CANTHO UNIVERSITY

COLLEGE OF ENGINEERING
FACULTY OF CHEMICAL ENGINEERING


Course: Modern Instrumental Methods of

Analysis
Assoc. Prof. Tran Thi Bich Quyen
Email: [email protected]
Phone: 0907500797
Nano-Electrochemistry Lab., Room 2.18, CTU Hi-tech Building,
Can Tho University
2025/01/05
Chapter 2. Fourier Transform Infrared Spectroscopy
(FT-IR)
 Contents
 Introduction
+ Brief history of development of FTIR
+ Theoretical background
 Components of FTIR spectroscopy
 Sampling techniques
 Instrumentation
 The working principles of Michelson interferometer
 Generating the spectrum
 Principle of Absorption
 FTIR Analysis
 Advantages of FTIR
 Limitations of FTIR
 Application of FTIR in textiles
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 Introduction
 Infrared spectrum is an important record which gives sufficient
information about the functional groups of a compound.
 The region from 0.8 m to 2.5 m is called Near IR, from 2.5 m to
15 m is called Mid IR or Ordinary IR and that from 15 m to 200 m
is called Far IR.
 FTIR stands for Fourier Transform Infrared Spectophotometer
– the preferred method of infrared spectroscopy.
 A method for measuring all of the infrared frequencies
simultaneously, rether than individually as with dispersive
instruments.

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 Brief History of Development of FT-IR
 FT-IR spectrometry was developed in order to overcome the
limitations encountered with dispersive instruments.
 The limitation of dispersive was the slow scanning process and
measuring individual infrared frequencies.
 A method for measuring all of the infrared frequencies
simulataneously and very simple optical was needed.
 Fourier had developed mathematical transform (FT) method in
1700.
 Albert Michelson had perfected FT-IR instrument in 1887 and
design the spectra of organic and his interferometer in 1891.
 FT-IR was combined with personal computers to make widely
used, versatile, and cost-effective method of analysis in 1980s.

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 What is Infrared Region?

 Infrared radiation lies between the visible and microwave

portions of the electromagnetic spectrum.
 Infrared waves have wavelengths longer than visible and shorter
than microwaves, and have frequencies which are lower than visible
and higher than microwaves.
 The Infrared region is divided into: Near, Mid and Far-
Infrared.
 Near-infrared refers to the part of the infrared spectrum that is
closest to visible light and far-infrared refers to the part that is
closer to the microwave region.
 Mid-infrared is the region between these two
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 What is Infrared Region? (con’t)

 The primary source of infrared radiation is thermal

radiation. (heat)

 It is the radiation produced by the motion of atoms and

molecules in an object. The higher the temperature, the
more the atoms and molecules move and the more
infrared radiation they produce.

 Any object radiates in the infrared. Even an ice cube,

emits infrared.

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 What is Infrared Region? (con’t)

According to Principle of IR,

 Molecular Vibration takes place as a result of

Absorption of IR radiation when – Applied Infrared
Frequency = Natural frequency of vibration

 Every bond or functional groups requires different

frequency for absorption. Hence characteristics Peak is
observed for every functional group or part of the
molecule.

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 Infrared Spectroscopy
For isopropyl alcohol, CH(CH3)2OH, the infrared
absorption bands identify the various functional
groups of the molecule
Transmittance (%)

Wavenumbers (cm-1)
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 Infrared Spectroscopy (con’t)
 Spectroscopy is the study of matter and its properties
by investigating light, sound, or particles that are emitted,
absorbed or scattered by the matter under investigation.

 It is the study of the interaction between light and

matter.

 Infrared frequencies of light are used to study

fundamental vibrations and associated rotational-
vibrational structure via vibrational resonance and
selective absorption.
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 Infrared Spectroscopy (con’t)
 Generally there are two types of infrared spectroscopy

 Dispersive infrared spectroscopy

 Fourier transform infrared spectroscopy

 Dispersive spectrophotometers, which use a monochromatic to

produce an infrared spectrum one resolution element at a time.

