Introduction

 Spectroscopy is the branch of science dealing

with the interaction of electromagnetic
radiation with atoms, molecules, or matter.
• Advantages
1. They require very less time for analysis.
2. Less sample quantity is required.
3. Sample materials remain unchanged during
analysis and can be reused.
4. They give accurate results.
 Types of spectra
Two types : Absorption and Emission spectrum
1. Absorption spectrum
When an atom or molecule undergo transition
from a lower energy level to a higher energy
level, it absorbs a photon of energy from the
incoming electromagnetic radiation. The
spectrum obtained is called an absorption
spectrum.
 2.Emission spectrum
When an atom or molecule undergo transition
from higher energy level to lower energy level, it
emits energy and the spectrum obtained is
called an emission spectrum.
 Molecular Energy Levels
Molecules possess four types of energy
1.Electronic energy :
Associated with electrons present in the molecule. The energy gaps between electronic
energy levels fall in UV- Visible region.
2. Vibrational energy
This is the energy associated with vibrations of molecules. The gaps between
vibrational energy levels fall in the IR region.
3.Rotational energy
When the molecule rotates, it is said to possess rotational energy. Rotational transitions
give spectrum in the microwave region.
4.Translational energy
Concerned with the overall movement of the molecules along the three axes

Total energy of the molecule:

E = E electronic + E vibrational + E rotational +E translational.
Since translational energy is negligible:
E = E electronic + E vibrational + E rotational.
Electronic transitions of a molecule are always accompanied by vibrational and
rotational transitions. Therefore discrete lines are not observed in the spectrum and
thus it as appears broad bands.
 Beer-Lambert’s Law
This law states that when a monochromatic light is
passed through a solution, the logarithm of ratio of
intensity of incident to transmitted light (Io/It) is
proportional to concentration of the solution, C and
path length (thickness- L) of the solution.

log I0 /It= ƐcL

where Io = intensity of incident radiation,
It = intensity of transmitted radiation
Ɛ - is a constant called molar extinction coefficient.
Deduce the differential and integral form of Beer
Lambert’s law
 Absorbance and Transmittance
• Absorbance (A) or optical density is the logarithm
of ratio of intensities of incident light to the
transmitted light.
A = log I0 /It
• Transmittance (T) is defined as the ratio of
intensities of transmitted to incident light.
T = It /I0
A = - log T
A = ƐcL
Transmittance T is %T /100 ( Eg: %T=40, T = 0.4)
 UV- Visible Spectroscopy
(Electronic Spectroscopy)
• Principle
When EM radiation falls on matter, it interacts
with atoms or molecules constituting it. The
energy of UV- Visible region corresponds to
energy for electronic excitations. Molecules
absorb energy in UV-Visible region and electrons
are promoted from bonding molecular orbital to
anti-bonding molecular orbital.
The wavelengths of radiation is UV(200-400 nm) or
visible(400-800 nm).
Classification of electronic transitions
Electronic Transitions in 1) ethene, 2) 1,3-butadiene
3) 1,3,5-hexatriene and 4) Benzene
 Instrumentation
The essential parts of UV – visible spectro-photometer are as follows:
• Radiation source: Both high and low voltage hydrogen lamps give rise to
continuous spectrum in the region between 200-370nm and a tungsten
filament lamp for the region 325-750nm. In modern instruments xenon
flash lamps are used.
• Monochromator/filter: This filter unit consists of an entrance slit, a
dispersing element and an exit slit. The dispersing element is generally a
prism or grating.
• Sample holder/cells: Modern instruments are double beam recording
spectrophotometers in which the light beam from the source is divided
into two identical parallel beams of equal intensity. These beams are
allowed to pass through the sample cell and reference cell containing the
sample and pure solvent respectively.
• Detectors: The two beams, one emerging from the sample cell and the
other from the reference cell, are then led to the detector system. The
detector converts the transmitted radiation into electrical energy.
• Recording system: The detector transmits the signals to a recorder which
gives the output.
Instrumentation
 Working of UV-Vis spectrophotometer
• A very dilute solution of the sample is prepared using a suitable solvent and is
taken in a transparent cuvette. The pure solvent is taken as reference in
another similar cuvette. The most commonly used solvents are water,
ethanol, hexane and cyclohexane.

