FOURIER TRANSFORM

INFRARED SPECTROSCOPY
Muhammad Iqbal

Workshop Karakterisasi Material

1 & 2 Maret 2016
Applications of FT-IR
• Polymer analysis
• Lubricant formulation and fuel additives
• Coatings and surfactants
• Foods research
• Pharmaceutical research
• Forensic investigations
• Environmental and water quality analysis
• Biochemical and biomedical research

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Information provided by FT-IR
• Qualitative aspect
identifies unknown materials

• Quantitative aspect
determines the amount of components in a mixture

3
Sample types
• Liquid
• Solid
• Gas

Organic compounds •
Inorganic compounds • 4
Why FT-IR spectroscopy?
• Non-destructive technique
• Good precision
• No external calibration
• High speed
• Signal-Noise ratio
• Mechanically simple

5
What is FT-IR spectroscopy?
• FT-IR stands for Fourier Transform Infra Red,
• IR radiation is passed through a sample. Some of the radiation
is absorbed by the sample and some of it is transmitted
• The resulting spectrum represents the molecular absorption
and transmission, creating a molecular “fingerprint”

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Electromagnetic spectrum

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Interaction between matter and energy

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Molecular spectra
Three basic types of molecular optical
spectra
1. Electronic or vibronic spectra (UV-
visible-near IR)
2. Vibrational or vibrational-
rotational spectra (IR region)
3. Rotational spectra (microwave
region)

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 Sample selection rules
• The energy associated with a quantum of light may be transferred to
the molecule if work can be performed on the molecule in the form of
displacement of charge.
• Selection rule: “A molecule will absorb infrared radiation if the change
in vibrational states is associated with a change in the dipole moment of
the molecule.”
• Vibrations which do not change the dipole moment are Infrared
Inactive (e.g. homonuclear diatomics).

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Infrared spectrum
of carbon dioxide

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Vibrational modes for a -CH2- Group

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Dispersive IR
• The original infrared instruments
• Prism or grating was used to separate individual frequencies
of energy emitted
• The detector measures the amount of energy at each
frequency which has passed through the sample.
• This results in a spectrum which is a plot of intensity vs
frequency

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 Dispersion Spectrometer VS FT-IR
To separate IR light, a grating is used
Detector Dispersion Spectrometer
Grating
Slit
• It takes several minutes to
measure an IR spectrum
Sample
• The detector receives only a
few % of the energy of original
To select the specified IR light, a slit is used light source
Light source

Fixed CCM
An interferogram is first made by
the interferometer using IR light.
FT-IR
• FT-IR takes only a few seconds
Detector
• The detector receives up to
B.S. 50% of the energy of original
light source
Sample

Moving CCM
The interferogram is calculated and 14
IR Light source transformed into a spectrum using a
Fourier Transform (FT).
FT-IR Spectrometer

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FT-IR Instrumentation
• Source: Infrared energy is emitted from a glowing black-
body source.
• Interferometer: beam enters the interferometer where
the “spectral encoding” takes place. The resulting
interferogram signal then exits the interferometer
• Beamsplitter takes the incoming beam and divides it into
two optical beams
• Sample: beam enters the sample compartment where it
is transmitted through or reflected off of the surface of
the sample
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FT-IR Instrumentation (cont)
• Detector: The beam finally passes to the detector for
final measurement
• Computer: measured signal is digitized and sent to the
computer where the Fourier transformation takes place
• Moving mirror in the interferometer is the only moving
part of the instrument
• Fixed mirror

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FT-IR spectroscopy
Interferometer
• Based on the use of an optical
modulator: interferometer
• Interferometer modulates radiation
emitted by an IR-source, producing
an interferogram that has all
infrared frequencies encoded into it Modulated IR
Beam
• Interferometer performs an optical
Fourier Transform on the IR Interferogram

radiation emitted by the IR source

• The whole infrared spectrum is Fourier
measured at high speed IR Spectrum
Transformation

• Spectral range is continuously

calibrated with He-Ne laser 18
• Fast, extremely accurate
measurements
 Michelson interferometer
• Simplest interferometer
design
• Beam splitter for dividing
Moving
the incoming IR beam into mirror
two parts
• Two plane mirrors for
reflecting the two beams IR Source
back to the beam splitter
where they interfere either
constructively or Stationary
mirror
destructively depending on
the position of the moving
mirror
OPD = Distance travelled by red beam
• Position of moving mirror is minus distance travelled by yellow beam 19
expressed as Optical Path
Difference (OPD)
 Interference
• Electromagnetic (EM) radiation destructive interference constructive interference
can be described as sine waves A A
having definite amplitude,
frequency and phase
• When EM-waves interact,
interference is observed
• Depending on the relative A A
phase of the waves,
interference is either
destructive or constructive Interference signal Interference signal

EM waves with same EM waves with same

amplitude and frequency, amplitude and frequency,
out of phase in phase (OPD = 0)
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Sequence for obtaining
spectrum
• Interferogram of background is obtained (without sample)
• System uses Fourier Transform to create single beam
background spectrum
• Interferogram of sample is obtained
• System uses Fourier Transform to create single beam
spectrum of sample
• System calculates the transmittance or absorbance spectrum

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 Measurement sequence

Transmittance spectrum

Interferogram with N2 Background

Interferogram with sample Single beam sample spectrum Absorbance spectrum

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What FT-IR Spectrometer do?
• collecting an interferogram
• simultaneously measuring
• acquiring and digitizing the interferogram
• outputting the spectrum

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What do we do?
• experimental setup
• sample preparation
• operating analysis
• spectrum interpretation
• drawing conclusion

