IR Spectroscopy

ELECTROMAGNETIC RADIATIONS

Molecular Molecular Electronic Valence band and Deep electronic

rotations vibrations Absorption shallow electronic core levels
levels (atoms) (atoms)

Infrared, UV absorption
Raman,

Microwave, Visible X-ray photoemission

 INTRODUCTION

• Absorption of Infra red radiations

by the molecules
• Wave number of electromagnetic
radiations involved are 4000cm-1 to
600cm-1
• Effective method for determining
the presence or absence of a wide
variety of functional groups in a
molecule.
 INTRODUCTION

WHAT HAPPENS WHEN A MOLECULE

ABSORBS IR RADIATIONS

Ionises ?

Electrons go to higher energy level?

Molecules vibrate?
 INTRODUCTION

The infrared rays are not large

enough to excite electrons, but
they induce vibrational
excitation of covalently bonded
atoms and groups.
What are Vibrations of molecules?

Any change in shape of the molecule-

stretching of bonds, bending of bonds
is called vibration

Hence vibrations are of two types

STRETCHING AND BENDING

stretching vibration 154 pm

10 pm
bending vibration

4o 10 pm
 Stretching vibrations

1. Symmetric stretching

2. Asymmetric stretching
 Bending vibrations

Scissoring

Rocking

Twisting

Wagging
 Bending vibrations

Scissoring

Rocking

Twisting

Wagging
Each stretching and bending vibrations take place at a characteristic
frequency

When a compound is exposed with radiation of a frequency (wave

number) exactly equal to the frequency of the vibrations the
molecule will absorb energy

Bond will stretch or bend little more

Amplitude of vibration increases but not the frequency

Wavelength of the light absorbed gives the indication of types of

bonds in the molecule
12500 – 4000 400- 50
4000 - 400cm-1
cm-1 cm-1
FUNCTIONAL GROUP REGION

• 4000 – 1400 cm-1

• Most of the functional groups show

absorption bands here

FINGERPRINT REGION

• 1400 – 600cm-1

• Each compound shows a unique

absorption pattern

• Overall pattern of absorption is the

characteristic of the compound
 HOOKES LAW

The restoring force of a spring is directly

proportional to the displacement of the spring
from the equilibrium position

K = force constant  = reduced mass

Absorption I R by the functional groups
TYPE OF BOND WAVE NUMBER

CN 2260-2220 Medium

CC 2260-2100 Weak
C=C 1680-1600 Medium
C=N 1650-1550 Medium
1600, 1500-1430
C=O 1780-1650
C-O 1250-1050
C-N 1230-1020
O-H (alcohol) 3650-3200
O-H (acid) 3300-2500

N-H 3500-3300
C-H 3300-2700
Basics
Calculate the wave number of stretching vibration of
a carbon carbon double bond force constant
k = 10  105 dynes cm-1

Calculate the wave number of stretching vibration of

a oxygen hydrogen single bond. Force constant
k = 5  105 dynes cm-1

Calculate the force constant of O-H bond. The wave

number of stretching vibration of a oxygen hydrogen
bond is 3330cm-1.
Condition for a molecule
to be IR active

• During vibrations if a
molecule undergoes a
change in the dipole
moment it becomes I R
active
ENERGY LEVELS OF A SIMPLE HARMONIC OSCILLATOR

Inter nuclear distance

INSTRUMENTATION
Source:
• Nernst Glower : oxides of Zr, Th, Ce,

Monochromator:
• Prism of NaCl or KBr or diffraction gratings

Detector
• thermopile : Thermocouples connected in series

Sample Holder
• Polished mineral salt like KBr, AgCl or CaF2

Mode of operation
• light source is split into 2 beams

Difference in the intensity is measured

1. Determination of force constant or bond
strength
2. Identification of the compound
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH 3500
CH 3300
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH 3500
CH 3300
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
1. Determination of force constant or bond
strength
2. Identification of the compound
3. Structural Elucidation
4. Determination of molecular shape
1. Determination of force constant or bond strength
2. Identification of the compound
3. Structural Elucidation
4. Determination of molecular shape
5. Quantitative Analysis
6. Study of Chemical reaction
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
mono substitited benzene 745 - 680
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
mono substitited benzene 745 - 680
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
mono substitited benzene 745 - 680
OH 3650
 NH2 3500
CH3 2970
=CH2 3080
 CH 3320
3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
mono substitited benzene 745 - 680
 BENZALDEHYDE
OH 3650
 NH2 3500
Aromatic C=C stretching
1600, 1580, 1460
CH3 2970
=CH2 3080
 CH 3320
Benzene 3060
C=O 1720
CO 1250
-CHO 2720, 2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
mono substituted benzene 745 - 680
 ANILINE
3000, 3400, 3500, 1600, 1580, 1460, 1300

