Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
4.1 Optical methods of analysis: Origin of spectra,
interaction of radiation with matter, fundamental laws of
spectroscopy and selection rules, validity of Beer-
Lambert’s law.
4.2 UV Spectroscopy: Types of electronic transitions.
4.3 Infrared spectroscopy: Fundamental and non-
fundamental molecular vibrations; IR absorption
positions of O, N and S containing functional groups; Effect
of H-bonding, conjugation, resonance and ring
size on IR absorptions.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
IR SPECTRA BASIC PRINCIPLES
Absorption of electromagnetic radiation from IR
region ( ranges from 4000- 400 cm-1)
causes stretching and bending vibrations in a
molecule so we call it as vibrational spectra.
IR spectroscopy is based on the interaction
between electromagnetic radiation and a
species with a permanent or induced dipole
moment.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
When a molecule absorbs electromagnetic
radiation in IR region, it undergoes vibrational or a
rotational transitions which causes net change in the
dipole moment in the molecule.- IR active, for example
HCl, CO etc),
if dipole moment does not change in molecules then
they are IR inactive (for example: O2, H2, N2 etc.)
means they do not absorb IR radiation.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
If the frequency of IR radiation matched
with the vibrational frequency of
molecule, then molecule absorbs
radiation.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
FINGERPRINT REGION
The region from 1500-600 cm-1 in IR spectrum is known
as Fingerprint region.
In this region number of bending vibration is more than
the number of stretching
vibration.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
WAVE NUMBER
It is the number of waves per unit distance. Typically, it is
measured using cm-1 and is given by-
IR spectra is plotted wave no on X-axis and %
Transmittance on Y axis
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
FUNDAMENTAL VIBRATION
These vibrations are arising when molecule promoted
from ground state to lower excited state.
The fundamental vibrations for linear and non-linear molecules are
determined by following way:
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
BASICALLY, IN ANY MOLECULE 2 TYPES OF
VIBRATIONS ARE SEEN 1) STRETCHING
2) BENDING
Mahavir Education Trust’s
Shah & AnchorChembur,
Kutchhi Engineering
Mumbai-400088
College
(Affiliated to University of Mumbai)
The fundamental vibrations.
a) Stretching vibration: Distance between two atom increase and
decrease but bond angle remains constant.
Types of stretching vibrations
i) Symmetric stretching vibration: In this case both the atoms
STRETCHED OR COMPRESSED IN THE SAME DIRECTION
ii) Asymmetric stretching vibration: In this vibration one atom
undergoes stretching and other atom undergoes compression
and vice versa.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Bending vibrations: Distance between two atom
remains constant but bond angle changes. These
vibrations can occur either in plane or out of
plane.
Types of bending vibrations
1) In plane bending vibrations:
i) Scissoring: both the atom move towards each
other just like scissor.
ii) Rocking: both the atoms move in same direction,
either in left side
or right side.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
2) Out of plane bending vibrations:
i) Wagging: both the atom move up and down with
respect to central atom.
ii) Twisting: one atom move up and other atom
move down with respect to central atom.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
SYMMETRIC STRECH ASYMMETRIC STRECH TWISTING
SCISORING ROCKING WAGGING
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
The pure vibration spectrum of a diatomic molecule
consists of mainly three signals: an intense signal for the
fundamental vibration, that arise from the transitions
from ground state (v = 0) to the first (v = 1) excited
vibrational level (Fig.3.3). The second is a weak signal for
its first overtone that is observed at roughly double the
frequency of the fundamental band; it is due to the
transitions from ground state (v = 0) to the second (v =
2) excited vibrational level. The third and the weakest
signal is observed at roughly triple the frequency of the
fundamental band; it is due to the transitions from
ground state (v = 0) to the third (v = 3) excited
vibrational level. It is called the second overtone.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
SELECTION RULES
1). A vibration is IR-active if it causes a change in the
molecule's dipole moment
2) The selection rule for vibrational spectroscopy is
Δʋ = ±1, ±2, ±3
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Absorption bands associated with C=O. bond stretching
are usually very strong because a large change in the
dipole takes place in that mode.
3.The rule of mutual exclusion, it states that, for
centrosymmetric molecules (molecules with a center
of symmetry, like carbon dioxide), vibrations that are
IR active are Raman inactive, and vice versa. So for
carbon dioxide there is 1 Raman band and two IR
bands.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Carbon dioxide is linear it has 3n−5=4
vibrations and they are pictured below.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Asymmetric stretch of CO2 occurs at 2350 cm-1
IR active
Bending vibration occurs at 667 cm-1 IR active
since both are degenerate gives one peak.
Thus spectrum of CO2 gives only 2 peaks.
Symmetric stretch does not have change in dipole
of the molecule it is not IR active
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
CS2 is another example like CO2 which has 4 fundamental
vibrations
Draw the asymmetric stretching and bending vibrations of
CS2
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Factor affecting vibrational frequency
Conjugation: As the conjugation increase, stretching
frequency decreases, because force content decrease due
to conjugation.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
b) Inductive effect and resonance effect:
Oxygen is more electronegative than nitrogen, therefore
nitrogen easily donate electron or lone pair of nitrogen
undergoes delocalization with C=O bond. Due to
delocalization double bond of C=O changes into partial
double bond therefore force constant decreases which
decrease the C=O stretching frequency.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Hydrogen bonding:
Intermolecular hydrogen bonding weakens the O-H
bond, thereby shifting
the band to lower frequency. For example, in Phenol
solution O-H stretching is efdfected because of H-
bonding.
vibration of phenol observed in the range from 3400-
3300 cm-1 When solution is diluted then O-H frequency
shifted towards higher frequency at 3600 cm-1
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
In case of methyl salisilate, intramolecular
hydrogen bonding lower
down the stretching frequency of O-H at
3200 cm-1
Intramolecular hydrogen bonding does not
change its frequency even in very dilute
solution
because upon dilution structure of
compound does not change.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Ring strain: As the size of the ring decrease,
vibrational frequency of C=O increase. For example.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Application of IR Spectroscopy
a) Identification of different functional group.
b) Distinction between intermolecular and intra-
molecular hydrogen bonding.
c) Identification of purity of the compound, if
compound is impure then
additional peaks are observed in the IR
spectrum.
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
d) Study of chemical reaction:
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Identification of geometrical isomers (cis-
trans).
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
Mahavir Education Trust’s
Shah & Anchor Kutchhi Engineering College
Chembur, Mumbai-400088
(Affiliated to University of Mumbai)
