UNIT IV: SPECTROSCOPIC TECHNIQUES & NON CONVENTIONAL ENERGY SOURCES

Part A: SPECTROSCOPIC TECHNIQUES

Electromagnetic spectrum-UV (laws of absorption, instrumentation, theory of electronic
spectroscopy, Frank-condon principle, chromophores and auxochromes, intensity shifts,
applications), FT-IR (instrumentation and IR of some organic compounds, applications)-magnetic
resonance imaging and CT scan (procedure & applications).
Part B: NON CONVENTIONAL ENERGY SOURCES
Design, working, schematic diagram, advantages and disadvantages of photovoltaic cell,
hydropower, geothermal power, tidal and wave power, ocean thermal energy conversion.

Part A: SPECTROSCOPIC TECHNIQUES:-

Electromagnetic radition:-
• Electromagnetic radiation is a form of energy that is produced by oscillating
electric and magnetic disturbance, or by the movement of electrically charged
particles traveling through a vacuum or matter.
• The electric and magnetic fields come at right angles to each other and
combined wave moves perpendicular to both magnetic and electric oscillating
fields thus the disturbance.

General Properties of all electromagnetic radiation:

1. Electromagnetic radiation can travel through empty space. Most other types
of waves must travel through some sort of substance. For example, sound
waves need either a gas, solid, or liquid to pass through in order to be heard.
2. The speed of light is always a constant. (Speed of light : 2.99792458 x 108 m
s-1)
3. Wavelengths are measured between the distances of either crests or troughs.
It is usually characterized by the Greek symbol λλ.

Amplitude:-

Amplitude is the distance from the maximum vertical displacement of the

wave to the middle of the wave. This measures the magnitude of oscillation
of a particular wave.

Wavelength
• Wavelength (λλ) is the distance of one full cycle of the oscillation. Longer
wavelength waves such as radio waves carry low energy; this is why we can
listen to the radio without any harmful consequences.
This wavelength frequently relationship is characterized by:
c=λν
where

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 • c is the speed of light,
• λλ is wavelength, and νν is frequency.

Frequency
Frequency is defined as the number of cycles per second, and is expressed as
sec-1 or Hertz (Hz). Frequency is directly proportional to energy and can be
express as: E=hν

where
E is energy,
h is Planck's constant, (h= 6.62607 x 10-34 J), and
ν is frequency.

Electromagnetic spectrum:-
• Electromagnetic waves have an extremely wide range of wavelengths,
frequencies, and energies.
• The highest energy form of electromagnetic waves are gamma (γ) rays and
the lowest energy form are radio waves.

Fig:-Electromagnetic spectrum with light highlighted

• As a wave’s wavelength increases, the frequency decreases, and as wave’s
wavelength decreases, the frequency increases.
• When electromagnetic energy is released as the energy level increases, the
wavelength decreases and frequency decreases.

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 • Thus, electromagnetic radiation is then grouped into categories based on its
wavelength or frequency into the electromagnetic spectrum.
• The different types of electromagnetic radiation shown in the electromagnetic
spectrum consists of radio waves, microwaves, infrared waves, visible light,
ultraviolet radiation, X-rays, and gamma rays. The part of the electromagnetic
spectrum that we are able to see is the visible light spectrum.

laws of absorption:-
• Absorption of light takes place when matter captures electromagnetic
radiation, converting the energy of photons to internal energy.
• Energy is transferred from the radiation to the absorbing species.

The Effect of Light Absorption on Matter:-

• Since the energy levels of matter are quantized, only light of energy that can
cause transitions from one existing energy level to another will be absorbed.
• We describe the energy change in the absorber as a transition or an excitation
from a lower energy level to a higher energy level.

Instrumentation and working of the UV spectrometers:-

Instrumentation and working of the UV spectrometers can be studied simultaneously.
Most of the modern UV spectrometers consist of the following parts-

 Light Source- Tungsten filament lamps and Hydrogen-Deuterium lamps are

most widely used and suitable light source as they cover the whole UV region .

 Amplifier- The alternating current generated in the photocells is transferred to

the amplifier. The amplifier is coupled to a small servometer.

 Recording devices- Most of the time amplifier is coupled to a pen recorder

which is connected to the computer. Computer stores all the data generated and
produces the spectrum of the desired compound.

