Fourier Transform Infrared (FT-IR) Spectroscopy:

Figure 38.01 displays the typical spectrum of Infrared (IR) range having short, medium and long
waves IR. It contains spectral fingerprinting range, i.e., frequencies at which they can detect
echoes of the vibrations of the molecules that make up a solid substance.

Figure 38.01: Schematic of Infrared spectrum (um refers micrometer) [1].

Ref.[1]. Infrared Process Heating Handbook for Industrial Applications, Industrial Heating
Equipment Association.

Fourier Transform Infrared (FT-IR) Spectroscopy:

For example, humans, at normal body temperature, radiate most strongly in the infrared, at a
wavelength of about 10 microns. Figure 38.02 shows a typical comparison of human body and
cat seen through visible light and IR. Comparing both the images, the red areas are the
warmest, followed by yellow, green and blue (coolest).
 Figure 38.02: Typical view of human body and cat through visible light and IR.

Fourier Transform Infrared (FT-IR) Spectroscopy:

Basics: This technique deals with interaction between a molecule and radiation from the IR
region of the electromagnetic spectrum (IR region = 4000 - 400 cm-1). The cm-1 unit is the
wavenumber scale and is given by 1/λcm.

IR radiation causes the excitation of the vibrations of covalent bonds within that molecule. These
vibrations include the stretching and bending modes. An IR spectrum shows the energy
absorptions as one 'scans' the IR region of the electromagnetic spectrum.

Figure 38.03: Vibrational modes of a water molecule.

The water molecule with its unsymmetrical structure can vibrate in three different modes, as
shown in Figure 38.03. The frequencies of such vibrations can be computed out of the mass and
bonding properties by using Hooke's Law. The liquid water primarily vibrates in the symmetric
stretching mode.

Fourier Transform Infrared (FT-IR) Spectroscopy:

Basics:
 Figure 38.04: Schematic of IR absorption and emission.

Infrared absorption occurs among the ground vibrational states, the energy differences, and
corresponding spectrum, determined by the specific molecular vibration(s) as shown in Figure
38.04. The infrared absorption is a net energy gain for the molecule and recorded as an energy
loss for the analysis beam.

Fourier Transform Infrared (FT-IR) Spectroscopy:

FT-IR has a natural reference point when the moving and fixed mirrors are the same distance
from the BS. This condition is called zero path difference or ZPD. The moving mirror
displacement, Δ, is measured from the ZPD.
 Figure 38.05: Block diagram of FT-IR setup.

The interference of waves with respect to mirror position is demonstrated in Figure 38.06.

Fourier Transform Infrared (FT-IR) Spectroscopy:

 Figure 38.06: Schematic representation of waves and their phases, input, output, and the two
arms of the interferometer as the scan goes from zero path difference condition to optical path
different (OPD)= λ . (a) OPD=0 case. (b) λ/4 OPD case. (c) λ/2 OPD case. (d) 3 λ/4 OPD case.
(e) 1 λ OPD case.

Fourier Transform Infrared (FT-IR) Spectroscopy:

The recombined beam passes through the sample, which absorbs all the different wavelengths
characteristic of its spectrum, and this subtracts specific wavelength from the interferogram. A
laser beam is superimposed to provide a reference for the instrument operation as shown in
38.07. The detector now reports a variation in energy versus time for all wavelengths
simultaneously as shown in Figures 38.08 and 38.09.
 Figure 38.07: Schematic diagram of FT-IR set up with laser beam superimposed.

Fourier Transform Infrared (FT-IR) Spectroscopy:

Relationship between light source spectrum and the signal output from an interferometer are
shown in Figure 38.08.
 Figure 38.08: Drawing of various nature of light and the signal output from interferometer.

Fourier Transform Infrared (FT-IR) Spectroscopy:

 Figure 38.09: A typical intensity pattern, output of a laser and optical path difference of FT-IR
interferometer.

Energy versus time is an odd way to record a spectrum, until you recognize the relationship
between time and frequency: they are reciprocals! A mathematical function called a Fourier
transform as described below allows us to convert an intensity versus time spectrum into an
intensity versus frequency spectrum.

where A(r) and X(k) are the frequency domain and time domain points, respectively for a
spectrum of N points.

Now, we have to simply Fourier transform for every point in the interferogram . As the output of
the detector is digitized, a small computer program will do the transform. All modern FT-IR
instruments are computer-interfaced.

Fourier Transform Infrared (FT-IR) Spectroscopy:

 Figure 38.10: An interferogram (top) and a spectrum (bottom) for Polystyrene measured using
FT-IR.

Figure 38.10 shows a typical interferogram and extracted spectrum extracted from interferogram
after Fourier Transformation.

There are several advantages to this design:

• All of the source energy gets to the sample, improving the inherent signal-to-noise ratio.

• Resolution is limited by the design of the interferometer. The longer the path of the moving
mirror, the higher the resolution.

• The digitization and computer interface allows multiple scans to be collected, also dramatically
improving the signal-to-noise ratio.

• Most of the computer programs today allow subtraction of a reference spectrum, correct the
baseline, edit spurious peaks or otherwise correct for sample limitations.

Fourier Transform Infrared (FT-IR) Spectroscopy:

 Figure 38.11: FT-IR spectrum of water [1].

The typical FT-IR spectrum for water molecule is shown in Figure 38.11. This clearly
demonstrates the various stretching bonds of water molecules as schematically shown in Figure
38.03.

Capabilities of Infrared Analysis:

1. Identification and quantitation of organic solid, liquid or gas samples.

2. Analysis of powders, solids, gels, emulsions, pastes, pure liquids and solutions, polymers, pure
and mixed gases.

3. FT-IR is widely used for research and development, quality control and quality assurance
applications.

4. Sample size ranging from 20 microns in length to very lagre areas pertaining to atmospheric
pollution studies.

Ref.[1]. http://webbook.nist.gov/cgi/cbook.cgi?ID=C7732185&Type=IR-SPEC&Index=1.

Fourier Transform Infrared (FT-IR) Spectroscopy:

Applications of Infrared Analysis:

1. Pharmaceutical research

2. Forensic investigations

3. Polymer analysis

4. Lubricant formulation and fuel additives

5. Foods research
6. Quality assurance and control

7. Environmental and water quality analysis methods

8. Biochemical and biomedical research

9. Coatings and surfactants

Quiz 38:

(Q38.1) What are the advantages of analyzing the sample using IR spectroscopy?

(Q38.2) Why does the fingerprint region of spectra become complex in analyzing?

(Q38.3) What is the working principle of Michelson Interferometer?

(Q38.4) How do we improve the FT-IR spectra?

(Q38.5) Why do we need to perform Fourier transformation?

(Q38.6) What are the materials can be analyzed using FT-IR?

Ref - NPTEL