CHAPTER

7 Fundamental Principles of
Organic Chemistry

Animation 7.1 : Organic Chemistry

Source and credit : Stackexchange
7. Fundamental Principles of Organic Chemistry [Link]

In This Chapter You Will Learn:

1. The special features of carbon chemistry with reference to its ability to
form chains, rings and isomers.
2. The importance of organic chemistry in daily life.
3. About the sources of carbon and its compounds like coal, petroleum and
natural gas with reference to their availability in Pakistan.
4. Refining, reforming and cracking of petroleum and to enlist products in a
tabular form.
5. How can petroleum serve as a source of different type of fuels.
6. About the classification of organic compounds based on the carbon
skeleton.
7. About functional groups and the dependence of chemical properties on
functional groups.
8. About the structural isomerism in organic compounds.
9. That cis-trans isomerism arises due to restricted rotation around a carbon-
carbon double bond.
10. How the hybridization theory can help us understand the type of bonding
and the shapes of organic compounds.

7.1 INTRODUCTION

More than 200 years ago, early chemists recognized organic compounds
distinct from inorganic compounds because of the differences in their or-
igin and properties. Organic compounds were considered as those ob-
tained from living things, plants or animals, and inorganic compounds were
those obtained from non-living or mineral sources.
The early chemists never succeeded in synthesizing organic compounds
and their failure led them to believe that organic compounds could be man-
ufactured only by and within living things and these compounds could nev-
er be synthesized from inorganic materials. This theory was referred to as
vital force theory. This theory was rejected by Friedrick Wohler when he
obtained urea (NH2)2CO , an organic compound in the urine of mammals,
from ammonium cyanate, NH4CNO, a substance of known mineral origin.

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NH 4CNO � (NH 2 ) 2CO

7.1.1 Modern Definition of Organic Chemistry.

Since the synthesis of urea from ammonium cyanate, millions of organic

compounds have been prepared and analyzed. All these compounds
contain carbon as an essential element. Apart from carbon, most of the
organic compounds also contain hydrogen. Other elements which may
also be present include oxygen, nitrogen, sulphur, etc. For historical and
conventional reasons a few of the carbon compounds such as CO,CO2,
carbonates, bicarbonates, etc are studied as inorganic compounds. It also
has been recognized that the chemical forces in organic compounds are
similar to those, which exist, in inorganic compounds. Thus it was felt that
organic chemistry should be redefined. According to the modern definition,
organic chemistry is that branch of chemistry which deals with the study of
compounds of carbon and hydrogen (hydrocarbons) and their derivatives.

7.2 SOME FEATURES OF ORGANIC COMPOUNDS

Following are some features of organic compounds.

(1) Peculiar Nature of Carbon
Carbon forms a large number of compounds. There are millions of
organic compounds known at present. The main reason for such a large
number of compounds is its unique property of linking with other carbon
atoms to form long chains or rings. This selflinking property of carbon is
called catenation. Carbon also forms stable single and multiple bonds
with other atoms like oxygen, nitrogen and sulphur, etc. It can thus
form numerous compounds of various sizes, shapes and structures.

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(2) Non-ionic Character of Organic Compounds

Organic compounds are generally covalent compounds, therefore, do not

give ionic reactions.

(3) Similarity in Behaviour

There exists a close relationship between different organic compounds.
This is exemplified by the existence of homologous series.
This similarity in behaviour has reduced the study of millions of compounds
to only a few homologous series.

(4) Complexity of Organic Compounds

Organic molecules are usually large and structurally more complex. For
example, starch has the formula (C6H10O5)n where n may be several thousands.
Proteins are very complex molecules having molecular masses ranging from
a few thousands to a million.

(5) Isomerism

Isomerism is a very common phenomenon in organic compounds.

Very often more than one compounds are represented by the same
molecular formula. However, they have different structural formulas.

(6) Rates of Organic Reactions

The reactions involving organic compounds are slow and in general the
yields are low. The slow rate of the organic reactions is due to the molecular
nature of organic compounds.

(7) Solubility

Most organic compounds are insoluble in water and dissolve readily

in non-polar organic solvents, such as, benzene, petroleum ether, etc.

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7.3 IMPORTANCE OF ORGANIC CHEMISTRY

The importance of organic chemistry can hardly be over emphasized.

Almost all the chemical reactions that take place in living systems,
including our own bodies, are organic in nature because they
involve such life molecules like proteins, enzymes, carbohydrates,
lipids, vitamins and nucleic acids, all contain thousand of carbon atoms.
We have become dependent upon organic compounds that occur in nature
for our food, medicines and clothing. Over the years,the chemists have learned
to synthesize plastics, synthetic rubber, medicines, preservatives, paints,
varnishes, textile fibres, fertilizers, pesticides, detergents, cosmetics, dyes,
etc. Many of these synthetic compounds prevent the shortages of naturally
occurring products.

7.4 SOURCES OF ORGANIC COMPOUNDS

Petroleum, coal and natural gas are vast reservoirs from which many
organic compounds are obtained. These are called fossil fuels and are
formed, over long period of time, from the decay of plants and animals.

Coal

It is believed that coal in nature was formed from the remains of the trees
buried inside the earth crust some 500 millions years ago. Due to the bacterial
and chemical reactions on wood it got converted into peat. Then, as a result
of high temperature and high pressure inside the earth crust, peat got
transformed into coal.

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Coal is an important solid fuel and becomes a source of organic compounds

when subjected to carbonization or destructive distillation. When coal
is heated in the absence of air (temperature ranging form 500-1000°
C); it is converted into coke, coal gas and coal tar. Coal tar contains a
large number of organic compounds, which separate out on fractional
distillation.
The total coal resources of Pakistan are estimated by the geological survey
of Pakistan to be 184 billion tonnes. About 80% of this coal is used to bake
bricks in lime kilns; besides, some quantity is used for domestic purposes.
Conscious efforts are being made by the government to induct coal into
industry by setting up coal based powrer units. The Sindh Coal Authority
and the directorates of Mineral Developments of the Punjab, Baluchistan
and Khyber Pakhtunkhwa are all keen to expand coal utilization in
power generation for which many incentives have been made available.

Animation 7.2 : What is coal seam gas

Source and credit: Aplng

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Natural Gas

Natural Gas is an important means of energy especially for countries like

Pakistan, which are deficient in the production of mineral oil and coal.
It is a mixture of low boiling hydrocarbons. Major portion of the natural gas
is methane. It is also formed by the decomposition of organic matter. In
Pakistan the gas, being cheaper, is used for power generation, in cement and
fertilizer industries; as a fuel in general industries and for domestic purposes.

Animation 7.3 : Coal fired power station

Source and credit: Gif2fly

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Petroleum

Mineral oil is called petroleum when it is in the refined form. It is thought to

have been formed by slow chemical and biochemical decomposition of the
remains of organic matters found between the sedimentary rocks. When
extracted from rocks it appears like a liquid of blackish colour known as
'crude oil'.
Table 7.1 Principal Fractions Obtained from Petroleum

Boiling Point
Fraction Composition Uses
Rang (oC)
CH 4- C4H10 Fuel,
Natural gas < 20
petrochemicals
Petroleum Ether 20 - 60 C5H12 , C6H14 Solvent
Ligroin, or Solvent, raw
60 - 100 C6H14 , C7H16
naphtha material
C4H10- C13H28
Gasoline 40- 220 Motor fuel
mostly C6H14- C8H18

Kerosene 175 - 325 C8H8 . C14H30 Heating fuel

Diesel and heating

Gas oil > 275 C12H26 . C18H38
fuel
Lubricating oils
Viscous liquids > C18H38 Lubrication
and greases
Paraffin M.p. 50 - 60 C23H48 - C29H60 Wax products
Asphalt, or Roofing, paving, fuel
Solids Residue
petroleum coke reducing agent

It is refined to get different petroleum fractions. At present four oil refineries

are in operation in our country. One oil refinery known as Attock Oil Refinery
is located at Morgah near Rawalpindi. It has about 1.25 million tonnes
oil refining capacity. Similarly, two oil refineries have been established at
Karachi which have about 2.13 million tonnes of oil refining capacity. Another
refinery known as Pak-Arab refinery is located at Mahmud Kot near Multan.
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The crude petroleum is separated by fractional distillation into a number

of fractions each corresponding to a particular boiling range, Table 7.1.

7.5 CRACKING OF PETROLEUM

The fractional distillation of petroleum yields only about 20% gasoline.

Due to its high demand this supply is augmented by converting surplus
supplies of less desirable petroleum fractions such as kerosene oil and
gas oil into gasoline by a process called cracking. It is defined as breaking
of higher hydrocarbons having high boiling points into a variety of lower
hydrocarbons, which are more volatile (low boiling). For example, a
higher hydrocarbons CI6H34 splits according to the following reaction.

C16 H 34 
Heat
700o
→ C7 H16 +3CH 2 =CH 2 +CH 3 -CH=CH 2
Alkane

This is the process in which C-C bonds in long chain alkane molecules are
broken, producing smaller molecules of both alkanes and alkenes. The
composition of the products depends on the condition under which the
cracking takes place. Cracking is generally carried out in the following ways.
(1) Thermal Cracking

Breaking down of large molecules by heating at high temperature and

pressure is called Thermal Cracking. It is particularly useful in the
production of unsaturated hydrocarbons such as ethene and propene.

(2) Catalytic Cracking

Higher hydrocarbons can be cracked at lower tem perature (500°C) and

lower pressure (2 atm), in the presence of a suitable catalyst. A typical
catalyst used for this purpose is a mixture of silica (SiO2) and alumina
(AI2O3). Catalytic cracking produces gasoline of higher octane number
and, therefore, this method is used for obtaining better quality gasoline.
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(3) Steam Cracking

In this process, higher hydrocarbons in the vapour phase are mixed with
steam, heated for a short duration to about 900°C and cooled rapidly.
The process is suitable for obtaining lower unsaturated hydrocarbons.

