Topic 5 - Alkenes

Topic 5 - Alkenes
• General formula: CnH2n.
• Can be cyclic – see cyclohexene below – what is the general formula
for cyclic alkenes?
• Unsaturated = have a double carbon-carbon bond which consists of a
sigma bond and a pi bond).
Topic 5 - Alkenes

What is the
difference
between cis and
trans?
Topic 5 – Alkenes – Double bond

• How  bonds are formed is shown below. The diagram on the left shows parallel
p orbitals of two separate carbon atoms overlapping sideways in an ethene
molecule. Notice that there is already a sigma bond (the black line) between
both carbon atoms. The diagram on the right shows the outcome which is a 
bond.

•  bonds are formed by the sideways overlap of 2 parallel p atomic orbitals. As p

orbitals have two lobes, the  bond has two regions of overlap and high electron
density, one above and below the axis between the nuclei of both atoms.
 Topic 5 – Alkenes – Double bond

1s2 2s2 2p2

ethane
Topic 5 – Alkenes - Bonding in ethene
Topic 5 – Alkenes – Double bond
Double bond =
• Strong sigma (σ-bond) bond formed when two 2s orbitals (or one 2s and one 2p
orbital) overlap along the axis between the two nuclei of the two carbon atoms.
• Weaker  bond which is formed when two 2p orbitals overlap sideways – one 2p
from each carbon atom – above and below the axis between the two nuclei of the
two carbon atoms. The  bond is weaker as the  electrons are further away from
the nuclei of both atoms so attracted less strongly.
Topic 5 – Alkenes – Double bond
Topic 5 – Alkenes
– Double bond
 Topic 5 – Alkenes – Geometric isomerism

Structural isomerism: same atoms but in different order or sequence in the molecule. Different structural
formula

Stereo isomerism: same atoms and in the same order/sequence in molecule so the same structural formula but
different spatial arrangement
Topic 5 – Alkenes – Geometric isomerism – cis-trans

This type of stereo isomerism occurs because free rotation of a carbon-carbon bond is
prevented either because it is a double bond or because the carbon-carbon bond is
part of a ring structure; this means that both are chemically different compounds!

Free rotation is impossible as there are two regions of overlap within the  bond;
above and below the axis between both nuclei; rotation would cause the overlapping
orbitals to separate and therefore break the bond.

As a result cis-trans isomerism happens in alkenes in which there are 2 different atoms
(or groups of atoms) on each carbon atom on either side of the double bond. The 
bond prevents the C=C from rotating and changing the position of the atoms on either
side.

.
Topic 5 – Alkenes – Geometric isomerism – cis-
trans
Two possible isomers:

 cis: two identical atoms of groups of atoms (substituents or R) are on the same side of
the double bond or on the same side of the reference plane passing through the double
bond – the plane is perpendicular to all the sigma bonds between the atoms and the
substituents or perpendicular to the trigonal plane of the molecule.

 trans: two identical groups on opposite side of the reference plane passing through the
double bond.
Topic 5 – Alkenes – Geometric isomerism – cis-trans

Draw cis and trans isomers for 1,2-

dibromoethene
Topic 5 – Alkenes – Geometric isomerism – cis-
trans
Draw cis and trans isomers for 1,2-
dibromoethene
Topic 5 – Alkenes – Geometric isomerism – cis-
trans
Topic 5 – Alkenes – Geometric isomerism – cis-trans

Cis-trans isomerism can be recognised by looking for:

 a double bond with two different atoms/groups joined to the atoms at either end of
the double bond; but both sets of different groups on either side of the double are
the same.

We only use the cis-trans convention of naming if the different atoms on each carbon
on either side of the double bond are the same.

If both sets of different atoms are not the same than we use a different convention
called the E/Z nomenclature and refer to the isomers as E/Z isomers.
Topic 5 – Alkenes – Geometric isomerism – E/Z

E/Z notation is a different set of rules used to describe a double-bond arrangement of 3 or 4

different atoms or groups of atoms around a double bond.

The E/Z convention involves ranking (giving it a relative priority) the R1 and R2 on the first
carbon atom around the double bond and ranking R3 and R4 on the second atom. The
ranking is done using the Cahn-Ingold-Prelog system (CIP) of assigning priority to the
substituent groups which uses the atomic number of the R groups.
Topic 5 – Alkenes – Geometric isomerism – E/Z
Rule 1: Look at the atom (or atom in the substituent group) bonded to the carbon of the
double bond. The atom with the higher atomic number has the higher priority.
Rule 2: If the atoms are the same, for example if they are both carbon atoms, apply the
same rule to the next bonded atom. This means that longer hydrocarbon chains have
higher priority.

When the two groups or substituents (R) with the highest precedence (importance) are on
the same side of the reference plane passing through the double bond the molecule is
referred to as the Z isomers (zusammen in German)(equivalent/same to cis).

