Infrared Spectroscopy

 Infrared spectroscopy
• Infrared spectroscopy ( vibrational spectroscopy) involves the
interaction of infrared radiation with matter.
• Absorption in the IR region arise from molecular vibrational
transitions
• Infrared spectrum of a compound represents its energy absorption
pattern in the infrared region and is obtained by plotting percent
absorbance or transmittance of infrared radiation as a function of
wavelength or wavenumber over a particular range
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.
 IR spectra mainly used in structure elucidation to
determine the functional groups.
IR region: 0.8 μm (800nm) to 1000 μm (1mm)

 1.Near IR: 0.8-2 μm

 2.Middle IR: 2-15 μm
 3.Far IR: 15-1000 μm

Most of the analytical applications are confined to

the middle IR region because absorption of organic
molecules are high in this region.
 PRINCIPLE OF IR SPECTROSCOPY

 Molecules are made up of atoms linked by bonds.

 The movement of atoms and the chemical bonds like spring

and balls (vibration)

This characteristic vibration are called Natural vibration.

 The energy of molecular vibration is quantized.
 Principle of IR Spectroscopy

1. As a covalent bond oscillates – due to the oscillation of the dipole of

the molecule – a varying electromagnetic field is produced

2. Greater the dipole moment change through the vibration, the more
intense the EM field that is generated
3.When a wave of infrared light encounters this oscillating EM field
generated by the oscillating dipole of the same frequency, the two
waves couple, and IR light is absorbed
• The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

“coupled” wave

EM oscillating wave
from bond vibration
 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.When applied infrared frequency=Natural frequency of Vibration
3.Change in dipole moment:
A molecule can only absorb IR radiation when its absorption cause a change in its electric
dipole.
A molecule is said to have an electric dipole when there is a slight positive and a slight negative
charge on its component of atoms
HCl , CO2 ,SO2 , HBr , CH4
Note :- All Homo Nuclear diatomic molecule IR inactive like H2 , O2, N2 .
• Degree of Freedom : Fundamental vibration of molecule depend
on degree of freedom.

i. Each atom has 3 degree of freedom depend on x, y, z direction .

ii. For a molecule containing n number of atom has 3n degree of freedom
iii. For non linear molecule 3 degree of freedom represented rotational and
translational motion .
iv. For non linear molecule (3n-6) degree of freedom represent
fundamental vibrations.
v. For linear molecule (3n-5) degree of freedom represent fundamental
vibrations
• Linear molecule CO2
o Total number of degree of freedom = 3n = 3*3 = 9
o Transitional = 3
o Rotational = 2
o Vibrational degree of freedom = 3n-5 = 3*3-5 = 4

• But in case of CO2

• the symmetric stretching frequency is not observed in the IR
spectrum because it is accompanied by a change in the dipole
moment of the molecule with vibration
 MOLECULAR VIBRATIONS
There are 2 types of vibrations:
1. Stretching vibrations

2. Bending vibrations

1. Stretching vibrations:
 Vibration or oscillation along the line of bond

 Change in bond length

 Occurs a t higher frequency: 4000-1250 cm-1

 2 types:

a) Symmetrical stretching

b) Asymmetrical stretching
 A) SYMMETRICAL STRETCHING:
Both bonds increase or decrease in length simultaneously.
H

B) ASYMMETRICAL STRETCHING
 In this, one bond length is increased and other is
decreased.

H
 2. BENDING VIBRATIONS
Vibration or oscillation not along the line of bond
Also called as deformations
In this vibrations bond angle is altered
 Occurs a t low frequency : 1400-666 cm-1
Two types:
a) In plane bending: E.g. scissoring, rocking

b) Out plane bending: E.g. wagging, twisting

 A) IN PLANE BENDING
i. Scissoring:
 This is a n in plane blending
 2 atoms approach each
other
 Bond angles are decrease

H
ii. Rockin g:
 Movement of atoms take place in the same
direction.

H
 B) OUT PLANE BENDING
i. Wagging:
 2 atoms move to one side of the plane. They move up and
down the plane.
H

ii. Twisting:
 One atom moves above the plane and another atom moves
below the plane.
H

H
IR STRETCHING FREQUENCIES
(

 = frequency

k = spring strength (bond stiffness)

= reduced mass (~ mass of largest atom)

Directly on the strength of the bonding between the two

atoms ( ~ k)
Inversely on the reduced mass of the two atoms (v ~
1/m)
 STRETCHING FREQUENCIES

 isolatedC=C 1640-1680 cm-1

 conjugated C=C 1620-1640 cm-1
 aromatic C=C approx. 1600
cm-1

 Frequency
 decreases
Conjugation with
lowers the increasing
frequency atomic weight.
 Frequency increases with increasing bond energy.
• Absorption frequencies in different bonds
• Fingerprint region in IR
In IR, the region below 1500 cm-1 is rich in many bands and the
region is known as fingerprint region
Here the no. of bending vibration are usually more than the
no. of stretching vibration
In this region small difference in the structure and constitution
of a molecule results significant changes in the absorption
bands
• Functional group region in IR
The functional group region runs from 4000 cm-1 to 1450 cm-1
The functional group region contains relatively few peaks
These are typically associated with the stretching vibrations
of functional groups
 Fingerprint group
Functional group region
region
CLASSIFICATION OF IR BANDS
Three types : strong (s), medium (m), or weak (w)

Depending on their relative intensities in the IR spectrum.

