NANO1261 Basic instrumental

techniques: FTIR
Dr Muhammad Raziq Rahimi Kooh @ Chern Yuan
2023
raziq.kooh@ubd.edu.bn
Centre for Advanced Material and Energy Sciences
Universiti Brunei Darussalam

1
Objectives
1. Define the term spectroscopy
2. Learn the basic about IR radiation and IR spectroscopy
3. Learn the components of IR spectroscopy
4. Understand the various techniques in IR spectroscopy
5. Learn to interpret IR spectrum
6. Explore various applications
7. Available tools for processing FTIR spectrum

2
Outline
1. Basic of spectroscopy
2. Instrument
3. Various IR techniques
4. Theory
5. IR-spectrum interpretation
6. Applications
7. Others: data processing software, web resources
8. Assignment

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Electromagnetic radiation

4
Types of energy transitions in each region of
the EM-spectrum

Spectroscopy – study of the interaction of EM radiation with matter to get spectra.

Spectra give information: bond angle, bond length, geometry, molecular structure, functional groups
5
 Definition of Spectroscopy
• Definition: Spectroscopy is the study of the absorption and emission of light and
other radiation by matter. It involves the splitting of light (or more precisely,
electromagnetic radiation) into its constituent wavelengths (a spectrum), which is
done in much the same way as a prism splits light into a rainbow of colors
• Spectroscopy is a fundamental tool of scientific study, with applications ranging
from materials characterization to astronomy and medicine. Spectroscopy
techniques are commonly categorized according to the wavelength region used,
the nature of the interaction involved, or the type of material studied.

Radiation Spectrometer Detector

source
Basic component of a spectroscopy

https://www.britannica.com/science/spectroscopy/Basic-properties-of-atoms 6
Type of spectroscopy

22 types of spectroscopy
https://microbenotes.com/types-of-spectroscopy/ 7
 Discovery of infrared radiation
• Infrared radiation was discovered by
William Herschel in 1800
• conducted an experiment measuring
the difference in temperature
between the colours in the visible
spectrum
• He placed thermometers within each
colour of the visible spectrum.
• The results showed an increase in
temperature from blue to red.

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Infrared (IR) spectrum In FT-IR, we look at the spectrum
using wavenumber, instead of
wavelength

Wavenumber = 1/wavelength

To convert from wavenumber (cm-1)

to nanometers, use the following
equation: 1/cm-1 x 107 = nanometers

• The range of IR region is 12800 ~ 10 cm-1 and can be divided into:

• near-infrared region (12800 ~ 4000 cm-1)
• mid-infrared region (4000 ~ 200 cm-1)
• far-infrared region (50 ~ 1000 cm-1)
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Infrared (IR) spectrum
• IR spectrum is molecular vibrational spectrum.
• When exposed to IR radiation sample molecules selectively absorb radiation of
specific wavelengths which causes the change of dipole moment of sample
molecules
• 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.
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 Dipole moment
• A dipole moment arises in any system in which there is a separation of charge. They can,
therefore, arise in ionic bonds as well as in covalent bonds. Dipole moments occur due to
the difference in electronegativity between two chemically bonded atoms.
• the dipole moment is created when the atoms of a molecule share the electrons
unequally
• unit to measure dipole moment of the molecules is D (Debye)

Net dipole moment = 0.816D Net dipole moment = zero

Net dipole moment = 1.855D
• Chlorine higher electron density than hydrogen, therefore has a significant dipole moment
• H2O molecule is a non-linear molecule due to the uneven distribution of the electron density. O2 is more
electronegative than H2 and carries a negative charge, while H has a partial positive charge.
https://byjus.com/chemistry/dipole-moment/ 11
 Vibrational modes
• A molecule consisting of (N) number of atoms has a total of 3N degrees of freedom,
corresponding to the Cartesian coordinates of each atom in the molecule.
• Number of vibrational modes can be calculated using the equations below:
• Linear Molecules: (3N - 5) vibrational modes
• Non-Linear molecules: (3N - 6) vibrational modes
Example 1 Water Molecule (non-linear)
• Total degree of freedom = 3 N = 3 (3) = 9
• Total vibrational mode = 3 (3) - 6 = 3
• O-H group is polar

