IR / FTIR Instrumentation

INTRODUCTION
• Infrared spectrum is an important record which gives
sufficient
information about the functional groups of a compound.

• The region from o.8 µ to 2.5µ is called Near IR, from 2.5µ to
15µ is called Mid IR or Ordinary IR and that from 15µ to 200µ
is called Far IR.

• FTIR stands for Fourier Transform Infra Red

Spectrophotometer — the preferred method of infrared
spectroscopy.

• A method for measuring all of the infrared frequencies

simultaneously, rather than individually as with dispersive
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FTIR spectroscopy is preferred over dispersive method of
IR 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 scan speed, collecting a scan every second.
It is mechanically simple with only one moving part.

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 Theory of
FTIR
 Fourier Transform Infrared (FT-IR) spectrophotometry 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 solution was developed which employed 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.

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 Most interferometers employ a beam-splitter which takes
the incoming infrared beam and divides it into two optical
beams.

One beam reflects off a flat mirror which is fixed in

place. The other beam reflects off a flat mirror which is on
a mechanism which allows this mirror to move a very short
distance (typically a few millimeters) away from the beam-
splitter.

The two beams reflect off of their respective mirrors and

are
recombined when they meet back at the beam-splitter.
 Because the path that one beam travels is a fixed length
and the other is constantly changing as its mirror moves,
the signal which exits the interferometer is the result of
these two beams “interfering” with each other. 6
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 The resulting signal is called an interferogram which has the
unique property that every data point (a function of the
moving mirror position) which makes up the signal has
information about every infrared frequency which comes
from the source.

 Because the analyst requires a frequency spectrum (a plot of

the intensity at each individual frequency) in order to make
an identification, the measured interferogram signal can not
be interpreted directly.

 Hence Fourier transformation is performed by the computer

which then presents the user with the desired spectral
information for analysis.
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 Infrared Light Absorption
Absorption of light by the Sample occurs when the
Energy carried by one or more wavelengths of the
light beam is correctly quantised to interact with
the Sample molecules.
Interaction can be due to electron transitions,
molecular vibrations and rotations.
For our application we need to look at vibration.
 Vibrating Molecules
 E1
Symmetrical
Molecule:

No Dipole
No Absorption
 (+)
E2
Heteronuclear
Molecule

d/dx =/= 0
(-)
Absorbs Energy
at  = E2 / h
 IR Absorption
IR radiation is of too low an energy to excite electronic
transitions
Absorption is limited to vibration and rotational levels
 IR Absorption - Summary

Intensity

I0

I
E=h

Absorption Energy () = E/h

 IR Absorption - Liquid Water

100

%T

0
3000 2000 1000

Wavenumbers / cm-1
 Methanol
Methanol

C-H
O-H

C-O
 IR Absorption - Methanol

• Band Assignments
– C-O 1019
– O-H 3300
– C-H (a) 2943
– C-H (s) 2830
– CH3 1449

4000 Wavenumbers 1000

 IR Absorption - Ethanol

• Band Assignments
– C-O 1044
– O-H 3323
– CH3 (a) 2972
– CH3 (s) 2927
– CH2 (a) 2831
– CH2 (s) 2886
4000 Wavenumbers 1000 – CH3 (bend) 1378
– C-C 879
 IR Absorption
The types of vibrations available to a molecule are
determined by the:
Number of atoms
Types of Atoms
Type of bonding between the atoms
As a result, IR absorption spectroscopy is a powerful tool
in characterizing pure organic and inorganic compounds.
iv.) Number of Vibrational Modes:
- for non-linear molecules, number of types of vibrations: 3N-6
- for linear molecules, number of types of vibrations: 3N-5
- why so many peaks in IR spectra
- observed vibration can be less then predicted because
‚ symmetry ( no change in dipole)
‚ energies of vibration are identical
‚ absorption intensity too low
‚ frequency beyond range of instrument

