Spectroscopic

Techniques
UV Visible and Infrared (IR)
Spectroscopy
• Course Objective:
To study spectroscopic techniques
for chemical analysis

• Course Outcome:
Identify chemical compounds based
on their structure.
Unit 5: Spectroscopic Techniques:
✓ Weightage : 18M
(only in End semester examination.)
✓ Teaching Hours: 08 hrs.
✓ Questions asked in ESE paper:
Q.5 a]7M, b] 6M, c] 5M
OR
Q.6 a]7M, b] 6M, c] 5M
 A) UV-Visible Spectroscopy
Content:
▪ Introduction,
▪ Interaction of electromagnetic radiation with matter
▪ Statement of Beer’s law and Lambert’s law,
▪ Absorption of UV radiation by organic molecule leading
to different electronic transitions,
▪ Terms involved in UV-visible spectroscopy-
chromophore, auxochrome, bathochromic shift,
hypsochromic shift, hyperchromic shift and
hypochromic shift,
▪ Instrumentation and basic principle of single beam
spectrophotometer,
▪ Applications of UV-visible spectroscopy.
 Spectroscopy
Introduction:
• Spectroscopy is branch of science deals with the study
of interaction of electromagnetic radiation with matter
• Spectroscopic methods of analysis are based on the
measurement of electromagnetic radiation absorbed
or emitted by the sample
• Physical and chemical properties of the sample
substance are directly related to the structure of the
sample and sample substance absorb radiations based
on its bonding and structure
• Structure elucidation can be done based on wavelength
absorbed by sample substance
 Spectroscopy
• Electromagnetic radiations consist of discrete packets
of energy which are called photons of light.
• Energy of photon of EMR is given by E = hc/ λ
• EMR travels at 3 x 108 m/sec. The speed of the wave is
given by Velocity = Wavelength x Frequency.
• These waves made of two components electrical and
magnetic. They oscillates in space perpendicular to
each other and perpendicular to the direction of
propogation.
• Wavelength of radiation is inversely proportional to its
energy.
Spectroscopy
Interaction of electromagnetic radiation
with matter
▪ Types of energies: Rotational, vibrational &
electronic energy.
▪ Molecular energy levels: Rotational, vibrational &
electronic energy levels.
▪ Interaction with EMR bring about changes in
outermost electrons present in the molecule these
changes depend on energy of EMR interacting.
▪ Energy associated with EMR can bring about either
electronic or vibrational or rotational excitations.
▪ Absorption spectrum: Definition & graph with
variables
 Spectroscopy
Spectroscopic methods of analysis are based on the
measurement of electromagnetic radiations absorbed or
emitted by the sample solution.

Most common photometric methods are,

1. Colorimetric: (400 to 800 nm)

2. UV spectroscopy (180 to 400 nm)
3. Visible spectroscopy (400 to 800 nm)
4. UV visible spectroscopy (180 to 800nm)
5. IR (0.76 to 15 micrometer)
 Spectroscopy
Interaction of electromagnetic radiation with
matter

UV visible Radiation: bring excitation of electrons in the

bond to higher energy anti bonding level

Absorption of IR: Cause vibration in certain covalent bonds

∆ E rotational < ∆ E vibrational < ∆ E electronic

 Fundamental Laws of Spectroscopy

Lambert’s law : When a beam of light is allowed to

pass through a transparent solution, the rate of
decrease in intensity of light is directly proportional
to thickness of solution.

Beer’s law: When a beam of light is allowed to pass

through a transparent solution, the rate of decrease
in intensity of light is directly proportional to
concentration of solution when thickness of solution
is kept constant.
Fundamental Laws of Spectroscopy
Range of UV-Visible Spectroscopy
▪ Range of wavelengths belong to UV and Visible region.
UV region: 10nm to 400nm
Visible region: 400nm to 800nm

▪ Subdivision of Ultraviolet region based on wavelengths:

Far UV (below 200nm) & Near UV(from 200 – 400nm)

▪ UV-Visible wavelengths are used in Quantitative as

well as Qualitative analysis in which absorption laws
are used.