 Photometer:-
An instrument for measuring the intensity of light or the relative intensity of a pair
of lights.Also called an illuminometer. It utilizes filter to isolate a narrow
wavelength region.

 Spectrophotometer:-
An instrument measures the ratio, or a function of the two, of the radiant power of
two EM beams over a large wavelength region.

 Colorimeter:-

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 An instrument which is used for measuring absorption in the visible region is
generally called colorimeter.

 Theory of electronic spectroscopy:-

• Electron spectroscopy is an analytical technique to study the electronic
structure and its dynamics in atoms and molecules.
• In general an excitation source such as x-rays, electrons or synchrotron
radiation will eject an electron from an inner-shell orbital of an atom.
• Detecting photoelectrons that are ejected by x-rays is called x-ray
photoelectron spectroscopy(XPS) or electron spectroscopy for chemical
analysis (ESCA).
• Detecting electrons that are ejected from higher orbitals to conserve energy
during electron transitions is called Auger electron spectroscopy (AES).
• Experimental applications include high-resolution measurements on the
intensity and angular distributions of emitted electrons as well as on the total
and partial ion yields.
Various methods emanate from the electron spectroscopy are:
• Electron spectroscopy for chemical Analysis Auger electron spectroscopy

Electron spectroscopy for chemical Analysis:-

In typical laboratory use, a sample is placed in the specimen chamber of a
scanning electron microscope (SEM). Because the SEM uses a beam of
electrons to illuminate the sample and produce the three dimensional images
often seen in lay news reports and publications as well as professional
journals, the sample must be able to conduct electricity

Auger electron spectroscopy (AES) is a common analytical technique used

specifically in the study of surfaces and, more generally, in the area of materials
science.

 Frank-condon principle:-
• The Franck–Condon principle is a rule in spectroscopy and quantum
chemistry that explains the intensity of vibronic transitions.
• Vibronic transitions are the simultaneous changes in electronic and vibrational
energy levels of a molecule due to the absorption or emission of a photon of
the appropriate energy.
• It states that when a molecule is undergoing an electronic transition, such as
ionization, the nuclear configuration of the molecule experiences no
significant change.
• This is due in fact that nuclei are much more massive than electrons and the
electronic transition takes place faster than the nuclei can respond.

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 • When the nucleus realigns itself with the new electronic configuration, the
theory states that it must undergo a vibration.

 CHROMOPHORE:
• The term chromophore was previously used to denote a functional group
of some other structural feature of which gives a color to compound.
• For example- Nitro group is a chromophore because its presence in a
compound gives yellow color to the compound.
• But these days the term chromophore is used in a much broader sense
which may be defined as “any group which exhibit absorption of
electromagnetic radiation in a visible or ultra-visible region “It may or
may not impart any color to the compound.
• Some of the important chromophores are: ethylene, acetylene, carbonyls,
acids, esters and nitrile groups etc.
 AUXOCHROMES:
• It is a group which itself does not act as a chromophore but when attached
to a chromophore, it shifts the adsorption towards longer wavelength
along with an increase in the intensity of absorption.
• Some commonly known auxochromic groups are: -OH, -NH2, -OR, -
NHR, and –NR2.
intensity shifts:-
There are four types of shifts observed in the UV spectroscopy-
a) Bathochromic effect:-
This type of shift is also known as red shift.
Bathochromic shift is an effect by virtue of which the absorption maximum
is shifted towards the longer wavelength due to the presence of an
auxochrome or change in solvents.

b) Hypsochromic shift- This effect is also known as blue shift. Hypsochromic

shift is an effect by virtue of which absorption maximum is shifted towards the
shorter wavelength. Generally it is caused due to the removal of conjugation
or by changing the polarity of the solvents.

c) Hyperchromic effect - Hyperchromic shift is an effect by virtue of which

absorption maximum increases. The introduction of an auxochrome in the
compound generally results in the hyperchromic effect.

d) Hypochromic effect- Hyperchromic effect is defined as the effect by virtue of

intensity of absorption maximum decreases. Hyperchromic effect occurs due
to the distortion of the geometry of the molecule with an introduction of new
group.

