Chemistry ESE Combined

Catalog
1.Spectroscopy CH132P.pdf ································································································································································ 1

2.Electrochemistry1.pdf ····································································································································································· 93
3.CORROSION ITS CONTROL modified.pdf ································································································································· 146
4.Thermodynamics.pdf ···································································································································································· 197
5.1WATER TECHNOLOGY.pdf ······················································································································································· 242
5.2 charecterisation.pdf ··································································································································································· 262
Spectroscopic Techniques and
Applications
MISSION VISION CORE VALUES

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Do’s and Don'ts for Students….
● Will be shared through the Google classroom or LMS

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Course Outcome
• Students will be able to explain the basic principles of IR spectroscopy

and UV Visible spectroscopy
• Students will be able to outline the oxidation and reduction reactions
which are relevant to study the concepts of corrosion science and
electrochemistry.
• Students will be able to analyze the various types of corrosion occurring
on metal surfaces by knowing electrochemical theory of corrosion
• Students will be able to explain the basic concepts of
thermodynamics, 1st law and 2nd law of thermodynamics
• Students will be able to illustrate the fundamentals of characterization
techniques and waste water treatment

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Spectroscopy
● The history of spectroscopy began with Isaac Newton's optics

experiments (1666–1672).
● Newton-"spectrum" to describe the rainbow of colors that combine to
form white light and that are revealed when the white light is passed
through a prism.
● Early 1800s, Joseph von made-dispersive spectrometers- spectroscopy
to become a more precise and quantitative scientific technique.
● Significant role in chemistry, physics, medical science and astronomy.

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Spectroscopy
It’s a branch of Science that deals with the interaction of matter with
electromagnetic radiation
or
In which electromagnetic radiation of particular wavelength /range of
wavelength is used for qualitative or quantitative analysis of matter
Matter
Anything which needed/occupies space in Universe and having mass is
called a matter.
Spectrum
A plot of the response as a function of wavelength/frequency is referred to
as Spectrum

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Spectrometry
• A spectrometer is a device for measuring these responses of light over
a wide range of the electromagnetic spectrum.
• It is widely used for spectroscopic analysis of sample materials.
• The incident light from the light source can be transmitted, absorbed
or reflected through the sample

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Electromagnetic Radiation
● Wave produced by the motion of Electrically charged particle with a

velocity. c = 3× 108 m/s (Photon)
● Consists of both Electric and Magnetic Components / Synchronized
oscillations of both Electric and Magnetic fields.
Image copied : https://en.wikipedia.org/wiki/File:Ondeelectromagnetique.svg

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Wave Parameters
Wavelength (λ)- It is the distance between two nearest parts of the
wave in the same phase.ie the distance between the nearest Crests or
Troughs and is measured in meters
Amplitude (A)- Length of the electrical vector at a maximum or minimum in

the wave.
https://en.wikipedia.org/wiki/File:Sine_wavelength.svg
https://qph.fs.quoracdn.net/main-qimg-
1ff351e5ca0d9c7f46123006590755e0

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Frequency (ν) - Number of cycles of a wave passing a fixed point per unit
time and is measured in Hertz (Hz)
1 Hz = 1 cycle per second
https://i.stack.imgur.com/y0qJV.png
Wavenumber (n) – It is the number of waves per unit distance / The

reciprocal of the wavelength in centimeters (cm-1)

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Relationship between frequency and wavelength
Velocity of light, c= ν λ (where c = 3× 108 m/s)
Relationship between frequency of light and Energy
E = h ν (where h is Plank’s Constant = 6.6261 × 10-34 J.s)
E= h c/ λ
E= mc2
mc2 = hc/ λ
λ = h/mc = h/mv (P=mv)

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Characteristics of EM Waves
• Electromagnetic waves are transverse in nature as they propagate by
varying the electric and magnetic fields such that the two fields are
perpendicular to each other
• Accelerated charges are responsible to produce electromagnetic waves.
• Electromagnetic waves have constant velocity in vacuum and it is nearly
equal to 3×108 ms−1
• Electromagnetic wave propagation does not require any material
medium to travel.
• The inherent characteristic of an electromagnetic wave is its frequency.
• Electromagnetic wave follows the principle of superposition.
• In an electromagnetic wave, the oscillating electric and magnetic fields
are in the same phase and their magnitudes have a constant ratio.
• The ratio of the amplitudes of electric and magnetic fields is equal to the
velocity of the electromagnetic wave.
• The energy is carried by the electric and magnetic fields of
electromagnetic waves are equal

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Electromagnetic Spectra
https://www.youtube.com/watch?v=HPcAWNlVl-8

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Types of Spectrum
Most spectroscopic methods are differentiated as either

• Atomic (Atomic Absorption Spectroscopy, Flame photometry)
• Molecular (UV- visible, IR Spectroscopy)
based on whether or not they apply to atoms or molecules.
• Absorption Spectroscopy
• Emission Spectroscopy
• Scattering Spectroscopy
The effect of interaction of electromagnetic rays with matter depends on

energy associated with the radiation and type of material.

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Absorption & Emission Spectroscopy

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Interaction of EMR with matter

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Interaction EMR with matter to give visible light
https://cdn.kastatic.org/ka-perseus-images/b8cb777559d81c6a6640187549bcd3907ebf0573.png

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Interaction of EMR with matter
1. Electronic Energy Levels:

• At room temperature the molecules are in the lowest energy levels E0.
• When the molecules absorb UV-visible light from EMR, one of the
outermost bond / lone pair electron is promoted to higher energy state
such as E1, E2, …En, etc. is called as electronic transition
• ΔE = hν = En - E0 where (n = 1, 2, 3, … etc)
• ΔE = 35 to 71 kcal/mole
2. Vibrational Energy Levels:

• These are less energy level than electronic energy levels.
• The spacing between energy levels are relatively small i.e. 0.01 to 10
kcal/mole.
• e.g. when IR radiation is absorbed, molecules are excited from one
vibrational level to another

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3. Rotational Energy Levels:

• These energy levels are quantized & discrete.
• The spacing between energy levels are even smaller than vibrational
energy levels.
∆Erotational < ∆Evibrational < ∆Eelectronic

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Molecular Energy Level Diagrams
• Explains the electronic structure of the molecules using quantum

mechanics
• Use of LCAO method (Linear combination of atomic orbitals)
• Suitable for diatomic molecules, but becomes complex in the case of
polyatomic molecules.
• Shown as short horizontal lines in the center, flanked by constituent
atomic orbital
• (AO) energy levels for comparison, with the energy levels increasing
from the bottom to the top.

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Construction of Molecular Energy Level Diagrams
• Atomic orbitals combine to form molecular orbitals

• Atomic orbitals can overlap in two different ways depending on their
phase relationship
• The phase (or sign) of an orbital is a direct consequence of the wave like
properties of electrons.
• Number of AO’s combine decides the number of MO’s
• Overlapping of sigma bonds are stronger compared to pi bond, so that
greater energy splitting will occur in sigma bonds
• Orbitals with same sign can interact constructively to give BMO with
high electron density at the centre

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• Orbitals with different sign (out of phase) can interact to form ABMO
with no electron density at the center (nodal plane)
• The filled MO high in energy is called HOMO and the MO just above
this is called LUMO
• Sometimes, atomic orbitals cannot be mixed due to energy or
symmetry problems, which results the formation of non-bonding
molecular orbitals.
• These orbitals are not contributing to bonding energetics.
• Bond Order = Electrons in BMO – Electrons in ABMO / 2

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Rules-Construction of Molecular Energy Level Diagrams
• Aufbau principle
Orbitals are filled starting with the lowest energy
• Pauli exclusion
The maximum number of electrons occupying an orbital is two, with
opposite spins
• Hund's rule
If there are several MO's with equal energy, the electrons occupy the MO's
one at a time before two electrons occupy the same MO

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Electronic Configuration of Diatomic Molecules

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MO Diagram of H2

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MO Diagram of NO

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MO Diagram of Methane

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Beer Lamberts Law
https://www.edinst.com/wp-content/uploads/2019/08/BLL-1.png

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Beer’s Law
According to this law, when a beam of monochromatic radiation is passed

through a solution of absorbing species, the intensity of beam of
monochromatic light decreases exponentially with increase in
concentration of absorbing species
-dI/dc α I
Lambert’s Law
Lambert’s law states that the rate of decrease of intensity of monochromatic

light with the thickness of the medium is directly proportional to the
intensity of incident
light.
-dI/dt α I

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Derivation of Beer Lambert’s Law

According to Beer’s law,
-dI /dc α I
The decrease in the intensity of light (I) with concentration(c) is
proportional to intensity of incident light (I)
-dI /dc = K I (K is proportionality constant)

-dI /I = K.dc
On integrating the above equation, ∫ -dI /I = ∫ K.dc
- ln I = K.c + b --------------------(1) (b constant of integration}

When concentration = 0, there is no Absorbance.
Hence I=I₀ and substituting in equation (1)
-ln I₀ = K × 0 +b
-ln I₀ = b

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Substituting the value of b in equation (1)

-ln I = K.c-ln I₀
ln I₀ - ln I = Kc {since log A- log B = log A/B}
So, ln I₀/ I = Kc
I₀/ I = ekc {removing natural log}
I/ I₀ = e-kc {making inverse on both sides}
I = I₀ e-kc ----------------------------(2) [Equation for Beer’s law]
According to Lambert’s law,
-dI/dt α I
This equation can be simplified by replacing ‘c’ with ‘t’ in (2)
I = I₀ e-kt ---------------------------------(3) [Equation for Lambert’s law]

Equation 2 & 3 can be combined to get
I = I₀ e-kct

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Converting natural log to base 10 & K= k/ 2.303
I/ I₀ = e-kct {rearranging terms}
I₀/ I = e kct {inverse on both sides}
Taking log on both sides,

log I₀/ I = Kct -------------------(4)
Here, Transmittance T = I/I₀ , & Absorbance, A = log 1/T

A = log 1/T
A = (log 1)/ (I/I₀) {Since T = I₀/I }
A =log I₀/I ------------------------(5)
Using equation 4&5, since A =log I₀/I and log I₀/I = Kct,
A= Kct
Instead of K, we can use ε Where ε = absorptivity, a constant dependent
upon the λ of the incident radiation and nature of absorbing material.
A = εct {Mathematical equation for Beer Lambert’s law}

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Beer Lambert’s – Graphical representation

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Colorimetry-Application of Beer Lamberts Law
• Wavelength region of 400-800nm

• Colored substance absorbs light of different λ in different manner and
hence get an absorption curve
• The λ at which maximum absorption takes place is called as λmax
• λmax is characteristic for every colored substance
• On plotting a graph of concentration v/s absorbance, we get a calibration
curve that is useful in determining the concentration or amount of a
substance substance in the given sample solution.

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Absorption Spectroscopy
• An analytical technique which concerns with the measurement of

absorption of electromagnetic radiation by various substances.
• e.g. UV (185 - 400 nm) / Visible (400 - 800 nm) Spectroscopy, IR
Spectroscopy (0.76 - 15 μm)
•
https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy
/Images/isopren1.gif

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U V Visible Spectroscopy
• The UV radiation region extends from 10 nm to 400 nm and the visible
radiation region extends from 400 nm to 800 nm.
Near UV Region: 200 nm to 400 nm
Far UV Region: below 200 nm
• Far UV spectroscopy is studied under vacuum condition.
• The common solvent used for preparing sample to be analyzed is either
ethyl alcohol or hexane.
• In UV/VIS spectroscopy, the transitions which result in the absorption of
EM radiation in this region are transitions btw electronic energy levels.

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Outline
• As light is absorbed by matter, the result is an increase in the energy
content of the atoms or molecules.
• When ultraviolet radiations are absorbed, this results in the excitation of
the electrons from the ground state towards a higher energy state.
• Molecules containing π-electrons or non-bonding electrons (n-electrons)
can absorb energy in the form of ultraviolet light to excite these
electrons to higher anti-bonding molecular orbitals.
• The more easily excited the electrons, the longer the wavelength of light
it can absorb. There are four possible types of transitions (π–π*, n–π*, σ–
σ*, and n–σ*), and they can be ordered as follows: σ–σ* > n–σ* > π–π* >
n–π*
• The absorption of ultraviolet light by a chemical compound will produce
a distinct spectrum which aids in the identification of the compound.

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Type of Transitions
● 3 types of electronic transitions
○ σ, п and n electrons
○ d and f electrons
○ Charge transfer electrons
What is σ,  and n electrons?

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CH2CH3 H H3C C C H
H C H propyne
C C
C C
H C H H H
H H C C
ethylbenzene
H
benzene C C
H H
1,3-butadiene

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Possible Electronic Transitions….
https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/Images/electrns.gif

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 to * transitions
• Never observed in normal UV/Vis spectra

• The absorption maxima are < 150 nm.
• The energy required to induce a σ to σ* transition is too great (see the
arrow in energy level diagram)
• This type of absorption corresponds to breaking of C-C, C-H, C-O, C-X,
….bonds

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n to * transitions
• Saturated compounds must contain atoms with unshared electron

pairs.
• Compounds containing O, S, N and halogens can absorb via this type
of transition.
• Absorptions are typically in the 150 -250 nm region and are not very
intense.
• ε range: 100 – 3000 Lcm-1mol-1
• Number of transitions are very small
• Sensitive to hydrogen bonding
• Example: ethers, aldehydes, amines etc

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Some examples of absorption due to n to σ* transitions
Compound λmax (nm) εmax

H 2O 167 1480
CH3OH 184 150
CH3Cl 173 200
CH3I 258 365
(CH3)2O 184 2520
CH3NH2 215 600

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n to * transitions
• Unsaturated compounds containing atoms with unshared electron

pairs
• These result in some of the most intense absorption in 200 – 700 nm
region.
• ε range: 10 – 100 Lcm-1mol-1
• Example: Oxygen and Nitrogen containing molecules
 to * transitions
• Unsaturated compounds to provide the  orbitals.