If the highest groups with the highest priority are on the opposite side of the reference
plane the molecule is an E isomer (equivalent to trans).
Topic 5 – Alkenes – Geometric isomerism – E/Z
Topic 5 – Alkenes – Geometric isomerism – E/Z
Topic 5 – Alkenes – Geometric isomerism – E/Z
Topic 5 – Alkenes – Geometric isomerism – E/Z
Topic 5 – Alkenes – Geometric isomerism – E/Z
Topic 5 – Alkenes – Geometric isomerism – E/Z
Topic 5 – Alkenes – Geometric isomerism – E/Z

Exercise: Draw the isomers

1. (E)-1-bromo-2-chloroethene and (Z)-1-bromo-2-chloroethene.

2. (E)-hept-3-ene and (Z)–hept-3-ene

Pearson Q29

Draw E/Z for oct

Topic 5 – Alkenes – Geometric isomerism – E/Z
Topic 5 – Alkenes – Geometric isomerism –
Topic 5 – Alkenes – Reactions
• As they are unsaturated alkenes are reactive. The  bond of the double bond is weaker
than a single σ-bond and is broken much easier.

• It is because of this greater reactivity that alkenes, especially ethene, are important starting
materials in organic synthesis of useful chemicals.

• It is important to note that alkenes also easily combust and undergo both complete and
incomplete combustion.
 Topic 5 – Alkenes – Addition reaction

Alkanes undergo addition reactions in which atoms from other molecules are added to
the molecule at either side of the double bond so any addition reaction increases the
number of atoms in the alkene molecule.

In an addition reaction two or more molecules are added together to form one
molecule.

During the addition reaction the double bond is converted to a single bond. The weaker
 bond of the double bond is replaced by a stronger single σ-bond ; this increases the
stability of the molecule.
 Topic 5 – Alkenes – Addition with halogen
Addition with bromine (bromination)
Occurs under normal conditions (even in the dark); the product is a colourless dihalogenoalkane.
 
Example: equations

Molecular C2H4 (g) + Br2 (l)  C2H4 Br2 (g)

Word ethene + bromine  1,2-dibromoethane (g)
Structural
 
 
 

Qualitative test for unsaturation   The bromination reaction is useful as it can be used to distinguish between an
alkane (no decolourization of bromine water occurs as it remains yellow/brown) and an alkene (bromine water which
is yellow or brown becomes colourless as 1,2-dibromoethane is a colourless compound). The amount of bromine
water which decolourizes gives an indication of the degree of unsaturation; the greater the amount of bromine
water which needs to be added before it retains its colour means the greater the degree of unsaturation; the greater
the number of double bonds.
Topic 5 – Alkenes – Addition with bromine –
Qualitative test for unsaturation
Topic 5 – Alkenes – Addition with hydrogen
Reaction with hydrogen (hydrogenation)

Does not occur under normal conditions but needs a finely divided nickel catalyst (to
break the strong H-H bonds) and some heat, 150 C – 200C, although it does also
occur at room temperature if platinum or palladium are used as catalysts.

Hydrogenation converts an alkene into an alkane.

Write symbol equation, word equation and structural equation for the reaction
between ethene and hydrogen.
Topic 5 – Alkenes – Addition with hydrogen halide

•Concentrated aqueous solutions of hydrogen halide at room

temperature; product is a halogenoalkane.
 
•Example: Write symbol, word and structural equation of reaction
between but-2- ene reacts and hydrogen chloride.
Topic 5 – Alkenes – Addition with steam
Reaction in which H and OH are introduced in the molecule: needs a strong
concentrated acid (e.g. H3PO4 or H2SO4) as catalyst, 300 C and 70 atm. The reaction is
used to make industrial ethanol.

Example: equations
Molecular C2H4 (g) + H2O (l)  C2H5 OH (l)
Word ethene + water  ethanol
Structural  
 
 
 

Other alcohols: Write symbol, word and structural equation showing the formation of
propene and steam to form propan-2-ol.
Topic 5 – Alkenes – Oxidation of double bond
• Product is a diol which is molecule with two hydroxyl groups.
• Conditions:
• Potassium manganate(VII) acts as an oxidizing agent and supplies an oxygen
atom. It also changes colour from purple to colourless.
• Dilute sulphuric acid solution
• Water provides the other oxygen and the hydrogens for the two hydroxyl
groups that will be added
• Symbol equation for the oxidation of ethene:
Topic 5 – Alkenes – Addition reactions
Topic 5 – Alkenes – Reactions
Topic 5 – Alkenes – Reactions
Topic 5 – Alkenes –
Topic 5 – Alkenes - Electrophilic addition

Reaction mechanism in electrophilic addition

 
Step 1: generation of electrophile and the formation of the carbocation
 
Because of the  electrons, the double bond in the alkene is an area of high electron density. This induces
polarisation (in a non-polar molecule e.g. a halogen molecule) or further polarisation (in a polar molecule e.g.
hydrogen halide and water) in the other reacting specie. The  electrons can do this because they are exposed
as they are above and below the axis between the two nuclei 

The cloud of  electrons then attracts the positively charged end of the halogen or hydrogen halide molecule.

