ALKENES

Assoc.prof. Lubomir Makedonski

Medical University of Varna

ALKENES INTRODUCING

What are alkenes?

Formulae

Alkenes are a family of hydrocarbons (compounds containing carbon

and hydrogen only) containing a carbon-carbon double bond. The
first two are:

ethene C2H4
propene C3H6

You can work out the formula of any of them using: CnH2n

The table is limited to the first two, because after that there are
isomers which affect the names.

Isomerism in the alkenes

Structural isomerism

All the alkenes with 4 or more carbon atoms in them show structural
isomerism. This means that there are two or more different
structural formulae that you can draw for each molecular formula.

For example, with C4H8, it isn't too difficult to come up with these
three structural isomers:

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There is, however, another isomer. But-2-ene also exhibits
geometric isomerism.

Geometric (cis-trans) isomerism

The carbon-carbon double bond doesn't allow any rotation about it.
That means that it is possible to have the CH3 groups on either end
of the molecule locked either on one side of the molecule or
opposite each other.

These are called cis-but-2-ene (where the groups are on the same
side) or trans-but-2-ene (where they are on opposite sides).

Physical properties of the alkenes

Boiling Points

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

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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.

Solubility

Alkenes are virtually insoluble in water, but dissolve in organic

solvents.

Chemical Reactivity

Bonding in the alkenes

We just need to look at ethene, because what is true of C=C in

ethene will be equally true of C=C in more complicated alkenes.

Ethene is often modelled like this:

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.
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The pi electrons are not as fully under the control of the carbon nuclei as the
electrons in the sigma bond and, because they lie exposed above and below the rest
of the molecule, they are relatively open to attack by other things.

The reactions of alkenes

Like any other hydrocarbons, alkenes burn in air or oxygen, but these reactions are
unimportant. Alkenes are too valuable to waste in this way.

The important reactions all centre around the double bond. Typically, the pi bond
breaks and the electrons from it are used to join the two carbon atoms to other
things. Alkenes undergo addition reactions.

For example, using a general molecule X-Y . . .

The rather exposed electrons in the pi bond are particularly open to attack by things
which carry some degree of positive charge. These are called electrophiles. If you
explore the rest of the alkene menu, you will find lots of examples of this kind.

MAKING ALKENES IN THE LAB

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.

The dehydration of ethanol to give ethene

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.

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The concentrated sulphuric acid is a catalyst. Write it over the
arrow rather than in the equation.

THE HYDROGENATION OF ALKENES

This page looks at the reaction of the carbon-carbon double bond in
alkenes with hydrogen in the presence of a metal catalyst. This is
called hydrogenation. It includes the manufacture of margarine from
animal or vegetable fats and oils.

The hydrogenation of ethene

Ethene reacts with hydrogen in the presence of a finely divided

nickel catalyst at a temperature of about 150°C. Ethane is produced.

This is a fairly pointless reaction because ethene is a far more

useful compound than ethane! However, what is true of the reaction
of the carbon-carbon double bond in ethene is equally true of it in
much more complicated cases.

THE HALOGENATION OF ALKENES

Reactions where the chlorine or bromine are in solution (for
example, "bromine water") are slightly more complicated and are
treated separately at the end.

Simple reactions involving halogens

In each case, we will look at ethene as typical of all of the alkenes.

There are no complications as far as the basic facts are concerned
as the alkenes get bigger.

Ethene and fluorine

Ethene reacts explosively with fluorine to give carbon and hydrogen

fluoride gas.

Ethene and chlorine or bromine or iodine

In each case you get an addition reaction. For example, bromine

adds to give 1,2-dibromoethane.

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The reaction with bromine happens at room temperature. 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. The reddish-brown bromine is decolourised as
it reacts with the alkene.

A liquid alkene (like cyclohexene) can be shaken 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 than
either of these.

Alkenes and bromine water

Using bromine water as a test for alkenes

If you shake an alkene with bromine water (or bubble a gaseous

alkene through bromine water), the solution becomes colourless.
Alkenes decolourise bromine water.

The chemistry of the test

This is complicated by the fact that the major product isn't 1,2-
dibromoethane. The water also gets involved in the reaction, and
most of the product is 2-bromoethanol.

However, there will still be some 1,2-dibromoethane formed, so at

this sort of level you can probably get away with quoting the simpler
equation:

ALKENES and HYDROGEN HALIDES

Symmetrical alkenes (like ethene or but-2-ene) are dealt with first.
These are alkenes where identical groups are attached to each end
of the carbon-carbon double bond. The extra problems associated
with unsymmetrical ones like propene are covered in a separate
section afterwards.

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Addition to symmetrical alkenes

What happens?

