alkynes;
• define geometric (cis / trans) isomerism and give examples;
• describe the general methods of preparing alkenes and alkynes in a laboratory;
• perform an experiment to prepare ethylene and ethyne in the laboratory;
• establish a test for unsaturation in alkenes and alkynes;
• explain chemical properties of alkenes and alkynes;
• describe the uses of ethylene and acetylene;
• Compare and contrast the properties of ethane, ethene and ethyne.
1.3.1 Alkenes or Olefins

Alkenes are unsaturated hydrocarbons whose molecules contain the carbon – carbon double bond
(C = C) as their functional group. An old name for this family of compounds that is still often used
is olefins. They form a homologous series represented by the general formula CnH2n, where n = 2,
3, 4…. Ethene (C2H4) and propene (C3H6) are the first two alkenes of the series. In ethene the
only carbon – carbon bond is the double bond. Propene has one carbon – carbon single bond and
one carbon – carbon double bond.
Table 1.5 The homologous series of alkenes and their physical constants
28
Physical Properties of Alkenes
At room temperature, alkenes containing two to four carbon atoms are gases. Those containing
five to seventeen carbon atoms are liquids, and those containing eighteen or more carbon atoms
are solids.
Alkenes are non-polar compounds. Therefore, their molecules are held together by weak
intermolecular forces. They are almost insoluble in polar solvents like water, but soluble in non-
polar solvents like ether, benzene, toluene and carbon tetrachloride.
Nomenclature of Alkenes
Many older names for alkenes are still in common use. Ethene is called ethylene, propene is
often called propylene, and 2 – methyl propene frequently bears the name isobutylene. Similarly,
1 – butene takes the common name butylene.
IUPAC system for branched alkenes
The IUPAC rules for naming alkenes are similar in many respects to those for naming alkanes.
1. Determine the base (parent) name by selecting the longest chain that contains the double bond
and change the ending of the name of the alkane of identical length from ane to ene.
29
2. a. Number the chain so as to include both carbon atoms of the double bond, and begin
numbering at the end of the chain nearer to the double bond. Designate the location of the
double bond by using the number of the first atom of the double bond as a prefix.
b. If the double bond is equidistant from each end, number the carbon atoms so that the
first substituent has the lowest number.
3. Write out the full name; numbering the substituents according to their position in the chain
and list them in alphabetical order.
4. If more than one double bond is present, indicate their positions by using the number of the
first carbon of each double bond and use the suffix -diene (for 2 double bonds), -triene (for 3
double bonds), -tetraene (for 4 double bonds), etc.
5. a. Cycloalkenes are named in a similar way. Number the cycloalkene so the double bond
carbons get numbers 1 and 2, and the first substituent is the lowest possible number. Examples:
30
b. If there is a substituent on one of the double bond carbons, it gets number 1

Isomerism
Alkenes with two and three carbon atoms have only one possible structure. Those containing four
or more carbon atoms exhibit isomerism. Alkenes show the following three types of isomerism:
1. Chain isomerism: This is due to the difference in the arrangement of the carbon atoms in the
longest continuous carbon chain.
2. Position isomerism: This is due to the difference in the position of the double bond in the
carbon chain.
31
Compounds (a) and (b) represent the position isomers of pentene, (c) and (d) are position isomers
of methyl butene; (a), (c) and (e) are the chain isomers, while all these compounds are the isomers
of C5H12.
3. Geometrical isomerism. This results from the difference in the relative spatial arrangement
of atoms or groups about the double bond. This isomerism exists because free rotation about
the double bond is not possible. To differentiate geometrical isomers, we use the prefix ‘cis’ if
two similar groups are on the same side of the double bond and ‘trans’ when the two similar
groups are on opposite sides of it; ‘cis’ means the same and ‘trans’ means across. As an
example, here are the geometrical isomers of 2-pentene.
Alkenes have more isomers than the corresponding alkanes.
Preparation of Alkenes
Alkenes are mainly obtained during fractional distillation of petroleum when the process called
cracking is carried out. In thermal cracking alkanes are passed through a chamber heated to a high
temperature. Larger alkanes are converted into alkenes. This process yields predominantly
ethylene.
In the laboratory, alkenes can be prepared by:
1. Dehydration of alcohols with concentrated sulfuric acid or alumina (Al2O3). Dehydration

means removal of water.
General reaction:
32
Example
2. Dehydrohalogenation of alkyl halides with a base (KOH). Dehydrohalogenation means

removal of hydrogen and a halogen atom. Alkyl halides are compounds of an alkyl group and
a halogen such as CH3Cl and CH3 – CH2 – Br.
General reaction:
Example
EXPERIMENT 1. 3
Laboratory Preparation of Ethene

Objective: To prepare ethene and study some of its properties
Materials required: Ethanol, concentrated H2SO4, water, bromine water, round-bottomed flask,
stopper, delivery tube, gas jars, pneumatic trough, thermometer, tripod, Bunsen burner, stand and
clamp, beehive shelf and wire gauze.
Procedure:
1. Arrange the set-up as shown in the figure below.

2. Pour ethanol into the flask and add concentrated H2SO4 through the thistle funnel; heat
carefully until the temperature reaches about 170°C. Discard the initially formed gas as it might
contain air; collect the next gas in two gas jars by downward displacement of water; perform
the following activities.
a. Insert a lighted splint into the first jar containing the gas and see what happens.
33
b. Add two drops of bromine water to the second gas jar, cover the jar and shake well.
Figure 1.6 Preparation of Ethene

a. What is the color and odor of the gas?
b. What is the substance left after combustion of the gas in the jar?
c. What change is observed when the gas is shaken with bromine water? Write equation for the
reaction.
d. Name the dehydrating agent used in the experiment.
e. Which method of preparation of an alkene is used in this experiment?
Write a laboratory report about the experiment and submit it to your teacher.
34
EXERCISE 1. 4
1. Write the molecular formulas of: alkane, alkene with one double bond, alkene with two
double bonds, cycloalkane and cycloalkene with no substituents comprising six carbons.
2. Which of the following compounds is / are capable of exhibiting cis /trans isomerism?
a. CH2 = CHCH2CH3 b. F2C = CH2 c. FCH = CHF d. 1 – Chloro-2-methypropene
3. The following names are given wrongly. Correct each of them.
a. 2 – methyl – 3 – pentene b. 5 – methyl cyclohexene c. 1, 1 – dimethyl propene
d. 1, 1, 2, 2 – tetramethyl ethene e. 1 – methyl – 1 – heptane
4. What is the product obtained from each of the following reactions?
a. Treating 3 – chloro – 2, 2 – dimethyl pentane with potassium hydroxide solution
b. Treating CH3CH(OH)CH2CH3 with concentrated H2SO4
Chemical Properties of Alkenes

Alkenes contain a double bond (one of which is strong bond while the other is weak) between
the two carbon atoms. They are more reactive than alkanes because the weak bond can be used
for further reaction. Alkenes undergo a variety of reactions.
1. Combustion reaction. Alkenes burn in oxygen with a luminous flame to form carbon
dioxide and water.
Example
C2H4 (g) + 3 O2 (g) → 2 CO2 (g) + 2 H2O (g) + heat
2. Addition reaction. Alkenes undergo mainly addition reactions. The addition occurs at the
carbon-carbon double bond.
35
a. Addition of halogens (halogenation): When a halogen molecule, X2, (where, X2 = Cl2 or

Br2) is added to alkenes, the product is a dihaloalkane.
General reaction:
Example
If bromine water (bromine in CCl4) is added to alkenes, the color of Br2 in CCl4 (reddish brown)
disappears. This is due to the addition of bromine (Br2) across the double bond. So, Br2 in CCl4 is
used to detect unsaturation (presence of multiple bond) in a compound.
b. Addition of hydrogen (Hydrogenation): Addition of hydrogen molecule to

alkenes in the presence of nickel or platinum catalyst at high temperature yields alkanes.
Example
c. Addition of hydrogen halides, HX (hydrohalogenation): Addition of hydrogen halide

