DRAWING ORGANIC MOLECULES

This page explains the various ways that organic molecules can be represented on paper
or on screen - including molecular formulae, and various forms of structural formulae.

Molecular formulae

A molecular formula simply counts the numbers of each sort of atom present in the
molecule, but tells you nothing about the way they are joined together.

For example, the molecular formula of butane is C4H10, and the molecular formula of
ethanol is C2H6O.

Molecular formulae are very rarely used in organic chemistry, because they don't give any
useful information about the bonding in the molecule. About the only place where you might
come across them is in equations for the combustion of simple hydrocarbons, for example:

In cases like this, the bonding in the organic molecule isn't important.

Structural formulae

A structural formula shows how the various atoms are bonded. There are various ways of
drawing this and you will need to be familiar with all of them.

Displayed formulae

A displayed formula shows all the bonds in the molecule as individual lines. You need to
remember that each line represents a pair of shared electrons.

For example, this is a model of methane together with its displayed formula:

Notice that the way the methane is drawn bears no resemblance to the actual shape of the
molecule. Methane isn't flat with 90° bond angles. This mismatch between what you draw
and what the molecule actually looks like can lead to problems if you aren't careful.

For example, consider the simple molecule with the molecular formula CH2Cl2. You might
think that there were two different ways of arranging these atoms if you drew a displayed
formula.

The chlorines could be opposite each other or at right angles to each other. But these two
structures are actually exactly the same. Look at how they appear as models.

One structure is in reality a simple rotation of the other one.

Note: This is all much easier to understand if you have

actually got some models to play with. If your school or
college hasn't given you the opportunity to play around with
molecular models in the early stages of your organic
chemistry course, you might consider getting hold of a cheap
set. The models made by molymod are both cheap and
easy to use. An introductory organic set is more than
adequate. Find them at www.molymod.com.
 Alternatively , get hold of some coloured Plasticene and
some used matches and make your own. It's cheaper, but
distinctly messier!

Consider a slightly more complicated molecule, C2H5Cl. The displayed

formula could be written as either of these:

But, again these are exactly the same. Look at the models.

The commonest way to draw structural formulae

For anything other than the most simple molecules, drawing a fully displayed
formula is a bit of a bother - especially all the carbon-hydrogen bonds. You
can simplify the formula by writing, for example, CH3 or CH2 instead of
showing all these bonds.

So for example, ethanoic acid would be shown in a fully displayed form and a
simplified form as:

You could even condense it further to CH3COOH, and would probably do this
if you had to write a simple chemical equation involving ethanoic acid. You
do, however, lose something by condensing the acid group in this way,
because you can't immediately see how the bonding works.

You still have to be careful in drawing structures in this way. Remember from
above that these two structures both represent the same molecule:
The next three structures all represent butane.

All of these are just versions of four carbon atoms joined up in a line. The
only difference is that there has been some rotation about some of the
carbon-carbon bonds. You can see this in a couple of models.

Not one of the structural formulae accurately represents the shape of butane.
The convention is that we draw it with all the carbon atoms in a straight line -
as in the first of the structures above.

This is even more important when you start to have branched chains of
carbon atoms. The following structures again all represent the same
molecule - 2-methylbutane.

The two structures on the left are fairly obviously the same - all we've done is
flip the molecule over. The other one isn't so obvious until you look at the
structure in detail. There are four carbons joined up in a row, with a CH3
group attached to the next-to-end one. That's exactly the same as the other
two structures. If you had a model, the only difference between these three
diagrams is that you have rotated some of the bonds and turned the model
around a bit.

To overcome this possible confusion, the convention is that you always look
for the longest possible chain of carbon atoms, and then draw it horizontally.
Anything else is simply hung off that chain.

It doesn't matter in the least whether you draw any side groups pointing up or
down. All of the following represent exactly the same molecule.
If you made a model of one of them, you could turn it into any other one
simply by rotating one or more of the carbon-carbon bonds.

How to draw structural formulae in 3-dimensions

There are occasions when it is important to be able to show the precise 3-D
arrangement in parts of some molecules. To do this, the bonds are shown
using conventional symbols:

For example, you might want to show the 3-D arrangement of the groups
around the carbon which has the -OH group in butan-2-ol.

Butan-2-ol has the structural formula:

Using conventional bond notation, you could draw it as, for example:

The only difference between these is a slight rotation of the bond between
the centre two carbon atoms. This is shown in the two models below. Look
carefully at them - particularly at what has happened to the lone hydrogen
atom. In the left-hand model, it is tucked behind the carbon atom. In the right-
hand model, it is in the same plane. The change is very slight.
It doesn't matter in the least which of the two arrangements you draw. You
could easily invent other ones as well. Choose one of them and get into the
habit of drawing 3-dimensional structures that way. My own habit (used
elsewhere on this site) is to draw two bonds going back into the paper and
one coming out - as in the left-hand diagram above.

Notice that no attempt was made to show the whole molecule in 3-

dimensions in the structural formula diagrams. The CH2CH3 group was left in
a simple form. Keep diagrams simple - trying to show too much detail makes
the whole thing amazingly difficult to understand!

Skeletal formulae

In a skeletal formula, all the hydrogen atoms are removed from carbon
chains, leaving just a carbon skeleton with functional groups attached to it.

For example, we've just been talking about butan-2-ol. The normal structural
formula and the skeletal formula look like this:

In a skeletal diagram of this sort

• there is a carbon atom at each junction between bonds in a chain and

at the end of each bond (unless there is something else there already
- like the -OH group in the example);
• there are enough hydrogen atoms attached to each carbon to make
the total number of bonds on that carbon up to 4.

Beware! Diagrams of this sort take practice to interpret correctly - and may
well not be acceptable to your examiners (see below).

There are, however, some very common cases where they are frequently
used. These cases involve rings of carbon atoms which are surprisingly
awkward to draw tidily in a normal structural formula.

Cyclohexane, C6H12, is a ring of carbon atoms each with two hydrogens

attached. This is what it looks like in both a structural formula and a skeletal
formula.
And this is cyclohexene, which is similar but contains a double bond:

But the commonest of all is the benzene ring, C6H6, which has a special
symbol of its own.

Note: Explaining exactly what this structure means needs

more space than is available here. It is explained in full in
two pages on the structure of benzene elsewhere in this site.
It would probably be better not to follow this link unless you
are actively interested in benzene chemistry at the moment -
it will lead you off into quite deep water!

Deciding which sort of formula to use

There's no easy, all-embracing answer to this problem. It depends more than

anything else on experience - a feeling that a particular way of writing a
formula is best for the situation you are dealing with.

Don't worry about this - as you do more and more organic chemistry, you will
probably find it will come naturally. You'll get so used to writing formulae in
reaction mechanisms, or for the structures for isomers, or in simple chemical
equations, that you won't even think about it.

There are, however, a few guidelines that you should follow.

What does your syllabus say?

Different examiners will have different preferences. Check first with your
syllabus. If you've down-loaded a copy of your syllabus from your examiners'
web site, it is easy to check what they say they want. Use the "find" function
on your Adobe Acrobat Reader to search the organic section(s) of the
syllabus for the word "formula".
You should also check recent exam papers and (particulary) mark schemes
to find out what sort of formula the examiners really prefer in given situations.
You could also look at any support material published by your examiners.
Note: If you are working to a UK-based syllabus and haven't
got a copy of that syllabus and recent exam papers, follow
this link to find out how to get them.

What if you still aren't sure?

Draw the most detailed formula that you can fit into the space available. If in
doubt, draw a fully displayed formula. You would never lose marks for giving
too much detail.

Apart from the most trivial cases (for example, burning hydrocarbons), never
use a molecular formula. Always show the detail around the important part(s)
of a molecule. For example, the important part of an ethene molecule is the
carbon-carbon double bond - so write (at the very least) CH2=CH2 and not
C2H4.

Where a particular way of drawing a structure is important, this will always be

pointed out where it arises elsewhere on this site.

THE NAMES OF ORGANIC COMPOUNDS

This page explains how to write the formula for an organic

compound given its name - and vice versa. It covers alkanes,
cycloalkanes, alkenes, simple compounds containing halogens,
alcohols, aldehydes and ketones. At the bottom of the page, you
will find links to other types of compound.

Background

How this page is going to tackle the problem

There are two skills you have to develop in this area:

• You need to be able to translate the name of an organic

compound into its structural formula.
• You need to be able to name a compound from its given
 formula.

The first of these is more important (and also easier!) than the
second. In an exam, if you can't write a formula for a given
compound, you aren't going to know what the examiner is talking
about and could lose lots of marks. However, you might only be
asked to write a name for a given formula once in a whole exam -
in which case you only risk 1 mark.

So, we're going to look mainly at how you decode names and turn
them into formulae. In the process you will also pick up tips about
how to produce names yourself.

In the early stages of an organic chemistry course people

frequently get confused and daunted by the names because they
try to do too much at once. Don't try to read all these pages in one
go. Just go as far as the compounds you are interested in at the
moment and ignore the rest. Come back to them as they arise
during the natural flow of your course.

Cracking the code

A modern organic name is simply a code. Each part of the name

gives you some useful information about the compound.

For example, to understand the name 2-methylpropan-1-ol you

need to take the name to pieces.

The prop in the middle tells you how many carbon atoms there are
in the longest chain (in this case, 3). The an which follows the
"prop" tells you that there aren't any carbon-carbon double bonds.

The other two parts of the name tell you about interesting things
which are happening on the first and second carbon atom in the
chain. Any name you are likely to come across can be broken up in
this same way.

Counting the carbon atoms

You will need to remember the codes for the number of carbon
atoms in a chain up to 6 carbons. There is no easy way around this
- you have got to learn them. If you don't do this properly, you won't
be able to name anything!

code no of carbons
meth 1
eth 2
prop 3
 but 4
pent 5
hex 6

Types of carbon-carbon bonds

Whether or not the compound contains a carbon-carbon double

bond is shown by the two letters immediately after the code for the
chain length.

code means

only carbon-carbon single

an
bonds

contains a carbon-carbon
en
double bond

For example, butane means four carbons in a chain with no double

bond.

Propene means three carbons in a chain with a double bond

between two of the carbons.

Alkyl groups

Compounds like methane, CH4, and ethane, CH3CH3, are members

of a family of compounds called alkanes. If you remove a hydrogen
atom from one of these you get an alkyl group.

For example:

• A methyl group is CH3.

• An ethyl group is CH3CH2.

These groups must, of course, always be attached to something

else.

Types of compounds

The alkanes

Example 1: Write the structural formula for 2-methylpentane.

Start decoding the name from the bit that counts the number of
carbon atoms in the longest chain - pent counts 5 carbons.

Are there any carbon-carbon double bonds? No - an tells you there

aren't any.

Now draw this carbon skeleton:

Put a methyl group on the number 2 carbon atom:

Does it matter which end you start counting from? No - if you

counted from the other end, you would draw the next structure.
That's exactly the same as the first one, except that it has been
flipped over.

Finally, all you have to do is to put in the correct number of

hydrogen atoms on each carbon so that each carbon is forming
four bonds.

If you had to name this yourself:

• Count the longest chain of carbons that you can find. Don't
assume that you have necessarily drawn that chain
horizontally. 5 carbons means pent.
• Are there any carbon-carbon double bonds? No - therefore
pentane.
• There's a methyl group on the number 2 carbon - therefore
2-methylpentane. Why the number 2 as opposed to the
number 4 carbon? In other words, why do we choose to
number from this particluar end? The convention is that you
number from the end which produces the lowest numbers in
the name - hence 2- rather than 4-.

Example 2: Write the structural formula for 2,3-dimethylbutane.

Start with the carbon backbone. There are 4 carbons in the longest
chain (but) with no carbon-carbon double bonds (an).
This time there are two methyl groups (di) on the number 2 and
number 3 carbon atoms.

Completing the formula by filling in the hydrogen atoms gives:

Note: Does it matter whether you draw the two methyl groups
one up and one down, or both up, or both down? Not in the
least! If you aren't sure about drawing organic molecules,
follow this link before you go on. Use the BACK button on
your browser to return to this page.

Example 3: Write the structural formula for 2,2-dimethylbutane.

This is exactly like the last example, except that both methyl groups
are on the same carbon atom. Notice that the name shows this by
using 2,2- as well as di. The structure is worked out as before:

Example 4: Write the structural formula for 3-ethyl-2-

methylhexane.

hexan shows a 6 carbon chain with no carbon-carbon double

bonds.

This time there are two different alkyl groups attached - an ethyl
group on the number 3 carbon atom and a methyl group on number
2.
Filling in the hydrogen atoms gives:

Note: Once again it doesn't matter whether the ethyl and

methyl groups point up or down. You might also have chosen
to start numbering from the right-hand end of the chain. These
would all be perfectly valid structures. All you would have
done is to rotate the whole molecule in space, or rotate it
around particular bonds.

If you aren't sure about this, then you must read about
drawing organic molecules before you go on.

If you had to name this yourself:

How do you know what order to write the different alkyl groups at
the beginning of the name? The convention is that you write them
in alphabetical order - hence ethyl comes before methyl which in
turn comes before propyl.

The cycloalkanes

In a cycloalkane the carbon atoms are joined up in a ring - hence

cyclo.

Example: Write the structural formula for cyclohexane.

hexan shows 6 carbons with no carbon-carbon double bonds.

cyclo shows that they are in a ring. Drawing the ring and putting in
the correct number of hydrogens to satisfy the bonding
requirements of the carbons gives:
The alkenes

Example 1: Write the structural formula for propene.

prop counts 3 carbon atoms in the longest chain. en tells you that
there is a carbon-carbon double bond. That means that the carbon
skeleton looks like this:

Putting in the hydrogens gives you:

Example 2: Write the structural formula for but-1-ene.

but counts 4 carbon atoms in the longest chain and en tells you
that there is a carbon-carbon double bond. The number in the
name tells you where the double bond starts.

No number was necessary in the propene example above because

the double bond has to start on one of the end carbon atoms. In the
case of butene, though, the double bond could either be at the end
of the chain or in the middle - and so the name has to code for the
its position.

The carbon skeleton is:

And the full structure is:

Incidentally, you might equally well have decided that the right-
hand carbon was the number 1 carbon, and drawn the structure as:

Example 3: Write the structural formula for 3-methylhex-2-ene.

The longest chain has got 6 carbon atoms (hex) with a double
bond starting on the second one (-2-en).

But this time there is a methyl group attached to the chain on the
number 3 carbon atom, giving you the underlying structure:
Adding the hydrogens gives the final structure:

Be very careful to count the bonds around each carbon atom when
you put the hydrogens in. It would be very easy this time to make
the mistake of writing an H after the third carbon - but that would
give that carbon a total of 5 bonds.

Compounds containing halogens

Example 1: Write the structural formula for 1,1,1-trichloroethane.

This is a two carbon chain (eth) with no double bonds (an). There
are three chlorine atoms all on the first carbon atom.

Example 2: Write the structural formula for 2-bromo-2-

methylpropane.

First sort out the carbon skeleton. It's a three carbon chain with no
double bonds and a methyl group on the second carbon atom.

Draw the bromine atom which is also on the second carbon.

And finally put the hydrogen atoms in.

If you had to name this yourself:

Notice that the whole of the hydrocarbon part of the name is written
together - as methylpropane - before you start adding anything else
on to the name.

Example 2: Write the structural formula for 1-iodo-3-methylpent-

2-ene.

This time the longest chain has 5 carbons (pent), but has a double
bond starting on the number 2 carbon. There is also a methyl group
on the number 3 carbon.

Now draw the iodine on the number 1 carbon.

Giving a final structure:

Note: You could equally well draw this molecule the other
way round, but normally where you have, say, 1-bromo-
something, you tend to write the bromine (or other halogen)
on the right-hand end of the structure.

Alcohols

All alcohols contain an -OH group. This is shown in a name by the

ending ol.

Example 1: Write the structural formula for methanol.

This is a one carbon chain with no carbon-carbon double bond

(obviously!). The ol ending shows it's an alcohol and so contains
an -OH group.

Example 2: Write the structural formula for 2-methylpropan-1-ol.

The carbon skeleton is a 3 carbon chain with no carbon-carbon

double bonds, but a methyl group on the number 2 carbon.

The -OH group is attached to the number 1 carbon.

The structure is therefore:

Example 3: Write the structural formula for ethane-1,2-diol.

This is a two carbon chain with no double bond. The diol shows 2
-OH groups, one on each carbon atom.

Note: There's no particular significance in the fact that this

formula has the carbon chain drawn vertically. If you draw it
horizontally, unless you stretch the carbon-carbon bond a lot,
the -OH groups look very squashed together. Drawing it
vertically makes it look tidier!

Aldehydes

All aldehydes contain the group:

If you are going to write this in a condensed form, you write it as

-CHO - never as -COH, because that looks like an alcohol.

The names of aldehydes end in al.

Example 1: Write the structural formula for propanal.

This is a 3 carbon chain with no carbon-carbon double bonds. The

al ending shows the presence of the -CHO group. The carbon in
that group counts as one of the chain.

Example 2: Write the structural formula for 2-methylpentanal.

This time there are 5 carbons in the longest chain, including the
one in the -CHO group. There aren't any carbon-carbon double
bonds. A methyl group is attached to the number 2 carbon. Notice
that in aldehydes, the carbon in the -CHO group is always counted
as the number 1 carbon.
Ketones

Ketones contain a carbon-oxygen double bond just like aldehydes,

but this time it's in the middle of a carbon chain. There isn't a
hydrogen atom attached to the group as there is in aldehydes.

Ketones are shown by the ending one.

Example 1: Write the structural formula for propanone.

This is a 3 carbon chain with no carbon-carbon double bond. The

carbon-oxygen double bond has to be in the middle of the chain
and so must be on the number 2 carbon.

Ketones are often written in this way to emphasise the carbon-

oxygen double bond.

Example 2: Write the structural formula for pentan-3-one.

This time the position of the carbon-oxygen double bond has to be

stated because there is more than one possibility. It's on the third
carbon of a 5 carbon chain with no carbon-carbon double bonds. If
it was on the second carbon, it would be pentan-2-one.

This could equally well be written:

© Jim Clark 2000

THE NAMES OF MORE ORGANIC
COMPOUNDS

This page continues looking at the names of organic compounds

containing chains of carbon atoms. It assumes that you have
already looked at the introductory page covering compounds from
alkanes to ketones.
Note: If you haven't already looked at that page, it would be a
good idea to do so before you go on. The names on this
second page aren't explained in quite as much detail as those
on the introductory page - it assumes that you have already
understood the main principles. If in doubt, follow this link first.
More types of organic compound

Carboxylic acids

Carboxylic acids contain the -COOH group, which is better written

out in full as:

Carboxylic acids are shown by the ending oic acid. When you
count the carbon chain, you have to remember to include the
carbon in the -COOH group. That carbon is always thought of as
number 1 in the chain.

Example 1: Write the structural formula for 3-methylbutanoic

acid.

This is a four carbon acid with no carbon-carbon double bonds.

There is a methyl group on the third carbon (counting the -COOH
carbon as number 1).

Example 2: Write the structural formula for 2-hydroxypropanoic

acid.

The hydroxy part of the name shows the presence of an -OH

group. Normally, you would show that by the ending ol, but this
time you can't because you've already got another ending. You are
forced into this alternative way of describing it.

The old name for 2-hydroxypropanoic acid is lactic acid. That name
sounds more friendly, but is utterly useless when it comes to writing
a formula for it. In the old days, you would have had to learn the
formula rather than just working it out should you need it.

Example 3: Write the structural formula for 2-chlorobut-3-enoic

acid.

This time, not only is there a chlorine attached to the chain, but the
chain also contains a carbon-carbon double bond (en) starting on
the number 3 carbon (counting the -COOH carbon as number 1).
Salts of carboxylic acids

Example: Write the structural formula for sodium propanoate.

This is the sodium salt of propanoic acid - so start from that.

Propanoic acid is a three carbon acid with no carbon-carbon
double bonds.

When the carboxylic acids form salts, the hydrogen in the -COOH
group is replaced by a metal. Sodium propanoate is therefore:

Notice that there is an ionic bond between the sodium and the
propanoate group. Whatever you do, don't draw a line between the
sodium and the oxygen. That would represent a covalent bond. It's
wrong, and makes you look very incompetent in an exam!

In a shortened version, sodium propanoate would be written

CH3CH2COONa or, if you wanted to emphasise the ionic nature, as
CH3CH2COO- Na+.
Note: The confusing thing about these salts (and even more
so for the esters that are coming up next) is that they are
named the wrong way round. In the formula, the sodium is at
the end, but appears first in the name. Why?

Salts are always named with the metal first - think of sodium
chloride or potassium iodide. So for consistency you would
need to reverse the formula of sodium propanoate -
NaOOCCH2CH3. But if you reverse the formula, you can't see
immediately that it is related to propanoic acid. So you learn to
live with the inconsistency.

Esters

Esters are one of a number of compounds known collectively as

acid derivatives. In these the acid group is modified in some way.
In an ester, the hydrogen in the -COOH group is replaced by an
alkyl group (or possibly some more complex hydrocarbon group).

Example 1: Write the structural formula for methyl propanoate.

An ester name has two parts - the part that comes from the acid
(propanoate) and the part that shows the alkyl group (methyl).

