Functional Group Analysis

Alkenes

CAPE Chemistry
Unit 2 Module 1
Prepared by C. Lucero
Objectives
1) Describe selected chemical reactions of alkenes
• Alkenes (C= C) with Br2 (l), Br2(aq),
• KMnO4(aq)/H+(aq)/(hot and cold);
• conc. sulphuric acid
• Hydrogen halides.
• Include hydrogenation of fats to produce trans– fats which are harmful.
• Equations for reactions of alkenes with KMnO4(aq)/H+(aq) are not required.
2) Explain the steps involved in the mechanism of selected chemical
reactions of alkene functional group
• Electrophilic addition of bromine and hydrogen bromide to alkenes.
• Include movement of electrons; to be indicated by curved arrows and fish
hook notation.
Alkenes
• Alkenes are a family of hydrocarbons (compounds containing carbon
and hydrogen only) containing one or more carbon-carbon double
bond.
• The alkenes that contain at least one double bond form a
homologous series with the General Formula CnH2n.
• Alkenes are non-polar molecules.
• They burn with a smoky flame.
• Alkenes are more reactive than alkanes because on the presence of a
double bond.
Physical Properties bp
• The boiling point of each alkene is very similar to that of the alkane
with the same number of carbon atoms. Ethene, propene and the
various butenes are gases at room temperature. All the rest that you
are likely to come across are liquids.

• In each case, the alkene has a boiling point which is a small number of
degrees lower than the corresponding alkane. The only attractions
involved are Van der Waals dispersion forces, and these depend on
the shape of the molecule and the number of electrons it contains.
Each alkene has 2 fewer electrons than the alkane with the same
number of carbons.
Bonding in Alkenes
The double bond between the carbon atoms is, of course, two pairs of
shared electrons. What the diagram doesn't show is that the two pairs aren't
the same as each other.

One of the pairs of electrons is held on the line between the two carbon
nuclei as you would expect, but the other is held in a molecular orbital
above and below the plane of the molecule. A molecular orbital is a region
of space within the molecule where there is a high probability of finding a
particular pair of electrons

In this diagram, the line between the two carbon atoms represents a normal
bond - the pair of shared electrons lies in a molecular orbital on the line
between the two nuclei where you would expect them to be. This sort of
bond is called a sigma bond.
The other pair of electrons is found somewhere in the shaded part above
and below the plane of the molecule. This bond is called a pi bond. The
electrons in the pi bond are free to move around anywhere in this shaded
region and can move freely from one half to the other.
https://www.chemguide.co.uk/organicprops/alkenes/background.html#top
Reactions of Alkenes
Alkenes are very reactive because of the presence of the double bond.
1) Addition of Hydrogen halides
2) Addition of Halogens
3) Addition of Sulphuric acid
4) Catalytic hydrogenation
5) Oxidation
Addition of Hydrogenhalides
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.
Alkene + Hydrogen halide  halogenoalkane
e.g. Ethene + Hydrogen bromide  bromoethane
Addition of Hydrogenhalides Mechanism for Symmetrical Alkenes –
Electrophilic Addition
An electrophile is chemical species which is attracted to electron-rich regions in other
molecules or ions. Because it is attracted to a negative region, an electrophile must be
something which carries either a full positive charge, or has a slight positive charge on
it somewhere.
Ethene and the other alkenes are
attacked by electrophiles. The
electrophile is normally the slightly
positive (+) end of a molecule like
hydrogen bromide, HBr.

https://www.chemguide.co.uk/mechanisms/eladd/hbrpolar.GIF
Addition of Hydrogenhalides Mechanism

An ion in which the positive charge is

carried on a carbon atom is called
a carbocation or a carbonium ion

In the final stage of the reaction the electrons in the lone

pair on the Y- ion are strongly attracted towards the
positive carbon atom. They move towards it and form a
co-ordinate (dative covalent) bond between the Y and the
carbon.
https://www.chemguide.co.uk/mechanisms/eladd/hbrpolar.GIF
Addition of Hydrogenhalides Mechanism for Asymmetrical
Alkenes – Electrophilic Addition The difference here is the
orientation of the addition - in
other words, which way around
the hydrogen and the halogen
add across the double bond.

Markovnikov's Rule
When a compound HX is added to an
unsymmetrical alkene, the hydrogen
becomes attached to the carbon with the
most hydrogens attached to it already.

https://www.chemguide.co.uk/mechanisms/eladd/hbrpolar.GIF
Student Activity 1
1) Show the structural formulae for the main product for each of the
following addition reactions:
(a) Ethene and hydrogen chloride
(b) But-2-ene and hydrogen bromide
(c) But-1-ene and hydrogen chloride
(d) Propene and hydrogen iodide
(e) 2-methylbut-2-ene and hydrogen iodide
 • The reaction with bromine happens at room
temperature.