(HCl, HBr or HI) to alkenes leads to the formation of alkyl halides. The product of the
reaction can be predicted by Markovnikov’s rule; which states that “when an alkene
reacts with a hydrogen halide, the hydrogen adds to the carbon atom of the double bond
that has greater number of hydrogen atoms, and the halogen to the carbon that has the
fewer number of hydrogen atoms”.
The same is true when an alkene reacts with water in an addition reaction to form an
alcohol.
36
General reaction:
Example
d. Addition of water (hydration): When alkenes are hydrated in the presence of an acid
catalyst, they produce alcohols, in accordance with Markovnikov’s rule.
General reaction:
Example
e. Oxidation of alkenes: Oxidation of alkenes with cold alkaline potassium permanganate

solution (KMnO4) forms diols (compounds containing two hydroxyl groups).
Example
37
Alkaline KMnO4 solution is another reagent used to test the presence of unsaturation in a
compound. The solution is called Baeyer’s reagent. If there is a carbon – carbon double bond
in the structure, the purple alkaline KMnO4 solution fades and a brown precipitate is formed.
f. Polymerization (self-addition) of alkenes: Polymerization is the union of small

molecules called monomers to form a large molecule called polymer
Example
Uses of Ethene (Ethylene)

➢ Ethene is used in the production of ethanol, and polymers such as polyethene, polyvinyl
chloride (PVC), polystyrene and Teflon.
➢ To make ethane-1, 2-diol used as anti-freezing for motor car radiators.
➢ For preservation as well as artificial ripening of fruits.
Cycloalkenes
These are unsaturated cyclic hydrocarbons. The carbon atoms are linked in such a manner as to
form a closed chain or a ring structure. They contain a double bond in the ring between carbon
atoms and are represented by the general formula CnH2n–2, where n is equal to or greater than 3.
Cycloalkenes are isomeric with alkynes of the same carbon number. This class of compounds are
named by prefixing “cyclo” to the name of alkenes containing the same number of carbon atoms.
EXERCISE 1. 5
1. Write the structure of each of the following compounds.
a. 3-methyl-3-heptene b. 3, 4-diethyl-1-hexene C. hepta-1,5-diene
2. Give the IUPAC name and molecular formula of the following compounds.
a b
. .
3. Complete each of the following equations and name the products.
a. CH3CH2CH= CH2 + HCl →
b. CH3CH2CH =CH2 + Br2 →
38
c. CH3CH2CH= CH2 + H2O →

d. CH3CH2CH = CH2 + ICl →
e. CH3CH = CHCH2CH3 + KMnO4 (alkaline) →
4. What do you expect or observe (if any) when:
a. Chlorine gas is added to ethane in the presence of light?
b. Bromine water is added to ethene in the presence and absence of light?
c. Chlorine gas is added to ethane in the absence of heat or light?
d. Alkaline KMnO4 aqueous solution is added to each of ethane and ethene?
(Challenge)
5. There are 17 chain, cyclic and geometric isomers with the formula C6H12.
a. Draw the structures of all these isomers.
b. How many of these are: (i) Chain isomers; (ii) position isomers (iii) geometric isomers?
1.3.2 Alkynes
Alkynes are unsaturated hydrocarbons possessing C ≡ C bond as their functional group. The
homologous series of alkynes is represented by the general formula CnH2n–2, where n ≥ 2. The
simplest member of the group is commonly known as acetylene (H–C≡C–H). The IUPAC names
for alkynes parallel those of alkenes, except that the family ending is -yne rather than -ene.
39
Table 1.6 Homologous series of alkynes and their physical constants.
Nomenclature of Alkynes
This class of compounds are commonly named as a derivative of acetylene.
Example
IUPAC System
The IUPAC names for alkynes are obtained by using the prefixes designating the carbon number
followed by the suffix ‘yne’ to indicate the presence of a triple bond between a pair of adjacent
carbon atoms.
40
Example
Isomerism
Alkynes show both chain and position isomerism, but not geometrical isomerism.
Example
1-Butyne and 2-butyne are position isomers.

Chain isomers of 1 – pentyne: HC ≡ C – CH2 – CH2 – CH2 – CH3
HC ≡ C – CH (CH3) – CH2 – CH3 HC ≡ C – CH2 – CH (CH3) – CH3
3 – methyl – 1 – pentyne 4 – methyl – 1 – pentyne
Physical Properties
Alkynes are non-polar compounds whose molecules are held together by weak intermolecular
forces. The strength of the intermolecular forces increases with increasing molecular size. The
physical properties of alkynes are almost similar to those of alkenes.
Preparation of Alkynes
Some of the general methods of preparation of alkynes are:
1. Dehydrohalogenation of vicinal (adjacent) dihalides with a base NaOH or KOH.

General reaction:
41
Example
2. Alkylation of sodium acetylide (dicarbide) with a primary alkyl halide.
General reaction:
Example
EXPERIMENT 1. 4
Laboratory Preparation of Ethyne
Objective: To prepare ethyne from calcium carbide and water.
Materials required: CaC2, H2O, bromine water, round-bottomed flask, separating funnel,
delivery tube, trough, beehive shelf and gas jar.
Procedure:
1. Arrange the set up as shown in the figure below. Put a layer of sand in a conical flask and
place calcium carbide on the sand.
2. Add water drop by drop from the separating funnel onto the calcium carbide. Watch carefully
and record your observation. Touch the flask with the tip of your finger.
42
3. Collect several jars of the gas over water and carry out the following tests:
a. Burn the gas as you did with methane and ethene.
b. Add a few drops of bromine water to the first jar filled with ethyne and note the changes.
Figure 1.7 Laboratory Preparation of Ethyne
Observation and analysis
a. What do you feel when you touch the flask? Is the reaction exothermic or endothermic?
b. How do you compare the color of the flame produced with that of methane and ethene?
Write a complete laboratory report and submit it to your teacher.
Chemical Properties of Alkynes

As a class, alkynes are more reactive than alkanes and alkenes. Why?
Alkynes are more unsaturated than alkanes and alkenes due to the presence of a carbon-carbon
triple bond. They can undergo combustion and addition reactions.
Some of the common reactions of alkynes are:
43
1. Combustion reaction: Alkynes burn with a smoky luminous flame, forming CO2 and water.
The smoky flame is due to the high percentage composition of carbon.
General reaction: CnH2n – 2 + ½ (3n – 1) O2 → n CO2 + (n – 1) H2O
Example
2 C4H6 + 11 O2 → 8 CO2 + 6 H2O + heat
C3H4 + 4 O2 → 3 CO2 + 2 H2O + heat
2. Addition reaction: Alkynes undergo addition reaction at the carbon-carbon triple bond.
Typical reactions are given as follows.
a. Addition of hydrogen (hydrogenation): In the presence of nickel or palladium catalyst,
alkynes produce alkanes with 2.0 mol of H2.
General relation:
Example
Partial hydrogenation of alkynes in the presence of Landler’s catalyst gives alkenes. Landler’s
catalyst is powdered palladium partially deactivated with lead acetate.
b. Addition of halogens: When molecule of an alkyne reacts with one and two molecules of
halogens, it gives a di haloalkene and a tetra halo alkane, respectively.
General Reaction:
44
Example
c. Addition of hydrogen halides: Alkynes add hydrogen halides to form a mono haloalkene
and a dihaloalkane. The addition reaction occurs according to Markovnikov’s rule.
General Reaction:
Example
45
3. Trimerization of Acetylene: Acetylene, on prolonged heating at 600 – 700oC, yields

benzene.
Properties and Uses of Acetylene

Acetylene is a colorless, sweet-smelling gas in pure form and is insoluble in water. It is usually
stored as a solution of acetone in steel cylinders. Combustion of acetylene with oxygen produces
an intensely hot flame of about 30000C. Thus, a large quantity of acetylene is used as a fuel in oxy-
acetylene torches for cutting and welding metals. Acetylene is also used to prepare acrylonitrile
which is a starting material for producing polyacrylonitrile, a raw material for textile fiber. It is
also used for making vinyl chloride which polymerizes to give polyvinyl chloride (PVC)
commonly used for making floor tiles, electrical insulators, shoe soles, water pipes, etc. Acetylene
is used to produce 1, 1, 2, 2-tetrachloroethane that serves as a solvent for wax, grease, rubber, etc.
Table 1.7 Comparison of some properties of Ethane, Ethene and Ethyne
EXERCISE 1. 6
1. Write the structures of all isomers of 1-pentyne (C5H8) and give their names. Group them
into chain isomers and position isomers.
2. Draw the structure for each compound.

