FT-IR - Fourier Transform Infra-Red

FT-IR Spectroscopy & Analysis of Materials

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 Presentation Over View

• Importance of IR Spectroscopy

• Working Principle of IR Spectroscopy

• Instrumentation

• Sampling Methods & Sample Criteria

• How to Read Infra-Red Spectra ?

• Case Study – Surface Activation of polyethylene by plasma

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 Importance of IR Spectroscopy
• IR Spectroscopy is used for qualitative identification
of organic and inorganic compounds.

• IR Spectroscopy is used for checking presence of

functional groups in organic compounds.

• Wavenumber with units of cm-1 is commonly used

• Wavenumber = number of waves of radiation per

centimeter

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 Working Principle of IR Spectroscopy
• Molecules are made up of atoms linked by
chemical bonds.
• A diatomic molecule is considered as a two
spherical masses (m1 & m2) connected with a
spring with a given force constant f.

~ν  1 f
2πc μ
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 Working Principle of IR Spectroscopy
• This characteristic vibrations are called Natural
frequency of vibration

• Applied Freq. = Natural Freq. of Vibration

• Absorption of IR radiation takes place and a

peak is observed.

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 IR Absorption in 2-Hexanone

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IR Absorption & Bond Vibration in 2 - Hexanone

The vibrations of a 2-hexanone molecule are not, of course,

limited to the simple stretching of the carbonyl bond. The
various carbon-carbon bonds also stretch and bend, as do
the carbon-hydrogen bonds.
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 IR Spectra of 2 - Hexanone

Functional Group Region

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 Instrumentation / Hardware
• A source - which provides the electromagnetic energy
required for the analysis

• A signal sorter (a dispersion or interference device for

resolving the frequencies from each other).

• A sample compartment

• A signal detector

• A computer (for data acquisition and analysis).

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 Instrumentation / Hardware
Older Generation Instrument- A Dispersive IR Spectrometer

Takes  10 – 20
minutes to scan entire
range

• Scanning instrument uses a frequency separation device (grating)

to resolve the IR radiation into individual frequencies.
• An exit slit isolates a specific frequency for passage to the
sample
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Modern IR Spectrometer – Optical Design

Light He-Ne gas laser

source

Beam splitter Interferogram

Movable mirror

Sample chamber

Fixed mirror
Detector
Interferometer
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 Fourier Transform of an Interferogram yields a Spectrum
Relative Intensity

Optical Path Difference Wavenumbers cm-1

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 Measuring a typical IR Spectra

% T = 100 x I/I0

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 Sampling Methods
Available with our instrument

• Transmission
• ATR
• Grazing Angle

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 Transmission Method
• Thin Films

• Solids (pallet Technique)

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 Sample criteria
for Transmission Method
For Analyzing Thin Films:
• Film should be in the free standing condition
and thickness should be ≤ 50μm
For Analyzing Solids by Pallet Technique:
• In this technique, a small amount of finely
ground solid sample is mixed with 100 times
its weight of potassium bromide and
compressed into a thin transparent pellet
using a hydraulic press.
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 ATR Sampling Method

• The infrared radiation interacts with the sample through

series of standing waves called evanescent waves.
• An evanescent wave is produced each time the infrared beam
is reflected from the inside surface of the crystal
• The evanescent waves penetrate the sample at each
reflection point.
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 How ATR method works ?
• IR beam is directed into a crystal of relatively higher
refractive index (mostly  2).

• IR beam reflects from the internal surface of the crystal

and creates an evanescent wave which projects
orthogonally in to the sample in intimate contact with
the ATR crystal

• Some of the energy of evanescent wave is absorbed by

the sample and reflected radiation is returned to the
detector.

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 Sample criteria for ATR Method
We can analyze following type of samples
• Soft polymers
• Rubbers
• Soft powders
• Pastes
• Gels
• Surface coatings
• Aqueous liquids

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 Sample criteria for ATR Method
We can Not analyze following type of samples
• Hard polymers
• Fibers
• Hard powders
• Films on Metals
• Brittle / Grindable solids
• Acidic liquids
• Caustic liquids

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 SAGA Sampling Method
Specular Apertured Grazing Angle

Specular reflection is defined as light reflecting

from a smooth surface (such as mirror) at a definite
angle

• Specular reflectance is a non-destructive method for surface

measurements using a mirror like reflection from shiny
sample surface.

• This method is used for analysis of thin films deposited on

reflective surfaces with thickness 1μm – 10 A°

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 How to Read / Interpret an IR Spectra ??

1. Which is the material

under test ?
2. What Functional Groups (identifying unknown
are Present in the material)
material under test ?

Functional Group Region Fingerprint Region

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 What do we mean by Functional Groups ??
• A functional group is a group of atoms with specific physical
& chemical properties. It is reactive part of the molecule.
• Most organic compounds have C – C and C – H bonds.
• However many organic compound possess other structural
features such as;
 Contains heteroatoms (atoms other than C / H)
 Contains  bonds
These specific structural features are responsible for chemical
reactivity of a molecule ; hence these structures are known as
‘functional groups’
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 How functional groups make the molecule reactive ?

Ethane contains only C- C and C-H bonds; hence it has no heteroatoms

/  bonds and so no reactive sites – Non Reactive Nature

Ethanol contains –OH molecule attached. It contains heteroatoms

which has two lone pairs of electrons which make it Reactive in nature.

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 How to identify unknown material ??
The region to the right-hand side of the diagram (from about 1500 to 500 cm-1)
usually contains a very complicated series of absorptions. These are mainly due
to all manner of stretching & bending vibrations within the molecule. This is
called the fingerprint region.

It is much more difficult to pick out individual bonds in this region than it is in
the "cleaner" region at higher wavenumbers. The importance of the fingerprint
region is that each different compound produces a different pattern of peaks in
this part of the spectrum.

