M.sc. SEM-1 IR Book (Reena Mam)

Notes for INFRARED SPECTROSCOPY
M.SC. SEM-1
SELECTED SPECTROSCPIC TECHNIQUE –I
(MCHE1SST/MICH1SST)
Department of Chemistry
Ganpat University
Dr. Reena V. Rathod
Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy
Spectroscopy: Spectroscopy is an instrumentally aided study of the interactions
between matter (sample being analyzed) and energy (any portion of the
electromagnetic spectrum). Using electromagnetic radiation to obtain information
about atoms and molecules that are too small to see so it is method of seeing un-
seeable.
1.UV-Visible radiations--------excitation of electrons---------UV-visible spectrum

2.IR-radiations------------------vibration changes in electrons--------IR spectrum
3.Radio frequency---------------spin rotational changes-------------N.M.R spectrum
Electromagnetic Radiation:
 The visible part of the electromagnetic spectrum is, by definition is radiation
visible to the human eye. Other detection systems reveal radiation beyond the
visible regions of the spectrum and these are classified as radiowave,
microwave, infrared, ultraviolet, X-ray and γ-ray.
 These regions are illustrated in below together with the processes involved in
the interaction of the radiation of these regions with matter. The electromagnetic
spectrum and the varied interactions between these radiations and many forms
of matter can be considered in terms of either classical or quantum theories. The
nature of the various radiations shown in below Figure have been interpreted by
Maxwell’s classical theory of electro- and magneto-dynamics – hence, the term
electromagnetic radiation.

Fig: Regions of electromagnetic spectrum
 According to this theory, radiation is considered as two mutually perpendicular

electric and magnetic fields, oscillating in single planes at right angles to each
other. These fields are in phase and are being propagated as a sine wave, as
shown in below Figure. The magnitudes of the electric and magnetic vectors are
represented by E and B, respectively.
Fig.: Representation of an electromagnetic wave
 This is known as the velocity of light, c, and has the value 2.997× 108 m s−1. If
one complete wave travelling a fixed distance each cycle is visualized, it may
be observed that the velocity of this wave is the product of the wavelength, λ
(the distance between adjacent peaks), and the frequency, ν (the number of
cycles per second).
Therefore: c = λν
 The presentation of spectral regions may be in terms of wavelength as meters
or sub-multiples of a meter. The following units are commonly encountered in
spectroscopy: 1 A˚ = 10−10 m 1 nm = 10−9 m 1 µm = 10−6 m
 Another unit which is widely used in infrared spectroscopy is the wavenumber,
ν, in cm−1. This is the number of waves in a length of one centimeter and is
given by the following relationship: ν = 1/λ = ν/c; This unit has the advantage
of being linear with energy.
 Work by Einstein, Planck and Bohr indicated that in many ways
electromagnetic radiation could be regarded as a stream of particles (or quanta)
for which the energy, E, is given by the Bohr equation,

E = hν
Where, h is Planck constant (h = 6.626 × 10−34 J s); ν is frequency
 Processes of change, including those of vibration and rotation associated with
infrared spectroscopy, can be represented in terms of quantized discrete energy
levels E0, E1, E2, etc., as shown in Figure 1.3. Each atom or molecule in a system
must exist in one or other of these levels. In a large assembly of molecules, there
will be a distribution of all atoms or molecules among these various energy
levels.
 Whenever a molecule interacts with radiation, a quantum of energy (or photon)
is either emitted or absorbed. In each case, the energy of the quantum of
radiation must exactly fit the energy gap E1 − E0 or E2 – E1, etc. The energy of
the quantum is related to the frequency by the following:
ΔE = hν
 Hence, the frequency of emission or absorption of radiation for a transition

between the energy states E0 and E1 is given by:
ν = (E1 − E0)/h
 Associated with the uptake of energy

of quantized absorption is some
deactivation mechanism whereby the
atom or molecule returns to its
original state. Associated with the loss
of energy by emission of a quantum of
energy or photon is some prior
excitation mechanism. Both of these
associated mechanisms are
represented by the dotted lines in Figure : Illustration of quantized
Figure. discrete energy level

Introduction to IR spectroscopy:
 Infrared spectroscopy deals with the recording of the absorption of radiations in
the infrared region of the electromagnetic spectrum.
 The position of a given infrared absorption is expressed in terms of wavelength
in micron (μ) or more commonly in terms of wavenumber v (cm-1) since it is
directly proportional to energy.
 The ordinary infrared region 2.5-15 μm (4000-667 cm-1) is of greatest practical
use to organic chemists. The region 0.8-2.5 μm (12,500- 4000 cm-1) is called
the near infrared and the region 15-200 μm (667-50 cm-1) the far infrared.
Near IR = carbohydrates and proteins

Middle IR = Organic molecules; Functional group
Far IR = Inorganic – coordination bonds and
quaternary ammonium compound
 The absorption of infrared radiation by a molecule occurs due to quantized

vibrational and rotational energy changes when it is subjected to infrared
irradiation. Thus, IR spectra are often called vibrational-rotational spectra.
 IR spectra have a large number of absorption bands and therefore provide plenty
of structural information about a molecule. Different bands observed in an IR
spectrum correspond to various functional groups and bonds present in the
molecule. Thus, IR spectroscopy is most widely used for the detection of
functional groups and identification of organic compounds.
 Energy of molecule = Electronic energy + Vibrational energy + Rotational
energy. IR spectroscopy is concerned with the study of absorption of infrared
radiation, which causes vibrational transition in the molecule. Hence, IR
spectroscopy also known as Vibrational spectroscopy.

Principle of IR spectroscopy:
 IR spectroscopy detects the absorption of light by a compound, in the IR region
of the electromagnetic spectrum.
To absorb light a molecule must have a bond within its structure that can exhibit
what is referred to as a ‘dipole moment’ which means electrons within a bond
are not shared equally.
 Electrons within the O–H bond are not equally shared meaning that the electrons
are more closely attracted to the oxygen than the hydrogen. As electrons are
negatively charged, this leads to the O of the bond bearing a slight negative
charge and the H a slight positive charge.
 This charge difference which enables the IR light to be absorbed by this
particular bond, giving rise to a peak within an IR spectrum. The basic principle
to get IR signal is mentioned below.
 Different bonds within functional groups which possess a dipole moment will
absorb at different areas of the IR spectrum, referred to as wavenumbers.