Halogenation of Alkenes • If you have a gaseous alkene like ethene, you can
bubble it through either pure liquid bromine or a
solution of bromine in an organic solvent like
tetrachloromethane.
Ethene and chlorine or bromine or iodine
• The reddish-brown bromine is decolourised as it
reacts with the alkene.
In each case you get an addition reaction. For example, • A liquid alkene (like cyclohexene) can be shaken
bromine adds to give 1,2-dibromoethane. with liquid bromine or its solution in
tetrachloromethane.
• Chlorine reacts faster than bromine, but the
chemistry is similar. Iodine reacts much, much
more slowly, but again the chemistry is similar.
• You are much more likely to meet the bromine case
Symmetrical than either of these.
The TRUE Mechanism
Halogenation of Alkenes with bromine water- Mechanism

Asymmetrical
Student Activity 2
2) Chlorine, bromine and iodine all react with alkenes such as ethene in
an addition reaction.
a) Write the equation for the chlorination of ethene, and name the
product.
b) Explain why this is called an addition reaction.
c) How does the vigour of the reaction change as you go from chlorine
to bromine to iodine?
Addition of Sulphuric Acid
Alkenes react with concentrated sulphuric acid in the cold to produce alkyl
hydrogensulphates. Ethene reacts to give ethyl hydrogensulphate.

The Mechanism - A hydrogen from the sulphuric acid

joins on to one of the carbon atoms, and the rest joins on
to the other one.
Hydrogenation
Ethene reacts with hydrogen in the presence of a finely divided nickel
catalyst at a temperature of about 150°C. Ethane is produced.

Some margarine is made by hydrogenating carbon-carbon double

bonds in animal or vegetable fats and oils. You can recognise the
presence of this in foods because the ingredients list will include words
showing that it contains "hydrogenated vegetable oils" or
"hydrogenated fats".
Hydrogenation

• A typical saturated fat might have the

structure:

• If there is only one carbon-carbon

double bond in each of the
hydrocarbon chains, it is called a
mono-unsaturated fat (or mono-
unsaturated oil, because it is likely to
be a liquid at room temperature.)

• If there are two or more carbon-

carbon double bonds in each chain,
then it is said to be polyunsaturated.
Preparation of Alkenes - Dehydration of
alcohols using aluminium oxide as catalyst
• The dehydration of ethanol to give ethene

• This is a simple way of making gaseous alkenes like ethene. If ethanol

vapour is passed over heated aluminium oxide powder, the ethanol is
essentially cracked to give ethene and water vapour.
Preparation of Alkenes-Dehydration of
alcohols using an acid catalyst
• The acid catalysts normally used are either concentrated sulphuric
acid or concentrated phosphoric(V) acid, H3PO4.
• Ethanol is heated with an excess of concentrated sulphuric acid at a
temperature of 170°C. The gases produced are passed through
sodium hydroxide solution to remove the carbon dioxide and sulphur
dioxide produced from side reactions.
• The ethene is collected over water.
Student Activity 3
• Draw the structures of the alkene(s) that might be produced if you
dehydrate:
• a) butan-1-ol, CH3CH2CH2CH2OH
• b) butan-2-ol, CH3CH2CH(OH)CH3
• c) pentan-3-ol, CH3CH2CH(OH)CH2CH3
Reactions of Alkenes with Cold, Dilute
KMnO4(aq)/H+(aq)

• The purple solution of KMnO4(aq)/H+(aq) turns colourless when

reacted with an alkene.
• The alkene is converted to a diol ( a compound with two OH groups).
• This reaction can be used to test if a compound is unsaturated.
H2C=CH2 + [O] + H2O  CH2OH – CH2OH
Reactions of Alkenes with Hot Concentrated
KMnO4(aq)/H+(aq)
• The C=C bond in the alkene is broken and a diol is formed.
• The diol is then immediately oxidised by the manganate(VII) to
ketones, aldehydes, carboxylic acids or carbon dioxide depending on
the type of alkene.
• A mixture of products is often formed.
Methylpropene + Hot conc KMnO4(aq)/H+(aq)  Propanone +CO2 + H2O

(CH3)2C=CH2 + 4[O]  (CH3)2C=O + CO2 + H2O

Summary
• Most of the reactions of alkenes are electrophilic addition reactions
• An electrophile is a positively charged species which attacks an area of high electron
density in a molecule.
• The double bond in alkenes is an area of high electron density.
• The major product formed when an alkene undergoes an electrophilic addition reaction
depends on the stability of the carbocation formed.
• Bromine water is used to test for presence of the C=C bonds.
• Alcohols formed when alkenes react with conc sulphuric acid and the product is then
hydrolysed with water.
• Cold dilute potassium manganate(VII) oxidises alkenes to diols.
• Hot conc potassium manganate(VII) oxidises alkenes to ketones, aldehydes, carboxylic
acids or carbon dioxide.
• The hydrogenation of fats or oils may produce trans fats which are harmful to health.