Examples:
1) HCl: 3(2)-5 = 1 mode

2) CO2: 3(3)-5 = 4 modes

- + - moving in-out of plane

See web site for 3D animations of vibrational modes for a variety of molecules
http://www.chem.purdue.edu/gchelp/vibs/co2.html
 Spectroscopy
• Method of “Seeing the
unseeable”
Atoms
Molecules

• using electromagnetic radiation to obtain

information about atoms and molecules that
are too small to see.
 Spectroscopy is an instrumentally aided study of the
interactions between matter (sample being analyzed) and
energy (any portion of the electromagnetic spectrum)

SPECTROPHOTOGRAPH
EMR ANALYTE

Conc. should be
lower

1.UV-Visible radiations--------excitation of electrons---------UV-visible spectrum

2.IR-radiations------------------vibration changes in electrons--------IR spectrum

3.Radio frequency---------------spin rotational changes-------------N.M.R

spectrum
 IR spectrophotometry
Energy of molecule = Electronic energy+
Vibrational energy + Rotational energy
• IR spectroscopy is concerned with the study of
absorption of infrared radiation, which causes
vibrational transition in the molecule.
Hence, IR spectroscopy also known as Vibrational
spectroscopy.
• IR spectra mainly used in structure elucidation to
determine the functional groups.
• IR region: 0.8 µm (800nm) to 1000 µm
(1mm) Sub divided
into

1.Near IR: 0.8-2 µm

2.Middle IR: 2-15 µm
3.Far IR: 15-1000 µm

Most of the analytical applications are confined

to the middle IR region because absorption of
organic molecules are high in this region.
•
Principle of IR spectroscopy
Molecules are made up of atoms linked by
chemical bonds. The movement of atoms and the
chemical bonds like like spring and balls (vibration)

• This characteristic vibration are called

Natural frequency of vibration.
• When energy in the form of infrared radiation is
applied then it causes the vibration between the
atoms of the molecules and when,
Applied infrared frequency = Natural frequency of
vibration
Then, Absorption of IR radiation takes place and a
peak is observed.
Different functional groups absorb characteristic
frequencies of IR radiation. Hence gives the
characteristic peak value.
Therefore, IR spectrum of a chemical substance is
a finger print of a molecule for its identification.
 Criteria for a compound to absorb IR
radiation
1. Correct wavelength of radiation
2. Change in dipole moment

1. Correct wavelength of radiation:

A molecule to absorb IR radiation, the natural
frequency of vibrations of some part of a
molecule is the same as the frequency of
incident radiation.
 2. Change in dipole moment
• A molecule can only absorb IR radiation
when its absorption cause a change in its
electric dipole
• A molecule is said to have an electric dipole
when there is a slight positive and a slight
negative charge on its component of atoms.
 If the dipole moment of a molecule would not change i.e. as
in Symmetric stretching the absorption spectra of radiation
cannot be obtained. Such spectra is called as Forbidden or
Inactive IR Spectra.

 If the molecule vibrate asymmetrically, the change in its

dipole moment takes place so absorption spectra of this
molecule can be obtained. This is called Active IR spectra.
 IR Spectroscopy is a qualitative analytical technique that
helps to indicate mainly the functional group of a molecule.

 When the IR radiation irradiated to the molecule the part of

molecule which is functional absorbs it, as a result of this
absorbance the molecular vibration increases.

 After the excitation of molecular vibration, these molecules

comes back to their original state by releasing that energy of
certain wave number which is recorded as transmittance on
the spectrophotometer.
 • Parameters
 The spectrophotometer give the spectra of certain wave by
indicating the quality of wave (i.e. its wavenumber) and the
quantity of wave that how much wave is absorbed by the
molecule (Transmittance).

Transmittance is the fraction of incident light electromagnetic radiation at a specified wavelength that
passes through a sample.(Lambert-Beer Law) It is a ratio so it has no unit.
 IR light or electromagnetic radiation is actually thermal
radiation. Its means that all of the heat which feel to us or
coming into the earth from sun is nothing but IR radiation.