• These result in some of the most intense absorption in 200 – 700 nm
region.
• ε range: 1000 – 10,000 Lcm-1mol-1
• Example: alkene

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Characteristics of Spectrum
• The λmax refers to the wavelength of the most absorbed radiation and is a
measure of the difference in the electronic energy levels involved in the
transition
• The intensity on the other hand is indicative of the probability of the
transition i.e., whether the transition is allowed or not
• It is also is a measure of the concentration of the absorbing species.

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Absorption and Intensity Shifts
• Bathochromic Shift or Effect. The shift of an absorption maximum to a

longer wavelength due to the presence of an auxochrome or solvent
effect is called a bathochromic shift or red shift.
• Hypsochromic Shift or Effect. The shift of an absorption maximum to a
shorter wavelength is called hypsochromic or blue shift.
• This is caused by the removal of conjunction or change in the solvent
polarity.
• Hyperchromic Effect: An effect which leads to an increase in absorption
intensity Emax is called hyperchromic effect.
• The introduction of an auxochrome usually causes hyperchromic shift.
• Hypochromic Effect: An effect which leads to a decrease in absorption
intensity Emax is called hypochromic effect.
• This is caused by the introduction of a group which distorts the
chromophore.

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Chromophores:
• The part of a molecule responsible for imparting color, are called as
chromospheres.
Or
• The functional groups containing multiple bonds capable of absorbing
radiations above 200 nm due to n→ π* & π → π* transitions. e.g. NO2 ,
N=O, C=O, C=N, C≡N, C=C, C=S, etc
Auxochromes:
• Substituents with unshared pair e's like OH, NH, SH ..., when attached to
π chromophore they generally move the absorption max. to longer λ.
• The functional group with non-bonding electrons that does not absorb
radiation in near UV region but when attached to a chromophore alters
the wavelength & intensity of absorption.
• e.g. Benzene λmax =255 nm, Phenol λmax =270 nm, Aniline λmax =280 nm

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Major Components of Spectrophotometer
• Light Source
• Monochromator
• Sample and reference cells
• Detector
• Amplifier
• Recorder

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Instrumentation of UV Spectroscopy
Light Source
• Tungsten filament lamps and Hydrogen-Deuterium lamps are most
widely used and suitable light source as they cover the whole UV
region.
Monochromator
• Monochromators generally is composed of prisms and slits.
• Most of the spectrophotometers are double beam spectrophotometers..
• The beam selected by the slit is monochromatic and further divided
into two beams with the help of another prism.
Sample and reference cells

• One of the two divided beams is passed through the sample solution
and second beam is passé through the reference solution.
• Both sample and reference solution are contained in the cells.
• These cells are made of either silica or quartz.
• Glass can’t be used for the cells as it also absorbs light in the UV region.

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Detector
• Generally two photocells serve the purpose of detector in UV
spectroscopy.
• One of the photocell receives the beam from sample cell and second
detector receives the beam from the reference
Amplifier
• The alternating current generated in the photocells is transferred to the
amplifier.
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.

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INSTRUMENTATION:
Single and Double Beam Spectrometer
Single-Beam: There is only one light beam or optical path from the
source through to the detector
Double-Beam: The light from the source, after passing through the
monochromator, is split into two separate beams one for the sample
and the other for the reference

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Single beam spectrophotometer

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Double beam spectrophotometer

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Advantages of single & double beam spectrophotometer
Single beam
• Simple in construction,
• Easy to use and economical
Double beam
• It facilitates rapid scanning over wide λ region.
• Fluctuations due to radiation source are minimized.
• It doesn’t require adjustment of the transmittance at 0% and 100%
• at each wavelength.
• It gives ratio of intensities of sample & reference beams
• simultaneously.

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Frank-Condon Principle – Electronic transitions are too fast

that there will be no change in the internuclear bond distance
Importance of selection rules
❖ Spin Selection rule (2s+1)
❖ Laporte selection rule (g –u, u – g)
Allowed Vs Forbidden Transitions
Transition Probability and Boltzmann Distribution

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Boltzmann Distribution

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MO Diagram of Ethane

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MO Diagram of Ethylene

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MO Diagram of 1,3 – butadiene

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Applications of UV-Visible spectroscopy:

1. Characterization of aromatic compounds and conjugated dienes or
other aliens.
2. Detection of impurities: For example, benzene is the common impurity
in cyclohexane and its presence can be detected by the absorption at
255 nm
3. Control of purification: The purification process should be continued till
the Compound which is being purified stops showing band due to
4. Determination of unknown concentration.
5. Determination of molecular weight.
6. Study of kinetics of chemical reactions.
7. Measuring the change in concentration of the reactants or products
which exhibit absorption in UV-Vis region

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References
• C. N. Banwell, “Fundamentals of Molecular Spectroscopy”, McGraw-Hill,

4thedn., 1995.
• Principles of Instrumental Analysis 6th Edition by Skoog. Holler,Crouch
• Atkins P.W. “Physical chemistry” ELBS 9 Edition 2009, London

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IR-Spectroscopy – Syllabus
● Principle - Number of vibrational modes - Vibrational energy states

of a diatomic molecule and -Determination of force constant of
diatomic molecule (Numerical) –Applications.

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Infra-Red (IR) Spectroscopy

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Interaction of Electromagnetic Radiation
Frequency ()
Wavelength ()
Radio-waves Microwaves Infra-red Visible Ultra-violet X-ray -ray

Region Region Region Region Region Region Region
Frequency 106 - 1010 1010 - 1012 1012 - 1014 1014 - 1015 1015 - 1016 1016 - 1018 1018- 1020
(HZ)
Wavelength 10m – 1 cm 1 cm – 100µm 100µm – 1µm 700 – 400 nm 400-10 nm 10nm – 100pm –
100pm 1 pm
NMR, ESR Rotational Vibrational Electronic Electronic
Spectroscopy spectroscopy Spectroscopy Spec.
Energy 0.001 – 10 Order of some Some 104 Some 100 Some 100s 107- 109 109- 1011
J/mole 100 J/mole J/mole kJ/mole kJ/mole J/mole J/mole

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Infrared radiations bring about changes in the vibration modes (stretching,

contracting and bending) of covalent bonds in a molecule
Examples:
Example: Vibrating HCl molecule

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Principle
• Molecules are flexible.
• Atoms in organic molecules are constantly vibrating around average
positions.
• Therefore, a vibrating bond can be thought of as two masses connected by a
spring.
• Molecules are vibrating in different modes i.e., different ways.

• Bond lengths and bond angles are continuously changing due to this
vibration.
• These vibrational changes depend on the spatial arrangement and masses of

the atoms in that particular molecule.
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67
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• If infrared radiations are passed through the naturally vibrating

molecules then IR waves matching with the vibrating frequencies of
molecule will be absorbed and increases the amplitude of vibration in
molecules.
• Because, IR radiations does not have sufficient energy to cause the
excitation of electrons, however, it causes atoms and groups of atoms of
organic compounds to vibrate faster about the covalent bonds which
connect them.
• The IR spectrum (vibrational spectra) appears as band and not as line
because; the vibrational changes are also accompanied by several
numbers of rotational changes.

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Various types of molecular vibrations
bond length changes bond angle changes

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Vibrations: Stretching and Bending
❑ Stretching vibration-change in the inter-atomic distance along the axis of the

bond between two atoms.
❑ Bending vibrations are characterized by a change in the angle between two
bonds and are of four types: scissoring, rocking, wagging, and twisting.

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Energy required
Stretching
> Bending
bond length changes bond angle changes
Energy needed to stretch a spring is more than that needed to bend it so the
stretching absorption of a bond will appear at a higher frequency than the
bending absorption of the same bond.
Stretching > Bending > Wagging / Twisting
❑ Bending is easier than stretching - happens at lower energy (lower
wavenumber)
❑ Bond Order is reflected in ordering - triple > double > single (energy)
with single bonds easier than double easier than triple bonds
❑ Heavier atoms move slower than lighter ones

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Different types of energy in atoms and molecules

ATOMS:
The electrons: Electronic energy. Increase the energy of one (or more) electrons in the
atom.
Nuclear motion: Translational energy. The atom can move around (translate) in space.
MOLECULES:
The electrons: Electronic energy. Increase the energy of one (or more) electrons
in the molecule.
Nuclear motion:
Translational energy. The entire molecule can translate in space.
Vibrational energy. The nuclei can move relative to one another.
Rotational energy. The entire molecule can rotate in space.

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N2

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CO2

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FUNDAMENTAL VIBRATION
 0 → 1 4
• The fundamental vibrations correspond 2

1
in the quantum treatment to the first 0
vibrational transition from the zeroth =1
vibrational level to the first,  0 →  1
• At the room temperature most molecules

are in the zeroth level.
4
3
2
1
0
=0
Vibrational-rotational energy
levels for a diatomic molecule

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Calculation of Oscillation Frequency

Hook’s Law
F=-kx F is the restoring force

x is the displacement from equilibrium
k is the force constant
The restoring force proportional to the displacement of particle from
its equilibrium position and the force constant k of the spring.

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The Simple Harmonic Oscillator Model: H2 molecule

•The oscillation of the bond is designated as simple harmonic motion.
In this case, energy curve is
parabolic,
1
E= k (r – req)2
2
H1 H2’
E2 H2”
E1
H2”
H1 H2’
The compression & extension of
a bond (like a spring) obeys
req
Hooke’s Law,
f = - k (r – req)

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Anharmonic molecular vibrations

• For a real molecule the potential energy curve is not a perfect parabola.
• The vibrational energy levels are converging (coming closer) because of
anharmonicity in the vibration
Fig. The energy diagram of molecule’s vibrational

model showing an
(a) ideal diatomic or
(b) (b) anharmonic diatomic oscillator.
req

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● The frequency of oscillation [υ] is dependent on the strength of the

bond and the mass of the particles involved in the bond
○ Stronger bonds vibrate more rapidly, but heavier atoms slow the
vibrations down
○ Reduced mass (μ) is used to simplify the result
m1m2 1 k
= =
m1 + m2 2 

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IR Absorptions
• Bonds absorb in four predictable regions of an IR spectrum.
Summary: The four regions of the IR spectrum

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Calculation of number of Fundamental vibrations
❑ How many vibrations are possible (= fundamental vibrations)?
• A molecule containing n atoms has 3n degrees of freedom (translational,

rotational, vibrational)
• In Linear molecule with n number of atoms has:
3 degrees called the translational degrees of freedom
2 degrees called the rotational degrees of freedom
3n – 5 degrees called the vibrational degrees of freedom
For Example: In CO2 the number of theoretical absorption bands could be

(3x3-5 = 4) four
Degrees of freedom
Molecule Total Translational Rotational Vibrational
3n 3n-5
HCl 6 3 2 1
CO2 9 3 2 4

CHRIST
• In non-linear molecule with n number of atoms has:

3 degrees called the translational degrees of freedom
3 degrees called the rotational degrees of freedom
3n – 6 degrees called the vibrational degrees of freedom
For Example: In CH4 the number of theoretical absorption bands could be

(3x5-6 = 9) nine.
Degrees of freedom
Molecule Total Vibrational
Translational Rotational
3n 3n-6
H2O 9 3 3 3
NH3 12 3 3 6
CH4 15 3 3 9

CHRIST
An IR spectrum
• In IR spectroscopy, an organic molecule is exposed to IR radiation. When the

radiant energy matches the energy of a specific molecular vibration,
absorption occurs.
• Compares intensity of IR striking sample (Iin) with intensity of IR leaving
sample (Iout)
• 100%T no light absorbed by sample
• 0% all light absorbed by sample

CHRIST
Instrumentation-An Infrared Spectrometer

CHRIST
• The IR radiation from the radiation source is passed through a

monochromator to select the appropriate wavelength.
• Then the IR radiation is passed through the sample.
• The transmitted light is detected, amplified and IR spectrum is recorded.
• In IR spectroscopy the following components are used.
• IR radiation source: Nernst glower is used to generate IR radiation. Nernst
glower is a moulded rod made of mixture of rare earth metal oxides
maintained at 1500C.
• Monochromator: Prism and grating made of metal halides like NaCl, KBr
etc., are used as monochromator to select appropriate wavelength.
• Detector: Thermocouple or bolometer is used as detector to detect the light
and to convert into electric signal.
• In IR spectroscopy gas, liquid or solution, solid substance can be used as
samples and the solvents like CCl4, CS2 and CHCl3 can be used as solvents.

