Module 3

Molecular Spectroscopy and Analytical Techniques

Introduction
Spectroscopy deals with the interaction of atoms or molecules or matter with electromagnetic radiation. Molecules
possess different quantum mechanical energy states such as electronic, vibrational, rotational and nuclear. The
transition can occur between these states by the absorption or emission of radiation.

Spectroscopy involves the production, measurement and interpretation of electromagnetic spectra arising from
emission or absorption of electromagnetic radiations by atoms or molecules. Detailed information regarding the
structure and bonding, as well as, various inter and intramolecular processes can be obtained from the analysis of
atomic and molecular spectra. The instruments used for the spectroscopic studies are known as spectrometers.

Based on the nature of interaction, the spectra can be broadly divided into the following types

1. Absorption spectrum: When an atom or molecule undergo a transition from the lower energy level, E1
to the higher energy level E1 with an absorption of a photon pf energy hv, the spectrum obtained is called
an absorption spectrum. The important spectral techniques such as UV – visible, IR, Microwave and NMR
belong to absorption spectra

2. Emission spectrum: When an atom or molecule undergo a transition from higher energy level, E; to
lower energy level, E, with an emission of a photon of energy hu, the spectrum obtained is called an
emission spectrum. For emission to be observed higher energy states have to be more populated than
lowerenergy states. Hydrogen spectrum, atomic emission spectrum (AES), fluorescence spectrum etc.
belongsto this class.

Based on the nature of the interacting species, the spectra can be divided into two categories
1. Atomic spectrum
It deals with the interaction of the electromagnetic radiation with atoms. During which the atoms absorb
radiation and gets excited from the ground state electronic energy level to another.
2. Molecular spectrum
It deals with the interaction of electromagnetic radiation with molecules. This results in transition between rotational,
vibrational and electronic energy levels. UV-Visible, IR, Microwave and NMR spectra are belonging to this category.
Differences between molecular spectra and atomic spectra

Sl.No. Atomic Spectra Molecular Spectra

It occurs from the interaction of

It occurs from the interaction of
1 molecules + electromagnetic
atom + electromagnetic radiation
radiation
Molecular spectra is a
2 Atomic spectra is a line spectrum
complicated spectra
It is due to vibrational, rotational
It is due to electronic transition in
3 and electronic transition in a
an element
molecule.

Electromagnetic spectrum
The range of photon energies is called the electromagnetic spectrum or It is the systematic arrangement of
electromagnetic waves in the increasing or decreasing order of any of its properties
The entire range (electromagnetic spectrum) is given by radio waves, microwaves, infrared radiation, visible
light, ultra-violet radiation, X-rays, gamma rays and cosmic rays in the increasing order of frequency and decreasing
order of wavelength.

Molecular energy levels

A molecule possesses four types of energies

1.Electronic energy (Eel): it is associated with the electrons present in a molecule, which can occupy various
molecular energy levels. The molecular orbitals can be bonding or antibonding. The energy gaps between electronic
energy levels falls in UV-visible region.

2. Vibrational energy (Evib): Atoms in a molecule can vibrate by keeping the position of center of mass constant,
the energy associated is called vibrational energy. The energy gaps between the vibrational energy levels falls in the
Infrared region.

3. Rotational energy (Erot): If a molecule rotates in space about an axis passing through its center of mass, it is
said to possess rotational energy. The energy gaps between rotational energy levels falls in the microwave region.
 4. Translational energy (Etrans): If the position of center of mass changes with time the molecule is said to
possess the translational energy.

The total energy, E total = (Eel) + (Evib) + (Erot) + (Etrans)

The UV-Spectrum always appear as broad band

Electronic transitions of a molecule are always always accompanied by vibrational and rotational transitions.
Thus, UV spectrum appears as broad band.

