FOURIER TRANSFORM

INFRA RED SPECTROSCOPY

(FTIR)
What is FTIR?
 FTIR stands for Fourier Transform Infra Red the
preferred method of infrared spectroscopy.
 An infrared spectroscopy measured the absorption of
IR radiation made by each bond in the molecule and
as a result gives spectrum which is commonly
designated as transmittance versus wavenumber
(cm−1).
 FTIR spectroscopy is a largely used technique to
identify the functional groups in the materials (gas,
liquid, and solid) by using the beam of infrared
radiations.
Spectroscopy

 The interaction of matter with any part of the

electromagnetic spectrum is called spectroscopy.
 Infrared Spectroscopy is the analysis of infrared light
interacting with a molecule. This can be analyzed in
three ways by measuring absorption, emission and
reflection. The main use of this technique is in
organic and inorganic chemistry. It is used by
chemists to determine functional groups in
molecules. IR Spectroscopy measures the vibrations
of atoms, and based on this it is possible to determine
the functional groups.
Infra Red
 The infra red region is lying between visible and
microwave end of the electromagnetic radiation
spectrum and divided into three main portions:
Near infrared (780 nm - 1400 nm)
Middle infrared (1400 - 3000 nm)
Far infrared (3000 nm -1000 nm)
This type of radiation is not energetic enough to excite
electrons, but it can cause the chemical bonds in
molecules to vibrate in different ways.
 The absorption of IR radiation is also quantized. The
molecule absorbed only those frequencies of IR
radiation which matched with the natural vibrational
frequency of the bonds and hence increases the
amplitude of vibrational modes of the molecules.
 The absorption of the IR radiations causes various
molecular motions in the molecule, which create a net
dipole moment. Therefore, a molecule is said to be IR
active if the molecule has a net dipole moment
(e.g., CH4, C2H6, NO2, TiO2), otherwise it will be
IR inactive (e.g., H2, O2, etc.).
 The energy changes in the infrared radiation are in the
order of 8 – 40 KJ/mole (1.9– 9.5 KCal/mol). The
energy in this range covers the stretching and bending
vibrations of various bonds in covalent molecules.
 Infrared Spectrum

 The plot of measured infrared light intensity (absorbance

or transmittance) versus its property, such as energy range
expressed in wavenumber (cm−1), is called an infrared
spectrum.
 The IR spectrum is recorded in absorbance mode, which
measures the amount of light absorbed by a sample, and its
intensity at y-axis is plotted in absorbance unit. The
absorbance spectrum is calculated from the following
relation:
A = log (I0/I )
Where A: absorbance.
I0 :intensity in the background spectrum.
I: intensity in the spectrum of sample.
 On the other hand, the y-axis of an infrared spectrum
can be also plotted in unit called percent transmittance,
which measures the percentage of light transmitted by
the compound and can be calculated as follows:
%T = 100 × (I/I0)
where % T: percent transmittance.
I0: intensity in the background spectrum.
I : intensity in the sample spectrum.
 Absorbance and transmittance are mathematically
related to each other, and they are inter convertible using
FTIR software. This conversion causes change of the
y-axis, but the peak positions are not affected.
 Modes of Vibrations
 Organic molecules mostly contain covalent bonds between the
atoms, which are not stiff and always agitating (exciting) at room
temperature. This movement of the bonds in molecule gives
various modes of vibration. There are two modes of vibrations:
1) Stretching vibration.
i) Symmetric vibrations
ii) Asymmetric vibrations
2) Bending vibration.
a)In-plane bending
i) Scissoring vibrations
ii) Rocking vibrations
b) Out-plane bending.
i) Wagging vibrations
ii) Twisting vibrations
 Stretching Vibration
If a molecule contain at least two or three identical
groups, then symmetric and asymmetric stretching
arises, for instance, CH2, NO2, and NH2 groups.
 symmetric stretch: the bond lengths of the participating
atoms either increase or decrease simultaneously.
 asymmetric stretch: one of the bond length increases,
while the other decreases.
The asymmetric stretching has higher energy than the
symmetric stretching.
 Bending Vibration
This type of vibration is also called deformation
vibration and causes change in the bond length There are
two types of bending vibrations:
 In-plane bending vibration – Scissoring and rocking
vibrations are the two types of in-plane bending
vibrations. In scissoring vibration both atoms are
moving toward each other or away from each other.
While in rocking vibration, the bond angles are
unchanged due to moments of participating atoms in the
same direction.
 Out of plane bending vibration – This vibration
includes wagging and twisting vibrations, where
the bond angle is changed. In wagging vibration,
both the atoms move toward a common side of the
plane. While in twisting vibration, both the atoms
go opposite to each other.
 Basic Principle of FTIR
 When IR radiation is bombarded on a sample, it absorbs
the light and creates various vibration modes. This
absorption relates precisely to the nature of bonds in the
molecule. The frequency ranges are measured as
wavenumber because it is directly related to the energy
and frequency, typically over the range of 4000–500 cm−1.
 Prior to the sample analysis, the background is recorded,
to avoid air and water vapor contamination peaks.
 The absorption spectrum indicating various vibrations of
the bonds presents in the molecule. Several modes arise
due to the various bond vibrations. So, in this way one can
easily identify the functional group in a molecule.
 FTIR Instrumentation
The typical FTIR spectrometer consists of :
 IR light source.
 Interferometer.
 Sample compartment.
 Detector.
 Computer.