CHRIST
IR absorption frequencies
Principal Correlation
Chart Region freq. (cm-1) what is found there??
XH region 3800 - 2600 OH, NH, CH (sp, sp2, sp3)
O−H 3600 cm-1
stretches
N−H 3500 cm-1 triple bond 2400 - 2000 CºC, CºN, C=C=C stretches
C−H 3000 cm-1 double bond 1900 - 1500 C=O, C=N, C=C stretches
CN 2250 cm-1 fingerprint 1500 - 400 many types of absorptions
CC 2150 cm-1 1400 - 900 C-O, C-N stretches
C=O 1715 cm-1 1500 - 1300 CH in-plane bends, NH bends
1000 - 650 CH out-of-plane bends
C=C 1650 cm-1
C−O 1100 cm-1
• An IR spectrum is a plot of the amount of transmitted light versus its

wavenumber.
• Frequencies in IR spectroscopy are reported using a unit called
wavenumber (): ~
 = 1/
CHRIST
IR absorption frequencies

CHRIST
IR Spectrum of some simple compounds…
(i) Alkanes…

CHRIST
(ii) Alkenes:…

CHRIST
(iii) Alkynes:…

CHRIST
For C-C, C=C and CC groups:

CHRIST
Applications
(i) Structure elucidation of organic compound

(ii) Structure identification
(iii)Identification of impurities
(iv)Study of reaction kinetics
(v) To ascertain hydrogen bonding in a molecule

UNIT – II:
ELECTROCHEMICAL
ENERGY SYSTEMS
Applied Chemistry (CH 132P)

Syllabus
# Single electrode potential-definition, origin, sign conventions.
# Derivation of Nernst equation. Standard electrode potential l-definition.
# Construction of Galvanic cell–classification - primary, secondary and

concentration cells, EMF of a cell–definition, notation and conventions.
# Reference electrodes–calomel electrode, Ag/AgCl electrode.
# Measurement of single electrode potential. Numerical problems on

electrode potential and EMF.
# Ion-selective electrode- glass electrode, determination of pH using glass

electrode.
Electrochemistry
The branch of chemistry which deals with the study of the
chemical changes which occur on passing electric current into certain
chemical systems and generation of electricity by carrying chemical
reactions.
ELECTROCHEMISTRY
ELECTRICAL ENERGY CHEMICAL ENERGY
REDUCTION REDOX REACTIONS OXIDATION
ELECTROCHEMICAL CELL
GALVANIC ELECTROLYTIC
GENERATE CURRENT REQUIRE CURRENT
Eg. Battery Eg. Electroplating
Electrolytic cell : chemical reactions by passing electric Current.
Electrochemical cell : the chemical reactions generate electricity
➢ OXIDATION : A species loses one or more electrons

M ↔ Mn+ + ne
➢ REDUCTION : A species gains one or more electrons

Mn+ + ne ↔ M
A species will lose electron when there is a counter part is accompanied by reduction
• Specific resistance of a conductor is the resistance of a conductor of unit length

and unit area of cross section.
• Cell constant (K) is a function of the electrode areas, the distance between the
electrodes and the electrical field pattern between the electrodes. The theoretical
cell just described has a cell constant of K = 1.0.
• Molar conductivity of a solution at a given concentration is the conductance of the
volume of solution containing one mole of electrolyte kept between two electrodes
with the unit area of cross section and distance of unit length.
• Specific conductivity (better known as conductivity) is the measure of the ability
of that material to conduct electricity. It is represented by the symbol “К”
Electrochemical cell
A Device Used To Transform Chemical Energy Of A Spontaneous Reaction Into
Electrical Energy Or To Bring About A Non Spontaneous Chemical Change Using
Electrical Energy From An External Source.
The Zinc/Copper galvanic cell
1.10 V
e-
e-
Porous Disk or
Salt Bridge
Zn(s) Cu(s)
e-
e-
a(Zn2+) = 1.00 a(Cu2+) = 1.00
Anode Cathode
SALT BRIDGE
It consists of an inverted U tube filled with a saturated solution of
KCl in agar-agar gel.
Functions
· It eliminates the liquid junction potential.
· It provides path for the flow of electrons between two half cells.
· Completes the circuit.
. Maintains electrical neutrality in the two compartments by migration
of ions through the porous material thus ensures the chemical reactions
proceed without hindrance.
· Prevents mixing of the electrode
solutions
Daniel cell - How to maintain potential in the
electrodes
• During cell reaction, Cl- diffuse from the salt bridge into the zinc half
cell or Zn2+ ions diffuses into the salt bridge to maintain the
potential of the zinc electrode.
• The K+ ions diffuse from salt bridge to the copper cell or diffusion of
SO42- ions from the copper electrode to the salt bridge.
Why KCl in salt bridge?
• KCl is used as size and charge density of both the ions are similar.
• the mobility and hence the current carried by both K+ and Cl- will be
same
• Ammonium nitrate also has the similar property like KCl, however it
is not used due to its explosive nature
Classification of Galvanic Cell
(1)Primary Galvanic Cell:-
Cell reactions are not completely Reversible, Cannot be
Recharged. Eg. Dry Cells
(2) Secondary Galvanic Cells:-

Cell reactions are Reversible, they are Rechargeable.
Recharging done by passing current through them in the direction
opposite to that of discharge current. Eg. Rechargeable battery
(3) Concentration Cells:-

Anode and Cathode are of the same material (metal or non-metal)
in contact with solutions of same electrolyte, but of different
concentrations.
Eg. A cell made of Cu-electrodes (cathode and anode) dipped in
solutions of different concentration.
How to represent a Cell ?
Zn(s) Zn+2(1M) Cu+2(1M) Cu(s)
Guidelines:-
1. First, write the LHS electrode, move across the salt bridge and
finally the RHS electrode.
2. Single vertical line or a semicolon indicate phase boundary between
metal and its solution.
3. Two vertical lines indicates salt bridge.
4. Concentration of the solution written in parenthesis.
5. Arrow indicates the direction of the flow of electrons.
Conventions
(1) Oxidation Half Cell is Written on LHS and reduction Half Cell is
written on RHS
(2) Cell potential (Ecell) is given +ve sign if the cell reaction is
spontaneous.
ie if the electrons travel from left to right in the external circuit.
(3) The term electrode potential always refers to Reduction Potential.

Cell Potential
• A combination of two electrodes is known as a electrochemical cell.
• Each electrode is known as half cell and reaction on each electrode is

known as half cell reaction (oxidation and reduction)
• The difference between the potential of the two half cells

constitutes the electromotive force (emf) or cell potential (Ecell)
E cell = reduction potential of reduced species – reduction

potential of oxidised species
Or
Ecell = ERight electrode – ELeft electrode
Ecell = Ecathode – Eanode

Electrode Potential
It is the measure of tendency of a metallic electrode to lose or gain

electrons, when in contact with a solution of its own salt.
Origin of Electrode Potential
• When an electrode is in contact with its ions it forms a potential

due to interaction between two phases.
• A metal dipped in its solution containing Mn+ ions, the metal

shows a tendency to pass into solutions as ions.
M Mn+ + ne
• Similarly, The ions from the solution shows a tendency to

discharge on to the metal.
Mn+ + ne M
• Both the tendencies reaches an equilibrium.

At equilibrium,
M Mn+ + ne
Helmholtz Double Layer

• When the reaction reaches equilibrium the metal passes into the solution
leaves the electrons on the surface of the electrodes.
• The positive ions collect around the electrode form a layer of positive
charge.
-
• Thus a double layer is formed known as -
-
Helmholtz double layer (HDL) -
-
• HDL is Similar to parallel plate capacitor -
- -
with a thickness of the radius (r1)of the ion.
- -
Guoy Chapman Layer
• The thin diffused region of ions beyond the HDL is known as

GCL.
• The electrode potential is largely determined by HDL.
• The electrode potential for each metal varies according to the
radius of the metal ion
HDL GCL
-
-
-
-
-
- -
-
- - -
- - -
Stern’s Adsorption theory
• Only a part of the ions in the solution stick to the electrode by electrostatic
forces forming Helmholtz double layer with a thickness corresponding to
radius of the metal ion.
• Remaining ions in the solutions or double layer are fixed to the surface
through adsorption and are diffusely spread out with decreasing charge
density.
Potential
Potential
(a) (b)
ri
Variation of potential with distance from metal-solution interface (a) HDL layer
(b) Stern layer
Nernst Equation
• Single electrode potential (Eel), change in free energy (ΔG) and
concentration (Mn+) are related by Nernst equation.
• According to thermodynamics,
decrease in free energy (-ΔG) represents the maximum amount of work

that can be obtained from a chemical reaction.
that is, -ΔG = Wmax (1)
• Work performed by a electrochemical cell depends on the number of

coulombs of electricity that flow and energy available per coulomb.
Work = number of coulombs x Energy available (2)

coulomb
Number of coulombs = no. of moles of electrons (n) x Faraday(F) (3)

• Energy available per coulomb is the cell potential, Ecell (Volt is equal to energy
per coulomb).
• Cell potential is maximum when the work derived from the cell is maximum.
thus, Wmax = n (mole of e) x F ( C mol-1) x E (J C-1) (4)
• From eqs (1) and (4),
ΔG = -nFE (5)
• Under standard conditions (concentration of all the species is unity) standard

free energy change is given by
ΔGo = -nFEo (6)
Where, Eo is called standard electrode potential.

• It is the potential when a metal is dipped in 1M solution of its ions or when an inert
electrode is in contact with a gas at a pressure of 1 atmosphere at 298 K.
For a reaction,
Mn+ + ne M
The equilibrium constant Kc is related to change in free energy by Vant Hoff

equation,
ΔG = ΔGo + RTlnKc
Kc = [M]/[Mn+] therefore,
ΔG = ΔGo + RT ln[M]/[Mn+]
ΔG = ΔGo + RT ln[M] – RT ln[Mn+]
Substituting from (5) and (6),

-nFE = -nFEo + RT ln[M] – RT ln[Mn+]
Dividing throughout by –nF,
E = Eo + RT/nF ln[Mn+] – RT/nF ln[M]
Under standard conditions [M] = 1, so above equation becomes,
E = Eo + RT/nF ln[Mn+]
Electrode potential increases with increase in the concentration of Mn+ ions
and increase in temperature.
R = 8.314 J K-1 mol-1, F = 96500 C mol-1, T = 298 K and converting in to
log to the base 10,
E = Eo + 0.059 log[Mn+]
n
Nernst Equation for Cell Potential
Ecell = Ecathode - Eanode
On substituting and rearranging the equations for Ecathode and Eanode
o
Ecell = Ecell + 0.059 log [species at cathode]
n [species at anode]
For a Daniel cell, the cell potential is given by,
o
Ecell = Ecell + 0.059 log [Cu+2]
2 [Zn+2]
Measurement of Standard Electrode Potential
• Measured by using Standard Hydrogen Electrode (SHE).

• Potential of SHE is taken as zero at all temperatures.
• Electrode whose potential to be measured coupled with SHE through
Salt Bridge.
• Potential measured using electronic voltmeter.
To measure the potential of the Zinc electrode, zinc electrode coupled

with SHE through Salt Bridge.
Zn(s) Zn+2(1M) HCl, [H+ = 1] H2(1 atm) Pt(s)

Zinc electrode SHE
Standard HYDROGEN Electrode
An electrode potential measured under standard
conditions;
Temperature at 298K,
1 Atmosphere pressure and
1 Mole of the activity of redox participants of the
half-reaction.
• The emf measured when a metal / metal ion

electrode is coupled to a hydrogen electrode
under standard conditions is known as the
standard electrode potential of that metal /
metal ion combination.
Sign Convention of Cell Potential
• -ve sign on the cell potential indicates the half-cell acts as the anode
by releasing electrons to the hydrogen electrode.
• +ve sign on the cell potential indicates the half-cell acts as the cathode
and accepts electrons from the hydrogen electrode.
• Electro Chemical Series : Metal ion-Metal electrodes are arranged

in the decreasing order of their reduction potential.
When elements are arranged in
decreasing order of their standard
electrode potential,
a series called electrochemical
series is obtained
This series can provide valuable

information regarding:
.
• Relative ease of oxidation and
reduction
• Replacement tendency
• Predicting spontaneity of
redox reactions
• Calculation of Equilibrium
Constant
Concentration Cells
A concentration cell is an electrochemical cell where the two electrodes
are the same material, the electrolytes on the two half-cells involve the
same ions, but the electrolyte concentration differs between the two
half-cells.
Eg: Two copper electrodes

dipped in copper sulfate
Cu
solutions of different
concentrations.
Cu(s) │Cu2+ (M1)║Cu2+ (M2) │Cu(s) Cu2+
Where M1 and M2 are the concentrations

of the copper sulphate solutions
Cu Cu2+(M1) + 2e Anode
Cu2+(M2) + 2e Cu Cathode
The net cell reaction is
Cu+2 (M2) Cu+2 (M1)
• The net cell reaction is the change in the concentration as a result

of which current flows.
• Continue until concentrations in the two half cells become equal.

Ecell = ER - EL
= Eo + 0.059 log[M2] Eo + 0.059 log[M1]
n n
Since Eo is same for both anode and cathode,
Ecell = 0.059 log [M2]

n [M1]
(i) When the two solutions are of same concentration,
log [M2]
=0
[M1]
and hence no current flow.
(ii) When M2/M1 > 1 (i.e., M2 > M1), log M2/M1 is positive,
Cell potential Ecell will be +ve.
Direction of spontaneous reaction is from the more concentrated solution (M2)

to less concentrated solution (M1).
(iii) Higher the ratio M2/M1, higher the cell potential.

