FTIR- Fourier Transform Infrared Spectroscopy
M.Sc. Chemistry Practical Inorganic
Chemistry (Paper- 4106)
Semester- IV
Dr. Neeraj Kumar and Dr. Sanjay Kumar Saroj
Inorganic Group- II
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Introduction
Spectroscopy is the study of the interaction
between matter and electromagnetic spectrum.
Electromagnetic radiation displays the properties of both
particles and waves.
The particle component is called a photon.
The energy (E) component of a photon is proportional to the
frequency. Where h is Planck’s constant and n is the frequency
in Hertz (cycles per second)
E = hn
also E=hc/λ
Infrared spectroscopy (IR spectroscopy) is the spectroscopy that
deals with the infrared region of the electromagnetic spectrum.
Frequency, n in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105
Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m
g-rays X-rays UV IR Microwave Radio
nuclear core electronic molecular molecular Nuclear Magnetic
excitation electron excitation vibration rotation Resonance NMR
(PET) excitation (p to p*) (MRI)
(X-ray
cryst.)
Visible
IR spectroscopy is an absorption technique.
Absorption of infrared radiation brings about changes in molecular
vibrations within molecules. So, it is a kind of vibrational spectroscopy.
The frequency at which a particular bond absorbs infrared radiation
will be different over a range of bonds and modes of vibration depending
on atom size, bond length and bond strength.
Hookes' Law
When can absorption occur?
1. Infrared absorption only occurs when infrared radiation interacts with
a molecule undergoing a permanent change in dipole.
2. Infrared absorption only occurs when the incoming infrared photon
has sufficient energy for the transition to the next allowed vibration
energy state.
If these two rules are not met ,no absorption can occur.
N2 or O2 has no infrared spectrum (no dipole change).
CO does have.
Vibration Types
• There are two different types of vibrational modes.
Vibrations can either involve a change in bond length
(stretching) or bond angle (bending).
Stretching Vibrations Bending vibrations
Vibrational Modes
1.Stretching – Vibration or oscillation along the line of the bond.
H H
C C
H H
symmetric asymmetric
2.Bending – Vibration or oscillation not along the line of the bond.
H H H H
C C C C
H H H
H
twist wag
scissor in plane rock out of plane
n Asym n Sym n Bending
What is FTIR
Fourier-transform infrared spectroscopy is a less intuitive
way to obtain the information.
Rather than shining a monochromatic beam of light at the
sample, this technique shines a beam containing many
frequencies of light at once and measures how much of
that beam is absorbed by the sample.
Fourier transform is to transform the signal from the time
domain to its representation in the frequency domain.
All FTIR spectrometers are based on the Michelson
Interferometer.
Instrumentation
Components of FTIR
IR Source Sample
compartment Detector
IR source
Nernst Glower heated rare earth oxide rod 1-50 µm
(~1500 K) (mid- to far-IR)
Globar heated SiC rod (~1500 K) 1-50 µm
(mid- to far-IR)
Tungsten filament 1100 K 0.78-2.5 µm
lamp (Near-IR)
Hg arc lamp plasma 50 - 300 µm
(far-IR)
CO2 laser stimulated emission lines 9-11 µm
The Sample Analysis Process
Interferogram : intensity vs time
after the Fourier transformation: intensity vs frequency:-an IR
spectrum
Theory and Instrumentation
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 known as an
interferogram.
Stationary mirror
HeNe laser
Beam Splitter
Source
Moving mirror
PMT
Sample
Detector
Optical Diagram of
Michelson Interferometer
Light He-Ne gas laser
source
Beam splitter Interferogram
Movable mirror
Sample chamber
DLATGS (deuterated L-
alanine doped triglycene
Fixed mirror sulphate)
Detector
Interferometer
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Interference Of Two Frequencies
Movable mirror
Fixed mirror
Movable mirror l
Same-phase -2l -l 0 2l
Continuous phase shift
Fixed mirror
Movable mirror Opposite-phase
Signal strength
Fixed mirror
Movable mirror
Same-phase -2l -l 0 l 2l
0 l
Interference pattern of light manifested by the optical-path difference
Detectors
The beam finally passes to the detector
Thermal detectors
•Thermocouples
•Bolometer
Photoconducting detectors
• most sensitive detectors.
Pyroelectric detectors
• much faster response time
• insulator material
• Triglycine sulphate
Absorption Regions
Advantages of FT-IR
Speed Because all of the frequencies are measured simultaneously.
• Sensitivity is dramatically improved with FT-IR ; detectors are much
more sensitive,higher signal to noise ratio.
• Mechanical Simplicity The moving mirror in the interferometer is the
only continuously moving part in the instrument. Thus, there is very
little possibility of mechanical breakdown.
• Internally Calibrated These instruments employ a He-Ne laser as an
internal wavelength calibration standard .These instruments are self-
calibrating and never need to be calibrated by the user.
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Disadvantages of FTIR
Cannot detect atoms or monoatomic ions - single atomic
entities contain no chemical bonds.
Cannot detect molecules comprised of two identical
atoms -such as N2 or O2.
Aqueous solutions are very difficult to analyze- water is a
strong IR absorber.
Complex mixtures - samples give rise to complex spectra.
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Applications of FT-IR
Pharmaceutical research
Forensic investigations
Polymer analysis
Foods research
Quality assurance and control
Environmental and water quality analysis
methods
Biochemical and biomedical research
coatings and surfactants
References
• Instrumental Methods of Analysis, Willard et al, 4th edition, CBS
Publishers and Co.
• Fourier Transform Infrared Spectroscopy, Peter R. Griffiths, 2nd
edition, John Wiley & Sons.
• http://www.photonics.com/Category.aspx?CatID=38300
• http://mtweb.mtsu.edu/nchong/Spectroscopy-CHEM6230.pdf
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