CHAPTER-I

MOLECULAR STRUCTURE AND SPECTROSCOPY

Syllabus: Molecular structure and Spectroscopy (9L): Introduction, Concept of atomic and molecular
orbitals, LCAO, Molecular orbitals of diatomic molecules, Molecular orbital energy level diagrams of
diatomic molecules (N2, O2 and F2). Pi-molecular orbitals of butadiene and benzene.
Spectroscopic techniques: Principles of spectroscopy, selection rules and applications of electronic
spectroscopy (UV & Visible). Vibrational and rotational spectroscopy (IR spectroscopy) - Applications.

Atom: A smallest indivisible particle of an element/matter/substance is called atom. In an atom,

subatomic particles like protons and neutrons are present inside the nucleus and negatively charged
electrons are present outside the nucleus.
Orbit: A fixed path in which electrons revolve around the nucleus of an atom is called orbit.
Orbital: A region having the highest probability of finding electrons (outside the nucleus) in an orbit
called orbital.
Atomic orbital: A mathematical function describing the location and wave-like behavior of an
electron in an atom called atomic orbital. This mathematical function can be used to calculate the
probability of finding any electron at any specific region around the atom’s nucleus.
Atomic orbitals are labelled as s, p, d and f orbitals. All four orbitals have different shapes.
The energies of orbitals are in order of s<p<d<f
The shapes of atomic orbitals are as follows
s-orbital: Spherical (it has one sub energy level)
p-orbital: Dumbbell (it has three sub energy levels)
d-orbital: Double dumbbell (it has five sub energy levels)
f-orbital: Diffused (complex) (it has seven sub energy levels)
➢ s-Orbital has only one sub energy level

S-orbital

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 ➢ p- Orbital has three sub-energy levels (Px, Py and Pz).

Px Py Pz

➢ d-Orbital has five sub-energy levels, i.e., dxy, dyz, dzx, dx2-y2 and dz2.

dxy dyz dzx dx2-y2 dz2

QUANTUM NUMBERS
Position and energy of electrons is completely described by four sets of quantum numbers.
1. Principal quantum number (n):
Principal quantum number was proposed by Neils Bohr and denoted by “n”.
It tells about the distance from the nucleus (or size of orbit) and energy of electron.
n = Integer with positive value
If, n = 1, i.e., 1st orbit; n = 2, i.e., 2nd orbit; n = 3, i.e., 3rd orbit; n = 4, i.e., 4th orbit.
Total no of electrons presents in a shell = 2n2
2. Azimuthal or Angular quantum number (l):
Azimuthal or Angular quantum number was proposed by Sommerfeld and it is denoted by ‘l’.
It describes the shape of orbitals (s, p, d and f).
Value of l is from 0 to (n-1).
l = 0 for s-orbital, l = 1 for p-orbital, l = 2 for d-orbital, l = 3 for f-orbital.
3. Magnetic quantum number (m or ml):
Magnetic quantum number was proposed by Lande and indicated by ‘m or ml’.
It describes about the number of orbitals and orientation of subshell.
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Magnetic quantum number values are (2l+1) and they are from –l····0····+l (including zero).
If, l = 0, then m = 1, i.e., 0
l = 1, then m = 3, i.e., -1, 0, +1
l = 2, then m = 5, i.e., -2, -1, 0, +1, +2
l = 3, then m = 7, i.e., -3, -2, -1, 0, +1, +2, +3
4. Spin quantum numbers (s or ms):
Spin quantum number was proposed by Beck (George Uhlenbeck)) and Goudsmit (Samuel Goudsmit)
and denoted by ms.
It describes the spin of electrons. Spin quantum numbers are only two, those are +1/2 and ̶ 1/2.
Clockwise direction ↑ 1 Anticlockwise direction ↓ 1
+ ̶
2 2

FILLING OF ATOMIC ORBITALS WITH ELECTRONS

1. Aufbau principle: Aufbau principle states that the electrons are filled into atomic orbitals from
lowest energy orbital to highest energy orbitals.
Example, carbon has 6 electrons. Electronic configuration is 1S2 2S2 2P2.
2. Hund’s rule: All degenerate orbitals in a subshell occupy with one electron before any orbital
occupy with two electrons, and all electrons in singly occupied orbitals have same spin.
Example: 3d: ↑ ↑ ↑ ↑ ↑
3. Pauli Exclusion Principle: Pauli exclusion principle states that, any two electrons do not have four
same quantum numbers in an atom.
Examples: Hydrogen ↑ Helium ↑↓ Lithium ↑↓ ↑
1S1 1S2 1S2 2S1

Molecule: Two or more atoms connected through chemical bonds is called molecule.
Molecular orbitals: A mathematical function describing the location and wave-like behavior of an
electron in a molecule called molecular orbital.

Shapes of Molecular Orbitals

Molecular orbitals are two types, σ-molecular orbitals and π-molecular orbitals. σ-Molecular orbitals
are formed when two atomic orbitals overlap along the internuclear axis. π-Molecular orbitals are
formed when two atomic orbitals overlap in sideways.

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1. Molecular orbitals from s-atomic orbitals (s-s overlap)
s-Atomic orbitals can overlap only through internuclear axis. Therefore, s-atomic orbitals produce
only σ-molecular orbitals and cannot give π-molecular orbitals. Molecular orbitals which are formed
through addition method are called as bonding molecular orbitals (BMO). Molecular orbitals which
are formed through subtraction method are called as antibonding molecular orbitals (ABMO).
(electron density between
nucleus is low)

(electron density between

nucleus is high)

2. Molecular orbitals from 2p-atomic orbitals (p-p overlap)

p-Atomic orbitals can overlap through internuclear axis as well as in sideways. Therefore, p atomic
orbitals can produce both σ and π-type molecular orbitals. When p-atomic orbitals overlap through
internuclear axis produce σ-molecular orbitals, and when p-atomic orbitals overlap through sideways
produce π-molecular orbitals. The strongest overlap occurs between the 2pz orbitals.

+ - + - σ*2pz
(ABMO)

- + + + -
2pz 2pz - + - σ2pz
(BMO)

- +
π*2px
+ -
- -
+
+ + 4 .-. π2px
2px 2px + (BMO)
 - + -
2pz 2pz - + - σ2pz
(BMO)

- +
π*2px
+ -
- -
+
+ + .-. π2px
2px 2px + (BMO)

- +
+ - π*2py
- - (ABMO)

+ + +
-
2py 2py π2py
+ (BMO)
Atomic orbitals from two different nuclei Molecular orbitals

MOLECULAR ORBITAL THEORY (MOT)

Molecular orbital theory (MOT) was developed by F. Hund and R. S. Mulliken. MOT clearly describes
the structure and properties of different molecules.
The important postulates of MOT are as follows
1. Only atomic orbitals having similar energy and proper symmetry combine each other to form
molecular orbitals.
2. Total number of molecular orbitals formed is equal to the total number of atomic orbitals
combined.
3. When n-number of atomic orbitals combine to form n-molecular orbitals, the wave functions are
𝑛
combined both in phase and out of phase to create ( ) bonding molecular orbitals (BMO), and
2
𝑛
( ) antibonding molecular orbitals (ABMO), respectively.
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4. Molecular orbitals which have lower energy than the corresponding atomic orbitals are called
bonding molecular orbitals (BMO). BMOs are formed through addition method.
5. Molecular orbitals which have higher energy than the corresponding atomic orbitals are called
antibonding molecular orbitals (ABMO). ABMOs are formed through subtraction method.
6. The electrons are filled in molecular orbitals following Aufbau rule, Hunds rule and Paulis
exclusion principle.
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7. Bond order (BO) = [𝑵𝒃 − 𝑵𝒂]/𝟐. Where, Nb is number of electrons present in BMO, and Na is
number of electrons present in ABMO.
8. A positive value of bond order reveals that the molecule exists and is stable. When the bond
order is zero, the molecule is unstable and does not exist.
9. If a molecule possesses one or more unpaired electrons in its molecular orbitals that molecule
will have paramagnetic property.
10. If a molecule doesn’t have any unpaired/lone pair electrons, it will have diamagnetic property.
LINEAR COMBINATION OF ATOMIC ORBITALS (LCAO)
Atomic orbitals can be expressed by wave functions (ψ) which represents the amplitude of electron
waves, but it may not be easy to solve for molecules.
To overcome this problem researchers developed an approximate method to obtain wave functions
for molecular orbitals known as linear combination of atomic orbitals (LCAO) method.
Consider the hydrogen molecule (H2) consisting of two hydrogen atoms HA and HB. Each hydrogen
atom in the ground state has one electron in 1s orbital, then the overall wave function of H2 molecule

is as follows. Here, orbitals are represented by wave function (ψ).

ψM.O = ψA ± ψB
ψBMO = ψA + ψB and ψABMO = ψA – ψB
A molecular orbital formed by addition of atomic orbitals is called bonding molecular orbitals (BMO).
Indeed, the probability of finding electron is in square form,

i.e., ψ2BMO = (ψA + ψB)2 and ψ2ABMO = (ψA – ψB)2

ψ2BMO = ψ2A + ψ2B + 2 ψAψB and ψ2ABMO = ψ2A + ψ2B – 2 ψAψB
A molecular orbital formed by subtraction of atomic orbitals is called antibonding molecular orbitals
(ABMO).
MOLECUALR ORBITAL ENERGY LEVEL DIAGRAN (MOED) OF VARIOUS DIASTOMIC MOLECULES
The relative energies of molecular orbitals in increasing order are found to be as follows.
For lighter molecules (having electrons ≤ 14):
σ1s < σ*1s < σ2s < σ*2s < (π2Px = π2Py) < σ2pz < (π*2Px = π*2Py) < σ*2pz.
For heavier molecules (having electrons >14).
σ1s <σ*1s < σ2s < σ*2s < σ2pz < (π2Px= π2Py) < (π*2Px=π*2Py) < σ*2pz.

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** MOLECULAR ORBITAL ENERGY LEVEL DIAGRAM OF NITROGEN MOLECULE (N2) **
➢ Atomic number of nitrogen (N) is 7. No of electrons in nitrogen atom (N) = 7. No of electrons in
nitrogen (N2) molecule = 14.
➢ Electronic configuration of Nitrogen atom is 1s2 2s2 2p3.
➢ The electronic configuration of N2 is: σ1s2 σ* 1s2 σ2s2 σ*2s2 (π2Px2 = π2Py2) σ2pz2.
➢ Bond order = (Nb-Na) / 2
Where, Nb = no of bonding electrons & Na = no of antibonding electrons.
Then, BO = (10-4)/2 = 3
In N2 molecule BO is three means a triple bond is present between two nitrogen atoms.
➢ N2 does not have any unpaired electrons, so, N2 has diamagnetic property.

σ*2pz
ABMO

π*2px= π*2py
2px 2py 2pz 2pz 2py 2px
σ2pz BMO

π2px= π2py

σ*2s
Energy

2S 2S
σ2s
σ*1s

1S 1S
Atomic Orbitals σ1s Atomic Orbitals
of N-Atom of N-Atom
Molecular Orbitals
of N2-Molecule

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** MOLECULAR ORBITAL ENERGY LEVEL DIAGRAM OF OXYGEN MOLECULE (O2) *
➢ Atomic number of oxygen (O) is 8. No of electrons present in oxygen atom (O) = 8. No of electrons
present in oxygen molecule (O2) = 16
➢ Electronic configuration of oxygen atom is 1s2 2s2 2p4
➢ The electronic configuration of oxygen molecule (O2) is
σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 (π2Px2= π2Py2) (π*2Px1=π*2Py1)
➢ Bond order = (Nb-Na)/2, Where, Nb = no of bonding electrons & Na = no of antibonding electrons.
Then, BO = (10-6)/2 = 2.
In O2 molecule BO is two means a double bond is present between two oxygen atoms.
➢ O2 molecule has two unpaired electrons, therefore O2 has paramagnetic property.
σ*2pz
ABMO

π*2px= π*2py
2px 2py 2pz 2pz 2py 2px
π2px= π2py BMO

σ2pz
σ*2s
Energy

2S 2S
σ2s
σ*1s

1S 1S
Atomic Orbitals σ1s Atomic Orbitals
of O-Atom of O-Atom
Molecular Orbitals
of O2-Molecule

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** MOLECULAR ORBITAL ENERGY LEVEL DIAGRAM OF FLUORINE MOLECULE (F2)
✓ Atomic number of fluorine (F) is 9. No of electrons present in fluorine atom (F) = 9. No of
electrons present in fluorine molecule (F2) = 18.
✓ Electronic configuration of oxygen atom is 1s2 2s2 2p5.
✓ The electronic configuration of oxygen molecule (F2) is:
σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 (π2Px2 = π2Py2) (π*2Py2 = π*2Px2).
✓ Bond order = (Nb-Na)/2, Where, Nb = no of bonding electrons & Na = no of antibonding electrons.
Then, BO = (10-8)/2 = 1.
✓ In F2 molecule the BO is one means a single bond is present between two fluorine atoms.
✓ F2 molecule doesn’t have unpaired electrons, so, F2 has diamagnetic property.
σ*2pz
ABMO

π*2px= π*2py
2px 2py 2pz 2pz 2py 2px
π2px= π2py BMO

σ2pz
σ*2s
Energy

2S 2S
σ2s
σ*1s

1S 1S
Atomic Orbitals σ1s Atomic Orbitals
of F-Atom of F-Atom
Molecular Orbitals
of F2-Molecule

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Pi (π) MOLECULAR ORBITALS OF 1,3-BUTADIENE
The structure of 1,3-butadiene is CH2=CH ̶ CH=CH2
Node: The probability of finding electron zero is called as node.
1,3-butadiene contains two double bonds that are in conjugation. It is built from 4 sp2 hybridized
carbon atoms, each contributing one p-atomic orbital containing one electron.

No of nodes = 3
π4* No of B.I. =0
No of anti B.I. = 3
No of nodes = 2
*
π3 No of B.I. =1
LUMO No of anti B.I. = 2
Energy

No of nodes = 1
π2 No of B.I. =2
HOMO No of anti B.I. = 1

π1 and π2 are BMO No of nodes = 0

π3* and π4* are ABMO
π1 No of B.I. =3
No of anti B.I. = 0
C1 C2 C3 C4
HOMO : Highest Occupied Molecular Orbital & LUMO : Lowest Unoccupied Molecular Orbital
B. I. = Bonding Interactions & anti B.I. = anti bonding interactions

The number of molecular orbitals for π-system is equal to the number of contributing p-orbitals.
Since butadiene consists of 4 individual p-orbitals, butadiene will contain 4 π-molecular orbitals.
The number of nodes between p-orbitals increases by one for each successive energy level, such
that the highest energy orbital has (n-1) nodes.

π1 Molecular orbital: π1 Molecular orbital is the lowest energy orbital, that has zero nodes
between the p-atomic orbitals. π1 MO has three bonding interactions between C1-C2, C2-C3 and
C3-C4. π1 -MO has zero antibonding interactions.

π2 Molecular orbital: π2-MO has one nodal plane between C2-C3. It has two bonding interactions
between C1-C2 and C3-C4 but one antibonding interaction between C2-C3.
π3* Molecular orbital: π3* has two nodal planes between C1-C2 & C3-C4. It has one bonding
interactions between C2-C3 and two antibonding interactions between C1-C2 & C3-C4.
π4* Molecular orbital: π4* MO has three nodal planes between C1-C2, C2-C3 and C3-C4. It has no
bonding interactions but three antibonding interactions between C1-C2, C2 –C3 and C3-C4.
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 The highest occupied molecular orbital (HOMO) is π2 in 1,3-butadiene.
In contrast, the anti-bonding π3* orbitals contain no electrons. The lowest unoccupied orbital
(LUMO) is π3* in 1,3-butadiene.

π-MOLECULAR ORBITALS OF BENZENE

Benzene (C6H6) is the simplest aromatic hydrocarbon. Benzene has a planar hexagonal structure.
All the carbon atoms are sp2 hybridized, each contributing one p-atomic orbital and one electron.
Since benzene contributes 6 individual p-orbitals, the π-system of benzene will contain 6-π molecular
orbitals.

No of B.I. = 0
3 nodes No of anti B.I. = 6

No of B.I. = 2 Benzene
No of anti B.I. = 4
No of B.I. = 0
No of anti B.I. = 4
2 nodes LUMO
Energy

1 nodes HOMO
No of B.I. = 2
No of B.I. = 4 No of anti B.I. = 2
No of anti B.I. = 2

No of B.I. = 6
0 node No of anti B.I. = 0

HOMO : Highest Occupied Molecular Orbital & LUMO : Lowest Unoccupied Molecular Orbital
B. I. = Bonding Interactions & anti B.I. = anti bonding interactions

❖ The molecular orbitals of benzene: π1, π2 and π3 are bonding molecular orbitals (BMO).
π 4*, π5* and π6* are antibonding molecular orbitals (ABMO).
❖ π1-Molecular orbital: π1-MO is the lowest-energy orbital. It has zero nodes between the p-
atomic orbitals. π1 MO has six bonding interactions and zero antibonding interactions.
❖ π2 & π3 Molecular orbitals: π2 and π3 Mos are degenerate molecular orbitals (means same energy
orbitals) and each has one nodal plane. π2 has four bonding interactions and two antibonding
interactions. π3 has two bonding interactions and two antibonding interactions.

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❖ π4* & π5* Molecular orbitals: π4* and π5* are degenerate molecular orbitals and have two nodal
planes. π4* has two bonding interactions and four antibonding interactions. π5* has zero bonding
interactions and four antibonding interactions.
❖ π6* Molecular orbitals: π6* MO has three nodal planes. It has zero bonding interactions and six
antibonding interactions.
❖ Benzene has 6π electrons which are filled in π1, π2 and π3 molecular orbitals.
❖ The highest occupied molecular orbital (HOMO) is π2 and π3 in benzene & the lowest unoccupied
molecular orbital (LUMO) is π 4*and π5* in benzene.

SPECTROSCOPY
Aim: Spectroscopy is an analytical tool to determine molecular structure and concentration of
unknown compounds.
Spectroscopy: Spectroscopy is the study of interaction between electromagnetic radiation (EMR) and
sample/compound/matter.

Electromagnetic radiation (EMR)

Electromagnetic radiation (EMR) consists of electromagnetic waves which are synchronized
oscillations of electric and magnetic fields. It is a type of energy, commonly known as light which is
produced by the movement of electrically charged particles travelling through a space or vacuum.
The electric and magnetic components are mutually perpendicular (90⁰) to each other.
EMR contains a range of wavelengths. Based on wavelength or energy EMR classified into different
categories as follows.
1) Gamma (γ) rays; 2) X-rays; 3) Ultraviolet (UV)-Visible; 4) Infrared (IR); 5) Microwave and 6) Radio
waves.

1. Gamma-rays 2. X-rays 3. Ultra-violet (UV)-Visible 4. Infrared (IR) 5. Microwave 6. Radio waves

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Wavelength (λ): The distance between two successive crests or troughs is known as wavelength.
Wavelength can be represented by λ. Units for wavelength: Å (10-8 cm), nm (10-9m), µm, cm.
Amplitude (A): Height of crest or depth of trough is called amplitude.
Wavenumber (γ): The number of waves present in unit length (cm) is known as wavenumber. It is
reciprocal of wavelength. Wavenumber can be represented by γ.
1
γ∝𝜆

Units: cm-1
Frequency (ν): The number of waves passed through a specific point in a given time (sec) is called
frequency. ν = c/λ.
Units: Hertz (Hz) or cycles/sec.

Wavelength (λ)
Crest

Amplitude

Trough
One oscillation

Various spectroscopic methods available for solving wide range of analytical problems.
The spectroscopy can be classified into two types:
1) Absorption spectroscopy: The absorbed radiation by molecule in the form of spectra.
Ex: UV-Visible spectroscopy, infrared (IR) spectroscopy, nuclear magnetic resonance (NMR)
spectroscopy, colorimetry, etc.
2) Emission spectroscopy: The emitted radiation by the molecules in the form of spectra.
Ex: Fluorescence and phosphorescence spectroscopy.
EMR used for analysis
UV-radiation (UV-Vis Spectroscopy)
IR-radiation (IR Spectroscopy)
Radio-radiation (NMR Spectroscopy)

UV-VISIBLE SPECTROSCOPY (ELECTRONIC SPECTROSCOPY)

Wavelength Range: UV-Visible radiation wavelength is 200-800 nm.
UV region is 200-400 nm & Visible region is 400-800 nm.
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Source for UV-Visible radiation: Tungsten lamp, Deuterium lamp, Mercury arc lamp, Xenon lamp.
Solvents: The most commonly used solvents are ethanol, water and hexane. The other solvents like
methanol, chloroform and ether can also be used.
In UV-Vis spectrum instead of sharp peaks broad bands will appear because of rotational and
vibrational transitions.
Energy levels of molecules: Molecules have different energy levels like, Electronic energy level (E),
Vibrational energy level (V) and Rotational energy level (R). The energy order of energy levels in the
molecules is as follows: ΔE > ΔV > ΔR Absorption of radiation in UV-Visible region causes transition
between electronic energy levels. Therefore, this is also called as electronic spectroscopy.

