M.Sc. Part I 1.3 INFRARED SPECTROPHOTOMETRY PPT.ppsx

INFRARED ABSORPTION SPECTROSCOPY
Syllabus
Instrumentation,
FTIR,
Advantages of FTIR,
Applications of IR,
Qualitative and quantitative analysis,
 Advantages and limitations of quantitative IR
methods.
2

INTRODUCTION:
• Infrared Spectroscopy is a powerful tool for
identifying pure organic and inorganic
compounds with the exceptions of few
molecular compounds such as O2, N2, and Cl2.
At temperature above absolute zero, all atoms
in molecules are in continuous vibration with
respect to each other .When the frequency of
specific vibrations are equal to the frequency
of the IR radiation directed on the molecule,
the molecules absorb IR radiation.
3

Infrared region
Near-infrared
(overtone region)
0.8-2.5 um
(12 500-4000 cm -1);
Middle infrared
(vibration-rotation
region)
2.5-50 um
(4000-200 cm -1);
Far-infrared
(rotation region)
50- 1000 um
(200-10 cm-1).
4

A molecule when absorb IR
radiation it undergoes
vibrations due to
Bonds may stretch
back and forth
Bonds may rotate
Bonds may bend
and flex
Groups on atoms
may “wag” and
“scissor
The molecule may
rotate and vibrate
in other ways
5

What is vibration
For a C-C bond with a bond
length of 154 pm, the
variation is about 10 pm.
For C-C-C bond angle a
change of 4o is typical.
This moves a carbon atom
about 10 pm.
4o 10
pm
10 pm
154 pm
stretching vibration
bending vibration
6

For a C-C bond with a bond
length of 154 pm, the
variation is about 10 pm.
Bond length 154 pm,
10 pm.
7

C
C
C
4o
10 pm
8
For C-C-C bond angle a change of 4o is typical. This moves a carbon atom about
10 pm.

How does the mass influence the vibration?
H2
I2
MM =2 g/mole
MM =254 g/mole
The greater the mass - the lower the wave number
9

10
Instrumentation
Radiation
source
Sample
handling
Detector Recorder

Radiation source:
• The various sources of radiation source are used
in I.R.
• Nernst Glower: A Nernst glower is heated to
1500-2000oc to get infrared radiation. Nernst
glower is a rod containing a mixture of
zirchonium,yttrium and erbium oxides. Platinum
leads are sealed into two ends of rods. The
Nernst Glower is 2 cm long and has diameter of
1.5 mm.Its IR output decreases with
temperature.
11

Glober Rod:
• The Glober rod is silicon carbide rod(SiC) which
on heating to 15000C emits IR radiation. Its
disadvantage is that SiC gets easily oxidized
hence it has shorter life than Nernst Glower;
However its advantage is that Its IR output
increases with increase in temperature.
12

Carbon dioxide Laser Source:
• For measurements in the middle-infrared region, 2.5-
50 PM, there are several differences between the
instruments used for UV/visible Spectrophotometry
and those designed for infrared determinations. These
changes are mainly dictated by the fact that glass and
quartz absorb strongly in the infrared region and
photomultipliers are insensitive to the radiation. Front-
surfaced mirrors are largely employed to avoid the
necessity of radiation passing through glass or quartz
layers as reflection from metallic surfaces is generally
very efficient in the infrared region. But absorption
cells and windows must be fabricated from infrared
transparent materials.
13

Sample Cells:
• 2 a) Sample Cells:
• The sample cells of metal halide like NaCl and
KBr are generally used.
• Quartz and glass are not used because it
absorbs strongly in IR region.
14

2 b) Sample Handling System:
• The solvent used for preparation of sample
solution should not absorb IR radiation.
• All solvents are dried to remove moisture before
used.
• Solvents commonly used in IR studies are hexane,
Chloroform, carbon tetrachloride, Dioxane,
carbon disulphide, ethanol ,methanol and in rare
case benzene.
• The solution concentration range from0.1% to
10%.
15

Sample handling and preparation
• Gaseous sample: Gaseous sample are taken in
10 cm long cells provided with NaCl windows
which are transparent to IR radiation.
• Liquid samples are pressed between two NaCl
plates which are held together by capillary
16

Sampling cuvettes for a) gaseous and b) liquid samples
17
Gaseous Sample Liquid samples