 IR is low energy, low frequency and long wavelength

radiation with low wave number that can only cause an
increase in molecular vibrations (i.e. stretching & bending).

 So by triggering molecular vibrations through irradiation

with infrared light provides mostly information about the
presence or absence of certain functional groups.
 MOLECULAR
VIBRATIONS

Fundament Non-
al fundamental
Vibrations Vibrations

Stretchin
Bending Over Tones,
g
Vibration Vibratio Combination
n Tones,
Fermi
Resonance
Symmetri Asymmetri In-plane Out Of Plane
c c Bending Bending

Scissorin Rocking Wagging Twisting

g
 Molecular
There are 2 types of vibrations:
vibrations
1.Stretching vibrations
2.Bending vibrations

1. Stretching vibrations:
▪Vibration or oscillation along the line of bond
▪Change in bond length
▪Occurs at higher energy: 4000-1250 cm-1
▪2 types:
•Symmetrical stretching
 2. Bending vibrations
• Vibration or oscillation not along the line
of bond
• These are also called as deformations
• In this, bond angle is altered
• Occurs at low energy: 1400-666 cm-1
• 2 types:
a)In plane bending: scissoring, rocking b)Out
plane bending: wagging, twisting
iii.) Types of Molecular Vibrations

Bond Stretching Bond Bending

symmetric In-plane rocking

asymmetric In-plane scissoring

Out-of-plane wagging

Out-of-plane twisting
 symmetric asymmetric In-plane scissoring

Out-of-plane twisting In-plane rocking Out-of-plane wagging

Another Illustration of Molecular Vibrations
 Vibration Modes

Types of molecular
vibrations. Note: +
indicates motion from
the page toward the
reader; - indicates
motion away from the
reader.
IR spectrum of ethanol
 THEORY
When a molecule absorb radiation with
frequency
a less than 100 cm-1 ,molecular
rotation takes place and if a molecule
absorb more energetic radiation in the
region of 104 to 102 , molecular
cm -1
vibration takes place.
A single energy change
accompanied by a large is number of
vibrational
rotational energy changes and the
vibrational spectra appear thusvibrational
as
rotational bands.
 FATE OF ABSORBED
RADIATION
There are 3 main process by which a molecule
can radiation, each of these
absorb an route
involve
proportional toincrease of energy
the light absorbed.
i.First route whichoccurs whenis absorption of
radiation leads to a higher rotational energy
level in a rotational transition.
ii.Second occurs when absorption of radiation
leads to a higher vibrational energy level in a
vibrational transition.
iii.Third occurs when absorption of radiation
leads to a higher electronic energy level in its
electronic transitions.
Energy level diagram
 In
FINGERPRINT REGION
IR, the region below 1500 cm-1 is rich in many
absorption bands and the region is known as
fingerprint region.
 Here the number of bending vibrations are
usually more than the number of stretching vibrations.
 In this region, small difference in the structure
and constitution of a molecule results significant
changes in the absorption bands.
 Many compounds show unique absorption bands
in this region and which is very useful for
the identification of the compound.
Fingerprint region can be sub-divided
into three:

i. 1500-1350 cm-1
– Here doublet near 1380 cm-1 and 1365 cm-1 shows
the of tertiary butyl group in the
presence
compound.
– ii.All classes compounds having groups like
1350-1000
of
alcohols, esters , lactones, acid anhydrates
cm-1 characteristic absorptions (s) due to
show
C – O stretching.
iii. Below 1000 cm-1
– Distinguishesbetween cis and trans
Spectrometer
components
Three basic components of FT system
are

• Radiation source
• Interferometer
• Detector

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Radiation
sources
Incandecent lamp

Nernst glower

Globar source

High pressure mercury

arc

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 Interferomete
• The heart of therFTIR 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.

