INFRARED

SPECTROSCOPY

BY AYESHA SHAHZADI
CONTENTS

• IR spectroscopy
• Regions of IR spectroscopy
• Principle of IR Spectroscopy
• Sample handling
• Source of light
• Vibrational modes
• Instrumentation of IR Spectroscopy
• Graph
• Applications of IR spectroscopy
IR SPECTROSCOPY

• IR spectroscopy deals with the infrared region of the electromagnetic spectrum, i.e. light
having a longer wavelength and a lower frequency than visible light.
• IR Spectroscopy detects frequencies of infrared light that are absorbed by a molecule.
Molecules tend to absorb these specific frequencies of light since they correspond to the
frequency of the vibration of bonds in the molecule.
• The IR spectroscopy concept can generally be analyzed in three ways: by measuring
reflection, emission, and absorption. The major use of infrared spectroscopy is to
determine the functional groups of molecules, relevant to both organic and inorganic
chemistry.
IR SPECTROSCOPY

• An illustration highlighting the different regions that light can be classified into is given
below.
• Light having a longer wavelength and a lower frequency than visible light.
IR SPECTROSCOPY

• The energy required to excite the bonds belonging to a molecule, and to make them
vibrate with more amplitude, occurs in the Infrared region. A bond will only interact with
the electromagnetic infrared radiation, however, if it is polar.
• The change in the vibrational energy leads to another corresponding change in the dipole
moment of the given molecule. The intensity of the absorption depends on the polarity of
the bond. Symmetrical non-polar bonds in N≡N and O=O do not absorb radiation, as they
cannot interact with an electric field.
 REGIONS OF IR SPECTRUM

• The infrared range covers 700-1000 nm (wavelength), or 14,286-12,800 cm-1

(wavenumber)
• The infrared spectrum or IR spectra can be categorized into two main regions, they are
like functional group region and fingerprint region. The functional group will be
identified in the chemical compound, and we all know each individual’s fingerprint is
different.
• The functional group frequency region 3600–1200 cm-1 and the “fingerprint” region
1200–600 cm-1 .
PRINCIPLE OF IR SPECTROSCOPY

• The principle of IR spectroscopy is related to the vibrational & rotational energy of a

molecule. Absorption of IR radiation causes an excitation of molecule from a lower to the
higher vibrational level. Each vibrational level is associated with a number of closely
placed rotational level.
SAMPLE HANDLING

• The term describes the ways in which the sample is transported and handled, both on the
way to the laboratory as well as during the processing stages.
1. Sampling of solids
Various techniques used for preparing solid samples are as follows:
• KBr disc formation
Take about 1-2mg of the solid sample and about 100mg of KBr. Mix thoroughly in a mortar
while grinding with the pestle and pressed (at 5000-10000 psi) into a disc, also known as a
pellet . KBr is optically transparent for the light in the range of IR measurement.
 SAMPLE HANDLING

• Mull formation
• In this technique a small quantity of sample is thoroughly ground in a clean mortar until the powder is
very fine. After grinding, the mulling agent (mineral oil or Nujol) is introduced. IR-transparent salt
plates (5mm in thickness and 25mm in diameter)are used to hold the sample in front of the beam in
order to acquire data.
• The most common mineral oil is Nujol, which is essentially a liquid paraffin based solution.
SAMPLE HANDLING

• Sampling of liquids
• Place a small drop of the compound on one of the KBr plates. Place
the second plate on top and make a quarter turn to obtain a nice even
film. Place the plates into the sample holder and run a spectrum.
• 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.
SOURCES OF LIGHT IN IR SPECTROSCOPY

The common radiation source for the IR spectrometer is an inert solid heated
electrically to 1000 to 1800 °C. Three popular types of sources are Nernst
filament (constructed of rare-earth oxides), Globar (constructed of silicon
carbide and Nichrome coil.
• Nernst glower is a cylindrical rod or tube composed of rare earth oxides such
as zirconium oxide(ZrO2), yttrium oxide (Y2O3) and erbium oxide
(Er2O3).Operates best in wavelengths from 2 to 14 micrometers.
• Globar :It’s a silicon carbide rod with a diameter of 5 to 10 mm and a length
of 20 to 50 mm that’s been electrically heated to 1,000 to 1,650°C (1,830 to
3,000 degrees Fahrenheit).The wavelength range of the emitted radiation is
from 1 to 50 µm.
 VIBRATIONAL MODES

• In general, a non-linear molecule with N atoms has 3N – 6 normal modes of vibration, but a linear molecule has 3N – 5
modes.

• Molecular vibrations are two types: stretching (that changes the bond length) and bending (that changes the bond angle).

