Module 1:

2.4 Describe selected chemical reactions of alkenes

2.5 Explain the steps involved in the mechanism of selected chemical reactions of alkene
functional group

Alkene

Alkenes have the general formula CnH2n .Their functional group is the carbon-carbon double
bond (-C=C-). The double bond is composed of a pi(p) and sigma (s) bond . Molecules with p
and bonds are said to be saturated.

Comparing Alkenes and Alkanes

The difference between alkenes and alkanes is that alkenes have a carbon- carbon double bond
and alkanes only have single bonds.

The bond energy of a C-C is 347kJmol-1 and C=C is 612 kJmol-1.So looking at the bond
dissociation energy we would expect alkenes to be less reactive than alkanes. This is not so for
three reasons:

1. First, a double bond consists of a p and a s bond.

The s bond is the same as in C-C (single) bond of the alkanes ( bond energy 347kJmol-1).
Since the energy value for the double bond is for the combination of pi and sigma bond,
hence the p bond must have energy of 612 - 347= 265 kJ mol-1.

Thus p bond part of the carbon -carbon double bond has less energy than the s bond
part and is relatively easy to break.

It is the pi bond of the double bond for alkenes that is broken (s bond remains intact)
which requires less energy than breaking the sigma bond of alkanes. Thus reason alkenes
are more reactive.
.
2. Second, the C=C forms an electron-rich area in the molecule, which can be easily
attacked by positively charged reagents called electrophiles
a. Electrophiles are ions or molecules (positively charged) which are electron deficient
or have an electron-deficient atom

b. Electron- deficiency in atoms is indicated by d+

c. Examples of electron deficient ions:

 Ions: H+ NO2+

d. Electrophilic molecules

Halogen molecules

Brd- - Brd+
Positively charged end

Hydrogen halides

Hd+ - Id-
Positively charged end

3. Thirdly, if the p part of the double bond is broken, each of the carbon atom is left
capable of forming a new bond.

 This allows addition reactions to take place (atoms added). The atoms become
attached to the freed electron of the carbon atoms.

 ‘On the other hand in alkanes atoms are forced to be removed so a new atom can
become attached. (substitution)’
 Reactions of Alkene
Reactions of alkenes with

o Liquid bromine (Br(l)) or Aqueous bromine (Br(aq))

o Hot and cold acidified KMnO4(aq)
o Concentrated H2SO4
o Hydrogen halides
o Hydrogenation of fats (C=C) to produce trans fats which are harmful

Reaction with Bromine molecule

The reaction of bromine with an alkene is an halogenations reaction. Unlike the reaction of
alkanes with halogens, halogenation of alkenes does not require ultraviolet (UV) light.

The reaction of bromine (halogen) with an alkene produces a dihalogeno alkane

 For example:

H H H H
H- C = C -H + Br2 H-C=C-H

Br Br

Mechanism

 The alkenes have a region of high electron density caused by the  electrons in its double
bond. The halogen molecule is non-polar but as it approaches the alkene it acquires a
temporary dipole.
Think, the halogen
molecule becomes
H H H H temporary polar
on approaching
H- C = C -H theH- C=C
alkene. -H
Why?
Br - Br Brα+

Br α-

The + end of the dipole is attracted to the electron rich  bond of the alkene
  The  bond attracts the Br and repels the electrons shared by the two bromine atoms,
thus strenghtening the dipole

 Finally the two electrons from the  bond form a bond with the Br and the electrons
shared by the bromine atoms are repelled away with the Br to form a Br ions. This
leaves a positively charged species called a carbocation. The carbocation is unstable and
is attacked by the negative Br - ions, forming the dihalogeno alkane

The mechanism is electrophilic addition because the Br2 is acting as an electrophile when
attracted to the electron rich double bond. The reaction occurs in two steps:
1. Formation of the carbocation, followed by

2. Rapid reaction with a negative ion.

Reaction with Hydrogen halides

Alkenes react with hydrogen halides (HCl, HBr, HI) to form a halogenoalkane. For example :
Ethene and hydrogen bromide.
For the reaction cold concentrated aqueous hydrogen bromide is used. The reaction is also
electrophilic addition and the mechanism is similar to when halogens react with alkenes. The
difference is that the hydrogen halide forms a permanent dipole.