Principle of UV-Visible spectroscopy: When a molecule is exposed to UV-Visible radiation, electron

present in the electronic ground state (E0) absorbs the UV-visible radiation and travels into the higher
energy electronic state (En). The transportation of electron from electronic ground state to electronic
excited state is called as electronic transitions.
Absorption Laws:
Monochromatic light is a single-wavelength light, where mono refers to single, and chroma means
color.
Beers Law: When a monochromatic light passed through a sample solution, the absorption of light
(A) is directly proportional to the concentration (c) of the solution. This law was proposed by Pierre
Bouguer. A ∝ c

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Lamberts Law: When a monochromatic light passed through a sample solution, the absorption of
light (A) is directly proportional to the path length (l) of the sample solution. This law was proposed

by Johann Heinrich Lambert. A ∝ l

Beer-Lamberts law: When a monochromatic light passed through a solution, absorption (A) of
radiation is directly proportional to the concentration of the solution (c) and the path length (l) of
the sample solution.
A ∝ cl
A = εcl

I0 = Intensity of incident light; ε = Molar extinction coefficient;

I = Intensity of transmitted light; c = Concentration of the solution;
l = path length of solution.

*** POSSIBLE ELECTRONIC TRANSITIONS IN UV-VISIBLE SPECTROSCOPY ***

The possible electronic transitions can be graphically shown as follows:

σ*-antibonding

π*-antibonding
Energy

n-bonding
n → π* n → σ*
π-bonding
π → π* π → σ*
σ-bonding
σ → π* σ → σ *

1. σ → σ* transition 4. n → π* transition
2. π → π* transition 5. σ → π* transition
3. n → σ* transition 6. π → σ* transition
Energy order: n - π* < π - π* < n - σ* < σ - σ*
1. σ → σ* transition: Molecules which are having only σ-electrons.
Examples: Alkanes (CH3-CH3) and cycloalkanes.

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2. π → π* transition: Molecules having σ and π electrons.
Examples: Alkenes (CH2=CH2), alkynes (CH≡CH) and aromatics.
3. n → σ* transition: Molecules having σ and n electrons.
Example: Alcohols (-CH2OH), alkyl halides (-CH2Cl), amines (-CH2NH2), etc.
4. n → π* transition: Molecules having σ, π and n electrons.
Examples: Carbonyls (-C=O), carboxylic acids (-COOH), esters (-COOR) and amides (-CONH2).
5. σ → π* transition and 6. π → σ* transitions: These transitions are only theoretically possible but
practically not allowed due to symmetry criteria.
Examples for different electronic transitions
1) CH3-CH3: Only σ → σ* transition is possible
2) CH2=CH2: π → π* and σ → σ* transitions are possible
3) Benzene.
π → π* and σ → σ* transitions.

4) CH3-CH2-Cl: n → σ* and σ → σ* transitions.

5) Amines (CH3CH2-NH2): n → σ* and σ → σ* transitions.
6) Acetic acid
π → π*, σ → σ*, n → σ* and n → π* transitions.
7) Acetone (CH3COCH3): n → π*, n → σ*, π → π*, and σ → σ* transitions.

Absorption spectrum
The intensity of the absorption varies as a function of wavelength is called as absorption spectrum.
The wavelength which corresponding to the maximum absorption intensity is called maximum
absorption wavelength (λmax). λmax depends on various factors like Chemical structure of the molecule
and solvent used to record spectrum.

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BASIC TERMINOLOGY IN ABSORPTION SPECTROSCOPY
Chromophore: Chromophore is a group of atoms or a part of a molecule that absorbs light.
Examples: C=C (λmax = 190 nm), C≡C (λmax = 205 nm), C=N (λmax = 207 nm), C≡N and N≡N, NO2, N=O,
C=O, etc.
Auxochrome: A group attached to chromophore that can change the absorption characteristics of
the chromophore is called auxochromes.
Examples: -OH, NH2, NR2, NHR, SH, OR, etc.

Benzene (λmax = 255 nm) Phenol (λmax = 275 nm) Aniline (λmax = 275 nm)

SHIFTS IN ABSORPTION SPECTRUM

a) Bathochromic shift or Red shift: Shift of maximum absorption wavelength (λmax) towards longer
wavelength due to substitution or solvent is called as bathochromic shift or red shift.

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 Benzene Phenol Benzoicacid P-Amino benzoicacid
(λmax = 255 nm) (λmax = 275 nm) (λmax = 230 nm) (λmax = 288 nm)

b) Hypsochromic shift or Blue shift: Shift of maximum absorption wavelength (λmax) towards
shorter wavelength due to substitution or solvent is called as hypsochromic shift or blue shift.

H+

Acidic medium

Aniline Anilinium chloride

(λmax = 275 nm) λmax = 265 nm

c) Hyperchromic shift: Increase in absorption intensity (ε) of a compound is called Hyperchromic

shift.

Benzene Cyanobenzene
ε = 7400 Mol-1 cm-1 ε = 13000 Mol-1 cm-1

d) Hypochromic shift: Decrease in absorption intensity (ε) of a compound is called as Hypochromic

shift.

Naphthalene 2-Methylnaphthalene
ε = 19000 Mol-1 cm-1 ε = 10250 Mol-1 cm-1

SELECTION RULES FOR UV-VISIBLE SPECTROSCOPY

1) The transition of only one electron from lower electronic energy level to higher electronic energy
level by the absorption of UV-Visible radiation is allowed, means provide more intense band.
Transitions involving two or more electrons are forbidden means provide less intense band or
not detected.
2) π – π* transitions are allowed because π & π* orbitals are in plane; thus, they readily overlap. n
– π* transitions are forbidden because n & π* orbitals are out of plane. So, they undergo poor
overlapping.

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3) Spin selection rule: During electronic transition retention of spin of electron is allowed. Inversion
of spin of electron is forbidden. Means ∆S = 0.
4) Angular momentum rule: The change in angular momentum should be 0 or ±1.
5) Multiplicity rule: Electron transition between the same spin multiplicity allowed (i.e., singlet to
singlet or triplet to triplet), whereas, singlet to triplet or triplet to singlet is forbidden.
6) Laporte rule: Electronic transitions involving molecular orbitals with same symmetry are
forbidden (less probable). Electronic transitions involving molecular orbitals with different
symmetry are highly probable.
Gerade (g) means molecular orbital having center of symmetry.
Ungerade (u) means the molecular orbital without center of symmetry.
i.e., allowed. g → u or u → g is allowed.
σ - g, π - u, σ* - u, π* - g
Applications of UV-Visible absorption spectroscopy
1. Structure elucidation of organic compounds: UV-Visible absorption spectroscopy is useful in the
structure elucidation of organic compounds such as the presence or absence of unsaturation or
hetero atoms etc.
2. Detection of impurities: Impurities present in organic compounds can be detected by UV-Visible
absorption spectroscopy.
3. UV-Visible absorption spectroscopy is used to find the conjugation in a molecule.
4. UV-Visible absorption spectroscopy can be used to find the molar concentration of the solution.
5. Detection of functional groups: UV-Visible absorption spectroscopy is used to detect the
presence of certain functional groups present in compounds.
6. Detection of geometrical isomers (Trans and Cis): In the case of geometrical isomers, trans
isomers exhibit slightly longer wavelength than the corresponding cis isomers.

INFRARED (IR) SPECTROSCOPY

Infrared (IR) spectroscopy is also called as rotational vibrational spectroscopy.
The spectroscopy which deals with the infrared (IR) radiation is called as IR spectroscopy.
IR spectroscopy is particularly used to identify different functional groups present in organic
molecules. IR spectroscopy is also useful in molecular structure determination.

19
A common laboratory instrument that uses this technique is a Fourier Transform Infrared (FTIR)
spectrometer.
Range: In terms of wavenumber IR region is from 12500 cm-1 to 50 cm-1. (The wavelength region
from 0.8 μm to 200 μm. But representation in wavelength is not common for IR spectroscopy).
Near IR region: 12500 – 4000 cm-1 (0.8 – 2.5 μm).
Mid IR region: 4000 – 667 cm-1 (2.5 – 15 μm), this is the main important region. Almost all
functional groups absorb in this region.
4000 – 1450 cm-1 is functional group region.
1450 – 667 cm-1 is fingerprint region.
Far IR region: 667 – 50 cm-1 (15 – 200 μm)
Source: Nernst glover, Mercury arc, IR-LEDs and Lasers, etc.

PRINCIPLE OF IR SPECTROSCOPY
When molecules absorb IR radiation, molecular vibrations and rotations takes place. That means the
molecules undergo lower vibrational, rotational energy level to higher vibrational rotational energy
level. Hence it is called as vibrational rotational spectroscopy.

Selection rules of IR Spectroscopy

➢ The most fundamental requirement for IR activity is that a vibration must cause change in the
dipole moment of the molecule. Means, the molecules which change their dipole moments is IR
active. Means the molecules having dipole moment is not equal to zero then those molecules are
IR active.

20
➢ If dipole moment is equal to zero then those molecules are IR inactive.
𝐃𝛍
≠ 0
𝐃𝐫
Examples: HCl, NaOH, KOH, CHCl3, NH3, H2O, C2H5OH, H2S: μ ≠ 0, Therefore IR active.
➢ The molecule which does not change their dipole moment during IR absorption is IR inactive.
H2, N2, Cl2, CH2=CH2, HC≡CH etc. are IR inactive.
❖ Exception: Carbon dioxide (CO2) though it is a linear molecule and μ = 0, but it changes its dipole
moment due to asymmetric stretching and asymmetric bending hence it is IR active.

Asymmetric stretching (IR active)

****Types of Molecular Vibrations

1. Stretching vibrations 2. Bending vibrations

a) Symmetrical stretching vibrations A) In plane bending vibrations
b) Asymmetrical stretching vibrations a) Scissoring bending vibrations
b) Rocking bending vibrations
B) Out of plane bending vibrations
a) Wagging bending vibrations
b) Twisting bending vibrations

1. Stretching vibrations
In stretching vibrations occurs a change in inter-atomic distance along the bond axis. That means
bond length changes in stretching vibrations.
Occurs at higher frequency 4000-1450 cm-1.
Depending on the movement of atoms stretching vibrations are two types: Symmetrical stretching
vibrations and asymmetrical stretching vibrations.
A) Symmetrical stretching vibration: Both the atoms in a molecule either move towards or away
from the central atom, but in the same direction.

21
B) Asymmetrical stretching vibration: In asymmetric stretching vibration, one atom approach
towards the central atom, while the other atom goes away from the central atom.

2. Bending vibrations
The position of the atoms changes relative to the original bond axis. Vibration or oscillation not along
the line of bond. In bending vibrations bond angle is altered.
Bending vibrations occur at lower frequency 1450 – 667 cm-1.
Bending vibrations are two types: (A) In plane bending vibration and (B) Out of plane bending
vibration.
A) In plane bending vibration B) Out of plane bending vibration
a) Scissoring a) Wagging
b) Rocking b) Twisting
A) In plane bending: In plane bending again two types.
a) Scissoring: In this type two atoms approach towards each other or go away from each other.

22
 b) Rocking: In this type, the moment of atoms moves in same direction.

B) Out of plane bending:

a) Wagging: In this type, two atoms move up or down the plane with respect to the central
atom.

b) Twisting: In this type, one of the atoms move up to the plane, while the other atom moves
down the plane with respect to the central atom.

Calculation of no of molecular vibrations in molecules

For linear molecules: No of vibrations = 3N-5.
Where N is the number of atoms present in molecule.
Eg: 1) CO2: N = 3, 3x3-5 = 4 vibrations
2) BeCl2: N = 3, 3x3-5 = 4 vibrations.
3) HC≡CH: N = 4, 3x4-5 = 7 vibrations.

23
For nonlinear molecules: No of vibrations = 3N-6.
Example: 1) NH3: N = 4, 3x4-6 = 6 vibrations.
2) H2O: N = 3, 3 x3-6 = 3. Therefore, water molecule has 3 vibrations.
Applications of IR spectroscopy
1. Identification of functional groups: IR spectroscopy is used to identify functional groups like
alkenes, alkynes, aldehyde, ketones, amines. i.e., C=C, C≡C, C=O, C-OH, CO-NH2, NH2, etc.
2. To distinguish geometrical isomers (Cis-trans): Geometrical isomers like Cis and Trans isomers can
be determined using IR spectroscopy. Generally, trans-isomers are IR inactive and cis-isomers are
IR active.

Cis-2-butene Trans-2-butene Cis-2-pentene Trans-2-pentene

μ≠0 μ =0 C-H bending C-H bending
IR active IR inactive 700 cm-1. 900 cm-1.

3. Distinguish between two types of hydrogen bonding (Intramolecular and intermolecular hydrogen
bonding).

o-dihydroxy benzene p-dihydroxy benzene

Intramolecular H-bonding Intermolecular H-bonding
3570 cm-1 3400 cm-1
4. Study of reaction progress:
Progress of the chemical reaction can be determined by examining the small portion of the
reaction mixture withdrawn from time to time. The rate of disappearance of a characteristic
absorption band of the reactant functional group and/or the rate of the appearance of the
characteristic absorption band of the product group to formation of product is observed.
5. Detection of impurities: IR spectroscopy is used to determine the impurities present in the sample.
6. IR spectroscopy is also useful in measuring the degree of polymerization in polymer manufacture.

24
7. IR spectrum is also useful in measuring in forensic analysis in both criminal and civil cases. For
example, in identifying in polymer degradation. It can be used in determining the blood alcohol
content of a suspected drunken driver.
8. IR spectroscopy has been successfully used in analysis and identification of pigments present in
paintings.
9. IR spectroscopy can also use in the food industry to measure the concentration of various
compounds in different food products.

Yours Dr. Mallesham Godumala

25
 CHAPTER-II
WATER TECHNOLOGY
Syllabus: Causes and effects of hardness of water, expression of hardness (CaCO3 equivalent), units
and types of hardness. Estimation of temporary and permanent hardness of water by EDTA method.
Numerical problems based on hardness of water. Potable water: characteristics, treatment of water
for domestic supply. Desalination of brackish water: Reverse osmosis. Alkalinity of water and its
determination. Boiler feed water: Boiler troubles (scale and sludge, priming, foaming, caustic
embrittlement and boiler corrosion) and its treatment: Internal treatment (colloidal, phosphate,
calgon conditioning of water). External treatment (ion –exchange process).

Chemical formula of water is H2O.

PH of water is neutral. Pure water is a colorless and odorless.
On the earth 70-75% of water is existing in the form of lakes, rivers and oceans and only 20-25% of
land is existing. Among these only 1% of water, we are using.
Sources of water
1) Rain fall
2) Surface water: Seas, Oceans and Rivers.
3) Underground water: Springs, Well and Borewell.
Impurities in water
Impurities present in water can be broadly classified into the following types.
1. Dissolved impurities: Inorganic salts like bicarbonates (HCO3-), chlorides (Cl-), sulphates (SO4-2),
and nitrates (NO3¯) of Sodium (Na+), Calcium (Ca+2), Magnesium (Mg+2), and Iron (Fe+2) ions.
2. Dissolved gases: Oxygen, nitrogen, carbon dioxide (CO2), oxides of nitrogen, oxides of Sulphur,
ammonia and hydrogen sulfide (H2S), etc.
3. Suspended impurities: Sand or clay and decayed organic substances.
4. Microorganisms: These include bacteria, fungi, and algae.

Types of water: Water can be broadly classified into two types, i.e., soft water and hard water.
1) Soft water: Water which gives lather readily with soap solution called soft water.

C17H35COONa + H2O C17H35COOH + NaOH

Sodium Stearate (Soap) Soft water Stearic acid Sodium hydroxide

C17H35COOH + H2O 26 Formation of lather

Stearic acid Soft water
 C17H35COONa + H2O C17H35COOH + NaOH
Sodium Stearate (Soap) Soft water Stearic acid Sodium hydroxide

C17H35COOH + H2O Formation of lather

Stearic acid Soft water
2) Hard water: Water which does not give lather with soap solution, but produce only white insoluble
precipitate (or scum) called hard water.

2C17H35COONa + Ca+2 (C17H35COO)2Ca + 2Na+

Sodium soap Hardness causing Calcium soap Sodium ions
(Water soluble) water (Water insoluble)

2C17H35COONa + Mg+2 (C17H35COO)2Mg + 2Na+

Sodium soap Hardness causing Magnesium soap Sodium ions
(Water soluble) water (Water insoluble)
Causes for hardness of water
Hardness: Hardness is the characteristic property of water, which prevents the lathering of soap. It
caused due to the presence of dissolved calcium (Ca+2) and magnesium (Mg+2) salts such as
bicarbonates (HCO3-), sulphates (SO4-2), chloridesb(Cl¯), and nitrates (NO3¯).
Types of hardness: Hardness is two types i.e., temporary and permanent hardness.
1. Temporary hardness: Temporary hardness caused due to the presence of bicarbonate (HCO3-)
salts of Calcium(Ca+2) and Magnesium (Mg+2), that is Ca(HCO3)2 and Mg(HCO3)2 in water. Temporary
hardness can be removed by boiling and filtering the water.

Heating
Ca(HCO3)2 CaCO3 + H2O + CO2
Calcium bicarbonate Calcium carbonate (insoluble)
Heating
Mg(HCO3)2 Mg(OH)2 + 2CO2
Magnesium bicarbonate Magnesium hydroxide (insoluble)

2. Permanent hardness: Permanent hardness causes due to the presence of chlorides (Cl¯), sulphates
(SO4-2) and nitrates (NO3¯) of Calcium (Ca+2) and Magnesium (Mg+2) ions, that is CaCl2, MgCl2, CaSO4,
MgSO4, Ca(NO3)2, and Mg(NO3)2. Permanent hardness can be removed by i) Ion exchange process, ii)
Lime soda process, and iii) Zeolite method.
Total Hardness = Temporary Hardness + Permanent Hardness

Units of hardness of water: Four types of units are available to express hardness of water.
1) ppm; 2) mg/L; 3) oF (Degree French); 4) oCl (Degree Clark).

27
1. ppm (parts per million): No of parts of CaCO3 equivalents hardness causing salts present in 106
parts of water.
2. mg/L: 1 milli gram of CaCO3 equivalents of hardness causing salts present in 1 liter (or 106 mg) of
water.
1ppm = 1mg/Lit.
3. Degree French (oF): 1 Part of CaCO3 equivalents of hardness causing salts present in 105 parts of
water.
4. oCl (Degree Clark): 1 part of CaCO3 equivalents of hardness causing salts present in 70,000 parts
of water. 1ppm = 0.07 oCl.

Relationship among the units of hardness: 1ppm = 1mg/L = 0.1 ⁰F = 0.07 ⁰Cl

Any water sample with hardness less than 150 is good and potable, while beyond 350 ppm is not
suitable for consumption.
Degree of hardness:
The hardness of water can be expressed in terms of equivalent amount of CaCO3. Because of two
reasons. i.e., i) CaCO3 is insoluble in water and doesn’t contribute hardness and ii) the molecular
weight of CaCO3 is 100 and its equivalent weight is 50, which is easy for calculation. The concentration
of hardness producing salts is calculated as

Weight of salt
The hardness of water in terms of CaCO3 equivalents = X 100
Molecular weight of salt

Equivalent weight = Molecular weight / total positive or negative charge

Problems
1) Calculate the total hardness in calcium carbonate equivalents (CaCO3) for the following water
sample. The water sample contains 81 mg/L of Ca(HCO3)2 (Molecular weight is 162).

81
The hardness of water in terms of equivalent amount of CaCO3 = X 100 = 50 mg/L
162

2) Calculate the total hardness in calcium carbonate equivalents (CaCO3) for the following water
sample. Sample water contains 11.1 mg/L of CaCl2 (Molecular weight is 111).

28
 11.1
The hardness of water in terms of equivalent amount of CaCO3 = X 100 = 10 mg/L
111
3) Sample water contains 9.5 mg/L of MgCl2 (Molecular weight is 95).

9.5
The hardness of water in terms of equivalent amount of CaCO3 = X 100 = 10 mg/L
95
4) Sample water contains 136 mg/L of CaSO4 (Molecular weight is 136).

136
The hardness of water in terms of equivalent amount of CaCO3 = X 100 = 100 mg/L
136

5) Sample water contains 40 mg/L of MgSO4 (Molecular weight is 120).

40
The hardness of water in terms of equivalent amount of CaCO3 = X 100 = 33.3 mg/L
120

6) Sample water contains 164 mg/L of Ca(NO3)2 (Molecular weight is 164).

164
The hardness of water in terms of equivalent amount of CaCO3 = X 100 = 100 mg/L
164

7) Sample water contains 148 mg/L of Mg(NO3)4 (Molecular weight is 148).

148
The hardness of water in terms of equivalent amount of CaCO3 = X 100 = 100 mg/L
148

8) Calculate the temporary, permanent and total hardness for the water containing Ca(HCO3)2 = 162
mg/L, CaCl2 = 111 mg/L, MgSO4 = 120 mg/L. *HCS is hardness causing salt.

