MODULE 2B
ALKENES
By the end of this module, you should be Key words
able to:
Addition reaction
Discuss the occurrence, synthesis, physical
properties and chemical properties of Electrophile
alkenes. Dehydration
Discuss the uses of alkenes.
Dehydrohalogenation
Ozonolysis
Oxidation
Introduction
Alkenes are a homologous series of hydrocarbons that contain a carbon-
carbon double bond. The number of hydrogen atoms in an alkene is double
the number of carbon atoms, so they have the general formula .
For example, the molecular formula of ethene is , while for propene it
is .
Below, are the names and structures of the first four alkenes:
Alkene Molecular formula Structural formula
Ethene
Propene
n-Butene
But-2-ene
Preparation of alkenes
Alkenes can be synthesized using different methods. Some of the methods
are indicated below:
1. Cracking of alkanes
You have already learnt that alkanes can be cracked to obtain shorter chain
alkanes which are useful as fuels. One of the products of cracking alkanes
are alkenes.
Hence cracking alkanes is one way of producing alkenes.
2. Dehydrohalogenation of alkyl halides
When alkyl halides are heated with concentrated sodium hydroxide in
ethanol as a solvent, alkenes are formed. The process is called
dehydrohalogenation.
3. Dehydration of alcohols
When alcohols are heated with concentrated Sulphuric acid at about 180 0C,
alkenes are formed.
4. Hydrogenation of alkynes
When hydrogen is passed over an alkyne vapour in presence of Lindlar’s
catalyst, alkenes are formed.
Physical properties of alkenes
Like alkanes, alkenes are non-polar compounds which are purely covalent.
Therefore, their physical properties are similar to those of alkanes of
comparable chain length.
a. Colour and smell
Most alkenes are colorless and odorless. However, ethene has a sweet
smell.
b. Solubility
Alkenes are insoluble in polar solvents such as water because they are
poorly covalent compounds. However, they are soluble in organic solvents
such as benzene, ether and acetone.
c. Melting and boiling points
Generally, the melting and boiling points of alkenes is low. Being purely
covalent, the main forces of attraction in the molecules are Vander Waals
forces. The forces are weak hence the low values of melting and boiling
points.
d. Physical states
Alkanes from C1to C4 are gases at room temperature. The next fourteen
alkenes are liquids while higher alkenes are solids at room temperature.
Chemical properties of alkenes
Alkenes are generally more reactive than alkanes because of the presence of a double bond. One of the
two bonds in alkenes is a weak pi bond and the electrons can easily be involved in bonding.
Electrophiles and nucleophiles
An electrophile is an atom, group of atoms or bond that is electron
seeking and has a positive charge or a partial positively charged part.
Example is H+
A nucleophile is an atom, group of atoms or bond with a negatively
charged centre that is able to donate electrons to another chemical
species.
An electrophilic addition reaction is a reaction in which a substrate is
initially attacked by an electrophile, and the overall result is the addition
of one or more relatively simple molecules across a multiple bond.
Most of the reactions of alkenes are electrophilic addition reactions.
1. Addition of hydrogen
Addition of hydrogen to a carbon-carbon double bond is
called hydrogenation. The overall effect of such an addition is the reductive
removal of the double bond. Alkenes react with hydrogen in the presence of
a catalyst to produce alkanes.
2. Addition of hydrogen halides
The mechanism for the addition of hydrogen halide to propene shown in the
reading is quite detailed. Normally, an organic chemist would write this
mechanism as follows:
However, the more detailed mechanism shown in the reading does allow you
to see the exact fate of all the electrons involved in the reaction.
In your previous chemistry course, you were probably taught the importance
of balancing chemical equations. It may come as a surprise to you that
organic chemists usually do not balance their equations, and often represent
reactions using a format which is quite different from the carefully written,
balanced equations that you studied. What is actually needed in organic
reaction is the main organic product and the mechanism of how it is formed.
All alkenes undergo addition reactions with the hydrogen halides. A
hydrogen atom joins to one of the carbon atoms originally in the double
bond, and a halogen atom to the other.
For example, with ethene and hydrogen chloride, you get chloroethane:
With but-2-ene you get 2-chlorobutane:
The addition of hydrogen halides is one of the easiest electrophilic addition
reactions because it uses the simplest electrophile: the proton. Hydrogen
halides have two ends where the hydrogen side acts as an electrophile and
the halide atom which acts as a nucleophile. First, the electrophile will attack
the double bond and take up a set of π electrons, attaching it to the
molecule. The resulting molecule will have a single carbon- carbon bond with
a positive charge on one of them. A chemical species with a positively
charged carbon atom is called a carbocation or carbonium ion. The next step
is when the nucleophile (halide) bonds to the carbocation, producing a new
molecule with both the original hydrogen and halide attached to the organic
reactant.
Mechanism of Electrophilic Addition of Hydrogen Halide to Ethene
Mechanism of Electrophilic Addition of Hydrogen Halide to an unsymmetrical
alkene such as Propene
All of the halides (HBr, HCl, HI, HF) can participate in this reaction and add on
in the same manner. Although different halides do have different rates of
reaction, due to the H-X bond getting weaker as X gets larger.
3. Addition of water
Alkenes react with water in the presence of mineral acids to form alcohols in
accordance with the Markonikov's rule. Since a molecule of water is added in
this reaction, this reaction is termed as hydration of alkenes.
4. Oxidation of Alkenes
(i) Alkenes are readily oxidised by cold, dilute, aqueous solution of potassium
permanganate to give compounds called diols.
(ii) Acidic potassium permanganate or acidic potassium dichromate (K 2Cr2O7) are
used to oxidise alkenes to ketones and/or carboxylic acids depending upon the
nature of alkene.
5. Ozonolysis of Alkenes
Ozonolysis of alkenes involves the addition of an ozone molecule (O 3) to alkene
to form ozonide which are reduced with zinc dust and water to give smaller
molecules.
SHAPE \* MERGEFORMAT
Ozonolysis is highly useful in detecting the position of the double bond in
alkenes because two different alkenes always give different products.
6. Polymerisation of Alkenes
In polymerisation, a large number of simple molecules, known as monomers,
combine to form a big molecule which is known as polymer. For example:
Ethene on heating to 473 K under a pressure of 1500 atm and in the presence of
a trace of oxygen gives a low-density polythene.
The polymers made artificially in this manner are called plastics. Plastics are
very important and useful materials in everyday life.
Uses of alkenes
1. Manufacture of plastics
Alkenes are very important compounds. They are starting materials for the
production of important materials called plastics. Plastics are produced
through the process of addition polymerization across the double bond.
2. Manufacture of ethanol
Ethanol is traditionally produced by the process of fermentation. However, ethanol
can also be manufactured on large scale by hydrolysis of alkenes in acid medium.
Ethanol produced in this way is used as methylated spirit, a solvent, running
automobiles among other uses.
3. Lower alkenes can be used as fuels and illuminants
4. Ethene is commonly used as a ripening agent for fruits.
5. Alkenes can be used as starting materials for many important organic
products such as alcohols, alkyl halides carbonyl compounds, organic acids
and esters.