INFRARED
SPECTROSCOPY
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i. >
fi e IR spectroscopy is the study of interaction
between infrared radiations and matter.
A. Infrared radiations refers broadly to that
part of electromagnetic spectrum between
visible and microwave region.
O.2um O.4um 0, 764m 1,0004m
Utraviolt RY Visible Infra-Red
wm” um soum “Ss 200mm
ae ~ Wi eae
(Ker i c—y
warmer cues
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ETHANOL
Transmittance INFRARED SPECTRUM
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
v j ] 1 | j
l l lL 1 |
3000. 2000. 1000.
Wavenumber (cm-1)
IR spectrum of ethanol
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PRINCIPLE
~~» The principle of IR spectroscopy Is related to
the vibrational and rotational energy of a
molecule.
e When the frequency of the IR radiation is
equal to the natural frequency of vibration, the
molecule absorb IR radiation.
e Absorption of IR_ radiation causes an
excitation of molecule from a lower to the
higher vibrational level.
e Each vibrational level is associated with a
number of closely placed rotational level.
e Therefore the IR spectroscopy is also called
as ‘vibrational-rotational spectroscopy”
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. e All the bonds in a molecule are not capable
of absorbing IR energy but those bonds
which are accompanied by a change in
dipole moment will absorb in the IR region
and such transitions are called IR active
transitions.
e The transitions which are not accompanied
by a change in dipole moment of the
molecule are not directly observed and are
considered as IR inactive.
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«_ e In IR spectroscopy the changes in the vibratione
~~ energy depends upon
Mass of the atoms present in a molecule
strength of the bonds
Arrangement of atoms within the molecule
e No two compounds except the enantiomers can
have the similar IR spectra.
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THEORY
e When a molecule absorb radiation with a
frequency less than 100 cm”! ,molecular
rotation takes place and if a molecule
absorod more energetic radiation in the
region of 10% to 10* cm’ _, molecular
vibration takes place.
eA single vibrational energy change is
accompanied by a large number of
rotational energy changes and thus the
vibrational spectra appear as vibrational
rotational bands.
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_FATE OF ABSORBED RADIATION
e There are 3 main process by which a molecule
“can absorb radiation, each of these route
involve an increase of energy which is
proportional to the light absorbed.
|. First route occurs when absorption of
radiation leads to a higher rotational energy
level in a rotational transition.
ii. Second occurs when absorption of radiation
leads to a higher vibrational energy level in a
vibrational transition.
iil. Third occurs when absorption of radiation
leads to a higher electronic energy level in its
electronic transiwtwwi.DoulonMsix.com
E
Electronic
energy levels
E2 x 4
v4= —.— <—— — —__—__—— Rotational Vi; brati: onal
energy
Vito SEI t
leiveilds levels |
A 6 C
Energy level diagram
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e Two criteria must be satisfied by a
molecule for the absorption of IR radiation:
The molecule should possess
vibrational and rotational frequency.
The molecule must give rise to
asymmetrical charge distribution.
e Three main type of absorption bands
occur in IR spectra:
Fundamental
Overtone
combinational
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80-4
Fundamental
40-4 band:
1 717 cm”
2
0 o ™
% $ &
me – ee “i. T se
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm)
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Transmittance (%)
FERMI RESONANCE
~~« Interactions which occur between fundamental and
overtone or combinational bands are known as
Fermi resonance.
e This phenomenon can be observed whenever two
fundamental or a fundamental and overtone bands
have nearly the same energy.
e Here molecule transfer its energy from fundamental
to overtone and back again and so that the each
level become partially fundamental or partially
overtone in character.
e As a result, two strong bands are observed in the
enerne instead of the expected strong and weak
ands.
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‘VW
VV
© E.g.: CO,
> It normally shows fundamental band at 1337
cm:’ and overtone at 1334.6 cm”.
° But due to the effect of Fermi resonance the
first band shift towards higher frequency and
give rise to two bands at 1285.5 cm” and
1388.3 cm’.