Start by thinking about propanoic acid - a 3 carbon acid with no

carbon-carbon double bonds.

The hydrogen in the -COOH group is replaced by an alkyl group -

in this case, a methyl group.

Ester names are confusing because the name is written backwards

from the way the structure is drawn. There's no way round this -
you just have to get used to it!

In the shortened version, this formula would be written

CH3CH2COOCH3.

Example 2: Write the structural formula for ethyl ethanoate.

This is probably the most commonly used example of an ester. It is

based on ethanoic acid ( hence, ethanoate) - a 2 carbon acid. The
hydrogen in the -COOH group is replaced by an ethyl group.

Make sure that you draw the ethyl group the right way round. A
fairly common mistake is to try to join the CH3 group to the oxygen.
If you count the bonds if you do that, you will find that both the CH3
carbon and the CH2 carbon have the wrong number of bonds.

Acyl chlorides (acid chlorides)

An acyl chloride is another acid derivative. In this case, the -OH

group of the acid is replaced by -Cl. All acyl chlorides contain the
-COCl group:

Example: Write the structural formula for ethanoyl chloride.

Acyl chlorides are shown by the ending oyl chloride. So ethanoyl

chloride is based on a 2 carbon chain with no carbon-carbon
double bonds and a -COCl group. The carbon in that group counts
as part of the chain. In a longer chain, with side groups attached,
the -COCl carbon is given the number 1 position.

Acid anhydrides

Another acid derivative! An acid anhydride is what you get if you

dehydrate an acid - that is, remove water from it.

Example: Write the structural formula for propanoic anhydride.

These are most easily worked out by writing it down on a scrap of

paper in the following way:

Draw two molecules of acid arranged so that the -OH groups are
next to each other. Tweak out a molecule of water - and then join
up what's left. In this case, because you want propanoic anhydride,
you draw two molecules of propanoic acid.

Amides

Yet another acid derivative! Amides contain the group -CONH2

where the -OH of an acid is replaced by -NH2.
Example: Write the structural formula for propanamide.

This is based on a 3 carbon chain with no carbon-carbon double

bonds. At the end of the chain is a -CONH2 group. The carbon in
that group counts as part of the chain.

Nitriles

Nitriles contain a -CN group, and used to be called cyanides.

Example 1: Write the structural formula for ethanenitrile.

The name shows a 2 carbon chain with no carbon-carbon double

bond. nitrile shows a -CN group at the end of the chain. As with
the previous examples involving acids and acid derivatives, don't
forget that the carbon in the -CN group counts as part of the chain.

The old name for this would have been methyl cyanide. You might
think that that's easier, but as soon as the chain gets more
complicated, it doesn't work - as the next example shows.

Example 2: Write the structural formula for 2-

hydroxypropanenitrile.

Here we've got a 3 carbon chain, no carbon-carbon double bonds,

and a -CN group on the end of the chain. The carbon in the -CN
group counts as the number 1 carbon. On the number 2 carbon
there is an -OH group (hydroxy). Notice that you can't use the ol
ending because you've already got a nitrile ending.

Primary amines

A primary amine contains the group -NH2 attached to a

hydrocarbon chain or ring. You can think of amines in general as
being derived from ammonia, NH3. In a primary amine, one of the
hydrogens has been replaced by a hydrocarbon group.
Example 1: Write the structural formula for ethylamine.

In this case, an ethyl group is attached to the -NH2 group.

This name (ethylamine) is fine as long as you've only got a short

chain where there isn't any ambiguity about where the -NH2 group
is found. But suppose you had a 3 carbon chain - in this case, the
-NH2 group could be on an end carbon or on the middle carbon.
How you get around that problem is illustrated in the next example.

Example 2: Write the structural formula for 2-aminopropane.

The name shows a 3 carbon chain with an amino group attached to

the second carbon. amino shows the -NH2 group.

Ethylamine (example 1 above) could equally well have been called

aminoethane.

Secondary and tertiary amines

You are only likely to come across simple examples of these. In a

secondary amine, two of the hydrogen atoms in an ammonia
molecule have been replaced by hydrocarbon groups. In a tertiary
amine, all three hydrogens have been replaced.

Example 1: Write the structural formula for dimethylamine.

In this case, two of the hydrogens in ammonia have been replaced

by methyl groups.

Example 2: Write the structural formula for trimethylamine.

Here, all three hydrogens in ammonia have been replaced by

methyl groups.
Amino acids

An amino acid contains both an amino group, -NH2, and a

carboxylic acid group, -COOH, in the same molecule. As with all
acids the carbon chain is numbered so that the carbon in the
-COOH group is counted as number 1.

Example: Write the structural formula for 2-aminopropanoic

acid.

This has a 3 carbon chain with no carbon-carbon double bonds. On

the second carbon (counting the -COOH carbon as number 1)
there is an amino group, -NH2.

© Jim Clark 2000

THE NAMES OF AROMATIC
COMPOUNDS

This page looks at the names of some simple aromatic

compounds. An aromatic compound is one which contains a
benzene ring. It assumes that you are reasonably confident about
naming compounds containing chains of carbon atoms (aliphatic
compounds).
Note: If you aren't sure about naming aliphatic compounds follow
this link before you go on.

Naming aromatic compounds isn't quite so straightforward as

naming chain compounds. Often, more than one name is
acceptable and it's not uncommon to find the old names still in use
as well.

Background

The benzene ring

All aromatic compounds are based on benzene, C6H6, which has a

ring of six carbon atoms and has the symbol:

Each corner of the hexagon has a carbon atom with a hydrogen

attached.
Note: If you don't understand this structure, it is explained in full
in two pages on the structure of benzene elsewhere in this site.
Following this link could well take you some time!

The phenyl group

Remember that you get a methyl group, CH3, by removing a

hydrogen from methane, CH4.

You get a phenyl group, C6H5, by removing a hydrogen from a

benzene ring, C6H6. Like a methyl or an ethyl group, a phenyl group
is always attached to something else.
Aromatic compounds with only one group attached to
the benzene ring

Cases where the name is based on benzene

chlorobenzene

This is a simple example of a halogen attached to the benzene

ring. The name is self-obvious.

The simplified formula for this is C6H5Cl. You could therefore

(although you never do!) call it phenyl chloride. Whenever you draw
a benzene ring with one other thing attached to it, you are in fact
drawing a phenyl group. In order to attach something else, you
have to remove one of the existing hydrogen atoms, and so
automatically make a phenyl group.

nitrobenzene

The nitro group, NO2, is attached to a benzene ring.

The simplified formula for this is C6H5NO2.

methylbenzene

Another obvious name - the benzene ring has a methyl group

attached. Other alkyl side-chains would be named similarly - for
example, ethylbenzene. The old name for methylbenzene is
toluene, and you may still meet that.

The simplified formula for this is C6H5CH3.

(chloromethyl)benzene

A variant on this which you may need to know about is where one
of the hydrogens on the CH3 group is replaced by a chlorine atom.
Notice the brackets around the (chloromethyl) in the name. This is
so that you are sure that the chlorine is part of the methyl group
and not somewhere else on the ring.

If more than one of the hydrogens had been replaced by chlorine,

the names would be (dichloromethyl)benzene or
(trichloromethyl)benzene. Again, notice the importance of the
brackets in showing that the chlorines are part of the side group
and not directly attached to the ring.

benzoic acid (benzenecarboxylic acid)

Benzoic acid is the older name, but is still in common use - it's a lot
easier to say and write than the modern alternative! Whatever you
call it, it has a carboxylic acid group, -COOH, attached to the
benzene ring.

Cases where the name is based on phenyl

Remember that the phenyl group is a benzene ring minus a

hydrogen atom - C6H5. If you draw a benzene ring with one group
attached, you have drawn a phenyl group.

phenylamine

Phenylamine is a primary amine and contains the -NH2 group

attached to a benzene ring.

The old name for phenylamine is aniline, and you could also
reasonably call it aminobenzene. Phenylamine is what it is most
commonly for UK-based exam purposes.
Note: In all cases where there is some possibility of alternative
 names, you need to know what your examiners are likely to call a
particular compound. Refer to your syllabus and recent exam
papers. If you are working to a UK-based syllabus for 16 - 8 year
olds, and haven't got these, follow this link to find out how to get
hold of them.

phenylethene

This is an ethene molecule with a phenyl group attached. Ethene is

a two carbon chain with a carbon-carbon double bond.
Phenylethene is therefore:

The old name for phenylethene is styrene - the monomer from

which polystyrene is made.

phenylethanone

This is a slightly awkward name - take it to pieces. It consists of a

two carbon chain with no carbon-carbon double bond. The one
ending shows that it is a ketone, and so has a C=O group
somewhere in the middle. Attached to the carbon chain is a phenyl
group. Putting that together gives:

phenyl ethanoate

This is an ester based on ethanoic acid. The hydrogen atom in the

-COOH group has been replaced by a phenyl group.

Note: If you aren't happy about naming esters, follow this link
before you go on.

phenol

Phenol has an -OH group attached to a benzene ring and so has a

formula C6H5OH.

Aromatic compounds with more than one group

attached to the benzene ring

Numbering the ring

Any group already attached to the ring is given the number 1

position. Where you draw it on the ring (at the top or in any other
position) doesn't matter - that's just a question of rotating the
molecule a bit. It's much easier, though, to get in the habit of
drawing your main group at the top.

The other ring positions are then numbered from 2 to 6. You can
number them either clockwise or anti-clockwise. As with chain
compounds, you number the ring so that the name you end up with
has the smallest possible numbers in it. Examples will make this
clear.

Some simple examples

Substituting chlorine atoms on the ring

Look at these compounds:

All of these are based on methylbenzene and so the methyl group

is given the number 1 position on the ring.

Why is it 2-chloromethylbenzene rather than 6-

chloromethylbenzene? The ring is numbered clockwise in this case
because that produces a 2- in the name rather than a 6-. 2 is
smaller than 6.
Warning! You will find all sorts of variations on this depending on
the age of the book you look it up in, and where it was published.
What I have described above isn't in strict accordance with the
 most modern interpretation of the IUPAC recommendations for
naming organic compounds.

The names should actually be 1-chloro-2-methylbenzene, 1-

chloro-3-methylbenzene, and so on. The substituted groups are
named in alphabetical order, and the "1" position is assigned to
the first of these - rather than to the more logical methyl group.

This produces some silly inconsistencies. For example, if you had

the exactly equivalent compounds containing nitro groups in place
of the chlorines, the names would change completely, to 1-
methyl-2-nitrobenzene, 1-methyl-3-nitrobenzene, etc. In this case,
the normal practice of naming the hydrocarbon first, and then
attaching other things to it has been completely wrecked.

Do you need to worry about this? NO! It is extremely unlikely that

you would ever be asked to name these in an exam, and it is
always easy to write a structure from one of these names -
however illogical it may be! There is a simple rule for exam
purposes. Unless you are specifically asked for the name of
anything remotely complicated, don't give it. As long as you have
got the structure right, that's all that matters.

2-hydroxybenzoic acid

This might also be called 2-hydroxybenzenecarboxylic acid. There

is a -COOH group attached to the ring and, because the name is
based on benzoic acid, that group is assigned the number 1
position. Next door to it in the 2 position is a hydroxy group, -OH.

benzene-1,4-dicarboxylic acid

The di shows that there are two carboxylic acid groups, -COOH,
one of them in the 1 position and the other opposite it in the 4
position.

2,4,6-trichlorophenol

This is based on phenol - with an -OH group attached in the

number 1 position on the ring. There are 3 chlorine atoms
substituted onto the ring in the 2, 4 and 6 positions.
methyl 3-nitrobenzoate

This is a name you might come across as a part of a practical

exercise in nitrating benzene rings. It's included partly for that
reason, and partly because it is a relatively complicated name to
finish with!

The structure of the name shows that it is an ester. You can tell
that from the oate ending, and the methyl group floating separately
from the rest of the name at the beginning.

The ester is based on the acid, 3-nitrobenzoic acid - so start with

that.

There will be a benzene ring with a -COOH group in the number 1

position and a nitro group, NO2, in the 3 position. The -COOH
group is modified to make an ester by replacing the hydrogen of
the -COOH group by a methyl group.

Methyl 3-nitrobenzoate is therefore:

 USING CURLY ARROWS IN
REACTION MECHANISMS

This page explains the use of curly arrows to show the movement
both of electron pairs and of single electrons during organic
reaction mechanisms.

You can jump straight to the movement of single electrons further

down this page if that is all you are interested in for the moment (for
example, if you are currently working on free radical reactions).

Using curly arrows to show the movement of electron

pairs

Curly arrows (and that's exactly what they are called!) are used in
mechanisms to show the various electron pairs moving around.
You mustn't use them for any other purpose.

• The arrow tail is where the electron pair starts from. That's
always fairly obvious, but you must show the electron pair
either as a bond or, if it is a lone pair, as a pair of dots.
Remember that a lone pair is a pair of electrons at the
bonding level which isn't currently being used to join on to
anything else.
• The arrow head is where you want the electron pair to end
up.

For example, in the reaction between ethene and hydrogen

 bromide, one of the two bonds between the two
carbon atoms breaks. That bond is simply a pair of
electrons.

Those electrons move to form a new bond with the

hydrogen from the HBr. At the same time the pair of electrons in
the hydrogen-bromine bond moves down on to the bromine atom.

There's no need to draw the pairs of electrons in the bonds as two

dots. Drawing the bond as a line is enough, but you
could put two dots in as well if you wanted to.

Notice that the arrow head points between the C

and H because that's where the electron pair ends
up. Notice also that the electron movement between the H and Br
is shown as a curly arrow even though the electron pair moves
straight down. You have to show electron pair movements as curly
arrows - not as straight ones.

The second stage of this reaction nicely illustrates how you use a
curly arrow if a lone pair of electrons is involved.

The first stage leaves you with a positive charge on the right hand
carbon atom and a negative bromide ion. You can think of the
electrons shown on the bromide ion as being the ones which
originally made up the hydrogen-bromine bond.
Note: There are another three lone pairs around the
outside of the bromide ion - making four in all. These
aren't normally shown because they don't actually do
anything new and interesting!

However, it is essential that you show the lone pair you

are interested in as a pair of dots. If you don't, you risk
losing marks in an exam.

The lone pair on the bromide ion moves to form a new bond
between the bromine and the right hand carbon atom. That
movement is again shown by a curly arrow. Notice again, that the
curly arrow points between the carbon and the bromine because
that's where the electron pair ends up.

That leaves you with the product of this reaction, bromoethane:

Note: You can read a full description of this

mechanism together with other similar reactions of
ethene and the other alkenes by following this link.
Using curly arrows to show the movement of single
electrons

The most common use of "curly arrows" is to show the movement

of pairs of electrons. You can also use similar arrows to show the
movement of single electrons - except that the heads of these
arrows only have a single line rather than two lines.

shows the movement of an electron pair

shows the movement of a single electron

The first stage of the polymerisation of ethene, for example, could

be shown as:

You should draw the dots showing the interesting electrons. The
half arrows show where they go. This is very much a "belt-and-
braces" job, and the arrows don't add much.

Whether you choose to use these half arrows to show the

movement of a single electron should be governed by what your
syllabus says. If your syllabus encourages the use of these arrows,
then it makes sense to use them. If not - if the syllabus says that
they "may" be used, or just ignores them altogether - then they are
as well avoided.

There is some danger of confusing them with the arrows showing

electron pair movements, which you will use all the time. If, by
mistake, you use an ordinary full arrow to show the movement of a
single electron you run the risk of losing marks.
STRUCTURAL ISOMERISM

This page explains what structural isomerism is, and looks at some
of the various ways that structural isomers can arise.

What is structural isomerism?

What are isomers?

Isomers are molecules that have the same molecular formula, but
have a different arrangement of the atoms in space. That excludes
any different arrangements which are simply due to the molecule
rotating as a whole, or rotating about particular bonds.

For example, both of the following are the same molecule. They
are not isomers. Both are butane.

There are also endless other possible ways that this molecule
could twist itself. There is completely free rotation around all the
carbon-carbon single bonds.
Note: Isomerism is much easier to understand if you have
actually got some models to play with. If your school or college
hasn't given you the opportunity to play around with molecular
models in the early stages of your organic chemistry course,
you might consider getting hold of a cheap set. The models
made by molymod are both cheap and easy to use. An
introductory organic set is more than adequate. Find them at
www.molymod.com.

Alternatively , get hold of some coloured Plasticene and some

used matches and make your own.

If you had a model of a molecule in front of you, you would have to

take it to pieces and rebuild it if you wanted to make an isomer of
that molecule. If you can make an apparently different molecule
just by rotating single bonds, it's not different - it's still the same
molecule.
Note: It's really important that you understand this. If you
aren't sure, then you must get hold of (or make) some models.

What are structural isomers?

In structural isomerism, the atoms are arranged in a completely

different order. This is easier to see with specific examples.

What follows looks at some of the ways that structural isomers can
arise. The names of the various forms of structural isomerism
probably don't matter all that much, but you must be aware of the
different possibilities when you come to draw isomers.

Types of structural isomerism

Chain isomerism

These isomers arise because of the possibility of branching in

carbon chains. For example, there are two isomers of butane,
C4H10. In one of them, the carbon atoms lie in a "straight chain"
whereas in the other the chain is branched.

Note: Although the chain is drawn as straight, in reality it's

anything but straight. If you aren't happy about the ways of
drawing organic molecules, follow this link.

Use the BACK button on your browser to return to this page.

Be careful not to draw "false" isomers which are just

twisted versions of the original molecule. For example,
this structure is just the straight chain version of butane
rotated about the central carbon-carbon bond.

You could easily see this with a model. This is the example we've
already used at the top of this page.
Pentane, C5H12, has three chain isomers. If you think you can find
any others, they are simply twisted versions of the ones below. If in
doubt make some models.

Position isomerism

In position isomerism, the basic carbon skeleton remains

unchanged, but important groups are moved around on that
skeleton.

For example, there are two structural isomers with the molecular
formula C3H7Br. In one of them the bromine atom is on the end of
the chain, whereas in the other it's attached in the middle.

If you made a model, there is no way that you could twist one
molecule to turn it into the other one. You would have to break the
bromine off the end and re-attach it in the middle. At the same time,
you would have to move a hydrogen from the middle to the end.

Another similar example occurs in alcohols such as C4H9OH

These are the only two possibilities provided you keep to a four
carbon chain, but there is no reason why you should do that. You
can easily have a mixture of chain isomerism and position
isomerism - you aren't restricted to one or the other.

So two other isomers of butanol are:

Note: It's essential if you are asked to draw isomers in an

exam not to restrict yourself to chain isomers or position
isomers. You must be aware of all the possibilities.

You can also get position isomers on benzene rings. Consider the
molecular formula C7H8Cl. There are four different isomers you
could make depending on the position of the chlorine atom. In one
case it is attached to the side-group carbon atom, and then there
are three other possible positions it could have around the ring -
next to the CH3 group, next-but-one to the CH3 group, or opposite
the CH3 group.

Functional group isomerism

In this variety of structural isomerism, the isomers contain different

functional groups - that is, they belong to different families of
compounds (different homologous series).

For example, a molecular formula C3H6O could be either propanal

(an aldehyde) or propanone (a ketone).

There are other possibilities as well for this same molecular formula
- for example, you could have a carbon-carbon double bond (an
alkene) and an -OH group (an alcohol) in the same molecule.

Another common example is illustrated by the molecular formula

C3H6O2. Amongst the several structural isomers of this are
propanoic acid (a carboxylic acid) and methyl ethanoate (an ester).

Note: To repeat the warning given earlier: If you are asked to

draw the structural isomers from a given molecular formula,
don't forget to think about all the possibilities. Can you branch
the carbon chain? Can you move a group around on that
chain? Is it possible to make more than one type of
compound?

Be careful though! If you are asked to draw the structures of

esters with the molecular formula C3H6O2, you aren't going to
get a lot of credit for drawing propanoic acid, even if it is a valid
isomer.

STEREOISOMERISM - GEOMETRIC
ISOMERISM

Geometric isomerism (also known as cis-trans isomerism or E-Z

isomerism) is a form of stereoisomerism. This page explains what
stereoisomers are and how you recognise the possibility of
geometric isomers in a molecule.

Further down the page, you will find a link to a second page which
describes the E-Z notation for naming geometric isomers. You
shouldn't move on to that page (even if the E-Z notation is what
your syllabus is asking for) until you are really confident about how
geometric isomers arise and how they are named on the cis-trans
system.

The E-Z system is better for naming more complicated structures

but is more difficult to understand than cis-trans. The cis-trans
system of naming is still widely used - especially for the sort of
simple molecules you will meet at this level. That means that
irrespective of what your syllabus might say, you will have to be
familiar with both systems. Get the easier one sorted out before
you go on to the more sophisticated one!

What is stereoisomerism?

What are isomers?

Isomers are molecules that have the same molecular formula, but
have a different arrangement of the atoms in space. That excludes
any different arrangements which are simply due to the molecule
rotating as a whole, or rotating about particular bonds.

Where the atoms making up the various isomers are joined up in a

different order, this is known as structural isomerism. Structural
isomerism is not a form of stereoisomerism, and is dealt with on a
separate page.
Note: If you aren't sure about structural isomerism, it might be
worth reading about it before you go on with this page.

