INSTRUMENTATION OF

INFRARED SPECTROSCOPY
 Infrared (IR) Spectroscopy

IR deals with the interaction of infrared radiation with matter.

The IR spectrum of a compound can provide important

information about its chemical nature and molecular structure.

Most commonly, the spectrum is obtained by measuring the

absorption of IR radiation, although infrared emission and
reflection are also used.
Widely applied in the analysis of organic materials, also useful
for polyatomic inorganic molecules and for organometallic
compounds.
 INFRARED REGION
NEAR INFRARED or OVERTONE: 1.2 -2.5 m,

MID INFRARED or VIBRATION: 2.5 - 25 m,

FAR INFRARED or ROTATION: 25 - 400 m,

0.78-1000 ɥM

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
Infrared (Mid-IR)
resonance
2.5 m 25 m 1m 5m
200 nm 400 nm 800 nm
BLUE RED
ORGANIC STRUCTURE DETERMINATION

How do we know

How atoms are connected together?

Which bonds are single, double, or

triple?

What functional groups exist in the

molecule? If we have a specific

 INSTRUMENTATIO
N
SOURCE SAMPLE MONOCHROMATOR DETECTOR READOUT

•Nernst Glower Gratin Thermal D

•Globar g Filter Recorder
•Incandescent wire source Thermocouple
•Hg Arc Thermopile
Thermister
Bolometer
Pyroelectric D
1. IR radiation source

Be continuous over the wavelength range

used.

Cover a wide wavelength range.

Be constant over long periods of time.

1. The Nernst Glower
Consist of cylindrical hollow rod or tube having a diameter of
1- 2 mm and length of 30 mm.

sealed by a platinum leads to the ends to permit

electrical connection.

It composed of a mixture of rare earth oxides such as

zirconium oxide (ZrO2), yttrium oxide (Y2O3) and thoria.

They electrically heated to about 2000 °C.

 It provide maximum radiation about 7100cm-1 (1.4 )

its lifetime depends on the operating temperature and the care

taken in handling it
2. The Globar source
It’s sintered silicon carbide rod, usually about 50 mm in length
and 5 mm in diameter

Heated to about 2000 °C.

It provide maximum radiation about 5200cm-1 .

The power consumption is normally higher than that of the

Nernst Glower
Water cooling is needed to cool the metallic electrodes attached
to the rod

Less convenient to use, more expensive & less intense than

Nernst Glower.
4. The Mercury
Arc.
Used for Far IR region (wave no<200cm-1).

It is a high pressure mercury arc which consist of a

quartz - jacketed tube containing Hg vapor at P > 1 atm.

When current passes through the lamp, mercury is

vaporized, excited, and ionized, forming a
plasma discharge at high pressure.

In the UV and visible regions, this lamp emits atomic

Hg emission lines that are very narrow and discrete, but
emits an intense continuum in the far-IR region.
3. Incandescent Wire Source
Lower intensity IR source but longer life than the
Globar or Nernst glower.

A tightly wound spiral of nichrome wire heated

to about 1100 k by an electric current.

A similar source is a rhodium wire heater sealed

in a ceramic cylinder.

Incandescent wire sources are longer lasting but

of lower intensity than the glower or globar.
2. MONOCHROMATORS
A. Prism:-
• Used as dispersive element.
• Constructed of various metal halide salts
• Sodium chloride is most commonly prism salt used.
• These salts are subjected to mechanical & thermal
instability or water solubility.
• Protection against damage must be continuously
exercised.
B. Grating
• Gratings are nothing but rulings made on some
materials like glass, quartz or alkylhalides depending
upon the instrument, The mechanism is that
diffraction produces reinforcement. The rays which
are incident upon the gratings gets reinforced with the
reflected rays.
 Advantages over
Prism:-
Made with materials like aluminium
which are not attacked by moisture.

Used over cosiderable wavelength range.

 3. Sample cell & Sampling of
substance
Infrared spectra may be obtained for gases, liquids or
solids (neat or in solution)

• Material containing sample must be transparent to

the IR radiation. So, the salts like NaCl, KBr are only
used.
 A. Sampling of solids
Various techniques used for preparing solid samples are as
follows:-
1. Solid run in Solution –
• In this technique, solid sample may be dissolved in a non-
aqueous solvent.

