Organic Chemistry: Alkenes

Ms. C.F.Zerafa

Alkenes

• General formula for alkenes with only one

double bond in the molecule is CnH2n where n is
the number of carbon atoms in the molecule

• Has at least one double bond consisting of a

sigma and a Pi bond between two adjacent
carbons in the molecule

• Unsaturated hydrocarbons

• More reactive than alkanes

• C=C attracts electrophiles i.e. positively charged

ions or electron deficient species

• The two carbons would be hybridized sp2 with all

atoms attached those two carbons in the same
plane as the sp2 hybrid carbons

• The geometry around the two sp2 carbons is

described as "trigonal planar"

• Shapes of molecules depend on the number of

sigma bonds and lone pairs (i.e. pairs of
electrons not used in bonding)

• Angle expected to be 120° but in actual fact it is

118° cos of the extra repulsion from the pi bond

• The Pi bond created by the overlap of two "p"

atomic orbitals that are parallel to one another is

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much weaker than the sigma bond created by

the overlap between two sp2 hybrid atomic
orbitals overlapping end to end with one another

• The dissociation energy (energy required to

break a bond) of all Pi bonds are about 60
kcal/mole whereas the dissociation energy for an
sp2 sigma bond is much greater

• Therefore during many chemical reactions

involving molecules that have Pi bonds and
sigma bonds, the Pi bond breaks without
disturbing the sigma bond

• This is most fortunate in that the molecule

escapes being fragmented which at the same
time the Pi electrons are released so they might
be used to form bonds with other atoms being
added to the molecule

IUPAC Rules For Alkenes

1. Determine the longest continuous chain of

carbons that have the double bond between two
of its carbons.

• By "longest continuous chain" is meant to

be able to trace through the carbons
without raising the tracer (or finger) off the
surface

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• The chain does not necessarily have to be

straight.

2. Number the carbons in the chain so that the

double bond would be between the carbons with
the lowest designated number

• You have to decide whether to number

beginning on the right end or left end of the
chain

• If it makes no difference to the double bond

then shift attention to the branched groups

3. Identify the various branching groups attached

to this continuous chain of carbons by name

4. Name the branched groups in alphabetical order

attaching (hyphenating) the carbon number it is
attached to along the continuous chain of
carbons to the front of the branch name

• If more than one of the same kind of

branched group is attached to the chain,

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identify the number carbon each group is

attached to as a series of numbers
separated by commas between each
number then a hyphen and finally use a
greek prefix attached to the branch name

5. Attach a numerical prefix indicating the lowest

carbon number the double bond is between onto
the normal alkane name

6. Drop the "ane" ending and add the "ene" ending

associated with the Alkene family

Here is an example:
Identify the IUPAC name for the following:
CH2=CH-CH-CH-CH3
| |
CH3 Br

1. Identify the longest continuous chain of carbons

with the double bond between two of them

Here we have five carbons

2. Number the carbon chain so the double bond is

between the lowest numbered carbons

Numbering from left to right would place the

double bond between carbon #1 and carbon #2

3. Identify and locate all branched groups,

alphabetically, attaching a prefixed number

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equal to the carbon number the branch is

attached to

Here we have a methyl group attached to

the #3 carbon and a halogen attached to
the #4 carbon. Halogens are named as
branches using the following:

o -F Fluoro
o -Cl Chloro
o -Br Bromo
o -I Iodo

So we would have 4-Bromo-3-methyl

4. Attach a numerical prefix (equal to the lowest

carbon number in which the double bond is
between) to the normal alkane name
corresponding to the number of carbons that
were in the continuous chain.