▪ In Quantitative analysis graph of absorbance against

concentrations is usually plotted.
 Absorption of UV radiation leading to
Electronic transitions in organic molecules
• Absorption of UV-visible radiation by a molecule brings
changes in the electronic energy of molecule because of
transition of valence electrons from lower energy to higher
energy
• Types of electrons present in organic molecule:
1. Sigma (σ) electrons: Electrons forming single bonds like
C-H bond present in saturated hydrocarbon
2. pi (π) electrons: Electrons forming double bonds like C=C
bond present in unsaturated hydrocarbon
3. Non bonded (ɳ) electrons: Non-bonded or lone pair of
electrons and not involved in bonding between atoms in
molecules. Lone pair of electrons present on Oxygen,
Nitrogen etc.
 Absorption of UV radiation leading to
Electronic transitions in organic molecules
• When energy is absorbed in UV Visible region,
electronic transitions occur:

➢ Possible Electronic Transitions:

1) σ→ σ* transition
2) π→ π* transition
3) ɳ→ σ*transition
4) ɳ→π*transition

➢ Forbidden Transitions:
1) σ→π*transition
2) 2) π →σ* transition
Electronic Energy Levels and Transitions
Electronic transitions in organic molecules
➢ Possible Electronic Transitions:

1. σ→ σ* transition: (Less than 150 nm)

Such transitions from occur only in the compounds
containing sigma electrons which are involved in single bonds
and no lone pair of electrons on any atom in the molecule from
sigma bonding orbital to the corresponding antibonding orbital.
Such transitions requires very large amount of energy, the
absorption band occurs in the far ultraviolet region.
e.g. Saturated Hydrocarbons like Methane, Ethane etc.
Methane (CH4) containing C-H bonds undergo this transition,
shows absorbance maxima at 125 nm
 Electronic transitions in organic molecules

➢ Possible Electronic Transitions:

2. π→ π* transition: (200 nm-700 nm)

Such transitions occur only in the compounds containing pi
electrons which are involved in multiple bonds in the molecule.
These electrons get excited from pi bonding orbital to the
corresponding antibonding orbital π* .
e.g. Unsaturated Hydrocarbons like alkenes, alkynes, nitriles,
aromatic compounds etc. show these transitions.
Generally alkenes absorb in the region of 180-200 nm while
compounds containing 2 or more conjugated bonds shows
absorbance maxima above 200 nm
Electronic transitions in organic molecules

➢ Possible Electronic Transitions:

3. ɳ→ σ* transition: (150 - 250 nm)

Such transitions occur in the saturated compounds
containing atoms with lone pair of electrons (non-bonding
electrons) like O, N, S and halogens. These electrons get excited
from non-bonding orbital to the antibonding orbital σ*.
e.g. Various functional groups show absorbance maxima at
shorter wavelength in the range of 150 - 250 nm
Electronic transitions in organic molecules

➢ Possible Electronic Transitions:

4. ɳ→π* transition: (200 nm-700 nm)

Such transitions occur in the compounds containing double
bonds involving hetero atoms with lone pair of electrons (non-
bonding electrons) like O, N, S and halogens. These electrons get
excited from non-bonding orbital to the antibonding orbital π*.
These transition requires minimum energy and show absorption
at longer wavelength between 200 to 700 nm
Electronic Transitions in Organic Molecules
 Content: UV-visible spectroscopy

Terms Involved in UV Visible Spectroscopy:

Definition and suitable examples to illustrate the following
terms:
➢ Chromophore:
➢ Auxochrome:
➢ Bathochromic shift:
➢ Hypsochromic shift:
➢ Hyperchromic shift:
➢ Hypochromic shift:
Terms involved in UV-visible spectroscopy
CHOMOPHORE: Any isolated covalently bonded unsaturated
group responsible for electronic absorption or shows
characteristic absorption in the UV Visible region.
E.g.: -C=C-, -C=O, NO2
Consequently chromophore is any substance (groups) which
absorbs radiation at particular wave length which may or may
not impart colour to the compound.
Chromophore types:
➢ The groups which contain electrons and undergo to *
transitions and
➢ The groups which contain both and n electrons and
undergo n to * and to * transitions.
Compounds which posses to * and n to * transitions
(150nm and 190nm) contains no chromophore within them.
Terms involved in UV-visible spectroscopy