a. 4-methyl-2-hexyne b. 3 – hexene – 2 - yne c. 3-methyl-1-hexyne
3. Complete the following reactions and name the major products:
a. CH3 – CH2 – CH = CH2 + HCl →
46
b. CaC2 + 2H2O →
c. CH3 – C ≡ CNa + CH3CH2Br →
d. CH3 – CH2 – C ≡ CH + 2HBr →
e. H – C ≡ C – H + Br2 →
f. H – C ≡ C – H + 2Br2 →
g. 1 - Methyl cyclohexene + HBr →
h. CH3-CHBr-CH2Br + 2 KOH →
4. Name the following compounds
5. Fill in the missing terms.

a. Propyne + H2 → ___X_______ b. X + HBr → ________
c. _______ + HCl → 2, 2 – dichloro butane
d. CH3CH2CH2CH = CHCH3 + alkaline KMnO4 → ___________
e. _________ + HBr → 1 – chloro – 1 – methyl cyclopropane
6. Correct the following wrongly given names.
a. 4, 5 – dichloro cyclopentene b. 1 – butyne – 3 – ene
c. 2 – Methyl cyclohexene d. 2 – chloro – 3 – pentyne
47
1.4 AROMATIC HYDROCARBONS

Competencies
At the end of this section you will be able to:
• define the term aromatic hydrocarbons;

• draw the structure of benzene;
• describe the major physical, chemical properties and reactions of benzene;
• carry out test-tube reactions with Br2 in CCl4, KMnO4, concentrated H2SO4.
The term aromatic is derived from the word ‘aroma’ meaning ‘fragrant’ or pleasant smell, which
was originally used to describe naturally occurring compounds with pleasant smell. At present, the
term is used without its original significance. Aromatic hydrocarbons are generally obtained from
petroleum and coal tar. They are characterized by the presence of a benzene ring or related
structures. Structures of some aromatic compounds are given below.
48
The number of pi (ℼ) electrons in benzene containing rings is given by the formula (4n + 2), where
n = 0, 1, 2, 3, etc.
Benzene
Benzene is the simplest aromatic hydrocarbon. Its molecular formula is C6H6. Friedrich A. Kekule,
in 1865, suggested that the six carbon atoms of benzene are arranged in the shape of a hexagon.
He also suggested a resonance hybrid structure. He represented benzene by the resonance
structures (figure below) in which the two structures shown make equal contribution for the
resonance hybrid or actual structure.
Figure 1.8 Resonance structures of benzene
The bonds in benzene are neither single nor double but have an intermediate character between
those of single and double bonds. All the carbon-carbon bonds in the molecule are the same in
length and reactivity. Since structures I and II given above are not the true structures of the
molecule, benzene is written, in most cases, in its resonance hybrid form as follows:
49
From structures I and II above, one may think that benzene has three double bonds and assume the
same chemical property as that of alkenes. But this is not true. Benzene and other aromatic
hydrocarbons are not as unsaturated as alkenes because the three double bonds in benzene are
delocalized due to resonance. They are more stable than alkenes. They undergo substitution
reactions to a far greater extent than addition reactions, which makes them different than alkenes.
Physical properties of benzene
Benzene is a flammable, colorless, and volatile liquid with a characteristic smell. It is nonpolar
and immiscible with water but miscible with non-polar solvents like ether and carbon tetrachloride.
It freezes at 5.4oC and boils at 80.4oC. It is a carcinogenic (cancer causing) substance. Benzene is
a good solvent for fats, gums, rubber etc., and is used in the manufacture of dyes, drugs and
explosives.
Nomenclature of Aromatic Hydrocarbons

Rule 1: As per IUPAC nomenclature system, it is important to place the substituent’s name
before the name of the compound as a prefix in any substituted aromatic hydrocarbon. For
example, nitrobenzene where the benzene ring is present along with a nitro group.
• Rule 2: Attach Greek numerical prefixes such as di, tri, and tetra to indicate similar
substituents group in case of compounds with more than one substituent group present in the
benzene ring.
50
• Rule 3: In case of compounds with two substituents, it is necessary to use terms such as ortho
(o), meta (m), and para (p) as prefixes to represent the relative positions. If substituent X is
attached to carbon.
Note: Ortho, meta and para are used in common names for two substituents only.
Chemical Properties of Benzene

Benzene and other aromatic hydrocarbons are more stable than alkenes and alkynes due to the
stability of the aromatic ring. It neither decolorizes bromine water (Br2 in CCl4) nor is reactive
towards cold potassium permanganate solution. However, benzene undergoes the following
reactions:
1. Combustion reaction: Benzene is highly inflammable. It burns with a smoky luminous
flame to form CO2 and H2O.
2 C6H6 + 15 O2 → 12 CO2 + 6 H2O + Heat
2. Substitution reaction: benzene chiefly undergoes substitution but not addition reaction. In
this reaction, hydrogen atom from the benzene ring is replaced by another atom or group.
51
a. Halogenation: Benzene reacts with bromine and chlorine in the presence of iron (III)
chloride or aluminum chloride catalyst to form substitution products.
b. Nitration: Concentrated nitric acid mixed with concentrated sulfuric acid reacts
with benzene at moderate temperatures to form nitrobenzene.
c. Sulfonation: Benzene reacts with concentrated sulfuric acid, H2SO4, at room

temperature to form benzene sulfonic acid.
d. Addition reaction: Benzene undergoes addition reaction under special conditions.
52
Example
In each of these reactions an atom or group has been substituted for one of the hydrogen
atoms in benzene. It basically resists addition.
Here is a summary for the properties of benzene in comparison to alkenes.
Reagent Benzene Cyclohexene
Br2 in CCl4 (brown) No reaction Rapid addition, color disappears
KMnO4 (aqueous) No reaction Rapid oxidation, color fades
HI No reaction Rapid addition
H2 in the presence of Ni Slow hydrogenation at 100 – Rapid addition at 25oC and
200 0C lower pressure
EXPERIMENT 1.5
Chemical Reaction of Toluene
Objective: To distinguish aromatic hydrocarbons from other unsaturated hydrocarbons

Materials required: Toluene, Br2 in CCl4, KMnO4, concentrated H2SO4, test tubes, test tube
rack, test tube holder, measuring cylinder, Bunsen burner and dropper.
Procedure:
1. Take three test tubes and place them in the test tube rack.
2. Add 5 mL of toluene (methylbenzene) to each of the three test tubes.
3. Add one or two drops of Br2 in CCl4 in the first test tube and add the same amount
of cold KMnO4 solution in the second test tube and observe the changes.
53
4. Add a few drops of concentrated sulfuric acid to the third test tube and, if necessary, heat
it gently, holding it with a test tube holder.
In which test tube does a reaction occur? Give reasons for the results of your observation.
Write a complete report of your observations and submit it to your teacher.
Uses of Aromatic Hydrocarbons

Aromatic hydrocarbons have great applications in both biological and synthetic processes. Some
uses of aromatic hydrocarbons are listed below.
Trinitrotoluene or TNT is widely used as explosive.

Methylbenzene is used as a solvent in model glues.
The green pigment found in plants, more commonly known as chlorophyll, consists of
aromatic hydrocarbons and is very important in the process of food production in plants.
Naphthalene is an important item in the production of mothballs
For the synthesis of drugs, dyes, and explosives, an aryl hydrocarbon known as
Phenanthrene is used
Plastic industry and petrochemical industries make use of aromatic hydrocarbons
extensively.
EXERCISE 1. 7
1. Describe the main reactions of benzene?

2. Benzene does not change the color of Br2 in CCl4 or that of KMnO4 solution; why?
3. Which compound is aromatic?
4. Write the IUPAC and common names of all dichloro benzenes.