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FINGERPRINT REGION
A
“win IR, the region below 1500 cm” is rich in many
absorption bands and the region is known as
fingerprint region.
e Here the number of bending vibrations are usually
more than the number of stretching vibrations.
e In this region, small difference in the structure and
constitution of a molecule results significant changes
in the absorption bands.
e Many compounds show unique absorption bands in
this region and which is very useful for the
identification of the compound.
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infra-red specturm of propa -Ol, CHsCH2CH20H
100
Tr —_ ——
4000 3000 2000 1500 1000 Soo
yvavenumber (crn!)
infra-red spect um of propan-P-ot alias gets
H
4000 3000 2000 1500 7000 soo
vrayve number (crm?)
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o — vansmilance (7)
e Fingerprint region can be sub-divided into
three:
cms
I. 1500-1350 cm”
Here doublet near 1380 cm! and 1365 cm! shows
the presence of tertiary butyl group in the
compound.
ii. 1350-1000 cm!
All classes of compounds having groups like
alcohols, esters , lactones, acid anhydrates show
characteristic absorptions (s) due to C — O
Stretching.
iii. Below 1000 cm!
Distinguishes between cis and trans alkenes and
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MmANKR And ANicithetititinne at nrtha mata NArna
VIBRATIONS
_ e Two types of vibrations are;
™~
1. Stretching
Symmetric
Asymmetric
2. Bending
scissoring
Rocking
Wagging
Twisting
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Many possible absorptions per molecule exist: stretching, bending…
Vibrational modes leadingto IR absorptions:
am
Se oe f -&
Symmetric stretching Symmetric bending Symmetric bending
vibration (both outside vibration in a plane vibration out of a plane
atoms move away from (scissoring) (twisting)
or toward the center)
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Asymmetric stretching
vibration (as one atom
moves toward the center,
the other moves away) Asymmetric bending
vibration in a plane
(rocking) Asymmetric bending
vibration out of a plane
(wagging)
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FACTORS INFLUENCING
ABSORPTION
“a Symmetry
Symmetric compounds do not possess dipole moment
and are IR inactive.
E.g. symmetric acetylene
| o=—C=C—”r
2. Coupling
> There are so many factors which cause coupled
vibration in IR and it will influence the intensity and
Shape of the absorption bands.
E.g. normally the band due to-€ OC bond is around at
1650 cm! but due to mechanical coupling of two C
C systems in allene give two bands at 1960 and 1970
cm
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3. Fermi resonance
> Fermi resonance results in an unexpected shift
in energy and intensity of the bands.
» E.g. the overtone of C–H deformation mode at
1400 cm’ is always in Fermi resonance with
the stretch of the same bond at 2800 cm”!
4. Hydrogen bonding
> It can change the shape and position of IR
bands.
> Stronger the H-bonding greater the absorption
shift.
Intermolecular- broad bands
Intra-molecular-sharp bands
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a
“6. Electronic effect
Electronic effects such as inductive, mesomeric
and field effect may cause shift in absorption
. bands due to the change in amscrtan frequency.
E.g. inductive— acetone(1715 cm” ) and
chloroacetone(1725 cm’)
mesomeric- acetophenone (1 693 cm:’) and P-
aminoacetophenone(16/77 cm‘)
6. Bond angles
Difference in bond angles can also leads to the
changes Is absorption bands.
E.g.
1815 1780 1745 1715 1715
oO —- 0 O O
A O
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Norma!
owiw w.DuloMix.com RING STRAIN
SAMPLING
~~ Samples of the same substance shows shift
in absorption bands as we pass from solid
to gases and hence the samples of different
phases have to be treated differently in IR
Spectroscopy.
« Sampling of solids
> Solids run in solution
© Mull technique
> Pressed pellet technique
° Solids films
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1.Solid run in solution
-e Dissolve solid sample in non-aqueous solvent
(which should be IR inactive) and place a drop
of this solution in alkali metal disc and allow to
evaporate, leaving a thin film which is then
mounted on a sepectrometer.
