MURULI’s CHEMISTRY PV=nRT 1

AVK PU COLLEGE, HASSAN.

MANAGED BY: Medhasvi Education Trust® QUARK ACADEMY
Subject:- I PUC - CHEMISTRY UNIT: 9 Max. Marks:- 15 MARKS
HYDROCARBON’s
-: SPLITTING OF MARKS :- EXPECTED TOPIC
MCQ [No. of Q-2] 2M Conformation of ethane, catalyst used in Electrophilic
substitution reaction, General formula of alkane,
alkene and alkyne. IUPAC naming, complete the
following reaction. Kekule structure.
FIB [No. of Q-1] 1M Catalyst used in Electrophilic substitution reaction,
General formula of alkane, alkene and alkyne.
Two mark questions 2M Wurtz reaction, Kolbe’s reaction, Markonikoff’s and
[No. of Q-1] anti Markonikoff’s rule, dehydrohalogenation,
decarboxylation reaction.
FIVE mark questions 10M Chlorination of methane, nitration, sulphonation,
[No. of Q-2] halogenation, Friedel craft alkylation & acylation of
benzene.
Maximum number of marks = 15M
INTRODUCTION:
The simplest organic compounds containing carbon and hydrogen are known as hydrocarbons. Petroleum
and coal are the two important natural hydrocarbons. Petroleum is an aliphatic hydrocarbon while coal is an
aromatic hydrocarbon.
Hydrocarbons are classified as
1) Open chain hydrocarbon (Acyclic hydrocarbon)
2) Close chain hydrocarbon (Cyclic hydrocarbon)
Open chain hydrocarbon: This hydrocarbon is also known as aliphatic hydrocarbon. Aliphatic
hydrocarbons or Acyclic hydrocarbon containing open chain of carbon atoms called aliphatic
hydrocarbons.
This is further classified into two types,
1) Saturated hydrocarbon 2) Unsaturated hydrocarbon
Saturated hydrocarbons contain chain of carbon atoms with single bond. This is also known as alkanes.
They are less reactive.
Eg: Methane (CH4), ethane (C2H6), propane (C3H8)
Unsaturated hydrocarbons contain chain of carbon atoms with double bonds or triple bonds. This is also
known as alkenes (carbon = carbon double bond) and alkynes (carbon ≡ carbon triple bond). They are
more reactive compared to saturated hydrocarbon (alkane).
Eg: Ethene (CH2 = CH2) → Alkenes
Ethyne (CH ≡ CH) → Alkynes
• Close chain hydrocarbon (Cyclic hydrocarbon): Cyclic hydrocarbons contain carbon – carbon cyclic
form with single bond or at least one benzene ring.
This is further classified into two types,
1) Alicyclic hydrocarbons
2) Aromatic hydrocarbons
Alicyclic hydrocarbons: Alicyclic hydrocarbons contain carbon-carbon in a ring or cyclic structure with
single or doubles. It is also called cyclo alkanes.
Eg: CH2 or

CH2 CH2
Cyclo propane, Cyclo butane
Aromatic hydrocarbons: Aromatic hydrocarbons contain at least one six membered carbon cyclic ring or
hexagonal carbocyclic rings or benzene ring with alternate single double bonds. This is also known as
arenas or aryls. They are burnt with sooty flame.
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Eg: Benzene, naphthalene, toluene etc…

This year we shall study only aliphatic and aromatic hydrocarbons.

Flow chart for hydrocarbons classification:

ALKANES (Paraffins)
Alkanes are saturated aliphatic hydrocarbons which contain only Carbon-Carbon single bond.
Characteristics of Alkanes:
1. General formula of alkanes is CnH2n+2, where ‘n’ is integer or number of carbon atoms (n=1, 2, 3…….).
2. Alkanes are generally inert towards most of the reagents. That is why alkanes are also called ‛paraffins’
(In Latin word ‟param” means - little and ‟affins” means – affinity or low reactivity).
Eg: Methane, ethane, propane, etc….
3. Alkanes are sp3 hybridized and hence forms four 𝜎 bonds.
4. Alkanes are Tetrahedron structure
5. Bond angle is 109028/
Eg: CH4

The chief source of alkanes is crude petroleum and natural gas. Methane (marsh gas) is formed by decay of
plants and animal tissue.

Nomenclature and Isomerism:

First three alkanes - methane, ethane and propane do not show isomerism but higher alkanes can have more
than one structure.
Eg: 1) Butane (C4H10) contains two chain isomers:

IUPAC name: Butane 2-methyl propane

2) Pentane (C5H12) contains three chain isomers:

IUPAC name: Pentane 2-methyl butane 2,2-dimethyl propane

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3) Hexane (C6H14) contains five chain isomers:

Example of simple unbranched alkanes:

Based upon the number of carbon atoms attached to a carbon atom, the carbon atoms are classified into four
types:
1) Primary carbon atoms: carbon atom attached to only one carbon atom is called primary carbon atom.
Terminal carbon atoms are always primary.
2) Secondary carbon atoms: carbon atom attached to two carbon atoms is known as secondary carbon
atoms.
3) Tertiary carbon atoms: carbon atom attached to three carbon atoms is called tertiary carbon atoms.
4) Quaternary or Neo carbon atoms: carbon atom attached to four carbon atoms is called quaternary or
neo carbon atoms.
Eg:

C1, C5 are primary, C3 is secondary, C4 is tertiary and C2 is neo or quaternary carbon atoms.
Write the IUPAC names and structures of given IUPAC name: [Que: NCERT page number - 377]
1) (CH3)3 C CH2C(CH3)3 → 2,2,4,4-tetramethylpentane
2) (CH3)2 C(C2H5)2 → 3,3-dimethylpentane
3) Tetra-tert-butyl methane → 3,3-di-tert-butyl-2,2,4,4-tetramethylpentane
4) 3,4,4,5- tetramethyl heptane

5) 2,5-dimethylhexane

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6) 2-ethylpentane

7) 3-ethyl-5-methylheptane

8)

General methods of preparation of alkanes:

1) From unsaturated hydrocarbons: Dihydrogen gas adds to alkene and alkynes in the presence of catalyst
like platinum or palladium or nickel to form alkanes. This process is called hydrogenation. This metal
absorbs a dihydrogen gas on their surfaces. This reaction is also known as Sabatier – Senderen’s reaction.
Eg: Ethene and propene is treated with dihydrogen / hydrogen in presence of Pt/Pd/ Ni catalyst at 573K to
form ethane & propane.