Fingerprint Region
How fingerprint region is important in identifying unknowns ?
 How to know what kind of functional groups are
present in material under test ??
Functional group region is divided in to 5 zones for better understanding

• Alcohols ( -- OH group)
Zone - 1
• Alkynes ( C – H)
• N-H Stretching (N – H)
3200 – 3700 cm -1

Functional Group Region

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 How to know what kind of functional groups are
present in material under test ??

• Aldehydes ( -- CHO)
• Carboxylic acids (-- COOH)
Zone - 2

2700 – 3200 cm -1

Functional Group Region

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 How to know what kind of functional groups are
present in material under test ??

• Alkynes ( C C)
• Nitriles(C N)
Zone - 3

2000 – 2300 cm -1

Functional Group Region

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How to know what kind of functional groups are
present in material under test ??

Zone - 4

• Carbonyls (--C=O)

1650 – 1800 cm -1

Functional Group Region

How to know what kind of functional groups are
present in material under test ??

• Alkenes ( C=C) Zone - 5

1680 – 1620 cm -1

Functional Group Region

 Case Study
Surface Functionalization of Polyethylene

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 Case Study
Surface Functionalization of Polyethylene
1720 cm -1 1640 cm -1
--C=O
C=C

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 Case Study
Surface Functionalization of Polyethylene

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 Resolution
• In order to resolve two
peaks in a spectrum three
data points are needed. One
on each peak and one point
in between.
• Data point spacing is
controlled by resolution
parameter and is ½ the
resolution.
• At resolution 4 cm-1, OPD is
0.25 cm and mirror
movement is  0.125 cm
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 Why there is He-Ne Laser in FT-IR ?
• Interferogram is not recoded continuously, but sampled at discrete intervals to give
different data points. The closer the spacing between data points, the greater the
wavenumber range of the spectrum.
• Monochromatic visible He-Ne laser beam is passed along with the polychromatic IR
light to provide a single wavelength interferogram that oscillates much more quickly
than anything in the IR (shorter wavelength).

The laser is used as an internal

clock to trigger data points
acquisition events.

IR data points might be taken at

every zero point of the laser
interferogram.

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 DIPOLE MOMENT (µ)
µ=Qxr

Q = charge and r = distance between charges

- Asymmetrical distribution of electrons in a bond renders the

bond polar

- A result of electronegativity difference

- µ changes upon vibration due to changes in r

- Change in µ with time is necessary for a molecule to absorb

IR radiation
 DIPOLE MOMENT (µ)
- The repetitive changes in µ makes it possible for polar molecules
to absorb IR radiation

- Symmetrical molecules do not absorb IR radiation since they

do not have dipole moment (O2, F2, H2, Cl2)

- Diatomic molecules with dipole moment are IR-active

(HCl, HF, CO, HI)

- Molecules with more than two atoms may or may not be

IR active depending on whether they have permanent
net dipole moment
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 Force constant for chemical bonds

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 Energy Distribution Curves for IR
Source

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 Out put of an interferometer = Interferogram

An interferogram has every infrared

frequency (or wavelength) encoded
in it

An interferogram
containing all IR
frequencies now
enters the sample
compartment

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 Absorbance / Transmittance
A Beer Lambert Law

A =  (absorptivity coefficient) x b (path length) x c (concentration)

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 Factors Affecting ATR Spectra
• Refractive indices of the ATR crystal and sample
• Depth of penetration
• Effective path length
• Number of reflections
• Quality of sample contact with ATR crystal

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 Some Common Functional Groups

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 Modes of vibrations

Region Origin of the absorption

antisymmetric symmetric
NIR Overtones and combination bands of
R R fundamental molecular vibrations
H H
stretching
R H R H
MIR fundamental molecular vibrations

R R FIR molecular rotations

H H in-plane
R H R H bending
scissoring rocking Molecule Degrees of freedom

R Non linear 3N -6
H R
H Linear 3N- 5
R H R H bending
 The Absorption Techniques of MIR and NIR Spectroscopy

The Harmonic Oscillator

The simplest classical model employed to have a didactic

insight on the interaction of radiation and matter in the NIR
V spectral region depicts a diatomic molecule as two spherical
masses (m1 and m2) connected with a spring with a given
-A force constant (k). Hook´s law states that the energy (E) of
0 this system is given by:

+A
E = (h/2π)√(k/µ) where μ is the reduced mass.

The molecular vibration can be described by a simplified

model supposing a harmonic oscillator for which the
potential energy (V), as a function of the displacement of the
atoms (x), is given by:
-A 0 +A V = ½ kx2
Displacement
The potential energy curve of such an oscillator is parabolic
in shape and symmetrical about the equilibrium bond length.

Harmonic Oscillator prepared by Carlos Ortega

 The Absorption Techniques of MIR and NIR Spectroscopy

For the harmonic oscillator the energy levels are equidistant and transitions are only allowed between
neighboring energy levels with:
Δn = ±1

According to the Boltzmann distribution, most molecules at room temperature populate the ground level n
= 0, and consequently the allowed, so-called fundamental, transitions between n = 0 and n = 1 dominate
the vibrational absorption spectrum.

For the harmonic oscillator Δn = ±1 and Ep = hv, which matches the predicted equal energy difference
between one state and the other of immediately higher energy. The figure at right shows the effect of
photon absorption on the energy and amplitude of vibration.
Fundamentals and Overtones

In the case of the anharmonic

oscillator, the vibrational
transitions no longer only obey
the selection rule n = 1. This
type of vibrational transition is
called fundamental vibration.
Vibrational transitions with n =
2, 3, ... are also possible, and
are termed overtones. Called
first, second, and so on,
overtones.