BEER LAMBERTS LAW

According to this law, "when a beam of monochromatic radiation is passed through a solution of an absorbing
substance, the rate of decrease of intensity of radiation 'dl with thickness of the absorbing solution 'dx' is proportional
to the intensity of incident radiation ‘I’ as well as the concentration of the solution 'C'.
It is mathematically represented as
-dl
αlC
dx
-dl
=klC--------(3)
dx
A = Cx
l0
Where, log = A = absorbance (or) Optical density.
l
k
=  = Molar absorptivity coefficient.
2.303
The equation is called Beer-Lambert’s law. Thus, the absorbance (A) is directly proportional to molar
concentration (C) and thickness (or) path length (x)

A = Cx
l0
log = A = absorbance (or) Optical density.
l
 T = It / I0
T % = It / I0 x 100
A = log 1/ T

Problem 1: - Find out the absorbance (or) optical density of a solution, if the transmittance of a solution is
18.5%.
Solution
Given: Percentage of transmittance (%T) = 18.5% (or) Transmittance (T) = 0.185.
l
 Absorbance (or) optical density,
A = log ( or ) − log T
T
= − log 0.185
Absorbance = 0.733
Problem 2:- The percentage transmittance of 5 x 10-4 M solution of disodium fumarate in a 1 cm cell is 19.2%.
Calculate (i) the absorbance (A), (ii) the molar absorption coefficient (  ) .

Solution
Given: % T= 19.2% (or) T=0.192; C = 5 ×10-4M
(i) Absorbance, A = -log T = - log 0.192 = 0.717
(ii) The molar absorption coefficient
A
=
Cx
0.717
=
5 10−4 1
= 1.434×103 mol dm-3cm-1
Problem 3: - A solution shows a transmittance of 20% when taken in a cell of 2.5 cm thickness. Calculate its
concentration if the molar absorption coefficient is 12,000 dm3 mol-1 cm-1.
Solution
Given: %T = 20%; T= 0.20; x = 2.5;  = 12,000 dm3 mol-1 cm-1
A = - log T = –log 0.20 = 0.699
We know that, A =  Cx
A 0.699
C = =
x 12, 000  2.5
= 2.33 10−5 mol dm−3
Problem 4: - Calculate the molar absorption of a solution 1×10-4 M. The absorbance of which is
0.20, when the path length is 2.5 cm.
Solution
Given: A=0.20; C=1×10-4; x = 2.5cm
We know that, A = Cx
 A 0.20
Molar absorptivity,  = =
Cx 110−4  2.5
Molar absorption = 800 dm3 mol–1 cm–1
Problem 5: - A monochromatic radiation is incident on a solution of 0.05 M concentration of an absorbing
substance. The intensity of the radiation is reduced to one-fourth of the initial value after passing through 10
cm length of the solution. Calculate the molar extinction co-efficient of the substance.
Solution
l
According to Beer-Lambert law, log = −Cx
l0
Given: C = 0.05 M; x = 10 cm; l = 1/4; l0 = 1;  =? The above equation may be written as
1 
− log  4 
− log ( l / l0 )  1  − ( −0.6020 )
= =  =
Cx 0.05 10 0.5
Molar extinction co-efficient  = 1.204 dm3 mol–1 cm–1
Problem 6
A-solution of thickness 2cm transmits 40% incident light. Calculate the concentration of the solution, given
that  = 6000 dm3 mol–1 cm–1
Solution
Given: % T = 40%; T = 0.40; x = 2.0 cm;  = 6000 dm3 mol–1 cm–1
A = –logT = –log 0.40 = 0.3980
We know that, A = Cx
A 0.3980
C= =
x 6000  2
Concentration = 3.316 x 10–5mol dm- 3.
Problem 7: - At definite wave length, an absorber when placed in a cell of 1 cm path length absorbs 20% of the incident
light. If the absorptivity of the absorber at this wave length is 2.0, find out its concentration.
Solution
Given: l = 100 –20 = 80; l0 = 100;  = 2; x = 1
l0
According to Beer-Lambert's law, log = xC
l
100
= log = 2  1 C
80
= log 1.25 = 2C = 0.0969 - 2C
C = 0.0969. + 2
Concentration = 0.048 g/lit
Problem 8: - A solution of thickness 2 cm transmits 40% incident light. Calculate the concentration of the solution,
given that
 = 5842 dm3 mol-1 cm–1
Given: %T = 40%; T= 0.40; x = 2 cm  = 5842 dm3 mol-1 cm- 1
A = –log T– log0.40 = 0.398
We know that, A =  Cx
A
C=
 x
0.398
C=
5842dm .mol−1.cm −1  2cm
3

