Infrared Spectroscopy:

The IR technique is used for the chemical identification and also for Quantitative
analysis.

Molecular spectroscopy involves the interaction of electromagnetic radiation with the

molecules of the material in question. Infrared (IR) region of the electromagnetic
spectrum lies between visible and microwave regions and therefore spans the
wavelengths from 0.78
are smaller than those associated with electronic transitions and fall in the IR region.
IR spectroscopy, therefore, is used to probe the vibrations in molecules and is also
known as vibrational spectroscopy.

IR absorption takes place in a region of longer wavelength and thus have a lesser
energy than UV-Vis range. The longer wavelength causes vibrational stretching and
bending of the atomic bonds within the molecule.

Photographic region 0.75 to 1.2 µm Middle IR Region

12500 to 8400 cm-1 0.8 to 2.5 µm
Very near IR Region 1.22 to 2.5 µm 4000 to 400 cm-1
8400 to 4000 cm-1
Ordinary IR region 2.5 to 15 µm Middle IR Region
4000 to 1250 cm-1 2.5 to 25 µm
Fingerprint Region 1432 to 910 cm-1 4000 to 400 cm-1

Far IR Region. 667 to 50 cm-1 Middle IR Region

25 to 250 µm
400 to 40 cm-1

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Mid-IR region ( = 2.5 - = 4000 400 cm-1) is the region of interest for
studying molecular vibrations, because in this range the important information about
the vibration in the molecule can be detected and hence structure of the compound
can be identified.

In the context of infrared spectroscopy, wavelength is measured in "wave numbers",

which have the unit cm-1. Wave number is the number of waves per cm, which can be
calculated from the wavelength.

compounds
because almost all molecules species can absorb IR radiation except a few homo
nuclear molecules like O2, N2 and Cl2.

Principle:

The technique is based on the fact, that a chemical substance shows absorption in IR
radiation.

In any molecule, atoms or group of atoms are connected by bonds. Photon energies
associated with infrared region are not large enough to excite electrons but may induce
vibrational excitations of covalently bonded atoms or groups. These covalent bonds are
not rigid, but they are analogous to springs which are stretched or bent.
Every bond or a portion of a molecule or a functional group requires different frequency

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for absorption. Hence, a characteristic peak is observed for every functional group or
a part of a molecule.

Criteria for a compound to absorb IR radiation are the change in dipole moment, and
applied IR frequency should be equal to the natural frequency of radiation. Otherwise
the compound will not give IR peaks.

When a beam of electromagnetic radiation is passed through a substance, the radiation

can be either absorbed or transmitted, depending on its frequency and the structure
of the molecules it encounters.

The bend intensity of an IR Spectrum may be expressed either in form of transmittance

(T) or absorption (A).

Transmittance can be defined as ratio of radiant power transmitted (It) by the sample
to the radiant power of incident (I0) on the sample, thus:

Transmittance, T =

Degrees of freedom and molecular vibrations

At non-zero temperatures, i.e. temperatures above 0 K, all the atoms in a molecule

are in motion. The molecule itself also is in translational and rotation motion. In a three
dimensional space, an atom in isolation has 3 degrees of freedom, corresponding to
the motion along the three independent coordinate axes. A molecule composed of N
atoms has a total of 3N degrees of freedom (Figure 10.2).

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 Figure 10.2 Degrees of rotational freedom for a diatomic (A) and a triatomic (B)
molecule

For a non-linear molecule, three of these 3N degrees of freedom correspond to

translational motion, three correspond to rotational motion while rest 3N-6 are the
vibrational degrees of freedom.

For a linear molecule, there are only two rotational degrees of freedom that correspond
to the rotation about the two orthogonal axes perpendicular to the bond (Figure 10.2).
A linear molecule, therefore, has 3N-5 vibrational degrees of freedom.

Let us have a look at the degrees of freedom of a diatomic molecule. A diatomic

molecule has a total of 3 × 2 = 6 degrees of freedom. Three of these six degrees of
freedom correspond to translational motion of the molecule; two of them define
rotational degrees of freedom; while one corresponds to the vibration of the atoms
along the bond.

The 3N-6 vibrational degrees of freedom (3N-5 for linear molecules) represent the
true/fundamental modes of vibration of a molecule.

IR spectroscopy is concerned with molecular vibration hence a vibrating bond can

therefore be considered a spring with its ends tethered to two atoms (Figure below).

Figure: Spring analogy of a bond vibration

If the masses of the atoms are m1 and m2, the frequency of stretching vibration of
the diatomic molecule

..............................................................................(10.1)

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Where, is the frequency of vibration, k is the spring constant, and is the reduced

mass i.e.