AUXOCHROME: Any saturated group with non bonded

electrons, which does not itself act as a chromophore but
whose presence brings about a shift of the absorption band
towards the red end of the spectrum (longer wavelength)
Auxochrome is a colour enhancing group.
The effect is due to its ability to extend the conjugation of a
chromophore by sharing the non bonding electrons
Auxochrome when attached to a chromophore, alters both
the wavelength and the intensity of the absorption
E.g. –NH2, -OH, -OR, -NHR, -SH etc.
Chromophore + Auxochrome = Newer Chromophore
Terms involved in UV-visible spectroscopy
BATHOCHROMIC SHIFT or RED SHIFT:
The shift of maximum absorption to a longer wavelength
due to substitution or solvent effect.
Causes:
1. An auxochrome
2. Change of solvent
E.g.: Absorption Maximum of Benzene λmax= 255 nm (εmax= 203)
While for Pheonl λmax= 270 nm and Aniline λmax= 280 nm (εmax=
1430)
In alkaline medium, p-nitrophenol shows red shift with
λmax=265 nm from λmax=255 nm. Because negatively charged
Oxygen delocalizes electron more effectively than the unshared
n electron pair present on –OH groups.
Terms involved in UV-visible spectroscopy

HYPSOCHROMIC SHIFT or BLUE SHIFT: The shift of

maximum absorption to a shorter wavelength.
Causes:
1) Change of solvent towards higher polarity or
2) Removal of conjugation
E.g.: Absorption Maximum of Aniline (conjugation of pair
electrons of nitrogen with benzene ring) λmax= 280 nm while
Aniline shows λmax= 203 nm as in acidic medium as it will
form –NH+3, due to removal of lone pair of electrons or due
to removal of –conjugation.
 Terms involved in UV-visible spectroscopy

HYPERCHROMIC EFFECT:
An increase in maximum absorption intensity
Cause: Introduction of auxochrome usually increases the
intensity of absorption

E.g. : Pyridine λmax= 257 nm and εmax= 2750 while pyridine

with –CH3 group shows increase in intensity of absorption that
is 2-methyl pyridine λmax= 262 nm and εmax= 3560
 Terms involved in UV-visible spectroscopy

HYPOCHROMIC EFFECT:
A decrease in maximum absorption intensity.
Cause: Due to introduction of any group to the compounds
which is going to alter the molecular pattern of the compound
or distort the original geometry results in a hypochromic shifts

E.g.: Biphenyl (or naphthalene) has an absorption λmax= 250

nm and εmax= 19000 whereas 2-methyl biphenyl has an
absorption of λmax= 237 nm and εmax= 10250
Effect of substituents on the position and
intensity of an absorption band

Source of Image: epgp.inflibnet.ac.in

 UV-Visible Spectra
➢ UV-Visible spectrophotometer on analysis of an analyte

solution gives data in the form of UV-Visible Spectra

➢ The UV-Vis spectra is a graph:

Absorbance verses wavelength () or

% Transmittance verses Wavelength ()

➢ It gives information about max

 UV-Visible Spectroscopy
max :It is defined as a particular wavelength at which
maximum absorbance is observed
It is a charactristic property of an analyte and
depends on strucutre of that analyte

 : It is called as molar extinction coefficient or

molar absorptivity
It is the extent of absorption for a solution of
specific concentration
 UV-Visible Spectroscopy
The UV-Vis spectra for isoprene is as follows:

Source: https://www.chemistry.msu.edu
Instrumentation: Single Beam UV Visible
Spectrophotometer

Block Diagram of Single Beam UV Visible Spectrophotometer:

Amplifier
Monochromator Sample /Recorde
Source Detector r
Cell

Components of Single Beam UV Visible Spectrophotometer:

1) Light Source: Provides wide range of UV Visible radiation

and sufficient intensity over required wavelength.
Eg: Deuterium/Hydrogen Discharge Lamp (190-290 nm);
Tungsten filament (370-780 nm)
Instrumentation: Single Beam UV Visible
Spectrophotometer
Amplifier
Monochromator Sample /Recorde
Source Detector r
Cell

2) Sample Holder: All UV Visible spectra are recorded for the

solution phase. Hence, Cells/Cuvettes made up of Glass or
Quartz are used. But Quartz Cells only are transparent in full
range of 200-780 nm.