0.398
= −1
= 3.4  10−5 mol.dm −3
11684dm .mol  2cm
3

UV-V1SIBLE SPECTROSCOPY
Principle
Ultraviolet (UV) Visible-spectra arises from the transition of valence electrons within a molecule or ion from a lower
electronic energy level (ground state E0) to higher electronic energy level (excited state El). This transition-occurs due
to the absorption of UV (wavelength 100–400 nm) or visible (wavelength 400–800 nm) region of the electronic
spectrum by a molecule or ion. The actual amount of energy required depends on the difference in energy between the
ground state and the excited state of the electrons.
E = E1 − E0 = hv
Types of transitions involved in organic molecules
Energy absorbed in the visible and UV region by a molecule causes transitions of valence electrons in the
molecule. These transitions are  → * , n → * , n → * &  → * . The energy level diagram for a molecule is shown
in the fig 1.1. The energy values for different transitions are in the following order.

1.  → * Transitions
 → * Transitions occur in the compounds, in which all the electrons are involved in single bonds and there are no
lone pair of electrons. The energy required for  → * transition is very large. This type of transition occurs below
150nm. The ordinary UV machines takes spectra only from 200-700nm and hence saturated hydrocarbons cannot be
detected using UV -vis spectrophotometer. The absorption band occurs in the far UV region' (120-136 nm). Example:
- Saturated hydrocarbons (CH4, CH3 - CH3, CH3 - CH2 - CH3, etc.,)
CH 4 : For  → * ;  max = 121.9nm

2. n → * Transitions
n → * Transitions occur in the saturated compounds containing N, O, S etc. having lone pair (non-bonding) of
electrons in addition to  → * transitions. The energy required for an n → * transition is less than that required
for a  → * transition. This absorption band occurs at longer wave length in the near UV region (180-200 nm). These
are also forbidden transitions. Absorption takes place below 200nm. Example: - ( CH 3 )3 N

3.  → * Transitions
 → * Transitions occur due to the transition of an electron from a bonding π orbital to an antibonding π* orbital. These
transitions can occur in any molecule having a π electron system. Selection rule determines whether transitions to a
particular π*orbital is allowed or forbidden. The unsaturated hydrocarbons containing double or triple bonds shows this
type of transition.
Eg: - C=C of ethylene molecule give an absorption maximum at 169nm.So normal UV machines will not show such
transitions. In case of molecule containing conjugated double bonds, these transitions can be observed from highest
occupied π molecular orbital (HOMO) to lowest unoccupied π molecular orbital (LUMO).

1,3-butadiene
It has four π molecular orbitals (Ψ1, Ψ2, Ψ3, Ψ4) formed by linear combination of four atomic orbitals (p orbitals). Here
Ψ1 &Ψ2 are bonding molecular orbitals and Ψ3 & Ψ4 are antibonding π molecular orbitals. In the ground state the four π
electrons occupy bonding molecular orbitals. Here the transition takes place from HOMO to LUMO with an absorption
maxima (ƛmax) at 217nm.

1,3,5-hexatriene
There are three double bonds in conjugation. It has six π molecular orbitals Ψ1, Ψ2, Ψ3, Ψ4, Ψ5, Ψ6 formed by linear
combination of six atomic orbitals (p orbitals). Here Ψ1, Ψ2, & Ψ3 are bonding molecular orbitals and Ψ4, Ψ5 & Ψ6 are
antibonding π molecular orbitals. In the ground state the six π electrons occupy bonding molecular orbitals. Here the
transition takes place from HOMO to LUMO with an absorption maxima (ƛmax) at 247nm.
Benzene
There are three double bonds in conjugation. It has six π molecular orbitals Ψ1, Ψ2, Ψ3, Ψ4, Ψ5, Ψ6 formed by linear
combination of six atomic orbitals (p orbitals). Here Ψ1, Ψ2, & Ψ3 are bonding molecular orbitals and Ψ4, Ψ5 & Ψ6 are
antibonding π molecular orbitals. In the ground state the six π electrons occupy bonding molecular orbitals. Here the
transition takes place from HOMO to LUMO with an absorption maxima (ƛmax) at 255nm. Here Ψ2, & Ψ3 are
degenerate orbital (same energy) and Ψ4 & Ψ5 are also degenerate.

As more and more double bonds come in conjugation the absorption comes to the visible region. In case of lycopene
a red coloured natural dye of tomato, there are 11 double bonds in conjugation therefore absorption maxima is observed
at 505nm.