Types of Single Electrodes
Important types of single electrodes are;
• Metal ion-Metal electrode : A metal is in contact with its own metal
ion solution. e.g., Cu+2/Cu, Zn+2/Zn, Ag+/Ag.
• Gas Electrode : A gas is in contact with an inert metal dipped in an
ionic solution of the gas molecules. e.g., Hydrogen electrode.
• Metal-Metal insoluble salt electrode : A metal is in contact with a
solution containing the anion of the salt. e.g., Calomel electrode,
Ag/AgCl electrode.
• Ion-Selective electrode : A membrane is in contact with an ionic
solution. e.g., Glass electrode, solid state electrode and liquid
membrane electrode.
Reference Electrodes
• Reference electrodes : Whose potentials are known and are used for the
determination of potential of other electrodes.
• Reference electrodes are of two types,
(i) Primary and (ii) Secondary
• Primary Reference electrode : e.g., Standard Hydrogen Electrode
(SHE).
• Whose potential is arbitrarily taken as zero at all temperatures.
• Secondary Reference electrode : Whose potential with respect to SHE
are known.
e.g., Calomel electrode, Ag/AgCl electrode
• Commonly used for the determination of electrode potential.
Standard Hydrogen Electrode
• Standard hydrogen electrode is a system in which hydrogen
ion and gaseous hydrogen are present in their standard states.
Pt, H2(1 atm), H+(1M)
H2(g) 2H+(1M) + 2e-
• potential is arbitrarily taken as zero at all temperatures.
Limitations of SHE :
• Difficulty in setting up of electrodes.
• The electrodes becomes inactive
in presence of impure gases in hydrogen
.
Calomel Electrode
KCl(sat), Hg2Cl2(sat), Hg(l)
# A small amount of mercury is placed at the bottom

of the vessel.
# A paste of solid mercurous chloride (calomel)
Hg2Cl2 , and mercury placed at the bottom of the
long glass tube above mercury.
# A saturated solution of KCl is placed over the solid
paste.
# Electrical connection is made through a platinum
wire dipped in the mercury at the bottom of the
vessel.
# This constitutes one half cell and it is connected to the
other half through a salt bridge.
Half-Cell Reaction of Calomel Electrode
The half cell reaction is
Hg2Cl2 + 2e- 2Hg + 2Cl-
The potential of the electrode depends on the concentration of the KCl.

For,
Saturated KCl, potential is +0.241 V
1 M KCl solution, potential is +0.280 V
0.1 M KCl solution, potential is +0.334 V
Advantages of calomel electrode

(i) Simple to construct
(ii) Cell potential is constant and reproducible
(iii) Cell potential does not vary with temperature.
Ion Selective Electrodes
# These Electrodes which are selectively sensitive to certain ions and
develop a potential proportional to the concentration of the ions.
# Contains a reference electrode and a membrane sensitive to particular
chemical species.
Ion selective membrane
Glass
Membrane Solid state
Liquid Membrane Gas Sensing
Membrane
Characteristics of a good membrane
• The membrane should also have low electronic conductivity.
• The membrane must have low solubility in the analyte solution – we don’t
want it to dissolve!!
• The membrane should possess high selectivity.
• The membrane should be highly permeable.
• Highly stable.
• The membrane should have excellent chemical durability..
(1) Glass Membrane:
• Glass electrode are responsive to univalent cations ( H+, Na+), This type of ISE
has good selectivity, but only for several single-charged cations.
Example: pH electrode
(2) Solid state Membrane:
• Solid state electrode are selective primarily to anions.
• It may be a homogenous membrane electrode or heterogeneous membrane
electrode.
• Homogenous membrane electrode: ion-selective electrodes in which the
membrane is a crystalline material (AgI/Ag2S).
Materials used for solid state membrane:

(1) LaF3 doped with EuF2 for the detection fluoride ions
(2) Pressed pellets of Ag2S + AgCl for the detection of chloride ions
(teflon body of electrode keeps the crystals in position with epoxy resin)
• Heterogeneous membrane electrode: ion-selective electrodes prepared of an
active substance, or mixture of active substances (silicone rubber or PVC).
Example: Fluoride ion selective electrode
(3) Liquid Membrane:
• Liquid membrane is a type of ISE based on water-immiscible liquid substances

produced in a polymeric membrane used for direct potentiometric
measurement.
• Used for direct measurement of several polyvalent cations (Ca+2 ion) as well as
a certain anions.
(1) Phosphate di-esters and neutral monocyclic crown ethers for cations
(2) Iron phenanthroline complex for anions.
Active materials in liquid membrane electrode is a large organic molecule, whose
job is to ferry the ion across the membrane (specifically interact with certain ions)
Pb2+
Reference
electrode
Pb2+
O O
O O
O O
Pb2+ PVC
(4) Gas Sensing Electrodes:
• Available for the measurement of ammonia, carbon dioxide and
nitrogen oxide.
• This type of electrode consist of permeable membrane and an
internal buffer solution.
• The pH of the buffer changes as the gas react with it.
• The change is detected by a
combination pH sensor within
the housing.
• This type of electrode does
not require an external
reference electrode.
Pollution Control
Agriculture and Fishery
-pH of acid rain, soil, surface water
-Soil and fertilizer for Nitrate,
-Contamination of surface water
Ammonium, Potassium to optimize
and ground water with ammonium
the use of fertilizer.
and nitrate
-Dissolved Oxygen and pH in ponds for
-Contamination of waste water with
fish breeding.
Cyanide, Cadmium, Mercury and Copper
Industrial Production
-Salinity and pH of Boiler Food and Quality Control
Worldwide -Nitrate and Nitrite in meat and
feed water
application vegetables
-Cyanide in plating baths
-Process (specific ions) -Chloride, Sodium, Nitrate and
Nitrite in baby food.
-Cadmium in fish
Medical Diagnosis and Hygiene Control

-Potassium in urine
-Contamination in various ions.
Determination of Concentration of metal ions
# A standard solution containing the same ion as the ion under
test is prepared and placed in the ion selective electrode.
# Test solution taken in a beaker and the above electrode is placed in to it.
(This forms One Half cell)
# A potential develops across the membrane.
# Potential is due to the membrane potential and the reference electrode.
# Half cell connected to a reference electrode. (forms a Cell)
Membrane
Reference Solution to be Internal Standard Reference

electrode 1 analyzed solution electrode 2
[Mn+] = c1 [Mn+] = c2
External Reference Electrode Ion Selective Electrode

The membrane potential is given by,
EMn+ = RT log c2
nF c1
C1 and c2 are concentrations of Mn+ in the solution to be
analyzed and the internal standard solution respectively.
The Cell Potential is given by,
Ecell = EMn+ _ Δ E*ref

Where, Δ E*ref is the difference in the
potentials of the reference electrodes, normally
its value is zero if identical reference electrodes
are used.
Since c2 is a constant, at a given temperature the
cell potential is given by,
EMn+ = constant - RT log c1
nF
Glass electrode
• A glass electrode is a type of ion-selective electrode made of a doped glass membrane
that is sensitive to a specific ion. The most common application of ion-selective glass
electrodes is for the measurement of pH.
• The pH electrode is an example of a glass electrode that is sensitive to hydrogen ions.
• Glass electrodes play an important part in the instrumentation for chemical analysis
and physico-chemical studies.
• The voltage of the glass electrode, relative to some reference value, is sensitive to
changes in the activity of certain type of ions.
Principle of Glass electrode

• A thin walled glass bulb containing an acid is immersed in another solution having H+
ions – Potential developed is Boundary potential Eb
• Eb – Potential is due to the difference in potential developed across the gel layer of the
glass membrane between two liquids.
• The difference in H+ ion concentration is given by the equation
Eb = E1-E2 = RT (lnc2-lnc1)
F
c1 and c2 are the comcentrations of H+ of the acid solution inside and outside the glass
bulb respectively
Eb = RT lnc1 + RT lnc2
F F
The concentration of the solution inside the glass bulb is constant hence the equation
reduces to
Eb = Constant + RT lnc2
F
Substituting R and F values and converting natural log at 298 K we get
Eb = L + 0.0591 log c2
L is a constant which depends on the pH of the solutions taken inside the glass bulb
& c2 = [H+] of the solution,
- log [H+] = pH therefore
Eb = L - 0.0591 pH
Is used to determine the pH of the solution
Boundary potential
Construction of Glass electrode
• Long glass tube with a thin walled bulb at one end

• Composition – Na2O 22%, CaO 6%, SiO2 72%
• It has low melting point, high electrical conductance and can sense H+ ions upto pH 9.
• Bulb contains 0.1 M HCl solution.
• Reference electrode ie Ag | AgCl electrode is places in the solution and connected with
platinum wires for electrical contact.
Representation
Ag | AgCl (s) | 0.1M HCl | glass
Working of Glass electrode
• The glass electrode is dipped in the test solution, the Na+ ions of glass membrane are
exchanged for H+ ions of the test solution
H+ + Na+ Gl- Na+ + H+ Gl-

Solution Membrane Solution Membrane
Due to the above reaction a boundary potential is established and is called as glass electrode
Potential EG.
The glass electrode Potential EG is given by
EG = Eb + E Ag/AgCl
Eb is 0 when c1 = c2,
However it has been seen that a small potential is still developed.
This is called asymmetric potential (Easy)
Hence the above equation can be written as
EG = Eb + E Ag/AgCl + Easy
But,
wkt Eb = L - 0.0591 pH substituting this in the above equation we get
EG = L - 0.0591 pH + E Ag/AgCl + Easy
Glass electrode
Determination of pH using Glass electrode
• The glass electrode is dipped in the test solution whose pH is determined.
• It is combined with the reference electrode such as calomel electrode via salt bridge.
• It is represented by
Saturated calomel electrode | solution of unknown pH | glass | 0.1 M HCl | AgCl | Ag
• The potential of the above cell, Ecell is measured using voltmeter connected to
potentiometer or pH meter as shown below
Ecell is the difference between EG and the calomel electrode potential ESCE
Ecell = EG + E SCE
= L1 - 0.0591 pH - E SCE Rearranging we get
pH = L1 - E SCE - Ecell
0.0591
L1 - E SCE is called as K, ie Glass electrode assembly constant. Therefore
pH = K - Ecell
0.0591
Determination of pH using pH meter

Problems
1. Calculate the E0 of Cu2+/Cu, given [Cu2+] = 0.018M and E of Cu2+/Cu =
0.296V
2. A cell uses Ag+| Ag and Zn|Zn2+ couple. Given E of Ag +| Ag= 0.85V, E
of Zn|Zn2+= - 0.70V. Calculate the cell voltage. Write the cell reaction
and which of the couple is negative for the cell?
3. A silver electrode dipped in a 1M solution of AgNO3 which is connected
by means of a salt bridge to a copper electrode dipped in an effluent
sample of Cu2+ ions. The cell potential measured was 0.56 V. Determine
the concentration of Cu2+ ions in effluent sample.(E0Ag+/Ag=0.80V;
E0 Cu2+/ Cu= 0.34V).
4. How many hours can a calculator work on an Hg cell having a cell
potential of 1.34V drawing 5×10-4 watt? The mass of HgO available is
5g.( molecular mass of HgO= 225gmol-1 and 1 watt=1Js-1, 2 mol
electrons involved for every mol of HgO).
5. For the Daniel cell involving the cell reaction Zn(s) + Cu2+ (aq) ⇌
Zn2+ (aq) + Cu, the standard free energies of formation of Zn(s), Cu(s),
Cu2+(aq), Zn2+(aq) are 0,0,64.4 kJ mol-1 and -154.0 kJmol-1 respectively.
Calculate the standard EMF of the cell.
6. The potential for a voltaic cell is 0.240 V at 250 C and the standard cell
potential is E0cell = 0.170 V. What is the concentration of the cadmium
ion solution? Cell representation is given as, Cd(s)/Cd+2(aq, M=?)//
Ni+2(aq, M =1.0M)/Ni(s)
7. Determine the EMF of the following electrochemical cell at 25oC:
H+ (C= 0.01M), H2 (1atm); Pt / Cu, Cu2+ (C=0.1M)
8. In the Daniel cell a) Calculate the cell potential if the Zn2+ and
Cu2+ concentrations are 0.1M and 1.0×10-9M respectively at 298K. b)
Calculate ΔG and ΔG0 for the reduction of 1.0M of Cu2+ by Zn at 298K.
(Faraday= 96.5kJmol-1V-1, E0cell = 1.10V).
Unit iii part A
CORROSION & its control
APPLIED CHEMISTRY CH132P/232P
Dr. Santhosh G
➢ One of the most significant problems faced by advanced industrial society.
➢ 30-40% iron and steel produced annually to replace the rusted materials.
➢ Touches everything – appliances used inside or outside home, on road, in sea, in

plants and in aerospace vehicles.
➢ Total cost of floods, hurricanes, fires, lightening and earthquakes are less than the
costs due to corrosion.
➢ Word corrosion derived from Latin word corrodere – means to gnaw
away.
➢ Metals undergo corrosion when exposed to air, water or other substances.
Example:- Rusting of iron, rusting weakens bridges, car bodies, etc.
Corrosion:- Defined as the destruction of the metals or alloys by the
surrounding environment through chemical or electrochemical changes.
➢ Pure metals have the natural tendency to revert back to their combined
states. Corrosion of a metal is the reversal of extraction.
Extraction
Metal ore Metal
Corrosion
➢ Erosion:- wearing away of nonmetallic coating materials such as

plastics, wood and ceramics by environment.
> Corrosion is continuous process and it is visible till it attains advance stage. In
metals the problems due to corrosion are
o Damage to the plants (chemical) and equipments.
o Wastage of raw materials which leads to the contamination of the products
➢ Atmospheric air and water are the main factors which initiate corrosion.
TYPES OF CORROSION
• Dry corrosion: Corrosion occurs in a dry environment. By direct attack of dry
gases through chemical reactions. Ex. Attack of dry oxygen or air on metals.
• Wet corrosion: Corrosion occurs in an aqueous environment. The metal
undergoes an electrochemical reaction with the moisture and oxygen present in
the atmosphere: Ex: Rusting of iron.