3) Monochromator: Converts polychromatic radiation into

monochromatic radiation using Prism/Filters/Gratings. Quartz
prism is used for UV region

4) Detector: Transducer which converts transmitted radiation

into electric signal/current. Commonly used are
Photomultiplier tube(PMT), Phototube etc
Instrumentation: Single Beam UV Visible
Spectrophotometer
Amplifier
Monochromator Sample /Recorde
Source Detector r
Cell

5) Amplifier: Amplify the signal received from detector

6) Recorder: Record output of the UV Visible spectrum data

and Display it either in the graphical manner as absorption
spectra or in the form of digital values of the Absorbance or
transmittance verses wavelength
Instrumentation: Single Beam UV Visible
Spectrophotometer

Source of radiation Sample holder (Cuvette)

Applications of UV-Visible
Spectroscopy
➢ Structural Information: max is the characteristic

property of a molecule due to presence of

chromophore along with auxochrome. By knowing

this value structural information can be extracted.

➢ Qualitative analysis: UV-Visible spectra of an

unknown sample can be matched with spectra of

known compound to analyse sample qualitatively.

Applications of UV-Visible
Spectroscopy
• Quantitative analysis: By use of UV-Visible
Spectroscopy, unknown concentration of analyte can
be evaluated. Here same analyte solution is prepared
with different concentration and its absorption is
determined. A graph is plotted with absorption verses
concentration, which gives a straight line.

• Now absorption of solution containing unknown

concentration is evaluated and by use of graph its
corresponding concentration can be determined.
Applications of UV-Visible
Spectroscopy
➢ Chemical Kinetics: According to Beer’s Law

absorbance is proportional to concentration. Hence

during the chemical reaction absorption intensity of

reactant decreases, while that of Product increases

which will help to study chemical kinetics.

➢ Detection of Impurity: Any change in the spectra of a

specific compound will indicate the presence of

impurity
B] Infra Red(IR) Spectroscopy
Content:
• Introduction,
• Principle of IR Spectroscopy,
• Types of vibrations: Stretching (symmetric & asymmetric)
and bending (scissoring, rocking, wagging and twisting),
• Conditions of absorption of IR radiations,
• Vibrations of diatomic and polyatomic molecules,
• Instrumentation with block diagram,
• Parts of IR spectrum, fundamental group region,
fingerprint region,
• Applications of IR spectroscopy
 Infra Red(IR) Spectroscopy
• IR spectroscopy is an important analytical technique
useful for chemical identification.

• IR spectra originate from the absorption of energy by a

molecule in IR region and the transition occur between two
vibration level.

• By measuring molecular vibrational frequencies, useful

information regarding molecule can be obtained.

• UV visible spectra provides good deal of information about

the structure of molecules that contain multiple bonds and
conjugated bonds.
 Infra Red(IR) Spectroscopy
• IR spectrum of an organic molecule provides good deal of
information about functional groups present in the
compound.

• IR spectroscopy is a type of absorption spectroscopy and

mainly used to determine functional group (carboxylic,
alcohol, ketone, aldehyde etc.).

• It is also called as vibrational and rotational spectroscopy.

• IR radiations of higher wavelength and lower energy are

mainly responsible for vibration and rotation of the bonds.

• The IR region of the electromagnetic spectrum which extends

from red end of visible spectrum to the microwave region may
be divided into three regions.
 Principle of IR Spectroscopy
➢ Atoms in molecules are not still, but they vibrate and
rotate in variety of ways in certain quantized energy
levels. These changes (vibrational, rotational) are
caused by absorption of IR radiations.

➢ The absorption process involves excitation of the

molecules to higher vibrational states and it is
quantized. It require definite amount of energy.

➢ The vibrations increase in amplitude when EMR raises

it to the next vibrational level.