Dividing equation 10.1 by gives:

............................................................................(10.2)

............................................................................(10.3)

.............................................................................(10.4)

The spring constant, k is the measure of the bond strength. The stronger the bond,
the higher the k, and consequently the higher is the frequency of vibration. This
treatment implies that the diatomic molecule is a simple harmonic oscillator. The
energy of a quantum harmonic oscillator is given by:

........................................................................(10.5)

Where, n h is the Plancks's constant

Each bond has its own vibrational frequency, but when an IR radiation of the same
frequency strikes the molecule, the molecule absorb some of the energy and thus the
amplitude of vibration is increased, which is expressed in terms of transmittance after
the absorption of IR radiation by the chemical substance.

The vibration in the molecule will takes place when the emitted IR radiation have the
same frequency as of the molecule can vibrate itself.

When the molecule is subjected to the IR radiation, the amount of radiation absorb or
transmitted by the molecule can be determined through detector and recorded. The
intensity of this radiation against the wave number will give a curve which shows a
number of bands and called IR spectrum of the molecule.

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Types of Vibrations in IR:

Simple diatomic molecules have only one bond, which may stretch. In polyatomic
molecules, each atom having a three degrees of freedom in three directions which are
perpendicular to each other. Thus, a molecule of n atoms has 3n degrees of freedom.

For a linear molecule, two degrees of freedom describe rotation and three degrees
describe translation, so the remaining 3n -5 are number of fundamental vibrations.
While for a non-linear molecule, three degrees of freedom describe rotation and three
degrees describe translation, so the remaining 3n -6 are number of fundamental
vibrations.

More complex molecules have more than one bonds and different types of vibrations
may occur. Vibrations fall into the two main categories of stretching and bending.

1. Stretching vibrations:
2. Bending Vibration / Deformation.

Stretching Vibration:

In this type of vibrations, the bond length is increased or decreased at regular intervals.
There are two types of stretching vibrations. Symmetrical stretching and asymmetrical
stretching.

a) Symmetrical stretching- In this type of stretching, bond length increase or

decrease symmetrically.

b) Asymmetrical stretching- In this type of stretching, length of one bond increases

and the other one decreases.

Bending Vibration / Deformation: In this type of vibrations, a change in bond angle

occurs between bonds with a common atom, or there is a movement of a group of

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atoms with respect to the remainder of the molecule without movement of the atoms
in the group with respect to one another.

The bending vibrations are also called as deformation vibrations. Deformation

vibrations are of two types.

a) In-plane bending vibrations: In these types of vibrations, there is a change

in bond angle. This type of bending takes place within the same plane. In plane
bending are of two types.
I. Scissoring in which bond angle decreases.
II. Rocking in which the bond angle is maintained but both bonds moves
within the same plane.

b) Out plane bending vibrations: This type of bending takes plane outside of the
plan of molecule.
I. Wagging in which both atoms move to one side of the plane
II. Twisting in which one atom is above the plane and the other is below
the plane

(+) sign: above movement in plane (coming forward).

(-) sign: above movement in plane (going backward).

Bending vibrations appear at lower frequency while for stretching vibrations higher
frequency is required.

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The force constant of bending vibration are generally less than stretching vibrations.
Thus bending vibration are more sensitive to change in experimental / environmental
conditions.

Requirement for IR Radiation Absorption:

Criteria for a compound to absorb IR radiation are the change in dipole moment, and
applied IR frequency should be equal to the natural frequency of radiation. Otherwise
the compound will not give IR peaks.

I. Correct Wavelength of the sample: A molecule absorbs IR radiation only

when the natural frequency of vibration of atom or groups of the atom of the
molecule is the same as the frequency of incident radiation. Molecules absorb
infrared radiation when the frequency of IR radiation is synchronized with a
natural vibration frequency of the molecule. When IR radiation is absorbed, the
molecule begins to vibrate with a greater amplitude (but with the same
frequency), and thus the molecule has gained energy.

II. Electrical Dipole: The IR radiation is absorbed by a molecule only when the
absorption causes a change in its electrical dipole. A molecule is said to have an
electrical dipole when it has a slight positive and slight negative charges on its
atom.

