Spectroscopy IR

Muhammad Abdullah
Department of BioMedical Engineering

University of Engineering and Technology New Campus
Kala Shah Kaku
SPECTROSCOPY:
• INFRARED SPECTROSCOPY:
• IR spectroscopy is the study of interaction
between infrared radiations and matter.
• Infrared radiations refers broadly to that part
of electromagnetic spectrum between visible
and microwave region.
IR spectrum of ethanol
PRINCIPLE:
• The principle of IR spectroscopy is related to the
vibrational and rotational energy of a molecule.
• When the frequency of the IR radiation is equal
to the natural frequency of vibration, the
molecule absorb IR radiation.
• Absorption of IR radiation causes an excitation of
molecule from a lower to the higher vibrational
level.
• Each vibrational level is associated with a
number of closely placed rotational level.
• Therefore the IR spectroscopy is also called as
“vibrational-rotational spectroscopy”
• 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.
• 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.
 In IR spectroscopy the changes in the vibrationa
energy depends upon
i. Mass of the atoms present in a molecule

ii. Strength of the bonds
iii. Arrangement of atoms within the molecule
 No two compounds except the enantiomers can

have the similar IR spectra.
THEORY:
 When a molecule absorb radiation with a
frequency less than 100 cm-1 ,molecular
rotation takes place and if a molecule
absorb more energetic radiation in the
region of 104 to 102 cm-1 , molecular
vibration takes place.
 A single vibrational energy change is
accompanied by a large number of
rotational energy changes and thus the
vibrational spectra appear as vibrational
rotational bands.
FATE OF ABSORBED RADIATION:
 There are 3 main process by which a molecule
can absorb radiation, of these route
each involve an increase of energy which is
proportional to the light absorbed.
i. 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.
iii. Third occurs when absorption of radiation leads
to a higher electronic energy level in its electronic
transitions.
Energy level diagram

Two criteria must be satisfied by
a molecule for the absorption of IR radiation:
i. The molecule should possess
vibrational and rotational frequency.
ii. The molecule must give rise to
asymmetrical charge distribution.
 Three main type of absorption bands occur in
IR spectra:
i. Fundamental
ii. Overtone
iii. combinational
FERMI RESONANCE:
 Interactions which occur between fundamental and
overtone or combinational bands are known as
Fermi resonance.
 This phenomenon can be observed whenever two
fundamental or a fundamental and overtone bands
have nearly the same energy.
 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.
 As a result, two strong bands are observed in the
spectrum, instead of the expected strong and weak
bands.
 E.g.: CO2
◦ It normally shows fundamental band at 1337
cm-1 and overtone at 1334.6 cm-1 .
◦ 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-1 and
1388.3 cm-1 .
FINGERPRINT REGION:
 In IR, the region below 1500 cm-1 is rich in many
absorption bands and the region is known as
fingerprint region.
 Here the number of bending vibrations are usually
more than the number of stretching vibrations.
 In this region, small difference in the structure and
constitution of a molecule results significant changes
in the absorption bands.
 Many compounds show unique absorption bands in
this region and which is very useful for the
identification of the compound.
FINGERPRINT REGION:
I. 1500-1350 cm-1
• Here doublet near 1380 cm-1 and 1365 cm-1 shows the presence of tertiary
butyl group in the compound.
II. 1350-1000 cm-1
• 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-1
• Distinguishes between cis and trans alkenes and mono and Di substitutions
at ortho, meta, para
VIBRATION
S
 Two types of vibrations are;
1. Stretching
i. Symmetric
ii. Asymmetric
2. Bending
i. Scissoring
ii. Rocking
iii. Wagging
iv. Twisting
FACTORS INFLUENCING
ABSORPTION
1. Symmetry
◦ Symmetric compounds do not possess dipole moment
and are IR inactive.
◦ E.g. symmetric acetylene
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 C C bond is around at
1650 cm-1 but due to mechanical coupling of two C
C systems in allene give two bands at 1960 and 1970
cm-1
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-1 is always in Fermi resonance with
the stretch of the same bond at 2800 cm-1.
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
5. Electronic effect
◦ 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)
6. Bond angles
◦ Difference in bond angles can also leads to the
changes is absorption bands.
◦ E.g.
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
1.Solid run in
solution
◦ 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.
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).
◦ 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.
Sampling of liquids
◦ Liquid sample can be sandwiched between
two alkali halide plates (NaCl , KBr ,
CaF2).
◦ The sample cell thickness is 0.01-0.05mm.
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.
 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 ,
CCl4, Carbon disulphide etc.
APPLICATIONS OF IR
SPECTROSCOPY
1. Identification of an organic compound

◦ 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. spectrum of n-hexanal
2. Qualitative determination of functional
groups
◦ 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
◦ 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-1
meta-880cm-1
para-830cm-1
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
Butan-2-one Butan-2-ol
(1710 cm-1) (3300 cm-
1)
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.
C==O – 1733 cm-1 O---H – 3300 cm-1

- 1710 cm-1 C==O – 1645
cm-

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Muhammad Abdullah

Department of BioMedical Engineering

i. Mass of the atoms present in a molecule

 No two compounds except the enantiomers can

1. Identification of an organic compound

C==O – 1733 cm-1 O---H – 3300 cm-1

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