What are stereoisomers?

In stereoisomerism, the atoms making up the isomers are joined up

in the same order, but still manage to have a different spatial
arrangement. Geometric isomerism is one form of
stereoisomerism.

Geometric (cis / trans) isomerism

How geometric isomers arise

These isomers occur where you have restricted rotation

somewhere in a molecule. At an introductory level in organic
chemistry, examples usually just involve the carbon-carbon double
bond - and that's what this page will concentrate on.

Think about what happens in molecules where there is unrestricted

rotation about carbon bonds - in other words where the carbon-
carbon bonds are all single. The next diagram shows two possible
configurations of 1,2-dichloroethane.
These two models represent exactly the same molecule. You can
get from one to the other just by twisting around the carbon-carbon
single bond. These molecules are not isomers.

If you draw a structural formula instead of using models, you have

to bear in mind the possibility of this free rotation about single
bonds. You must accept that these two structures represent the
same molecule:

But what happens if you have a carbon-carbon double bond - as in

1,2-dichloroethene?

These two molecules aren't the same. The carbon-carbon double

bond won't rotate and so you would have to take the models to
pieces in order to convert one structure into the other one. That is a
simple test for isomers. If you have to take a model to pieces to
convert it into another one, then you've got isomers. If you merely
have to twist it a bit, then you haven't!
Note: In the model, the reason that you can't rotate a carbon-
carbon double bond is that there are two links joining the
carbons together. In reality, the reason is that you would have
to break the pi bond. Pi bonds are formed by the sideways
overlap between p orbitals. If you tried to rotate the carbon-
carbon bond, the p orbitals won't line up any more and so the
pi bond is disrupted. This costs energy and only happens if the
compound is heated strongly.

If you are interested in the bonding in carbon-carbon double

bonds, follow this link. Be warned, though, that you might have
 to read several pages of background material and it could all
take a long time. It isn't necessary for understanding the rest of
this page.

Drawing structural formulae for the last pair of models gives two
possible isomers.

In one, the two chlorine atoms are locked on opposite sides of the
double bond. This is known as the trans isomer. (trans : from latin
meaning "across" - as in transatlantic).

In the other, the two chlorine atoms are locked on the same side of
the double bond. This is know as the cis isomer. (cis : from latin
meaning "on this side")

The most likely example of geometric isomerism you will meet at

an introductory level is but-2-ene. In one case, the CH3 groups are
on opposite sides of the double bond, and in the other case they
are on the same side.

The importance of drawing geometric isomers properly

It's very easy to miss geometric isomers in exams if you take short-
cuts in drawing the structural formulae. For example, it is very
tempting to draw but-2-ene as

CH3CH=CHCH3

If you write it like this, you will almost certainly miss the fact that
there are geometric isomers. If there is even the slightest hint in a
question that isomers might be involved, always draw compounds
containing carbon-carbon double bonds showing the correct bond
angles (120°) around the carbon atoms at the ends of the bond. In
other words, use the format shown in the last diagrams above.
How to recognise the possibility of geometric isomerism

You obviously need to have restricted rotation somewhere in the

molecule. Compounds containing a carbon-carbon double bond
have this restricted rotation. (Other sorts of compounds may have
restricted rotation as well, but we are concentrating on the case
you are most likely to meet when you first come across geometric
isomers.) If you have a carbon-carbon double bond, you need to
think carefully about the possibility of geometric isomers.

What needs to be attached to the carbon-carbon double

bond?
Note: This is much easier to understand if you have actually
got some models to play with. If your school or college hasn't
given you the opportunity to play around with molecular models
in the early stages of your organic chemistry course, you might
consider getting hold of a cheap set. The models made by
molymod are both cheap and easy to use. An introductory
organic set is more than adequate. Find them at
www.molymod.com.

Alternatively , get hold of some coloured Plasticene and some

used matches and make your own.

Think about this case:

Although we've swapped the right-hand groups around, these are

still the same molecule. To get from one to the other, all you would
have to do is to turn the whole model over.

You won't have geometric isomers if there are two groups the
same on one end of the bond - in this case, the two pink groups on
the left-hand end.

So . . . there must be two different groups on the left-hand carbon

and two different groups on the right-hand one. The cases we've
been exploring earlier are like this:
But you could make things even more different and still have
geometric isomers:

Here, the blue and green groups are either on the same side of the
bond or the opposite side.

Or you could go the whole hog and make everything different. You
still get geometric isomers, but by now the words cis and trans are
meaningless. This is where the more sophisticated E-Z notation
comes in.

Summary

To get geometric isomers you must have:

• restricted rotation (often involving a carbon-carbon double

bond for introductory purposes);
• two different groups on the left-hand end of the bond and
two different groups on the right-hand end. It doesn't matter
whether the left-hand groups are the same as the right-hand
ones or not.

Note: The rest of this page looks at how geometric isomerism

affects the melting and boiling points of compounds. If you are
meeting geometric isomerism for the first time, you may not
need this at the moment.

If you need to know about E-Z notation, you could follow this
link at once to the next page. (But be sure that you understand
 what you have already read on this page first!)

Alternatively, read to the bottom of this page where you will

find this link repeated.

The effect of geometric isomerism on physical properties

The table shows the melting point and boiling point of the cis and
trans isomers of 1,2-dichloroethene.

isomer melting point (°C) boiling point (°C)

cis -80 60

trans -50 48

In each case, the higher melting or boiling point is shown in red.

You will notice that:

• the trans isomer has the higher melting point;

• the cis isomer has the higher boiling point.

This is common. You can see the same effect with the cis and
trans isomers of but-2-ene:

isomer melting point (°C) boiling point (°C)

cis-but-2-ene -139 4

trans-but-2-ene -106 1

Why is the boiling point of the cis isomers higher?

There must be stronger intermolecular forces between the

molecules of the cis isomers than between trans isomers.

Taking 1,2-dichloroethene as an example:

Both of the isomers have exactly the same atoms joined up in

exactly the same order. That means that the van der Waals
dispersion forces between the molecules will be identical in both
cases.

The difference between the two is that the cis isomer is a polar
molecule whereas the trans isomer is non-polar.
Note: If you aren't sure about intermolecular forces (and also
about bond polarity), it is essential that you follow this link
before you go on. You need to know about van der Waals
dispersion forces and dipole-dipole interactions, and to follow
the link on that page to another about bond polarity if you need
to.

Use the BACK button on your browser to return to this page.

Both molecules contain polar chlorine-carbon bonds, but in the cis

isomer they are both on the same side of the molecule. That
means that one side of the molecule will have a slight negative
charge while the other is slightly positive. The molecule is therefore
polar.

Because of this, there will be dipole-dipole interactions as well as

dispersion forces - needing extra energy to break. That will raise
the boiling point.

A similar thing happens where there are CH3 groups attached to

the carbon-carbon double bond, as in cis-but-2-ene.

Alkyl groups like methyl groups tend to "push" electrons away from
themselves. You again get a polar molecule, although with a
reversed polarity from the first example.

Note: The term "electron pushing" is only to help remember

what happens. The alkyl group doesn't literally "push" the
electrons away - the other end of the bond attracts them more
strongly. The arrows with the cross on (representing the more
positive end of the bond) are a conventional way of showing
this electron pushing effect.

By contrast, although there will still be polar bonds in the trans

isomers, overall the molecules are non-polar.
The slight charge on the top of the molecule (as drawn) is exactly
balanced by an equivalent charge on the bottom. The slight charge
on the left of the molecule is exactly balanced by the same charge
on the right.

This lack of overall polarity means that the only intermolecular

attractions these molecules experience are van der Waals
dispersion forces. Less energy is needed to separate them, and so
their boiling points are lower.

Why is the melting point of the cis isomers lower?

You might have thought that the same argument would lead to a
higher melting point for cis isomers as well, but there is another
important factor operating.

In order for the intermolecular forces to work well, the molecules

must be able to pack together efficiently in the solid.

Trans isomers pack better than cis isomers. The "U" shape of the
cis isomer doesn't pack as well as the straighter shape of the trans
isomer.

The poorer packing in the cis isomers means that the

intermolecular forces aren't as effective as they should be and so
less energy is needed to melt the molecule - a lower melting point.

E-Z NOTATION FOR GEOMETRIC

ISOMERISM
This page explains the E-Z system for naming geometric isomers.
Important! If you have come straight here via a search engine
(including the Google site search on the Main Menu of
Chemguide), you should be aware that this page follows on
from an introductory page about geometric isomerism. Unless
you are already confident about how geometric isomers arise,
and the cis-trans system for naming them, you should follow
this link first. You will find links back to this current page at
suitable points on that page.

The E-Z system

The problem with the cis-trans system for naming geometric

isomers

Consider a simple case of geometric isomerism which we've

already discussed on the previous page.

You can tell which is the cis and which the trans form just by
looking at them. All you really have to remember is that trans
means "across" (as in transatlantic or transcontinental) and that cis
is the opposite. It is a simple and visual way of telling the two
isomers apart. So why do we need another system?

There are problems as compounds get more complicated. For

example, could you name these two isomers using cis and trans?

Because everything attached to the carbon-carbon double bond is

different, there aren't any obvious things which you can think of as
being "cis" or "trans" to each other. The E-Z system gets around
this problem completely - but unfortunately makes things slightly
more difficult for the simple examples you usually meet in
introductory courses.

How the E-Z system works

We'll use the last two compounds as an example to explain how

the system works.

You look at what is attached to each end of the double bond in

turn, and give the two groups a "priority" according to a set of rules
which we'll explore in a minute.

In the example above, at the left-hand end of the bond, it turns out
that bromine has a higher priority than fluorine. And on the right-
hand end, it turns out that chlorine has a higher priority than
hydrogen.

If the two groups with the higher priorities are on the same side of
the double bond, that is described as the (Z)- isomer. So you would
write it as (Z)-name of compound. The symbol Z comes from a
German word (zusammen) which means together.
Note: I'm not getting bogged down in the names of these
more complex compounds. As soon as I put the proper full
names in, the whole thing suddenly looks much more
complicated than it really is, and you will start to focus on
where the whole name comes from rather than on if it is a (Z)-
or (E)- isomer.

If the two groups with the higher priorities are on opposite sides of
the double bond, then this is the (E)- isomer. E comes from the
German entgegen which means opposite.

So the two isomers are:

Summary

• (E)- : the higher priority groups are on opposite sides of the

double bond.
 • (Z)- : the higher priority groups are on the same side of the
double bond.
Note: I wish I could think of a really good way to remember
this for non-German speakers - but I can't! If you have a way of
remembering it which might help other students, please get in
touch with me via the address on the about this site page.

Personally, I remember it as exactly the opposite of what you

might expect from the shapes of the letters E and Z. In the
case of the E, all the horizontal bits are on the same side of the
letter; in the case of Z, the horizontal bits are on different sides.
That's exactly the opposite of the arrangement of the groups in
E and Z isomers. It's a fairly unsatisfying way to remember it,
but it will have to do until someone gives me a better one!

Since writing this, I've had another suggestion which is Z =

"zame zide" and E = "epposite". I think that would work well if
English is your first language, but if it isn't, I'm not sure that you
will understand what is going on! More suggestions would be
welcome.

Rules for determining priorities

These are known as Cahn-Ingold-Prelog (CIP) rules after the

people who developed the system.

The first rule for very simple cases

You look first at the atoms attached directly to the carbon atoms at
each end of the double bond - thinking about the two ends
separately.

• The atom which has the higher atomic number is given the
higher priority.

Let's look at the example we've been talking about.

Just consider the first isomer - and look separately at the left-hand
and then the right-hand carbon atom. Compare the atomic
numbers of the attached atoms to work out the various priorities.
Notice that the atoms with the higher priorities are both on the
same side of the double bond. That counts as the (Z)- isomer.

The second isomer obviously still has the same atoms at each end,
but this time the higher priority atoms are on opposite sides of the
double bond. That's the (E)- isomer.

What about the more familiar examples like 1,2-dichloroethene or

but-2-ene? Here's 1,2-dichloroethene.

Think about the priority of the two groups on the first carbon of the
left-hand isomer.

Chlorine has a higher atomic number than hydrogen, and so has

the higher priority. That, of course, is equally true of all the other
carbon atoms in these two isomers.

In the first isomer, the higher priority groups are on opposite sides
of the bond. That must be the (E)- isomer. The other one, with the
higher priority groups on the same side, is the (Z)- isomer.

And now but-2-ene . . .

This adds the slight complication that you haven't got a single atom
attached to the double bond, but a group of atoms.

That isn't a problem. Concentrate on the atom directly attached to

the double bond - in this case the carbon in the CH3 group. For this
simple case, you can ignore the hydrogen atoms in the CH3 group
entirely. However, with more complicated groups you may have to
worry about atoms not directly attached to the double bond. We'll
look at that problem in a moment.

Here is one of the isomers of but-2-ene:

The CH3 group has the higher priority because its carbon atom has
an atomic number of 6 compared with an atomic number of 1 for
the hydrogen also attached to the carbon-carbon double bond.

The isomer drawn above has the two higher priority groups on
opposite sides of the double bond. The compound is (E)-but-2-ene.

A minor addition to the rule to allow for isotopes of, for

example, hydrogen

Deuterium is an isotope of hydrogen having a relative atomic mass

of 2. It still has only 1 proton, and so still has an atomic number of
1. However, it isn't the same as an atom of "ordinary" hydrogen,
and so these two compounds are geometric isomers:

The hydrogen and deuterium have the same atomic number - so

on that basis, they would have the same priority. In a case like that,
the one with the higher relative atomic mass has the higher priority.
So in these isomers, the deuterium and chlorine are the higher
priority groups on each end of the double bond.

That means that the left-hand isomer in the last diagram is the (E)-
form, and the right-hand one the (Z)-.

Extending the rules to more complicated molecules

If you are reading this because you are doing a course for 16 - 18
year olds such as UK A level, you may well not need to know much
about this section, but it really isn't very difficult!

Let's illustrate this by taking a fairly scary-looking molecule, and

seeing how easy it is to find out whether it is a (Z)- or (E)- isomer
by applying an extra rule.

Focus on the left-hand end of the molecule. What is attached

directly to the carbon-carbon double bond?

In both of the attached groups, a carbon atom is attached directly

to the bond. Those two atoms obviously have the same atomic
number and therefore the same priority. So that doesn't help.

In this sort of case, you now look at what is attached directly to

those two carbons (but without counting the carbon of the double
bond) and compare the priorities of these next lot of atoms.

You can do this in your head in simple cases, but it is sometimes

useful to write the attached atoms down, listing them with the
highest priority atom first. It makes them easier to compare. Like
this . . .

In the CH3 group:

The atoms attached to the carbon are H H H.

In the CH3CH2 group:

The atoms attached directly to the carbon of the CH2 group are C H
H.

In the second list, the C is written first because it has the highest
atomic number.

Now compare the two lists atom by atom. The first atom in each list
is an H in the CH3 group and a C in the CH3CH2 group. The carbon
has the higher priority because it has the higher atomic number. So
that gives the CH3CH2 group a higher priority than the CH3 group.

Now look at the other end of the double bond. The extra thing that
this illustrates is that if you have a double bond, you count the
attached atom twice. Here is the structure again.
So, again, the atoms attached directly to the carbon-carbon double
bond are both carbons. We therefore need to look at what is
attached to those carbons.

In the CH2OH group:

The atoms attached directly to the carbon are O H H.

In the CHO group:

The atoms attached directly to the carbon of the CH2 group are O
O H.

In both lists, the oxygens are written first because they have a
higher atomic number than hydrogen. In the CHO group list, the
oxygen is written twice because of the C=O double bond.

So, what is the priority of the two groups? The first atom in both
lists is an oxygen - that doesn't help. Look at the next atom in both
lists. In the CH2OH group, that's a hydrogen; in the CHO list, it's an
oxygen.

The oxygen has the higher priority - and that gives the CHO group
a higher priority than the CH2OH group.

The isomer is therefore a (Z)- form, because the two higher priority
groups (the CH3CH2 group and the CHO group) are both on the
same side of the bond.

That's been a fairly long-winded explanation just to make clear how

it works. With a bit of practice, it takes a few seconds to work out in
any but the most complex cases.

One more example to make a couple of additional minor points . . .

Here's an even more complicated molecule!

Before you read on, have a go at working out the relative priorities
of the two groups on the left-hand end of the double bond, and the
two on the right-hand end. There's another bit of rule that I haven't
specifically told you yet, but it isn't hard to guess what it might be
when you start to look at the problem. If you can work this out, then
you won't have any difficulty with any problem you are likely to
come across at this level.

Look first at the left-hand groups.

In both the top and bottom groups, you have a CH2 group attached
directly to the carbon-carbon double bond, and the carbon in that
CH2 group is also attached to another carbon atom. In each case,
the list will read C H H.

There is no difference between the priorities of those groups, so

what are you going to do about it? The answer is to move out along
the chain to the next group. And if necessary, continue to do this
until you have found a difference.

Next along the chain at the top left of the molecule is another CH2
group attached to a further carbon atom. The list for this group is
again C H H.

But the next group along the chain at the bottom left is a CH group
attached to two more carbon atoms. Its list is therefore C C H.

Comparing these lists atom by atom, leads you to the fact that the
bottom group has the higher priority.

Now look at the right-hand groups. Here is the molecule again:

The top right group has C H H attached to the first carbon in the
chain.
The bottom right one has Cl H H.

The chlorine has a higher atomic number than carbon, and so the
bottom right group has the higher priority of these two groups.

The extra point I am trying to make with this bit of the example is
that you must just focus on one bit of a chain at a time. We never
get around to considering the bromine at the extreme top right of
the molecule. We don't need to go out that far along the chain - you
work out one link at a time until you find a difference. Anything
beyond that is irrelevant.

For the record, this molecule is a (Z)- isomer because the higher
priority groups at each end are on the same side of the double
bond.

Can you easily translate cis- and trans- into (Z)- and (E)-?

You might think that for simple cases, cis- will just convert into (Z)-
and trans- into (E)-.

Look for example at the 1,2-dichloroethene and but-2-ene cases.

But it doesn't always work! Think about this relatively

uncomplicated molecule . . .

This is clearly a cis- isomer. It has two CH3 groups on the same
side of the double bond. But work out the priorities on the right-
hand end of the double bond.

The two directly attached atoms are carbon and bromine. Bromine
has the higher atomic number and so has the higher priority on that
end. At the other end, the CH3 group has the higher priority.

That means that the two higher priority groups are on opposite
sides of the double bond, and so this is an (E)- isomer - NOT a
(Z)-.

Never assume that you can convert directly from one of these
systems into the other. The only safe thing to do is to start from
scratch in each case.

Does it matter that the two systems will sometimes give different
results? No! The purpose of both systems is to enable you to
decode a name and write a correct formula. Properly used, both
systems will do this for you - although the cis-trans system will only
work for very straightforward molecules.

© Jim Clark 2007

STEREOISOMERISM - OPTICAL
ISOMERISM

Optical isomerism is a form of stereoisomerism. This page explains

what stereoisomers are and how you recognise the possibility of
optical isomers in a molecule.

What is stereoisomerism?

What are isomers?

Isomers are molecules that have the same molecular formula, but
have a different arrangement of the atoms in space. That excludes
any different arrangements which are simply due to the molecule
rotating as a whole, or rotating about particular bonds.

Where the atoms making up the various isomers are joined up in a

different order, this is known as structural isomerism. Structural
isomerism is not a form of stereoisomerism, and is dealt with on a
separate page.
Note: If you aren't sure about structural isomerism, it might be
worth reading about it before you go on with this page.

What are stereoisomers?

In stereoisomerism, the atoms making up the isomers are joined up

in the same order, but still manage to have a different spatial
arrangement. Optical isomerism is one form of stereoisomerism.
Optical isomerism

Why optical isomers?

Optical isomers are named like this because of their effect on plane
polarised light.
Help! If you don't understand about plane polarised light,
follow this link before you go on with this page.

Simple substances which show optical isomerism exist as two

isomers known as enantiomers.

• A solution of one enantiomer rotates the plane of

polarisation in a clockwise direction. This enantiomer is
known as the (+) form.

For example, one of the optical isomers (enantiomers) of the

amino acid alanine is known as (+)alanine.

• A solution of the other enantiomer rotates the plane of

polarisation in an anti-clockwise direction. This enantiomer is
known as the (-) form. So the other enantiomer of alanine is
known as or (-)alanine.
• If the solutions are equally concentrated the amount of
rotation caused by the two isomers is exactly the same - but
in opposite directions.

• When optically active substances are made in the lab, they

often occur as a 50/50 mixture of the two enantiomers. This
is known as a racemic mixture or racemate. It has no
effect on plane polarised light.
Note: One of the worrying things about optical isomerism is
the number of obscure words that suddenly get thrown at you.
Bear with it - things are soon going to get more visual!

There is an alternative way of describing the (+) and (-) forms

which is potentially very confusing. This involves the use of the
lowercase letters d- and l-, standing for dextrorotatory and
laevorotatory respectively. Unfortunately, there is another
different use of the capital letters D- and L- in this topic. This is
totally confusing! Stick with (+) and (-).