Principally, FTIR is a method of obtaining infrared

spectra, which includes initially the collection of an
interferogram of a sample signal using an
interferometer and then performance of a Fourier
transform on the interferogram to obtain the spectrum.
IR light source
Different types of lamps are generally used in
FTIR with different ranges.
 For the mid-IR radiation, the silicon carbide is
heated to approximately 1200 K.
 Higher temperature source like tungsten-
halogen lamp is used for the near-IR range
(shorter wavelengths).
 For the far-IR, especially, a mercury discharge
lamp gives higher output than a thermal source.
 Interferometer
 The beam enters the interferometer where the ‘spectral
encoding’ takes place. The interferometer divides
radiant beams, generates an optical path difference
between the beams, and then recombines them in order
to produce repetitive interference signals measured as
a function of optical path difference by a detector. As
its name implies, the interferometer produces
interference signals, which contain infrared spectral
information generated after passing through a sample.
 Sample compartment
This is where specific frequencies of energy, which are
uniquely characteristic of the sample, are absorbed.
IR spectra can be measured using liquid, solid, or gaseous
samples.
 A drop of a liquid can be placed as a thin film between
two salt plates which are transparent to infrared light at
most important frequencies.
 A solid can be ground with KBr and pressed into a disk
that is placed in the light beam.
 Gases are placed in a longer cell with polished salt
windows.
 Detector
The beam finally passes to the detector for final
measurement. Detectors convert photon energy
into electrical charge by the internal
photoelectric effect.
Computer:
The measured signal is digitized and sent to the
computer where the Fourier transformation
takes place. The final infrared spectrum is then
presented to the user for interpretation and any
further manipulation.
 
Interferometer and Interferogram:
 The beam enters the interferometer as it is divided into two
light beams, which travel in different paths and the
difference in distance is known as optical path difference.
 After these two beams travel in their different paths, they
are united into one beam, then the light beam leaves the
interferometer where either constructive interference or a
destructive interference occurs.
 If the measured light intensity versus optical path difference
is plotted, the graph obtained is called an interferogram .
 The IR beam contains a large number of wavelengths
(wavenumbers) each with a unique Fourier-frequency. The
detector measures the sum of these individual interference
patterns.
Fourier Transform of Interferogram to
Spectrum
 It is a mathematical method to transform a function
into a new function. an interferogram is a
superposition of cosine waves For instance, an
interferogram is a plot of infrared intensity versus
optical path difference (OPD), which can be
measured in centimeters. When an interferogram is
Fourier transformed, a function is obtained that is a
plot of infrared intensity versus cm−1. therefore, a plot
of infrared intensity versus wavenumber is an FTIR
spectrum.
 Analytical information of FTIR:
 FTIR can be analyzed by two techniques namely: Qualitative
and Quantitative
 (i) Qualitative analysis:
IR spectroscopy is mainly used in two ways: structural
elucidation and compound identification.
 Structural Elucidation:
Because of complex interactions of atoms within the molecule,
IR absorption of the functional groups may vary over a wide
range. However, it has been found that many functional groups
give characteristic IR absorption at specific, narrow frequency
ranges regardless of their relationship with the rest of the
molecule. Generalized tables of the positions and relative
intensities of absorption bands have been established and used to
determine the functional groups present or absent in a molecule.
Range (cm-1) Functional group
3200–3500 Alcohols, O-H stretch
3100–3500 N-H stretch, Primary and secondary amines and
amides
3000 - 3100 Alkenes, C–H stretch
2260–2220 Nitrile, C≡N
2950–2850 Alkanes, C-H stretch
1750–1680 Ketone, C = O
1750–1735 Ester, C = O
1690–1630 Amide, C=O
1550-1640 Amines,N-H bend
1300–1000 Acids, C-O
1050 - 1150 Alkoxy, C-O
900 -690 Aromatics, C-H out- of- plane bend
 Compound Identification:
Since the IR spectrum of every molecule is unique, one of
the most positive identification methods of an organic
compound is to find a reference IR spectrum that matches
that of the unknown compound.
The transmittance spectra provide better contrast between
intensities of strong and weak bands because
transmittance ranges from 0 to 100 % T whereas
absorbance ranges from infinity to zero.
Quantitative analysis
Beer’s law states that the intensities of absorption
bands are linearly proportional to the concentration of
each component in a homogeneous mixture or
solution.
A = εlc
where, A :absorbance.
ε: molar absorptivity.
l: path length.
c : concentration of the sample.
Advantages of FTIR
 Its a non-destructive technique for materials.
 Its sensitivity is better because it measures all
frequencies simultaneously rather than scanning through
the individual frequencies
 Less energy is needed from the source and less time (1
to 2 seconds) is needed for a scan.
 Internally Calibrated: These instruments employ a
reference laser as an internal wavelength calibration
standard.
 Mechanical Simplicity: The moving mirror in the
interferometer is the only continuously moving part in
the instrument.
Limitations of FTIR
 Minimal elemental information is given for most
samples.
 Background solvent or solid matrix must be
relatively transparent in the spectral region of
interest.
 Molecule must be active in the IR region.