HYDROCARBON

BY VINOD CHAUDHARI

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HYDROCARBONS The compounds which contains only carbon and hydrogen elements are
called Hydrocarbons.
HYDROCARBONS

Open chain (aliphatic) Closed chain (Cyclic)

C
|
C—C—C—C—C
|
C

Saturated Un saturated Saturated (alicyclic) Un saturated

Alkanes

Aromatic Non aromatic

Alkenes Alkynes

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 ALKANES

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Alkanes: Alkanes are aliphatic saturated hydrocarbons containing [ C—C ] single covalent
bonds.

 They are represented by the common general formula CnH2n+2 , where ‘n’ is the
number of carbon atoms.

 They are commonly also known as Paraffins

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Isomerism in alkanes:
ISOMERISM

STRUCTURAL ISOMERISM STEREO ISOMERISM

CHAIN ISOMERISM
CONFIRMATIONAL CONFIGURATIONAL
POSITION ISOMERISM

FUNCTIONAL ISOMERISM GEOMETRICAL OPTICAL

METAMERISM

TAUTOMERISM

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Chain isomerism in alkanes:
Two or more alkanes having same molecular formula but differ in the arrangement of carbon
atoms in a chain are known as chain isomers and the type is termed as chain isomerism.
Example: 1. Chain isomers of butane (C4H10)

H H H H H H H
| | | | | | |
H —C—C—C—C— H H —C—C—C— H
| |
|
H H H H
| | |
H H |
H —C—H
n-Butane |
H Isobutane (2-Methylpropane)
2. Chain isomers of pentane (C5H12)
CH3
CH3—CH2—CH2—CH2—CH3 CH3—CH—CH2—CH3 |
| CH3—C—CH3
CH3 |
n-Pentane
CH3
Isopentane
Neopentane
(2-Methylbutane)
(2,2-Dimethylpropane)

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 H H
| •
CH4 H—C—H H •C• H
| •
H
H

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Conformation in ethane:
 Alkanes have only single bonded atoms.
 Single covalent bond is formed by coaxial overlap of orbitals and is called sigma bond.
 As a direct consequence of coaxial overlap of orbitals, a sigma bond is cylindrically
symmetrical and the extent of orbital overlap is unaffected by rotation about the single
bond and therefore C—C bonds undergo rotation.
 The atoms bonded to one carbon of a C—C single bond change their relative position
with reference to the atoms on the other carbon of that bond on rotation of that C—C
bond.
 The resulting arrangements of the atoms in space about the C—C single bond are called
conformations.
 Innumerable conformations result on complete rotation of a C—C single bond through
360°
Out of infinite conformations of ethane molecule two are extreme and called staggered
and eclipsed conformation.
They are represented by Sawhorse formula and Newman projection formula.

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 https://www.chemtube3d.com/stethanenewman/

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Methods of preparation of Alkanes:
1. From Unsaturated hydrocarbons ( Alkenes and Alkynes ):

H H H H
Pt or Pd
H—C C—H + H—H H—C— C—H
or Δ Ni
Ethene H H
Ethane
Pt or Pd
CH3—CH CH2 + H—H CH3—CH2—CH3
or Δ Ni
Propene Propane
H H
Pt or Pd
H—C C—H + 2 H—H H—C— C—H
or Δ Ni
Ethyne
H H
Ethane

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 Pt or Pd
CH3—C CH + 2H—H CH3—CH2—CH3
or Δ Ni
Propyne Propane
2. From alkyl halide:
a. By reduction: Reducing agent: Zn + dilHCl Zn + 2HCl ----> ZnCl2 + 2 [H]

Δ
Zn + dil HCl
R—X + 2 [H] R—H + HX
Alkyl halide Nascent hydrogen Alkane
Example
Δ
Zn + dil HCl
1. CH3—Br + 2 [H] CH4 + HBr
Methyl bromide Methane
Δ
Zn + dil HCl
2. CH3—CH2—Cl + 2 [H] CH3—CH3 + HCl
Ethyl chloride Ethane