How optical isomers arise

The examples of organic optical isomers required at A' level all

contain a carbon atom joined to four different groups. These two
models each have the same groups joined to the central carbon
atom, but still manage to be different:
Obviously as they are drawn, the orange and blue groups aren't
aligned the same way. Could you get them to align by rotating one
of the molecules? The next diagram shows what happens if you
rotate molecule B.

They still aren't the same - and there is no way that you can rotate
them so that they look exactly the same. These are isomers of
each other.

They are described as being non-superimposable in the sense

that (if you imagine molecule B being turned into a ghostly version
of itself) you couldn't slide one molecule exactly over the other one.
Something would always be pointing in the wrong direction.
Note: Unless your visual imagination is reasonably good, this
is much easier to understand if you have actually got some
models to play with. If your school or college hasn't given you
the opportunity to play around with molecular models, you
might consider getting hold of a cheap set. The models made
by molymod are both cheap and easy to use. An introductory
organic set is more than adequate. Find them at
www.molymod.com.

Alternatively , get hold of some coloured Plasticene and some

used matches and make your own.

What happens if two of the groups attached to the central carbon

atom are the same? The next diagram shows this possibility.

The two models are aligned exactly as before, but the orange
group has been replaced by another pink one.

Rotating molecule B this time shows that it is exactly the same as

molecule A. You only get optical isomers if all four groups attached
to the central carbon are different.

Chiral and achiral molecules

The essential difference between the two examples we've looked at

lies in the symmetry of the molecules.

If there are two groups the same attached to the central carbon
atom, the molecule has a plane of symmetry. If you imagine slicing
through the molecule, the left-hand side is an exact reflection of the
right-hand side.

Where there are four groups attached, there is no symmetry

anywhere in the molecule.

A molecule which has no plane of symmetry is described as chiral.

The carbon atom with the four different groups attached which
causes this lack of symmetry is described as a chiral centre or as
an asymmetric carbon atom.

The molecule on the left above (with a plane of symmetry) is

described as achiral.

Only chiral molecules have optical isomers.

The relationship between the enantiomers

One of the enantiomers is simply a non-superimposable mirror

image of the other one.

In other words, if one isomer looked in a mirror, what it would see is

the other one. The two isomers (the original one and its mirror
image) have a different spatial arrangement, and so can't be
superimposed on each other.

If an achiral molecule (one with a plane of symmetry) looked in a

mirror, you would always find that by rotating the image in space,
you could make the two look identical. It would be possible to
superimpose the original molecule and its mirror image.

Some real examples of optical isomers

Butan-2-ol

The asymmetric carbon atom in a compound (the one with four

different groups attached) is often shown by a star.

It's extremely important to draw the isomers correctly. Draw one of

them using standard bond notation to show the 3-dimensional
arrangement around the asymmetric carbon atom. Then draw the
mirror to show the examiner that you know what you are doing, and
then the mirror image.

Help! If you don't understand this bond notation, follow this

link to drawing organic molecules before you go on with this
page.
Notice that you don't literally draw the mirror images of all the
letters and numbers! It is, however, quite useful to reverse large
groups - look, for example, at the ethyl group at the top of the
diagram.

It doesn't matter in the least in what order you draw the four groups
around the central carbon. As long as your mirror image is drawn
accurately, you will automatically have drawn the two isomers.

So which of these two isomers is (+)butan-2-ol and which is

(-)butan-2-ol? There is no simple way of telling that. For A'level
purposes, you can just ignore that problem - all you need to be able
to do is to draw the two isomers correctly.

2-hydroxypropanoic acid (lactic acid)

Once again the chiral centre is shown by a star.

The two enantiomers are:

It is important this time to draw the COOH group backwards in the

mirror image. If you don't there is a good chance of you joining it on
to the central carbon wrongly.

If you draw it like this in an exam, you won't get the mark for that
isomer even if you have drawn everything else perfectly.

2-aminopropanoic acid (alanine)

This is typical of naturally-occurring amino acids. Structurally, it is

just like the last example, except that the -OH group is replaced by
-NH2

The two enantiomers are:

Only one of these isomers occurs naturally: the (+) form. You can't
tell just by looking at the structures which this is.

It has, however, been possible to work out which of these

structures is which. Naturally occurring alanine is the right-hand
structure, and the way the groups are arranged around the central
carbon atom is known as an L- configuration. Notice the use of the
capital L. The other configuration is known as D-.

So you may well find alanine described as L-(+)alanine.

That means that it has this particular structure and rotates the
plane of polarisation clockwise.

Even if you know that a different compound has an arrangement of

groups similar to alanine, you still can't say which way it will rotate
the plane of polarisation.

The other amino acids, for example, have the same arrangement of
groups as alanine does (all that changes is the CH3 group), but
some are (+) forms and others are (-) forms.

It's quite common for natural systems to only work with one of the
enantiomers of an optically active substance. It isn't too difficult to
see why that might be. Because the molecules have different
spatial arrangements of their various groups, only one of them is
likely to fit properly into the active sites on the enzymes they work
with.

In the lab, it is quite common to produce equal amounts of both

forms of a compound when it is synthesised. This happens just by
chance, and you tend to get racemic mixtures.
Note: For a detailed discussion of this, you could have a look
 at the page on the addition of HCN to aldehydes

© Jim Clark 2000 (modified 2004)

INTRODUCING ALKANES AND

CYCLOALKANES

This is an introductory page about alkanes such as methane,

ethane, propane, butane and the rest. It deals with their formulae
and isomerism, their physical properties, and an introduction to
their chemical reactivity.

What are alkanes and cycloalkanes?

Alkanes

Formulae

Alkanes are the simplest family of hydrocarbons - compounds

containing carbon and hydrogen only. They only contain carbon-
hydrogen bonds and carbon-carbon single bonds. The first six are:

methane CH4
 ethane C2H6
propane C3H8
butane C4H10
pentane C5H12
hexane C6H14

You can work out the formula of any of them using: CnH2n+2

Isomerism

All the alkanes 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, C4H10 could be either of these two different

molecules:

These are called respectively butane and 2-methylpropane.

Note: If you aren't confident about naming organic
compounds, the various ways of drawing organic compounds,
or structural isomerism, then you really ought to follow these
links before you go on.

You should read the whole of the page about drawing organic
molecules, but there is no need to read the other two beyond
where they talk about alkanes.

Use the BACK button on your browser to return to this page.

Cycloalkanes

Cycloalkanes again only contain carbon-hydrogen bonds and

carbon-carbon single bonds, but this time the carbon atoms are
joined up in a ring. The smallest cycloalkane is cyclopropane.
If you count the carbons and hydrogens, you will see that they no
longer fit the general formula CnH2n+2. By joining the carbon atoms
in a ring, you have had to lose two hydrogen atoms.

You are unlikely to ever need it, but the general formula for a
cycloalkane is CnH2n.

Don't imagine that these are all flat molecules. All the cycloalkanes
from cyclopentane upwards exist as "puckered rings".

Cyclohexane, for example, has a ring structure which looks like

this:

This is known as the "chair" form of cyclohexane - from its shape

which vaguely resembles a chair.
Note: This molecule is constantly changing, with the atom on
the left which is currently pointing down flipping up, and the
one on the right flipping down. During the process, another
(slightly less stable) form of cyclohexane is formed known as
the "boat" form. In this arrangement, both of these atoms are
either pointing up or down at the same time.

Physical Properties

Boiling Points

The facts
The boiling points shown are all for the "straight chain" isomers
where there are more than one.

Notice that the first four alkanes are gases at room temperature.
Solids don't start to appear until about C17H36.

You can't be more precise than that because each isomer has a
different melting and boiling point. By the time you get 17 carbons
into an alkane, there are unbelievable numbers of isomers!

Cycloalkanes have boiling points which are about 10 - 20 K higher

than the corresponding straight chain alkane.

Explanations

There isn't much electronegativity difference between carbon and

hydrogen, so there is hardly any bond polarity. The molecules
themselves also have very little polarity. A totally symmetrical
molecule like methane is completely non-polar.
Note: If you aren't sure about electronegativity and polarity,
then you really ought to follow this link before you go on.

Use the BACK button on your browser to return to this page.

This means that the only attractions between one molecule and its
neighbours will be Van der Waals dispersion forces. These will be
very small for a molecule like methane, but will increase as the
molecules get bigger. That's why the boiling points of the alkanes
increase with molecular size.
Note: If you aren't sure about Van der Waals forces, then you
should follow this link before you go on.

Use the BACK button on your browser to return to this page.

Where you have isomers, the more branched the chain, the lower
the boiling point tends to be. Van der Waals dispersion forces are
smaller for shorter molecules, and only operate over very short
distances between one molecule and its neighbours. It is more
difficult for short fat molecules (with lots of branching) to lie as
close together as long thin ones.

For example, the boiling points of the three isomers of C5H12 are:

boiling point
(K)
pentane 309.2
2-methylbutane 301.0
2,2-
282.6
dimethylpropane

The slightly higher boiling points for the cycloalkanes are

presumably because the molecules can get closer together
because the ring structure makes them tidier and less "wriggly"!

Solubility

The facts

What follows applies equally to alkanes and cycloalkanes.

Alkanes are virtually insoluble in water, but dissolve in organic

solvents. The liquid alkanes are good solvents for many other
covalent compounds.

Explanations

Solubility in water

When a molecular substance dissolves in water, you have to

• break the intermolecular forces within the substance. In the

case of the alkanes, these are Van der Waals dispersion
forces.

• break the intermolecular forces in the water so that the

substance can fit between the water molecules. In water the
main intermolecular attractions are hydrogen bonds.
Note: If you aren't sure about hydrogen bonds, then you
should follow this link before you go on.
 Use the BACK button on your browser to return to this page.

Breaking either of these attractions costs energy, although the

amount of energy to break the Van der Waals dispersion forces in
something like methane is pretty negligible. That isn't true of the
hydrogen bonds in water, though.

As something of a simplification, a substance will dissolve if there is

enough energy released when new bonds are made between the
substance and the water to make up for what is used in breaking
the original attractions.

The only new attractions between the alkane and water molecules
are Van der Waals. These don't release anything like enough
energy to compensate for what you need to break the hydrogen
bonds in water. The alkane doesn't dissolve.
Note: The reason that this is a simplification is that you also
have to consider entropy changes when things dissolve. If you
don't yet know about entropy, don't worry about it!

Solubility in organic solvents

In most organic solvents, the main forces of attraction between the

solvent molecules are Van der Waals - either dispersion forces or
dipole-dipole attractions.

That means that when an alkane dissolves in an organic solvent,

you are breaking Van der Waals forces and replacing them by new
Van der Waals forces. The two processes more or less cancel
each other out energetically - so there isn't any barrier to solubility.

Chemical Reactivity

Alkanes

Alkanes contain strong carbon-carbon single bonds and strong

carbon-hydrogen bonds. The carbon-hydrogen bonds are only very
slightly polar and so there aren't any bits of the molecules which
carry any significant amount of positive or negative charge which
other things might be attracted to.

The net effect is that alkanes have a fairly restricted set of

reactions.

You can

• burn them - destroying the whole molecule;

 • react them with some of the halogens, breaking carbon-
hydrogen bonds;
• crack them, breaking carbon-carbon bonds.

These reactions are all covered on separate pages if you go to the

alkanes menu (see below).

Cycloalkanes

Cycloalkanes are very similar to the alkanes in reactivity, except for

the very small ones - especially cyclopropane. Cyclopropane is
much more reactive than you would expect.

The reason has to do with the bond angles in the ring. Normally,
when carbon forms four single bonds, the bond angles are about
109.5°. In cyclopropane, they are 60°.

With the electron pairs this close together, there is a lot of repulsion
between the bonding pairs joining the carbon atoms. That makes
the bonds easier to break.

The effect of this is explored on the page about reactions of these

compounds with halogens which you can access from the alkanes
menu below.

© Jim Clark 2003

THE COMBUSTION OF ALKANES AND

CYCLOALKANES
This page deals briefly with the combustion of alkanes and
cycloalkanes. In fact, there is very little difference between the two.

Complete combustion

Complete combustion (given sufficient oxygen) of any hydrocarbon

produces carbon dioxide and water.

Equations

It is quite important that you can write properly balanced equations

for these reactions, because they often come up as a part of
thermochemistry calculations. Don't try to learn the equations -
there are far too many possibilities. Work them out as you need
them.

Some are easier than others. For example, with alkanes, the ones
with an even number of carbon atoms are marginally harder than
those with an odd number!

For example, with propane (C3H8), you can balance the carbons
and hydrogens as you write the equation down. Your first draft
would be:

Counting the oxygens leads directly to the final version:

With butane (C4H10), you can again balance the carbons and
hydrogens as you write the equation down.

Counting the oxygens leads to a slight problem - with 13 on the

right-hand side. The simple trick is to allow yourself to have "six-
and-a-half" O2 molecules on the left.

If that offends you, double everything:

Note: You might well come across either

version of these equations. The ones with the
halves left in are often used in calculation work.

Forgive me if you find this last bit on equations

 unbearably trivial - not everybody does! Just be
grateful that you have been well taught.

Trends

The hydrocarbons become harder to ignite as the molecules get

bigger. This is because the bigger molecules don't vaporise so
easily - the reaction is much better if the oxygen and the
hydrocarbon are well mixed as gases. If the liquid isn't very volatile,
only those molecules on the surface can react with the oxygen.

Bigger molecules have greater Van der Waals attractions which

makes it more difficult for them to break away from their neighbours
and turn to a gas.
Note: If you aren't sure about Van der Waals
forces, then you should follow this link before
you go on.

Use the BACK button on your browser to return

to this page.

Provided the combustion is complete, all the hydrocarbons will burn

with a blue flame. However, combustion tends to be less complete
as the number of carbon atoms in the molecules rises. That means
that the bigger the hydrocarbon, the more likely you are to get a
yellow, smoky flame.

Incomplete combustion

Incomplete combustion (where there isn't enough oxygen present)

can lead to the formation of carbon or carbon monoxide.

As a simple way of thinking about it, the hydrogen in the

hydrocarbon gets the first chance at the oxygen, and the carbon
gets whatever is left over!

The presence of glowing carbon particles in a flame turns it yellow,

and black carbon is often visible in the smoke. Carbon monoxide is
produced as a colourless poisonous gas.

Why carbon monoxide is poisonous

Oxygen is carried around the blood by haemoglobin (US:

hemoglobin). Unfortunately carbon monoxide binds to exactly the
same site on the haemoglobin that oxygen does.
The difference is that carbon monoxide binds irreversibly - making
that particular molecule of haemoglobin useless for carrying
oxygen. If you breath in enough carbon monoxide you will die from
a sort of internal suffocation.

THE HALOGENATION OF ALKANES AND

CYCLOALKANES

This page describes the reactions between alkanes and

cycloalkanes with the halogens fluorine, chlorine, bromine and
iodine - mainly concentrating on chlorine and bromine.

Alkanes

The reaction between alkanes and fluorine

This reaction is explosive even in the cold and dark, and you tend
to get carbon and hydrogen fluoride produced. It is of no particular
interest. For example:

The reaction between alkanes and iodine

Iodine doesn't react with the alkanes - at least, under normal lab
conditions.
Note: I can't discover the truth about this! Some sources say
that it doesn't react; others say that it reacts very slowly. I have
found it impossible to find all the data I need to estimate
whether there might be a temperature at which the reaction
becomes feasible. The information needed depends too much
on what assumptions you make about the physical states of
the reactants and products - for example, whether the iodine is
present as a solid, a gas or a solution.

If you have any hard information, could you contact me via the
address on the about this site page.

The reactions between alkanes and chlorine or bromine

There is no reaction in the dark.

In the presence of a flame, the reactions are rather like the fluorine
one - producing a mixture of carbon and the hydrogen halide. The
violence of the reaction drops considerably as you go from fluorine
to chlorine to bromine.

The interesting reactions happen in the presence of ultra-violet light

(sunlight will do). These are photochemical reactions, and
happen at room temperature.

We'll look at the reactions with chlorine. The reactions with bromine
are similar, but rather slower.

Methane and chlorine

Substitution reactions happen in which hydrogen atoms in the

methane are replaced one at a time by chlorine atoms. You end up
with a mixture of chloromethane, dichloromethane,
trichloromethane and tetrachloromethane.

Note: Follow this link if you aren't happy about naming organic
compounds.
 Use the BACK button on your browser to return to this page.

The original mixture of a colourless and a green gas would produce

steamy fumes of hydrogen chloride and a mist of organic liquids.
All of the organic products are liquid at room temperature with the
exception of the chloromethane which is a gas.

If you were using bromine, you could either mix methane with
bromine vapour, or bubble the methane through liquid bromine - in
either case, exposed to UV light. The original mixture of gases
would, of course, be red-brown rather than green.

You wouldn't choose to use these reactions as a means of

preparing these organic compounds in the lab because the mixture
of products would be too tedious to separate.

The mechanisms for the reactions are explained on separate

pages.
Note: If you want the methane-chlorine mechanism, follow this
link.

If you want the methane-bromine mechanism, follow this one.

Use the BACK button on your browser to return to this page.

Larger alkanes and chlorine

You would again get a mixture of substitution products, but it is

worth just looking briefly at what happens if only one of the
hydrogen atoms gets substituted (monosubstitution) - just to show
that things aren't always as straightforward as they seem!

For example, with propane, you could get one of two isomers:

Note: If you aren't sure about isomerism, you might like to

follow this link.

Use the BACK button on your browser to return to this page.

If chance was the only factor, you would expect to get 3 times as
much of the isomer with the chlorine on the end. There are 6
hydrogens that could get replaced on the end carbon atoms
compared with only 2 in the middle.

In fact, you get about the same amount of each of the two isomers.

If you use bromine instead of chlorine, the great majority of the

product is where the bromine is attached to the centre carbon
atom.

The reasons for this are beyond UK A level chemistry.

Cycloalkanes

The reactions of the cycloalkanes are generally just the same as

the alkanes, with the exception of the very small ones - particularly
cyclopropane.

The extra reactivity of cyclopropane

In the presence of UV light, cyclopropane will undergo substitution

reactions with chlorine or bromine just like a non-cyclic alkane.
However, it also has the ability to react in the dark.

In the absence of UV light, cyclopropane can undergo addition

reactions in which the ring is broken. For example, with bromine,
cyclopropane gives 1,3-dibromopropane.

This can still happen in the presence of light - but you will get
substitution reactions as well.

The ring is broken because cyclopropane suffers badly from ring

strain. The bond angles in the ring are 60° rather than the normal
value of about 109.5° when the carbon makes four single bonds.

The overlap between the atomic orbitals in forming the carbon-

carbon bonds is less good than it is normally, and there is
considerable repulsion between the bonding pairs. The system
becomes more stable if the ring is broken.

© Jim Clark 2003

CRACKING ALKANES

This page describes what cracking is, and the differences between
catalytic cracking and thermal cracking used in the petrochemical
industry.

Cracking

What is cracking?

Cracking is the name given to breaking up large hydrocarbon

molecules into smaller and more useful bits. This is achieved by
using high pressures and temperatures without a catalyst, or lower
temperatures and pressures in the presence of a catalyst.

The source of the large hydrocarbon molecules is often the

naphtha fraction or the gas oil fraction from the fractional distillation
of crude oil (petroleum). These fractions are obtained from the
distillation process as liquids, but are re-vaporised before cracking.

There isn't any single unique reaction happening in the cracker.

The hydrocarbon molecules are broken up in a fairly random way
to produce mixtures of smaller hydrocarbons, some of which have
carbon-carbon double bonds. One possible reaction involving the
hydrocarbon C15H32 might be:

Or, showing more clearly what happens to the various atoms and
bonds:
This is only one way in which this particular molecule might break
up. The ethene and propene are important materials for making
plastics or producing other organic chemicals. The octane is one of
the molecules found in petrol (gasoline).

Catalytic cracking

Modern cracking uses zeolites as the catalyst. These are complex

aluminosilicates, and are large lattices of aluminium, silicon and
oxygen atoms carrying a negative charge. They are, of course,
associated with positive ions such as sodium ions. You may have
come across a zeolite if you know about ion exchange resins used
in water softeners.

The alkane is brought into contact with the catalyst at a

temperature of about 500°C and moderately low pressures.

The zeolites used in catalytic cracking are chosen to give high

percentages of hydrocarbons with between 5 and 10 carbon atoms
- particularly useful for petrol (gasoline). It also produces high
proportions of branched alkanes and aromatic hydrocarbons like
benzene.

For UK A level (and equivalent) purposes, you aren't expected to

know how the catalyst works, but you may be expected to know
that it involves an ionic intermediate.
Note: You should check your syllabus to find out exactly what
you need to know. If you are studying a UK-based syllabus and
haven't got one, follow this link.

Use the BACK button on your browser to return quickly to this

page.

The zeolite catalyst has sites which can remove a hydrogen from
an alkane together with the two electrons which bound it to the
carbon. That leaves the carbon atom with a positive charge. Ions
like this are called carbonium ions (or carbocations).
Reorganisation of these leads to the various products of the
reaction.
 Note: If you are interested in other examples of catalysis in
the petrochemical industry, you should follow this link. It will
lead you to information on reforming and isomerisation (as well
as a repeat of what you have just read about catalytic
cracking).

