"FTIR SPECTROSCOPY:

A QUANTITATIVE APPROACH TO FORENSIC

ANALYSIS"

PRESENTED BY- NISHA BHAGAT

CLASS-M.SC.(2ND SEMESTER)
ROLL NO-: 24151003
 CONTENTS :

1. HISTORY
2. IR REGION OF EMR SPECTRUM
3. FTIR SPECTROSCOPY
4. PRINCIPLE OF FTIR
5. SAMPLE PREPARATION
6. ATR SAMPLING
7. INSTRUMENTATION
8. ADVANTAGES &
DISADVANTAGES OF FTIR
9. FORENSIC APPLICATIONS OF
FTIR
 HISTORY :

• Chemical IR spectroscopy was emerged as a science in 1800 by Sir

William Herschel
• Firstly most IR instrumentation was based on prism or grating
monochromators
• Michelson invented interferometer in 1880s
• In 1949 Peter Fellgett obtained the first IR spectrum by using FTIR
spectrometer
• In 1960s commercial FTIR spectrometers appeared
• In 1966 Cooley- Tukey developed an algorithm, which quickly does a
Fourier transform
IR REGION OF ELLECTROMAGNETIC SPECTRUM:

10-200 cm-1 200-4000 cm-1 4,000 - 14,000 cm-1

 FTIR ( FOURIER TRANSFORM INFRARED)
SPESPECTROSCOPY

• FTIR stands for Fourier Transform Infrared, the preferred method of infrared
spectroscopy.
• It is a powerful tool for identifying the type of chemical bond present in a molecule
• In infrared spectroscopy, IR radiation is passed through a sample. Some of the
infrared radiation is absorbed by the sample and some of it is passed through
(transmitted).
• The resulting spectrum represents the molecular absorption and transmission, creating
a molecular fingerprint of the sample.
• Like a fingerprint no two unique molecular structure produce the same infrared
spectrum. This makes infrared spectroscopy useful for several types of analysis.
 CONT.

• FTIR have greatly extended the capabilities of IR and applied to many areas that are
difficult to analyze by dispersive instrument.
• In dispersive IR , IR light is separated into it’s individual frequency by dispersion using
a grating monochromatic
• All frequencies and intensities can be simultaneously determined. FTIR gives a plot of
intensity v/s frequency.
• The instrument used for FTIR is Scanning Michelson interferometer.
• FTIR frequencies are allowed to intersect to produce an interference pattern and this
pattern is analyzed mathematically using “FOURIER TRANSFORM”, to determine the
individual frequencies and their intensities.
 PRINCIPLE OF FTIR SPECTROSCOPY:

Radiation emitted from the source is split into two light beam with a beamsplitter in
the interferometer. The fixed and moving mirror reflect each of the beam to the
beamsplitter, where the two beams recombine into one and falls on the detector. The
two beams combine constructively or destructively, varying as the optical path
difference , when the moving mirror is moved. When the combined beam is
transmitted through the sample, it is detected as an interferogram and contains all
infrared information on the sample. The infrared spectrum is obtained from the
interferogram by the mathematical process of Fourier transformation.
 SAMPLE PREPARATION:
(A) SOLID SAMPLES:
1.Solids run in solution
2. Cast Films: Prepared by casting a solution of the sample onto a substrate.
3. Mull technique : Grind sample with oil or Nujol to create a mull.
4. KBr pressed pellet: Mix sample with KBr powder and compress into a pellet.

(B) LIQUID SAMPLES

1. Solution Cells: Prepare a solution of the sample in a suitable solvent and place it in a
solution cell.
2. Cast Film: Cast a thin film of the liquid sample on a salt plate or other substrate.

