UNIT 3

IR SPECTROSCOPY

Infra-red spectrum is an important record which gives sufficient information about the structure of a
compound.

The absorption of infra-red radiations causes the various bands in a molecule to stretch and bent with
respect to one another.

The ordinary infra-red region extends from 2.5 μ to 15 μ. The region from 0.8 μ to 2.5 μ is called near
infra-red region and that from 15 μ to 200 μ is called far infra-red region.

The absorption of infra-red radiations can be expressed either in terms of wavelength (λ) or in wave
number (𝜈̅ ).

Mostly infra-red spectra of organic compounds are plotted as percentage transmittance against wave
number.

Principle

The absorption of infra-red radiations causes an excitation of molecule from a lower to the higher
vibration level.

We know that each vibrational level is associated with a number of closely spaced rotational levels.
Clearly, the infra-red spectra is considered as vibrational-rotational spectra.

All the bonds in a molecule are not capable of absorbing infra-red energy but only those bonds which
are accompanied by a change in dipole moment will absorb in the infra-red region.

Such vibrational transitions which are accompanied by a change in the dipole moment of the molecule
are called infra-red active transitions.

On the other hand, the vibrational transitions which are not accompanied by a change in dipole moment
of the molecule are not directly observed and these are infra-red inactive.

For example, vibrational transitions of C=O, N-H, O-H etc. bands are accompanied by a change in dipole
moment and thus, absorb strongly in the infra-red region.

But transitions in carbon-carbon bonds in symmetrical alkenes and alkynes are not accompanied by the
change in dipole moment and hence do not absorb in the infra-red region.
Molecular Vibrations

Absorption in the infra-red region is due to the changes in the vibrational and rotational levels.

There are two types of molecular vibrations or fundamental vibrations:

Stretching

Bending

Stretching: In this type of vibrations, the distance between the two atoms increases or decreases but the
atoms remain in the same bond axis.

Bending: In this type of vibrations, the positions of the atoms change with respect to the original bond
axis.

Types of stretching vibrations

There are two types of stretching vibrations:

Symmetric stretching: In this type, the movement of the atoms with respect to a particular atom in a
molecule is in the same direction.

Asymmetric stretching: In these vibrations, one atom approaches the central atom while the other
departs from it.

Types of Bending vibrations

There are four types of bending vibrations:

Scissoring: In this type, two atoms approach each other.

Rocking: In this type, the movement of the atoms takes place in the same direction.
Wagging: Two atoms move up and down the plane with respect to the central atom.

Twisting: In this type, one of the atoms move up the plane while the other moves down the plane with
respect to the central atoms.

Modes of vibration of linear triatomic molecule (CO2)

Carbon dioxide is a linear triatomic molecule.

The number of fundamental modes of vibration = 3𝑁 − 5

= 3(3) − 5 = 9 − 5

=4

These four modes are:

During the symmetrical stretching there is no change in dipole moment. Hence this symmetrical
stretching will not absorb radiation and it is infra-red inactive.

During the asymmetrical stretching there is a change in dipole moment and hence this mode is infrared
active.

Inplane bending mode.

Out of plane bending mode. The 3 and 4 bending modes result in a change in dipole moment and hence
these two are infra-red active.

Modes of vibration of non-linear triatomic molecule (H2O)

Water is a non-linear (bent) triatomic molecule.

The number of fundamental modes of vibration = 3𝑁 − 56

 = 3(3) − 6 = 9 − 6

=3

All the three vibrational modes result in a change in dipole moment. Hence these three vibrations are
infra-red active.

Selection Rules

Infra-red light is absorbed only when a change in dipole character of the molecule takes place.

(i) If a molecule has a centre of symmetry, then the vibrations are centrosymmetric and are inactive in
the infra-red but are active in the Raman.

(ii) The vibrations which are not centrosymmetric are active in infra-red but inactive in Raman.

Fermi resonance

In infra-red spectrum, absorption bands are spread over a wide range of frequencies. It may happen that
the energy of an overtone level coincide with the fundamental mode of different vibration. A type of
resonance occurs as in the case of coupled pendulums. This type of resonance is called Fermi resonance.

Vibrational Frequency

The value of the stretching vibrational frequency of a bond can be calculated by the application of
Hook’s law which may be represented as,

𝑘
𝑐 1 𝑚1 𝑚2
= 𝜈̅ = [ ]
𝜆 2𝜋𝑐 𝑚1 + 𝑚2

1 𝑘
= √
2𝜋𝑐 𝜇

where, μ is the reduced mass.

m1 and m2 are the masses of the atoms in a particular bond.

k is force constant
c is velocity of radiation.

The value of vibrational frequency depends upon:

Bond strength and

Reduced mass.

Factors influencing Vibrational frequencies

1. Coupled vibrations

We expect one stretching absorption frequency for an isolated C-H bond. But in the case of methylene (-
CH2-) group, two absorptions occur which correspond to symmetric and asymmetric vibrations as
follows.

In such cases, asymmetric vibrations occur at higher wave number compared with the symmetric
vibrations. These are called coupled vibrations.