2) From alkyl halides: [Wurtz reaction]

i) Wurtz reaction: When two molecules of alkyl halide heated with sodium metal in the presence of dry
ether as a catalyst to form higher alkanes. It is called Wurtz reaction.

R-X + 2 Na + X-R R-R + 2NaX

Alkane
Eg: When two molecules of methyl chloride heated with sodium metal in the presence of dry ether to form
ethane.
CH3-I + 2Na + I-CH3 CH3-CH3 + 2NaI
Methyl chloride Ethane

CH3-CH2-Br + 2Na + Br-CH2-CH3 CH3-CH2-CH2-CH3 + 2NaBr

Ethyl bromide n- butane
Note: It is used for the preparation of higher alkanes containing even number of carbon atoms. Methane
cannot be prepared by this method.
2) By reduction of alkyl halides: Alkyl halides except fluorides on reduction with hydrogen molecule in
the presence of palladium to give alkane.

Note: The other reducing agents used for above reduction are
1) Zn – Cu couple in ethanol 2) HI in presence of red phosphorous 3) Zn / HCl
3) From acids: (Using carboxylic acid)
a) Decarboxylation: Dry distillation of sodium or potassium salt of saturated monocarboxylic acid with
soda lime gives alkanes. The removal of carbon dioxide from molecules having –COOH group by using
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soda lime is called decarboxylation. Soda lime (mixture of sodium hydroxide and calcium CaO) is called
decarboxylating agent.
Eg: When sodium acetate react soda lime to form alkane.

b) From Kolbe’s electrolytic method: [Electrolytic decarboxylation reaction]

An aqueous solution of sodium or potassium salt of fatty acids (carboxylic acid) on electrolysis gives higher
alkanes are formed at the anode and hydrogen gas is liberated at the cathode. It is called Kolbe’s electrolytic
method. Methane cannot be prepared by this method.
Eg: Sodium or potassium acetate solution is electrolysed to form ethane.
2CH3COONa + 2 H2O CH3 – CH3 + 2CO2 + H2 + 2NaOH
Eg: When concentrated solution of sodium acetate is electrolyzed ethane will be formed.
Ionization: CH3COONa ⇌ CH3COO̶ + Na+
H2O OH ̶ + H+
Cathode: 2H+ + 2e̶ H2
̶
Anode: CH3COO + 2e-
CH3ͦ + CO2
CH3ͦ + CH3ͦ CH3ͦ - CH3ͦ
CH3ͦ + CH3ͦ C2H6
Physical properties:
• Alkanes are almost colourless and odourless.
• Alkanes nonpolar molecules that is insoluble in water and soluble in organic solvents (like ether,
benzene, carbon tetrachloride etc..) because they have covalent character.
• Lower alkanes (C1 – C4) are gases, intermediate alkanes (C5 ̶ C17) are liquids and higher alkanes (> C17)
are waxy solids.
• They only have strong sigma bonds due to the weak force.
• Boiling point: They possess low boiling points. If molecular mass increases, the boiling point of alkanes
increases due to increase of Vander waal’s forces (pentane < hexane < heptane < octane). Amongst
isomeric alkanes, boiling point decreases as the surface area decreases with increase in branching. Thus
the boiling points of isomeric pentanes decrease in the order, n-pentane (309K), isopentane (301K) and
neopentane (282.5K).
• Melting point: They possess low melting points. Melting points of alkanes increase as the molecular
mass increases but unlike boiling points, this increase is not regular.

Chemical properties of alkanes [Chemical reactions]:

1. Substitution reactions: One or more hydrogen atoms of alkanes can be replaced by halogens, or nitro
group or sulphonic acid group. Lower alkanes do not undergo nitration and sulphonation reactions. Those
reactions in which hydrogen atoms of alkanes are substituted are known as substitution reactions.

a. Halogenation: It is a type of substitution reaction, halogens react with alkanes in presence of high
temperature (573 – 773K) or in the presence of diffused sun light or ultraviolet light to from a mixture of
various halogen products. It is called halogenations.
The rate of reaction of alkanes with halogens is F2 > Cl2 > Br2 > I2. The rate of replacement of hydrogens of
alkanes is 30 > 20 > 10. Fluorination is too violent to be controlled. Iodination is very slow and a reversible
reaction. It can be carried out in the presence of oxidising agents like HIO3 or HNO3. Halogenation reaction
is also known as free radical mechanism.
Eg: Chlorination of methane

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When chlorine reacts with methane in the presence of diffused sunlight a hydrogen atom of methane is
replaced by a halogen atom consequently forming methyl chloride, dichloromethane, chloroform and carbon
tetra chloride.

Mechanism of chlorination of methane (free radical mechanism): It involves in three steps

Step 1: Chain initiation: Chlorine molecule absorbs energy from sunlight and undergoes homolysis to give
two chlorine free radicals.