Criteria for a compound to absorb IR radiation:
1. Correct wavelength of radiation: A molecule to absorb IR radiation, the natural
frequency of vibrations of some part of a molecule is the same as the frequency of
incident radiation.
2. Change in dipole moment: A molecule can only absorb IR radiation when its
absorption cause a change in its electric dipole
Mode of the vibration in IR spectroscopy:
IR absorption spectra originate from transitions in vibrational and rotational energy
levels within a molecule. On absorption of IR radiation, vibrational and rotational
energies of the molecule are increased. When a molecule absorbs IR radiation
below 100 cm -1, the absorbed radiation causes transitions in its rotational energy
levels. When a molecule absorbs IR radiation in the range 100-10,000 cm-1, the
absorbed radiation causes transitions in its vibrational energy levels. These energy
levels are also quantized, but vibrational spectra appear as bands rather than
discrete lines. The energy differences between various rotational energy levels of
a molecule are far less than that between its vibrational energy levels. Thus, a
single transition in vibrational energy levels is accompanied by a large number of
transitions in rotational energy levels and so the vibrational spectra appear as
vibrational-rotational bands instead of discrete lines.
Various atoms in a molecule may be regarded as balls of different masses and the
covalent bonds between them as weightless tiny springs holding such balls
together.
Atoms in a molecule are not still but they vibrate. The two types (modes) of
fundamental molecular vibrations known are: (a) stretching and (b) bending
vibrations.

(i) Stretching Vibrations: In stretching vibrations, the distance between two
atoms increases or decreases, but the atoms remain in the same bond axis.
Stretching vibrations are of two types:
(a) Symmetrical stretching: In this mode of

vibration, the movement of atoms with
respect to the common (or central) atom is
simultaneously in the same direction along
the same bond axis (Fig. a).
(b)Asymmetrical Stretching: In this
vibration, one atom approaches the common
atom while the other departs from it (Fig. b).
(ii) Bending Vibrations: In such vibrations, the positions of the atoms change
with respect to their original bond axes (angle). Bending vibrations are of four
types:
(a) Scissoring: In this mode of vibration,
the movement of atoms is in the
opposite direction with change in their
bond axes as well as in the bond angle
they form with the central atom (Fig.
3.3(a)).
(b) Rocking: In this vibration, the
movement of atoms takes place in the
same direction with change in their
bond axes (Fig. 3.3(b)). Scissoring and
rocking are in-plane bendings.
(c) Wagging. In this vibration, two

atoms simultaneously move above and
below the plane with respect to the
common atom (Fig.c).

(d) Twisting. In this mode of vibration, one of the atom moves up and the other
moves down the plane with respect to the common atom (Fig. d).
Infrared radiation is absorbed when, due to a molecular vibration the oscillating

dipole moment interacts with the oscillating electric field of the infrared beam. An
absorption band appears only when a molecular vibration produces a change in the
dipole moment of the molecule. Otherwise, the vibration is said to be infrared
inactive and it will show no absorption band in the infrared spectrum. Usually,
larger the change in dipole moment, the higher is intensity of absorption.
We know that lesser energy is required to bend a spring than that required for
stretching it. Analogously, bending vibrations of a band require lesser energy than
its stretching vibrations. Thus, the absorption bands resulting from bending
vibrations appear at lower wavenumbers those that resulting from stretching
vibrations of the same band. Stretching vibrations usually cause peaks of high
intensity. A typical IR spectrum showing various mode of vibrations is given in
below figure:
Fig: IR Spectra
of Octane
Frequency of stretching and banding vibrations of octane (C-H str and banding)

Number of Fundamental Vibrations:
The IR spectra of polyatomic molecules may exhibit more than one vibrational
absorption bands. The number of these bands corresponds to the number of
fundamental vibrations in the molecule which can be calculated from the degrees
of freedom of the molecule.
The degrees of freedom of a molecule are equal to the total degrees of freedom of
its individual atoms. Each atom has three degrees of freedom corresponding to the
three Cartesian Coordinates (x, y and z) necessary to describe its position relative
to other atoms in the molecule. Therefore, a molecule having (n) atoms will have
3(n) degrees of freedom.
In case of a non-linear molecule, three of the degrees of freedom describe rotation
and three describe translation. Thus, the remaining (3n - 3 - 3) = 3n - 6 degrees of
freedom are its vibrational degrees of freedom or fundamental vibrations, because
Total degrees of freedom (3n) = Translational + Rotational + Vibrational degrees
of freedom
In case of a linear molecule, only two degrees of freedom describe rotation
(because rotation about its axis of linearity does not change the positions of the
atom) and three describe translation. Thus, the remaining (3n - 2 - 3) = 3n - 5
degrees of freedom are vibrational degrees of freedom or fundamental vibrations.
The number of vibrational degrees of freedom for the linear carbon dioxide
molecule can be calculated as follows:

Number of atoms (n) = 3
Total degrees of freedom (3n) = 3 x 3 = 9
Rotational degrees of freedom = 2
Translational degrees of freedom = 3
Therefore, vibrational degrees of freedom = 9 - 2 - 3 = 4
Since each vibrational degree of freedom corresponds to a fundamental vibration
and each fundamental vibration corresponds to an absorption band, for carbon
dioxide molecule there should be four theoretical fundamental bands.
For a non-linear molecule ethane (C2H6), the vibrational degrees of freedom can
be calculated as:
Number of atoms (n) = 8
Hence, vibrational degrees of freedom = 24- 3- 3 = 18
Thus, theoretically there should be 18 absorption bands in the IR spectrum of
ethane.
It has been observed that in actual IR spectra, the theoretical number of
fundamental bands are rarely obtained because there are certain factors which
decrease, whereas certain factors increase the number of bands.
The following factors decrease the theoretical number of fundamental bands:
(i) The frequencies of fundamental Vibrations which fall outside of the
region 4000-667 cm-1
(ii) Fundamental bands which are so weak that they are not observed.
(iii) Fundamental bands which are so close that they coalesce.
(iv) The occurrence of a degenerate band from several absorptions of the same
frequency in highly symmetrical molecules such as carbon dioxide.

(v) Certain fundamental vibrational bands which do not appear in the infrared
spectrum due to lack of the required change in dipole-moment of the
molecule, e.g. in carbon dioxide molecule. The carbon dioxide molecule
is linear and has four fundamental vibrations (3 x 3)- 5 = 4 (as shown in
below figure) Thus, four theoretical fundamental bands are expected but
actually it shows only two. The symmetrical Stretching vibration in
carbon dioxide is IR inactive because it produces no change in the dipole
moment of the molecule. The two bending vibrations are equivalent and
absorb at the same wavenumber (667.3 cm-1). Thus, the IR spectrum of
carbon dioxide shows only two fundamental absorption bands, one at
2350 cm-1 due to asymmetrical stretching vibration, and the other at 667.3
cm-1 due to the two bending vibrations.
Fig.: Fundamental vibrations of the linear carbon dioxide molecule (+ and – signs
indicate movements perpendicular to the plane of paper)
In a molecule having a center of symmetry, the vibrations which are symmetrical

about the center of symmetry are IR inactive. For example, the symmetrical
stretching vibrations of carbon dioxide and the symmetrical C=C Stretching
vibrations of ethylene do not result in an absorption band in the IR spectra. It
should be noted that ethylene shows bands for C-H stretching vibrations. Similarly,
symmetrical di-atomic molecules such as H2, N2, O2 and Cl2 do not absorb IR
radiation, but unsymmetrical di-atomic molecules like carbon monoxide and
iodine chloride (I-Cl) absorb IR radiation.

