IR Spectroscopy

Introduction:
The infrared (IR) spectroscopy deals with studying absorption of
infrared radiation by chemical compounds. The IR radiation
corresponds to the region between visible and microwave region of
electromagnetic spectrum. The IR spectrum is mainly used to determine
the functional groups present in a compound and elucidate the structure
of compound.
The energy of a molecule=Electronic energy + Vibrational energy +
Rotational energy. Different compounds when absorb infrared radiation
give rise to vibrational transitions characteristic to the molecular
structure and those transitions are recorded as IR Spectra.
The infrared range covers from 14,290—200 cm—1.
It is further subdivided into three regions:
1. Near IR region: 14290—4000cm —1 (0.75 to 2.5μ)
2. Mid IR region: 4000—666cm —1(25 to 2.5μ)
3. Far IR region:700— 200cm —1(25 to 1000μ)
Out of these three regions the Mid IR region is widely used in pharmaceutical
studies.
Overall, the IR region is broadly divided into:
Finger print region (400-1500cm —1): This region of IR spectrum provides
characteristic peaks for different part of a molecule and helps in qualitative
identification of compounds.
Group frequency region (4000—1500cm —1): Peaks with respect to different
functional groups are observed in this region.
Principle
Molecules consist of atoms or group of atoms that are connected by
bonds which are analogous to springs. These bonds are flexible in
nature in the molecules and they move continuously to gain vibrations
having some frequency. This frequency of vibration is characteristic to
the different parts of the molecule and hence, it can be called as the
natural frequency of vibration. When we apply an external infrared
frequency and it matches the natural frequency of vibration within a
molecule the applied energy is then absorbed by the molecule and an
infrared peak is observed. These peaks are characteristic to different
functional group and parts of the molecule and they are unique for every
molecule. Hence the IR spectroscopy is considered as the fingerprint
analysis of a molecule.
The IR region is measured in terms of Wavenumber and it is expressed
as:
“It is the number of waves present per cm i.e.
Wavenumber = 1/Wavelength (μm) × 104
A compound can be analyzed by IR radiation only if:
1. There is a change in dipole movement
2. There should be a resonance in applied and natural IR frequency
Fundamental modes of vibrations in a polyatomic molecule are mainly
two types of vibrations that are present within a molecule.
They are:
1. Stretching vibration: In stretching vibration, the length of a bond is
changed i.e. either increased or decreased. It is of two types:
A] Symmetrical stretching: Here the two bonds increase or decreases in
length in a symmetric
pattern.
B] Asymmetrical stretching: Here when one bond length increases the
other ones decreases.
Bending vibration: Bending vibrations are of two sub-types.
• In plane bending
• Out-of-plane bending
When there is a change in bond angle during the vibration it is called is in
plane bending and the bending of bonds occur within a plane. The in plane
bending can be again of two subtypes known as scissoring where the bond
angle decreases and rocking with the bond angle is unaltered however both
the bond moves within the same plane. In case of out of plane bending the
bending occurs in different planes of the molecule and is again subdivided
into two types. Wagging where both atoms move to one side of the plane and
Twisting where one atom remains above the plane whereas the other one
below the plane.
The total number of fundamental vibrations for any given polyatomic molecule
having "n” number of atoms can be determined using the expression:
A] 3n- 6 for the nonlinear molecule
B] 3n- 5 for the linear molecule
However, few other kinds of vibrations can also be found in infrared spectrum
known as overtones, combination bands, difference bands and Fermi resonance.
The overtone vibrations occur at twice or thrice the value of fundamental
vibrations.
Combination bands are the bands that result because of coupling of fundamental
Frequencies
Difference bands are noticed at the frequency which is actually the difference of
two bands.
Fermi resonance bands are produced because of coupling between fundamental
vibration and an overtone or because of a combination band.
According to the expression stated above for linear or non-linear molecules it
is very difficult to obtain the predicted number of vibrations. There may be a
variation in the predicted number of bands and observed number of bands due
to:
1] More number of bands may be produced due to:
Overtones
Combination bands
2] Less bands may be obtained:
When a vibration doesn't involve a change in dipole moment
When the fundamental bends fall outside the region of 4000 to 400 cm-1
When the bands are too weak to be observable
When the vibrations occur very close to each other such that they coalesce
In a symmetrical molecule many absorptions with same frequency produce a
degenerate band
Factors effecting vibrations:
Following are the factors that affect vibrational frequencies in a
molecule
A] Coupled vibration
• An isolated C-H bond has only one stretching vibration frequency
where as the methylene group shows two stretching vibrations both
symmetrical and asymmetrical.
• Because of mechanical coupling or interaction between CH stretching
vibrations in the CH2 group.
• Asymmetric vibrations develop at a higher frequency or wave
numbers than stretching vibrations
• Such vibrations are called coupled vibrations because these vibrations
occur at a different frequency than the required for an isolated CH
stretching
B]Fermi resonance
• Coupling of two fundamental vibration modes produces 2 new modes
of vibration. With frequencies higher and lower than the observed in
absence of interaction.
• This interaction takes place between fundamental vibrations and
overtones or combination tone vibration and they are collectively
called us Fermi resonance.
• In Fermi resonance molecule transfer energy from fundamental
vibrations into overtone or combination level and back.
• The resonance pushes the two levels apart and mixes their character
and each level has some amount of fundamental and some amount of
overtone or combination tone characters.
C]Electronic effects
Changing the absorption frequencies for a particular group takes place
when the substituent in the neighborhood of the particular group is
changed. They include
• Inductive effect: Inclusion of alkyl group gives +ve Inductive effect
producing decreased absorption frequency. Adding an electronegative
atom or group produces –ve inductive effect leading to increased
absorption frequency.
• Mesomeric effect: It produces lengthening or weakening of a bond
leading to lowering of absorption frequency.
• Field effect: In ortho substituted compounds, the lone pair of electrons
on two atoms influence each other through space interactions and
change the vibrational frequencies of both the groups. Example: Ortho
halo acetophenone. This is called field effect.
D]Hydrogen bonding
• It occurs in any system having a proton donor group and a proton
acceptor. If the sorbital of the proton effectively overlaps the P or 𝜋
orbital of the acceptor group.
• The stronger the hydrogen bond, the longer the OH bond, the lower
the vibration frequency and broader and more intense will be the
absorption.
• Intermolecular bonds produce broad bands whereas intramolecular
hydrogen bonds produce sharp and well defined bands.
Sample handling
The sample cells usually comprise transparent ionic substances such as
sodium chloride (NaCl) or potassium bromide (KBr). However, KBr is
preferred because of its compatibility with the instrumental measurement
process. The infrared samples can be considered of three forms such as:
Liquids:
A drop of liquid is placed within the KBr plates with the thickness less
than 0.01 mm.
Around 1-10mg of sample is required to prepare the solution.
Aqueous solutions are not preferred as they tend to dissolve the sample
cells so the solvent should be anhydrous and mostly organic solvents such
as chloroform is preferred.
Solid solutions:
To prepare a solid solution 1 to 10 mg volumes of 0.1 to 1.0 ml of 0.05 to 10%
solution are required for placement within a cell of 0.1 to 1mm thickness. CCl4
is used for this purpose which absorbs strongly at 785 cm-1. Care should be
taken to avoid solution combinations that react instantaneously.

Solids:
The solid samples can be prepared using pressed pellet technique where the
sample is placed in KBr pellets are prepared in form of thin transparent layer
using a hydraulic press. However, as KBr is hygroscopic in nature care should
be taken to minimise its atmospheric exposure. Another technique called as
Nuzol-Mull technique (popularly called as Mull Technique) may be used where
the mixing up of the sample with a mineral oil (Nujol) is done and afterwards a
thin film of the liquid can be applied on the liquid sample cell for measurements.
Techniques used for Sampling
Various techniques used for preparing solid samples are as follows.
a) Mull technique: In this technique, the finely crushed sample is mixed
with Nujol (mulling agent) in n 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 the path of IR beam, and the spectrum is recorded.
b) Solid run in Solution – In this technique, the solid sample may be
dissolved in a non-aqueous solvent provided 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 the solvent is evaporated to dryness, leaving a thin film
of the solute.
c) Case film technique – If the solid is amorphous in nature,
then the sample is deposited on the surface of a KBr or NaCl
cell by evaporation of a solution of the solid and ensuring that
the film is not too thick to pass the radiation.

d) Pressed pellet technique – In this technique, a small amount

of finely ground solid sample is mixed with 100 times its
weight of potassium bromide and compressed into a thin
transparent pellet using a hydraulic press. These pellets are
transparent to IR radiation and are used for analysis.
Sampling of liquids
Liquid sample cells can be sandwiched using liquid samples of highly
purified alkali halides, normally NaCl. Other salts, such as KBr and
CaF2, can also be used. Aqueous solvents cannot be used because they
cannot dissolve alkali halides. Organic solvents like chloroform can be
used. The sample thickness should be selected so that the transmittance
lies between 15-20%. For most liquids, the sample cell thickness is
0.01-0.05 mm. Some salt plates are highly soluble in water, so the
sample and washing reagents must be anhydrous.
Sampling of gases
The sample cell is made up of NaCl, KBr etc., similar to the liquid
sample cell. A sample cell with a long path length (5 – 10 cm) is needed
because the gases show relatively weak absorbance.
Instrumentation
Sources of radiation
• The source of energy should produce a very narrow beam of IR
radiation
• The radiation should be intense enough to detect the analyte
• It should be steady
• It should cover the desired wavelength range
Following are some of the sources of IR radiation used in IR
spectrophotometers:
1. Incandescent lamp
This lamp is particularly used in near-IR instruments. However, it is
least preferred over other sources as it has low spectral emission.
2. Nernst Glower
• It contains a hollow rod composed of rare earth oxides such as zirconia, yttria and
thoria.
• It is in non-conducting at room temperature and requires heating by external
means to bring it to a conducting state.
• The glower is heated to a temperature within the 1000-1800° C range.
• It gives a maximum radiation of 7100 cm-1
• It has the disadvantage of frequent mechanical failure
3. Globar source
• It is a rod prepared from centred Silicon carbide
• It is heated up to a temperature between 1300-1700°C
• It emits maximum radiation at 5200cm-1
• It has a disadvantage in that its radiation is less intense than Nernst
glower
4. Mercury arc lamp
It is a device made up of a quartz-jacketed tube containing mercury
vapour at a pressure greater than 1 atmosphere.
It is highly effective in the far-IR region where the other radiation
sources fail to provide continuous radiation.
Wavelength selectors
• They help select continuous IR radiation in the desired wavelength
region.
• They generally contain a chopper and a complex system of
monochromators.
• The choppers are generally used to enhance the instrument's signal-to-
noise ratio and moderate the radiation intensity that reaches the
detector.
• The monochromator is used to select its desired frequency of radiation
which will be then allowed to an incident on the detector
These monochromators are of two types:
1. Prismatic monochromator: They are made of glass/quartz and coated
with alkyl halides.
A] Mono Pass (Radiation passes only once through the prism)
B] Double Pass (Radiation passes twice through the prism)
2. Grating monochromator: They are grooves made of aluminium and
provide better radiation dispersion than prisms.
A] Reflection gratings
B] Transmittance grating
Detectors
1. Golay cell
• It contains a small metal cylinder which is closed by a black metal
plate at one end and buy a flexible metal die programme at the other
end
• The cylinder is filled with xenon and sealed.
• When IR radiation is allowed to fall on the black metal plate it heats
the gas, which expands it.
• The signal detected by the phototube is then modulated according to
the power of the radiant beam.
2. Bolometer
• It is made up of a thin metal conductor.
• When radiation falls on this conductor, its temperature changes as the resistance
of a metallic conductor changes with temperature. The degree of change in
resistance is regarded as the measurer amount of radiation that is incident on the
bolometer.
• It follows the principle of the Wheatstone bridge.
• When there is no radiation incident on the bolometer, the bridge remains balanced.
In case radiation is incident on the bolometer, the bridge becomes unbalanced due
to the changes in electrical resistance. There is a flow of current through the
galvanometer.
3. Thermocouple
• It is based on the principle that electric current flows when there are two dissimilar
metal wires connected at both ends, and a temperature difference is present
between the two ends.
• The end exposed to the IR spectrometer is called the Hot junction.
• To increase energy-gathering efficiency, it is usually made up of a black body.
• The other connection, i.e. Cold junction, is thermally insulated and carefully
protected from stray light.
• The electricity flowing through is directly proportional to the energy difference
between the two connections.
4. Thermistor
• Thermistors are usually made up of fused mixture of metallic oxides.
• As the temperature of the mixture increases its electrical resistance
decreases and accordingly the measurements are performed in the
higher spectrophotometer.
5. Pyroelectric detector
• The pyroelectric detector is a thermal sensor of infrared radiation requiring no bias. While, in
principle, a pure capacitor (hence theoretically noiseless), the detector has a varying noise
contribution as a function of frequency due to a load resistor, series loss resistance, and amplifier.
• The actual sensor is a pyroelectric crystal exhibiting spontaneous polarization. The spontaneous
polarization and dielectric constant of the crystal are temperature dependent.
• A change in incident power raises the detector temperature causing an electric charge to appear
across the electrode surfaces cut perpendicular to the crystal's ferroelectric axis.
• The evacuated detector package incorporates an electrode triglycine sulfate flake mounted on a low
thermal and electrical conductivity substrate, a field effect transistor, a load resistor, and an infrared
transparent window.
Applications
IR spectroscopy is applied for qualitative as well as quantitative analysis of drugs in
Pharmaceutical industry.
• It is used for the identification of drug substances
• It identifies the impurities present in a drug sample
• It helps in the study of hydrogen bonding, intermolecular and intramolecular type
• It is widely used in the study of polymers
• It helps in the determination of Cis- Trans isomers present in a mixture of compounds
• It elucidates reaction mechanisms
• It is a great tool investigation of rotational isomerism
• It identifies functional groups present in any sample
• It estimates relative stability of confirmation
• It distinguishes between Sis and trance I so much
• It can predict the keto-enol tautomerism
• It helps in establishing the quality of tea leaves