INFRA-RED SPECTRUM

At the end of this topic, students should be able to:

• explain the origin of absorption in IR spectroscopy;

• describe the basic steps involved in analyzing samples by IR spectroscopy;

• deduce the functional groups present in organic compounds from IR spectra;

• cite examples of the use of IR spectroscopy in the monitoring of air pollutants.

The background to infra-red spectroscopy

How an infra-red spectrum is produced?

The visible light is made up of a continuous range of different electromagnetic frequencies - each frequency can be
seen as a different colour. Infra-red radiation also consists of a continuous range of frequencies - it so happens that
our eyes can't detect them.

If you shine a range of infra-red frequencies one at a time through a sample of an organic compound, you find that
some frequencies get absorbed by the compound. A detector on the other side of the compound would show that
some frequencies pass through the compound with almost no loss, but other frequencies are strongly absorbed.

How much of a particular frequency gets through the compound is measured as percentage transmittance.

A percentage transmittance of 100 would mean that all of that frequency passed straight through the compound
without any being absorbed. In practice, that never happens - there is always some small loss, giving a
transmittance of perhaps 95% as the best you can achieve.

A transmittance of only 5% would mean that nearly all of that particular frequency is absorbed by the compound.
A very high absorption of this sort tells you important things about the bonds in the compound.
What an infra-red spectrum looks like?

A graph is produced showing how the percentage transmittance varies with the frequency of the infra-red radiation.

Notice that an unusual measure of

frequency is used on the horizontal axis.
Wavenumber is defined like this:
What causes some frequencies to be absorbed?

Each frequency of light (including infra-red) has a certain energy. If a particular frequency is being absorbed as it
passes through the compound being investigated, it must mean that its energy is being transferred to the compound.
Energies in infra-red radiation correspond to the energies involved in bond vibrations.

Bond stretching

In covalent bonds, atoms aren't joined by rigid links - the two atoms are held together because both nuclei are attracted
to the same pair of electrons. The two nuclei can vibrate backwards and forwards - towards and away from each other -
around an average position.
The diagram shows the stretching that happens in a carbon-oxygen single bond. There will, of course, be other atoms
attached to both the carbon and the oxygen. For example, it could be the carbon-oxygen bond in methanol, CH3OH.
.

The energy involved in this vibration depends on things like the length of the bond and the
mass of the atoms at either end. That means that each different bond will vibrate in a
different way, involving different amounts of energy.
Bonds are vibrating all the time, but if you shine exactly the right amount of energy on a
bond, you can kick it into a higher state of vibration. The amount of energy it needs to do
this will vary from bond to bond, and so each different bond will absorb a different
frequency (and hence energy) of infra-red radiation.
Bond bending

As well as stretching, bonds can also bend. The diagram shows the bending of the bonds in a water molecule. The effect of
this, of course, is that the bond angle between the two hydrogen-oxygen bonds fluctuates slightly around its average value.
Imagine a lab model of a water molecule where the atoms are joined together with springs. These bending vibrations are
what you would see if you shook the model gently.

Again, bonds will be vibrating like this all the time and, again, if you shine exactly the right amount of
energy on the bond, you can kick it into a higher state of vibration. Since the energies involved with the
bending will be different for each kind of bond, each different bond will absorb a different frequency of
infra-red radiation in order to make this jump from one state to a higher one.
 Tying all this together

Look again at the infra-red spectrum of propan-1-ol, CH3CH2CH2OH:

In the diagram, three sample absorptions are picked out to show you the bond vibrations
which produced them. Notice that bond stretching and bending produce different
troughs in the spectrum.
 THE FINGERPRINT REGION OF AN INFRA-RED SPECTRUM

What is the fingerprint region?

This is a typical infra-red spectrum:

Each trough is caused because energy is being absorbed from that

particular frequency of infra-red radiation to excite bonds in the
molecule to a higher state of vibration - either stretching or bending

Some of the troughs are easily used to identify particular bonds in a

molecule. For example, the big trough at the left-hand side of the
spectrum is used to identify the presence of an oxygen-hydrogen bond in
an -OH group.

The region to the right-hand side of the diagram (from about 1500 to 500 cm-1) usually contains a very complicated series
of absorptions. These are mainly due to all manner of bending vibrations within the molecule. This is called the fingerprint
region.

It is much more difficult to pick out individual bonds in this region than it is in the "cleaner" region at higher
wavenumbers. The importance of the fingerprint region is that each different compound produces a different pattern of
troughs in this part of the spectrum.
Using the fingerprint region
Compare the infra-red spectra of propan-1-ol and propan-2-ol. Both compounds contain exactly the same bonds. Both
compounds have very similar troughs in the area around 3000 cm-1 - but compare them in the fingerprint region between
1500 and 500 cm-1.