The appearance of the following types of additional (non-fundamental) bands
increases the number of bands as compared to that expected from the
theoretical number of fundamental vibrations. All these bands have one-tenth to
one-hundredth intensity of the fundamental bands.
i) Overtone Bands These may arise if a molecule is excited, e.g. from its first
vibrational energy level to the third vibrational energy level; the energy
required is almost twice of that required for the excitation to second
vibrational energy level. In this way, if there are two fundamental bands at x
and y cm-1, then the overtone bands can be expected, e.g. at 2x, 2y, 3x and
3y cm-1. The intensity of the overtone decreases as the order of the overtone
increases, e.g. the second overtone (3x or 3y) is less intense than the first
overtone (2x or 2y). Consequently, second and higher overtones are rarely
observed, whereas first overtones are observed only for strong bands.
ii) Combination Bands: If there are two fundamental bands at x and y cm-1,
then the combination bands can be expected, e.g. at (x + y), (x + 2y) and (2x
+ y) cm-1
iii) Difference Bands: If there are two fundamental bands at x and y cm-1, then
the difference bands can be expected, e.g. at (x- y), (x -2y) and (2x- y) cm-1
Calculation of Vibrational Frequencies:

The stretching vibrations of two bonded atoms may be regarded as the vibration
of two balls connected by a spring, a situation for which Hooke's law applies. Thus,
an approximate value for the Stretching vibrational frequency, i.e., the stretching
absorption frequency of a bond, can be calculated by Hooke's law as mentioned
below
Vibrational Frequency (ῦ) = 1/2πc√𝒌/µ
Where
𝑚1 𝑋 𝑚2
µ= are the reduced masses; and m1 and m2 are the mass of the atom
𝑚1+𝑚2
involved in particular bond.
k= force constant of bond in dyne/cm.
c= velocity of light (2.99 x 1010 cm/sec)
ῦ = vibrational frequency of bond in cm-1 (wave number)

 The force constant of a bond is related to its bond strength. The value of force
constant is approximately 5 X 105 dynes/cm for single bonds and approximately
twice and thrice of this value for double and triple bonds, respectively. The force
constant is a characteristic property of a bond and like other physical constants,
it is another physical constant. The frequencies of IR absorptions are commonly
used to calculate the force constants of various bonds.
 Applying Eq. (3.1) (Hooke's law), the frequency of the C-H Stretching
vibration can be calculated as follows: here the atomic mass of carbon is 12 and
that of hydrogen is 1. Thus,
ῦ = 3032cm-1
C-H stretching vibrations of CH3 and CH2 groups are generally observed in the
range 2850-3000 cm-1.
The value of stretching vibrational frequency depends on the bond strength and
the reduced mass. The stretching vibrational frequency of a bond increases with
an increase in the bond strength or decrease in the reduced mass of the bonded
atoms.
Due to the greater bond strength (value of f) of C=C and C=O bonds, they are
expected to absorb at higher stretching frequencies than that of C-C and C-O,
respectively. Similarly, O-H stretching absorption appears at a higher frequency
than that of C-C because of the lower value of reduced mass for O-H compared
to that for C-C. For the same reason, we would predict O-H stretching vibration
to be of higher frequency than O-D Stretching vibration.
On the basis of reduced mass, we can expect that F-H bond should absorb at a
lower Stretching frequency than the C-H bond. Actually, F-H absorbs at a
higher frequency (4138 cm-1) than the C-H group (3040 cm-1). This can be
explained because there is an increase in the force constant when we proceed
from left to right in the first two periods of the periodic table and this increase
is more effective than the mass increase which tends to lower the absorption

frequency. Thus, the relative contributions of bond strengths and atomic masses
must be considered while applying the Hooke's law for predicting the
vibrational frequencies of bond Stretchings.
Factors Affecting Vibrational Frequencies:
It should be noted that any factor which affects the force constant of a bond will
affect its stretching frequency. There are various interrelated factors which shift
the vibrational frequencies from their expected values. For this reason, the values
of vibrational frequencies of the bonds calculated by the application of Hooke's
law are not exactly equal to their observed values.
The force constant of a bond changes with the electronic and steric effects of the
other groups present in the molecule, and so the vibrational frequencies are shifted
from their normal values. Following are some important factors which affect the
vibrational frequencies of bonds.
1) Coupled Vibrations:
 For an isolated C-H bond, only one Stretching vibrational frequency is expected
but a methylene group shows two absorptions corresponding to symmetrical
and asymmetrical Stretchings as mentioned in figure below:
 This is because there is mechanical coupling or interaction between the C-H

stretching vibrations in the CH2 group. In all such cases, asymmetric stretching
vibrations occur at higher frequencies or wavenumbers than the symmetric
stretching vibrations. The C-H coupled vibrations if CH2 groups are of different
frequencies than that of CH3 groups. Coupling accounts for the two N-H
Stretching bands in the region 3077- 3497 cm-1 in the spectra of primary amines
and primary amides.

 A strong vibrational coupling is present in carboxylic acid anhydrides in which
symmetrical and asymmetrical stretching vibrations appear in the region 1720-
1825 cm-1 and are separated by about 60 cm-1. Here, two carbonyl groups are
coupled through the oxygen. The interaction is very effective probably because
of the partial double band character in the carbonyl oxygen bonds due to
resonance which also keeps the system planar for effective coupling.
 The asymmetrical Stretching band in acyclic anhydrides is more intense,
whereas the symmetrical stretching band is more intense in cyclic anhydrides.
This characteristic can be used for differentiating acyclic and cyclic anhydrides.
Following are the requirements for effective coupling interaction:

i) Interaction is greatest when the individual absorption frequencies of the
coupled groups are nearly the same.
ii) Strong coupling between stretching vibrations occur when the groups
have a common atom between them.
iii) Coupling is negligible when groups are separated by one or more carbon
atoms and the vibrations are mutually perpendicular.
iv) Coupling between bending vibrations can occur when there is a common
bond, e.g. there is coupling between the bending vibrations of the adjacent
C-H bonds in aromatic rings.
v) If the stretching bond forms one side of the changing angle, then coupling
between stretching and bending vibrations can take place.
2) Fermi Resonance:
 The coupling between fundamental vibrations and overtone or combination tone
vibrations of very similar frequency is known as Fermi resonance (after Enrico
Fermi who first observed it in the case of CO2). In Fermi resonance, a molecule
transfers its energy from fundamental vibrational level to overtone or
combination tone level and back.

