Fourier Transform Infrared

(FT-IR) Spectroscopy

Theory and Applications

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 Outlines

Introduction on Infrared Spectroscopy?

Theory of FT-IR
How does FTIR Works
Sample Preparation
Infrared Peak Positions, Intensities and
Widths
Application of FTIR
FT-IR Advantages and Disadvantages?

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 Regions of Electromagnetic Spectrum-the colour of light

Fig. 18-2
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 What is Infrared Radiation(IR)?
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.
Infrared radiation ranges in wavelength from 700nm to 1mm,
which covers the most interesting range of molecular
vibration.
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 The Infrared region is divided into: near, mid and far-infrared.
Near-infrared refers to the part of the infrared spectrum
that is closer 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.

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? (Cont.)

Humans, at normal body temperature, radiate most

strongly in the infrared, at a wavelength of about 10
microns (A micron is the term commonly used in astronomy
for a micrometer or one millionth of a meter). In the image
to the left, the red areas are the warmest, followed by
yellow, green and blue (coolest).
The image to the right shows a cat in the infrared. The yellow-
white areas are the warmest and the purple areas are the
coldest. This image gives us a different view of a familiar
animal as well as information that we could not get from a
visible light picture. Notice the cold nose and the heat from
the cat's eyes, mouth and ears.
 WHAT IS FTIR?
FTIR spectroscopy is an important technique
used to identify organic, polymeric, and in
some cases, inorganic materials.

The FTIR spectroscopy method uses infrared

light to scan test samples and observe
chemical properties
 WHAT IS FTIR?

An easy way to identify the presence of certain

functional groups in a molecule.

Fourier-transform infrared spectroscopy is a

vibrational spectroscopic technique, meaning it takes
advantage of asymmetric molecular stretching,
vibration, and rotation of chemical bonds as they are
exposed to designated wavelengths of light.
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.
 Infrared Spectroscopy
Infrared spectroscopy is the study of the interaction of infrared
light with matter.

The fundamental measurement obtained in infrared

spectroscopy is an infrared spectrum, which is a plot of measured
infra intensity versus wavelength, ( or wavenumber, 1/) of
light.

An instrument used to obtain an infrared spectrum is called an

infrared spectrometer.

There are several kinds of spectrometers in the world used to

obtained infrared spectra. The most prevalent type of
spectrometer is called a Fourier Transform Infrared Spectrometer
(FTIR).
 Infrared Spectroscopy
The infrared spectroscopy is sensitive to the presence of
chemical functional groups in a sample.
The bonds between atoms in the molecule stretch and bend,
absorbing infrared energy and creating the infrared
spectrum.

Symmetric Stretch Antisymmetric Stretch Bend

A molecule such as H2O will absorb infrared light when the

vibration (stretch or bend) results in a molecular dipole moment
change
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 Energy levels in Infrared Absorption

Excited
states
hn

Infrared Absorption and

Emission
h(n2 - n1)
n (overtone)
3
n h(n1 - h(n1 -
n0 ) n 0) Ground
n2 (vibrational
n
1
) states
0

Infrared absorption occurs among the ground vibrational states,

the energy differences, and corresponding spectrum, determined
by the specific molecular vibration(s). The infrared absorption is a
net energy gain for the molecule and recorded as an energy loss
for the analysis beam.
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 Necessary conditions for infrared absorbance to take place.
A molecule must possess a vibration
The energy of the infrared light that used for shinning on
the molecule must equal a vibrational energy level
difference in the molecule.
Only the resonated vibration with the same frequency
will be absorbed.

Example 1:

N2 (nitrogen) has NO infrared spectrum, as theres no dipole change.

However, CO (carbon monoxide ) DOES have one:

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 What is a FTIR Spectrometer?
A spectrometer is an optical instrument used to measure
properties of light over a specific portion of the
electromagnetic spectrum, 5 microns to 20 microns.

FTIR (Fourier Transform InfraRed) spectrometer is a obtains an

infrared spectra by first collecting an interferogram of a
sample signal using an interferometer, then performs a
Fourier Transform on the interferogram to obtain the
spectrum.

An interferometer is an instrument that uses the technique of

superimposing (interfering) two or more waves, to detect
differences between them. The FTIR spectrometer uses a
Michelson interferometer.

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 How does FTIR works?
As infrared is an absorption technique,
infrared passes through the sample, and is
then detected.