Besides increasing the yield of gasoline, cracking has also produced large
amounts of useful by-products, such as ethene, propene, butene and
benzene. These are used for manufacturing drugs, plastics, detergents,
synthetic fibres, fertilizers, weed killers and important chemicals like ethanol,
phenol and acetone.
7.6 REFORMING

The gasoline fraction present in petroleum is generally not of good quali-

ty. When it burns in an automobile engine, combustion can be initiated
before the spark plug fires. This produces a sharp metallic sound called
knocking which greatly reduces the efficiency of an engine. The quality
of a fuel is indicated by its octane number. As the octane number increas-
es, the engine is less likely to produce knocking. Straight- chain hydrocar-
bons have low octane numbers and make poor fuels. Experiments have
shown that isooctane or 2,2,4- trimethyl pentane burns very smooth-
ly in an engine and has been arbitrarily given an octane number of 100.
The octane number of gasoline is improved by a process called reform-
ing. It involves the conversion of straight chain hydrocarbons into branched
chain by heating in the absence of oxygen and in the presence of a catalyst.

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The octane number of a poor fuel can also be improved by blend-

ing it with a small amount of additive like tetraethyl lead (TEL). Tetraeth-
yl lead (C2H5)4 Pb, is an efficient antiknock agent but has one serious disad-
vantage; its combustion product, lead oxide, is reduced to metallic lead
which is discharged into the air through the exhaust pipe and causes
air pollution.

7.7 CLASSIFICATIONS OF ORGANIC COMPOUNDS

There are millions of organic compounds. It is practically not possi-

ble to study each individual compound. To facilitate their study, or-
ganic compounds are classified into various groups and sub-
groups. They may be broadly classified into the following classes.

1. Open chain or Acyclic compounds.

2. Closed chain or Cyclic (or ring) compounds.
(1) Open Chain or Acyclic Compounds

This type of compounds contain an open chain of carbon atoms.

The chains may be branched or non-branched (straight chain). The
open chain compounds are also called aliphatic compounds.
Straight Chain (or non- branched) Compounds

Those organic compounds in which the carbon atoms are connected in

series from one to the other.

CH 3 -CH 2 -CH 2 -CH 3 H 2C= CH-CH 2 -CH 3 CH 3 -CH 2 -CH 2 -CH 2 -OH
n-Butane 1-Butene 1-Butanol

Branched chain compounds

Those organic compounds in which the carbon atoms are attached on the sides
of chain.

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(2) Closed Chain Compounds or Cyclic Compounds

These compounds contain closed chains or rings of atoms and are known as
cyclic or ring compounds. These are of two types;
(a) Homocyclic or carbocycli compounds
(b) Heterocyclic compounds
The classification of organic compounds into various classes is shown in Fig.
7.1.
(a) Homocyclic or Carbocyclic Compounds

The compounds in which the ring consists of only carbon atoms,

Homocyclic or carbocyclic compounds.
Homocyclic compounds are further classified as :
1. Alicyclic compounds
2. Aromatic compounds

Fig:7.1 Classification of organic compounds.

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(1) Alicyclic Compounds

The homocyclic compounds which contain a ring of three or more

carbon atoms and resembling aliphatic compounds are called alicyclic
compounds. The saturated alicyclic hydrocarbons have the general
formula CnH2n. Typical examples of alicyclic compounds are given below.
One or more hydrogen atoms present in these compounds may be
substituted by other group or groups.

(2) Aromatic Compounds

These carbocyclic compounds contain at least one benzene ring, six carbon
atoms with three alternate double and single [Link] bonds are usually
shown in the form of a circle. Typical examples of aromatic compounds are
given below.

The aromatic compounds may have a side-chain or a functional group

attached to the ring. For example:

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The aromatic compounds may also contain more than one benzene rings fused
together.

(b) Heterocyclic Compounds

The compounds in which the ring consists of atoms of more than one kind are
called heterocyclic compounds or heterocycles. In heterocyclic compounds
generally one or more atoms of elements such as nitrogen (N), oxygen
(O) or sulphur (S) are present. The atom other than carbon viz, N, 0, or S,
present in the ring is called a hetero atom.

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7.8 FUNCTIONAL GROUP

An atom or a group of atoms or a double bond or a triple bond whose

presence imparts specific properties to organic compounds is called a
functional group, because they are the chemically functional parts
of molecules.
The study of organic chemistry is organized around functional groups.
Each functional group defines an organic family. Although over six mil-
lion organic compounds are known, there are only a handful of func-
tional groups, and each one serves to define a family of organic com-
pounds. The examples of functional groups are outlined in Table 7.2.
TABLE 7.2 FUNCTIONAL GROUPS
Class of compounds
Functional group Example

Formula Name

C C None Alkane CH — CH3

C C Double bond Alkene H2C = CH2

C C Triple bond Alkyne HC=CH

Halo (fluoro, chloro,
-X(X=F,Cl,Br,I) Alkyl halide CH3-CH2-Cl
bromo, iodo)
OH Hydroxyl group Alcohol or alkanol CH3-CH2-OH
NH2 Amino group Amine CH3-CH2-NH2

C NH Imino group Imine CH2=NH

C O C Ether linkage Ether CH3-CH2-O-CH2-CH3

O O
C Formyl group Aldehyde or alkanal CH3-C
H H
R CH3
C O Carbonyl Ketone or alkanohe C O
R CH3

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O O
Carboxylicacid CH3-C
C Carboxyl group
(oralkanoicacid) OH
OH
O
C X Acid halide Acid halide CH3 C Cl

O
C NH2 Acid amide Acid amide CH3 C NH2

O O
R C Ester group Ester CH3-C
OH OCH3

SH Mercapto Thioalcohol or Thiol CH3-CH2-SH

Alkyl cyanide or alkane CH3-C N

C N Cyano
nitrile
O
N Nitro Nitro compounds C6H5NO 2
O

7.9 HYBRIDIZATION OF ORBITALS AND THE SHAPES OF

MOLECULES

Although the most stable electronic configuration of a carbon atom

(having two partially filled 2p orbitals) requires it to be divalent, car-
bon is tetravalent in the majority of its compounds. In order to explain
this apparent anamoly, it is assumed that an electron from the 2s orbit-
al is promoted to an empty 2pz orbital, giving the electronic configuration:

Ground state electronic configuration of carbon = 1s2 2s2 2p1x 2p1y 2p°z
Excited state electronic configuration of carbon = 1s2 2s1 2p1x 2p1y 2p1z

The excited state configuration can explain the tetravalency of carbon but
these four valencies will not be equivalent. Orbital hybridization theory
has been developed to explain the equivalent tetravalency of carbon.

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According to this theory the four atomic orbitals of carbon belonging

to valence shell may be mixed in different ways to explain the
bonding and shapes of molecules formed by carbon atoms.

sp3 Hybridization

In order to explain the bonding and shapes of molecules in which carbon is

attached with four atoms, all these four atomic orbitals are mixed together to
give rise to four new equivalent hybrid atomic orbitals having same shape and
energy. This mode of hybridization is called tetrahedral or sp3 hybridization.

All these four sp3 hybrid orbitals are degenerate (having equal energy) and
are directed at an angle of 109.50 in space to give a tetrahedral geometry.
When a carbon atom forms single bonds with other atoms, these
hybrid orbitals overlap with the orbitals of these atoms to form four
sigma bonds. This type of hybridization explains the bonding and
shapes of all those compounds in which carbon atom is saturated.

x y
z

Fig. 7.2 sp3 hybridization of carbon to give methane (CH4)

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In the formation of methane, the four hybrid atomic orbitals of carbon overlap
separately with four 1s atomic orbitals of hydrogen to form four equivalent
C-H bonds. The shape of methane thus formed is very similar to the actual
methane molecule. All the four hydrogen atoms do not lie in the same plane.

109.50

In ethane, CH3 - CH3, the two tetrahedrons of each carbon are joined together
as shown in the above figure. Further addition of a carbon atom with ethane
will mean the attachment of another tetrahedron. At this stage, it is necessary
to answer an important [Link] where does the energy come to
excite the carbon atom?
The answer to this question is simple. Before excitation the carbon should
make two covalent bonds releasing an adequate amount of energy. After
excitation, however, it will form four covalent bonds releasing almost double
the amount of energy. This excess energy is more than that needed to excite
the carbon atom. So a tetravalent carbon atom is expected to be more stable
than a divalent carbon atom.

sp2 Hybridization

In order to explain the bonding in unsaturated compounds, two more modes

of hybridization have been developed.

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The structure of alkenes can be explained by sp2 mode of hybridizaton.

In this type one 2s and two 2p orbitals of carbon are mixed together
to give three equivalent and coplanar sp2 hybridized orbitals, Fig. 7.3.

Each sp2 hybrid orbital is directed from the centre of an equilateral triangle
to its three corners. The bond angle between any two sp2 hybrid orbitals is
120°.The unhybridized 2pz orbital will remain perpendicular to the triangle
thus formed.

Fig. 7.3 sp2-hybridization of carbon.

In the formation of ethene molecule, three sp2 orbitals of each carbon atom
overlap separately with sp2 orbital of another carbon and 1s orbitals of two
hydrogen atoms to form three s bonds. This gives rise to what is called the
s-frame work of ethene molecule. The unhybridized orbitals of each carbon
atom will then overlap in a parallel fashion to form a π - bond, Fig. 7.4

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π - bond
Fig. 7.4 Formation of ethene.

sp-Hybridization

The structure of alkynes can be explained by yet another mode of

hybridization called sp hybridization. In this type one 2s and one 2p orbitals
of the carbon atom mix together to give rise to two degenerate sp hybridized
atomic orbitals. These orbitals have a linera shape with a bond angle 180o.

The two unhybridized atomic orbitals, 2py and 2pz are perpendicular to these
sp hybridized orbitals.
Ethyne molecule is formed when two sp hybridized carbon atoms
join together to from a s-bond by sp-sp overlap. The other sp orbital
is utilized to form a s- bond with 1s orbital of hydrogen atom.

