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Infra red

Spectroscopy
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Selection Rules
Polar Molecules (Water) and molecules
whose polarity changes (Carbon Di Oxide)
are IR active
V = 1

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Number of Vibrations
The number of fundamental vibration can be
calculated as followed:
Linear poly atomic exhibits 3N5 vibrations
Non linear molecules can exhibit 3N6 vibrations
N is the number of atoms in a molecule

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Vibrations in Water molecule


Polar So IR Active
Non linear therefore 3N6 vibrations are
possible
3(3) 6 = 9 6 = 3 possible vibrations
Usually Two stretching and one bending
occurs
Stretching both sym. and asym.
Bending wagging occurs
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Stretching (Water Molecule)


Symmetric

Asymmetric

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In plane
Rocking

Scissoring

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Out of plane
Wagging

Twisting

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Vibrations of water molecule


Symmetrical Stretching

Wagging

Asymmetrical Stretching

% Transmission Vs Wave number


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Vibrations in Carbon Di Oxide


molecule
Non Polar However polarity changes on IR
absorption hence IR active
Linear therefore 3N5 vibrations are
possible
3(3) 5 = 4 ( a maximum of 4 , however it
is not necessary that all 4 should occur.
Only vibrations that brings about a change
in dipole occurs others do not occur)
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IR - CO2 Stretching Vibrations


Asymmetric ( IR
Active)

Symmetric (IR inactive)

symmetric no change in dipole IR


inactive
asymmetric Change in dipole IR active
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IR CO2 Bending Vibrations


Vertical (out plane active)

Horizontal (in plane inactive)

In- plane bending :No change - IR inactive


Out plane : Dipole changes IR active

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IR Spectrum Of CO2

% Absorption Vs Wave number


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IR Instrumentation
and
Applications

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IR - Instrumentation
There are Three basic components in an Infra
red Spectrophotometre
A stable Source of radiant energy
A monochromator for isolating a desired
narrow region of IR radiation ( single wave
length)
A detector for measuring the transmitted
radiation.
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Block Diagram of IR Spectroscopy

Source Lamp

Wavelength
Selector
(Monochromator)

Sample

Detector

Signal Processor
and Readout

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Sources
Inert solid , electrically heated to 15001500-2200K
Commonly used sources Electrically heated
Nernst Glower (Rare
(Rare earth oxides )
Globar Source (Silicon
(Silicon carbide rod)
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Special sources
Tungsten Filament Lamp
Used in nearnear-IR region of 4,0004,000-12,800 cm-1

Mercury Arc
- Used in Far IR region
CO2 Laser (tunable)
- Used to monitor atmospheric conditions
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Monochromator
Glass and Quartz absorb very strongly
beyond 4 micro metre.
Hence cannot be used as monochromator
or cell material in IR region
Alkali halides (NaCl / KBr / NaBr) do
not absorb in IR region.
Hence prisms made up of these materials
are used as monochromators
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Cells
The most commonly used cells are made
from NaCl , as it is transparent to IR and
inert towards the analyte
NaCl is highly hygroscopic and after every
use cell has to be washed with CHCl3 and
dried with a stream of dry nitrogen.
Should always be kept in a dessicator

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Infrared Detectors
Thermocouples (Thermocouples are a
widely used type of temperature sensor and
can also be used to convert heat into electric
power)
Bolometres (A very sensitive device for
detecting and measuring small amounts of
thermal radiation and radiant energy
It is used specifically to IR in presence of MW )
A highly sensitive device called thermopile is
used in modern instruments
(themopile is an array of thermocouples)
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Applications of IR Spectroscopy
It is the only method known for
detecting toxic chemicals and
explosives enclosed in a sealed
container made of plastic, paper
and materials other than metals ie
non conducting containers.
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Qualitative Tool
Each functional group shows typical
absorption pattern. Hence this is very helpful
in establishing the structure of an organic
compound.
For ex. Ketone carbonyl shows strong
absorption at 1720 -1740 cm-1 irrespective of
whether it is aliphatic or aromatic ketone.

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Very useful in determining the


position isomers
IR spectrum of super imposable
isomers are also super imposable

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Useful Data
Molecular symmetry
Dipole moments
Bond length etc.,

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Quantitative Tool

The Presence of impurity


can be easily identified by
comparing IR spectrum of
pure and impure samples.
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IR Spectrum of Cocaine

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Spectrum of a Single Grain of a


Suspected Drug in coke (cocaine
(cocaine))

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Other Applications

Presence of intra and inter


molecular hydrogen
bonding can be
established.
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Atmospheric monitoring

Pollutants like CO
-1
(2170 cm ) and HC
-1
(3000 2800cm ) in air
samples can be
determined.
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IR spectrum of each molecule is unique, hence it can


serve as a signature or fingerprint to identify the
molecule. This feature, along with the fact that it is a
non--destructive technique, have made infrared
non
spectroscopy a valuable method in chemical analysis.
Areas in which it is used extensively include
pharmaceutical analysis, quality control in industrial
processes, environmental chemistry, geology and
astronomy.
One difficulty, however, is that the infrared (IR)
spectra of molecules with more than a few atoms can
be very complicated
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