Use the BACK button on your browser if you want to return

quickly to this page.

Thermal cracking

In thermal cracking, high temperatures (typically in the range of

450°C to 750°C) and pressures (up to about 70 atmospheres) are
used to break the large hydrocarbons into smaller ones. Thermal
cracking gives mixtures of products containing high proportions of
hydrocarbons with double bonds - alkenes.
Warning! This is a gross oversimplification, and is written to
satisfy the needs of one of the UK A level Exam Boards (AQA).
In fact, there are several versions of thermal cracking designed
to produce different mixtures of products. These use
completely different sets of conditions.

If you need to know about thermal cracking in detail, a Google

search on thermal cracking will throw up lots of useful leads.
Be careful to go to industry (or similarly reliable) sources. You
will find a Google search box at the bottom of the Main Menu
(link below). Remember to search the whole web rather than
Chemguide otherwise you will just end up back here again!

Thermal cracking doesn't go via ionic intermediates like catalytic

cracking. Instead, carbon-carbon bonds are broken so that each
carbon atom ends up with a single electron. In other words, free
radicals are formed.
Reactions of the free radicals lead to the various products.

INTRODUCING ALKENES

This is an introductory page about alkenes such as ethene,

propene and the rest. It deals with their formulae and isomerism,
their physical properties, and an introduction to their chemical
reactivity.

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:

Note: If you aren't confident about naming organic

compounds, the various ways of drawing organic
compounds, or structural isomerism, then you really
ought to follow these links before you go on.

Use the BACK button on your browser to return to this

 page.

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).

Note: If you aren't confident about geometric

isomerism, then it is essential that you follow this link
before you go on.

Use the BACK button on your browser to return to this

page.

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 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.
Note: If you aren't sure about Van der Waals forces,
then you should follow this link before you go on.

You will find the boiling points of the alkanes explained

in some detail on the introductory alkanes page.
 Everything said there applies equally to the alkenes.

You will find the way geometric isomerism affects

melting and boiling points explained towards the bottom
of the page you get to by following this link.

Use the BACK button on your browser to return to this

page.

Solubility

Alkenes are virtually insoluble in water, but dissolve in organic

solvents.
Note: The reasons for this are exactly the same as for
the alkanes. You will find a detailed explanation on the
introductory alkanes page.

Use the BACK button on your browser to return to this

page.

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.
Note: This diagram shows a side view of an ethene
molecule. The dotted lines to two of the hydrogens
show bonds going back into the screen or paper away
from you. The wedge shapes show bonds coming out
towards you.

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.
Note: Check your syllabus to see if you need to know
how a pi bond is formed. If you are studying a UK-
based syllabus and haven't got a copy of that syllabus,
find out how to get one by following this link.

If you do need to know about the bonding in ethene in

detail, follow this link as well.

Use the BACK button on your browser to return to this

page.

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.
Note: If you need to know about organic reaction
mechanisms, it would be a good idea to read the page
explaining the background to electrophilic addition
before you start looking at individual cases from the
alkenes menu.

In fact, if you are only really interested in mechanisms,

then look at that page and then explore the rest of the
electrophilic addition menu in the mechanisms section
of this site.

© Jim Clark 2003

MAKING ALKENES IN THE LAB

This page looks at ways of preparing alkenes in the lab by the

dehydration of alcohols.

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.

To make a few test tubes of ethene, you can use this apparatus:

It wouldn't be too difficult to imagine scaling this up by boiling some

ethanol in a flask and passing the vapour over aluminium oxide
heated in a long tube.

Dehydration of alcohols using an acid catalyst

The acid catalysts normally used are either concentrated sulphuric

acid or concentrated phosphoric(V) acid, H3PO4.

Concentrated sulphuric acid produces messy results. Not only is it

an acid, but it is also a strong oxidising agent. It oxidises some of
the alcohol to carbon dioxide and at the same time is reduced itself
to sulphur dioxide. Both of these gases have to be removed from
the alkene.
It also reacts with the alcohol to produce a mass of carbon. There
are other side reactions as well, but these aren't required by any
current UK A level (or equivalent) syllabus.

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.

WARNING! This is potentially an extremely dangerous
preparation because of the close proximity of the very hot
concentrated sulphuric acid and the sodium hydroxide solution.
I knew of one chemistry teacher who put several students into
hospital by getting it wrong! That was many years ago before
safety was taken quite so seriously as it is now.

The concentrated sulphuric acid is a catalyst. Write it over the

arrow rather than in the equation.
Note: You will find the mechanism for the dehydration of
alcohols in the mechanism section of this site. You will also
find a discussion of how to cope with questions about the
dehydration of more complicated alcohols if you follow a link at
the bottom of that page.

Use the BACK button (or the HISTORY file or GO menu) on

your browser if you want to return to this page.

The dehydration of cyclohexanol to give cyclohexene

This is a preparation commonly used at this level to illustrate the

formation and purification of a liquid product. The fact that the
carbon atoms happen to be joined in a ring makes no difference
whatever to the chemistry of the reaction.

Cyclohexanol is heated with concentrated phosphoric(V) acid and

the liquid cyclohexene distils off and can be collected and purified.

Phosphoric(V) acid tends to be used in place of sulphuric acid

because it is safer and produces a less messy reaction.
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.

Hydrogenation in the lab

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.
Note: You will find the mechanism for this hydrogenation
reaction described in some detail in the catalysis section of this
site.

Use the BACK button on your browser to return to this page.

Margarine manufacture

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".

The impression is sometimes given that all margarine is made by

hydrogenation - that's simply not true.

Animal and vegetable fats and oils

These are similar molecules, differing in their melting points. If the

compound is a solid at room temperature, you usually call it a fat. If
it is a liquid, it is often described as an oil.

Their melting points are largely determined by the presence of

carbon-carbon double bonds in the molecule. The higher the
number of carbon-carbon double bonds, the lower the melting
point.

If there aren't any carbon-carbon double bonds, the substance is

said to be saturated. A typical saturated fat might have the
structure:
Molecules of this sort are usually solid at room temperature.

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.)

A typical mono-unsaturated oil might be:

If there are two or more carbon-carbon double bonds in each chain,

then it is said to be polyunsaturated.

For example:

For simplicity, in all these diagrams, all three hydrocarbon chains in

each molecule are the same. That doesn't have to be the case -
you can have a mixture of types of chain in the same molecule.
Making margarine

Vegetable oils often contain high proportions of polyunsaturated

and mono-unsaturated fats (oils), and as a result are liquids at
room temperature. That makes them messy to spread on your
bread or toast, and inconvenient for some baking purposes.

You can "harden" (raise the melting point of) the oil by
hydrogenating it in the presence of a nickel catalyst. Conditions
(like the precise temperature, or the length of time the hydrogen is
passed through the oil) are carefully controlled so that some, but
not necessarily all, of the carbon-carbon double bonds are
hydrogenated.

This produces a "partially hydrogenated oil" or "partially

hydrogenated fat".

You need to hydrogenate enough of the bonds to give the final

texture you want. However, there are possible health benefits in
eating mono-unsaturated or polyunsaturated fats or oils rather than
saturated ones - so you wouldn't want to remove all the carbon-
carbon double bonds.
Note: There is constant (and constantly changing) controversy
about the health risks and benefits of eating the various types
of fat. If you do a Google search on this topic, you will find all
sorts of conflicting information. Look carefully at the reliability
of the source of that information before you try to make up your
mind. Just because it is on the internet doesn't mean that it is
right!

You will find a Google search box on the Main Menu page (link
below). Don't forget that you need to search the whole web
and not just chemguide - otherwise you will just end up back
here!

The flow diagram below shows the complete hydrogenation of a

typical mono-unsaturated oil.
The downside of hydrogenation as a means of hardening fats
and oils

There are some probable health risks from eating hydrogenated

fats or oils. Consumers are becoming more aware of this, and
manufacturers are increasingly finding alternative ways of
converting oils into spreadable solids.

One of the problems arises from the hydrogenation process.

The double bonds in unsaturated fats and oils tend to have the
groups around them arranged in the "cis" form.
Note: If you don't know what this means, you will find more
about it towards the bottom of the introductory page about
esters. If you don't understand what cis and trans isomers are,
you won't make any sense of what comes next!

Use the BACK button on your browser to return to this page.

The relatively high temperatures used in the hydrogenation process

tend to flip some of the carbon-carbon double bonds into the
"trans" form. If these particular bonds aren't hydrogenated during
the process, they will still be present in the final margarine in
molecules of trans fats.

The consumption of trans fats has been shown to increase

cholesterol levels (particularly of the more harmful LDL form) -
leading to an increased risk of heart disease.

Any process which tends to increase the amount of trans fat in the
diet is best avoided. Read food labels, and avoid any food which
contains (or is cooked in) hydrogenated oil or hydrogenated fat.
Note: As I said earlier, ideas about this change all the time. It
would be worth doing a Google search on trans fatty acids.
The US Food and Drugs Administration (FDA) has a useful up-
to-date fact sheet about them, and the Google search will find
it for you amongst a lot of other information.

© Jim Clark 2003 (modified 2004)

THE HALOGENATION OF ALKENES

This page looks at the reaction of the carbon-carbon double bond

in alkenes such as ethene with halogens such as chlorine, bromine
and iodine. This is called halogenation.

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. This isn't a useful reaction, and you aren't
likely to need it for exam purposes in the UK at this level (A level or
equivalent).

Ethene and chlorine or bromine or iodine

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

adds to give 1,2-dibromoethane.
 Note: Follow this link if you aren't happy about naming organic
compounds

Use the BACK button on your browser to return to this page.

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.
Note: If you are interested in the mechanism for the addition
of bromine to alkenes you will find it in the mechanism section
of this site.

Use the BACK button on your browser to return to this page.

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:

Note: Check your syllabus, past papers and mark schemes to

find out what you need to be able to do. If you are studying a
UK-based syllabus (A level or equivalent) and haven't got any
of these, follow this link to find out how to get hold of them. If
you are working at a lower level, use the simpler equation.

If you are interested in the mechanism for this reaction, I'm

afraid that you won't find it on this site because it isn't on any of
the UK-based syllabuses. You can, however, deduce it fairly
easily if you know the mechanism for the addition of pure
bromine. Instead of the intermediate ion being attacked by a
bromide ion, it is much more likely to be hit by a lone pair on an
oxygen of a water molecule, followed by loss of a hydrogen ion
from the product.

© Jim Clark 2003

ALKENES and HYDROGEN HALIDES

This page looks at the reaction of the carbon-carbon double bond

in alkenes such as ethene with hydrogen halides such as hydrogen
chloride and hydrogen bromide.

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.

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:

Note: Follow this link if you aren't happy about naming organic
compounds

Use the BACK button on your browser to return to this page.

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.
Warning! The mechanism for this reaction is almost invariably given
for the reaction involving the alkene and the simple molecules H-Cl or
H-Br or whatever. In the presence of water, these molecules will
already have reacted with the water to produce hydroxonium ions,
H3O+, and halide ions. The mechanism will therefore be different -
involving an initial attack by a hydroxonium ion. Avoid this problem by
using the pure gaseous hydrogen halide.

If you choose to follow this link to the mechanism, use the BACK button
on your browser to return to this page.

Reaction rates

Variation of rates when you change the halogen

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.
Note: If you should know about the mechanism, but are a bit uncertain
about it, then you should spend some time exploring the electrophilic
addition mechanisms menu before you go on, and then come back to
this page later. You should look at the addition of hydrogen halides to
unsymmetrical alkenes as well as symmetrical ones.

This will take you some time. Use the BACK button (or, more efficiently,
the HISTORY file or GO menu) on your browser to return to this page.

If you don't need to know about the mechanisms, skip over the next bit!

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.
Note: If you aren't sure about pi bonds, you will find a simple mention
of them in the introductory page on alkenes

You will find more about the electron pushing effect of alkyl groups on a
page about carbocations in the mechanism section of this site. That is
also important reading if you are to understand the next bit.

Use the BACK button on your browser to return to this page later.

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:
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.
Didn't understand this? You should have followed the link to the
page about carbocations mentioned above!

Use the BACK button on your browser to return to this page afterwards.

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:

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 CH3
group are totally irrelevant.
Warning! Markovnikov's Rule is a useful guide for you to work out
which way round to add something across a double bond, but it isn't the
reason why things add that way. As a general principle, don't quote
Markovnikov's Rule in an exam unless you are specifically asked for it.

You will find the proper reason for this in a page about the addition of
hydrogen halides to unsymmetrical alkenes in the mechanism section
of this site.

Use the BACK button on your browser if you want to return to this
page.

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.

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.
Note: All this is explored in detail on the page about free radical
addition of HBr to alkenes in the mechanism section of this site.

© Jim Clark 2003

 ALKENES and SULPHURIC ACID

This page looks at the reaction of the carbon-carbon

double bond in alkenes such as ethene with concentrated sulphuric
acid. It includes the conversion of the product into an alcohol.

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.
Important! Learn this structure for sulphuric acid. Sketch it over
and over again until you can't possibly get it wrong.

Follow this link if you want the mechanism for this reaction.

Use the BACK button on your browser to return to this page.

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.

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 CH3
group are totally irrelevant.
Warning! Markovnikov's Rule is a useful guide for you to work
out which way round to add something across a double bond,
but it isn't the reason why things add that way. As a general
principle, don't quote Markovnikov's Rule in an exam unless you
are specifically asked for it.

You can find more about this in the mechanism section of this
site. You will find the mechanism for this reaction discussed in
detail if you follow this link.

Use the BACK button (or HISTORY file or GO menu, if you have
to explore several pages) on your browser if you want to return
to this page.
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

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.
Note: You can find out about the manufacture of alcohols by
direct hydration by following this link.
ALKENES and POTASSIUM
MANGANATE(VII)

This page looks at the reaction of the carbon-carbon double bond

in alkenes such as ethene with potassium manganate(VII) solution
(potassium permanganate solution).

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:

Note: This type of equation is quite commonly used in organic

chemistry. Oxygen written in square brackets is taken to mean
"oxygen from an oxidising agent". The reason for this is that a more
normal equation tends to obscure the organic change in a mass of
 other detail - as you will find below!

The full equations are given below, although you probably won't need
them.

The full equation depends on the conditions.

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

manganese(II) ions.

Note: If you want to know how to write equations for redox reactions
like this you could follow this link, and explore in the redox section of
this site.

Use the BACK button (or HISTORY file or GO menu) on your browser
to return to this page later.

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.
Note: You might possibly remember that further up the page it says
that potassium manganate(VII) is often made slightly alkaline by
adding sodium carbonate solution. Where are the hydroxide ions in
this?

Carbonate ions react with water to some extent to produce

hydrogencarbonate ions and hydroxide ions. It is the presence of
these hydroxide ions that gives sodium carbonate solution its pH in
the 10 - 11 region.
Complications

(. . . and you thought this was already complicated enough?)

The product, ethane-1,2-diol, is itself quite easily oxidised by

manganate(VII) ions, and so the reaction won't stop at this point
unless the potassium manganate(VII) solution is very dilute, very
cold, and preferably not under acidic conditions.

That means that this reaction has little use as a way of preparing
ethane-1,2-diol. Its only real use is in testing for carbon-carbon
double bonds - and even then it isn't very good!
Note: Ethane-1,2-diol is an alcohol, although unlike simple ones like
ethanol it contains two -OH groups. The oxidation of alcohols is
explored on another page if you are interested.

That page deals with the oxidation of alcohols by acidified potassium

dichromate(VI) solution - a slightly less powerful oxidising agent than
potassium manganate(VII). The essential chemistry will be the same,
although manganate(VII) ions eventually oxidise ethane-1,2-diol all
the way to carbon dioxide and water. You only need read the first part
of that page about oxidation of primary alcohols.

Use the BACK button on your browser to return to this page if you
choose to follow this link.

Using the reaction to test for carbon-carbon double bonds

If an organic compound reacts with dilute alkaline potassium

manganate(VII) solution to give a green solution followed by a dark
brown precipitate, then it may contain a carbon-carbon double
bond. But equally it could be any one of a large number of other
compounds all of which can be oxidised by manganate(VII) ions
under alkaline conditions.

The situation with acidified potassium manganate(VII) solution is

even worse because it has a tendency to break carbon-carbon
bonds. It reacts destructively with a large number of organic
compounds and is rarely used in organic chemistry.

You could use alkaline potassium manganate(VII) solution if, for

example, all you had to do was to find out whether a hydrocarbon
was an alkane or an alkene - in other words, if there was nothing
else present which could be oxidised.

It isn't a useful test. Bromine water is far more clear cut.

Note: You will find details of the use of bromine water in testing for
carbon-carbon double bonds in the page about the reactions of
alkenes with halogens.
THE DIRECT HYDRATION OF ALKENES

This page looks at the production of alcohols by the direct

hydration of alkenes - adding water directly to the carbon-carbon
double bond.

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:

Note: This is a bit of a simplification! When the gases from the reactor
are cooled, then excess steam will condense as well as the ethanol.
The ethanol will have to be separated from the water by fractional
distillation.

All the sources I have looked at gloss over this, so I don't have any
details. I assume it is a normal fractional distillation of an ethanol-water
mixture.

You can find a full explanation of the reasons for the reaction conditions
by following this link to the physical chemistry part of this site.

If you are interested in the mechanism for this reaction you will find it by
following this link.

Use the BACK button (or HISTORY file or GO menu) on your browser if
you want to return to this page later.

Manufacturing other alcohols

If you start from an unsymmetrical alkene like propene, you have to

be careful to think about which way around the water adds across
the carbon-carbon double bond.

Markovnikov's Rule says that when you add a molecule HX across

a carbon-carbon double bond, the hydrogen joins to the carbon
atom which already has the more hydrogen atoms attached to it.

Thinking of water as H-OH, the hydrogen will add to the carbon

with the more hydrogens already attached. That means that in the
propene case, you will get propan-2-ol rather than propan-1-ol.

The conditions used during manufacture vary from alcohol to

alcohol. The only conditions you will need for UK A level purposes
are those for making ethanol.
Note: I haven't included the mechanism for the hydration of these
more complicated alkenes anywhere on the site, but it isn't too difficult
to work out for yourself if you know the mechanism for the hydration of
ethene, and know about the stability of carbocations (carbonium ions).

The water adds to the propene in the way shown above because the
secondary carbocation formed during the process is more stable than
the primary one formed if the addition was the other way around.

These two pages are in two different parts of this site, so it would be
best to come back to this page using the BACK button on your browser
to get from one to the other if you are interested.
THE POLYMERISATION OF ALKENES

This page looks at the polymerisation of alkenes to produce

polymers like poly(ethene) (usually known as polythene, and
sometimes as polyethylene), poly(propene) (old name:
polypropylene), PVC and PTFE. It also looks briefly at how the
structure of the polymers affects their properties and uses.

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

Temperature: about 200°C

Pressure: about 2000 atmospheres
Initiator: a small amount of oxygen as
 an impurity
Note: If you want the mechanism for this reaction, you can get
it by following this link to the mechanism section of the site.

Use the BACK button on your browser if you want to return to

this page.

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.
Note: Various sources quote estimated values for the
proportion of low density poly(ethene) which is crystalline.
These vary from 50% to 75%. I have no idea what the correct
value is!

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)").
Note: Follow this link if you don't understand van der Waals
forces.

Use the BACK button on your browser to return to this page.

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

Temperature: about 60°C

Pressure: low - a few atmospheres
Catalyst: Ziegler-Natta catalysts or
 other 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.
Note: Despite the names, HDPE is only about 3% denser than
LDPE! HDPE has a density of about 0.95 g cm-3 compared with
about 0.92 for LDPE.

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) which you may need to know about, but we'll start
from the beginning with a general structure which fits all of them.
Note: You should check your syllabus to find out exactly how
much you need to know. It is pointless getting bogged down in
this if you don't need to! If you are studying a UK-based
syllabus and haven't got a copy of that syllabus, follow this link
to find out how to get one.

Use the BACK button (or HISTORY file or GO menu) on your

browser to return to this page later.

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:

The three variations on this structure

You have got to remember that the diagrams above are 2-

dimensional. Real poly(propene) chains are 3-dimensional. There
are three different sorts of poly(propene) depending in how the CH3
groups are arranged in space.

These are called isotactic, atactic and syndiotactic

poly(propene). The commonly used version is isotactic
poly(propene).

Isotactic poly(propene)

A bit of the isotactic poly(propene) chain looks like this:

Note: Dotted lines show bonds going back into the screen or
paper, and wedge shapes show them coming out towards you.
If you aren't very happy about the various ways of drawing
organic structures it might be worth following this link before
 you go on.

Use the BACK button on your browser to return to this page.

This very regular arrangement of the CH3 groups makes it possible

for the chains to pack close together and so maximise the amount
of van der Waals bonding between them. That means that isotactic
poly(propene) is quite strong either as a solid object or when it is
drawn into fibres.

This is the common form of poly(propene) which is used to make

plastic crates and ropes amongst many other things. Look for the
letters PP near the recycling symbol.

Atactic poly(propene)

In atactic poly(propene) the CH3 groups are orientated randomly

along the chain.

This lack of regularity makes it impossible for the chains to lie

closely together and so the van der Waals attractions between
them are weaker. Atactic poly(propene) is much softer with a lower
melting point.

