CHAPTER -2

INFRARED SPECTROSCOPY

2.1 INTRODUCTION
Infrared spectroscopy deals with the interaction light and molecules lt is
used to study and identify chemical substances or functional groups in solid
liquid or gaseous forms. The method or techique of infrared spectroscopy is
conducted with an instrument called an infrared spectrometer which
produces an infrared spectrum.An IR spectrum can be visualized in a graph of
infrared light absorbance (or transmittance) on the vertical axis versus
frequency or wavelength on the horizontal axis. Typical units of frequency
used in IR spectra are reciprocal centimeter (some times called wave numbers)

With the symbol cm-1.Unit of IR, wave length are commonly given in
micrometers having symbol (um) which are related to wave numbers in a
reciprocal way.A common laboratory instrument that uses this techique is a
fourier transform infrared (FTIR) spectroscopy.

2.2 THEROY AND SELECTION RULES

Infrared spectroscopy is a powerful analytical technique used to study the
vibrational modes of molecules. When a molecule absorbs infrared radiation, its
vibrational energy changes, leading to characteristic peaks in the infrared spectrum.
These peaks can be used to identify the types of functional groups present in a
molecule, and to determine its structure and composition. The theory of infrared
spectroscopy is based on the concept of molecular vibrations. A molecule is made up
of atoms that are bonded together by chemical bonds, and these bonds can vibrate in
different ways. Infrared radiation corresponds to the energy required to excite these
vibrations, so when a molecule absorbs infrared radiation, it undergoes changes in its
vibrational energy.

The vibrational energy of a molecule is quantized, meaning that it can only take
on certain discrete values. These values correspond to the different vibrational modes
of the molecule, which are determined by its geometry and the types of chemical
bonds present. Each vibrational mode has a characteristic frequency, which is
determined by the masses of the atoms involved and the strength of the chemical
bonds. Infrared spectroscopy works by measuring the absorption of infrared radiation
by a sample, and plotting the resulting spectrum as a function of frequency. The
spectrum shows peaks at frequencies corresponding to the vibrational modes of the
molecule, and the position and shape of these peaks can be used to identify the types
of functional groups present in the sample.

Infrared spectroscopy measures the frequency of absorption when a sample is

irradiated with infrared electromagnetic radiation. It is a technique used to study the
vibrations between atoms because atomic vibrational excitation occur in the infrared
region of the electromagnetic spectrum. The bonds between atoms can be thought of
as a spring connecting two masses. In the spring-mass analogy the moving system can
be approximated by as simple harmonic oscillator. The frequency of oscillation is
proportional to root of K/m, where K is the spring constant and m is the mass of the
object. In a similar approximation, the frequency of vibration between two atoms as
unique and varies depending on the strength of the bond (k) and size of the atom (m)
when the frequency of electromagnetic radiation matches the natural frequency of
vibration between atoms, the atoms are able to absorb this energy and exhibit
vibration. This vibration can be detected as signal if they produce a change in the
dipole moment between two atoms which can interact with electric field.

2.3 DIFFERENT REGIONS OF INFRARED SPECTROSCOPY

Infrared (IR) radiation is a type of electromagnetic radiation with longer

wavelengths than visible light. The IR spectrum can be divided into three regions:
near-infrared, mid-infrared, and far-infrared.

Near-infrared (NIR) region:

This region has the shortest wavelengths among the three IR regions, ranging
from 0.75 to 2.5 micrometres. Near-infrared radiation is used in applications such as
fibre optics communication, spectroscopy, and remote sensing.
Mid-infrared (MIR) region:

This region has wavelengths ranging from 2.5 to 50 micrometres. Mid-infrared

radiation is used in a variety of applications, including chemical analysis,
environmental monitoring, and medical diagnostics.

Far-infrared (FIR) region:

This region has the longest wavelengths among the three IR regions, ranging
from 50 to 1000 micrometres. Far-infrared radiation is used in applications such as
thermal imaging, astronomy, and remote sensing.

2.4 INSTRUMENTATION
Fourier-Transform Infrared(FT-IR) spectroscopy is based on the idea of the
interference of radiation between two beams to yield an interferogram, in which a
signal is produced as a function of the change in path length between the two bearms.
The two domains of distance and frequency are inter convertible by the mathematical
method of Fourier transformation. The building blocks of all FT-IR instrument have
the following chain.