 Michelson interferometers, which use a moving mirror adjustment

to create an interferogram, from which all resolution elements are
determined simultaneously.

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What is FTIR?
 What is FTIR? (con’t)
 FT-IR stands for Fourier Transform InfraRed, the preferred method
infrared spectroscopy.

 Fourier infrared spectroscopy is the study of interactions between matter

and electromagnetic fields in the IR region.

 In this spectral region, the EM waves mainly couple with the molecular
vibrations.

 A molecule can be excited to a higher vibrational state by absorbing IR

radiation.

 It covers a range of techniques, mostly based on absorption spectroscopy.

 This makes infrared spectroscopy useful for several types of analysis.

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 What information can FTIR provide?

It can identify known materials

Identify structure of compounds based on feature

vibration of functional groups

It can determine the quality or consistency of a sample

It can determine the amount of components in a

mixture
 Infrared spectroscopy can result in a positive identification
(qualitative analysis of every different kind of material).
 With modern softwave algorithms, infrared is an excellent tool
for quantitative analysis.
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 What is FTIR? (con’t)
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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 Regions of IR
The Electromagnetic Spectrum

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 Regions of IR (con’t)

IR region is subdivided into three regions, near IR, mid IR and far IR.
 Regions of IR (con’t)

- Near-IR: có số sóng: 400-10 cm-1 (wavelength: 1000- 25

μm)
- Mid-IR 4000 - 400 cm-1 (25- 2,5 μm)
- Far-IR 14000- 4000 cm-1 (2,5 – 0,8 μm)
The spectrum and Molecular Effects
FT Optical System Diagram
Comparison of FTIR
 Sampling techniques
1. Liquid samples:
3. Gas samples:
 Neat sample
 Short path cell
 Diluted solution  Long path cell
 Liquid cell
2. Solid samples:
 Neat sample
 Cast films
 Pressed films
 KBr pellets
 Mull
Instrumentation
Instrumentation
 Working principles of Michelson Interferometer
 Light from the light source is directed to the beam splitter.

 Half of the light is reflected and half is transmitted.

 The reflected light goes to the fixed mirror where it is reflected back
to the beam splitter.

 The transmitted light is sent to the moving mirror and is also

reflected back towards the mirror.

 At the beam splitter, each of the two beams (from the fixed and
moving mirrors) are split into two:
One goes back to the source and
The other goes towards the detector
Working principles of Michelson Interferometer (con’t)

 The two beams reaching the detector come from the same source and have
an optical path difference determined by the positions of the two mirrors.

 That means they have a fixed phase difference and the two beams interfere.

 The two beams interfere constructively or destructively for a particular

frequency by positioning the moving mirror.

 If the moving mirror is scanned over a range, a sinusoidal signal will be

detected for that frequency with its
Maximum corresponding to constructive interference and
Minimum corresponding to destructive interference.
 This sinusoidal signal is called interferogram – detector signal (intensity)
against optical path difference.
Model of Michelson Interferometer (con’t)

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 The Sample Analysis Process
The noraml instrumental process is as follows:
1. The Source: Infrared energy is emitted from a glowing black-body source.
The beam passes through an aperture which controls the amount of energy
presented to the sample (and, ultimately, to the detector).
2. The Interferometer: The beam enters the interferometer where the
“spectral encoding” takes place. The resulting interferogram signal then exits
the interferometer.
3. The Sample: The beam enters the sample compartment where it is
transmitted through or reflected off of the surface of the sample, depending on
the type of analysis being accomplished. This is where specific frequencies of
energy, which are uniquely characteristic of the sample, are absorbed.
4. The Detector: The beam finally passes to the detector for final
measurement. The detectors used are the detector for final measurement. The
detectors used are specially designed to measure the special interferogram
signal. 2025/1/6 28
 The Sample Analysis Process (con’t)
5. The 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.