3506 cm-1 3585 cm-1 1885 cm-1

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IR intensity = 0.17 IR intensity = 1.0 IR intensity = 0.15
 Vibrational modes

Example 2: Carbon dioxide (linear)

• Total vibrational modes = 3 (3) – 5 = 4
• CO2 has 2 stretching modes, symmetric and asymmetric:
• The CO2 symmetric stretch is not IR active because there is no change in dipole
moment because the net dipole moments are in opposite directions and as a
result, they cancel each other.
• In the asymmetric stretch, O atom moves away from the C atom and generates a
net change in dipole moments and hence absorbs IR radiation at 2350 cm-1. The
other IR absorption occurs at 666 cm-1.
• Bending: does not cause a dipole moment change because the polar directions
cancel each other
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Molecular vibration

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IR (2)
• capable to analyze all gas, liquid and solid samples
• common used region for infrared absorption spectroscopy is 4000 ~
400 cm-1 (Mid-IR range) because the absorption radiation of most
organic compounds and inorganic ions is within this region
• advantages:
1. The signal-to-noise ratio of spectrum is significantly higher than the
previous generation infrared spectrometers.
2. The accuracy of wavenumber is high. The error is within the range of ± 0.01
cm-1.
3. The scan time of all frequencies is short (approximately 1 s).
4. The resolution is extremely high (0.1 ~ 0.005 cm-1).
5. The scan range is wide (1000 ~ 10 cm-1).
6. The interference from stray light is reduced. Due to these advantages, FTIR
Spectrometers have replaced dispersive IR spectrometers.
15
Mid IR range
• Functional group region (4000 – 1500 cm-1)
• Fingerprint region (1500-909 cm-1)
• Aromatic region
• ortho, meta, para substitution

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FTIR as a tools
For:
• Basic sample characterisation
• detection of impurities
• Kinetics of reaction
• Quantitative analysis
• Study of covalent bond
• Shape / geometry of an inorganic compound
• Water detection

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Instrument basic
Components:
1. IR source
2. Interferometer
3. Sample compartment
4. Detector
5. Fourier-transform

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Instrument basic

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 Function of individual component
• Source: Infrared energy is
emitted from a glowing black-
body source.
• Interferometer: The beam
enters the interferometer
where the “spectral encoding”
takes place. The resulting
interferogram signal then
exits the interferometer.
• Sample: beam transmitted
through or reflected off the
surface of sample
• Detector: Measuring the
interferogram signal
• Computer: digitized the
signal and mathematical
technique known as Fourier
transformation
Further reading: URL
20
 Michelson interferometer
• the core of FTIR spectrometers, is used
to split one beam of light into two so
that the paths of the two beams are
different
• the Michelson interferometer
recombines the two beams and
conducts them into the detector where
the difference of the intensity of these
two beams are measured as a function
of the difference of the pathseams are
different
• consists of two perpendicular mirrors
(one stationary and one movable) and a
beamsplitter

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Fourier transform
• Mathematical technique based on trigonometry (Sin, cosine)
• Clean up raw signal into interpretable form

Fast fourier transformation

For curious mind

https://youtu.be/spUNpyF58BY

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Sampling techniques
There are four major sampling techniques in FTIR:

 Transmission.
 Attenuated Total Reflection (ATR)
 Specular Reflection.
 Diffuse Reflectance

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Methods
1. Nujol mull method
2. Pressed pellet
3. Liquid sample
4. ATR
5. Handheld direct measurement

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 To obtain IR-spectrum
1. Nujol-mull method for solid sample

Sample
How much?
Paraffin oil or Mounting
mineral oil
FTIR
Grind

Spectrum of nujol mull

Sandwich
Spread
onto kbr
plate

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Mull’s method
• Finely ground solid mixed with nujol (mineral oil) to make a thick
paste and then sandwiched between IR transmitting windows
• The windows are placed in holder and mounted in a path of IR beam
and the spectrum is run
• This method is good for quantitative analysis