Step 2: Chain propagation: Chlorine free radical attacks the methane molecule to form methyl free radicals
and HCl.

The methyl free radicals thus obtained attacks the second molecules of chlorine to form methyl chloride
and another chlorine free radical.

The above two reactions are repeated and setup a chain of reactions. In this propagation step various
halogenated products are formed.

Step 3: Chain termination: the chain terminates when highly reactive free radical react among themselves
forming stable molecules.

2) Combustion: (Oxidation)
Combustion Alkanes on heating in the presence of air or dioxygen are completely oxidized to carbon
dioxide and water with the evolution of large amount of heat.
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General reaction of combustion:

Due to the evolution of large amount of heat during combustion alkanes are used as fuels. During
incomplete combustion of alkane with insufficient amount of air or oxygen carbon black is formed which is
used in ink printer ink and filters.

3) Controlled oxidation:
Alkanes on heating with a regulated supply of air or oxygen with suitable catalyst at high temperature and
high pressure to give alcohols or aldehyde or ketones and carboxylic acids.

Ordinarily alkanes resist oxidation but alkanes having tertiary H-atom can be oxidized to corresponding
alcohols by potassium permanganate.

4) Isomerisation:
The process of conversion of one isomers into another isomer is called Isomerisation.
Higher alkanes (n – alkanes) on heating in presence of anhydrous AlCl3 and hydrogen chloride gas form
branched chain isomers. Major products are given below. Some minor products are also possible which you
can think over. Minor products are generally not reported in organic reactions.

5) Aromatisation: The conversion of aliphatic hydrocarbons into aromatic compounds is called

aromatisation.
Eg: When n-hexane is passed through chromium or vanadium or molybdenum oxide is supported at 5000C
heat at 10-20 atmospheric pressure to give benzene.

6) Pyrolysis [cracking]: The thermal decomposition of organic compounds is called pyrolysis. When
pyrolysis applied in alkanes, the process is known as cracking.
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When alkanes are heated to high temperatures in the absence of air, the higher alkanes molecules break
up into smaller molecules of lower alkanes, alkenes and hydrogen. Methane is heated at 1273K in the
absence of air to form carbon black and hydrogen.

When ethane is heated in the absence of air at 723K to form ethylene and hydrogen.

7) Reaction with steam: Methane reacts with steam at 1273K in the presence of nickel catalyst to form
carbon monoxide and hydrogen. This method is used for industrial preparation of hydrogen gas.

Note: Nitration: Alkanes react with fuming nitric acid to form nitro alkanes. Ethane reacts with nitric acid
vapours at 673 – 723K to form nitro ethane.

Sulphonation: Alkanes react with fuming sulphuric acid to form alkane sulphonic acid. Lower
alkanes cannot be sulphonated.

Conformation in alkanes:
The different arrangements of the atoms in space that results from the rotation of groups about C-C bond
axis are called conformers or conformations or rotomers.
Alkanes can have infinite number of conformations by rotation around-C-C-single bonds. But the rotation
around a C-C single bond is not completely free. The repulsive interaction between the electron clouds
which affects the stability of a conformation is called torsional strain. The magnitude of torsional strain
depends upon the angle of rotation about C-C single bond. This angle is called dihedral angle or torsional
angle.
Conformation of ethane
Infinite numbers of conformations are possible in ethane molecule due to free rotation around the carbon -
carbon single bond about its axis. However, there are two extreme cases. They are
1. Eclipsed conformation 2. Staggered conformation
Eclipsed conformation: The conformation in which hydrogen atoms attached to two carbons are as closed
together as possible is called eclipsed conformation.
Staggered conformation: The conformation in which hydrogen atoms attached two carbons are as far apart
as possible is called staggered conformation
Any other intermediate conformation is called skew conformation.
Chemists have adopted two ways of representing conformational isomers.
1. Sawhorse representations 2. Newman projections
The saw horse formulas in eclipsed and staggered conformations of ethane are as follows:

The Newmen projections of eclipsed and staggered conformations of ethane are as follows

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Relative stability of conformations of ethane:

The different conformations of ethane are not of equal stability. The staggered confirmation is the most stable
conformation. In the staggered conformation of ethane, a hydrogen atom on one carbon atom has a 600
torsional angle with respect to the nearest hydrogen atom on the other carbon so that steric hindrance is
minimized. It has minimum energy and maximum stability. The eclipsed conformation is the least stable
confirmation with maximum energy. The staggered conformation is more stable than eclipsed
conformation by about 12.55kJ/mole. Since the energy difference between the two extreme forms is very
small, even at ordinary temperatures, the ethane molecule gains thermal or kinetic energy sufficient enough to
overcome this energy barrier of 12.5 kJ mol-1 through intermolecular collisions. Thus the rotation about
carbon-carbon single bond in ethane is almost free for all practical purposes. It has not been possible to
separate and isolate different conformational isomers of ethane. However, at any given moment, most of the
ethane molecules would exist in staggered conformation due to its minimum energy and maximum stability.
The skew or gauche form stability is in between the eclipsed and staggered forms. The stability order of
conformers is staggered > skew or gauche > eclipsed

ALKENES (olefins):
Alkenes are unsaturated aliphatic hydrocarbons containing carbon-carbon double bond. They are represented
by the general formula CnH2n, where n = 2,3,4,5….. alkenes are also called olefins because they form oily
liquids on reaction with chlorine or bromine. Examples,

IUPAC nomenclature of alkenes:

Alkenes are named according to the IUPAC rules discussed in unit 12. Some of the examples are given
below:
CH2 = CH2 Ethene
CH3 – CH2 = CH2 Propene