It is formed as a waste product during the manufacture of isotactic

poly(propene) and its uses are limited. It is used, for example, in
road paint, in making roofing materials like "roofing felt", and in
some sealants and adhesives.

Syndiotactic poly(propene)

Syndiotactic poly(propene) is a relatively new material and is

another regularly arranged version of poly(propene). In this case,
every alternate CH3 group is orientated in the same way.

This regularity means that the chains can pack closely, and van der
Waals attractions will be fairly strong. However, the attractions
aren't as strong as in isotactic poly(propene). This makes
syndiotactic poly(propene) softer and gives it a lower melting point.
Because syndiotactic poly(propene) is relatively new, at the time of
writing uses were still being developed. It has uses in packaging -
for example, in plastic film for shrink wrapping food. There are also
medical uses - for example, in medical tubing and for medical bags
and pouches. There are a wide range of other potential uses -
either on its own, or in mixtures with isotactic poly(propene).

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.

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.
Note: If you aren't happy about the various sorts of
intermolecular forces, it is important to follow this link.

If you don't understand about electronegativity and polar

bonds, then follow this one as well.

Use the BACK button (or HISTORY file or GO menu) on your

browser to return to this page.

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).
Note: There won't be any dipole-dipole attractions between
the chains in addition to dispersion forces (unlike PVC). The
fluorines are arranged regularly around the carbon backbone.
Although each bond is very polar, overall they cancel each
other out.

(In fact, there might even be some repulsions because the

outsides of the chains all consist of slightly negative fluorine
atoms, but these obviously aren't enough to have a significant
effect on the strong dispersion forces. I haven't been able to
find any mention of this either in textbooks or on the Web.)

You might like to read about CCl4 (a simple example of a non-

polar molecule containing polar bonds) on the main page about
electronegativity (different from the link above).

Use the BACK button on your browser to return to this page.

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.
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
Note: Despite an extensive Web search, I haven't found any
convincing explanation for the non-stick properties of PTFE at
the molecular level. Many sources talk about it in terms of
surface tension or surface energy, which actually beg the
question. Unless you can explain the origin of these in terms of
attractions or repulsions at the molecular level, it seems to me
that you aren't actually explaining anything just by using a
posh-sounding term!

If you are interested, you will find a discussion of how far I've
got in coming up with an answer to this on a page about the
non-stick properties of PTFE in the section of questions that I
can't answer to my satisfaction!

© Jim Clark 2003

EPOXYETHANE ( ETHYLENE OXIDE )

This page looks at the manufacture of epoxyethane from ethene, and then at
some of the products that are made from epoxyethane.

The manufacture of epoxyethane

Conditions

Temperature: about 250 - 300°C

Pressure: about 15 atmospheres

Catalyst: silver

Problems and hazards during manufacture

The main problem comes in controlling the temperature. The reaction is

exothermic and so the temperature will tend to rise unless it is carefully
controlled.

At higher temperatures the ethene burns in the oxygen to produce carbon

dioxide and water which means that the temperature would increase even
more - and the whole thing get completely out of hand!

Two hazards during manufacture come from the nature of epoxyethane. It is

• poisonous and carcinogenic (cancer producing);

• highly inflammable or explosive in contact with air.

The reactivity of epoxyethane

Ring strain
The reason that epoxyethane is so reactive is that bonding pairs in the ring of
atoms in the molecule are forced very close together. The bond angles are
about 60° rather than about 109.5° when carbon atoms normally form single
bonds.

The overlap between the atomic orbitals in forming the carbon-carbon and
carbon-oxygen bonds is less good than it is normally, and there is
considerable repulsion between the bonding pairs. The system becomes
more stable if the ring is broken.

When epoxyethane reacts a carbon-oxygen bond is always broken and the

ring opens up.

Uses of epoxyethane

Manufacture of ethane-1,2-diol (ethylene glycol)

Acid catalysed hydrolysis of epoxyethane

Epoxyethane reacts with water in the presence of an acid catalyst (very dilute
sulphuric acid) at a temperature of about 60°C. Ethane-1,2-diol is produced.

A large excess of water is used to try to prevent the product from reacting with
the original epoxyethane. Ethane-1,2-diol is an alcohol (because it contains
simple -OH groups), and alcohols react with epoxyethane (see below).

Even in the presence of a large excess of water, this reaction happens as

well:

The product is still an alcohol, and similar reactions can also lead to quite long
chains.

Uses of ethane-1,2-diol

Ethane-1,2-diol is used as an antifreeze in car engines. It is added to the

cooling water to prevent it from freezing under very cold conditions.
Ethane-1,2-diol is also used in the manufacture of polyesters such as
poly(ethylene terephthalate). You may have come across this as a fibre used
to make clothes (perhaps under the brand name Terylene), or as a clear
material used to make plastic drinks bottles (PET).

The reaction of epoxyethane with alcohols

This is a reaction which students at this level often find difficulty remembering.
It is actually probably easier to work out than remember. Think of it as an
extension of the reaction with water.

Alcohols have the formula R-OH, where R is an alkyl group. Water can be
thought of as H-OH.

The reaction of epoxyethane with water can be colour-coded like this:

Now do the same thing with the alcohol:

Product molecules of this type are used as solvents.

Notice that the product is still an alcohol. It has an -OH group at the right-hand
end of the molecule. If the epoxyethane is in excess, the reaction can
continue. (In fact, it continues to some extent even if the epoxyethane isn't in
excess.)

The product from this reaction is again an alcohol, and can go on to react with
even more epoxyethane! What you get eventually is a chain with a structure:

Compounds of this type are used as plasticisers (added, for example, to PVC
to make it more flexible) or as non-ionic surfactants (detergents). To make the
surfactant, you would start with a fairly long chain alcohol to produce a
molecule such as:
 RADICAL CHAIN
MECHANISM
FOR REACTION OF
METHANE WITH Br2

Step 1 (Initiation)
Heat or uv light cause the
weak halogen bond to
undergo homolytic
cleavage to generate two
bromine radicals and
starting the chain
process.

Step 2 (Propagation)
(a) A bromine radical
abstracts a hydrogen to
form HBr and a methyl
radical, then
(b) The methyl radical
abstracts a bromine atom
from another molecule of
Br2 to form the methyl
bromide product and
another bromine radical,
which can then itself
undergo reaction 2(a)
creating a cycle that can
repeat.

Step 3 (Termination)
Various reactions
between the possible
pairs of radicals allow for
the formation of ethane,
Br2 or the product, methyl
bromide. These reactions
remove radicals and do
not perpetuate the cycle.

Isomerism in Organic Chemistry

Isomerism is the phenomenon whereby certain compounds, with the same molecular
formula, exist in different forms owing to their different organisations of atoms. The concept of
isomerism illustrates the fundamental importance of molecular structure and shape in organic
chemistry.

Structural Isomerism

Structural Isomers have different structural formulae because their atoms are
linked together in different ways.

It arises owing to:

• arrangement of Carbon skeleton

e.g. The formula C4H10 represents two possible structural formulae, butane and
methylpropane:

• position of Functional group

e.g. propan-1-ol and propan-2-ol

 • different Functional groups

e.g. the molecular formula C2H60 represents both ethanol and methoxymethane.

Cyclic alkanes are isomeric with alkenes, e.g. cyclopropane and propene

Isomer Map

Stereoisomerism

Stereoisomers have the same structure and bond order but their atoms and
groups of atoms are arranged differently in space. They have different spatial
arrangements and their molecules are not superimposable. There are two types:

• Geometric Isomerism

Involves a double bond, usually C=C, that does not allow free rotation about the
double bond (unlike a C-C single bond). They are not superimposable.

e.g. cis-but-2-ene and trans-but-2-ene

Stereoisomers may possess quite different physical properties, such as melting

point, density and solubility in water (look up those of maleic acid and fumaric
acid). Ring structures and other steric factors also result in geometric isomerism.
 Isomer Map

• Optical isomerism

Involves an atom, usually carbon, bonded to four different atoms or groups of

atoms. They exist in pairs, in which one isomer is the mirror image of the other.

e.g. butan-2-ol

These isomers are referred to as enantiomers. The central carbon atom to which
four different atoms or groups are attached, is called an asymmetrical carbon
atom.

Enantiomers have identical physical constants, such as melting points and boiling
points, but are said to be optically active since they can be distinguished from
each other by their ability to rotate the plane of polarised light in opposite
directions. A mixture of enantiomers in equal proportions is optically inactive, and
is called a racemic mixture. Use an organic chemistry textbook to find out more
about optical isom

Case study 1a.3 The chain isomerisation of alkanes

Chain Isomerization is used in the petrochemical industry to produce more branched

alkanes with a higher octane number, from linear alkanes, for fuels more suitable for petrol
engines. The proportions of the 'isomers', as well as the hydrocarbon chain length, in crude oil
does not match specific market demands. Straight chain alkanes are heated with a suitable
catalyst to break up the chains and more branched alkanes, as well as lower alkanes are
formed on recombination of the fragments (see examples below).

For a given carbon number of an alkane, the more branched the alkane, the higher the
octane number. The higher the octane number of a fuel/molecule, the less the tendency it
has to cause auto-ignition resulting in 'knocking' or 'pinking' in the car engine.

(1) is linear heptane,

a chain isomer of C7H16, and octane number = 0.

(2) is 2,2,4-trimethylpentane,

a highly branched chain isomer of C8H18, octane number = 100 (used to be called 'iso-
octane').

The known tendency of a mixture of (1) and (2) to auto-ignite are compared with other
fuels/molecules to give them their individual 'octane rating'.
Using skeletal formula, one possible isomerisation reaction of pentane C5H12 is shown
below. They are reversible reactions, so changing reaction conditions, can change the
position of the equilibrium.

(3) pentane, octane number 62 (4) 2-methylbutane, octane

number 93

Case study 1b.1 Positional isomers of molecular formula C3H7Br

In the uv light catalysed reaction of bromine and propane gases, the free radical
substitution reaction can produce two initial mono-substitution products. [full mechanism]

CH3CH2CH3 + Br2 {CH3CH2CH2Br or CH3CHBrCH3} + HBr

(1) 1-bromopropane, , bpt 71oC, primary halogenoalkane,

(2) 2-bromopropane, , bpt 59oC, secondary halogenoalkane,

They are both low boiling colourless liquids, but the more compact molecule (2) has a lower
boiling point. Chemically they are very similar e.g. both undergoing all the nucleophilic
substitution reactions with ammonia, cyanide ion, and hydroxide ion etc. In the case of the
latter, (1) would give the primary alcohol, propan-1-ol and (2) would give the secondary
alcohol, propan-2-ol. [lots of named halogenoalkane structures]

For higher bromoalkanes e.g. 1-bromobutane CH3CH2CH2CH2Br and 2-bromobutane

CH3CH2CHBrCH3, another chemical difference will show up refluxing with ethanolic
potassium hydroxide by which, following an elimination reaction,

1-bromobutane can only form but-1-ene CH3CH2CH=CH2, but 2-bromobutane can form two
isomeric elimination products, namely

but-1-ene CH3CH2CH=CH2, and but-2-ene CH3CH=CHCH3, i.e. you can eliminate either side
of the C-Br bond.

Case study 1b.2 Two linear positional isomers of molecular formula

C5H10

(1) , pent-1-ene, bpt 30oC,

(2) , pent-2-ene, cis bpt 37oC, trans bpt 36oC,

They are very similar physically e.g. relatively non-polar volatile colourless liquids, with similar
low boiling points. Chemically similar e.g. all the usual electrophilic addition reactions of any
alkene, though may, or may not be, some 'isomeric consequences' as regards both their
formation or addition reaction products and some examples are outlined below. Unlike
pent-1-ene, pent-2-ene can also exist as geometric isomers.

Both can be formed in cracking pentane or higher alkanes in which various isomers of C5H10
would be formed. In the laboratory they can be made by elimination reactions e.g. (a) the
'dehydration' of isomeric pentanols with conc. sulphuric acid or (b) or by hydrolysing
bromoalkanes by refluxing with ethanolic potassium hydroxide. The formation of more than
one isomer of the pentenes depends on the position of the -OH in alcohols or the -Br in
bromoalkanes e.g.

(a)(i) CH3CH2CH2CH2CH2OH ==> CH3CH2CH2CH=CH2 + H2O

Pentan-1-ol (above) can only give 1 isomer, pent-1-ene, but pentan-2-ol (below)

(a)(ii) CH3CH2CH2CHOHCH3 ==> {CH3CH2CH2CH=CH2 or CH3CH2CH=CHCH3} + H2O

can give 2 isomers, pent-1-ene and pent-2-ene, because elimination of a -H (as well as the
-OH) can take place either side of the >CH-OH group from an adjacent C-H, which is not
possible with pentan-1-ol with the -OH group on the end carbon.

(b)(i) CH3CH2CH2CH2CH2Br + KOH ==> CH3CH2CH2CH=CH2 + H2O + KBr

1-bromopentane can only give 1 isomer, pent-1-ene (above), but 2-bromopentane (below)

(b)(ii) CH3CH2CH2CHBrCH3 + KOH ==> {CH3CH2CH2CH=CH2 or CH3CH2CH=CHCH3} + H2O

+ KBr

can give two isomers, pent-1-ene and pent-2-ene, because elimination of a -H (as well as the
-Br) can take place either side of the >CH-Br group from an adjacent C-H, which is not
possible with 1-romopentane with the -Br group on the end carbon.

You can also derive many other isomers from the molecular formula C5H10 e.g.
methylbutenes (chain/positional isomers wrt pentenes), methylcyclobutane and
dimethylcyclopropanes (both chain/functional group isomers wrt pentenes).

Case study 1b.5 The alcohols based on C4H10O or C4H9OH

The molecular formula C4H10O can lead to a multitude of isomers including different 'types'
or 'classes' of alcohols based on the formula C4H9OH, resulting in some differences in
physical and chemical properties which are summarised below.

(1) butan-1-ol, bpt 118oC, is a primary alcohol and

oxidised to an aldehyde (butanal) using aqueous sulphuric acid/potassium dichromate(VI). Its
fully linear structure gives it the highest boiling point.

(2) butan-2-ol, bpt 100oC, is a secondary alcohol and oxidised to

a ketone (butanone) using aqueous sulphuric acid/potassium dichromate(VI).

(3) 2-methylpropan-1-ol, bpt 108oC, is primary alcohol and

oxidised to an aldehyde (2-methylpropanal) using aqueous sulphuric acid/potassium
dichromate(VI)
(4) 2-methylpropan-2-ol, bpt 83oC, is a tertiary alcohol and not readily
oxidised because the strong C-C chain would have to be broken. It gives the lowest boiling
point because it has the most compact structure (for explanation see case study 1a.1)

(1) and (2) are positional isomers of each other (same chain structure), as is (3) wrt (4).
The pairs (8)/(9) and (10)/(11) are chain isomers of each pair. From the molecular formula
C4H10O you can also derive three ethers, (5) ethoxyethane, (6) 1-methoxypropane and (7) 2-
methoxypropane.

(5) , (6) , (7)

Case study 1b.6 Halogenoalkane isomers of C4H9Cl

From this molecular formula, both chain and positional isomers can be derived, as well as
illustrating the three classes of halogenoalkanes and a few physical and chemical
differences are summarised below. The alcohols formed by hydrolysis of C4H9Cl are
considered in case study 1b.5 above. Skeletal formulae are used in the examples below.

(1) 1-chlorobutane, bpt 79oC, , a primary halogenoalkane, in a HCl

elimination reaction only but-1-ene is formed. The most 'linear' structure gives the highest
boiling point. On hydrolysis with aqueous sodium hydroxide, the primary alcohol butan-1-ol is
formed.

(2) 2-chlorobutane, bpt 67oC, , a secondary halogenoalkane, in HCl elimination

but-1-ene and but-2-ene are formed. On hydrolysis the secondary alcohol butan-2-ol is
formed.

(3) 1-chloro-2-methylpropane, bpt 68oC, , a primary halogenoalkane, in HCl

elimination 2-methylpropene is formed. On hydrolysis the primary alcohol 2-methylprop-2-ol
is formed.

(4) 2-chloro-2-methylpropane, bpt 51oC, , a tertiary halogenoalkane, in HCl

elimination 2-methylpropene is formed. The most 'compact' structure gives the lowest boiling
point. On hydrolysis the tertiary alcohol 2-methylprop-2-ol is formed.

They are all volatile colourless liquids and all undergo the usual nucleophilic substitution
reactions of any halogenoalkanes. There can chemical differences in e.g. (4) is likely to react
via the 2 step 'unimolecular' SN1 carbocation mechanism (carbocation stability is tert > sec >
prim), and (1) is more likely to go by the SN2 'bimolecular' one step mechanism. Also, with
ethanolic/aqueous sodium hydroxide, con-current elimination is much more likely with
tertiary halogenoalkanes than primary ones. See also bromobutanes for an example of
differences in elimination products, mechanisms of haloalkane reactions and [lots of
halogenoalkane structures]
Case study 1c.1 Functional group isomers of C2H6O

(1) ethanol, an alcohol, bpt 79oC,

(2) methoxymethane, an ether, bpt -25oC,

The highly polarised Oδ--Hδ+ bond arises from the difference in oxygen/hydrogen
electronegativity (O>>H). This results in alcohol molecules being much more polar than
ethers and the formation of 'hydrogen bonding' between alcohol molecules (however
misnamed!). Hydrogen bonding is the strongest intermolecular force and the resulting
increased inter-molecular forces raises the boiling point of alcohols quite considerably
compared to the isomeric ether. The Cδ+-Oδ- is polar, but the two polarities of the C-O-C
linkage tend to cancel each out. The lower alcohols tend to be more soluble in the highly
polar solvent water (water-alcohol H bonding) than the less polar ether molecules are.

Their structural differences leads to quite different chemical reactions and products, apart
from combustion! Alcohols have a diverse chemistry via the C-OH group which ethers lack
giving them quite a limited chemistry. However the lack of reactivity/chemistry of ethers
makes ethers very useful as solvents for other reactants!

(a) Alcohols like (1) react with carboxylic acids to form esters via the -OH group, ethers
cannot.

CH3CH2OH + CH3COOH ==> CH3COOCH2CH3 + H2O

Ethanol forms the ester ethyl ethanoate when heated with ethanoic acid and a little conc.
sulphuric acid.

(b) Alcohols can be dehydrated to form alkenes, ethers cannot.

CH3CH2OH ==> CH2=CH2 + H2O

Ethanol forms ethene when heated with conc. sulphuric acid.

(c) Alcohols rapidly react with sodium metal

2CH3CH2OH + 2Na ==> CH3CH2O-Na+ + H2

Ethanol Case study 1c.3 Functional group isomers of C3H6O

Some physical similarities e.g. low boiling colourless polar liquids or gases, (1) and (2) also
show chemical similarities, as do (3) and (4), but there are significant chemical differences
between all four shown below.

(1) , propanal (an aldehyde), bpt 49oC, adds HCN to give hydroxynitrile,
gives yellow-orange ppt with 24DNPH, produces the primary alcohol, propan-1-ol, on
reduction, readily oxidised to propanoic acid, gives silver mirror with ammoniacal silver nitrate
and red-brown ppt with Fehlings/Benedicts reagent. I2 reaction?
(2) , propanone (a ketone), bpt 56oC, adds HCN to give hydroxynitrile,
gives yellow-orange ppt with 24DNPH, produces secondary alcohol, propan-2-ol, on
reduction, NOT readily oxidised, NO silver mirror with ammoniacal silver nitrate and NO red-
brown ppt with Fehlings/Benedicts reagent. I2 reaction?

(3) , prop-2-ene-1-ol (a bi-functional molecule alkene/alcohol or enol),

bpt 97oC, higher bpt due to hydrogen bonding via -OH (not possible with 1 and 2 above),
gives electrophilic addition reaction of Br2, H2O, HI etc. like any other alkene, reacts with
sodium to give H2 and forms esters with carboxylic acids or acid chlorides just like alcohols
do, NO reaction with ammoniacal silver nitrate, Fehlings/Benedicts reagent or 24DNPH.

(4) , cyclopropanol (an alicyclic secondary alcohol), bpt ?, very unstable,

difficult to study, and readily isomerises to (1) propanal (see case study 1c.4 below.
Theoretically has the chemistry of a secondary alcohol e.g. oxidised to the ketone
cyclopropanone, reacts with sodium to give H2, forms esters with carboxylic acids or acid
chlorides.

(5) , methoxyethene (a bi-functional ether-alkene), bpt 5oC, gives

electrophilic addition reaction of Br2, H2O, HI etc. like any other alkene, but no aldehyde,
ketone or alcohol chemistry.

(6) , 1,2-epoxypropane (a cyclic-ether), bpt 35oC, no alkene, aldehyde,

ketone or alcohol chemistry.

(7) , 1,3-epoxypropane (a cyclic-ether), bpt 49oC, no alkene, aldehyde, ketone

or alcohol chemistry.

Again, for a 'small' molecular formula, C3H6O2 packs quite an isomeric punch! but don't worry
too much, (1) to (2) are ones whose detailed structure, naming, physical properties and
chemical reactions you should be very familiar with. (3) to (5) you should cope with in a
functional group concept Q and (6) to (7) I wouldn't worry too much about!

forms the salt sodium ethoxide and hydrogen.