26
Nujol
• Nujol is a brand of mineral oil by Plough Inc., cas number 8012-95-1, and density
0.838 g/mL at 25 °C, used in infrared spectroscopy.
• It is a heavy paraffin oil so it is chemically inert and has a relatively uncomplicated IR
spectrum, with major peaks between 2950-2800, 1465-1450, and 1380–1370 cm−1.
• The empirical formula of Nujol is hard to determine exactly because it is a mixture
but it is essentially the alkane formula CnH(2n + 2) where n is very large.
• To obtain an IR spectrum of a solid, a sample is combined with Nujol in a mortar and
pestle or some other device to make a mull (a very thick suspension), and is usually
sandwiched between potassium- or sodium chloride plates before being placed in
the spectrometer.
• For very reactive samples, the layer of Nujol can provide a protective coating,
preventing sample decomposition during acquisition of the IR spectrum.
• When preparing the sample it is important to keep the sample from being saturated
with Nujol, this will result in erroneous spectra since the Nujol peaks will dominate,
silencing the actual sample's peaks.

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 Common IR window materials
Hygroscopic

Hygroscopic, soft, easily polished,

commonly used in making pellets

Hygroscopic, soft

Attacked by HF

Attacked by acids, avoid ammonium salts

Further reading URL

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Maintenance of IR windows

Depend on material
KBr plates sensitive to humidity 29
Making KBr window using pellet press

Die pressing set Dried KBr (Oven at 110oC)

Clean with chloroform and

store with desiccant

Pressed at 8-10 t
pressure

Connect to vacuum pump

Hydraulic pellet press 30
 2. Pressed pellet technique: KBr Plate method
(Slowest method)
If pressed pellet
is too opaque,
and did not get
Dried KBr Grind good reading,
Pellet press, mount and
analyse then reduce
amount of
Sample sample and try
Ratio of Sample: KBr 1:40 sample:
1:10 to 1:100 (depends KBR ratio
on sample material)

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 Nujol method vs pressed pellet method
Nujol method Pressed pellet method
Speed faster Slower due to longer
preparation time
Sample For reactive sample Standard method for most
conventional analysis
Maintenance Need to maintain the No need for sandwich plates
plates used as window
Interference Some interfering peaks No interfering peak apart from
from mineral oil moisture in KBr

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3. liquid sample

Advantage
•Convenient to handle and clean with solvents after analysis
Disadvantages
•Aqueous solvents cannot be used as they dissolve alkali halides
•Path length cannot be adjusted depending on solution concentration
•It is difficult to fill the sealed cell with viscous samples 33
 4. ATR (attenuated total
reflectance)
• An IR beam is reflected off the surface of a crystal from
the underside and interacts with a sample of lower
refractive index placed onto the surface of the crystal
• Recording the intensity of the light reflected before and
after placing a sample on the crystal surface produces
the characteristic infrared spectrum of your sample
• the IR beam does not exit the surface of the crystal at
the crystal/sample interface. Instead, the electric
component of the light propagates into the rarer
sample medium. This is known as called an evanescent
wave, and it decreases exponentially as it propagates
into the sample. As a result, the penetration depth of
ATR spectroscopy is very short, the exact depth
depending on several factors including the sample type
and the wavelength of the light. 34
 Future reading: URL

4. ATR (attenuated total For both solid and

liquid samples
reflectance)
Advantages
• Simple
• Little preparation
• Stronger absorbance
• Small amount of sample
• Suitable for biological sample, powder, thin film,
and even liquid
Disadvantage
• light absorbance is hard to quantify due to
scattering
Halal science – there was an interest to develop FTIR as fast identification tool for
detecting lard DOI: 10.1007/s11746-001-0338-4 35
 Crystal choice: Depends on
ATR crystal materials your application