• Stretching : When there is a continuous change in the interatomic distance along the axis of the bond between two atoms.

• Example : Alcohol show stretching in alcohol in O-H bond with frequency of 3200-3600 (broad

• Bending: It is the variation of the angle of the bond caused by a vibration.

• The scissoring mode of the CH2 group gives rise to a characteristic band near 1465 cm−1 in IR and Raman spectra. This
band often overlaps with CH3 antisymmetrical bending in the 1470-1430 cm−1 region.
STRETCHING

• Symmetrical stretching- In this type of stretching,

bond length increase or decrease symmetrically.
• Asymmetrical stretching- In this type of
stretching, length of one bond increases and the
other one decreases.
 BENDING

• Bending vibrations can be either in-plane (as;

scissoring, rocking) or out-of-plane (as; wagging,
twisting).
• Scissoring : The movement of two atoms toward
and away from each other.
• Rocking: The atoms swing back and forth
concerning the central atom of a molecule
BENDING

• Wagging: Two atoms move to same side of plane. They

move up and down the plane.
• Twisting: In this one atom moves above the plane and
other moves below the plane.
 INSTRUMENTATION

• An infrared spectrophotometer is an instrument that passes infrared light through an organic

molecule and produces a spectrum that contains a plot of the amount of light transmitted.
• The basic components of a IR spectrometer include a radiation source, Sample and reference cells,
monochromator, detector and a recorder.
• Source of light :Nernst filament, Globar and Nichrome coil.
• Reference cell: The reference cell is filled with a non-absorbing gas. The detector cell is filled
with the analyte (i.e., carbon monoxide, which has an IR absorption band in the region from 2050-
2250 cm-1). NIST(National Institute of Standards and Technology) provides Standard spectra of
Reference Material for Infrared spectroscopy.
 INSTRUMENTATION

• Monochromator: It is used to disperse or separate a broad

spectrum of IR radiation into individual narrow IR frequencies.
• Detector: Detects the intensity of radiation falling on it. Should
absorb the heat completely from the IR radiation incident on it.
Formed from a very fine metal wire such as platinum, silver,
antimony or bismuth.
INSTRUMENTATION

• Recorder: It records IR-spectrum as a plot of frequency of absorbed radiation and

intensity of absorption in terms of transmittance.
GRAPH

• An IR spectrum can be visualized in a graph of infrared light absorbance (or

transmittance) on the vertical y-axis frequency, wavenumber or wavelength on the
horizontal x-axis. Typical units of wavenumber used in IR spectra are reciprocal
centimeters, with the cm-1
APPLICATIONS OF IR SPECTROSCOPY

1.Identification of functional group and structure elucidation

• Entire IR region is divided into group frequency region and fingerprint region. Range of
group frequency is 4000-1500 cm-1 while that of finger print region is 1500-400 cm-1.
• In group frequency region, the peaks corresponding to different functional groups can be
observed. According to corresponding peaks, functional group can be determined.
• Each atom of the molecule is connected by bond and each bond requires different IR
region so characteristic peaks are observed. This region of IR spectrum is called as finger
print region of the molecule. It can be determined by characteristic peaks.
 APPLICATIONS OF IR SPECTROSCOPY

2. Identification of substances
IR spectroscopy is used to establish whether a given sample of an organic substance is
identical with another or not. This is because large number of absorption bands is
observed in the IR spectra of organic molecules and the probability that any two
compounds will produce identical spectra is almost zero. So if two compounds have
identical IR spectra then both of them must be samples of the same substances.
• IR spectra of two enatiomeric compound are identical. So IR spectroscopy fails to
distinguish between enantiomers.
 APPLICATIONS OF IR SPECTROSCOPY

For example, an IR spectrum of benzaldehyde is observed as follows.

C-H stretching of aromatic ring- 3080 cm -1

C-H stretching of aldehyde- 2860 cm-1
and 2775 cm-1
C=O stretching of an aromatic aldehyde- 1700 cm-1

C=C stretching of an aromatic ring- 1595 cm-1

• C-H bending- 745cm-1

685 cm-1
• No other compound then benzaldehyde produces same IR spectra as shown above.
APPLICATIONS OF IR SPECTROSCOPY

3. Studying the progress of the reaction

• Progress of chemical reaction can be determined by examining the small portion of the reaction
mixture withdrawn from time to time. The rate of disappearance of a characteristic absorption band
of the reactant group and/or the rate of appearance of the characteristic absorption band of the
product group due to formation of product is observed.
4. Detection of impurities
• IR spectrum of the test sample to be determined is compared with the standard compound. If any
additional peaks are observed in the IR spectrum, then it is due to impurities present in the
compound.