➢ For a molecule to absorb IR the vibrations and

rotations within a molecule must cause a net change in
dipole moment of the molecule.
 Principle of IR Spectroscopy
➢ If the frequency of the radiation matches the
vibrational frequency of the molecule then the radiation
will be absorbed causing a change in the amplitude of
the molecular vibrations.

➢ The type of IR wavelength absorbed by the molecule

depends on the types of atoms and chemical bonds in
the molecule.

➢ The IR spectrometer measures the absorption at each

frequency in turn and so produce the IR spectrum.
Infrared spectroscopy is the study by measurements of
the wavelength and intensity of the absorption of infrared
radiation by a sample.
• IR Radiation (0.8 μ to 15 μ) which has longer
wavelength, low energy and capable of affecting both
the vibrational and rotational energy levels in the
molecules
• The unit commonly used is wavenumbers (cm-1 )
Wavenumber is proportional with energy (E) and
frequency (v), but reciprocal with wavelength.

Range of IR: 0.8 μ to 15 μ or 4000-400 cm-1

• IR Spectrum shows Transmittance and Wavenumbers
• IR Spectrum of an organic compound reveals good
information about functional groups
 Division of IR Region
The Whole IR region is subdivided into 3 parts:

1)Near Infrared Radiation :0.8 to 2.5μ(12500-4000 cm-1)

Energy range: (1.55-0.5eV)

2)Middle Infrared Radiation: 2.5 to15μ(4000-667cm-1)

a) Functional Group: 2.5 to 7.7 μ(4000 -1300cm-1)

b) Finger Print: 7.7 to 11 μ(1300 - 909cm-1)
c) Aromatic Region:11 to 15 μ (909 - 667cm-1)

3) Far Infrared Radiation: 15 μ to 200 μ (667-50cm-1)

Energy range for Middle & Far IR: (0.5-0.0012eV)

Conditions for absorption of IR radiation
1. Correct frequency of radiation:
Energy of IR radiation is insufficient to cause
electronic excitation but can cause vibrational or
rotational excitations in molecule.
• If the frequency of the radiation matches the
vibrational frequency of the molecule then radiation
will be absorbed, causing a change in the amplitude
of molecular vibration.
• For a molecule to absorb IR, the vibrations or rotations
within a molecule must cause a net change in the
dipole moment of the molecule.
• When the frequency of ER is equal to that of
alternating electrical field produced by change in
the dipole moment vibrational motions are excited in
the molecule, and the radiation is absorbed.
Conditions for absorption of IR radiation
2. Electric dipole:

✓ Molecule must give rise to change in dipole moment

due to absorption of IR radiation.

Thus, Vibrational Modes are IR active only if a

change in dipole moment occurs during the vibration
What kind of sample be able to absorb IR light?
• Only vibration which alters molecule dipole moment
(the magnitude of positive and negative charge between
two bonded atoms) and having the IR absorption
frequency in the IR region
• Gas molecules such as O2, H2 and Cl2 don’t have a
dipole moment, means no IR absorption occurs
• SO2 and CO2 have a dipole moment so it will give IR
absorption or show IR spectrum
• Every functional group has their own IR absorption
• The more complex molecule structure, the more complex
IR absorption
• It is used to identify any functional group presents in a
molecule structure
Conditions for absorption of IR light
Selection Rule: Requirement that absorption of a
Vibrational quantum be accompanied by a change in
dipole moment is known as Selection Rule

IR active transition: The vibrational transitions which

results in a change in dipole moment of a molecule are
absorbed in IR are known as IR active transitions
Eg: CO2, SO2 , CHCl3

IR inactive transition: The vibrational transitions

which do not results in a change in displacement of a
molecule are not absorbed in IR are known as IR inactive
transitions
Eg: H , N , Cl , CCl
 Types of Vibrations

➢ Covalent bonds are not rigid but almost elastic

➢ A molecule can be said to resemble a system of balls of different

masses, corresponding to a atoms of a molecule

➢ The bonds between two atoms are analogous of spring of a

molecule

➢ A molecule is constantly vibrating; its bond stretch, contract or

bend with respect to each other

➢ There are two modes of vibrations

 Types of Vibrations

Modes of vibrations: Two modes of vibrations

1) Stretching Vibrations:
i) Symmetric Stretching Vibrations
ii) Asymmetric Stretching Vibrations