In general, such absorption of an infrared light quantum can occur only if the
dipole moment of the molecule is different in the two vibrational levels. The
variation of the dipole moment with the change in interatomic distance during
the vibration corresponds to an oscillating electric field that can interact with the
oscillating electric field associated with electromagnetic radiation. The
requirement that absorption of a vibrational quantum be accompanied by a
change in dipole moment is known as a selection rule. Such a vibrational
transition is said to be infrared-active. Vibrational transitions that do not result
in a change of dipole moment of the molecule during vibration are not observed
directly and are referred to as infrared-inactive transitions. The greater the
change in dipole moment the stronger the infrared absorption.

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Sample Preparation

IR spectroscopy is used for the characterization of solid, liquid or gas samples. Material
containing sample must be transparent to the IR radiation. So, the salts like NaCl, KBr
are only used.

Sampling of solids: Various techniques used for preparing solid samples:

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 a path
of IR beam and the spectrum is recorded.

b) Solid run in Solution In this technique, 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 alkali metal disc and 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 ensured 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 it is used for analysis.

Sampling of liquids:

Liquid sample cells can be sandwiched using liquid sample cells 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

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Sampling of gases

The sample cell is made up of NaCl, KBr etc. and it is 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 of IR Spectroscopy:

A usual optical materials like Glass or Quartz absorb IR radiation, consequently the
application for measuring IR radiation (spectrum) is highly different from UV-Vis
Spectroscopy.

Two types of infrared spectrometers are commercially available: Dispersive and Fourier
Transform Infrared (FTIR) spectrometers.

Dispersive spectrometer: A dispersive spectrometer is very similar in design to a

UV/visible spectrophotometer. It has a radiation source, a grating monochromator, and
a detector. The IR radiation generated by the source is dispersed into different
frequencies by a monochromator. The selected frequencies go through sample and
reference cells and the transmitted light is measured by the detector. The infrared
sources are usually inert solids that are electrically heated to radiate infrared radiation.
The detectors usually are either thermal sensors such as thermocouples and
thermistors or the semiconductor materials that conduct following absorption of IR
radiation (absorption of photon causes transition of electrons from the valence band to
the conduction band).

Fourier Transform Spectrometer: A Fourier transform spectrometer uses an

interferometer in place of the monochromator. An interference of polychromatic
radiation is generated using an interferometer, usually a Michelson interferometer.
Absorption of any particular wavelength will bring a change in the interferogram which
gets detected. An interferogram is a time domain signal and is converted to frequency
domain signal though Fourier Transformation.

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In IR spectroscopy generally double beam spectrometer is used. The main parts of IR
spectrometer are as follows:

1. radiation source
2. Monochromators
3. sample cells and sampling of substances
4. detectors
5. recorder

Radiation Source:

IR instruments require a source of radiant energy which emit IR radiation which must
be steady, intense enough for detection and extend over the desired wavelength. An
inert solid is electrically heated to a temperature in the range 1500-2000 K. The heated
material will then emit infrared radiation. Various sources of IR radiations are as
follows.

a) Nernst glower: is a cylinder (1-2 mm diameter, approximately 20 mm long) of

rare earth oxides. Platinum wires are sealed to the ends, and a current passed
through the cylinder. The Nernst glower can reach temperatures of 2200 K.

b) The incandescent wire source is a tightly wound coil of nichrome wire,

electrically heated to 1100 K. It produces a lower intensity of radiation than the
Nernst or Globar sources thus used in the near IR instrument but has a longer
working life.

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 c) Glober source: is a silicon carbide rod (5mm diameter, 50mm long) which is
electrically heated to about 1500 K. Water cooling of the electrical contacts is
needed to prevent arcing. The spectral output is comparable with the Nernst
glower, execept at short wavelengths (less than 5 mm) where it's output
becomes larger.

d) Mercury arc: In far IR instruments high pressure Murcury arc is used which is
usually a quartz mercury lamp for spectrum > 50 mm.

Monochromator:

A monochromator is a means of separating wavelengths of the source radiation. The

monochromator is used to separate polychromatic radiation into a suitable
monochromatic form.

Various types of monochromators are prism, gratings and filters. Prisms are made of
Potassium bromide, Sodium chloride or Caesium iodide. Filters are made up of Lithium
Fluoride and Diffraction gratings are made up of alkali halides. Prism: Gives no
resolution of radiation and is generally used for entire range , Filters: gives no
resolution in the IR region when the significant Stretching vibration are located.
Grating: It can replace the prism monochromator to give high resolution of radiation.
In this combination small prism is used.