4. n → π* Transitions
n —> π* transitions are shown by unsaturated molecule containing hetero atoms like N, O & S. It occurs due to the
transition of non-bonding lone pair of electrons to the antibonding orbitals. This transition shows a weak band, and
occurs in longer wavelength with low intensity.

Examples: - (i) Aldehyde & ketone having no C = C & C  C )

n —> π * transition occurs in the range of 270-300 nm.

(ii) Aldehyde & ketone ( (having double bond).

n →π* transition occurs in the range of 300-350 nm.

Instrumentation of UV-Vis spectrophotometer

A spectrophotometer is a device which detects the percentage transmittance of light radiation when light of certain
intensity and frequency range is passed through the sample. Thus the instrument compares the intensity of transmitted
light with that of incident light.

Components: - The various components of a visible UV spectrometer are as follows.

1. Radiation source
In visible - UV spectrometers, the most commonly used radiation sources are hydrogen (or) deuterium lamps.
2 Monochromators
The monochromator is used to disperse the radiation according to the wavelength. The essential elements of a
monochromator are an entrance slit, a dispersing element an exit slit. The dispersing element may be a prism or grating
(or) a filter.
3. Cells (sample cell and reference cell)
The cells, containing samples or reference for analyzing
4. Detectors
There are three common types of detectors used in UV visible spectrophotometers. The detector converts the radiation,
falling on which, into current. The current is directly proportional to the concentration of the solution.
5. Recording system
The signal from the detector is finally received by the recording system. The recording is done by recorder pen.
Working of UV and visible spectrophotometer
The radiation from the source is allowed to pass through the monochromator unit. The monochromator unit allows a
narrow range of wavelength to pass through an exit slit. The beam of radiation coming out of the monochromator is
split into two equal beams. One-half of the beams (the sample beam) are directed to pass through a transparent cell
containing a solution of the compound to be analyzed. The half (the reference beam) is directed to pass through
an identical cell that contains only the solvent. The instrument is designed in such a way that it can compare the
intensities of the two beams. If the compound absorbs light at a particular wavelength, then intensity of the sample
beam (I) will be less than that of the reference beam (l0). The instrument gives output graph, which is a plot of
wavelength Vs absorbance of the light. This graph is known as an absorption spectrum.

Block diagram of UV-visible spectrophotometer

UV-Visible spectrum
It is a plot of Absorbance (A) against wavelength (ƛ) of light. The wavelength of maximum absorbance (ƛmax) is a
characteristic value. Different compounds may have different absorption maxima and absorbance.
 Applications of UV- Visible or Electronic spectroscopy
1. For the detection of aromatic compounds, conjugated dienes etc.
2. For the characterization of dyes and colorants.
3. Detection of impurities. For e.g. benzene is a common impurity in cyclohexane which can be detected by
the absorption at 255nm.
4. Determination of unknown concentration. This is done by comparing the absorbance with the absorbance
of the standard solution.
5. Study of kinetics of chemical reactions. If a reaction involve shift of absorption frequency or wavelength,
the rate of such reaction can be easily monitored.
6. Widely used in medical lab for quantitative estimation of blood sugar, cholesterol etc. These tests are done
by measuring the absorbance after developing colour with suitable reagents.

INFRARED SPECTROSCOPY

IR spectroscopy deals with the infrared region of the electromagnetic spectrum. The range in the electromagnetic
spectrum extending from 12500 to 50 cm- 1 is commonly referred to as the infrared (IR). This region is further divided
into three sub regions.
1. Near infrared: - This region is from 12500 to 4000 cm–1
2. Infrared (or) ordinary IR: - This region is from 4000 to 667 cm–1
3. Far infrared: - This region is from 667 to 50 cm–1
Principle

Principle: Vibrational or IR spectroscopy involves the transitions between vibrational energy levels of a molecule,
having change in dipole moment with vibration of a bond. These transitions are brought about by absorbing IR
radiations falling in the range 500 - 4000 cm-1
Origin of IR spectra