Source Interferometers Sample Detector

Figure 2.1 Schematic representation of FT-IR Spectrometer

Source:
In the mid IR several type of sources are used. They are either a Iamp
filament, or a hollow rod, 1-3 mm in diameter and 2-4 cm long, made of fused
mixtures of zirconium oxide or rare earth oxides (Nernst source) heated by
Joule effect by means of an internal resistor. These sources are heated to
1500"C, without a protective shield. They dissipate power of the order of a
hundred watts by emitting radiation over a large domain ranging from visible
to thermal IR.

Interferometers:

The most common interferometer used in FT-IR spectrometry is a

Michelson Interferometer, which consists of two perpendicularly arranged
plane mirrors, one of which an travel in a direction perpendicular to the plane.
A beam splitter (semi-reflecting film) bisects the planes of these two mirrors.
The beam splitter material has to be chosen according to the region to be
examined.

Figure 2.2 Fourier Transform Infrared Spectrometer

Sample:

For solid samples pellet technique is used. In Pellet technique the

first setup is to grind the sample very finely with potassium bromide.
The mixture is then pressed into transparent pellets with the help of a
dye. This is then placed in the IR beam in a suitable sample holder
Detector:
 There are two commonly used detectors employed for the mid-
infrared region. The normal detector for routine use is a pyroelectric
device incorporating Deuterium Tri-Glycine Sulfhates(DTGS) in a
temperature-resistant alkali halide window. For more sensitive work,
Mercury Cadmium Telluride(MCT) can be used, but has to be cooled to
liquid nitrogen temperature. A detector must have adequate sensitivity
to the radiation arriving from the sample and monochromatic over the
entire spectral region required.

2.5 SAMPIE HOLDING TECHNIQUES

Recording of IR spectra of solid sample are more difficult because the
particles reflect and scatter the incident radiation, and therefore, transmittance
is always low. Three different techniques are employed commonly in
recording the spectra.

Mull technique:

In this method, a slurry or mull of the substance is prepared by

grinding it into a fine powder and dispersing it in the mulling agent such as
paraffin oil (nujol), hexachlorobutadiene and perfluorokerosene (fluorolube).
It is smeared between two cell windows which are then held together. The
mull spreads out as a very thin film and the window set up is placed in the
path of the IR beam. The main disadvantage of this technique is the
interference due to the absorption bands of the mulling agent. The absorption
bands of nujol are found at 719, 1,376, 1,462, and 2,915 cm which interfere
with certain important group frequencies. For best results the size of the
sample particles must be less than that of the wavelength of radiation used.

Pellet technique:

The first step in this method is to grind the sample very finely with
potassium bromide. The mixture is then pressed into transparent pellets with
the help of suitable dies. This is then placed in the IR beam in a suitable
holder. This method has the following advantages:

 Absence of interfering bands

 Lower scattering losses
 Higher resolution of spectra
 Possibility of storage for future studies
 Ease in examination
  Better control of concentration and homogeneity of sample

The main disadvantage is that anomalous spectra may result from physical
and chemical changes induced during grinding. A common change of this
type is the absorption of water from atmosphere.

Solid films:

Spectra of solids may also be recorded by depositing a thin film of a

solid on a suitable window material. A concentrated layer of the solution of
the substance is allowed to evaporate slowly on the window material forming
a thin uniform film. Thickness can be adjusted by changing the concentration
of the solution. Interference caused by multiple reflections between parallel
surfaces affect the accuracy of measurements.

2.6 FOURIER TRANSFORM INFRARED SPECTROSCOPY

Fourier Transform Infrared (FTIR) spectroscopy first developed by

astronomers in the early l950s to study the infrared spectra of distant
stars has now been developed into a very powerful technique for the
detection of very weak signals from the environmental noise. It is a
simple mathematical technique to resolve a complex wave into its
frequency components. The conventional IR spectrometers are not of
much use for the far IR region (20 400 cm) as the sources are weak and
detectors insensitive. FTIR has made this energy limited region more
accessible. It has made the middle infrared (400-4,000 cm-1) also more
useful.