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b. Wurtz synthesis:
Δ
Dry ether
R—X + 2 Na + X—R R—R + 2 NaX
Alkyl sodium Alkyl Higher
halide halide alkane
Example Δ
Dry ether
1. CH3—I + 2 Na + I—CH3 CH3—CH3 + 2 NaI
Methyl iodide Ethane

Δ
Dry ether
2. CH3—CH2—Br + 2 Na + Br—CH2—CH3 2 NaBr
Ethyl bromide
+
CH3—CH2—CH2—CH3
n-Butane

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c. From Grignard reagent :
Δ
Dry ether
R—X + Mg R—Mg—X
Alkyl halide Alkyl magnesium halide
Δ
Dry ether X
R—Mg—X + H—O—H R—H + Mg
Alkane OH
Example
Δ
Dry ether
1. CH3—I + Mg CH3—Mg—I
Methyl iodide methyl magnesium iodide

Δ
Dry ether I
CH3—Mg—I + H—O—H CH4 + Mg
Methane OH

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 Δ
Dry ether
2. CH3—CH2—Br + Mg CH3—CH2—Mg—Br
Ethyl bromide Ethyl magnesium bromide
Δ
Dry ether Br
CH3—CH2—Mg—Br + H—O—H CH3—CH3 + Mg
Ethane OH
Physical Properties:
 Polarity: The electronegativity of carbon and hydrogen is nearly same. Hence C—H and C
—C bonds are non-polar covalent bonds and alkanes are thus, non-polar.
 Nature of intermolecular forces:
 Since, alkanes are non-polar molecules, the forces which hold alkanes molecules together
are the vander Waal’s forces (weak forces of attraction).
 The strength of these forces depends on the surface area of molecules, larger the surface
area of molecules, stronger are the forces.

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 Melting and boiling point:
• Alkanes have low melting or boiling points because of the very weak intermolecular forces
between alkane molecules.
• Melting and boiling point of homologous alkanes increases with increase in the (molecular
mass and size ) chain length.

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• The intermolecular forces are relatively stronger in straight chain alkanes than in branched
chain alkanes. Therefore straight chain alkanes have higher melting and boiling points than
branched chain alkanes.

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 Solubility: Alkanes are non-polar molecules hence alkanes are insoluble in water (polar
solvent) but readily soluble in non-polar solvent. (like – ether, acetone etc.).
Chemical properties of alkanes:
 Alkanes are saturated aliphatic hydrocarbons in which all the four valencies of each carbon
atom in a chain satisfied by four single covalent bonds, hence they do not undergo reaction
under normal temperature.
 Alkanes are not attacked by acids, bases, oxidising agents and reducing agents.
 Alkanes can undergo only substitution reaction under some specific conditions.
Substitution reaction of alkanes:

1. Halogenation of alkanes:
Reaction in which one or more hydrogen atoms of alkanes are replaced by one or more
halogen atoms is known as halogenation.
The order of reactivity of halogens with alkanes is F2>Cl2>Br2>I2

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 a. Chlorination of alkanes: Alkanes when treated with chlorine in presence of ultra-violet
radiation or at high temperature, hydrogen atom of alkane is
replaced by chlorine atom to form corresponding alkyl chloride.
U.V or Δ
R—H + Cl—Cl R—Cl + HCl
Alkane Alkyl chloride
Example:
1. Chlorination of methane:
U.V or Δ
CH4 + Cl—Cl CH3—Cl + HCl
Methane Chloromethane
(Methyl chloride)
U.V or Δ
CH3—Cl + Cl—Cl CH2Cl2 + HCl
Chloromethane Dichloromethane
(Methyl chloride) (Methylene di chloride)
U.V or Δ
CH2Cl2 + Cl—Cl CHCl3 + HCl
Dichloromethane Trichloromethane
(Methylene di chloride) (Chloroform)
U.V or Δ
CHCl3 + Cl—Cl CCl4 + HCl
Trichloromethane Tetrachloromethane
(Chloroform)
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 U.V or Δ
2. CH3—CH3 + Cl—Cl CH3—CH2—Cl + HCl
ethane Chloroethane
(Ethyl chloride)
1° 2° 1° U.V or Δ
3. CH3—CH2—CH3 + Cl—Cl CH3—CH2—CH2—Cl
Propane 1-Chloropropane
(minor)
+
The ease removal of hydrogen atom in alkane is
CH3—CH—CH3
|
3°> 2° > 1°
Cl
2-Chloropropane
(major)