• Consists of three active components-

• A moving mirror
• A fixed mirror
• A beam splitter
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 1 .Mirrors in an FTIR are generally made of metal. The
mirrors 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, ant to focus light from the sample
onto the detector.
2.The beam splitter can be constructed of a material such
as Si or Ge deposited in a thin coating onto an IR-
transparent substance. The germanium or silicon is coated
onto the highly polished substrate by vapour deposition.

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- A common beam splitter material for the mid-IR region is
germanium and the most common substrate for this region
is KBr. Both the substrate and the coating must be optically
flat. KBr is an excellent substrate for the mid-IR region.

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 Schematic diagram of Michelson Interferometer.
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 Construction: The two mirrors are perpendicular to each other.
The beam-splitter is a semi-reflecting device and is often made by
depositing a thin film of Germanium onto a flat KBr substrate.

Working: Radiation from the broadband IR source is

collimated and directed into the interferometer, and impinges
on the beam- splitter.
•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. 14
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 Schematic diagram of FTIR spectrometer

Fixed mirror Michelson

interferomete
r
Moving mirror
positions

To
detector sample

ZPD
¼λ ¼λ
• Dueterated triglycine sulphate
(DTGS) cadmium
Mercury
• (MCT)
telluride • NERNST GLOWER
IR
Source • GLOBAR SOURCE
• HIGH PRESSURE MERCURY
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ARC LAMP 53
 FTIR spectrophotometer
FTIR spectrophotometer obtains an infrared spectra
by collecting an interferogram of a sample signal
using an interferometer and then performs a Fourier
transform on the interferogram to obtain a spectrum.

Fourier transform defines a relationship between

signal in time domain and its representation in
frequency domain.

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1/31/2016 55
• The sampling rate is controlled by an internal,
independent reference, a modulated
monochromatic beam from a Helium-Neon Laser
focused on a separate detector.

Source interferomete sample detector

r

interferogram (encoded data of sample at each

frequency)

decoding by FT IR Spectra 18

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 When the mirror is moved at a constant velocity, the
intensity of radiation reaching the detector varies in a
sinusoidal manner to produce the interferogram. The
interferogram (which has every infrared frequency
encoded into it) is the record of the interference signal. It
is a time domain spectrum and records the detector
response changes versus time within the mirror scan.
If the sample happens to absorb at this frequency, the
amplitude of the sinusoidal wave is reduced by an amount
proportional to the amount of sample. The IR signal after
interaction with the sample is uniquely characteristics of
the sample. The beam finally arrives at the detector and is
measurde by the detector.

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 Cont...
The detected interferogram can not be directly
interpreted. It has to be decoded with a well-known
mathematical technique in term of Fourier Transformation.

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 SAMPLING
Samples of the same substance shows shift
in absorption bands as we pass from
solid to gases and hence the samples of
different phases have to be treated
differently in IR spectroscopy.
Sampling of solids
◦ Solids run in solution
◦ Mull technique
◦ Pressed pellet technique
◦ Solids films
 1.Solid run in solution
◦ Dissolve solid sample in non-aqueous
solvent (which should be IR inactive) and place
a drop of this solution in alkali metal disc and
allow to evaporate, leaving a thin film which
is then mounted on a sepectrometer.
◦ E.g. of solvents – acetone, cyclohexane,
chloroform, carbon tetrachloride etc.
• Mull technique
◦ Finely powdered sample + mulling agent
(Nujol) and make a thick paste (mull). Transfer
the mull to the mull plates and the plates
are squeezed together to adjust the thickness it
is then mounted in spectrometer.
◦ Finely powdered sample is mixed with about 100
3.Pressed pellet technique
times its weight of KBr in a vibrating ball mill and
the mixture is then pressed under very
high pressure in an evacuable die to form a
small pellet( 1-2mm thick and 1cm in diameter).
◦ Advantages:-
 Eliminates bands which appear due to
mulling agent.
 Pellets can be stored for longer period of time.
 Concentration of sample can be adjusted.
◦ Disadvantages:-
 Not suitable for polymers which
are difficultto
bind with KBr.
 High pressure may change the
crystallinity of the sample.
• Solid films.
◦ Here amorphous solid is dissolved in
volatile solvents and this solution is poured
on a rock salt plate (NaCl or KBr), then
Sampling of
liquids
◦ Liquid sample can be sandwiched between
two alkali halide plates (NaCl , KBr , CaF2).
◦ The sample cell thickness is 0.01-0.05mm.
Sampling of
gases
◦ Here gases sample is introduced into a glass
cell made up of NaCl.
◦ Very few organic compounds can be examined
as gases.
◦ E.g.: 1,4-dioxane.
Sampling of solutions
◦ Here 1-5% of solution is placed in a
solution cell made up of metal halides and
a second cell containing the pure solvent
act as a
reference.
◦Important solvents used are:-chloroform
CCl4, Carbon disulphide etc. ,
 Detectors in FTIR
Two most popular detectors for FTIR
spectrometer
are
• Pyroelectric Detector: Deuterated triglycine
sulphate (DTGS).
• Photon-sensitive semiconducting Detectors:
Mercury cadmium teluride (MCT)