For Solid samples following two methods are
used .
KBr Pallet Method: An alkali halide (AR Grade ) KBr
pallet is prepared by grinding 1 mg of sample with 100-
200 mgs of KBr.
The pallet is dried to remove moisture and pressed
under high pressure into small transparent disc of 10
mm and thickness 1-2 mm.
The disc can directly used in sampling area of the
spectrophotometer.
Mull Method: A mull is prepared by grinding 5 mgs of
sample of solid sample with few drops of mulling oil.
The mulling oil commonly used is is high boiling
petroleum oil called nujol.
The mull is then pressed between two NaCl windows.
18

Solid sample:
Die assembly for making KBr pellets
19

Detector:
• The various detectors used in IR spectroscopy
are as ;
 Thermocouple
 A bolometer
 The Golay pneumatic detector
20

The Thermocouple:
• The Thermocouple: It is made by welding together
two wires of metals 1 and 2 in such a manner that a
segment of metal 1 is connected to two terminal wires
of metal 2. One junction between metals 1 and 2 is
heated by the infrared beam, and the other junction is
kept at constant temperature: small changes in
ambient temperature are thus minimized. To avoid
losses of energy by convection, the couples are
enclosed in an evacuated vessel with a window
transparent to infrared radiation. The metallic
junctions are also covered with a black deposit to
decrease reflection of the incident beam
21

A Bolometer:-
• A bolometer is essentially a thin blackened platinum
strip in an evacuated glass vessel with a window
transparent to the infrared rays: it is connected as one
arm of a Wheatstone bridge, and any radiation
absorbed raises the temperature of the strip and
changes its resistance. Two identical elements are
usually placed in the opposite arms of a bridge; one of
the elements is in the path of the infrared beam and
the other compensates for variations in ambient
temperature. Both the above receptors give a very
small direct current, which may be amplified by special
methods to drive a recorder.
23

The Golay Pneumatic Detector
 It is sometimes used, consists of a gas-filled chamber which
undergoes a pressure rise when heated by radiant energy.
 Small pressure changes cause deflections of one wall of the chamber,
this movable wall also functions as a mirror and reflects a light beam
directed upon it to a photocell, the amount of light reflected bearing
a direct relation to the gas-chamber expansion, and hence to the
radiant energy of the light from the monochromator.
 This detector responds to the total light energy received as distinct
from energy received per unit area (thermocouples and bolometers).
 When infrared radiation is incident on the detector there is a change
in polarisation which can be employed to produce an electrical signal.
The detector will only produce a signal when the intensity of the
incident radiation changes.
 These detectors are of especial value in FT-IR where rapid response
times are needed and for this purpose they use deuterium triglycine
sulphate as the detecting medium in an evacuated chamber.
24

• In FT IR instruments, Instruments collect the
response at all the wavelengths simultaneously. In
these multiplex instruments the monochromator is
replaced by an Interferometer and the response of
the sample to the whole range of IR radiation is
suitably modulated and collected in the time domain.
• These are then decoded using the Fourier
transformation. Therefore it is named the Fourier
transform infra red spectrometer (FT-IR).
• The basic instrument design for an FT-IR instrument is
quite simple. A schematic diagram showing different
components is given in Fig.
• The IR radiation from the source is first directed into
an interferometer from where it is passed through
the sample compartment and then it reaches to the
detector.
25

Interferometers as wavelength
selector In FTIR Spectroscopy:
• A device that allows all wavelengths of light to be measured
simultaneously, eliminating the need for a wavelength selector
interferometer simultaneously allows source radiation of all wavelengths
to reach the detector. Radiation from the source is focused on a beam
splitter that transmits half of the radiation to a fixed mirror, while
reflecting the other half to a movable mirror.
• The radiation recombines at the beam splitter, where constructive and
destructive interference determines, for each wavelength, the intensity of
light reaching the detector.
• As the moving mirror changes position, the wavelengths of light
experiencing maximum constructive interference and maximum
destructive interference also changes.
• The signal at the detector shows intensity as a function of the moving
mirror’s position, expressed in units of distance or time. The result is
called an interferogram, or a time domain spectrum. The timedomain
spectrum is converted mathematically, by a process called a Fourier
transform, to the normal spectrum (also called a frequency domain
spectrum) of intensity as a function of the radiation’s energy
27

28
Qualitative Applications
The most important qualitative application of the mid-IR
spectrometry is in the determination of the structures of
organic and biochemical species.
It is achieved in an empirical method wherein the signals
in the IR spectra are identified with the help of
correlation tables (briefly discussed below). Besides
structure determination, we shall discuss how the IR
spectra can be used in establishing the identity of a
molecule? And also, how does it help in monitoring the
progress of a reaction?