Electrochemical theory of CORROSION
➢ When a metal like iron exposes to air, following electrochemical changes occurs,
(i) Formation of Galvanic cell:- Anodic and cathodic areas are formed resulting in
minute Galvanic cells.
(ii) Anodic reaction:- Oxidation takes place by release of two electrons, results in
corrosion of iron.
Fe → Fe2+ + 2 e-
(iii) Cathodic reaction:- Reduction occurs by the flow of electrons from anode to
cathode.
➢ Reduction can takes place in 3 different ways,
(i) If solution is aerated and almost neutral, oxygen reduced in the presence of H2O
to OH-
O2 + 2H2O + 4e → 4 OH-
➢ If the solution is deaerated and neutral, water reduced to H2 and OH-.
2H2O → 2H+ + 2 OH-
2H+ + 2e-→ H2
2H2O + 2e-→ H2 + 2 OH-
➢ If the solution is deaerated and acidic, the H+ ions are reduced to H2.
2H+ + 2e-→ H2
➢ Metal ions formed at the anode combines with OH- ions to form the metal
hydroxide and finally the hydrated metal oxide (rust).
2Fe2+ + 4OH-→ Fe(OH)2
2 Fe(OH)2 + O2 + (n-2) H2O→ Fe2O3. nH2O

Diagrammatic representation of
Electrochemical theory of CORROSION
AI R
Water film /
moisture
Anodic area Cathodic Area
Anodic reaction : Fe → Fe2+ + 2 e-
Cathodic reaction : O2 + 2H2O + 4e → 4 OH-

Rate of CORROSION
Rate of corrosion = icorr / nF grams per second
icorr = corrosion current
n = charge of the ion
F = Faraday constant
The total current due to the cathodic and

anodic reaction must be equal but opposite in sign
( icorr) = -Σia = Σic

Reason behind the formation of galvanic cell /
corrosion
➢ Due to the presence of heterogeneities at the interface of metal and
environment.
➢ The heterogeneities may develop due to several reasons,
❖ Difference in concentration of air or oxygen (area in contact with

more air or oxygen act as cathode, while area in contact with less air or
oxygen acts as anode).
❖ Contact of two different metals (Example:- copper and iron –

copper acts as cathode and iron acts as anode).
❖ Stress in the metal (area under strain acts as the anode).

Types of corrosion
▪ Differential metal corrosion
▪ Differential aeration corrosion
▪ Stress corrosion
▪ Grain boundary corrosion

1. Differential metal corrosion
> A potential difference is developed if two different metals are in contact with
each other. Metal acts as the anode undergoes corrosion and the metal act as the
cathode is unaffected.
➢ Metals higher in electrochemical series act as anode to the metal below to it.
Example:- Fe is anodic to Cu, Ni and Sn
but, Fe is cathodic to Zn and Mg.
Therefore, Fe corrodes in contact with Cu, Ni and Sn. Whereas , Zn and Mg corrodes
in presence of iron.
➢ Anode: Highly electropositive/ metallic/ lower electrode potential/ lower position
in electrochemical series.
➢ The rate of corrosion depends on the amount of current passes from anode to
cathode.
➢ Higher the potential difference, higher the corrosion.
Example: Iron / copper : Iron undergoes corrosion
e-
Fe Zn
Fe Cu
e-
Example: Iron and Zinc : zinc undergoes

corrosion and iron is unaffected
2. Differential aeration corrosion
➢ Occurs due to the difference in the concentrations of air over the surface of
the metal.
➢ A strip of pure iron partially immersed in an aerated solution of sodium

chloride.
➢ Concentration of oxygen is high at the surface than inside the solution.
➢ Area near the water line (above the surface of the water) acts as cathodic area.
➢ Lower concentration of
oxygen at the bottom part makes
it anodic area.
➢ Electrons pass from bottom
portion to top portion and
corrosion products forms at the
junction.
➢ Examples for differential aeration corrosion,
(i) water-line corrosion and (ii) pitting corrosion
(i) Water-line corrosion:-
➢ Observed mainly in steel water tanks.
➢ Metal just below the water-line is more anodic (less oxygenated).
➢ The meniscus (creep) which is immediately above the water-line is more

oxygenated, acts as the cathode and is unaffected.
➢ This type of corrosion commonly observed in ships floating in seawater for
long periods of time.
(ii) Pitting corrosion:-
➢ Caused by the deposition of dust particles on metal surface.
➢ The portion covered by dust particles will be less aerated compared to the
exposed surface.
➢ The exposed portion becomes cathodic and the covered portion becomes
anodic.
➢ In the presence of electrolytes and moisture,

corrosion starts beneath the dust resulting in a
pit.
➢ The formation of small anodic area and the
presence of large exposed cathodic area
accelerates the rate of corrosion.
3. Stress corrosion
➢ Two samples of steel, one of which is under stress, are placed in a corrosive
environment, stressed specimen corrodes at a faster rate.
➢ Stress can be due to ,
Poor design, Riveting, Cold working, Welding, Bending, Pressing, Quenching.
➢ Stressed portion becomes anode with respect to the unstressed portion under
corrosive environment.
➢ Presence of both stress and specific environment are necessary for stress
corrosion to occur.
➢ Cracking ceases when either

the corrosive environment or
the tensile stress is
eliminated.
Reason behind STRESS CORROSION ?
➢ The atoms are displaced slightly due to stress which results in the
formation of the anodic zone of higher potential.
➢ The stress produces strains which results in localized zones of high

energy.
➢ These high energy zones are easily attacked even by the mild
corrosive agents.
Example, Crack progress in a plane perpendicular to the stress.
Stress is a force that can cause a change in a physical body
Strain is the change in shape or form of an object when stress is applied

What type of corrosive environment
required for a stress corrosion ?
Corrosive Metal / Alloy Corrosive environment

Mild steel Sodium hydroxide
Low carbon steel Nitrates (Ca(NO3)2, NaNO3)
Stainless steel Metal chlorides (MgCl2, ZnCl2, LiCl, NaCl )
Brackish / sea water
Solution of NaOH and H2O2
Nickel Strong solution of alkalis (NaOH or KOH)
Brass Vapours of NH3 and Ammoniacal solution
➢ Example for stress corrosion - Intercrystalline Corrosion or Caustic
Embrittlement in boilers.
CAUSTIC EMBRITTLEMENT
➢ Fine cracks are formed at the stressed portion of the mild boilers.
➢ The alkaline impurities present in the water penetrate through the fine cracks
by capillary action.
➢ During heating water evaporates and caustic soda settles in the cracks.
➢ An electrochemical cell is set up between the iron under stress (ANODE) and
the iron in the main body which is free from stress (CATHODE).
➢ Iron surrounded by dilute NaOH is the cathode and the iron under stress acts
as the anode and gets corroded resulting in boiler failure.
Iron under Concentrated Dilute NaOH
Iron
stress NaOH (in boiled
(main body)
(anode) (in the cracks) water)
a. Factors affecting rate of corrosion
Primary factors (Due to Metal ) Secondary factors (Due to Environment)
Electrode potential pH
Anodic and cathodic areas Temperature
Nature of surface of the metal Conductance of the medium
Surface protective film Humidity
Polarization of the electrode Presence of the impurities in the

surface environment
Hydrogen over voltage Acid fumes
Surface state of the metal Hydrogen sulphide

1. Potential difference
➢ The potential difference between the anodic and cathodic area is known as the
corrosion potential.
➢ The larger the potential difference higher is the rate of corrosion.
➢ Potential difference between iron and copper is 0.78 V, which is more than Fe
and Sn (0.3 V). Therefore, Fe corrodes faster in contact with Cu than in contact
with Sn.
➢ Farther the positions of the metals in electrochemical series, greater the intensity
of corrosion of the anodic metal.
➢ Use of dissimilar metals avoided to minimize this type of corrosion.
➢ But the actual rate of corrosion is determined by the polarization of the electrode
areas.
2. Anodic & cathodic areas
➢ Corrosion occurs fast if ANODE is small and CATHODE area is large.
Example:- Coating of zinc on iron protects iron ; iron acts as cathode and
zinc acts as anode.

3. Nature of corrosion product
➢ The product of corrosion is a thin oxide layer over the surface of the metal.
➢ This layer determines the further corrosion rate of the material.
➢ The oxide layer acts as protective layer if the layer composition is stoichiometric,
highly insoluble and nonporous with low ionic and electronic conductivity.
➢ The layer prevents further corrosion.
➢ Example:- Al, Ti and Cr develops such layers. Stainless steel (18% Cr and 8% Ni)
builds a thin films (20 Ao), but a highly protective film of Cr2O3.
➢ Ta, Zr and Mo forms a protective layer and this layer is capable of self repairing
oxide layer when it is damaged.

4. Polarization of electrode surface
➢ Corrosion is due to the flow of electrons from anodic area to cathodic area.
➢ Magnitude of current depends on the extent of polarization of the electrodes.
➢ There is an irreversible tendency around the electrodes which tend to oppose

the direction of current flow. This is called polarization of electrodes.
➢ Polarization: The deviation of the potential of an electrode from the open circuit
potential due to irreversible reactions around the electrode.
➢ This tendency makes anode to become more cathodic and vice versa.
➢ Therefore, as a result of polarization effect, potential difference between the

electrodes decreases steadily and hence the current flowing from anode to
cathode which in turn reduces the corrosion.
➢ When corrosion begins the concentration of electrolyte around the electrode
surface and the bulk of the electrolyte changes.
➢ For corrosion to progress, species must be supplied or removed from medium

by diffusion.
➢ Diffusion is low in non-conducting medium, at low temperature and at low

concentration.
➢ Under these conditions electrodes gets polarized and rate of corrosion

decreases.
➢ The deviation in potential finally reaches equilibrium (steady state) at which

the rate of oxidation at anode is equal to the reduction at cathode.
➢ The potential at steady state is called corrosion potential Ecorr . The current
corresponding to this steady state is called corrosion current (icorr);
where, icorr = ia = ic
Greater the polarization of the electrodes on anode or cathode smaller is
the corrosion current and smaller the corrosion, this is applicable even if the
potential difference between the electrodes is high.
Anodic polarization: If the anode alone undergoes polarization the rate of

corrosion is controlled by the potential of the anode alone known as anodic
polarization.
Cathodic polarization: If the cathode alone undergoes polarization the rate

of corrosion is controlled by the potential of the cathode alone known as
cathodic polarization.
Mixed control: If both the electrode undergoes polarization.

5. Surface state of a metal
➢ The rate of corrosion is high.
If surface of metal is rough and uneven.
Presence of cracks and bends.
Presence of acid environment.

Secondary factors
a. pH
➢ Rate of corrosion increases with decrease in pH.
➢ At pH greater than 10 corrosion ceases due to a protective coating of
hydrous oxide is formed.
➢ At pH between 3-10 the presence of oxygen is essential for corrosion.
➢ At pH less than 3 corrosion happens even in absence of air due to
evolution of hydrogen from cathodic areas.

b. Temperature
➢ Rate of corrosion increases with increase in temperature due to,
• Increase in conductance of aqueous medium
• Increase in rate of diffusion
• Decreases passivity which increases rate of corrosion again.

c. Humidity
➢ The rate of corrosion increases with humidity.
➢ Above a certain relative humidity known as critical humidity corrosion
takes place at rapid rate.
Less than 60% of relative humidity iron rusts very slowly beyond this value it
undergoes rusting much faster rate, due to porous capillary structure.
➢ The capillaries get filled at relative humidity and at critical humidity the
pores are filled.
➢ An increase beyond critical humidity will allow water to penetrate the
surface results in severe rusting of iron.

D. Presence of impurities in atmosphere
➢ 0.01% of SO2 and relative humidity of 50% after 60 days negligible corrosion.
➢ 0.01% of SO2 and relative humidity of 90% exhibits severe corrosion in one day.
➢ Rate of corrosion decreases in presence of CO2 due to two reasons :

1. CO2 modifies gel structure of rust becomes less permeable.
2. CO2 forms insoluble basic carbonate on the surface which offers protection to metal.
➢ High levels of H2S reduces corrosion in steels, this is due to
Formation of metal sulphide at temperature above 600C accompanied by liberation of
hydrogen .
E. Acid fumes
➢ HCl and H2SO4 are used in industry.
➢ These alloys are used to protect the metals from H2SO4
(i) Cast iron with 14.5% Si – Duriron
(ii) Lead alloys
Chemical lead - (0.06% copper)
Hard lead – (4-15% Sb)
Zn, Cd, Ni, Fe are not resistant to H2SO4 fumes.