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 Encoding
-A beam splitter will divide the incoming infrared
light into two optical beams.

-One beam will reflects off a flat mirror fixed in a

place, another beam reflects off a flat mirror which
is allows to move for a short distance.

-Two beams are allow to reflect off of the

respective mirrors and recombined when they
meet at beam splitter again.
-One beam travelled a fix distance and the
other is constantly changing as the mirror
moves.

-The interference of these two beams forms a

beam (interferogram) which consists of all
frequencies of infrared light.

-This is the reason why FT-IR consumes less

time than dispersive spectrometer.
 Fixed Mirror
F

Moving Mirror 1

M
B
2 IR
Beam Splitter

Sample

Detector

Beam splitter is designed to transmit half of the radiation and reflect

half of it
Beam 1 travel the distance of 2FB, whereas beam 2 travels a
distance of 2 MB
The difference between FB and MB is called the optical path
difference
Two beams reflect off and recombined together at the beam splitter.
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 This combined beams produce an interference pattern, or
interferogram. The interference pattern varies with the
displacement of the moving mirror.

Interference of two beams of light

Fixed mirror
Same-phase interference
wave shape
Movable mirror

Fixed mirror
Opposite-phase interference
wave shape
Movable mirror
Fixed mirror
Same-phase interference

wave shape
Movable mirror Light intensity versus
0 l
optical path difference
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 When the interferogram signal is transmitted through or reflected
at sample surface, the specific frequencies of energy are absorbed
by the sample due to the vibration of functional groups.

Lastly, arrives at the detector and is measured by the detector.

Decoding by using a well known mathematical technique, Fourier

transformation.

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 Sample Preparation
Solid sample
1. KBr Method.
Sample is ground into powder and a purified salt (usually
potassium bromide, KBr) is used to mix with the powder and
the mixture is crushed in a mechanical die press to form a
translucent pellet as an IR sample.

2. Film Method
- mostly for polymer sample. Polymer sample is first dissolved
in a good solvent to form a solution. A drop of this solution is
deposited on the surface of a KBr or NaCl cell.
- This solvent is then evaporated to form a film on the cell,
analyzed directly
- The films should not be too thick for the light to pass through.

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3. Reflection method.
- For nontranslucent samples or films, a reflection at the
sample surface is measured.
- the reflection rate should be high enough for obtaining an IR
spectrum.

Liquid sample
1. Fill into an IR transparent glass sample cell
2. Sandwiched between two plates of a high-purity salt (usually
sodium chloride or potassium bromide).

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 Infrared Peak Positions
Chemical bonds in different environments will absorb varying
intensities and at varying frequencies. Thus IR spectroscopy involves
collecting absorption information and analyzing it in the form of a
spectrum.

The frequencies at which there are absorptions of IR radiation

("peaks" or "signals") can be correlated directly to bonds within the
compound in question.

Because each interatomic bond may vibrate in several different

motions (stretching or bending), individual bonds may absorb at
more than one IR frequency.

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Stretching absorptions usually produce stronger peaks than bending,
however the weaker bending absorptions can be useful in differentiating
similar types of bonds (e.g. aromatic substitution).

It is also important to note that symmetrical vibrations do not cause

absorption of IR radiation. For example, neither of the carbon-carbon
bonds in ethene or ethyne absorb IR radiation.

Over time organic chemists have recorded and catalogued the types and
locations of IR absorptions produced by a wide variety of chemical bonds
in various chemical environments. These data can be quickly referenced
through tables of IR absorption ranges and compared to the spectrum
under consideration.

Tables of IR absorptions are arranged by functional group -- it some

versions these may be further subdivided to give more precise
information.

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 Table of IR Absorptions

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 Infrared Spectral Interpretation
This involved 10 steps
1. Use quality data.
The better the spectrum, the more accurate the
analysis.
Try to do some purification or software methods to
improve the appearance of a spectrum

2. Avoid mixtures (if possible)

3. Use other knowledge of the sample

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4. Read the spectrum quickly from left to right noting the presence or
absence of the following intense group wavenumbers.
Band Position in cm-1 Functional Group
3500-3200 X-H ( O-H or N-H)
3200-2800 C-H
X=Y (C=C, C=N)
2250-2000

1800-1600 X=Y (C=O)

less than 1000 X=Y (C=C, benzene rings)

5. Assign the intense bands

6. Track down the secondary bands of the functional groups whose
presence suspect based on evidence gathered in steps 4 and 5.
7. Assign other bands as needed
8. Write down the functional groups you think exist in the sample
9. Get help from spectral database, library searching or interpretation
software.
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 Infrared Peak Intensities and
Widths
Peak intensities are useful in infrared spectral interpretation
because it can distinguish between the spectra of different
functional groups .