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 Generating the Spectrum
Interferogram is determined experimentally in FTIR spectroscopy, and
the corresponding spectrum – frequency against intensity plot, is
computed using Fourier transform.
This transformation is carried out automatically and the spectrum is
displayed.

 The detector sees all the frequencies simultaneously.

 It is imperative to record a relevant background spectrum for each sample
examined.
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 Generating the Spectrum (con’t)
Background spectrum:

 The empty beam background (no sample in the light path) is

recorded first.

 This spectrum shows the instrument energy profile.

Sample spectrum:

 The sample is placed in the combined beam.

 The sample spectrum is the ratio of the spectrum containing

sample against that of the background.
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 Principle of Absorption
 At temparetures above absolute zero, all the atoms in molecules are in
continuous vibration with respect to each other.
 As a molecule vibrates, a regular fluctuation in the dipole moment
occurs.
A Dipole Moment = Charge Imbalance in the molecule
 When the frequency of a specific vibration is equal to the frequency of
the IR radiation directed on the molecule, the molecule absorbs the
radiation and amplitude of the vibration increases.
 Principle of Absorption (con’t)
 The major types of molecular vibrations are Stretching and Bending
 Stretching – along the line of the chemical bond
 Bending – out of the line with the chemical bond.

 The absorbed Infrared radiation and the associated energy is

converted into these type of motions.
 Stretching > Bending
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 Principle of Absorption (con’t)
Stretching Bending
 Change in inter-atomic  Change in angle between two
bonds.
distance along bond axis
1. Twisting
 Stretching absorptions
2. Rocking
usually produce stronger peaks
3. Wagging
than bending
4. Scissoring
 IR Chart

 This Chart is a result of interaction bet. IR-radiations and matter.

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Four Regions of Chart

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Table of Characteristic IR Absorptions

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Table of Characteristic IR Absorptions (con’t)

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 FT-IR Analysis
In fiber characterization by FTIR, analysis is done in two ways:
1. Qualitative Analysis
 For qualitative identification purposes, the spectrum is commonly presented
as transmittance vs wavenumber.
 It is possible to identify a functional group of a molecule by comparing its
vibrational frequency on an IR stored data bank.
 Functional groups have their characteristic fundamental vibrations which
give rise to absorption at certain frequency range in the spectrum.
 However, several functional groups may absorb at the same frequency range,
and a functional group may have multiple-characteristic absorption peaks,
especially for 1500-650 cm-1, which is called the fingerprint region.
 In addition, the size of the peaks in the spectrum is a direct indication of the
amount of material present.
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 Fingerprint Region
 More complex and more difficult to interpret.
 Small structural differences results in significant in spectral
differences.
 Complete interpretation impossible.
 Complete identification requires 100% match between sample’s and
standard’s spectra in the fingerprint region.
Fingerprint Region (con’t)

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Fingerprint Region (con’t)
 Properties of Peaks
1. Intensity (weak, medium or strong),
2. Shape (broad or sharp), and
3. Position (cm-1) in the spectrum.

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Properties of Peaks (con’t)

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 FT-IR Analysis (con’t)
2. Quantitative Analysis
 Absorbance (A) is used for quantitative analysis due to its linear
dependence on concentration.
 It is given by Beer-Lamber Law; absorbance is directly proportional
to the concentration and path length of sample:

Where:
A – is absorbance,
e – the molar extinction coefficient or molar absorptivity,
c – the concentration and
l – the path length (or the thickness) of sample.
 Thus the intensity of the peaks in the FT-IR spectrum is proportiona
to the amount of substance present, for identical e and c.
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Characterization of Cotton by FTIR spectra

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Characterization of Polyester by FTIR spectra

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Characterization of Nylon by FTIR spectra

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Characterization of Ethanol by FTIR spectra

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FTIR spectra

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FTIR spectra

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FTIR spectra

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FTIR spectra

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FTIR spectra

2025/1/6 54
 Definitions
Wavelength
 The wavelength is the distance between two identical points on two
adjacent identical waves in a beam.
Wave number
 Wave number is defined as the reciprocal of the wavelength expressed
in cm. Unit are cm-1.
 Wave numbers are normally the units along the X-axis in Infrared
spectra.