The pattern in the fingerprint region is completely different and could therefore be used to identify the
compound.

So . . . to positively identify an unknown compound, use its infra-red spectrum to identify what sort of compound it is by
looking for specific bond absorptions. That might tell you, for example, that you had an alcohol because it contained an -
OH group.

You would then compare the fingerprint region of its infra-red spectrum with known spectra measured under exactly the
same conditions to find out which alcohol (or whatever) you had.
 INTERPRETING AN INFRA-RED SPECTRUM
The infra-red spectrum for a simple carboxylic acid
Ethanoic acid
You will see that it contains the following bonds:
carbon-oxygen double, C=O carbon-oxygen single, C-O
oxygen-hydrogen, O-H carbon-hydrogen, C-H carbon-carbon single, C-C

The carbon-carbon bond has absorptions which occur over a wide range of wavenumbers in the fingerprint region - that
makes it very difficult to pick out on an infra-red spectrum.
The carbon-oxygen single bond also has an absorbtion in the fingerprint region, varying between 1000 and 1300 cm-1
depending on the molecule it is in. You have to be very wary about picking out a particular trough as being due to a C-O
bond.
The other bonds in ethanoic acid have easily recognised absorptions outside the fingerprint region.
The C-H bond (where the hydrogen is attached to a carbon which is singly-bonded to everything else) absorbs somewhere
in the range from 2853 - 2962 cm-1. Because that bond is present in most organic compounds, that's not terribly useful!
What it means is that you can ignore a trough just under 3000 cm-1, because that is probably just due to C-H bonds.

The carbon-oxygen double bond, C=O, is one of the really useful absorptions, found in the range 1680 - 1750 cm-1. Its
position varies slightly depending on what sort of compound it is in.
The other really useful bond is the O-H bond. This absorbs differently depending on its environment. It is easily recognised in
an acid because it produces a very broad trough in the range 2500 - 3300 cm-1.
 The infra-red spectrum for ethanoic acid looks like this:

The possible absorption due to the C-O single bond is queried

because it lies in the fingerprint region. You couldn't be sure
that this trough wasn't caused by something else.

The infra-red spectrum for an alcohol The O-H bond in an alcohol absorbs at a higher wavenumber than it
Ethanol does in an acid - somewhere between 3230 - 3550 cm-1. In fact this
absorption would be at a higher number still if the alcohol isn't
hydrogen bonded - for example, in the gas state. All the infra-red
spectra on this page are from liquids - so that possibility will never
apply.

Notice the absorption due to the C-H bonds just under 3000 cm-1, and
also the troughs between 1000 and 1100 cm-1 - one of which will be
due to the C-O bond.
 The infra-red spectrum for an ester
Ethyl ethanoate

This time the O-H absorption is missing completely. Don't

confuse it with the C-H trough fractionally less than 3000 cm-1.
The presence of the C=O double bond is seen at about 1740 cm-
1.

The C-O single bond is the absorption at about 1240 cm-1. Whether or not you could pick that out would depend
on the detail given by the table of data which you get in your exam, because C-O single bonds vary anywhere
between 1000 and 1300 cm-1 depending on what sort of compound they are in. Some tables of data fine it down,
so that they will tell you that an absorption from 1230 - 1250 is the C-O bond in an ethanoate.
 The infra-red spectrum for a ketone
Propanone

You will find that this is very similar to the infra-red spectrum for ethyl ethanoate, an ester. Again, there
is no trough due to the O-H bond, and again there is a marked absorption at about 1700 cm-1 due to the
C=O.

Confusingly, there are also absorptions which look as if they might be due to C-O single bonds - which,
of course, aren't present in propanone. This reinforces the care you have to take in trying to identify any
absorptions in the fingerprint region.

Aldehydes will have similar infra-red spectra to ketones.

 The infra-red spectrum for a hydroxy-acid
2-hydroxypropanoic acid (lactic acid)

This is interesting because it contains two different sorts of O-H bond - the one in the acid and the simple "alcohol" type in
the chain attached to the -COOH group.

The O-H bond in the acid group absorbs between 2500 and 3300, the one in the chain between 3230 and 3550 cm-1. Taken
together, that gives this immense trough covering the whole range from 2500 to 3550 cm-1. Lost in that trough as well will
be absorptions due to the C-H bonds.

Notice also the presence of the strong C=O absorption at about 1730 cm-1.
 The infra-red spectrum for a primary amine
1-aminobutane

Primary amines contain the -NH2 group, and so have N-H bonds. These absorb somewhere between 3100 and 3500
cm-1. That double trough (typical of primary amines) can be seen clearly on the spectrum to the left of the C-H
absorptions.