5. Change the "ane" ending to "ene"

4-Bromo-3-methylpent-1-ene

Identify the IUPAC name for the following:

CH3-CH-CH2-CH-CH=CH2
| |
CH3 CH2-CH2-CH3

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Alkene Isomerism

Structural Isomerism

Alkenes three carbons or higher have cycloalkanes

as structural isomers. For example C4H8 have
three structural isomers:

cyclobutane

CH2=CH-CH2-CH3 But-1-ene

CH3-CH=CH-CH3 But-2-ene

CH2=C-CH3
|
CH3 2-methyl Propene

Geometrical Isomerism

Alkenes in which the sp2 carbons each have

different groups attached to them will have a
different isomerism which differ not in the
connectivity but how the atoms are positioned to
one another in three dimensional space

Whenever you have two molecules that have the

same molecular formula and the same
connectivity but differ in the way the atoms are
positioned to one another in 3-D space then you
have geometrical isomers also referred to as
"cis-trans" isomerism

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Since spatial orientation is the distinguishing factor

these are classified as "stereoisomers"

There are two kinds of stereoisomers, optical and

geometric

If both sp2 carbons in an alkene have different

groups attached to the sp2 carbon then we have
the potential for geometrical or cis-trans
isomerism

For example, if we consider the following

structure:
CH2=CH-CH2-CH3

 One of the sp2 carbons have identical atoms

attached to it specifically two hydrogens.
 Therefore there would be no possibility of
cis-trans isomerism here

However if we had the following:

CH3-CH=CH-CH2-CH3

The sp2 carbon on the left has a methyl and a

hydrogen attached to it, two non-identical
groups, and the sp2 carbon on the right has
a ethyl and a Hydrogen attached to it which
are also non-identical groups

This alkene will have cis-trans forms

If the methyl on the first sp2 carbon and the

ethyl on the second sp2 carbon were on

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opposite sides of the double bond then we

would have the trans isomer and we would
place the word "trans" in front of the IUPAC
name

On the other hand if the methyl group on the

first sp2 carbon and the ethyl group on the
second sp2 carbon were on the SAME side
of the double bond then we would have the
"cis" form.

The reason these are different isomers is

because of the restricted rotation around
the two sp2 carbons

Those carbons can not rotate around each

other like two sp3 carbons can because of
the "p" orbital overlap that must be
maintained to have the Pi bond

If those carbons try to rotate that will reduce

the amount of overlap between those "p"
orbitals that maintain the Pi Bond

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Since they cannot rotate the groups attached

to these two carbons remain fixed in space

This kind of stereoisomerism is also found in

cycloalkanes and cycloalkenes

The cis isomer will have significantly different

physical properties and to some extent different
chemical behavior when compared to the trans
isomer

Example 1: The cis form of 1,2-dichloroethene has

a higher boiling point than the trans form (cis =
60°C while trans = 48°C) cos’ the cis form has a
dipole moment while the trans doesn’t i.e. the
cis form is polar while the trans is non-polar

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 Therefore, the cis form would have dipole-

dipole interactions while the trans form would
have Van der Waals’ forces

Example 2: But-2-enedioic acid – the cis form on

warming loses water to form the anhydride, but
the trans form won’t cos’ in the trans

 In the trans, the double bond must be rotated

before and this requires additional energy

Example 3: Cyclohexane derivatives

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Physical Properties of Alkenes

• The boiling points and solubilities of alkenes are

very similar to the alkanes

• Both families have members that are non-polar

• Alkenes are also referred to as "olefins" - means

fat dissolving since fats are relatively non-polar
as alkenes are

Chemical Reactions Involving the Preparation of

Alkenes

1. Industrial Preparation from oil

• Products made from ethene, propene and

butene have commercial importance

• These are manufactured in large scale and

made as a product of the conversion
processes carried out during the fractional
distillation of oil particularly cracking

• Cracking: breaking up larger molecules into

smaller ones

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• Alkane vapour is passed over heated catalyst

(SiO2 and Al2O3)

2. Dehydration of alcohols (Principal Lab

Preparation)

• 3 ways to do this:

1. Alcohol vapour passed over Al2O3 heated

to a temperature of 300 - 350°C
(industrial preparation – good yields)

2. Alcohol mixed with concentrated (syrupy)

H3PO4 at 200 – 250°C

3. Alcohol is mixed with excess conc. H2SO4

and heated to about 170°C

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 Convenient way to prepare ethene

but different products form from
ethanol and sulphuric acid when the
conditions are altered