• A beam of light from light source is split into two equal beams. One is passed
through sample and the other through reference. The intensities of emerging
light beams are measured by electronic detectors and compared.

• If the sample does not absorb light of a given wavelength, then I = Io.
However, if the sample absorbs light then I is less than Io, and this difference
is detected and recorded. Graph is plotted with absorbance Vs wavelength.
 Applications of UV- visible
spectroscopy
1. Identification of unknown compounds .
2. Detecting impurities in organic compounds .
3. Characterization of aromatic compounds and
conjugated dienes.
4. Study of kinetics of chemical reactions.
5. Determination of unknown concentration.
6. To determine the ozone present in the
environment, by measuring its spectrum.
7. Detection of blood sugar, cholesterol, etc.
 Practice Questions
1. Which molecule will absorb at longest wavelength in UV? Explain.

2. Arrange the molecules in the increasing order of their λmax.

Justify your answer. (3)

3. Which of the following molecules can give UV-visible spectrum (200nm - 800nm)?

a) CH4 b) N2 c) Butadiene d) Benzene

 IR SPECTROSCOPY
Principle
• Molecular spectra resulting from transitions between the
vibrational energy levels of a molecule on the absorption of
IR radiations are termed IR spectra.
• During the vibration of a molecule, if there occurs a change
in dipole moment, it will lead to the generation of an
oscillating electric field and interact with the
electromagnetic radiation.
• Vibrational spectra is given in the infrared region 500 to
4000 cm-1
• The requirement for a molecule to show IR spectrum is that
the dipole moment should change during vibration.
 Types of molecules give IR spectrum
• Homonuclear diatomic molecules like H2, O2,
N2, etc do not give IR spectrum as they do not
possess a dipolemoment change with
stretching vibration
• a hetero nuclear diatomic molecule like HCl,
undergo stretching vibration and the dipole
moment change occurs.
 Vibrational modes in LINEAR molecule
FOR A LINEAR MOLECULE
NO: OF VIBRATIONAL DEGREES OF FREEDOM = 3N-5, WHERE N = NUMBER OF ATOMS
CONSTITUTING THE MOLECULE
 Vibrational modes in NON LINEAR molecule

