VIJAYANAGARA COLLEGE

HOSPETE,VSKUB
department of PG studies and research
in chemistry

INFRARED SPECTROSCOPY
PRESENTED BY
PRATIBHA .K
Introdution
 Infrared radiation was discovered in 1800 by
astronomer Sir William Herschel .
 Infrared spectroscopy provides a wealth of information

on
 1. Transition between Vibrational & rotational energy

levels in molecules.
 2.Symmetry , purity & structure of organic compounds.
 The frequency or wavelength absorption depends on

the masses of the atoms , the force constants of the

bonds & the geometry of the atoms.
 Infrared (IR) Is an electromagnetic radiation (EMR)
with wavelengths longer than those of visible light.
 Infrared technique is based upon the simple fact that
a chemical substance shows marked selective
absorption in infrared region .
 Infrared spectrum of a compound represents it’s
energy absorption pattern in the infrared region & is
obtained by plotting absorbance or transmittance of
IR radiation as a function of wavelength or wave
number over a particular range.
 Regions of infrared spectrum :
IR Radiation refers that part of the Electromagnetic
spectrum which lies between the visible & microwave
regions. The IR region has been subdivided as follows .
 1. Photographic region: Ranges from visible to 0.8 µm .
 2. near infrared region (overtone region): Ranges from

0.8 µm to 2.5 µm .
 3.mid infrared region (vibration – rotation): Ranges from

2.5 µm to 15 µm .
 4. far infrared region (Rotation region): Ranges from 15

µm to 200 µm .
 INFRARED INSTRUMENTATION
 The IR instrumentation has divided into Dispersive
& Inter ferometric methods .
 Dispersive spectrometer :
 It uses a grating or prism to disperse the radiation

from the source into the spectral elements according

to Bragg’ s law nλ= 2d sinθ . And a detector to
measure the energy of each spectral element.
 Filters are used to eliminate the higher order bands

of lower wavelength radiation.

 A condensing system focuses the radiation on the
entrance slit of a monochromator , that selects a narrow
band of radiation.
 A second condensing system focuses the energy from
the exit slit of the monochromator on to a detector.
 The signals are amplified & a recorder records the
signals.
 The energy of each spectral element is measured along
the frequency domain & vibrational & rotational bands
are observed directly from the spectrum
SINGLE BEAM SPECTROPOTOMETER
 A single beam spectrophotometer records the energy
of the radiation reaching the detector after passing
through a sample .
 These are simple ,sensitive ,accurate, versatile & are

used to study fine details.

 Disadvantages:
 When the spectra of the solution is recorded ,The

absorption bands due to solvent are also

obtained ,thus making the interpretation of bands
more difficult.
DOUBLE BEAM SPECTROPHOTOMETER
 The optical null & ratio recording spectrophotometers
are most common.
 The main difference between these two instruments

lies in the manner in which the energy measured by

the detector is recorded as spectra.
 Components of Double beam IR
Spectrophotometer
1.Radiation Source .
2.Monochromator and Optical material.
3.Sampling area .
4. Detector.
5. Instrument for the measurement of response of the
recorder.
 1 .Radiation Source
 IR radiation is produced by electrically heating a
source .
 Usually a Nerst glower or a Globar to 1273 –

2073K.
 Globar is a small rod of silicon carbide usually 5cm

in length and 0.5 cm in diameter.

 The Nerst filament is fabricated from a binder and

oxides of Thorium , Cerium , Zirconium,& Yttrium.

 Nichrome wire , carbon arc , Rhodium wire &

Tungsten filament lamp are also used as light source.