Why HCl is More Corrosive Than H2SO4
➢ Higher solubility of chlorides.
➢ Higher mobility of chloride ions.
➢ These alloys are resistant to HCl fumes,
1. High silicon iron alloy containing molybdenum – DURICHLOR
2. A nickel alloy with high molybdenum content – CHLORIMENT

GALVANIC SERIES Mg
Zn
➢ The galvanic series determines the electrochemical potential Al
Cd
and nobility of metals and metal alloys.
Mild steel
➢ The series in which the metals are arranged in an increasing Cast iron
Pb
order of their electrode potential values.
Sn
➢ This table is made by studying the corrosion of metals in the Brass

Ni
environment without the removal of oxide film. Stainless
steel
➢ A metal higher in the series is more anodic and undergoes Ag
Ti
corrosion faster compared to metals present below.
Au
• When two metals are submerged in an electrolyte, while also
electrically connected by a metallic conductor, the less noble will
experience galvanic corrosion.
• The less noble metals becomes the anode and corrodes faster than it
would all by itself, while the other becomes the cathode and corrodes
slower than it would alone.
Corrosion control
➢ Corrosion can be controlled by the preventing the formation of galvanic cells.
This can be done in different ways,
1. Design and selection of materials

2. Protective coatings
(i) Inorganic coating
(a) Metal coatings:- anodic and cathodic
(b) Surface conversion coatings:- anodizing and phosphating
(ii) Organic Coatings
Example:- paints and enamels
3. Cathodic protection
4. Anodic protection
5. Corrosion inhibitors
1. Design and selection of materials
1. Avoid use of dissimilar metal, choose materials having closer potential values.
2. Cathode must be small anode must be of large surface area
3. Anode should not be painted when in contact with cathode this decreases
anodic area.
4. Bolt, nut, rivets must be made up of materials which can act as cathode.
5. An insulator is needed to avoid contact between two dissimilar metals.
6. Porous materials like asbestos, wood and magnesia should not be used as
insulators since they hold liquids and they act as electrolytic conductors.
7. Gaps must be avoided since some liquids can trap which results in differential
, , aeration corrosion.
8. Welded joints are preferred than nuts, bolts and rivets in low pressure boilers and
chemical plants.
9. Stress corrosion can be avoided by annealing.
10. Prior designing of the equipment includes,
a. Supported legs instead of large blocks to facilitate air circulation and prevention
of stagnant pool and damp areas.
b. Smooth edges which can avoid dust accumulation which prevents pitting
corrosion and differential aeration corrosion.

2. Metal Coatings
➢ Corrosion can be controlled by covering the substrate or base metal by another
metal, known as metal coating.
i. Inorganic metal coatings
➢ There are two types of inorganic metal coating,
a. Anodic metal coating
b. Cathodic metal coating
a. Anodic metal coating
➢ The metal / equipment to be protected are coated using metals which are
highly anodic. Example:- Hot dipping, galvanizing, etc.
➢ The anodic coating if peels off undergoes corrosion slowly due to the large
anodic area and small cathodic areas.

Hot Dipping
➢ Dipping the base metal (metal to be protected) into molten anodic metal.
➢ The coating metal is melted at a relatively low temperature.
➢ The base metal must with stand this temperature without undesirable changes in its
physical and chemical properties.
➢ Process of Coating zinc on iron by hot dipping is called Galvanizing.
➢ Galvanization of iron includes following steps,
(i) Degreasing of iron with organic solvents.
(ii) Pickling sheet is washed with sulphuric acid and later rinsed with water.
(iii) The sheet is treated with aqueous solution of ZnCl2 and NH4Cl and dried.
(iv) The sheet is dried and dipped in molten zinc (430-4700C).
(v) Excess zinc over the iron surface is removed by rolling wiping or passing
trough blast air.
b. Cathodic Metal Coatings
➢ Cathodic metal coatings are coating with metals which are catodic to the specimen.
Example:- Coating of copper , Nickel and chromium on iron.
➢ They should cover the surface of the specimen without leaving a pin hole.
➢ Otherwise, rapid corrosion of the base metal takes place due to large cathodic and
small anodic area.
➢ The process of coating tin on iron is called Tinning.
➢ Tinning is the process of thinly coating sheets of wrought iron or steel with tin, and
the resulting product is known as tinplate.
➢ Involves following steps,
(i) Degreasing of iron with organic solvents.

(ii) Pickling sheet is washed with sulphuric acid and later rinsed with water.
(iii) The sheet is treated with aqueous solution of ZnCl2 and NH4Cl and dried.
(iv) The sheet is dried and dipped in molten tin
(v) Excess tin over the iron surface is removed by rolling.
(vi) The coated tin is dipped in palm oil to avoid oxidation.
Cathodic Metal Coatings - Advantages of Tinning
➢ Tin is non toxic.

➢ Tinning gives a fine film which completely covers the surface and avoid
corrosion.
➢ Tinning is economical than electroplating.
3. Organic coatings
➢ Metallic surfaces can be coated with paints or enamels with the capacity to inhibit corrosive
attack. The term organic coating is used when the layer thickness is less than 0.4 mm.
➢ Coatings thicker than 0.4 mm are referred to as mastics or linings.
➢ Coating of meal surface with organic coating involves two stages.
Preparation of metal surfaces (I stage)

1. Removal of rust by mechanical brushing followed by pickling in dilute sulphuric acid
2. Treating with wash primer (consists of phosphoric acid). This converts residual rust into
insoluble adherent phosphate coating.
3. Coating with priming paint containing corrosion inhibitive pigment such as zinc chromate
red lead or heavy metal benzoate.
Zinc rich paint-consisting of epoxies, chlorinated
hydrocarbons, and other polymers; or inorganic
based on organic alkyl silicates
Multi coat of paint (II stage)
1. The undercoat of pigment is given to decrease the permeation of
water, finally the surface is provided with multicoat of paint.
4. Anodic Protection
➢ Metals like Ti and alloys like stainless steel readily gets passive and
cannot be offered cathodic protection.
➢ Anodic protection involves deposition of an oxide film on a metal
surface by applying anodic current in an oxidising environment.
➢ Minimum potential required to protect the metal can be obtained from
potential-current curve.
Y
➢ Initially current increases along AB,

Passive
C
shows the dissolution (corrosion) of --------------------------------------------
Potential
the metal.
---------------------------------
B
Ep
➢ When current reaches Icri, oxide layer Active
(passivation) starts forming. A
Ip Current Icri X
➢ Potential at Icri is called passivating potential (Ep).
➢ Above Ep (along BC) current flow decreases to very low value – passivating current Ip.
➢ Ip is the minimum protective current density to maintain passivation.
➢ At this stage, an increase in potential will not corrode the metal as the metal is in a highly
passive state.
➢ Anodic protection is used for carbon steel storage tanks containing extreme pH
environments including concentrated sulfuric acid and 50 percent caustic soda where
cathodic protection is not suitable due to very high current requirements
➢ Advantage:- (i) Requires only a very small amount of current.
➢ Disadvantages:-
(i) Cannot be applied to metals which do not passivate.
(ii) Corrosion rate cannot be reduced to zero.
➢ Finds application mainly in the transportation of concentrated acids using steel containers.
Potentiostat
➢ A schematic arrangement for anodic protection In

Out
device consists of
ΔE
•Generator cable of producing high current density
•An auxiliary platinum electrode
•A reference calomel electrode Reference electrode
------------------------------
•A potentiostat to maintain constant potential ---
Pt
•A specimen kept in oxidizing atmosphere as anode. Oxidizing medium
Metal
➢ Working,
(i) The potential is first increased to (Ep) for initial corrosion to occur.
(ii) Then potential is slightly increased to (Ef ) flade potential where current
decreases to small value.
(iii) Potential is kept constant to Ep and current is maintained at ip.
5. Corrosion Inhibitors
➢ Chemicals which slow down anodic or cathodic reactions by forming a
film over anode or cathode.
➢ Two types,
(i) Anodic Inhibitors
(ii) Cathodic Inhibitors

(i) Anodic inhibitors
➢ Oxidising agents; chromates, molybdates, tungstates, nitrites, etc.
➢ Oxidizes the surface of the anode forming a thin protective layer of oxide or
chromate, thus decreases the rate of anode reaction.
➢ Chromates and nitrites maintain the protective layer even in the absence of oxygen.
➢ Chromates used as inhibitors in the IC engines, rectifiers and cooling towers.
➢ To achieve inhibition concentration of the inhibitors should exceed a minimum
value, if it is below that concentration, they increases the corrosion rate.
➢ Critical concentration for chromates and nitrites are in the range of 10-3 to 10-4 M.
(ii) Cathodic inhibitors
➢ Inhibits cathodic reactions like liberation of H2 and OH- .
➢ Organic cathodic inhibitors are,
amines, mercaptans thioureas and sulphoxides – effective towards acidic
medium.
➢ Forms a protective layer on cathode and prevents corrosion.
➢ Inorganic cathodic inhibitors are,
➢ sulphates of Mg, Mn, Ni and Zn in neutral or alkaline medium.
➢ React with OH- liberated at cathode forming insoluble hydroxides which
form a protective film over cathodic area.
➢ Neutral hydroxide layer does not conduct electrons and hence no corrosion.
Thermodynamics
MISSION VISION CORE VALUES

CHRIST is a nurturing ground for an individual’s Excellence and Service Faith in God | Moral Uprightness
holistic development to make effective contribution to Love of Fellow Beings
the society in a dynamic environment Social Responsibility | Pursuit of Excellence
CHRIST
Session Guidelines
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Do’s and Don'ts for Students….
● Will be shared through the Google classroom or LMS

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Course Outcome
• Students will be able to explain the basic principles of IR spectroscopy

and UV Visible spectroscopy
• Students will be able to outline the oxidation and reduction reactions
which are relevant to study the concepts of corrosion science and
electrochemistry.
• Students will be able to analyze the various types of corrosion occurring
on metal surfaces by knowing electrochemical theory of corrosion
• Students will be able to explain the basic concepts of
thermodynamics, 1st law and 2nd law of thermodynamics
• Students will be able to illustrate the fundamentals of characterization
techniques and waste water treatment

CHRIST
Syllabus
Definition of thermodynamic terms: system, surrounding etc. Types of

systems, intensive and extensive properties.
First law of thermodynamics, internal energy, enthalpy, relation between
internal energy & enthalpy, heat capacity, free energy.
Second law of thermodynamics, Spontaneous & non-spontaneous reactions,
Gibbs-Helmholtz equation & related problems. Clausius-Clapeyron
equation, Lavoisier & Laplace law.

CHRIST
What is Thermodynamics?
The science of energy, that concerned with the ways in which energy is
stored within a body.
Energy transformations – mostly involve heat and work movements.
All of thermodynamics depends on the law of :

CONSERVATION OF ENERGY
Energy cannot be created or destroyed, but can only be transformed from

one form to another.
If PE of products is less than reactants, the difference must be released

as KE.

CHRIST
System, surroundings and boundary
• System: A quantity of matter or a region in space chosen for study.

• Surroundings: The mass or region outside the system
• Boundary: The real or imaginary surface that separates the system
from its surroundings.

CHRIST
Type of system (isolated system)
• Isolated system – neither mass nor energy can cross the selected
boundary
• Example (approximate): coffee in a closed, well-insulated thermos
bottle

CHRIST
Type of system (Closed system)

• Closed system – only energy can cross the selected boundary
• Examples: a tightly capped cup of coffee

CHRIST
Type of system (Open system)

• Open system – both mass and energy can cross the selected
boundary
• Example: an open cup of coffee

CHRIST
Intensive and extensive properties
• Intensive properties are those properties whose value is

independent upon the amount of substance present in the system.
Eg:- temperature, boiling point
• Extensive properties are those properties whose value does depends
upon the amount of substance present in the system.
Eg:- Volume, mass, size

CHRIST

CHRIST
Reversible Processes
• In a reversible process the system changes in such a way that the

system and surroundings can be put back in their original states by
exactly reversing the process.
• Changes are infinitesimally small in a reversible process.

CHRIST
Irreversible Processes
• Irreversible processes cannot be undone by exactly reversing the
change to the system.
• All Spontaneous processes are irreversible.
• All Real processes are irreversible.

CHRIST
FIRST LAW OF THERMODYNAMICS

• Energy cannot be created nor destroyed.
• Therefore, the total energy of the universe is a constant.
• Energy can, however, be converted from one form to another or
transferred from a system to the surroundings or vice versa.

CHRIST
ENTHALPY
• It is total energy of the system
• Specific Enthalpy,
• Unit of Enthalpy (H) is kJ
• Unit of Specific Enthalpy (h) is kJ/kg
• Most chemical reactions occur at constant P, so

CHRIST
∆H = Hfinal - Hinitial
If Hfinal > Hinitial then ∆ H is positive Process is ENDOTHERMIC
If Hfinal < Hinitial then ∆ H is negative Process is EXOTHERMIC

CHRIST
What is Internal Energy?

• An energy form which is inherent in every systemarises from the
molecular state of motion of matter.
• The symbol E is used for the internal energy and the unit of
measurement is the joules (J).
• Internal energy increases with rising temperature and with changes of
state or phase from solid to liquid and liquid to gas.
• The heat reservoirs store internal energy, and the heat engines convert
some of this thermal energy into various types of mechanical, electrical
and chemical energies.

