INTRODUCTION

Organic chemistry is the study of compounds that contain carbon, though some carbon
containing compounds such as carbon II Oxide, Carbon IV Oxide, are inorganics. It is one of the
major branches of chemistry. It involves the studies of the structure, properties, composition,
reactions, and preparation (by synthesis or by other means) of carbon-based compounds,
hydrocarbons, and their derivatives. The word organic came from the believe that compounds
obtained from living organisms were too complex to be obtained synthetically.
There are over six million organic compound characterized ranging from the foods we eat, (made
of carbohydrates, lipids, proteins, and vitamins), plastics, synthetic and natural fibers, dyes and
drugs, insecticides and herbicides, ingredients in perfumes and flavoring agents, and petroleum
products and hence organic compounds are sorted into groups (organic families) defined by
functional groups. Such groups include the hydrocarbons, alcohols, ethers, aldehydes, ketones,
carboxylic acids, esters e.t.c.
What do you understand by functional groups?
Functional groups are small structural units within molecules at which most of the compound's
chemical reactions occur.
HYDROCARBONS
Hydrocarbons are organic compounds that consist of only C and H atoms. Its major source is
petroleum. We have four types of hydrocarbons and they are alkanes, alkenes, alkynes, and
aromatic hydrocarbons. The main thing that distinguishes the four types of hydrocarbon is bond
between carbon atoms.
CUT
Hydrocarbons can be acyclic or cyclic. An acyclic hydrocarbon can exist as straight chain or
branched chain while a cyclic hydrocarbon can be aromatic or non aromatic.
Straight chain hydrocarbon.
H H H H H H
| | | | | |
H-C-C-C-C-C-C-H
| | | | | |
H H H H H H

n-hexane

Branched Chain Hydrocarbon

H
|
H
H H H-C-H H H
|
| |
|
| |
H---C---C-C---C---C-C-H
|
| |
|
| |
H-C-H H H
H
H H
|
H-C-H
|
H

3-methyl Octane
Cyclic hydrocarbon (Non aromatic)

Aromatic hydrocarbon

Cyclohexane

Benzene

STOP
These four types can be grouped into two i.e saturated (alkanes) and the other three belongs to
the unsaturated hydrocarbon group.
Hydrocarbons have the following common characteristics:

All hydrocarbon burns (though some are flammable and others combustible).

All hydrocarbons have some degree of toxicity.

All hydrocarbons are insoluble in water.

SATURATED HYDROCARBONS (ALKANES)

Alkanes also called paraffins are saturated hydrocarbon in which each carbon is bonded to four
other atoms through single covalent bonds. Alkanes have the general formula CnH2n+2, where n is
any integer. (paraffin means little affinity)
Methane (CH4) is the simplest saturated alkane, its single carbon atom is bonded to four
hydrogen atoms.

EXERCISE
What is Isomerism?
Write out the structures and names of all the Isomers of pentane.
PROPERTIES OF ALKANES
Physical properties

Change of state occur as the number of carbon increases, unbranched alkanes methane,
ethane, propane, and butane are gases; pentane through hexadecane are liquids while the
homologues larger than hexadecane are solids.

Boiling point increases number of carbon atoms increases, the more atoms there
are the greater the intermolecular van der Waals forces, greater intermolecular
force means more energy needed to separate the molecules and the more
energy required, the higher the boiling point.

ASSIGNMENT
Explain why the boiling point of a straight chain hydrocarbon is greater that of a
branched hydrocarbon of equal number of carbon atoms.

Melting point also increases with molecular mass but not in a regular pattern as
boiling points.

They are non polar and hence are immiscible with water but are soluble in most
organic solvent.

Chemical properties

Alkanes are relatively unreactive because they have strong, nonpolar covalent
bonds. Also, since they are already completely saturated, they cant undergo
addition reactions but they undergo substitution reactions. Two important reactions
that the alkanes do undergo are combustion and halogenation.

Combustion

Alkanes burns in oxygen in an exothermic reaction according to the reactions below

Complete combustion
CH4(g) + 2O2(g) > CO2(g) + 2H2O(l)
Incomplete combustion
2CH4(g) + 3O2(g) > 2CO(g) + 4H2O(l)
The greater the number of carbon atoms, the more energy produced and the greater the
amount of oxygen needed for complete combustion.

Halogenation of alkanes

Bromine will react with carbon-carbon single bonds in alkanes by replacing an H with Br
by substitution, however, the reaction is generally slow and requires light to act as a
catalyst.