It is also used to determine the concentration of molecules in

the sample.

Peak intensities are determined by the vibration of the

molecules.

Different functional groups give rise to bands with different

peak widths and this property can be used to distinguish
between them.
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 Example 1

molecular wavenumber wavelength

vibration (cm-1) (m)
C-Cl 700-800 14.3-12.5
C-C 750-1100 13.3-9.1
C-O 1000-1300 10-7.7
C=C 1610-1680 6.2-6.0
C=O 1670-1750 6.0-5.7
O-H (acids) 2500-3300 4.0-3.0
C-H 2850-3300 3.5-3.0
O-H (alcohols) 3200-3550 3.1-2.8
N-H (primary
3350-3500 3.0-2.9
amines)

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 (1) The infrared (ir) spectrum of hexane, CH3CH2CH2CH2CH2CH3.
Bond types present
- C-H stretches
(2850-3300 cm-1)

(2)The infrared (ir) spectrum of 1-hexene, H2C=CHCH2CH2CH2CH3.

Bond types present
- C-H stretches
(2850-3300 cm-1)
-C=C stretches
(1610-1680 cm-1)

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 (3) The infrared (ir) spectrum of ethanol, CH3CH2OH.
Bond types present
- O-H (alcohol) stretches
(3200-3550 cm-1)
- C-H stretches
(2850-3300 cm-1)

(4) The infrared (ir) spectrum of octanal

Bond types CH3CH2CH2CH2CH2CH2CH2CH
present ||
- C-H stretches O
(2850-3300 cm-1)
- C=O stretches
(1670-1750 cm-1)

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 (5) The infrared (ir) spectrum of 2-pentanone,
CH3CH2CCH2CH3
ll
O

Bond types present

-C-H stretches
(2850-3300 cm-1)
-C=O stretches
(1670-1750 cm-1)

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 Capabilities of Infrared Analysis
Identification and quantization of organic solid, liquid or gas
samples.
Analysis of powders, solids, gels, emulsions, pastes, pure
liquids and solutions, polymers, pure and mixed gases.
Infrared used for research, methods development, quality
control and quality assurance applications.
Samples range in size from single fibers only 20 microns in
length to atmospheric pollution studies involving large areas.

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 Applications of Infrared Analysis
Pharmaceutical research
Forensic investigations
Polymer analysis
Lubricant formulation and fuel additives
Foods research
Quality assurance and control
Environmental and water quality analysis
methods
Biochemical and biomedical research
Coatings and surfactants
Etc.

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 Advantages of Infrared spectroscopy
It is an universal technique and inexpensive.

Infrared spectra are information rich; the peak position, intensities, widths
and shapes in a spectrum all provide useful information.

Relatively fast and easy technique. Normally, the result can be obtained
within 5 minutes.

Better sensitivity and brightness

- Allows simultaneous measurement over the entire wavenumber range
- Requires no slit device, making good use of the available beam

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High wavenumber accuracy
- Technique allows high speed sampling with the aid of laser light
interference fringes
- Requires no wavenumber correction
-Provides wavenumber to an accuracy of 0.01 cm-1

Resolution
- Provides spectra of high resolution

Stray light
- Fourier Transform allows only interference signals to contribute to
spectrum.
Background light effects greatly lowers.
-Allows selective handling of signals limiting intreference

Wavenumber range flexibility

- Simple to alter the instrument wavenumber range

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 Disadvantages of Infrared Spectroscopy
Not well suited for certain samples. The sample must contain chemical
bonds to have an infrared spectrum. The presence of the functional
groups is a must. Atoms or monoatomic ions do not have infrared
spectra. Such as Helium, argon and Pb2+ dissolved in water do not have
infrared spectra.

Molecules consist of two identical atoms, such as and

(homonuclear diatomic)do not absorb infrared radiation.

If the samples composition is complex, spectrum will be complex and it

will be hard to know which infrared bands are due to which molecules.

Aqueous solutions are difficult to analyze. Infrared spectroscopy is not

used to analyze trace amounts of material dissolved in water.
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