The photons in the IR region are not energetic enough to cause electronic transitions. Infrared radiation is absorbed
by organic molecules and converted into energy of molecular vibration, either stretching or bending. An IR
spectrum is a plot of wavenumber (X-axis) vs percentage transmittance (Y-axis). Since the energy required is less
for rotational transitions, the resulting spectra is called vibrational- rotational spectrum.
For example when a hetero nuclear diatomic molecule like HCl undergo stretching vibration the dipole moment
changes with change in inter nuclear distance (dipole moment is the product of charge and distance) and shows IR
activity. Whereas homo nuclear diatomic molecules like H2, O2, N2 etc. are not vibrationally active as they possess
 no change in dipolemoment with stretching vibration.
Criteria for a compound to be IR active
When energy in the form of IR radiation is applied, it causes vibration of atom in a molecule if;
i) Correct wavelength of radiation: - frequency of incident radiation must exactly correspond to the frequency of
particular vibration mode

ii) Change in dipole moment (charge x distance): - The dipole moment of the molecule must vary during vibration
so that interaction with radiation is possible.

Molecular Vibrations
Since atoms in a molecule are continuously vibrating, molecules are also vibrating. There are two kinds of fundamental
vibrations in the molecule.
1. Stretching vibrations
During stretching the distance between two atoms decreases or increases, but bond angle remains unaltered.
Types of stretching vibrations
(a) Symmetric stretching: - In this type the movement of the atoms with respect to a particular atom in a
molecule is in the same direction. As a result of symmetric stretching in a molecule bond length increases
or decreases.

(b) Asymmetric stretching vibrations: - In these vibrations, one atom approaches the central atom while the
other departs from it. As a result of asymmetric stretching bond length changes.

2. Bending (or) deformation vibrations

During bending bond angle increases and decreases but bond distance remains unaltered.
Types of bending vibrations
(a) Scissoring: - In this type, the atoms move away and come close to each other in the same plane just like
blades of scissor.
(b) Rocking: - In this type, the movement of atoms take place in the same direction.
(c) Twisting: - In this type, one of the atoms moves up the plane while the other moves down the plane with
respect to the central atom.
(d) Wagging; - In this type, two atoms move up and below the plane with respect to the central atom.

Number of stretching and bending vibrations

The number of fundamental (or) normal vibrational modes of a molecule can be calculated as follows.
1. For Non-linear molecule
A non-linear molecule containing ‘n’ atoms has (3n - 6) fundamental vibrational modes.
2. For linear molecules
A linear molecule containing ‘n’ atoms has (3n-5) fundamental vibrational modes.
Illustrations
1. Water (n = 3)
Water is a bent (non-linear) triatomic molecule, and has 3n–6 = (3×3–6) = 3 fundamental vibrational modes.
They are symmetric stretching, asymmetric stretching and a bending mode. These modes and their corresponding
frequencies are shown below

In general stretching frequencies are much higher than bending frequencies. This is because; more energy is
required to stretch a bond than to bend it. All the above 3 vibrations are said to be active (change in dipole moment
during the vibration) in the IR region and the IR spectrum of water exhibits 3 absorption bands at 1596, 3652 and 3756
cm–1 corresponding to the bending, symmetric stretching and the asymmetric stretching vibrations respectively.Thus,
for a vibration to be active in IR, the dipole moment of the molecule must change.
2. Carbon dioxide (n = 3)
Carbon dioxide is a linear triatomic molecule, and has 3n- 5 = (3 x 3 - 5) = 4 fundamental vibrational modes.
Symmetric stretching, asymmetric stretching and two bending vibrations in two mutually perpendicular planes. These
modes and corresponding frequencies are shown (Fig. 1.5).

Of the four normal modes of vibration of C02, only three are IR active. The asymmetric stretching and two bending
vibrations involve change in dipole moment so they are IR active. But the symmetric stretching vibration does not
involve any change in the dipole moment (IR inactive). Thus, though there are three active vibrations, two of them
(two bending vibrations) have the same frequency, so the IR spectrum of CO2 exhibits only two bands i.e. one at 666
cm-1 for bending vibration and another at 2350 cm–1 for asymmetric stretching.
Applications of IR spectroscopy

1. Identity of the compound can be established

2. Detection of functional groups
3. Testing purity of a sample
4. Study of progress of a chemical reaction
5. Determination of shape or symmetry of a molecule
6. Determination of force constant (k)
A simple harmonic oscillator can be considered as a model for vibrating diatomic molecule. Consider two atoms of
masses m1 and m2 connected by means of chemical bond of force constant k. According to classical mechanics the
fundamental frequency of vibration ν0 is given by