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:

What happens if you add the hydrogen to the carbon atom at the
right-hand end of the double bond, and the chlorine to the left-hand
end? You would still have the same product.

The chlorine would be on a carbon atom next to the end of the chain
- you would simply have drawn the molecule flipped over in space.

That would be different of the alkene was unsymmetrical - that's

why we have to look at them separately.

Conditions

The alkenes react with gaseous hydrogen halides at room

temperature. If the alkene is also a gas, you can simply mix the
gases. If the alkene is a liquid, you can bubble the hydrogen halide
through the liquid.

Alkenes will also react with concentrated solutions of the gases in

water. A solution of hydrogen chloride in water is, of course,
hydrochloric acid. A solution of hydrogen bromide in water is
hydrobromic acid - and so on.

There are, however, problems with this. The water will also get
involved in the reaction and you end up with a mixture of products

Reaction rates

Variation of rates when you change the halogen

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Reaction rates increase in the order HF - HCl - HBr - HI. Hydrogen
fluoride reacts much more slowly than the other three, and is
normally ignored in talking about these reactions.

When the hydrogen halides react with alkenes, the hydrogen-

halogen bond has to be broken. The bond strength falls as you go
from HF to HI, and the hydrogen-fluorine bond is particularly strong.
Because it is difficult to break the bond between the hydrogen and
the fluorine, the addition of HF is bound to be slow.

Variation of rates when you change the alkene

This applies to unsymmetrical alkenes as well as to symmetrical

ones. For simplicity the examples given below are all symmetrical
ones- but they don't have to be.

Reaction rates increase as the alkene gets more complicated - in

the sense of the number of alkyl groups (such as methyl groups)
attached to the carbon atoms at either end of the double bond.

For example:

There are two ways of looking at the reasons for this - both of which
need you to know about the mechanism for the reactions.

Alkenes react because the electrons in the pi bond attract things

with any degree of positive charge. Anything which increases the
electron density around the double bond will help this.

Alkyl groups have a tendency to "push" electrons away from

themselves towards the double bond. The more alkyl groups you
have, the more negative the area around the double bonds becomes.

The more negatively charged that region becomes, the more it will
attract molecules like hydrogen chloride.

The more important reason, though, lies in the stability of the

intermediate ion formed during the reaction. The three examples
given above produce these carbocations (carbonium ions) at the
half-way stage of the reaction:

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The stability of the intermediate ions governs the activation energy
for the reaction. As you go towards the more complicated alkenes,
the activation energy for the reaction falls. That means that the
reactions become faster.

Addition to unsymmetrical alkenes

What happens?

In terms of reaction conditions and the factors affecting the rates of

the reaction, there is no difference whatsoever between these
alkenes and the symmetrical ones described above. The problem
comes with the orientation of the addition - in other words, which
way around the hydrogen and the halogen add across the double
bond.

Orientation of addition

If HCl adds to an unsymmetrical alkene like propene, there are two

possible ways it could add. However, in practice, there is only one
major product.

This is in line with Markovnikov's Rule which says:

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 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.

In this case, the hydrogen becomes attached to the CH2 group,

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

Notice that only the hydrogens directly attached to the carbon

atoms at either end of the double bond count. The ones in the CH 3
group are totally irrelevant.

A special problem with hydrogen bromide

Unlike the other hydrogen halides, hydrogen bromide can add to a

carbon-carbon double bond either way around - depending on the
conditions of the reaction.

If the hydrogen bromide and alkene are entirely pure

In this case, the hydrogen bromide adds on according to

Markovnikov's Rule. For example, with propene you would get 2-
bromopropane.

That is exactly the same as the way the other hydrogen halides add.

If the hydrogen bromide and alkene contain traces of organic

peroxides

Oxygen from the air tends to react slowly with alkenes to produce
some organic peroxides, and so you don't necessarily have to add
them separately. This is therefore the reaction that you will tend to
get unless you take care to exclude all air from the system.

In this case, the addition is the other way around, and you get 1-
bromopropane:

This is sometimes described as an anti-Markovnikov addition or as

the peroxide effect.

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Organic peroxides are excellent sources of free radicals. In the
presence of these, the hydrogen bromide reacts with alkenes using
a different (faster) mechanism. For various reasons, this doesn't
happen with the other hydrogen halides.

This reaction can also happen in this way in the presence of ultra-
violet light of the right wavelength to break the hydrogen-bromine
bond into hydrogen and bromine free radicals.

ALKENES and SULPHURIC ACID

The addition of sulphuric acid to alkenes

The reaction with ethene

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.

Confused by all this? Don't be!