ROH + H2SO4 RHSO4 + H2O

 140°C and excess alcohol: 1 molecule

of water is taken from 2 molecules of
alcohol to give diethyl ether
C2H5OC2H5

 At moderate temperature: equimolar

proportions of alcohol and acid give
ethylhydrogensulphate

 The problem with this method is that

the sulphuric acid is also an oxidizing
agent under these conditions and
some charring of the alcohol as well
as oxidation and rearrangement of
the alkene takes place

• Dehydration of alcohols is a type of

elimination reaction i.e. removal of atoms
from a molecule which leads to the formation
of double (or triple) bonds or ring structures

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• The sulphuric acid generates two entities –

(i) Electrophile: H+

(ii) Nucleophile: HSO4-

3. From halogenoalkanes

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• Nucleophiles used for such transformations

are strong bases like: hot concentrated
aqueous sodium /potassium hydroxide,
alcoholic potassium hydroxide (i.e. KOH
dissolved in alcohol) and sodium/potassium
alkoxides (which are obtained by reacting
alcohols with the metals e.g. Na + C2H5OH
gives C2H5O-Na+ and ½ H2)

• Process called “dehydrogenation” and it is an

example of an elimination reaction

Vicinal Dihalides

• Compounds that have two halogen atoms on

adjacent carbon atoms can have both of the
halogens removed by heating with zinc dust

• The term vicinal is used when two species

are sited very close to each other in a
molecule – specifically on two carbon atoms
that are bonded to each other

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• With two vicinal halogens, the 1,2-

dibromopropane can easily be converted to
propene:

• In general

Reactions of the Alkenes

• Main reaction: addition i.e. chemical attack at

the double bond

• X+ electrophile attacks cloud of π electrons cos’

they are more susceptible to attack i.e. they are
more exposed than the σ electrons

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1. Combustion

• When alkenes are burnt in an atmosphere

that is rich in oxygen and if the temperature
is high enough, the alkenes burn giving CO2
and H2O

• If the temperature is not high enough or if

the oxygen present is in short supply,
carbon, as soot, and CO will also form

• Burning alkenes tend to give a sootier flame

than the alkane

• As the unsaturation increases, the molecules

do not appear to have enough time to break
all the necessary bonds within the flame
region, to give the colourless, combustion
products expected

2. Hydrogenation of alkenes

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• Catalysts are substances that changes the rate

(velocity) of a chemical reaction without being
consumed or appearing as part of the product

• Catalysts act by lowering the activation energy

of reactions, but they do not change the relative
potential energy of the reactants and products

• Finely divided metals, such as platinum,

palladium and nickel, are among the most
widely used hydrogenation catalysts

• Plant oils: sunflower and peanut are

polyunsaturated i.e. have more than one C=C
bond

 These are less valuable than animal fats

e.g. butter

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• In margarine, the softness depends on the

degree of hydrogenation (when soft, some C=C
remain)

• Animal fats are esters of saturated carboxylic

acids

3. Halogenation

• Alkenes combine with halogens to produce

dihalides

• Order of increasing reactivity I2<Br2<Cl2<F2

room temperature

H2C=CH2(g) + Cl2(g)  ClCH2CH2Cl(l)

1,2-dichloroethane

H2C=CH2(g) + Br2(CCl4)  BrCH2CH2Br(CCl4)

Reddish brown colourless

• Removal of colour of bromine solutions: test for

alkenes and unsaturated compounds (no
evolution of HBr)

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• With bromine water, get bromoalcohol

(decolourisation)
H2C=CH2(g) + Br2(aq) + H2O(l)  BrCH2CH2OH +HBr(aq)

2-bromoethanol

• Mechanism:

 Different than alkanes cos’ double bond is

center of chemical reactivity due to the
presence of 2 π electrons

 Alkene additions involve:

(i) Electrophile in 1st step

(ii) Intermediate: carbocation

(iii) Attack by nucleophile

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 As Br2 approaches the alkene, the π electron

cloud interacts with the approaching Br2
molecule – the Br-Br bond gets polarized

 The π electrons become more attached to

the partially positive Br atom and thus there
is simultaneous attack of the δ+ Br and
displacement of δ- Br (Br- is a good leaving
group)

 Formation of brominium ion

 Bulky intermediate

 Positive charge stabilized by

delocalisation

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 Rigid and attacked only from the

side opposite the bromine i.e.
stereospecific

 The Br- can attack either C leading to

racemic mixtures

 Methyl groups stabilize the carbocation

intermediate and transition state that
precedes it cos’ methyl groups are electron
releasing and thus reduces the positive
charge on the carbocation! React faster (14
times more than ethene)!

Carbocation CH2=CH-
CH3(+) < CH3CH2(+) < (CH3)2CH(+) ≅ < C6H5CH2(+) ≅ (CH3)3C(+)
Stability CH2(+)

4. Hydrohalogenation

 Symmetrical Alkenes

o Alkenes react with hydrogen bromide in the cold

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o The double bond breaks and a hydrogen atom

ends up attached to one of the carbons and a
bromine atom to the other.

o Hydrogen bromide is chosen as a typical

hydrogen halide

o Bromine is more electronegative than hydrogen.

That means that the bonding pair of electrons is
pulled towards the bromine end of the bond, and
so the hydrogen bromide molecule is polar.

o In the case of ethene, bromoethane is formed

Mechanism:

Electrophilic addition reactions involving the

other hydrogen halides

The facts

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o Hydrogen chloride and the other hydrogen

halides add on in exactly the same way

o For example, hydrogen chloride adds to ethene

to make chloroethane:

o The only difference is in how fast the reactions

happen with the different hydrogen halides

o The rate of reaction increases as you go from HF

to HCl to HBr to HI.

HF slowest reaction
HCl
HBr
HI fastest reaction

o The reason for this is that as the halogen atoms

get bigger, the strength of the hydrogen-
halogen bond falls

o As you have seen in the HBr case, in the first

step of the mechanism the hydrogen-halogen
bond gets broken

o If the bond is weaker, it will break more readily

and so the reaction is more likely to happen.

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The mechanisms

o The reactions are still examples of electrophilic

addition.
o With ethene and HCl, for example:

o This is exactly the same as the mechanism for

the reaction between ethene and HBr, except
that we've replaced Br by Cl

o All the other mechanisms for symmetrical

alkenes and the hydrogen halides would be done
in the same way.

 Asymmetrical Alkenes

o An unsymmetrical alkene is one like propene in

which the groups or atoms attached to either
end of the carbon-carbon double bond are
different.

o For example, in propene there are a hydrogen

and a methyl group at one end, but two
hydrogen atoms at the other end of the double
bond.

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o But-1-ene is another unsymmetrical alkene.

Electrophilic addition reactions involving

hydrogen bromide

The facts

o As with all alkenes, unsymmetrical alkenes like

propene react with hydrogen bromide in the cold

o The double bond breaks and a hydrogen atom

ends up attached to one of the carbons and a
bromine atom to the other.

o In the case of propene, 2-bromopropane is

formed.

o This would normally be written in a more

condensed form as

o The product is 2-bromopropane.

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Organic Chemistry: Alkenes
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o This is in line with Markovnikov's Rule which

says:

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.

o In this case, the hydrogen becomes attached to

the CH2 group, because the CH2 group has more
hydrogens than the CH group

o Notice that only the hydrogens directly attached

to the carbon atoms at either end of the double
bond count

o The ones in the CH3 group are totally irrelevant

The mechanism

o This is an example of electrophilic addition.

o The addition is this way around because the

intermediate carbocation (previously called a
carbonium ion) formed is secondary

o This is more stable (and so is easier to form)

than the primary carbocation which would be

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produced if the hydrogen became attached to

the centre carbon atom and the bromine to the
end one

o If the halogen is given the symbol X, the

equation for the reaction with propene is:

The mechanism

o These are still examples of electrophilic

addition.

o Again using X to stand for any halogen:

o Again, the intermediate carbocation formed is

secondary

o This is more stable than the primary carbocation

ion which would be formed if the hydrogen
attached to the centre carbon atom and the X to
the end one

o If it is more stable it will be easier to make.