5. Draw the structures of the following compounds
54
a. 1,3-dichlorobezene b. o – bromo chlorobenzene c. 2-bromotoluene

d. ethylbenzene e. m – chloro methyl benzene
6. Correct the following wrongly given names
a. 1, 4, 5 – trichloro benzene b. 2 – bromochlorobenzene c. 5 – nitrotoluene
1.5 NATURAL SOURCES OF HYDROCARBONS

Competencies
After completing this subunit, you will be able to:
• list the major natural sources of hydrocarbons and their uses;

• describe natural gas;
• mention the products of the fractional distillation of crude oil;
• describe the composition of coal and its destructive distillation;
Natural gas
The principal sources of hydrocarbons are natural gas, crude oil and coal. Natural gas is found in
association with petroleum or alone. It is found in underground deposits several hundreds or
thousands of meters below the earth’s surface, where it originated from the decay and
decomposition of animal and plant remains millions of years ago.
Natural gas mainly contains only the more volatile alkanes, that is, those of low molecular mass;
it consists chiefly of methane and progressively smaller amounts of ethane, propane, butane and
higher alkanes. Other gases such as, CO2, N2, O2 and H2S, may also be present in natural gas. The
composition of natural gas varies, depending on its place of origin. Natural gas is widely used as
a fuel. It is advantageous over liquid and solid fuels and also other gases, except H2, due to its very
high heat of combustion.
Petroleum
The word petroleum is derived from two Latin words, ‘petra’ meaning rock, and ‘oleum’ meaning
oil. Thus, petroleum means rock oil. The term petroleum (crude oil) refers to a broad range of
fossil hydrocarbons that are found as gases, liquids or solids beneath the surface of the earth. Crude
oil is generally found along with natural gas in the form of a dark-colored viscous liquid, which is
a complex mixture of hydrocarbons. It mainly contains alkanes, cycloalkanes and aromatic
55
hydrocarbons. It also contains organic compounds consisting of nitrogen, sulfur and oxygen in
small amounts.
Refining of crude oil

Crude oil or petroleum is obtained by drilling wells until the oil-bearing region is reached. After
the crude oil is brought to the surface of the earth, it must be refined before it can be used. Crude
oil is refined or separated into several components by fractional distillation based on differences
in boiling ranges of its fractions.
Figure 1. 8 Fractional Distillation of Petroleum.
The major products (fractions) obtained from fractional distillation of petroleum and their
uses are given below.
56
Table 1.8 Common petroleum products
Most hydrocarbons present in petroleum are long-chain hydrocarbons. However, there is a very
high demand for petrol or gasoline, which contains hydrocarbons, composed of five to ten carbon
atoms. Therefore, the amount of petrol obtained by fractional distillation of crude oil does not
satisfy the demand for it. To satisfy the demand and maximize the output of petrol or gasoline, the
process called cracking is carried out during fractional distillation.
Cracking is the decomposition of large hydrocarbon molecules into smaller ones by the application
of heat (thermal cracking or pyrolysis) or in the presence of catalysts (catalytic cracking).
Example
Hydrogen gas can be added during cracking to saturate the alkenes formed in the process.
Coal
57
Coal is formed naturally by the decomposition of plant matter over several millions of years. It is
not a pure form of carbon. It is an important source of aromatic hydrocarbons. Heating mineral
coal in the absence of air is called destructive distillation of coal or coking of coal. By this process,
it gives volatile products and coke. When cooled, the volatile products separate into coal gas and
a liquid, called coal tar. Aromatic hydrocarbons and many other substances are isolated from coal
tar by fractional distillation. Coke, which is a solid and relatively pure form of carbon, is used as
a fuel in the blast furnace during the extraction of iron. It is also used to produce gaseous fuels,
such as water gas (mixture of H2 + CO) and producer gas (mixture of N2 + CO).
EXERCISE 1. 8
1. What are the major natural sources of hydrocarbons?
2. Which hydrocarbons are the main constituents of petroleum?
3. What is destructive distillation?
4. Which fraction of petroleum is in very high demand?
5. What process should be carried out during fractional distillation of crude oil to maximize
the output of petrol or gasoline?
6. Describe the main use of
a. Petroleum ether c. Kerosene e. Bitumen
b. Gasoline d. diesel oil
7. The heats of combustion of methane, ethane, propane and benzene, all in the gaseous state
are, 890 kJ, 1560 kJ, 2220 kJ and 3300 kJ per mole, respectively. When 1.0 g of the respective
hydrocarbon is burned in excess oxygen, which one produces:
(a) more heat? (b) more carbon dioxide?
8. What are the advantages of using H2 gas as a fuel compared to C6H6?
1.6 ALCOHOLS
Competencies
After completing this section, you will be able to:
• define alcohols and tell their functional group;

• write the general formulas of monohydric alcohols;
• give IUPAC names for given alcohols;
58
• classify monohydric alcohols based on the number of alkyl groups attached

to the carbon atom carrying the hydroxyl group;
• describe the physical properties of alcohols;
• explain general methods of preparation of alcohols;
• explain the industrial preparation of ethanol and perform an experiment to prepare
ethanol from sugar;
• explain the chemical reactions of alcohols such as oxidation, reaction with active
metals, esterification and dehydration;
• carry out an activity to show chemical reactions of alcohols with active metals;
• write the general structural formulas for the derivatives of alcohols: aldehydes,
ketones, carboxylic acids and simple esters;
• write the molecular formulas and names of the derivatives of alcohols.
Most people think of two common alcohols: the substance that intoxicates people and the one used
in clinics and hospitals. However, there are many types of alcohol. The only alcohol present in all
alcoholic beverages is called ethanol. Other alcohols are used for different purposes.
Alcohols are hydroxyl derivatives of hydrocarbons that can be obtained by replacing one or more
hydrogen atom(s) of a hydrocarbon with the hydroxyl (–OH) group, which the functional group
of alcohols.
Examples
1.6.1 Classification of Alcohols

Alcohols are generally classified as monohydric, dihydric and tri hydric depending on the number
of hydroxyl (–OH) groups they contain in their molecular structure.
Monohydric alcohols are alcohols containing only one hydroxyl group.
Examples
59
Dihydric alcohols are those containing two hydroxyl groups per molecule. They are also
named glycols or diols.
Example
Tri hydric alcohols are those containing three hydroxyl groups in their molecular structure.
If there are three or more hydroxyl groups per molecule, they are called polyhydric alcohols.
1.6.2 Nomenclature of Alcohols

An alcohol can be considered to be derived from a hydrocarbon by the replacement of at least
one H atom by hydroxyl group. Hence, alcohols can be systematically named by using the
suffix -ol to replace the terminal -e in the corresponding alkane name.
60
Table 1. 9 IUPAC names, condensed structures and physical constants of the first six
monohydric alcohols
Structure of mono IUPAC name Melting Boiling Density

hydric alcohol point (0C) point (0C) g/mL
CH3OH Methanol -97 64.7 0.92
CH3CH2OH Ethanol -117 78.3 0.789
CH3CH2CH2OH 1-Propanol -126 97.2 0.804
CH3(CH2)2CH2OH 1-Butanol -90 117.7 0.810
CH3(CH2)3CH2OH 1-Pentanol -78.5 138 0.817
CH3(CH2)4CH2OH 1-Hexanol -52 156.5 0.819
In the IUPAC system of nomenclature of alcohols containing side chains or –OH groups in
different positions, the longest chain to which the –OH group is attached, is chosen as a parent
structure. The chain is then numbered, starting from the end closer to the carbon atom to which
the –OH group is bonded. The other rules are similar to the nomenclature of hydrocarbons.
Examples
Classification of monohydric alcohols

Carbon atoms can be classified as primary (1°), secondary (2°), tertiary (3°) and quaternary
(4°) if they are bonded to one, two, three and four carbon atoms, respectively.
61
Example
Primary alcohols are those which have the hydroxyl group connected to a primary carbon.
They can also be defined as molecules containing a “–CH2OH” group.
Example
Secondary alcohols are those in which the carbon atom bonded to the hydroxyl group is attached
to two alkyl groups or contains an –OH group bonded to a secondary carbon atom.
62
Example
Tertiary alcohols are those in which the carbon atom bonded to the hydroxyl group is attached
to three hydrocarbon (alkyl) groups or contain –OH group attached to a tertiary carbon atom.
Example
1.6.3 Physical properties of Alcohols

The hydroxyl group in an alcohol is polar due to the high electronegativity of oxygen. As a
result, there is significant hydrogen bonding in alcohols.
Figure 1.9 Hydrogen bonding between molecules of an alcohol
Due to the hydrogen bonding in alcohols, they have higher melting and boiling points than
hydrocarbons of comparable molecular size (mass). Hydrogen bonding is also the cause for even
63
lower members to be liquids at room temperature. The boiling point of more branched isomer is
lower than that of its isomeric straight-chain alcohol; for example,
boils at 82.5°C. Dihydric and the tri hydric alcohols have higher boiling points than monohydric
alcohols of similar molecular size (mass). Ethane-1, 2-diol (dihydric alcohol, molecular mass =
62), boils at 197°C, while 1-propanol (monohydric, molecular mass = 60) boils at 97.2°C.
The first three alcohols: methanol, ethanol and 1-propanol are miscible with water. The solubility
in water decreases with increasing carbon number. The water solubility of dihydric and tri hydric
alcohols are higher than those of monohydric alcohols of similar molecular mass.
EXERCISE 1. 9
1. Classify the following monohydric alcohols as primary, secondary or tertiary alcohols.

