Infrared (IR) Spectroscopy

Navaneetha Krishnan J
Asst. Prof. (Biotech)
Introduction
• Infrared light is part of the electromagnetic spectrum between visible light and
microwaves, with wavelengths ranging from 780 nm to 1 mm.
• Infrared Spectroscopy generally refers to the analysis of the interaction of a molecule
with infrared light.
• IR spectroscopy (which is short for infrared 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 is one of the most common and widely used spectroscopic techniques
employed mainly by inorganic and organic chemists due to its usefulness in determining
structures of compounds and identifying them.
• Wavenumbers tell us the number of wavelengths per unit distance and are given in units
of cm-1.
• Light with shorter wavelengths and higher energy will have a larger wavenumber, while
light that has longer wavelengths will have lower energy and wavenumbers.
Categories of IR radiations

Near IR waves; Mid IR waves and Far IR waves

Categories of IR radiations
Wave number in IR spectroscopy
• The reciprocal centimeter is the number of wave cycles in one centimeter; whereas,
frequency in cycles per second or Hz is equal to the number of wave cycles in 3*1010 cm
(the distance covered by light in one second).
 Different types of vibrations in IR spectroscopy

• The atoms in chemical compounds are constantly moving and vibrating in different ways.
• Even in a simple molecule like water there are six different ways the molecule can vibrate: the
symmetric stretch, the antisymmetric stretch, the deformation or bending vibration, rocking,
twisting, and wagging.
Principle of IR spectroscopy
• Atom size, bond length and bond strength vary in molecules and so the frequency at which a
particular bond absorbs infrared radiation will be different over a range of bonds and modes of
vibration.
• When a molecule absorbs infrared light, it undergoes a spectroscopic transition from a lower to
an upper vibrational energy level.
• Mid-infrared is energetic enough to excite molecular vibrations to higher energy levels.
• Not all the atomic bonds can absorb IR. The bonds accompanied by a change in dipole moment
are only IR active. E.g. polar molecules like water, HCl.
• Measuring the absorption of infrared radiation by a material provides very useful information
about structure.
• The frequency for a particular bond is more or less independent of other bonds in the
compound; therefore, determination of the frequencies in the infrared region which are absorbed
by a compound gives information about the types of bonds which are present.

The dipole moment is a measure of charge asymmetry. Polar bonds such as O–H and C=O have large charge asymmetry and
hence large dipole moments. Covalent bonds like C–C single bonds have little charge separation and hence small dipole
moments.
• Since no two organic compounds have the same IR spectrum, a compound can be identified with
certainty by comparing its spectrum with that of a known pure compound. If they are identical,
then they are one and the same.
• An infrared spectrometer analyses a compound by passing infrared radiation, over a range of
different frequencies, through a sample and measuring the absorptions made by each type of
bond in the compound. This produces a spectrum, normally a ‘plot’ of % transmittance against
wavenumber.
 Functional regions vs Fingerprint regions
• The functional group region runs from 4000 cm-1lto 1450 cm-1, and the fingerprint region
from 1450 cm-1lto 500 cm-1.
• The functional group region contains relatively few peaks. These are typically associated
with the stretching vibrations of functional groups.
• In the fingerprint region, the spectra usually consist of bending vibrations within the
molecule. The pattern of peaks is more complicated, and it is much more difficult to pick
out individual bonds in this region.
• The fingerprint region is important because each different compound produces its own
unique pattern of peaks (like a fingerprint) in this region.
Characteristic infrared absorptions of functional groups
Types of IR spectrometers
There are four types of instruments for infrared absorption measurements
available:
1. Dispersive grating spectrophotometers for qualitative measurements
2. Nondispersive photometers for quantitative determination of organic
species in the atmosphere
3. Reflectance photometers for analysis of solids
4. Fourier transform infrared (FT-IR) instruments for both qualitative and
quantitative measurements.
 IR spectrometer - Instrumentation
The main parts of the IR spectrometer (dispersive type) include:
1. IR radiation source
2. Sample container
3. Beam chopper/splitter
4. Monochromator
5. Detector
6. Recorder
1. IR Light source
• Infrared sources consist of an inert solid that is electrically heated to a temperature between 1,200 and
1,500 ̊ C. The heated material will then emit infra red radiation.
• E.g. Nernst glower, Globar source, Nichrome coil, Carbon dioxide laser
• A globar is a rod of silicon carbide (5 mm diameter, 50 mm long) which is electrically heated to about 1200 ̊
C.
2. Samples/Sample handling
• Preparing solid samples often involves creating pellets or thin films. When making pellets, the sample is
typically ground into a fine powder and mixed with a non-absorbing medium like potassium bromide
(KBr).
• The mixture is then pressed under high pressure to form a transparent pellet through which the IR beam can
pass.
• Liquids are generally placed in specially designed IR cells or cuvettes made from materials like calcium
fluoride or barium fluoride, which do not absorb IR radiation.
• Samples that are liquid at room temperature are usually analysed in pure form or in solution. The most
common solvents are Carbon Tetrachloride (CCl4) and Carbon Disulfide (CS2).
• The spectrum of a gas can be obtained by permitting the sample to expand into an evacuated cell, also
called a cuvette.
• Analyzing gasses with IR spectroscopy requires cells with much longer path lengths than those for liquids
or solids. This is because gasses at standard pressure and temperature have lower molecular densities.
 Nernst glower

Globar source

Pelleting assembly for solid samples

3. Beam chopper / splitter:
• It reflects or transmits the sample beams alternately into the monochromator.
• The reference and sample beams are alternately focused on the detector for optical
comparison of transmitted light of reference and sample.
4. Monochromator
• The monochromator is a device that is used to disperse or separate a broad spectrum of IR
radiation into individual narrow IR frequencies.
• After the incident radiation travels through the sample species, the emitted wavefront of
radiation is dispersed by a monochromator (gratings and slits) into its component
frequencies.
• A combination of prisms or gratings with variable-slit mechanisms, mirrors, and filters
comprise the dispersive system.
• Narrower slits give better resolution by distinguishing more closely spaced frequencies of
radiation and wider slits allow more light to reach the detector and provide better system
sensitivity.
5. Detector
• Detectors are devices that are used to convert the analog spectral output into an
electrical signal.
• The detector in an IR spectrometer captures the IR radiation that has interacted with the
sample.
• The detectors can be classified into three categories, thermal detectors, pyroelectric
detectors and photo-conducting detectors each with varying sensitivity and response
times.
6. Recorder
• A recorder is used to record the IR spectrum. The electrical signals generated by detector
are further processed by the computer using a mathematical algorithm into a final
spectrum.
Infrared Spectrum
• The infrared spectrum is used to identify structures of many organic and inorganic molecules
because functional groups give rise to characteristic bands both in terms of intensity and
frequency or wavelength.
• The spectrum diagram for 2-hexanone is given below the picture:
Fourier transform infrared spectrometer (FTIR)
• An FTIR instrument uses an interferometer, which consists of a source, beam splitter, two
mirrors, a laser and a detector.
• Interferometer is used to identify samples by producing an optical signal with all the IR
frequencies encoded into it.
• The resulting interference waveform, called an “interferogram”, produced by the FT
instrument encodes all the information across all the wavelengths measured.
• Utilizing the Fourier Transform technique, they convert the interferogram obtained from the
IR radiation into a detailed spectrum.
• FTIR spectrometers are renowned for their efficiency and accuracy.
• These spectrometers are known for their rapid scanning capabilities, high signal-to-noise
ratio, and ability to collect spectral data across a wide range simultaneously.
• FTIR spectrometers are versatile, suitable for analyzing gasses, liquids, and solids, and are
used in applications ranging from chemical identification to environmental monitoring
and pharmaceutical quality control.
Interferometer
Applications of IR spectroscopy
1. Identification of organic compounds: The identity of organic compounds can be
established from the fingerprint region. If the fingerprint region of an unknown
compound exactly matches the fingerprint region of the known compounds, the
identity of the compound is confirmed.
2. Analysis of functional groups: Different functional groups produce different IR
absorption bands. As a result, IR spectra can be used to identify functional groups.
3. Conformational analysis: This technique is quite useful in determining the relative
stability of various conformations of cyclic compounds.
4. Food Quality Control: In the food industry, IR spectroscopy is used to detect
contaminants, analyze nutritional components, and monitor changes during food
processing.
Applications of IR spectroscopy……

5. Environmental Analysis: IR spectroscopy is pivotal in assessing the impact of

industrial activities on the environment. It enables the detection of greenhouse gases
and the monitoring of air and water pollution levels.
6. Pharmaceutical industries: Beyond basic identification and quantification, IR
spectroscopy is instrumental in understanding the interactions and stability of
different pharmaceutical compounds.
7. Forensic science: The technique can be used in forensic science to identify
polymer degradation and determine the blood alcohol content of a suspected drunk
vehicle driver. It's used to analyze paint chips, plastic fragments, and other trace
evidence, providing crucial information that can link suspects to crime scenes.
FTIR spectrometer and IR microscope