MSc(III Sem) IR Spectroscopy 2023

IR Spectroscopy
Introduction:
IR spectroscopy gives information on molecular vibrations or more precisely on
transitions between vibrational and rotational levels in molecules. This will help in finding
the molecular structure of the molecule.
The ordinary infrared region extends from 2.5μ to 15μ. The region from 0.8μ to 2.5μ
is called near IR. And that from 15μ to 200μ is called far IR region.

Near infra red Far infra-red region

IR region

12500 4000 667 50cm-1

wave number

The absorption of Ir radiation can be expressed either in terms of wave length (λ) or in wave
number (γ). The Ir spectrum of organic compounds is plotted as percentage transmission
against wave number.
1
Wave number = 𝑤𝑎𝑣𝑒𝑙𝑒𝑔𝑡ℎ 𝑖𝑛 𝐶𝑚
If wavelength (λ) is 2.5μ = 2.5 × 104 cm, then,
1
Wave number (ў) = 2.5×104 = 4000 Cm-1.
Therefore, the ordinary IR region covers 4000 Cm-1 to 667 Cm-1. (15μ = 667 Cm-1).
Principle of IR spectroscopy
Absorption of IR radiations causes an excitation of molecule from a lower to higher
vibrational levels. IR spectra are considered as vibrational-rotational spectra. All the bonds
in the molecules are not capable of absorbing IR energy but only those bonds which are
accompanied by a change in dipole moment will absorb in the IR region. Such vibrational
transitions which are accompanied by a change in the dipole-moment of the molecule are
called IR active transitions.
In IR spectroscopy (region 2.5μ to 15μ), the absorbed energy brings about
predominant changes in vibrational energy. The vibrational energy depends upon,
1. Mass of atom present in a molecule
2. Strength of the bonds and
3. The arrangement of atoms within the molecule.
Types of vibrations: when IR light is passed through the sample, the vibrational and
rotational energies of the molecules are increased. Two kinds of fundamental vibrations are,
stretching and bending.
1. Stretching: in this type of vibrations, the distance between the two atoms increases
or decreases. But the atoms remain in the same bond axis.

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 MSc(III Sem) IR Spectroscopy 2023

There are two types of stretching vibrations,

Symmetric stretching: in this type, the moment of the atoms with respect to a particular
atom in a molecule is in the same direction.
Asymmetric stretching: in these vibrations, one atom approaches the central atom
while the other departs from it.
2. Bending: in this type of vibrations, the positions of the atoms change with respect to
the original bond axis. We know that more energy is required to stretch a spring than
that required to bend it.
Types of bending vibrations: bending vibrations are of two types:
i) Scissoring: in this type, two-atoms approach each other.
ii) Rocking: in this type, the movement of the atoms takes place in the same
direction.
iii) Wagging: two atoms move ‘up and down’ the plane with respect to the central
atom.
iv) Twisting: in this type, one of the atoms move up the plane while the other moves
down the plane with respect to the central atoms

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 MSc(III Sem) IR Spectroscopy 2023

Characteristic group frequencies and skeletal frequencies:

Stretching vibrations (single bonds):

Structural unit Frequency, cm-1

sp C—H 3310-3320
sp2 C—H 3000-3100
sp3 C—H 2850-2950
sp2 C—O 1200
sp3 C—O 1025-1200
Stretching vibrations (multiple bonds):
Structural unit Frequency, cm-1
C C 1620 – 1680
C C 2100 – 2200
C N 2240 – 2280
Stretching vibrations (carbonyl groups):

Structural unit Frequency, cm-1

Aldehydes and ketones 1710-1750
Carboxylic acids 1700-1725
Acid anhydrides 1800-1850 and 1740-1790
Esters 1730-1750
Amides 1680-1700
Bending vibrations of alkenes:

RCH = CH2 910 – 990

R2 = CH2 890
CIS- RCH = CHR’ 665 – 730
TRANS - RCH = CHR’ 960 – 980
R2C = CHR’ 790 – 840

Bending vibrations of derivatives of benzene:

Structural unit Frequency, cm-1

Monosubstituted 730-770 and 690-710
Ortho-disubstituted 735-770
Meta-disubstituted 750-810 and 680-730
Para-disubstituted 790-840
Stretching vibrations (single bonds):

