Unit V – IR spectroscopy

Course Instructor- Dr.Shailesh Dhoke

 Topics Covered

 Principle of Infrared Spectroscopy

 Types of vibrations in molecules
 Interpretation of IR Spectrum
 Instrumentation of IR Spectroscopy
 Applications of IR Spectroscopy
 Introduction
Infrared spectroscopy is a very important tool for the determination of the structure of a
compound.
It is also called vibrational spectroscopy as it involves the transition between vibrational
energy levels.
Infrared radiations do not have sufficient energy to bring about electronic excitation;
however, it causes atoms and groups to vibrate about the covalent bond connecting them. As
these vibrations are quantized, the compound absorbs the infrared energy in different regions
of the spectrum.
An infrared spectrum is obtained when the frequency of molecular vibration
corresponds to the frequency of the infrared radiation absorbed.
Apart from vibrational changes, rotational changes also occur in the molecule, hence some
fine structures are obtained on the vibrational band.
The IR region of electromagnetic spectrum extends from 0.8 μ to 200 μ (12,500 cm–1 to
50 cm–1) but the most important region for the purpose of study is 2.5 μ to 15 μ (4000 cm–1
to 667 cm–1). Molecular vibrations are detected and measured in this region.
The region from wavelength 0.8 μm to 2.5 μm (12,500 to 4000 cm–1) is called near
infrared (Near IR) and that from 25 μm to 1000 μm (400 to 10 cm–1) is called far infrared
region.
 Principle of IR Spectroscopy
Interaction Between Infrared Radiations and Molecular Vibrations

When a beam of IR radiation of varying frequency passes through a sample

(heteronuclear diatomic molecules) , it absorbs energy when the energy matches the
difference between the vibrational energy levels of its bonds.
This energy is utilized for stretching, the atoms in the covalent bond or bending the two
covalent bonds on an atom.
Infrared spectrum consisting of absorption bands are thus obtained and are usually plotted
as frequency or wave number VS percentage transmittance.

vs

The position of the infrared absorption band is specified in frequency units expressed not
in hertz but in wave numbers, cm–1 or by its wavelength l (μm).

Band intensity is expressed either in terms of absorbance (A) or transmittance (T).

 Interaction Between Infrared Radiations and Molecular Vibrations

The mechanism of transfer of energy between the radiation and the vibrating molecule is
as follows:
The Energy of Vibration is given by

Where h is Planks constant, ν is the vibration quantum number having values 0,1,2…

and νm is the frequency in cycles/s given by

Where
k is the force constant, which gives the idea of the toughness or the strength of the bond.
µ is the reduced mass given by

Where m1 and m2 are the masses of the atoms of the bond

The energy difference between successive vibrational levels is given by

Note:
All types of molecules cannot interact with IR radiation. Only those molecules which
exhibit change in dipole moment during a vibration can exhibit IR spectra.
Evidently, the homo-nuclear diatomic molecules like H2, O2, N2, Cl2, etc do not show
change in dipole moment during vibration. Consequently, these do not exhibit IR spectra
(IR Inactive).
The hetero- nuclear diatomic / polyatomic molecules like HCl, BeCl2, NH3, CH4, CO2,
C6H6, etc shows change in dipole moment and thus they exhibit IR spectra (IR Active).
 Criteria for A compound to Absorb IR Radiation

1.Correct Wavelength of Radiation.

A molecule to absorb IR radiation, the natural frequency of vibration of some part of a
molecule is same as the frequency of incident radiation.
i,.e The natural frequency of vibration of the molecule must equal the frequency of the
incident radiation

2. Change in Dipole Moment

A molecule can only absorb IR radiation when its absorption cause a change in its electric
dipole.
A bond or molecule must have a permanent dipole moment. If not, then, some of its
vibration must produce an induced dipole moment in order to have an absorbance in the
IR spectrum
 Types /Modes of Vibrations
There are two types of molecular vibrations. (a) Stretching and (b) Bending
Note that it takes more energy to stretch a spring then to bend it; hence, stretching
vibrations appear at a higher frequency as compared to the bending vibrations.

(a)Stretching Vibrations:
In this type of vibrations, the inter-atomic distance between the atoms increases or
decreases but the atoms remain in the same bond axis.
Stretching can be of two types: (i) Symmetric (ii) Asymmetric
(i) Symmetric stretching: In symmetric stretching, the movement of the atoms
with respect to a particular atom is in the same direction.
(ii) Asymmetric stretching: In these vibrations, one atom approaches the central
atom and the other departs from it.

Symmetric stretching Asymmetric stretching

b) Bending vibrations:
In these types of vibrations, the position of the atom changes with respect to the
original bond axis but the distance between the atoms remains constant.
Bending vibrations are of two types.

(i) In-plane bending vibrations:

In this type, the atoms remain in the same plane as the nodal plane of the system.
These, also, are of two types.

Scissoring: In this type, the two atoms approach each other and move away like the
two arms of a scissors .