a. 1-pentanol b. 2-pentanol c. 2-methyl-2-butanol d. cyclohexanol
2. Give reason for each of the following observations.
a. Ethanol has higher boiling point than ethane.
b. 2 – Propanol boils at lower temperature than 1 – propanol
c. Ethane diol is more soluble in water than ethanol
d. Butane is a gas while butanol is a liquid.
1.6.4 Preparation of Alcohols

The general laboratory methods of preparing alcohols are:
a. Acid-catalyzed hydration of alkenes
General Reaction:
64
Example
b. Hydrolysis of alkyl halides

Warming alkyl halides with sodium hydroxide produces alcohols.
General Reaction:
Example
c. Hydrolysis of esters
Heating esters with potassium hydroxide produces alcohols.
General Reaction:
Example
65
The two methods, b and c, involve the replacement of other groups by –OH. Hence, they are
examples of substitution reaction.
Ethanol (Ethyl Alcohol), CH3CH2OH
Ethanol is the second member of the homologous series of monohydric alcohols. It is the
constituents of all alcoholic beverages. ‘Tella’, ‘Tej’, beer, wine, ‘Katikalla’, ouzo, gin and
whisky contain ethanol. Here are industrial methods of preparing ethanol.
a. Fermentation of carbohydrates such as sugar
Fermentation is the slow decomposition of carbohydrates such as sucrose, starch and cellulose in
the presence of suitable enzyme. The final products are ethanol and carbon dioxide:
Fermentation can produce alcoholic beverage whose ethanol content is 12 – 15% only. The
alcohol kills the yeast and inhibits its activity when the percentage is higher. To produce
beverages of higher ethanol content, distillation of the aqueous solution is required. Most liquor
factories in Ethiopia use molasses, a by-product of sugar industries, as a raw material to
produce ethanol. In the brewing industry, germinated barley called malt (in Amharic ‘Bikil’) is
used as the starting material. The whole process taking place in breweries is summarized as
follows:
b. Catalytic hydration of ethene

In this process, ethene is treated with steam at 573 K and 60 atm pressures in the presence of
phosphoric acid, H3PO4, catalyst. Most ethanol is manufactured at present by this method.
66
EXPERIMENT 1.6
Preparation of ethanol by fermentation
Objective: To prepare ethanol from sugar.
Materials required: Conical flask, glass rod, distillation flask, condenser, spatula,
thermometer, watch glass, Bunsen burner, beaker, stopper and delivery tube.
Sugar, ammonium phosphate or ammonium sulphate, yeast, Ca (OH)2.
Procedure
1. Take 50 mL of distilled water in a conical flask, add 15 g of sugar to it and stir. Add about
1 gram of yeast and a small amount of ammonium phosphate or ammonium sulphate to the
solution. Arrange the setup as shown below, and let the flask stand for three days at a warm
place.
Figure 1.10 (a) The Fermentation of sugar

Observation and analysis
a. What is the purpose of adding yeast to the solution?
b. Why do we add ammonium phosphate or ammonium sulphate to the sugar solution?
67
c. What happened to the calcium hydroxide solution at the end of the first or second day?
Which gas is produced?
d. What is the smell of the solution in the flask after three days?
e. What has happened in the flask containing sugar solution as it stood for three days?
2. After three days, filter the solution, and arrange the set up as in Figure 1.10 (b). Pour 20
mL of the filtrate in a distilling flask, heat the solution, and collect the liquid in a receiver.
Figure 1.10 (b) Separation of ethanol by distillation

Points to observe
a. Observe the color and identify the smell of the distillate.
b. Pour a small amount of the distillate on a watch glass, strike a match and bring the flame
close to the distillate. Does it catch fire?
Write complete laboratory report on this experiment and submit it to your teacher.
Properties and Uses of Ethanol
Ethanol is a colorless liquid with a pleasant smell and a burning taste. It boils at 78.3°C and
freezes at –117°C. It is inflammable and burns with a blue flame. It is miscible with water, non-
poisonous and has an intoxicating effect. It is a hypnotic (sleep producer).
68
As mentioned earlier, ethanol is a constituent of all alcoholic beverages. It is a good solvent for
many organic compounds that are insoluble in water, such as paints, dyes, perfumes etc. It is also
used as a fuel for cars and spirit lamps. Ethanol can be made unfit for drinking by mixing it with
other non – food materials, such as methanol or iodine. This mixture is called denatured alcohol.
For example, methylated spirit is a mixture of 95% ethanol and 5% methanol. Currently,
Ethiopia uses 5% ethanol with 95% benzene as fuel for cars.
1.6.5 Chemical Properties of Alcohols

Alcohols contain a hydrocarbon skeleton with the functional group (–OH). Which part of
alcohols is responsible for most of their chemical properties?
Reactions of alcohols may involve the cleavage of the oxygen hydrogen bond (C— O — H)
or the carbon-oxygen bond (— C — O – H).
The reactions of alcohols involving the –O–H bond cleavage are:
a. Alcohols react with strongly electropositive metals like Na, K and Ca to form alkoxides
and liberating H2 gas.
General reaction:
Example
EXPERIMENT 1. 7
Reactions of alcohols with active metals
Objective: To observe the reaction of alcohols with sodium and magnesium.

Materials required: Ethanol, sodium and magnesium metals. Test tubes, test tube holder, test
tube rack, measuring cylinder, Bunsen burner, scissors or knife.
Procedure:
Take two test tubes and add 2 - 5 mL of ethanol to each of the test tubes. Cut a very small piece
69
of sodium with a knife and drop it slowly into the first test tube.
Take magnesium ribbon and drop it in the second test tube.
1. What do you observe:

a. in the 1st test tube? b. in the 2nd test tube?
2. Is there evolution of gas? If so, what do you think this gas is?
3. If no reaction occurs in any of the test tubes, heat the mixture gently using a Bunsen burner
and write your observation.
4. Which bond of the alcohol is broken in the reaction?
5. Write a balanced equation for the reaction (s) you observe.
6. What type of metals react in this manner?
b. Oxidation of alcohols: The oxidation products of alcohols depend on the type of alcohol and
nature of the oxidizing agent. Oxidation of alcohols is a very important method for the
production of other oxygen-containing compounds of hydrocarbons, such as aldehydes,
ketones and carboxylic acids.
i. Oxidation of primary alcohols in the presence of mild oxidizing agent yields aldehydes.
General reaction:
Example
Strong oxidizing agents, such as acidified KMnO4 or K2Cr2O7 and CrO3 in H2SO4, oxidize
primary alcohol first to aldehydes and then to carboxylic acids. It is difficult to stop the
reaction at the aldehyde stage.
70
Example
Note that aldehydes are represented by the general structural formula or

RCHO, where R is an alkyl group. In the case of methanol, R = H. For naming aldehydes,
use the suffix -al to replace the terminal -e in the corresponding alkane name. The suffix “-
al” indicates the functional group –CHO. Carbon of the functional group is always assigned
number 1 in naming these compounds.
Table 1.10 Condensed structures and IUPAC names of some aldehydes
ii. Oxidation of secondary alcohols yields ketones.
General reaction:
71
Example
The general structural formula of ketones is: or RCOR’ where R and R’

may be the same or different but never H.
The IUPAC names of ketones are obtained by using the suffix -one to replace the terminal –e
in the corresponding alkane name. The suffix ‘-one’ indicates the functional group. Unlike
aldehydes, the position of the functional group must be indicated in the name of higher ketones.
To do so, the longest chain containing the functional group is chosen as a parent and then the
carbon atoms of the chain are numbered starting from the end closer to the carbonyl group.
iii. Tertiary alcohols and ketones are generally resistant to oxidation. However, they can
undergo oxidation under drastic conditions to form a mixture of carboxylic acids.
72
Example
The general structural formula of carboxylic acids is or simply R– COOH where

R – is an alkyl group. The first member of carboxylic acids is methanoic acid where R = H. The
IUPAC names of carboxylic acids are derived by replacing the final -e of the corresponding alkane
with -oic acid. The suffix ‘-oic acid’ represents the functional group –COOH. The molecular
formulas, condensed structure and IUPAC names of the first six straight chain carboxylic acids
are given below.
Table 1.11. Formulas, condensed structures and IUPAC names of some carboxylic acids
c. Esterification:
Alcohols react with carboxylic acids to form esters. This reaction is known as esterification.
73
EXPERIMENT 1.8
Reaction of alcohols with organic acids