CH3CH3 + Br2

light/ slow

CH3CH2Br + HBr

Brownish red

Colourless

Pungent Smell

Alkanes also react with other halogens [chlorine (Cl2), fluorine (F2) and Iodine (I2)]. For
example, in the presence of ultraviolet light or at high temperatures chlorine reacts with excess
methane (CH4) to give methyl chloride (CH3Cl).
CH4 + Cl2 CH3Cl + HCl
With more chlorine, a mixture of products is obtained: CH3Cl, CH2Cl2, CHCl3, and CCl4.
Fluorine (F2), the lightest halogen, combines explosively with most hydrocarbons.
Iodine (I2) is relatively unreactive. Fluorinated and iodinated alkanes are produced
by indirect methods.

General preparation of alkanes

(i)

Decarboxylation ie the removal of CO2 from molecules having - COOH gp.

Saturated monocarboxylic acid salt of sodium potassium on dry distillation
with soda lime gives alkane.

RCOONa

soda lime/-CO

or RCOONa + NaOH

R-H
CaO

R-H + Na2CO3

The alkane formed always contains one carbon atom less than the original acid. This
method gives a good yield in the case of lower members but poor yield for higher
members. (Use a specific example).
(ii) By hydrogenation of alkenes: Sabatier and senderen's method :
Alkenes and alkynes on catatlytic hydrogenation give alkanes
CH2 = CH2 + H2

Ni, 200oC

CH3-CH3

CHCH + 2H2

Ni, 200oC

CH3-CH3

If Pt or Pd are used as catalyst, reaction occurs at normal temperature.

(iii)

By Reduction of Carbonyl compounds (Clemmensen reduction):

The reduction of carbonyl compounds by amalgamated zinc and conc. HCl
yields alkanes.

CH3CHO + 2H2
(iv)

Zn+Hg/HCl

CH3CH3 + H2O

Reduction of alkyl halides(haloalkanes):

Alkyl halides on reduction with nascent hydrogen form alkanes.
R-X

[2H]

R-H + HX

Reduction of alkyl halides generally gives a high yield and form pure hydrocarbons.
Other methods use in the preparation of alkanes includes : the kolbes electrolysis,
double decomposition of grignard reagents, Wurtz reaction, hydroboration of alkenes,
reduction of alcohols, aldehydes, ketones or fatty acids and their derivatives e.t.c.

Cycloalkanes with general formular (CH2)n are saturated hydrocarbons containing rings of carbon
atoms linked together by single bonds. The chemical properties of cycloalkanes changes in a much more
dramatic way with increasing n than do those of the acyclic hydrocarbons. The melting and boiling points of
cycloalkanes are somewhat higher than those of the corresponding alkanes, they are also hydrophobic in nature
and are less dense than water.

UNSATURATED HYDROCARBONS
Alkenes are hydrocarbons with carbon-to-carbon double bonds (R 2C=CR2) and
alkynes are hydrocarbons with carbon-to-carbon triple bonds (RCCR). These are
called unsaturated hydrocarbons because they have fewer hydrogen atoms than

does an alkane with the same number of carbon atoms. The general formula of
alkenes is CnH2n and that of alkyns is CnH2n-2.

Physical properties of alkenes

The physical properties of alkenes are similar to those of the alkanes. The boiling
points of straight-chain alkenes increase with increasing molar mass, just as with
alkanes. Like other hydrocarbons, the alkenes are insoluble in water but soluble in
organic solvents.

Chemical properties of alkenes

Unsaturated hydrocarbons i.e alkenes and alkynes are quite reactive. In fact, they
serve as building blocks for many familiar plasticspolyethylene, vinyl plastics,
acrylics and other important synthetic materials (e.g., alcohols, antifreeze, and
detergents).
Alkenes are valued mainly for addition reactions, in which one of the bonds in the
double bond is broken. Each of the carbon atoms in the bond can then attach
another atom or group while remaining joined to each other by a single bond.

(i)

Hydrogenation Of alkenes.

This is the reaction of alkenes with hydrogen (H2) in the presence of a catalyst such as nickel
(Ni) or platinum (Pt).