Rocking In this type, both the atoms move in the same direction.
.

Scissoring Rocking
(ii) Out-of-plane bending vibrations:
In this type, the atoms move out of the nodal plane with respect to the central atom that
results in change in bond angle between bonds. These, also, are of two types.

Wagging: In this type, both the atoms swing up and down with respect to the central
atom.

Twisting: In this type, one atom moves up the plane and the other moves down the plane
with respect to the central atom.

Wagging Twisting

Note:
In a rocking, wagging or twisting coordinate, the bond lengths within the groups
involved do not change but the angles change.
Rocking is distinguished from wagging by the fact that the atoms in the group stay in the
same plane.
 Stretching and Bending Vibrations of H2O Molecule
Water molecule has non – linear structure. It has three fundamental vibrational modes
which are corresponding to the frequencies 3652 cm – 1 (Symmetric stretching
vibration), 3756 cm – 1 (Asymmetric stretching vibration) and 1596 cm – 1 (Bending
vibration) respectively. All the three vibrations are IR active and giving IR spectra at
various frequencies
 Stretching and Bending Vibrations of CO2 Molecule
Carbon dioxide molecule has linear structure and has four fundamental vibrational modes which
are corresponding to the frequencies 1340 cm – 1 (Symmetric stretching vibration), 2350 cm –
1 (Asymmetric stretching vibration) and twice 666 cm – 1 (In plane bending vibration and Out of

plane bending vibration) respectively.

In symmetrical stretching, both bonds are shortened or elongated to the same extent. Hence there
is no change in dipole moment. So it is IR inactive.
In asymmetrical stretching, one of the bonds is shortened and the other is elongated. Hence there
is change in bond length and dipole moment. So it is IR active.
In bending, both in-plane and out of plane bending involves variation of bond angle. Hence there
is change in bond angle and dipole moment. So it is IR active.
 Number of Fundamental Vibrations for Polyatomic Molecules
If an atom moving in a three-dimensional space, three coordinates (x, y, z) are adequate
to explain the motion of a particle is; so its degree of freedom is three but its motion is
purely translational.
If a molecule is made of N atoms or ions, the degree of freedom becomes 3N ( because
each atom has three degrees of freedom), but these atoms are bonded together, all motions
are not translational; some become rotational and others vibrational.

i.e 3N = Translational Modes + Rotational Modes + Vibrational Mode

For non-linear molecules: all rotational motions can be described in terms of rotations
around three axes, hence, it possesses 3N − 6 degrees of freedom for normal vibrational
motion.
Total degree of freedom = 3N
Translational degree of freedom = 3
Rotational degree of freedom = 3
Therefore, Vibrational degree of freedom = 3N – 3 – 3 = 3N – 6
Hence, number of fundamental bands for non-linear molecules = 3N – 6
W here N = number of atoms in a molecule.
 Solved Problems on Non-Linear Molecules
Calculate the theoretical number of vibrational degrees of freedom in the following:
(a) C6H6 is a non-linear molecule where n = 12 (6C + 6H)
Vibrational degree of freedom = 3n – 6 = 3 × 12 – 6 = 30

(b) H2O is a non-linear molecule with n = 3

Vibrational degree of freedom = 3n-6 = 3 × 3 – 6 = 3

(c) SO2 is a non-linear molecule with n = 3

Vibrational degree of freedom = 3n – 6 = 3 × 3 – 6 = 3

(d) N2O is a non-linear molecule with n = 3

Vibrational degree of freedom = 3n – 6 = 3 × 3 – 6 = 3

(e) NH3 is a non-linear molecule with n = 4

Vibrational degree of freedom = 3n-6 = 3 × 4 – 6 = 6

(f) CH4 is a non-linear molecule with n = 5

Vibrational degree of freedom = 3n-6 = 3 × 5 – 6 = 9
 For a linear molecule:
Rotation about the axis of linearity does not bring about any change in the position of
atoms while rotation about the other two axes, changes the position of the atoms. Hence,
linear molecule has two degrees of rotation and possesses 3N-5 degree of freedom for
vibration.
Total degree of freedom = 3N
Translational degree of freedom = 3
Rotational degree of freedom = 2
Vibrational degree of freedom = 3N – 3 – 2 = 3N – 5
Hence, Number of fundamental vibrational modes for a linear molecule = 3N − 5
where N = number of atoms in a molecule.
Solved Problems on Linear Molecules
Calculate the theoretical number of vibrational degrees of freedom in the following:
(a) C2H2 is a linear molecule where n = 4 (2C + 2H)
Vibrational degree of freedom = 3n – 5 = 3 × 4 – 5 = 7
(b) CO is a linear molecule with n = 2, Vibrational degree of freedom = 3n-2 = 3 × 2 – 5 = 1
(c) HCl is a linear molecule with n = 2, Vibrational degree of freedom =3n – 5= 3×2 – 5 = 1
(d) CO2 is a linear molecule with n = 3, Vibrational degree of freedom = 3n – 5= 3×3–5 = 4
 Instrumentation in IR Spectroscopy

Block Diagram of an IR Spectrophotometer

The instrument consists of the following.