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 b. Bromination of alkanes:
Bromination takes place in presence of ultra-violet radiation to form corresponding alkyl
bromides.
Example:
U.V or Δ
1. CH3—CH3 + Br—Br CH3—CH2—Br + HBr
ethane Bromoethane
(Ethyl bromide)
1° 2° 1° U.V or Δ
2. CH3—CH2—CH3 + Br—Br CH3—CH2—CH2—Br +
Propane 1-Bromopropane
(minor)
CH3—CH—CH3
|
Br
2-Bromopropane
(major)

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 1° 3° 1° U.V or Δ
3. CH3—CH—CH3 + Br—Br CH3—CH—CH2—Br
| |
1° CH3 CH3
2-Methylopropane 1-Bromo-2-methylopropane
+
CH3
CH3—C—CH3
|
Br
2-Bromo-2-methylopropane

1° 2° 2° 1° U.V or Δ
4. CH3—CH2—CH2—CH3 + Br—Br CH3—CH2—CH2—CH2—Br
Butane 1-Bromobutane
(minor)

+ CH3—CH—CH2—CH3
|
Br 2-Bromobutane
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Mechanism of halogenation of alkanes:
The reaction proceeds through the free radical chain mechanism.
The radical chain mechanism is characterized by three steps: 
initiation, propagation and termination.
Step 1: Initiation
The first step in the reaction is the heat- or light-induced homolytic cleavage of a molecule of
chlorine (the weakest bond in the mixture).

U.V or Δ

Chlorine free radicals

Step 2: Propagation
The next two steps in the mechanism are called propagation steps.
In the first propagation step: One of the chlorine atoms abstracts a hydrogen atom from a
methane molecule to form hydrogen chloride and methane free radical.
In the second propagation step: The methyl radical abstracts a chlorine atom from another
Cl2 molecule yielding chloromethane and a new chlorine free radical..

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Methane
Methyl free radical

Methyl chloride

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Step 3: Chain termination:
In the termination steps, all the remaining radicals combine (in all possible manners) to form
more product (CH3Cl), more reactant (Cl2) and even combinations of the two methyl radicals to
form a side product of ethane (CH3CH3).

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2. Combustion :

Alkanes on heating in the presence of air or dioxygen are completely oxidised to carbon
dioxide and water with evolution of a large amount of heat .

Δ
CH4 + 2 O2 CO2 + 2 H2O
Methane
ΔcH° = - 890 KJ mol-1

Δ
C4H10 + 13/2 O2 4 CO2 + 5 H2O
Butane
ΔcH° = - 2875.84 KJ mol-1

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3. Pyrolysos:
Alkanes on heating at higher temperature in absence of air decomposes to lower alkanes,
alkenes and hydrogen etc. This process is known as pyrolysis or cracking.