• Provided that there is no chemical interaction

with the solvent and the solvent is not absorbed in the
range to be
studied.

• A drop of solution is placed on the surface of alkali metal disc

solvent is to dryness leaving a thin film of the solute.
 2. Solid film technique
• If the solid is amorphous in nature.

• Then the sample is deposited on the surface of a KBr

or NaCl cell by evaporation of a solution of the solid.
• Ensured that the film is not too thick to pass
the radiation
 3. Pressed pellet technique
• In this technique, a small amount of finely ground solid
sample is mixed with 100 times its weight of potassium
bromide and compressed.
• To form thin transparent pellet(1-2mm thick & 1cm in
diameter) using a hydraulic press.
• These pellets are transparent to IR radiation and it is used for
analysis.
Advantages:-
• Kbr pellets stored for long period of time.
• Resolution of spectrum is superior.

Disadvantages:-
• Always have a band at 3450cm-1 due to OH group of
moisture.
• Due to high pressure(~25000 psig) polymorphic
changes occurs.
• Not successful for polymers. (diffcult to grind with
Kbr.)
 4. Mull technique
In this technique, the finely crushed sample is mixed with Nujol
(mineral oil) in a marble or agate mortar, with a pestle to make
a thick paste.

A thin film is applied onto the salt plates.

This is then mounted in a path of IR beam and the spectrum is

recorded.
 2. Sampling of liquids
Liquid sample cells can be sandwiched using liquid sample cells of highly purified
alkali halides, normally NaCl. & KBr can also be used.

Aqueous solvents cannot be used because they cannot dissolve alkali halides.
Organic
solvents like chloroform can be used.

The sample thickness should be selected so that the transmittance lies between 15-
20%.

For most liquids, the sample cell thickness is 0.01-0.05 mm.

Some salt plates are highly soluble in water, so the sample and washing reagents must
be anhydrous
 3. Sampling of gases

The sample cell is made up of NaCl, KBr etc

It is similar to the liquid sample cell.

A sample cell with a long path length (5 – 10 cm) is needed

because the gases show relatively weak absorbance.

Gas analysis are not commonly used because of lack of

sensitivity.
 DETECTORS
• The detectors can be classified into three
categories:
1. Thermal detectors:- Their responses depend upon
the heating effect of radiation .
2. Pyroelectric detectors:- Pyroelectric effect depends
on the rate of change of the detector temperature rather than
on the temperature itself.
3. Photoconducting detectors:- Most sensitive .
 Thermocouples

A thermocouple is made by welding together at each end two wires made

from different metals.

If one welded joint (called the hot junction) becomes hotter than the other
joint (the cold junction), a small electrical potential develops between the
joints
In IR spectroscopy, the cold junction is carefully screened in a protective box
and kept at a constant temperature.

The hot junction is xposed to the IR radiation, which increases

the temperature of the junction.

The potential difference generated in the wires is a function of the

temperature difference between the junctions and, therefore, of the
intensity of IR radiation falling on the hot junction.

Response time ~60m sec.

To enhance sensitivity several thermocouples connected in series
are called a “thermopile”
 Bolometer
A bolometer is a type of resistance thermometer.

It consist of thin metal conductor.

A bolometer is made one arm of Wheatstone Bridge.

A similar strip of metal used as balancing arm of bridge.

When no radiation fall on bolometer.

Bridge remain balance.

 When IR radiation fall.

Unbalanced, due to change in resistance.

Current flow through Galvanometer

Amount of current flow.

Measure the intensity of radiation.

Response time ~4m sec.

Functioning of a bolometer
 THERMISTORS

Made of fused mixture of metal oxides.

As the temp. of mixture increases, it’s electrical

resistance decreases. (opposed to Bolometer)

Response time very slow...

 GOLAY CELLS:

• These are sensitive gas thermometers.