Ge is suitable for materials

with a high refractive index
and for surface studies owing
to its smaller penetration
depth

Most common
• avoid harder samples and
point loads as these can
cause the crystal to
shatter
• ensure the crystal is not
exposed to acidic or
strongly basic samples as
these can cause the
formation of toxic36fumes
Black: KBr method
Blue: ATR

37
 5. Handheld FTIR

• Non-destructive
• Mobile
2kg • Fast, on-the-go
• Applications include analysis of polymers,
coatings, composites, bulk material, cleaning
verification, and even historical artifacts and
artwork

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Video references
• Making KBR plates using hydraulic press
https://youtu.be/eKqorNb2pGU
• Nujol mull method (without grinding)
https://youtu.be/AEprOM8sy-Y
• ATR Basic
https://youtu.be/q0evGXCK-sY
• Agilent Handheld-FTIR
https://youtu.be/sa00gWvnzBM

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Basic operation
• Number of scans: 32 recommended – reduce noise (5min / sample)
• Resolution: 0.5, 1, 2, 4, 8, 16 cm-1
• Select %Transmittance or Absorbance
• Do a background scan of the air
• Caution: Humidity

40
Background (spectrum of air)

Background spectrum will

contain information about
the species of gases and
solvent molecules, which
may then be subtracted
away from our sample
spectrum in order to gain
information about just the
sample

41
 Absorbance
Expression of DATA

42 Transmittance
 Expression of DATA
Absorbance

Absorbance
1000 1000 3000
3000

43
Theory – molecular vibration

44
Molecular vibration

45
Interpretation of spectrum

46
Simplified correlation chart

47
IR Spectrum of 2-Hexanone

Resource on interpretation of FTIR spectrum

48
www.uma.pt/jrodrigues/disciplinas/QINO-II/Teorica/IR.pdf
 Fingerprint region
Unique area

• Fingerprint region is also known as the vibration region

• Occurred between 400 cm-1 and 1500 cm-1
• usually contains a large number of peaks,
• mainly due to all manner of bending vibrations within
the molecule
• difficult to identify individual peaks.
• However, the fingerprint region of a given compound is
unique and, therefore, can be used to distinguish
between compounds.

https://chem.libretexts.org/Ancillary_Materials/Reference/Organic_Chemistry_Glossary/Fingerprint_Region#:~:te
49
xt=The%20region%20between%20400%20cm,used%20to%20distinguish%20between%20compounds.
 2-hexanone vs 3-hexanone
MF: C6H12O MW: 100.16g/mol
MF: C6H12O MW: 100.16g/mol

https://webbook.nist.gov/cgi/cbook.cgi?ID=C589388&Mask=80 50
 https://www.chemguide.co.uk/analysis/ir/fingerprint.html

Fingerprint example 2 isomer

Propan-1-ol and propan-2-ol contain exactly the same bond Both compounds have very similar troughs in the area
around 3000 cm-1 - but compare them in the fingerprint region between 1500 and 500 cm-1. The pattern in the
fingerprint region is completely different and could therefore be used to identify the compound.
51
Fingerprint example 3: cis- and trans-N-phenylamides

https://pubs.rsc.org/en/content/articlelanding/2009/cp/b822310f 52
Spectrum of Nujol

53
Spectrum of Nujol + ferrocene

Ferrocene in nujol (highlighted region represents peaks from nujol)

54
Look from journal article KBR pressed method Alexandria Engineering Journal
Volume 54, 2015, Pages 1253-1263

Casuarina leaves Casuarina leaves + Dyes

Functional group analysis

Interpretation
(1) Shift of peaks
(2) new peaks 55
 APPLICATIONS
Characterisations • Microplastic Food Science
• Polymer studies • Authentication of edible
• Minerals • Archeology oil
• Catalyst • Purity • Detection of illegal food
assessment additives
• Archeology
• Functional • Detection of porcine
• Biomass group analysis fats in Halal Science
• Medical field • Detection of dangerous
fake food

56
 FTIR for polymer
Hardwood

softwood

The intensity ratio of two lignin peaks for different woods show
a higher 1505-to-1600 cm-1 ratio for softwood than hardwood. cellulose
The intensity ratio of carbonyl absorption to two lignin
absorptions shows a higher value for hardwoods.