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 Advantages of FTIR
FTIR instruments have distinct advantage over dispersive
spectrometers.
1. Simpler mechanical design.
2. Elimination of Stray light and emission contributions.
3. Powerful data station.
4. Majority of molecules in the universe absorb mid-infrared light,
making it a highly useful tool.
5. Universal technique.
6. Sensitive, fast and easy.
7. Relatively inexpensive and provides rich information.
8. Sensitive to “molecules”- anything that contains chemical bonds.
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 Limitations of FTIR

 It cannot be used to detect all the vibration modes in a molecule.

 It is not possible to know molecular weight of substance.
 It is not possible to know whether it is pure compound or a
mixture of compound.
 Interferogram are difficult to interpret without first performing a
Fourier transform to produce a spectrum.
 Accuracy of FT-IR remains true if there is no change in
atmospheric conditions throughout the experiment.

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 Application of FTIR in Textile
 Identification of compounds by matching spectrum of unknown
compound with reference spectrum (fingerprinting).
 Identification of functional groups in unknown substances.
 Identification of reaction components and kinetic studies of
reactions.
 Identification of molecular orientation in polymer films.
 Detection of molecular impurities or additives present.
 The same way it determines Percentage of trash particles or
foreign matter present in fiber, yarn or fabric.
 Identification of polymers, plastics, and resins.
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 Raman spectrometer

Modern Raman spectrometer

Model of Gas Laser He-Ne

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 Raman spectrometer

Laser sources:
- Laser ion Argon.
- ND : Laser YAG.
- Titanium: Laser Sapphire.
- Diode laser.

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Difference between IR and Raman spectroscopy
2025/1/6 62
 Raman (SERS) spectra

Phổ Raman ứng với từng nồng độ khác nhau của H2SO4

2025/1/6 63
Raman (SERS) spectra

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 Raman (SERS) spectra
(A) 1511 1649
1619
1364

1571
1315 1386
Intensity (a.u)

Intensity (a.u)
1181
613 776 1127
(a)
1331
(b) 1565
1204
(c) 1147 (d)
(d) (c)
(e) 951
(f) (b)
(a)
600 800 1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
-1 -1
Raman shift (cm ) Raman shift (cm )

Raman spectra of: (a) CEA antigen (10 ng/mL),

(A) Representative 532 nm excited SERS (b) R6G/antibody (15 mM)–CEA antigen (100
spectra with various concentrations of ng/mL), (c) Au@SiO2 NRs/antibody without
R6G: (a) 10-8 M, (b) 10-10 M, (c) 10-12 M, CEA antigen, and (d) Au@SiO2 NRs/antibody–
(d) 10-14 M, (e) 10-15 M, and (f) 10-16 M on CEA antigen (10 ng/mL) at 532 nm and low
Au@SiO2 NRs (~70 nm core/shell 1-2 power: 1 mW.
nm).
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 Raman (SERS) spectra

(A) 1619
50 (B)
1386
40
Intensity (a.u)

Intensity*1619
1331
1565 30
1204
1147
951 (a) 20
(b)
(c)
(d) (e) 10
(f)
(g)
(h) 0
-16 -15 -14 -13 -12 -11 -10 -9 -8 -7
1000 1200 1400 1600 1800
-1 Log [CEA antigen (g/mL)]
Raman shift (cm )
(A) Representative 532 nm excited SERS spectra with various concentrations of CEA
antigen: (a) 10 ng/mL, (b) 1 ng/mL, (c) 100 pg/mL, (d) 10 pg/mL, (e) 1 pg/mL, (f) 100
fg/mL, (g) 10 fg/mL, and (h) 1 fg/mL on Au@SiO2 NRs/antibody. (B) A logarithmic
plot of CEA concentration vs. signal intensity for the bands at 1619 cm-1.

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Many Thanks for your
attention!