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FT-IR Spectroscopy Techniques Explained

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0% found this document useful (0 votes)
30 views7 pages

FT-IR Spectroscopy Techniques Explained

Uploaded by

Harshmeek Kaur
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Fourier transform Infrared spectroscopy (FT-IR)

The discovery of the fast Fourier transform algorithm and the concurrent introduction
of sophisticated computers permitted the new generation of infrared instrumentation,
called Fourier transform infrared spectrometer. The Fourier transform infrared
spectrographs have replaced the conventional infrared spectrographs.

In FT-IR the grating monochromator is replaced by Interferometer to obtain best


results. Fourier transform Infrared spectroscopy (FT-IR) is the technique for
measurement of infrared spectra in which the amount of energy absorbed is not
recorded but when the frequency of the infra-red light is varied, the IR light is guided
through an interferometer instead of monochromator.

FT-IR spectrometer consists of following components:

1. IR radiation source
2. Beam splitter
3. Fixed mirrors
4. Moving mirrors
5. Collimating mirrors
6. Detector

Working Principle of FTIR:

In FT-IR, Michelson interferometer is used to produce a new signal of a much lower


frequency which contains the same information as the original IR signal. The output
from the interferometer is an interferogram.

INSTRUMENTAL TECHNIQUES | Compiled by Mohamed Eeman


Radiation leaves the source and is split by the beam splitter.

Half is reflected to a stationary mirror and then back to the splitter. This radiation
has travelled a fixed distance.

The other half of the radiation from the source passes through the splitter and
is reflected back by a movable mirror. Therefore, the path length of this beam
is variable.

The two reflected beams recombine at the splitter, and they interfere (e.g. for
any one wavelength, interference will be constructive if the difference in path
lengths is an exact multiple of the wavelength. If the difference in path lengths
is half the wavelength then destructive interference will result).

If the movable mirror moves away from the beam splitter at a constant speed,
radiation reaching the detector goes through a steady sequence of maxima and
minima as the interference alternates between constructive and destructive
phases.

Because all wavelengths emitted by the source are present, the interferogram
is extremely complicated. The moving mirror must travel smoothly; a frictionless
bearing is used with electromagnetic drive. The position of the mirror is
measured by a laser shining on a corner of the mirror. A simple sine wave
interference pattern is produced. Each peak indicates mirror travel of one half

INSTRUMENTAL TECHNIQUES | Compiled by Mohamed Eeman


the wavelength of the laser. The accuracy of this measurement system means
that the IR frequency scale is accurate and precise.

In the FT-IR instrument, the sample is placed between the output of the
interferometer and the detector. The sample absorbs radiation of particular
wavelengths. Therefore, the interferogram contains the spectrum of the
source minus the spectrum of the sample.

An interferogram of a reference (sample cell and solvent) is needed to obtain


the spectrum of the sample.

After an interferogram has been collected, a computer performs a Fast Fourier


Transform, which results in a frequency domain trace (i.e intensity vs.
wavenumber).

The detector used in an FT-IR instrument must respond quickly because


intensity changes are rapid (the moving mirror moves quickly). Pyroelectric
detectors or liquid nitrogen cooled photon detectors must be used. Thermal
detectors are too slow.

To acheive a good signal to noise ratio, many interferograms are obtained and
then averaged. This can be done in less time than it would take a dipersive
instrument to record one scan.

The conventional IR instrument are called Dispersive Instrument. When Dispersive


Instrument is coupled with computer and microprocessor based apparatus then the
instrument is called Fourier Transform Infrared Spectrometer (FT-IR).

Any waveform can be shown in one of two ways; either in frequency domain or time
domain. Dispersive IR instruments operate in the frequency domain.

If we wished to record a trace in the time domain, it could be possible to do so by


allowing radiation to fall on a detector and recording its response over time. In practice,
no detector can respond quickly enough (the radiation has a frequency greater than

INSTRUMENTAL TECHNIQUES | Compiled by Mohamed Eeman


1014 Hz). This problem can be solved by using interference to modulate the i.r. signal
at a detectable frequency.

The Michelson interferometer is used to produce a new signal of a much lower


frequency which contains the same information as the original IR signal. In FT-IR
Instrument, the resultant absorption of radiation by sample is a spectrum in the time
domain which is called interferogram.

In interferometers, in FT-IR, a small red helium neon laser is used to pass a


monochromatic beam through the interferometer. This red helium neon laser gives the
wavelength around 600nm as a source of radiation.