Structural unit Frequency, cm-1

O—H (alcohols) 3200-3600
O—H (carboxylic acids) 3000-3100
N—H 3350-3500

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 MSc(III Sem) IR Spectroscopy 2023

Finger print region: one of the important functions of IR spectroscopy is to determine the
identity of two compounds. Two identical compounds have exactly the same spectra when
run in the same medium under similar conditions. The region below 1500 cm-1 is rich in
much absorption which is caused by bending vibrations and those resulting from the
stretching vibrations of C-C, C-O and C-N bonds. In a spectrum, the number of bending
vibrations is usually more than the number of stretching vibrations. The said region is
usually rich in absorption bands and shoulders. It is called finger print region. Some
molecules containing the functional group show similar absorptions above 1500 cm-1 but
their spectra differ in finger print region.
For example, alcohols, esters, lactones, acid anhydrides show characteristic absorption s in
this region due to C-O stretching. Cis and trans alkenes can be distinguished. Higher value
indicates hydrogen atoms in the alkenes are trans with respect to each other.

Factors affecting group frequencies and band shapes:

1. Conjugation: conjugation of carbonyl group with an olefinic bond or aromatic ring results
in the delocalization of the π electrons of both unsaturated groups and reduces the double
bond character of both the bonds causing a lowering of carbonyl frequency from 1718(cm-1)
to about 1690 cm-1 and C=C stretching frequency from 1645 cm-1 to 1620 cm-1. The lowering
of absorption frequency can be explained as follows

2. Resonance and inductance: 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. Consider the numbers of absorption in the following
compounds: (a) Acetone 1715cm-1, (b) chloroacetone 1725cm-1, (c) dichloroacetone
1740cm-1 (d) tetrachloroacetone 1750, 1778cm-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. For
example, formaldehyde and acetaldehyde exhibit wave numbers at 1750 and1745cm-1
respectively. Conjugation lowers the absorption frequency of C=O stretching whether the
conjugation is due to β-unsaturation or due to an aromatic ring.

3. Hydrogen bonding and ring strain: Hydrogen bonding brings about remarkable
downward frequency shift. Stronger the hydrogen bonding, greater is the absorption shifts
towards lower wave number than the normal value. Two types of hydrogen bonds can be
readily distinguished in Infra-red technique. Generally intermolecular hydrogen bonds give
rise to broad bands whereas bands arising from intramolecular hydrogen bonds are sharp and
well defined. In aliphatic alcohols, a sharp band appears at 3650cm-1 in dilute solutions due to
free O – H group while a broad band is noticed at 3350cm-1 due to hydrogen bonded O –H
group. Alcohols are strongly hydrogen bonded in condensed phases. These ar usually
associated as dimmers and polymers which result in broadening of bands at lower absorption
frequencies.

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 MSc(III Sem) IR Spectroscopy 2023

4. Tautomerism, Cis-trans isomerism: Tautomeric equilibria can be studied with the help of
IR spectroscopy. Most common systems like keto-enol, mercaptothiamide contain a group
such as C=O, OH, NH or C=S with characteristic frequency which makes it possible to
deduce the spectrum as to which form predominates.

Instrumentation of Infrared (IR) Spectroscopy

The main parts of the IR spectrometer are as follows:
1. Radiation source, 2. Sample cells and sampling of substances, 3. Monochromators, 4.
Detectors and 5. Recorder.

A. IR radiation sources:
IR instruments require a source of radiant energy which emits IR radiation which must be
steady, intense enough for detection, and extend over the desired wavelength.
Various sources of IR radiations are as follows.
1. Nernst glower
2. Incandescent lamp
3. Mercury arc
4. Tungsten lamp
5. Glober source
6. Nichrome wire
B. Sample cells and sampling of substances:
IR spectroscopy has been used for the characterization of solid, liquid, or gas samples.
i. Solid – Various techniques are used for preparing solid samples such as pressed pellet
technique, solid run in solution, solid films, mull technique, etc.
ii. Liquid – Samples can be held using a liquid sample cell made of alkali halides. Aqueous
solvents cannot be used as they will dissolve alkali halides. Only organic solvents like
chloroform can be used.
iii. Gas– Sampling of gas is similar to the sampling of liquids.

