THE CHEMISTRY

OF ALKENES
 THE STRUCTURE OF ALKENES

General are members of a homologous series

hydrocarbons - contain only C and H
general formula is CnH2n - for non-cyclic alkenes
unsaturated - atoms can be added to their formula
contain a C=C double bond somewhere in their structure
 THE STRUCTURE OF ALKENES

General are members of a homologous series

hydrocarbons - contain only C and H
general formula is CnH2n - for non-cyclic alkenes
unsaturated - atoms can be added to their formula
contain a C=C double bond somewhere in their structure
Structure spacial arrangement around the C=C is planar
the bond angles are 120°
 HYBRIDISATION OF ORBITALS

2p
The electronic configuration of a 2
carbon atom is 1s22s22p2 2s

1 1s

If you provide a bit of energy you 2p

2
can promote (lift) one of the s 2s
electrons into a p orbital. The
configuration is now 1s22s12p3
1 1s

The process is favourable because the of arrangement of

electrons; four unpaired and with less repulsion is more stable
 HYBRIDISATION OF ORBITALS - ALKENES
Alternatively, only three orbitals (an s and two p’s) combine or
HYBRIDISE to give three new orbitals. All three orbitals are
equivalent. The remaining 2p orbital is unchanged.
2s22p2 2s12p3 3 x sp2 2p

In ALKENES, the three

sp2 orbitals repel each
other into a planar
arrangement and the 2p
orbital lies at right angles
to them
 THE STRUCTURE OF ALKENES

Covalent bonds are formed An sp2 orbital from each carbon

by overlap of orbitals. overlaps to form a single C-C bond.

The resulting bond is called

a SIGMA (δ) bond.
 THE STRUCTURE OF ALKENES

The two 2p orbitals also overlap to form a second bond. This is

known as a PI (π) bond.

For maximum overlap and hence the strongest bond, the 2p

orbitals are in line.

This gives rise to the planar arrangement around C=C bonds.

 ORBITAL OVERLAP IN ETHENE - REVIEW

two sp2 orbitals overlap to form a sigma two 2p orbitals overlap to form a pi
bond between the two carbon atoms bond between the two carbon atoms

s orbitals in hydrogen overlap with the sp2 the resulting shape is planar
orbitals in carbon to form C-H bonds with bond angles of 120º
 PHYSICAL PROPERTIES OF ALKENES

Boiling point trends are similar to those shown in alkanes

increases as they get more carbon atoms in their formula
more atoms = greater intermolecular Van der Waals’ forces
greater intermolecular force = more energy to separate molecules
greater energy required = higher boiling point
the lower members are gases at room temperature and pressure
cyclohexene C6H10 is a liquid
for isomers, greater branching = lower boiling point

C2H4 (- 104 °C) C3H6 (- 48°C) ....... C6H10 (83°C)

Melting point general increase with molecular mass

the trend is not as regular as that for boiling point.

Solubility alkenes are non-polar so are immiscible (don’t mix with) with water
miscible with most organic solvents.
 CHEMICAL PROPERTIES OF ALKENES
ELECTROPHILIC ADDITION MECHANISM

The main reaction of alkenes is addition

Because of the extra electron density in a

C=C double bond, alkenes are attacked
by species which ‘like’ electrons.

These species are called electrophiles; they

possess a positive or partial positive charge
somewhere in their structure.

Examples include... hydrogen halides

concentrated H2SO4
 CHEMICAL PROPERTIES OF ALKENES
ELECTROPHILIC ADDITION OF BROMINE
TEST FOR UNSATURATION

The addition of bromine dissolved in tetrachloromethane (CCl4) or water (known as

bromine water) is used as a test for unsaturation. If the reddish-brown colour is
removed from the bromine solution, the substance possesses a C=C bond.

A PLACE A SOLUTION OF BROMINE

IN A TEST TUBE

B ADD THE HYDROCARBON TO BE

TESTED AND SHAKE

C IF THE BROWN COLOUR

DISAPPEARS THEN THE
HYDROCARBON IS AN ALKENE

A B C

Because the bromine adds to the alkene, it no longer exists as

molecular bromine and the typical red-brown colour disappears
 Addition to unsymmetrical alkenes

When a hydrogen halide react with an unsymmetrical alkenes, there are

two possible addition products as the hydrogen atom is placed on one or
other carbon of the double bond. Thus propylene with HBr can form n-
propylbromide and isopropyl bromide. But it has been established
experimentally that isopropyl bromide is obtained predominantly.

Br
Isopropyl bromide
CH3 CH C H3
(MAJOR PRODUCT)

CH2 CH C H3 HBr
Br

CH2 C H3 N-propyl bromide

CH2
(MINOR PRODUCT)
 Markovnikov Rule
Russian chemist Markovnikov studied a number of addition reactions and
formulated an empirical rule:

In the ionic addition of an unsymmetrical reagent (H-G), the hydrogen

or positive end of the reagent becomes attached to the carbon atom
of the double bond bearing the larger number of hydrogen atom.

R H

+ H G

H H

Where, HG=
Unsymmetrical
reagent; R-alkyl
 Carbocation Stabilities

A carbocation is an ion with a positively-charged carbon atom.

 Explanation : Mechanism

The mechanism of addition reaction of halogen halides to unsymmetrical

alkenes involves the formation of carbonium ion (carbocation).

Step 1: Formation of a cyclic intermediate and Br -

Br   
H
H  

CH 2  CH  CH3  HBr  CH 2  CH  CH3  CH2  CH  CH3  Br 

Step 2 : the cyclic intermediate is capable of forming two carbonium ions,

one primary and one secondary.
 
CH3  C H  CH3
 2 carbonium ion (more stable)
H

CH2  CH  CH3

C H 2  CH 2  C H 3
1 carbonium ion (less stable)

Step 3: The more stable carbonium ion react with the nucleophile Br- to
give the isopropyl bromide , the major product.
Br

CH3  C H  CH3  Br-  CH3  C H  CH3
Isopropyl bromide
(major product)
 Modern Statement of Markovnikov’s Rule
With this understanding of the mechanism for the ionic addition of
hydrogen halides to alkenes, we can now give the following modern
statement of Markovnikov’s rule.

“In the ionic addition of an unsymmetrical reagent to a double bond,

the positive portion of the adding reagent attaches itself to a carbon
atom of the double bond so as to yield the more stable carbocation
as an intermediate”.

An Exception to Markovnikov’s Rule

This exception concerns the addition of HBr to alkenes when the addition
is carried out in the presence of peroxides (i.e., compounds with the
general formula ROOR).
When alkenes are treated with HBr in the presence of peroxides, an anti-
Markovnikov addition occurs in the sense that the hydrogen atom
becomes attached to the carbon atom with the fewer hydrogen atoms.

This anti-Markovnikov addition occurs only when HBr is used in the

presence of peroxides and does not occur significantly with HF, HCl,
and HI even when peroxides are present.