Applied Polymer Science, 71(12), 1969-1975

57
 FTIR in synthesis
• Synthesis of
polyurethane foam
using waste oil
• FTIR to confirm the
presence of polyol
in waste oil
• Polyol as ingredient
for synthesis of
polyurethane foam

https://iopscience.iop.org/article/10.1088/1757-899X/271/1/012062
58
IOP Conf. Ser.: Mater. Sci. Eng. (2017) 271, 012062
FTIR for catalyst
The CO-FTIR spectra of the reduced catalysts (Fig. 4)
exhibit a low frequency band (LF) at 2038–
2042 cm−1 unambiguously attributed to CO linearly
bonded to metallic ruthenium, Ru0, and other bands at
higher wavenumbers (HF) assigned to
Run+(CO)x multicarbonyls
It is important to point out the low intensity of the
Ru(c,r)/Al and Ru(c,w,r)/Al spectra in comparison with that
of Ru(r)/Al. The lower CO uptake by the first two catalysts
can be due to the lower metal dispersion but also to the
different nature of the Ru species present

Applied Surface Science 210.3-4 (2003): 222-230

59
 Commercial Library available, but expensive
FTIR in mineralogy
• Position and shape of the OH stretching band
in the IR spectra of smectites is influenced
mainly by the nature of the octahedral atoms
to which the hydroxyl groups are coordinated.
• The absorption at 3620 cm−1, found in the
spectrum of montmorillonite, is typical for
smectites with high amount of Al in the
octahedra
• The position of the OH band at 3567 cm−1 is
characteristic for nontronites in which FeFeOH
grouping dominates in the octahedral sheets.
The OH stretching region of hectorite and
saponite reflects their trioctahedral character
with mainly Mg3OH units in the octahedral
IR spectra of kaolinite (a), dickite (b), chrysotile (c), SAz-1 montmorillonite
(d), nontronite (e), hectorite (f) and saponite (g) in the OH stretching (A) sheet, absorbing near 3680 cm−1.
and 1300-400 cm−1 (B) regions.
Vibrational spectroscopy 31.1 (2003): 1-10 60
FTIR + mathematical tools for analysis
• For processing multiple FTIR spectra (e.g. 100 FTIR spectra)
• Machine learning: neural networks, random forests, support vector machine
• Discriminator analysis
• Dimension reduction: Principal component analysis
• Software: Weka data mining workbench (FREE), SPSS (not free),
Matlab (not free)
• Write your own codes (Python, R)
• reading
• https://ieeexplore.ieee.org/stamp/stamp.jsp?arnumber=9000861
• https://link.springer.com/article/10.1007/s00216-019-02063-y

61
 FTIR in Halal Science
Spectra of pure mixed ghee along with the addition of pig
body fat in the wavenumber range (a)3030-2785 cm−1
(b)1786–1680 cm−1 (c)1490–919 cm-1.
PMG- Pure Mixed Ghee (1:1- Pure cow ghee and Pure
buffalo ghee) PBF = Pig Body Fat.

Journal of Molecular Structure 1153 (2018): 275-281. 62

 Application in food science: Fatbergs from sewerage Waste oil from sewerage

Gutter oil / sewer oil

• processing of waste oil collected from
sources such as restaurant fryers, grease
traps, slaughterhouse waste, and fatbergs
• Gutter oil is acceptable as a raw ingredient
for producing soap, rubber, bio-fuel, and
cosmetics
• Illegal for food processing
Grease trap
• toxic causing diarrhea and abdominal pain.
• long-term consumption can lead to stomach
and liver cancer.
• Testing of some samples of gutter oil has
revealed traces of polycyclic aromatic
hydrocarbons (PAH): dangerous organic
pollutants capable of causing cancer with
long-term consumption.
https://en.wikipedia.org/wiki/Gutter_oil 63
FTIR + Machine learning (1)
• 135 samples: FTIR
data of edible and
adultered oil range
3100–2900, 1800–
1700, 1500–1400,
and 1200–1100 cm−1
• Fit into supervised
learning:
discriminator analysis
• 100% identified oil
mixed with gutter oil

https://www.sciencedirect.com/science/article/pii/S0308814622006239
64
Food Chemistry 2022, 385, 132661
FTIR + Machine learning (2)