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Applications of UV spectroscopy:-
1. Detection of functional groups- UV spectroscopy is used to detect
the presence or absence of chromophore in the compound.
This is technique is not useful for the detection of chromophore in
complex compounds.
The absence of a band at a particular band can be seen as an
evidence for the absence of a particular group.

2. Detection of extent of conjugation- The extent of conjugation in the

polyenes can be detected with the help of UV spectroscopy. With the
increase in double bonds the absorption shifts towards the longer
wavelength.
3. Identification of an unknown compound- An unknown compound
can be identified with the help of UV spectroscopy. The spectrum of
unknown compound is compared with the spectrum of a reference
compound and if both the spectrums coincide then it confirms the
identification of the unknown substance.
4. .Determination of configurations of geometrical isomers- It is
observed that cis-alkenes absorb at different wavelength than the
trans-alkenes. The two isomers can be distinguished with each other
when one of the isomers has non-coplanar structure due to steric
hindrances.

 FT-IR:-
• FTIR stands for Fourier transform infrared, the preferred method of infrared
spectroscopy.

• When IR radiation is passed through a sample, some radiation is absorbed

by the sample and some passes through (is transmitted).

• The resulting signal at the detector is a spectrum representing a molecular

‘fingerprint’ of the sample.

• The usefulness of infrared spectroscopy arises because different chemical

structures (molecules) produce different spectral fingerprints.

So, what is FTIR?

• The Fourier Transform converts the detector output to an interpretable

spectrum.
• The FTIR generates spectra with patterns that provide structural insights.

How does FTIR work and why use it?

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The FTIR uses interferometry to record information about a material placed in the IR
beam. The Fourier Transform results in spectra that analysts can use to identify or
quantify the material.

• An FTIR spectrum arises from interferograms being ‘decoded’ into

recognizable spectra
• Patterns in spectra help identify the sample, since molecules exhibit specific
IR fingerprints.

 IR of some organic compounds:-

• IR (infrared) spectroscopy is useful in organic chemistry because it enables
you to identify different functional groups.
• This is because each functional group contains certain bonds, and these
bonds always show up in the same places in the IR spectrum.
• To generate the IR spectrum, different frequencies of infrared light are
passed through a sample, and the transmittance of light at each frequency is
measured.
• Different functional groups produce bond absorptions at different locations
and intensities on the IR spectrum.
• This table lists the locations and intensities of absorptions produced by typical
functional groups.

 Sampling and applications of FTIR:-

• FTIR can be a single purpose tool or a highly flexible research instrument.

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 With the FTIR configured to use a specific sampling device – transmission or
ATR for instance – the spectrometer can provide a wide range of information:

• Most commonly, the identification of an unknown

• Quantitative information, such as additives or contaminants
• Kinetic information through the growth or decay of infrared absorptions
• Or more complex information when coupled with other devices such as TGA,
GC or Rheometry
Ultimately, FTIR can be a cost-effective answer machine.

Magnetic resonance:-
• Magnetic Resonance (MR) spectroscopy is a noninvasive diagnostic test for
measuring biochemical changes in the brain, especially the presence of tumors.
• While magnetic resonance imaging (MRI) identifies the anatomical location of a
tumor, MR spectroscopy compares the chemical composition of normal brain tissue
with abnormal tumor tissue.

How does MR spectroscopy work?

• MR spectroscopy is conducted on the same machine as conventional MRI. The MRI
scan uses a powerful magnet, radio waves, and a computer to create detailed
images.
• MR spectroscopy analyzes molecules such as hydrogen ions or protons.
• Proton spectroscopy is more commonly used.
• There are several different metabolites, or products of metabolism, that can be
measured to differentiate between tumor types:
o Amino acids o
Lipid o Lactate
o Alanine
o N-acetyl aspartate
o Choline o
Creatine o
Myoinositol

Magnetic Resonance Imaging (MRI) & CT scan

• MRI is a non-invasive imaging technology that produces three dimensional
detailed anatomical images.
• It is often used for disease detection, diagnosis, and treatment monitoring.
• It is based on sophisticated technology that excites and detects the change in the
direction of the rotational axis of protons found in the water that makes up living
tissues

How does MRI work?

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 • MRIs employ powerful magnets which produce a strong magnetic field that forces
protons in the body to align with that field.
• When a radiofrequency current is then pulsed through the patient, the protons are
stimulated, and spin out of equilibrium, straining against the pull of the magnetic
field.
• To obtain an MRI image, a patient is placed inside a large magnet and must
remain very still during the imaging process in order not to blur the image.