CH3—CH=CH—CH3 + H2
But-2-ene
Δ
CH3—CH2—CH2—CH3 CH3—CH=CH2 + CH4
773K
n-Butane Propene Methane
CH2=CH2 + CH3—CH3
Ethene Ethane

C6H12 + H2
Hex-3-ene
Δ
C4H8 + C2H6
C6H14 773K
But-2-ene Ethane
n-Hexane
C3H6 + C2H4 + CH4
Propene Ethene Methane

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4. Aromatisation or Reforming:

Alkanes containing six or more carbon atoms, when heated under pressure in the presence of
suitable catalysts ( V2O5, Cr2O3, Mo2O3 ) get cyclised to give aromatic hydrocarbons.
V2O5
CH3—CH2—CH2—CH2—CH2—CH3 + 4 H2
773 K / 10-20 atm
n-Hexane
Benzene
CH3
V2O5
CH3—CH2—CH2—CH2—CH2—CH2—CH3
773 K / 10-20 atm
n-Heptane

Methyl benzene
(Toulene)
+
4 H2

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Uses of Alkanes:

 First four alkanes are used as a fuel mainly for heating and cooking purpose. For
example, LPG and CNG.

 CNG, petrol, diesel are used as fuels for automobiles.

 Lower liquid alkanes are used as solvent.

 Alkane with more than 35 carbon atoms (tar) are used for road surfacing.

 Waxes are high molecular weight alkanes. They are used as lubricants. They are
also used for the preparation of candles and carbon black.

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 ALKENES

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Alkenes:
 Alkenes are unsaturated hydrocarbons containing a carbon-carbon double bond (C=C)
in their molecules.

 Alkenes have general formula CnH2n, where n = 2,3,4 ...

 Alkenes are also known as olefins.

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 Structure of alkene:
In alkenes, two carbon atoms in the parent chain are bonded through a double bond.
In alkenes, the doubly bonded carbon atoms undergo sp2 hybridisation. Ethene (C 2H4) is the
simplest alkene. Its structural formula is:

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Isomerism in alkenes:
Alkenes show three types of isomerism:
(a) Chain isomerism (b) Position isomerism (c) Geometrical isomerism
Chain isomerism:
Two or more alkenes having same molecular formula but differ in the arrangement of
carbon atoms in the chain are called chain isomers.
Example: 1. Chain isomers of butene (C4H8)

CH3—CH2—CH=CH2 CH3—C=CH2
But-1-ene
CH3 2-Methylpropene
2. Chain isomers of pentene (C5H10)

CH3—CH2—CH2—CH=CH2 CH3—CH—CH=CH2
Pent-1-ene 3-Methylbut-1-ene
CH3
CH3—CH2—C=CH2
2-Methylbut-1-ene
CH3
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Position isomerism:
Two or more alkenes having same molecular formula, same arrangement of carbon atoms in
the chain but differ in the position of double bond in chain are known as position isomers.
Example: 1. Position isomers of butene (C4H8)

CH3—CH2—CH=CH2 CH3—CH=CH—CH3
But-1-ene But-2-ene

2. Position isomers of pentene (C5H10)

CH3—CH2—CH2—CH=CH2 CH3—CH2—CH=CH—CH3
Pent-1-ene Pent-2-ene

3. Position isomers of Hexene (C6H12)

CH3—CH2—CH2—CH2—CH=CH2 CH3—CH2—CH2—CH=CH—CH3
Hex-1-ene Hex-2-ene
CH3—CH2—CH=CH—CH2—CH2
Hex-3-ene
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Geometry Isomerism
Alkenes having same molecular formula, same structural
formula but differ in the spatial arrangement of the
groups about a carbon – carbon double bond are called
geometrical isomers and the phenomenon is known as
geometrical isomerism.
This type of isomerism is also known as cis – trans isomerism

X Y X Y
C C
|| ||
C C
X Y Y X
cis-isomer trans-isomer

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Example: 1. Geometrical isomers of But-2-ene (C4H8)
CH3—CH=CH—CH3
H3C H H3C H
C C
|| ||
C C
H3C H H CH3
cis-But-2-ene trans-But-2-ene
2. Geometrical isomers of Hex-3-ene (C6H12) CH3—CH2—CH=CH—CH2—CH3
H5C2 H H5C2 H
C C
|| ||
C C
H5C2 H H C2H5
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Alkenes with general formula RCH=CHR, R1R2C=CR2R1, R1CH=CR1R2, R1CH=CR2R3, R1CH=CHR2 and
R1R2C=CR3R4 exhibit cis-trans isomerism