ν0 = 1/ 2π √ k/μ where μ is the reduced mass of the system is given by μ = m1m2 / m1+ m2
k = 4 π2 ν02 μ
In IR spectroscopy ν0 = ν and ν = c ν
k = 4 π2 c2 (ν) 2 μ
Problems

The CO molecule absorbs infrared frequency of 2140cm-1. Calculate the force constant of the chemical bond, given
that atomic masses of C= 12 amu and O = 16amu.
k = 4 π2 c2 (ν) 2 μ
μ = m1m2 / m1+ m2
= 12x 1.66 x 10-27kg x 16x 1.66x10-27kg / 12x1.66 x 10-27kg x 16x 1.66x10-27 kg
= 1.4 x 10-26kg
Frequency of absorbed IR radiation (ν) is equal to fundamental vibrational frequency of the molecule (ν0)
k = 4 π2 ν2 μ
ν=cν
k = 4 π2 c2 ν2 μ Given that ν = 2140cm-1
k = 4 x 3.142 x (3x108ms-1)2 x (2140x102 m-1)2 x 1.14x 10-26 kg = 1853Nm-1

Scanning Electron Microscopy (SEM)

Scanning Electron Microscopy (SEM) is an important surface characterization technique used in nanotechnology.
It is a powerful magnification to that utilizes focused beam of electrons toobtain information.
The resolution power of electron microscopy is very high (~10 nm) since electrons are used for illumination
(wavelength of electrons are 105 times shorter than that of light). Therefore nano-sized particles can be seen with the
help of SEM.
Principle:
SEM produces images of a sample by scanning the surface with a focused beam of electrons. The interaction of
electron beam with the atoms near the surface of the sample results in the production of secondary electrons (SE),
back scattered electrons (BSE) and X-rays. These signals are then detected by appropriate detectors and can be used
to obtain information about the surface topography and composition. The high- resolution, three-dimensional images
produced by SEM makes them invaluable in a variety of science and industry applications.

Secondary electrons (SE): They are electrons that are directly knocked out from the atom by primary/incidental
electron beam. They have low energy (< 50eV) and give information about topography

Back scattered electrons (BSE): They are incidental electrons that are reflected backwards. They have high energy
(> 50eV) compared to SE. They give information about topography and composition. BSE comes from deeper
regions of the sample whereas SE originates from the surface and that's why BSE and SE carry different types of
information.

X- rays: X-rays, emitted from beneath the sample surface, can provide element and mineral information
Auger Electrons: When core electrons are removed, leaving a vacancy, an electron from the higher energy level
may fall into the vacancy and resulting a release of energy. Mostly this energy emission us in the form of photonand
can transfer this energy to another electron which is ejected from the atom. These second ejected electron from the
valence shell is known as auger electrons

Instrumentation
SEMs consist of the following components:

1. Electron Source: Generates beam of energetic electrons. They are of two types:
a. Thermionic gun (produces electron beam at high temperature, eg:- W filament, LaB6 etc)
b. Field emission gun (produces electron beam under strong electric field)
2. Anode: Accelerates the electron beam. As the velocity of the electron increases wavelength decreases
(according to the De Broglie relation, λ = h/mV) and thus enhances the resolution power.
 3. Vacuum chamber: High vacuum minimises the scattering of electron beam.
4. Condenser lens: It is the electromagnetic lens used to focus the electron beam into small,
thin andcoherent beam. Generally tubes wrapped in coils, known as solenoids, are used as
condenser lenses.
5. Objective lens: It is also an electromagnetic lens. Electron beam passes through the
scanning coils ofobjective lens that deflect the beam in raster fashion over a rectangular area of
sample surface.
6. Sample chamber: The sample is kept in the sample chamber.
7. Detectors: There are suitable detectors to detect SE, BSE and X-rays.
8. PC control: To provide the SEM image.

Working: Electron gun generates a beam of energetic electrons which are accelerated using the anode.
The accelerated electrons are then focused into a coherent beam using condenser lens. Objective lens then
focuses thebeam onto the stage, where the solid sample is placed. SE, BSE and X-rays produced from the
sample are detectedusing suitable detectors and black and white, three dimensional images are obtained
after processing. SEM data provides information about size, shape, texture and composition of the
sample. Image magnification can be up to10 nanometers and, although it is not as powerful as its TEM
counterpart.