OH 3650
 NH2 3500
Aromatic C=C stretching
1600, 1580, 1460
CH3 2970
=CH2 3080
 CH 3320
Benzene 3060
C=O 1720
CO 1250
-CHO 2720,
2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
 ETHYL ALCOHOL
3630, 2996, 2924, 1050,

OH 3650
 NH2 3500
Aromatic C=C stretching
1600, 1580, 1460
CH3 2970
=CH2 3080
 CH 3320
Benzene 3060
C=O 1720
CO 1250
-CHO 2720,
2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
 Benzoic acid
2500 – 3300, 1680, 3000,1600, 1580, 1460 ,1300

OH 3650
 NH2 3500
Aromatic C=C stretching
1600, 1580, 1460
CH3 2970
=CH2 3080
 CH 3320
Benzene 3060
C=O 1720
CO 1250
-CHO 2720,
2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
 Benzonitrile
2230, 1600, 1580, 1460, 3060(aro C-H)

OH 3650
 NH2 3500
Aromatic C=C stretching
1600, 1580, 1460
CH3 2970
=CH2 3080
 CH 3320
Benzene 3060
C=O 1720
CO 1250
-CHO 2720,
2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
 Benzonitrile
2230, 1600, 1580, 1460, 3060(aro C-H)

OH 3650
 NH2 3500
Aromatic C=C stretching
1600, 1580, 1460
CH3 2970
=CH2 3080
 CH 3320
Benzene 3060
C=O 1720
CO 1250
-CHO 2720,
2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
 Toluene
2940, 1600, 1580, 1460, 3060(aro C-H), 730-770(-CH3)

OH 3650
 NH2 3500
Aromatic C=C stretching
1600, 1580, 1460
CH3 2970
=CH2 3080
 CH 3320
Benzene 3060
C=O 1720
CO 1250
-CHO 2720,
2820
CC 2150
C=C 1680
C N 2260
C=N 1650
CN 1230
 RAMAN SPECTROSCOPY
When radiation passes through a transparent
medium, the species present scatter a fraction of
the beam in all directions.

In 1928, the Indian physicist C. V. Raman

discovered that the visible wavelength of a small
fraction of the radiation scattered by certain
molecules differs from that of the incident beam
and furthermore that the shifts in wavelength
depend upon the chemical structure of the
molecules responsible for the scattering.
Similarity between IR & Raman

• Finger pints of the • Finger pints of the

molecular structure molecular structure
• Internal vibrations of • Internal vibrations of
the covalently bonded the covalently bonded
molecule molecule
• Lattice structures of • Lattice structures of
the ionic molecules in the ionic molecules in
the crystalline state the crystalline state
Differences between IR & Raman

Raman IR
• Water is used as a • Water is opaque to IR
solvent in Raman radiation
• Raman spectra can be • IR spectra of lquids
obtained for gases, and solids are diffused
soids, & liquids
Differences between IR & Raman

Raman IR
• Scattering of light by • Absorption of light by
vibrating molecules vibrating molecules
• Polarisability of the • Dipole moment in the
molecule is the molecule is the
deciding factor deciding factor
• Homonucear diatomic • Homonucear diatomic
molecules (N2, O2, Cl2) molecules (N2, O2, Cl2)
are often found to be are often found to be IR
Raman active inactive
 Mutual Exclusion Principle

Symmetric molecules
IR-active vibrations are not Raman-active.
Raman-active vibrations are not IR-active.

O=C=O O=C=O

Raman active Raman inactive

IR inactive IR active
Instrumentation
 Sample Illumination System
Sample handling for Raman spectroscopic
measurements is simpler than for infrared
spectroscopy because glass can be used for
windows, lenses, and other optical components
instead of the more fragile and atmospherically less
stable crystalline halides. In addition, the laser
source is easily focused on a small sample area and
the emitted radiation efficiently focused on a slit.
Consequently, very small samples can be
investigated. A common sample holder for
nonabsorbing liquid samples is an ordinary glass
melting-point capillary.
 Sample Illumination System
• Liquid Samples: A major advantage of sample
handling in Raman spectroscopy compared with infrared
arises because water is a weak Raman scatterer but a
strong absorber of infrared radiation. Thus, aqueous
solutions can be studied by Raman spectroscopy but not
by infrared. This advantage is particularly important for
biological and inorganic systems and in studies dealing
with water pollution problems.
• Solid Samples: Raman spectra of solid samples are
often acquired by filling a small cavity with the sample
after it has been ground to a fine powder. Polymers can
usually be examined directly with no sample
pretreatment.
 Raman Spectrometers
Raman spectrometers were similar in design and
used the same type of components as the classical
ultraviolet/visible dispersing instruments. Most
employed double grating systems to minimize the
spurious radiation reaching the transducer.
Photomultipliers served as transducers. Now
Raman spectrometers being marketed are either
Fourier transform instruments equipped with
cooled germanium transducers or multichannel
instruments based upon charge-coupled devices.