2.7 ADVANTAGES OF FOURIER TRANSFORM INFRARED

SPECTROSCOPY
The FT-IR spectrometer has several major advantages over the
dispersive instrument.

 It's sensitivity is better because it measures all frequencies

simultaneously rather than scanning through the individual
frequencies.
 Less energy is needed from the source and less time is needed for a
scan.
  Organic and Inorganic compound can be identified easily using Fourier
Tranforn Infrared Spectrascopy.
 Resolution and accuracy are also improved because a laser beam is used
alongside the Infrared Spectroscopy beam to control the speed of
themoving mirror and to time the collection of data points.

2.8 INTERPRETATION OF INFRARED SPECTROSCOPY

Infrared (IR) spectroscopy is a technique used to analyze the
vibrational modes of molecules. IR spectra provide information about
the functional groups present in a molecule, as well as its overall
structure and bonding.

The interpretation of an IR spectrum involves identifying the peaks and

bands that correspond to different vibrational modes of the molecule.
Here are some general guidelines for interpreting an IR spectrum:

 Identify the fingerprint region: The fingerprint region is the

portion of the IR spectrum below 1500 cm^-1. It contains a
complex pattern of peaks that are unique to each molecule and
can be used for identification.

 Identify functional groups: Functional groups are specific

arrangements of atoms in a molecule that give it certain chemical
properties. They can be identified by the presence of
characteristic peaks in the IR spectrum. For example, the presence
of a strong peak at around 1700 cm^-1 indicates the presence of a
carbonyl group (C=O).

 Identify other important peaks: Other important peaks to look for

include the stretching vibrations of C-H bonds (around 3000-3100
cm^-1) and the bending vibrations of C-H bonds (around 1300-
1500 cm^-1).

 Consider the intensity and shape of the peaks: The intensity of a

peak is related to the number of bonds in the molecule that are
undergoing the particular vibrational mode. The shape of the
peak can also provide information about the symmetry of the
molecule.
  Compare to known spectra: Finally, the interpretation of an IR
spectrum can be confirmed by comparing it to known spectra of
similar molecules.

Overall, interpreting an IR spectrum requires a good understanding of

the chemistry of functional groups and molecular vibrations, as well as
some experience and intuition.

2.9 APPLICATICATION
Applications of infrared spectroscopy are of varied types. The advent of
FTIR created renewed interest in the field of IR spectroscopy. It is one of the
most widely used analytical tools available today. The rapidly increasing
demand for routine analysis of a wide range of compounds and the data
handling capabilities have generated this interest.

2.9.1 IDENTIFICATION OF MOLECULAR

CONSTITUENTS

Identification of molecular constituents is done by assigning the

experimentally observed bands to possible functional groups and
stretching and bending vibrations of bonds. The vibrational
spectrum of a molecule consists of two major regions the group
frequency region and the finger print region. A simple way of
identifying a compound is by matching its IR spectrum to that of a
known sample. The use of group frequency concept for identifying
the constituents of a molecule is best illustrated with the help of an
example.

Spectrum of Cd(HCOO)2 . 2H2O :

The FTIR spectrum (500-4,000 cm-1) of the solid, Figure 2.3, can be
interpreted in terms of the vibrations of HCOO- and H2O groups as
the metal oxygen linkages are weak and appear below 400 cm-1. In
the OH stretching frequency region, there is a medium intense broad
band at 3,382 cm-1 with asymmetries around 3,432 and 3,257 cm-1.
This group is due to the asymmetric and symmetric stretching
modes of water molecules. The CH stretching mode of HCOO - ion
is responsible for the intense sharp band at 2862 cm The asymmetric
stretching vibration vas (COO-) and the bending vibration of water
usually occur in the region 1,560-1,620 cm-1 Hence the intense broad
band (FWHM = 200 cm-1) at 1588 cm-1 can be assigned to these
modes and the one at 1,358 cm to vs(COO -).

Figure 2.3 Infrared spectrum of Cd(HCOO)2 . 2H2O

The other two sharp intense bands at 1,405 and 764 cm-1 are
assigned to inplane OCH bending and OCO deformation modes
respectively. The lowering of the frequency of stretching modes of
water shows the system is considerably hydrogen bonded.