Objective: To investigate the reaction of ethanol and ethanoic acid.
Material required: Ethanol, ethanoic acid, concentrated sulfuric acid, test tube, test tube
holder, Bunsen burner, beaker, water and glass rod.
Procedure:
1. Pour 2 mL of ethanol and 4 mL of acetic acid in a test tube. Add a few drops of
concentrated sulfuric acid to the mixture of the alcohol and acid.
2. Hold the test tube containing the mixture with a test tube holder and heat it gently from
three to five minutes. Allow the contents to cool, add it to a beaker half-filled with water.
Stir the mixture and smell the product.
a. What smell did you recognize? What do you think is the origin of this smell?
b. Write a balanced chemical equation to show what has happened on heating the mixture.
c. What is the purpose of adding drops of concentrated sulfuric acid to the mixture?
Write a laboratory report in groups and present it to the class.
74
The general structural formula of esters is: or simply RCOOR where R and R’
are alkyl groups. If the acid used is methanoic, then R = H. In the nomenclature of esters, they
are considered as derivatives of both carboxylic acids and alcohols.
In naming esters, the alcohol derivative comes first followed by the acid derivative. The alcohol
part is changed into alkyl group (e.g. ethanol to ethyl) followed by the acid part changing the
suffix “-ic acid” to “-ate” (e.g. ethanoic to ethanoate). Here are some examples of esters.
The reactions of alcohols involving the – C – O bond cleavage include:
a. Dehydration of alcohols: Heating alcohols in the presence of dehydrating agent, like

concentrated H2SO4, yield alkenes.
General reaction:
75
Example
The overall tendency of alcohols to undergo dehydration is in the following order:
b. Reactions of alcohols with hydrogen halides produce alkyl halides:
Examlpe
EXERCISE 1.10
1. Which skeleton is common in the functional groups of:
a. alcohols and carboxylic acids b. aldehydes and ketone
2. Write the structures of the following compounds.
a. 3, 3 – dimethyl – 2 – butanol b. 3 – bromo propanal
c. cyclo hexanone d. 4 – chloro – 2 – butanone
e. 3 – hydroxyl butanoic acid f. propyl methanoate
3. Name the alcohol and carboxylic acid that make up each of the following esters?
a. butyl butanoate b. ethyl methanoate c. cyclo hexyl propanoate
4. Complete each of the following reactions.
a. CH3CH2I + NaOH → b. CH3OH + HCOOH →
76
c. CH3CH(OH)CH3 + H2SO4 → d. CH3COOCH2CH3 + KOH →

e. CH3CH2CH2OH + HBr → f. CH3OH + KMnO4 / H+ →
5. Consider the following organic compounds.
a. Pentanone b. 1 – Pentanol c. Pentane d. Pentanoic acid e. ethyl ethanoate
a. Arrange the given compounds in decreasing order of boiling point.
b. Which of the above compounds is more soluble in water than the others? Which
one is the least soluble in water and why?
c. Which of the above compounds exhibit hydrogen bonding?
1.7 INDUSTRIAL AND AGRICULTURAL APPLICATIONS OF ORGANIC

COMPOUNDS
Competencies
After completing the section, you will be able to:
• discuss the uses of organic compounds in the manufacture of beverages; pharmaceuticals;

soaps and detergents; dry cleaning agents; fuels;
• conduct an experiment to prepare soap from naturally existing esters;
• discuss the uses of organic chemicals in the manufacture of pesticides and herbicides;
• discuss the importance and manufacture of urea.
Industrial application
Organic chemicals are used for the manufacturing of a large number of industrial products that
have a variety of uses. Some of these products include alcoholic beverages, pharmaceuticals,
soaps and detergents etc.
a. Alcoholic beverages
A potable (meaning drinkable) liquid containing ethanol of 0.5 % or more by volume is termed
as ‘alcoholic beverage’. Alcohol is a volatile fluid obtained from a fermented sugar or starch.
The ethanol content of all alcoholic beverages is not the same. It ranges from small to higher
concentrations. These alcoholic beverages can be either un distilled or distilled. The un distilled
alcoholic beverages include beer, wine, “Tella”, ‘Tej’, etc. while ouzo, gin, brandy, whisky,
‘Katikalla’, and vodka are among the distilled alcoholic beverages.
77
Beer: Beer is one of the alcoholic beverages widely manufactured and consumed in most parts
of the world. The common raw materials for its production are barley and hops. Although
the types of beer produced in the world are many, the average beer has alcohol content
between 3 to 6 % by volume.
Wine: Wine is un distilled alcoholic beverage. The most common raw material for producing
wine is grapes. In the production process, grapes are first crushed and then steamed. The
liquid derived from crushing is called must. It then goes to a tank where fermentation
takes place. Then it passes to a settling tank, where sediments are allowed to settle, and it
proceeds from there to a filter. The clear liquid is cooled in a refrigerator and pasteurized
as it passes through a flash pasteurizer. Most wines have an alcohol content varying from
10 to15 % by volume.
Liquor: Compared with beer and wine, liquor contains higher concentration of ethanol. It is not
possible to obtain an alcoholic beverage of more than 15% alcohol by volume through
fermentation. This is because the yeast cells are not able to stay alive in alcohol of higher
concentration. To get alcoholic beverages with higher percentage, the alcohol must be
separated from the solution by fractional distillation.
The alcoholic beverages like ouzo, gin, cognac, whisky, etc. are made by distillation. In
most distilled beverages, the percentage ranges between 30 to 45% alcohol by volume.
However, some alcoholic beverages like Araki can be made to have higher percentage.
b. Pharmaceuticals
Organic chemicals are used to manufacture drugs and medicines for various uses. These drugs
and medicines are collectively known as pharmaceuticals. Some of these are given below.
Pharmaceutical Uses Example
Analgesics reduce pain Aspirin, paracetamol
Antiseptics prevent infections in wounds by acriflavine

killing bacteria
Sedatives Hypnotics (sleep – producers) and Barbiturates (barbituric

make a person feel calm and relaxed acid), cocaine, morphine
Disinfectants Disinfect or kill bacteria Dettol
Sulfonamides Antibiotics Penicillin
78
c. Soaps and detergents

Organic chemicals are used for the synthesis of soaps and detergents. For example, animal fat
and vegetable oils are used for manufacturing soap. Fats and oils are naturally – occurring esters
of glycerol and the higher fatty acids. Long open-chain alcohols and alkyl benzene sulfonic acid
can be used for the production of detergents.
Soaps and detergents are substances used to remove dirt. They are also called surfactants or
surface-active agents. This is because they reduce the surface tension of water and change the
surface properties. Soaps are either sodium or potassium salts of higher (long-chain) carboxylic
acids. The sodium salts are called hard soaps and those of potassium salts are soft soaps. All are
prepared by boiling animal fat or vegetable oil with a base. The reaction that produces soap is
called saponification.
Some forms of soaps:
79
Detergents contain either a sulfate or a sulfonate group. One example of detergents is sodium
lauryl sulfate, C12H25SO3O- Na+. It is prepared by first reacting dodecyl (lauryl) alcohol with
sulfuric acid followed by mixing it with sodium hydroxide.
The reaction equation is:
Some forms of detergents
Differences between soaps and detergents

Soaps Detergents
They are sodium or potassium They are sodium or potassium salts of
salts of fatty acids sulfonic acid
Their polar end is – COO– Na+ The polar end is – SO3 –Na+
They do not work well with hard, They are effective in all types of water
acidic and saline water (they don’t (produce lather easily)
give lather easily)
They are fully biodegradable Those with branched – chain hydrocarbons
may be non – biodegradable
80
EXPERIMENT 1.9
Preparation of Soap
Objective: To prepare soap from animal fat or vegetable oil.
Materials required: Animal fat or vegetable oil, NaOH, NaCl, measuring cylinder, beaker, glass
rod, Bunsen burner, filter paper, funnel, conical flask, and test tube.
Procedure:
Measure 3 mL vegetable oil or 3 g animal fat and place it in a 100 – mL beaker; add 3 mL of
ethanol and 3 mL of 5 M NaOH. Stir the mixture vigorously with a glass rod and gently heat over
a flame for 15 minutes or until it turns in to a paste. When the paste begins to form, stir very
carefully to prevent frothing. Once the paste has formed, set the beaker on the bench to cool. Add
about 15 mL of saturated NaCl solution to the paste mixture and stir thoroughly. This process is
called salting out the soap. Filter off the soap mixture by suction filtration and wash the collected
soap precipitate with 15 mL of ice water.
a. Why do we add ethanol during the preparation?