2. Bond strength

The vibrational frequency increases when the bond strength increases.

e.g., C=C and C=O stretching will have higher frequencies than C-C and C-O stretching.

3. Reduced mass

The vibrational frequency, increases when the reduced mass of the system decreases.

e.g., O-H stretching will have higher frequencies than C-C and C-O stretching.

4. Electronic Effects

Vibrational frequency changes are due to the electronic effects which include inductive effect,
mesomeric effect, fields effects etc.,

Under the influence of these effects, the force constant or the bond strength changes and thus the
vibrational frequency shifts from the normal value.

5. Hydrogen bonding

Vibrational frequency decreases with increasing the strength of hydrogen bonding.

e.g., N – H has higher frequency than O – H.

Instrumentation of IR Spectroscopy

There are three basic components in an infra-red spectrophotometer:

A stable source of radiant energy

A monochromator

A detector

Radiation sources

The two most common sources used in IR spectrophotometers are:

Nernst Glower

Globar

Nernst Glower

This is a tube made of a fused mixtures of the oxides of zirconium, yttrium and thorium, 1 mm in
diameter and 2 cm in length.

The ends of the rod are attached to mounted ceramic tubes and platinum leads are used for electrical
connections.

Globar

This is made up of a small cylindrical rod of silicon carbide.

It is usually placed in a water cooled brass tube with a slit provided for the emission of radiation.

Aluminium electrodes are used for electrical connections.

Monochromators

To obtain monochromatic light, optical prisms or gratings can be used.

Detectors

Thermal detectors are used for detecting transmitted radiation in the infra-red region.

Two types of detectors are used in IR spectrophotometers. They are:

Thermocouple

Bolometers

Thermocouple
It uses heat sensitive junctions of two different semiconductor materials (or) metals to generate a small
voltage difference when the temperature changes.

Two dissimilar metals silver and platinum are placed together and the radiation to be measured is
focused on one of the junctions, which is connected to a receiver plate.

The receiver plate absorbs the incident radiation and converts it to heat.

The temperature difference between the hot and cold junctions sets up a small voltage difference
between these two junctions. The resulting current, which can be measured, is directly proportional to
the intensity of the incident light.

Bolometers

A bolometer is a device whose resistance changes as the temperature changes.

Bolometer diagram: Gopalan book

page 241

Rd and Rf represent the resistances of the detector and reference bolometer respectively.

The reference bolometer has a higher resistance compared to the resistance of the detector bolometer.

The change in resistance Rd due to the incident infra-red radiation will induce a current flow which can
be measured by the galvanometer.

The change in resistance is directly proportional to the intensity of the incident radiation.

Cells

The most commonly used cells are made from sodium chloride, as this material is transparent to infra-
red radiation and inert toward the samples.

Cells after use, should be carefully cleaned by washing with pure chloroform and drying with a stream of
dry nitrogen.

Sodium chloride cells, when not in use, should be kept in a desiccator.

Working technique

IR instrument

Y.R sharma page 90

Light from the source is split into two beams. One of the beams is passed through the sample under
examination and is called the sample beam. The other beam is called the reference beam.
When the beam passes through the sample, it becomes less intense due to the absorption of certain
frequencies.

Now there will be a difference in the intensities of the two beams.

The two beams are made to fall on a segmented mirror M (chopper) with the help of two mirrors M1
and M2.

The chopper (M) which rotates at a definite speed reflects the sample and the reference beams to a
monochromator grating (B).

As the grating rotates slowly, it sends individual frequencies to detector (D) which converts infra-red
energy into electrical energy. It is then amplified with the help of amplifier (A).

Due to the difference in intensities of the two beams, alternating currents start flowing from the
detector to the amplifier.

The amplifier is coupled to a small motor (E) which drives an optical wedge (F).

The movement of the wedge is in turn coupled to a pen recorder which draws absorption bands based
on the calibrated chart.

Sampling techniques

Solid samples

Three methods are available for the analysis of solid samples in IR spectrophotometers. They are:

KBr pellet technique

Mull technique

Solid film

KBr pellet technique

KBr pellets are prepared by grinding sample and KBr in the ratio 1:100

Then this pellets are made into a disc after drying and pressing it under elevated temperature and high
pressure.

The disc is mounted on a holder and then the spectrum is recorded.

Mull technique

The sample is prepared by adding mulling reagent and made into a paste. Then this paste is placed
between two glass plates and then the spectrum is recorded.

Important mulling reagents are:

Nujol

Hexachloro butadiene

Chloro fluoro carbon

Nujol is the most commonly used mulling reagent.

Nujol also shows some absorption bands for –CH3 and –CH2- stretching and bending vibrations.

Solid film

Sample is dissolved in volatile solvent and made into a sample solution. Then this solution is added as
drops on KBr/NaCl pellets. The solvent is allowed to evaporate.

This method is applicable in qualitative analysis than quantitative analysis.

Liquid samples

The simplest technique consists of sampling a liquid in a thin film squeezed between two sodium
chloride plates.