Applications

1. SEM helps in the characterizations of solid materials.

2. It can detect and analyse surface fractures, surface contamination and provide in formation
inmicrostructures.

3. It helps to reveal spatial variations in chemical compositions and to identify crystalline

structures,

4. It is used as an essential research tool in fields such as life science, nano-science,

gemmology, medicaland forensic science.

5. SEMs have practical industrial and technological applications such as semiconductor

inspection,production line of miniscule products and assembly of microchips for computers.
 Thermal Analysis
Thermal analysis deals with the study of properties of materials with change in temperature. There are
different techniques available for thermal analysis which include thermogravimetric analysis (TGA),
differential thermal analysis (DTA), dielectric thermal analysis (DETA) etc. These methods are based
on the measurement of dynamic relationship between temperature and any one of the properties such
as mass change, heat change, mechanical change, phase change etc.

Dielectric Thermal Analysis

Dielectric analysis is a collective term used for a group of techniques that are employed for the
measurement of dielectric properties of a material as a function of time, temperature or frequency. One
such technique is dielectric thermal analysis (DETA), where the change in dielectric properties of
a material under an applied voltage is recorded with change in temperature. It is used to study
the thermal and dielectric properties of a material simultaneously and provides information
about dielectric changes with temperature.

Instrumentation

1. Sample holder/capacitor: Sample is placed in between with the two parallel metal plate electrodes.
Proper electrical contact should be maintained between the sample and electrodes. A grounded
electrode surrounding one of the plates, called a guard ring, is sometimes used to reduce stray electric
fields to improve the performance.
2. Programmable furnace: Furnace with temperature programming facility is used to ramp up and down
the temperature of the sample. It is used to provide the suitable heating rate also.
3. Temperature sensor: Thermocouples are used as the temperature sensors, which will record the
temperature of the sample.
4. Frequency generator: Sinusoidal voltage (alternating current) is provided through the frequency
generator. It allows the study of dielectric properties of the sample at different frequencies.
5. Environment control equipment: It is used to provide the suitable atmosphere (eg. air, inert gas) for
the sample as per requirement.
6. Temperature control equipment: Prevents the over heating of the sample.
7. Dielectric analyzer: It is the key component of DETA which acts as the detector and detects the
relative permittivity and dielectric lose for every change in temperature. It includes an impedence
analyser or LCR meter to measure the dielectric properties of the sample.
8. Recorder: Computer will record the data and DETA curve is obtained as a plot between temperature
and relative permittivity or dielectric loss. Known standard materials such as low-density
polyethylene (LDPE), alumina etc. are used as reference material to calibrate the system. Many DTA
instruments use a dual-compartment holder for measuring the dielectric properties of both the sample
and a reference material under identical conditions.
 Working
Sample in the form of thin film, powder, sheet, pellet etc; is placed in between the two electrodes and
an alternating electric field is applied. The temperature of the sample is increased at a control rate using
programmable furnace under suitable environmental condition. The response signal is detected and
analysed using dielectric analyser. In general, the sinusoidal voltage is applied to one of the electrodes
and the response is then measured at the second electrode. The dielectric response is recorded for every
change in temperature under a constant frequency. Temperature of the sample is monitored using the
thermocouple. DETA plot is obtained between temperature vs relative permittivity or dielectric loss.
Figure shows the DETA profile of PET at different frequencies; the glass-rubber transition of the
polymer can be observed as a step increase in ’ and a peak in ’’ around 150°C.

Applications of DETA

1. Used to analyse food, pharmaceuticals, polymers, plastics, glasses, ceramics, proteins etc.
2. Used to identify the phase transition temperatures like glass transition temperature in polymers,
especially for those which are not easily detected using other thermal tech-nique.
3. Used to study the curing profile of thermoset, flow behaviour and phase transitions like melting,
crystallization etc. in polymers, composite materials etc.
4. Used to study epoxy curing process and the related rheological properties in the fabrication of polymer-
matrix composite materials.
5. Study of dielectric properties at different temperatures is used for the development of new insulating
materials and energy storage materials.
Advantages of DETA
1. It can be used to analyze solid, semi-solid and liquid materials.
2. It is more sensitive compared to other thermal analysis techniques.