The reaction of propene with hydrogen bromide

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o The double bond in all alkenes is made up of two

different parts

o One pair of electrons lies on the line between

the two nuclei where you would expect them to
be. This is called a sigma bond.

o The other pair lies in an orbital above and below

the plane of the rest of the molecule, and is
called a pi bond

o The pi bond is weaker than a sigma bond and is

very vulnerable to attack.

o As the HBr approaches the pi bond, the

electrons in that bond are attracted towards the
slightly positive hydrogen atom

o That repels the electrons in the hydrogen-

bromine bond down towards the bromine.

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o The electron movements continue until a new

bond is made between one of the carbon atoms
and the hydrogen

o The bromine now has both electrons from the H-

Br bond, and so is negatively charged as a
bromide ion.

o The problem is that there are two possible ways

that the pi bond electrons could move

o They could form a bond between the hydrogen

and the left-hand carbon:

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o Or they could form a bond with the right-hand

one:

o It's the second of these changes that happens

more readily

o In that case, a secondary carbocation is formed

- and that's more energetically stable than the
primary one formed in the first possibility.

o Because the secondary ion is more energetically

stable, it will form more easily and so the
reaction needs less activation energy.

o Once the ions have been formed, the lone pair

on the bromide ion is strongly attracted towards
the positive carbon atom

o It moves towards it and forms a bond.

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That leaves you with the over-all mechanism:

5. Concentrated Sulphuric Acid

The electrophilic addition reaction between

ethene and sulphuric acid

The facts

 Alkenes react with concentrated sulphuric

acid in the cold to produce alkyl
hydrogensulphates

 Ethene reacts to give ethyl

hydrogensulphate.

 The structure of the product molecule is

sometimes written as CH3CH2HSO4, but the
version in the equation is better because it
shows how all the atoms are linked
up. You may also find it written as
CH3CH2OSO3H.

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 The mechanism is exactly the same as the one

with hydrogen bromide

 As you will find out, the formula of the product

follows from the mechanism in an inevitable way

The mechanism for the reaction between

ethene and sulphuric acid

Sulphuric acid as an electrophile

 The hydrogen atoms are attached to very

electronegative oxygen atoms which means that
the hydrogens will have a slight positive charge
while the oxygens will be slightly negative

 In the mechanism, we just focus on one of the

hydrogen to oxygen bonds, because the other
one is too far from the carbon-carbon double
bond to be involved in any way.

The mechanism

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 The slightly positive hydrogen atom in the

sulphuric acid acts as an electrophile, and is
strongly attracted to the electrons in the pi bond

 The electrons from the pi bond move down

towards the slightly positive hydrogen atom

 In the process, the electrons in the hydrogen-

oxygen bond are repelled down until they are
entirely on the oxygen atom, producing a
negative ion.

So the first stage of the reaction is:

 The ion with a positive charge on the carbon

atom is called a carbocation or carbonium ion
(an older term)

 Why is there a positive charge on the carbon

atom?

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 The pi bond was originally made up of an

electron from each of the carbon atoms

 Both of those electrons have been used to make

a new bond to the hydrogen

 That leaves the right-hand carbon an electron

short - hence positively charged.

 In the second stage of the mechanism, the lone

pair of electrons on the oxygen atom is strongly
attracted to the positive carbon and moves
towards it until a bond is formed.