HCS Amount of HCS M.Wt. Hardness in terms of CaCO3

162
Ca(HCO3)2 162 162 X 100 = 100 mg/L
162
111
CaCl2 111 111 X 100 = 100 mg/L
111
120
MgSO4 120 120 X 100 = 100 mg/L
120

29
 Temporary hardness = Hardness due to Ca(HCO3)2
= 100 mg/L
Permanent hardness = Hardness due to Cl2, SO4
= 100 + 100 = 200 mg/L
Total hardness = Permanent hardness + Temporary hardness
= 100 + 200 = 300 mg/L
9) Calculate the temporary, permanent and total hardness of a sample of hard water containing the
following dissolved salts per liter.
Mg(HCO3)2 = 14.6 mg/L, Ca(HCO3)2 = 16.2 mg/L, MgCl2 = 9.5 mg/L, CaSO4 = 13.6 mg/L.

HCS Amount of HCS M.Wt. Hardness in terms of CaCO3

14.6
Mg(HCO3)2 14.6 146 X 100 = 10 mg/L
146
16.2
Ca(HCO3)2 16.2 162 X 100 = 10 mg/L
162
9.5
MgCl2 9.5 95 X 100 = 10 mg/L
95

13.6
CaSO4 13.6 136 X 100 = 10 mg/L
136

Temporary hardness = Hardness due to Ca(HCO3)2 and Mg(HCO3)2

= 10 + 10 = 20 mg/L
Permanent hardness = Hardness due to Cl2, SO4
= 10+10 = 20 mg/L
Total hardness = Permanent hardness + Temporary hardness
= 20 + 20 = 40 mg/L
10) Calculate the total, temporary and permanent hardness of a sample of hard water containing the
following dissolved salts per liter.
Mg(HCO3)2 = 7.3 mg/L, Ca(HCO3)2 = 32.4 mg/L, CaCl2 = 11.1 mg/L, MgCl2 = 19 mg/L, MgSO4 = 60 mg/L.

30
 HCS Amount of HCS M.Wt. Hardness in terms of CaCO3
7.3
Mg(HCO3)2 7.3 146 X 100 = 5 mg/L
146
32.4
Ca(HCO3)2 32.4 162 X 100 = 20 mg/L
162
11.1
CaCl2 11.1 111 X 100 = 10 mg/L

60
MgSO4 60 120 X 100 = 50 mg/L
120

19
MgCl2 19 95 X 100 = 20 mg/L
95

Temporary hardness = Hardness due to Ca(HCO3)2 and Mg(HCO3)2

= 20 + 5 = 25 mg/L
Permanent hardness = Hardness due to Cl2, SO4
= 10 + 50 + 20 = 80 mg/L
Total hardness = Permanent hardness + Temporary hardness
= 25 + 80 = 105 mg/L

Quality of water for different uses:

Purpose Quality requirement

Drinking Tasty, clear and free from color, odor, turbidity and pathogens
Domestic washing Soft water producing lather readily.
Textile dying Free from color, turbidity, organic matter, Iron (Fe) and Magnesium (Mg)
Boiler feed water Free from dissolved salts, suspended impurities, silica and dissolved
gases.
Drugs and Soft and clear, free from pathogens, color, odor and suspended
pharmaceuticals impurities.
Construction Not too hard, should contain less amount of chlorides.

31
 Paper industry Free from color, turbidity, organic matter, iron (Fe), manganese (Mn),
silica and alkalinity.

ESTIMATION OF HARDNESS OF WATER BY EDTA METHOD

➢ EDTA is Ethylene Diamine Tetra Acetic acid
➢ EDTA method is used to determine total temporary, permanent and hardness of water.
➢ Involves the volumetric titration. It is a complexometric titration (colored complex is used to
determine the end point of the titration)
➢ Titrant: EDTA (Ethylene Diamine Tetra Acetic acid). The structure is shown below

EDTA Structure
➢ Indicator: Eriochrome Black-T (EBT)
➢ Analyte: Water
➢ Buffer: Ammonium chloride (NH4Cl) + Ammonium hydroxide (NH4OH) (PH: 9-10)
Principle: EDTA has low solubility in water, but its disodium salt dissolves in water quickly &
completely. EDTA is a hexa dentate ligand. It binds the metal ions in water to give stable chelate
complex. Hence it is called as complexometric titration method. This method has greater accuracy,
convenience & more rapid.
Initially buffer solution (NH4Cl + NH4OH) is added to the hard water to maintain the PH at 9-10.
When 3 drops of Eriochrome Black-T (EBT) indicator is added to the hard water sample at PH 9-10,
water turns to wine-red colored solution due to the formation an unstable complex of EBT with Ca+2
and Mg+2 present in hard water. When wine-red colored solution is titrated with EDTA, wine-red
color gets converted into blue color due to the formation of colorless stable complex and free EBT
indicator. The liberated free indicator has blue color at pH 9-10. So, the color changes from wine-red
to blue is considered as the end point.
Indicator EBT becomes wine red in color when bound with metal ions while remaining blue in
color when free from metal ions. While EDTA (which is ethylene diamine tetra acetic acid) is colorless
whether it’s bound to metal ions or not. So, the addition of the EBT indicator in the sample (water
containing metal) makes it wine red in color as EBT binds with metal ions. EBT indicator binds with
metal ions loosely, while EDTA binds with metal ions strongly. So, when all metal ions are bound to

32
EDTA, indicator EBT remains free in the water sample, therefore the solution turns blue. Wine red
color to blue color is considered as an end point.

Hard water + EBT Buffer Solution Metal – EBT

(Ca+2, Mg+2) (Blue color) (Unstable complex)
PH = 9 - 10 (Wine-red)
Buffer Solution
M – EBT + EDTA Metal – EDTA + EBT
(Wine-red) PH = 9 - 10 (color less) (Blue color)
(Stable complex)

Metal-EDTA structure Eriochrome black-T (EBT)

Procedure: 5 steps are involved in EDTA method.

1) Preparation of standard hard water (SHW)
2) Standardization of EDTA.
3) Estimation of total hardness
4) Estimation of permanent hardness
5) Estimation of temporary hardness.
1) Preparation of standard hard water (SHW) (M1)
Standard solution means a solution for which the concentration is accurately known. 1.0 g of CaCO3
is dissolved in 1L distilled water and few drops of HCl is added. It is known as a 0.1 N standard hard
water.
2) Standardization of EDTA (M2): Take 50 ml of standard hard water into a conical flask + add 10 ml
of buffer solution + 3- drops of eriochrome black-T (EBT), then it turns to wine-red color. Then titrate
with EDTA. When wine-red color converted to blue color will be considered as an end point.
M 1V 1 = M 2V 2
M1 = Molarity of standard hard water (0.1 N)
33
 V1 = Volume of standard hard water taken into conical flask (50 mL)
M2 = Molarity of EDTA to be measured
V2 = Volume of EDTA (Burette reading)
3) Estimation of Total hardness of hard water sample: Take 50 mL of sample hard water (i.e., tap
water) in a conical flask + add 10 mL of buffer solution (NH4Cl + NH4OH) + 3-drops of EBT indicator,
then it turns to wine-red color. Then titrate with EDTA. When wine-red color converted to blue color
will be considered as an end point.
M 2V 2 = M 3V 3 → M3 = M2V2/V3
M2 = Molarity of EDTA, V2 = Volume of EDTA (Burette reading)
M3 = Molarity of hard water to be measured
V3 = Volume of hard water taken into conical flask (i.e., 50 mL).
By multiplying M3 with 105 gives total hardness in ppm units.
4) Estimation of permanent hardness: Take 100 mL of sample hard water and boil it continuously
to get to 50 mL. Then filter it and add 50 mL of distilled water to the filtered water and make it to
100 mL.
Δ
100 mL of hard water sample 50 mL of hard water + 50 mL of distilled water
Take 50 mL of the above prepared hard water sample into 250 mL conical flask + add 10 mL of buffer
solution (NH4Cl + NH4OH) + 3 drops of EBT indicator, then it turns to wine-red color. Then titrate with
EDTA. When wine red color converted to blue color will be considered as an end point.
M 2V 2 = M 4V 4
M4 = M2V2/V4
M2 = Molarity of EDTA
V2 = Volume of EDTA (Burette reading)
M4 = Molarity of hard water to be measured
V4 = Volume of hard water taken into conical flask (i.e., 50 mL)
By multiplying M4 with 105 gives permanent hardness (in ppm units).
5) Estimation of temporary hardness:
Total hardness = Permanent hardness + Temporary hardness
Temporary hardness = Total hardness – Permanent hardness.
Result: The hardness of the given water sample has been found to be as follows:
Total hardness = ------------------------------------ ppm
34
Permanent hardness = ------------------------------ ppm
Temporary hardness = ----------------------------- ppm

Potable Water and it’s Characteristics

Water which is safe for drinking is called as potable water.
Characteristics of Potable water
❖ Should be clean, colorless and odorless
❖ PH must be between 6.5 – 8.0
❖ Should be free from pathogenic bacteria
❖ Should not contain dissolved gases like CO, CO2, NH3, H2S etc
❖ The optimum hardness of water must be 125 ppm
❖ Turbidity should not exceed 25 ppm
❖ The maximum concentration of total dissolved solids (TDS) must not exceed 500 ppm
❖ Must be free from heavy metals like Lead (Pb), Arsenic (As), Chromium (Cr) and Manganese
(Mn), etc.
❖ Water should not be corrosive.

TREATMENT OF WATER FOR DOMESTIC SUPPLY

This treatment involves the removal of colloidal impurities, suspended impurities and pathogenic
bacteria. Municipal water treatment method involves the following several steps.
1. Screening, 2. Aeration, 3. Sedimentation, 4. Coagulation, 5. Filtration, 6. Sterilization and
disinfection, 7. Storage and supply distribution of water.
1. Screening: All the floating impurities like leaves, sticks, bio-related impurities can be removed in
the screening process

Raw water Removes floating materials

Screen with holes

2. Aeration: In this process air will be sent into the water. Then the hazardous gases like carbon
monoxide (CO), carbon dioxide (CO2), NH3, H2S etc will be removed. Further, it removes certain metal
ion impurities like Iron (Fe+3) and Manganese (Mn+2) by precipitating as metal hydroxides (Fe(OH)3
and Mn(OH)2.

35
3. Sedimentation: Water is allowed to stand undisturbed for 3-6 hours. Suspended particles settle
down and clear water raises to top which can be drawn out with pumps. Almost 75% of suspended
impurities can be settled down. Sedimentation step is carried out without adding any chemicals.
4. Coagulation: Helps in the removal of colloidal and suspended impurities by adding coagulants like
Alum (K2SO4, Al2(SO4)3) and NaAlO2, etc. Coagulants can interact with impurities and increase the
particle size and facilitate to easy settlement.
5. Filtration: This also helps in the removal of colloidal and suspended impurities which are not
removed by sedimentation method. Also, color, smell and most of the bacteria can be removed.
Two types of sand filters are used here.
Slow sand filter and Rapid sand filter/pressure sand filter.

Water Inlet -- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
Fine Sand
Course Sand
Fine Gravel
Course Gravel
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -
- - - - - - - - -- Water Outlet

6. Sterilization and disinfection:

The process of removing harmful bacteria is called sterilization. Methods adopted for sterilization are
as follows
a) Boiling
b) By passing ozone O3 → O2 + [O] (Nascent oxygen disinfectant)
c) Chlorination: There are three chlorinating agents.
By chloramine : Cl2 + NH3 → ClNH2 (Chloramine) + HCl
ClNH2 + H2O → HOCl (Hypochlorous acid) + NH3.
By bleaching : CaOCl2 + H2O → Cl2 + Ca(OH)2
powder Cl2 + H2O → HOCl + HCl

36
 By chlorination : Process of addition of calculating amount of Cl2 to water to kill the
bacteria.
Cl2 + H2O → HOCl + HCl.
Only calculated amount of Cl2, must be added, otherwise excess of present as residual Cl2, which
causes bad taste, bad odor and toxicity.
Break point of chlorination: The minimal amount of chlorine which is required to kill pathogenic
bacteria.

Destruction of Chloramine
Formation of Chloramine

Break Point
oxidation of reducing agents

Residual chlorine
Killing of bacteria and
Residual Cl2

A B C

Chlorine (Cl2) gas passed

A = Killing of bacteria and oxidation of reducing the impurities

B = Formation of chloramine; C = Destruction of chloramine; D = Residual chlorine.
Advantages of breaking point of chlorine:
It destroys all types of pathogenic bacteria. Color, taste and organic impurities can be removed.

DESALINATION OF BRACKISH WATER

Brackish means salty. Water having dissolved salts with an average of 3.5% is known as brackish
water. Such water is not useful for drinking.
Desalination: The process of removal of dissolved salts (e.g., NaCl) from water.
Water quality is usually graded as
Fresh water : Less than 100 mg/L of dissolved salts
Brackish water : 10 g – 35 g/L of dissolved salts
Sea water : > 35 g/L of dissolved salts
The following techniques are carried out for desalination of Brackish water:
1) Reverse Osmosis, 2) Electrodialysis & 3) Distillation.

37
***1) REVERSE OSMOSIS****
Osmosis: When two solutions of different concentrations are separated by a semi permeable
membrane (SPM), solvent flows from a lower concentration region to a higher concentration region
is called as Osmosis. This process is a natural process. This natural process can be reversed by
applying a pressure higher than the osmatic pressure on the high concentration side. Then, the
solvent flows from higher concentration solution to lower concentration solution, which is called
reverse osmosis.
The external pressure which is required to stop the flow of solvent from low concentration
region to high concentration region is called osmatic pressure.
Semi permeable membranes having the pores in the range of (0.0001 – 0.001 mm in diameter) and
these are made by cellulose triacetate or cellulose butyrate or polyamide.

Osmosis Reverse Osmosis

Applied Pressure Pure Water

Semi Permeable Semi Permeable

Membrane (SPM) Membrane (SPM)

Contam Contam
inants inants

Direction of Water Flow Direction of Water Flow

Advantages of RO technique are as follows
1. It can remove ionic and non-ionic, inorganic, colloidal and high molecular weight organic
impurities.
2. The lifetime of membrane is quite high (>1 year).
3. The maintenance cost is only the replacement of membrane.
4. Reverse osmosis is the final category of membrane filtration (also known as super-filtration or
hyper-filtration). It removes particles with size up to 0.1 nm

38
BOILER FEED WATER
Boilers are two types, steam boilers (generates steam) and hot water boilers. Steam boilers can be
used in Power generation, Food processing industry, Textile industry, Paper industries, Building
materials, etc. The water which is used in boilers called boiler feed water. The water has to meet
specific requirements. If hard water is used in boilers, those boilers get the following troubles.

Boiler troubles: Boilers troubles are as follows

1) Scales and sludges (formation of deposits)
2) Priming and foaming (carry over)
3) Boiler corrosion
4) Caustic embrittlement
1) Scales and sludges (formation of deposits)
On continuous evaporation of water in boilers the concentration of insoluble matters increases
progressively, which leads to boiler troubles.
Scale: A hard and sticky precipitate, which stick on the inner wall of the boiler called Scale. These are
formed by CaCO3, CaSO4, Ca(HCO3)2, Mg(OH)2 etc. in hot portion of boiler.
Disadvantages of scale formation
Scale is a poor conductor of heat, so they tend to waste time and heat.
It decreases the efficiency and safety of boilers. May lead to explosion.
Removal of scales
i. With the help of scraper or piece of wood or wire brush, if they are loosely adhering.
ii. By giving thermal shocks, if they are brittle.
iii. By dissolving them in chemicals like 5-10% HCl or EDTA solution.
Sludge: Sludges are loose, soft and non-sticky precipitate. The sludge formed by the CaCl2, MgCl2,
MgCO3, MgSO4 etc.
Disadvantages of Sludge formation
Sludge is poor conductor of heat, so they tend to waste time and heat.
It decreases the efficiency and safety of boilers.
Excessive sludge formation disturbs the working of boiler.

39
 Water
- -- -- -- -
- -
- - - - - - - - -- -- -- -- -- --
- - - - - - - - - - - - - - -
- - - - - - - - - - - - - - - -
- - - - - - - - - - - - - - - -
- - - - - - - - - - - - - - - -
Loose and non-sticky
- - - - - - - - - - - - - - - -
precipitate suspended - - - - - - - - - - - - -
in water (Sludge) - - - - - - - - - -
Hard adhering
coating on inner
walls of boiler (Scale)
Heat Heat
Prevention of Scale and Sludge formation
➢ By using well softened water and Blow-down operation (replacing the concentrated water with
fresh water).
2) Priming and foaming
Priming: When a boiler is steaming (i.e., producing stream) rapidly, some particles of the liquid water
are carried along-with the stream. This process of wet-stream formation is called priming.
Reasons
(a) Due to the presence of huge dissolved solids. (b) Improper boiler design. (c) Sudden boiling. (d)
Sudden increase in steam-production rate.
Priming can be avoided by
i) Fitting “mechanical steam purifiers”, maintaining of low water levels in boilers.
ii) By using well softened water and Blow-down operation.
Foaming: The production of persistent foam or bubbles along with stream in boilers is called as
foaming.
Reasons: Foaming is due to the presence of substances like oils (which greatly reduce the surface
tension of water).
Foaming can be avoided by adding anti-foaming chemicals like castor oil.
When, priming or foaming happens dissolved salts may enter the parts of other machinery,
where stream is being used, thereby decreasing the life of the machinery.
3. Boiler corrosion
Damage of boilers by its environment is called as boiler corrosion. Corrosion in boilers is due to the
presence of (i) Dissolved O2, (ii) Dissolved CO2 and (iii) Dissolved mineral acids (HCl and H2SO4).

40
I) Dissolved oxygen (O2): Water usually contains about 8 mL of dissolved oxygen per liter at room
temperature. That oxygen interacts with Iron (Fe) and produces rust.
2Fe + 2H2O + O2 → 2Fe(OH)2
4Fe(OH)2 + O2 → 2Fe2O3.2H2O (Rust)
Removal of dissolved oxygen:
1) By adding calculated quantity of hydrazine (N2H4)
N2H4 + O2 → N2 ↑ + 2H2O
(Hydrazine)
2) By mechanical de-aeration means without adding chemicals also can remove the dissolved gases.
4. Caustic Embrittlement:
Caustic embrittlement is the phenomenon in which the boiler material becomes brittle due to the
accumulation of caustic substances. Caustic Embrittlement is a type of boiler corrosion.
The NaOH containing water flows into the hair-cracks, always present in the inner side of boiler by
capillary action.
Fe + 2NaOH → Na2FeO2 (Sodium Ferroate) + H2O
This causes embrittlement of boiler parts, particularly stressed parts (like bends, joints, rivets, etc.)
causing even failure of the boiler.
Caustic Embrittlement can be avoided by
• By using sodium sulfate (Na2SO4) as the softening agent, instead of sodium carbonate. Sodium
sulfate prevents the infiltration of caustic soda solutions.
• By adding Tannin or Lignin to boiler water, since these blocks the hair-cracks, thereby preventing
infiltration of caustic soda solution.

TREATMENT OF BOILER FEED WATER OR SOFTENING OF WATER:

There are two types of treatments
1) Internal treatment
2) External treatment.

