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MOLECULAR SPECTROSCOPY
AND
ANALYTICAL TECHNIQUES
SYLLABUS
Molecular Spectroscopy and Analytical Techniques
[Link]-Types of spectra- Molecular energy levels - Beer Lambert’s
law – Numerical problems
2. Electronic Spectroscopy – Principle, Types of
electronic transitions –Role of conjugation in absorption maxima-
Instrumentation-Applications
[Link] spectroscopy – Principle-
Number of vibrational modes - Vibrational modes of CO2 and H2O –
Applications
[Link] Analysis: Dielectric Thermal Analysis (DETA) of Polymers-
Working and Application.
[Link] Microscopic Techniques: SEM - Principle, instrumentation and
Applications.
 SPECTROSCOPY

• It is the branch of science that deals with study of interaction matter

with light or
• It is the branch of science that deals with study of interaction of
matter with electromagnetic radiation
• Electromagnetic radiation of particular wavelength or range of wave
length is used for qualitative and quantitative analysis of matter
• Matter : anything which can occupy space in universe and having
mass
• electromagnetic radiation :
wave produced by motion of electrically charged particle
consist of 2 component:electrical and magnetic field
Properties of waves
• Wavelength(λ):distance between two nearest crest or trough
• Frequency: Number of wavecycle in a given time,measured in
hertz(Hz)
• Amplitude: wave`s height or length
• Relationship between frequency and wavelength
velocity (speed) of propogation :

Relation between frequency of light and energy

ELECTROMAGNETIC
RADIATION
• The particle in matter has different types of energy associated with
them
They are
1. Rotational energy
2. Vibrational energy
3. Electronic energy
INTERACTION OF ELECTROMAGNETIC RADIATION WITH MATTER
• Absorption of Radiation
1. Electronic energy level
molecules are present at lowest energy level E0
molecule absorb energy(UV/Visible)promoted to higher energy
level
Difference in energy ( ΔE) = En – E0
= 35 to 71 kcl/mol
2. Vibrational energy level
Molecule absorb energy (IR)-promoted from one vibrational level to
another vibrational level
Difference in energy ( ΔE) = 0.01 to 10 kcl/mol
Less energy required than electronic energy level
Rotational energy level
Energy required is smaller than vibrational energy level
ΔErota < ΔEVibr < ΔE elec

