Infrared Spectroscopy
Dr. Roli Verma
HoD, Chemistry
JSS Academy of Technical Education,
Noida
Infrared Spectroscopy
Infrared Spectroscopy
• Total = Electronic energy + Vibrational
Energy of molecule
energy + Rotational energy.
• IR spectroscopy is concerned with the study of
absorption of infrared radiation, which causes
vibrational transitions in the molecule.
• Hence ,IR spectroscopy also known as
VIBRATIONAL SPECTROSCOPY
Energy levels for a molecule. Possible transitions that occur:
(A): Pure rotational Transitions,
(B) rotational-Vibrational Transitions,
(C) Rotational-Vibrational-Electronic Transitions
Infrared Region
• Infrared spectroscopy can be rationalized as the spectroscopy that
deals with electromagnetic radiation of infrared frequency. As
previously explained, there are three well defined infrared regions;
each of them has the potential to provide different
• information:
• Far-Infrared (400-33 cm-1): vibrations of molecules containing heavy
atoms, molecular skeleton vibrations and crystal lattice vibrations
• Mid-Infrared (4000-400 cm-1): useful for organic analysis
• Near Infrared (12820-4000 cm-1): overtones; very useful for
quantitative analysis
• Infrared spectroscopy is one of the most useful and widely used
methods to perform structural analysis.
Finger Print Region
Principle of IR Spectroscopy
Types of Vibrations
Bending Vibrations
How to calculate Wave Number??
• Since an IR spectrum is a plot of % transmittance vs. wave number,
the bond vibration energies vary as you move horizontally on the graph.
Thus, the horizontal position of the absorption band corresponds to a
different energy.
• The strength of the bond and the masses of the bonded atoms are crucial
in determining the stretching energy.
• The best way to understand the following concepts is to imagine two
atoms connected by a spring. Imagine you have your bonded atoms – the
stronger the bond is, the tighter the spring, and the more energy is
required to stretch it.
• For example, triple bonds are stronger than double bonds which are in
turn stronger than single bonds.
• Moreover, the lighter the atoms are, the more energy is required to
vibrate the atoms.
•
• Shows the relationship of bond strength and
atomic mass to the wave- number at which a
molecule will absorb IR radiation.
•As the force constant increases, the vibrational
frequency (wavenumber) also increases.
•The force constants for bonds are:
As the mass of the atoms increases, the vibration
frequency decreases.
•The region of an IR spectrum where bond
stretching vibrations are seen depends primarily
on whether the bonds are single, double, or triple
or bonds to hydrogen.
• Each molecule has a different number of fundamental
vibrations depending on the number of atoms in the
molecule. These represent the different ways in which the
molecule can have its bonds stretched or bent. All
stretching or bending modes have a certain associated
energy or frequency in the usual ground state. When a
photon of infrared light is absorbed whose energy is equal
to the difference between the ground state and the first
excited state, then this is a fundamental absorption. Energy
is absorbed only when the particular vibration mode
involves a changing dipole moment during the vibration.
Fundamental Vibrations
• Molecules of n atoms will have 3n degrees of
freedom.
• Since its atoms may have its movement resolved
along x, y and z axes.
• Movement of the whole molecule as a rigid unit will
take up six of these degrees of freedom, three
translational and three rotational
(two rotational in the case of linear molecules).
•So, for vibrational motions where atoms move relative
to each other, we have 3n-6
(3n-5 for linear molecules) fundamental vibrations
•(vibrations responsible for number of theoretically
expected absorption bands in IR).
• H 2O
• Three atoms (non-linear). due to the uneven distribution of the electron
density. O2 is more electronegative than H2 and carries a negative charge,
while H has a partial positive charge.
• degrees of freedom 3 X 3= 9
• 3n-6 (fundamental vibrations).
• 9 - 6 = 3 (fundamental vibrations). which correspond to the following
stretching and bending vibrations. The vibrational modes are illustrated
below:
The vibrational modes of H2O
CO2
• CO2 is a linear molecule and thus has the formula (3N-5). It has 4 modes
of vibration (3(3)-5).
• The CO2 symmetric stretch is not IR active because there is no change in
dipole moment because the net dipole moments are in opposite
directions and as a result, they cancel each other. In the asymmetric
stretch, O atom moves away from the C atom and generates a net change
in dipole moments and hence absorbs IR radiation at 2350 cm-1. The
other IR absorption occurs at 666 cm-1. CO2 symmetry with D∞hD∞h
• CO2 has a total of four of stretching and bending modes but only two are
seen. Two of its bands are degenerate and one of the vibration modes is
symmetric hence it does not cause a dipole moment change because the
polar directions cancel each other. The vibrational modes are illustrated
below:
The vibrational modes of CO2
Factors affecting IR signals
Physical State
APPLICATIONS OF IR SPECTROSCOPY
• Identification of functional groups & structure
elucidation of organic compounds.
• Quantitative analysis of a number of organic compounds.
• Study of covalent bonds in molecules.
• Studying the progress of reactions.
• Detection of impurities in a compound.
• Ratio of cis-trans isomers in a mixture of compounds.
• Shape of symmetry of an inorganic molecule.
• Study the presence of water in a sample.
• Measurement of paints and varnishes.
LIMITATIONS OF IR SPECTROSCOPY
• Cannot determine the molecular weight of the
compound.
• Does not give information about the relative position of
different functional groups in a molecule.
• From the single IR spectrum of an unknown substance,
it is not possible to know whether it is pure compound
or a mixture of compound.
• Sample cells are made of halaogen salts which are
susceptible to moisture.
• Gas samples cannot be analyzed as they lack sensitivity.