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ν = 1/λ Where: λ in cm
Converting wavelength (µ
(µm ) into
wavenumber (cm-1) and reverse
cm-1 = 10,000/µm
µm = 10,000/cm-1
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Infrared Spectroscopy
Region Wavelength Wavenumber
µm cm-1
Near 0.78 - 2.51 12800 – 4000
Middle 2.5 – 50 4000 – 200
Far 50 - 1000 200 – 10
IR - Applications
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Infrared Spectroscopy
Infrared Spectroscopy
Vibrational Bending IR
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Infrared Spectroscopy
Infrared Spectroscopy
Infrared Spectroscopy
Molecular Vibrations:
Vibrations:
Atoms in molecules fluctuate
continuously
Interaction in complex molecules
4
Infrared Spectroscopy
Vibrations:
Stretching – continuous change
in the distance between atoms
along the bond within
molecule
Bending – change in the angle
between two bonds; types:
scissoring, rocking, wagging
and twisting
Stretching IR
IR Spectroscopy - Absorption
s s
s
s
s
s
s
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Mid-
Mid-range IR Spectra
Spectroscope Components
Absorption
Fluorescence
Phosphorescence
Scattering
Infrared Spectroscopy
Infrared Source:
Usually inert solid material electrically heated to
1500 – 2200K; maximum radiation 5000 – 5900 cm-1
(2 to 1.7 µm)
Nernst Glower – rare earth oxides formed in to
cylinder – electrically heated to 1200K to
2200K; 1 – 9 µm
Globar Source – silicon carbide rod; heated to
1300K to 1500K; spectrum similar to Nernst
with higher energy at the 5 µm
Mercury arc – for spectrum > 50 µm
Tungsten Filament Lamp – near infrared 2.5 to 0.78
µm
6
Tungsten-
Tungsten-Halogen Lamps for NIR
IR Radiation Sources
7
Spectroscopy – Radiation Source
Blackbody
Radiation
Characteristics
NIR
8
Infrared Spectroscopy
Infrared Spectroscopy
¾ Pyroelectric – temperature dependent
capacitors
- Dielectric material, pyroelectric
material such as triglycine sulfate
between electrodes
- One electrode is expose to IR radiation
- Change in temperature change charge
distribution in material and
current is measured
¾ Lasers – monochromatic radiation; tunable
CO2 laser emits at 1100 – 900 cm-1 –
pollution control
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Spectroscopy – Radiation Source
Infrared Spectroscopy
Instrumentation:
Monochromators
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Spectrometers
FT – Fourier Transformed
Mathematical transformation
converting the signal measured as
function of time into a function of
reciprocal time – frequency – time
series
Fast algorithm available to apply
this transformation
Interferometer
We can measure the radiation intensity at all
wavelength simultaneously and can reconstruct
it in the form of intensity vs. wavelength
(spectrum). The wavelength have to be
encoded in a well-
well-defined manner as happen in
interferometer. Wavelength and their
corresponding intensities will overlap – the
overlap is used to plot spectrum.
In this case mathematical methods can be
applied to describe spectrum – Fourier analysis
- deconvoluting
An instrument that does this without a
monochromator is called a multiplex
instrument
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Michelson Interferometer - FTIR
Mirror moves a distance Reference
equal to 1/4λ at constant
speed
ZPD
Zero
Pathlength
Difference
Radiation from
splitter Signal at detector
Fix and mobile mirrors
In Phase
are at equal distance from
Constructive
splitter or when the path
Interference
difference is integral
multiple of wavelength
Out of Phase
Mobile mirror moves 1/4λ
Destructive
and beam will be combined
Interference
1800 out of phase
Michelson Interferometer
f = 2ν
2ν/λ
Where: f – frequency
ν – velocity of moving mirror
λ – wavelength of radiation
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Interferometer
For monochromatic radiation a plot of the
signal (intensity) vs. difference in pathlength
form interferogram and is describe by cosine
function
The interferogram it is a record of the
interference signal at the detector – detector
response in time – time domain
If sample absorbs radiation at a specific
frequency – change of amplitude of
frequency will change
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Interferogram -
Infrared Spectroscopy
Infrared Spectroscopy
Sample Handling
Gases – examined without
preparation; water have to be
eliminated (Pathlength up to 40m
used)
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Reflectance Cell for IR
To extent radiation
pathlength and attenuate signal
Infrared Spectroscopy
Solid samples:
samples:
– used as solution in compatible solvent
(CCl4; CS2); variety of cells used made
from salts
– Pressed to pellet form with KBr –
scattering – particles; heat and moisture
sensitive material; salts selected based on
absorption – Cut off: KBr 400cm-1; CsI
200cm-1
– Mulling – dispersing substance in small
amount of mineral oil (Nujol
(Nujol)) or
fluorinated hydrocarbons (mull). Mixture
is placed between plates of the cell
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IR – Sample Holder
Liquid sample
Cuvette
Card
IR Cuvette
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IR – Solvents Limitation
Horizontal Lines Indicates Useful Region
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Infrared Spectroscopy - Patterns
Infrared Spectroscopy
Mid-
Mid-Range IR Spectra
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Michelson Interferometer
Infrared Spectroscopy
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Interferogram Formation
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