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NCERT Problem 13.7: Write IUPAC names of the following compounds:

(i) 2, 8-dimethyl-3,6-decadiene (𝜎 bonds = 33, 𝜋 bonds = 2)

(ii) 1, 3, 5, 7 octatetraene (𝜎 bonds = 17, 𝜋 bonds = 4)
(iii) 2-n-propylpent-1-ene (𝜎 bonds = 23, 𝜋 bonds = 1)
(iv) 4-ethyl-2, 6-dimethyl-dec-4-ene (𝜎 bonds = 41, 𝜋 bonds = 1)
Structure of alkenes:
In alkenes, the carbon atom of the double bond undergoes sp2 hybridization. Hence they are having triangular
planar geometry with the three sp2 hybrid orbitals directed towards three corners of an equilateral triangle
with a bond angle of 1200.
Eg: Structure of ethene

✓ Alkenes are more reactive than alkanes due to the presence of weaker pi bond. The reactions of alkenes
are essentially the reactions of pi bond.
✓ The bond length of carbon-carbon double bond in alkenes (134 pm) is less than the bond length of
carbon-carbon single bond (154 pm) in alkanes.
Isomerism in alkenes:
Alkenes show both structural isomerism and geometrical isomerism.
Structural isomerism: Structural isomerism is commonly referred to as constitutional isomerism. It is a
type of isomers having same molecular formula but different structural formula.
Alkenes higher than propene show structural isomerism.
The structural isomerism of the formula C4H8 are:

Geometrical isomerism (cis-trans isomerism):

Two compounds having the same molecular formula and structural formula but differs in the special
arrangement of atoms or groups across the carbon-carbon double atom double bond are called geometrical
isomers. The phenomenon is called geometrical isomerism. It is due to the restricted rotation across the
carbon-carbon double bond.
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They are two forms of geometrical isomers;

✓ The isomers in which the two similar atoms or groups lie on the same side of the double bond is called
Cis isomers.
✓ The isomers in which the two similar atoms or groups lie on the opposite side of the double bond is
called Trans isomers.
For example: 2-butene exhibits Cis – Trans isomerism as shown below

Question 1: Trans isomers are more able than cis isomers. Why?
Ans: Trans isomers are more stable than cis isomers because in cis isomers, the bulky groups are on the
same side of the double bond. The steric repulsion (hindrance) of the group makes the cis isomers less stable
than the trans isomers in which the bulky groups are far apart (they are on the opposite side of the double
bond).
Question 2: cis form of alkenes is formed to be more polar than the trans form.
Ans: Dipole moment of cis – but-2-ene is 0.33 Debye. Whereas, dipole moment of the trans form is almost
zero.
Due to different arrangement of atoms (or) group in space, these isomers differ in their properties like
melting point, boiling point, dipole moment, solubility etc….
Methods of preparation of alkene:
1) From alkynes:
Alkenes can be obtained by partial reduction of alkynes with calculated amount of hydrogen gas in the
presence of Lindlar’s catalyst (Pd on charcoal partially deactivated with BaSO4 or CaCO3 or quinoline. This
catalyst prevents further hydrogenation) gives alkenes while reduction with Na in liquid ammonia (Birch
reduction) gives trans alkenes.

Note: Acetylene is hydrogenated in presence of Lindlar’s catalyst to form ethylene (Ethene)

2) Dehydrohalogenation of alkyl halides:

Alkyl halides are heated with alcoholic potassium hydroxide (KOH) to form alkenes.
Eg: Ethyl halide is heated with alc. KOH solution to from ethylene (ethene)

According to Saytzeff’s rule, highly substituted alkene is the predominant product in the
dehydrohalogenation of alkyl halides.

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According to Saytzeff’s rule, the carbon around the double bond which is highly alkylated (which as
maximum number of carbon atom) that is the major product.

3) Dehalogenation of vicinal dihalides:

Vicinal Di halides: The two halogen atom is replace the two hydrogen atom in a adjacent carbon atom.

Vicinal dihalides are heated with zinc dust in an alcoholic solution to form alkenes.
Eg: 1) 1,2 di bromo ethane is heated with zinc dust in an alcoholic solution to form ethylene (ethene).

2) 1,2 di bromo propane is heated with zinc dust in an alcoholic solution to form propene.

From alcohol by acidic dehydration:

Alcohols on heating with concentrated Sulphuric acid at 443K to form alkenes with the elimination of water
molecules hence it is called acidic dehydration of alcohols. This reaction is also the example of 𝛽-
elimination reaction, since -OH group takes out one hydrogen atom from 𝛽-carbon atom.

Physical properties:
• The first three members are gases, the next 14 members are liquid and the higher ones are solids.
• Alkenes are insoluble in water soluble but soluble in alcohol, ether and organic solvent.
• All other alkenes are colourless and odourless.
• They show regular increases in boiling point with increases in size (for every –CH2 group added
increases boiling point by 20 to 30K)

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Chemical properties:
Alkenes are more reactive due to presence of weak 𝜋 bonds. Electrophilic addition reactions are involved in
alkanes due to availability of 𝜋 electrons. This reaction is also called as electrophilic addition reaction.
Addition reaction:
a) Addition of dihydrogen (Sabatier – Senderen’s): When alkene is treated with dihydrogen in the
presence of Ni/Pt/Pd as a catalyst to form alkanes. This reaction is called hydrogenation. This reaction is
exothermic reaction. (A reaction that releases energy from the system in the form of heat)

When ethene is heated with dihydrogen in the presence of Ni as catalyst to form ethane.

b) Addition of halogen:
Alkenes react with halogens to form dihaloalkanes in inert solvent like carbon tetra chloride (CCl4). The
order of reactivity is chlorine > bromide > Iodine.

Eg: 1) Ethene react with bromide to form 1,2-dibromoethane in inert solvent like carbon tetra chloride.

2) Propene react with bromide to form 1,2-dibromopropane in inert solvent like carbon tetra chloride.

Bromination reaction is used as a test for unsaturation.

NOTE: order of reactivity is HI>HBr>HCl>HF
Addition of hydro halo acids (hydrogen acids):
Alkenes react with concentrated aqueous solution of halogen acids gives haloalkanes. The order of reactivity
of hydro halo acids as HI > HBr > HCl.
a) Addition of HBr to symmetrical alkene:
HBr adds to symmetrical alkenes (alkenes containing similar groups on either side of double bond) to form
alkyl bromides.

Eg: 1) HBr adds to ethene to form bromo ethane.

2) HBr adds to butene to form bromo butane.

b) Addition of HBr to unsymmetrical alkene (Markovnikov’s rule):

Addition of HBr to unsymmetrical alkene takes place according to Markovnikov’s rule. The rule states that
“negative part of the unsymmetrical molecules gets attached to the unsaturated carbon atom of the
alkene or alkyne containing less number of hydrogen atoms’’.
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Mechanism: The mechanism of this reaction involves the following steps:

Step 1: Formation of electrophile (H+)
HBr heterolitically ionizes giving a proton [electrophile (H+)] and bromide ion

Step 2: The electrophile, H+ which attaches to the double bonded carbon atom to form carbocation.

The order of stability is 30 > 20 > 10 (In this 20 > 10)

The secondary carbocation (II) is more stable than 10 carbocation (I). Thus, secondary carbocation (II) is
formed.
Step 3: The secondary carbocation (II) is attacked by Br- ion to form stable product 2-bromo propane.

Anti-Markovnikov’s rule: (Peroxide effect or Kharash effect):

In presence of peroxide, addition of HBr to propene (alkene) take place against to the Markovnikov’s rule.
This is called peroxide effect or Kharash effect or Anti-Markovnikov’s rule.

Mechanism: This reaction proceeds via free radical chain mechanism as follows:
Step 1: Formation of peroxide free radicals: dibenzoyl peroxide undergoes homolytic cleavage to give
free radical

Step 2: When electrophile attacks to the peroxide free radicals to form bromide free radical.

Step 3: The bromide free radical, which attaches to the double bonded carbon atom to form free
radicals.

Step 4: Secondary free radical (I) is more stable than primary free radical (II). Hence the reaction proceeds
via secondary free radical (I) resulting in the formation of n-propyl bromide.

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d) Addition of sulphuric acid (H2SO4):

In according of Markovnikov’s rule alkenes readily add concentrated sulphuric acid to form alkyl hydrogen
sulphate.
Eg: 1) Ethene reacts with concentrated H2SO4 to gives ethyl hydrogen sulphate.

2) Propene reacts with concentrated H2SO4 to give iso propyl hydrogen sulphate.

e) Addition of water (Hydration of alkenes):

Alkenes react with water in presence of a few drops of concentrated H2SO4 to form alcohols. It is also
follows Markovnikov’s rule.
Eg: 1) Ethene reacts with water in presence of concentrated H2SO4 to form ethyl alcohol (ethanol).

2) Propene reacts with water in presence of concentrated H2SO4 to form propan-2-ol.

Oxidation reaction of alkenes:

• Alkene can be readily oxidized. The product of oxidation depends on the type of oxidising agent used.
• The cold and dilute alkaline KMnO4 solution is known as Baeyer’s reagent.
With cold alkaline KMnO4:
When alkenes are oxidised with cold alkaline KMnO4. Dihydroxy compounds (vicinal glycols) are formed.
The KMnO4 gets decolourised. This reaction is used as a test for unsaturation called Baeyer’s test.
Eg: 1) ethylene (ethene) reacts with cold and cold alkaline dilute KMnO4 solution at 273K to form ethylene
glycol.

2) Propene gives propane 1,2 di-ol when treated with the cold alkaline KMnO4.

Ozonolysis: (Addition of ozone)

The addition of ozone to alkene form ozonides and decomposition of ozonides with water and zinc to give
carbonyl compounds is termed ozonolysis. This reaction is useful to locate the position of the double bond
(or) other unsaturated compounds
Eg: 1) Ethene reacts with ozone to give ethene ozonide which on reductive hydrolysis gives formaldehyde
(carbonyl compound)

2) Propene reacts with ozone to give propene ozonide which on reductive hydrolysis gives acetaldehyde
& formaldehyde (carbonyl compound)

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Polymerisation reaction:
It is a process in which large number of a simple molecule combines under suitable condition to form a
polymers or large molecules or macro molecules.

(or) Polymerisation is a process by which large number of simple molecules join together to form giant
molecules called polymers. This simple molecule is called monomers. Alkenes undergo addition
polymerisation when heated under pressure, in the presence of suitable catalyst.
Eg: 1) When ethene is heated to 10000 C (no elimination of simple molecules like water, HX under 1000
atm pressure in presence of oxygen polythene is formed.

Similarly, when propene is polymerized in the presence of catalyst, it forms polypropylene.

Uses of polymers:
• Polymers are used for the manufacture of plastic bags, pipes, radio and TV etc…
• Polyethene is used in the plastic glouse, bottles etc…

ALKYNE
Alkynes are unsaturated aliphatic hydrocarbons containing carbon-carbon containing triple bond. They are
represented by general formula is CnH2n-2. Where n = 2, 3, 4……..
Some important alkynes are:

• Alkynes are also called as acetylene series because the first member of the alkyne series is acetylene
• Alkynes are more reactive than alkenes and alkanes because of the presence of two weaker 𝜋-bonds and
they readily undergo electrophilic addition reaction.

