You are on page 1of 32

INFRARED

SPECTROSCOPY

INFRARED SPECTROPHOTOMETER

Classification of analytical
techniques
1.Separation techniques Chromatography
2.Spectrophotometric SPECTROSCOPY
3. Electro analytical

Potentiometry,conductometry
4. Titrimetric analysis Titrations

SPECTROSCOPY
Spectroscopy is the branch of science deals

with the study of interaction of


electromagnetic radiation with matter.
Electromagnetic radiation is a type of energy
that is transmitted through space at enormous
velocities.
EMRANALYTESPECTROPHOTOGRAPH

concentration should be lower

IR SPECTROSCOPY
INTRODUCTION
Infrared spectroscopy (IR) measures the bond
vibration frequencies in a molecule and is
used to determine the functional groups.
The infrared region of the spectrum
encompasses radiation with wave numbers
ranging from about 12,500 to 50cm-1 (or)
wave lengths from 0.8 to 200.
Infrared region lies between visible and
microwave region.

The infrared region constitutes 3 parts


a) The near IR (0.8 -2.5m) (12,500-4000cm-1)
b) The middle IR (2.5 -15m) (4000-667cm-1)
c) The far IR (15-200m) (667-50cm-1)
most of the analytical applications are confined to the

middle IR region because absorption of organic


molecules are high in this region.
Wave number is mostly used measure in IR absorption
because wave numbers are larger values & easy to
handle than wave length which are measured in m.

E = h = hc/ = hc
It gives sufficient information about the structure of a
compound.

PRINCIPLE OF IR SPECTROSCOPY
The absorption of infra red radiation excitation of

molecule.
Vibrational transitions which are accompanied by a
change in dipole moment of the molecule are
called infrared active transitions. Because they
absorb the ir region.
Atoms or groups of atoms are connected by
bonds. These are non rigid in nature.
Due to continuous motion of the molecule they
maintain vibration with frequency.
Applied frequency = natural frequency of vibration

MOLECULAR
VIBRATIONS
There are 2 types of vibrations.
1) Stretching vibrations
2) Bending vibrations
) 1)Stretching vibrations: in this bond length

is altered.
) They are of 2 types
) a) symmetrical stretching: 2 bonds increase
or decrease in length.

b) Asymmetrical stretching: in this one bond length is increased


and other is decreased.

2)Bending vibrations:
These are also called as deformations.
In this bond angle is altered.
These are of 2 types
a) in plane bending scissoring, rocking
b) out plane bending wagging, twisting

Scissoring:
This is an in plane bending.
In this bond angles are decreased.2 atoms

approach each other.

Rocking:
In this movement of atoms takes place in
same direction.

Wagging:
It is an out of plane bending.
In this 2 atoms move to one side of the plane.

They move up and down the plane.

Twisting:
In this one atom moves above the plane and
the other atom moves below the plane.

NUMBER OF VIBRATIONAL MODES


A molecule can vibrate in many ways, and

each way is called a vibrational mode.


If a molecule contains N atoms, total number
of vibrational modes
For linear molecule it is (3N-5)
For non linear molecule it is (3N-6)
Eg: H2O, a non-linear molecule, will have

336=3 degrees of vibrational freedom,


or modes.

FREQUENCY
occurs when atoms in a molecule are in

periodic motion while the molecule as a whole has


constant translational and rotational motion.
The frequency of the periodic motion is known as a
vibration frequency.
The value of stretching vibrational frequency of a
bond can be calculated by the application of hookes
law.
/c = = 1/2c[k/m1m2/m1+m2]1/2
= 1/2ck/
Where, reduced mass
m1&m2 masses of the atoms
k force constant
c velocity of radiation

Factors influencing
vibrational
frequencies
Calculated value of frequency of absorption for

a particular bond is never exactly equal to its


experimental value.
There are many factors which are responsible
for vibrational shifts
1) Vibrational coupling:
) it is observed in compounds containing CH2 &
-CH3.
EG. Carboxylic acid anhydrides
amides
aldehydes

2)Hydrogen bonding:
Hydrogen bonding brings about remarkable

downward frequency shifts.


Stronger the hydrogen bonding, greater is the
absorption shift towards lower wave length
than the normal value.
There is 2 types of hydrogen bonding
a) inter molecularbroad bands
b) intra molecular sharp bands
hydrogen bonding in O-H and N-H compounds
deserve special attention.
Eg: alcohols&phenols
enols & chelates

3)Electronic effects:
In this the frequency shifts are due to electronic

effects which include conjugation, mesomeric effect,


inductive effect.
a) conjugation: conjugation lowers the absorption
frequency of C=O stretching whether the
conjugation is due to ,- unsaturation or due to an aromatic
ring.
b) mesomeric effect: a molecule can be represented
by 2or more structures that differ only in the
arrangement of electrons.
c) inductive effect: depends upon the intrinsic
tendency of a substituent to either release or
withdraw electrons.

INSTRUMENTATION
There are 2 types of infrared

spectrophotometer, characterized by the


manner in which the ir frequencies are handled.
1) dispersive type
2) interferometric type

In dispersive type the infrared light is


separated into individual frequencies by
dispersion, using a grating monochromator.

In interferometric type the ir


frequencies are allowed to interact to produce
an interference pattern and this pattern is then
analyzed, to determine individual frequencies
and their intensities.