 Overall mechanism is therefore

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6. Hydration of Alkenes

Two ways:

(a) The alkene initially adds to conc.

sulphuric acid and the resulting alkyl
hydrogen sulphate is then hydrolysed
by heating with excess water:

(b) Alternatively, an industrial process

similar to the above reaction is
carried out but harsher conditions are
used and conc. Phosphoric acid is the
preferred catalyst here

7. Oxidation

(i) Hydroxylation (formation of the diol)

 When an alkene is reacted with alkaline KMnO4,

the diol is formed

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 In basic solution the purple permanganate anion

is reduced to the green manganate ion,
providing a nice color test for the double bond
functional group

N.B. This reaction is very sensitive to conditions used as the oxidizing power
of the permanganate is very high in acid environments so much so that the carbon
chain can easily be broken down to give lower carboxylic acids and/or carbon
dioxide. Since the purple permanganate, MnO4−, colour is discharged in such a
reaction, this is often used as a test for presence of double bonds

(ii) Oxidative Cleavage of Double Bonds

Ozonolysis

 In determining the structural formula of an

alkene, it is often necessary to find the

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location of the double bond within a given

carbon framework

 One way of accomplishing this would be to

selectively break the double bond and mark
the carbon atoms that originally formed that
bond

 For example, there are three isomeric

alkenes that all give 2-methylbutane on
catalytic hydrogenation. These are 2-
methylbut-2-ene (compound A), 3-methyl-
but-1-ene (compound B) and
2-methylbut-2-ene (compound C), shown in
the following diagram

 If the double bond is cleaved and the

fragments marked at the cleavage sites, the
location of the double bond is clearly
determined for each case

 A reaction that accomplishes this useful

transformation is known, called ozonolysis

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 Since the ozonolysis reaction effects a more

complex change than a simple addition
reaction, its mechanism has been
extensively studied

 Reactive intermediates called ozonides have

been isolated from the interaction of ozone
with alkenes, and these unstable
compounds may be converted to stable
products by reductive workup (Zn dust in
water or alcohol)

(iv)Direct combination with oxygen using

suitable catalysts

 Depending on the catalyst chosen, oxygen

can be made to react specifically with
ethene either to give an epoxide when
silver is used as the catalyst or an
aldehyde when an aqueous mixture of
Cu(II) and Pd(II) chlorides is used to
catalyse the reaction

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8. Polymerisation

 Under conditions of temperature and

pressure, molecules of ethene react with one
another to form larger molecules having the
same empirical formula a ethene but a
molecular weight many times greater

 Original conditions: 1000 atm and trace of

oxygen

 Occurs by free radical mechanism

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 Free radical addition polymerization must take

place at high temperatures and pressures,
approximately 300°C and 2000 atm

 There are problems with the lack of control in

the reaction, specifically with the creation of
variably branched chains

 Also, as termination occurs randomly, when two

chains collide, it is impossible to control the
length of individual chains

 Finally, reactions involving larger molecules

such as polypropene are difficult

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 For this reason new mechanisms for addition

polymerization were developed

 An early replacement was the Ziegler-Natta

catalyst

 The problem of branching occurs during

propagation, when a chain curls back on itself
and breaks - leaving irregular chains sprouting
from the main carbon backbone

 Branching makes the polymers less dense and

results in low tensile strength and melting
points

 Developed by Karl Ziegler and Giulio Natta in

the 1950s, Ziegler-Natta catalysts
(triethylaluminium in the presence of a metal
(IV) chloride) largely solved this problem

 Instead of a free radical reaction, the initial

ethene monomer inserts between the
aluminium atom and one of the ethyl groups in
the catalyst

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Ms. C.F.Zerafa

 The polymer is then able to grow out from the

aluminium atom and results in almost totally
unbranched chains

 With the new catalysts, the tacticity

(stereochemistry) of the polypropene chain, the
alignment of alkyl groups, was also able to be
controlled

 However there were further complications to be

solved

 If the Ziegler-Natta catalyst was poisoned or

damaged then the chain stopped growing

 Also, Ziegler-Natta monomers could be only

small, and it was impossible to control the
molecular mass of the polymer chains

 Again new catalysts, the metallocenes

(consisting of an aromatic organic ligand bound
to a metal), were developed to tackle these
problems

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Organic Chemistry: Alkenes
Ms. C.F.Zerafa