 O—H AND N—H STRETCHING

 Both of these occur around 3300 cm-1, but they look

different:

 Alcohol O—H is broad with rounded tip.

 Primary amine (RNH2 ) is broad with two sharp spikes
 Secondary amine (R2 NH) is broad with one sharp
spike.
 No signal for a tertiary amine (R3N) because there

is no hydrogen.
• Factor influencing absorption
 Symmetry
Symmetric compounds do not posses dipole moment and
they are IR inactive
E.g.- symmetric acetylene

Hydrogen bonding
It can change the shape and position of IR bands
Strongers the H-bonding greater the absorption shift
Intramolecular- broad band
Intermolecular- sharp bands
• Electronic effect
o Electronic effects such as inductive, mesomeric and field
effect may cause shift in absorption bands due to the change
in absorption frequency
E.g. Inductive- acetone(1715 cm-1 ) and
chloroacetone (1725 cm-1 )
mesomeric- acetophenone(1693 cm-1 ) and
P-aminoacetophenone (1677 cm-1 )
• Bonds angles
o Difference in bond angles can also leads to the changes in
absorption bands
o E.g.-
INDUCTIVE EFFECT
The introduction of alkyl group causes +I effect which results in the lengthening or the
weakening of the bond. Hence the force constant is lowered and wave number of
absorption decreases.

Let us compare the wave numbers of v (C=O) absorptions for the following compounds :
 Formaldehyde (HCHO) 1750 cm-1.
 Acetaldehyde (CH3CHO) 1745 cm-1.
 Acetone (CH3COCH3) 1715 cm-1.

 Introduction of an electronegative atom or group causes –I effect which results in the bond
order to increase.

 Hence the force constant increases and the wave number of absorption rises.
E.g. Inductive- acetone(1715 cm-1 ) and
chloroacetone (1725 cm-1 )
  Mesomeric effect :-
• It causes lengthening or the weakening of a bond leading in the
lowering of absorption frequency.
• As nitrogen atom is less electronegative than oxygen atom, the electron
pair on nitrogen atom in amide is more labile and participates more in
conjugation.
• Due to this greater degree of conjugation, the C=O absorption
frequency is much less in amides as compared to that in esters.
 Hydrogen bonding
• It occurs in any system containing a proton donor group(X-H) and a
proton acceptor. if the s-orbital of the proton can effectively overlap
the P or π orbital of the acceptor group.

• The stronger the hydrogen bond, the longer the O-H bond, the lower
the vibration frequency and broader and more intense will be the
absorption band.

• The N-H stretching frequencies of amines are also affected by

hydrogen bonding as that of the hydroxyl group but frequency shifts
for amines are lesser than that for hydroxyl compounds.

• Because nitrogen is less electronegative than oxygen so the hydrogen

bonding in amines is weaker than that in hydroxy compounds.
• Intermolecular hydrogen bonds gives rise to broad bands, while intramolecular
hydrogen bonds give sharp and well defined bands.

• The inter and intramolecular hydrogen bonding can be distinguished by dilution.

• Intramolecular hydrogen bonding remains unaffected on dilution and as a result the

absorption band also remains unaffected where as in intermolecular, bonds are
broken on dilution and as a result there is a decrease in the bonded O-H absorption .
 IR SPECTRUM OF ALCOHOLS

 IR spectrum of alcohols broad, intense O—

H stretching absorption around 3300 cm-1.
 The broad shape is due to the hydrogen bonding

interactions of alcohol molecules.

 IR SPECTRUM OF AMINES

 The IR spectrum of amines show a broad N—H

stretching absorption centered around 3300 cm-
1.
 IR SPECTRUM OF AMIDES

 strong absorption for the C═O a t 1630–1660 cm-1.

 there will N—H absorptions a t around 3300 cm-1.
• Applications of IR spectroscopy
Identifications of an organic compound
o The identity of an organic compound can be established from its
fingerprint region by comparing the sample spectrum with the known
spectrum of the compound.
o E.g.- spectrum of n-heptanal
2. Qualitative determination of functional groups
o The presence or absence of absorption bands help in
predicting the presence of certain functional group in the
compound
3. Distinction between 2 types of H-bonding
o If a compound having intra-molecular H-bonding it will show broad bands
in IR spectrum and if a compound having intermolecular H-bonding then
it will show sharp well defined bands.
o E.g.- o-nitrophenol shows broad bands due to intra-molecular H-bond
whereas p-nitrophenol shows sharp bands due to intermolecular H-
bonding

4. Qualitative analysis
o It can be done by measuring the intensity of the absorption bands.
o E.g.- xylene exists as mixture of 3 compounds which shows absorption
bands at.
ortho- 740 cm-1
meta - 880 cm-1
para - 830 cm-1
5. Study of chemical reactions

o It is useful for studying the chemical reactions.

o E.g. – reduction of butan-2-one to from butan-2-ol

LiAlH4

O OH
Butan-2-one Butan-2-ol
(1710cm-1) (3300cm-1)
 Bibliography
•Pavia, D. L., Lampman, G. M., & Kriz, G. S. (1979). Introduction to
spectroscopy: A guide for students of organic chemistry. Philadelphia:
W.B. Saunders Co.

•Bruice, P. Y. (2004). Organic chemistry. Upper Saddle River, NJ:

Pearson/Prentice Hall.

•Sharma Y.R.(2015).Elementary Organic spectroscopy principles and

chemical applications, S.Chand publishing.