For samples that contain water, plates may be constructed with calcium fluoride.

A drop of the liquid sample is placed on the top of the sodium chloride plate and another sodium
chloride plate is placed on it.

The pair of sodium chloride plates enclosing the liquid film is then placed in the path of the sample
beam.

Gaseous samples

The gaseous sample is introduced into a gas cell. The walls of the cell are made of sodium chloride.

Sodium chloride windows allow the cell to be placed directly in the path of the sample beam.

The gas cell is usually 10 cm long.

Solution

The liquid sample can be dissolved in a suitable solvent and the spectrum of this solution is recorded.

Usually 1 – 5 % solution is placed in the sample cell.

Some important solvents which may be used are:

Chloroform

Carbon tetrachloride
Carbon disulphide

1. Light (or) radiation source

A number of radiation sources are used in IR spectrometer. Some of the radiation sources are:

Incandescent lamp

Nernst glower

Globar

Mercury arc lamp

Incandescent lamp

The incandescent lamp produces white light and it is used only for near IR region.

Nernst glower

It is the most important radiation source in IR spectrometer. It consists of a rod of the sintered mixture
of the oxides of Zr, Y and Er.

The rod is electrically heated up to 1500 oC to produce IR radiation.

Globar

It consists of SiC (silicon carbide) rod and it is applicable for > 650 cm-1 frequency.

Mercury arc lamp

It is applicable only for far IR region.

Monochromators

To obtain monochromatic light, two types of monochromators are used in IR spectrometers. They are:

Prism monochromators
Grating monochromators

Prism monochromators

Glass and quartz cannot be used in prism material because they strongly absorb the IR light. Instead of
them, NaCl (or) certain alkali metal halides are commonly used.

Since NaCl is hygroscopic, temperature should be maintained. NaCl is used as monochromator up to 625
cm-1

LiF, CaF2 and CsI are used as monochromators below 625 cm-1.

Grating monochromators

For higher frequencies of radiation, gratings are used instead of prism monochromators. Gratings gives
high resolution than prism.

Applications of IR spectroscopy

1. Identification of an Organic compound

The identification of an organic compound can be established from its finger print region (1400-900 cm-
1
).

The identity of an organic compound is confirmed if its finger print region exactly matches with the
known spectrum of that compound.

2. Structure determination

This technique helps to establish the structure of an unknown compound.

All major functional groups absorb at their characteristic wave numbers. From the data available due to
absorption frequencies, the probable structure can be predicted.

Example:

The infra-red spectra of amino acids exhibit bands for ionized carboxylic acid and amine salts (-NH3+). No
band for free –NH2 and –COOH groups is observed. Clearly, amino acids exist as zwitter ions as below:

3. Qualitative analysis of functional groups

The presence or absence of absorption bands help in predicting the presence of certain functional
groups in the compound.

The presence of oxygen reveals that the group may be –OH, C=O, COOR, -COOH, anhydride etc.
4. Distinction between two types of hydrogen bonding

It is known that in hydrogen bonding, the electron cloud transfers from a hydrogen atom to the
neighbouring electronegative atom.

This technique helps to distinguish between intra molecular and inter molecular hydrogen bonding.

Example:

o-Nitro phenol exhibits intra molecular hydrogen bonding whereas p-nitro phenol exhibits inter
molecular hydrogen bonding.

Intra molecular hydrogen bonded compound does not show any shift in absorption on dilution whereas
inter molecular hydrogen bonded compound does.

5. Qualitative analysis

It helps to make a quantitative estimation of an organic mixture. The estimation of the compounds of a
mixture can be done by:

measuring the intensities of absorption band for a pure component

knowing the optical density of the absorption band for a pure component.

It is known that commercial xylene exists as a mixture of three isomers, i.e., -ortho, -meta, and para
xylenes. The separation of the mixture cannot be easily done.

However, the percentage composition of the mixture can be determined by taking the IR spectrum of
the mixture. Bands are formed at

(i) 740 cm-1 for –ortho isomer

(ii) 880 cm-1 for –meta isomer

(iii) 830 cm-1 for the –para isomer

6. Study of a Chemical reaction

This technique is quite useful for studying chemical reactions.

Consider the reaction of a saturated aliphatic ketone to form secondary alcohol.

Ketone forms a strong band at about 1710 cm-1. When it is subjected to reduction, it forms 2-butanol
which absorbs at 3300 cm-1 due to O-H stretching.

The progress of reaction can be studied from time to time and the reduction will complete when a
strong band due to C=O stretching will be missing and only one band due to O-H stretching is present.

7. Study of keto-enol tautomerism

Diketones and ketoesters exhibit keto-enol tautomerism provided they have α-hydrogen atom in them.

The infra-red spectrum of such a compound contain bands due to C=O, O-H and C=C bonds.

Example:

Consider ethyl acetoacetic ester. It exists in keto-enol isomers in equilibrium.

The lowering of ν C=O stretching absorption in the enolic form is due to intra molecular hydrogen
bonding which is established by resonance.