C. Monochromators: Various types of monochromators are prism, gratings and filters.

Prisms are made of Potassium bromide, Sodium chloride or Caesium iodide. Filters are
made up of Lithium Fluoride and Diffraction gratings are made up of alkali halides.

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 MSc(III Sem) IR Spectroscopy 2023

D. Detectors: Detectors are used to measure the intensity of unabsorbed infrared radiation.
Detectors like thermocouples, Bolometers, thermisters, Golay cell, and pyro-electric detectors
are used.
E. Recorders: Recorders are used to record the IR spectrum.

Sample Preparation:
IR spectroscopy is used for the characterization of solid, liquid or gas samples. Material
containing sample must be transparent to the IR radiation. So, the salts like NaCl, KBr are
only used.
1. Sampling of solids
Various techniques used for preparing solid samples are as follows
a) Mull technique: In this technique, the finely crushed sample is mixed with Nujol
(mulling agent) in n a marble or agate mortar, with a pestle to make a thick paste. A thin film
is applied onto the salt plates. This is then mounted in a path of IR beam and the spectrum is
recorded.
b) Solid run in Solution – In this technique, solid sample may be dissolved in a non-
aqueous solvent provided that there is no chemical interaction with the solvent and the
solvent is not absorbed in the range to be studied. A drop of solution is placed on the surface
of alkali metal disc and solvent is evaporated to dryness leaving a thin film of the solute.
c) Case film technique – If the solid is amorphous in nature then the sample is deposited on
the surface of a KBr or NaCl cell by evaporation of a solution of the solid and ensured that
the film is not too thick to pass the radiation.
d) Pressed pellet technique – In this technique, a small amount of finely ground solid
sample is mixed with 100 times its weight of potassium bromide and compressed into a thin
transparent pellet using a hydraulic press. These pellets are transparent to IR radiation and it
is used for analysis.
2. Sampling of liquids
Liquid sample cells can be sandwiched using liquid sample cells of highly purified alkali
halides, normally NaCl. Other salts such as KBr and CaF2 can also be used. Aqueous solvents
cannot be used because they cannot dissolve alkali halides. Organic solvents like chloroform
can be used. The sample thickness should be selected so that the transmittance lies between
15-20%. For most liquids, the sample cell thickness is 0.01-0.05 mm. Some salt plates are
highly soluble in water, so the sample and washing reagents must be anhydrous
3. Sampling of gases
The sample cell is made up of NaCl, KBr etc. and it is similar to the liquid sample cell. A
sample cell with a long path length (5 – 10 cm) is needed because the gases show relatively
weak absorbance.

Applications of IR spectroscopy:
1. Identification of an organic compound: The identity of an organic compound can
be established from its finger print region (1400 – 900). The identity of an organic compound
is confirmed if its ginger print region exactly matches with the known spectrum of that
compound. It may be noted that the compounds containing the same functional groups may
have similar absorptions above 1500cm-1 but they differ considerably in finger print region.

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 MSc(III Sem) IR Spectroscopy 2023