Mechanism

Intermediate carbocation

Markovinikov’s rule
An alkene with two carbon atoms reacting with a hydrogen halide only one product is produced.
When ethene reacts with HBr the only product formed is: 1-bromoethane as shown above.
When an alkene with three (3) or more carbons in the chain reacts with a hydrogen halide, more
than one products is formed. For example, when propene reacts with hydrogen bromide, it is
possible for two products to be formed: 1-bromoethane and 2-bromoethane.

The products are almost entirely 2-bromopropane. This is due to what is known as
Markovnikov’s rule.
The rule states that when hydrogen halides add to alkenes the hydrogen adds onto the
carbon atom that already has the most hydrogen atoms.
The reason for this is due to the stability of the intermediate carbocation. Two possible
carbocation formed:
 REM. The Carbocations are formed
after the hydrogen of the
hydrogen halide is attached

The first carbocation is more stable because the positive charge on the carbon is stabilized
by two methyl (CH3-) group pushing electrons towards it while
Hence this carbocation is favoured which leads to the 2-bromopropane being formed as the
major product.
All akyl groups have the tendency to release or push electrons towards any carbon atom to
which it is attached. This is called the positive inductive effect while the negative inductive
effect is when electrons are pulled away from the carbon atom by atoms bonded to it.

Reaction of Alkenes with Acidified KMnO4

Reaction with cold acidified KMnO4

Alkenes react with cold acidified potassium manganate (VII) to produce a diol. A diol is an
organic compound with two alcohol (-OH) or hydroxide groups
The reaction is an oxidation reaction (addition of oxygen) and the purple potassium manganate
(VII) is reduced to brown precipitate of manganese(iv) oxide
This reaction is also used as an alternative to bromine water to test for double bonds.
For Example: Ethene and cold acidified KMnO4
Reaction with hot acidified KMnO4

When alkenes react with hot acidified potassium permanganate the double bond of the alkene
is cleaved (broken). Different products can be produced from the cleavage depending on the
alkene molecule Products such as:

 carbon dioxide
 organic acids (salt of the organic acid) or
 Ketones
For example:

jj

Reaction with concentrated Sulphuric acid

Concentrated sulphuric acid(cold) also adds on across the double bond. The reaction is
exothermic and occurs at room temperature. The reaction is

When water is added to the product an alcohol is formed and the sulphuric acid regenerated.
This reaction is called hydrolysis. Hydrolysis means using water to break covalent bonds.

The overall reaction is

This is a two step reaction:

 Reaction with cold concentrated H2SO4

 Then warm and add water.

It is a useful way of converting alkenes to alcohols in the laboratory

Markovinikov’s rule also applies in the reaction of sulphuric acid with an alkene. The hydrogen
bonds to the carbon which already has the most hydrogen attached.

So:

Reaction with hydrogen

The reaction of alkenes with hydrogen is called hydrogenation . The reaction can be carried out
at 140oC using highly porous nickel catalyst called Raney nickel.
Industrially the hydrogenation reaction is used to produce margarines. Vegetable oils such as
palm oils are compounds that consist of esters of long-chain carboxylic acids which contain
double bonds (unsaturated). They are converted to margarines (‘hardened’) by reducing the
number of double bonds (hydrogenation),which means the compounds are saturated. The
reaction is carried out under controlled conditions so the margarine can be made soft or hard as
required.

There is medical evidence to show that saturated fats (those containing few double bonds) are
dangerous to health.

• Monosaturated fats: contains one double bond

• Polysaturated fats: contains two or more double bonds.

The double bonds in the unsaturated fats and oils tend to have the groups around them arranged
in the ‘cis’ form. The relatively high temperatures used in the hydrogenation process tend to
flip some of the C-C double bonds into the trans form.

If these particular bonds are not hydrogenated in the process they will still be present in the final
product as trans fats. The consumption of the trans fat has been shown to increase cholesterol
levels (particularly the more harmful LDL form). They are thought to contribute to and increase
the risk of heart and circulatory disease.