b. What is the purpose of adding saturated NaCl solution to the paste mixture?
Write a laboratory report and present it to the class.
d. Dry cleaning
The qualities of some clothes decrease when they are washed with water using ordinary soap. In
order to avoid this, other chemicals are used for washing purposes that remove dirt in the same
manner as soaps. Dry cleaning refers to the use of different chemicals that are capable of dissolving
grease and other dirt stains in a similar manner as soaps without the use of water. The most
commonly used chemicals in dry cleaning are organic chemicals such as tetra chloro methane,
CCl4; tetrachloroethylene, Cl2C = CCl2; benzene and gasoline.
e. Fuels
The term fuel refers to any material that is capable of burning to produce energy, heat and light.
Most fuels occurring in nature are organic compounds. However, some inorganic substances like
hydrogen, producer gas and water gas are also used as gaseous fuels.
81
The most widely used fuels at present are of organic origin. This includes petroleum which chiefly
contains alkanes. Natural gas which is used as a fuel for stoves contains mainly methane. Gasoline
which is a fuel for internal combustion engines also contains alkanes. Paraffin wax, used to make
candles, is another fuel which is a mixture of alkanes containing more than twenty carbon atoms.
Besides its use as a constituent of all alcoholic beverages, ethanol can also be used as a fuel for
internal combustion engines. At present, it is one of the substances that we can rely on for use as
a fuel for automobiles. The use of ethanol as a fuel is now practiced in Ethiopia by mixing it with
petrol. Ethanol and other plant seed oils can be classified as bio fuels.
Agricultural Applications
Organic compounds also play an important role in agriculture, especially by controlling the
damages caused by insects, rodents, fungi, birds and weeds. In other words, organic chemicals
can be used in the manufacture of pesticides and herbicides.
What is the distinction between pesticides and herbicides?
Pesticides are the chemicals used for controlling the damage that can be caused by fungi,
insects and other pests that attack crops. Among the pesticides, Bordeaux mixture is used as
fungicide. Other chemicals like DDT, Aldrin, dieldrin and malathion are used as insecticides.
Herbicides are the chemicals that are applied on agricultural lands to remove unwanted plants
or weeds. Some examples of compounds that are used as herbicides include paraquat, diquat,
ammonium sulfamate, ammonium glyphosinate, sodium chlorate, etc.
Fertilizers: In order to increase crop productivity, we use either synthetic or natural fertilizers.
Synthetic fertilizers are grouped into three classes as nitrogen, potash and phosphate fertilizers.
Nitrogen is one of the essential plant nutrients. It is absorbed by plants in the form of nitrate ion,
NO3–. Nitrogen enables green plants to synthesize amino acids and proteins, and it is also a
constituent of DNA molecules.
To provide nitrogen for plants, nitrogen-containing fertilizers are usually added to the soil.
These include, ammonium salts like NH4Cl, (NH4)2SO4; (NH4)2HPO4 (DAP), nitrates like
KNO3 and urea. Urea is one of the most important nitrogen fertilizers. It is a component of
urine. On an industrial scale, urea is manufactured by the dehydration of ammonium carbamate:
82
It can also be prepared by direct combination of ammonia and carbon dioxide at 180°C and
pressure of about 140 atm.
83
Check list
Key terms of the unit
• addition reaction • halogenation

• alcohol • herbicide
• aldehyde • homologous series
• alkane • hydrogenation
• alkene • hydrohalogenation
• alkyl halide • isomers
• alkyl radicals • ketone
• alkynes • lifeforce theory
• benzene • Markovinov’s rule
• biogas • Natural gas
• carboxylic acid • nitration
• chain isomerism • organic compound
• cracking • pesticide
• crude oil • petroleum
• cycloalkanes • pharmaceuticals
• cycloalkenes • polymerization
• decarboxylation • position isomers
• dehydrohalogenation • resonance structures
• destructive distillation • saturated hydrocarbons
• detergents • soaps
• elimination reaction • substitution reaction
• ester • sulfonation
• fermentation • unsaturated hydrocarbons
• fertilizer • vitalism
• functional group • Wurtz reaction
• geometric isomerism
84
UNIT SUMMARY
• Until about 1850 many chemists believed that organic compounds must have their origin in living
organisms and consequently could never be synthesized from inorganic material. This idea was
known as the “vital force” theory.
• Organic chemistry is the study of hydrocarbons and their derivatives, both natural and synthetic.
Hydrocarbons are compounds composed of carbon and hydrogen atoms only.
• Organic compounds are classified based on the functional group they contain in their structures.
Functional group is a part of a molecule that determines the chemical and physical properties of a
compound.
• Saturated hydrocarbons contain only single bonds between carbon atoms while unsaturated
hydrocarbons are those containing one or more double or triple bonds between carbon atoms.
• A homologous series is a list of compounds in which each member of the group differs from the
next member by the constant – CH2 – group.
• Alkanes are saturated hydrocarbons represented by the general formula CnH2n +2, n ≥ 1. They are
named by using prefixes that indicate the number of carbon atoms followed by the suffix ‘ane.’
• Isomerism is the existence of two or more compounds of the same molecular formula but different
structures. The different compounds are called isomers.
• Alkenes are unsaturated hydrocarbons containing a carbon – carbon double bond as their functional
group. Their general formula is CnH2n. The suffix ‘ene’ in their names indicate the functional group.
• Alkynes are unsaturated hydrocarbons containing a carbon – carbon triple bond as their functional
group. They are represented by the general formula CnH2n – 2. In alkenes and alkynes, n ≥ 2. The
suffix ‘yne’ indicates the triple bond as a functional group.
• Alkenes and alkynes undergo mainly addition reaction while the major reaction in alkanes is
substitution. All the three types of hydrocarbons undergo combustion reaction readily.
• Aromatic hydrocarbons are compounds containing benzene ring (s).
• Even though benzene contain double bonds, it is not an alkene. It undergoes substitution reaction.
• The natural sources of hydrocarbons are crude oil, natural gas and coal.
• Crude oil is a complex mixture of alkanes (main component), and also cycloalkanes and aromatics.
Crude oil is separated into a number of useful fractions by fractional distillation.
85
• Alcohols are compounds containing the hydroxyl (– OH) group as their functional group and
saturated alcohols are represented by the general formula CnH2n +1OH.
• Alcohols are classified depending on the number of hydroxyl groups they contain as monohydric,
dihydric and tri hydric alcohols.
• Monohydric alcohols are classified as primary (1o), secondary (2o) and tertiary (30) alcohols.
• The name of alcohols end with the suffix ‘ol’ which indicates the presence of – OH group.
• Primary alcohols oxidize to give aldehydes and then to carboxylic acids while secondary alcohols
oxidize to form ketones.
• Organic compounds have industrial applications such as in the production of alcoholic beverages
and pharmaceuticals. Organic chemicals are also used in the production of fertilizers, pesticides and
weed killers for agricultural consumption.
• Organic compounds have applications as fuels, and to produce soaps, detergents and for dry
cleaning.
86
REVIEW EXERCISE ON UNIT 1

Part I: Which of the following statements are true?
a. Hydrocarbons that do not possess rings are aliphatic compounds.
b. Decaying of animals and vegetation is a major source of hydrocarbons
c. A simple alkene can be transformed back into alkane by adding hydrogen
d. All carbon containing compounds are organic.
e. A weed killer is a pesticide.
f. Antiseptics are sleep inducing drugs.
g. ‘Tella’ is a distilled alcoholic beverage.
h. Soaps and detergents are surfactants.
i. Alkanes easily undergo addition reactions.
j. Benzene burns with a sooty flame.
k. Biogas mainly contains n-butane.
l. Addition of ICl to propene produces 2-iodo-1-chloroprane
Part II: Multiple choice Type Questions
1. Which straight-chain alkane is a structural isomer of 3-propylheptane?

a. nonane b. decane c. hexane d. pentane
2. The hydrocarbon end of a soap molecule is
a. Hydrophobic and attracted to grease
b. Hydrophilic and attracted to water
c. Hydrophobic and attracted to water
d. hydrophilic and attracted to grease
3. The IUPAC name for the alcohol CH3 CH(OH)CH2CH(CH3)CH3 is
a. 2–methylhexan–4–ol c. 2–methyl–4–pentanol
b. 2–methyl–2–pentanol d. 4–methylpentan–2–ol
4. Which of the following hydrocarbons does not belong to the homologous series of alkanes?
a. C3H8 b. C8H18 c. C6H10 d. C10H22
5. Which of the following alkanes is a liquid at room temperature?
a. CH4 b. C6H14 c. C4H10 d. C3H8
6. The hydrocarbon used as a fuel in an oxyacetylene torch is:
87
a. C2H2 b. C2H4 c. C4H10 d. CH4

