Advanced Analytical Techniques

Topic: IR Spectroscopy
Submitted to: Dr. Abdullah Shakir

Submitted by: Muhammad Shafeeq and Tahir

Mushtaq

Roll No: Mphil-11 and 15

1st Semester
Part1:
• By Muhammad Shafeeq
Judges
1. Mphil Roll No=1
2. Mphil Roll No=2
3. Ms Roll No=1
Contents
• What is IR spectroscopy
• Basic Terms
• Principle
• Molecular vibration
• Component of instrument.
• Working of instrument
• Applications
• Advantages
• Disadvantages
Introduction of Spectroscopy
Spectroscopy is the study of the interaction
between matter and radiated energy or
radiation.
IR spectroscopy
Infrared spectroscopy (IR spectroscopy) is the
spectroscopy that deals with the infrared region of
the electromagnetic spectrum, that is light with a
longer wavelength and lower frequency than
visible light.

As with all spectroscopic techniques, it can

be used to identify and study chemicals.
Types of IR region
• The IR regions extends from 0.8μm to 200μm of
wavelength and 12500cm−1 to 100 cm −1 of
frequency.
IR region Wavelength Frequency

Near Infrared 0.8μm to 2.5μm 12500cm−1 to 4000cm−1

Middle Infrared 2.5μm to 15μm 4000cm−1 to 667cm−1

Far Infrared 15μm to 200μm 667cm−1 to 100cm−1

Basic Terms:
• Electric Field:
• An imaginary area around a charge from where it implies a
force on another charge.
• Magnatic Field:
• The change in electric field is
Called magnatic field.
Dipole Moment
• A bond dipole moment is a measure of the polarity of a
chemical bond between two atoms in a molecule. It involves
the concept of electric dipole moment, which is a measure of
the separation of negative and positive charges in a system.
Bond Angel:
• A bond angle is the angle formed between three atoms across
at least two bonds.
• Bond Length:
• The bond length is defined to be the
average distance between the nuclei of two
atoms bonded together in any given molecule.
 Principle of IR
spectroscopy
IR radiation does not have enough energy to
induce electronic transitions as seen with UV.

Absorption of IR is restricted to compounds with

small energy differences in the possible vibrational
and rotational states.

For a molecule to absorb IR, the vibrations or

rotations within a molecule must cause a net
charge in the dipole moment of the molecule.
1. Correct wavelength of radiation
2. Change in dipole moment

The alternating electrical field of the radiation

interacts with fluctuations in the dipole moment of
the molecule.

If the frequency of the radiation matches the

vibrational frequency of the molecule then radiation
will be absorbed , causing a change in the amplitude
of molecular vibration.
Infrared Spectroscopy
The IR Spectroscopic Process
As a covalent bond oscillates – due to the
oscillation of the dipole of the molecule – a
varying electromagnetic field is produced

The greater the dipole moment change through the

vibration, the more intense the EM field that is
Infrared Spectroscopy
The IR Spectroscopic Process
When a wave of infrared light encounters this oscillating
EM field generated by the oscillating dipole of the same
frequency, the two waves couple, and IR light is absorbed

The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer “coupled” wave

EM oscillating wave
from bond vibration
Molecular vibrations

There are 2 types of vibrations:

1. Stretching vibrations
2. Bending vibrations
Stretching vibrations
Vibration or oscillation along the line of bond
Change in bond length
Occurs at higher energy: 4000-1250 cm-1

2 types:
a) Symmetrical stretching
b) Asymmetrical stretching
Symmetrical stretching: 2 bonds
increase or decrease in length
simultaneously.
H
C
H

Asymmetrical stretching: in this, one

bond length is increased and other is
decreased.
H
C
H
Bending vibrations
Vibration or oscillation not along the line of bond
These are also called as deformations
Occurs at low energy: 1400-666 cm-1

2 types:
a) In plane bending: scissoring, rocking
b) Out plane bending: wagging, twisting
Scissoring
This is an in plane blending
2 atoms approach each other H
C
Bond angles are decrease
H

Rocking
Movement of atoms take place in the same
direction.
H
C
H
Wagging
2 atoms move to one side of the plane. They
move up and down the plane.
H
C
H

Twisting
One atom moves above the plane and another
atom moves below the plane.

