FTIR

INTRODUCTION
IR spectroscopy is Absorption spectroscopy in which molecular
vibrations observed due to absorption of IR radiation.

Infrared radiation was discovered in 1800 by William Herschel.

Infrared absorption spectroscopy is the method which scientists
use to determine the structures of molecules.

When exposed to infrared radiation, sample molecules selectively

absorb radiation of specific wavelengths which causes the change
of dipole moment of sample molecules.
Consequently, the vibrational energy levels of sample molecules
transfer from ground state to excited state
The frequency of the absorption peak is determined by the vibrational energy
gap.
The number of absorption peaks is related to the number of vibrational
freedom of the molecule.
The intensity of absorption peaks is related to the change of dipole moment
and the possibility of the transition of energy levels.
Therefore, by analyzing the infrared spectrum, one can readily obtain abundant
structure information of a molecule.
Most molecules are infrared active except for several homonuclear diatomic
molecules such as O2, N2 and Cl2 due to the zero dipole change in the vibration
and rotation of these molecules.
 Vibrational motion
The absorption of the electromagnetic radiation by matter leads to many Type of vibrations
1. The dipole moment of the molecule must change during the vibration.
2. Homonuclear diatomic molecules such as Hydrogen (H2), Nitrogen (N2) and Oxygen (O2) no
infrared absorption is observed because its dipole moment remains zero.
Molecular vibrations:
1. The positions of atoms in a molecules are not fixed.
2. The Vibrational corresponds to the absorption of energy by a molecule
3. Main categories of stretching and bending.
Stretching Vibrations:
•Change in inter-atomic distance along bond
axis.
•Stretching absorptions usually produce
stronger peaks than bending.

Bending Vibrations :
Change in angle between two bonds.
1. Twisting
2. Rocking
3. Wagging
4. Scissoring
 The range of EMR between the visible and microwaves region is called INFRARED region
Stretching vibrations occurs in F.G. region.
 Peaks in this region are characteristic of specific
kinds of bonds, and therefore can be used to
identify whether a specific functional group is
present.

Bending vibrations occurs in F.P. region.

The region to the right-hand side of the diagram
(from about 1650 to 500 cm-1).
It usually contains a large number of peaks, making
it difficult to identify individual peaks.
However, the fingerprint region of a given
compound is unique and, therefore, can be used to
 Development of IR Spectrometers
The first generation IR spectrometer was invented in late 1950s.
It utilizes prism optical splitting system.
The prisms are made of NaCl.
The requirement of the sample’s water content and particle size is
extremely strict.
Further more, the scan range is narrow.
Additionally, the repeatability is fairly poor.
As a result, the first generation IR spectrometer is no longer in use.
 The second generation IR spectrometer was introduced to the world in 1960s.
 It utilizes gratings as the monochrometer.
 The performance of the second generation IR spectrometer is much better compared with IR
spectrometers with prism monochrometer,
 But there are still several prominent weaknesses such as low sensitivity, low scan speed and poor
wavelength accuracy which rendered it out of date after the invention of the third generation IR
spectrometer.
 Dispersive Infrared Spectrophotometer

The basic components of a dispersive IR spectrometer include

Radiation source, Monochromator, and Detector.
Radiation Source: Inert solids (Nernest glower)that are heated (1500-2000K)
electrically to promote thermal emission of radiation in the infrared region of
the electromagnetic spectrum.
Monochromator: a device used to disperse or separate a broad spectrum of
IR radiation into individual narrow IR frequencies. Gratings & Slits are used.
Detector: Photon/quantum detectors- causes electrons to be excited to a
higher energy level
Thermal detectors – Thermocouple, thermopiles
• Working condition:
Dispersive IR spectrophotometers are generally double-beam, recording instruments
which use reflection grating for dispersing radiation.
Dispersive spectrometers have a double-beam design with two equivalent beams from
the same source passing through the sample and reference chambers as independent
beams.
These reference and sample beams are alternately focused on the detector by making
use of an optical chopper, such as, a sector mirror.
One beam will proceed, traveling through the sample, while the other beam will pass
through a reference species for analytical comparison of transmitted photon wavefront
information.
After the incident radiation travels through the sample species, the emitted wavefront of
radiation is dispersed by a monochromator (gratings and slits) into its component
frequencies.
A combination of prisms or gratings with variable-slit mechanisms, mirrors, and filters
comprise the dispersive system.
Narrower slits gives better resolution by distinguishing more closely
spaced frequencies of radiation and wider slits allow more light to reach
the detector and provide better system sensitivity.
The emitted wavefront beam (analog spectral output) hits the detector
and generates an electrical signal as a response.
 Ftir
FT-IR stands for Fourier Transform InfraRed, the preferred method of
infrared spectroscopy.
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 structures produce the same
infrared spectrum.
• Fourier transform infrared spectroscopy is preferred over dispersive or
filter methods of infrared spectral analysis for several reasons:

• • It is a non-destructive technique
• • It provides a precise measurement method which requires no external
calibration
• • It can increase speed, collecting a scan every second
• • It can increase sensitivity – one second scans can be co-added together
to ratio out random noise
• • It has greater optical throughput
• • It is mechanically simple with only one moving part
Fourier Transform Infrared (FT-IR) spectrometry was developed in order
to overcome the limitations encountered with dispersive instruments.
The main difficulty was the slow scanning process.
 A method for measuring all of the infrared frequencies simultaneously,
rather than individually, was needed.
 A very simple optical device called an “interferometer”
The interferometer produces a unique type of signal which has all of the
infrared frequencies “encoded” into it.
The signal can be measured very quickly, usually on the order of one
second or so.
Thus, the time element per sample is reduced to a matter of a few
seconds rather than several minutes.
 The invention of the third generation IR spectrometer, Fourier transform infrared
spectrometer

 Marked the abdication of monochromatic and the prosperity of interferometer.

 With this replacement, IR spectrometers became exceptionally powerful. Consequently,

various applications of IR spectrometer have been realized.
Fourier Transform, named after Joseph Fourier.

is capable of decomposing a complicated waveform

into a sequence of simpler elemental waves
 FTIR collects all wavelengths simultaneously and scans
at once.
 FTIR works based on Michelson Interferometer which
having
• Beam splitter
• Fixed mirror
• Movable mirror

Fourier transform
function
Inerferometer: A device that separates a beam of
light into two ray beams, usually by means of
reflection, and that brings the rays together to
produce interference, used to measure wavelength.

The heart of the FTIR is a Michelson Interferometer.

The monochromator is replaced by an

interferometer, which divides radiant beam, then
recombines them in order to produce repetitive
interference signals measured as a function of
optical path difference as the name implies, the
interferometer produces interference signals, which
contain IR spectral information generated after
passing through a sample.
Beam Splitter:
Made up of Si or Ge deposited in a thin coating onto an IR transparent
Substance.
A common beam splitter material for the mid-IR region is germanium and
the most common substrate for this region is KBr.
The beam splitter is made of a special material that transmits half of the
radiation striking it and reflects the other half.
Radiation from the source strikes the beam splitter and separates into two
beams.
One beam is transmitted through the beam splitter to the fixed mirror
and the second is reflected off the beam splitter to the moving mirror.
The fixed and moving mirrors reflect the radiation back to the beam splitter.
Again, half of this reflected radiation is transmitted and half is reflected at
the beam splitter, resulting in one beam passing to the detector and the
second back to the source.
• Mirrors:
Mirrors are made up of metal and are polished on the front surface
and may be gold coated to improve corrosion resistance.
Commercial FTIRs use a variety of flat and curved mirrors to move
light within the spectrometer,
 to focus the source onto the beam splitter,
to focus light from the sample onto the detector.
Stationary Mirror:
The stationary mirror in an FTIR interferometer is nothing more
than a flat highly reflective surface.
Moving Mirror:
There is present only one moving part in an FTIR spectrometer, its
oscillating mirror.
Air bearings are used in FTIR spectrometers because of the higher
Construction: The two mirrors are perpendicular to each other.
Working: Radiation from the broadband IR source is collimated and
directed into the interferometer, and impinges on the beamsplitter.
 At the beam-splitter half of the IR beam is transmitted to the fixed
mirror and the remaining half is reflected to the moving mirror.
After the divided beams are reflected from the two mirrors, they are
recombined at the beam-splitter.
 Due to changes in the relative position of the moving mirror,
an interference pattern is generated. The resulting beam then
passes through the sample and is eventually focused on the
detector.
 Detectors in FTIR
Two most popular detectors for FTIR spectrometer are

