INFRARED SPECTROSCOPY

RECAP
Spectroscopy is the Study of interaction between matter and electromagnetic radiation
e.g., IR Spectroscopy is concerned with the study of absorption of infrared radiation, which causes vibrational
transition of bonds in molecules. So it is also called vibrational Spectroscopy .

IR Spectroscopy mainly used to identify the functional group, but also gives information likes
No. of bond, Specific stereo-isomer, Atomic arrangement in the molecule.
 IR Region

Near IR Mid IR Far IR

Wave Length: 0.8 – 2.5 μm Wave Length: 2.5 – 5.0 μm Wave Length: 50 – 1000 μm
Wave number: 12,500 – 4,000 cm-1 Wave number: 4,000 – 200 cm-1 Wave number: 200 – 10 cm-1

Interfered with UV radiation FIR is also closer to the radio-wave

and gives extra IVCT region and sometimes interact/form
[Intervalence charge transfer] extra unwanted band spectra on the
band on IR spectra due to IR spectrum.
delocalization of electron

MIR is appropriate for the IR spectroscopy. Because it gives fully IR peak on IR spectrum.
So, We used 2.5 – 5.0 μm wavelength in IR Spectroscopy
 PRINCIPLE OF IR SPECTROSCOPY

When IR radiation interact with sample molecule, the sample molecule will absorb the specific applied quantized IR
light which is matched with the internal vibrational frequency of the molecule and other residual frequencies are
transmitted via the sample. Due to absorption of IR radiation, the net change of dipole moment in molecule is
occurred and causes vibration of bonds in the molecule like Stretching and bending vibration. The transmitted light is
detected by the detector and IR spectrum interpreted on the computer screen by analysis of the transmitted light.

IR Radiation
(Mid IR)
Sample Transmitted
Range: 4000 – 400 cm-1 (absorbs Specific frequency) Light

Position change of Atoms in a molecule

due to net change of dipole Moment

Change in amplitude of molecular Vibration % 𝑜𝑓 𝑇

Stretching & Bending Vibration Wave number, cm-1

 Molecular Vibration

Stretching Vibration Bending vibration

Higher Frequency Lower Frequency

Symmetric Asymmetric In-Plane Out of Plane

Stretching Stretching Bending Bending

Scissoring Bending Rocking Bending

Twisting Bending Wagging Bending

NOTE: No. of bending vibration is usually more than the no. of stretching vibration in IR spectrum.
a) Stretching Vibration involves a continuous change in interatomic
distance along the axis of bond between 2 atoms.

In Symmetric Stretching, the bond length increase & decrease

symmetrically.
In Asymmetric Stretching, length of one bond increase & the other
one decrease at the same time without changing bond angle.

b) Bending vibration involves the change of angle between two atoms

Scissoring is the movement of two atoms toward and away from each
other. So bond angle decrease and increase with time.

Rocking in which the bond angle is maintained but bonds moves within
the same plane. Changing angle b/w a group of atoms.

Wagging in which both atoms move to one side of the plane. Changing
angle b/w the plane a group of atoms

Twisting in which one atom is above the plane and the other is below
the plane. Changing angle b/w the plane 2 groups of atoms
 W H AT A R E T H E C O N D I T I O N S O R C R I T E R I A T O A B S O R B I R R A D I AT I O N ? ?

Those are,
✓ When applied infrared frequency in equal to natural frequency of vibration, then the absorption take place
and a peak is observed.

✓ Molecules must undergo change in dipole moment.

✓ Only molecules give IR absorption.

Note: It is important to remember that it is not necessary for a compound to have a

permanent dipole moment to be IR active.
M O D E S O F M O L E C U L E W I T H R E S P E C T T O E L E C T R O M A G N E T I C R A D I AT I O N ?

Modes are,
I. Translation
II. Rotational To explain this, We should know about degrees of freedom ??
III. Vibrational

Now, The total no. of degrees of freedom = ( Translation + Rotational + Vibrational ) degrees of freedom
𝑜𝑟, Vibrational degree of freedom = 3N - (Translation + Rotational ) degrees of freedom
∴ Vibrational degree of freedom = 3N - ( 3 + Rotational ) degrees of freedom
No. of atoms in the molecule
For Linear molecule,
Vibrational degrees of freedom = 3N - ( 3 + 2 ) = 3N - 5
For Non-Linear molecule,
Vibrational degree of freedom = 3N - ( 3 + 3 ) = 3N - 6

E.g. Vibrational degrees of freedom of CO2 = 3 × 3 − 5 = 4

Vibrational degrees of freedom of H2O = 3 × 3 − 6 = 3
 Calculation of For Single bond, K= 5× 105 dyne / cm
Vibrational frequency Double bond, K = 10 × 105 dyne / cm
Triple bond, K = 15× 105 dyne / cm
 W H AT I S I R S P E C T R U M ?

IR Spectrum is the graphical plot of % transmittance versus vibrational frequency in wavenumbers.