Preparation of Alkenes:
(I) Elimination reactions (1,2-elimination):
The reaction in which two atoms or groups are eliminated or removed from adjacent carbon
atoms are called 1,2-elimination reactions
Sp3 hybridized Sp2 hybridized

| | | |
—C —C— 1,2-elimination —C = C—
| | -XY Alkene
X Y

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i) Dehydrohalogenation of alkyl halides:
Alkyl halides when heated with alcoholic solution of alkali (NaOH or KOH), halide atom from
σ carbon and hydrogen from β carbon atom are eliminated to form corresponding alkenes.
|β | | |
α
—C—C— + KOH Δ KCl + H2O + —C = C—
alc
| | Alkene
H X
Alkyl halide
Example:
H H
β α Δ
1. H—C—C—H + KOH KCl + H2O + H2C=CH2
alc
Ethene
H Cl
Bromoethane
(Ethyl bromide)

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 H H H
α
2. β β Δ
H3C—C—C—C—H + KOH
alc
KCl + H2O +

H Cl
2-ChloroButane
H3C—CH=CH—CH3 + H3C—CH2—CH=CH2
But-2-ene But-1-ene

The ease of dehydrohalogenation

of alkyl halides accordingly is in
Saytzeff rule: In dehydrohaloge
the order 3° > 2° > 1°
the preferred product is the alke
has the greater number of alkyl
attached to doubly bonded ca
atoms.

The ease of formation of alkenes:

R2C=CR2 > R2C=CHR > R2C=CH2 ,
RCH=CHR > RCH=CH2
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2. Dehydration of alcohols:
Alcohols on heating with sulphuric acid form alkenes with elimination of water molecule.
The reaction is known as catalyzed dehydration of alcohols.

|β |α Δ
—C—C— H2O + H2C=CH2
| | Conc. H2SO4
Alkene
H OH The ease of dehydratio
Alcohol alcohols is in the order 3°
Example:
H H
β α Δ
1. H—C—C—H H2O + H2C=CH2
Ethene
H OH
Ethanol
(Ethyl alcohol)

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2. H H
Δ H2O + H3C—CH2—CH=CH2
H3C—CH2—C—C—H
But-1-ene
H OH
Butan-1-ol

H H H
α
3. β β Δ H3C—CH=CH—CH3
H3C—C—C—C—H H2O + But-2-ene
+
H OH H3C—CH2—CH=CH2
Butan-2-ol But-1-ene

H CH3 H CH3
4. β α β Δ
H—C—C—C—H H2O + H3C—C=CH2
H OH H 2-Methylpropene
2-Methylpropan-2-ol
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3. By dehalogenation of vicinaldihalides Geminal Dihalides
Vicinal dihalides when heated with metal zinc, two halogen atoms from adjacent carbon
attached to the sam
atoms are eliminated to form corresponding alkenes.
Dihalides are the
compounds having two
halogen atoms in their
molecules
| | | | Vicinal Dihalides
—C—C— + Zn Δ ZnX2 + attached to two adja
—C = C—
| | Alkene
X X —
Vicinal dihalide
Example:
H H
β α Δ
1. H—C—C—H + Zn ZnBr2 + H2C=CH2
Ethene
Br Br
1,2-Dibromoethane
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 H H
2. α α Δ
H3C—C—C—H + Zn ZnBr2 + H3C—CH=CH2
Ethene
Br Br
1,2-Dibromopropane
II. Addition reaction:
The Alkynes can be partially reduced to alkenes with calculated quantity of dihydrogen in
presence of Lindlar’s catalyst ( palladised charcoal deactivated partially with quinoline)
Pd-C R R
R—C C—R C=C
quinoline
Alkyne H H
cis-Alkene
Na R H
R—C C—R C=C
liq NH3
Alkyne H R
trans-Alkene
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