• Detection of porcine fats using support vector machine algorithm

Meat Science Volume 92, Issue 4, December 2012, Pages 65

506-510
FTIR in medicinal
+ ML (3) Cells 2022, 11(3), 458

66
67
 Spectragryph
https://www.effemm2.de/spectragryph/down3.html

Tutorial from youtube channel:

Friedrich Menges
https://www.youtube.com/channel/UCpjrKBe7
m_Exf6-zRPIeJjw/videos 68
IRPal 2.0 (free)
The program IRPal is a powerful tool for the
interpretation of IR-spectra of organic
compounds. It not only gives the user one or
more functional groups that feature absorption
band(s) for a selected wavenumber, but relates
that information to the possible existence of
other bands in the spectrum that could confirm
these assignments.

file size of 1.61 MB

Last update: 27 March, 2018

https://irpal.software.informer.com/download/

69
 Crystalsleuth

• User-friendly
• Small size
• Free
• Can be used for UV/vis, Raman, FTIR
• Download link for crystal sleuth
• https://rruff.info/about/about_download.php
• Need Labview runtime (free) for software to work
• note: Labview runtime (free) ≠ Labview (notfree)
• https://www.ni.com/en-us/support/downloads/software-products/download.labview-
runtime.html
70
Other softwares for processing spectra
Protea (freetrial ?? Days)
• https://www.environmental-expert.com/software/protea-free-ftir-
software-106267
EssentialFTIR (30days free)
• https://www.essentialftir.com/download.shtml
• OriginLab (Not free)

71
Webtool: Free IR frequency lookup

https://www.specac.com/en/resources/infrared-frequency-tool 72
 Free lab poster: quick guide (#not sponsored)

https://www.specac.com/en/documents/user-manuals/if-freq-poster 73
74
https://pubchem.ncbi.nlm.nih.gov

Pubchem
• great resource for known
compound
• Good for checking purity
• Contain many other spectra
information e.g.

NMR, LC-
MS, MS-MS,
RAMAN

75
 NIST chemical webbook

https://webbook.nist.gov/cgi/cbook.cgi?ID=C591786&Type=IR-SPEC&Index=1 76
 Theoretical simulation for known
and unknown molecules
Gaussian
software
package

Predicting UV/VIS, FTIR, NMR and RAMAN spectrum

77
Using DFT for to calculate frequency
FT-IR spectra of 2-amino-4-
methyl benzonitrile: (a)
observed in solid phase,

(b) calculated
with HF/6-31 G∗

(c) calculated with

B3LYP/6-31G∗
Spectrochimica Acta Part A:
Molecular and Biomolecular
Spectroscopy
Volume 96, 2012, Pages 480-
484 78
Suggested Reading
• https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Book
%3A_Physical_Methods_in_Chemistry_and_Nano_Science_(Barron)/
04%3A_Chemical_Speciation/4.02%3A_IR_Spectroscopy
• https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_
Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_and_
Theoretical_Chemistry)/Spectroscopy/Vibrational_Spectroscopy/Infr
ared_Spectroscopy/How_an_FTIR_Spectrometer_Operates
• https://www.pharmaresearchlibrary.com/wp-
content/uploads/2013/04/Infrared-Spectroscopy-Fundamentals-and-
Applications-Barbara-Stuart.pdf
• https://assets.thermofisher.com/TFS-
Assets/CAD/brochures/BR50555_E_0513M_H_1.pdf

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 End of this Lecture !
Continue with RAMAN
Lecture

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