Emission of radiation
Electromagnetic radiation is produced when excited particle
(ions,atoms,molecule) relax to lower energy level by giving up their
excess energy as photons
 TYPES OF SPECTRA
[Link] spectrum
• Whenever electromagnetic radiation interacts with atoms and molecules of
matter, the electrons in these atoms may absorb energy and jump to a higher
energy state, losing their stability.
• In order to regain their stability, they need to move from the higher energy state to
the previous lower energy state.
• To accomplish this job, these atoms and molecules emit radiation in various
regions of the electromagnetic spectrum.
• This spectrum of radiation emitted by electrons in the excited atoms or molecules
is known as an emission spectrum.
• However, the emission spectrum of atoms in the gas phase do not exhibit a
continuous spread of wavelength from one colour to others. Rather, the emitted
light consists of a specific wavelength having dark spaces existing between them.
Such kind of spectra is known as atomic spectra or line spectra.
[Link] spectrum
This spectrum is constituted by the frequencies of light transmitted with dark bands
when the electrons absorb energy in the ground state to reach higher energy states.
This type of spectrum is produced when atoms absorb energy
The dark line pattern is seen exactly in the same place where
coloured lines are seen in the emission spectrum. The spectrum thus obtained is
known as the absorption spectrum.
Emission spectra can emit all the colours in an electromagnetic
spectrum, while the absorption spectrum can have a few colours missing due to the
redirection of absorbed photons. The wavelengths of light absorbed help figure out
the number of substances in the sample.
BEER – LAMBERT LAW
When a monochromatic radiation is passed through the solution,
thedecrease in the intensity of radiation with thickness of the solution
is directly proportional to the intensity of the incident light as well as
concenteration of the solution
Let I be the intensity of incident radiation,X be
the thickness of the solution.C be the concenteration of the
[Link],
NUMERICAL PROBLEM
Electronic spectroscopy(UV Visible spectroscopy)
• EM radiation in the 10-800 nm region is capable of interactin with the
molecule give rise toelectronic transition
• 10-400 : UV Region
• 400-800: visible region
• UV radiation having wavelength less than 200 nm is difficult to handle
and not commonly used.
• It involve the study of electronic transition from lower to higher
energy levels in a molecular species by absorption of energy in the UV
and Visible light
FRANCK – CONDON PRINCIPLE
• The principle useful in explain the nature of electronic transition
and vibrational structure of electronic spectra
• In a molecule ,individual atom vibrate about mean position and
therefore ,the internuclear distance changes continuously
• According to FC principle,an electronic transition is rapid that
the vibrating molecule doesnot change its internuclear distance
appreciably during transition
• During electronic transition,the internuclear distance remain
same and straight line representing the transition between
electronic state will be vertical
• The transition between electronic state occur vertically in a
potential energy diagram
• The intensity distribution of line in the spectra of molecule is
not same .The variation of intensity are explained on the basis of
FC principle
Types of electronic transitions
• A molecule undergo various type of electronic transition
• All molecule have σ orbital and the σ*orbital
• Molecule with doublebond having π and π* orbitals
• Molecule containing heteroatoms(O,N,S) have nonbonding orbital(n)
Role of conjugation in absorbtion maxima
Instrumentation
 Application
• Identification of compound:identification of aromatic hydrocarbon
containing fused rings such as naphthalene ,[Link] greater
the number of fused ring ,the more complex the spectrum [Link]
spectrum of each compound is uniquely characteristic of its structure
• Detection of functional group
• Identification of geometrical isomers:trans isomers have higher
absorption maximum compared to cis counterpart
• Study of conjugation:presence of conjugation generally shift higher
absorption maxima to higher [Link] is useful in distinguishing
conjugated compound from non conjugated compound
• Impurity detection
• Study of strain
• Study of tautomeric equilibria
• Study of coordination complex
• Provide a host of information regarding nature and type of metal
ion,ligand present and type of interaction present in them
• Quantitative estimation in organic and inorganic chemistry
 Vibrational spectroscopy (IR spectroscopy)
• PRINCIPLE:
• The principle of IR spectroscopy is related to the vibrational and rotational
energy of a molecule
• When a frequency of the IR radiation is equal to the natural frequency of
vibration,the molecule absorb IR radiation
• Absorbtion of IR radiation causes an excitation of molecule from a lower to
the higher vibrational energy level
• Each vibrational level is associated with the number of closely packed
rotational [Link] is also called vibrational rotational spectroscopy
• The band correspond to the characteristic functional group and the band
present in a chemical [Link] spectrum of a compound is considered
as a fingerprint for its chemical identification
Normal mode of vibration
Vibrational mode of CO2

carbondioxide is triatomic molecule (n=3).For molecule has 3n degree

of [Link] linear molecule there will be (3n -5) fundamental
vibration
3n-5 =3(3)-5
= 9-5
=4

The mode of vibrations

• In symmetrical stretching,there is a partial charge separation due to 2
oxygen atom,the magnetic moment get cancelled each other,
molecule is nonpolar –IR inactive
• In asymmetrical stretching: one end is stretched and other end is
[Link] produce a fluctuating dipole moment – IR active
• Bending: there are 2 bending vibration ,differ only in their direction
and have same frequency and IR active
Vibrational mode of H2O
DIELECTRIC THERMAL ANALYSIS (DETA) OF
POLYMERS
DETA is a combination of dielectric analyisis and thermal analysis
to study the thermal and dielectric property of metal

• Dielectric thermal analysis (DETA) is a materials science technique in

which an oscillating electric field is used to analyze changes in the
physical properties of a number of polar materials
• This thermal analysis technique can be used with materials in a range
of forms, from thin films and sheet materials to powders or liquids
PRINCIPLE
• The sample is placed in contact with two
electrodes (the dielectric sensor). When a
sinusoidal voltage is applied, the charge carriers
inside the sample are forced to move: positively
charged particles migrate to the negative pole and
vice versa. This movement results in a sinusoidal
current with a phase shift.
• In the frequency range (up to 1 MHz), the charge
carriers are mainly ions (often present as catalysts
or impurities) and additionally dipole alignment
takes place within the electrical field.
• Sample is subjecting to a varying electric field while
simultaneously measuring its temperature
• [Link] Analyser
• This is the instrument used for dielectric measurement
• It applies an electricfield to the sample and measure its
response in terms of dielectric permittivity & dielectric loss
as a function of temperature and frequency
• 2. Furnace
• The sample is subjected to controlled temperature changes
during the analysis
• The furnace maintain the desired temperature while
dielectric properties are measured
• [Link] holder
• The sample holder consist of 2 parallel plate made of
conductive material sandwich the sample being analysed
• The plate serve as electrodes for applying the electric field
to sample
• [Link] generator
• It is the important component of dielecric analyser
• DETA involves measurement at different frequencies
• It allow the user to study the dielectric response over a range of
frequencies
• [Link] Acquistition system
• This system records and processes the data obtained during the
analysis
• It capture the dielectric response of the sample and convert it in to
meaningful data,such as dielctric loss and dielectric permitivitty
• [Link]
• Used to maintain desired temperature inside the furnace
• Thermocouples are temperature sensors placed near the sample to
monitor the sample temperature
DATA INTERPETATION
APPLICATION
• Dielectric thermal analysis can be used in investigations into the
curing behavior of thermosetting resin systems, adhesives, paints,
and composite materials. Dielectric thermal analysis can also be used
to characterize polar materials including:

• PVC – polyvinyl chloride

• PVDF – polyvinylidene fluoride

• PMMA – poly(methyl methacrylate)

• PVA – poly(vinyl acetate)

• Polymer properties examined by DETA are permittivity (ε’), the measure of
the degree of alignment of the molecular dipoles to the electrical field, and
the loss factor (ε”), which represents the energy required for the
reorientation of the dipoles and ions. The dissipation factor (tan δ = ε”/ε’)
and the conductivity (σ-1) are also examined.

• With DETA, the dielectric constant and polarizability of polymers are easily
detected during phase transitions such as the glass transition (Tg), a unique
characteristic of polymers in which a material will transition from a hard
state (glassy) to a viscous state as the temperature of the polymer is
increased. Other transitions include melting and crystallization and
secondary transitions.

• Other applications of dielectric thermal analysis are monitoring curing

kinetics of epoxy and urethane systems.

• Used to study the dielectric properties of various material

ADVANTAGE
• Data can be gathered from samples in a wide range of forms, from
solids and liquid, to powders or pellets.
• DETA is also more sensitive than DSC, allowing it to obtain better data
on samples
• dielectric thermal analysis is able to offer frequencies beyond 100 Hz.
DISADVANTAGE
• Sensitivity of DETA can be affected by various factors such as sample
size,sample preparation
• Preparation of sample for DETA can be difficult for obtaining accurate
results
• Interpretation of DETA require experience and expertise
• DETA is not available like other technique
• DETA performed in a limited and specific temperature range,which is
difficult to maintain
SCANNING ELECTRON MICROSCOPY (SEM)
• SEM is a type of electron microscope that is capable of producing
high resolution image of a sample surface
• SEM image have characteristic 3D appearance and is useful in judging
the surface structure of a sample
• Principle:
• SEM work on the principle of scattering of electron on the surface of
sample
• It is a type of electron microscope which produce images of sample
by scanning the surface with a focused beam of electron
• Electron will interact with the atom present in the sample and
produce various signal
• Inforamation of the sample is obtained
Instrumentation
• Electron beam is thermionically emmited from an
electric gun fitted with a tungsten filament
cathode
• The beam is recorded by anode
• The beam travel through electromagnetic
field,lens which focus the beam down towards
the sample
• When the beam touches the surface of sample ,it
produce [Link] electron [Link] scattered
electron [Link]
• The emitted secondary electron are collected by
secondary electron detector and converted in to
signal that is sent to the screen which produce
final image
• Additional detector collect other rays produce
corresponding image
Main components are
[Link] gun :
2 types:
[Link] gun :apply thermal energy to the tungsten
filament to produce electron
Tungsten is used because
[Link] melting point b. low vapourpressure c. it is cheap
2. field emission gun : creat strong electricfield to pull electron
away from atom
2. Condenser lens:
Made up of magnet capable of bending the path of electron
Condenser lens focus and control electron beam
[Link] coil :
This consist of 2 solenoid oriented in such a way that to create 2
magnetic field perpendicular to each other
4. Chamber
This is the place where specimen is kept
[Link]
The device detect various way that electron beam interact with sample
object
Secondary electron detected by Secondary electron detector,this
detector produce most detailed images of an object surface
Other detectors such as backscattered electron detector and xray
detector
APPLICATION
• Used in a variety of industrial,commercial and research application
• Used in material science for research
• Forensic investigation
• Analysis of gunshot residue
• Measuring effect of climate
• Identifying new bacteria
• Work with in the field of genetics
• Identifying diseases and viruses
• Testing new medicines
 ADVANTAGE

• Provide 3D topography image of sample

• Important research tool to study surface morphology in
biological,medical,forensic science
• Cheaper than TEM
• It needed minimal sample preparation
• Scanning speed is high & produce image in lessthan in 5 minute
 DISADVANTAGE
• Size of SEM is large
• Require vaccum for its operator
• It can image only solid and inorganic sample
• Require special training to operate
• Require stable power supply,cooling system
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