Past Paper Question:


1. Give a block diagram of FTIR and explain the process involved in
interferometer.

INSTRUMENTAL TECHNIQUES | Compiled by Mohamed Eeman


Advantages of Fourier transform IR over dispersive IR;
Improved frequency resolution
Improved frequency reproducibility (older dispersive instruments must be
recalibrated for each session of use)
Higher energy throughput
Faster operation
Computer based (allowing storage of spectra and facilities for processing
spectra)
Easily adapted for remote use (such as diverting the beam to pass through an
external cell and detector, as in GC - FT-IR)

Disadvantages of FT-IR over Dispersive instruments


More expensive
They require precision for mirror movement
Detection of the compound is influenced by water vapor, path length and
chemical interference.

Application of IR Spectroscopy:

a) In Forensic Applications: Applications such such identification of drugs and


poisons, Determination of impurities, Identification and Examination of Gun Shot
Residue (GSR) and explosive substances, Examination of polymers and polythene
and Identification and examination of paint, dye, etc.

b) Identification of functional groups: As has already been discussed, IR


spectroscopy allows identification of functional groups. Carbonyl (C=O) is an
interesting functional group worth discussing. Carbonyl is a double bond (high
spring constant, k) with very high polarity. Stretching vibration of carbonyl group
causes large changes in the dipole moment consequently resulting in a very intense
absorption band. Furthermore, the frequency of carbonyl stretching does not differ
significantly for aldehydes, ketone, carboxylic acids, and esters. The large intensity

INSTRUMENTAL TECHNIQUES | Compiled by Mohamed Eeman


and relatively unchanged frequency of carbonyl stretching allows easy identification
of the carbonyl compounds (It is important to note that carbonyl stretching
frequency can be much lower for amides and much higher for anhydrides and acid
chlorides).

c) Identification of compounds: The fingerprint region of the IR spectrum is unique


to each compound. It is possible to identify a compound from its IR spectrum if the
spectrum for the compound is already known and available for comparison. This is
particularly useful in pharmaceutical research and development. A patented drug,
if suspected to be synthesized by another pharmaceutical company, can easily be
identified by comparing the IR spectra in the fingerprint region.

d) Presence of impurities: Comparison of the IR spectra of the given compound with


the spectra of pure compound helps in the assessment of its purity. It is important
to ascertain the purity of the active molecule and the excipients used in preparing
drug formulations.

e) Structural transitions in lipids: Structural lipids are those that are organized in
bilayers in biological membranes. Glycerophospholipids constitute the major class
of the structural lipids (Figure 10.7). The lipids have several structural phases such
as a gel phase with all-transconformation and a liquid crystalline phase
where gauche conformations are also present. Methylene ( CH2 ) stretching
vibrations give the most intense absorption band in lipids as expected for a molecule
having long hydrocarbon chains.

Both CH2 stretching and bending vibrations are sensitive to the conformations of
the lipids and therefore provide information about the transition of lipids between
different phases. Vibration modes of the head group and the interfacial region also
provide useful information about local acyl chain conformation. Carbonyl stretching
vibration (1750 1700 cm-1) in the ester bond is sensitive to the conformation of
the local acyl chain conformation.

f) Protein and peptide structure: Infrared spectroscopy is routinely used to study


the structures of proteins and peptides. Like CD spectroscopy, the region of interest
in determining the conformation of the polypeptide backbone is the peptide bond.
The peptide group results in nine distinct bands, labeled as amide A, B, and I-VII.
Amide I is the most useful band in studying the polypeptide backbone conformation.

INSTRUMENTAL TECHNIQUES | Compiled by Mohamed Eeman


Amide I band (1700 1600 cm-1) arises largely due to the carbonyl stretching with
small components of C N stretching and N H bending. The frequency of carbonyl
stretching vibration is sensitive to the H-bonding, and therefore to the conformation
of polypeptide backbone.

g) Studying the progress of the reaction: Progress of chemical reaction can be


determined by examining the small portion of the reaction mixure withdrawn from
time to time. The rate of disappearance of a characteristic absorption band of the
reactant group and/or the rate of appearance of the characteristic absorption band
of the product group due to formation of product is observed.

h) Quantitative analysis: The quantity of the substance can be determined either in


pure form or as a mixure of two or more compounds. In this, characteristic peak
corresponding to the drug substance is chosen and log I0/It of peaks for standard
and test sample is compared. This is called base line technique to determine the
quantity of the substance.

INSTRUMENTAL TECHNIQUES | Compiled by Mohamed Eeman

Common questions

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The interferogram serves as a crucial intermediate step in the data acquisition process of an FT-IR spectrometer. It captures the time domain signal that results from the interference of light beams traveling along different paths in the Michelson interferometer. This complex signal reflects changes in intensity as a function of the movement of the interferometer's moving mirror. After obtaining an interferogram, it undergoes a Fast Fourier Transform to convert it into a frequency domain spectrum, showcasing intensity versus wavenumber, thus providing detailed spectral information about the sample .