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Fig. 7.6 Formation of ethyne

The two unhybridized p orbitals on a carbon atom will overlap separately with
the p orbitals of the other carbon atom to give two π -bonds both perpendicular
to the s -framework of ethyne. The presence of a s and two π bonds
between two carbon atoms is responsible for shortening the bond distance.

7.10 ISOMERISM

The concept of isomerism is an important feature of organic compounds. Two or

more compounds having the same molecular formula but different structural
formulas and properties are said to be isomers and the phenomenon is called isomerism.
The structural formula of a compound shows the arrangement of atoms and bonds
present in it.

The simplest hydrocarbon to have structural isomers is butane (C4H10).

The alkanes, methane, ethane and propane do not show the phenom-
enon of isomerism because each exists in one structural form only. If
we study the structural formula of butane or other higher hydrocar-
bons of the alkane family, we will observe that it is possible to arrange the
atoms present in the molecule in more than one way to satisfy all valencies.
This means that it is possible to have two or more different arrangements for
the same molecular [Link] example, butane molecule can have two dif-
ferent arrangements as represented by the following structural formulas:

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CH 3 -CH 2 -CH 2 -CH 3

n-Butane

Isobutane

This fact has been supported by an experimental evidence that there

are two compounds with different physical properties but with the same
molecular formula of C4H10.
Isomerism is not only possible but common if the compound contains
more than three carbon atoms. As the number of carbon atoms in a
hydrocarbon increases, the number of possible isomers increase very rapidly.
The five carbon compound, pentane, has three isomers. When the number
of carbon atoms increases to thirty, the number of isomers amount to over
four billions.

7.10.1 Types of Isomerism

(1) Structural Isomerism

The structural isomerism is not confined to hydrocarbons only. In

fact, all classes of organic compounds and their derivatives show the
phenomenon of structural isomerism. The structural isomerism arises due
to the difference in the arrangement of atoms within the molecule. The
structural isomerism can be exhibited in five different ways. These are :
(i) The Chain Isomerism.

This type of isomerism arises due to the difference in the nature of the carbon
chain. For example, for pentane (C5H12), the following arrangements are
possible.

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CH 3 -CH 2 -CH 2 -CH 2 -CH 3

n-Pentane

(ii) Position Isomerism.

This type of isomerism arises due to the difference in the position of the
same functional group on the carbon chain. The arrangement of carbon
atoms remains the same. For example,
(a) Chloropropane can have two positional isomers given below.

CH 3 -CH 2 -CH 2 -Cl

1-Chloropropane

(b) Butene (C4H8) can have two positional isomers.

CH 3 -CH 2 -CH=CH 2 CH 3 -CH=CH-CH 3

I-Butene 2-Butene

(iii) Functional Group Isomerism

The compounds having the same molecular formula but different functional
groups are said to exhibit functional group isomerism. For example, there
are two compounds having the same molecular formula C2H6O , but different
arrangement of atoms.

CH 3 -O-CH 3 CH 3 -CH 2 -OH

Diethyl
Dimethyl etherether Eethyl alchohal
Ethyl alcohol

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(iv) Metamerism

This type of isomerism arises due to the unequal distribution of carbon atoms
on either side of the functional group. Such compounds belong to the same
homologous series. For example, diethyl ether and methyl n-propyl ether are
metamers.

CH 3 − CH 2 − O − CH 2 − CH 3 CH 3 − O − CH 2 − CH 2 − CH 3
Diethyl ether Methyl n-propyl ether
For a ketonic compound having the molecular formula C5H10O, the following
two metamers are possible.

(v) Tautomerism

This type of isomerism arises due to shifting of proton from one atom to other
in the same molecule.

(2) Cis-trans Isomerism or Geometric Isomersim

Two carbon atoms joined by a single bond are capable of free rotation about
it. However, when two carbon atoms are joined by a double bond, they
cannot rotate freely. As a result, the relative positions of the various groups
attached to these carbon atoms get fixed and gives rise to cis- trans isomers.

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Such compounds which possess the same structural formula, but differ
with respect to the positions of the identical groups in space are called cis-
trans isomers and the phenomenon is known as the cis-trans or geometric
isomerism.

The necessary and sufficient condition for a compound to exhibit geomet-

ric isomerism is that the two groups attached to the same carbon must be
different.

2-Butene can exist in the form of cis and trans isomers.

Similarly 2-pentene and l-bromo-2-chloropropene also show cis-trans

isomerism.

In the cis-form, the similar groups lie on the same side of the double bond
whereas in the trans-form, the similar groups lie on the opposite sides of the
double bond.
The rotation of two carbon atoms joined by a double bond could happen only
if the π bond [Link] ordinarily costs too much energy, making geometric
isomers possible.

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KEY POINTS
1. Chemical compounds were classified as organic and inorganic compounds based
upon their origin. Organic compounds are obtained from living things whereas
inorganic compounds are obtained from mineral sources.
2. It was thought that organic compounds could not be synthesized in the laboratory
from inorganic sources.
3. Organic chemistry is now-a-days defined as the chemistry of carbon compounds.
4. Most of the commercially important compounds we use everyday are organic in
nature.
5. Coal, petroleum and natural gas are important sources of organic compounds.
6. The process of cracking is developed to increase the yield of lower hydrocarbons
which serve as important fuels commercially.
7. Organic compounds are classified into acyclic and cyclic compounds.
8. The study of organic chemistry is organized around functional groups. Each
functional group defines an organic family.
9. The type of bonding and the shapes of different type of compounds formed by
carbon can be explained by sp3, sp2 and sp modes of hybridization.
[Link] having the same molecular formula but different structural formulas
are called isomers. There are four different type of structural isomers.
[Link] arises due to restricted rotation around a carbon- carbon double bond
is called cis-trans isomerism.

EXERCISE

Q l. Fill in the blanks

i) Organic compounds having same molecular formula but different ______are called
isomers.
ii) The state of hybridization of carbon atom in ______ is sp2.
iii) Alkenes show______ due to restricted rotation around a carbon-carbon double
bond.
iv) Heating an organic compound in the absence of oxygen and in the presence
of________as a catalyst is called cracking.

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v) A group of atoms which confers characteristic properties to an organic

compound is called _________ .
vi) 2-Butene is________of 1-butene.
vii) Carbonyl functional group is present in both_________and ketones.
viii) A heterocyclic compound contains an atom other than______ in its ring.
ix) The quality of gasoline can be checked by finding out its_____ .
x) A carboxylic acid contains___________ as a functional group.

Q.2 Indicate true or false.

(i) There are three possible isomers forpentane.
(ii) Alkynes do not show the phenomenon of cis-trans isomerism.
(iii) Organic compounds can not be synthesized from inorganic compounds.
(iv) All close chain compounds are aromatic in nature.
(v) The functional group present in amides is called an amino group.
(vi) Government of Pakistan is trying to use coal for power generation.
(vii) Crude petroleum is subjected to fractional sublimation in order to separate
it into different fractions,
(viii) A bond between carbon and hydrogen serves as a functional group for
alkanes.
(ix) o-Nitrotoluene and p-nitrotoluene are the examples of functional group
isomerism.
(x) Almost all the chemical reactions taking place in our body are inorganic
in nature.

Q 3. Multiple choice questions. Encircle the correct answer.

(i) The state of hybridization of carbon atom in methane is:
(a) sp3 (b) sp2 (c) sp (d) dsp2

(ii) In t-butyl alcohol, the tertiary carbon is bonded to:

(a) two hydrogen atoms (b) three hydrogen atoms
(c) one hydrogen atom (d) no hydrogen atom

(iii) Which set of hybrid orbitals has planar triangular shape.

(a) sp3 (b) sp (c) sp2 (d) dsp2

(iv) The chemist who synthesized urea from ammonium cyanate was:
(a) Berzelius (b)Kolbe (c) Wholer (d) Lavoisier
27
7. Fundamental Principles of Organic Chemistry [Link]

(v) Linear shape is associated with which set of hybrid orbitals?

(a) sp (b) sp2 (c) sp3 (d) dsp2

(vi) A double bond consists of:

(a) two sigma bonds (b) one sigma and one pi bond
(c) one sigma and two pi bonds (d) two pi bond

(vii) Ethers show the phenonenom of:

(a) position isomerism (b) functional group isomerism
(c) metamerism (d) cis-trans isomerism

(viii) Select From the following the one which is alcohol:

(a) CH3-CH2-OH (b) CH3-O-CH3
(c) CH3COOH (d) CH3-CH2-Br

Q 4. How organic compounds are classified? Give suitable example of each type.
Q 5. What are homocyclic and heterocyclic compounds? Give one example of
each.
Q 6. Write the structural formulas of the two possible isomers of C4H10.
Q 7. Why is ethene an important industrial chemical?
Q 8. What is meant by a functional group? Name typical functional groups
containing oxygen.
Q 9. What is an organic compound? Explain the importance of Wohler’s work in
the developrnent of organic chemistry.
Q 10. Write a short note on cracking of hydrocarbons.
Q 11. Explain reforming of petroleum with the help of suitable example.
Q 12. Describe important sources of organic compounds.
Q13. What is orbital hybridization? Explain sp3 sp2 and sp modes of hybridization
of carbon.
Q14. Explain the type of bonds and shapes of the following molecules using
hybridization approach.
CH3 - CH3, CH2 = CH2, CH = CH, HCHO, CH3CI
Q 15. Why there is no free rotation around a double bond and a free rotation
around a single bond ? Discuss cis-trans isomerism.

28
CHAPTER

8 ALIPHATIC
HYDROCARBONS

Animation 8.1 : Cycloalkanes

Source and credit : Stackexchange
8. ALIPHATIC HYDROCARBONS [Link]

In This Chapter You Will Learn:

1. How to name the aliphatic hydrocarbons according to IUPAC
rules.
2. The synthesis of alkanes, alkenes and alkynes and their important
reactions.
3. The comparison of reactivity of s bond and p bond.
4. About the free radical nature of reactions of alkanes and electrophilic
addition of alkenes and alkynes.
5. The comparison of reactivities of alkanes, alkenes and alkynes.