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Gas samples
• A gas sample cell consists of a cylinder of glass or sometimes a
metal. The cell is closed at both ends with an appropriate window
materials (NaCl/KBr) and equipped with valves or stopcocks for
introduction of the sample.
• Long pathlength (10 cm) cells – used to study dilute (few
molecules) or weakly absorbing samples.
• Multipass cells – more compact and efficient instead of long-
pathlength cells. Mirrors are used so that the beam makes several
passes through the sample before exiting the cell. (Effective
pathlength  10 m).
• To resolve the rotational structure of the sample, the cells must be
capable of being evacuated to measure the spectrum at reduced
pressure.
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Volcanic gas sample

FTIR

IR Source
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Liquid samples
• Pure or soluted in transparent solvent – not water (attacks
windows)
• The sample is most often in the form of liquid films
(“sandwiched” between two NaCl plates)
• Adjustable path length (0.015 to 1 mm) – by Teflon spacer

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 Regions of transparency for common infrared solvents

The horizontal lines indicate regions where solvent transmits at least 25% of the 28
incident radiation in a 1-mm cell.
 Solid samples
• Spectra of solids are obtained as alkali halide discs (KBr), mulls (e.g.
Nujol, a highly refined mixture of saturated hydrocarbons) and films
(solvent or melt casting)

Alkali halide discs:

1. A milligram or less of the fine ground sample mixed with about 100 mg
of dry KBr powder in a mortar or ball mill.
2. The mixture compressed in a die to form transparent disc.

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Solid samples
Mulls
1. Grinding a few milligrams of the powdered sample with a mortar or
with pulverizing equipment. A few drops of the mineral oil added
(grinding continued to form a smooth paste).
2. The IR of the paste can be obtained as the liquid sample.

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FTIR Accessories

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FTIR Accessories

transmission reflectance

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diffuse reflectance specular

Group frequencies
• With certain functional or structural groups, it has been found that their
vibrational frequencies are nearly independent of the rest of the
molecule – group frequencies.

Carbonyl group 1650 to 1740 cm-1 various aldehydes and ketones

• Calculations show that for most groups of interest, characteristic

frequencies of stretching vibrations should lie in the region 4000 to 1000
cm-1. In practical, the region from 4000 to 1300 cm-1 is often called the
group frequency region.
• The presence of various group vibrations in the IR spectrum is of great
assistance in identifying the absorbing molecule.
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34
 Fingerprint region
• In the region from  1300 to 400 cm-1, vibrational frequencies are affected
by the entire molecule, as the broader ranges for group absorptions in the
figure below – fingerprint region.
• Absorption in this fingerprint region is characteristic of the molecule as a
whole. This region finds widespread use for identification purpose by
comparison with library spectra.

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Organic compounds

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 Infrared Spectrum of Hexane

bending
C—H stretching
bending bending

CH3CH2CH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

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Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw-Hill Companies, Inc. All rights reserved.
 Infrared Spectrum of 1-Hexene

C=C

C=C—H H—C
H2C=C

H2C=CHCH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

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Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Stretching vibrations (single bonds)
sp C—H 3310-3320
sp2 C—H 3000-3100
sp3 C—H 2850-2950
sp2 C—O 1200
sp3 C—O 1025-1200

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Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Stretching vibrations (multiple bonds)

C C 1620-1680

—C C— 2100-2200

—C N 2240-2280
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 Infrared Absorption Frequencies

Structural unit Frequency, cm-1 C O

Stretching vibrations (carbonyl groups)

Aldehydes and ketones 1710-1750
Carboxylic acids 1700-1725
Acid anhydrides 1800-1850 and 1740-1790
Esters 1730-1750
Amides 1680-1700
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Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Bending vibrations of alkenes

RCH CH2 910-990

R2C CH2 890

cis-RCH CHR' 665-730

trans-RCH CHR' 960-980

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R2C CHR' 790-840
Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Bending vibrations of derivatives of benzene
Monosubstituted 730-770 and 690-710
Ortho-disubstituted 735-770
Meta-disubstituted 750-810 and 680-730
Para-disubstituted 790-840

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 Infrared Spectrum of tert-butylbenzene

Ar—H
C6H5C(CH3)3

H—C
Monsubstituted
benzene

3500 3000 2500 2000 1500 1000 500

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Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Infrared Absorption Frequencies: functional groups

Structural unit Frequency, cm-1

Stretching vibrations (single bonds)
O—H (alcohols) 3200-3600
O—H (carboxylic acids) 3000-3100
N—H 3350-3500

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 Infrared Spectrum of 2-Hexanol

H—C

O—H
CH3CH2CH2CH2CHCH3

OH

3500 3000 2500 2000 1500 1000 500

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Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Inorganic analysis
• Inorganic analysis has been done less frequently compared to
organic
• Some typical inorganic compounds are not molecules but have
ionic structure, vibrational spectra in the typical IR region do
not exist, too weak or not characteristic enough
• Most inorganic compounds include heavy atoms, their
vibrations do not appear in common middle infrared region
(4000 - 400 cm-1) but in far infrared region (under 400 cm-1)
• Spectra of typical inorganic compounds have usually broad
bands
• Inorganic chemists prefer other than spectral analytical
methods
• Infrared spectra of inorganic compounds are more difficult to
be obtained
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Inorganic compounds

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References
• Introduction to spectroscopy, Donald L. Pavia
• Infrared spectroscopy in conservation science, Michele R.
Derrick, Dusan Stulik, James M. Landry
• Introduction to open-path FTIR measurements of
volcanic gases, Mike Burton, 2015
• Introduction to Fourier transform infrared spectrometry,
Thermo Nicolet Corporation, 2001
• Infrared Spectroscopy: Fundamentals and Applications,
Barbara Stuart
• NICODOM IR Inorganics, 1803 IR spectra of inorganics,
NICODOM 1993-2006
• http://www.thermoscientific.com/ 49