Nomenclature of alkynes:
In the common system, alkynes are named as the derivative of acetylene.
Eg: H – C ≡ C – H Acetylene
CH3 – C ≡ C – H Methyl acetylene
CH3 – C ≡ C – CH3 Dimethyl acetylene
The IUPAC nomenclature of Alkynes is similar to that of alkene, except the -ene ending is replaced with
-yne. The chain is membered from the end closest to the triple bond.
Eg: 1) HC ≡ CH ethyne 2) CH3 – C ≡ CH propyne
3) CH3 – CH2 – C ≡ CH But-1-yne 4) CH3 – CH2 – C ≡ C– CH3 pent-2-yne

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5) CH3 – CH2 – CH2 – C ≡ CH pent-1-yne

Note: Organic compounds containing both double and triple bonds are named as en-yne along with their
carbon atoms.

Isomerism: Alkyne shows two types of structural isomerism.

1) Position isomerism: due to the differ in the position of the triple bond in the carbon chain.
2) Chain isomerism: due to differ in the carbon chain
Eg: Three isomers are possible in C5H8

Structure I and II are position isomers

Structure I and III or II and III are chain isomers
Structure of triple bond (structure of acetylene):
In acetylene (ethyne), the each carbon atom undergoes sp-hybridization. The two sp hybrid orbitals are
oriented diagonally opposite to each other with resulting in the linear structure with a bond angle of 1800.
Now the each carbon atom is having two unhybridised p-orbital. Which are mutually perpendicular to each
other.

Preparation of alkynes: (preparation of Ethyne)

1) From calcium carbide
Acetylene (ethyne) is prepared by treating calcium carbide with water.
CaC2 + 2H2O → C2H2 + Ca(OH)2
Calcium carbide Acetylene
Note: Industrially, Calcium carbide is obtained by heating quickly lime with coke. Quick lime can be
obtained by heating lime stone.
CaCO3 → CaO + CO2
CaO + 3C → CaC2 + CO
2) From 1,2 dibromo ethane:
Acetylene (ethyne) is prepared by heating 1,2 dibromo ethane with alcoholic potash (or) sodamide .

Note:
Vinyl halide: Vinyl is often used to describe any alkenyl group. Alkenyl halide formula RCH = CHX.
Sometime called vinyl halides.
Physical properties:
1) They are insoluble in water.
2) They are quit soluble in the usual solvent of low polarity (Eg: C6H6, ether, CCl4)
3) They are less dense than water.
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4) Their B.P shows the usual increase with increasing carbon.

Chemical properties of alkynes: Alkynes show acidic nature
1) Addition reaction:
a) Addition of hydrogen: When alkyne is treated with hydrogen in the presence of Ni or Pt as a catalyst at
250 ͦ C to form alkane.

Eg: When ethylene is heated with hydrogen in the presence of Ni as catalyst to form ethane.

Note: When ethyne is heated with hydrogen in presence of Lindlar’s catalyst (Palladium supported over
barium sulphate), ethene is formed.

b) Addition of halogens: When alkynes are treated with halogens (chlorine or bromine) in the dark,
forming di-haloalkenes first and finally tetra-haloalkanes. This reaction get accelerated in presence of light
(or) halogen carrier.

Eg: 1) When ethyne is treated with bromine molecule to form tetra bromo ethane is formed.

2) When ethyne is treated with bromine molecule to form 1, 1, 2, 2-tetra bromo ethane is formed.

The order of reactivity of halogens is Cl2 > Br2 > I2

c) Addition of hydrogen acids (Hydro halo acid or addition of HX):
Additional information: Geminal dihalides: It means if two hydrogen atoms are replaced by halogen in a
same carbon.

When alkyne reacts with hydrogen acids according to Markovnikov’s rule to form alkane halides.

Eg: When ethyne (acetylene) reacts with hydrogen bromide (HBr) to form bromo ethene and finally 1,1
dibromo ethane.

The rate of addition of halogen acids follows the order, HI > HBr > HCl
d) Addition of hypochlorous acid (HOCl):
Alkynes react with hypochlorous acids to form di-halo aldehyde or ketones.
Eg: Acetylene reacts with hypochlorous acids to form di-chloro acetaldehyde.

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e) Addition of water:
Alkynes are immiscible and do not react with water. But when an alkyne is passed through dil.H2SO4 in
presence of mercuric sulphate (HgSO4) at 333K addition of one molecule of water taken place to form
carbonyl compound.

Eg: 1) When ethyne is passed through dil.H2SO4 in presence of HgSO4 at 333K, Ethanal is formed.

2) When propyne is passed through dil.H2SO4 in presence of HgSO4 at 333K propanone (acetone) is
formed.

f) Polymerisation:
Alkynes undergo polymerisation on heating in the presence of catalyst. The nature of products depends upon
conditions of polymerisation.
1) Cyclic polymerisation: When ethyne (acetylene) is passed through a red hot iron tube, it polymerises to
form benzene.

(or)

2) Linear polymerisation: Acetylene undergoes linear polymerisation to form poly acetylene or polyethyne
under suitable condition.