CHRIST
The different components of internal energy of a system are

CHRIST
The physical and chemical processes that can change the internal
energy of a system are

CHRIST
Internal energy for systems with same temperature

CHRIST
The relationship between the enthalpy of the system and the internal
energy of the system is
H = E + PV
The change in the enthalpy of the system during a chemical reaction is equal
to the change in its internal energy plus the change in the product of the
pressure times the volume of the system.
ΔH = Δ E + Δ(PV)
If the reaction is run at constant pressure, the change in the enthalpy that
occurs during the reaction is equal to the change in the internal energy of the
system plus the product of the constant pressure times the change in the
volume of the system.
Δ H = Δ E + P Δ V (at constant pressure)

CHRIST
Substituting the first law of thermodynamics into this equation gives the
following result.
Δ H = (qp + w) + P Δ V
Assuming that the only work done by the reaction is work of expansion
gives an equation in which the P Δ V terms cancel.
Δ H = (qp - P Δ V) + P Δ V
Thus, the heat given off or absorbed during a chemical reaction at constant
pressure is equal to the change in the enthalpy of the system.
Δ H = qp (at constant pressure)

CHRIST
The relationship between the change in the internal energy of the system
during a chemical reaction and the enthalpy of reaction can be
summarized as follows.
1. The heat given off or absorbed when a reaction is run at constant

volume is equal to the change in the internal energy of the system.
Δ Esys = qv
2. The heat given off or absorbed when a reaction is run at constant

pressure is equal to the change in the enthalpy of the system.
Δ Hsys = qp

CHRIST
What is Heat Capacity?

The heat capacity of a substance can be defined as the amount of heat
required to change its temperature by one degree.
Mathematically,
Q=CΔT
Where Q is the heat energy required to bring about a temperature change of

ΔT and C is the heat capacity of the system under study.

CHRIST
What is specific Heat Capacity?
The specific heat of a substance is the amount of energy required to raise
the temperature of 1 gram of the substance by 1oC .
Mathematically it is given as: Q=msΔT
Here Q is the amount of heat energy required to change the temperature of
m (kg) of a substance by ΔT, s is the specific heat capacity of the system.
Specific Heats of Some Common Substances
Substance Specific Heat (J/goC)
Water (l) 4.18
Water (s) 2.06
Water (g) 1.87
Ammonia (g) 2.09
Ethanol (l) 2.44
Aluminum (s) 0.897
Carbon, graphite (s) 0.709
Copper (s) 0.385
Gold (s) 0.129
Iron (s) 0.449
Lead (s) 0.129
Mercury (l) 0.140
Silver (s) 0.233

CHRIST
Gibbs Free Energy (G)
The energy associated with a chemical reaction that can be used to do

work.
The free energy of a system is given by enthalpy (H) minus the product
of the temperature (Kelvin) and the entropy (S) of the system:
G = H - TS
Free energy of reaction (G)
The change in the enthalpy (H) of the system minus the product of the
temperature (Kelvin) and the change in the entropy (S) of the system:
ΔG=ΔH-TΔS

CHRIST
Standard-state free energy of reaction (Δ G°)
The free energy of reaction at standard state conditions:
Δ G° = Δ H° - T Δ S°
Standard-state conditions
The partial pressures of any gases involved in the reaction is 1 atm.
The concentrations of all aqueous solutions are 1 M.

CHRIST
Limitations of the first law of thermodynamics
1. No restriction on the direction of the flow of heat

2. The first law does not indicate whether heat can flow from a cold end
to a hot end or not.
For example: we cannot extract heat from the ice by cooling it to a
low temperature. Some external work has to be done.
3. Does not specify the feasibility of the reaction: first law does not specify
that process is feasible or not
example: when a rod is heated at one end then equilibrium has to be
obtained which is possible only by some expenditure of energy.
4. Practically it is not possible to convert the heat energy into an
equivalent amount of work.

CHRIST
Second Law of Thermodynamics
The entropy of the universe does not change for reversible processes and
increases for spontaneous processes.
Reversible (ideal):
Δ S Universe = Δ S System + Δ S Surroundings = 0
Irreversible (real, spontaneous):
Δ S Universe = Δ S System + Δ S Surroundings > 0

CHRIST
Spontaneous Processes
• Spontaneity does not imply that the reaction proceeds with great
speed. For example, the decay of diamonds into graphite is a
spontaneous process that occurs very slowly, taking millions of years.
• The rate of a reaction is independent of its spontaneity, and instead
depends on the chemical kinetics of the reaction.
• Every reactant in a spontaneous process has a tendency to form the
corresponding product.
• This tendency is related to stability.
• For spontaneous processes, the change in Gibbs free energy is negative
(ΔG<0).
• Examples of spontaneous processes:
1) Heat flows from hotter body to a colder body.
2) A solid KCl spontaneously dissolves in water.

CHRIST
• Spontaneous processes are those that

can proceed without any outside
intervention.
• The gas in vessel B will spontaneously
effuse into vessel A, but once the gas is
in both vessels, it will not spontaneously

CHRIST
• Processes that are spontaneous in one

direction are non spontaneous in the
reverse direction.

CHRIST
• Processes that are spontaneous at one temperature may be

nonspontaneous at other temperatures.
• Above 0°C it is spontaneous for ice to melt.
• Below 0°C the reverse process is spontaneous.

CHRIST

CHRIST
Non-Spontaneous Processes
• An endergonic reaction (also called a nonspontaneous reaction or an

unfavorable reaction) is a chemical reaction in which the standard change in
free energy is positive, and energy is absorbed. (ΔG>0).
• The total amount of energy is a loss (it takes more energy to start the reaction
than what is gotten out of it) so the total energy is a negative net result.
• Endergonic reactions can also be pushed by coupling them to another reaction,
which is strongly exergonic, through a shared intermediate.
• A non-spontaneous processes does not takes place on its own.
• It needs continuous external influence.
• Once started, a non-spontaneous processes will stop, when the continuous
external force is withdrawn.
• Examples of non-spontaneous processes:
1) Flow of heat from inside of refrigerator to the room. Room is at
higher temperature than refrigerator.
2) Boiling of water.

CHRIST

CHRIST

CHRIST
Gibbs free energy and spontaneity
When a process occurs at constant temperature and pressure, P, we can

rearrange the second law of thermodynamics and define a new quantity
known as Gibbs free energy:
Gibbs free energy
G=H−TS where H, is enthalpy, T, is temperature (in kelvin), S, is the

entropy.
When using Gibbs free energy to determine the spontaneity of a process,

we are only concerned with changes in G, rather than its absolute value.
The change in Gibbs free energy for a process is thus written as ΔG, which
is the difference between Gibbs free energy of the products, and the Gibbs
free energy of the reactants.

CHRIST
Spontaneity in terms of free energy change is given by

∆G = ∆H - T∆S
∆G = (-ve) spontaneous
∆G = 0 Equilibrium
∆G = (+ve) Non-Spontaneous
This equation takes into account both the concepts (a) energy factor
and other (b) entropy factor

CHRIST
Depending upon the signs of ∆H and T ∆ S. and their relative magnitudes the
following possibilities arise:
When both ∆ H and T ∆ S are negative: Energy factor favors and randomness
oppose then:
if ∆ H <T ∆ S(non-spontaneous), ∆ G= +ve
When both ∆ H = T ∆ S the process is in equilibrium and ∆ G =0
when both ∆ H and T ∆ S are positive: Energy factor opposes and randomness
favours then:
If ∆ H >T∆ S process is non spontaneous, ∆ G =+ve
If ∆ H<T ∆ S process is spontaneous, ∆ G= -ve
If ∆ H=T ∆ S the process is in equilibrium, ∆ G=0
When ∆ H = -ve and T ∆ S =+ve, process is spontaneous and ∆ G= -ve
When ∆ H = +ve and T ∆ S =-ve, process is non spontaneous and ∆ G= +ve
Effect of temperature on spontaneity of process

Endothermic process at high t-> spontaneous
Exothermic process at low t-> spontaneous

CHRIST
Gibbs Helmholtz equation
• It is used for predicting the spontaneity of a process.

Applications of the Gibbs-Helmholtz equation:
• Used in the calculation of the change in enthalpy using the change in
Gibbs energy when the temperature is varied at constant pressure.
• Used in the calculation of the change in enthalpy for a reaction with
temperature other than 298K.
• Used in the calculation of the effect of temperature change on the
equilibrium constant.

CHRIST
CLAUSIUS–CLAPEYRON EQUATION
Relates the latent heat (heat of transformation) of vaporization or

condensation to the rate of change of vapor pressure with temperature
or
in the case of a solid-liquid transformation, it relates the latent heat of
fusion or solidification to the rate of change of melting point with
pressure

CHRIST
Lavoisier and Laplace’s law (1782)
This law may be stated in the general form as the heat change
accompanying a chemical reaction in one direction is exactly equal in
magnitude, but opposite in sign, to that associated with the same
reaction in the reverse direction.
This law states that; the heat change (or enthalpy change) of a chemical
reaction is exactly equal but opposite in sign for the reverse reaction.
This is evident from the following two fractions:
(a) CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) [here, ∆H0 = -890.3 kJ mol-1]
(b) CO2 (g) + 2H2O (l) → CH4 (g) + 2O2 (g) [here, ∆H0 = +890.3 kJ mol-1]
Thus, it can be concluded that ∆Hforward reaction = ∆Hbackword reaction

CHRIST
Examples
1.
S(s) + O2(g) → SO2(g) ΔH = -296.9 kJ
SO2(g) → S(s) + O2(g) ΔH = +296.9 kJ
2.
C(s) + O2 → CO2 (g); ΔH = – 94.3 kcal
CO2 → C(s) + O2; ΔH = + 94.3 kcal.

Water Technology
Impurities in water, Biochemical Oxygen Demand and Chemical Oxygen

Demand. Numerical problems on BOD and COD. Sewage treatment.
Purification of water- Desalination - Flash evaporation- Electro dialysis and
Reverse Osmosis.
1
Impurities present in water
Dissolved impurities: The main dissolved impurities are bicarbonates, chlorides

and sulphates of calcium, magnesium and sodium. Traces of nitrates nitrites,
silicates ammonium and ferrous salts are also seen. The water in contact with lime
stone contains calcium bicarbonate react with the CO2 dissolved in water.
CaCO3 + H2O +CO2 → Ca(HCO3)2

Water which is in contact with magnesite contains magnesium bicarbonate.
MgCO3 + H2O + CO2 → Mg(HCO3)2
Suspended Matter: Inorganic or organic in nature, the inorganic materials include

sand clay silica hydroxides of iron aluminium. The organic suspensions are
decaying vegetable matter due to microorganisms.
Dissolved gases: Oxygen, carbon dioxide, sulphur dioxide, ammonia and oxides
of nitrogen derived from atmosphere are present in the form of dissolved gases.
Organic matter: Decay of vegetable and animal matter including bacteria.

Hardness of water
• Hardness is due to the presence of divalent metal ions of calcium and

magnesium.
• There are two types of hardness namely temporary hardness and permanent
hardness.
• Removal of hardness of water is known as softening.
Temporary hardness: bicarbonates of calcium and magnesium. This can be

removed by boiling.
Permanent hardness: due to chlorides and sulphates of calcium and magnesium.

This can be removed by chemical treatment.
3
Determination of hardness using EDTA
• Hardness of water is expressed in terms of ppm of CaCO3.
• Hardness is determined using standard EDTA solution.
• Ethylene diamine tetra acetic acid (EDTA) is a hexadentate ligand forms
complexes with Ca2+ and Mg2+.
• The hardness is determined by titrating a known volume of water against
standard EDTA solution in presence of Eriochrome black-T as indicator at a
pH of 10.
• EBT forms a wine red colored complex with metal ions.
• On addition of EDTA the metal ions starts forming complex with free metal
ions.
• At the equivalence point, the indicator will become free from metal ions and
the free indicator is imparts blue colour to the solution.
• The end point is the colour change from wine red to blue colour, since the
reaction involves the release of H+ ions from the EDTA, the change in the
pH value can be controlled by addition of buffer solution.
• The temporary hardness is determined by boiling the water sample; this
converts soluble bicarbonates into insoluble carbonates.
• This solution is filtered to remove the precipitated calcium carbonates. The
filtrate is titrated against EDTA.
5
Total hardness = Permanent hardness + Temporary hardness
1000 ml of 1 M EDTA reacts with = 100 g of CaCO3
1 ml of 1M EDTA reacts with = (100/ 1000)g of CaCO3
V1 ml of 1 M EDTA = V1 (Burette Reading) X (100/ 1000)g of CaCO3

Consider we use 0.01 M of EDTA and 50 ml of water sample then
V1 ml of 0.01 M EDTA = V1 X 0.01 (100/ 1000)g of CaCO3
50 ml (parts) of water sample = V1 X 0.01 (100/ 1000)g of CaCO3
1 part of water sample = V1 X 0.01 (100/ 1000 x 50)g of CaCO3
1 ppm of water sample = V1 X 0.01 X 106 (100 / 1000 x 50)g of CaCO3
= 20 x V1 g of CaCO3
Total hardness of water = 20 x V1 ppm of CaCO3 equivalent