 According to quantum mechanics, the resonance pushes the two levels apart and
mixes their character, consequently each level has partly fundamental and partly
overtone or combination tone character. Thus, Fermi resonance give rise to a
pair of transitions of almost equal intensity, and so the resulting absorption
bands usually appear as a doublet.
 For example (as seen in Section 3.5), the symmetrical Stretching vibration of
CO2 is IR inactive. For this Stretching, Raman spectrum shows a strong band at
1337 cm-1. The two bending vibrations (Fig. 3.4) are equivalent and absorb at
the same frequency, of 667.3 cm-1 The first overtone of this is 2 x 667.3 = 1334.6
cm-1 Since it is very close to the frequency of the fundamental
vibration(symmetrical stretching), Fermi resonance occurs. Thus, there is
mixing of 1337 cm-1 (fundamental) and 1334.6 cm-1 (overtone) levels in
accordance with Fermi resonance to give two bands at 1285.5 cm-1 and at
1388.3 cm-1 with the intensity ratio 1: 0.9, respectively.
 The absorption of aldehydic C-H appears as a doublet at -2820 cm-1and -2720
cm-1 due to the interaction of C-H Stretching vibration (fundamental) and the
first overtone of C-H bending.
 Cyclopentanone shows carbonyl absorption at 1746 and 1750 cm-1; This
splitting is due to Fermi resonance with an overtone or combination band of an
a-methylene group and the carbonyl band.
 Fermi resonance is observed only when the interacting groups are so located in
the molecule that there is considerable mechanical coupling and that the
fundamental and overtone or combination-tone vibrational levels are of the
same symmetry species.
3) Hydrogen Bonding:
 Hydrogen bonding remarkably lowers the Stretching frequencies of both the
groups involved in it, and also changes the shape and intensity of the absorption
bands. Usually, absorption bands become more intense and broad on hydrogen
bonding. The stronger the hydrogen bond, lower is the O-H Stretching
frequency. Thus, the value of O-H stretching frequency is a test for hydrogen
bonding as well as a measure of the strength of hydrogen bonds.
 Non-hydrogen-bonded (free) O-H group of alcohols and phenols show sharp
and strong absorption bands in the region 3590-3650 cm-1; Sharp, non-hydrogen

bonded O-H bands are observed only in the vapour phase, in very dilute
solution, in non-polar solvents or when hydrogen bonding is prevented by steric
hindrance.
 Pure samples and concentrated solutions of alcohols and phenols show broad
O-H stretching bands in the region about 3200-3600 cm-1 due to intermolecular
hydrogen bonding. The N-H Stretching frequencies of amines are also affected
by hydrogen bonding in the same way as that of the hydroxyl group but
frequency shifts for amines are lesser than that for hydroxyl compounds. This
is because nitrogen is less electronegative than oxygen and so the hydrogen
bonding in amines is weaker than that in hydroxy compounds.
 For example, non-hydrogenbonded primary amines exhibit two bands, one near
3400 cm-1 and the other near 3500 cm-1 due to symmetrical and asymmetrical
N-H stretching modes, respectively. In pure amines, these bands respectively
appear in the range 3250- 3330 cm-1 and 3330-3400 cm-1 due to intermolecular
hydrogen bonding in liquid or solid state, and in concentrated solutions,
carboxylic acids exist as dimers due to strong intermolecular hydrogen bonding.
 The strong hydrogen bonding between C=O and OH groups lowers their
Stretching frequency. Because of more polar O-H bond, carboxylic acids form
stronger hydrogen bond than alcohols.
 Carboxylic acid dimers show very broad, intense O-H Stretching absorption in
the region 2500-3000 cm-1, whereas non hydrogen-bonded carboxylic acids
(monomers) show the O-H absorption near 3550 cm-1. Hydrogen bonding
weakens the C=O bond, i.e. its force constant is reduced, resulting in absorption
at a lower frequency than the monomer. Thus, C=O stretching bands of
monomers of saturated carboxylic acids appear at 1760 cm-1, whereas that of
dimers appear at about 1710 cm-1. In many cases, some O-H groups are
hydrogen bonded and some are free. Hence, bands due to both may be observed.

Why does hydrogen bonding lower the absorption frequency?
 On hydrogen bonding, the original O-H bond is lengthened (weakened) due to
electrostatic attraction between the hydrogen atoms of one molecule and oxygen
atom of the other, and thus the force constant of the O-H bond is reduced
resulting in a decrease in its stretching frequency.
Further, the hydrogen bond may be regarded as a resonance hybrid of the

following resonating structures, consequently the O-H bond is weakened and
its stretching frequency is lowered
 Distinction between inter- and intramolecular hydrogen bondings: In very

dilute solutions (in non-polar solvents), intermolecular distances are too large
to form intermolecular hydrogen bonds. On the other hand, in pure liquids,
solids and concentrated solutions, the molecules are closer to form
intermolecular hydrogen bond. Thus, intermolecular hydrogen bonding is
concentration dependent.
 On dilution with non-polar solvents, intermolecular hydrogen bonds are broken.
Hence, there is decrease in intensity or disappearance of the hydrogen-bonded
O-H stretching band and increase in intensity or appearance of free O-H
stretching absorption. Thus, in very dilute solutions (in non-polar solvents,
concentration < -0.01 M), the O-H Stretching frequency is shifted to a higher
frequency in case of intermolecular hydrogen bonding.
 Intra-molecular hydrogen bonding is within the same molecule, hence it is
not affected by change in intermolecular distances. Thus, intra-molecular
hydrogen bonds are unaffected by dilution, and so the absorption band is also
unaffected. Intra-molecular hydrogen bonding (chelation) is very strong in

enols and compounds like methyl salicylate etc., due to resonance stabilization
of the chelate ring. For example, in enols, the O-H group involved in chelation
shows broad absorption band in the range 2500-3200 cm-1, whereas the C=O
stretching band in enolic form occurs at 1630 cm-1 and that in the keto form at
1725 cm-1. From the relative intensities of the two bands, it is possible to
determine ratio of the keto and enol forms.
4) lnductive and Mesomerie (Resonance) Effects:

Absorption frequencies of a particular group are affected by electronic effects,
especially inductive and mesomeric (resonance) effects of the nearby groups.
These effects are generally interrelated and their individual contribution can
only be estimated approximately.
Strength (force constants) of a particular bond is changed by these effects and
hence its Stretching frequency is also changed with respect to the normal values.
Both of these effects may operate in the same direction or opposite to each other
where one dominates the other.
Inductive effect:
A carbonyl compound may be considered as a resonance hybrid of the
following structures:
 The Stretching frequency of a carbonyl group decreases with increasing number

of alkyl groups attached to it. This is due to +I effect of alkyl groups which
favors structure (II) and lengthens (weakens) the carbon-oxygen double bond,
and hence its force constant is decreased resulting in the lowering of the C=O
Stretching frequency.