What is MRI used for?

• MRI scanners are particularly well suited to image the non-bony parts or soft tissues
of the body.
• They differ from computed tomography (CT), in that they do not use the damaging
ionizing radiation of x-rays.
• The brain, spinal cord and nerves, as well as muscles, ligaments, and tendons are seen
much more clearly with MRI than with regular x-rays and CT; for this reason MRI is
often used to image knee and shoulder injuries.
• In the brain, MRI can differentiate between white matter and grey matter and can also
be used to diagnose aneurysms and tumors.
• Because MRI does not use x-rays or other radiation, it is the imaging modality of
choice when frequent imaging is required for diagnosis or therapy, especially in the
brain.
• However, MRI is more expensive than x-ray imaging or CT scanning.
• One kind of specialized MRI is functional Magnetic Resonance Imaging (fMRI.)
• This is used to observe brain structures and determine which areas of the brain
“activate” (consume more oxygen) during various cognitive tasks.
• It is used to advance the understanding of brain organization and offers a potential
new standard for assessing neurological status and neurosurgical risk.

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UNIT-4 (ADVANCED CONCEPTS/TOPICS IN CHEMISTRY)
Computational chemistry: Introduction, Ab Initio studies
Molecular switches: characteristics of molecular motors and machines, Rotaxanes and Catenanes
as artificial molecular machines, prototypes – linear motions in rotaxanes, an acid-base controlled
molecular shuttle, a molecular elevator, an autonomous light-powered molecular motor

Computational chemistry:-
 Introduction:-
• Computational chemistry is a branch of chemistry that uses
computer simulation to assist in solving chemical problems.
• It uses methods of theoretical chemistry, incorporated into
efficient computer programs, to calculate the structures and
properties of molecules and solids.
• It is necessary because, apart from relatively recent results
concerning the hydrogen molecular ion (dihydrogen caution, see
references therein for more details), the quantum many-body
problem cannot be solved analytically, much less in closed form.
• While computational results normally complement the information
obtained by chemical experiments, it can in some cases predict
hitherto unobserved chemical phenomena.
• It is widely used in the design of new drugs and materials.
• Examples of such properties are structure (i.e., the expected
positions of the constituent atoms), absolute and relative
(interaction) energies, electronic charge density distributions,
dipoles and higher multipolar moments, vibrational frequencies,
reactivity, or other spectroscopic quantities, and cross sections
for collision with other particles.

 Ab Initio studies:-
• Ab initio methods are based entirely on quantum mechanics and
basic physical constants.
• The programs used in computational chemistry are based on
many different quantum-chemical methods that solve the
molecular Schrödinger equation associated with the molecular
Hamiltonian.
• Methods that do not include any empirical or semi-empirical
parameters in their equations – being derived directly from

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 theoretical principles, with no inclusion of experimental data – are
called ab initio methods.

Fig: ab intio methods

Molecular switches: - A molecular switch is a molecule that can

be reversibly shifted between two or more stable states.
characteristics of molecular motors and machines:-
• Molecular motors:- o Molecular motors are natural (biological)
or artificial molecular machines that are the essential agents of
movement in living organisms. o In general terms, a motor is a
device that consumes energy in one form and converts it into
motion or mechanical work;
o For example, many protein-based molecular motors harness
the chemical free energy released by the hydrolysis of ATP in
order to perform mechanical work. o In terms of energetic
efficiency, this type of motor can be superior to currently
available man-made motors.
o One important difference between molecular motors and
macroscopic motors is that molecular motors operate in the
thermal bath, an environment in which the fluctuations due to
thermal noise are significant.
• Molecular machines:- o A molecular machine, nanite, or Nano
machine, is a molecular component that produces quasi-
mechanical movements (output) in response to specific stimuli
(input).
o In biology, macromolecular machines frequently perform tasks
essential for life such as DNA replication and ATP synthesis.
o The expression is often more generally applied to molecules
that simply mimic functions that occur at the macroscopic level.