2.9.2 ELUCIDATION OF MOLECLAR STRUTURE

Elucidation of molecular structure is possible with the help

of IR spectroscopy only if Raman results are also taken into
consideration since both are complementary to each other. However,
we shall restrict ourselves to certain cases where one can get
information from IR alone.

As already indicated, from the observed P, Q, R branches of

the IR spectra o polyatomic molecules, an estimate of the rotational
 constants are possible from which the moments of inertia and
interatomic distances can be determined. This procedure is possible
even for molecules with zero dipole moment, if they exhibit rotational
fine structure of the vibration band. Study of the influence of nuclear
spins on the intensities of fine structure components of vibrational
spectrum permits the understanding of groupings of atoms in
molecules.

2.9.3 STUDY OF PHASE TRANSITION

In the area of ceramics, infrared spectroscopy is mainly used for

characterization purposes. As an example, consider the heat treatment
(45°C-1,200°C) of boehmite (AIOOH) which is of the most widely used
precursor gels in the preparation of high temperature ceramics,
abrasives and composites. Heat treatment causes dehydration,
rearrangement of OH groups, the formation of a number of transition
phases and finally the stable a-alumina which is then sintered at high
temperatures to get the final ceramic. Characterization of such
transition phases by XRD method has limitation in the early stages of
precursor decomposition due to its amorphous nature and the
nanosize particles. In view of the fact that particle size and state of
aggregation have a strong effect on the IR spectra, it is expected to be
an efficient tool in the characterization of the dehydroxylation
behaviour of boehmite precursor gel.

Aluminium can have different types of co-ordinations with

oxygen. If the AlO6, coordination is octahedral, the Al-0 stretching and
bending modes are expected in the region 500-750 cm-1 and 330-450 cm
respectively. However, a AlO4, tetrahedral coordination is expected to
give stretching modes in the narrow range 750-850 cm and bending
modes between 250-320 cm-1. The spectrum of boehmite gel at 45°C,
Figure (2.4.a) shows a very broad band with peaks at 485, 625 and 742
cm-1 indicating that the Al-0 bonding in boehmite gel is octahedral. The
band at 485 cm is assigned to the bending mode of AlO6 octahedron.
The spectra of samples heat treated at temperatures 400, 600 and 800°C
showed a shoulder around 800 cm indicating the onset of tetrahedral
coordination. This shows that the y-alumina phase contains both
octahedral and tetrahedral (small percentage) Al-0 coordination. The
samples heat treated at temperatures 900, 1,000 abd 1,050°C showed a
well defined band, Figure (2.4.b), (c), (d), around 840 cm in addition to
 the bands in the region 500-650 cm-1. That is, botlh octahedral and
tetrahedral Al-0 coordinations exist in the &phase (up to 1,050°C). As the
temperature is increased 1,100°C (0 phase), Figure (2.4), the tailing off
of the intensity profile in the high frequency side shows the absence of
tetrahedral coordination.

Figure 2.4 FTIR spectra of boehmite gel heat treated

2.9.4 BIOLOGICAL APPLICATIONS

With the advent of FTIR techniques a new awakening has

taken place in the biological applications of IR spectroscopy. Use of IR
spectroscopy to applications of biological and biomedical significance
was relatively slow due to the following constraints.

 Each functional group in a biological macromolecule contributes

to the IR spectrum, which is very complex. Overlapping and
mixing of vibrational modes make the analysis very difficult

 Most biological systems of interest are aqueous based and often

surface specific as well. Hence complex optical techniques are
often needed.

 The molecular or cellular systems that are being studied are

generally complex, and therefore. sample handing techniques
and experimental design are as difficult as spectroscopic
consideration.
  Most biological experiments require instruments with extremely
high signal to ng ratio. Only research grade FTIR spectrometers
are usable for biomedical applications.

2.9.5 OTHERS APPLICATIONS

IR spectroscopy is extensively used in different areas for varying

purposes. Some of them are the study of inter-and intramolecular
interactions, distinguishing free and hindered internal rotation,
chemical reaction kinetics, pollution studies, hydrogen bonding, surface
chemistry, catalytic processes, establishment of molecular symmetry
and so on

Summing up, the IR instrumentation has advanced to a level

generally beyond most of the spectroscopes’ ability to interpret. The
current challenge facing them is that of proper experimental design,
interpretation of spectra and use of appropriate data processing.