Edexcel IAL Chemistry A-level

Topic 5: Alkenes
Detailed notes

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Introduction to Alkenes

Alkenes are unsaturated hydrocarbons with at least one carbon-carbon double bond. They are
part of a homologous series with the general formula CnH2n. Cycloalkenes are a type of alkene
hydrocarbon, where the carbon atoms are arranged in a closed ring.

Structure and Reactivity

The carbon double bond is an area of high electron density making it susceptible to attack from
electrophiles (species that are attracted to ∂-areas). It consists of a normal covalent σ bond and a
π bond.

Example:

Test for Alkenes

Bromine water is used to identify an alkene double bond and other unsaturated compounds.
Alkenes cause bromine water to change colour from orange-brown to colourless. This is
because the C=C bond can ‘open up’ to accept bromine atoms, and thus become saturated.

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Geometric isomerism

Stereoisomers
These have a different spatial arrangement. A type of stereoisomerism is E-Z isomerism, where
limited rotation around a double carbon bond means that functional groups can either be
‘together’ or ‘apart’. The E isomer (german for entgegen meaning apart) has functional groups on
opposite sides. The Z isomer (german for zusammen meaning together) has functional groups
together on the same side of the double bond.

Example:

Cahn-Ingold-Prelog (CIP) Priority Rules

There is a priority of different groups in molecules that can display E-Z isomerism. The first atom
which is directly bonded to the carbon with the double bond with the higher Ar is given the higher
priority. These groups are used to determine if it is the E or Z isomer.

Example:

Therefore this molecule is the Z isomer as the highest priority

atoms are on the same side.

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How to determine a more complicated E/Z isomers

Compound A

● Step 1: Apply the CIP priority rules

○ Look at R1 and R3:
■ Carbon is the first atom attached to the C=C bond, on the left hand side
○ Look at R2 and R4:
■ Carbon is the first atom attached to the C=C bond, on the right hand side
○ This means that we cannot deduce if compound A is an E or Z isomer by applying
the CIP priority rules to the first atom attached to the C=C bond
■ Therefore, we now have to look at the second atoms attached
■
● Step 2: Apply the CIP priority rules (using the second atoms)
○ Look again at R1 and R3:
■ The second atoms attached to R1 are hydrogens and bromine
■ The second atoms attached to R3 are hydrogens and another carbon
■ We can ignore the hydrogens as both R groups have hydrogens
■ Bromine has a higher atomic number than carbon, so bromine is the
higher priority
■ Therefore, the CH2Br group has priority over the CH3CH2 group
○ Look again at R2 and R4:
■ The second atoms attached to R2 are hydrogens and chlorine
■ The second atoms attached to R4 are hydrogens
■ Chlorine has a higher atomic number than hydrogen, so chlorine is the
higher priority
■ Therefore, the CH2Cl group has priority over the CH3 group
■
● Step 3: Deduce E or Z
○ In compound A, the two highest priority groups are on the same side (both above)
the C=C bond
■ Therefore, compound A is the Z isomer

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Cis- and Trans- isomers
Stereoisomers can be named in the same process as above, but instead using Cis- for when the
groups are on the same side and trans- for when they are different sides. Cis- and trans- differs
from E/Z isomerism in that cis- and trans- can only be used when there are hydrogen atoms to
compare the two other groups to. When there are more groups present, you have to assign E/Z
isomerism by using the Cahn-Ingold-Prelog (CIP) priority rules described above.

Reactions of alkenes

The carbon-carbon double bond in alkenes makes them reactive. During their reactions, the
double bond opens up to form single bonds to other atoms.

Alkanes
Alkenes can undergo electrophilic addition with hydrogen to produce alkanes. The C=C bond
opens up and forms single bonds to each of the hydrogen atoms. This reaction requires a nickel
catalyst.

Example:

Halogenaoalkanes
Halogenoalkanes are organic compounds with single carbon bonds only and halogen functional
groups. Alkenes undergo addition reactions with halogens to form di-substituted
halogenoalkanes, and with hydrogen halides to form mono-substituted halogenoalkanes. The
mechanism for this reaction is given on the following page of these notes.

Alcohols
Alcohols are organic compounds with a hydroxyl functional group. Alkenes undergo addition
reactions with steam to form alcohols. This reaction requires an acid catalyst, such as phosphoric
acid.

Example:
CH2CH2 + H2O → CH3CH2OH

Diols, alcohols with two hydroxyl functional groups, can also be formed from alkenes through an
oxidation reaction. The double bond is oxidised by acidified potassium manganate(VII)
(KMnO4). The manganate ions must be cold, dilute and acidified.

Example:
CH2CH2 + H2O + [O] → CH2(OH)CH2(OH)

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Electrophilic Addition

Alkenes undergo electrophilic addition about the double bond.

Electrophiles
These are electron acceptors and are attracted to areas of high electron density. Some of the
most common electrophiles are:

● HBr
● Br2
● H2SO4

Electrophilic Addition
Electrophilic addition is the reaction mechanism that shows how electrophiles attack the double
bond in alkenes. When the double bond is broken, a carbocation forms. This is a carbon atom
with only three bonds, meaning it has a positive charge.

Mechanism: Alkene + Halogen → Dihalogenoalkane

The π bond causes the bromine molecule to gain a temporary

dipole so that electrons are transferred.

Mechanism: Alkene + Hydrogen Halide → Halogenoalkane

Example: Electrophilic addition of hydrogen bromide to ethene

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Example: Electrophilic addition of hydrogen bromide to propene

Hydrogen bromide is polar due to the difference in the electronegativities of hydrogen and
bromine. The electron pair in the double bond attracts Hδ+, forming a covalent bond between
carbon and hydrogen. This produces a positively charged carbocation intermediate which
attracts the negatively charged bromide ion. The hydrogen joins to the carbon atom which is
bonded to the most hydrogen atoms. The bromide ion bonds to the carbon atom which is joined to
the most carbon atoms. This is why 2-bromopropane forms more often than 1-bromopropane in
the mechanism of propene with hydrogen bromide. Further explanation of stability is given below.

Inductive effects of alkyl groups

When a hydrogen halide bonds to an unsymmetrical alkene, there are two possible products. The
quantities of each product produced depends on the stability of the carbocation intermediate.
Carbocations with more alkyl groups are more stable. This is because alkyl groups have a
positive inductive effect on the carbon atom and feed electrons towards the positive charge. The
more stable carbocation
is more likely to form so
there will be higher
quantities of this
product. It is often
referred to as the major
product.

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Addition Polymers

Addition polymers are produced from alkenes, where the double bond is broken to form a
repeating unit. Alkenes are short chain monomers which join together to form long chain
polymers.

Example:

The repeating unit must always be shown with extended bonds through the brackets, showing
that it bonds to other repeating units on both sides.

Uses of Polymers
Polymers are unreactive hydrocarbon chains with multiple strong, non-polar covalent bonds.
This makes them useful for manufacturing many everyday plastic products such as poly(ethene)
shopping bags.

However, the unreactive nature of the bonds in addition polymers means they are not
biodegradable and cannot be broken down by species in nature.

Disposal of Polymers
Addition polymers are non-biodegradable which means disposal of them can be difficult. Waste
polymers can be processed in different ways. Some can be recycled, some are used as
feedstock for cracking and some are incinerated to produce energy for other industrial
processes. Incineration can release toxic gases which must be removed to reduce the impact on
the environment.

Scientists are developing biodegradable polymers to overcome the various disposal issues.

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