2) Bending Vibrations:
i) Scissoring
ii) Rocking
iii) Wagging
iv) Twisting
 Types of Vibrations

Stretching and Bending Vibrations:

 Stretching Vibrations
• Characterized by change in inter-nuclear distance, thus
the distance between two atoms increases or
decreases, but atoms remain in the same bond axis.
These modes are further divided into:
a) Symmetrical Stretching and b) Asymmetrical Stretching
 Bending Vibrations
• Characterized by change of angle between two covalent
bonds, due to change in the position of the atoms
relative to the original bond axis. These modes are
further divided into four types:
a) Scissoring, b) Rocking c) Wagging and d) Twisting
 Fundamental Modes of Vibrations
• Stretching and bending occur at a certain quantized
frequencies.
• A particular vibration will absorb radiations only if it
causes change in Dipole Moment of the molecule.
• Vibrational frequency increases with the increase in the
bond strength
• No. of fundamental modes of vibrations for a molecule
can be calculated from the no of atoms in a molecule
and its geometry.
• Molecule containing N atoms have 3N degrees of freedom
• 1) For linear molecule: 3N-5 possible modes of vibration
• 2) For non-linear molecule: 3N-6 possible modes of
vibration
 Fundamental Modes of Vibrations
Examples:

Molecule Atoms (N) Geometry of Fundamental

Molecule modes of
vibrations

NO 2 Linear 1
CO2 3 Linear 4
H2O 3 Non-linear 3
NH3 4 Non-linear 6
CH4 5 Non-linear 9
 Regions in IR spectrum

• Middle IR Region
• 4000- 667 cm-1 (2.5 to 15µ)
• Divided into three sub regions as

I. Functional group region: 4000- 1300 cm-1 (2.5 to 7.7µ)

II. Finger print region: 1300- 909 cm-1 (7.7 to11µ)
III. Aromatic region: 909- 667 cm-1 (11 to 15µ)
 Functional group region
▪ The region extends from: 2.5-7.7 µ (4000-
1300cm-1)

▪ It contains absorption bands due to stretching

vibrations of functional groups such as O-H,
N-H, C-H, multiple bonds, carbonyl group may
be aldehyde or ketone etc.

▪ Useful for Organic Chemists

 Intensity Trends
• Follows change in dipole caused by
vibrating atoms
– Polar bonds (strong bond dipoles) absorb
strongly
• O-H
• C=O, C=N
• C-O
– Nonpolar bonds absorb weakly
• C=C, C≡C
• Follows overlapping bands
– CH bands tend to overlap
– Molecules contain many CH
– CH absorptions tend to be strong
 Energy Trends
• Energy follows vibration frequency of atoms
• light atoms vibrate more rapidly: C-H, N-H, S-H, O-H
vibrations (2500-3700 cm-1)
• Multiple bonds vibrate less rapidly:
Triple bonds (2500-2000 cm-1) :
C≡C (2100-2200 cm-1 )
C≡N (2240- 2280 cm-1)
Double bonds (2000-1500 cm-1):
C=O (1680-1750 cm-1)
C=C (1620-1680 cm-1)
Single bond : C-O (1025-1200 cm-1)

• 1500-400 cm-1, an absorption that involves the

deformation of other bondings.
 IR Spectrum Distribution
1. 4000-2500 cm-1, absorption of atom which is
bond to H atom, ex: C-H, O-H and N-H
2. 2500-2000 cm-1, triple bond, ex: C≡C , C≡N
3. 2000-1500 cm-1, double bond, ex: C=O, C=C,
C=N
4. 1500-400 cm-1, an absorption that involves the
deformation of other bondings.

