LECTURE NOTES

ON
INFRARED SPECTROSCOPY
ENGINEERING CHEMISTRY
[Link] 1st year

By
Dr. Divya Pratap Singh
Assistant Professor
 INFRARED (IR) SPECTROSCOPY

OR

VIBRATIONAL SPECTROSCOPY
• Infrared spectroscopy is used in identification of functional groups in pure
compounds.
• Infra-red (IR) does not have sufficient energy to induce electronic transition
as seen in UV spectroscopy. When molecule absorbed electromagnetic
radiation in IR region, 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 does not
absorb IR radiation. IR region ranges from 4000-400 cm-1.
• If the frequency of IR radiation matched with the vibrational frequency of
molecule, then molecule absorb radiation.
• IR spectroscopy based on Hooke’s law, suppose two atoms or masses are
connected through spring (bond), then frequency of vibration can be
represented by following equation:
1 𝗆 1 𝗆
ν= √ or ῡ =
2π μ
√
2πc μ

Where, 𝜅 is force constant of the bond, ῡ is wave-number (cm-1), ν is the

frequency, c is speed of light and 𝜇 is reduce mass (m1 and m2 are the
masses of atoms)

m1 × m2
μ =
(m1 + m2)

• Stronger the bond, greater the value of force constant (𝜅), higher the
frequency vibration or wave-number (cm-1). For example,
C−C C=C C≡C
5 dynes
force constant 5 x 105 10 x 105 15 x 10 ( )
cm
wavenumber (cm−1) 1200 1650 2100
• IR spectrum is divided mainly into two region as follows;
 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:

Molecule Degree of freedom

Linear 3n-5
Non-linear 3n-6
Where, ‘n’ is number of atom present in the molecule

The vibrations discuss below are 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 same direction.

ii) Asymmetric stretching vibration: In this vibration one atom undergoes

stretching and other atom undergoes compression and vice versa.

b) 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.

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.
 OVERTONES AND COMBINATION BANDS
When molecule absorbed electromagnetic radiation in IR region, and then
molecule promoted from ground state to second, third or even fourth vibrational
excited state. These bands are known as Overtones. The intensity of these bands is
very weak. It is helpful in characterization of aromatic compounds.

When two fundamental vibrational frequencies (ν1 + ν2) in a molecule couple to

give rise to a new vibrational frequency within the molecule, it is known as
combination band.

COUPLED VIBRATIONS
The coupled vibrations are observed in group like –CH2, NH2 etc. In these groups
same atoms are attached to the central atom. When –CH2 undergoes vibration by
the absorption of IR radiation, due to internal perturbation, energy of one C-H
bond is transfer to neighboring C-H bond which enhance its vibrational frequency.
Therefore two stretching vibrational frequencies for –CH2 group is observed at
2950 cm-1 (asymmetric stretching) and 2860 cm-1 (symmetric stretching).

FERMI RESONANCE
When fundamental vibration coupled with overtones or combination band, the
coupled vibration is called Fermi resonance or when molecule absorb IR radiation
then it transfers its energy or intensity from fundamental vibration to overtones,
then Fermi resonance is observed. As we know that the intensity of overtones band
is very weak as compare to fundamental vibrations. But, due to transfer of energy,
the strong band is observed for overtones along with the fundamental frequency.
Fermi resonance is generally observed in carbonyl groups. For example, in
benzoyl chloride –C=O stretching vibration observed at 1790 cm-1 and 1745 cm-1.
The lower frequency band at 1745 cm-1 is observed due to combination of
overtones of CH bending vibration at 875 cm-1 with the fundamental vibration of
C=O stretching.

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.

Number of molecules contains same functional group & show similar peak above
1500 cm-1 but they show different peak in finger print region. Therefore we can say
that each and every molecule have unique peak or band which is observed in finger
print region, it is just like the finger print of human.
IR correlation chart

Types of vibration Frequency (cm-1)

Alkane C-C stretching 1200
C-H stretching 3000-2840
-CH2 bending 1465
-CH3 bending 1375
CH2 rocking 720
Alkenes C=C stretching 1650
=C-H stretching 3095-3010
=C-H bending 1000-650
Alkynes C≡C stretching 2100
≡C-H stretching 3300
≡C-H bending 700-600
Aromatic C=C stretching 1600, 1500, 1450
=C-H stretching 3040-3010
=C-H bending Below 900
C=O stretching Amide 1680
Carboxylic acid 1710
Ketone 1715
Aldehyde 1725
Ester 1735
Acid chloride 1800
Anhydride 1760 (I), 1810 (II)
C-O Stretching 1300-1000
O-H Alcohol, phenol
Free 3600
H-bonded 3400-3200
Carboxylic acid 3400-2400
Amine -N-H stretching 3440 (as), 3350 (s)
-N-H bending 1650-1580
C-N stretching 1350-1000
Amide -N-H stretching 3370 (as), 3150 (s)
-N-H bending 1650-1560
Nitriles C≡N 2250
Imines C=N 1690-1640
Nitro group (NO2) N=O 1550 (as), 1350 (s)
Alkyl halide (C-X) C-F 1350
C-Cl 750
C-Br, C-I <660
Factor affecting vibrational frequency
a) Conjugation: As the conjugation increase, stretching frequency decreases,
because force content decrease due to conjugation.

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.

c) Hydrogen bonding:
Intermolecular hydrogen bonding weakens the O-H bond, thereby shifting
the band to lower frequency. For example, in neat solution O-H stretching
 vibration of phenol observed in the range from 3400-3300 cm-1. When
solution is dilute then O-H frequency shifted towards higher frequency at
3600 cm-1.

Whereas 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.

d) Ring strain: As the size of the ring decrease, vibrational frequency of C=O
increase. For example.

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.
d) Study of chemical reaction:

e) Identification of geometrical isomers (cis-trans).