1) Internal treatment: The principle involved in internal treatment is the conversion of scale
forming salts into sludges. Internal treatment methods are generally followed by blow-down
operation. So that an accumulated sludge is removed. Important internal condition methods are:
a) Colloidal conditioning: In low pressure boilers scale formation can be avoided by adding organic
substances like kerosene, tannin, agar-agar (a gel) etc, which get coated over the forming

41
precipitates, thereby yielding non-sticky and loose deposits which can be easily removed by blow-
down operators.
b) Carbonate conditioning: Scale formation in low pressure boilers can be avoided by adding sodium
carbonate to boiler water, where CaSO4 is converted into calcium carbonate, a sludge which can be
removed by blow don operation.
CaSO4 + Na2CO3 ↔ CaCO3 + Na2SO4
c) Phosphate conditioning: In high pressure boilers, scale formation can be avoided by adding sodium
phosphate, which reacts with calcium and magnesium salts forming non-adherent and easily
removable soft sludge of calcium and magnesium phosphates, which can be removed by blow-down
operation.
3CaCl2 + 2Na3PO4 → Ca3(PO4)2 + 6NaCl
The main phosphates employed are (a) NaH2PO4, sodium dihydrogen phosphate (acidic); (b)
Na2HPO4, disodium hydrogen phosphate (weakly alkaline); (c) Na3PO4, trisodium phosphate
(alkaline).
d) Calgon conditioning: The word Calgon means Calcium gone, i.e., the removal of Ca +2. Sodium
hexameta phosphate {Na2[Na4(PO3)6]} is Calgon. When we add Calgon to boiler water, it prevents the
scale and sludge formation by forming soluble complex compound with CaSO4.
Na2[Na4(PO3)6] + 2CaSO4 → Na2[Ca2(PO3)6] + 2Na2SO4
(Calgon) (Soluble complex ion)

2. EXTERNAL TREATMENT OF BOILER FEED WATER

Treating the water before feeding it into boiler is called external treatment.
i) ION EXCHANGE PROCESS (DEIONIZATION OR DE-MINERALIZATION)
This process removes almost all the ions present in water. Ion exchangers are resins (Polymers).
Based on the functional groups, resins are two types: (These functional groups are responsible for
the ion exchanging process).
Cations are the positively charged ions and Anions are the negatively charged ions.
(i) Cation exchange resin: In this step cations (Na+, K+, Ca+2, Mg+2, etc) present in hard water are
exchanged with H+ ions of resin. Cation exchange resins contain acidic functional groups like -SO3H
or -COOH. Example: Sulphonated polystyrene
R-H + M+ → R-M + H+

42
(ii) Anion exchange resin: In this step, anions (Cl-, SO4-2, HCO3-) present in hard water are exchanged
with OH- of the resins. Anion exchange resins contain basic functional groups like quaternary
ammonium salts etc. Example: Polystyrene with quaternary ammonium salt.
R-OH + Aˉ → R-A + OHˉ

Step-I Step-II
Water passed through cation chamber Na+, K+, Water passed through anion chamber, then
Ca+2, Mg+2, etc are exchanged with H+ ions of Cl-, SO4-2, HCO3- etc. ions are exchanged with
resin. OH- of the resin.
R-H + Na+ → R-Na + H+ R-OH + Cl- → R-Cl + OH-
2R-H + Mg+2 → R2-Mg + 2H+ 2R-OH + SO4-2 → R2SO4 + 2OH-
2R-H + Ca+2 → R2-Ca + 2H+ Free from almost all the ions and it is neutral
Water is acidic in nature. (deionized or demineralized water)

Cation Exchange Resin Anion Exchange Resin

HO OH

HO OH

Diagram of Ion Exchange Method

43
REGENERATION OF RESINS:
The exhausted cation exchange resin is regenerated by passing dilute HCl solution through it.
R-Ca + 2HCl → R-H2 + CaCl2
R-Na + HCl → R-H + NaCl
The exhausted anion exchange resin is regenerated by passing dilute NaOH solution through it.
R-Cl + NaOH → R-OH + NaCl
Advantages
✓ The water hardness can be reduced up to 2 ppm, hence it is suitable for use in high pressure
boilers.
✓ Highly acidic or highly basic water can be softened by using this process.
Limitations
▪ The resins used in the process are quite expensive.
▪ If water contains turbidity, the efficiency of the process will be reduced.
▪ Water containing Fe and Mn cannot be treated because they form stable product with the resins.

44
LIME SODA PROCESS
In this process lime [Ca(OH)2] and soda [Na2CO3] are used to precipitate the dissolved salts of Ca+2
and Mg+2 as insoluble CaCO3 and Mg(OH)2, which can be removed by settling or filtration. Lime reacts
with Ca-based temporary hardness salts, Mg-based permanent salts, CO2, acids, bicarbonates and
alum. However, lime cannot remove Ca-based permanent salts.
Ca(OH)2 + Ca(HCO3)2 → 2CaCO3 ↓ + 2H2O
Ca(OH)2 + MgCl2 → Mg(OH)2 ↓ + CaCl2
Ca(OH)2 + MgSO4 → Mg(OH)2 ↓ + CaSO4
Soda can remove all Calcium (Ca) based permanent hardness causing salts.
Na2CO3 + CaCl2 → CaCO3 ↓ + 2NaCl
Na2CO3 + CaSO4 → CaCO3 ↓ + Na2SO4
Precautions to be followed
• Only calculated amounts of lime and soda should be added. Because the excess amount of
reagents causes boiler troubles like corrosion and caustic embrittlement.
• Proper time must be given to complete the reactions.
Lime soda process is of two types: Cold lime soda process & Hot lime-soda process
1) Cold lime soda process: If the entire process is carried out at room-temperature it is called cold
lime soda process. However, at room temperature the precipitates formed are finely divided, so they
do not settle down easily. Therefore, a small amount of coagulants [NaAlO2 or Al2(SO4)3] should be
added.
NaAlO2 + 2H2O → NaOH + Al(OH)3
In this process, raw water and required amount of lime, soda and coagulants are pored at room
temperature from the top in to the inner chamber. A fitted paddle stirrer can vigorously stir the
water, then the raw and chemicals flow down. The softened water rising up and passes through a
wood fiber filter.

45
2) Hot-lime soda process
In hot lime soda process, water is treated with lime [Ca(OH)2] and soda [Na2CO3] at 80 – 150 oC.
Coagulant is not needed.

In hot lime soda process, three steps are taken.

(a) Reaction tank: Raw water, chemicals and superheated steam are passed into reaction tank, where
all three are mixed thoroughly. The beginning and ending reaction occur in this tank.
(b) Conical sedimentation tank: From the reaction tank, the contents go to this tank, so hot sludge
settle down.
(c) Sand filter: It acts as filter and ensure complete removal of sludge from the softened water.
46
 Cold Lime Soda Method Hot Lime Soda Method

Carried at room temperature Carried at 80 – 150 oC

Coagulant is added. No need of coagulant.
Dissolved gases are not removed. Dissolved gases are also removed.
Obtained water hardness is of 60 ppm Obtained water hardness is of 15-20 ppm
Slow process Fast process

Advantages of lime soda process

It is more economical.
Less amount of coagulant is needed.
It increases the pH value, thereby corrosion is reduced.
Fe, Mn and minerals are reduced.
Disadvantages of lime soda process
For efficient and economical softening careful operation is required.
Disposal of large amount of sludge is a problem.
This can remove hardness up to 15 ppm which is not good for boilers.
Alkalinity of water
Alkalinity: The capacity of water to neutralize acids called alkalinity. It can measure the presence of
the hydroxide (OHˉ), carbonate (CO32ˉ) and bicarbonate (HCO3ˉ) ions which are naturally present in
water. Three types of ions (OHˉ, CO32ˉ and HCO3ˉ) are mainly responsible for alkalinity. Different ions
cause different pH.
Alkalinity of water can be determined using titrimetric analysis.
Principle: OHˉ + H+ → H2O (complete neutralization of OHˉ)
CO32ˉ + H+ → HCO3ˉ (half neutralization of carbonate)
HCO3ˉ + H+ → H2CO3 (complete neutralization of carbonate)
OHˉ and CO32ˉ: Basic PH (>7) Phenolphthalein indicator is used.
HCO3ˉ: Acidic PH (<7) Methyl orange indicator is used.
Phenolphthalein: Colorless
Pink to light yellow
Methyl orange: Light yellow to red.

Yours: Dr. Mallesham Godumala

47
 CHAPTER-III
ELECTROCHEMISTY, BATTERIES and CORROSION
SYLLABUS: Electrode, electrode potential, galvanic cell, cell reactions and cell notation, cell EMF,
types of electrodes (Normal Hydrogen Electrode, calomel electrode), Determination of pH, Nernst
equation, Numerical problems.

Electrochemistry is an important branch of chemistry. It deals with the relation between the electrical
energy and chemical entity. It is the study of “conversion of electrical energy into chemical energy
and chemical energy into electrical energy”.
Electrode: A metal rod dipped in its own salt solution is called as electrode.
Examples for metal electrode:
Zinc electrode: Zn/ZnSO4
Copper electrode: Cu/CuSO4
Magnesium electrode: Mg/MgSO4
Silver electrode: Ag/AgNO3

n Electrode Cu Electrode Ag Electrode

n - - - Cu
- - - - - - - Ag
- - - -
- - - - - - -
- - - - - - - - - - - - - -

- - - - - - -
- - - - - - -
Zn/ZnSO4 Cu/CuSO4 Ag/AgNO3

Electrode potential (Ecell): The tendency of a metal to loosen electrons (oxidation) or taken electrons
(reduction) when it is placed in its own salt solution called electrode potential. Means, when a metal
[M] placed into its own salt solution containing its own ions [Mn+], then the metal may undergo either
oxidation or reduction.
If metal undergoes oxidation, then the positive metal ions will pass into the solution
M → Mn+ + ne- (Oxidation)
If the metal undergoes reduction, then the negative ions may get deposited over the metal.
Mn+ + ne- → M (Reduction)
48
Standard electrode potential (𝑬𝟎𝒄𝒆𝒍𝒍 ): The tendency of metal to loosen electrons (oxidation) or taken
electrons (reduction) when it is placed in its own salt solution having 1.0 M (unimolar) concentration
at 25 ⁰C is called as standard electrode potential.
Cell (Galvanic Cell or Electrochemical cell): Cell is made up of two electrodes, i.e., anode half-cell
and cathode half-cell. Oxidation reaction takes place at one electrode called as anode half-cell and
reduction reaction takes place at another electrode called as cathode half-cell.
Cell = Anode half-cell + Cathode half-cell.
Cell reactions: In an electrochemical cell, flow of electrons takes place from one electrode to another
electrode due to the oxidation reaction at anode and reduction reaction at cathode. So, the net
chemical change can be obtained by adding the two half-cell reactions called as cell reaction. Cell
reaction = Anode half-cell reaction + Cathode half-cell reaction
Example, Galvanic cell [Zn/ZnSO4//CuSO4/Cu]
Anode half-cell reaction: Zn → Zn+2 + 2e- (Oxidation)
Cathode half-cell reaction: Cu+2 + 2e- → Cu (Reduction)
Cell reaction or net reaction: Zn + Cu+2 → Zn+2 + Cu
Electromotive Force (EMF) or Cell Potential: In an electrochemical cell, a potential difference which
is required to flow of electricity from anode to cathode is called as electromotive force (emf) or cell
potential.
Representation and notation of electrochemical cells
The Galvanic cell or electrochemical cells are represented on the paper with the help of symbolic
representation of single electrodes.
Example: Galvanic cell is represented as Zn/ZnSO4//CuSO4/Cu
Steps for construction of Cell:
(i) Single vertical line (/): It represents a phase boundary between metal and its salt solution.
Zn/ZnSO4 (Anode half-cell), CuSO4/Cu (Cathode half-cell).
(ii) Anode half-cell is written on left side and cathode half-cell is written on right side.
(iii) Anode half-cell and cathode half cells are separated by two vertical lines (//) called salt bridge.
Example: Zn/ZnSO4//CuSO4/Cu
(iv) Symbolic formation electrode, like the Platinum electrode is often enclosed in a bracket.
Mg/Mg+2//H+/H2 (Pt)
(v) The emf value of a cell is written on the right side of the cell diagram.

49
 Zn/ZnSO4//CuSO4/Cu E = 1.12 eV
NERNST EQUATION: This equation gives the relationship between electrode potential, concentration
of the products and reactants, and absolute temperature.
Let us consider a cell reaction
aA + bB → cC + dD
Where, a, b, c, d represent the number of moles of A, B, C and D components, respectively. The
Nernst equation for the cell is

C c D d
2.303 RT
Ecell = Eo cell
log
nF A a B b

0.0591 C c D d
log
Ecell = Eocell a b
n A B

Where, R = gas constant = 8.314 J K-1mol-1, T = 298 K, F = 96500 coulombs (Faraday), n = no of

electrons involved in the cell reaction,
𝑜
𝐸𝑐𝑒𝑙𝑙 = Standard electrode potential & Ecell = Cell potential (EMF)
Nernst equation is used to determine single electrode potential and also cell potential.

Electrochemical cell: Cell which converts electrical energy into chemical energy or chemical energy
into electrical energy called electrochemical cell.
Galvanic cell/Voltaic Cell/Daniel Cell: A device which converts chemical energy into electrical energy
due to spontaneous redox reaction.

50
Salt bridge: It is an inverted U-shaped glass tube, which contains a paste of KCl or KNO3 or NH4NO3
with Agar-agar.
Use of salt bridge: Salt bridge completes the circuit and allows the passage of electric current.
It also maintains the electric neutrality in both half cells.
Types of electrodes:
1) Working electrode, 2) Reference electrode & 3) Counter electrode

Reference electrode: The electrode which is used to determine the electrode potential of another
electrode is called reference electrode. The best example for reference electrode is standard
hydrogen electrode (SHE), whose electrode potential at all temperatures is ‘zero’.
The most commonly used reference electrodes are:
1) Standard Hydrogen Electrode (SHE) or Normal Hydrogen electrode (NHE)
2) Standard Calomel electrode (SCE)

1) Standard Hydrogen Electrode (SHE) or Normal Hydrogen Electrode (NHE):

(a) Introduction: Standard Hydrogen Electrode (SHE) is a primary reference electrode used to
determine electrode potential and pH of any unknown sample solution.
(b) Construction: Standard Hydrogen Electrode (SHE) consists of Pt electrodes coated with Pt black
immersed in a 1.0 M acidic solution (H+ ions) maintained at 25 ⁰C. A stream of pure hydrogen is bubbled
around the platinum foil at a constant pressure of one atmosphere (1 atm). The gas at the Pt electrode

forms H+ ions and electrons.

Pt wire

H2 gas (1atm)
Glass envelop

Pt electrode coated
with Pt black
Acidic solution
(H+, 1.0M)

(c) Cell Representaion: (Pt), H2 (g)/H+ solution (1.0 M)

SHE acts as both anode and cathode.

51
 If it acts as anode H2 ⇌ 2H+ + 2e-
If it acts as cathode 2H+ + 2e- ⇌ H2
(d) Determination of pH of any sample solution using standard hydrogen electrode
Hydrogen electrode can be employed to find the pH value of an unknown solution. For this, the
solution pH is to be determined is taken in a vessel and an electrode is half dipped in it. The half cell
so formed is connected to a standard hydorgen electrode (having a solution of 1N HCl) through a salt
bridge. The emf of the cell is determined by potentiometer. Since emf of the reference electrode is
zero, the observed emf gives directly the emf of the half-cell containing the solution under test.
Potentiometer

Glass envelop
H2 gas (1atm) H2 gas (1atm)
Salt bridge

----------------------------
-- ------------------------- Pt electrode coated
---------------------------- with Pt black
----------------------------
----------------------------
----------------------------

Hydrogen electrode (HE) Acidic solution Acidic solution Standard Hydrogen electrode
(Anode) (H+, pH to be determined) (H+, 1.0M) (SHE) (Cathode)

The cell represented as;

Anode (Pt), H2 (g)/H+ (pH to be determined)//Acidic solution (H+ = 1M)/H2 (g), (Pt) (Cathode)
Ecell = Eanode + Ecathode
H2 ⇌ 2H+ + 2e-
Ecell = EHE + ESHE 0.0591 [P]
Ecell = E°cell - log
= (0.0591 pH) + 0 n [R]
= 0.0591pH
0.0591 [H+] 2
𝐸𝑐𝑒𝑙𝑙 Ecell E°cell log
pH = = -
0.0591 2 [H2]

0.0591 [H+] 2
Ecell = 0 - log
2 1
0.0591
Ecell = - 2 x log [H+]
2
Ecell = 0.0591pH

52
(B) STANDARD CALOMEL ELECTRODE (SCE)
(a) Introduction: Standard calomel electrode (SCE) is a secondary reference electrode used to
determine electrode potential and pH of any unknown solution.
(b) Construction:

Pt wire

Salt bridge Saturated KCl

solution

Hg2Cl2 and Hg
paste

Mercury
Calomel Electrode

(c) Cell Representaion: Standard calomel electrode representation: Hg/Hg2Cl2, Saturated KCl
Predominantly it acts as cathode. Hg2Cl2 + 2e- → 2Hg + 2Cl-
Hg2Cl2 → 2Hg+ + 2Cl-
2Hg+ + 2e- → 2Hg
Hg2Cl2 → 2Hg + 2Cl-
Electrode potential of calomel electrode depends on the concentration of electrolyte.
If saturated KCl is used as an electrolyte, the electrode potential is 0.241 V.
If 1.0N KCl is used as an electrolyte, the electrode potential is 0.280 V.
If 0.1N KCl is used as an electrolyte, the electrode potential is 0.333 V.
Determination of pH of unknown solution using standard calomel electrode:
To determine the pH of an unknown solution, a Standard Hydrogen Electrode (SHE) containing
solution of unknown pH is coupled with standard calomel electrode.

53
The above cell can be represented as
(Pt), H2(g)/H+ (pH to be determined) // Sat.KCl/ Hg2Cl2, Hg
(Anode) (Cathode)
Ecell = Ecathode + EAnode
H2 ⇌ 2H+ + 2e-
Ecell = ESCE + EHE 0.0591 [P]
Ecell = E°cell - log
Ecell = 0.241 + 0.0591pH n [R]
0.0591pH = Ecell – 0.241
0.0591 [H+] 2
pH = Ecell – 0.241 Ecell = E°cell - log
2 [H2]
0.0591
0.0591 [H+] 2
Ecell = 0 - log
2 1
0.0591
Ecell = - 2 x log [H+]
2
Ecell = 0.0591pH

Problems based on Nernst equation:

1) Calculate the single electrode potential of the following electrochemical cell reaction.
Cu+2/Cu where E0Cu+2/Cu = 0.36V
(0.01M)
Ans: Net reaction: Cu+2 + 2e- → Cu (Reduction)
0 0.0591 [𝑃]
Nernt Equation: Ecell = Ecell - log [𝑅]
𝑛

54
 ECu+2/Cu = 0.0591 Cu
log
n Cu+2

= 0.0591 [1]
0.36 - log [0.01]
2

= 0.0591
0.36 - log [102]
2

= 0.0591
0.36 - x 2 log [10]
2

= 0.36 - 0.0591
ECu+2/Cu = 0.3009V
2) Calculate the single electrode potential of the following electrochemical cell reaction.
Ag+/Ag where E0Ag+/Ag = 0.8V
(0.01M)
Ans: Net reaction: Ag+ + e- → Ag (Reduction)
0 0.0591 [𝑃]
Nernt Equation: Ecell = Ecell - log [𝑅]
𝑛

EAg+/Ag = 0.0591 [Ag]

log
n Ag+

= 0.0591 [1]
0.8 - log [0.01]
2

= 0.0591
0.8 - log [102]
2

= 0.0591
0.8 - x 2 log [10]
2

= 0.8 - 0.0591
ECu+2/Cu = 0.7409V
3) Calculate the single electrode potential of the following electrochemical cell reaction.
(Pt) Cl2/Cl- where E0Cl2/Cl- = 1.36V
(0.01M)
Ans: Net reaction: Cl2 + 2e- → 2Cl- (Reduction)
0 0.0591 [𝑃]
Nernt Equation: Ecell = Ecell - log [𝑅]
𝑛

ECl2/Cl- = 0.0591 [Cl-]2

- log
n Cl2

= 0.0591 [0.01]2
1.36 log
2 1

55
 = 0.0591
1.36 - log [10-2]2
2

= 0.0591
1.36 - x (-4) log [10]
2

= 1.36 + 0.1182
ECl2/Cl- = 1.4782V
4) Calculate the single electrode potential of the following electrochemical cell reaction.
Zn/Zn+2 where E0Zn+2/Zn = -0.76V
(0.1M)
Ans: Net reaction: Zn → Zn+2 + 2e- (Oxidation)
0 0.0591 [𝑃]
Nernt Equation: Ecell = 𝐸𝑐𝑒𝑙𝑙 - log [𝑅]
𝑛

Ecell = 0 0.0591 [𝑃]

𝐸𝑐𝑒𝑙𝑙 - log [𝑅]
𝑛

EZn/Zn+2 = 0.0591 n+2

log
n n

= 0.0591 [0.1]
0.76 - log
2 [1]

= 0.76 - 0.0295 log [10-1]

= 0.76 + 0.0295
EZn/Zn+2 = 0.7895 V
5) Calculate the EMF of cell potential of the following electrochemical cell reaction.
Zn/Zn+2//Ag+/Ag where E0Zn/Zn+2 = 0.76V and E0Ag+/Ag = 0.8V
(1.0M) (1.0M)
0 0 0
Ans: 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐴𝑛𝑜𝑑𝑒 + 𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒
= E0Zn/Zn+2 + E0Ag+/Ag
= 0.76 + 0.80
0
𝐸𝑐𝑒𝑙𝑙 = 1.56V
Reaction at anode : Zn → Zn+2 + 2e-
Reaction at cathode : 2Ag+ + 2e- → 2Ag
Net cell reaction : Zn + 2Ag+ → Zn+2 + 2Ag
0 0.0591 [𝑃]
Nernt Equation: Ecell = Ecell - log [𝑅]
𝑛

Ecell = 0.0591 [Zn+2] Ag 2

log
n [Ag+]2 n

56
 = 0.0591 1 [1]2
1.56 log
2 [1]2 1

= 0.0591
1.56 - log [1]
2

= 1.56 + 0
Ecell = 1.56V
6) Calculate the EMF of cell potential of the following electrochemical cell reaction.
Fe/Fe+2//Cu+2/Cu where E0Fe+2/Fe = -0.44V and E0Cu+2/Cu = 0.34V
(0.1M) (0.01M)
0 0 0
Ans: 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐴𝑛𝑜𝑑𝑒 + 𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒
= E0Fe+2/Fe + E0Cu+2/Cu
= 0.44 + 0.34
0
𝐸𝑐𝑒𝑙𝑙 = 0.78V
Reaction at anode : Fe → Fe+2 + 2e-
Reaction at cathode : Cu+2 + 2e- → Cu
Net cell reaction : Fe + Cu+2 → Fe+2 + Cu
0 0.0591 [𝑃]
Nernt Equation: Ecell = Ecell - log [𝑅]
𝑛

Ecell = 0.0591 Fe+2 Cu

log
n Fe Cu+2

= 0.0591 0.1 1
0.78 log
2 1 0.01

= 0.0591
0.78 - log [10]
2

= 0.78 - 0.0295
Ecell = 0.7504V
7) Calculate the EMF of cell potential of the following electrochemical cell reaction.
Zn/Zn+2//Ag+/Ag where E0Zn/Zn+2 = 0.76V and E0Ag+/Ag = 0.8V
(0.1M) (0.01M)
0 0 0
Ans: 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐴𝑛𝑜𝑑𝑒 + 𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒
= E0Zn/Zn+2 + E0Ag+/Ag
= 0.76 + 0.80

57
 0
𝐸𝑐𝑒𝑙𝑙 = 1.56V
Reaction at anode : Zn → Zn+2 + 2e-
Reaction at cathode : 2Ag+ + 2e- → 2Ag
Net cell reaction : Zn + 2Ag+ → Zn+2 + 2Ag
0 0.0591 [𝑃]
Nernt Equation: Ecell = Ecell - log [𝑅]
𝑛

Ecell = 0.0591 [Zn+2] Ag 2

log
n [Ag+]2 n

= 0.0591 [0.1] [1]2

1.56 log
2 0.01 2 [1]

0.0591 10 1
1.56 log
2 10 2 2

= 0.0591
1.56 - log [103]
2

= 1.56 - 0.0295 x 3
= 1.56 - 0.08865
Ecell = 1.47V

BATTERIES
Introduction to cell and battery, Primary (lithium cell) and secondary cells, (lead-Acid cell, and
Lithium-ion cells). Fuel cells – Hydrogen – Oxygen fuel cell, advantages and engineering applications
of fuel cells. Introduction to super capacitors.