INTRODUCING ARENES (AROMATIC
HYDROCARBONS)

This page looks at the structures and physical properties of the

simplest arenes (benzene and methylbenzene), together with a
very brief introduction to their reactivity. Much of this is covered in
detail elsewhere on the site - in sections on bonding and
mechanisms, for example. You will find links to all of these pages.

What are arenes?

Arenes are aromatic hydrocarbons. The term "aromatic" originally

referred to their pleasant smells, but now implies a particular sort of
delocalised bonding (see below).

The arenes are based on benzene rings. The simplest of them is

benzene itself, C6H6. The next simplest is methylbenzene (old
name: toluene) which has one of the hydrogen atoms attached to
the ring replaced by a methyl group - C6H5CH3.

The structure of benzene

The structure of benzene is covered in detail in two pages in the

organic bonding section of this site. It is important to understand
these thoroughly to make sense of benzene and methylbenzene
chemistry. Unless you have read these pages recently, you should
spend some time on them now before you go any further on this
page.
 Note: You will find two pages dealing with the bonding in
benzene. One deals with the Kelulé structure, and the other
with the modern delocalised structure.

You should read both of these pages starting with the one
about the Kelulé structure. You will find a link to the second
page at the bottom of the first one.

This is likely to take you some time because you will

probably have to follow up other links as well in order to fully
understand the second page. Don't try to short-cut this.

Use the BACK button (or more likely, the HISTORY file or
GO menu) on your browser to return to this page later.

What you need to understand about benzene is:

• Benzene, C6H6, is a planar molecule containing

a ring of six carbon atoms each with a hydrogen
atom attached.

The six carbon atoms form a perfectly regular hexagon. All

the carbon-carbon bonds have exactly the same lengths -
somewhere between single and double bonds.

• There are delocalised electrons above and below the plane

of the ring.

This diagram shows one of the molecular orbitals containing

two of the delocalised electrons, which may be found
anywhere within the two "doughnuts". The other molecular
orbitals are almost never drawn.

• The presence of the delocalised electrons makes benzene

particularly stable.
• Benzene resists addition reactions because that would
involve breaking the delocalisation and losing that stability.
•

Benzene is represented by this symbol, where the circle

represents the delocalised electrons, and each corner of the
hexagon has a carbon atom with a hydrogen attached.
The structure of methylbenzene (toluene)

Methylbenzene just has a methyl group attached to the benzene

ring - replacing one of the hydrogen atoms.

Attached groups are often drawn at the top of the ring, but you may
occasionally find them drawn in other places with the ring rotated.
Note: If you have to count up the hydrogens in a diagram of
this kind, don't forget that there isn't a hydrogen atom at any
corner of the hexagon where there is something else
attached. The molecular formula of methylbenzene, for
example, is C7H8. Check that you get that answer from this
diagram!

Physical properties

Boiling points

In benzene, the only attractions between neighbouring molecules

are van der Waals dispersion forces. There is no permanent dipole
on the molecule.

Benzene boils at 80°C - rather higher than other hydrocarbons of

similar molecular size (pentane and hexane, for example). This is
presumably due to the ease with which temporary dipoles can be
set up involving the delocalised electrons.
Note: If you aren't happy about van der Waals dispersion
forces then you should follow this link before you go on.

Use the BACK button on your browser to return to this page.

Methylbenzene boils at 111°C. It is a bigger molecule and so the

van der Waals dispersion forces will be bigger.

Methylbenzene also has a small permanent dipole, so there will be

dipole-dipole attractions as well as dispersion forces. The dipole is
due to the CH3 group's tendency to "push" electrons away from
itself. This also affects the reactivity of methylbenzene (see below).
Melting points

You might have expected that methylbenzene's melting point would

be higher than benzene's as well, but it isn't - it is much lower!
Benzene melts at 5.5°C; methylbenzene at -95°C.

Molecules must pack efficiently in the solid if they are to make best
use of their intermolecular forces. Benzene is a tidy, symmetrical
molecule and packs very efficiently. The methyl group sticking out
in methylbenzene tends to disrupt the closeness of the packing. If
the molecules aren't as closely packed, the intermolecular forces
don't work as well and so the melting point falls.

Solubility in water

The arenes are insoluble in water.

Benzene is quite large compared with a water molecule. In order

for benzene to dissolve it would have to break lots of existing
hydrogen bonds between water molecules. You also have to break
the quite strong van der Waals dispersion forces between benzene
molecules. Both of these cost energy.

The only new forces between the benzene and the water would be
van der Waals dispersion forces. These aren't as strong as
hydrogen bonds (or the original dispersion forces in the benzene),
and so you wouldn't get much energy released when they form.

It simply isn't energetically profitable for benzene to dissolve in

water. It would, of course, be even worse for larger arene
molecules.

Reactivity

Benzene

It has already been pointed out above that benzene is resistant to

addition reactions. Adding something new to the ring would need
you to use some of the delocalised electrons to form bonds with
whatever you are adding. That results in a major loss of stability as
the delocalisation is broken.

Instead, benzene mainly undergoes substitution reactions -

replacing one or more of the hydrogen atoms by something new.
That leaves the delocalised electrons as they were.
Note: The delocalisation is, in fact, broken during a
 substitution reaction, but reforms at the end. If you are
interested in the mechanisms for benzene's substitution
reactions you could follow this link.

Should you want to come back to this page later, it would

probably be best to use the HISTORY file or GO menu on
your browser.

Methylbenzene

You have to consider the reactivity of something like

methylbenzene in two distinct bits:

For example, if you explore other pages in this section, you will find
that alkyl groups attached to a benzene ring are oxidised by
alkaline potassium manganate(VII) solution. This doesn't happen in
the absence of the benzene ring.

The tendency of the CH3 group to "push" electrons away from itself
also has an effect on the ring, making methylbenzene react more
quickly than benzene itself. You will find this explored in other
pages in this section as well.
MANUFACTURING ARENES

This page looks at the manufacture of arenes such as benzene and

methylbenzene (toluene) by the catalytic reforming of fractions from petroleum
(crude oil).

Catalytic reforming

What is reforming?

Reforming takes straight chain hydrocarbons in the C6 to C8 range from the

gasoline or naphtha fractions and rearranges them into compounds containing
benzene rings. Hydrogen is produced as a by-product of the reactions.

For example, hexane, C6H14, loses hydrogen and turns into benzene. As long
as you draw the hexane bent into a circle, it is easy to see what is happening.

Similarly, methylbenzene (toluene) is made from heptane:

The process

The feedstock

The feedstock is a mixture of the naphtha or gasoline fractions and hydrogen.

The hydrogen is there to help prevent the formation of carbon by
decomposition of the hydrocarbons at the high temperatures used. The
carbon would otherwise contaminate the catalyst.

The catalyst

A typical catalyst is a mixture of platinum and aluminium oxide. With a

platinum catalyst, the process is sometimes described as "platforming".

Temperature and pressure

The temperature is about 500°C, and the pressure varies either side of 20
atmospheres.

Converting some of the methylbenzene into benzene

Methylbenzene is much less commercially valuable than benzene. The methyl

group can be removed from the ring by a process known as "dealkylation".

The methylbenzene is mixed with hydrogen at a temperature of between 550

and 650°C, and a pressure of between 30 and 50 atmospheres, with a
mixture of silicon dioxide and aluminium oxide as catalyst.

NITRATION OF BENZENE AND

METHYLBENZENE

This page looks at the facts about the nitration of benzene and
methylbenzene. The mechanisms for these reactions are covered
elsewhere on the site, and you will find links to these.

The nitration of benzene

Nitration happens when one (or more) of the hydrogen atoms on

the benzene ring is replaced by a nitro group, NO2.

Benzene is treated with a mixture of concentrated nitric acid and

concentrated sulphuric acid at a temperature not exceeding 50°C.
The mixture is held at this temperature for about half an hour.
Yellow oily nitrobenzene is formed.

You could write this in a more condensed form as:

The concentrated sulphuric acid is acting as a catalyst and so isn't

written into the equations.

At higher temperatures there is a greater chance of getting more

than one nitro group substituted onto the ring. You will get a certain
amount of 1,3-dinitrobenzene formed even at 50°C. Some of the
nitrobenzene formed reacts with the nitrating mixture of
concentrated acids.

Notice that the new nitro group goes into the 3 position on the ring.
Nitro groups "direct" new groups into the 3 and 5 positions. The
reasons for this "directing effect" are beyond UK A level.
Note: The numbering on the ring goes clockwise around the
ring starting with number 1 at the top.

It is also possible to get a third nitro group attached to the ring (in
the 5 position). However, nitro groups make the ring much less
reactive than the original benzene ring. Two nitro groups on the
ring make its reactions so slow that virtually no trinitrobenzene is
produced under these conditions.
Note: Follow this link if you want the mechanism for the
nitration of benzene.

You will find the mechanism for the nitration of nitrobenzene

(the reaction producing 1,3-dinitrobenzene) at the bottom of
the page you will get to by following this second link.

If you choose to follow either of these links, use the BACK

button (or the HISTORY file or GO menu) on your browser to
return to this page later.

The nitration of methylbenzene (toluene)

Methylbenzene reacts rather faster than benzene - in nitration, the

reaction is about 25 times faster. That means that you would use a
lower temperature to prevent more than one nitro group being
substituted - in this case, 30°C rather than 50°C. Apart from that,
the reaction is just the same - using the same nitrating mixture of
concentrated sulphuric and nitric acids.

You get a mixture of mainly two isomers formed: 2-

nitromethylbenzene and 4-nitromethylbenzene. Only about 5% of
the product is 3-nitromethylbenzene. Methyl groups are said to be
2,4-directing.

For 2-nitromethylbenzene:

. . . and for 4-nitromethylbenzene:

Note: You will find the mechanism for the nitration of

methylbenzene by following this link.

Use the BACK button (or HISTORY file or GO menu) on your

browser to return to this page later.

Just as with benzene, you will get a certain amount of dinitro

compound formed under the conditions of the reaction, but virtually
no trinitro product because the reactivity of the ring decreases for
every nitro group added. From an experimental point of view this is
just as well. Trinitromethylbenzene used to be called trinitrotoluene
or TNT!

The reason for the 2,4-directing effect of the methyl group is

beyond UK A level, but the increased reaction rate can be
explained up to a point.

The reactivity of a benzene ring is governed by the electron density

around the ring. Methyl groups tend to "push" electrons towards the
ring - increasing the density, and so making the ring more attractive
to attacking reagents.

This is actually a simplification. In order to understand the rate

effect properly you have to think about the stability of the
intermediate ions formed during the reactions, because this affects
the activation energy of the reactions. This is also the basis for the
directing effect and is again beyond UK A level.

Warning! I have deliberately chosen not to use the strict

IUPAC names for the compounds in this section, because I
see them as illogical and inconsistent with the older names for
these compounds. The names for the compounds with one
nitro group substituted into methylbenzene should be methyl-2-
nitrobenzene and methyl-4-nitrobenzene. The reason for these
names is that you should strictly name the attached groups in
alphabetical order.

It seems to me to be illogical on three counts. Firstly, it breaks

up the name of the hydrocarbon, so that it is no longer
immediately obvious that you are talking about a derivative of
methylbenzene.

Secondly, it doesn't relate to the older names for these

compounds. Methyl-4-nitrobenzene, for example, used to be
called para-nitrotoluene. The "para" refers to the 4 position.
You could equally have called it 4-nitrotoluene. My name of 4-
nitromethylbenzene is a direct translation of this. I think that's
entirely logical!

Thirdly, you can end up with completely different names for

compounds which are structurally similar. For example, if you
think about substituting chlorines into these positions instead of
nitro groups you will have to completely change the names for
purely alphabetical reasons. That's silly!

I may well be in a minority of one on this, but I am sticking to

my guns on it. In fact, IUPAC is much more flexible about
these things than they are sometimes given credit for. I doubt if
it would worry them, although it might upset your teachers or
lecturers. Obviously, if you are working in a system which still
calls methylbenzene "toluene", none of this bothers you!

HALOGENATION OF BENZENE AND

METHYLBENZENE

This page looks at the reactions of benzene and methylbenzene

(toluene) with chlorine and bromine under various conditions. The
mechanisms for several of these reactions are covered elsewhere
on the site and you will find links to these other pages.

The halogenation of benzene

Substitution reactions

Benzene reacts with chlorine or bromine in the presence of a

catalyst, replacing one of the hydrogen atoms on the ring by a
chlorine or bromine atom.

The reactions happen at room temperature. The catalyst is either

aluminium chloride (or aluminium bromide if you are reacting
benzene with bromine) or iron.

Strictly speaking iron isn't a catalyst, because it gets permanently

changed during the reaction. It reacts with some of the chlorine or
bromine to form iron(III) chloride, FeCl3, or iron(III) bromide, FeBr3.

These compounds act as the catalyst and behave exactly like

aluminium chloride, AlCl3, or aluminium bromide, AlBr3, in these
reactions.

The reaction with chlorine

The reaction between benzene and chlorine in the presence of

either aluminium chloride or iron gives chlorobenzene.

or, written more compactly:

The reaction with bromine

The reaction between benzene and bromine in the presence of

either aluminium bromide or iron gives bromobenzene. Iron is
usually used because it is cheaper and more readily available.

or:

Note: Follow this link if you want the mechanism for the
halogenation of benzene.
 Use the BACK button on your browser to return to this page
later.

Addition reactions

In the presence of ultraviolet light (but without a catalyst present),

hot benzene will also undergo an addition reaction with chlorine or
bromine. The ring delocalisation is permanently broken and a
chlorine or bromine atom adds on to each carbon atom.

For example, if you bubble chlorine gas through hot benzene

exposed to UV light for an hour, you get 1,2,3,4,5,6-
hexachlorocyclohexane.

Bromine would behave similarly.

The chlorines and hydrogens can stick up and down at random

above and below the ring and this leads to a number of geometric
isomers. Although there aren't any carbon-carbon double bonds,
the bonds are still "locked" and unable to rotate.

One of these isomers was once commonly used as an insecticide

known variously as BHC, HCH and Gammexane. This is one of the
"chlorinated hydrocarbons" which caused so much environmental
harm.
Note: Geometric isomerism is explored on another page,
although only with regard to carbon-carbon double bonds.

It isn't too difficult to relate this to the ring case. For example,
the chlorine atoms in the 1 and 2 positions on the ring could
both be pointing up above the ring (or down below it) or one
could be pointing up and the other one down. That
corresponds exactly to the cis and trans positions that you are
probably familiar with in carbon-carbon double bonds.

Use the BACK button on your browser to return to this page if

you choose to follow this link.

The halogenation of methylbenzene

Substitution reactions

It is possible to get two quite different substitution reactions

between methylbenzene and chlorine or bromine depending on the
conditions used. The chlorine or bromine can substitute into the
ring or into the methyl group.

Substitution into the ring

Substitution in the ring happens in the presence of aluminium

chloride (or aluminium bromide if you are using bromine) or iron,
and in the absence of UV light. The reactions happen at room
temperature.

This is exactly the same as the reaction with benzene, except that
you have to worry about where the halogen atom attaches to the
ring relative to the position of the methyl group.

Methyl groups are 2,4-directing, which means that incoming

groups will tend to go into the 2 or 4 positions on the ring -
assuming the methyl group is in the 1 position. In other words, the
new group will attach to the ring next door to the methyl group or
opposite it. The reason for the directing effect is beyond UK A level.

With chlorine, substitution into the ring gives a mixture of 2-

chloromethylbenzene and 4-chloromethylbenzene.

With bromine, you would get the equivalent bromine compounds.

Note: You will find the mechanism for this reaction half way
down the page you will get to by following this link.

Use the BACK button on your browser to return to this page

later.

Substitution into the methyl group

If chlorine or bromine react with boiling methylbenzene in the

absence of a catalyst but in the presence of UV light, substitution
happens in the methyl group rather than the ring.

For example, with chlorine (bromine would be similar):

The organic product is (chloromethyl)benzene. The brackets in the

name emphasise that the chlorine is part of the attached methyl
group, and isn't on the ring.

One of the hydrogen atoms in the methyl group has been replaced
by a chlorine atom. However, the reaction doesn't stop there, and
all three hydrogens in the methyl group can in turn be replaced by
chlorine atoms.

That means that you could also get (dichloromethyl)benzene and

(trichloromethyl)benzene as the other hydrogen atoms in the
methyl group are replaced one at a time.

If you use enough chlorine you will eventually get

(trichloromethyl)benzene, but any other proportions will always lead
to a mixture of products.
Note: You will find the mechanisms for these reactions spread
over 3 pages (depending on how much detail you want) which
you can get to by following this link

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Addition reactions

I haven't been able to track down anything similar to the reaction

between benzene and chlorine in which six chlorine atoms add
around the ring.

That perhaps isn't surprising. Chlorine adds to benzene in the

presence of ultraviolet light. With methylbenzene under those
conditions, you get substitution in the methyl group. That is
energetically easier because it doesn't involve breaking the
delocalised electron system.

Whether you would get addition to the ring if you used a large
excess of chlorine and did the reaction for a long time, I don't know.
Once all the hydrogens in the methyl group had been substituted,
perhaps you might then get addition to the ring as well.

None of this is needed for any of the UK A level syllabuses.

Note: If you have any solid information on this (either that the
reaction definitely does or definitely doesn't happen), I would
be grateful if you could contact me via the address on the
about this site page.

FRIEDEL-CRAFTS REACTIONS
OF BENZENE AND
METHYLBENZENE

This page gives details of the Friedel-Crafts reactions of benzene

and methylbenzene (toluene). The mechanisms for some of these
reactions are covered elsewhere on the site and you will find links
to those as you go along.

Friedel-Crafts acylation

Friedel-Crafts acylation of benzene

What is acylation?

An acyl group is an alkyl group attached to a carbon-oxygen double

bond. If "R" represents any alkyl group, then an acyl group has the
formula RCO-. Acylation means substituting an acyl group into
something - in this case, into a benzene ring.

The most commonly used acyl group is CH3CO-. This is called the
ethanoyl group, and in this case the reaction is sometimes called
"ethanoylation". In the example which follows we are substituting a
CH3CO- group into the ring, but you could equally well use any
other acyl group.

The facts

The most reactive substance containing an acyl group is an acyl

chloride (also known as an acid chloride). These have the general
formula RCOCl.
Benzene is treated with a mixture of ethanoyl chloride, CH3COCl,
and aluminium chloride as the catalyst. The mixture is heated to
about 60°C for about 30 minutes.

A ketone called phenylethanone (old name: acetophenone) is

formed.
Note: Don't worry too much about the name "phenylethanone"
- all that matters is that you can draw the structure.

You may find slight variations on the conditions for this

reaction. Various recipes I have found vary the temperature
and time - for example by having a slightly lower temperature
for a longer time.

or, if you want a more compact form:

The aluminium chloride isn't written into these equations because it

is acting as a catalyst. If you wanted to include it, you could write
AlCl3 over the top of the arrow (see below).
Note: You will find the mechanism for this reaction in the
mechanisms section of this site.

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later.

Friedel-Crafts acylation of methylbenzene (toluene)

The reaction is just the same with methylbenzene except that you
have to worry about where the acyl group attaches to the ring
relative to the methyl group.

Normally, the methyl group in methylbenzene directs new groups

into the 2- and 4- positions (assuming the methyl group is in the 1-
position). In acylation, though, virtually all the substitution happens
in the 4- position.

Note: The reason for the 2,4-directing effect of the methyl

 group is beyond UK A level. The reason that you get virtually
none of the 2- isomer in this instance is because of the size of
the incoming acyl group. Everything gets too cluttered (and
therefore less stable) if you try to put the acyl group next door
to the methyl group.

Friedel-Crafts alkylation

Friedel-Crafts alkylation of benzene

What is alkylation?

Alkylation means substituting an alkyl group into something - in this

case into a benzene ring. A hydrogen on the ring is replaced by a
group like methyl or ethyl and so on.

The facts

Benzene reacts at room temperature with a chloroalkane (for

example, chloromethane or chloroethane) in the presence of
aluminium chloride as a catalyst. On this page, we will look at
substituting a methyl group, but any other alkyl group could be
used in the same way.

Substituting a methyl group gives methylbenzene.

or:

Note: The methylbenzene formed is more reactive than the

original benzene, and so the reaction doesn't stop there. You
get further methyl groups substituted around the ring. You can
improve your chances of just getting monosubstitution by using
a large excess of benzene.

You won't have to worry about this for UK A level purposes.

You will find the mechanism for this reaction in the

mechanisms section of this site.

Use the BACK button on your browser to return to this page

later.

Friedel-Crafts alkylation of methylbenzene (toluene)

Again, the reaction is just the same with methylbenzene except that
you have to worry about where the alkyl group attaches to the ring
relative to the methyl group.

Unfortunately this time there is a problem! Where the incoming

alkyl group ends up depends to a large extent on the temperature
of the reaction.

At 0°C, substituting methyl groups into methylbenzene, you get a

mixture of the 2-.3- and 4- isomers in the proportion 54% / 17% /
29%. That's a higher proportion of the 3- isomer than you might
expect.