2000-1500 cm-1, double bond, ex: C=O, C=C, C=N

C=O (1680-1750)
 Fingerprint region
▪ The region extends from: 11-15 µ (1300-
909 cm-1)
▪ It is the most complex part of IR spectrum.
▪ The absorption bands in this region are due
to stretching as well as bending vibrations.
▪ This region is not useful for interpretation
but can be used for identification of
compounds.
▪ If FP region of 2 samples are identical then
these samples are also identical.
 Aromatic Region
• 11-15 µ (909-667 cm-1)
• This region is useful for determination
of aromatic character.
• The absorption bands in this region are
due to bending vibrations.
• The absorption bands in this region
provides information about aromatic
substitution pattern such as ortho,
meta and para substitution.
Bond Type of Range of Abso.
Compound
C-H Alkane 2800-3000
=C-H Alkene 3000-3100
=-C-H Alkyne 3200-3300
Ar-H Aromatic Rings 3000-3100
-O-H Alcohols(Phenols) 3200-3600
(Broad)
-C-H (C=O) Aldehyde 2720 (1700)
Ketone 1700
C==O Carboxylic Acid 1730
(OH) (3300-2700
Broad)
 Parts of IR Spectrum
▪ The IR spectrum is basically a plot of transmitted
(or absorbed) frequencies vs. intensity of the
transmission (or absorption).
▪ Frequencies appear on the x-axis in units of inverse
centimeters i.e. cm-1 (wave numbers), and intensities
are plotted on the y-axis in percentage units.
▪ IR is most useful in providing information about the
presence or absence of specific functional groups.
▪ IR can provide a molecular fingerprint that can be
used while comparing samples.
▪ IR can provide information about aromatic
substitution pattern.
 Instrumentation of IR spectroscopy

➢ Schematic / block diagram with function &

material of each component

▪ Source

▪ Monochromator

▪ Sample cell

▪ Detector

▪ Amplifier & recorder

Instrumentation of IR Spectroscopy

Mirror
Mirror
Reference Cell
(KBr)

Chopper Beam
(to send light Monochromator Detector Amplifier/
Source Recorder
alternately)

Sample Cell
Mirror
Mirror
 Instrumentation of IR Spectroscopy
Source: Provides IR radiation
• Common IR radiation source are inert solids that are
heated electrically to a range of 10000C to 18000C to
promote thermal emission of radiation in IR region of
EM spectrum
Most common sources are:
1) Nernst filament/Glover :composed of rare earth
oxides such as Zirconium, Yettrium and Erbium or
mixture of LnxOy
2) Globar : Rod (5mm D & 50mm L) of Silicon Carbide
3) Incandescent Wire: Nichrome coil
• All produce continuous radiations, but with different
radiation energy profiles. Beam is divided into 2
equivalent beams, one passing through sample and
the other as reference beam
 Instrumentation of IR Spectroscopy
• Reference Cell and Sample Cell: Keep the sample
(Solid/Liquid/ Gas/Solution) to be analyzed and the
material of cells are transparent to IR region.
Cells are commonly made up of Alkali metal halides such
as: NaCl, KBr and KCL
Solid Sampling: Solid is dissolved in non aqueous solvent. A
drop of solution placed on the disc of alkali halide. Solvent is
dried to give thin film on surface.
Amorphous solid are deposited on KBr or NaCl plates/cell by
evaporation of solution of solid
Sample mixed with mineral oil (Nujol) to make fine paste and
thin film of paste applied on the KBr pellet
Sample is finely ground with KBr and pressed to pellet
Liquid Sampling: Liquids sandwiched using cells made up of
KBr or NaCl
Gas Sampling: Gases are filled in KBr/NaCl cells
Instrumentation of IR Spectroscopy
• Chopper Beam:
Splitter, Used to send the transmitted radiation
alternatively to the monochromator
• Monochromator: Converts polychromatic radiation
into monochromatic radiation Consists of
Prism/ Filters/Diffraction Gratings made up of Alkali
halides (NaCl, KBr, LiF)
Detectors: Transducer converting radiation into electric
signal or current. Various types:
Thermal Detectors:
Thermocouple : Consists of Antimony and Bismuth wires
welded to form 2 junctions wherein one becomes hotter
(due to IR) and other one is colder. PD gets developed
between two junctions as a result of Temperature
difference. Current is directly α IR falling on detector
Instrumentation of IR Spectroscopy
Bolometer: Thin metal (Pt/Ni) conductor based on
thermal radiation; used to measure increase in the
resistance (in turn current flow changes) with the
increase in temperature (per 0 C)
Thermister: Fused Metal oxide mixture, Increasing
Temperature, Decreasing resistance by 5%/0 C
Golay Detector: Contains Xenon and Used as a Gas
sensing thermometer
Photoconducting Detectors
Semiconductor Detectors
Amplifier: Used to amplify the signal
Recorder: IR Spectra gets Displayed
Applications of IR Spectroscopy

➢Determination of structure & functional group.