IR Spectrum

%T
Functional Group Region Finger-print Region
4,000 – 1500 cm-1 1500 – 500 cm-1

Identifies the functional group with the Identifies the exact molecule with the
consequence of changing stretching vibration consequence of changing bending vibration
Wave Number, cm-1
Only stretching mode of vibration, so this Both Stretching and bending, but bending is
𝐼 𝐼𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑇𝑟𝑎𝑛𝑠𝑚𝑖𝑡𝑡𝑒𝑑 𝑙𝑖𝑔ℎ𝑡
T= = region contains few peaks. more than stretching
𝐼∙ Intensity of incident light
 Peaks
of Functional Group

Shape Intensity
(Width of peak)
(height of peak)

Strong A strong band covers most of the y-axis

Broad Sharp
Medium A medium band falls to about half of the y-axis
Due to H-bonding or
Presence of water Weak A weak band falls to about one third or less of the y-axis
molecules

Factors affecting the Peak intensity :

Electronegativity difference α Polarity α Dipole moment α More Intense Peak
FA C T O R S A F F E C T I N G F O R V I B R AT I O N A L F R E Q U E N C I E S O F T H E F U N C T I O N A L G R O U P

1. Effect of different mode of vibration: V. frequency of stretching is higher than the bending mode of bond
1
2. Reduced Mass of atoms α
𝑉𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦

3. More Vibration frequency = More Force-Contact (K)

4. Electronic effect:
Conjugation / Resonance α vibrational frequency

1
5. H-bonding effect α 𝑉𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦

6. Multiplicity of bond: No. of bond α Vibrational frequency

7. Nature of Hybridization: % of S- character α Bond Strength α α

1
V. frequency
𝐵𝑜𝑛𝑑 𝑙𝑒𝑛𝑔𝑡ℎ
 H O W T O I N T E R P R E T / A N A LY Z E I R S P E C T R A ? ?

IR spectra isn’t generally used to determine the whole structure of an unknown molecule. But IR
spectra is great for identifying certain specific groups.
Here an overview of the IR window from 4000 to 500 cm-1 with various region of interest highlighted.

Basically 80% of the most useful information for our purpose can be obtained by looking at 3600 to 1600 cm-1 specific
area of spectrum.
An even more compressed overview looks like this…
NO. Peak take place Common Symbols of Examples of bond of
between (cm-1) bond functional group

ZONE 1 3600 – 2700 X –H O-H bond, C–H bond, N-H bond

ZONE 2 2700 – 1900 X≡X C≡N or C≡C bond

ZONE 3 1900 – 1500 X=O, X=X C=O bond, C=C bond

ZONE 4 1500 -- 1000 X –O , X –X C-O bond, C – C Bond

Here, X symbol will be Oxygen [O] or Carbon [C] or Nitrogen [N]

For Zone 1:
a) O-H bond stretching at 3650 – 3200 cm-1 with strong intensity & broad ‘U’ elongated shape

b) Terminal alkynes (≡C–H bond) stretching at 3340 – 3250 cm-1 with stronger & sharper peak
 c) N-H bond stretching mainly occurred for Primary & Secondary amine:
For primary amine, stretching at 3500 – 3200 cm-1 with two signal. These are medium
in intensity & broad shape.
For secondary amine, stretching at 3500- 3200 cm-1 with one signal . These are weak
intensity & sharp shape

d) =C–H Stretching at 3100 cm-1 with weak intense & sharp peak

e) - C–H Stretching at 2900 – 2800 cm-1 with medium intense & sharp peak

NOTE: for aromatic compound, out of plane =C–H bending peak at 900 – 690 cm-1
For Zone 2:

a) C≡C bond stretching at 2200 – 2000 cm-1 with variable intense & shape peak

b) C≡N bond stretching at 2260 – 2220 cm-1 with variable intense & shape peak

For Zone 3:

a) C=O bond stretching peak

for aldehyde at 2200 – 2000 cm-1 , Ketone at 1700- 1725 cm-1, Carboxylic acid at 1715 cm-1, Ester at 1750 – 1735 cm-1
b) C=C bond stretching peak at 1660 – 1600 cm-1

c) C=C bond stretching for aromatic compound peak at 1510 – 1450 cm-1

For Zone 4:
a) C–C bond stretching: peak at 1200 – 1000 cm-1

b) C–O bond stretching: peak at 1150 – 1000 cm-1

A P P L I C AT I O N O F I R S P E C T R O S C O P Y

i. Identification of an organic compound

ii. Structure determinations

iii. Identification of functional group

iv. Studying the progress of reaction

v. Distinction between two types of hydrogen bonding

vi. Study of Cis-trans isomerization

vii. Determination of impurities in compound

viii. Presence of water in sample

 L I M I TAT I O N S O F I R S P E C T R O S C O P Y

a. Doesn’t give information about the relative position of different functional groups in a molecule.

b. From the single IR spectra of an unknown substance, it is not possible to know whether it is
pure compound or a mixture of compound.

c. Sample cells are made of halogen salts which are susceptible to moisture
FIGURE: FOURIER TRANSFORM SPECTROPHOTOMETER

Working Function: The source energy strikes the beam splitter and produces two beams of roughly the same
intensity. One beam strikes the fixed mirror and returns to the beam splitter. The other beam goes to the
moving mirror. When these two beams meet up again at the beam splitter, they recombine. The recombined
beam passes through the sample……..

Radiation source: NERST glower or Global Source which produce Mid IR