Infrared Spectroscopy

The IR region of the electromagnetic spectrum has much less energy that the UV/Vis region.
Certain energies in the UV/Vis region causes electrons to be excited to higher energy levels. In
the IR region however, there is only sufficient energy to cause vibrations in molecules. There are
many possible vibrational levels associated with each electron state.
IR spectroscopy is a subset of spectroscopy that deals with the IR region of the electromagnetic
spectrum. The main goal of IR spectroscopy is to determine the functional group present in the
molecule and it is used alongside other techniques to determine the structure of organic
molecules.
1.1

Explain the origin of absorption in IR spectroscopy

IR radiation is not energetic enough to cause electronic transitions but it can induce
vibrational and rotational transitions within the ground electronic state of the molecule.
Absorption in the rotational levels may given rise to a series of peaks for each vibrational
state. However, rotation is often prevented in solid or liquid samples and the effects of
these energy changes are not detected. Thus infrared spectra show closely spaced
absorption peaks resulting from transitions among the various vibrational energy levels.
Absorption of infrared wavelengths can cause bonds to stretch, bend or twist in
characteristics ways. The energies associated with stretching vibrations are different from
one another and that of bending or twisting vibrations. A molecule can vibrate in a
number of ways which is related to the number of atoms and hence the number of bonds
in the molecule.
A molecule absorbs IR radiation whose frequency is the same as the natural vibration of
the bonds in the molecule. The energy associated with the vibrations is quantized. The
energy absorbed also increases the amplitude of the vibration of the bonds.
Picture a diatomic molecule as two spheres connected by a spring. When the molecule
vibrates, the atoms move towards or away from each other at certain frequencies. The
energy absorbed is related to how much the spring is stretched or compressed. These

vibrational frequencies are related to the strength of the chemical bonds and the masses of
the atoms. Molecules differ from sets of spheres and springs in that vibrational
frequencies are quantized meaning only certain energies for the system are allowed.
An atom has three degrees of freedom corresponding to motion in the three Cartesian
coordinates (x, y, z). A polyatomic molecule has a total of 3n degrees of freedom where n
is the number of atoms in the polyatomic molecule. Additionally, three degrees of
freedom are used to represent translation (movement of molecule as a whole) in the three
coordinates and three degrees of freedom are also used to represent rotation in the three
coordinates. It should be noted that in linear molecules while there are three degrees of
freedom for either movement or vibration, there are only two degrees of freedom to
rotate.
Therefore, the number of vibrations for a polyatomic molecule is equal to 3n 6. But for
a linear molecule, the number of vibrations is 3n 5.
Selection Rules for IR
Not all bonds within a molecule absorb energy at IR wavelengths even though the
frequency of the radiation exactly matches that of bond vibration. The molecule absorbs
only if there is some type of charge separation within the molecule (the molecule is polar
and hence has a dipole) or if the vibration results in a change in the dipole moment of the
molecule.
Symmetrical bonds such as those in Hydrogen and Chlorine do not absorb IR radiation
because stretching does not change the dipole moment and bending cannot occur with
only two atoms in a molecule. IR spectra for diatomic or triatomic molecules are
relatively easy to understand, however absorption spectra become much more complex as
the number of atoms in the molecule increase. This is due to the increase in the number of
possible vibrations.
Vibrations can be divided into two types, depending on whether the bond length or angle
is changing.
Bond length change results in stretching (symmetric and asymmetric)
Bond angle change results in bending (scissoring, rocking, wagging and twisting)

N.B. Heavier atoms vibrate at lower frequencies but stronger bonds vibrate at higher
frequencies.
Why does Hydrogen gas show no absorption in IR?
# of vibrations = 3(2) 5 = 1
There is no change in the dipole moment, since the vibrations cancel out each other. This
also occurs with Nitrogen.
Why is Carbon Dioxide IR active?
# of vibrations = 3(3) 5 = 4
Carbon dioxide is a linear molecule. There are four of vibrations.

There are three bands in the IR spectrum for carbon dioxide (two occur at the same
wavelength). This is due to asymmetric stretching and two different types of bending.