7. The general formula that represents the olefin homologous series is:
a. CnH2n+1 b. CnH2n+2 c. CnH2n–2 d. CnH2n
8. The major reaction that alkenes undergo is:
a. Elimination b. substitution c. addition d. decomposition
9. Benzene is an unsaturated hydrocarbon; it mainly undergoes:
a. Addition b. elimination c. polymerization d. substitution
10. Which of the following compounds is a ketone?
a. CH3CHO b. CH3COOH c. CH3COCH3 d. CH3COOCH3
11. Which of the following classes of hydrocarbons is the most reactive?
a. Alkane b. alkene c. alkyne d. aromatic hydrocarbon
12. The compounds CH3OH and CH3COOH react in the presence of an acid catalyst to form:
a. Carboxylic acid b. Ketone c. Aldehyde d. Ester
13. Which hydrocarbon is the main constituent of natural gas and biogas?
a. C2H6 b. C4H10 C. CH4 d. C6H14
14. During fractional distillation of crude oil, the process of cracking is carried out to:
a. separate the crude oil into different fractions
b. vaporize the liquid components
c. maximize the output of petrol or gasoline
d. separate alkanes from alkenes
15. Ethyne decolorizes Br2 in CCl4. This is due to the formation of:
a. 1,1-dibromoethane b. 1,1,2,2-dibromoethene
b. 1,2-dibromoethene d. 1,1,2,2-dibromoethane
16. The following reaction can be classified as:
CH4 + Br2 → CH3Br + HBr

a. Addition reaction c. elimination reaction
b. substitution reaction d. Chlorination reaction
17. Which one of the following substance is not used in dry cleaning?
a. C6H6 b. CCl4 C. Cl2C = CCl2 d. CH3COOH
18. The compound with the structure given below is
88
a. secondary alcohol c. tertiary alcohol

b. primary alcohol d. dihydric alcohol
19. Which of the following alcohols is the easiest to dehydrate?
20. Alcohols that yield ketones on oxidation are classified as

a. Primary alcohols c. secondary alcohols
b. Dihydric alcohols d. tertiary alcohols
21. Which one of the following structure represents hex–2–ene?
a. CH2=C(CH3)CH2CHCH3 c. CH3CH = CHCH2CH2CH3
b. CH3C = CCH(C2H5)CH3 d. CH3CH2CH=CHCH2CH3
22. What is the molecular formula of the following compound?
a. C8H10 b. C6H6 c. C6H8 d. C8H6

23. The name of a compound with the structure
a. cis-2-pentane c. trans-3-pentene
89
b. cis-2-pentene d. trans-2-pentyne
24. Soap is formed from:
a. two hydrophobic compounds
b. a physical change when fats are heated
c. two hydrophilic compounds
d. oils or fats by reacting with an alkali
25. Molecules that have the same molecular formula but different structural formulas are called
a. Isotopes b. Structural isomers c. Allotropes d. Alloy
Part III: Nomenclature based problems

26. Give the IUPAC names for the following compounds
90
27. Write the structural formulas of the following compounds

a. 2-methyl-2-butanol
b. 3-bromo-2-chlorohex-1-ene
c. 4-ethyl-2,2,3-trimethylhexane
28. Complete the following chemical equations
91
29. Complete the following reaction equations
30. It is believed that “Tella” (local beer) causes hangover and turns sour if kept open for days.
Predict the derivatives of this local beverage that are associated with these properties and write
the reactions taking place.
92

Uploaded by

Uploaded by

UNIT ONE: INTRODUCTION TO ORGANIC CHEMISTRY

• elaborate the historical development of organic compounds;

HISTORY OF ORGANIC CHEMISTRY

AgCNO (aq.) + NH4Cl (aq.) → AgCl (s) + NH4CNO (aq.)

Classification of Organic Compounds

1. Classify each of the following compounds as either organic or inorganic.

a. C3H8O b. CaCl2 c. Aspirin d. C3H4NO e. Salt f. HCN

a. CH2O b. CH4O c. CH4NO d. C2H6O

5. Identify the functional group in each of the following compounds.

a. CH3CH2COCH2CH3 b. CH3CH2COOH c. CH3CH2CH2OH d. CH3COOCH3

1.2 SATURATED HYDROCARBONS

Molecular formula Condensed form Saturated Unsaturated

C3H8 CH3CH2CH3 Propane ✓

C3H6 CH2 = CHCH3 Propene ✓

C3H4 CH3C ≡ CH Propyne ✓

1.2.1 Alkanes or Paraffins

1.2.2 Physical Properties of Alkanes

Figure 1.1 Structure of methane

1.2.3 Nomenclature (naming) of Alkanes

i. a prefix: indicating the number of carbon atoms

Prefix Number of carbon atoms Prefix Number of carbon atoms

Meth- One Hex- Six

Eth- Two Hept- Seven

Prop- Three Oct- Eight

But- Four Non- Nine

Pent- Five Dec- Ten

Common Names of Alkanes

a. H3C — CH2 — CH2 — CH2 — CH2—CH2—CH3 n- Heptane

IUPAC System Nomenclature of Alkanes

Table 1.4 Formulas, names and structures of some alkyl groups.

The system of naming organic compounds is based on the recommendations of IUPAC.

a. IUPAC names from given structures

b. Structural formulas from given IUPAC names

Isomers of butane (C4H10)

Isomers of pentane (C5H12)

Pentane has three isomers:

1.2.5 Preparation of Alkanes

1. Hydrogenation of alkenes with a metal catalyst.

2R – X + Zn → R–R + ZnX2 (Zinc halide)

2CH3CH2 – Br + Zn → CH3CH2CH2CH3 + ZnBr2

Laboratory Preparation of Methane

Figure 1.3 Preparation of methane

Carry out the following activities with the collected gas:

graphically depicted in the figure below.

Figure 1.4 Reactions in the production of biogas

Production of Methane from Cow Dung

Figure 1.5 Preparation of methane gas from cow dung.

1.2.6 Chemical Properties of Alkanes

The major reactions of alkanes are the following:

CnH2n+2 + ½ (3n + 1)O2 → n CO2 + (n + 1) H2O + heat

ii. Chain propagating step: This is a step which consumes

1.3 UNSATURATED HYDROCARBONS

• define unsaturated hydrocarbons, alkenes and alkynes;

1.3.1 Alkenes or Olefins

Physical Properties of Alkenes

b. If there is a substituent on one of the double bond carbons, it gets number 1

Alkenes have more isomers than the corresponding alkanes.

In the laboratory, alkenes can be prepared by:

1. Dehydration of alcohols with concentrated sulfuric acid or alumina (Al2O3). Dehydration

2. Dehydrohalogenation of alkyl halides with a base (KOH). Dehydrohalogenation means

Laboratory Preparation of Ethene

1. Arrange the set-up as shown in the figure below.

Figure 1.6 Preparation of Ethene

Observation and analysis:

a. CH2 = CHCH2CH3 b. F2C = CH2 c. FCH = CHF d. 1 – Chloro-2-methypropene

3. The following names are given wrongly. Correct each of them.

a. 2 – methyl – 3 – pentene b. 5 – methyl cyclohexene c. 1, 1 – dimethyl propene

d. 1, 1, 2, 2 – tetramethyl ethene e. 1 – methyl – 1 – heptane

4. What is the product obtained from each of the following reactions?

a. Treating 3 – chloro – 2, 2 – dimethyl pentane with potassium hydroxide solution

b. Treating CH3CH(OH)CH2CH3 with concentrated H2SO4

Chemical Properties of Alkenes

a. Addition of halogens (halogenation): When a halogen molecule, X2, (where, X2 = Cl2 or

b. Addition of hydrogen (Hydrogenation): Addition of hydrogen molecule to

c. Addition of hydrogen halides, HX (hydrohalogenation): Addition of hydrogen halide

e. Oxidation of alkenes: Oxidation of alkenes with cold alkaline potassium permanganate

f. Polymerization (self-addition) of alkenes: Polymerization is the union of small

Uses of Ethene (Ethylene)