IR Spectroscopy

Content

• Introduction
• Principle
• Types of Vibrations
• Instrumentation
• Application of IR Spectroscopy
• Infrared spectroscopy is the measurement of the interaction of IR radiation with
compounds.
Introduction
• IR region involves the range between region 4000-400 cm-1 (780nm to 1mm)
• IR radiation causes the excitation of molecules from lower to higher vibrational
levels.
• Near IR (780-1.4µm), Mid IR (1.4-3µm) and far IR (3µm-1mm)
• It is basically used in identification of compound by determining its structure and
functional groups
 Principle

• When IR Spectra radiation passed through a IR active compounds. The

compounds absorb the IR radiation when the frequency of IR is the same as the
vibrational frequency of the compound and get excited.
• Every bond or portion of a molecule or functional group requires different
frequency for absorption.
 Types of vibrations

• There are different types of vibrations:

Vibrations

Stretching Bending

Symmetric Asymmetric In-plane Out-plane

scissoring Rocking Wagging Twisting

• Stretching:
In this, the distance between the two atoms increases or decreases but in the same axis.
They further divide into two types:
1. Symmetric: Movement of atoms are in same direction.

2. Asymmetric: Movement of atoms are in opposite direction.

• Bending(Deformation):
- In this, position of atoms changes with respect to the original bond axis.
- Stretching absorption of a bond appears at higher frequencies than the bending absorption.
- They further divide into two types:
1. In-plane bending: In-plane comprises the scissoring and rocking vibrations.
a) Scissoring: Two atoms approaches each other.
b) Rocking: Movement of atoms in same direction in same plane.
2. Out-plane bending: Out-plane comprises the wagging and twisting.
a) Wagging: In this, two atoms move up and down the plane with respect to the central atom.

b) Twisting: In this, one atom moves up the plane and the other moves down with respect to the
central atoms.(3)
Reference
 Instrumentation

• The main parts of the IR spectrometer are as follows:

1. Radiation source
2. Sample cells and sampling of substances
3. Monochromators
4. Detectors
5. Recorder
1. Radiation Sources
• IR instruments require a source of radiant energy which emits IR radiation which
must be steady, intense enough for detection, and extend over the desired wavelength.
• Various sources of IR radiations are as follows.
1. Nernst glower
2. Incandescent lamp
3. Mercury arc
4. Tungsten lamp
5. Nichrome wire
2. Sample cells and sampling of substances:
• IR spectroscopy has been used for the characterization of solid, liquid, or gas samples.
i. Solid – Various techniques are used for preparing solid samples such as pressed
pellet technique, solid run in solution, solid films, mull technique, etc.
ii. Liquid – Samples can be held using a liquid sample cell made of alkali halides.
Aqueous solvents cannot be used as they will dissolve alkali halides. Only organic
solvents like chloroform can be used.
iii. Gas– Sampling of gas is similar to the sampling of liquids.
3. Monochromators:
 Various types of monochromators are prism, gratings filters.
 Prisms are made of Potassium bromide, Sodium chloride or Caesium iodide.
 Filters are made up of Lithium Fluoride and Diffraction gratings are made up of alkali
halides.
4. Detectors:
• Detectors are used to measure the intensity of unabsorbed infrared radiation.
• Detectors like thermocouples, Bolometers, thermistors, Golay cell, and pyro-electric
detectors are used.

5. Recorders:
• Recorders are used to record the IR spectrum.
• A thermocouple is a type of thermal detector that places two
different metals (e.g. bismuth and antimony together). When
the metals are heated by IR radiation, a small voltage,
proportional to the temperature at the junction between the 2
metals, is sent out (the Peltier effect).
• A bolometer is a thermal infrared detector. In order to obtain
significant heating it must be thermally insulated from its heat
sink (typically the substrate) by a support having a low thermal
conductance G.
• Thermistor bolometers are fast, sensitive infrared detectors
with good responsivity from 1 to 15 microns. The detectors
consist of a thin flake of thermistor material mounted on a
thermal sink. The time constant of the detectors is determined
by the type of thermal sink on which the flakes are mounted.
• The Golay cell detector consists of a small metal cylinder enclosed by a rigid metal plate.
• Separated by a flexible membrane or diaphragm, the chamber encloses an IR-active gas
on one side and an LED light source (focused on the membrane) on the other.
• When the IR radiation falls on the chamber, the gas absorbs the radiation and expands
due to the heat generated.
• The resultant increase in the pressure causes the diaphragm to deform.
• The LED light focusing on the membrane deflects and the beam gets reflected toward
the photodiode array detector.
• The fraction of the beam reaching the photodiode depends on the curvature of the
flexible membrane which in turn depends on the IR radiation absorbed by the gas and
which in turn depends on the IR radiation that has reached the detector.
• Golay cell detector can be used in the far IR region where the radiation energy is less.
Golay cell
 Applications:
• It has been of great significance to scientific researchers in many fields such as:
• Protein characterization
• Space exploration.
• Analysis of gaseous, liquid or solid samples
• Identification of compounds
• Quantitative analysis(5)