Consider 50 ml of water sample after heating requires V2 ml of 0.01 M EDTA
Permanent hardness = 20 X V2 g of CaCO3
Temporary hardness = total hardness – permanent hardness= 20 x (V1-V2)

ppm CaCO3 equivalent
Biological oxygen demand
Biochemical oxygen demand or B.O.D. is the amount of dissolved oxygen
needed by aerobic biological organisms in water to oxidise the organic material
present in a one litre of water sample over a five day period at 200C.
The BOD value is most commonly expressed in milligrams of oxygen consumed

per litre of sample during 5 days of incubation at 20 °C.
7
Chemical oxygen demand
• Chemical oxygen demand is defined as the amount of oxygen consumed
in the chemical oxidation of organic and inorganic wastes present in one
litre of waste water.
• Potassium dichromate is a strong oxidizing agent under acidic conditions.
Most commonly, a 0.25N solution of potassium dichromate is used for
COD determination,
• An excess amount (10 ml) of standard solution of potassium dichromate
is added to the measured volume (V) of waste water sample with known
volume of sulphuric acid.
• Once oxidation is complete, the amount of excess potassium dichromate
is titrated against standard solution of ferrous ammonium sulfate (FAS)
using Ferroin as indicator.
• Once all the excess dichromate has been reduced, the Ferroin indicator
changes its colour from blue-green to reddish-brown.
• The amount of ferrous ammonium sulfate added is equivalent to the
amount of excess potassium dichromate added to the original water
sample.
8
• A blank sample is created by adding all reagents (e.g. acid and
oxidizing agent) to a volume of distilled water.
• COD is measured and compared for both water and blank samples.
• The oxygen demand in the blank sample is subtracted from the COD
for the original sample to ensure a true measurement of organic
matter.
Calculation of COD
• Volume of K2Cr2O7 required for the water sample = (b-a)

• Where the titrant vale for the blank titration = b
• Titrant value for the experimental titration = a
• Volume of water sample taken = V
• Normality of ferrous ammonium sulphate = N
• COD of the sample = [N x (b-a) x 8 gL-1] / V
Sewage treatment
Sewage treatment is the process of removing contaminants from wastewater

and household sewage. It includes physical, chemical, and biological
processes to remove physical, chemical contaminants and biological
contaminants.
The sewage is classified into Domestic sewage and Industrial effluents. The
treatment is classified into
Pretreatment
Primary treatment
Secondary treatment
Tertiary treatment
Pre-treatment includes the removal of materials that can be easily collected

from the raw wastewater before they damage or clog the pumps and
skimmers of primary treatment clarifiers (trash, tree limbs, leaves, etc.).
Primary treatment
• In the primary treatment, sewage flows through large tanks, commonly

called "primary clarifiers“or "primary sedimentation tanks."
• Then the water is passed into a sedimentation tank where it is allowed to
settle.
• The non-settleable solids are removed by coagulation by treatment with
coagulating agents like alum, ferric chloride or lime.
Secondary treatment (biological treatment / activated sludge process)
• The waste water after primary treatment is allowed to flow into large
tanks.
• Activated sludge containing microorganism is sprayed over the water.
• These microorganism form thin layer over the primary treated water and
thrive on organic wastes in sewage.
• Air is passed vigorously from bottom of the tank, to bring good contact
between the organic wastes and bacteria in presence of sunlight and air to
improve the aerobic oxidation of organic matter occurs.
• Sludge formed removed by settling or filtration.
• Part of sludge reused & rest is used as fertilizer.
• Residual water is chlorinated, to remove bacteria then discharged into
running water.
• This process operates at 90-95% efficiency of BOD treatment. It treated
water contains a high concentration of phosphates, heavy metal ions,
colloidal impurities and non-degradable organic compounds, then the
water is subjected to tertiary treatment.
Tertiary treatment
• Treatment of lime for removal of phosphates as insoluble calcium

phosphates.
• Treatment with sulphur ions for removal of heavy metal ions as insoluble
sulphides.
• Treatment with activated charcoal to adsorb remaining organic
compounds.
• Treatment with alum to remove the colloidal impurities not removed in
previous treatments to further reduce the BOD level.
Desalination
• Desalination or desalinisation refers to any of several processes that

remove some amount of salt and other minerals from water. Several
methods are available for desalination, such as
• Flash evaporation
• Reverse osmosis
• Electrodialysis
Flash evaporation:
• This method is used to remove the volatile impurities present in water. In
flash evaporation water is heated to a high temperature under pressure
without changing the phase (liquid to gas), then is evaporated quickly
(flash) in successive flashing units each operating at a lower pressure than
the previous one.
• The flash water from each unit is condensed and supplied to the next unit
for further flashing and condensation, till the volatile impurities are
completely removed.
Schematic of a 'once-through' multi-stage flash
desalinator
A - Steam in
B - Seawater in
C - Potable water out
D - Brine out (waste)
E - Condensate out
F - Heat exchange
G - Condensation collection
H - Brine heater
Osmosis
• Osmosis is a natural process.
• When two liquids of different concentration are separated by a semi
permeable membrane, the fluid has a tendency to move from low to high
solute concentrations for chemical potential equilibrium.
• The phenomenon of movement of solvent from an area of low solute
concentration (high Water Potential), to an area of high solute concentration
(low water potential) through a semi permeable membrane is known as
osmosis.
• The movement of a pure solvent to equalize solute concentrations on each
side of a membrane generates osmotic pressure
Reverse osmosis:
• Applying an external pressure to reverse the natural flow of pure solvent,
is known as reverse osmosis.
Principle:
• Reverse osmosis (RO) is a membrane technical filtration method that
removes many types of large molecules and ions from solutions by applying
pressure to the solution when it is on one side of a selective membrane.
• The result is that the solute is retained on the pressurized side of the membrane
and the pure solvent is allowed to pass to the other side.
18
Electrodialysis:
• Electrodialysis is used to transport salt ions from one solution to another
solution through an ion-exchange membrane under the influence of an
applied electric potential difference.
• The passage of electric current through a solution of salt results in migration
of cations towards cathode and anions towards the anode.
• The use of semi permeable cation

exchange membranes permits the passage
of only cations and anion exchange
membranes permits the passage of
anions.
• An electrodialysis unit consists of a
chamber carrying a series of
compartments fittted with closely spaced
alternate cation and anion exchange semi
permeable membranes between the
cathode and anode.
19
Thank You
20
Characterization of Catalysts
1
X-ray Photoelectron Spectroscopy (XPS)
Principle
• Surface of the specimen is irradiated by X-ray with the energy of hν.
• Mono-energetic photon knocks out the electron from atoms in the surface region.
Photons with higher energy hν penetrate deeper into the samples surface. Electrons
emitted by photons from lower energy X-rays originates from inner atomic energy
levels and were bound to atomic nuclei with the binding energy Eb.
• Electrons emitted in this manner are referred to as photoelectrons.
An example of a photoelectron
emitted due an incident photon
The binding energy is the energy required to break a nucleus into its constituent protons and neutrons
Theory
• XPS spectra are obtained by irradiating a material with a beam of X-rays while
simultaneously measuring the kinetic energy and number of electrons that
escape from the top 0 to 10 nm of the material being analyzed.
• So in this particular technique we are utilizing x-ray to excite a particular
material, then generate photoelectrons and eventually get a spectrum to finally,
evolve with the chemical analysis.
• It is also called electron spectroscopy, because electron which is emitted as the
photoelectron, that is being captured for the chemical analysis of a particular
material.
• We can analyze its elemental composition, chemical formula, empirical formula
and chemical or electronic state of the elements. So, we can easily determine
the overall nature of a particular element and its electronic state
3
• XPS detects all elements except Hydrogen and Helium.
• Detection limits for most of the elements (on a modern instrument) are in
the parts per thousand range. Detection limits of parts per million
(ppm) are possible, but require special conditions: concentration at top
surface or very long collection time (overnight).
Why Ultra High Vacuum

• Remove adsorbed gases from the sample.
• Eliminate adsorption of contaminants on the sample.
• Prevent high voltage breakdown.
• Increase the mean free path for electrons, ions and photons.
• Electron counting detectors in XPS instruments are typically one meter
away from the material irradiated with X-rays.
• This long path length for detection requires low pressures.
Einstein’s Photoelectric Equation
• An electron, which is negatively charged, is attracted to the nucleus of an atom
because of the positive charge that is there.
• The amount of energy that is required to be given to the electron to pull it away from
this attractive (Coulombic) force is called the binding energy.
• Sometimes binding energy is also called as work function
• Ephoton denotes the energy of the incident photon, which is equal to h𝜈

• Φ denotes the threshold energy of the metal surface
• Ekinetic denotes the kinetic energy of the photoelectron, which is equal to ½mev2 (me =
mass of electron = 9.1 X 10-31 kg)
5
Features of XPS
• A typical XPS spectrum is a plot of the number of electrons detected
(sometimes per unit time) (Y-axis, ordinate) versus the binding energy of the
electrons detected (X-axis, abscissa).
• Each element produces a characteristic set of XPS peaks at characteristic
binding energy values that directly identify each element that exists in or on the
surface of the material.
• The number of detected electrons in each of the characteristic peaks is directly
related to the amount of element within the XPS sampling volume.
• Signals detected from analytes at the surface much stronger than the signals
detected from analytes deeper below the sample surface.
• 1–20 minutes for a broad survey scan that measures the amount of all detectable
elements.
• 1–15 minutes for high resolution scan that reveal chemical state differences
• 1–4 hours for a depth profile that measures 4–5 elements.
• The minimum analysis area ranges from 10 to 200 micrometres.
7
Quantification of XPS
8
Powder X-ray Diffraction
• X-ray diffraction (XRD) is an characterization technique followed for
determining the crystal structure of materials.
• It detects crystalline materials having crystal domains greater than 3-5 nm.
It is used to characterize bulk crystal structure, particle size and chemical
phase composition.
• X-ray is a form of electromagnetic radiation have wavelength of from
0.01-0.7 nm.
• The spacings between lattice planes in the crystal are comparable to X-
rays.
• When an incident beam of X-rays interacts with the target atom, X-ray
photons are scattered in different directions.
• Scattering is elastic when there is no change in energy between the
incident photon and the scattered photon.
• In inelastic scattering the scattered photon loses energy.
• These scattered waves may super impose.
• Diffraction from different planes of atoms produces a diffraction
pattern, which contains information about the atomic arrangement
within the crystal.
• The X-ray beams incident on a crystalline solid will be diffracted by the
crystallographic planes.
• Bragg's law for diffraction. It is given as sinθ=nλ/2d; where n = an
integer λ = wave length of the radiation d = spacing between two planes
or layers θ = diffraction peak at a specific angle.
• The spacing between diffracting planes of the atoms determines the
peak positions. The peak intensity is determined by the atoms are in the
diffracting plane.
Bragg's Law refers to the simple equation
nλ = 2d sinθ
The rays of the incident beam are always in phase
and parallel up to the point at which the top beam
strikes the top layer at atom z.
The second beam continues to the next layer where
it is scattered by atom B.
The second beam must travel the extra distance
AB + BC if the two beams are to continue
traveling adjacent and parallel.
This extra distance must be an integral (n) multiple of the wavelength (λ) for the
phases of the two beams to be the same: nλ = AB +BC eq. (1)
Recognizing d as the hypotenuse of the right triangle Abz,

we can use trigonometry to relate d and to the distance (AB + BC).
The distance AB is opposite so, AB = d sinθ eq. (2)
Because AB = BC eq. (1) becomes, nλ = 2AB eq. (3)
Substituting eq. (2) in eq. (3) we have,
nλ = 2d sinθ
4000
3000
Intensity
2000
1000
10 20 30 40 50 60 70 80
Angle (2)
Amorphous Pattern Crystalline Pattern
16
Thank You
17

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Catalog

MISSION VISION CORE VALUES

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Do’s and Don'ts for Students….

● Will be shared through the Google classroom or LMS

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• Students will be able to explain the basic principles of IR spectroscopy

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● The history of spectroscopy began with Isaac Newton's optics

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● Wave produced by the motion of Electrically charged particle with a

Image copied : https://en.wikipedia.org/wiki/File:Ondeelectromagnetique.svg

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Amplitude (A)- Length of the electrical vector at a maximum or minimum in

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Wavenumber (n) – It is the number of waves per unit distance / The

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Relationship between frequency and wavelength

Velocity of light, c= ν λ (where c = 3× 108 m/s)

Relationship between frequency of light and Energy

E = h ν (where h is Plank’s Constant = 6.6261 × 10-34 J.s)

λ = h/mc = h/mv (P=mv)

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Most spectroscopic methods are differentiated as either

The effect of interaction of electromagnetic rays with matter depends on

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Absorption & Emission Spectroscopy

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Interaction of EMR with matter

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Interaction EMR with matter to give visible light

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Interaction of EMR with matter

1. Electronic Energy Levels:

2. Vibrational Energy Levels:

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3. Rotational Energy Levels:

∆Erotational < ∆Evibrational < ∆Eelectronic

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Molecular Energy Level Diagrams

• Explains the electronic structure of the molecules using quantum

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Construction of Molecular Energy Level Diagrams

• Atomic orbitals combine to form molecular orbitals

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Rules-Construction of Molecular Energy Level Diagrams

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Electronic Configuration of Diatomic Molecules

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Beer Lamberts Law

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According to this law, when a beam of monochromatic radiation is passed

Lambert’s law states that the rate of decrease of intensity of monochromatic

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Derivation of Beer Lambert’s Law

-dI /dc = K I (K is proportionality constant)