°E.g. of solvents — acetone, cyclohexane,
chloroform, carbon tetrachloride etc.
2.Mull technique
> Finely powdered sample + mulling agent
(Nujol) and make a thick paste (mull). Transfer
the mull to the mull plates and the plates are
Squeezed together to adjust the thickness it is
then mounted in spectrometer.
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‘ 3.Pressed pellet technique
> Finely powdered sample is mixed with about 100
< times its weight of KBr in a vibrating ball mill and
~— the mixture is then pressed under very high
– pressure in an evacuable die to form a small
pellet( 1-2mm thick and 1cm in diameter).
10 tons pressure
|
Piston
Die —>
Sample mixture —> ——
Die —>
= —— $——> Vacuum
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> Advantages:-
-Eliminates bands which appear due to mulling
agent.
– Pellets can be stored for longer period of time.
– Concentration of sample can be adjusted.
» Disadvantages:-
-Not suitable for polymers which are difficult to
bind with KBr.
*High pressure may change the crystallinity of
the sample.
4. Solid films.
> Here amorphous solid is dissolved in volatile
solvents and this solution is poured on a rock
Salt plate (NaCl or KBr), then the solvent is
evaporated by gentle heating.
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=
a
“Sampling of liquids
° Liquid sample can be sandwiched between
~~ two alkali halide plates (NaCl , KBr , CaF.).
come
_e The sample cell thickness is 0.01-0.05mm.
=
a——— NaCl plate
——— Liquid sample
NaCl plate
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e Sampling of gases
> Here gases sample is introduced into a glass
cell made up of NaCl.
> Very few organic compounds can be examined
as gases.
> E.g.: 1,4-dioxane.
e Sampling of solutions
> Here 1-5% of solution is placed in a solution
cell made up of metal halides and a second
cell containing the pure solvent act as a
reference.
Important solvents used _ are:-chloroform J
CCl,, Carbon disulphide etc.
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APPLICATIONS OF IR
SPECTROSCOPY
C| 1 Identification 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.
E.g. soectrum of n-hexanal
Hexanal
INFRARED SPECTRUM
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‘ 4 A i A 4 4 A i ius A ‘ iL aa ee a ae a ee ee es
3000 2000 1000
Wavenumber (cm-1)
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NIST Chemistry WebBook (http://webbook.nist.gov/chemistry)
Relative Transmittance
/ 2. Qualitative determination of functional
groups
e The presence or absence of absorption bands
help in predicting the presence of certain
functional group in the compound.
Table 13.4 Important IR Stretching Frequencies
Type of bond Wavenumber (cm~!) Intensity
C==N 2260—2220 medium
C=C 2260—2 100 medium to weak
C=C 1680—1600 medium
C=N 1650—1550 medium
©) ~1600 and ~1500—1430 strong to weak
C=O 1780—1650 strong
C—O 1250—1050 strong
CN 1230—1020 medium
O—H 3650—3200 strong, broad
(alcohol)
O-—H 3300—2500 strong, very broad
(carboxylic acid)
N—H 3500—3300 medium, broad
C—H 3300-2700 medium
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3. Distinction between 2 types of H-bonding
© 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.
» 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. Quantitative analysis
© It can be done by measuring the intensity of the
absorption bands.
E.g. xylene exists as mixture of 3 compounds
which shows absorption bands at
ortho-740cm”!
meta-880cm:!
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5. Study of chemical reactions
__° It is useful for studying the chemical reactions.
E.g.: reduction of butan-2-one to form butan-2-ol
Ame wy
O OH
Butan-2-one Butan-2-ol
(1710 cm”) (3300 cm”)
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6. Study of keto-enol tautomerism
_~° Diketones and ketoesters exhibit keto-enol
~~ tautomerism and this can be studied using IR
spectrum of the compound.
° E.g.: Ethyl acetoacetic etser.
O O oo
Keto Enol
C==O — 1733 cm”! O—H — 3300 cm!
– 1710 cm”! C==O — 1645 cm:
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THANK YOU
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