 For example, HCHO, CH3CHO and CH3COCH3 show Vc=o absorption at
1750, 1730 and 1715 cm-1, respectively. It should be noted aldehydes absorb at
higher frequency than ketones as +I effect increase in ketone so it lower the
absorption frequency.
 Similarly, when a group with -I effect is attached to a C=O group, it favors
structure (I) and its Stretching frequency is increased due to increase in the bond
order (force constant) of the carbon-oxygen double bond. For example,
CH3COCH3, CH3COCHl2 and CHCl2COCHCl2 show Vc=o bands at 1715,
1740 and 1780 cm-1, respectively.
 Amides show Vc=o band at a lower frequency than that of esters. Due to lesser
electronegativity of nitrogen than oxygen, its lone pair of electrons are more
readily involved in resonance than that of oxygen. Thus, the carbon-oxygen
double bond character is more reduced by resonance in amides than that in
esters resulting in a much lower Vc=o frequency of amides than that of esters.
For example, benzamide shows Vc=o band at 1663 cm-1 and methyl benzoate
at 1735 cm-1.
Conjugation or Resonance or mesomeric effect:

 Conjugation of a carbonyl group with an olefinic double bond or an aromatic
ring lowers the stretching frequency of the C=O groups by about 30 cm-1. This
is because the double bond character of the C=O group is reduced by mesomeric
effect.
 For example, the stretching frequency of C=O group in acetone is 1720 cm-1,
whereas aceto-phenone shows vC=O band at 1697 cm-1 due to its conjugation
with the aromatic ring. In this case, -I effect of the sp2 -carbon of the ring is
dominated by the +M effect of the ring.

 Identification of organic molecule from characteristic absorption band:
IR spectrum:
• FEATURESOF IR SPECTRUM: An IR spectrum is a plot of per cent

transmittance (or absorbance) against wavenumber (frequency or
wavelength). A typical infrared spectrum is shown below. A 100 per cent
transmittance in the spectrum implies no absorption of IR radiation.
• When a compound absorbs IR radiation, the intensity of transmitted

radiation decreases. This results in a decrease of per cent transmittance and
hence a dip in the spectrum. The dip is often called an absorption peak or
absorption band.
• Different types of groups of atoms (C-H, O-H, N-H, etc…) absorb infrared
radiation at different characteristic wavenumbers. No two molecules will
give exactly the same IR spectrum (except enantiomers)
• Simple stretching : 1600-4000cm-1 ; Complex vibrations: 400 -1400 cm-1
There are two types of region in IR spectra from where one can obtain the
information about the molecule
1) The Functional group region: Identify the functional group with the
consequence of changing stretching vibrations. Range from 4000 to 1600cm-1
2) The fingerprint Region: identify the exact molecule with the consequences of
changing bending vibrations. Range from 1600 to 625cm-1

Fingure print region:
 It is not possible for any two different compounds (except enantiomers) to have
exactly the same IR spectrum. Therefore, the IR spectrum of a compound is
called its fingerprint.
 The region below 1500 cm-1 is called fingerprint region because every
compound has unique absorption pattern in this region, just as every person has
unique fingerprints.
 The fingerprint region contains many absorption bands caused by bending
vibrations as well as absorption bands caused by C-C, C-O like in alcohols,
ethers, esters, etc. and C-N (e.g. in amines, amino acids, amides, etc.) stretching
vibrations.
 Since the number of bending vibrations in a molecule is much greater than its
Stretching vibrations, the fingerprint region is rich in absorption bands. Thus,
the superimposability of IR bands of the spectra of any two different compounds
becomes impossible in this region. However, similar compounds may show
very similar spectra above 1500 cm-1.
 The use of IR spectroscopy to confirm the identity of a compound with the help
of an authentic sample is more reliable than taking mixed m.p. or comparing
other physical properties. If two pure samples give different IR spectra under
same conditions, they represent different compounds.
 If the samples give the superimposable IR spectra, they represent the same
compound. For example, the IR spectra of two Stereoisomerie steroids,
androsterone and epiandrosterone, show three strong bands above 1500 cm-1,
viz. araund 3600, 2950 and 1740 cm-1 due to O-H, C-H and C=O stretching
vibrations, respectively. However, the absorption patterns in the fingerprint

region of their IR spectra are quite different showing them to be different
compounds.
Characteristic absorption frequency of different functional groups: Different
functional groups absorb the IR radiation at different frequency, the absorption
frequency of various functional group is mentioned in table below:
Frequency Table:

Interpretation of various functional group:
O-H stretching:The O-H stretching region
• O-H: 3600 cm-1 (alcohol, free)
• O-H: 3300cm-1 (alcohol & acids. H-bonding)
N-H stretching region: N-H 3300-3400cm-1

IR Spectrum of Tertiary Amine – N,N, -Dimethylaniline:
C-H Stretching: Hybridization of Carbon effect on the stretching frequency

of C-H bond. Various types of carbon shows different region of C-H str frequency
as shown in table below.
C-H bending: The C-H bending region …..CH2 bending ~1465 cm-1
• CH3 bending (asym) appears near the CH2 value ~ 1460 cm-1
• CH3 bending (sym) ~ 1375 cm-1
C=C Stretching:
• C=C double at 1650cm-1 is often weak or not even seen
• C=C benzene ring shows peak near 1600 and 14000 cm-1,
one or two at each value – conjugation lower the value

• When C=C is conjugated with C=O it is stronger and
comes at a lower frequency
IR spectra of alkane and alkene are mentioned below:
IR spectra of Alkane – Hexane
IR Spectra of alkene
: The triple bond stretching region

C≡N 2250cm-1; C≡C 2150cm-1

• The cyano group often gives a strong, sharp peak due to its large dipole
moment
• The carbon-carbon triple bond gives sharp peak, but it is often week due to
lack of a dipole. This is especially true if it is at the center of a symmetric
molecule. : R-C≡C-R
Nitrile – propanenitrile
C=O Stretching -The carbonyl stretching region:

• This region stretches from about 1800 to 1650 cm-1 – right in the
middle of the spectrum and the base value is 1715 cm-1 (ketone)
• The bonds are very strong due to the large dipole moment.
• C=O is often one of the strongest peak in the spectrum, C=O is
sensitive to its environment so each C=O comes at a different
frequency as mentioned in table below

Ketone – 2- Butanone (base =1715)
-1
C-O Stretching:The C-O band appears in the range of 1300 to 1000 cm
• Ether, alcohol, ester and carboxylic acids have C-O bands
IR spectrum of Ether – Dibutyl Ether (base =1100)
-1
N=O stretching: N=O Stretching --- 1550 and 1350cm asymmetric and
-1
symmetric stretching. Often the 1550cm peak is stronger than other one
IR Spectrum of Notroalkane – 2 Nitropropane

-1
C-X stretching: C-Cl 785 to 540 cm – often hard to find amongst
the fingerprint band. C-Br and C-I – appears the outside of infrared
spectroscopy. C-F bonds can be found easily, but are not that common.
Recent advances in I.R. spectroscopy including FTIR, ATR, etc.