Cell: A cell is a single unit of device that converts chemical energy into electrical energy.
Cells are two types:
Galvanic cell: Electrochemical cells which convert chemical energy to electrical energy. Here,
Anode (-Ve charge) and Cathode (+Ve charge).
Electrolytic cell: Electrochemical cells which convert electrical energy to chemical energy. Here,
Anode (+Ve charge) and Cathode (-Ve charge)
Battery: Battery is the collection of cells that converts chemical energy into electrical energy.

58
Cells and batteries can store chemical energy and release it as electrical energy when required.
Battery has 3 main components: Anode (-Ve charge), Cathode (+Ve charge) & Electrolyte.
Characteristics of Battery
a) A battery should have high capacity (very small variation of voltage during discharge).
b) Battery should have high energy efficiency.
c) A battery should have high cycle life means it should have more number of charging and
discharging cycles before failure.
d) Long shelf-life is required.
e) High tolerance to different service conditions such as variation in temperature, vibration shock
etc.
f) Cost should be affordable.
Types of batteries: Batteries are two types. Primary battery/cell and Secondary battery/cell.
Primary cells/battery Secondary cells/battery
1. The cell in which all reactions are not 1. Cells in which reactions are reversible. It
reversible called as primary cell. Once can be used for many cycles by charging and
reactants are converted to products, the cell discharging.
becomes dead.
2. These are not rechargeable 2. These are rechargeable
3. These can be used only once 3. These can be used for many times
4. These are cheap 4. These are expensive
5. Ex: Lithium cell, Dry cell 5. Ex: Lead acid storage cells, Lithium-ion cell

1) LITHIUM CELLS (A Primary cell):

In Lithium cell, Lithium (Li) acts as anode
Depending on the cathode and electrolyte Lithium cells are classified into two types.
a) Lithium Cell with Solid Cathode (LSC): Ex. Li-MnO2
b) Lithium cell with Liquid Cathode (LLC): Ex. Li-SO2 and Li-SOCl2
a) Lithium Cell with Solid Cathode (LSC): In these cells the cathode is solid.
Li-MnO2 is the example for LSC
Anode: Li
Cathode: MnO2

59
Electrolyte: Propylene carbonate and 1,2-dihydroxyehtane.
At Anode: Li Li+ + e-
At Cathode: Li+ + e- + MnO2 LiMnO2

Net Cell reaction: Li + MnO2 LiMnO2

Li-MnO2 battery delivers voltage about 3V.

Applications:
(i) Cylindrical type of batteries is used in cameras and remotes etc.
(ii) Coin type batteries are used in wrist watches and calculators.

b) Lithium Cell with Liquid Cathode (LLC): In these cells the cathode is liquid.
Li-SO2 and Li-SOCl2 are the examples for LLC
Li-SO2: Anode: Li
Cathode: SO2
Electrolyte: Propylene carbonate or acrylonitrile
At Anode: Li Li+ + e-
At Cathode: Li+ + e- + 2SO2 LiS2O4

Net Cell reaction: Li + 2SO2 LiS2O4

Li-SOCl2: Anode: Li
Cathode: SOCl2
Electrolyte: SOCl2

At Anode: 4Li 4Li+ + 4e-

At Cathode: 4Li+ + 4e- + 2SOCl2 4LiCl + SO2 + S

Net Cell reaction: 4Li + 2SOCl2 4LiCl + SO2 + S

These batteries deliver voltage up to about 3.3 – 3.5 V

Applications:
They are used in electronic circuit boards.
They have many military and space applications.
They can be used in medical devices like neuro stimulations and drug delivery system.

60
SECONDARY CELLS
Secondary cells act as both galvanic/voltaic and electrolytic cells. When it converts chemical energy
into electrical energy functions as voltaic cell and while converting electrical energy into chemical
energy functions as electrolytic cells.
2) LEAD-ACID STORAGE CELL: Lead storage battery is also known as the lead acid battery. It is a kind
of rechargeable battery. It is a secondary storage battery. This secondary storage battery can undergo
reversible chemical reaction. Lead storage batteries are the energy storage device.
Anode: Lead (Pb) plates
Cathode: Pb plates coated with PbO2
Electrolyte: Diluted H2SO4 (38%)

Construction:

Pb (Anode) Pb plate coated with PbO2

(Cathode)

2H+ SO4 2 H2SO4 (38 )

When Lead-Acid storage battery converting chemical energy into electrical energy it is said to be
presenting discharging phase.
DISCHARGING PHASE

At Anode: Pb Pb+2 + 2e-

Pb+2 + SO4-2 PbSO4

Net reaction at anode: Pb + SO4-2 PbSO4 + 2e- - - - - - - - - - - - - (1)

At Cathode: PbO2 + 2e- + 4H+ Pb+2 + 2H2O

Pb+2 + SO4-2 PbSO4
Net reaction
at Cathode: PbO2 + 2e- + 4H+ + SO4-2 PbSO4 + 2H2O - - - - - - - - - - - - (2)

Overall reaction during discharging (1) + (2)

61
 Reaction at anode: Pb + SO4-2 PbSO4 + 2e-
Reaction at Cathode: PbO2 + 2e- + 4H+ + SO4-2 PbSO4 + 2H2O

Net Cell reaction: Pb + PbO2 + 4H+ + 2SO4-2 2PbSO4 + 2H2O + Energy

Lead-acid battery delivers voltage 2V.

In this case, PbSO4 completely converts anode and cathode the cell stops functioning as voltaic cell,
at this condition cell needs to be recharged.
Charging can be done by sending electricity with voltage more than 2V.

Charging Phase: When Lead-acid storage cell converts the electrical energy into chemical energy it is
said to be in the charging phase, during charging, the chemical reactions taking place in the
discharging phase will be reversed (Reverse to reactions 1 &2).

Net reaction at anode: PbSO4 + 2e- Pb + SO4-2

Net reaction at Cathode: PbSO4 + 2H2O PbO2 + 2e- + 4H+ + SO4-2

Net Cell reaction: 2PbSO4 + 2H2O + Energy Pb + PbO2 + 4H+ + 2SO4-2

Car battery contains six Lead-acid storage cells that means car battery delivers voltage above 12V.
Generally, by decreasing temperature by 1 ⁰C, there will be decrease in voltage about 1.5 x 10-4 V.
With this reason starting of car is quite difficult in cold climate. At that condition car battery needs
to be heated.
Applications: Lead-acid batteries are used for supplying electricity for automobiles (all kind of
vehicles), electronic devices, laboratories, hospitals, railways, broad-casting stations, etc.

3) LITHIUM ION CELL

Anode: LiCoO2 (LiNiO2 or LiMnO4) mixed with conductor and binder
Cathode: Carbon mixed with binder.
Electrolyte: LiPF6 in organic solution.

62
 Voltameter

------------------------------------
------------------------------------
1st Metal foil coated ------------------------------------ 2nd Metal foil
with LiCoO2 + ------------------------------------ coated with
binder + conductor ------------------------------------ Carbon + binder
(Anode) ------------------------------------ (Cathode)
------------------------------------

Electrolyte (LiPF6)
DISCHARGING PHASE: When cell converts chemical energy into electrical energy is said to be
present in discharging phase.

Reaction at anode: LimCoO2 Lim-nCoO2 + nLi+ + ne-

Reaction at Cathode: C + nLi+ + ne- CLin

Net Cell reaction: LimCoO2 + C Lim-nCoO2 + CLin

Lithium-ion cell delivers voltage about 4.1V

RECHARGING PHASE: Charging can be done by sending current with voltage more than 4.1V, then
chemical reaction taking place in discharging phase will be reversed.

Reaction at anode: Lim-nCoO2 + nLi+ + ne- LimCoO2

Reaction at Cathode: CLin C + nLi+ + ne-

Net Cell reaction: Lim-nCoO2 + CLin LimCoO2 + C

Applications:
Lithium-ion batteries used in laptops and mobile phones.

Fuel Cell
Fuel cell is an electrochemical cell, where chemical energy is converted into electrical energy by
sending reactants into the battery. The basic principle of fuel cell is identical to that of an
electrochemical cell. But only the difference is that chemical energy provided by oxidant and fuel are
stored outside of battery/cell. Example: Hydrogen – oxygen fuel cells (H2 - O2).

63
Characteristics of Fuel cells: Energy conversion is very high & thermal pollution is low.

Hydrogen-Oxygen Fuel Cell (H2 - O2)

Similar to a galvanic cell, fuel cell also has two half cells. Both half cells have porous carbon/graphite
electrode with a catalyst (platinum or lead or silver). The electrodes are placed in the aqueous
solution of NaOH or KOH which acts as an electrolyte. Hydrogen is supplied at anode and oxygen is
supplied at cathode.

The two half-cell reactions are as follows:

2
At Anode: 2H2 + 4OH 4H2O + 4e
At Cathode: O2 + 4e + 2H2O 4OH

Net reaction: 2H2 + O2 2H2O (Fresh water)

The EMF of this cell is measured to be 1.23V. A number of such fuel cells are stacked together in
series to make a battery.

Applications of Hydrogen-Oxygen Fuel Cell (H2 - O2):

1. The most important application of a fuel cell is its use in Space Vehicles, Submarine or Military
Vehicles.
2. The product H2O is valuable source of fresh water by the Astronauts.
3. It is hoped that fuel cell technology will bring a revolution in the area of energy production. 4. Fuel
cell batteries for automotive will be a great boom for the future.
64
Advantages of Hydrogen-Oxygen Fuel Cell (H2 - O2):
Energy conversion is very high in Hydrogen-Oxygen fuel cell.
It has low thermal pollution.
Low maintenance cost.
It is an energy storage system for space applications.
Product H2O is a drink water source for Astronauts.

Disadvantages of Hydrogen-Oxygen Fuel Cell (H2 - O2):

❖ The actual lifetime of Hydrogen-Oxygen (H2 - O2) fuel cell is not known.
❖ Initial cost of Hydrogen-Oxygen fuel cell is very high
❖ Storage of large amount of Hydrogen is difficult and the problems of durability.

CORROSION (MID-II Syllabus)

Introduction: (I) Types of corrosion: Chemical corrosion and Electrochemical corrosion. (ii) Factors
affecting the rate of corrosion: Nature of the metal: Galvanic series, Anodic index, Purity of metal and
Nature of corrosion-product & Nature of environment: Effect of temperature, Effect of pH, Humidity.
(iii) Corrosion control methods: Cathodic protection: sacrificial anode method and impressed current
cathode method. Protective coatings: metallic coatings (anodic and cathodic), methods of
applications of metallic coatings: electroplating (of copper) and electroless plating (of Nickel).

INTRODUCTION
Metals and alloys (combination of two or more metals) are used for fabrication or construction of
engineering materials. If the metals or alloy-based components are not properly maintained, they
slowly decay by the action of atmospheric gases, moisture and other chemicals. “The process of
decay of metal by environmental attack is called as corrosion”.
When metals undergo corrosion they convert into their oxides, hydroxides, carbonates, sulphides,
etc.
Examples: (i) Rusting of iron (Fe) – when Iron (Fe) is exposed to the atmospheric conditions, a layer
of Reddish-brown scale formed is called as rusting of Iron [Fe2O3.xH2O].

Reddish-brown film
Environment
Fe Fe

65
(ii) Formation of Green film on the surface of Copper (Cu) when exposed to open atmosphere
containing CO2 due to the formation of basic carbonate [CuCO3 + Cu(OH)2].
Green film
Environment
Cu Cu

Units for corrosion: mm/year or inches/year.

Reasons for corrosion

1. The metals exist in nature in the form of their “Raw materials or Ores’’ in the stable forms like
oxides, chlorides, silicates, carbonates and sulphides.
2. Metals are extracted by giving some amount of energy to ore of the metal. So, the extracted metal
has high energy and it is thermodynamically unstable. Hence, metals have natural tendency to go
back to their stable ore form (oxides, chlorides, sulphides, carbonates and silicates).

Corrosion (oxidation) Metallic

Metal compound (Or)
Ore of metal
(High energy, Metal extraction
thermodynamically unstable) (Reduction) (Low energy,
thermodynamically stable)
[Corrosion is the reverse process of metal extraction]

Disadvantages
1. Life span and efficiency of metallic parts of machinery and fabrications is reduced.
2. Metals loss metallic properties like electrical conductivity, flexibility and elasticity.
3. Wastage of metal in the form of its compounds.

TYPES OF CORROSION
(1) Chemical corrosion (or) Dry corrosion
(2) Electrochemical corrosion (or) Wet corrosion

(1) CHEMICAL CORROSION (OR) DRY CORROSION

Attack of atmosphere on the surface of a metal in the absence of moisture is called Dry corrosion or
chemical corrosion. This type of corrosion occurs mainly through the direct chemical action of
atmospheric gases like O2, N2, halogens, H2S, SO2.

66
Dry corrosion is classified into three types.
(A) Oxidation corrosion, (B) Corrosion by other gases & (C) liquid metal corrosion.
(a) Oxidation corrosion: Attack of oxygen (O2) on the surface of any metal in the absence of moisture
called oxidation corrosion.
Generally, at low-temperature alkali and alkali earth metals undergo oxidation corrosion. At high
temperature the remaining all metals undergo oxidation corrosion [except silver (Ag), Gold (Au) and
Platinum (Pt)].
Mechanism:

Formation of Metal oxide [MO] at the

point of meeting Mn+ & O-2

O-2 Mn+

O-2 Mn+

O-2 Mn+

O2 Mn+

O-2 Mn+

O-2 Mn+

M M+2 + 2e- (Oxidation)

1/2O2 + 2e- O-2 (Reduction)

Net Reaction: M + 1/2O2 M+2 + O-2 MO (Metal Oxide)

✓ The extent of corrosion depends upon the nature of the metal oxide formed on the surface.

Following are the types of metal oxides [MO] formed on metals.

(a) Stable metal oxide layer: The metal oxide layer formed is stable and it prevents further corrosion.
Stable MO layer

Metal + O2 Metal No further corrosion

Eg.: Al, Cu, Sn, Pb, etc. form stable oxide layers on surface, thus preventing further oxidation.

67
(b) Unstable metal oxide layer: The oxide layer formed decomposes back to metal and oxygen.
Therefore, oxidation corrosion is not possible in such cases. Ex: Ag, Au and Pt do not undergo
oxidation corrosion.

Unstable MO layer
Long time MO decompose
Metal + O2 Metal Metal + O2
Rapidly

(c) Volatile metal oxide layer: The metal oxide layer formed is volatile in nature and evaporates as
soon as it is formed. Example: Mo- molybdenum forms volatile MoO3 layer.

Fresh surface for

Volatile Metal Oxide further attack
Evaporation
Metal + O2 Metal Metal
of MO

(d) Porous metal oxide layer: If the metal oxide layer is porous, that layer has pores or cracks. In this
case the atmospheric oxygen penetrates through the pores or cracks and corrode the underlying
metal surface. This cause continuous corrosion till the complete conversion of metal into its oxide.
Example: Alkali and alkaline earth metals (Li, Na, K, Mg etc).

Porous metal oxide

Further attack through
Metal + O2 Metal
pores and cracks continues

**Pilling Bedworth rule**

“The extent of protection given by the metal oxide layer to the parent metal” is Pilling Bedworth rule.
It is expressed in terms of Specific Volume Ratio.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑀𝑒𝑡𝑎𝑙 𝑂𝑥𝑖𝑑𝑒 𝐿𝑎𝑦𝑒𝑟

Specific Volume Ratio =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑃𝑎𝑟𝑒𝑛𝑡 𝑀𝑒𝑡𝑎𝑙

Specific volume ratio increases the further oxidation corrosion decreases.

Specific volume ratio decreases the further oxidation corrosion increases.
Example. The specific volume ratio of W, Cr, and Ni are 3.6, 2.0 and 1.6, respectively. Ni has lower
specific volume ratio, so it undergoes rapid oxidation corrosion.

68
(B) Corrosion by other gases
Gases like CO2, SO2, Cl2, F2 and H2S also cause corrosion of metals in absence of moisture.
The rate of corrosion depends on the reactivity of gases on metal surface.
Examples: (i) Attack of Cl2 on Ag forms stable AgCl layer.

Stable ‘AgCl’ that

Ag + Cl2 Ag prevents corrosion

(ii) Attack of Cl2 on Sn forms volatile SnCl4 layer.

Volatile ‘SnCl4’
Sn + Cl2 Sn [Fresh metal for
further attack]

(iii) Attack of H2S on steel forms porous ‘FeS’ layer.

Porous ‘FeS’ layer

Steel + H2S Steel [Further corrosion
takes place]

(c) Liquid Metal Corrosion

“Attack of liquid metal on the surface of any solid metal in absence of moisture”. It is due to inter
penetration of liquid metal through the solid metal (or) dissolution of solid metal in liquid metal.
Example: Attack of Mercury (Hg) on any metal.

2) ELECTROCHEMICAL CORROSION OR WET CORROSION*****

Attack of atmosphere on the surface of a metal in presence of moisture is called as Electrochemical
Corrosion or Wet Corrosion.
In this, formation of electrochemical cells takes place.
Electrochemical cell involves,
i) Anode and cathodes, which are separated by conducting medium (electrolyte)
ii) At anode, metal undergoes oxidation to form metallic ions
M → Mn+ + ne-
iii) At cathode, H+ ions/H2O/O2 takes electrons and forms non-metallic ions like OH- or O-2
iv) Metallic ions formed at anode and non-metallic ions formed at cathode combines each other and
forms corrosion product (like Rust) between anode and cathode.

69
Wet corrosion takes place in two ways
a) Evaluation of Hydrogen (H2) & b) Absorption of Oxygen (O2)
a) Evaluation of Hydrogen (H2):
This type of wet corrosion mainly occurs in “acidic medium” and also possible in neutral medium
(H2O).
In hydrogen evolution type corrosion, anodic areas are large and cathodic areas are small.
In acidic medium:

------------------------------- Acidic medium

- - - - -H+ - - - - - - - - - - - -- - - - -H+ - - - - - - (Electrolyte)
- - - - - - -H+ - - - - - - - - - - - - - - - - - - - - - -
- - - - - - - - - - - - -+ - - - -- - - - - - - - - - -H+ - - Small cathodic area
2 H + 2e H2
F F 2 2 2
F F 2
Large Anode Area Large Anode Area
e- e-

Fe Metal

At Anode: Fe Fe+2 + 2e-

At Cathode: 2H+ + 2e- H2

Net reaction: Fe + 2H+ Fe+2 + H2

In neutral medium (H2O):

At Anode: Fe Fe+2 + 2e-

At Cathode: 2H2O + 2e- 2OH- + H2

Net reaction: Fe + 2H2O Fe+2 + 2OH- + H2

Fe(OH)2
4Fe(OH)2 + O2 + 2 H2O → 4Fe(OH)3 → 2[Fe2O3.3H2O] [Rust]

70
(b) Absorption of Oxygen (O2):

• This type of corrosion takes place in basic or neutral medium in presence of oxygen.
• Usually, in presence of oxygen the surface of iron is coated with a thin film of iron oxide.
• If the film develops cracks, anodic areas are created on the surface and the rest of the metal
surface acts as cathodes.
In absorption of oxygen type corrosion, anodic areas are small and cathodic areas are large.

