Infrared Spectroscopy
Infrared Spectroscopy
• The study of the interaction of electromagnetic radiation with
vibrational or rotational resonances (i.e., the harmonic
oscillations associated with the stretching or bending of the
bond) within a molecular structure is termed infrared
spectroscopy.
• Almost any compound having covalent bonds, whether organic or
inorganic, absorbs various frequencies of electromagnetic
radiation in the infrared region of the electromagnetic spectrum.
• This region lies at wavelengths : 800 nm to 1 mm.
• For chemical purposes, we are interested in the vibrational
portion of the infrared region. It includes radiation with
wavelengths (λ) between 2.5 µm and 25 µm (1 µm = 10−6 m).
The IR Absorption Process
• Molecules are excited to a higher energy state when they absorb
infrared radiation. The absorption of infrared radiation is, like
other absorption processes, a quantized process.
• In the absorption process, those frequencies of infrared radiation
that match the natural vibrational frequencies of the molecule in
question are absorbed, and the energy absorbed serves to
increase the amplitude of the vibrational motions of the bonds
in the molecule.
• Note, that not all bonds in a molecule are capable of absorbing
infrared energy, even if the frequency of the radiation exactly
matches that of the bond motion. Only those bonds that have a
dipole moment that changes as a function of time are capable of
absorbing infrared radiation.
• Symmetric bonds, such as those of H2 or Cl2, do not absorb infrared
radiation. A bond must present an electrical dipole that is changing at
the same frequency as the incoming radiation for energy to be
transferred. The changing electrical dipole of the bond can then
couple with the sinusoidally changing electromagnetic field of the
incoming radiation. Thus, a symmetric bond that has identical or
nearly identical groups on each end will not absorb in the infrared.
• For the purposes of an organic chemist, the bonds most likely to be
affected by this restraint are those of symmetric or pseudosymmetric
alkenes (C=C) and alkynes (C Ξ C).
Molecular vibrations
• The positions of atoms in a molecule are not
fixed; they are subject to a number of different
vibrations. Vibrations fall into the two main
categories of stretching and bending.
Stretching
• In this type of vibration, the distance between the two
atoms increases or decreases but the atoms remain in
the same bond axis.
• Stretching vibrations are two types-
• Symmetric stretching: In this type, the movement of
the atoms with respect a particular atom in a molecule
is in the same plane.
• Asymmetric stretching: In this type, one of the atom
moves toward the central atom while the other moves
away from it.
Bending
• In this type of vibration, the position of the atoms
changes with respect to the original bond axis.
• Bending vibrations are four types-
Rocking: Movement of the atoms takes place in the
same direction.
Scissoring: Two atoms move toward and away from
each other.
Wagging: two atoms move up and below the plane
with respect to the central atom.
Twisting: One of the atoms moves up the plane,
while the other moves down the plane with respect
to the central atom.
Dispersive infrared spectrophotometer
• Dispersive IR spectrophotometer consists of
the following parts.
a) Radiation source
b) Sample compartment
c) Monochromator
d) Detector
e) Recorder
Radiation source
• An inert solid is electrically heated to a temperature in the range
1500-2000 K. The heated material will then emit infrared
radiation.
Sample compartment
• After preparation of the sample (solid, liquid or gas), it is
inserted into a holder and then placed in the sample
compartment in the path of the IR beam. For solutions, a
reference cell is needed that contain solvent only. After
passing through the sample and reference, the beams are
chopped by a mirror which focuses each beam alternately
into the entrance slit of the monochromator.
• Glass and plastics absorb strongly throughout the IR region
of the spectrum. Thus cells are constructed by ionic
substances like-
– Sodium chloride
– Potassium bromide
• 3. Monochromator: A monochromator selects
specific frequency from other extraneous
radiation using either a prism or a diffraction
grating.
• 4. Detector: The detector senses the difference
and determines which frequencies have been
absorb by the sample and which frequencies
remain unaffected and send a signal which is
amplified by an amplifier.
Recorder
The amplified detector signal is recorded as % of
transmitted light vs. frequency on a chart.
Preparation of sample
• IR spectra may be obtained from all phases:
solid, liquid and gaseous.
• Vapor or gaseous phase: The vapor or gas is
introduced into a special cell usually about
10cm long which is then placed directly in the
path of one of the infrared beams. The end
walls of the cell are usually made of sodium
chloride which is transparent to infrared from
4000 to 650 cm-1.
• Liquids: The liquids are usually examined as a
thin film sandwiched between two polished
salt plates made of NaCl or KBr. The pair of
plates is inserted in a holder which is then
placed in the path of the IR beam. It is the
simplest of all procedures. KBr is transparent
throughout the 4000 to 400 cm-1.
Solids
• Three methods are commonly used for preparing a solid
sample for measurement of IR absorption.
• a) KBr disc: About 1mg of the sample is finely ground with
about 300mg of KBr in a mortar. The mixture is pressed
into a disk using a special mould and hydraulic press. Under
pressure KBr melts and seals the compound into a matrix
and form a KBr disk. The KBr disk can be inserted into a
holder which is then placed in the spectrophotometer.
• b) As Nujol mull (in the form of suspension): About 1mg of
the sample is finely ground in a mortar with a drop of
nujol mull. The mull is then placed between flat plates of
NaCl.
• c) In solution: The compound is dissolved to give a 1-5%
solution in CCl4 or CHCl3. The solution is introduced into a
special NaCl cell. A second cell of equal thickness but
containing pure solvent is placed in the path of the other
beam of the spectrometer in order to cancel the solvent
absorption. For aqueous solutions, special calcium fluoride
cells are used
Application 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.
2. Identification of substances
• Each atom of the molecule is connected by
bond and each bond requires different IR
region so characteristic peaks are observed. It
contains a very complicated series of
absorptions. These are mainly due to all
manner of bending vibrations within the
molecule. This region of IR spectrum is called
as finger print region of the molecule.
Identification of a compound can be revealed
by comparing its finger print region with the
spectra of authentic sample with identical
conditions.
• 3. 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.
• 4. Quantitative analysis
• The quantity of the substance can be
determined either in pure form or as a mixture
of two or more compounds.