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Ftir1 PH308

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32 views10 pages

Ftir1 PH308

Uploaded by

Harshita Tripathi
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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03-05-2023

Fourier Transform IR Spectroscopy

Perkin Elmer, USA. Model: spectrum one

What is FTIR

• Fourier-transform infrared spectroscopy is a


vibrational spectroscopic technique, meaning it
takes advantage of asymmetric molecular
stretching, vibration, and rotation of chemical
bonds as they are exposed to designated
wavelengths of light.
• Fourier transform is to transform the signal from
the time domain to its representation in the
frequency domain

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03-05-2023

Introduction
• Absorption peaks in an infrared absorption spectrum arise
from molecular vibrations
• Absorbed energy causes molecular motions, which create a
net change in the dipole moment.

Wavelength and Wavenumber

• Wavelength = 1 / Wavenumber
• For the IR, wavelength is in microns.
• Wavenumber is typically in 1/cm, or cm-1.
• 5 microns corresponds to 2000 cm-1.
• 20 microns corresponds to 500 cm-1.

• 15 microns corresponds to 667 cm-1.


Much ‘terrestrial’ IR energy at the
wavenumber.

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03-05-2023

Theory and Instrumentation

• Light enters the spectrometer and is split by the beam


splitter. The figure above shows what is referred to as the
Michelson interferometer

Theory and Instrumentation(contd.)


• The light originates from the He-Ne laser
• Half of the light is reflected 90 degrees and hits a
fixed mirror, while the other half passes through
the beam splitter and hits the moving mirror
• The split beams are recombined, but having
traveled different distances, they exhibit an
interference pattern with each other
• As they pass through the sample, the detector
collects the interfering signals and returns a plot of
response v. mirror displacement known as an
interferogram

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03-05-2023

FTIRs Often Use MCT Detectors:


Mercury Cadmium Telluride

HgCdTe or Mercury cadmium telluride (also Cadmium Mercury Telluride,


MCT is an alloy of CdTe and HgTe and is sometimes claimed to be the
third semiconductor of technological importance after Silicon and
Gallium(III) arsenide. The amount of cadmium (Cd) in the alloy (the alloy
composition) can be chosen so as to tune the optical absorption of the
material to the desired infrared wavelength.

Mathematics

I ( )

• Optical path difference is 


• Intensity in the detector I ( ) has maxima at
 = n , n = 0,1,2
and minima at  = ( n + 1 / 2)

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03-05-2023

Mathematics (contd.)
• The resulting interferogram is described as an
infinitely long cosine wave

• B ( ) cos( 2 ) where B( ) =intensity as F(v)

• For non-monochromatic source treat each frequency
as if it resulted in a separate cosine train.

Mathematics (contd.)

• An infrared source is typically approximated as


a black body radiator and the summation can
be replaced by an integral.

I ( ) =  B( ) cos(2 )d
0

• At  = 0, signal always has a strong maxima


called Centreburst.
• Outwards from the centreburst the cosine
waves cancel and reinforce and the amplitude of
the interferogram dies off.

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03-05-2023

Mathematics (contd.)

• Spectroscopists are interested in the spectrum


in the frequency domain i.e intensity versus
wavenumber
• If the mathematical form of the interferogram
is known,spectrum in the frequency domain
can be calculated by Fourier Transformation

B( ) =  I ( ) cos(2 )d
−

For mathematical validity this integration


must be carried out over all possible values
of delta i.e + to – 

Measurement Techniques
Using FTIR, most of the work is done in the absorption spectra
area, though some emission spectroscopy is also done.

• 1. If there is no sample present, the spectrum is that of a


black body radiator modified by any transmission
characteristics of the interferometer components.
• 2. If the interferometer chamber is not evacuated or
purged with dry gas some absorption from the atmospheric
CO2 and H20 is observed. This is called the background
spectrum.
• 3. When the sample is introduced, the spectrum now is a
superposition of the absorption bands of the sample on an
uneven background.
• 4. To obtain %T with wavenumber, we ratio the single
beam sample spectrum with the background spectrum.

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03-05-2023

Measurement Techniques(contd.)

Apodization

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03-05-2023

Energy transitions

For the vibrational motion of a diatomic molecule, the


permanent electric dipole moment can be expanded in a
Taylor series about the equilibrium internuclear
separation

Hence
can be expressed as

Energy transitions(contd.)

Therefore, diatomic molecules will only exhibit a


vibrational absorption spectrum if there is a
change in dipole moment with the vibrational
motion

Theory also dictates transition between  = 1

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03-05-2023

Applications
Applications are vast and diverse. Some of them are

•Compositional analysis of organic, inorganic and


polymers
•Biological and biomedical fields like detection of
water in biological membranes
•Analysis of Aircraft exhausts
•Measurement of toxic gas in fuels
•Combustion
•Gas analysis and lots more

Advantages and Disadvantages


• FT – IR can take wavelength readings across the whole IR region
simultaneously and smoothly, making this a very rapid technique.
• The technique is non-invasive and non-destructive. Its resolution
of 0.125 cm-1 is not spectacular in comparison to other vibrational
techniques and it will not give the same detailed structural
information that NMR, MS, or X-ray crystallography give.
• IR spectroscopy is notoriously sensitive to the absorption of
water, and it has the tendency to overwhelm all of the other peaks.
If there is significant moisture in the sample the penetration
distance of the light decreases. It may be advantageous to go with
Raman in place of IR in the case of excess moisture.
• Spectra in the frequency domain can never be eyeballed
conclusively. They are always subject to some sort of
manipulation, leading some to believe that the data can say
whatever the experimenter wants it to say depending on how it is
manipulated.

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03-05-2023

Advantages
• Much higher signal to noise ratio. Felgett’s
advantage=
• Greater throughput of power.
• Hard to do samples having low transmission and
weak spectra can be done with FTIR.
• Greater wavenumber accuracy. Most FT
instruments have an accuracy of +/- 0.01 cm-1.

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