Neutral aqueous solution of electrolyte (NaCl)

O2 + H2O + 2 e 2OH O2 + H2O + 2 e 2OH

Rust
Metal oxide

Large Cathodic Area Large Cathodic Area

e
Small Anodic Area

Fe Fe+2 + 2e
Fe Metal

At Anode: Fe Fe+2 + 2e
At Cathode: O2 + H2O + 2e 2OH

Net reaction: Fe + O2 + H2O Fe+2 + 2OH

Fe(OH)2
If there is enough oxygen is present, Ferrous hydroxides [Fe(OH)2] will be converted to Ferric
hydroxides [Fe(OH)3] followed by rust.
(𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛) (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛)
4Fe(OH)2 + O2 + 2 H2O → 4Fe(OH)3 → 2[Fe2O3.3H2O] [Rust]
Differences between Dry corrosion and wet corrosion
Dry corrosion Wet corrosion
1. The process of attacking of atmosphere 1. The process of attacking of atmosphere
on metal surface in absence of moisture on metal surface in presence of moisture.

71
 2. It is a slow process. 2. It is a rapid process
3. It is a uniform corrosion. 3. It is non-uniform corrosion.

M ta Metal

4. It is explained by absorption mechanism 4. Explained by electrochemical mechanism

5. In this corrosion, product is formed at the 5. In this process corrosion product takes
place where corrosion is taking place. place in between anode and cathode.

***FACTORS EFFECTING THE RATE OF CORROSION***

Always corrosion is the relation between METAL and ENVIRONMENT. Therefore, the rate of corrosion
depends on the nature of metal and nature of environment.

1. Nature of Metal 2. Nature of Environment

(a) Position of metal in the Galvanic Series (a) Temperature

(b) Purity of Metal (b) Humidity
(c) Nature of surface film (c) pH
(d) Nature of Corrosion product

1. NATURE OF METAL
(a) Position of metal in the Galvanic Series:
Metals present at the top of the Galvanic Series undergo rapid corrosion due to high oxidation
potential.
Metals present at bottom of the Galvanic Series undergo less corrosion due to low oxidation
potentials.
Mg, Mg-alloy, Zinc, Al, Fe, Steel, Pb-Sn alloy, Pb, Sn, Brass, Cu, Bronze, Ag, Graphite, Ti, Au, Pt
𝐷𝑒𝑐𝑟𝑒𝑎𝑠𝑖𝑛𝑔 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑟𝑟𝑖𝑠𝑖𝑜𝑛
→
(b) Purity of Metal
As purity of metal decreases the rate of corrosion increases, and as purity of metal increases
corrosion decreases.
𝟏
% Of purity of Metal ∝
𝑹𝒂𝒕𝒆 𝒐𝒇 𝑪𝒐𝒓𝒓𝒐𝒔𝒊𝒐𝒏

72
Impurity presents in metal causes heterogeneity which results the formation of electrochemical cell.
Hence, the rate of corrosion increases.
Example: Zinc metal.

% Of purity 99.999 99.99 99.9 99

Rate of Corrosion 1 2650 5000 7200

(c) Nature of surface film: According to Pilling Bedworth rule;

𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝑴𝒆𝒕𝒂𝒍 𝑶𝒙𝒊𝒅𝒆 𝑳𝒂𝒚𝒆𝒓
Specific Volume Ratio (SVR) ∝
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝑷𝒂𝒓𝒆𝒏𝒕 𝑴𝒆𝒕𝒂𝒍

If SVR increases, the rate of corrosion (Non porous,

decreases. protective surface film
Metal

If SVR decreases, the rate of corrosion (Porous, non-

increases. Metal protective surface film)

(d) Nature of corrosion product

(i) Volatility of corrosion product: If the corrosion product is volatile, it evaporates as soon as it is
formed and gives fresh metal to further attack.

Fresh surface for

Volatile Metal Oxide further attack
Evaporation
Molybdenum O2 Mo Molybdenum
of MO

(ii) Solubility of corrosion product:

If corrosion product is soluble in corroding medium, then the rate of corrosion is High.
If corrosion product is insoluble in corroding medium, then the rate of corrosion is Low.

H2SO4 corroding medium

------------
------------
------------
------------
H2SO4
------------ ------------
------------ PbSO4
Pb Pb

Corrosion product PbSO4 is insoluble in H2SO4, so rate of corrosion of Pb is low.

73
2. NATURE OF ENVIRONMENT
(a) Temperature: The rate of corrosion increases with increase in temperature.
Rate of corrosion ∝ Temperature
Reasons: As temperature increases, the rate of reaction increases and diffusion of gases on metal
surface increases.

(b) Humidity in air: The rate of corrosion increases with increase in humidity/moisture present in air.

Rate of corrosion ∝ Humidity of air.

Reasons: (i) Humidity present in atmosphere provides water to the electrolyte which is essential
for setting up of an electrochemical cell.
(ii) The metal oxide film formed has the tendency to absorb moisture which creates another
electrochemical cell.
Example: (i) Fe undergoes rapid corrosion in wet conditions than the case of dry conditions.
Critical Humidity: The humidity above which the rate of corrosion increases rapidly is called as
critical humidity.

(c) pH: In acidic medium metals undergo rapid corrosion compared to neutral/basic medium.
𝟏
pH ∝
𝑹𝒂𝒕𝒆 𝒐𝒇 𝒄𝒐𝒓𝒓𝒐𝒔𝒊𝒐𝒏

Acidic medium: PH < 7 - Corrosion is More

Basic medium: PH > 7 - Corrosion is Less

Fe undergoes rapid corrosion in H2CO3 than H2O and NaOH.

CORROSION CONTROLLING METHODS

Corrosion controlling methods are two types: (i) Cathodic protection & (ii) Metallic coatings.

(I) CATHODIC PROTECTION

The method of protecting the base metal by forcibly making it to behave like a cathode there by
preventing corrosion is called as Cathodic Protection. It is classified into two types.
(a) Sacrificial Anodic Protection & (b) Impressed Current Cathodic Protection.

(A) SACRIFICIAL ANODIC PROTECTION

In this method, the metal to be protected (base metal) is connected to a more anodic metal (having
high oxidation potential metal) through a wire, then the newly introduced metal acts as anode and

74
undergoes corrosion, whereas the base metal acts as cathode i.e., that will be protected from
corrosion. The attached more anodic metal is called Sacrificial Anode. Generally, sacrificial anodes
are Mg, Al and Zn.

Base Metal Mg/Zn/Al (Sacrificial Metal Anode)

APPLICATIONS
1) Marine structures and Ship hulls can be protected from corrosion.

‘’‘’ ‘’‘’ ‘’‘’ ‘’‘’ ‘’‘’ ‘’‘’

‘’‘’ ‘’‘’ ‘’‘’ ‘’‘’ ‘’‘’ ‘’‘’
Base Metal

Sacrificial
Anode ( n)

Water

2) Underground pipelines can be protected

Ground level

Mg

Underground pipeline Sacrificial Metal Anode

3) Industrial Hot Water tank can be protected.

75
 ------------
------------ Sacrificial Anode
Base Metal ------------ (Mg/Zn/Al)
------------
------------

(B) IMPRESSED CURRENT CATHODIC PROTECTION

In this method, an impressed current is allowed through the circuit from an external DC source in the
opposite direction to nullify the corrosion current. The result is that the anode metal is converted
into cathode and protected from corrosion.

DC line

Ground level
Graphite
--------
Underground pipeline Base metal. Back fill
Initially acts as Anode but after Composed of Gypsum
passing current acts as cathode

Applications
1. Underground pipelines can be prevented from corrosion
2. Marine structure can be prevented from corrosion
3. Hot water tanks can be prevented from corrosion
4. Condensers can be prevented from corrosion
5. Transmission line towers can be prevented from corrosion

Limitations
i) Capital investment and maintenance cost is very high
ii) Regular inspection is needed
iii) Industrial current using in this method ways correction of adjacent pipe lines.

(II) METALLIC COATINGS

The process of coating of a pure metal (coating metal) on the surface of the base metal which is to
be protected (base metal) is called metallic coating.
76
 Metal II (Coating Metal)
Base Metal

Based on coating, metallic coatings are classified into two types.

i) Anodic coating and ii) Cathodic coating.

A) ANODIC COATING: The process of coating more anodic metal (high oxidation potential metal) on
the surface of the base metal is called anodic coating. Ex: Coating of Mg/Al/Zn on any base metal like
Iron (Fe) or Steel.

More Anodic Metal ( n)

Base Metal

Anodic coating prevents corrosion of base metal due to its high oxidation potential, i.e., anodic
coating undergoes corrosion while base metal protected from corrosion.

Corrosion Environment
Anodic Coating Exposed part of base Anodic Coating
(Anode) Metal (Cathode) (Anode)

e e

Base Metal

If anodic coating contains pores, breaks and discontinues the unexposed part of base metal acts as
cathodic part (cathode). Hence, no corrosion takes place to the base metal until entire anodic coating
gets corrosion.
B) CATHODIC COATING: The process of coating more cathodic metal (Low oxidation potential metal)
on the surface of base metal is called cathodic coating.
Coating of Tin (Sn) on Iron (Fe) is known as Tinning.

More Cathodic Metal (Sn)

Base Metal

77
Cathodic coating prevents corrosion of base metal due to its noble behaviour towards corrosion, i.e.,
less tendency towards corrosion due to high reduction potential.

Corrosion Environment
Cathodic Coating Exposed part of Cathodic Coating
(Cathode) Base Metal (Anode) (Cathode)

e e

Base Metal

If cathodic coating contains pores, breaks and discontinuity then unexposed part of base metal acts
as anode and corrosion takes place of base metal. Hence, no corrosion takes place to base metal
when cathodic coating free from pores, breaks and discontinuity.
Example: Tinning (coating of Sn on base metal)
Difference between anodic coating and cathodic coating
Anodic coating Cathodic coating
i) Coating of more anodic metal on the i) Coating of more cathodic metal on the
surface of base metal surface of base metal
ii) The coated metal should have high ii) The coated metal should have low
oxidation potential than the base metal oxidation potential than the base metal
iii) The coated metal should have low iii) The coated metal should have high
reduction potential than the base metal reduction potential than the base metal
iv) It prevents corrosion of base metals iv) It prevents corrosion of base metals by its
artificially noble behavior
v) If it contains pores, breaks and v) If it contains pores, breaks and
discontinuity, the base metal acts as discontinuity, the base metal acts as anode
cathode and prevents corrosion and forms corrosion
vi) No corrosion forms until entire anodic vi) No corrosion forms unless the coating
coating gets corrosion contains pores, breaks and discontinues.
Ex: Galvanization Ex: Tinning
78
METHODS AND APPLICATIONS OF METALLIC COATING
1) Electroplating, 2) Electroless plating & 3) Galvanisation.
1) ELECTROPLATING/ELECTRODEPOSITION (of Copper)
Coating of a coat metal on the surface of any base metal by passing a direct current called
Electroplating.

Electrolyte to refill the loss in the case of inert anode

Cu
DC Line
+
Wooden Tank

Cathode (Article to be
Mn+ electroplated)
- - - Mn+- - - - -
Electrolyte (Solution of
soluble salt of coating metal)

Anode (made of pure metal to be deposited on other metal)

❖ In this method article to be electroplated subjected to solvent cleaning using trichloroethylene to

remove oils and grease. Then the article is subjected to acid picking using dilute HCl to remove
oxides.
❖ The cleaned article is made as the cathode of electrolytic cell.
❖ The pure metal to be deposited is made as the anode of the cell. Anode and cathodes are dipped
into the electrolytic solution of soluble salt of coating metal.
❖ When electricity is passed through electrodes, the anode metal undergoes oxidation and forms
metal ions. The liberated electrons accumulate at cathode. The formed metal ions migrate
towards cathode and deposited on the surface of article (cathode) which results the formation of
smooth, bright and thin layer of coating metal on the surface of base metal (article).
❖ Example: Electroplating of Copper (Cu) on the surface of article (base metal) with smooth and
bright layer should maintain the following conditions.
Anode : Cu pellets

79
 Cathode : Article to be electroplated (Base metal)
Electrolyte : CuSO4 or AgCuCl2.
Temperature : 40 – 70 ⁰C
Current density : 20 – 30 mA/cm2
Applications
• Metals and non-metals can be electroplated.
• In this case of metals electroplating increases corrosion resistance and chemical resistance
strength, hardness and surface properties.
• In the case of non-metals like plastic, glass and wood, electroplating increases strength and
improves decorative values.
2) ELECTROLESS PLATING/AUTOCATALYTIC PLATING (OF NICKEL)
Coating of a coat metal on the surface of any base metal by using reducing agent instead of electricity
is called electroless plating. In this process, the reducing agent supplies electrons for the reduction
of Metal Ions into Metal.

M+ + R M + R
Metal ion Reducing agent Metal

Following are the requirements for electroless plating

a) The coating metal should be in the form of salt soluble.
b) Reducing agents like Formaldehyde or Sodium Hypophosphite are used.
c) Accelerators like fluorides and Succinates are used to accelerate the reduction rate.
d) To improve the brightness of the coat, brighteners like Pb+2 and Cd+2 are added.
e) Buffer solution used to maintain PH and temperature.

Example: Electroless plating of Nickel (Ni) on the surface of ABS

ABS = Acrylonitrile Butadiene Styrene

80
 Ni

---------------------
NiSO4 + Sodium hypophosphite
---------------------
ABS (NaH2PO2) + Sodium succinate +
Cd+2 + Sodium acetate
---------------------
In this process, reducing agent (NaH2PO2) converts Ni+2 ions into Ni
Ni+2 + H2PO2ˉ+ H2O → Ni + H2PO3ˉ + 2H+
The formed (Ni) will be deposited on the surface of catalytically active ABS (non-metal) or (metal).
Applications
In the case of metals, electroless plating increases corrosion resistance, strength, hardness and
surface properties.
In case of non-metals, electroless plating increases strength.

Yours: Dr. Mallesham GODUMALA

81
 CHAPTER IV
Stereochemistry, Reaction Mechanism and Synthesis of Drug Molecules (9L)
Structural isomers and stereoisomers, configurations, symmetry and chirality, enantiomers,
diastereomers, optical activity. Conformational analysis of n-butane.
Organic reactions and synthesis of drug molecules:
Introduction to reactions involving substitution (SN1 & SN2), addition (addition of HBr to propene,
Markownikoff and Anti Markownikoff addition), Elimination reactions: Dehydro halogenation of alkyl
halides. Saytzeff rule. Redox reactions, oxidation (oxidation of alcohols using KMnO 4 & CrO3),
reduction (reduction of carbonyl compounds by LiAlH4 & NaBH4). Synthesis & uses of commonly used
drug molecules: paracetamol and Asprin.

Stereo chemistry: “The study of properties (physical, chemical and biological) of molecules with
respective to spatial arrangement of atoms or groups in 3-dimensions” is called as stereochemistry.
Or Stereochemistry is a branch of chemistry that deals with the three-dimensional arrangement of
atoms/groups in molecules.

Isomers: Compounds having same molecular formula but different chemical and physical properties
called isomers. This phenomenon is called as isomerism.

Isomers

Structural Isomers or Stereo Isomers

Constitutional isomers

Chain Isomers

Positional Isomers Configurational Stereo Isomers Conformational

Stereo Isomers

Functional Isomers
Geometrical Isomers Optical Isomers
Metamers
Cis Isomers Enantiomers

Tautomers Trans Isomers Diastereomers

82
Structural Isomers:
Compounds having same molecular formula but different structures called as Structural isomers.

Chain Isomers: Compounds having same molecular formula but differ in length/nature of carbon
cain is called as chain isomers. This phenomenon is called as chain isomerism.
Example-1: Butane [C4H10]

CH3 CH2 CH2 CH3 CH3 CH CH3

n-Butane CH3 Iso-Butane

Example-2: Pentane [C5H12] CH3

CH3 CH2 CH2 CH2 CH3 CH3 CH2 CH CH3 CH3 C CH3

n-Pentane CH3 CH3

Iso-Pentane Neo-Pentane

Positional Isomers: Compounds having same molecular formula but differ in position of
functional group called Positional isomers. This phenomenon is called as positional isomerism.
Example-1: Chloropropane [C3H7Cl]

CH3 CH2 CH2 Cl CH3 CH CH3

1-Chloropropane Cl 2-Chloropropane
Example-2: Hydroxypropane [C3H7OH]

CH3 CH2 CH2 OH CH3 CH CH3

1-Hydroxypropane OH 2 Hydroxypropane

Example-3: Dichlorobenzene [C6H4Cl2]

o-Dichlorobenzene m-Dichlorobenzene p-Dichlorobenzene

Functional isomers: Compounds having same molecular formula but differ in functional groups
called as functional isomers and the phenomenon is called as functional isomerism.

83
 1) CH2=CH-CH=CH2 CH3-C≡C-CH3
1,3-Butadiene 2-Butyne

2) CH3 CH2 CH2 OH CH3 CH2 O CH3

1-Hydroxypropane Methoxyethane

O O
3) CH3 C CH3 CH3 CH2 C H
Propanone Propanal

**Metamers: Compounds having same molecular formula but different alkyl groups around the
same functional group is called as metamers.

1. Ethers

CH3 CH2 CH2 O CH3 CH3 CH2 O CH2 CH3

Methyl propyl ether Diethyl ether

2. Thioethers

CH3 CH2 CH2 S CH3 CH3 CH2 S CH2 CH3

Methyl propyl thioether Diethyl thioether

**Tautomers: Compounds having same molecular formula, that are readily interconvertible and
exist dynamic equilibrium called tautomers and this phenomenon is called as tautomerism. (or)
Compounds which are having same molecular formula, and involves 1,3-proton transfer called
tautomers and this phenomenon is called tautomerism.

O OH

1) CH3 C CH3 ⇌ CH3 C CH2

Keto form Enol form
(Propanone) (Isopropenol)

84
 O OH

2) CH3 C NH2 ⇌ CH3 C NH

Amide form Iminol form

Stereo isomers
Compounds having same molecular formula but different spatial arrangement of atoms or groups
called stereo isomers and this phenomenon is called as stereo isomerism.

Configurational stereo isomers

The stereo isomers which are not interconvertible by rotation called configurational isomers. These
are classified into two types.

(i) Geometrical Isomers **

Compounds having same molecular formula but different geometry called as Geometrical isomers.
These are two types.

(a) Cis Isomers: Compounds having same molecular formula and both identical/similar groups are
present on the same side of the double bond called Cis isomers.

(b) Trans Isomers: Compounds having same molecular formula and both identical/similar groups are
present on the opposite side of the double bond called Trans isomers.

Cis 2-butene Trans 2-butene Cis-1,2-dibromoethene Trans-1,2-dibromoethene

Cis-1,2-dichloroethene Trans-1,2-dichloroethene Cis-1,2-diFluoroethene Trans-1,2-diFluoroethene

(ii) Optical isomers: Configurational isomers which rotate plane polarized light called optical
isomers. These are two types.

85
(a) ***Enantiomers: Compounds having same molecular formula that are “Non-Superimposable
Mirror images” called enantiomers.
(i) Mirror (ii) Mirror (iii) Mirror

Mirror (ii) Mirror

(i)
CHO CHO COOH COOH

H OH HO H H OH HO H

CH2OH CH2OH CH3 CH3

D-Glyceraldehyde L-Glyceraldehyde D-Lactic acid L-Lactic acid

(iii) Mirror (iv) Mirror

COOH COOH
COOH COOH
HO H H OH
H NH2 2HN H HO H
H OH

COOH COOH
CH3 CH3
D-Alanine L-Alanine D-Tartaric acid L-Tartaric acid

Properties of enantiomers
1. Enantiomers have same physical properties, means they have same melting point (MP), same
boiling point (BP), same solubility, same density, same colour, etc.
2. Enantiomers have same chemical properties; means they have same reactivity towards acids and
bases.
3. Enantiomers should be optically active (means they have chiral carbon).
4. Enantiomers have same degree of rotation of plane polarized light but they rotate light in
opposite direction.
5. Mixture of enantiomers called racemic mixture.
6. Enantiomers can be separated from racemic mixture by Mechanical Separation.

86
(b) ***Diastereomers: Compounds having same molecular formula, that are Non-
Superimposable and Non-Mirror images called Diastereomers.

Cis 2-butene Trans 2-butene Cis-1,2-dibromoethene Trans-1,2-dibromoethene

Non-Mirror Non-Mirror
COOH COOH COOH COOH

HO H HO H H OH HO H

H OH HO H HO H HO H

COOH COOH COOH COOH

D-Tartaric acid Meso-Tartaric acid D-Tartaric acid Meso-Tartaric acid

Properties of Diastereomers
1. Diastereomers have different physical properties, means they have different melting point (MP),
different boiling point (BP), different solubility, different density, different colour, etc.
2. Diastereomers have different chemical properties; means they have different reactivity towards
acids and bases.
3. Diastereomers may or may not optically active.
4. Diastereomers have different degree of rotation of plane polarized light.
5. Diastereomers can be separated by Fractional Distillation.