 2.Monochromator & Optical material
 The separation of desired frequencies can be achived by
means of monochromators.
 Prisms & Gratings are used for this purpose.
A monochromator
 1. disperses the Radiation according to it’s wave number
components .
 2. Restricts the radiation falling on the detector into a
narrow wave number range.
 Most IR Spectrometers use Prisms of alkali halides.
 Prisms of LiF or CaF2 give more resolution in the region
where the significant stretching vibrations are located.
 The most common Prism material used is Nacl for
the entire region from 4000 – 650 cm-1 .
 Crystalline KBr & CsBr are satisfactory for the Far

IR region .
 LiF provides prism material in the near IR region.
 Fused silica & glass are also used as Optical

materials.
 Prisms suitable for use below 250 cm -1 are not

commercially available . therefore , it is necessary to

use gratings in order to obtain spectra below 250 cm -1
 Gratings disperse the energy into more than one order
and the undesirable wavelengths are separated with
high quality filters.
 Both transmission & interference filters have been

developed for IR region.

 3. Sample Handling
 Compounds may be examined in the vapour phase , as
pure liquids in solution & in solid state.
 Crystalline sample can be used for the study of IR

dichroism & informations regarding molecules in the

molecules in the lattice can be obtained.
A. Gaseous sample :
 The Vapour is introduced into a special cell,usually about

10 cm long , the can be placed directly in the path of one

the IR beams.
 Most organic compounds have too low a vapour pressure

for this phase to be useful.

 Only a few thermally stable metal carbonyl ,
cyclopentadienyl compounds & certain acetyl acetone
complexes can be examined in the gas phase.
B. Liquid samples :
 Liquids are usualy handled pure ,i.e without solvent

because all solvents have their own absorption spectra .

 Ex: Ccl is useful in the 4000 – 1350 cm -1 region .
4
 Cs2 is used in the range 1330 – 625 cm-1 region .
 In resricted wave length regions acetone , alcohol,
water, chloroform, cyclohexane also give satisfactory
results.
 C. Solid Sample:
 A wide variety of techniques is used for measurement of IR
absorption spectra of solid materials .
 Solid samples may be used in the form of solution, powder,
glassy film or pellet.
(1) Solids run in solution:
 If the solid is soluble in some suitable solvent, it’s solution
can be made and run in one of the cells for liquids.
 Suitable solvents are limited in number and none are totally
transparent.
 Ex: Cs2 (Carbon disulphide)is transparent below 1330 cm -1 .
 (2) Solid films:
 Amorphous solid samples may be cast into films from
solution on an IR transmitting window or solid melted
between salt plates and allowed to cool into a film.
 This technique is recommended for rapid qualitative
analysis but not for quantitative analysis.
(3) Mull Technique :
 The most convenient & Routine method is called
Mulling.
 The powdered sample is mixed with little high boiling
petroleum ,usually Nujol.
The oil has a few absorption bands specifically at
about 2857, 1449,& 1389 cm-1 . C-H stretching
and C-H bending absorption bands occur in these
region .
 Use Nujol ,Fluorolube or Hexachlorobutadiene

makes possible a scan ,essentially free of interfering

bands , over the 4000 cm-1 to 666cm-1 ( 2.5 to 15 µm)
regions.
 (4) Pressed pellet technique :
 This technique depends on the fact that dry ,

powdered KBr can be pressed under high pressure in

vacuo to form transparent discs which are inserted
into a special holder of the spectrometer.
 In conjunction with mull method , it can yield more

information about the sample .

 Some polymers yield their best spectra in KBr disc.
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 (4) Detector
 Detector is a device that usually change the Thermal radiant energy
into electrical energy.
 The IR detectors may be selective or non selective.
 The selective detector are those whose response is markedly
dependent upon the wave length of the incident radiation .
 EX: Photo cell, photo graphic plates , photo conductive cell.
 The non – selective detectors are those whose response is directly
proportional to incident energy but relatively independent of wave
length.
 Ex: Thermo couples, bolo meters and pneumatic cell.
 (5) Recorder
 Computer is used as recorder, in which all the
electrical energy (which is converted by detector) is
stored as a data.
 We can get the data in the form of spectrum.
Fourier Transform infrared spectroscopy or
Interferometry

 Principle: The simple interference of radiation where

the absorption spectrum is obtained through the
interference Technique.
 Two radiation beams with the same wave length (λ)

& amplitude lead to optical interference.