FOR A NON-LINEAR MOLECULE

NO: OF VIBRATIONAL DEGREES OF FREEDOM = 3N-6, WHERE N = NUMBER
OF ATOMS CONSTITUTING THE MOLECULE
All the three vibrational modes are IR active.
 Applications of IR spectroscopy
1. The force constant of different bonds in a molecule can be
determined.
2. The purity of a sample can be detected.
3. Unknown compounds can be identified by comparing their IR
spectrum with that of a known compound.
4. The presence of certain functional groups can be detected
from the stretching vibrations of the bond present in that
functional groups.
5. IR spectroscopy can be used to distinguish between intra
molecular and inter molecular hydrogen bonding.
Eg: In p-hydroxy phenol there exist intermolecular hydrogen
bonding. On dilution, it weakens and a shift in absorption
frequency occurs. In o-hydroxy phenol there exist intramolecular
hydrogen bonding and it is not affected by dilution.
 Dielectric Thermal Analysis (DETA)
Principle : Dielectric Thermal Analysis (DETA) is a valuable technique for exploring the
change in dielectric properties of a material under an applied voltage with change in
temperature. The applied sinusoidal voltage will polarize the sample resulting a
sinusoidal current with phase shift. This is used to study thermal behavior of polymers,
including glass transition, melting, and crystallization temperatures.
Dielectric polarisation in materials
1. Concentration Polarisation: When a material containing mobile ions is subjected to
electric field, positive ions concentrate near the negative plate and negative ions
concentrate near the positive plate. It is a slow process and are suitable for low
frequency and low voltage applications.
2. Orientation Polarisation: When a material containing polar covalent bonds are
subjected to an electric field, the positive ends of the dipole orient towards the
negative plate. These types of materials (PVC) are suitable for making insulators.
3. Electronic Polarisation: Materials like polyethylene has no polar covalent bonds ,
therefore when placed in electric field, electron clouds around atoms lose its
spherical symmetry resulting in small induced polarisation. These materials can be
used as an insulating material in high frequency low voltage applications such as
radio frequency communication cables.
 Instrumentation
1. Sample holder – Sample is placed in between two parallel metal
plate electrode.
2. Programmable furnace: This is used to ramp up and down the
temperature of the sample to provide a suitable heating rate.
3. Temperature sensor: Thermocouple to record the temperature of
the sample continuously.
4. Frequency generator: To provide sinusoidal voltage. It allows the
study of dielectric properties.
5. Environmental control: To provide suitable atmosphere ( eg: air,
inert gas) for the sample as per requirement.
6. Temperature control : To prevent overheating of the sample.
7. Dielectric analyzer : To detect the relative permittivity and
dielectric lose for every change in temperature (Impedence
analyzer or LCR meter).
8. Recorder: Computer will record the data and DETA curve is
obtained as a plot between temperature and relative permittivity.
Block diagram of DETA
 Working of DETA
• Sample Preparation: The polymer sample is typically
prepared as a thin film or pellet and placed between two
electrodes in a dielectric measurement cell. The sample is
usually in a controlled atmosphere or vacuum to prevent
interference from moisture or other contaminants.
• Measurement Setup: An alternating electric field is applied
to the sample. This field induces polarization in the
polymer, and the dielectric response is measured.
• Temperature Scanning: The temperature of the sample is
monitored using thermocouple.
• Data Collection & Analysis : As the temperature changes,
the dielectric constant and loss are recorded. DETA plot is
obtained between temperature vs relative permittivity.
These properties reflect how the polymer's ability to store
and dissipate electrical energy changes with temperature.
Applications of Dielectric Thermal Analysis (DETA)

• Material Characterization: Thermal properties analysis to control processing

conditions and Molecular Dynamics to Provide insights into the molecular mobility
and relaxation processes within the polymer.
• Polymer Quality Control: It helps to detect any deviations from expected
performance due to variations in polymer composition or processing.
• Development of New Polymers: To design and optimize the development of new
polymer materials by providing information on how different modifications affect
thermal and dielectric properties. This is important for developing polymers with
tailored properties for specific applications.
• Thermal Stability Studies: Evaluates the thermal stability of polymers by
monitoring changes in dielectric properties at elevated temperatures. This is
important for assessing the longevity and performance of materials in practical
applications.
• Environmental and Safety Assessments: Assists in understanding how polymers
react to temperature variations, which is important for applications exposed to
fluctuating environmental conditions.
Advantages
It can be used to anlyze solid, semi-solid and liquid materials.
It is more sensitive compared to other thermal analysis techniques.
 Scanning Electron Microscopy(SEM)
Principle
In SEM an electron beam is focused over a
surface to create an image. Electrons in the
beam interact with sample producing signals.
The signals give information about the surface
composition.
Instrumentation

Electron gun-source of electron

Condenser lens –compress electrons

to narrow beam

Objective lens-it focuses the electron

beam to the sample

Detector – Detect signals

 Working of SEM
The process begins with an electron gun generating a beam of
energetic electrons. The beam is focused on the solid sample.
When the incident electrons come in contact with the sample ,
energetic electrons are released from the surface of the
sample. Detectors attract different types of scattered electrons.
There are different types of scattered electrons.
• Backscatter electrons (BSE)are incidental electrons reflected
backwards. They come from deeper regions of the sample.
• Secondary electrons (SE) originate from the surface of the
sample.
The scatter patterns give information on the properties of the
sample. SEM produces black and white three dimensional
images.
 Advantage
• 3D IMAGE
• Instrument fast and easy to operate
• Data is available in digital form
Dis advantage
• Expensive and large instrument
• Technical skill needed
• Risk of radiation associated with electrons
Applications of SEM
1.SEM helps in characterization of solids.
2.Can detect and analyze surface fractures.
3.Can be used to identify crystalline structures.
4.It is a research tool in different fields.
5.Have technological applications such as assembly of microchips
for computers.