Structure Elucidation of Organic
Molecules by IR Spectra
• For structure determination of organic molecules, the
infrared spectrum can be broadly divided into two regions.
• The region spanning from 3600 to 1200 1 cm− is called the
functional group region
• The region that includes all frequencies below 1200 cm-1
is called the fingerprint region.
• The two regions put together are important in the
determination of the identity of a molecule.
• It is almost impossible to assign all the possible frequencies
observed in the IR spectrum. However, identification of the
• characteristic features in the functional group region that
includes stretching vibrations, of typical functional groups
found in organic molecules, is quite important.
29

Quantitative analysis :
• Infrared spectra are recorded using either or
both absorbance and percentage transmission
just as they are in visible/ultraviolet electronic
spectra, and the Beer-Lambert relationship:
• for a mixture of compounds the observed
absorbance at a particular wavelength (or
frequency) will be the sum of the absorbances
for the individual constituents of the mixture
at the wavelength:
30

2) Calibration Curve Method:
31

Standard addition methods:
These are not widely applied in quantitative infrared
spectrophotometry, being limited to determinations of low
concentration components in multicomponent mixtures.
The solutions are made from a series of increasing
concentrations of the pure analyte (similar to a normal
calibration graph set of concentrations) but to each is
added a constant, known amount of the sample containing
the unknown concentration. All the solutions are diluted to
a fixed volume and their absorbance’s measured in a fixed-
path-length cell by scanning over the chosen absorption
band.
A plot of the absorbance against the concentration of the
pure analyte does not pass through zero as all the
absorbance values are enhanced by an equal amount due
to the presence of the unknown concentration in the added
sample. Extrapolation of the graph back to the abscissa (the
horizontal axis) gives the concentration of the unknown as
a negative value (Graph)
33

Other Miscellaneous applications:
• i) IR spectroscopy is widely used in both research and industry
as a simple and reliable technique for measurement, quality
control and dynamic measurement.
• ii) IR spectroscopy has been highly successful for applications
in both organic and inorganic chemistry.
• iii) By measuring at a specific frequency over time, changes in
the character or quantity of a particular bond can be
measured. This is especially useful in measuring the degree of
polymerization in polymer manufacture.
• iv) IR spectroscopy is useful for identifying substances and
confirming their identity. Therefore it also has a forensic
purpose: with the use of IR spectroscopy alcohol, drugs, fibers
and paint could be analyzed.
35

• v) IR spectroscopy has also been successfully
utilized in the field of semiconductor
microelectronics:
• for example, this technique can be applied to
semiconductors like silicon, gallium arsenide,
gallium nitride , zinc selenide, amorphous
silicon, and silicon nitride.
• vi) Techniques have been developed to assess
the quality of tea-leaves using IR spectroscopy.
36

Advantages of quantitative IR methods.
1) Any sample in any state can be studied.
2) Liquid sample solutions ,pastes powders, films
fibres, gases and surfaces can be examined with
judious choice of sampling technique.
3) Application of IR spectroscopy varies from
laboratory to laboratory to other.
4) Quanitative analysis is based on Beers Lamberts
Law.
5) Apparent deviations arises from either chemical
or instrumental defects.
37

5) The baseline technique involves selection of
an absorption band of the substance under
analysis.
6) The transmittance speed is measured at
point of maximum absorption.
7) The value of Po is plotted against
concentration
8) Many possible error are eliminated by base
line technique.
9) The same cell is used for all determination
38

limitations of quantitative IR methods.
1) Molecular weight of substance is not
determined by this technique.
2) It is frequently non-adherence to Beers Law
of Complexity spectra.
3) Narrowness of spectra and effect of stray ray
radiations make the measurements of
absorbance upon slit width and wavelenght
setting.
39

4) Generally IR spectroscopy does not provide
information of the relative positions of
different functional groups in a molecule.
5) From single IR spectrum of an unknown
substance ,It is not possible to know whether
pure compound or mixture of compound,For
Ex. Mix. Of parafin and alcohol will give the
same IR spectra as high molecular weight of
alcohol.
40

M.Sc. Part I 1.3 INFRARED SPECTROPHOTOMETRY PPT.ppsx

More Related Content

Similar to M.Sc. Part I 1.3 INFRARED SPECTROPHOTOMETRY PPT.ppsx (20)

Recently uploaded (20)

M.Sc. Part I 1.3 INFRARED SPECTROPHOTOMETRY PPT.ppsx