The product is an alkane having the same carbon skeleton as the alkene. The above reaction is
applicable in the food industries for the conversion of vegetable oil to margarine.
(ii)

Halogenation of alkenes

Alkenes also readily undergo halogenationthe addition of halogens. Indeed, the reaction with
bromine (Br2) can be used to test for alkenes. Bromine solutions are brownish red. When we add
a Br2 solution to an alkene, the colour of the solution disappears because the alkene reacts with
the bromine.
H2C=CH2 + Br2

1,2-Dibromoethane (Colourless)

Another important addition reaction is that between an alkene and water to form an alcohol. This
reaction, called hydration, requires a catalyst usually a strong acid, such as sulfuric acid (H2SO4).
H2C=CH2 + H2O

H2SO4

CH3CH2OH

(iii)

Addition of halogen acids

Alkenes with concentrated aqueous solution of halogen acids give haloalkanes. The
order of reactivity is HI > HBr > HCl for example

H3C-CH=CH-CH3 + HBr
2-Butene

H3C-CH2-CH(Br)-CH3
2-bromobutane

A symmetrical alkenes give only one product, due to the equivalence of the two carbon
atoms (the H and X may add to the molecule in any way). In asymmetrical alkenes, the
addition of a halogen acid takes place in a manner where by the halogen atom (the
negative part of the molecule to be added) adds to the carbon atom, which has lesser
number of hydrogen atoms on it. For example, in the case of propene, the product
obtained is 2-iodopropane and not 1-iodopropane.

H3C-CH=CH2 + HI

H3C-CH(I)-CH3

This rule of the addition of halogen acids to an asymmetrical alkene is known as

Markownikoff's rule.

Peroxide effect (anti-Markownikoff's rule)

The mode of addition of hydrogen bromide to unsymmetrical alkenes in the presence of
oxygen and peroxides is contrary to Markownikoff rule. This addition of HBr to
unsymmetrical alkenes against the Markownikoff's rule is known as peroxide effect, or
anti-Markownikoff's rule.
For instance, the reaction of propene with HBr in the presence of peroxides, forms 1bromopropane instead of 2-brompropane
CH3-CH=CH2 + HBr

CH3-CH2-CH2Br1 -bromopropane

The mode of addition of hydrogen chloride or hydrogen iodide is not affected by the
presence of peroxides.

(iv)

Addition of water (Hydration of alkenes)

Water molecule adds to an alkene molecule across the double bond in the presence of
dilute acids and a catalyst. For example, ethane gives ethanol when a mixture of ethene
and steam is passed over phosphoric acid and silica under a pressure 65 atm, and at
300C.

CH2=CH2 + H2O

H3PO4/300oC,65atm

CH3-CH2-OH

Ethene

(v)

Ethanol

Addition of oxygen

Lower alkenes are mixed with air and passed under pressure over a silver catalyst at
200-400C. This gives epoxides by adding one atom of oxygen across the double bond.
The epoxides so obtained are used in detergents.

CH2=CH2 + 1/2O2

Ag, 200-400oC

Ethene
(vi)

Ethene-epoxide
Oxidation

Alkenes can be readily oxidized, but the nature of the products depends upon the
oxidizing agent used.
With cold, alkaline KMnO4
When alkenes are oxidised with cold, alkaline KMnO4, dihydroxy compounds (diols or
glycols) are formed. The KMnO4 gets decolorized. This reaction is therefore, used as
Bayer's test for unsaturation i.e the presence of double or triple bonds in any molecule.
Ethene gives ethane-1,2-diol.

CH2=CH2 + H2O + O
Ethene

KMnO4 Alkaline, cold

Ethane 1,2-diol

(vii)

Substitution reactions

At elevated temperatures (500C), higher alkenes give substitution products with

chlorine. For example,
CH3-CH=CH2 + Cl2

ClCH2-CH=CH2 +HCl

propene

3-chloropropene

(viii)

Polymerization

Addition polymerization is a process by which a large number of molecules of the same

species (monomers) join together to form a giant molecule, called a polymer. Alkenes
undergo addition polymerization when heated under pressure, in the presence of
suitable catalysts. When ethene is heated to 1000C under 1000 atm pressure in presence
of oxygen, we get polyethene.
nCH2=CH2

O2

Ethene

-(-CH2-CH2-)npolyethene

ETHYNE

Ethyne with general formula C2H2n-2 has a triple bond between the two carbon atoms.
Physical properties
Physical state
The first three members (ethyne, propyne and butyne) are colourless and odorless
gases. Due to the presence of phosphine as an impurity ethyne (acetylene) has garlic
smell. The next eight members are liquids, and higher members are solids under normal
conditions of temperature and pressure.
Solubility
Alkynes are insoluble in water, but are fairly soluble in organic solvents such as, alcohol,
ether, acetone etc.
Melting and boiling points
The melting and boiling points of alkynes increase with molecular mass.