8.1 INTRODUCTION

Hydrocarbons are organic compounds which contain carbon and hydro-

gen only. The number of such compounds is very large because of the prop-
erty of catenation. Hydrocarbons have been divided into various class-
es on the basis of structure of the chain or size and nature of the ring.

2
8. ALIPHATIC HYDROCARBONS [Link]

If all the valencies of the carbon atoms in a molecule are fully satisfied and
these cannot further take up any more hydrogen atoms, then the
hydrocarbons are named as saturated hydrocarbons or alkanes.
The compounds of carbon and hydrogen in which all the four valen-
cies of carbon are not fully utilized and they contain either a double or
a triple bond, such compounds are called unsaturated hydrocarbons.
Those unsaturated hydrocarbons which contain a double bond are
called alkenes while those containing a triple bond are called alkynes.
Classification of hydrocarbons has been’ shown at page 136.

8.2 NOMENCLATURE

8.2.1 Common or Trivial Names:

In the early days, the compounds were named on the basis of their history,
the method of preparation or name of the person working on it, e.g., the name
marsh gas was given to methane because it was found in marshy places.
Acetic acid derives its name from vinegar (Latin, acetum means vinegar).
Organic compounds were named after a person, like barbituric acid after
Barbara. Such a system may have a certain charm but is never manageable.
For alkanes with five or more carbon atoms, the root word is derived from
the Greek or Latin numerals indicating the number of carbon atoms in
a molecule, and the name is completed by adding ‘ane’ as a suffix, e.g.
pentane (C5H12), hexane (C6H14), heptane (C7H16), etc. The common or
trivial names are applicable to all isomers of a given molecular formula.
The prefixes n, iso, neo are, however, to differentiate between isomers.

3
8. ALIPHATIC HYDROCARBONS [Link]

CH3 CH2 CH2 CH3 H3C CH CH3

|

n-butane CH3
Isobutane

CH3 CH2 CH2 CH2 CH3

n-pentane

CH3
|
H3C CH CH2 CH3 H3C C CH3
| |

CH3 CH3
Isopentane Neophentane

These prefixes have only limited use, as they are not workable with
complex molecules. Moreover, common names give only minimum
information about the structure of the [Link] are similarly
named by replacing the ending -ane of the name of alkane with ylene. e.g.

CH3
|
H3C C=CH2
H2C=CH2 H3C CH =CH2
Ethylene Propylene Isobutylene

4
8. ALIPHATIC HYDROCARBONS [Link]

8.2.2 IUPAC Names

In 1889 the solution for naming the organic compounds systematically
was sought by International Chemical Congress. A report was accepted in
1892 in Geneva but it was found incomplete. In 1930, International Union of
Chemistry (IUC) gave a modified report which is also referred as Liege Rules.
This report was further modified by International union of Pure and
Applied Chemists (IUPAC) in the year 1947. Since that date the union
has issued periodic reports on rules for the systematic nomenclature of
organic compounds, the most recent of which was published in the year
1979. IUPAC system of nomenclature is based on the following principle.
‘Each different compound should have a different name’.
Thus through a systematic set of rules, the IUPAC system provides
different names for more than 7 million known organic compounds.

Nomenclature of Alkyl Groups:

If we remove one hydrogen atom from an alkane, we obtain what is
called an alkyl group. These alkyl groups have names that end in —
[Link] the alkane is unbranched and the hydrogen atom that is
removed is a terminal hydrogen atom, the names are straight forward:

Alkane Alkyl Group Abbreviation

CH3 H CH3 Me-
Methane Methyl
Et-
CH3 CH2 H CH3CH2

Ethane Ethyl
Pr-
CH3 CH2 CH2 H CH3CH2CH2

Propane n-propyl
n-Bu-
CH3 CH2 CH2 CH2 H CH3CH2CH2CH2

n-Butane n-Butyl

5
8. ALIPHATIC HYDROCARBONS [Link]

8.2.3 Nomenclature of Alkanes

Branched-chain alkanes are named according to the following rules.

1. Locate the longest continuous chain of carbon atoms; this chain determines
the parent name for the alkane. We designate the following compound as
a hexane because the longest continuous chain contains six carbon atoms.

H3C CH2 CH2 CH2 CH CH3

|

CH3
The longest continuous chain may not always be obvious from the way the
formula is written. Notice, for example, that the following alkane is designated
as a heptane because the longest chain contains seven carbon atoms.

[Link] the longest chain beginning from the end of the chain nearer the
substituent. Applying this rule, we number the two alkanes shown above in
the following way.

6
8. ALIPHATIC HYDROCARBONS [Link]

[Link] the numbers obtained by the application of rule 2 to designate the

location of the substituent group. The parent name is placed last, and the
substituent group, preceded by the number designating its location on
the chain, is placed first. Numbers are separated from words by a hyphen.
The systematic names ot the two compounds shown above will then be:

4. When two or more substituents are present, give each substituent a number
corresponding to its location on the longest chain. For example, we designate
the following compound as 4 -ethyl-2 -methylhexane.

The substituent groups should be listed alphabetically (i.e. ethyl before methyl).
In deciding on alphabetical order disregard multiplying prefixes such as “di”
and “tri”.
5. When two substituents are present on the same carbon atom, use that
number twice.

7
8. ALIPHATIC HYDROCARBONS [Link]

[Link] two or more substituents are identical, indicate this by the use of the
prefixes di, tri , tetra , and so on. Then make certain that each and every substituent
has a number. Commas are used to separate numbers from each other.

Application of these six rules allows us to name most of the alkanes that we
shall encounter. Two other rules, however, may be required occasionally.

[Link] two chains of equal length compete for selection as the parent chain,
choose the chain with the greater number of substituents.

8
8. ALIPHATIC HYDROCARBONS [Link]

8. When branching first occurs at an equal distance from either end of the
longest chain, choose the name that gives the lower number at the first point of
difference.

8.2.4 Nomenclature of Alkenes:

The IUPAC rules for naming alkenes are similar in many respects to those for naming
alkanes.

[Link] the longest continuous chain that contains the C = C as the parent
chain. Change the ending of the name of the alkane of identical length
from — ane to — ene, e.g.,

[Link] the chain so as to include both carbon atoms of the double

bond. Numbering begins from the end nearer to the double bond.

9
8. ALIPHATIC HYDROCARBONS [Link]

[Link] the location of the double bond by using the number of the first
atom of the double bond as a prefix.

1 2 3 4 5
1 2 3 4
H2 C = CH CH2 CH3 H2 C = CH CH2 CH2 CH3
1-Pentene
1-Butene
[Link] the locations of the substituent groups by the numbers of the
carbon atoms to which they are attached.

[Link] the parent chain contains more than one double bonds, they are alkadienes
for two, alkatrienes for three and so on.

1 2 3 4
= =
CH2 CH CH CH2
1,3-Butadiene

8.2.5 Nomenclature of Alkynes:

[Link] largest continuous carbon chain containing triple bond is selected.

The name of the identical alkane is changed from ane to — yne. e.g.

2 1 3 2 1
CH ≡ CH H3 C C ≡ CH
Ethyne
Propyne
10
8. ALIPHATIC HYDROCARBONS [Link]

[Link] position of triple bond is shown by numbering the alkyne, so that minimum
number is assigned to the triple bond.

4 3 2 1
H3 C CH2 C ≡ CH
1-Butyne

[Link] a hydrocarbon contains more than one triple bonds, it is named as

alkadiyne and triyne, etc. depending on the number of triple bonds.

6 5 4 3 2 1
HC ≡ C CH2 CH2 C ≡ CH

1,5 - Hexadiyne
[Link] both double and triple bonds are present in the compound then ending
enyne is given to the root.

[Link] possible number is assigned to a double or a triple bond irrespective

of whether ene or yne gets the lower number.

1 2 3 4 5 1 2 3 4 5
HC ≡ C CH=CH CH3 =
H2 C CH C=
≡ C CH3
3 - Penten - 1- yne 1- Penten - 3 - yne
[Link] case a double and a triple bond are present at identical positions, the double
bond is given the lower number.

11
8. ALIPHATIC HYDROCARBONS [Link]

8.3 ALKANES OR PARAFFINS

Alkanes are the simplest organic compounds made up of carbon and

hydrogen only. They have a general formula of CnH2n+2. In these compounds
the four valencies of carbon atoms are satisfied by single bonds to either other
carbon atoms or hydrogen atom. They are, therefore known as Saturated
Hydrocarbons. Methane (CH4) is the simplest member of this family. Each
carbon atom in alkane is sp3 hybridized and has a tetrahedral geometry.
8.3.1 General Methods of Preparations
(1) Hydrogenation of Unsaturated Hydrocarbons
(Sabatier-Sendem’s Reaction)

Hydrogenation of alkenes or alkynes in the presence of nickel at 200-300OC

yields alkanes.

R CH = CH2 + H2  Ni
200−300o C
→ R CH2 CH3

Alkene

e.g CH2 = CH2 + H2  Ni

200−300o C
→ CH3 CH3

Ethane
The hydrogenation can also be carried out with platinum or
palladium at room temperature but they are expensive than nickel.
The method is of industrial importance. Production of vegetable ghee
by the catalytic hydrogenation of vegetable oil (unsaturated fatty acids)
is an example of the application of this method on industrial scale.
(2) From Alkyl Halides:
An alkane is produced when an alkyl halide reacts with zinc in the
presence of an aqueous acid.

