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Spectroscopy Spectroscopy Radiation Source Radiation Source
Infrared Spectroscopy Infrared Spectroscopy
Instrumentation: Instrumentation:
Classic Classic dispersive dispersive radiation from the radiation from the
source is passed through the sample source is passed through the sample
focused on monochromator and dispersed focused on monochromator and dispersed
as continuous spectrum on detector; as continuous spectrum on detector;
difference in intensity is recorded: difference in intensity is recorded:
T(%) = I T(%) = I
s s
/I /I
R R
x 100 x 100
peaks of absorbance peaks of absorbance
Monochromators Monochromators
Prism and slit Prism and slit
Prism and filter Prism and filter
Grating and slit Grating and slit
Grating and filter Grating and filter
This type of equipment is called This type of equipment is called - -
Dispersive spectrometer or Dispersive spectrometer or
spectrophotometer spectrophotometer
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Spectrometers Spectrometers
CO CO
2 2
and H and H
2 2
O O absorption in IR absorption in IR
sealed optic compartment sealed optic compartment filled or filled or
flush continuously with dry nitrogen flush continuously with dry nitrogen
Double beam systems to compensate Double beam systems to compensate
Single beam will provide erratic Single beam will provide erratic
spectra spectra humidity and temperature humidity and temperature
Mirrors made of polished metals Mirrors made of polished metals
For spectra moving grating or prisms For spectra moving grating or prisms
Only about 5% of current instruments Only about 5% of current instruments
are dispersive type are dispersive type
FT Fourier Transformed
Mathematical transformation Mathematical transformation
converting the signal measured as converting the signal measured as
function of time into a function of function of time into a function of
reciprocal time reciprocal time frequency frequency time time
series series
Fast algorithm available to apply Fast algorithm available to apply
this transformation this transformation
Interferometer
We can measure the radiation intensity at all We can measure the radiation intensity at all
wavelength simultaneously and can reconstruct wavelength simultaneously and can reconstruct
it in the form of intensity vs. wavelength it in the form of intensity vs. wavelength
(spectrum). The wavelength have to be (spectrum). The wavelength have to be
encoded in a well encoded in a well- -defined manner as happen in defined manner as happen in
interferometer. Wavelength and their interferometer. Wavelength and their
corresponding intensities will overlap corresponding intensities will overlap the the
overlap is used to plot spectrum. overlap is used to plot spectrum.
In this case mathematical methods can be In this case mathematical methods can be
applied to describe spectrum applied to describe spectrum Fourier analysis Fourier analysis
- - deconvoluting deconvoluting
An instrument that does this without a An instrument that does this without a
monochromator is called a multiplex monochromator is called a multiplex
instrument instrument
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Michelson Interferometer Michelson Interferometer - - FTIR FTIR
ZPD
Zero
Pathlength
Difference
Mirror moves a distance
equal to 1/4 at constant
speed
Reference
Wave Interaction in Interferometer Wave Interaction in Interferometer
In Phase
Constructive
Interference
Out of Phase
Destructive
Interference
Fix and mobile mirrors
are at equal distance from
splitter or when the path
difference is integral
multiple of wavelength
Signal at detector
Mobile mirror moves 1/4
and beam will be combined
180
0
out of phase
Radiation from
splitter
Michelson Interferometer Michelson Interferometer
As the mirror moves, detector sees signal as a As the mirror moves, detector sees signal as a
function of path length difference in the form function of path length difference in the form
of cosine curve of cosine curve
The frequency of signal will be: The frequency of signal will be:
f = 2 f = 2 / /
Where: Where: f f frequency frequency
velocity of moving mirror velocity of moving mirror
wavelength of radiation wavelength of radiation
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Interferometer Interferometer
For monochromatic radiation a plot of the For monochromatic radiation a plot of the
signal (intensity) vs. difference in pathlength signal (intensity) vs. difference in pathlength