Chemical properties

Combustion
Alkynes burns in air or oxygen with smoky flame, CO2 and H2O are the product of their
combustion.
Alkynes give electrophilic addition reactions as they show reactivity due to the presence
of bonds. This property is similar to alkenes but alkynes are less reactive than alkenes
towards electrophilic addition reactions due to the compact CC electron cloud. Some
typical electrophilic addition reactions given by alkynes are:
Addition of hydrogen
An alkyne reacts with hydrogen in the presence of catalyst (Pt or Ni) at 250C, first
forming alkenes and finally alkane.

CH=CH + H2

Ni

Ethyne

CH2=CH2 + H2
Ethene

Ni

CH3CH3
Ethane

Addition of halogens
Alkynes react with halogens (Cl2 or Br2) in the dark, forming dihaloalkenes first and
finally tetrahaloalkanes. The reaction gets accelerated in the presence of light or halogen
carriers.

CH=CH + Cl2
Ethyne

CHCl=CHCl
Dichloroethane

CHCl2-CHCl2
Tetrachloroethane

The order of reactivity of halogens with alkyns is Cl2 > Br2 > I2.

Addition of halogen acids

Alkynes react with halogen acids according to the Markownikoff's rule i.e. the carbon
atom carrying the least number of hydrogen atoms will have the negative part of the
addendum attached to it.
H3C-C=CH + HBr

H3C-CBr=CH2

H3C-CBr2-CH3

Propyne

2-bromo propene

2,2-dibromopropane

The rate of addition of halogen acids follows the order, HI > HBr > HCl.
Alkynes can also undergo nucleophilic addition reactions e.g.
Addition of water
In the presence of sulphuric acid and mercuric sulphate at 60C, alkynes add on one
water molecule to give aldehydes or ketones.
CH=CH + H2O

HgSO4/H2SO4

H2C=CHOH

CH3CHO

Substitution reactions

Hydrogen atoms in ethyne and 1-alkynes, linked to the carbon atom having a triple bond on it,
are acidic in nature. Due to this acidic nature, alkynes form metallic salts called alkynides e.g.,
sodium, silver and copper(ous) salts. Since ethyne (acetylene) has two acidic hydrogen atoms, it
gives dimetal salts.
CH=CH

Na(liquid NH3)

CH=CNa

Na

CNa=CNa

Polymerization
On heating alkynes undergo polymerization in the presence of catalyst. The nature of
products depends upon the conditions e.g when ethyne (acetylene) is passed through a
hot copper tube, it polymerizes to benzene.

3CH=CH

Hot Cu tube

C6H6

When passed through a solution of cuprous chloride in ammonium chloride, ethyne

undergoes linear polymerization.
Oxidation
Oxidation of alkynes gives mono or dicarboxylic acids.
For example,
Alkaline KMnO4 oxidises ethyne to oxalic acid.

oxalic acid(ethanedioic acid)

With chromic acid, ethyne gives acetic acid. (CH3COOH)

DIENES
Dienes are unsaturated hydrocarbons containing two carbon-carbon double bonds per
molecule. Their general formula is CnH2n-2. Dienes and alkynes are functional isomers.
Classification of dienes
Depending upon the relative positions of the two double bonds dienes are classified as:
Isolated dienes
In these dienes the double bonds are separated by more than one single bond and are
called isolated dienes. For example:
Cumulated dienes
When the double bonds are present between successive carbon atoms such dienes are
called cumulated dienes or allenes. For example:
Conjugated dienes
When the double bonds are separated by a single bond, dienes are termed as conjugated
dienes. For example:
Relative stabilities of dienes
A conjugated diene is more stable as compared with non-conjugated dienes. The relative
order of stability of dienes is:Conjugated diene > Isolated diene > Cumulated diene
The evidence in favour of maximum stability of conjugated dienes can be obtained from the
values of heats of hydrogenation

As more heat is given out during hydrogenation of 1,4-pentadiene (an isolated diene) as
compared with 1,3-pentadiene (a conjugated diene), it indicates that 1,4-pentadiene has
more energy than 1,3-pentadiene and hence is less stable than it.