Chiral carbon/Chiral centre/Dissymmetric centre

Carbon which is attached to four different atoms or groups called as chiral carbon.

a (i) (ii) (iii)

CHO COOH COOH

c * H * OH H * OH H * NH2

b d e
CH2OH CH3 CH3
* Chiral carbon D-Glyceraldehyde D-Lactic acid D-Alanine

87
Chirality: Molecule which is nonsuperimposable on its mirror image called as chirality.
Mirror (ii) Mirror
(i)
CHO CHO COOH COOH

H OH HO H H OH HO H

CH2OH CH2OH CH3 CH3

D-Glyceraldehyde L-Glyceraldehyde D-Lactic acid L-Lactic acid

Optical activity
The ability of a substance to rotate the plane polarized light that is passed through it called optical
activity. The compounds exhibiting optical activity are called as optically active compounds.
Note: Plane polarized light consists of waves in which the direction of vibration is the same for all
waves.

Or

Ordinary light Prism Plane Sample Clockwise Anti

polarized Light clockwise

Optical activity of compounds can be measure using Polarimeter.

Conditions for optical activity

❖ Molecule must contain chiral centre.
If a compound rotates plane polarized light in the clockwise direction (or right side) called as
dextrorotatory (d).

Dextrorotatory

Plane polarized Light Sample Clockwise

If a compound rotates plane polarized light in the anti-clockwise direction (or left side) called as
levorotatory (l).

88
 Levorotatory

Plane polarized Light Sample Anti-clockwise

Examples: (ii) (iii) (iv)

(i) CHO COOH COOH COOH

H * OH H * OH H * NH2 H H

CH2OH CH3 CH3 CH3

D-Glyceraldehyde D-Lactic acid D-Alanine (Optically Inactive)
(Optically Active) (Optically Active) (Optically Active)

CONFIGURATION
The arrangement of atoms/groups at chiral centre or chiral carbon is known as configuration.
Configuration is two types.

(i) Relative configuration/[DL] configuration & (ii) Absolute configuration/[RS] configuration

(I) RELATIVE CONFIGURATION/[DL] CONFIGURATION

In relative [or DL] configuration the arrangement of atoms or groups at chiral centre can be studied
by taking reference isomer. Here, Glyceraldehyde is used as reference isomer to determine
configuration of different isomers. Therefore, this configuration is called as relative configuration.
Rules for DL configuration
(i) Draw the molecule in Fischer Projection.
a
b d
c
(ii) If the molecule contains more than two chiral centres, Identify the bottom most chiral centre
from lower side.

89
(iii) Then at the chiral centre, if OH/NH2 group or highly electronegative group present at Right Side
of the Fischer projection of chiral centre, that configuration is said to be ‘D’.
(iv) If OH/NH2 group or highly electronegative group present at Left Side of the Fischer projection of
chiral centre, that configuration is said to be ‘L’
Examples

(i) CHO CHO (ii) COOH COOH

H OH HO H H OH HO H

CH2OH CH2OH CH3 CH3

D-Glyceraldehyde L-Glyceraldehyde D-Lactic acid L-Lactic acid

(iii) COOH COOH (iv) COOH COOH

HO H H OH
H NH2 H NH2
H OH HO H

CH3 CH3 COOH COOH

D-Alanine L-Alanine
D-Tartaric acid L-Tartaric acid

ABSOLUTE CONFIGURATION/[RS] CONFIGURATION

Cahn, Ingold, Prelog (CIP) rules are followed to assign the priorities at chiral carbon.
(i) Draw the molecule in a Fischer projection.
a
b d
c
(ii) Give the priorities to the groups attached to chiral carbon based on atomic number. Priority:
High atomic number > Low atomic number.

Cl (3)

(4) F Br (2)

I (1)

90
(iii) If isotopes (having same atomic number but different mass number) are attached to chiral
carbon then give priority based on mass number.
Priority: High Mass number > Low Mass number.

Cl (1)

(2) CH3 D (3)

H (4)
(iv) If first attached atom at chiral carbon is same then go to the next attached atom for deciding
priority.

(1) NH2 (3) NH2 (4) NH2

(2) (3)
(4) H CH2Cl (4) H OH (2) CH3HN OH (2)

(3) CH2OH (1) OCH3 (1) OCH3

(v) If chiral carbon attached to double or triple bonds, then that atom is considered as two and three
single atoms, respectively.

O (2) HC=O
C O C
O
N (4) H OH (1)
C N C N
N (3) CH3OH

(vi) After given priority, the lowest priority group should be present on the vertical line. Then, if the
priority of atoms at chiral carbon is clockwise direction that configuration is called “R”. If the
priority of atoms at chiral carbon is anticlockwise that configuration is “S”.
(vii) If the lowest priority group present on horizontal line, then the configuration will be reversed.
Means R becomes S and S becomes R.
Examples

91
 (2) Br (1) I (2) CHO

(1) I Cl (4) F Br (4) H OH

(3) (2) (1)
(4) F (3) Cl (3) CH2OH
Clockwise “R” Clockwise but least priority Anticlockwise but least
group is horizontal line. So, priority group is horizontal
“S” Configuration line. So, “R” Configuration

(3) NH2 (4) NH2 (2) COOH

(3)
(1) H3CO OH (2) CH3HN OH (2) (4) H OH (1)

(4) H (1) OCH3 (3) CH3

Anticlockwise but least Anticlockwise. So, “R” Anticlockwise but least
priority group is horizontal Configuration priority group is horizontal
line. So, “R” Configuration line. So, “R” Configuration
(2)
(2) COOH (2) COOH COOH
(1) S (4)
HO H
(1) Cl CH3 (1) H CH3 (3)
(3) (3) (4) H (3) OH (1)
S
(4) H (4) Cl H
Clockwise “R” (2)
Clockwise but least priority
group is horizontal line. So, “S”
Configuration

Conformational Isomers
Compounds having same molecular formula and which can be interconvertible by rotating the
molecule around the single bond (C-C) are called conformational isomers.

92
**CONFORMATIONAL ANALYSIS OF n-BUTANE

Molecular formula of n-Butane is (C4H10): CH3-CH2-CH2-CH3

I, Fully Eclipsed II III, Partially Eclipsed

(0⁰, 360⁰) Gauche (60⁰) (120⁰)

VI V, Partially Eclipsed IV, Staggered/Anti

Gauche (300⁰) (240⁰) (180⁰)
Steric hindrance between groups in conformations is CH3 – CH3 > CH3 – H > H - H
Energy order of conformations of n-butane is I > III, V > II, VI > IV
Fully Eclipsed > Partially Eclipsed > Gauche > Staggered.
Energy is inversely proportional to the stability order of conformation of n-butane. Therefore, the
stability order of n-butane conformers is as follows.
IV > II, VI > III, V > I
Staggered > Gauche > Partially Eclipsed > Fully Eclipsed

Potential energy diagram of n-butane conformation is as follows.

93
 Dihedral angle (o)

REACTION MECHANISM

Introduction: Organic reactions are chemical reactions involving organic compounds. Reaction
mechanism is in chemical reactions the detailed process by which chemical substances are
transformed into other substances. The reactions may involve the interaction of atoms, groups, ions,
electrons and free radicals.
Organic reactions are mainly three types.
(i) Substitution reactions, (ii) Addition reactions & (iii) Elimination reactions.

1. SUBSTITUTION REACTIONS
The chemical reactions in which atoms or groups are replaced by another atom or groups called as
substitution reactions. These are two types.
(A) Nucleophilic substitution reactions & (B) Electrophilic substitution reactions.

94
(A) NUCLEOPHILIC SUBSTITUTION REACTIONS
A chemical reaction in which one nucleophile is replaced by another nucleophile. These reactions
may carried out in two ways.
(a) SN1 reaction or Unimolecular Substitution Reaction.
(b) SN2 reaction or Bimolecular Substitution Reaction.

(A) SN1 REACTION OR UNIMOLECULAR SUBSTITUTION REACTION.

(i) In SN1, S means Substitution N means Nucleophilic and 1 means unimolecular reaction.
(ii) In SN1, the rate of reaction depends only on the concentration of alkyl halide but not on
Nucleophile.
Rate ∝ [Alkyl Halide]
(iii) The rate is depending on only alkyl halide, therefore it is called a First order reaction.
(iv) SN1 is a two-step process.
(v) Polar solvents (methanol or water) favour SN1 reaction.
(vi) Carbocation is the reaction intermediate
(vii) SN1 reactions are mainly shown by tertiary alkyl halides.
Example: Reaction between tert-butyl bromide with aq. KOH

CH3 CH3 CH3

Br + aq. KOH OH + HO
H3C H3C H3C
CH3 CH3 CH3
Tert butyl bromide Tert butyl alcohol

Mechanism: SN1 reaction takes in two steps.

STEP-I: In first step, the carbon-halogen bond slowly breaks to from carbocation intermediate.

CH3 CH3

Slow
Br + + Br
H3C H3C
CH3 CH3
Tert butyl bromide Carbocation

95
STEP-II: Carbo cation rapidly combines with nucleophile (OH-) from either side.

CH3 CH3 CH3

OH-
+ OH + HO
Fast
H3C H3C H3C
CH3 50% CH3 50 CH3
Carbocation Tert butyl alcohol

(B) SN2 REACTION OR BIMOLECULAR SUBSTITUTION REACTION.

(i) In SN2, S means Substitution, N means Nucleophilic, and 2 means Bimolecular reaction.
(ii) In SN2, the rate of reaction depends on both that is the concentration of alkyl halide and
Nucleophile.
Rate ∝ [Alkyl Halide] [Nucleophile]
(iii) The rate is depending on both; therefore, it is called a Second order reaction.
(iv) SN2 proceeds in a Single step process.
(v) Non-polar solvents favour SN2 reaction.
(vi) A Transition state is the reaction intermediate and 100% inversion product (also called as
Walden Inversion)
(vii) SN2 reactions are mainly shown by Primary alkyl halides.

Example: Reaction between Methyl bromide with aq. KOH

CH3Br + OH- CH3OH + Br-

Mechanism: SN2 reaction involves in a single step. Therefore, the breaking of carbon-halogen bond
and making of carbon-nucleophile bond occurs simultaneously.
In SN2 reaction, nucleophile attacks the carbon from opposite side to the halogen. In that stage,
carbon atom is partially bonded to both nucleophile and leaving group. That state is called as
transition state (or activated complex).
That transition state is highly unstable, so, it converts to alcohols as an inversion product.

96
 H H H H
Slow Fast OH H
H Br + OH HO C Br
H
H
Methyl Bromide H Methyl alcohol
Transition state (100% inversion product)

In SN2 reaction inverted product is formed. This phenomenon is called Walden Inversion.

2. ADDITION REACTIONS
The Addition reaction in which two or more molecules combine and forms one product without the
loss of any atom.
Unsaturated molecules like alkenes, alkadienes and alkynes involve addition reaction.
Addition reactions are initiated by electrophiles, nucleophiles or free radicals.
Depending on initiators, addition reactions are three types; (a) Electrophilic addition reactions, (b)
Free radical addition reactions & (c) Nucleophilic addition reactions

(a) ELECTROPHILIC ADDITION REACTIONS

The addition reactions which are initiated by electrophiles (positively charged species or electron
deficient) are called Electrophilic addition reactions.
CH2=CH2 + HBr → H-CH2-CH2-Br
(Ethene) (Bromo ethene)
HC≡CH + HBr → H-CH=CH-Br
Acetylene (Bromoethene)

Addition of HBr to unsymmetrical alkenes

CH3 CH2 CH2 Br

1-Bromopropane (Minor)
CH3 CH=CH2 + HBr
Br
Propene
CH3 CH CH3
2-Bromopropane (Major)

Formation of major product can be explained by Markovnicov’s Ru ***

“When an asymmetrical reagent is added to unsymmetrical alkene, then negative half of the reagent
will attach to the carbon atom containing lesser number of hydrogen atoms” is Markovnicov’s Rule.

97
 Br
Example: CH3-CH=CH2 + HBr CH3 CH CH3
Propene 2 Bromopropane (Ma or)

Mechanism: It involves three steps.

Slow
Step-1: HBr ionizes to form H+ and Br- ions. HBr H+ + Br-

Step-2: Proton (H+) reacts with π-bond of alkene and gives carbocation as follows.

CH3-CH2-CH2+
H+ 1o-Carbocation (Less stable)
CH3 CH=CH2
Propene +
CH3-CH-CH3
o
2 -Carbocation (More stable)
Step-3: More stable 2⁰-carbocation reacts with Br- and forms 2-bromopropane as a major product.
Br
+
CH3-CH-CH3 CH3-CH-CH3
2o-Carbocation 2-Bromopropane (Major)

(b) FREE RADICAL ADDITION REACTIONS

Addition reactions which are initiated by free radicals called free radical addition reactions.

ANTI MARKOVNICOV’S RULE (OR) KHARASCH EFFECT (OR) PEROXIDE EFFECT***

When an asymmetrical reagent is added to unsymmetrical alkene, then negative half of the reagent
will attach to the carbon atom containing more number of hydrogen atoms is Anti Markovnicov’s
Rule. This will occur in presence of peroxide; therefore, this is also called as Peroxide effect or
Kharasch effect.

H2O2
Example: CH3-CH=CH2 + HBr CH3-CH2-CH2-Br
Propene hν 1-Bromopropane (Major)

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Mechanism: It takes in three steps.
Step-1: Peroxide cleaves and forms alkoxide free radical.

hν
R̶ O ̶ O ̶ R 2RO

2RO + HBr ROH + Br

Step-2: Bromine radical (Br.) attacks at π-bond of propene and forms two types of free radicals.

CH3 CH CH2 Br
2o Free radical (Mor sta )
CH3 CH=CH2 + Br
Br
Propene
CH3 CH CH2
1o Free radical (Less stable)

Step-3: 2o free radical reacts with HBr and forms 1-bromopropane as major product.

HBr
CH3 CH CH2 Br CH3 CH2 CH2 Br + Br
2o Free radical 1 Bromopropane

3. ELIMINATION REACTIONS
The chemical reactions in which, two or more atoms/groups attached to adjacent carbons are
eliminated to form double bond or triple bond called elimination reaction.
Example: Dehydrohalogenation: When alkyl halides react with alc. KOH dehydrohalogenation takes
place.
H alc. KOH
R CH CH2 X R CH CH2

Alkyl halide Alkene

Elimination reactions are classified into two types.
(i) E1 elimination reactions & (ii) E2 elimination reactions.

(i) E1 elimination reactions

E1 stands for Unimolecular elimination. In this type, the rate of elimination depends on only alkyl
halide but not on nucleophile. Therefore, it is a first order reaction.
This reaction is preferred in 2o and 3o alkyl halides.
99
 Br
Ethanol
CH3 C CH3 CH3 C CH2
NaOH
CH3 CH3
2-Bromo-2-methylpropane 2-methylpropene

Mechanism: This involves two steps

Step-1: Ionization of tert-butyl bromide and forms carbonium ion.
Br
Slow
CH3 C
+
CH3 + Br
-
CH3 C CH3
CH3 CH3
2-Bromo-2-methylpropane Carbocation
Step 2: Carbocation loses a proton from the adjacent carbon to give alkenes.

CH3
+
C CH2 + OH
- Fast
CH3 C CH2 + H2O

CH3 H CH3
Carbocation 2-methylpropene
(ii) E2 elimination reactions
E2 stands for Bimolecular elimination. In this type, the rate of reaction depends on the concentration
of both alkyl halide and nucleophile. Therefore, it is a second order elimination reaction.
Rate ∝ [Alkyl Halide] [Nucleophile]
E2 reaction preferentially occurs in 1o-alkyl halides.

alc. KOH
Example: R CH2 CH2 Br R CH CH2 + HBr
Alkyl halide Alkene
Mechanism: This is a one-step reaction.
In this type a proton is attracted by nucleophile and removal of halogen takes place simultaneously
in a single step. At the same time double bond formation will be formed. That state is called as
transition state.

100
 -
OH H HO H
Slow
R C
Fast -
R C CH2 CH2 R CH CH2 + H2O + Br
H Br H Br Alkene

Alkyl halide Transition state

***Saytzeff rule
Saytzeff rule says that, in an elimination reaction if two types of products are possible, then more
substituted alkene is the major product.

H H H H CH3 CH CH CH3 + HBr

OH 2-Butene (Major) [Saytzeff Product]
H C C C C H

H H Br H CH3 CH2 CH CH2 + HBr

2-Bromobutane 1-Butene (Minor) [Hoffmann Product]

2-Bromobutane on reaction with alcoholic KOH forms more substituted 2-butene as a major product,
while less substitutes 1-butene is the minor product.

REDOX REACTIONS
An oxidation-reduction reaction called redox reaction.
Redox reaction is a type of chemical reaction that involves transfer of electrons between two species.

Oxidation of alcohols with KMnO4 and CrO3

(a) Oxidation of alcohols with KMnO4 (Potassium permanganate)
(i) Structure:

+
O OK
Mn
O
O

(ii) It is a crystalline substance

(iii) Soluble in water and alcohols
(iv) In soluble in organic compounds.
Applications: KMnO4 converts 1o alcohols into aldehydes.

101
 H O
KMnO4
R C OH R C H
H
1o Alcohol Aldehyde

H O
KMnO4
CH3 C OH CH3 C H
H
Ethanol Acetaldehyde

KMnO4 oxidizes 2o alcohols into ketone

H O
H KMnO4 O
R C OH KMnO4 R C R
R C OH R C R
R
R
2ooAlcohol Ketone
2 Alcohol Ketone
H O
H O
KMnO4
CH KMnO4
CH33 CC OH OH CH3 CC
CH3
CH3
CH3
CH
CH33
22 Propanol
Propanol Acetone
Acetone

KMnO4 cannot react with 3o-alcohols due to the absence of Hydrogens

CH3
KMnO4
CH3 C OH No reaction
CH3
3o Butanol

Oxidation of alcohols with Chromium trioxide (CrO3)

(i) Structure

102
 O

O Cr O

(ii) It is a crystalline substance

(iii) Soluble in organic solvents

(a) Jones reagent (CrO3 + aq. H2SO4 + acetone)

➢ Jones reagent converts primary (1o) alcohols into Aldehydes.

H O
CrO3 + aq. H2SO4
R C OH R C H
Acetone
H Aldehyde
1o Alcohol
H O
CrO3 + aq. H2SO4
CH3 C OH CH3 C H
Acetone
H Acetaldehyde
Ethanol

➢ Jones reagent converts secondary (2o) alcohols into Ketones.

H O
CrO3 + aq. H2SO4
R C OH R C R
Acetone
R Ketone
2o Alcohol
H O
CrO3 + aq. H2SO4
CH3 C OH CH3 C CH3
Acetone
CH3 Acetone
2-Propanol

(b) Sarett reagent (CrO3 + Pyridine)

➢ Sarett Reagent converts primary (1o) alcohols into Aldehydes.

103
 H O
CrO3 + Pyridine
R C OH R C H
H Aldehyde
1o Alcohol

H O
CrO3 + Pyridine
CH3 C OH CH3 C H
H Acetaldehyde
Ethanol

➢ Sarette Reagent converts Secondary (2o) alcohols into Ketones.

H O
H CrO3 + Pyridine O
CrO3 + Pyridine
R C OH R C R
R C OH R C R
R Ketone
R Ketone
2o Alcohol
2o Alcohol
H O
H CrO3 + Pyridine O
CrO3 + Pyridine
CH C OH CH3 C CH3
CH3 3C OH CH3 C CH3
CH Acetone
CH3 3 Acetone
2-Propanol
2-Propanol

(c) Collins Reagent (CrO3 + Pyridine + CH2Cl2)

➢ Collins Reagent converts primary (1o) alcohols into Aldehydes.

104
 H O
CrO3 + Pyridine
R C OH R C H
CH2Cl2
H Aldehyde
1o Alcohol
H O
CrO3 + Pyridine
CH3 C OH CH3 C H
CH2Cl2
H Acetaldehyde
Ethanol

➢ Collins Reagent converts Secondary (2o) alcohols into Ketones.

H
H O
O
CrO3 ++ Pyridine
CrO Pyridine
3
R
R C
C OH
OH R
R C R
C R
CH2Cl
CH Cl2
2 2
R Ketone
Ketone
R
2oo Alcohol
2 Alcohol
H
H O
O
CrO3 ++ Pyridine
CrO Pyridine
3
CH3
CH C
C OH
OH CH3
CH C
C CH3
CH
3 3 3
CH2Cl
CH Cl2
2 2
CH3 Acetone
Acetone
CH3
2-Propanol
2-Propanol

Note: Tertiary alcohols do not react with Jones, Sarette and Collins reagent due to absence of
hydrogens.

CH3
ones, Sarette
CH3 C OH No reaction
Collins Reagent
CH3
3o Butanol

105
Reduction of carbonyl compounds (C=O) with Lithium Aluminium Hydride
(LiAlH4) and Sodium Borohydride (NaBH4).
(a) Reduction of carbonyl compounds (C=O) with Lithium Aluminium Hydride (LiAlH4)
Structure

H H
Al Li+
H
H

It is a white crystalline substance

Solvents: Ether, Tetrahydrofuran.
Reaction with Carbonyl compounds (Aldehydes and Ketones)
(i) LiAlH4 converts Aldehydes into 1o-Alcohols.

O H
LiAlH4
R C H R C OH
Aldehyde o
H 1 Alcohol

O H
LiAlH4
CH3 C H CH3 C OH
Acetaldehyde H Ethanol

(ii) LiAlH4 converts Ketones into 2o-Alcohols.