This causes the polar bond in the halogen or hydrogen halide molecule break (heterolytic fission!). The
positive end of the molecule now becomes a separate positive ion called an electrophile.
The electrophile joins the alkene molecule forming a carbocation.

The  bond in the alkene is used to bond the halogen or hydrogen onto a carbon in the double bond which
makes the other carbon atom in the double bond positive as it has lost its share in the  bond. The partial
negative part of the halogen molecule becomes an anion.
Topic 5 – Alkenes - Electrophilic addition
Step 2: attack to neutralise carbocation
 
Electrostatic attraction (=ionic) between the positively charged carbon
atom or carbocation and the negative ion from the halogen or
hydrogen halide molecule results in a quick neutralisation forming the
end product.
 
Topic 5 – Alkenes - Electrophilic addition –
hydrogen bromide to ethene

Heterolytic fission
Topic 5 – Alkenes - Electrophilic addition – hydrogen
bromide to ethene (different diagram part 1)
Topic 5 – Alkenes - Electrophilic addition HBr and ethene
Topic 5 – Alkenes - Electrophilic addition –
bromine to ethene – Part 1
Topic 5 – Alkenes - Electrophilic addition –
bromine to ethene – part 2
Topic 5 – Alkenes - Electrophilic addition -
bromine to ethene.
Topic 5 – Electrophilic addition of hydrogen
bromide to an asymmetrical alkene - propene
Electrophilic addition reaction with a hydrogen halide involving unsymmetric alkene: two
products
 
When a hydrogen halide (= example of an unsymmetrical molecule) combines with an
unsymmetrical alkene, e.g. propene, two intermediate carbocations are formed, each one
giving its own halogenoalkane product (isomers). The proportion of these products is
determined by the rule explained below.
 
For instance, in the addition of a hydrogen bromide to propene there are two possible
products; one product with the bromine on the second carbon (2-bromopropane) or one
product with the bromine on the first carbon (1-bromopropane).

When such a reaction occurs we need to use Markovnikov’s rule to predict which product,
2-bromopropane or 1-bromopropane, would be the more common or major.
Topic 5 – Electrophilic addition of hydrogen
bromide to an asymmetrical alkene - propene

Markovnikov’s rule:
 
In case of the addition of a hydrogen halide (HBr) to an asymmetrical alkene, the

major product is the one in which the hydrogen of the hydrogen halide attaches

itself to the carbon carrying the larger number of hydrogen which in this case is the

2-bromopropane.
 Topic 5 – Electrophilic addition of hydrogen
bromide to an asymmetrical alkene - propene

Minor product

Which product is favoured? Major product

Topic 5 – Electrophilic addition of hydrogen
bromide to an asymmetrical alkene - propene
 Topic 5 – Electrophilic addition - Markovnikov
rule
Reason for the rule: stability of carbocation produced:
 
The reason for the rule is that during this addition reaction two carbocations are formed; the
carbocation - a secondary carbocation - which leads to the production of 2-bromopropane is
more stable than the carbocation – a primary carbocation - which leads to the production of 1-
bromopropane.

The product which is produced by the more stable carbocation is the major product which is
the product of the secondary carbocation

The stability of a carbocation depends on the number of alkyl groups. Tertiary carbocations
(e.g.(CH3)3 C+ ) are even more stable than the secondary ones (CH3)2 CH+ . CH3CH2CH2+ is the
least stable.
Topic 5 – Electrophilic - addition hydrogen
bromide + ethene - Markovnikov rule
Topic 5 - Electrophilic addition
Topic 5 - Electrophilic addition
 Topic 5 – Alkenes – Polymerization
(addition)
• Polymerization = adding together a large number of small alkene molecules
(monomers) to form a large molecule called a polymer.
• The double bond in the alkenes is used to add the molecules together.
Topic 5 – Alkenes – Polymerization
(addition)

monomer

polymer
Topic 5 – Alkenes – Polymerization (addition)
Topic 5 – Alkenes – Polymerization
(addition)
Topic 5 – Alkenes – Polymerization
(addition)
Topic 5 – Alkenes – Polymerization
(addition)
Identifying the monomer
• The diagram below is not a repeat unit. Identify the monomer and write
its formula
Topic 5 – Alkenes – Identifying the monomer
Topic 5 – Polymer disposal problems
Problems:
• Addition polymers are non-biodegradable (= cannot be broken by microbes).
• Running out of landfill sites to bury the polymer waste.
• When incinerated toxic gases can be released.

Solutions
• Remove the toxic waste gases when incinerating addition polymers.
• Produce biodegradable plastics.
Skeletal formula – Name and draw structural
formula
Task 1 Task 2