H
C
H
Infrared Absorption by molecules
 
• Absorption frequency depends on

- Masses of atoms in the bonds

- Geometry of the molecule

- Strength of bond

- Other contributing factors

 What vibrations change the dipole moment of a
molecule?
• Asymmetrical stretching/bending and internal
rotation change the dipole moment of a molecule.
• Asymmetrical stretching/bending are IR active.

• Symmetrical stretching/bending does not. So Not

IR active

• Only vibrations that cause a change in ‘polarity’

(Dipole moment) give rise to bands in IR spectra –
(A dipole moment ​is a measurement of the
separation of two oppositely charged bodies.)
Part2:
• By Tahir Mushtaq
Judges
1. Muzzamil Rani
2. M. Faizan
3. Arshia
 IR Spectrum

•Wavenumber = number of waves of radiation per

centimeter
INSTRUMENTATION AND SAMPLE HANDLING
 INSTRUMENT:

DOUBLE-BEAM IR SPECTROPHOTOMETER:
• A double-beam IR spectrophotometer consists of the same
basic components as the UV/VIS spectrophotometer and
operates in a similar manner.

• Radiation Source → Monochromator → Beam Splitter →

Sample Compartment ( Reference Beam and Sample
Beam) → Detector → Recorder
Ray diagram
 SAMPLING:
• For IR spectral study, the sample can be used in any physical state which
may be:
• Gas : For gas sample, a multiple path cell is used.
• Liquid : A drop of a liquid organic compound is placed between a pair of
polished sodium chloride or potassium bromide plates, referred to as salt
plates. A spectrum determined by this method is referred to as a neat
spectrum since no solvent is used.
• Solid: A solid sample is examined either as a Nujol mull (A mixture of high
boiling paraffinic hydrocarbons) or as a KBr disc. A solid sample can be
examined in as a solution in a suitable solvent.
• Carbon tetrachloride, Carbon disulfide and Chloroform are the most
commonly used solvents for infrared spectral study.
 IR Radiation Source
• IR instruments require a source of radiant energy
which emit IR radiation which must be:
• Nernst: This is composed of a mixture of Zr, Th
and Yt, which is formed in to a hollow rod.

• Globar: This is a bonded Si-C rod.

• When heated electrically to about 1500’C, these

rods emit infrared radiations
 Method:
• A beam of IR is passed through the sample.

• It’s intensity is constantly compared with the intensity of a

reference beam as the wavelength or frequency of the radiation is
varied.

• The spectrophotometer records the result as a spectrum showing

absorbance or transmittance versus wavelength or frequency.
The IR Spectrum:
 Regions/ Parts of IR Spectrum:
There are two region in IR Spectra from which we can
obtained the
information about the quality of molecule .

 The Functional Group region: Identifies the functional

group with the consequence of changing stretching
vibrations. Ranges from 4000 to 1600 cm-1.

 The Fingerprint region: Identifies the exact molecule with

the consequence of changing bending vibrations. Ranges
from 1600 to 625cm-1. 
Functional Group Region:
 Individual/clear peaks are visible
 These peaks are of functional group
 Wave no of each peak is matched with a reference
list
 Majorly stretching vibrations are present
Fingerprint region

 Multiple peaks are visible

 tells us that which molecule is present
 Every component has its fingerprint region
which is compared with spectrum library
 Stretching and bending vibrations
Interpretation of IR spectra:
• An IR spectrum is a plot of per cent transmittance
(or absorbance) against wavenumber (frequency
or wavelength). A typical infrared spectrum is
shown below:
FEATURES OF AN IR
SPECTRUM
• Different types of groups of atoms (C-H, O-H,
N-H, etc…) absorb infrared radiation at different
characteristic wavenumbers.
• No two molecules will give exactly the same IR
spectrum 
Uses of IR spectra

• Identification of functional groups on a molecule

– this is a very important tool in organic
chemistry
• Spectral matching can be done by computer
software and library spectra .
Limitation
• IR does not provide detailed information or proof
of molecular formula or structure. It provides
information on molecular fragments, specifically
functional groups.
• Therefore it is very limited in scope, and must be
used in conjunction with other techniques to
provide a more complete picture of the molecular
structure.