All you need to do is to learn the structure of sulphuric acid. A

hydrogen from the sulphuric acid joins on to one of the carbon
atoms, and the rest joins on to the other one. Make sure that you
can see how the structure of the sulphuric acid relates to the
various ways of writing the formula for the product.

The reaction with propene

This is typical of the reaction with unsymmetrical alkenes. An

unsymmetrical alkene has different groups at either end of the
carbon-carbon double bond.

If sulphuric acid adds to an unsymmetrical alkene like propene,

there are two possible ways it could add. You could end up with one
of two products depending on which carbon atom the hydrogen
attaches itself to.

However, in practice, there is only one major product.

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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.

In this case, the hydrogen becomes attached to the CH2 group,

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

Notice that only the hydrogens directly attached to the carbon

atoms at either end of the double bond count. The ones in the CH 3
group are totally irrelevant.

Using these reactions to make alcohols

Making ethanol

Ethene is passed into concentrated sulphuric acid to make ethyl

hydrogensulphate (as above). The product is diluted with water and
then distilled.

The water reacts with the ethyl hydrogensulphate to produce

ethanol which distils off.

Making propan-2-ol

More complicated alkyl hydrogensulphates react with water in

exactly the same way. For example:

Notice that the position of the -OH group is determined by where the
HSO4 group was attached. You get propan-2-ol rather than propan-1-
ol because of the way the sulphuric acid originally added across the
double bond in propene.

Using these reactions

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These reactions were originally used as a way of manufacturing
alcohols from alkenes in the petrochemical industry. These days,
alcohols like ethanol or propan-2-ol tend to be manufactured by
direct hydration of the alkene because it is cheaper and easier.

ALKENES and POTASSIUM MANGANATE(VII)

Oxidation of alkenes

Experimental details

Alkenes react with potassium manganate(VII) solution in the cold.

The colour change depends on whether the potassium
manganate(VII) is used under acidic or alkaline conditions.

If the potassium manganate(VII) solution is acidified with dilute

sulphuric acid, the purple solution becomes colourless.

If the potassium manganate(VII) solution is made slightly alkaline

(often by adding sodium carbonate solution), the purple solution first
becomes dark green and then produces a dark brown precipitate.

Chemistry of the reaction

We'll look at the reaction with ethene. Other alkenes react in just
the same way.

Manganate(VII) ions are a strong oxidising agent, and in the first

instance oxidise ethene to ethane-1,2-diol (old name: ethylene
glycol).

Looking at the equation purely from the point of view of the organic
reaction:

The full equation depends on the conditions.

Under acidic conditions, the manganate(VII) ions are reduced to

manganese(II) ions.

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Under alkaline conditions, the manganate(VII) ions are first reduced
to green manganate(VI) ions . . .

. . . and then further to dark brown solid manganese(IV) oxide

(manganese dioxide).

This last reaction is also the one you would get if the reaction was
done under neutral conditions. You will notice that there are neither
hydrogen ions nor hydroxide ions on the left-hand side of the
equation.

THE DIRECT HYDRATION OF ALKENES

Manufacturing ethanol

Ethanol is manufactured by reacting ethene with steam. The

reaction is reversible.

Only 5% of the ethene is converted into ethanol at each pass

through the reactor. By removing the ethanol from the equilibrium
mixture and recycling the ethene, it is possible to achieve an overall
95% conversion.

A flow scheme for the reaction looks like this:

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THE POLYMERISATION OF ALKENES
Poly(ethene) (polythene or polyethylene)

Low density poly(ethene): LDPE

Manufacture

In common with everything else on this page, this is an example of

addition polymerisation.

An addition reaction is one in which two or more molecules join

together to give a single product. During the polymerisation of
ethene, thousands of ethene molecules join together to make
poly(ethene) - commonly called polythene.

The number of molecules joining up is very variable, but is in the

region of 2000 to 20000.

Conditions

Temperatur
about 200°C
e:
Pressure: about 2000 atmospheres
a small amount of oxygen as an
Initiator:
impurity

Properties and uses

Low density poly(ethene) has quite a lot of branching along the hydrocarbon chains,
and this prevents the chains from lying tidily close to each other. Those regions of the
poly(ethene) where the chains lie close to each other and are regularly packed are
said to be crystalline. Where the chains are a random jumble, it is said to be
amorphous. Low density poly(ethene) has a significant proportion of amorphous
regions.
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One chain is held to its neighbours in the structure by van der Waals dispersion
forces. Those attractions will be greater if the chains are close to each other. The
amorphous regions where the chains are inefficiently packed lower the effectiveness
of the van der Waals attractions and so lower the melting point and strength of the
polymer. They also lower the density of the polymer (hence: "low density
poly(ethene)").