1. If the radiation beams are in Phase the beams will
interfere constructively & the resultant amplitude
will be twice as high.
2. If the radiation beams are out of Phase by (1/2)
(2n+1) λ ( half integral number of wave length),
the beams will interfere destructively &
cancelling out each other .
 FTIR Spectrometer

It consists of
 1. an optical system which uses an interferometer.
 2. Computer which stores data ,performs

computation on the data &plots the spectra.

 FT Spectrometer consists of two perpendicular mirrors,
one oof which is a Stationary mirror and other a movable
mirror.
 Between these two mirrors is a beam splitter set at

45degree from the initial position of the movable mirror.

 A parallel beam of radiation from the IR Source is passed

on to the mirrors through the beam splitter.

 The beam splitter divides the beam and transmits half the

incoming radiation to the fixed mirror and the other half

to the movable mirror.
 The composition of beam splitter on the spectral region.
 For Example , in the mid-IR region (4000-400 cm-1) , a
beam splitter of germanium coated on a kBr plate is used .
 Germanium reflects the radiation while KBr transmits most
of the desirable radiation .
 In the far-IR region ,germanium coated on CsI is used.
 Upon reflection from the fixed and moving mirrors the light
is recombined at the beam splitter.
 The path length of one of the return beams is changed in
order to create an overall phase difference to cause an
interference pattern.
 The recombined radiation is then directed through the
sample and focused on to the detector.
 The detector measures the amount of energy at discrete
intervals of mirror movement .
Factros affecting group frequencies and
band shape.
 The value of absorption frequency is also shifted
science the force constant of bond changes with it’s
electronic states
 Frequency shifts also occur while working with the

same substance in different states.

 In the vapour state a substance usually absorb at higher

frequency than that of the solid and liquid states.

 Following are some of the factors responsible for

shifting the vibrational frequencies from their normal

valves.
 1.Vibrational coupling / coupled
vibrations:
 An isolated C-H bond exhibits one stretching frequency but
in case of methylene(CH2) groip, two absorptions occur
which corresponds to symmetric and asymmetric as shown
in below fig. respectively


 In such cases, asymmetric vibrations always occur at
higher wave number than symmetric vibrations.these are
known as coupled vibration.
 Since these vibration occur at different frequencies that
required for an isolated C-H stretching.
 Similarly ,coupled vibration of –CH3 group occur at
different frequencies compared to –CH2 group.
 Some times it happens that two different vibrational
levels have almost same species ( i.e –CH2 or -CH3group)
 Then a mutual perturbation of energy may occur resulting
in the shift of one towards lower frequency while the
other to wards higher frequency.
2.Electrical /Electronic Effect
 The changes in the absorption frequencies for a particular
group take place when the substituents in the
neighborhood of that particular group are changed.
 The frequency shift are due to electronic effect which

include :
a. Inductive effect
b.Mesomeric effect
c. Field effect
Under the influence of these effects,the force constant or
the bond length or strength changes and it’s absorption
frequency shifts from the normal value .
a. Inductive effect
 The introduction of an electronegative atom or group
causes –I effect which results in the bond order to
increase.
 The force constant increases and hence the wave

number of absorption rises.