Sample Cell and Sampling of Substances:

IR spectroscopy is used for the characterization of solid, liquid or gas samples. Material
containing sample must be transparent to the IR radiation. So, the salts like NaCl, KBr
are only used:

a) Solid - Various techniques are used for preparing solid samples such as pressed
pellet technique, solid run in solution, solid films, mull technique etc.

b) Liquid samples can be held using a liquid sample cell made of alkali halides.
Aqueous solvents cannot be used as they will dissolve alkali halides. Only organic
solvents like chloroform can be used.

c) Gas sampling of gas is similar to the sampling of liquids.

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Detectors:

Detectors used in infrared spectrophotometers usually convert the thermal radiant

energy into electrical energy, which can subsequently be plotted on a chart recorder.
Two Types of the detectors are commonly used:

a) Thermal Detectors, in which the infrared radiation produces a heating effect

that alters some physical property of the detector.
b) Photon Detectors, which use the quantum effects of the infrared radiation to
change the electrical properties of a semiconductor.

c) In near IR region Photoconductivity cell is generally used while in far IR region

thermal detectors are used.

Photon Detectors:

The more sensitive infrared detectors rely on a quantum interaction between the
incident photons and a semiconductor - the result producing electrons and holes. This
is the internal photoeffect. A sufficiently energetic photon that strikes an electron in
the detector can raise that electron from a nonconducting state into a conducting state.
As conductors, electrons contribute to the current flow in one of two ways, depending
on the configuration of the semiconductor. These are referred to as photovoltaic or
photoconductive cell.

a) Photoconductive Cells commonly used are indium antimonide (InSb) or Hg-Cd-

Te (MCT), which have high sensitivity and very quick response time in infrared
detection. These detectors operate at liquid nitrogen temperature which reduces
noise. The radiant energy falling on the detector is converted into measurable
electrical energy.

b) Pyroelectric detectors are made from a single crystalline wafer of a pyroelectric

material, such as triglycerine sulphate. The properties of a pyroelectric material
are such that when an electric field is applied across it, electric polarisation
occurs (this happens in any dielectric material). In a pyroelectric material, when
the field is removed, the polarisation persists. The degree of polarisation is
temperature dependant. So, by sandwiching the pyroelectric material between

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 two electrodes, a temperature dependant capacitor is made. The heating effect
of incident IR radiation causes a change in the capacitance of the material.
Pyroelectric detectors have a fast response time. They are used in most Fourier
transform IR instruments.

c) Photoelectric detectors such as the mercury cadmium telluride detector

comprise a film of semiconducting material deposited on a glass surface, sealed
in an evacuated envelope. Absorption of IR promotes nonconducting valence
electrons to a higher, conducting, state. The electrical resistance of the
semiconductor decreases. These detectors have better response characteristics
than pyroelectric detectors and are used in FT-IR instruments - particularly in
GC - FT-IR

Thermal Detectors

Because infrared radiations are essentially radiant heat, thermal detectors are used to
detect changes in the radiations. Thermal detectors are made as small as possible to
reduce their heat capacity so that for a given amount of energy there will be a large
temperature rise. In order to make the detector rapid in response it must be able to
dissipate the heat very rapidly. There are three main types of detector.

a) Thermocouples: Thermocouples consist of a pair of junctions of different

metals; for example, two pieces of bismuth fused to either end of a piece of
antimony. The thermocouple uses the principle that the change in temperature
of a junction of two dissimilar metals creates an electromotive force (emf) which
may be measured.

b) Bolometers: The bolometer uses the principle that the electrical resistance of
a pure metal or semi-conductor is temperature-sensitive. If a constant potential
is applied to such a detector the variation of the resistance with temperature
may be measured by the variations in the current flowing in the circuit.

c) Golay cell: In the Golay cell the detector is a small metal cylinder enclosed by
a blackened metal plate at one end and a flexible metallised diaphragm at the

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 other. The cylinder is filled with a gas and sealed. As IR radiation falls on the
blackened plate the gas in the cylinder expands deforming the diaphragm. Light
from a lamp inside the detector is focused on the diaphragm. The light is
reflected from the metallised diaphragm and falls onto a photocell. Movement of
the diaphragm moves the light beam across the photocell. The output of the
photocell is proportional to the expansion of the gas.

Amplifiers and Recorders:

The radiant energy received by the detector is converted into measurable electrical
signal and is amplified by the amplifiers. The amplified signal is registered by a recorder
or a plotter. The recorder is driven with a speed which is synchronized with that of a
monochromator, so that, the pen moving across the chart, records the transmittance
of the sample as a function of the wavenumber.

Past Paper Questions:

1. Describe the molecular vibration occurred in IR-Spectroscopy with

diagram?
2. Give the instrumentation and applications of Atomic Absorption
Spectroscopy?

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