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INFRA RED

PRESENTATIO
N

INTRODUCTION
Infrared spectroscopy (IR
spectroscopy) is the subset of
spectroscopy that deals with the
infrared region of the
electromagnetic spectrum. It covers
a range of techniques, the most
common being a form of
absorption spectroscopy. As with
all spectroscopic techniques, it can
be used to identify compounds or

The infrared portion of the


electromagnetic spectrum is divided
into three regions
Near infra red-0.8 to 2.5m (128004000cm-1)
Middle infrared-2.5 to 50m (4000200)
Far infrared- 50 to 1000m (200 to
10)
Mostly used is from 4000 to 670

At 0degrees kelvin the atoms of a molecule


are still vibrating
Vibration within infra red region
If radiated with infra red radiation of
apprioprate wavelength energy is absorbed
Leads to increase in vibrations and amplitude
Change in dipole moments of the molecule.
Spectrometer then measures the energy
absorbed at different wavelengths or wave
numbers to give a spectrum.

Vibrations can result from stretching


bonds
Can also be by bending or
deformation of bonds.
Some molecules are infrared inactive
eg. ethene.
Most functional groups due to
stretching.

PRINCIPLE

I.R deals with vibrational energy


inherent in a molecule.
Increase in the vibrational energy of
either a bond or a functional group
Frequency of vibration directly
proportional to the strength of the
spring but inversely proportional to
the masses of the atoms connected
to the spring-Hookes Law

Types of vibrational modes


Stretching and bending
Stretching can be symmetrical or assymetrical
Bending can either be
rocking,wagging,scissoring and twisting
Vibrational modes should cause a change in
the dipole moment of the bond in order to be
I.R active
Intensity of the absorption bands are
proportional to the change in dipole moment
that the bond undergoes when it stretches

Factors affecting stretching


vibration frequencies

Bond strength
Mass of atoms
Hydrogen bonding
Electronegative atoms
Conjugation

Interpretation of spectrum
Between 3650-3100per cm,the
functional groups OH and NH
appear
Around 1700per cm,the C=O absorbs
I.R radiation
Around 1600per cm,the C=C
stretching of unsymmetrical alkenes
and aromatics and carbon nitrogen
stretching occurs at this
wavenumber

Interpretation of
spectrum(contd)
The fingerprint region is
characteristic of the molecule as a
whole and is observed between
1500-650per cm.

PROCEDURE

Sample preparation
Gaseous samples require little
preparation beyond purification, but
a sample cell with a long pathlength
(typically 5-10cm) is normally
needed, as gases show relatively
weak absorbances.

Liquid samples can be sandwiched between


two plates of a high purity salt (commonly
sodium chloride, or common salt, although a
number of other salts such as
potassium bromide or calcium fluoride are
also used). The plates are transparent to the
infrared light and will not introduce any lines
onto the spectra. Some salt plates are highly
soluble in water, so the sample and washing
reagents must be anhydrous (without water).

Solid samples can be prepared in


four major ways. The first is to crush
the sample with a mulling agent
(usually nujol) in a marble or agate
mortar, with a pestle. A thin film of
the mull is applied onto salt plates
and measured.

The second method is to grind a


quantity of the sample with a
specially purified salt (usually
potassium bromide) finely (to remove
scattering effects from large
crystals). This powder mixture is then
crushed in a mechanical die press to
form a translucent pellet through
which the beam of the spectrometer
can pass

The third technique is the Cast Film technique,

which is used mainly for polymeric materials.


The sample is first dissolved in a suitable, non
hygroscopic solvent. A drop of this solution is
deposited on surface of KBr or NaCl cell. The
solution is then evaporated to dryness and the
film formed on the cell is analysed directly. Care
is important to ensure that the film is not too
thick otherwise light cannot pass through. This
technique is suitable for qualitative analysis.

The final method is to use microtomy


to cut a thin (20-100 micrometre)
film from a solid sample. This is one
of the most important ways of
analysing failed plastic products for
example because the integrity of the
solid is preserved

It is important to note that spectra


obtained from different sample
preparation methods will look slightly
different from each other due to
differences in the samples' physical
states

INSTRUMEINTATION
we will be limiting our attention to
instrumentation concerned with
spectroscopy in the middle region
(4000 - 200cm-1). It is absorption in
this region which gives structural
information about a compound

Light from the IR source is reflected from a mirror, through the

reference cell, through an attenuator system and onto a second


mirror. The beam is attenuated by interposing a device that
removes a continuous, but controllable fraction of the light from
the reference beam. The attenuator usually takes the form of a
comb, the teeth of which are cut so that the amount of light
attenuated is linearly related to the lateral movement of the
comb through the beam. After passing through the attenuator to
the second mirror, the attenuated light passes through a chopper
to a grating, where light of a specific wavelength is selected and
passes to an IR sensor. A second beam of light from the source is
reflected through the sample cell by a plane mirror and then, by
means of another mirror, also passes through the chopper to the
grating and then to the IR sensor.

The chopper arranges for the sensor to alternately receive light that has
been transmitted through the cell, and light that has passed through
the attenuator. The servo system of the attenuator adjusts the light
transmission until both beams have the same intensity. The amount of
light that is absorbed is indicated by the position of the attenuator.
More simply, the amount of light of the chosen wavelength which is
absorbed by the sample, is measured by attenuating the reference
beam until its intensity is equivalent to that of the beam transmitted
through the sample. The resolution is controlled by the width of the slit
which is adjustable. In the older versions of this type of IR spectrometer,
an analog plotter, mechanically associated with the attenuator,
recorded the spectrum. Even if modified to provide an output that is
proportional to absorption, the big disadvantage of this type of
spectrometer for use in combined systems is its very slow rate of
scanning.