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 o The term is also common in nanotechnology where a number
of highly complex molecular machines have been proposed
that are aimed at the goal of constructing a molecular
assembler.
Rotaxanes and Catenanes as artificial molecular machines:-
• Rotaxanes:- o A rotaxane is a mechanically interlocked
molecular architecture consisting of a "dumbbell shaped molecule"
which is threaded through a "macro cycle" (see graphical
representation). o The name is derived from the Latin for wheel
(rota) and axle (axis).
o The two components of a rotaxane are kinetically trapped since
the ends of the dumbbell (often called stoppers) are larger than
the internal diameter of the ring and prevent dissociation
(unthreading) of the components since this would require
significant distortion of the covalent bonds.

• Catenanes as artificial molecular machines:- o An artificial

molecular machine consists of molecule or substituent
components jointed together in a specific way so that their mutual
displacements could be initiated using appropriate outside stimuli.
o Such an ability of performing mechanical motions by
consuming external energy has endowed these tiny machines
with vast fascinating potential applications in areas such as
actuators, manipulating atoms/molecules, drug delivery,
molecular electronic devices, etc.
o To date, although vast kinds of molecular machine archetypes
have been synthesized in facile ways, they are inclined to be
defined as switches but not true machines in most cases
because no useful work has been done during a working cycle.
Prototype:-
o A prototype is an early sample, model, or release of a product built to test a
concept or process. o It is a term used in a variety of contexts including
semantics, design, electronics, and software programming.
o A prototype is generally used to evaluate a new design to enhance precision
by system analysts and user.

Basic prototype categories:-

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Prototypes explore different aspects of an intended design:
• A Proof-of-Principle Prototype serves to verify some key functional aspects of
the intended design, but usually does not have all the functionality of the final
product.
• A Working Prototype represents all or nearly all of the functionality of the final
product.
• A Visual Prototype represents the size and appearance, but not the
functionality, of the intended design.
• A Form Study Prototype is a preliminary type of visual prototype in which the
geometric features of a design are emphasized, with less concern for color,
texture, or other aspects of the final appearance.
• A User Experience Prototype represents enough of the appearance and
function of the product that it can be used for user research.
• A Functional Prototype captures both function and appearance of the intended
design, though it may be created with different techniques and even different
scale from final design.

Rotaxane:-
• A rotaxane is a mechanically interlocked molecular architecture consisting of a
"dumbbell shaped molecule" which is threaded through a "macrocycle" .
• The name is derived from the Latin for wheel (rota) and axle (axis).
• The two components of a rotaxane are kinetically trapped since the ends of the
dumbbell (often called stoppers) are larger than the internal diameter of the ring
and prevent dissociation (unthreading) of the components since this would
require significant distortion of the covalent bonds.

An acid-base controlled molecular shuttle:-

• This paper describes the acid/base-mediated three-state translational
isomerization of two [2]rotaxanes, each containing N-alkylaniline and N,N-
dialkylamine centers as binding sites for threaded dibenzo[24]crown8 units.
• Under neutral conditions, the dialkylamine unit predominantly recognized
the crown ether component through cooperative binding of a proton; when
both amino units were protonated under acidic conditions, both translational
isomers were generated; the addition of a strong base caused aniline–crown
ether interactions to dominate.
• The three states of the rotaxane featuring the 3,5-diphenylaniline terminus in
its dumbbell-shaped component were accompanied by distinct absorptive
outputs that were detectable using UV spectroscopy.

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A molecular elevator:-
• We report the incrementally staged design, synthesis, characterization, and
operation of a molecular machine that behaves like a nano scale elevator.
• The operation of this device, which is made of a platform like component
interlocked with a trifurcated riglike component and is only 3.5 nanometers by
2.5 nanometers in size, relies on the integration of several structural and
functional molecular subunits.
• This molecular elevator is considerably more complex and better organized
than previously reported artificial molecular machines.

An autonomous light-powered molecular motor:-

Molecular motor runs all by itself, without external intervention, on a tank of
chemical fuel

Motor proteins are essential for moving muscles in animals and transporting
molecules across cell membranes.
Researchers have now mimicked them by designing and creating the first synthetic
motor that runs autonomously—without further intervention—on chemical fuel.
Mother Nature isn’t easy to emulate, so an artificial chemically powered motor that
works like a motor protein “is a major advance,”
Earlier non autonomous chemically powered motors required constant intervention
they had to be fed a sequence of compounds to complete each operating cycle.

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