In an FT-IR spectrometer, the interference pattern generated by the Michelson interferometer plays a crucial role in determining the spectral output. Radiation from the source is split by the beam splitter, with one part reflected to a stationary mirror and the other to a moving mirror. These parts recombine and interfere at the beam splitter upon returning. Constructive interference occurs when the path length difference is a multiple of the wavelength, while destructive interference occurs at half wavelengths. The resultant cyclic maxima and minima create an interferogram, which is subsequently converted to a frequency domain trace using a Fast Fourier Transform. Thus, the interference pattern contains all spectral information before the calculation of the final spectrum .

FT-IR spectroscopy aids in identifying functional groups by analyzing characteristic absorption bands specific to certain groups, such as the carbonyl group's intense band due to its high polarity and spring constant. It allows differentiation between compounds, although carbonyl stretching frequency differences are minimal among aldehydes, ketones, carboxylic acids, and esters. Regarding impurity detection, FT-IR enables purity assessment by comparing the IR spectrum of the given compound with that of a pure compound. Discrepancies in spectral patterns may indicate the presence of impurities .

The accuracy of the FT-IR frequency scale is crucial to the reliability of spectroscopic data analysis, as it ensures precise identification of absorption bands corresponding to molecular vibrations. With an accurate frequency scale, researchers can trust the exact wavelength measurements that are critical in determining the presence and quantity of functional groups, detecting impurities, and identifying molecular structures. The use of a laser to monitor the moving mirror's position in the Michelson interferometer maintains this accuracy, ensuring that interpretations of spectral data are consistent and reliable across different measurements .

FT-IR spectroscopy is highly useful in forensic science for several key applications. It aids in identifying drugs and poisons, determining impurities, and examining residues from gunshots and explosives. Additionally, FT-IR is instrumental in analyzing polymers, polyethylene, and the composition of paint and dyes, all of which can be critical in forensic investigations to gather evidence or verify materials involved in criminal activities .

The identification of the fingerprint region in FT-IR spectroscopy plays a vital role in compound analysis due to its uniqueness to each molecule. This region, typically between 600-1500 cm⁻¹, contains complex and specific vibrational modes arising from entire molecular frameworks rather than isolated functional groups. It serves as a molecular 'signature' allowing precise compound identification by comparing to known spectra within databases. In pharmaceutical research, it verifies the molecular integrity against patented drugs and detects any synthesis by unauthorized entities, affirming authenticity and compliance with established spectral profiles .

Fourier Transform Infrared (FT-IR) spectroscopy offers several advantages over traditional dispersive IR instruments. These include improved frequency resolution and reproducibility, higher energy throughput, faster operation, and the ability to store and process spectra digitally. FT-IR's computer-based system also allows for flexibility in adapting for remote use by redirecting the beam through external cells and detectors . Moreover, FT-IR provides a more efficient signal-to-noise ratio by averaging multiple interferograms faster than dispersive instruments, which require more time to record a single scan .

The interaction of light with components of an FT-IR spectrometer is essential to derive data about the sample. The light source emits IR radiation that is split into two beams by a beam splitter within the Michelson interferometer. One beam reflects off a stationary mirror and the other off a moving mirror. As the moving mirror shifts, the beams recombine and their interference pattern at the detector changes, producing an interferogram that encodes spectral data. The sample interrupts this light path between the interferometer and the detector, selectively absorbing certain frequencies and modifying the interferogram. The recorded interferogram represents both the source spectrum and the sample's absorption characteristics, which a computer processes using a Fast Fourier Transform to create an IR spectrum showing intensity versus wavenumber .

FT-IR spectroscopy can monitor a chemical reaction's progress by observing changes in characteristic absorption bands within the IR spectrum over time. As the reaction proceeds, distinct absorption bands corresponding to reactants may decrease in intensity, while bands representing products appear or grow in intensity. By periodically analyzing small samples from the reaction mixture, the rates of disappearance of reactant bands and appearance of product bands provide insight into the reaction kinetics and progress .

Precision in mirror movement is critical in an FT-IR spectrometer because the accuracy of the produced interferogram directly depends on the precise control of the mirror's path. This precision is crucial for maintaining the correct path length difference necessary for reliable interference patterns and accurate spectral data. Precision is maintained using a frictionless bearing with an electromagnetic drive for the moving mirror, and its position is monitored by a laser fixed to a corner of the mirror. This setup ensures smooth, consistent movement, providing accurate positioning that determines the frequency scale's precision and accuracy .

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