Aromatic hydrocarbons or Arenes

Organic compounds containing at least one benzene ring called aromatic hydrocarbons. They are also called
arenes or aryls. Aromatic is derived from “aroma” means fragrance.
Eg:

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Hetero cyclic aromatic compound:

Other aromatic compound:

Characteristics of aromatic compounds:

• Aromatic compound is ring structure like 1) Planner structure
2) Alternative 𝜋 bond
• Exhibit resonance, it show high resonance energy processes.
• Follows (4n+2) rule, to calculate the 𝜋 electrons. n = 0, 1, 2, 3, 4……
• Do not undergo addition reaction like alkene or alkynes.
• Not affected strong oxidizing agents like KMnO4 and K2Cr2O7
• Does not decolourise Br2/H2O.
• They undergo substitution reaction.
• They bun with sooty (soocty) flame.
Structure of benzene:
➢ The molecular formula of benzene is found to be C6H6.
➢ To explain the structure of benzene
1) Kekule structure 2) Dewar structure 3) Claus structure 4) Armstrong structure
5) Landenberg structure 6) Levine and Cole structure
Kekule structure is accepted but remaining are not accepted.

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➢ One mole of benzene on catalytic hydrogenation reacts with 3 moles of hydrogen to form cyclohexane.

➢ Under drastic condition one mole of benzene reacts with 3 moles of a chlorine to form an addition
product benzene hexa chloride [BHC]

Similarly, benzene reacts with 3 moles of ozone to form benzene triozonide

Question: What are the two reactions will confirm the presence of 𝜋 bonds?
Ans: Hydrogenation and chlorination reaction of benzene confirm the presence of 3 𝜋 bonds.
➢ To account for the above facts Friedrich August Kekule in 1865 proposed a ring structure for benzene.
He assumed the presence of alternative single and double bonds in the molecules.

Some objections to Kekule structure:

1) The benzene structure gives two types of ortho di substituted products. They are shown below:

In the above structure both 1,2 and 1,6 positions are called ortho position. But they are not identical. In
both structure C1 and C2 are connected by a single bond but C1 and C6 are connected by a double bond.
two types of ortho di substituted products should be possible. Both are not identical. Hence the Kekule
structure cannot explain the partial observation.
2) Failed to explain the reasons why benzene does not undergoes oxidative degradation with alkaline
KMnO4.
Aromaticity or aromatic character:
Benzene undergoes substitution reaction in spite of the high degree of unsaturation. This behaviour is called
as aromaticity (or) aromatic character. Aromatic character of benzene can be explained on the basis of
1) Resonance structure
2) Orbital structure
3) Huckel rule (or) (4n+2) rule
Huckel rule (or) (4n+2) rule:
This rule states that cyclic planar, conjugated systems containing a total of (4n+2) delocalised 𝜋 electrons
possess a degree of unsaturation and behaves as aromatic compounds. Where n = 0, 1, 2, 3……..
Eg: 1) Benzene has a 6 𝜋 electrons due to 3 double bonds. Hence benzene is automatic compound.

(4n+2), (4(1)+2), 4+2 = 6𝜋 electrons

2) Naphthalene 10 𝜋 electrons due to 5 double bonds. Hence benzene is automatic compound.

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(4n+2), (4(2)+2), 8+2 = 10𝜋 electrons

So, the necessary condition for a compound to attain aromaticity is,

1) The molecule must be cyclic.
2) The molecules must be planner.
3) It must have a conjugated system of (4n+2) 𝜋 electrons.
Methods of preparation of benzene:
1) From Ethyne:
When Ethyne is passed over heated iron tube at 773 K, benzene is formed.

2) From soda sodium benzoate:

When sodium benzoate is heated with the soda lime, decarboxylation take place to form benzene.

Note: The composition of NaOH + CaO is soda lime.

Role of soda lime: It keeps a reaction dry. It acts as a decarboxylating agent to removal of CO2.
3) From phenol: When phenol is a distilled with zinc dust, benzene is formed.

Physical properties:
• Benzene is a colourless and volatile liquid.
• Its boiling point is boiling point is 80°C and freezing 5.5°C. It has characteristic order.
• It is highly inflammable and burns with sooty flame.
• It is lighter than water.
• It is immiscible with water but miscible with organic solvent such as alcohol, ether
• Benzene itself it is a good solvent. Fats, resins, rubbers etc….. Dissolved in it.
• It is a nonpolar compound and its dipole moment is zero.
• Aromatic hydrocarbons are colourless and has a characteristic or pleasant odour [naphthalene]
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Chemical properties of benzene:

Benzene is quite stable and gives substitution reactions. Because of the high electron density on the ring, the
electron deficient group attacks it with easy to electrophilic substitution reactions. Some typical reactions
given by benzene are described below:
1) Electrophilic substitution reactions:
The substitution of hydrogen atom of benzene ring by an electrophile is called electrophilic substitution
reaction.
“An electrophile is an electron deficient chemical species, which can form a new bond by accepting an
electron pair. It may be either neutral (or) positively charged.
Eg: 𝑵𝑶𝟐 ⊕ - Nitronium ion (charged electrophile)
𝑩𝒓⊕ - Bromonium ion (charged electrophile)
𝑪𝒍⊕ - Chloronium ion (charged electrophile)
𝑺𝑶𝟑 ⊕ - Sulphur tri oxide (Neutral electrophile)
𝑪𝑯𝟑 ⊕ - Methyl carbocation (charged electrophile)
a) Nitration of benzene:
Benzene on heating with nitrating mixture (Conc. HNO3 and Conc. H2SO4) gives nitrobenzene. This
reaction is known as nitration of benzene.

Mechanism: It involves the following steps.

Step: 1) The formation of electrophile (𝑵𝑶𝟐 ⊕ ):
Conc. nitric acid with Conc. sulphuric acid to give the electrophile, 𝑵𝑶𝟐 ⊕ (Nitronium ion).

Step: 2) The electrophile, 𝑵𝑶𝟐 ⊕ attacks the molecule of benzene to give carbocation (earlier called a
carbonium ion)

The carbocation is stabilised by resonance and it is the resonance hybrid of the following resonance forms.