2. Structure determination: the technique helps to establish the structure of an

unknown compound. All major functional groups absorb at their characteristic wave
numbers.
It is known that the IR spectra of amino acids sxhibit bands for ionized carboxylic acids
and amine salts (NH3+). No band for free –NH2 and –COOH groups is observed. Clearly,
amino acids exist as zwitter ions as below.
NH3+ - CH – COO-
Similarly, from the IR bands of suluphuric acid, it is said that the compound contains
NH3+ and SO3- and not free groupsas –NH2 and SO3H.
3. Qualitative analysis of functional groups: the presence or absence of absorption
bands help in predicting the presence of certain functional groups in the compound. The
presence of oxygen reveals that the group may be –OH, C = O, COOR, - COOH, anhydride
etc., but an absorption band between 3600-3200cm-1 limits the possibilities. The band in this
region may be due to –O – H. This region also speak of absorption in case of –NH2, NH
groups. In case of –NH2, two absorption bands appear in the above region. NH group give
only one band. Its distinction from O-H str can be made from the extent of hydrogen bonding
which is stronger in -OH compounds and causes more lowering in wave number.
Each band in a spectrum can be attributed to stretching or bending mode of a bond.
Almost all the fundamental vibrations appear in the mid-infrared region. For instance, 4000 –
2500 cm-1 region usually can be assigned to stretching modes of O-H, N-H or C-H. Triple-
bond stretching modes appear in the region of 2500 – 2000 cm-1. C=C and C=O stretching
bands fall in the 2000 – 1500 cm-1 region. Hence, characterization of functional groups in
substances according to the frequencies and intensities of absorption peaks is feasible, and
also structures of molecules can be proposed. This method is applicable to organic molecules,
inorganic molecules, polymers, etc.
4. Quantitative analysis: The quantity of the substance can be determined either in pure
form or as a mixture of two or more compounds. In this, characteristic peak corresponding to
the drug substance is chosen and log I0/It of peaks for standard and test sample is compared.
This is called base line technique to determine the quantity of the substance.
5. Identification of substances: IR spectroscopy is used to establish whether a given
sample of an organic substance is identical with another or not. This is because large number
of absorption bands is observed in the IR spectra of organic molecules and the probability
that any two compounds will produce identical spectra is almost zero. So if two compounds
have identical IR spectra then both of them must be samples of the same substances. IR
spectra of two enatiomeric compound are identical. So IR spectroscopy fails to distinguish
between enantiomers.
For example, an IR spectrum of benzaldehyde is observed as follows.
C-H stretching of aromatic ring- 3080 cm-1
C-H stretching of aldehyde- 2860 cm-1 and 2775 cm-1
C=O stretching of an aromatic aldehyde- 1700 cm-1
C=C stretching of an aromatic ring- 1595 cm-1
C-H bending- 745 cm-1 and 685 cm-1
No other compound then benzaldehyde produces same IR spectra as shown above.

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 MSc(III Sem) IR Spectroscopy 2023

6. Studying the progress of the reaction: Progress of chemical reaction can be determined
by examining the small portion of the reaction mixure withdrawn from time to time. The rate
of disappearance of a characteristic absorption band of the reactant group and/or the rate of
appearance of the characteristic absorption band of the product group due to formation of
product is observed. 4. Detection of impurities IR spectrum of the test sample to be
determined is compared with the standard compound. If any additional peaks are observed in
the IR spectrum, then it is due to impurities present in the compound.
7. Distinction between two types of hydrogen bonding: this technique is quite valuable to
distinguish between the types of hydrogen bonding, intra or intermolecular hydrogen
bonding. For example: o-nitro phenol exhibits intramolecular hydrogen bonding whereas p-
nitrophenol exhibits intermolecular hydrogen bonding. Intramolecular hydrogen bonded
compound does not show any shift in the aborption on dilution whereas intermolecular H-
bonded does.
8. Study of keto-enol tautomerism: diketones and ketoesters exhibit keto-enol
tautomerism provided they have α-H atom in them. The infra –red spectrum of such a
compound contain bands due to C = O , O – H and C = C bonds. Consider ethyl acetoacetic
ester. It exists in koto-enol isomers in equilibrium.
O O H
O O
C C
C C
H2C C OC2H5 H3C C
H2 H OC2H5

VC = O str 1733, 1710 cm-1(s) vO-H str- 3300cm-1 (b)

vC=Ostr 1645 cm-1 (s)
The lowering of ν C = O stretching absorption in the enolic form is due to intra-molecular
hydrogen bonding which is established by resonance. The appearance of the above bands
clearly confirm koto-enol tautomerism in acetoacetic ester. Similar absorption bands are also
noted in case of β-dikotones.
O O
HO O
H2
H3C C C C CH3
H3C C C C CH3
H
(keto)
(enol)
9. Geometrical Isomerism: it is known that a vibration is infra-red active only if it causes a
change in dipole – moment of the molecule. Also the intensity of absorption depends upon
the change in the dipole moment. This technique clearly makes a distinction between cis and
trans isomers. Consider 1, 2- dichloro ethane. Its geometrical isomers are:
H H
Cl Cl
C C

C C
H Cl Cl H
 = 1.85 D =0

For most of the vibrations, the change in the diplole-moment occurs in the cis isomer. On the
other hand, trans isomer is non-polar with dipole moment equal to zero.

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 MSc(III Sem) IR Spectroscopy 2023

Accordingly the C = C str absorption peak at 1580cm-1 is not observed in case of trans-
isomer since the vibration in it does not produce any change in the doloe moment. On the
other hand, this peak (1580cm-1) appears due to C = C str in cis isomer.

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9 Dr. NN MSCW, M