form interferogram and is describe by cosine form interferogram and is describe by cosine
function function
The interferogram it is a record of the The interferogram it is a record of the
interference signal at the detector interference signal at the detector detector detector
response in time response in time time domain time domain
If sample absorbs radiation at a specific If sample absorbs radiation at a specific
frequency frequency change of amplitude of change of amplitude of
frequency will change frequency will change
Interferometer Detector Signal Interferometer Detector Signal
Sampling the Interferogram Sampling the Interferogram
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Interferogram Interferogram - -
Infrared Spectroscopy Infrared Spectroscopy
Fourier Transform (FTIR) Fourier Transform (FTIR)
Advantage Advantage
entire spectrum obtained within a few entire spectrum obtained within a few
milliseconds milliseconds
hundreds of complete spectra can be hundreds of complete spectra can be
obtained on a sample obtained on a sample
spectrometer is recording spectrometer is recording interferograms interferograms, ,
which are later which are later deconvoluted deconvoluted
Better signal to noise ratios obtained than Better signal to noise ratios obtained than
in dispersive instruments in dispersive instruments
Infrared Spectroscopy Infrared Spectroscopy
Sample Handling Sample Handling
Gases Gases examined without examined without
preparation; water have to be preparation; water have to be
eliminated (Pathlength up to 40m eliminated (Pathlength up to 40m
used) used)
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Reflectance Cell for IR Reflectance Cell for IR
To extent radiation
pathlength and attenuate signal
Infrared Spectroscopy Infrared Spectroscopy
Solid samples Solid samples: :
used as solution in compatible solvent used as solution in compatible solvent
(CCl (CCl
4 4
; CS ; CS
2 2
); variety of cells used made ); variety of cells used made
from salts from salts
Pressed to pellet form with KBr Pressed to pellet form with KBr
scattering scattering particles; heat and moisture particles; heat and moisture
sensitive material; salts selected based on sensitive material; salts selected based on
absorption absorption Cut off: KBr 400cm Cut off: KBr 400cm
- -1 1
; ; CsI CsI
200cm 200cm
- -1 1
Mulling Mulling dispersing substance in small dispersing substance in small
amount of mineral oil ( amount of mineral oil (Nujol Nujol) or ) or
fluorinated hydrocarbons (mull). Mixture fluorinated hydrocarbons (mull). Mixture
is placed between plates of the cell is placed between plates of the cell
Pellet Sample Die for IR Pellet Sample Die for IR
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IR IR Sample Holder Sample Holder
Liquid sample Liquid sample
Cuvette Cuvette
Card Card
IR IR Cuvette Cuvette
Spectral Cards Absorption Spectra Spectral Cards Absorption Spectra
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IR IR Solvents Limitation Solvents Limitation
Horizontal Lines Indicates Useful Region
IR Optics Materials IR Optics Materials Mid IR Mid IR
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Infrared Spectroscopy Infrared Spectroscopy - - Patterns Patterns
Infrared Spectroscopy Infrared Spectroscopy
Coupling of vibrations Coupling of vibrations - - bonds at bonds at
singular central atom singular central atom change in the change in the
characteristics of vibrations characteristics of vibrations
Mid Mid- -Range IR Spectra Range IR Spectra
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Michelson Interferometer Michelson Interferometer
Solvents Properties for IR Solvents Properties for IR
Infrared Spectroscopy Infrared Spectroscopy
Instrumentation Instrumentation - - Fourier transform Fourier transform
Interference pattern Interference pattern interferogram interferogram
complex waveform that contains complex waveform that contains
information about all frequencies in the information about all frequencies in the
measured infrared region. Using measured infrared region. Using
mathematical operation termed a mathematical operation termed a Fourier Fourier
transform transform to to deconvolute deconvolute the interferogram the interferogram
to produce a spectrum in frequency domain; to produce a spectrum in frequency domain;
the same as in dispersive spectrometer the same as in dispersive spectrometer
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Interferogram Formation Interferogram Formation