1. Pyroelectric Detector:

Deuterated triglycine sulphate (DTGS).
2. Photon-sensitive semiconducting Detectors:
Mercury cadmium teluride (MCT)
Pyroelectric Detector:
Pyroelectric materials change their electric polarization as a
function of temperature.
These materials may be insulators, ferroelectric materials or
semiconductors.
 A dielectric placed in an electrostatic field becomes polarized with
the magnitude of the induced polarization depending on the
dielectric constant.
The induced polarization generally disappears when the field is
removed.
Pyroelectric materials, however, stay polarized and the polarization
is temperature dependent.
• It consists of a thin single crystal of pyroelectric material
placed between two electrodes.
• Upon exposure to IR radiation, the temperature and the
polarization of the crystal changes. The change in the polarization
is detected as a current in the circuit connecting the electrodes.
• The signal depends on the rate of change of polarization
with temperature and the surface area of the crystal.
• These crystals are small: they vary in size from about 0.25 to
12.0 mm².
• Pyroelectric material used as an IR detector is
• Deuterated triglycine sulfate(DGTS),
• Lithium tantalite(LiTaO3) and
• Strontium barium niobate.
Photon Detectors
Here semiconductors are used. Semiconductors are materials
that are insulators when no radiation falls on them but
become conductors when radiation falls on them.
 Exposure to radiation causes very rapid change in their
electrical resistance and therefore a very rapid response to
the IR signal.
The response time of a semiconductor detector is the time
required to change the semiconductor from an insulator to a
conductor.
It consists of a thin film of suitable semiconductors like lead
telluride or germanium which are non conducting at lower energy
state.
When the radiation falls on these, they are raised to higher level
which can conduct and produce a signal which is
proportional to amount of radiations.
In this, there is drop of electrical resistance and if small voltage is
applied there is large increase in current which can be applied and
indicated on meter or recorder.
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.
Four regions of Chart
• 3700 – 2500 cm-1 Single bonds to hydrogen
• 2300 – 2000 cm-1 Triple bonds
• 1900 - 1500 cm-1 Double bonds
• 1400 - 650 cm-1 Single bonds (other than hydrogen)
• Properties of peaks
• Intensity (weak, medium or strong),
• Shape (broad or sharp), and
• Position (cm-1) in the spectrum
Properties of peaks
 Sample Preparation
• Transmission radiation passes through a sample
• Reflectance Radiation reflected from the sample surface.

Infrared Reflectance Spectroscopy

• 1. Attenuated Total Reflection
• 2. Diffuse Reflectance
• 3. Specular reflectance

Infrared Transmission Spectroscopy

• 1. Transmission Solid
• 2. Transmission liquid
• 3. Transmission gas
Transmission Solid ----- Potassium
Bromide disk

 2 mg sample powder.
300 mg KBr( spectroscopic grade) into an agate
mortar.
Grind the powders together until it become like
fine flour.
Transfer the ground mixture into the cylinder
bore.
Place the die assembly into a hydraulic press.
Increase pressure in the press to 15 tons .
• Carefully release the vacuum, and remove the die from the press.
• Dismantle the die, and transfer the KBr disk to a spectrometer disk
holder Avoid touching the faces of the disk.
• Mount the disk holder in the spectrometer.

• If the disk is not translucent

• Uneven distribution in powder in die
• Too much sample
• Too much KBr powder
• Poorly dispersed sample
• Water in die
• Pressed at too low pressure or at too low time
• Transmission Liquid
• A drop of the sample is placed between two potassium
bromide or sodium chloride circular plates,
• This produce a thin capillary film.
• Nujol Mull:
• The sample is ground using an agate mortar and pestle to
give a very fine powder
• A small amount is then mixed with Nujol to give a paste .
• Several drops of this paste are then applied between two
sodium chloride plates (these do not absorb infrared in the
region of interest).
• The plates are then placed in the instrument sample holder
ready for scanning.
• Infrared Reflectance Spectroscopy
• Attenuated Total Reflection
• Diffuse Reflectance
• Specular reflectance
• Attenuated Total Reflection
• The beam is directed onto optical dense crystal , internal
reflectance create waves that extend to the sample in
contact with crystal surface.
 Advantages of FTIR
FTIR instruments have distinct advantage over dispersive spectrometers.
Simpler mechanical design.
Elimination of Stray light and emission contributions.
Powerful data station.
Majority of molecules in the universe absorb mid-infrared light, making it a highly
useful tool.
Universal technique.
 Sensitive, fast and easy.
Relatively inexpensive and provides rich information.
 Sensitive to “molecules”-anything that contains chemicalbonds.
• Disadvantages of FT-IR
• Cannot detect atoms or monoatomic ions – single
atomic entities contain no chemical bonds.
• Cannot detect molecules comprised of two identical
atoms symmetric-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.
• Applications
• Identification of an organic compound.
• Structure determination.
• Study of chemical reaction.
• Study of Keto-Enol tautomerism.
• Study of complex molecules.
• Detection of impurities in a compound.
• Conformational analysis.