UNIT–II
• IR spectroscopy
• Introduction
• Fundamental modes of vibrations in poly atomic molecules.
• Sample handling.
• Factors affecting vibrations.
• Instrumentation-
• Sources of radiation, wavelength selectors,
• Detectors- Golay cell, Bolometer, Thermocouple, Thermister, Pyroelectric
detector.
• Applications.
IR SPECTROSCOPY
BY [Link]
Molecular Vibrations
Molecules are made up of atoms linked by chemical bonds.
The movement of atoms and bonds are like spring and balls (vibration).
These characteristic vibrations are called as Natural frequency of vibration.
MOLECULAR
VIBRATIONS
Fundamental Non-
Vibrations fundamental
Vibrations
Stretching Bending Over Tones,
Vibration Vibration Combination
Tones,Fermi
Resonance
In-plane Out Of
Symmetric Asymmetric Bending
Plane
Bending
Scissoring Rocking Wagging Twisting
a) Metal halide prisms:
• prisms which are made up of KBr are used in the
wavelength region from 12-25µm.
• LiF prisms are used in the wavelength region from 0.2-
6µm.
• CeBr prisms used in wavelength region from 15-38µm.
b) NaCl prisms:
• Used in the whole wave length region from 4000-
650cm-1.
• they have to be protected above 20•c because of
hygroscopic nature.
c) Gratings:
• They offer better resolution at low frequency than prisms.
SAMPLING CELL AND SAMPLING OF
SUBSTANCES
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.
Sample handling
Bolometer
• A bolometer consists of an absorptive
element, such as a thin layer of metal.
• Most bolometers use semiconductor or
superconductor absorptive elements rather
than metals.
Thin layer of
metal Any radiation on
connected to the absorptive
element raises its The
a reservoir temperature temperature
above that of the change can be
reservoir. measured
directly with an
attached
thermometer.
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.
• Thermopile detectors are voltage-generating
devices, which can be thought of as miniature
arrays of thermocouple junctions.
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, triglycerine sulphate
• They are used in FTIR instruments.
• It involves multiple scanning.
The Principle involved
• properties is electric
of a pyro electric polarization.
material are such that when an
electric field is applied across it, electric polarisation occurs
(this happens in any dielectric material).
In a pyroelectric material, when the field is removed, the polarisation persists.
The degree of polarisation is temperature dependant. So, by sandwiching the pyroelectric
material between two electrodes, a temperature dependant capacitor is made.
The heating effect of incident IR radiation causes a change in the capacitance of the material.
Pyroelectric detectors have a fast response time.
Golay detectors
• The material should be
inert in nature.
• used in non dispersive IR
instruments.
• Response time is 0.01 sec.
• Principle involved is Metal cylinder and flexible
diaphragm
expansion of gases.
Temperature increases
Gas is expended and diaphragm
Small metal cylinder deforms
Flexible silvered diaphragm
detect as a signal
Whole chamber is filled with xenon gas.
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.
APPLICATIONS:
[Link] of functional group and structural elucidation.
The peaks corresponding to every functional group in the
sample appears in group frequency region –4000-1500 cm-1
which is useful in structural elucidation. Finger print region
is useful in identifying the sample including the isomer.
[Link] estimation:
The structure of the sample can be confirmed if the IR
spectrum of the sample and standard are identical (spectral
matching).
[Link] of impurities in a drug sample.
Impurities give extra peaks in the spectrum when compared
with the spectrum of pure drug thus presence of impurities
can be confirmed.
[Link] study the progress of reaction:
• The disappearance of a characteristic absorption
frequency of a reactant shows the progress of the
reaction. Spectra of samples taken at different time
intervals can be used in studying the progress of
reaction.
[Link] identify and find the ratio of geometrical isomers
(cis, trans) in a mixture
[Link] of tautomers.
[Link] find the shape of symmetry of a molecule.
8. Presence of water in a sample can be identified using
IR spectrum which shows characteristic absorption of
water in 3 regions 3600-3200 cm-1, 1650cm-1, 600-300
cm-1.
[Link] analysis:
• The quantitative estimation of the substance can be determined in pure
form or as a mixture oftwo or more components.
• Two methods are used: 1) cell in cell-out method.2) Base line method.
• In cell-in-cell-out method the unknown concentration of sample is
determined using calibration curve of the standard or using beers law by
the comparison of log I0/It (absorbance) of the standard and sample.
• In baseline method tangents are drawn and I0 and It are measured and
absorbance is plotted against concentration and unknown concentration
is determined.
Applications
• QUALITATIVE ANALYSIS
1. Identification of Substances
2. Determination of Molecular Structure
3. Studying Progress of Reactions
4. Detection of Impurities
5. Isomerism in Organic Chemistry
6. Functional Group Isomerism
7. APPLICATIONS OF IR SPECTROSCOPY TO INORGANIC COMPLEXES
8. Shape of Symmetry of a Molecule
9. Identification of Functional Groups
10. Presence of Water in Sample
QUANTITATIVE ANALYSIS
Based on the determination of one of the functional groups.