 Ex: acetone –CH -CO-CH - 1715 cm-1
3 3

Chloroacetone - CH3-CO-CH2Cl -1725 cm -1

Dicholroacetone – CH3–CO-CH2Cl2 – 1740 cm-1
 The introduction of alkyl group causes + I effect which
results in weakening of the bond .
 Hence the force constant is lowered and wave number

of absorption decreases.
 Ex: formaldehyde -1750 cm-1
 Acetaldehyde - 1745 cm-1
 Conjugation lowers the absorption frequency of C=O

stretching whether the due to aromatic ring .

b. Mesomeric effect
 It causes lengthening or the weakening of a bond
leading to the lowering of absorption frequency .
 In most of the cases mesomeric effect works along with

inductive effect.
 Ex :
 In case where the lone pair of electron present on an
atom is in conjugation with the double bond of a group
the mobility of the lone pair of electrons matters.
 As N-atom is less electronegative than oxygen atom the
electron pair on N –atom in amide is more labile and
participates more in conjugation.
 Due to greater extent of conjugation , the C=O

absorption frequency is much less in amide as

compared to that in ester.
 3. Field effect
 In the ortho substituted compounds the lone pair of

electrons on two atoms influence each other through

space interaction and change the vibrational
frequencies of both the groups this effect is known as
Field effect.
 Consider ortho haloacetophenone . The non- bonding
electrons present on oxygen atom cause electrostatic
repulsions. this results in a change in the state of
hybridization of C=O group and also makes it to go out
of the plane of the double bond .
 Conjugation diminished and absorption occurs at a

higher frequency or wave number , thus for substituted

compounds, cis-isomer absorbs at a higher frequency
than the trans isomer .
3. Hydrogen Bonding
 Stronger the hydrogen bonding greater is the
absorption shift towards lower wave number than the
normal value.
 Generally bands due to intramolecular (with in )

hydrogen bonds give rise to broad bands.

 The absorption frequency difference b/w free and

associated molecule is smaller in case of intramolecular

H-bonding than that in intermolecular association.
 On dilution i.e if dilution increases bond becomes

sharp in intermolecular H- bonding and vibrational

frequrncy shifts at higher frequency.
 Since N-atom is less electronegative than O-atom so
hydrogen bonding in amines is weaker than that in
alcohols.
 Thus amines show N-H stretching at 3500 cm-1 .in

dilute solution absorption occurs at 3300 cm-1.

 The O-H group involved in chelation gives rise to

broad absorption b/w 3000to 2500 cm-1 .

 The frequency of CO absorption occur at 1630 cm-1

( enolic )that in keto form 1725 cm-1.

4. Ring structure /bond angle
 If the ring strain increses ,bond angle increases .hence
the energy increases.
 Angle strain increases carbonyl frequency .
 Therefore absorption frequency increases.
 Smaller angle requires more p character
 Greater the s- character results in shortening and

shorter of C=O bond and the C=O stretch occurs at

higher frequency.
co-relation Chart
 is a list of absorption peaks and frequencies, typically
reported in wavenumber, for common types of
molecular bonds and functional groups.
 Application of IR Spectroscopy
1. Qualitative Analysis :
IR Spectroscopy is particularly useful in the qualitative
identification of compound or components of a mixture.
2. Identification of functional group & structure
elucidation :
Entire IR region is divided into group frequency region
& Finger print region. Range of group frequency is 4000
– 1500 cm-1 while that of finger print region is 1500 –
400 cm-1 .
 In group frequency region , the peaks corresponding
to different functional groups can be observed.
According to corresponding peaks , functional groups
can be determined.
Each atom of the molecule is connected by bond and
each bond requires different IR region so
characteristic peaks are observed. This region of IR
spectrum is called as fingerprint region of the
molecule .It can be determined by characteristic
peaks.
3. Studying the progress of the reaction :
Progress of chemical reaction can be determined by
examining the small portion of the reaction mixture
Withdrawn from time to time .
The rate of disappearance of a characteristic
absorption band of the reactant group or the rate of
appearance of the characteristic absorption band of
the product group due to formation of product is
observed .
4. Purity of sample :
Pure sample show fairly sharp and well resolved
absorption bands while the spectrum of crude sample
may be exhibit poorly resolved broad bands.
 Reference
 Instrumental methods of chemical
Analysis
H. KAUR
Thank - you