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 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.

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 Cont...
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.
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 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.

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 Cont...
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.

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 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 chemical
bonds.
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 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.
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Applications
1. Identification of an organic compound.

2. Structure determination.

3. Study of chemical reaction.

4. Study of Keto-Enol tautomerism.

5. Study of complex molecules.

6. Detection of impurities in a
compound.

7. Conformational analysis.
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6. Elementary organic spectroscopy. Y. R. Sharma. Pg
No:137- 140.
7. Instrumental methods of Analysis. Willard, Merritt. Pg
No:302-305.

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 APPLICATIONS OF IR
SPECTROSCOPY
1. Identification of an organic compound
◦ The identity of an organic compound can be
established from its fingerprint region by
comparing the sample spectrum with the
known spectrum of the compound.
◦ E.g. spectrum of n-hexanal
2. Qualitative determination of functional
groups
◦ The presence or absence of absorption bands
help in predicting the presence of certain
functional group in the compound.
◦ 3.
If aDistinction
compoundbetween 2 types of H-bonding
having intra-molecular H-bonding
it will show broad bands in IR spectrum and if a
compound having intermolecular H-bonding then
it will show sharp well defined bands.
◦ E.g. o-nitrophenol shows broad bands due to intra-
molecular H-bond whereas p-nitrophenol shows
sharp bands due to intermolecular H-bonding.
• Quantitative analysis
◦ It can be done by measuring the intensity of the
absorption bands.
◦ E.g. xylene exists as mixture of 3 compounds
which shows absorption bands at
ortho-740cm-1 meta-880cm-1 para-830cm-1
◦ 5.
It isStudy
useful forof chemical
studying reactions
the chemical reactions.
◦ E.g.: reduction of butan-2-one to form butan-2-ol

Butan-2-one Butan-2-ol
(1710 cm-1) (3300 cm-1)
cm-1

6. Study of keto-enol tautomerism

◦ Diketones and ketoesters exhibit keto-enol tautomerism
and this can be studied using IR spectrum of the
compound.
◦ E.g.: Ethyl acetoacetic etser.

C==O – 1733 cm-1 O---H – 3300 cm-1

- 1710 cm-1 C==O – 1645 cm-
1
 Referenc
e
1. Instrumental analysis. Skoog, Holler, Crouch. Pg
No:488-493.
2. Fundamentals of Analytical chemistry. F James Holler,
Stanley R. Crouch. Pg No:749-750.
1. Introduction to Instrumental Analysis. Robert D.
Braun. Pg No:372-373.
2. Instrumental methods of Chemical Analysis. Gurudeep
R. Chatwal, Sham K.Anand. Pg No:2.49-2.59.
1. Text book of Quantitative Chemical Analysis. Vogel’s et
al.,Pg No:680-681.
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