Here the instrumentation required to obtain an infrared spectrum is described;
Fourier-transform infrared spectrometers are now predominantly used and have
improved the acquisition of infrared spectra dramatically. Reflectance methods,
such as the attenuated total reflectance, diffuse reflectance and specular reflectance
approaches, as well as photoacoustic spectroscopy, are also in use. Infrared
microspectroscopy has emerged in recent years as an effective tool for examining
small and/or complex samples. Infrared spectroscopy has also been combined with

other well-established analytical techniques such as chromatography and thermal
analysis; Such as combination techniques.
1) Dispersive Infrared Spectrometers: The first dispersive infrared instruments
employed prisms made of materials such as sodium chloride. The popularity of
prism instruments fell away in the 1960s when the improved technology of
grating construction enabled.
 The dispersive element in dispersive instruments is contained within a
monochromator. Below Figure shows the construction of infrared spectrometer
which uses a grating monochromator.
 Figure shows double-beam arrangement in which radiation from a source is

divided into two beams with the help of mirror.
 The IR radiation source used is must be sufficiently intense over the
wavenumber range and transmittance range. Commonly, the Globar- which is
constructed of silicon carbide and Nernst filament, which is a mixture of the
oxides of zirconium, yttrium and erbium is used as source in this technique.
 These beams pass through a sample and a reference path of the sample
compartment, respectively. The information from these beams is regulated to
obtain the required sample spectrum.
 In this instrument the dispersion of radiation occurs when energy falling on the
entrance slit is collimated onto the dispersive element (Grating) and the
dispersed radiation is then reflected back to the exit slit, beyond which lies the
detector.

 Detector is used to detect the disperse radiation, a detector must have adequate
sensitivity to the radiation arriving from the sample and monochromator over
the entire spectral region required. Most detectors have consisted of
thermocouples of varying characteristics.
Limitation or problem with dispersive IR instrument:
1) The essential problem of the dispersive spectrometer lies with its
monochromator. This contains narrow slits at the entrance and exit which limit the
wavenumber range of the radiation reaching the detector to one resolution width.
2) Samples for which a very quick measurement is needed, for example, in the
eluent from a chromatography column, cannot be studied with instruments of low
sensitivity because they cannot scan at speed.
These limitations may be overcome through the use of a Fourier-transform infrared
spectrometer.
2) Fourier-Transform Infrared Spectrometers:
 Fourier-transform infrared (FTIR) spectroscopy is based on the idea of the
interference of radiation between two beams to yield an interferogram. The
latter is a signal produced as a function of the change of pathlength between
the two beams.
 The two domains of distance and frequency are interconvertible by the
mathematical method of Fourier-transformation. The basic components of an
FTIR spectrometer are shown schematically in Figure below.

 The radiation emerging from the source is passed through an interferometer
to the sample before reaching a detector.
 Upon amplification of the signal, in which high-frequency contributions have
been eliminated by a filter, the data are converted to digital form by an
analog-to-digital converter and transferred to the computer for Fourier-
transformation.
Michelson Interferometers: The most common interferometer used in FTIR
spectrometry is a Michelson interferometer, which consists of two perpendicularly
plane mirrors, one of which can travel in a direction perpendicular to the plane as
mentioned in figure. A semi-reflecting film (beam splitter), bisects the planes of
these two mirrors.
 The beam splitter material has to be chosen according to the region to be

examined. If a collimated beam of monochromatic radiation of wavelength λ
(cm) is passed into an ideal beam splitter, 50% of the incident radiation will be
reflected to one of the mirrors while 50% will be transmitted to the other mirror.
The two beams are reflected from these mirrors, returning to the beam splitter
where they recombine and interfere.

 The beam which emerges from the interferometer at 90◦ to the input beam is
called the transmitted beam and this is the beam detected in FTIR spectrometry.
 The moving mirror produces an optical path difference between the two arms
of the interferometer. Which further produce the constructive and destructive
interference of radiation.
 Sources and Detectors FTIR spectrometers use a Globar or Nernst source for
the mid-infrared region. There are two commonly used detectors employed for
the mid-infrared region. The normal detector for routine use is a pyroelectric
device incorporating deuterium tryglycine sulfate (DTGS) in a temperature-
resistant alkali halide window. For more sensitive work, mercury cadmium
telluride (MCT) can be used.
Fourier-Transformation: The essential equations for a Fourier-transformation
relating the intensity falling on the detector, I(δ), to the spectral power density at a
particular wavenumber, ν¯, given by B(ν¯), are as follows:
∞
I(δ) = ∫0 𝐵(ν¯)cos (2πνδ¯ )dν¯ …………………. (1)
which is one half of a cosine Fourier-transform pair, with the other being:
+∞
B(ν¯) = ∫−∞ I(δ)cos (2πνδ¯ )dδ ………………(2)
These two equations are interconvertible and are known as a Fourier-transform

pair.
The first shows the variation in power density as a function of the difference in
pathlength, which is an interference pattern. The second shows the variation in
intensity as a function of wavenumber.Each can be converted into the other by the
mathematical method of Fourier-transformation.
Advantages: FTIR instruments have several significant advantages over older
dispersive instruments.
1) Improvement in the SNR per unit time, proportional to the square root of the
number of resolution elements being monitored. This results from the large
number of resolution elements being monitored simultaneously.
2) FTIR spectrometry does not require the use of a slit or other restricting
device, the total source output can be passed through the sample

continuously. This results in a large gain in energy at the detector, hence
translating to higher signals and improved SNRs.
3) Another strength of FTIR spectrometry is its speed advantage. The mirror
has the ability to move short distances quite rapidly, which make it possible
to obtain spectra on a millisecond timescale.
3) Attenuated Total Reflectance Spectroscopy:

Attenuated total reflectance (ATR) spectroscopy utilizes the phenomenon of total
internal reflection as shown in below figure
Fig.: Schematic of a typical attenuated total reflectance cell