➢Study of kinetics of chemical reaction.

➢Distinction between intra & inter molecular

hydrogen bonding.

➢Detection of impurities.

➢Study of isomerism.

➢Detection of size of ring ketones.

 Applications of IR spectroscopy

1. Identification of functional group and

structure elucidation
The IR spectrum is divided in two parts:

1) Group frequency region (4000-1400 cm-1 )

2) Fingerprint region (1400-400 cm-1)

In Group frequency region, each peak corresponds to

specific functional group .

For example: If IR Spectrum shows a broad peak in the

region 3500-3200, it indicates presence of O-H group of

alcohol or phenol.
 Applications of IR spectroscopy
1. Identification of functional group and structure
elucidation

• Hence based on the peaks observed in functional group

region functional group present in sample can be determined.

• These functional group helps to determine the possible

structure of sample.

• Also peaks in the finger print region helps to decide

characteristic peaks of a particular bond between two atoms,

based on vibration frequency of that bond.

• Such peaks will also help to determine structure of sample

 Applications of IR spectroscopy
2. Identification of substances
• Depending upon the number of atoms present in a
molecule and whether the structural arrangement is
linear or non-linear. Large number of absorption bands
are observed in the IR spectra of organic molecule.

• Hence the two molecules having same IR spectra is not

possible.

• Hence based on the IR spectral data the two samples

are identical or not can be decided.

• So if two compounds have identical IR spectra then

both of them must be samples of the same substances.
 Applications of IR spectroscopy
2. Identification of substances
IR spectra of two enatiomeric compounds are identical. So IR
spectroscopy fails to distinguish between enantiomers. For
example, an IR spectrum of benzaldehyde is observed as follows.

No other compound then benzaldehyde produces same IR

spectra as shown above.
 Applications of IR spectroscopy
3. Detection of impurities
• IR spectrum of an organic molecule does not matches
with any other molecule.

• Now if a test sample to be determined is compared with

the standard spectra of same compound, then both
should have same spectral pattern.

• If any additional peaks are observed in the IR spectrum,

then it suggest these additional peaks are due to
impurities present in the compound.
 Applications of IR spectroscopy
4. Quantitative analysis
• In case of Quantitative analysis baseline technique is
used to determine quantity of a substance or a mixture.
• Here absorbance (log I0/It ) of chosen characteristic peaks
of substance under analysis is compared with the same
characteristic peaks of same pure sample of known
concentration.
• This comparison will be helpful to find quantity of analyte
substance.
• The method can be used to determine quantity of a
substance either in pure form or in the form of mixture of
two or more compounds.
 Applications of IR spectroscopy
5. Progress of Reaction
In case of chemical reaction of organic molecule,
generally one functional group gets converted to another.
That means one functional group will disappear and another
gets formed.

If a small portion of reaction mass is analyzed by IR

spectrophotometer then progress of reaction can be
determined.

Just for example if C=O is converted to -OH then sharp peak

of C=O will disappear and broad band of –OH will appear.
 References

1) Instrumental Methods of Chemical Analysis by Chatwal

2) Elementary Organic Spectroscopy by Sharma Y. R.

Thank You
 Principles
• When the certain molecules are exposed to IR
light, it will absorb the energy to make the atoms
of molecules vibrating
• The vibration frequency depend on the amount of
atoms and the length and the strength of atomic
bonding
• Molecule vibration is stimulated by absorption
radiation in the same frequency with the
frequency of its origin vibrations
 Principles IR Spectroscopy
• Atoms in a molecule are not still. They vibrate
& rotate in variety of ways (in certain quantized
energy levels) due to absorption of IR radiation
• ER of IR region is absorbed to various extents
by all substances
• The absorption involves excitation of molecules
to higher Vibrational States and therefore, is
Quantized
The vibrations increase in amplitude when ER
raises it to the next vibrational level.