FT-IR - Fourier Transform InfraRed

FT-IR Spectroscopy & Analysis of Materials

Mrs. Purvi Kikani
Dave

10/5/16

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
10/5/16

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
commonly used
Wavenumber
10/5/16

units

number

of

of

cm-1

is

waves

of3

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.

~ 1 f
2c
10/5/16

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.
10/5/16

IR Absorption in 2-Hexanone

10/5/16

Basics of IR Spectroscopy
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 carboncarbon bonds also stretch and bend, as do the
10/5/16
7
carbon-hydrogen
bonds.

IR Spectra of 2 - Hexanone

Functional Group Region

10/5/16

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
analysis).
10/5/16

(for

data

acquisition

and
9

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
10/5/16
10

Modern IR Spectrometer Optical

Design
Light
source

Movable mirror

He-Ne gas laser

Beam splitter

Interferogra
m
Sample chamber

Fixed mirror

Detector

Interferometer
10/5/16

11

Relative Intensity

Fourier Transform of an Interferogram

yields a Spectrum

Optical Path Difference

10/5/16

Wavenumbers cm-1

12

Measuring a typical IR Spectra

% T = 100 x
I/I0

10/5/16

13

Sampling Methods
Available with our instrument

Transmission
ATR
Grazing Angle

10/5/16

14

Transmission Method
Thin Films
Solids (pallet
Technique)

10/5/16

15

Sample criteria
for Transmission Method
For Analyzing Thin Films:
Film should be in the free standing
condition and thickness should be 50m
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.
10/5/16

16

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
10/5/16
The evanescent waves penetrate the sample at17

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.
10/5/16

18

Sample criteria for ATR

Method

We can analyze following type of samples

Soft polymers
Rubbers
Soft powders
Pastes
Gels
Surface coatings
Aqueous liquids

10/5/16

19

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
10/5/16

20

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
1m 10 A
10/5/16

21

How to Read / Interpret an IR

Spectra ??

2.
What
Functional
Groups are Present in
the
material under
test ?

Functional Group Region

10/5/16

1.Which is
the
material
under
test
?
(identifying
unknown
material)

Fingerprint Region
22

What do we mean by Functional

Groups
?? of atoms with
A functional group
is a group
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
otherfor
These specific
structuralheteroatoms
features are(atoms
responsible
chemical than
reactivity
C / H) of a molecule ; hence these
structures are known as functional groups
Contains bonds
10/5/16
23

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.
10/5/16

24

How to identify unknown

The region to the right-hand
side of the
material
??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 ??

onal group region is divided in to 5 zones for better understa

Zone 1

3200 3700
cm -1

10/5/16

Alcohols ( -- OH group)
Alkynes ( C H)
N-H Stretching (N H)

Functional Group Region

27

How to know what kind of functional

groups are present in material under
test ??
Zone 2

Aldehydes ( -- CHO)
Carboxylic acids (-- COOH)

2700 3200
cm -1

10/5/16

Functional Group Region

28

How to know what kind of functional

groups are present in material under
test ??
Zone 3

Alkynes ( C C)
Nitriles(C N)

2000 2300
cm -1

10/5/16

Functional Group Region

29

How to know what kind of functional

groups are present in material under
test ??
Carbonyls (-C=O)

Zone 4

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

10/5/16

32

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

10/5/16

-1

1640 cm

-1

C=C

33

Case Study
Surface Functionalization of Polyethylene

10/5/16

34

Thank you

10/5/16

35

Resolution

10/5/16

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

the
At resolution 4 cm-1,
resolution.
OPD is 0.25 cm and
mirror movement is
0.125 cm
36

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.
10/5/16

37

DIPOLE MOMENT ()
=Qxr
Q = charge and r = distance between charges
- Asymmetrical distribution of electrons in a bond renders the
bond polar
- A result of electronegativity difference
- changes upon vibration due to changes in r
- Change in with time is necessary for a molecule to absorb
IR radiation

DIPOLE MOMENT ()
- The repetitive changes in 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

10/5/16

40

Force constant for chemical

bonds

10/5/16

41

Energy Distribution Curves for IR

Source

10/5/16

42

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
10/5/16

43

Absorbance / Transmittance
A Beer Lambert Law

absorptivity coefficient) x b (path length) x c (concent

10/5/16

44

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

10/5/16

45

Some Common Functional Groups

10/5/16

46

Modes of vibrations
Region

antisymmetric
R
R
R

symmetric

H
H
H

R
H
scissoring

R
H
rocking

Origin of the absorption

Overtones and combination

bands of fundamental
molecular vibrations

MIR

fundamental molecular
vibrations

FIR

molecular rotations

stretching

in-plane
bending

H
H

NIR

bending

Molecule

Degrees of
freedom

Non linear
Linear

3N -6
3N- 5

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
spectral region depicts a diatomic molecule as two spherical
masses (m1 and m2) connected with a spring with a given
force constant (k). Hooks law states that the energy (E) of
this system is given by:

V
-A
0
+A

E = (h/2)(k/)

where 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
Displaceme
nt

+A

V = kx2

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:

n = 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 n = 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.