A beam of radiation entering a crystal will undergo total internal reflection when
the angle of incidence at the interface between the sample and crystal is greater
than the critical angle, where the latter is a function of the refractive indices of the
two surfaces.
The beam penetrates a fraction of a wavelength beyond the reflecting surface and
when a material that selectively absorbs radiation is in close contact with the
reflecting surface, the beam loses energy at the wavelength where the material
absorbs. The resultant attenuated (reduce) radiation is measured and plotted as a
function of wavelength by the spectrometer and gives rise to the absorption
spectral characteristics of the sample.
The depth of penetration in ATR spectroscopy is a function of the wavelength (λ),
the refractive index of the crystal (n2), and the angle of incident radiation (θ). The
depth of penetration (dp), for a non-absorbing medium is given by the following:
dp = (λ/n1)/ {2π[sin θ − (n1/n2)2]½}

where n1 is the refractive index of the sample. The crystals used in ATR cells are
made from materials that have low solubility in water and are of a very high
refractive index. Such materials include zinc selenide (ZnSe), germanium (Ge) and
thallium–iodide (KRS-5).
Advantages: This techniques used for samples that are difficult to analyse by the
conventional transmittance methods.
Combination techniques:
1) Chromatography–Infrared Spectroscopy:
 Infrared spectroscopy may be combined with each of a number of possible
chromatographic techniques, with gas chromatography–infrared spectroscopy
(GC– IR) being the most widely used. GC– IR allows for the identification of
the components eluting from a gas chromatograph.
 In GC, the sample in a gaseous mobile phase is passed through a column
containing a liquid or solid stationary phase. The retention of the sample
depends on the degree of interaction with the stationary phase and its volatility:
The sample is introduced into the column, housed in an oven, via injection at
one end and a detector monitors the effluent at the other end.
 A common method for coupling a gas chromatograph to an FTIR spectrometer
is to use a light pipe, i.e. a heated flow cell which allows the continuous
scanning of the effluent emerging from the GC column. Below figure shows a
schematic diagram of a typical GC– IR system.
Fig.: Layout of a typical GC– IR system

 The nature of this technique requires that interferograms are collected over short
time intervals. Data can be displayed in real time and are commonly monitored
as the changing spectrum of the GC effluent and the changing infrared
absorption as a function of time. The latter is known as a Gram–Schmidt
chromatogram.
 Liquid chromatography (LC) may also be used in conjunction with infrared
spectroscopy [10]. In this technique, the effluent from a liquid chromatograph
is passed through a liquid flow-through cell. Supercritical fluid chromatography
(SFC), where supercritical CO2 is commonly used as a mobile phase, can be
used with FTIR spectroscopy to improve detection limits.
2)Thermal Analysis–Infrared Spectroscopy:
 Thermal analysis methods provide information about the temperature
dependent physical properties of materials. However, it is not always possible
to gain information about the chemical changes associated with changes in
temperature by using standard thermal analysis equipment.
 Thermal analysis apparatus is combined with an infrared spectrometer in order
to obtain a complete picture of the chemical and physical changes occurring in
various thermal processes.
 The most common approach is to combine FTIR spectroscopy with a thermal
method such as thermogravimetric analysis (TGA) to obtain an evolved gas
analysis (EGA). The latter involves the measurement and characterization of
the gaseous products which evolve from a sample when it is heated.
 Below Figure presents a schematic layout of a typical thermal analysis–infrared
spectroscopy system.
Fig.: Layout of a typical thermal analysis–infrared spectroscopy system.

 In this, a sample is placed in a furnace while being suspended from a sensitive
balance.
 The change in sample mass is recorded while the sample is maintained either at
a required temperature or while being subjected to a programmed heating
sequence.
 A TGA curve may be plotted as sample mass loss as a function of temperature
or in a differential form where the change in sample mass with time is plotted
as a function of temperature.
 The evolved gases can be carried from the furnace to the spectrometer where
they can be examined in a long-pathlength gas cell. Data may be illustrated as
a function of time by using a Gram–Schmidt plot
Basic Terminology which help to to interpreat IR spectrum: (Mode of the

spectrum, type of peak and intensity)
TRANSMISSION and ABSORPTION spectrum
When a chemical sample is exposed to the action of IR light, it can absorb some
frequencies and transmit the rest. Some of the light can also be reflected back to
the source. Spectrum can be monitored (recorded) in absorption mode or
Transmission mode. AN IR SPECTRUM
AN IR SPECTRUM IN
IN TRANSMISSION
ABSORPTION MODE
MODE

CLASSIFICATION OF IR BANDS:
IR bands can be classified as strong (s), medium (m), or weak (w), depending on
their relative intensities in the infrared spectrum. A strong band covers most of the
y-axis. A medium band falls to about half of the y-axis, and a weak band falls to
about one third or less of the y-axis
INFRARED ACTIVE BONDS: Not all covalent bonds display bands in the IR
spectrum. Only polar bonds do so. These are referred to as IR active. The intensity
of the bands depends on the magnitude of the dipole moment associated with the
bond:
• Strongly polar bonds such as carbonyl groups (C=O) produce strong bands
• Medium polarity bonds and asymmetric bonds produce medium bands.
• Weakly polar bond and symmetric bonds produce weak or non observable bands.
INFRARED BAND SHAPES: Infrared band shapes come in various forms. Two
of the most common are narrow and broad, as shown below.

SOLVED EXAMPLES:
1. How many bands due to fundamental vibrations do you expect to observe
in the IR spectrum of water?
Solution: Water molecule is a nonlinear molecule, hence its vibrational degree of
freedom, i.e. fundamental vibrations will be equal to 3n-6 and can be calculated as
follows: Number of atoms (n) = 3
Hence, vibrational degrees of freedom (3n - 6) = 9 - 3 - 3 = 3
Thus, there will be three fundamental modes of vibration. These are symmetrical
Stretching, asymmetrical stretching and bending vibrations.
All these modes of vibrations are IR active and are non-degenerate. Thus, three
absorption bands corresponding to these three fundamental modes of vibration are
expected in the IR spectrum of water (observed absorption bands occur at 3652,
3756 and 1595 cm-1)
2. Using IR spectroscopy, how will you distinguish the following isomeric

compounds: (i) CH3CH2C=CH and CH3C=CCH3
(ii) CH3CH2OH and CH3OCH3
(iii) (CH3)3N and CH3CH2NHCH3

Solution:
(i) CH3CH2C=CH will show strong absorption bands at -3300, 2100 and 625 cm-1
due to =C-H Stretching, C=C stretching and =C-H bending vibrations,
respectively. All these bands will be absent in the IR spectrum of CH3C=CCH3. It
should be noted that Vc ...c band will also be absent in the IR spectrum of
CH3C=CCH3 because the symmetrical Substitution makes the C=C stretching
frequency IR inactive.
(ii) CH3CH2OH will show absorption bands in the region 3200-3600 cm-1 due to
Stretching vibration of intermolecularly hydrogen-bonded O-H group and at 1050
cm-1 due to Vc=o· These bands will be absent in the IR spectrum of CH3OCH3. lt
will show an absorption band around 1100 cm-1 due to C-O-C stretching.
(iii) CH3CH2NHCH3 will show a medium band in the region 3310-3550 cm-1 due
to N-H stretching. This band will be absent in IR spectrum of (CH3)N.
3. How will you distinguish o-hydroxybenzaldehyde (salicylaldehyde) and m-

hydroxybenzaldehyde on the basis of IR spectroscopy?
Solution: In salicylaldehyde, due to intramolecular hydrogen bonding, Va-H and
Vc=o bands are shifted to lower wavenumbers. Since it is intramolecular, change
in concentration does not cause any shift in Va-Hand Vc=o absorption bands. In
case of m-hydroxybenzaldehyde, O-H and Vc=o bands occur at a still lower
wavenumber due to intermolecular hydrogen bonding. In this case, VO-H and Vc=o
bands shift to higher wavenumbers on dilution with a nonpolar solvent.