12
8. ALIPHATIC HYDROCARBONS [Link]

R X + Zn + H+ + X − 
→ R H + ZnX 2
Alkyl halide Alkane

CH3 I + Zn + H+ + I− 
→ CH4 + ZnI2
Methyl iodide Methane

CH3 CH2 CH CH3

|

Br + Zn + H+ + Br − 
→ CH3 CH2 CH2 CH3 + ZnBr
2-Bromo-butane n-Butane

Alkanes can also be prepared from alkyl halides using palladium-charcoal

as acatalyst. The method is known as Hydrogenolysis (hydrogenation
accompanied by bond cleavage)

R X + H2 
Pd/C
∆
→R H+H X
(3) Decarboxylation of Monocarboxylic Acids
i) When sodium salts of fatty acids are heated with soda-lime (prepared
by soaking quick lime (CaO) with caustic soda solution and drying
the product). They eliminate a molecule of CO2 to form alkanes.

e.g

13
8. ALIPHATIC HYDROCARBONS [Link]

ii) Kolbe's Electrolytic Method

When a concentrated solution of sodium or potassium salt of a mono
carboxylic acid is electrolysed, an alkane is produced. This method
is only suitable for the preparation of symmetrical alkanes i.e. those
of the type R—R. Methane cannot be prepared by this method.

2RCOO−Na + + 2 H2O 

Electrolysis
→R R+2CO2 + 2NaOH+H2
It is known to involve the following mechanism.
When potassium salt of acetic acid is electrolysed, acetate ion migrates
.
towards the anode gives up one electron to produce acetate free
.
radical (CH3COO), which decomposes to give a methyl free radical
(CH3) and [Link] such methyl radicals combine to give ethane.

At Anode

O
||
2H3C C O   + 2CO
→ 2CH3 2

 + CH
CH  → H3C CH3
3 3
At Cathode

2H2O + 2e− 
→ 2OH + H2

2K + + 2OH 
→ 2KOH
This reaction has limited synthetic applications as it forms a number of side
products.
14
8. ALIPHATIC HYDROCARBONS [Link]

(4) From Carbonyl Compounds (Aldehydes or Ketones)

The carbonyl groups of aldehydes or ketones are reduced to methyl or

methylene group respectively by either Clemmensen or Wolf-Kishner’s
reduction. In the former reaction a ketone is reduced to an alkane
using zinc amalgam and hydrochloric acid whereas in the later an
aldehyde is reduced to alkane with hydrazine in the presence of KOH.

3
Acetone Propane

(5) From Grignard Reagents

Alkyl halides react in anhydrous ether with magnesium to
form alkyl magnesium halides, known as Grignard Reagent.
They decompose on treatment with water or dilute acid to give alkanes.

ether

15
8. ALIPHATIC HYDROCARBONS [Link]

8.3.2. Physical Properties

1. Alkanes containing upto four carbon atoms are colourless, odourless gases
while pentane to heptadecane (C5 to C17) are colourless, odourless liquids. The
higher members from C18 onwards are waxy solids which are also colourless and
odourless.
2. Alkanes are non-polar or very weakly polar and are insoluble in polar solvents
like water, but soluble in non-polar solvents like benzene, ether, carbon tetra
chloride,etc.
3. Their physical constants like boiling .points, melting points, density, etc increase
with the increase in number of carbon atoms, whereas solubility decreases
with increase in molecular mass. The boiling point increases by 20 to 30°C
for addition of each CH2 group to the molecule. The boiling points of alkanes
having branched chain structures are lower than their isomeric normal chain
alkanes, e.g. n-butane has a higher boiling point-0.50 C than isobutane (-1 1 .7°C).
[Link] melting points of alkanes also increase with the increase in molecular mass
but this increase is not so regular.

8.3.3. Reactivity of Alkanes

The alkanes or paraffins (Latin: parum = little, affins = affinity) under ordinary
condition are inert towards acids, alkalis, oxidizing and reducing agents.
However, under suitable conditions, alkanes do undergo two types of reactions.
1. Substitution Reactions
2. Thermal and Catalytic Reactions

These reactions take place at high temperature or on absorption of

light energy through the formation of highly reactive free radicals.

The unreactivity of alkanes under normal conditions may be explained on the

basis of the non-polarity of the bonds forming them. The eletronegativity values
of carbon (2.5) and hydrogen (2.1) do not differ appreciably and the bonding
electrons between C-H and C-C are equally shared making them almost non-
polar. In view of this, the ionic reagents such as acids, alkalies, oxidizing agents,
etc find no reaction site in the alkane molecules to which they could be attached.

16
8. ALIPHATIC HYDROCARBONS [Link]

Inertness of s-bond
The unreactivity of alkanes can also be explained on the basis of inertness of a
s-bond. In a s -bond the electrons are very tightly held between the nuclei which
makes it a very stable bond. A lot of energy is required to break it. Moreover
the electrons present in a s-bond can neither attack on any electrophile nor a
nucleophile can attack on them. Both these facts make alkanes less reactive.

8.3.4 Reactions

1. Combustion
Burning of an alkane in the presence of oxygen is known as Combustion.
Complete combustion of an alkane yields CO2, H2O and heat.

The amount of heat evolved when one mole of a hydrocarbon is burnt to

CO2 and H2O is called heat of combustion, e.g;

CH4 ( g ) + 2O2 ( g ) 

Flame
→ CO2 ( g ) + 2H2O ( g ) + 891kJmol-1
Although the reaction is highly exothermic, it requires very
high temperature to initiate it, e.g. by a flame or a spark.
Combustion is the major reaction occurring in the internal combustion
engines of automobiles. A compressed mixture of alkanes and air burns
smoothly in the internal combustion engine and increases its efficiency.

2. Oxidation
Oxidation of methane under different conditions gives different products.
i) Incomplete oxidation occurs in a limited supply of oxygen
or air and results in the formation of CO and carbon black.

3CH4 ( g )+ 4O2 ( g ) 

Flame
→ 2CO ( g ) + 6H2O ( g ) + C ( s )

17
8. ALIPHATIC HYDROCARBONS [Link]

ii) Catalytic Oxidation: Lower alkanes when burnt in the presence of metallic
catalysts, at high temperature and pressure, result in the formation of useful
products.

CH4 + [O] 

→ H3C Cu
400o C/200atm
OH
Methyl alcohol
H3C OH + O  Cu
400o C/200atm
→ HCHO+H2O

Formaldehyde

HCHO + [O]  Cu

400o C/200atm
→ HCOOH
Formic acid
HCOOH + [O] 
→ CO2 + H2O Cu
400o C/200atm

Catalytic oxidation of alkanes is used industrially to prepare

higher fatty acids used in soap and vegetable oil industries.

3. Nitration:

It is a substitution reaction of alkanes in which a hydrogen atom of an

alkane is replaced by nitro group (-NO2). Alkanes undergo vapour-phase
nitration under drastic condition (at 400-500°C) to give nitroalkanes, e.g.

450o C
CH4 + HONO2 
→ CH3NO2 + H2O
Nitromethane
Nitroalkanes generally find use as fuels, solvents, and in organic synthesis.

18
8. ALIPHATIC HYDROCARBONS [Link]

4. Halogenation
Alkanes react with chlorine and bromine in the presence of sunlight
or UV light or at high temperature resulting in the successive
replacement of hydrogen atoms with halogens called halogenation.
Extent of halogenation depends upon the amount of halogen used.
Reaction of alkanes with fluorine is highly violent and results in
a mixture of carbon, fluorinated alkanes and hydrofluoriq acid.
Iodine does not substitute directly because the reaction is too slow
and reversible. The order of reactivity of halogens is F2>Cl2>Br2>I2.
Halogenation is believed to proceed through free radical mechanism.
It involves the following three steps.

hυ )Initiation(
Step I Cl Cl  → Cl − + Cl −

]
hυ
Step 2 H3C H + Cl�  → CH�3 + HCl )Propagation(
hυ
CH�3 + Cl Cl  → CH3 Cl + Cl�

)Termination(
Step 3 CH�3 + Cl� 
→ CH3 Cl

By repetition of step II, a mixture of halogen substituted products are

[Link] reaction is not synthetically so important.

19
8. ALIPHATIC HYDROCARBONS [Link]

� �
Cl CH2 + Cl Cl → Cl CH2 Cl + Cl

Dichloromethane

Chloroform

Tetrachloromethane or
carbon tetrachloride

20
8. ALIPHATIC HYDROCARBONS [Link]

8.3.5 Uses of Methane

Methane is used:

(i) as a fuel and as an illuminating gas.

(ii) for the preparation of methylchloride, dichloromethane, chloroform and
carbon tetrachloride.
(iii) for the industrial preparation of methyl alcohol, formaldehyde and hydrogen
cyanide.
(iv) for the preparation of carbon black used in paints, printing inks and
automobile tyres.
(v) is used to manufacture urea fertilizer.

8.4 ALKENES

Alkenes have two hydrogen atoms less than the coresponding saturated
hydrocarbons. They are also known as Olefins (derived from Latin word
olefiant meaning oil forming) because lower members form oily products
on treatment with chlorine or bromine. The simplest olefin is C2H4, ethene.

Alkene having one double bond are known as mono-enes with general
formula CnH2n. Alkenes containing two double bonds are called dienes.

8.4.1 General Methods of Preparation

1. Dehydrohalogenation of Alkyl Halides

Alkyl halides on heating with alcoholic potassium hydroxide undergo
dehydrohalogenation i.e. elimination of a halogen atom together with a hydrogen
atom from adjacent carbon atoms.

21
8. ALIPHATIC HYDROCARBONS [Link]

R CH2 CH2 →

Alc. KOH
R CH =CH2 + KX + H2O
|

H2 C CH2 + KOH 

Alcohol
→ H2C=CH2 + KBr + H2O
| |

H Br

H3C CH2 CH2 Br + KOH 

Alcohol
→ H3C =
CH CH2 + K Br + H2O
2. Dehydration of Alcohols
Alcohols when dehydrated in the presence of a catalyst give alkene .
The best procedure is to pass vapours of alcohol over heated alumina.

Al2O3
R CH2 CH2 
340−450o C
→ R CH=CH2 + H2O
|
Alkene
Alcohol OH
P4O10, (conc)H2SO4 and H3PO4 are also used for dehydration. The ease of
dehydration of various alcohols is in the order. Ter. alcohol > Sec. alcohol >
Pri .alcohol
Thus
75% H2SO4
R CH2 CH2 
140−170o C
→ R CH=CH2 + H2O
|

OH
Primary Alcohol
60% H2SO4
R CH2 CH CH3 
100o C
→ R CH=CH CH3 + H2O
|

OH
Secondary Alcohol

Tertiary Alcohol
22
8. ALIPHATIC HYDROCARBONS [Link]

3. Dehalogenation of Vicinal Dihalides

Vicinal dihalides have two halogens on adjacent carbon atoms. Dehalogenation
occurs when dihalide is treated with Zinc dust in an anhydrous solvent like
methanol or acetic acid.