(C) GASEOUS SAMPLES

1. Gas Cells: Use specialized gas cells to contain and analyze gas samples.
2. Gas Sampling Bags: Collect gas samples in sampling bags and then transfer to a gas cell.
ATR(ATTENUATED TOTAL REFLECTANCE) SAMPLING

ATR sampling is based on the principle of total internal reflection. When an infrared beam
passes through a high-refractive-index material (e.g., a crystal) and hits a sample in contact
with the crystal, the beam is partially absorbed by the sample and partially reflected back
into the crystal.
ATR ACCESSORIES:
1. ATR crystals: diamond, zinc selenide, or germanium.
2. ATR cells: Hold the sample in place
SAMPLE PREPARATION
1. Clean the ATR crystal
2. place sample on crystal
 1. IR source

2. Interferometer -

Moving Mirror

- Fixed Mirror

4. Beam splitter
I N S T R U M E N TAT I O N
OF FTIR 5. Sample cell or chamber
S P E C T R O S C O P Y: 6,.Laser

7.. Detector

- Thermal detectors

- Photonic Detector

8. Computer – FOURIER TRANSFORM

9. Recorder
IR SOURCE:

• 1.GLOBAR SOURCE: A rod of sintered silicon carbide

• 50mm in length and 4mm in diameter.
• heated to a temperature between 1300 -1700°C
• 2.NERNST GLOWER: hollow rod composed of rare earth oxides such as Zirconium,
thorium, and yttrium.
• 30 mm in length and 2mm in diameter
• heated upto a temperature between 1000 -1800°C.
• 3.NICHROME COILS: These coils were once popular IR sources and did not require
cooling as they ran at lower temperatures (1100°C). A black oxide film forms on coil, giving
acceptable emissivity.
MICHELSON INTERFEROMETER:

• Invented by Albert Abraham Michelson in 1880.

 BEAM SPLITTER:

• At the heart of the interferometer is an optical device called a beamsplitter.

• Beam splitter in most FTIRs consists of a thin film of germanium or
potassium bromide(KBr) or Zinc selenide(ZnSe) sandwiched between two
infrared transparent windows.
• A beamsplitter is designed to transmit some of the light incident upon it and
some of the light reflect it. The light transmitted by the beamsplitter travels
toward the fixed mirror, and the light reflected by the beamsplitter travels
toward the moving mirror. Once the light beams reflect from these mirrors
they travel back to the beamsplitter, where they are recombined into a
single beam that leaves the interferometer, interacts with the sample, and
strikes the detector.
 LASER:

Most FTIR instruments employ a Helium-Neon laser as an internal

wavelength calibration standard.

This laser emits a precise and stable frequency, which is used to calibrate
the FTIR instrument's spectrum.

The He-Ne laser beam is used to control the movement of the mirror,
ensuring accurate and precise scanning of the infrared spectrum.
DETECTORS:
A. THERMAL DETECTORS

• Detect changes in temperature of an absorbing material lithium tantalate (LiTaO3), lead

selenide (PbSe), germanium etc. Many temperature dependent phenomena can be
followed to measure the effects of the incident IR radiation.
• – The output obtained from them may be in the form of:-
• – Electromotive form (thermocouples).
• – A change in resistance of an conductor (bolometer) or semiconductor (thermistor
bolometer)
• – The movement of diaphragm caused by expansion of gas (neumatic detector)
• – Which may lead to change in illumination of subsidIary photocell (Golay detector).
PHOTONIC DETECTORS:

• Here some semiconductors are used.

• Exposure to radiation causes very rapid change in their electrical resistance and therefore
a very rapid response to the IR signal.
• The incident IR radiation causes electronic excitations between the ground and first
excited states, which in photoconductive detectors result in a change in resistivity which
is monitored
• The response time of a semiconductor detector is the time required to change the
semiconductor from an insulator to a conductor.
• Materials such as lead selenide(PbSe), indium gallium arsenide(InGaAs), indium
antimonide(InSb) and Mercury cadmium telluride(HgCdTe, also called MCT) are
intrinsic semiconductors commonly used.
 ADVANTAGES& DISADVANTAGES OF FTIR:

ADVANTAGES DISADVANTAGES

FELGETT : Better speed and sensitivity Cannot detect atoms or monoatomic ions - single
atomic entities contain no chemical bonds.
JACQUINOT: Increased information
Cannot detect molecules comprised of two
CONNES: internal calibration identical atoms symmetric-such as N2 or O2

Majority of molecules absorb mid-infrared Aqueous solutions are very difficult to analyze -
light, making it a highly useful tool water is a strong IR absorber.
Universal technique..
Complex mixtures - samples give rise to complex
Sensitive to “molecules”-anything that spectra.
contains chemical bonds.
FORENSIC APPLICATIONS OF FTIR: