14.

2 Alkenes

Hydrocarbon
 CONTENTS

• Alkenes

• Structure of double bond

• Nomenclature

• Isomerism in alkenes

• Preparation of alkene

• Properties of alkenes

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Alkenes

• Alkenes are unsaturated hydrocarbons containing carbon-carbon double bond (C═C)in

their molecules. They have the general formula CnH2n.
• The simplest member of alkene family is ethene, C2H4
• The alkenes are also called olefins (Greek olefiant meaning oil forming) because the
larger member of the series (such as ethylene, propylene, etc. react with chlorine to form
oily products.

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Structure of double bond
• Carbon-Carbon double bond in alkenes consists of one strong sigma(σ) bond (bond
enthalpy about 397kJmol-1 due to head on overlapping of sp2 hybridised orbitals and one
weak pi bond(bond enthalpy about 284 kJmol-1)obtained by lateral or sideways
overlapping of the two 2p orbitals of the two carbon atom.
• The double bond is shorter in bond length (134pm) than the single bond (154pm).
• Alkenes are easily attacked by reagents or compounds which are in search of electron
(electrophilic reagents) because they behave as source of loosely held mobile electron.
• The presence of weaker pi bond makes alkenes unstable molecules in comparison to
alkanes and thus, alkenes can be changed into single bond compounds by combining
with the electrophilic reagents

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Structure of double bond

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Nomenclature
• According to IUPAC system alkenes are named
similar to alkanes with the following modification:
• The longest continues chain should include both
the carbon atoms of the double bond.
• The suffix used for alkene is –ene
• The chain is numbered from the end that gives the
lower number to the first carbon atom of the
double bond.
• If there are two or more double bonds the ending
ane of the alkane is replaced by adiene or atiene

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Isomerism in Alkenes

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Structural isomerism
Alkene show the following types of structural isomerism
I. Chain isomerism:
The isomer differ with respect to the chain of carbon atoms. as in alkanes, ethene (C2H4)
and propene(C3H6) can have only one structure but alkenes higher than propene have
different structures.

II. Positional isomerism

The isomers differ in the position of the double bonds

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Geometrical isomerism
• The compounds which have the same structural formula but
differ in the spatial arrangement of atoms or groups of atoms
about the double bond are called geometrical isomers and
the phenomena is known as geometrical isomerism.
• The isomers in which similar atoms or groups lie on the same
side of the double bond is called cis-isomers while the other in
which they are displaced on opposite sides, is called trans-
isomerism.
• Cis-isomer is more polar than trans-isomers
• These are distinguished on the basis of their physical
properties such as melting point, boiling point

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Preparation of alkenes

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From Alkynes
• Alkynes can be reduced to alkenes using palladium charcoal (palladised charcoal)
catalyst partially deactivated with poison like Sulphur compounds or quioline. Partially
deactivated palladised charcoal is known as Lindlar’s catalyst.
• Alkynes can also be reduced to alkenes with sodium in liquid ammonia (called Birch
reduction).

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From Alkyl Halides
• Alkene can be prepared from alkyl halides(usually bromides or iodides) by treating with
alcoholic potash(potassium hydroxide dissolved in ethanol).
• This reaction removes a molecule of HX and therefore, the reaction is called
dehydrohalogenation.
• In this reaction, the hydrogen atom is eliminated from β carbon atom (carbon atom next
to the carbon to which halogen is attached). Therefore, the reaction is also called β–
elimination reaction

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From Alkyl Halides
• Nature of halogen atom and the alkyl group determine rate of the reaction.
• It is observed that for halogens, the rate is: Iodine > Bromine > Chlorine while for alkyl
group it is Tertiary > Secondary > Primary

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From Vicinal Dihalides
Dihalogen derivatives of alkanes in which two halogens atoms are attached to adjacent
carbon atoms (called vicinal dihalogen derivatives) are converted to alkenes by heating
with zinc dust in ethyl alcohol

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From Alcohols
• Alkenes are prepared from alcohols by heating with protonic acids such as sulphuric
acid at about 443K. This reaction is called dehydration of alcohols.

• This reaction is also an example of β-elimination reaction because –OH group takes out
one hydrogen atom from the β- carbon atom.

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Properties of alkenes
Physical properties
Melting point
• In general, alkenes have higher melting point than the corresponding alkanes.
• This is due to the reason that p-electrons of a double bond are more polarizable than s-
electron of single bonds. As a result, the intermolecular force of attraction are stronger in
alkenes than alkanes.
• The melting and boiling point of alkenes in general, increase with increase in molecular
mass

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Properties of alkenes
Physical properties
Boiling point
• The boiling points of alkene show a regular gradation with the increase in number of
carbon atoms like alkanes.
• In general, for each added –CH2 group the boiling point rises by 20˚-30˚.

Dipole moments
• Alkenes are weakly polar. The p-electron of the double bond can be easily polarized.
• Therefore, their dipole moments are higher than those of alkanes. The dipole moment of
alkene depends upon the position of the groups bonded to the two double bonded
carbon atoms.

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Properties of alkenes
Dipole moments
• Alkenes are weakly polar. The p-electron of the double bond can be easily polarized.
• Therefore, their dipole moments are higher than those of alkanes. The dipole moment of
alkene depends upon the position of the groups bonded to the two double bonded carbon
atoms.
• The symmetrical trans alkenes are non-polar and hence have zero dipole moment.
• However, unsymmetrical trans-alkenes have small dipole moment because the two dipoles
opposes each other but they do not cancel out each other exactly since they are unequal.
• On the other hand, both symmetrical and asymmetrical cis-alkenes are polar and hence
have finite dipole moments.
• This is because the two dipoles of individual bonds are on the same side and hence have a
resultant dipole moment

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Properties of alkenes
Solubility
• Alkenes are lighter than water. These are insoluble in water because they are non-polar.
• However, they readily dissolve in organic solvents like alcohol, benzene, ether, carbon
tetrachloride, etc

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Properties of alkenes
Chemical properties
Addition of hydrogen
• Alkenes add up on molecule of dihydrogen gas in the presence of finally divided nickel,
palladium or platinum to form alkanes.

Addition of halogens
• Halogens like bromine or chlorine add up to alkene to form vicinal dihalides.
• The reddish orange colour of bromine solution in carbon tetrachloride is discharged
when bromine adds up to an unsaturation site.
• This reaction is used as a test for unsaturation.
• Addition of halogen to alkene is an example of electrophilic addition reaction.

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Properties of alkenes
Addition of hydrogen halides
• Hydrogen halides (HCl, HBr, HI) add up to alkenes to form alkyl halides.
• The order of reactivity of the hydrogen halides is HI>HBr>HCl.
• Like addition of halogens to alkenes, addition of hydrogen halides is also an example of
electrophilic addition reaction

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Markovnikov’s Rule
During the addition across unsymmetrical multiple bond, the negative part of the
addendum (attacking molecule)joins with the carbon atom which carries smaller number
of hydrogen atoms while the positive part goes to the carbon atom with more hydrogen
atom.

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Properties of alkenes
Addition of sulphuric acid
Cold concentrated sulphuric acid adds to alkenes in accordance with Markovnikov rule to
form alkyl hydrogen sulphate by the electrophilic addition reaction

Addition of water
In the presence of a few drops of concentrated sulphuric acid alkenes react with water to
form alcohols, in accordance with the Markovnikov rule

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Properties of alkenes
Oxidation
I. Hydroxylation
Alkenes react with cold dilute aqueous or alkaline potassium permanganate solution to
form 1,2-diols called glycols.
The glycols contain two –OH groups on adjacent carbon atoms.
This reaction of addition of two hydroxyl groups to each end of double bond is called
hydroxylation of the double bond.

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Properties of alkenes
Oxidation
II. Oxidative cleavage of alkenes
• When alkene is treated with hot acidic potassium permanganate or potassium
dichromate solution the alkene gets split up at the double bond forming carboxylic acids
or ketones.
• This is also called oxidative cleavage of alkanes.

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Properties of alkenes
Ozonolysis
• Alkenes are oxidised with ozone to form ozonides which are unstable compounds. These
• are reduced with zinc and water forming aldehydes and ketones.
• The reaction is called ozonolysis.

Polymerisation
• Polymerisation is a process in which a large number of simple (same or different)
molecules combine to form a bigger molecule of higher molecular mass.
• The small molecule are called monomers while the bigger molecule are called
macromolecules or polymers.

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