O H
LiAlH4
R C R R C OH
Ketone R 2o Alcohol
H O
LiAlH4
CH3 C OH CH3 C CH3
CH3 Acetone
2-Propanol

106
**** Cinnamaldehyde on reduction with LiALH4 forms following products.

LiAlH4
Ph CH2 CH2 CH2OH
RT
Ph CH CH CHO
LiAlH4
Cinnamaldehyde Ph CH CH CH2OH
0 – 5oC

(a) Reduction of carbonyl compounds (C=O) with Sodium Borohydride (NaBH4)

Structure

H H
-
B Na+
H
H

It is crystalline compound
Solvent: Water, alcohol
Reaction with Carbonyl compounds (Aldehydes and Ketones)
(i) NaBH4 converts Aldehydes into 1o-Alcohols.

O H
NaBH4
R C H R C OH
Aldehyde o
H 1 Alcohol

O H
NaBH4
CH3 C H CH3 C OH
Acetaldehyde H Ethanol

(ii) NaBH4 converts Ketones into 2o-Alcohols.

O H
NaBH4
R C R R C OH
Ketone R 2o Alcohol
H O
NaBH4
CH3 C OH CH3 C CH3
107
CH3 Acetone
2-Propanol
 R C R R C OH
Ketone R 2o Alcohol
H O
NaBH4
CH3 C OH CH3 C CH3
CH3 Acetone
2-Propanol

**** In Cinnamaldehyde NaBH4 reduces only aldehydes but not double bonds.

NaBH4
Ph CH CH CHO Ph CH CH CH2OH
RT
Cinnamaldehyde Cinnamyl alcohol

LiAlH4 is more reactive, therefore less selective. But, NaBH4 is less reactive, therefore more selective.

Synthesis and uses of commonly used drug molecules (Aspirin and

Paracetamol)
ASPIRIN
Aspirin prepared by reaction of salicylic acid with acetic anhydride in presence of acid (H3PO4) as
catalyst.

Salicylic acid Acetic anhydride Acetyl salicylic acid Acetic acid

(Aspirin)

• It is an Electrophilic Substitution reaction.

• In this H+ ions of Salicylic acid are substituted with acetyl group (CH3-C=O). So, it is called as
acetylation reaction.

Uses
✓ Aspirin reduces Fever
✓ Aspirin is used as a pain killer, means it reduces headache, Muscle ache, Stomach ache, Tooth
ache, etc.
✓ It also prevents blood clotting.

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Side Effects

Upset of stomach. Kidney problems, Hearing problems, Yellowing of eyes and skin.

PARACETAMOL

It is prepared by the reaction between p-aminophenol and acetic anhydride in presence of dil. H2SO4
as a catalyst.

Acetic acid
P-Aminophenol Acetic anhydride Paracetamol

• It is an electrophilic substitution reaction

• In this reaction H+ ions of NH2 in p-amino phenol substituted with acetyl group (CH3-C=O). So, it
is called as acetylation reaction.

Uses
✓ Paracetamol reduces Fever
✓ Paracetamol is used as a pain killer, means it reduces headache, Muscle ache, Stomach ache,
Tooth ache, etc.
✓ Paracetamol also acts as anti-inflammatory (reduces swelling).

Side Effects
o It causes diarrhoea. Leads to vomiting.
o Low blood pressure.
o Over sweating.

Yours: Dr. Mallesham Godumala

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 UNIT-V: ENGINEERING MATERIALS(9L)
BIODEGRADABLE POLYMERS: Introduction, Preparation and properties of Polyhydroxy butyrate
(PHB), Polyhydroxy butyrate-co-β-Hydroxy valerate (PHBV), Polyglycolic acid (PGA), Polylactic acid
(PLA), Poly (Î-caprolactone) (PCL). Applications of biodegradable polymers.

LUBRICANTS: Introduction, Classification with examples, characteristics of a good lubricant and

properties of lubricants: Viscosity and viscosity index, cloud point, pour point, flash & fire point.

REFRACTORIES: Classification with examples, characteristics and Properties of refractory materials

(Refractoriness, RUL test & Thermal spalling).
CERAMICS: Introduction, chemical bonding and applications.

1. BIODEGRADABLE POLYMERS
A polymer is a molecule made up of numerous small molecules (called monomers) joined together
to form a larger molecule. Poly which means many, and mer which means unit.
“The polymers which degrade by the enzymatic action of naturally occurring microorganism and
bacteria” are called Biodegradable polymers.
Oxygen, water, heat and sunlight can also cause degradation of the polymers apart from enzymes
and microbes.
(i) The degradation of the polymers may be due to breaking of chemical bonds (or)
(ii) Rearrangement of chemical bonds.

Properties of Biodegradable polymers

1. Until degraded, biodegradable polymers can retain good mechanical integrity.
2. Since biodegradable polymers have extremely strong carbon backbones that are difficult to crack.
Degradation usually begins at the end-groups.
3. Biodegradable polymers should produce non-toxic materials.
4. The degradation rates of biodegradable polymers can be regulated.
5. Biodegradable polymers are hydrophilic (attracts water).
Biodegradable polymers are of two types, i.e., Natural Biodegradable Polymers and Synthetic
Biodegradable Polymers.

110
The following are the factors controlling the rate of degradation.
Naturally occurring biodegradable polymers. These natural polymers are beautiful for environment
degradation. The rate of degradation and the formation of metabolite depends on the structural
complexity of material and the environment conditions related for degradation.
The biodegradable polymers which are found in nature called as Natural biodegradable polymers.
These are generally nontoxic and easily available. Naturally biodegradable polymers are four types.
(a) Polysaccharides: Ex. Starch and Cellulose
(b) Proteins: Ex. Gelatin, Fibrin, Silk and Wool
(c) Polyesters: Ex: Polyhydroxyalkanoates
(d) Others: Ex. natural Rubbers and Lignin.

The biodegradable polymers which are preparing in laboratory or man-made called Synthetic
biodegradable polymers. Synthetic biodegradable polymers have been developed in order to dispose
them similar to that of naturally occurring polymers.
The common examples of synthetic biodegradable polymers are given bellow.
(i) Poly Glycolic acid (PGA), (ii) Polylactic acid (PLA), (iii) Polyhydroxybutyrate (PHB)
(iv) Polyhydroxy butyrate-co-β-hydroxy valerate (PHBV) and (v) Polycaprolactone (PCL).

i) Polyglycolic acid (PGA): PGA polymer can be obtained by the self-condensation of Glycolic acid.

O O
Condensation
n HO CH2 C OH O CH2 C
Heat n
Glycolic acid Polyglycolic acid
ii) Polylactic acid (PLA): PLA polymer can be obtained by the self-condensation of Lactic acid.

O O
Condensation
n HO CH C OH O CH C
n
CH3 CH3
Lactic acid Polylactic acid
iii) Polyhydroxy butyrate (PHB): PHB polymer can be obtained by the self-condensation of 3-
hydroxybutanoic acid.

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 O Condensation O
n HO CH CH2 C OH O CH CH2 C
CH3 CH3 n

3-Hydroxybutanoic acid PHB

iv) Polyhydroxybutyrate-co-β-hydroxyvalerate (PHBV): PHBV is a copolymer formed by
reaction between two different monomers. The condensation of 3-hydroxybutanoic acid and 3-
hydroxypentanoic acid produce PBHV polymer. In this polymer, the monomer units are joined by
alternate linkages.

O O
HO CH CH2 C OH + HO CH CH2 C OH
CH3 CH2
3-Hydroxybutanoic acid CH3 3-Hydroxypentanoic acid
Condensation

O O
O CH CH2 C O CH CH2 C
CH3 CH2 n
PHBV CH3

The properties of PHBV depend on the ratio of both the monomers involved in polymerization.
Presence of excess of 3-hydroxybutanoic acid provides stiffness and the presence of excess of 3-
hydroxypentanoic acid provides flexibility.

v) Polycaprolactone (PCL): PCL polymer can be obtained by the condensation polymerization of

caprolactone (6-hydroxy hexanoic acid).

5 O O
Heat Catalyst
4 1 n HO (CH2)5 C OH O (CH2)5 C
n
3 2
Caprolactone 6-Hydroxyhexanoic acid Polycaprolactone (PCL)

112
APPLICATION OF BIODEGRADABLE POLYMERS
1) Medical applications
a) Surgical sutures: The biodegradable polymers are used as surgical implants in blood vessels for
controlled long term drug release and also used as absorbable surgical sutures for the treatment of
eyes.
b) Bone fixation devices: It is proved that biodegradable polymers like PGA and PLA are used as bone
fixation devices because they have better compatibility with bones and lignan compared to metal.
The other advantage is that sometimes the metal implants need to be removed while that is not the
case with biodegradable polymers. Removal of metal sometimes may cause bone weakness and
refractures. The biodegradable polymers when used for bone fixation allow free movement of
ligaments and bones.
c) Vascular graft: Gelatin is used as a vascular graft in the treatment of cardiovascular diseases.

2) Agriculture
a) Biodegradable polymers are useful in manufacture of plant bags, pots etc.
b) In horticulture for making threads, fertilizer bags and seed bags.
c) They used to prepare ropes and fishing nets.

3) Packaging
Biodegradable polymers are used to prepare bags, cups and bottles etc.

2. REFRACTORIES
Refractories are inorganic materials that can resist at high temperature, without softening or without
suffering a deformation in shape. Or any substance that is difficult to fuse is a refractory. A refractory
is a material which doesn’t melt easily because its fusion temperature is very high.
Refractories are widely used for providing high temperature resistant lining for furnace, rocket
nozzles and for domestic heating appliances.

Classification of Refractories
Refractories are classified into three types as follows. 1) Based on Fusion Temperature
2) Based on Chemical Composition & 3) Based on Oxide Content.

1) On the basis of Fusion Temperature

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a) Normal refractory: Refractories having fusion temperature of 1580 ⁰C – 1780 ⁰C are called as
normal refractory. Example: Fire clay refractory
b) High refractory: Refractories having fusion temperature of 1780 ⁰C – 2000 ⁰C are called as High
refractory. Example: Chromite refractory
c) Super refractory: Refractories having fusion temperature above 2000 ⁰C are called as super
refractory. Example: Zirconia refractory.

2) On the basis of Chemical Composition

a) Acidic refractories: Refractories consist of acidic materials like Alumina (Al2O3) and Silica (SiO2) are
called acidic refractories. They are not attacked or affected by acidic materials but are attacked by
basic materials. Example: Alumina, Silica and Fireclay.
b) Basic refractories: Refractories consist of basic materials like CaO or MgO are called basic
refractories. They are resistant to basic slags but are attacked by acidic slags.
Example: Magnesite and Dolomite bricks.
c) Neutral refractories: Refractories consist of weakly acidic or weakly basic materials are called
neutral refractories. They are chemically stable towards both acids and bases. Example: Graphite,
Zirconium and Silicon carbide (SiC) etc.

3) On the basis of Oxide Content

a) Single oxide refractories: Refractories having single oxide are called single oxide refractories.
Example: Alumina, Magnesia and Zirconia.
b) Mixed refractories: Refractories having mixed oxides are called mixed refractories. Example:
Chromite (FeO.Cr2O3).
c) Non-oxide refractories: Refractories are not having any oxides are called non-oxide refractories.
Example: Borides, carbides, nitrides etc.

Characteristics of refractory materials

A good refractory material should have the following characteristics
1) The softening temperature should be much higher than the operating temperature.
2) They should have high refractoriness.
3) They should have high Refractoriness Under Load (RUL)
4) They should have Low Thermal Spalling (getting cracks or removing upper layer)

114
5) They should have Low Permeability (the ability of a substance to allow gases or liquids to go
through it)
6) They should Not Crack at Operating Temperatures.
7) They should be chemically inert

PROPERTIES of REFRACTORIES
Refractories have the following properties
a) Refractoriness: The ability of a material to resist at high temperatures without appreciable
deformation or softening under given working conditions called refractoriness. It is usually expressed
in softening or fusion temperature of the material. Usually, as the temperature increases a material
softens and deforms but a refractory should resist such a tendency. Higher the softening temperature
more valuable is the refractory. So, a good refractory should possess high refractoriness.
b) Refractoriness Under Load (RUL): RUL is a measure of the resistance behaviour of a refractory body
to the combined effects of rising temperature and load.
Since reactants are changed into the refractory lined furnaces, the refractory should resist such heavy
loads at high temperatures.
Example: Fire clay refractories collapse at temperature below to their fusion temperature, when
appreciable load is applied. On the other hand, Silica refractories withstand of heavy load even at
high temperature. Hence, the RUL test is performed to know the safe upper temperature limit up to
which the refractory can be used.
c) Thermal spalling: High temperature and its fluctuations induces uneven expansion and contraction
of refractory material which ultimately leads to cracking and breaking of refractory bricks. This
phenomenon is called as thermal spalling.
The spalling resistance order for some of the refractories is
Silicon carbide > Fireclay bricks > Magnesite > Silica bricks
Thermal spalling can be minimized by
(i) Avoiding sudden fluctuations in temperature
(ii) Proper furnace design.
(iii) Proper selection of refractory material with high thermal conductivity and low coefficient of
thermal expansion.

115
 3. LUBRICANTS
A substance which reduces the friction when introduced between two surfaces is lubricant. The
phenomenon is known as lubrication.
Criteria of a good lubricant: Any substance which shows the process of lubrication must satisfy certain
functions as follows
• A lubricant is to reduce the friction.
• The lubricant should keep moving parts apart.
• It should transfer heat and acts as coolant
• It should reduce the wear and tear as well as surface deformation caused due to rubbing action
of a two sliding surfaces.
• It prevents rust and corrosion thereby reduces the maintenance and running cost of the machines.
• It acts as a seal
• It carries away contaminants, otherwise damage the surface of the machinery.
• It should also reduce the loss of energy in the form of heat.
• Lubricant minimizes the liberation of frictional heat, the expansion of metals can be reduced.

PROPERTIES OF LUBRICANTS
Mainly lubricant has three properties. 1) Viscosity, 2) Flash and Fire points & 3) Cloud and Pour points.
1) Viscosity: Viscosity is the property of a fluid that determines its resistance to flow. It is an indicator
of flow ability of a lubricating oil. Viscosity is two types.
a) Absolute viscosity: It is the indirect force per unit area required to maintain a ‘unit velocity
gradient’ between two parallel layers. Units in C.G.S. are ‘Poise’.
b) Kinetic viscosity: It is the ratio of absolute viscosity to the density for any fluid. Units in C.G.S. are
‘Stokes’.
Viscosity Index (VI): The variation of viscosity of a liquid with temperature is called viscosity index.
For every 1 ⁰C rise in the temperature viscosity index decreases by 2%. The mathematical expression
for viscosity index is

𝐿−𝑈
VI = X 100
𝐿−𝐻
Where, L = Viscosity of standard oil having a viscosity index of zero at 38 ⁰C. U = Viscosity of test oil
at 38 ⁰C, H = Viscosity of the standard oil having a VI of 100 at 38 ⁰C.
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Measurement of Viscosity
The instrument which is used for measuring viscosity is known as viscometer. The commonly used
viscometer is Redwood Viscometer. This consists of the following essential parts.
i) Oil cup: It is a Silver (Ag)-plated brass cylinder. The upper end of the cup is open. The bottom of
the cylinder is fitted with an agate jet. The jet is opened or closed by a “valve rod”, which is a
small silver-plated brass ball fixed to a short wire. A thermometer is fitted to the lid which gives
the oil temperature.
ii) Heating bath: Oil cup is surrounded by a water bath fitted with a thermometer and a stirrer. the
thermometer provides the temperature of the water.
iii) Stirrer: The stirrer has flour blades for stirring the water to maintain uniform temperature. The
stirrer also has a circular shield at the top to prevent any water splashing into the oil present in
cup.
iv) Levelling Screws: The entire apparatus rests on three legs provided at their bottom with levelling
screws.

Thermometers

Stirrer Shield

Pointer
Metallic Oil Cup
Stirrer blade
Water bath
Valve rod
Heating tube
Agate jet

Kohlrausch
flask
Levelling screws

Working: Initially the oil cup is cleaned and valve rod is placed on the agate jet to close it. Oil to be
tested is filled in the cup up to the pointer level. Kohlrausch flask is kept below the jet outlet to collect

117
the oil. Water is filled in the bath and side tube is heated slowly with constant stirring. At the desired
temperature heating is stopped and the valve from jet hole is lifted. The time taken to collect 50mL
oil in the Kohlrausch flask to be noted. Higher the time taken to flow, higher the viscosity of the oil.

2) Flash and Fire points

Flash point is the lowest temperature at which the lubricating oil gives enough vapours, when a test
flame brought near to it.
Fire point is the lowest temperature at which the vapours of the lubricating oil burn
continuously at least for 5 seconds, when a test flame brought near to it. Generally, fire point is 5 to
40 times higher than the flash point.
Measurement: Flash and Fire points are measured by “Pensky-Marten’s apparatus”.
Oil Cup: Pensky Marten’s apparatus consists of an oil cup made up of brass with 5.0 cm depth and
5.5 cm diameter. The lid of the cup has four openings for introducing thermometer, stirrer, test flame
and for passage of air.
Stirrer: The lid is provided with a stirrer having two blades.
Shutter: The shutter is provided at the top of the cup. By moving the shutter, the opening in the lid
opens and flame from the flame exposure device is dipped into this opening. After introducing the
test flame, the test flame returns back to its original position where it is lighted by a pilot burner.
Air bath: The oil cup is surrounded by an air-bath which is heated by a gas burner.

Working: The lubricating oil to be tested is filled into the oil cup up to the levelling mark and then
heated by a burner. Stirring is done with the help of stirrer and heat is applied so as to raise the oil
temperature of about 5⁰C per minute.

118
 At every 1⁰C rise of temperature, test flame is introduced at the opening with the help of
shutter for a moment. The temperature at which distinct vapours appear inside the cup is recorded
as the Flash point. The procedure is continued till the oil vapour catches fire and burns for five
seconds. That temperature is recorded as the Fire point.

3) Cloud point and Pour point

The temperature at which the lubricating oil becomes cloudy or hazy upon cooling is called cloud
point.
The temperature at which the oil ceases to flow or pour is called as pour point.
The cloud and pour points indicate the suitability of lubricants in cold conditions. The lubricant used
in machines should have low cloud and pour point than the operating conditions (means lower than
the operating temperature).
Determination of cloud point and Pour point: It is determined by cloud point and pour point
apparatus.

Thermometer

Flat bottomed test tube

Air-jacket
Jar
Oil

Cork Dish

Cooling Mixture
(Ice + Salt)

The apparatus consists of a flat-bottomed test tube kept in an air jacket. The jacket is surrounded by
freezing mixture (Ice + CaCl2) contained in a jar. The test tube is half filled with test oil. Two
thermometers are introduced in the oil and in the freezing mixture for noting temperature. As the
cooling proceeds slowly in jacket the temperature falls continuously with every degree fall of
temperature of the oil. The tube is withdrawn from air jacket for a moment to check and then
immersed immediately. The temperature at which cloudiness is noticed is recorded as a Cloud point.
119
After cloud point, the cooling is still continued the temperature at which oil doesn’t flow in the test
tube, even when kept horizontal for 5 sec is recorded as Pour point.

4. CERAMICS
Ceramics are inorganic non-metallic materials that are processed for use at high temperatures.
Example: Silica, Alumina, Fire clay, Glass etc.

Classification of Ceramics
1) Based on chemical composition
Oxides Ex: SiO2, Al2O3
Carbides Ex: SiC
Nitrides Ex: Si3N4
Sulphides Ex: Ag2S
2) Based on their applications
Clay products: Structural clay products (Tiles, Bricks etc)
White wares (Porcelain and China clay)
Chemical stone ware (Sanitary fixtures, Sinks, Bath tub).
Refractories: Fire clay, Dolomite, Zircon, Magnesia etc.
Glass: Insulated glass, Safety glass, Hard glass, Soft glass, Flint glass, Borosilicate glass or Pyrex glass,
Vitreosil etc.
Advanced ceramics: Glazed ceramics, Porcelain.

Properties of Ceramics
Ceramics possess the following properties.
Extreme hardness
High wear resistance
Corrosion resistance
Heat resistance
Low electrical conductivity
Low thermal conductivity
Low thermal expansion and contraction
Low ductility (Flexibility)
Low density

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 High strength at elevated temperature
Very brittle.

Applications of Ceramics
Consumer uses: Glassware, windows, tiles, lenses, microwave, home electronics, pottery, etc
Automotive: Catalytic converters, ceramic filters, sensors, ceramic rotors, pressure sensors, softly
glass etc.
Aerospace: Thermal barriers, high temperature glass windows, fuel cells, etc.
Medical: Orthopaedic devices, dental restoration and bone implants.
Computers: Insulators, resistors, capacitors, super conductors, ferroelectric components etc.
Industries: Bricks, cement, membranes, filters and lab equipment.
Communications: Fiber optic/laser, TV, Radio components and Microphones, etc.

Yours: Dr. Mallesham GODUMALA

All the very best

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