CH3OH
R CH CH2 Zn  → H2C=CH R+ ZnX 2
| |

X X Alkene

CH3OH
H3C CH CH CH3 + Zn  → H3C CH=CH CH3 + ZnBr2
| |
2-Butene
Br Br

4. Electrolysis of Salts of Dicarboxylic acid

(Kolbe’s Electrolytic Method)
When sodium or potassium salts of the dicarboxylic acid like succinic acid
are subjected to electrolysis in an aqueous solution, alkenes are formed.

H2C COO-Na + H2C COO- + 2Na+

| Ionization |
�� �� ��H2�O� ��
��
H2C COO-Na + H2C COO-
Disodium Succinate

At Anode

23
8. ALIPHATIC HYDROCARBONS [Link]

At Cathode
2H2O + 2e− → 2OH− + H2
2Na + + 2OH− → 2NaOH

5. Partial Hydrogenation of Alkynes: -

Controlled hydrogenation of alkynes with hydrogen gas in an equimolar ratio

over heated catalysts, gives alkenes. The catalyst is finely divided palladium
supported on BaSO4 and poisoned by treatment with quinoline (Lindlar’s catalyst).

Cis-Alkene
A trans alkene can be obtained by treating an alkyne with Na in liquid NH3 at -33°C.

trans-Alkene
8.4.2 Physical Properties

1. First three members i.e. ethene, propene and butene are gases at room
temperature while C5 to C15 are liquids and the higher members are solids.
2. They are insoluble in water but soluble in alcohol.
3. They have characteristic smell and burn with luminous flame.
4. Unlike alkanes, they show weakly polar properties because of sp2
hybridization.
24
8. ALIPHATIC HYDROCARBONS [Link]

8.4.3 Reactivity of a p-bond

In the formation of a p-bond, the partially filled p-orbitals overlap in a
parallel fashion. The probability of finding electron is thus away from
the line joining the two nuclei. Due to this reason p-electrons are less
firmly held between the nuclei. A p-bond is, therefore, a weak bond as
compared to a s-bond. During a reaction it breaks comparatively easily
rendering alkenes as reactive group of compounds. Moreover, the
loosely held p-electrons are more exposed to attack by the electrophilic
reagents. Alkenes, therefore, undergo electrophilic reactions very easily.

8.4.4 Reactions of Alkenes

A. Addition Reactions
1. Addition of Hydrogen (Hydrogenation)
Hydrogenation is a process in which a molecule of hydrogen is added to an
alkene in the presence of a catalyst and at moderate pressure (1-5 atm.) to
give a saturated compound. The process is known as Catalytic Hydrogenation.

It is a highly exothermic process and the amount of heat evolved when one
mole of an alkene is hydrogenated is called Heat of Hydrogenation. The heat
of hydrogenation of most alkenes is about 120kJmole -1 for each double bond
present in a molecule. The catalysts employed are Pt, Pd and Raney nickel.
Raney Nickel
It is prepared by treating a Ni — Al alloy with caustic soda.

Ni Al + NaOH+ H2O → Ni + NaAlO2 + 3 H2

2

Most alkenes are hydrogenated over Raney nickel at about 100°C and upto 3-
atmosphere pressure.

3-Methyl-l-butene iso Bentane

25
8. ALIPHATIC HYDROCARBONS [Link]

Catalytic hydrogenation of alkenes is used in the laboratory as well as

in industry. In industry, it is used for the manufacture of vegetable ghee
from vegetable oils. In the laboratory, it is used as a synthetic method
as well as an analytical tool, as the reaction is generally quantitative.

2. Addition of Hydrogen Halides

Alkenes react with dry gaseous hydrogen halides to form alkyl
halides. The order of reactivity of halogen aicds is HI > HBr > HC1.

R CH=CH2 + HX → R CH CH3

|

H2C=CH2 + HCl →H3C CH2

|

Cl
The addition of a hydrogen halide to an alkene takes place in two steps.
Alkene accepts the proton of hydrogen halide to form a carbocation.

26
8. ALIPHATIC HYDROCARBONS [Link]

The carbocation then reacts with the halide ion.

The addition of hydrogen halide over an unsymmetrical alkene is governed by

Markownikov’s Rule. The rule states that; in the addition of an unsymmetrical
reagent to an unsymmetrical alkene, the negative part of the adding
reagent goes to that carbon, constituting the double bond, which has least
number of hydrogen atoms.

27
8. ALIPHATIC HYDROCARBONS [Link]

3. Addition of Sulphuric Acid

When alkenes are treated with cold concentrated sulphuric acid, they are
dissolved because they react by addition to form alkyl hydrogen sulphate.
For example,

These alkylhydrogen sulphates on boiling with water decompose to

give corresponding alcohols. The overall reaction involves the addition
of water to an alkene and it is, therefore, called hydration reaction.

100o C
H3C CH2 O SO3H + H2O 
→ H3C CH2 OH + H2SO4
4. Addition of Halogens
The alkenes on treatment with halogen in an inert solvent like carbon tetrachloride
at room temperature give vicinal dihalides or 1,2 dihalogenated products.
For example,

Br2 and Cl2 are effective electrophilic reagents. Fluorine is too reactive to control
the reaction. Iodine does not react.
Mechanism:
a. A bromine molecule becomes polarized as it approaches the alkene. This
polarized bromine molecule transfers a positive bromine atom to the alkene
resulting in the formation of a bromonium ion.

28
8. ALIPHATIC HYDROCARBONS [Link]

b. The nucleophilic bromide ion then attacks on the carbon of the bromonium
ion to form vic. dibromide and the colour of bromine is discharged. A trans
product is formed.

Bromonium ion 1, 2-Dibromoethane

This test is used for the detection of a double bond.
5. Addition of Hypohalous acid (HOX)
If the halogenation of an alkene is carried out in an aqueous solution,
haloalcohol is formed called a Halohydrin. In this reaction, molecules of the
solvent become reactants too.

X 2 + H2O 
→ HOX + HX

Halohydrin

B. OXIDATION REACTIONS

1. Addition of Oxygen
Alkenes when mixed with oxygen or air and passed over a silver oxide
catalyst at high temperature and pressure, add an atom of oxygen to form
epoxides. Epoxides serve as the starting substances for the industrial
production of glycols.

29
8. ALIPHATIC HYDROCARBONS [Link]

2. Hydroxylation
When alkenes are treated with mild oxidizing reagents like dilute
(1%) alkaline KMn04 solution (Baeyer's Reagent) at low temperature,
hydroxylation of duoubie bond occurs resulting in the formation of
dihydroxy compounds known as vicinal glycols. The pink colour of KMnO4
solution is discharged during the reaction. It is also a test for the presence of
unsaturation in the molecules. For example,

3. Combustion
Alkenes burn in air with luminous flame and produce CO2 and H2O
vapours. Ethene forms a highly explosive mixture with air or oxygen.

C2H4 + 3O2 → 2CO2 + 2H2O + heat

4. Ozonolysis
Ozone (O3) is a highly reactive allotropic form of oxygen. It reacts vigorously
with alkenes to form unstable molozonide. It rearranges spontaneously to
form an ozonide.

30
8. ALIPHATIC HYDROCARBONS [Link]

Ozonides are unstable compounds and are reduced directly by treatment with zinc
and H2O. The reduction produces carbonyl compounds (aldehydes or ketones).

H2O2 + Zn → ZnO + H2O

Ozonolysis is used to locate the position of double bond in an alkene.

C. Polymerization

In this ‘process small organic molecules (monomers) combine together to form

larger molecules known as [Link] at 400°C and 100 atm pressure,
polymerize to polythene or polyethylene.

A good quality polythene is obtained, when ethene is polymerized in the

presence of aluminium triethyl Al(C2H5)3 and titanium tetrachloride catalysts
(TiCl4).
8.4.5 Uses of Ethene:
Ethene is used:
1. for the manufacture of polythene, a plastic material used for making toys,
cables, bags, boxes, etc.
2. for artificial ripening of the fruits.
3. as a general anaesthetic.
4. for preparing ‘Mustard gas’ a chemical used in World War I. The name comes
from its mustard like odour. It is not a gas, but a high boiling liquid that is
dispersed as a mist of tiny droplets. It is a powerful vesicant i.e., causes blisters.

31
8. ALIPHATIC HYDROCARBONS [Link]

5. as a starting material for a large number of chemicals of industrial use such

as glycols (antifreeze), ethyl halide, ethyl alcohol, etc.

8.5 ALKYNES

Unsaturated hydrocarbons which contain a triple bond are called Alkynes.

They have the general molecular formula CnH2n-2 and contain two hydrogen
atoms less than the corresponding alkenes.
The first member of the Alkyne series has the formula C2H2 and is known as
Ethyne or Acetylene.

8.5.1 General Methods of Preparation

1. Dehydrohalogenation of Vicinal Dihalides

Vicinal dihalide on treatment with a strong base eliminates two mole-

cules of hydrogen halides from two adjacent carbons to give an alkyne.

Alkyne

1,2-Dihalide

32
8. ALIPHATIC HYDROCARBONS [Link]

HC CH + KOH 
Alcohol
− HBr 80oC
→ HC=CH2
| | |

Br Br Br
1,2-Dibromoethane Vinyl bromide

=HC CH + KOH 

Alcohol
− HBr 150oC
→ HC ≡ CH
| |

Br H
Ethyne
The second molecule of hydrogen halide is removed with great difficulty and
requires drastic conditions.

2. DehalogenationofTetrahalides

Tetra haloalkanes on treatment with active metals like Zn, Mg, etc. form
alkynes.

