CH2213: Analytical Chemistry

Lecture -23
FTIR Spectroscopy
Professor Manickam Jayakannan
Department of Chemistry
IISER Pune, INDIA
E-mail: jayakannan@iiserpune.ac.in
Website: http://www.iiserpune.ac.in/~jayakannan/

Date: 5th April 2022

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 IR (Vibrational) Spectroscopy

Infrared Absorption: Infrared radiation generally is not energetic enough to cause electronic transitions,
but it can induce transitions in the vibrational and rotational states associated with the ground electronic
state of the molecule. Four of these transitions are depicted in the lower left part of (!1 to !4).
For absorption to occur, the radiation source has to emit frequencies corresponding exactly to the
energies indicated by the lengths of the four arrows. 2
 Stretching & Bending Vibration

Stretching absorptions of a bond appear at higher frequencies in the infrared

spectrum than the bending absorptions of the same bond.

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Determination of Vibrational Frequencies

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Determination of Vibrational Frequencies

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Absorptions in the 6 to 15 micrometer region is dependent on the
molecular environment; this region is Finger print region
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The vibrational frequency of a bond is expected to increase when the bond strength
increases, and also when the reduced mass of the system decreases.
We can then predict that:
ü C=C and C=O str will have higher frequencies than C-C and C-O str, respectively:
ü C-H and O-H str absorptions at higher frequencies than C-C and C - O str.
ü Similarly, we would predict O-H str to be of higher frequency than O-D str.
ü On the basis of mass, we expect X-H str frequencies to fall along the series C-H, N-H, 0-H,
F-H ; in fact they rise, mainly owing to increasing electronegativity.
Note: Without accurate data on force constants, however, some caution should be exercised in
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predicting exact trends other than in this general way .
FT-IR Instrumentation

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FT-IR Instrumentation

Attenuated Total Reflectance (ATR)

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FT-IR: Conjugation Effect

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FT-IR: Resonance Effect

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FT-IR: Reaction Monitoring

N3 12
FT-IR: Amides and Esters

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 H-Bonding Interactions
The hydrogen bond can be regarded as a resonance hybrid of I and II (approximating
overall to III), so that hydrogen bonding involves a lengthening of the original O-H bond.
This bond is consequently weakened (that is, its force constant is reduced), so the
stretching frequency is lowered.

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 H-Bonding Interactions
Enols and chelates. Hydrogen bonding in enols and chelates is particularly strong,
and the observed O-H str frequencies may be very low (down to 2800 cm-1). Since
these bonds are ' not easily broken on dilution by an inert solvent, free O-H str may
not be seen at low concentrations.

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The sharp band appears at 3650 cm-1 in addition to the broad band at 3350 cm-1. The sharp band is
O-H str in free alcohol molecules; the broad band is O-H str in hydrogen-bonded alcohol molecules .

Source: Michigan State University 16