4. Give suitable explanation for the following:
(a) Stretching frequencies of C-C, C=C and C≡C fall in the regions which are in
increasing order 800-1200 cm-1, 1650-1670cm-1 and 2100-2260 cm-1, respectively.
(b) The VO-H band appears near 3570 cm-1, whereas the VO-D band appears near
2630 cm-1.
(c) 2-t-butylphenol has two VO-H bands-one at 3608 cm-1 and the other at 3643
cm-1, whereas 2,6-di-t-butylphenol has only one band at 3642 cm-1
Solution:
(a) According to Hooke's law, the stretching frequency of a bond increases with
an increase in the force constant, i.e., bond strength. Thus, the stretching
frequencies of carbon-carbon single, double and triple bonds increase in the
order of their increasing bond strengths, i.e. the increasing order of stretching
frequencies is C-C < C=C < C≡C.
(b) According to Hooke's law, the stretching frequency of a bond increases as

the reduced mass of the bonded atoms decreases. Since hydrogen has lesser
atomic mass than deuterium, the O-H Stretching frequency (near 3570 cm-1)
is higher than the O-D stretching frequency (near 2630 cm-1).
(c) In 2-t-butylphenol, two bands are present at 3608 and 3643 cm-1 showing that
some molecules are intermolecularly hydrogen bonded, whereas in others
OH is not hydrogen bonded due to steric hindrance by the bulky-t-butyl
group.
2-t-butylphenol 2,6-di-t-butylphenol
In 2,6-di-t-butylphenol, because of the presence of two bulky-t-butyl groups

in the ortho position of the OH group, the OH groups of two different

molecules are not able to approach close enough to form intermolecular
hydrogen bond. Thus, 2,6-di-t-butylphenol shows only one VO-H band at
3642 cm-1 due to nonhydrogen-bonded OH group.
6. Giving reasons arrange the following compounds in order of decreasing frequency of

carbonyl absorption in their IR spectra:
Solution: The following is decreasing order of frequency of carbonyl absorption

(c) > (a) > (b)
Cyclohexane carboxaldehyde (c) is a saturated aldehyde, hence will absorb around
1730 cm-1. Due to conjugation of the C=O group with the double bonds of the
benzene ring, the VC=O absorption of benzaldehyde (a) will be shifted to lower
frequency (1700 cm-1). In Salicylaldehyde (b), the lowering is due to conjugation
as weil as intramolecular hydrogen bonding (chelation), thus the Vc=o absorption
frequency is further lowered (1665 cm-1).

Question bank:
1. In terms of transitions, how does IR spectroscopy differ from UV
spectroscopy? And arrange the following transitions in order of their increasing
energy requirement: Vibrational, electronic and rotational
2. Write notes on:
(a) Stretching and bending vibrations
(b) Fingerprint region
(c) Fermi resonance
(d) Hydrogen Bonding
3. Comment on the following:
(a) Hydrogen bonding raises the wavelength of IR absorption.
(b)Vc=o frequency for ethyl acrylate is lower than that for ethyl propionate.
(Hint. Due to conjugation.)
4. Calculate the number of fundamental vibrations in the following molecules: (i)
Methane (ii) Ethanol (iii) Acetylene (iv) Ethylene (v) Oxygen
5. How will you distinguish the two members of each of the following pairs of
compounds using IR spectroscopy:
(a) CH3COOH and HCOOCH3
(b) ClCH2CH2CH2COOH and CH3OCH2CH2COC1
(c) CH3CH2CHO and CH2=CH-CH2OH
6. Discuss the factors which affect the IR absorption frequency of a functional
group.
7. Giving examples discuss how inductive and mesomeric effects influence the
carbonyl absorption frequency?
8. The IR spectrum of methyl salicylate shows absorption bands at 3300, 3050,
2990, 1700, 1590 and 1540 cm-1 Which of these bands are due to which of the
following groups?
C=O, CH3, O-H and aromatic ring
9. Ethylacetate shows Vc=o absorption at 1735 cm-1, whereas phenyl acetate at
1770 cm-1. Explain.

10. Arrange the following compounds in order of increasing absorption frequency
of their carbonyl groups. Give reason for your answer. C6H5CHO, CH3CHO,
CH3COCl and CH3COCH3
11. Using IR spectroscopy, how will you distinguish?
(a) Intermolecular and intramolecular hydrogen bonding
(b) cis-cinnarnic acid and trans-cinnamic acid
12. Indicate which of the following vibrationswill be IR active or inactive?
Moleeule Mode of vibration
(i) CHz =CHz C = C Stretching
(ii) CHz=CHz C-H stretching
(iii) N2 N == N Stretching
(iv) SO2 Symmetrical stretching
(v) CO2 Symmetrical Stretching
(vi) CH3-CH3 C-C Stretching

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Notes for INFRARED SPECTROSCOPY

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

1.UV-Visible radiations--------excitation of electrons---------UV-visible spectrum

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

 According to this theory, radiation is considered as two mutually perpendicular

Fig.: Representation of an electromagnetic wave

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

 Hence, the frequency of emission or absorption of radiation for a transition

 Associated with the uptake of energy

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Near IR = carbohydrates and proteins

 The absorption of infrared radiation by a molecule occurs due to quantized

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

(a) Symmetrical stretching: In this mode of

(c) Wagging. In this vibration, two

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared radiation is absorbed when, due to a molecular vibration the oscillating

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

In a molecule having a center of symmetry, the vibrations which are symmetrical

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Calculation of Vibrational Frequencies:

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

 This is because there is mechanical coupling or interaction between the C-H

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Following are the requirements for effective coupling interaction:

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Further, the hydrogen bond may be regarded as a resonance hybrid of the

 Distinction between inter- and intra- molecular hydrogen bondings: In very

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

4) lnductive and Mesomerie (Resonance) Effects:

 The Stretching frequency of a carbonyl group decreases with increasing number

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Conjugation or Resonance or mesomeric effect:

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

• FEATURESOF IR SPECTRUM: An IR spectrum is a plot of per cent

• When a compound absorbs IR radiation, the intensity of transmitted

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

N-H stretching region: N-H 3300-3400cm-1

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

C-H Stretching: Hybridization of Carbon effect on the stretching frequency

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

IR spectra of Alkane – Hexane

: The triple bond stretching region

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

C=O Stretching -The carbonyl stretching region:

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

IR Spectrum of Notroalkane – 2 Nitropropane

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

Recent advances in I.R. spectroscopy including FTIR, ATR, etc.

Infrared Spectroscopy M.Sc. SEM-1 Dr. Reena V. Rathod

 Figure shows double-beam arrangement in which radiation from a source is