At 25°C, the proportions change to 3% / 69% / 28%. In other words

the proportion of the 3- isomer has increased even more. Raise the
temperature some more and the trend continues.

The reason for this is again beyond UK A level.

Note: The problem in this case lies in the fact that the methyl
groups attaching to the ring can fall off again and reattach
somewhere else in the presence of the aluminium chloride.
You can get equilibria set up between the various isomers.

The reason for the 2,4- directing effect of the methyl group in
methylbenzene lies in the fact that the 2- and 4- isomers form
faster than the 3- isomer. However, in this case, the 3- isomer
is the most thermodynamically stable of the three. If you raise
the temperature, or allow more time, the equilibria set up
favour the most stable product.

You do NOT have to worry about this for A level purposes.

Friedel-Crafts alkylation industrially

The manufacture of ethylbenzene

Ethylbenzene is an important industrial chemical used to make

styrene (phenylethene), which in turn is used to make polystyrene -
poly(phenylethene).

It is manufactured from benzene and ethene. There are several

ways of doing this, some of which use a variation on Friedel-Crafts
alkylation. What follows is the method required by the UK A level
Exam Board, AQA.

The reaction is done in the liquid state. Ethene is passed through a

liquid mixture of benzene, aluminium chloride and a catalyst
promoter which might be chloroethane or hydrogen chloride. We
are going to assume it is HCl (because that's what AQA want!).
Promoters are used to make catalysts work better.

There are two variants on the process. One (the Union Carbide /
Badger process) uses a temperature no higher than 130°C and a
pressure just high enough to keep everything liquid.

The other (the Monsanto process) uses a slightly higher

temperature of 160°C which needs less catalyst. (Presumably -
although I haven't been able to confirm this - the pressure would
also need to be higher to keep everything liquid at the higher
temperature.)

or:

Again, the aluminium chloride and HCl aren't written into these
equations because they are acting as catalysts. If you wanted to
include them, you could write AlCl3 and HCl over the top of the
arrow.
Note: You will find the mechanism for this reaction in the
mechanisms section of this site. This will show exactly what
the HCl and aluminium chloride are doing in the reaction.

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later.

ASSORTED REACTIONS OF BENZENE

AND METHYLBENZENE

This page gives details of some reactions of benzene and

methylbenzene (toluene) not covered elsewhere in this section. It
deals with the combustion, hydrogenation and sulphonation of
benzene and methylbenzene (toluene), and with the oxidation of
side chains attached to benzene rings.

Remember that benzene, methylbenzene and similar hydrocarbons

based on benzene rings are collectively known as arenes.

Combustion

Like any other hydrocarbons, benzene and methylbenzene burn in

a plentiful supply of oxygen to give carbon dioxide and water. For
example:

For benzene:

. . . and methylbenzene:

However, for these hydrocarbons, combustion is hardly ever

complete, especially if they are burnt in air. The high proportion of
carbon in the molecules means that you need a very high
proportion of oxygen to hydrocarbon to get complete combustion.
Look at the equations.

As a general rule, the hydrogen in a hydrocarbon tends to get what

oxygen is available first, leaving the carbon to form carbon itself, or
carbon monoxide, if there isn't enough oxygen to go round.

The arenes tend to burn in air with extremely smoky flames - full of
carbon particles.

You almost invariably get incomplete combustion, and the arenes

can be recognised by the smokiness of their flames.

Hydrogenation

Hydrogenation is an addition reaction in which hydrogen atoms are

added all the way around the benzene ring. A cycloalkane is
formed. For example:

With benzene:

. . . and methylbenzene:
These reactions destroy the electron delocalisation in the original
benzene ring, because those electrons are being used to form
bonds with the new hydrogen atoms.

Although the reactions are exothermic overall because of the

strengths of all the new carbon-hydrogen bonds being made, there
is a high activation barrier to the reaction.

The reactions are done using the same finely divided nickel
catalyst that is used in hydrogenating alkenes and at similar
temperatures (around 150°C), but the pressures used tend to be
higher.
Note: Pressure values quoted can be anywhere from about 20
atmospheres to 200 atmospheres. I have no way of knowing
which is right!

This hydrogenation reaction is important in estimating the

delocalisation energy for benzene. You can find more about
this by following this link to a page about the Kekulé structure
for benzene.

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later.

Sulphonation

Sulphonation involves replacing one of the hydrogens on a

benzene ring by the sulphonic acid group, -SO3H.

The sulphonation of benzene

There are two equivalent ways of sulphonating benzene:

• Heat benzene under reflux with concentrated sulphuric acid

for several hours.
• Warm benzene under reflux at 40°C with fuming sulphuric
acid for 20 to 30 minutes. Fuming sulphuric acid, H2S2O7,
can usefully be thought of as a solution of sulphur trioxide in
concentrated sulphuric acid.
Or:

The product is benzenesulphonic acid.

Note: You will find the mechanism for this reaction by
following this link.

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The sulphonation of methylbenzene

Methylbenzene is more reactive than benzene because of the

tendency of the methyl group to "push" electrons towards the ring.
Exactly how this increases the rate of reaction is beyond UK A level
- it is rather more complicated than just an increase in the electron
density of the ring.

The effect of this greater reactivity is that methylbenzene will react

with fuming sulphuric acid at 0°C, and with concentrated sulphuric
acid if they are heated under reflux for about 5 minutes.

As well as the effect on the rate of reaction, with methylbenzene

you also have to think about where the sulphonic acid group ends
up on the ring relative to the methyl group.

Methyl groups have a tendency to "direct" new groups into the 2-

and 4- positions on the ring (assuming the methyl group is in the 1-
position). Methyl groups are said to be 2,4-directing. The origin of
this directing effect is also beyond UK A level.

So you get a mixture which mainly consists of two isomers. Only

about 5 - 10% of the 3- isomer is formed.

The main reactions are:

and:
In the case of sulphonation, the exact proportion of the isomers
formed depends on the temperature of the reaction. As the
temperature increases, you get increasing proportions of the 4-
isomer and less of the 2- isomer.

This is because sulphonation is reversible. The sulphonic acid

group can fall off the ring again, and reattach somewhere else. This
tends to favour the formation of the most thermodynamically stable
isomer. This interchange happens more at higher temperatures.

The 4- isomer is more stable because there is no cluttering in the

molecule as there would be if the methyl group and sulphonic acid
group were next door to each other.

Side chain oxidation in alkylbenzenes

An alkylbenzene is simply a benzene ring with an alkyl group

attached to it. Methylbenzene is the simplest alkylbenzene.

Alkyl groups are usually fairly resistant to oxidation. However, when

they are attached to a benzene ring, they are easily oxidised by an
alkaline solution of potassium manganate(VII) (potassium
permanganate).

Methylbenzene is heated under reflux with a solution of potassium

manganate(VII) made alkaline with sodium carbonate. The purple
colour of the potassium manganate(VII) is eventually replaced by a
dark brown precipitate of manganese(IV) oxide.

The mixture is finally acidified with dilute sulphuric acid.

Overall, the methylbenzene is oxidised to benzoic acid.

Interestingly, any alkyl group is oxidised back to a -COOH group on

the ring under these conditions. So, for example, propylbenzene is
also oxidised to benzoic acid.
 Note: These are flow schemes - deliberately not full
equations. To be honest, I don't really know whether you could
write an accurate single equation for anything more
complicated than a methyl group attached to the ring. In other
cases, you will certainly get some carbon dioxide produced,
but possibly some other organic molecules as well depending
on the conditions.

The separation of the benzoic acid is beyond the scope of this

site. The sulphuric acid converts benzoate ions (formed under
the alkaline conditions) into benzoic acid. The problem lies in
separating solid benzoic acid from solid manganese(IV) oxide.

This reaction has some similarities to the oxidation of alkenes

by potassium manganate(VII), which you might also like to
have a look at if it is on your syllabus.

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later if you choose to follow this link.

Part IV AROMATIC HYDROCARBONS (Arenes)

The five reactions described are electrophilic substitution reactions involving the
generation of a powerful electrophile (electron pair acceptor) which subsequently
attacks the electron rich Π ο τ δ ν ε τ σεν ε ρ Α .δ ν ο β ελβ υ ο δ
εη τ φο µε τ σ ψ σ νορ τ χ ε λ ε )ι π( εη τ σω ο λ λ α
σνο ι τ υ τ ι τ σ β υ σ εσυ α χ ε β ,ν ο ι τ ι δ δ α ναη τ
ρεη τ α ρ ,ν ο ι τ υ τ ι τ σ β υ σ ογρ ε δ ν υ .τ χ α τ ν ι
νιαµ ε ρ οτ γν ι ρ ενε ζ ν ε β ελβ α τ σ ψρ ε ϖ

The electrophilic substitution of an arene - nitration

• for benzene : C6H6 + HNO3 ==> C6H5NO2 + H2O [see mechanism 19 below]
• for methyl benzene: C6H5CH3 + HNO3 ==> O2NC6H4CH3 + H2O
• The nitrating mixture consists of concentrated nitric acid (source of the nitro group
-NO2) and concentrated sulphuric acid which acts as a catalyst and as a strong
acid.

mechanism 19 - electrophilic substitution in the nitration of the benzene ring

• [mechanism 19 above] Benzene is converted into nitrobenzene, when R = H.
• When R = CH3, methylbenzene will form a mixture of the three possible substitution
products methyl-2/3/4-nitrobenzene,
o and methyl-3-nitrobenzene is the minority product, the mechanism above
would show the formation of one of the major products methyl-2-
nitrobenzene.
• Step (1) The sulphuric acid protonates the nitric acid (strong acid, but weaker
than H2SO4)
• Step (2) The protonated nitric acid loses a water molecule via a sulphuric acid
molecule, to generate the electrophile, the nitronium ion, NO2+. This is a much
more powerful electrophile, i.e. electron pair acceptor, than the original nitric acid,
and is needed to attack the very stable aromatic ring of benzene.
o Steps (1) and (2) can be written as: 2H2SO4 + HNO3 ==> NO2+ + H3O+ +
2HSO4-
• Step (3) An electron pair from the delocalised ι π electrons of the benzene ring
forms a C-N bond with the electron pair accepting nitronium ion forming a highly
unstable carbocation. It is very unstable because the stable electron arrangement of
the benzene ring is partially broken to give a 'saturated' C (top right of ring).
• Step (4) The hydrogensulphate ion (HSO4-, formed in step (1), abstracts a proton
from the highly unstable intermediate carbocation to give the nitro-aromatic product
and reform the sulphuric acid catalyst as well as the stable benzene ring.
o Note that the hydrogensulphate ion, HSO4- has been shown in the style of
-
:O-SO2-OH, to emphasize the importance a lone pair on the oxygen
abstracting the proton from the aromatic carbocation.

• GENERAL COMMENT to compare aromatic electrophilic substitution with the

electrophilic addition with alkenes:
o Like alkenes, arenes are susceptible to electrophilic attack because of
the high electron density of the ι π electrons involved in the carbon-
carbon bonding and both show little reactivity towards nucleophilic reagents.
o However two points should be considered because of the particular stability
of the aromatic (benzene) ring.
1. This makes aromatic compounds less reactive than alkenes, which
readily undergo addition rather than substitution.
2. Aromatics do not usually undergo addition because this will remove
the stability conferred on the molecule by the benzene ring. By under
going substitution rather than addition, the stable aromatic ring is
preserved.
• FURTHER COMMENTS
o The overall nitration reaction is the substitution of -H by -NO2

The electrophilic substitution of an arene - chlorination (example of

aromatic halogenation)

• C6H6 + Cl2 ==> C6H5Cl + HCl [see mechanism 21 below]

• Chlorine is bubbled into a mixture of the arene and anhydrous aluminium chloride
catalyst. Other catalysts like anhydrous iron(III) chloride can be used, and they are
collectively known as halogen carriers.
 mechanism 21 - electrophilic substitution by halogen in a benzene ring

• [mechanism 21 above] When R = H, benzene forms chlorobenzene.

o Step (1) The non-polar and uncharged chlorine molecule is not a strong
enough an electrophile to disrupt the ι π electron system of the benzene
ring. The aluminium chloride reacts with a chlorine molecule to form a
positive chlorine ion Cl+ which is a much stronger electron pair accepting
electrophile and a tetrachloroaluminate(III) ion (either this or an AlCl3-Cl2
complex - details not needed for A level).
o Step (2) An electron pair from the delocalised ι π electrons of the benzene
ring forms a C-Cl bond with the electron pair accepting positive chlorine ion
forming a highly unstable carbocation. It is very unstable because the stable
electron arrangement of the benzene ring is partially broken to give a
'saturated' C (top right of ring).
o Step (3) The tetrachloroaluminate(III) ion, formed in step (1), abstracts a
proton from the highly unstable intermediate carbocation to give the chloro-
aromatic product, hydrogen chloride gas and reform the aluminium chloride
catalyst.
• Also consider C6H5CH3 + Cl2 ==> ClC6H4CH3 + HCl
• when R = CH3, methylbenzene forms a mixture of chloro-2/3/4-methylbenzene.
o chloro-3-methylbenzene is the minority product and the mechanism above
would show the formation of chloro-2-methylbenzene.
• FURTHER COMMENTS
o The overall halogenation reaction is the substitution of -H by -Cl
o Bromination can be carried in the same way by mixing bromine, the
aromatic hydrocarbon (arene) with a halogen carrier catalyst such as
anhydrous AlBr3 or FeBr3.
o Why do aromatic compounds tend to react by electrophilic substitution
BUT alkenes tend to react by electrophilic addition?
 They both interact with electrophiles because they both have
'electron rich' electron pair donating bonding systems i.e. the >C=C<
double bond in alkenes and the delocalised ∏ electrons of the
benzene ring, but the benzene ring has a particularly high stability
which is preserved on substitution. For the same reason alkenes are
generally more reactive than arenes.
o If methyl benzene is reacted with chlorine in the presence of uv light,
substitution takes place in the alkyl side chain. In other words it behaves like
an alkane and undergoes a free radical substitution reaction. The initial
product is chloromethylbenzene, C6H5CH2Cl, and further substitution products
can be formed C6H5CHCl2 and C6H5CCl3. This illustrates the significance of
changing reaction conditions which function via a different mechanism to give
a different product.
 initiation:
 Cl-Cl ==> Cl. + Cl.
 chain propagations:
 Cl. + C6H5CH3 ==> HCl + C6H5CH2.
 then C6H5CH2. + Cl-Cl ==> C6H5CH2Cl + Cl.
 chain terminations:
 2C6H5CH2. ==> C6H5CH2CH2C6H5 or 2Cl. ==> Cl2 or C6H5CH2.
+ Cl. ==> C6H5CH2Cl
 The electrophilic substitution of an arene - alkylation (Friedel-Crafts
reaction)

• C6H6 + R3C-Cl ==> C6H5-CR3 + HCl (R = H, alkyl, aryl) [see mechanism 23 below]
• The arene is refluxed with a chloroalkane and anhydrous aluminium chloride catalyst.

mechanism 23 - electrophilic substitution by an alkyl group in the benzene ring

• [mechanism 23 above] If R' = H, benzene would form methylbenzene if

chloromethane was used.
o Step (1) The weakly polar and uncharged halogenoalkane molecule is not a
strong enough an electrophile to disrupt the ι π electron system of the
benzene ring. The aluminium chloride reacts with the halogenoalkane
molecule to form a carbocation which is a much stronger electron pair
accepting electrophile than the original acid chloride (either this or an AlCl3-
R3Cl complex - details not needed for A level).
o Step (2) An electron pair from the delocalised ∏ electrons of the benzene
ring forms a C-C bond with the electron pair accepting carbocation forming a
second highly unstable carbocation. It is very unstable because the stable
electron arrangement of the benzene ring is partially broken to give a
'saturated' C (top right of ring).
o Step (3) is a proton transfer, as the tetrachloroaluminate(III) ion [formed in
step (1)], abstracts a proton from the highly unstable intermediate
carbocation to give the alkyl-aromatic product, hydrogen chloride gas and
reform the aluminium chloride catalyst.
• If R' = CH3 methylbenzene: C6H5CH3 + R3C-Cl ==> R3C-C6H4CH3 + HCl
• A mixture of polysubstituted alkyl aromatic compounds are formed.
o e.g. using chloromethane, 1,2- or 1,3- or 1,4-dimethylbenzene will be formed,
 so if R=H, the mechanism above would show the formation of 1,2-
dimethylbenzene.

• FURTHER COMMENTS
o The overall alkylation reaction is the substitution of -H by -CR3
o Bromoalkanes can also be used for alkylation, but more expensive. Similar
catalysts can be used e.g. anhydrous AlBr3 or FeBr3.

The electrophilic substitution of an arene - acylation (Friedel-Crafts reaction)

• for R = H, benzene: C6H6 + R'COCl ==> C6H5COR' + HCl [see mechanism 25

below]
• Benzene is refluxed with an acid chloride and anhydrous aluminium chloride
catalyst and a ketone is formed.
mechanism 25 - electrophilic substitution by an acyl group in the benzene ring

• [mechanism 25 above] If ethanoyl chloride, CH3COCl, was used (R=CH3-), benzene

forms phenylethanone, C6H5-CO-CH3.
o Step (1) Although the acid chloride molecule is polar, it is still not a strong
enough electrophile to disrupt the ι π electron system of the benzene ring.
The aluminium chloride reacts with an acid chloride molecule to form a
carbocation (acylonium ion, RCO+) which is a much stronger electron pair
accepting electrophile than the original acid chloride (either this or an AlCl3-
RCOCl complex - details not needed for A level).
o Step (2) An electron pair from the delocalised ι π electrons of the benzene
ring forms a C-C bond with the electron pair accepting carbocation forming a
second highly unstable carbocation. It is very unstable because the stable
electron arrangement of the benzene ring is partially broken to give a
'saturated' C (top right of ring.
o Step (3) is a proton transfer, as the tetrachloroaluminate(III) ion [formed in
step (1)], abstracts a proton from the second highly unstable intermediate
carbocation to give the ketone product, hydrogen chloride gas and reforming
the aluminium chloride catalyst.
• for R = CH3, benzene: C6H5CH3 + R'COCl ==> R'COC6H4CH3 + HCl
o and again there is the potential to form three position isomers by substituting
in the 2, 3 or 4 position on the ring.
• FURTHER COMMENTS
o The overall acylation reaction is the substitution of -H by RCO

The electrophilic substitution of an arene - sulphonation

• for R = H, benzene: C6H6 + SO3 ==> C6H5SO2OH [see mechanism 44 below]

• or C6H6 + H2SO4 ==> C6H5SO2OH + H2O
• Benzene is heated with concentrated sulphuric acid or even better, 'fuming' sulphuric
acid, which has a higher sulphur trioxide content and more efficient at introducing the
sulphonic acid group into the benzene ring.

mechanism 25 - electrophilic substitution by an acyl group in the benzene ring

• [mechanism 44 above]
o Step (1) Sulphur trioxide is formed (or already present). It is a powerful
electrophile, i.e. electron pair acceptor because of the effect of the three
very electronegative oxygen atoms bonded to the central sulphur atom.
o Step (2) An electron pair from the delocalised ι π electrons of the benzene
ring forms a C-S bond with the electron pair accepting sulphur trioxide
forming a second highly unstable carbocation. It is very unstable because the
stable electron arrangement of the benzene ring is partially broken to give a
'saturated' C (top right of ring).
o Step (3) A hydrogensulphate ion removes a proton and the complete
benzene ring is reformed giving the anion of the aromatic sulphonic acid.
o Step (4) is a proton transfer to give the sulphonic acid.
• for R = CH3, benzene: C6H5CH3 + H2SO4 ==> CH3C6H4SO2OH + H2O
o and again there is the potential to form three position isomers by substituting
in the 2, 3 or 4 position on the ring, the mechanism diagram shows the
formation of methyl-2-benzenesulphonic acid.
• FURTHER COMMENTS
o The overall sulfonation reaction is the substitution of -H by -SO2OH

The orientation of products in aromatic electrophilic substitution

reactions

• Certain groups, already present, can increase the electron density of the
benzene ring and make the aromatic compound more reactive towards
electrophiles such as those described above. However the effect seems to enhance
the reactivity at the 2 and 4 substitution positions more than the 3 substitution
position.
o Groups that increase reactivity are e.g. -CH3, -Cl, -OH, -NH2, -NHCOCH3,
and favour substitution at the 2 and 4 positions (typically 90-100%
combined).
o They all, by some means, have a small, but significant, electron donating (+I
inductive effect) on the ring of ι π electrons.
o For example, methyl benzene is significantly more reactive than benzene
and when nitrated, over 90% of the products are either methyl-2-
nitrobenzene or methyl-4-nitrobenzene.
• Certain groups, already present, can decrease the electron density of the
benzene ring and make the aromatic compound less reactive towards
electrophiles such as described above. However the effect seems to decrease the
reactivity at the 2 and 4 substitution positions more than the 3 substitution position.
o Groups that decrease reactivity, by some means, are e.g. -NO2, COOH,
-CHO, -SO2OH, and favour substitution at the 3 position (typically 70-90%)
and their effect does fit in with them all being strongly electronegative
groupings giving a -I inductive effect.
o For example, nitrobenzene is much less reactive than benzene and on
nitration, 93% of the product is 1,3-dinitrobenzene.