• Xenon gas is contained in a small
cylindrical chamber which contains a
blackened membrane on one side while
other side has a flexible diaphragm;
silvered outside.
• A beam of light is reflected from the
silvered surface to cathode at a vacuum
phototube.
• When IR radiations fall on the
blackened membrane it is heated which
in turn heats the xenon gas by conduction
resulting in increase in pressure causes
distortion of silvered diaphragm
• As a result the fraction of reflected light
which strikes the active surface of
phototube is changed leading to change in
photocurrent this is related to the falling
IR radiations.
There are 2 types of infrared spectrophotometer, characterized by the
manner in which the ir
frequencies are handled.
– 1) dispersive type (IR)
– 2) interferometric type(FTIR)

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.
A method of obtaining an Infrared spectrum by measuring the interferogram of a
sample using an interferometer, then performing a Fourier Transform upon the
interferogram to obtain the spectrum.
It is single beam instrument.
The Interferometer:

An device in which two or more radiation beams interfere with each other after
passing through different optical paths. The interferometer produces a unique
type of signal which has all of the infrared frequencies “encoded” into it. The
output is an interferogram or interference record. The two domains of Distance
and Frequency are inter convertible by the mathematical method of Fourier
transformation.
Majority of commercially avaiable FT-IR are based on an inetrferometer
commonly Michelson interferometer.
Michelson Interferometer
Michelson Interferometer:interferometer:

It has three basic components a beam splitter, fixed mirror, and a

moveable mirror.
Beam splitter is semi-reflecting device so that 50% oof light impinging
on it is transmitted while the remaining 50% is reflected. It is either a
Partially silvered mirror or thin film of germanium (Ge) sendwiched
btw two KBr plates.
IR light received from source is split into two identical beams by the
beam splitter such that one beam is reflected to the fixed flat mirror
while the other beam is transmitted to the moveable flat mirror.
The two beams are reflected back by their respective mirrors to
recombine at the beam splitter to again form one beam which passes
through the sample and is then focused on detector. Of course, each
of the two beams reflected back by their respective mirror is again split
into two equal halves by the beam splitter, one half of each beam goes
to detector while the other half of each beam goes back to the
source.The sample can be use directly without the prepration of mull or
KBr discs or solution.
 Detectors in FTIR:
1.Pyroelectric detectors a thin, Pyroelectric crystals such as deuterated
triglycine sulfate (DTGS) or LITA (lithium tantalate), When a
pyroelectric material is polarized by an electric field, it remains
polarized after the field is removed due to an effect called residual
electric polarization. This residual polarization is sensitive to changes
in temperature.

2. Photoconductive detectors show an increase in electrical conductivity

when illuminated with IR radiation, They have a rapid response and
high sensitivity. The most commonly used photoconductive detector
is the MCT (Mercury Cadmium Telluride), which must be cooled to
liquid nitrogen temperatures for proper operation.
 Pyroelectric detectors:
• They are constructed from single crystalline water of pyroelectric material
which are dielectric materials which have special thermal & electrical
properties.
• Eg deuterated triglycine sulphate
• When an electric field is applied across any dielectric material electrical
polarization takes place.
• The magnitude of polarization is a function of dielectric
constant of that material
• This pyroelectric crystal is sandwiched between 2 electrodes which are IR
transparent.
• The pyroelectric crystal acts as a temperature dependent capacitor.
• When IR radiations fall there is a change in the temperature which alters the
charge distribution across the crystal which can be detected as a current in an
external circuit connecting to two sided of capacitor.
• Magnitude of current is directly proportional to surface area of crystal and rate of
change of polarization with temperature.
Photo conducting detector:
They consists of a thin film of semiconductor material such as lead
sulphide, mercury cadmium telluride or Indium antimonide deposited on
Non conducting glass surface & sealed into an evacuated envelope to
protect semiconductor from atmosphere.
Absorption of radiation by these materials promote non- conducting
valence electrons to a higher energy conducting state thus decreasing
electrical resistance of semiconductor.
41
Interferogram
The light signal measured by the detector is known as
Interferogram.
An interferogram is time domain interference signal, and
represents the detector's response to the itensity changes
against time within the mirror scan.
Movement of the moveable mirror back and forth once is known
as scan.
Fourier Transformation:
The time domain interferogram obtained as detector's response
cannot be interpreted as such. It is subjected to fourier
transformation (a mathematical operation performed by an
attached computer) which converts it into a frequency-domain
spectrum.
Comparison between Dispersive IR and FTIR:
PROPERTIES DISPERSIVE IR FTIR
1.Components Many moving parts result in Only mirror moves during an experiment
mechanical slippage.
2.Calibration Calibration against reference spectra Use of laser provides high frequency precision (to 0.01
required to measure frequency cm-1 (Connes’ advantage)
1.Stray light Stray light within instrument causes spurious Stray light does not affect detector, since all signals are modulated.
readings
2.Resolution In order to improve resolution, only small Much larger beam aperture used; higher energy throughput
amount of IR beam is allowed to (Throughput or Jacquinot’s advantage).
pass through the slits.
3.No. of Only narrow-frequency radiation falls All frequencies of radiation fall on detector
Frequency on the detector at any one time. simultaneously; improved S/N obtained quickly (Multiplex
or Fellgett’s advantage)