(i)

=
(ii) HC CH + Zn 
→ HC ≡ CH + ZnBr2
| |

Br Br
3. Electrolysis of Salts of Unsaturated Dicarboxylic Acids
Kolbe's electrolytic method involves electrolysis of aqueous solution of Na
or K salts of unsaturated dicarboxylic acids.

33
8. ALIPHATIC HYDROCARBONS [Link]

At Anode

Ethyne

At Cathode
2H2O + 2e− → 2OH−

2K + + 2OH− → 2KOH

Industrial Preparation of Ethyne
On industrial scale ethyne is prepared by the reaction of calcium
carbide (CaC2) with water Calcium carbide is prepared by heating lime
(CaO) and coke (C) at a very high temperature in an electric furnace.

2000oC
CaO+3C 
→ CaC2 +CO
34
8. ALIPHATIC HYDROCARBONS [Link]

8.5.2 Physical Characteristics

1. They are colourless, odourless, except acetylene which has a garlic like
odour,
2. The first three members are gases (ethyne, propyne, butyne) at room
temperature, The next eight members (C5 - C12) are liquids and higher
members are solids.
3 The melting points, boiling points and densities increase gradually with
the increase in molecular masses.
4 They are nonpolar and dissolve readily in solvents like ether, benzene and
carbon tetrachloride.

8.5.3 Reactivity of Alkynes

In alkynes, the carbon atoms are held together by a triple bond, a s-bond and
two p-bonds. The electron density between the carbon atoms is very high
which draws atoms very close to each other. Electrons in a triple bond are,
therefore, less exposed and thus less reactive towards electrophilic reagents.

8.5.4 Reactions
A. Addition Reactions:
Alkynes undergo addition reactions like alkenes but add two molecules of the
reagent instead of one.
1. Addition of Hydrogen:
Alkynes react with hydrogen gas in the presence of a suitable catalysts
like finely divided Ni, Pt, or Pd. Initially alkenes are formed which
then take up another molecule of hydrogen to form an alkane.

35
8. ALIPHATIC HYDROCARBONS [Link]

HC ≡ CH + H2 →
Ni
heat
H2C=CH2
Ethyne Ethene

CH2 =CH2 + H2 →

Ni
heat
H3C CH3
Ethene Ethene

2. Addition of Halogens:
One or two molecules of halogens can be added to alkynes giving
dihalides and tetra halides [Link] and bromine add readily
while iodine reacts rather slowly.

3. Addition of Halogen Acids:

Alkynes react with hydrogen chloride and hydrogen bromide to form

dihaloalkanes. The reaction occurs in accordance with Markownikov’s rule.

36
8. ALIPHATIC HYDROCARBONS [Link]

HC ≡ CH + H Br 
→ H2C=CH
|
Ethyne
Br
Vinyl bromide

1, 1- Dibromoethane

4. Addition of Water:

Water adds to alkynes in the presence of mercuric sulphate dissolved in

sulphuric acid at 75°C. The reaction is important industrially. For example,

HgSO4
HC ≡ CH + Hä+ OHä- 
H2SO4
→ H2C=CH O H
Vinyl alcohol

Vinyl alcohol is an unstable enol. The enol has the hydroxy group attached
to a doubly bonded carbon atom and isomerises to acetaldehyde.

Acetaldehyde
All other alkynes give ketones.

37
8. ALIPHATIC HYDROCARBONS [Link]

5. Addition of Ammonia and Hydrogen Cyanide:

NH3and HCN react with ethyne in the presence of suitable catalysts, to

give nitriles.

Al2O3
HC ≡ CH + NH3 
300o C
→ H3C C ≡ N + H2
Methyl Nitrile

Cu2Cl2 /NH4Cl
HC ≡ CH + HCN  ∆
→ CH2 =CH CN
Acrylonitrile

B. Oxidation Reactions

1. Ethyne on oxidation with strong alkaline KMnO, gives glyoxal.

38
8. ALIPHATIC HYDROCARBONS [Link]

2. Combustion:
Alkynes when burnt in air or oxygen produce heat and evolves CO2
and H2O. The reaction is highly exothermic for acetylene and the
resulting oxyacetylene flame is used for welding and cutting of metals.

2HC ≡ CH + 5O2 → 4CO2 + 2H2O + heat

C. Polymerization

Alkynes polymerize to give linear or cyclic compounds depending upon the

temperature and catalyst used. However, these polymers are different from
the polymers of the alkenes as they are usually low molecular weight polymers.

1. Conversion of Acetylene to Divinyl Acetylene

When acetylene is passed through an acidic solution of cuprous chloride

and ammonium chloride and then allowed to stand for several hours at
room temperature, vinyl acetylene and divinyl acetylene are obtained.

Cu2Cl2 ,NH4Cl
HC ≡ CH + HC ≡ CH →
300o C
=H2C CH C ≡ CH
Vinyl acetylene
(1- Buten-3-yne

Cu2Cl2 ,NH4Cl
H2C=CH C ≡ CH+HC ≡ CH → =H2C CH C ≡ C=CH CH2
Divinyl acetylene
(l,5-Hexdiene-3-yne)
If HCl is added to vinyl acetylene, chloroprene is obtained which readily
polymerize to neoprene, used as synthetic rubber.
Cu2Cl2 ,NH4Cl
H2C=CH C ≡ CH+(conc.)HCl → H2C = CH C=CH2
|
Vinyl acetylene
Cl
Chloroprene

39
8. ALIPHATIC HYDROCARBONS [Link]

Chloroprene 
Polymerization
→ Neoprene ( synthetic rubber )

2. Conversion of Acetylene to Benzene

When acetylene is passed through a copper tube at 300°C, it polymerizes to

benzene.

D. Acidic Nature of Alkynes

In ethyne and other terminal alkynes like propyne, the hydrogen atom
is bonded to the carbon atom with sp-s overlap. An sp hybrid orbital has
50% s-character in it and renders the carbon atom more electronegative
than sp2 and sp3 hybridized carbons. As a result, the sp hybridized
carbon atom of a terminal alkyne pulls the electrons more strongly
making the attached hydrogen atom slightly acidic.

H C ≡ Cä- Hä+

1. When 1-alkyne or ethyne is treated with sodamide in liquid ammonia

or passed over molten sodium .alkynides or acetylides are obtained.

R C ≡ CH + NaNH2 liq NH3

 →R C ≡ C-Na + +NH3
→ Na +C- ≡ C-Na + +H2
HC ≡ CH + 2Na 
Sodium acetylide

40
8. ALIPHATIC HYDROCARBONS [Link]

Sodium acetylide is a very valuable reagent for

chemical synthesis and is essentially ionic in nature.
Acetylides of copper and silver are obtained by passing acetylene in the
ammoniacal solution of cuprous chloride and silver nitrate respectively.

HC ≡ CH + Cu2Cl2 + 2 NH4OH 
→ CuC ≡ CCu+ 2 NH4Cl +2H2O
Dicopperacetylide
(Reddish brown ppt.)

HC ≡ CH + 2AgNO3 + 2 NH4OH 
→ AgC ≡ CAg+ 2 NH4NO3 +2H2O
Disilver acetylide
(white ppt.)
Silver and copper acetylides react with acids to regenerate alkynes.

AgC ≡ CAg + H2SO4 (dil.) 

→ HC ≡ CH + Ag 2SO4

AgC ≡ CAg + 2HNO3(dil.) 

→ HC ≡ CH + 2AgNO3
These alkynides are used for the preparation, purification, separation, and
identification of alkynes.

8.5.5 Uses of Ethyne

Ethyne is used:
1. in oxyacetylene torch which is in turn used for welding and cutting metals.
2. for the preparation of alcohols, acetic acid and acetaldehyde.
3. for the manufacture of polymers like PVC, polyvinyl acetate, polyvinyl ethers,
orlon and neoprene rubber.
4. to prepare acetylene tetrachloride a solvent for varnishes, resins, and rubber.
5. for ripening of fruits.

8.5.6 Comparison of Reactivities of Alkanes, Alkenes and Alkynes

The general decreasing reactivity order of alkanes, alkenes and alkynes is as
follows:

Alkenes > Alkynes > Alkanes

41
8. ALIPHATIC HYDROCARBONS [Link]

It has already been explained that a p -bond in alkenes is not only weak
but its electrons are more exposed to an attack by an electrophilic reagent.
Both these facts make the alkenes a very reactive class of compounds.
Alkynes although contain two p -bonds are less reactive than alkenes
towards electrophilic reagents. This is because the bond distance between
the two triple bonded carbon atoms is very short and hence the p
-electrons are not available to be attacked by electrophilic [Link]
are, however, more reactive than alkenes towards nucleophilic reagents.

KEYPOINTS

1. Hydrocarbons are made up of carbon and hydrogen only. Saturated

hydrocarbons are called alkanes. They do not contain functional groups.
2. Alkanes react with halogens by a free radical mechanism to give haloalkanes.
Then mechanism consists of three steps, initiation, propagation and termination.
3. Alkenes are unsaturated hydrocarbons with at least one C=C. The double bond
is composed of a s and a p bond. Carbon atoms in alkenes are sp2 hybridized.
4. Alkenes are very reactive compounds. They undergo electrophilic reactions
very easily.
5. Addition of unsymmetrical reagent to an unsymmetrical alkene takes place in
accordance with the Markownikov's rule.
6. Alkenes can be very easily oxidized with cold KMnO4 solution, O2 or ozone.
With ozone both the bonds between carbon atoms are cleaved.
7. Hydrocarbons containing a triple bond are known as alkynes or acetylenes.
8. Alkynes undergo addition reactions and two molecules of a reagent are added
in it.
9. Ethyne and other terminal alkynes contain a weakly acidic hydrogen and they
react with ammoniacal cuprous chloride and ammoniacal silver nitrate to give
acetylides
10. The decreasing reactivity order of alkanes, alkenes and alkynes are as
follows:
Alkenes > Alkynes > Alkanes

42
8. ALIPHATIC HYDROCARBONS [Link]

EXERCISE

Q.1. Fill in the blanks.