Step: 3) The carbocation loses a proton to HSO4- (bisulphate ion) to give the product nitrobenzene.

b) Halogenation of benzene:
Benzene on heating with a halogen in the presence of ferric chloride or Fe or I2 (halogen carrier) catalyst
gives helo benzene.

Eg:

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Mechanism of halogen of benzene: It is involved in the following steps.

Step: 1) The formation of an electrophile X+ (halonium ion)
The catalyst to FeCl3 combines with a molecule of halogen to give an electrophile, X+

Step: 2) The electrophile attacks the molecule of benzene to give carbocation.

The carbocation is stabilized by resonance and it is the resonance hybrid of the following resonance forms.

Step: 3) The carbocation combines with FeCl3X- to give the products to halobenzene and hydrogen halide.
The catalyst FeCl3 gets regenerated.

Similarly, learn the mechanism of chlorination of benzene by replacing X2 by Cl2 and X by Cl.
c) Sulphonation of benzene:
Benzene on heating with concentrated sulphuric acid gives benzene sulphonic acid. This is called
sulphonation of benzene.

Mechanism of halogen of benzene: It is involved in the following steps.

Step: 1) The formation of an electrophile SO3
Two molecules of H2SO4 interact to give the neutral electrophile, sulphur trioxide.

Step: 2) The electrophile SO3 attacks the molecule of benzene to give carbocation.

The carbocation is stabilized by resonance and it is the resonance hybrid of the following resonance forms.

Step: 3) The carbocation combines with HSO-4 to give benzene sulphonate ion which gets protonated to
give benzene sulphonic acid.

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d) Alkylation of benzene by Friedel-Crafts reaction:

Benzene on heating with the mono haloalkane (alkyl halide) in the presence of anhydrous aluminium
chloride gives alkyl benzene. This is called Friedel – Craft Alkylation reaction.

Role of AlCl3:
• It act as a catalyst.
• It act as a halogen carrier.
• It act as a Lewis acid catalyst such as FeCl3 or AlCl3 is to form carbocation & and removal of the
halides.
Mechanism of alkylation of benzene: It involves the following steps
Step: 1) Formation of electrophile R+
The catalyst AlCl3 combines with the molecule of haloalkanes to give the electrophile R+

Step: 2) The electrophile R+ attacks the molecules of benzene to give carbocation.

The carbocation is stabilized by resonance and it is the resonance hybrid of the following resonance forms.

Step: 3) The carbocation combines with AlCl3X- to give the product alkyl benzene and hydrogen halide.
The catalyst AlCl3 is regenerated.

Conversion of benzene to toluene (methyl benzene):

Benzene reacts with methyl chloride in presence of anhydrous AlCl3 to form toluene.

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e) Acylation of benzene by Friedel-Crafts reaction:

Benzene reacts with acid chloride in presence of anhydrous aluminium chloride gives aromatic ketone.
This is called Friedel – Craft Acylation reaction.

Eg: Benzene reacts with acetyl chloride (ethnyl chloride) in presence of anhydrous aluminium
chloride to form acetophenone.

Mechanism of alkylation of benzene: It involves the following steps

Step: 1) Formation of an electrophile, CH3CO+

Step: 2) The electrophile CH3CO+ attacks the molecules of benzene to give carbocation.

The carbocation is stabilized by resonance and it is the resonance hybrid of the following resonance forms.

Step: 3) The carbocation loses a proton to AlCl4- to give the product and catalyst AlCl3 is regenerated.

2) Combustion:
When benzene is heated in air, it burns with sooty flame producing CO2 and H2O.

3) Addition of hydrogen: In the presence of finely divided nickel, under pressure, benzene undergoes
hydrogenation to give cyclohexane.

4) Addition of halogens: Benzene undergoes addition reactions with chlorine in the presence of sunlight
and gives benzene hexachloride (BHC or gammaxane or indane).

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Directive in place of a functional group in mono substituent benzene:

All six hydrogen atom in benzene are identical therefore only one type of mono substituted product is
possible.
Eg: Formation of chlorobenzene. All six hydrogen atoms are identical. Therefore chlorine atom attached to
anyone of the carbon atom.
The second substituent group is attached or replaced by hydrogen atom in ortho, para and meta directing
groups. This depends on the first substituent group. Only two possible products are possible. They are called
directing groups.
1) Ortho and para directing groups:
The group which directs the incoming group to ortho and para positions are called ortho and para directing
groups.
It usually involves saturated compounds.
Ӧ—H O—H O—H O—H :O—H :O—H
̶ ̶
≡

2) Meta directing groups:

The group which direct the incoming group to Meta position are called meta directing group. It usually
involves unsaturated compounds.
It is deactivating group further substitution is not possible.
Eg: NO2, CHO, COOH, COOR, CN etc.

Carcinogenicity and toxicity: Benzene and many of its poly nuclear compounds are toxic and A
carcinogenic (cancer producing property). This may be due to the ability of a compound to damage the
genome or disruption of cellular metabolism, finally damage DNA and cause cancer. The polynuclear
hydrocarbons are formed due to incomplete combustion of organic materials like tobacco, coal and
petroleum.
Eg:

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"ವಿದ್ಯಾ ಭ್ಯಾ ಸ ಯಾವ ದಿಕ್ಕಿ ನಲ್ಲಿ ಮನುಷ್ಾ ನನುು ನಡೆಸುವುದೋ ಅದೋ ಅವನ
ಭವಿಷ್ಾ ವನುು ನಿರ್ಧರಿಸುವುದು". - ಪ್ಲ ೇಟೇ

MURULI. R.M. [Lecturer in Chemistry]