(i) Light source: Infrared radiations are produced by electrically heating Globar or a
Nernst filament to 1000–1800°C. Globar is a rod of silicon carbide, whereas the Nernst
filament is a high resistance element composed of sintered oxides of zirconium, cerium
and thorium.
(ii) Filter or monochromator: A monochromator separates the polychromatic source to
radiation into suitable wavelength.
 Optical prisms or Diffraction gratings are used to obtain monochromatic light. Prisms
are made of sodium chloride or alkali metal halides.
 Light reflected from the grating is diffracted to get the light of specific wavelength and
splits into two beams of equal intensity.
 Then one beam is passed through the sample to be examined and other through the
reference.
(iii) Sample holder: Cells are made of NaCl or alkali metal halides as they do not absorb
IR radiations. Solid samples are ground with KBr and made into a disc. The sample
should be absolutely dry as water absorbs strongly in the IR region. Solvents used for
IR are chloroform, carbon tetrachloride, carbon disulphide, etc.

(iv) Detectors: Thermocouple based detectors are used. Light from the source is split into
beams, one of which passes through the sample and the other through the reference. The
beam on passing through the sample becomes less intense. There is a difference in
intensity of the two beams. This is detected and recorded and an IR spectrum is
obtained.

It is important to note here that IR light is absorbed only when the dipole moment of the
molecule is different in the two vibrational levels and the oscillating dipole moment due to
molecular vibrations interacts with the oscillating electric vector of the infrared beam.
 Sample Preparation for IR Spectroscopy Study

Sampling of solid can be done by :

a) Solid run in solution: solid substance is dissolved in non-aqueous solvent. A drop of
solution is placed on the disc of alkali halide. Solvent is dried to give thin film on
surface.

b) Solid film technique – used for amorphous solid, sample is deposited on KBr or NaCl
cell by evaporation of solution from solid.

c) Pressed pallet technique – sample is finally ground with KBr and pressed to pellet.

d) Mull technique - Sample is mixed with Nujol (mineral oil) and mulled to make fine
paste. A thin film is applied on KBr pellet.

Sampling of liquids – Liquid sample can be sandwiched using sample cells of KBr and
NaCl

Sampling of gases – Sample cells made of KBr or NaCl can be used for the purpose.
 Regions of IR Spectrum
Infrared spectrum is usually studied under two regions
(a) Functional group region (4000 – 1500 cm–1)
The higher frequency region 4000 – 1500 cm–1 is called the functional group region. The
characteristic stretching frequencies of all the important functional groups such as OH,
NH2, C O, etc., lie in this region.

(b) Finger print region (1500 – 667 cm–1)

The region below 1500 cm–1 (1500–667 cm–1) is rich in absorptions caused by bending
vibrations and those resulting from the stretching vibrations of C—C, C—O and C—N
bonds. These bands are unique to an organic compound just like finger prints are
characteristic to an individual. Hence, this region is termed as the fingerprint region.
 Applications of IR Spectroscopy

1. Determination of functional groups: Most of the functional groups have

characteristic IR absorption frequencies., therefore functional group present in
unknown compound can be identified.
2. Determination of Purity of Sample: Whenever a compound has an impurity,
reduction in the sharpness of individual bands, appearance of extra bands and a
general blurrd appearance of the spectrum is observed. IR spectroscopy method of
detection of impurities is used for quality control of many chemicals or drugs.
3. Study of kinetics of a chemical reaction: Majority of the organic reactions involve
changes in functional groups. IR Spectroscopy is very useful in following the
progress of such reactions.
Cyclohexanol  Cyclohexanone
Alcohol group Ketone group
(-OH) 3550 cm-1 (C=O) 1710 cm-1

4. Study of Hydrogen bonding: Hydrogen bonding decreases the frequency of

absorption. Stronger the hydrogen bonding, greater is the shift in frequency of IR
absorption.
Aliphatic – OH free – 3650 cm-1
Aliphatic –OH hydrogen bonded – 3350 cm-1
5. Shape of symmetry of a molecule: IR spectroscopy is used to deduce the shape or
symmetry of a molecule. For example NO2 molecule gives three peaks at 750 cm-1 , 1323
cm-1 and 1616 cm-1 . The formula for non linear molecule is 3n-6 also predicts three
fundamental vibration. This proves that NO2 is a bent molecule and not a linear molecule
which should give four peaks according to the formula for linear molecules 3n-5.

6. Geometrical Isomers can be distinguished by their IR spectra.

Trans isomers are more symmetric than Cis isomers. Hence the trans-isomer has little
change in dipole moment in the presence of IR radiation and shows a simpler spectrum
than the cis-isomer. This characteristic property led to their easy identification.