MOLECULAR ABSORPTION

SPECTROMETRY -IR

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 Introduction to Molecular
Absorption
• A spectroscopic technique used to
measure the absorption of radiation as a
function of wavelength.

• During this process, a sample is hit with

photons from a light source and the
frequency produced from the molecules is
recorded for analysis.

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 Introduction
Quantitative and qualitative analyses
IR Spectroscopy

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 Infrared Spectroscopy
• IR- Spectroscopy detects the absorption of
light by a compound in the IR region of
the Electromagnetic spectrum

• To absorb light, a molecule must have a

bond with its structure that can exhibit a
“dipole moment”.

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 Infrared Spectroscopy
• Infrared absorption:
– Energy of IR photon insufficient to cause
electronic excitation but can cause vibrational or
rotational excitation
– It can induce transitions in the vibrational and
rotational states
– Molecules absorb specific frequencies that are
characteristic of their structure.
– These absorptions are resonant frequencies, i.e.
the frequency of the absorbed radiation matches
the transition energy of the bond or group that
vibrates.

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 A Functional Group Chart
4000 3600 3200 2800 2400 2000 1600 1200 800 group
O-H str

NH str
COO-H
=C-H
str
Csp3-H
≡C-H
-(C=O)-
H
C≡N
C≡C
C=O
-C=N
-C=C
phenyl
C-O
C-N
F Cl C-X I
Br
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 Infrared Spectroscopy
• In order for a vibrational mode in a molecule to be "IR
active,"
• It must be associated with changes in the dipole.
• For molecules with N atoms in them, linear molecules
have 3N – 5 degrees of vibrational modes.
• Nonlinear molecules have 3N – 6 degrees of
vibrational modes
• As an example H2O, a non-linear molecule, will have 3
× 3 – 6 = 3 degrees of vibrational freedom, or modes.

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 Infrared Spectroscopy
• Number of vibrational modes
Symmetrical Antisymmetrical
stretching stretching Scissoring

Rocking Wagging Twisting

+ + + -

Out of plane Out of plane

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 Regions of Frequencies
Spectral Frequency Wavenumber Wavelength
Region (Hz) (cm-1) (λ,nm)
Near -to 3.8 x 1014 12800 to 780 to 2500
visible- IR to 1.2 x 4000
(NIR) 1014
Combinatio
n bands

Mid 1.2 x 1014 4000 to 200 2500 to 50000

Infrared to 6.0 x
Fundmental 1012
bands for
organic
molecules
Far IR 6.0 x 1012 200 to 10 50000 to
Inorganics to 3.0 x 1000000
organometal 1011
lics Rule of mutual exclusion:
If a molecule has a centre of symmetry:
IR vibration inactive
Vice versa
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 Infrared Instruments
• Three types of spectrometers:
– Dispersive IR instruments
• Introduction
–It uses a diffraction grating in a monochromator
to disperse the different wavelengths of light.
–It separates the wavelengths of light in the
spectral range and directs each wavelength
individually through a slit to the detector.

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 Infrared Instruments
• Three types of spectrometers:
– Fourier transform infrared spectrometer
• Introduction
–An FT-IR instrument uses a system called an
interferometer to collect a spectrum.
–It consists of a source, beam splitter, two
mirrors, a laser and a detector.
Fixed mirror

Movable Source
mirror

B
Detector

Sample
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 Infrared Instruments
• Three types of spectrometers:
– Filter spectrometer
• Introduction
–Infrared photometers designed to monitor
the concentration of air pollutants, such
as carbon monoxide, nitrobenzene, vinyl
chloride, hydrogen cyanide, and pyridine,
are often used to ensure compliance

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 FT-IR Instruments
• The process of collecting an infrared spectrum in an
FT-IR spectrometer

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 FTIR absorption bands
• IR spectroscopy is often used to identify structures
because functional groups give rise to characteristic
bands both in terms of intensity and position

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 FTIR: Isotope effects
• The different isotopes in a particular species may give
fine detail in infrared spectroscopy.
• For example, the O–O stretching frequency of
oxyhemocyanin is experimentally determined to be 832
and 788 cm−1 for ν(16O–16O) and ν(18O–18O),
respectively.
• The wavenumber of absorbance, ν can be calculated:

• where k is the force constant for the bond, c is the speed

of light, and μ is the reduced mass of the A–B system:
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 FTIR Spectra

FTIR Spectra of CNT

- 4000 -1600 cm-1 ⇒functional group region.

- 1600- 400 cm-1 ⇒ fingerprint region. 35
 Tutorial Questions
1. Give advantages of FTIR over dispersive instruments. (4 marks)

2. The infrared range of the electromagnetic spectrum is divided

into three regions. Name them and give their relation to the
visible spectrum? (3 marks)

3. Why are photomultiplier tubes unsuited for the detection of

infrared radiation? (3 marks)

4. A ketone possesses an absorption band with a peak centred

around 1710 cm-1. From this information deduce a value for the
force constant of the C=O double bond. (5 marks)

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