 Example of metallocene: ferrocene Fe(C5H5)2

 Due to their structure they have less premature

chain termination and branching

Properties and Uses of polythene

Property Low Density Polyethylene (LDPE) High Density Polyethylene (HDPE)
Melting Point ~115oC ~135oC
low crystallinity (50-60% crystalline) highly crystalline (>90% crystalline)
Main chain contains many side chains of contains less than 1 side chain per 200
Crystallinity 2-4 carbon atoms leading to irregular carbon atoms in the main chain leading to
packing and low crystallinity long linear chains that result in regular
(amorphous) packing and high crystallinity
more flexible than HDPE due to lower more rigid than LDPE due to higher
Flexibility
crystallinity crystallinity
not as strong as HDPE due to irregular strong as a result of regular packing of
Strength
packing of polymer chains polymer chains
retains toughness & pliabilty over a wide
Heat
temperature range, but density drops off useful above 100oC
Resistance
dramatically above room temperature.
good transparency since it is more
less transparent than LDPE because it is
Transparency amorphous (has non-crystalline regions)
more crystalline
than HDPE
0.91-0.94 g/cm3 0.95-0.97 g/cm3
Density
lower density than HDPE higher density than LDPE
Chemical chemically inert chemically inert

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Organic Chemistry: Alkenes
Ms. C.F.Zerafa

Properties Insolvent at room temperature in most

solvents.
Good resistance to acids and alkalis.
Exposure to light and oxygen results in
loss of strength and loss of tear
resistance.

Schematic
diagram

sandwich bags, cling wrap, car covers,

freezer bags, water pipes, wire and cable
Uses squeeze bottles, liners for tanks and
insulation, extrusion coating
ponds, moisture barriers in construction

Production of LDPE
Production of LDPE by addition polymerization
requires:

• temperature range of 100-300oC

• very high pressure 1500-3000 atmospheres
• oxygen or an organic peroxide such as dibutyl
peroxide, benzoyl peroxide or diethyl peroxide
as initiator.
An initiator is a substance which is added in
small quantities and is decomposed by light or
heat to produce a free radical (R.). A free radical
is formed when a covalent bond is broken and a
bonding electron is left on each part of the
broken molecule. Since the O-O covalent bond is
weak, free radicals are easily formed from
oxygen or peroxides.
• benzene or chlorobenzene used as the solvent
since both polymer (polythene) and monomer
(ethene) dissolve in these compounds at the
temperature and pressure used.
Water or other liquids may be added to dissipate
the heat of reaction as the polymerization
reaction is highly exothermic.

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Organic Chemistry: Alkenes
Ms. C.F.Zerafa

CH2=CH2 R. ----- .
+ CH2-CH2-R
ethene initiator >
. ----- .CH2-CH2-CH2-
CH2=CH2 + CH2-CH2-R
> CH2-R
Process continues to form polythene
(polyethylene) [-CH2-CH2-]n

Production of HDPE

Production of HDPE by addition polymerization

with a supported metal oxide catalyst requires:

• temperature ~300oC
• 1 atmosphere pressure (101.3kPa)
• aluminium-based metal oxide catalyst
(metallocene catalyst)

In general:

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Organic Chemistry: Alkenes
Ms. C.F.Zerafa

Tests for alkenes.

 Elemental analysis, which is the commonest

(traditional!), test to carry out only gives
presence of carbon and hydrogen if a simple
alkene is analysed

 Empirical formulae calculations already

indicate the presence of the unsaturation

 Chemical tests for this functionality must

then be performed to confirm suspicions

 Reliable tests for alkenes is that with

(a) Either bromine water which rapidly
decolorizes (- the brown colour of the
bromine is discharged) or
(b) With acidified potassium permanganate
solution which similarly gives rapid
-
decolorisation of the purple MnO4
(c) With alkaline KMnO4, a green colour would
be formed if an alkene is present

 The position of the double bond in the

molecule was then found through analyses
of products obtained by ozonolysis of the
alkene.

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