1. Ozone reacts with ethene to form___________ .
2. Lindlar’ s catalyst is used for___________ of alkynes.
3. Divinyl acetylene is a ______________ acetylene.
4. Vicinal dihalides have two halogens on_________carbon atoms.
5. Ethyne is acidic in character because of__________ hybridization.
6. Halohydrins are formed due to addition of__________ in ethene.
7. Ethylene glycol is produced when__________ reacts with cold alkaline KMnO4
solution.
8. Mustard gas is a high boiling _____________ .
9. Ethyne has_____________ like odour.
10. Ethyne is obtained by the reaction of________ with calcium carbide.

Q.2. Indicate True or False.

1. Addition of HX to unsymmetriacal alkanes takes place according to
Markownikov’s rule.
2. Methane reacts with bromine water and its colour is discharged.
3. Mustard gas is a blistering agent.
4. Methane is also called marsh gas.
5. Ethyne is a saturated compound.
6. Baeyer’s reagent is used to locate a double bond in an alkene.
7. Alkanes usually undergo substitution reactions.
8. Benzene is a polymer of ethene.
9. Acrylonitrile can be obtained from ethyne.
10. Ethyne is more reactive towards electrophilic reagents than ethene.

43
8. ALIPHATIC HYDROCARBONS [Link]

Q. 3. Multiple choice questions. Encircle the correct answer.

i) Preparation of vegetable ghee involves
(a) Halogenation (b) Hydrogenation
(c) Hydroxylation (d) Dehydrogenation

ii) Formula of chloroform is:

(a)CH3Cl (b) CCI4 (c)CH2CI2 (d)CHCl3

iii) The presence of a double bond in a compound is the sign of

(a) Saturation (b) Unsaturation (c) Substitution (d)None

iv) Vinyl acetylene combines with HCl to form

(a) Polyacetylene (b) Benzene
(c) Chloroprene (d) Divinyl acetylene

v) The addition of unsymmetrical reagent to an unsymmetrical alkene is in

accordance
with the rule
(a) Hund’s rule (b) Markownikov’s rule
(c) Pauli’s Exclusion Principle (d) Aufbau Principle

vi) Synthetic rubber is made by polymerization of

(a) Chloroform (b) Acetylene
(c) Divinylacetylene (d) Chloroprene

vii) b-b’- dichloroethyl sulphide is commonly known as

(a) Mustard gas (b) Laughing gas
(b) Phosgene gas (d) Bio-gas

ix) When methane reacts with Cl2 in the presence of diffused sunlight the
products
obtained are:
(a) Chloroform only (b) Carbon tetrachloride only
(c) Chloromethane and dichloromethane (d) Mixture of a, b, c

x) Which one of the following gases is used for artificial ripening of fruits.
(a) Ethene (b) Ethyne (c) Methane (d) Propane

44
8. ALIPHATIC HYDROCARBONS [Link]

Q. 4. Write the structural formula for each of the following compounds

,
i) 2-Methylpropane. ii) Neopentane.
iii) 3-Ethylpentane. iv) 4-Ethyl-3,4-dimethylheptane.
v) 2,2,3,4-Tetramethylpentane vi) 4-iso-Propylheptane.
vii) 2,2-Dimethylbutane. viii) 2,2-Dimethylpropane.
Q. 5. Write down names of the following compounds according to
IUPAC-system.

)i( )ii( (CH3 )3 C CH2 C ( CH3 )3

)iii( )iv( (CH3 )2 CH CH

|
CH ( CH3 )2

CH3

)v( CH3CH2C(CH3 )2CH(CH2CH3 )CH3 )vi( (CH3CH2 )3 CH

)vii( CH3C(CH3 )2 ( CH2 )2 CH3 )viii( (C6H5 )3 CH

Q. 6. What are the rules for naming alkanes? Explain with suitable examples.
Q. 7. (a) Write down the structural formulas for all the isomeric hexanes and name
them according to IUPAC system
(b) The following names are incorrect. Give the correct IUPAC names,
i) 4-Methylpentane ii) 3,5,5-Trimethylhexane
iii) 2-Methyl-3-Ethylbutane
Q.8. (a) Explain why alkanes are less reactive than alkenes? What is the effect of
branching on the melting point of alkanes ?
(b) Three different alkanes yield 2-methylbutane when they are hydrogenated
in the presence of a metal catalyst. Give their structures and write equations
for the reactions involved.
45
8. ALIPHATIC HYDROCARBONS [Link]

Q.9. (a) Out line the methods available for the preparation of alkanes.
(b) How will you bring about the following conversions?
i) Methane to ethane. ii) Ethane to methane,
iii) Acetic acid to ethane. iv) Methane to nitromethane.

Q.10. (a) What is meant by octane number? Why does a high octane fuel has a less
tendency to knock in an automobile engine?
(b) Explain free radical mechanism for the reaction of chlorine with methane
in the presence of sunlight .
Q. 11. (a) Write structural formulas for each of the following compounds.
i) Isobutylene ii) 2,3,4,4-Tetramethyl-2-pentene
iii) 2 ,5-Heptadiene iv) 4,5-Dimethyl-2-hexene
v) Vinylacetylene vi) 1,3-Pentadiene
vii) 1-Butyne viii) 3-n-Propyl-1, 4-pentadiene
ix) Vinyl bromide x) But-1 -en.3 -yne
xi) 4-Methyl-2-pentyne xii) Isopentane
(b) Name the following compounds by IUPAC system.

)i( H3C CH=CH ( CH2 )2 CH3 )ii(

(CH3 )2 C=CH2

)iii( CH3 CH2 CH2 C=CH2 )iv(

|
CH2 =CH CH=CH2
CH ( CH3 )2

)v( CH2 =C CH2CH2CH3 )vi(

|
CH ≡ C CH3
C2H5

)vii( )viii(
CH3 C≡C CH3 =
CH2 CH C≡C CH=CH2

)ix( CH ≡ C CH=CH C ≡ CH )x(

CH2 =CH C ≡ CH

46
8. ALIPHATIC HYDROCARBONS [Link]

Q. 12. (a) Describe different methods for the preparation of alkenes. How would
you establish that ethylene contains a double bond?
(b) Give structure formulas of the alkenes expected to form by the
dehydrohalogenation of the following compounds with a strong base:
i) 1 -Chloropentane ii) 2-C hloro-3-methy lbutane
iii) l-Chloro-2,2-dimethyl propane.

Q. 13. (a) Write down chemical equations for the preparation of propene from the
following compounds.

i) CH3 — CH2 — CH2 — OH ii) CH3 — C = CH

iii) iso-Propyl chloride

(b) Write skeleton formula showing only the arrangement of carbon atoms
for all the possible alkenes of the molecular formula C5H10.

Q. 14. (a) How may ethene be converted into ethyl alcohol?

(b) Starting from ethene, outline the reactions for the preparation of
following compounds.
i) 1,2-Dibromoethane ii) Ethyne iii) Ethane
iv) Ethylene glycol

(c) How will you bring about the following conversions:

i) 1-Butene to 1-Butyne ii) 1-Propanol to CH3—CH—CH2CI

Q. 15. Show by means of chemical equations how the following cycle of changes
may be affected.

Q. 16. Write down structural formulas for the products that are formed when
1-butene will react with the following reagents:

47
8. ALIPHATIC HYDROCARBONS [Link]

i) H2, Pt ii) Br2 in CCI4

iii) Cold dil. KMnO4\OH iv) HBr
v) O2 in the presence of Ag vi) HOCI
vii) dil. H2SO4

Q. 17. In the following reactions, identify each lettered product.

i) conc.H2SO4
Ethyl alcohol  Br2
→ A  → B →
alcoholic
C
KOH
Br2
ii) Propene  → D →
alcoholic
KOH
E →
HCN
F
Q.18. After an ozonolysis experiment, the only product obtained was acetalde-
hyde CH3CHO. Can you guess the structural formula of this compound.
Q. 19. (a) The addition of sulphuric acid to an alkene obeys Markownikov’s rule.
Predict the structures of the alcohols obtained by the addition of the acid
to the following compounds.
i) Propene ii) 1-Butene iii) 2-Butene
(b) Predict the most likely product of the addition of hydrogen chloride to
2-methyl-2-butene. Explain the formation of this product.

Q. 20. Why are some hydrocarbons called saturated and others unsaturated?
What type of reactions are characteristics of them?
Q.21. (a) Describe methods for the preparation of Ethyne.
(b) How does ethyne react with:
i) Hydrogen ii) Halogen acid
iii) Alkaline KMnO4 iv) 10% H2SO4 in the presence of HgSO4.
v) Ammonical cuprous chloride
(c) Mention some important uses of methane, ethene and ethyne.

Q.22 . Describe how you could distinguish ethane, ethene and ethyne from one
another by means of chemical reactions.

Q.23. (a) How will you synthesize the following compounds starting from ethyne.

48
8. ALIPHATIC HYDROCARBONS [Link]

i) Acetaldehyde ii) Benzene

iii) Chloroprene iv) Glyoxal
v) Oxalicacid vi) Acrylonitrile
vii) Ethane viii) Methyl nitrile
(b) Write a note on the acidity of ethyne.

Q. 24. (a) Compare the reactivity of ethane, ethene and ethyne.

(b) Compare the physical properties ot alkanes, alkenes and alkynes.

Q. 25. How does propyne react with the following reagents.

(a) AgNO3/NH4OH
(b) Cu2CI2/NH4OH
(c) H2O/H2SO4/HgSO4

Q. 26. A compound has a molecular formula C4H6, when it is treated with

excess hydrogen in the presence of Ni-catalyst, a new compound C4H10
is [Link] C4H6 is treated with ammoniacal silver nitrate a white
precipitate is formed. What is the structural formula of the given compound.

Q.21. (a) Identify A and B.

PCl5
CH3CH2CH2OH  → A  
Na/Ether
→ B

(b) Give the general mechanism of electrophilic addition reactions of

alkenes.

49