The main parts of an IR spectrometer are as

follows
1) IR radiation source
2) monochromators
3) sample cells
4) detectors
Infrared sources:
require a source of IR radiant energy.
The rod is electrically heated to 1500K to produce
IR radiations.
a) Nernst glower or Nernst filament: they are made up of sintered
mixtures of oxides of Zr, Th, Ce, Y, Er, etc.
Used in near IR region.
Intensity of radiation produced is more intense.
Used for detection of carbohydrates & proteins.

b) globar source: made up of silicon carbide.

They are self starters.


used in middle IR region.
used to detect simple functional groups.
C) incandescent lamp: it is made up of
nichrome wire.
used in near IR
instruments.
Has a low spectral
emissivity.
It is heated up to 1100K.
Used to detect complex organic molecules
d) mercury arc: high pressures are used.
used in far IR region.

e) tungsten lamp: they heated up to 3500K

used in mid IR region.


intensity of radiation is mild.
used to detection of organic functionalgrps

MONOCHROMATORS
They convert polychromatic light into mono
chromatic light.
They must be constructed of materials which
transmit the IR.
They are of 3 types.
a) metal halide prisms
b) NaCl prisms
c) gratings

a) metal halide prisms:


prisms which are made up of KBr are used in
the wavelength region from 12-25m.
LiF prisms are used in the wavelength region
from 0.2-6m.
CeBr prisms used in wavelength region from
15-38m.
b) NaCl prisms:
Used in the whole wave length region from
4000-650cm-1.
they have to be protected above 20c because of
hygroscopic nature.
c) gratings:
They offer better resolution at low frequency than prisms.

sample cells
Sample cells made up of alkali halides like

NaCl or KBr are used.


Aqueous solvents cannot be used as they
dissolve alkali halides.
Only organic solvents like chloroform is used.
IR spectroscopy has been used for the
characterization of solid, liquid, gas samples.

detectors
They convert the radiation into electrical signal.
There are mainly 5 types of detectors used in IR.
Thermo couple detectors:
made up of bismuth& antimony coated

by metal oxides. If wires of 2 dissimilar


metals joined head to tail, then a difference
in temperature between head & tail causes
a current to flow in the wire. This current
proportional to the intensity of radiation.
also called as thermopile
detectors.
material should be thermally
active. used in dispersive instruments.
Response time is 30 seconds.
They give responses for all frequencies.

Thermister detectors
These are made up of sintered oxides

of Mn, Co, Ni.


The material sh0uld be thermally
sensitive.
The response time is 4 seconds .

pyro electric detectors


These are made up of TGS, LiTaO3.
They are used in FTIR instruments.
It involves multiple scanning.
Principle involved is electric polarization.

Golay detectors
The material used is CO2.
The material should be

inert in nature.
used in non dispersive IR
instruments.
Response time is 0.01 sec.
Principle involved is
expansion of gases.

Photo conductive
detectors
Photoelectric detectors such as the mercury

cadmium telluride detector comprise a film of


semiconducting material deposited on a glass
surface, sealed in an evacuated envelope.
Absorption of IR promotes nonconducting
valence electrons to a higher, conducting
state.
These detectors have better response
characteristics than pyroelectric detectors and
are used in FT-IR instruments - particularly in
GC - FT-IR.

DISPERSIVE
INSTRUMENTS
These are often double-beam recording

instruments, employing diffraction gratings for


dispersion of radiation.
These 2 beams are reflected to a chopper
which consists of rotating mirror.
It sends individual frequencies to the detector
thermopile.
Detector will receive alternately an intense
beam & a weak beam.
This alternate current flows from detector to
amplifier.

INTERFEROMETRIC INSTRUMENTS
THE MICHELSON INTERFEROMETER:

It is used to produce a new signal of a much lower

frequency which contains the same information as


the original IR signal.
The output from the interferometer is an
interferogram.
Radiation leaves the source and is split.
Half is reflected to a stationary mirror and then back
to the splitter.
The other half of the radiation from the source
passes through the splitter and is reflected back by
a movable mirror. Therefore, the path length of this
beam is variable. The two reflected beams
recombine at the splitter, and they interfere .
interference alternates between constructive and
destructive phases.
The accuracy of this measurement system means
that the IR frequency scale is accurate and precise.

FOURIER TRANSFORM IR
SPECTROMETER
In the FT-IR instrument, the sample is placed between the

output of the interferometer and the detector. The sample


absorbs radiation of particular wavelengths.
An interferogram of a reference is needed to obtain the
spectrum of the sample.
After an interferogram has been collected, a computer
performs a Fast Fourier Transform, which results in a
frequency domain trace (i.e intensity vs wavenumber).
The detector used in an FT-IR instrument must respond quickly
because intensity changes are rapid .
Pyroelectric detectors or liquid nitrogen cooled photon
detectors must be used. Thermal detectors are too slow.
To achieve a good signal to noise ratio, many interferograms
are obtained and then averaged. This can be done in less time
than it would take a dispersive instrument to record one scan.

Advantages of Fourier
transform IR over dispersive IR
Improved frequency resolution
Improved frequency reproducibility (older

dispersive instruments must be recalibrated


for each session of use)
Faster operation
Computer based (allowing storage of spectra
and facilities for processing spectra)
Easily adapted for remote use (such as
diverting the beam to pass through an
external cell and detector, as in GC - FT-IR)