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.
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.