SOURCES

An inert solid is electrically heated to a

temperature in the range 1500-2000 K. The


heated material will then emit infra red radiation
The Nernst glower mixture of oxides of

zirconium, yttrium and thorium. Platinum wires


are sealed to the ends, and a current passed
through the cylinder. The Nernst glower can
reach temperatures of 2200 K.

The Globar source- a small rod of silicon carbide


which is electrically heated to about 1500 K. Water
cooling of the electrical contacts is needed to
prevent arcing. The spectral output is comparable
with the Nernst glower, execept at short
wavelengths (less than 5 mm) where it's output
becomes larger.
The incandescent wire source is a tightly wound
coil of nichrome wire, electrically heated to 1100 K.
It produces a lower intensity of radiation than the
Nernst or Globar sources, but has a longer working
life.

DETECTORS
Thermocouples consist of a pair of junctions of

different metals; for example, two pieces of


bismuth fused to either end of a piece of
antimony
Pyroelectric detectors made from a single

crystalline wafer of a pyroelectric material, such


as triglycerine sulphate. Most developed
detector and have a fast response time. They are
used in most Fourier transform IR instruments.

Photoelectric detectors- mercury


cadmium telluride detector , lead
sulphide photon detector. These
detectors have better response
characteristics than pyroelectric
detectors and are used in FT-IR
instruments

MONOCHROMATORS
May be either a prism or grating.
Most common prisms material is
NaCl (transparent from 4000-650cm1). Suffers from low resolution
KBr may be used (extends range to
400)
Other CsBr, CsI

Gratings are now preffered as they


give better resolution at high
frequency than prisms. If used filter
req. as the prism reflects or allows
various radiations.

types
Dispersive infra red spectophotometers
These are often double-beam recording
instruments, employing diffraction gratings for
dispersion of radiation.
Radiation from the source is flicked between the
reference and sample paths. Often, an optical null
system is used. This is when the detector only
responds if the intensity of the two beams is
unequal. If the intensities are unequal, a light
attenuator restores equality by moving in or out of
the reference beam. The recording pen is attached
to this attenuator

Fourier transform infrared (FTIR)


spectrophotometer is a measurement
technique for collecting infrared spectra.
Instead of recording the amount of
energy absorbed when the frequency of
the infra-red light is varied
(monochromator), the IR light is guided
through an interferometer. After passing
through the sample, the measured signal
is the interferogram. Performing a
mathematical Fourier transform on this
signal results in a spectrum identical to
that from conventional (dispersive)
infrared spectroscopy.

Adv.
Improved frequency resolution
Improved frequency reproducibility (older
dispersive instruments must be recalibrated for
each session of use)
Higher energy throughput
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)

MODERN
ADVANCEMENT

THERMO NICOLET NEXUS 670 FTIR Spectrometer

NEXUS 670 FTIR Spectrometer with


Thermo-Nicolet microscope

OUTGAS 6 FTIR

The M500 Quick Scan I.R


Spectrophotometer

APPLICATION
IDENTITY
Substances that give the same IR Spectra are

identical,however although IR Spectrum is


unique for any given chemical compound,there
is the exception of optical isomers,which have
identical spectra.

A collection of reference spectra for


use with monographs as published in
the British Pharmacopoeia(BP)helps
in verifying identity of drugs or drug
products

CONFIRMATON OF IDENTITY
Most IR Spectra especially in the fingerprint
region(1500-650) contain some considerable
detail and direct comparison of two spectra
which have been recorded under the same
sampling conditions offers one of the most
reliable ways of examining the identity or
unidentity of two samples

Detection of IMPURITIES
IR may prove to be useful if only the
impurity absorbs strongly in a
regionwhere the main component is
reasonably transparent eg.
Adrenalone in adrenaline

Recognition of functional
groups
The IR Spectrum is capable of yielding

considerable information about the


bonds present in a molecule.
Since functional groups have vibrational

groups,within well defined regions of


this range

Recog cont
This makes IRSpectrum the

SIMPLEST,most RAPID and often most


RELIABLE means for assigning a
compound its class,thus contributing to
structure elucidation of organic molecules.

QUANTITATIVE ANALYSIS
The application of IR for quantitative
analysis has diminished with the
advent of newer techniques such as
Gas Chromatography,HPLC,NMR and
Spectrofluorimetry.

Quantitative cont
The quantitative analysis is based on
the fact that the intensity or depth of
an absorption band in a substances
is reflected to the concentration of
the material associated with that
band

QUANTITATIVE ANALYSIS
CONTD
For solutions (of drug formulations)
the Beer Lamberts law holds and
since the IR Spectrophotometers
measures band intensities linearly in
%T and therefor log.in Absorbance,A.

cont
A plot of Absorbance against concentration
for a series of standards using a calibration
curve, the absorbance of the unknown can
be measured and the curve used to read
the concentration and vice versa.eg
determination of amount of
phenobarbitone in phenobarbitone tablets.

QUANTITATIVE CONTROL OF
CHEMICAL RXN AND SEPARATION
IR provides a convenient and simple method
for checking each stage of synthesis or for
monitoring Chromatographic Separation or
progress of organic reactions especially if
they involve suitable spectral changes
eg.include the oxidation of a secondary
alcohol(3570cm-1) to ketone (1725cm-1)and
chromatographic separation of a 5membered-ring ketone(1750cm-1)and a 6memberedisomer(1750cm-1)