INFRARED SPECTROSCOPY

INTRODUCTION:-

• Infrared spectroscopy deals with the interaction between molecule and radiation
from the IR-region which ranges from 4000 – 400 cm unit is the wave number .
IR region lies between the visible and the microwave region.

• IR region having longer wavelength as compared to visible region it lies below

the red colour of the visible region.

• Infrared spectroscopy is also known as vibrational spectroscopy. The absorption

of infrared radiations is associated with the excitation of the molecules from the
ground state to a higher vibrational energy state.

E = hv

• These vibrations include the stretching and the bending modes.

STRETCHING VIBRATIONS ; The periodic movement between the bonded atoms along
the bond axis such that the interatomic distance is increases or decreases.

BENDING VIBRATIONS ; The periodic movement that cause a change in the angle
between bonds i.e the position of atoms changes relative to the original bond axis ; the
interatomic distance remain same.

• When infrared radiations are passed from the organic compound only those
frequencies are absorbed which are match with the vibrational frequency .

• Before and after absorption frequency remain same but there is change in
amplitude.
 IR active and IR inactive molecules / vibrations ;-

INFRARED ACTIVE VIBRATIONS ; Those vibrations which cause dipole moment

(polar molecules) to fluctuate and thus produce a fluctuating electric field and it will
interact with the fluctuating electric field of EMR having matching frequency and cause
the absorption such vibrations are known as infrared active vibrations. These vibrations
occur in symmetrical molecules.

INFRARED INACTIVE VIBRATIONS ; Those vibrations that does not cause a change in
the dipole moment ( non-polar molecules ) will not interact with the infrared radiations,
and therefore known as infrared-inactive vibrations.

FACTORS AFFECTING VIBRATIONAL FREQUENCY:-

A) SRENGTH OF BOND ; The strength of bond which is directly proportional

proportional to vibrational frequency.

C=C > C=C > C-C

B) MASSES OF THE BONDED ATOMS ; The mass of the bonded atoms is

inversely proportional to the vibrational frequency .

PREPARATION OF SAMPLES FOR IR SPECTROSCOPY : -

• Sample cells are made up of ionic substances e.g ; NaCl and KBr instead of glass
and plastic.
• NaCl and KBr both are transparent in IR region .
KBr transparency range is 4000-400 cm.

NaCl transparency range is 4000-650 cm.

Samples used for analysis may be sloid, liquid and gas.

1) LIQUID SAMPLE ; preparation Neat liquid method is used.

 2) SOLID SAMPLE ; preparation three methods are used,
 KBr pellets.
 Nujor Mull method.
 Solution method.

3) GASEOUS SAMPLE ; Multiple gas cells are used.

INSTRUMENTATION :-

1) Dispersive IR spectrophotometer.
2) Fourier transform IR spectrophotometer.

1) DISPERSIVE IR SPECTROPHOTOMETER ;-

i) SOURCE ; Nernst Filament is used and it is electrically heated

1000-1800 C and emit radiations in the form of heat of different
frequency and wave number.

ii) BEAM SPLITTER ; It splits IR in two beams of equal intensities.

iii) MONOCHROMATOR ; It is a wavelength selector and having the

diffraction gratings and allows the singal wavelength to pass and
reach the detector.

iv) DETECTOR ; It convert the thermal energy into the electric energy
and it is based on thermoelectric effect. It is made up of two wires
of dissimilar metal. When IR radiations strike with wires heat is
absorb electrons flow from hot wire to cold wire and generate an
electric current.

v) AMPLIFIER ; It amplifies the current coming from the detector.

vi) RECORDER ; Represent the IR spectrum of the unknown sample

by showing peaks in different peaks in different regions.

IR spectra consist of two regions ;-

i) Functional group region  4000-1600 cm.
ii) Finger print region  1600-400 cm.
2)FOURIER TRANSFORM IR SPECTROPHOTOMETER :-

Light from the source is split into two beams by a half-silvered mirror, one is reflected
off the semi transparent mirror , goes to the top mirror and then reflects back, goes to
through the semi-transparent mirror , to the detector . The other first goes through the
semi-transparent mirror to the mirror on the right reflects back to the semi-transparent
mirror then reflects back from the semi-transparent mirror into the detector.

All IR radiations enter in the cell at the same time and detect too.

Interferogram convert these signals into neat IR spectrum by applying fourier transform
operation.
 INTERPRETATION OF IR SPECTRA

It is used for the determination of functional groups in organic compound. Complete

structure of compound is not determined only the functional groups are detected.

GROUPS SPECTRA RANGE PEAK

APPEARANCE
Nitro group 1600 – 1300 cm Two strong
absorption bands.
Hydroxyl group (OH) 4000 – 3000 cm Strong absorption
and broad peak
appear.
Amides (NH ) 4000 – 3000 cm Medium and sharp
absorption band
Ester ( C-O) 1300 – 1000 cm Strong band.
Anhydrides 1800 – 1600 cm Two strong
absorption peaks
appear.
Aldehyde 3000 – 2500 cm Weak and small
peaks.
Ketones 1800 – 1600 cm No strong
absorption peak
appear
Aromatic ring 1600 – 1400 cm No of medium
absorption bands.
                

APPLICATIONS OF INFRARED SPECTROSCOPY:­

i) Structure determination.
ii) Detection of impurities.
iii) Progress of a chemical reaction.
iv) Percentage composition of a mixture.