1.2

Describe the basic steps involved in analysing samples by IR spectroscopy

Layout of a Typical IR Spectrometer

A beam of IR radiation is produced from an IR source (electrically heated

filament).
The radiation is passed through the sample cell and the reference cell.
The level of IR radiation of the beam passing through the sample is compared
with that coming through the reference cell.
The diffraction grating or prism is rotated so that different wavelengths of IR
radiation are brought to the detector.
The recorder plots a graph of % transmission against wavenumber

The diffraction grating, prism, mirrors and cells cannot be made from glass
because glass absorbs IR radiation. The cells are often made from potassium
bromide or calcium fluoride. These substances do not absorb IR radiation.
This arrangement is advantageous because the infrared radiation is not energetic
enough to bring about photodecomposition which may occur if samples are
exposed to an ultraviolet-visible source.
Sample Preparation
Material containing the sample must be transparent to IR radiation. So salts like NaCl and
KBr are only used.
1. Sampling Solids
Multi-technique
The finely crushed sample is mixed with Nujol/paraffin oil (mulling agent) in
a marble or agate mortar, with a pestle to make a thick paste. A thin film is
applied onto the salt plates. This is then mounted in a path of IR beam and the
spectrum is recorded.

Solid run in Solution

Solid sample may be dissolved in a non-aqueous solvent provided that there is
no chemical interaction with the solvent and the solvent is not absorbed in the
range to be studied. A drop of solution is placed on the surface of the alkali
metal disc and solvent is evaporated to dryness leaving a thin film of solute.

Case film technique

If the solid is amorphous in nature then the sample is deposited or the surface
of a KBr or NaCl cell by evaporation of a solution of the solid and ensured
that the film is not too thick to pass the radiation.

Pressed pellet technique

A small amount of finely ground solid is mixed with 100 times its weight of
KBr and compressed into a thin transparent pellet using a hydraulic press.
These pellets are transparent to IR radiation and is used for analysis.

2. Sampling of Liquids

Liquid sample cells can be sandwiched using special liquid cells of highly purified
alkali halides, normally NaCl. Other salts such as KBr and Ca F2 can also be used.
Aqueous solvents cannot be used because they cannot dissolve alkali halides. Usually
the liquid is diluted to a concentration of about 0.2 M using a suitable organic solvent
like chloroform. The sample thickness should be selected so that transmittance lies
between 15-20%. For most liquids, the sample cell thickness is 0.01-0.05mm. Some
salt plates are highly soluble, so the sample and washing reagents must be anhydrous.
3. Sampling of Gases
The sample cell is made up of NaCl, KBr and it is similar to the liquid sample cell. A
sample cell with a long path length (5-10cm) is needed because the gases show
relatively weak absorbance.

Characteristics of an IR spectrum
The energy absorbed as a result of molecular vibrations depends on the masses of the
atoms and the bond strength.

Each type of bond absorbs IR radiation of a specific frequency.

Different types of vibration in particular bonds give rise to the absorptions in
particular regions of the spectrum, e.g. the absorption due to C H stretching
vibrations are at higher frequencies than the absorption due to C H bending

vibrations.
The IR spectrum shows the percentage (%) of radiation transmitted. it appears as

a series of dips (peaks) where particular bonds have absorbed radiation.

The position of the peaks is given by the wavenumber measured in cm1 .

wavenumber =

frequency Hertz
spe ed of light

Even though an IR spectrum is characteristic for an entire molecule, there are certain
groups of atoms that give rise to absorption bands near the same wave number regardless
of the rest of the molecule. These persistent characteristics enable you to identify major
structural features of the molecule after a quick inspection of the spectrum and the use of
a co-relation table. This table provides the bond and the characteristic absorption range in
wave numbers.

The IR spectrum is a graphical display of % transmittance versus wave number (

1
). It

shows the frequency of IR radiation absorbed and the % of incident light that passes
through the molecule without being absorbed. This is done for each wave number
absorbed. A typical IR spectrum has two regions:

> 1000 wave number (bond spotting region)

< 1000 wave number (fingerprint region)

The fingerprint region is < 1000 wave number and it is unique for each molecule. There
is a database available of all fingerprint regions for molecules. To identify a molecule,
one can simply perform IR spectroscopy and match its fingerprint region to its database
fingerprint region and determine the exact molecule. However, the region most studied in
IR is > 1000 wave number where certain bonds and function groups are identified.
When we observe an IR spectrum, the absorption bands are observed for intensity and
width. The more intense an absorption bond, the more polar is the molecule. The width of
an absorption band is proportional to the degree of hydrogen bonding involved.
Therefore, absorption bands are said to be strong, medium or low intensity (polarity) and
broad or narrow (degree of hydrogen bonding).
6.3

Comment on the limitations associated with the use of IR spectroscopy

It cannot be used to identify substances that are non-polar.

It cannot be sued to identify substances that are electrolytes or have ionic

components.
It provides information about the types of groups present, including functional

groups, but not always about the structure of the molecule as a whole.
Minimal elemental information is given for most samples.
The background solid or solvent matrix must be completely transparent in the

spectral region of interest (not absorbing)

The molecule must be active in IR, i.e. a minimum of one vibrational movement

must alter the dipole present

With IR, it is not possible to know the relative molecular mass of the substance
Frequently does not adhere to Beer Lamberts Law. Thus IR has limited

quantitative applications.
Deviations arise from chemical or instrumental defects.
Stray radiation makes measurements difficult due to the narrowness of the
spectrum.

6.4

Deduce the functional groups present in organic compounds from IR spectra

When identifying groups from IR spectra, we match the peaks (dips) with known values
for these groups.

Look for the carbonyl bond, C = O. This is a strong, intense bond at the 1680
1750 cm1 region. This band is usually the most intense band in the spectrum.
It will have a medium width. If you see a carbonyl bond, look for other bands
associated with functional groups which has a carbonyl group by going to Step 2.
If no carbonyl is present, go to Step 3.

If a C = O band is present, you would want to determine if it is part of a

carboxylic acid, ester, aldehyde or ketone. At this time, you will not be able to
distinguish between an aldehyde or ketone and you will NOT be asked to do so.

For acids, look for indications that an O H is also present. It has a broad
absorption band (because of hydrogen bonding) near to 3300 2500 cm1 .
There will also be a C O band near the 1300 1100 cm1 and the C = O
band in acids is between 1725 1700 cm1 .
For esters, look for C O of medium frequency near to 1300 1100 cm1 .
There will be no OH absorption band.
For aldehydes and ketones, look for aldehyde type C H absorption band.

If no carbonyl band appears in the spectrum, look for an alcohol O H band

which is a broad band between 3600 3300 cm1 and look also for a C O
bond at 1275 1050 cm1 .

If no carbonyl and no OH is present, start thinking alkenes. Look for a weak

absorption of the C = C near 1650 cm1 and C H stretch at 3000 cm1 .
For an aromatic double bond, however, look for a C = C absorption band which is
medium to strong absorption in the region 1650 1450 cm1 .

If none of the above is present, you may have an alkane where the main
absorption is the C H stretch near 3000 cm1 . The spectrum would be simple
with another bond between 1470 1350 cm1 caused by the C H bond.
Also, it the alkane has any CH 3

groups present, we might observe a band near

1375 cm1 .

If the spectrum cannot be identifies, look for an amine NH and wave number
3500 3350 cm1 medium intensity peak.

6.5

Cite examples of the use of IR spectroscopy in the monitoring of air pollutants.

Uses of IR Spectroscopy

Determination of functional groups in organic molecules. It is not used to identify

a molecule unless the fingerprint region is matched.

Determination of molecular composition of surfaces
Identification of chromatographic effluents
Quantitative determination of compounds in mixtures (Beer Lamberts Law)
Determination of molecular conformation
Determination of molecular orientation

Applications of IR Spectroscopy

Identification of compounds by matching spectrum of unknown compounds to the

database spectrum, i.e. the fingerprint regions

Identification of functional groups of unknown substances
Identification of reaction components and kinetic studies
Identification of molecular orientation in polymer films
Identification of polymers, plastics and resins
Detection of molecular impurities or additives present ranging from as low as

0.01% to 1%.
Analysis of formulations such as insecticides and co-polymers.
To monitor pollutants in the air
Fourier transform IR spectroscopy can be used to detect and measure pollutants in
the air such as carbon monoxide, sulphur dioxide and ozone. It can also be used to
measure the concentration of carbon dioxide in the air. The method uses the
fingerprint regions of the IR spectrum to identify particular molecules.
To measure the concentration of carbon dioxide:
Draw the polluted air through a sample chamber
A beam of IR radiation is continuously passed through the sample
chamber and a reference chamber (with no carbon monoxide present). Any
decrease in intensity of the beam at a particular wavenumber is due to the

presence of carbon monoxide.

A detector measures the difference in IR radiation between the two

chambers and the amount of CO recorded automatically.

Since different pollutants have characteristic IR spectra, with maximum
absorbance at particular wavenumbers, this method can measure several
pollutants at the same time.