Low density poly(ethene) is used for familiar things like plastic carrier bags and other
similar low strength and flexible sheet materials.

High density poly(ethene): HDPE

Manufacture

This is made under quite different conditions from low density poly(ethene).

Conditions

Temperatu
about 60°C
re:
Pressure: low - a few atmospheres
Ziegler-Natta catalysts or other
Catalyst:
metal compounds

Ziegler-Natta catalysts are mixtures of titanium compounds like titanium(III) chloride,

TiCl3, or titanium(IV) chloride, TiCl4, and compounds of aluminium like aluminium
triethyl, Al(C2H5)3. There are all sorts of other catalysts constantly being developed.

These catalysts work by totally different mechanisms from the high pressure process
used to make low density poly(ethene). The chains grow in a much more controlled -
much less random - way.

Properties and uses

High density poly(ethene) has very little branching along the hydrocarbon chains -
the crystallinity is 95% or better. This better packing means that van der Waals
attractions between the chains are greater and so the plastic is stronger and has a
higher melting point. Its density is also higher because of the better packing and
smaller amount of wasted space in the structure.

High density poly(ethene) is used to make things like plastic milk bottles and similar
containers, washing up bowls, plastic pipes and so on. Look for the letters HDPE
near the recycling symbol.

Poly(propene) (polypropylene): PP

Poly(propene) is manufactured using Ziegler-Natta and other modern

catalysts. There are three variants on the structure of poly(propene)

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which you may need to know about, but we'll start from the
beginning with a general structure which fits all of them.

The general structure

If your syllabus simply mentions the structure of poly(propene) with no more detail,
this is adequate.

The trick is to think about the shape of the propene in the right way:

Now line lots of them up in a row and join them together. Notice that the double
bonds are all replaced by single bonds in the process.

In a simple equation form, this is normally written as:

Poly(chloroethene) (polyvinyl chloride): PVC

Poly(chloroethene) is commonly known by the initials of its old

name, PVC.

Structure

Poly(chloroethene) is made by polymerising chloroethene,

CH2=CHCl. Working out its structure is no different from working out
the structure of poly(propene) (see above). As long as you draw the
chloroethene molecule in the right way, the structure is pretty
obvious.

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The equation is usually written:

It doesn't matter which carbon you attach the chlorine to in the

original molecule. Just be consistent on both sides of the equation.

The polymerisation process produces mainly atactic polymer

molecules - with the chlorines orientated randomly along the chain.
The structure is no different from atactic poly(propene) - just replace
the CH3 groups by chlorine atoms.

Because of the way the chlorine atoms stick out from the chain at
random, and because ot their large size, it is difficult for the chains
to lie close together. Poly(chloroethene) is mainly amorphous with
only small areas of crystallinity.

Properties and uses

You normally expect amorphous polymers to be more flexible than

crystalline ones because the forces of attraction between the
chains tend to be weaker. However, pure poly(chloroethene) tends
to be rather hard and rigid.

This is because of the presence of additional dipole-dipole

interactions due to the polarity of the carbon-chlorine bonds.
Chlorine is more electronegative than carbon, and so attracts the
electrons in the bond towards itself. That makes the chlorine atoms
slightly negative and the carbons slightly positive.

These permanent dipoles add to the attractions due to the

temporary dipoles which produce the dispersion forces.
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Plasticisers are added to the poly(chloroethene) to reduce the effectiveness of these
attractions and make the plastic more flexible. The more plasticiser you add, the
more flexible it becomes.

Poly(chloroethene) is used to make a wide range of things including guttering, plastic

windows, electrical cable insulation, sheet materials for flooring and other uses,
footwear, clothing, and so on and so on.

Poly(tetrafluoroethene): PTFE

You may have come across this under the brand names of Teflon or
Fluon.

Structure

Structurally, PTFE is just like poly(ethene) except that each

hydrogen in the structure is replaced by a fluorine atom.

The PTFE chains tend to pack well and PTFE is fairly crystalline.
Because of the fluorine atoms, the chains also contain more
electrons (for an equal length) than a corresponding poly(ethene)
chain. Taken together (the good packing and the extra electrons)
that means that the van der Waals dispersion forces will be stronger
than in even high density poly(ethene).

Properties and uses

PTFE has a relatively high melting point (due to the strength of the attractions
between the chains) and is very resistant to chemical attack. The carbon chain is so
wrapped up in fluorine atoms that nothing can get at it to react with it. This makes it
useful in the chemical and food industries to coat vessels and make them resistant to
almost everything which might otherwise corrode them.
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Equally important is that PTFE has remarkable non-stick properties - which is the
basis for its most familiar uses in non-stick kitchen and garden utensils. For the same
reason, it can also be used in things like low-friction bearings

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