4.Scan speed Slow scan speeds make dispersive Rapid scan speeds permit monitoring samples
instruments too slow for monitoring systems undergoing rapid change.
undergoing rapid change (e.g.
GC effluents)

5.Source Sample subject to thermal effects from Short scan times, hence sample is not subject to thermal
effects the source due to length of scan time. effects.
6. IR from Any emission of IR radiation by sample Any emission of IR radiation by the sample will not be
sample itself will fall on detector due to the conventional detected.
positioning of the sample before the
monochromator.

7.Advantage Double beam optics permit continuous Single beam optics; background spectrum collected
of Beam real-time background substraction. separately in time from sample spectrum.
optics Can result in error if background spectra not collected frequently.
 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)
• Energy limiting accessories such as diffuse reflectance or FT-IR
microscopes
• High resolution experiments (as high as 0.001 cm-1 resolution)
• Trace analysis of raw materials or finished products
• Depth profiling and microscopic mapping of samples
• Kinetics reactions on the microsecond time-scale
• Analysis of chromatographic and thermogravimetric sample fractions
Comparison between Dispersive IR and FTIR:
46
 Applications of IR Spectroscopy:
(Functional group analysis)
Structure determination:
IR spectroscopy is mainly used for determination of structure of organic
compounds by correlation and interpretation of IR spectra (Cannot differentiate
enantiomers).
Identification of Substances:
• To compare spectrums.
• No two samples will have identical IR spectrum.
• Criteria: Sample and reference must be tested in identical conditions, like
physical state, temperature, solvent, etc.
Determination of Molecular Structure
• Used along with other spectroscopic techniques. Identification is done based
on position of absorption bands in the spectrum. Eg.: C=O at 1717 cm-1.
• Absence of band of a particular group indicates absence of that group in the
compd.
Detection of Impurities
• Determined by comparing sample spectrum with the spectrum of pure reference
compound.
• Eg.: ketone impurity in alcohols.
• Detection is favoured when impurity possess a strong band in IR region where
the main substance do not possess a band.
Progress of Reactions
• Observing rate of disappearance of characteristic absorption band in reactants
or
•Rate of increasing absorption bands in products of a particular
product. Presence of Water in Sample
If lattice water is present, spectra will contain 3 characteristic
bands  at 3600-3200cm-1, 1650cm-1 and 600-300cm-1.
Application In Industry
Determine impurities in raw materials (to ensure quality products). For Quality Control
checks; to determine the % of required product. Identification of materials made in
industrial research labs, or materials of competitors. E.g.: Impurity in bees wax (with
petroleum wax)
IR Absorptions:
Sr. Characteristic
Functional Group
No. Absorption(s) (cm-1)
1 Alkyl C-H Stretch 2950 - 2850 (m or s)
Alkenyl C-H Stretch 3100 - 3010 (m)
2
Alkenyl C=C Stretch 1680 - 1620 (v)
Alkynyl C-H Stretch ~3300 (s)
3
Alkynyl C=C Stretch 2260 - 2100 (v)
Aromatic C-H Stretch ~3030 (v)
4 Aromatic C-H Bending 860 - 680 (s)
Aromatic C=C Bending 1700 - 1500 (m,m)
5 Alcohol/Phenol O-H Stretch 3550 - 3200 (broad, s)
6 Carboxylic Acid O-H Stretch 3000 - 2500 (broad, v)
7 Amine N-H Stretch 3500 - 3300 (m)
8 Nitrile C=N Stretch 2260 - 2220 (m)
Aldehyde C=O Stretch 1740 - 1690 (s)
Ketone C=O Stretch 1750 - 1680 (s)
9 Ester C=O Stretch 1750 - 1735 (s)
Carboxylic Acid C=O Stretch 1780 - 1710 (s)
Amide C=O Stretch 1690 - 1630 (s)
10 Amide N-H Stretch 3700 - 3500 (m)
KETONE:
AMINES:
ACIDS: