Chemistry-BTL-QB-with Solutions-2021

GURU NANAK INSTITUTIONS TECHNICAL CAMPUS
(Autonomous)
Question Bank with Blooms Taxonomy Level (BTL)
Academic Year : 2020-21

Subject Name with code : Chemistry,18BS0CH01
Class : B.Tech - 1styear
Name oftheFaculty : All Facultyembers
Blooms Taxonomy Levels (BTL)
1. Remembering
2. Understanding
3. Applying
4. Analyzing
5. Evaluating
6. Creating
Blooms CO’
Q.No s
Questions Taxono
my
Levels
Unit-1
PART-A
1 Give the reasons for crystal field splittingofd-orbital’s (Dec 2018 Level-4 CO1
[R18])
Crystal Field Theory is one of the most important theory for explaining nature of bonding in
coordination compounds.
1. CFT regards a complex as a combination of central metal ion surrounded byother
ions or neutral molecules which are calledligands.
2. The ionic ligands are regarded as pointcharges.
3. The bonding between metal cations and ligands are purely electrostatic innature.
4. The electrostatic attraction between the metal ion and ligands are due to theshared
pair ofelectrons.
5. The electrostatic field of approachingligands.
6. The interaction between the electrons, cation (central metal ion) and these of ligands
are entirelyrepulsive.
Theserepulsiveforcesthatareresponsibleforcausingthespillingofd-orbitalsofthe
metalcation.
2 Write the energy level diagram for N2 molecule (Dec 2018 [R18]) Level-3 CO1
3 What is the bond order for Li 2, N2, O2?(Dec 2018 SNIST [R18]) Level-1 CO1
Ans
Bond order for Li2 = 1
Bond order for N2 = 3
Bond order for O2 = 2
4 Define electro negativity and explain its variation along period.(Jan 2019 Level-1 CO1
CVR [R18])
Ans Electronegativity: The relative tendency of an atom in a molecule to attract a shared pair of
electrons towards itself is termed as Electronegativity.
The value of electronegativity of an element describes the ability of its atom to compete for
electronswiththeotheratomtowhichitisbonded.Electronegativityishowevernottheproperty of an
isolated atom. Electronegativity is measured on a number of scale levels, the most commonly
used are of Pauling orMullikan.
Variation along a period: As the nuclear charge increases from going left to right in a period
because the electrons enter the same shell, the shielding is less effective.
element Li Be B C N O F
electronegativity 1.0 1.5 2 2.5 3 3.5 4
5 What is the molecular geometry of Ni (CO)4 ? Explain..(Jan 2019 CVR Level-2 CO1
[R18])
Ans The molecular geometry of Ni (CO)4is Tetrahedral,
In [Ni(CO)4 ] , nickel is present in zero oxidation state {Ni = 3d8 4s2}.
CO is a very strong ligand, so it can pair the upaired electrons. Hence, the 4s electrons
goesto the 3 d orbital. Now, 3 d orbital is completely filled, but 4s and 4p are still available.
These 4 orbitals form a degenerate set of orbitals and hybridization is sp3
6 Sketch the shapes of S, P and d-orbital’s (Dec 2018 GNITC [R18]) Level-3 CO1
Ans S Orbital:
PORBITALS
dORBITALS
7 Why IP2 is greater than IP1? Give reasons?.(Jan 2019 CVR [R18]) Level-3 CO1
Ans IP2 is greater than IP1, because
The amount of energy required to remove the most loosely bound electron from an isolated
gaseous atom is called First ionization energy (IP1).
The amount of energy required to remove an electron from a unipositive ion is called Second
ionization energy (IP2).
8 Give II molecular orbitals of 1,3 – butadiene (Dec 2018 SNIST [R18]) Level-3 CO1
Ans
9 Give an account of LCAO. (Dec 2018 [R18]) Level-3 CO1

Ans Linear combination of Atomic orbitals (LCAO): A Molecular orbital (MO) is constructed by
combination of two Atomic orbitals (AO’s) and this method is known as Linear combination of
Atomic orbitals (LCAO).
1. Electrons may be considered either as particle or wave. An electrons in an atom may
therefore be described by a wave function (), which is a solution to Schrodinger wave
equation.
2. According to Molecular orbital Theory(MOT) the electrons in a molecule are said to
occupy Molecular orbitals(MO’s)
3. The wave function describing a Molecular orbitals (MO’s) may be obtained by the
method ofLCAO.
Let us consider, ψ(A) and ψ(B) are two atomic orbitals which are combining to form Molecular
orbitals (MO’s) for A-B bond.
molecular orbitals will also be wave functions and they can be represented as:
ψ(Mob) = ψ(A)+ ψ(B) ψ(Mob) = bonding molecular orbital wave function
ψ(Moab) = ψ(A) -ψ(B) ψ(Moab) = anti bonding molecular orbital wave
function
10 Explain the band structure of solids. (Jan 2019 CVR [R18], May/June Level-2 CO1
2019 [ R18]),OCT/NOV2020[R18]
Ans Bandstructureofsolids:Thisisthequantummechanicaltreatmentofthemetallicbondandissimilar to
molecular orbitals approach of covalent bond. A very large number of atoms in the order of 1023or more
are brought together so that their atomic orbitals undergo linear combination to form exactly same
number of molecularorbitals.
Theenergiesofthesemolecularorbitalsaresocloselyspacedthattheyappearstobea continuumknown as
quasi-continuous energy band. Hence it is known as band structure ofsolids.
11 What are the differences between atomic and molecular orbitals?(May Level-2 CO1
2019 [R18])OCT/NOV2020[R18])
Ans Atomic orbitals Molecular orbitals
1. Atomic orbitals are regions around the 1. Molecular orbitals are regions around
nucleus where electrons have a high molecules where electrons are most likely to
probability of beingfound. befound.
2. Orbitals allow the atom to be bound to 2. In addition to consisting of different shapes
other atoms to form molecules through and energy levels, there are also bonding
the sharing or exchanging of electrons in orbitals which make molecules more stable
higherorbitals. and anti-bonding orbitals which can make
3. Theyconsistofvariousenergylevelsand them less stable.
theorbitalscontainingthemost electrons 3. While atomic orbitals occur around a single
will depend on the amount of energy nucleus, molecular orbitals occur around a
absorbed by theatom. cluster of nuclei within amolecule.
4. They can be of different shapes which 4. Molecularorbitalscanmakeamoleculestable or
consist of multiple energylevels. unstable depending on how manyelectrons
5. Electrons of higher energy are inorbitals are in the bonding or anti-bondingorbitals.
farther from thenucleus.
6. Atomic orbitals have no effect on the
stability of anatom.
12 What do you understand by linear combination of atomic orbitals? (May Level-2
CO1
2019 [R18])
therefore be described by a wave function (), which is a solution to schrodinger wave
equation.
method ofLCAO.
orbitals (MO’s) for A-B bond.
ψ(Mob) = ψ(A)+ ψ(B) ψ(Mob) = bonding molecular orbital wavefunction
function
13 Give the molecular orbital Energy level diagrams of O2 (May/June 2019 [ Level-3 CO1
R18]),OCT/NOVJNTUH2020[R18]
Ans
14 How effective nuclear charge is expressed? Effective nuclear charge Level-3 CO1
increases down the group. Justify?(Dec/Jan 2020 GNITC [R18])
Ans The effective nuclear charge (often symbolized as Zeff or Z*) is the net
positive charge experienced by an electron in a multi-electron atom. The term “effective”
is used because the shielding effect of negatively charged electrons prevents higher orbital
electrons from experiencing the full nuclear charge.
Important factors:-The effective nuclear charge, Zeff, increases down a group which
draws electrons closer towards the nucleus, decreasing atomic radius.
The principal quantum number, n, of electron orbitals that increases down a group and due
to the quantum mechanical nature of electrons, the radius of these electron orbitals
increases with increasing n, thus increasing in size as you go down the group
15 What is meant by bond order? What is the bond order for N2 (Dec/Jan Level-1 CO1
2020 GNITC [R18]),(Jan 2020 SNIST [R18])
Ans Bond order (BO): BO is defined as half of the difference between the number of
electrons present in the bonding and the anti bonding orbitals.
Bond order (BO) = ½ [Number of bonding orbital electrons - Number of anti-bonding
orbital electrons]
Bond order (BO) ) for N2 = ½ [10-4]=3
16 what are atomic and molecular orbitals? (Dec/Jan 2020[R18]),(Jan2020 Level-1 CO1
AGI[R18])
Ans Atomicorbitals:-Atomicorbitalsareregionsaroundthenucleuswhereelectronshaveahighprobability of
being found.
Molecularorbitals;-Molecularorbitalsareregionsaroundmolecules whereelectronsaremostlikelyto
befound.
17 Explain insulators on the basis of band theory (Dec/Jan 2020[R18]) Level-2 CO1
Ans An important parameter in the band theory is the Fermi level, the top of the available electronenergy
levelsatlowtemperatures.Thepositionof theFermilevelwiththerelationtotheconductionbandis
a crucial factor in determining electrical properties.
If the large energy difference is there between conduction band and valance band called as
insulators.
18 What do you understand by HOMO and LUMO draw HOMO of 1,3 Level-1 CO1
butadiene. (Jan2020 AGI[R18])
Ans HOMO and LUMO are the orbitals most likely to be involved in chemical reactivity.
Chemical reactions involve the redistribution of electrons (creation and destruction of bonds,
oxidation, reduction, …)
The HOMO is the orbital of highest energy that is still occupied, so energetically it is the
easiest to remove electrons from this orbital. This could be simply donating electron density
to form a bond (act as a Lewis base) or it could be oxidation.
The LUMO is the lowest lying orbital that is empty, so energetically it is the easiest to add
more electrons into this orbital…Lewis acid; reduction.
PART-B
1 Explain about Crystal field theory (CFT)? (Dec 2018[R18]),(Dec
Level-2 CO1
2018 SNIST [R18]),OCT/NOV2020GNITC[R18]
Ans Crystal Field Theory is one of the most important theory for explaining nature of
bonding in coordination compounds.
 It deals with electrostatic interactions between metal ion and the ligands forming
complexeswithvaryinggeometrieslikeoctahedral,tetrahedral, squareplanaretc.
 According to this theory, the donor electrons of the incoming ligands due totheir
negative charges attract the positively charged metalion.
 Besides this, there is repulsive interaction between d electrons present on the metal
ion and theligands.
Salient features of CFT:
1. Crystal field theory has been developed by Bethe andVleck.
2. CFT regards a complex as a combination of central metal ion surrounded by otherions
or neutral molecules which are calledligands.
pair ofelectrons.
8. Theserepulsiveforcesthatareresponsibleforcausingthespillingofd-orbitalsofthe
metalcation.
9. The bond between the metal and the surrounding ligands are purelyionic.
10. If the ligand approaching more towards metal ion, the splitting of d-orbitals more.
2 Mention the difference between atomic and molecular orbitals? (Dec CO1
Level-4
2018 [R18],(May/June 2019 [ R18]),OCT/NOV2020GNITC[R18])
Ans Atomic orbitals Molecular orbitals

7. Atomic orbitals are regions around the 5. Molecular orbitals are regions around molecules
nucleus where electrons have a high wher electrons are most likely to befound.
probability of beingfound. 6. In addition to consisting of different shapes and energ
8. Orbitals allow the atom to be bound to levels, there are also bonding orbitals which mak
other atoms to form molecules through molecules more stable and anti-bonding orbitals whic
the sharing or exchanging of electrons in can make them lessstable.
higherorbitals. 7. While atomic orbitals occur around a single nucleus
9. Theyconsistofvariousenergylevelsand molecular orbitals occur around a cluster of nucle
theorbitalscontainingthemost electrons within amolecule.
will depend on the amount of energy 8. Molecular orbitals can make a molecule stable o
absorbed by theatom. unstable depending on how many electrons are in th
10. They can be of different shapes bonding or anti-bondingorbitals.
which consist of multiple energylevels.
11. Electrons of higher energy are in
orbitals farther from thenucleus.
12. Atomicorbitalshavenoeffectonthe
stability of anatom.
3 Write a note on molecular orbital theory? OrWhat is LCAO? Explain (Dec CO1
Level-3
2018 [R18], May/June
2019 [ R18]),(Jan 2020 SNIST [R18]), (Aug 2019 SNIST
[R18]),OOCT/NOV2020[R18])
Ans
IntheVBT,theindividualityofatomicpropertiesoftheconstitutingatomsformingamolecule is
retained too some extent. Whereas, in the molecular orbital theory it is considered that
molecularorbitalsareformedbythelinearcombinationofthetwoconstitutingatomicorbitals wave
functions.
A Molecular orbital (MO) is constructed by combination of two Atomic orbitals (AO’s) and
this method is known as Linear combination of Atomic orbitals (LCAO).
Linear combination of Atomic orbitals (LCAO):
therefore be described by a wave function(), which is a solution to schrodinger
wave equation.
method ofLCAO.
Letusconsider,ψ(A)andψ(B)aretwoatomicorbitalswhicharecombiningtoformMolecular
orbitals (MO’s) for A-Bbond.
ψ(Mob) = ψ(A)+ψ(B) ψ(Mob) = bonding molecular orbital wave function
ψ(Moab) = ψ(A)-ψ(B) ψ(Moab) = anti bonding molecular orbital wave functionThe
MOT given by R. S. Mullican and F. Hund incorporates the followingpoints
1. When nuclei of two atoms comes close to each other, their Atomic orbitals (AO’s)
interacts, to form Molecular orbitals (MO’s) in which the identity of both the atomic
orbitals islost.
2. The number of Molecular orbitals (MO’s) is equal to the number of Atomicorbitals
(AO’s) involved in their formation.
3. Just as Atomic orbitals in an atom are quantized, similarly Molecular orbitals(MO’s)
are also believed to bequantized.
4. The electrons in the Atomic orbitals (AO’s) are influenced by one nucleus,
the electrons in the Molecular orbitals (MO’s) are influenced by all thenuclei.
5. Electrons are filled in the Molecular orbitals (MO’s) in the same way as they are filled
in Atomic orbitals (AO’s), following Aufbau principle, Hund’s rule of maximum
multiplicity.
6. The Molecular orbitals are represented by ϭ, ϭ*, ∏,∏*etc.
Bonding Molecular orbitals: Theyare formed by the additive effect of the Atomic
orbitals (AO’s). ψ(Mob) = ψ(A) + ψ(B) ψ(Mob) = bonding molecular orbital

wave function
It increases the electron density between the nuclei. These orbitals have lower energy than the
Atomic orbitals (AO’s) from which they are formed.
Bonding Molecular orbitals stabilizes the molecule, these are represented by ϭ, ∏ etc.
Anti-Bonding Molecular orbitals: They are formed by the substractive effect of the Atomic
orbitals (AO’s).
ψ(Moab) = ψ(A) - ψ(B) ψ(Moab) = anti bonding molecular orbital wave function
It decreases the electron density between the nuclei. These orbitals have higher energy than
theAtomic orbitals (AO’s) from which they are formed.
Anti-Bonding Molecular orbitals destabilizes the molecule, these are represented by
ϭ*, ∏* etc. The order of energy of Molecular orbitals (MO’s) has been determined
from spectroscopic data. The energy generally increases in the following order as we
move from left to right.
Ϭ1s Ϭ*1s Ϭ2s Ϭ*2s Ϭ2pz ∏2px = ∏2py ∏*2px = ∏*2pyϬ*2pz
In the case of homo nuclear diatomic molecules of second row element of the periodic
table up to N2, the Ϭ2pz orbitals are higher energy than the ∏2px = ∏2py Molecular
orbitals. For these atoms the order is:
Ϭ1s Ϭ*1s Ϭ2s Ϭ*2s ∏2px=∏2py Ϭ2pz ∏*2px=∏*2py Ϭ*2pz
Filling of electrons in Molecular orbitals in MOT: For simple homo atomic molecules,
the filling of electrons are carried out in a similar fashion as in atomic orbitals.
Following rules are followed:
1. Aufbau principle: the orbitals with lowest energy is to be filled first of all. i.e.,
electrons enter various molecular orbitals in the order of their increasingenergies.
2. Pauli Exclusion Principle: the maximum number of electrons in a
molecular orbitals cannot exceed two and these should have oppositespins.
3. Hund’s rule: pairing of electrons takes place only when each molecular orbitals
of the same energy has at least one electroneach.
4. A bond between two atoms is said to be found when the total number of
electrons in bonding orbitals is greater than the number of anti bondingorbitals.
5. Bond order (BO): BO is defined as half of the difference between the numberof
electrons present in the bonding and the anti bondingorbitals.
Bond order (BO) = ½ [Number of bonding orbital electrons - Number of anti-
bonding orbital electrons]
4 Explain the crystal field splitting of d- orbitals by the ligands in

octahedral complex with coordinationnumber 6. (Dec 2018 Level-2 CO1
SNIST [R18], May/June 2019 [ R18]), (Jan 2019SNIST [R18])
Ans
Crystal Field Theory is one of the most important theory for explaining nature of bonding
in coordination compounds.

pair ofelectrons.
metalcation.
10. If the ligand approaching more towards metal ion, the splitting of d-orbitalsmore.
Crystal field splitting in octahedralcomplexes:

In an octahedralcomplex,
 Theligandsapproachthecentralmetalatomalongtheaxis,asresulttheaxialorbitals
(dz2anddx2-y2)experiencegreaterrepulsionthannon-axial(dx,dyanddz)orbitals.
 The degenerate d-orbitals split into two degenerate sets, one set consists of lower
energy and more stable dx, dyz and dzx orbitals (t2g orbitals) and the other less
stable higher energy dz2and dx2-y2 (eg)orbitals.
 This splitting of degenerate orbitals under the influence of ligands is termed as
crystal field splitting and the energy separation between them is denoted by “o”
where “o” stands foroctahedral.
 Theenergyoft2gorbitalsisdecreasedby0.4oor4Dqandtheenergyofegorbitals rises
by 06 o or 6 Dq above the hypothetical degenerated-orbitals.
 Thecrystalfieldsplittingenergyodependsonthefieldproducedbytheligandand the
charge on the metalion.
5 What is the role of doping in band structure.(Dec 2018 SNIST CO1
Level-4
[R18]),(June 2019 SNIST [R18]),
Ans
Effect of doping on conductance:
Doping is nothing but adding N or P type impurities to a pure semiconductor. So these impurities will
contain electrons or holes based on their impurity. When these kind of doping takes place in
semiconductorsandvoltageisapplied,theseelectronswillconductelectricity.Incaseofholes,electrons due
to potential excitation jump from their original positions to these holes and form immobile ions at that
point, whereas equal amount of holes are created from where these electrons jumped. Thus
conductivity increases due todoping.
Doping means the introduction of impurities into a semiconductor crystal to the defined modification
of conductivity. Two of the most important materials silicon can be doped with, are boron (3 valence
electrons = 3- valent) and phosphorus (5 valence electrons = 5-valent). Other materials are aluminum,
indium (3-valent) and arsenic, antimony (5-valent).
The dopant is integrated into the lattice structure of the semiconductor crystal, the number of outer
electrons define the type of doping. Elements with 3 valence electrons are used for p-type doping, 5-
valued elements for n-doping. The conductivity of a deliberately contaminated silicon crystal can be
increased by a factor of 106.
Doped semiconductors are electrically neutral. The terms n- and p-type doped do only refer to the
majoritychargecarriers.Eachpositiveor negativechargecarrierbelongstoafixednegativeorpositive
chargeddopant.
N- and p-doped semiconductors behave approximately equal in relation to the current flow. With
increasingamountofdopants,thenumberofchargecarriersincreasesinthesemiconductorcrystal.Here it
requires only a very small amount of dopants. Weakly doped silicon crystals contain only 1 impurity
per 1,000,000,000 silicon atoms, high doped semiconductors for example contain 1 foreign atom per
1,000 siliconatoms.
Bytheintroductionofadopantwithfiveouterelectrons,inn-dopedsemiconductorsthereisanelectron in the
crystal which is not bound and therefore can be moved with relatively little energy intothe
conduction band. Thus in n-doped semiconductors the donator energy level is close to the conduction
band edge, the band gap to overcome is very small.
Analog, through introduction of a 3-valent dopant in a semiconductor, a hole is available, which may
be already occupied at low-energy by an electron from the valence band of the silicon. For p-doped
semiconductors the acceptor energy level is close the valence band.
Whenweaddimpuritiestosemiconductorswecallthemdopantsandtheprocessiscalleddoping.The result is
a dilute (100 -1000 ppm) substitutional solidsolution.
Band model of doped semiconductors
6 Discuss the variation of atomic size and Ionization potential along a CO1
Level-2
period and group in the periodic table. (Jan 2019 CVR [R18 ]
Ans Atomic size: In homo-nuclear diatomic molecules the distance from the centre of one nucleus
to the centre of another nucleus gives the bond length and half of this bond length is atomic
radius.
An ion is formed when an atom undergoes a loss or gain of
electrons.M(g) M+ (g) + e– (cationformation)
M (g)+e– M– (g) (anionformation)
Acationisformedwhenanatomlosesthemostlooselyboundelectronfromits
outermost shell. The atom acquires a positive charge and becomes an ion (a
cation).
A cation is smaller than its atom.
On the removal of an electron, the positive charge of the nucleus acts on lesser number of
electrons than in the neutral atom and thus greater pull is exerted by the nucleus, resulting in a
smaller size of the cation.
An anion is bigger than its atom because on receipt of an electron in the outermost orbit the
numberof negativechargesincreaseanditoutweighsthepositivecharges,thustheholdofthe
nucleusontheshellsdecreaseresulting inanincreaseinthe sizeoftheanion.
A cation is always smaller than its atom and an anion is always bigger than its atom e.g.
Na+ is smaller than Na, Cl- is bigger thanCl.
The Radius of Sodium in Its Three Known Oxidation

States
Na+ Na0 Na−

Type Cation (+1) Atom (0) Anio
n (-1)
Electron 1s22s22p6 1s22s22p63s 1s22s

Configuration 1 22p6
3s2
Radius (pm) 102 154 202
Ionization Energy/ Ionization Potential: The amount of energy required to remove the most
loosely bound electron from an isolated gaseous atom is called ionization energy (IE).
Ionization energy (IE) is also called as ionization potential (IP) because it is measured as the
minimum potential required to remove the most loosely held electron from the rest of the
atom.
IE or IP units: electron volts (eV) per atom or kilo joules per mole of atoms
(kJ mol-1). 1 eV per atom = 96.64 kJ mol-1 = 23.05 k cal mol-1
Factors affecting Ionization Energy:

1. Size of theatom
2. Charge on thenucleus
3. Screeningeffect
4. Electronic arrangement
In period: The ionization energy increases with increasing atomic number in a period.
element Li Be B C N O F Ne
Ionization energy 520 899 801 1056 1402 1314 1651 2050
In group: The ionization energy gradually decreases in moving from top to bottom in a
group.
element Li Na K Rb Cs
Ionization energy 520 496 419 403 376
7 Draw the energy level diagram of N2 molecule and find its bond CO1
order? (Jan 2019 CVR [R18 ]),OCY/NOV2020GNITC[R18]) Level-3
Ans

orbital electrons]
Bond order (BO) ) = ½ [10-4]=3

8 Explain the band structure of solids with their conducting behavior C
Level-2
(Jan 2019 CVR [R18 ]),NOV2020JNTUH[R18]. O
1
Ans Band structure of solids: This is the quantum mechanical treatment of the metallic bond and is
similar to molecular orbitals approach of covalent bond. A very large number of atoms in the order of
1023or more are brought together so that their atomic orbitals undergo linear combination to form
exactly same number of molecular orbitals.
The energies of these molecular orbitals are so closely spaced that they appears to be a continuum known
as quasi-continuous energy band. Hence it is known as band structure of solids.
9 Explain the salient features of CFT? May/June 2019 [ R18]) Level-2 CO1
Ans Crystal Field Theory is one of the most important theory for explaining nature of bonding
in coordination compounds.
pair ofelectrons.
metalcation.
10 Give the crystal field splitting of d orbitals in tetrahedral CO1
geometry(May/June Level-2
2019 [ R18]),(June 2019 SNIST[R18])
Ans Crystal field splitting in Tetrahedral Complexes:
 Aregulartetrahedralgeometryisobtainedwhenametalcationoratomisplaced the
centre of a cube and 4 ligands occupy the alternate corners of thecube.
 The x, y and z axes are passed through the centre of the faces of thecube.
 None of the ligands approaches directly any of the metald-orbitals.
 Instead they all approach to some degree in between the metald-orbitals.
 The crystal field splitting in tetrahedral complex is denoted by “t”, where “t”
stands fortetrahedral.
 Thedxy,dyzanddzxorbitalsofmetalcation,experiencemorerepulsionfromthe
ligandsandareofhigherenergythanthose ofthedx2-y2anddz2orbitals.
 The dxy, dyz and dzx orbitals (“t2” set orbitals) are 0.4 t above the bary-centre
andthedx2-y2anddz2(“e”set)orbitalsare0.6tbelowthebary-centre.Therefore
theenergyoft2orbitalisraised and“e”set orbitalsisloweredfromthecenter.The “g”
subscript this not used with “t2” and “e” sets because the tetrahedral complexes
have no inversioncentre.
 It has been observed that the energy separation between “e” and “t2” orbitals in
tetrahedral complexes is smaller than in octahedral complexes, because d-
orbitals are not directly under the influence of the ligand and the number of
ligands is smaller.
The crystal field splitting in tetrahedral complexes is shown as
11 Draw the molecular orbital diagram O2 molecule and predict the magnetic
Level-3 CO1
behavior of it? (May 2019 [ R18]),(Jan 2020 AGI[18])
Ans
∏*2px = ∏*2py molecular orbitals contains single electrons So, it is paramagnetic in nature.
12 Discuss the salient features of crystal field theory and explain the crystal
field splitting of transition metal ion d-orbitals in square planar Level-2 CO1
geometries.(May 2019 [ R18]),(Aug 2019 SNIST [R18])
Ans Salient features of CFT:
pair ofelectrons.
metalcation.
Square planar complex:
In a square planar complex, there are four ligands around the
metal ion. The electrons of ligands are only attracted to xy-
plane.
Any orbital in the xy-plane has a higher energy level.
So,thedx2-y2anddxyorbitalsenergywillbeincreasesanddz2&dzxorbitalenergywillbe
decreases. Thus in square planar geometry, the order of energy of differentd-orbitals
Dyz = dzx < dz2 < dxy < dx2-y2
interact with two ligands in the sp complex while in octahedral complexes the interactions
takes placewith
13 Explain the band structure of solids. Discuss how the dopping influence CO1
Level-2
the conductance of them. (May 2019 [ R18])
Effect of doping on conductance:
Doping is nothing but adding N or P type impurities to a pure semiconductor. So these impurities will
contain electrons or holes based on their impurity. When these kind of doping takes place in
semiconductorsandvoltageisapplied,theseelectronswillconductelectricity.Incaseofholes,electrons due
to potential excitation jump from their original positions to these holes and form immobile ions at that
point, whereas equal amount of holes are created from where these electrons jumped. Thus
conductivity increases due todoping.
Doping means the introduction of impurities into a semiconductor crystal to the defined modification
of conductivity. Two of the most important materials silicon can be doped with, are boron (3 valence
electrons = 3- valent) and phosphorus (5 valence electrons = 5-valent). Other materials are aluminum,
indium (3-valent) and arsenic, antimony (5-valent).
The dopant is integrated into the lattice structure of the semiconductor crystal, the number of outer
electrons define the type of doping. Elements with 3 valence electrons are used for p-type doping, 5-
valued elements for n-doping. The conductivity of a deliberately contaminated silicon crystal can be
increased by a factor of 106.
Doped semiconductors are electrically neutral. The terms n- and p-type doped do only refer to the
majoritychargecarriers.Eachpositiveor negativechargecarrierbelongstoafixednegative orpositive
chargeddopant.
N- and p-doped semiconductors behave approximately equal in relation to the current flow. With
increasingamountofdopants,thenumberofchargecarriersincreasesinthesemiconductorcrystal.Here it
requires only a very small amount of dopants. Weakly doped silicon crystals contain only 1 impurity
per 1,000,000,000 silicon atoms, high doped semiconductors for example contain 1 foreign atom per
1,000 siliconatoms.
Bytheintroductionofadopantwithfiveouterelectrons,inn-dopedsemiconductorsthereisanelectron in the
crystal which is not bound and therefore can be moved with relatively little energy into the conduction
band. Thus in n-doped semiconductors the donator energy level is close to the conduction bandedge,
thebandgaptoovercomeisverysmall.
Analog, through introduction of a 3-valent dopant in a semiconductor, a hole is available, which may
be already occupied at low-energy by an electron from the valence band of the silicon. For p-doped
semiconductors the acceptor energy level is close the valence band.
Whenweaddimpuritiestosemiconductorswecallthemdopantsandtheprocessiscalleddoping.The result is
a dilute (100 -1000 ppm) substitutional solidsolution.
Band model of doped semiconductors
14 Draw neatly, the molecular orbital diagrams of Butadiene and C
Level-3
Benzene.(May 2019 [ R18]),(Jan 2020 AGI[18]) O
1
Ans
15 Explain the bond order in N2. (May/June 2019 [ R18]) .Level-2 CO1
Ans Bond order (BO) = ½ [Number of bonding orbital electrons - Number of anti-bonding
orbital electrons]
Bond order (BO) ) = ½ [10-4]=3, Triple bond is present in between two nitrogen atoms
16 What is LCAO? Explain (Dec/Jan 2020 GNITC [R18]) .Level-2 CO1
therefore be described by a wave function (), which is a solution to Schrodinger wave
equation.
6. ThewavefunctiondescribingaMolecularorbitals(MO’s)maybeobtainedbythemethod
ofLCAO.
orbitals (MO’s) for A-Bbond.
ψ(Mob) = ψ(A)+ ψ(B) ψ(Mob) = bonding molecular orbital wavefunction
function
17 Explain about conductors and insulators on the basis of band theory
.Level-2 CO1
(Dec/Jan 2020 GNITC [R18])
Themolecularorbitalsformedaredelocalized,i.e.,belongtothecrystalas awhole.Thebandgap/fermi level is
shown infigure:
18 Give the salient features of CFT. What are its applications (Dec/Jan 2020
.Level-2 CO1
GNITC [R18])

pair ofelectrons.
metalcation.
Applications :Crystal Field Theory is one of the most important theory for explaining nature
of bonding in coordination compounds.
CFT qualitatively describes the strength of the metal-ligand bonds. Based on the strength of
the metal-ligand bonds, the energy of the system is altered.
19 Write an account on π molecular orbitals of butadiene (Dec/Jan 2020

Level-3 CO1
GNITC [R18])
Pi – molecular orbitals of Butadiene:

The structure of 1,2-Butadiene consists of two conjugated double bonds. The structure has
four sp2 hybridized C atoms. Each atom contributes a p atomic orbital consisting of one
electron.
molecular orbitals for which we need to make an in-phase and an out-of-phase combination
20 Explain molecular energy level diagram of N2 molecules (Dec/Jan
Level-3 CO1
2020[R18])

orbital electrons]
Bond order (BO) ) = ½ [10-4]=3, Triple bond is present in between two nitrogen atoms
21 Explain the π molecular orbitals of butadiene (Dec/Jan 2020[R18]), (Jan Level-3 CO1
2019 SNIST [R18])
A Pi – molecular orbitals of Butadiene:

ns
The structure of 1,2-Butadiene consists of two conjugated double bonds. The structure has
four sp2 hybridized C atoms. Each atom contributes a p atomic orbital consisting of one
electron.
molecular orbitals for which we need to make an in-phase and an out-of-phase combination
22 Discuss the Crystal field splitting of d orbitals in octahedral and
Level-2 CO1
tetrahedral fields (Dec/Jan 2020[R18])
Crystal field splitting in octahedralcomplexes:

In an octahedralcomplex,
 Theligandsapproachthecentralmetalatomalongtheaxis,asresulttheaxialorbitals
(dz2anddx2-y2)experiencegreaterrepulsionthannon-axial(dx,dyanddz)orbitals.
 The degenerate d-orbitals split into two degenerate sets, one set consists of lower
energy and more stable dx, dyz and dzx orbitals (t2g orbitals) and the other less
stable higher energy dz2and dx2-y2 (eg)orbitals.
 This splitting of degenerate orbitals under the influence of ligands is termed as
crystal field splitting and the energy separation between them is denoted by “o”
where “o” stands foroctahedral.
 Theenergyoft2gorbitalsisdecreasedby0.4oor4Dqandtheenergyofegorbitals rises
by 06 o or 6 Dq above the hypothetical degenerated-orbitals.
 Thecrystalfieldsplittingenergyodependsonthefieldproducedbytheligandand the
charge on the metalion.
The crystal field splitting in octahedral complexes is shown as:
 Ligands that produce strong field and causes large splitting are known as strong field
ligands.
 Ligands that produce weak field and causes small degree of splitting are knownas
weak field ligands.
 Themagnitudeofoandthedistributionofelectronsinthed-orbitalsislargely
influenced by the ligand fieldstrength.
Crystal field splitting in Tetrahedral Complexes:
 Aregulartetrahedralgeometryisobtainedwhenametalcationoratomisplaced the
centre of a cube and 4 ligands occupy the alternate corners of thecube.
 The x, y and z axes are passed through the centre of the faces of thecube.
 None of the ligands approaches directly any of the metald-orbitals.
 Instead they all approach to some degree in between the metald-orbitals.
 The crystal field splitting in tetrahedral complex is denoted by “t”, where “t”
stands fortetrahedral.
 The dxy, dyz and dzx orbitals of metal cation, experience more repulsion from the
ligandsandare ofhigherenergythanthoseofthedx2-y2anddz2orbitals.
 Thedxy,dyzanddzxorbitals(“t2”setorbitals)are0.4tabovethebary-centreand the
dx2- y and dz (“e” set) orbitals are 0.6 t below the bary-centre. Therefore the
2 2
energyoft2orbitalisraisedand“e”setorbitalsis lowered fromthe center.The “g”

subscriptthisnotusedwith“t2”and“e”setsbecausethetetrahedralcomplexeshave no
inversioncentre.
 It has been observed that the energy separation between “e” and “t2” orbitals in
tetrahedral complexes is smaller than in octahedral complexes, because d-orbitals
are not directly under the influence of the ligand and the number of ligands is
smaller.
The crystal field splitting in tetrahedral complexes is shown as

Blooms CO’s
Q.No
Questions Taxono
my
Levels
Unit-2
PART–A
1 Why do you express hardness of water in CaCO3 equivalence? (Dec 2018 Level-3 CO2
[R18])
Ans The concentration of hardness as well as non-hardness consisting ions is, usually,
expressed in terms of equivalents of CaCO3. The choice of CaCO3 in particular is due to
its molecular weight 100 (Equivalent weight =50) and moreover, it is the most insoluble
salt that can be precipitated in water treatment.
2 What is caustic embrittlement? How do you prevent it (Dec 2018 [R18], Level-1 CO2
May 2018 [R15], May 2018[ R13], May 2019 [ R16])
Ans Caustic embrittlement is a term used for the appearance of cracks inside the boiler particularly at those
places which are under stress such as riveted joints due to the high concentration of alkali leading to
the failure of the boiler. The cracks have appearance of brittle fracture hence the failure is called
caustic embrittlement.
The boiler feed water containing carbonates and bicarbonates of alkali metals,
sodium hydroxide and a small quantity of silica or sodium silicate is purified by lime soda process. During
the softening process by lime-soda process, free Na2CO3is usually present in small portion in the soft water
which decomposes to give sodium hydroxide and carbon dioxide at high pressure of theboilers.
Na2CO3 + H2O 2NaOH + CO2
1. The pH of the feed water should be carefully adjusted to8-9.

2. Byusingsodiumphosphateassofteningreagentinsteadofsodiumcarbonate.
3. By adding tannin or lignin to boiler water which blocks the hair cracks and pits
thatarepresentonthesurfaceoftheboilerplatethuspreventingtheinfiltrationof caustic sodasolution.
4. The addition of sodium sulphate to boiler water blocks the hair cracks and pits present on the
surface of the boiler plate, thereby preventing caustic soda infiltration intothem.
The sodium sulphate is added to boiler water so that the ratio
The sodium sulphate is added to boiler water so that the ratio [Na_2 SO_(4 ) concentration]/[NaOH
concentration]
4 Which salts are responsible for temporary and permanent hardness of Level-3 CO2
water.(Dec 2018 [R16]) ,(Jan 2020 SNIST [R18])
Ans Temporary Hardness/Carbonate hardness/Alkaline hardness
Temporary hardness is caused by the presence of dissolved
bicarbonateofcalciumandmagnesium.Thishardnesscanberemoved by boiling of water,
when bicarbonates are converted into insoluble carbonates.
Ca(HCO3)2 CaCO3↓ + H2O +CO2↑
Calcium bicarbonate
Mg (HCO3)2 MgCO3↓ + H2O +CO2↑
Magnesium bicarbonate
Permanent Hardness/Non-carbonate hardness/Non-alkaline hardness
Permanenthardnessiscausedbythedissolvedsaltsofcalciumand
magnesium, other than bicarbonates. They are chlorides, sulphates,
nitrates, etc. Unlike temporary hardness, permanent hardness cannot
be removed by boiling. Removal of this hardness requires certain
special chemical treatment methods.
5 What is hard water ?What are the salts that causes hardness to water?( May/June- Level-2 CO2
2017[R16], May 2019 [ R16])
Ans Hardnessinwateristhatcharacteristic,which“preventsthelathering of soap”. This is due
to the presence of soluble salts of calcium, magnesium and other heavy metals
inwater.
Hardwaterdoesnotgivelathereasilywithsoap,butproducesa
whitescumorprecipitatewithsoap.Thisisduetotheformationof insoluble soaps of
calcium and magnesium when the calcium and magnesium ions react withsoap.
 (Soaps are sodium and potassium salts of higher fatty acids such as oleic acid, palmitic acid and stearicacid).
2C17H35COONa + Ca+2 (C17H35COO)2Ca+ 2Na+
Sodiumstearate Precipitate
2C17H35COONa + Mg+2 (C17H35COO)2Mg+ 2Na+
6 How are the salts from sea water removed? (May/June2017[R16]) Level-3 CO2
Ans The process of removing common salt (sodium chloride) from the
waterisknownasdesalination.Thewatercontainingdissolvedsalts with a peculiar salty
taste is called brackishwater.
Reverse osmosis is the technique of removing salts from sea water. A pressure higher
than the osmotic pressure is applied on the solution, the solvent will flow from the
solution into the pure solvent through SPM. Since the flow of solvent is in the reverse
direction to that observed in the usual osmosis, the process is called reverse osmosis.
7 Differentiate hardwater and soft water? (Sep 2017 [R15]) Level-4 CO2
Ans Hardness of water
Hardnessinwateristhatcharacteristic,which“preventsthe
latheringofsoap”.Thisisduetothepresenceofsolublesaltsof
calcium, magnesium and other heavy metals inwater.
Hardwaterdoesnotgivelathereasilywithsoap,butproducesa
whitescumorprecipitatewithsoap.Thisisduetotheformationof insoluble
soaps of calcium and magnesium when the calcium and magnesium
ions react with soap.
 (Soaps are sodium and potassium salts of higher fatty acids such as oleic acid, palmitic acid and
stearicacid).
2C17H35COONa + Ca+2 (C17H35COO)2Ca+ 2Na+
2C17H35COONa + Mg+2 (C17H35COO)2 Mg + 2Na+
Therefore, soap can produce lather only after all the hardness
causingionsareprecipitatedasinsolublesoap.Henceitrequireslarge
quantity of soap to produce lather. Thus, water which does not
producelatherreadilywithsoapiscalledHardwater.Ontheother hand,
water which produces lather easily with soap is called Soft water.
8 What are the various units of hardness give the relationship between Level-4 CO2
them? (Dec 2016[R16])
Ans 1. Parts per million (ppm) is the parts of CaCO3 equivalent hardness per 106 parts of
water.
i.e. 1 ppm = 1 part of CaCO3 eq. hardness in 106 parts ofwater.
2. Milligrams per litre (mg/L) is the number of milligrams of CaCO3 equivalent hardness
present per litre of water.Thus,
1 mg/L = 1 mg of CaCO3 equivalent hardness per 1 litre of water.
But 1 litre of water weighs 1 Kg.
1Kg=1000g=1000×1000mg=106 mg.
3. Clarke’sdegree(oCl)isnumberofgrains(1/7000lb)/(65mg)of
CaCO3 equivalent hardness per gallon (10 lb)/(4.546 lit) of water.
4.
4. Degree French (oFr) is the parts of CaCO3equivalent hardness per 105 parts of
water.Thus,
1oFr = 1 part of CaCO3 hardness equivalent per 105 parts ofwater.
5. Milliequivalentperlitre(m.eq/L)isthenumberofmilliequivalents of hardness present per
litre.Thus,
1m.eq/L=1m.eq.ofCaCO3perlitreofwater.
1ppm= 1mg/L= 0.1oFr= 0.07oCl= 0.02m.eq./L 1oCl= 1.43oFr=
14.3ppm= 14.3mg/L= 0.286m.eq./L
9 Calgon Treatment prevents scale formation in Boilers. Give Level-2 CO2

reasons.(May 2016 [R15]),(June 2019 SNIST[R18])
Ans 1.Calgonconditioning:SodiumhexametaphosphateNa2[Na4(PO3)6]
or(NaPO3)6iscalledcalgon.Thisformssolublecomplexcompounds with CaSO4 which
causes no boilertroubles.
Na2[Na4(PO3)6] ⇌ 2 Na+ + [Na4P6O18]2-
Calgon
2 CaSO4+[Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4
Soluble complex ion
The treatment of boiler feed water with calgon is called calgon conditioning.
10 Write two balanced equations to describe when hard water is heated.(May 2016 Level-3 CO2
[R15])
Ans Ca(HCO3)2 CaCO3↓ + H2O +CO2↑
Calcium bicarbonate
11 Define temporary and permanent hardness of water.(May 2016 [R13]) Level-1 CO2
Temporary hardness is caused by the presence of dissolved
bicarbonateofcalciumandmagnesium.Thishardnesscanberemoved by boiling of water,
when bicarbonates are converted into insoluble carbonates.
Calcium bicarbonate
Permanent Hardness/Non-carbonate hardness/Non-alkaline hardness
Permanenthardnessiscausedbythedissolvedsaltsofcalciumand
magnesium, other than bicarbonates. They are chlorides, sulphates, nitrates, etc.
Unlike temporary hardness, permanent hardness cannot be removed by boiling.
Removal of this hardness requires certain special chemical treatment methods.
12 Discuss the disinfectations of water by chlorination.(May 2016 [R13]),(Jan 2020 Level-2 CO2
AGI[18])
Ans Chlorination:chlorineisthemostwidelyuseddisinfectantinmunicipal
water treatment. The high popularity of chlorine is due to the following reasons:
1. It is readily available either in the liquid or in the gaseous form.
2. It has powerful bactericidalproperty.
3. It does not introduce any impurities inwater.
4. It iseconomical.
Mechanism of chlorination: When chlorine is added to water, it produces two species,
namely, ionized hydrochloric acid and unionized hypochlorous acid at lower pH values of
6.5.
Cl2 + H2O HOCl + H+ + Cl- (pH6.5)
Hypochlorous acid is found to be a powerful bactericidal. Gleen and Stumpf, reported
that the death of pathogenic bacteria is due to the reaction of unionized hypochlorous
acid with the enzymes in the cells of the micro-organisms which are essential for their
metabolism.
At higher pH value of 8, hypochlorous acid undergoes appreciable ionization and exists
as hypochlorite ion (OCl-) and H+ ion.
Hypochlorite ion is a weak bactericidal because it cannot deactivate the enzymes in the
cells of the micro-organisms. Therefore, chlorine is a powerful disinfectant at lower pH
values.
HOCl ⇌ H+ + OCl-
Limitations:
1. High residual chlorine produces unpleasant taste andodour.
2. Excesschlorinepresentinwaterattacksmucousmembrane and
causesirritation.
ChlorineproducestoxiccompoundssuchasCHCl3,CCl4,etc.
byreactingwithorganicpollutantspresentinwater.Thelong term consumption of such
water may damage liver, kidney, etc.
13 What you understand by Reverse osmosis..(Oct 2016 [R13]) Level-2 CO2

Ans A pressure higher than the osmotic pressure is applied on the solution, the solvent will
flow from the solution into the pure solvent through SPM. Since the flow of solvent is
in the reverse direction to that observed in the usual osmosis, the process is called
reverse osmosis. Thus, in reverse osmosis method pure solvent, water is
separatedfromitscontaminantsratherthanremovingcontaminants
from the water. This membrane filtration is often called as “super- filtration” or “hyper-
filtration”.
Method: In the reverse osmosis process pressure of the order 15-40
Kg/cm2 is applied to the sea water or impure water to force its pure water out through
SPM, leaving behind the dissolved salts or solids both ionic as well as non-ionic.
The membrane consists of very thin films of cellulose acetate,
affixed to either side of a perforated tube. However, more recently superior
membranes made of polymethacrylate and polyamide polymers have come into use.
Advantages of reverse osmosis:

a. Process issimple.
b. Involves no phasechange.
c. Requires lowenergy.
d. It deals with the problem of removing colloidal silica which is not removed by
othermethod–demineralization.
Life time of SPM (cellulose acetate) is quite high, 2 years and can be
replacedwithinminutes,therebyprovidingnearlyuninterrupted water supply.
14 Explain the causes of caustic embrittlement in Boilers and suggest a Level-2 CO2
remedy? (Jun 2015 [R13])
the softening process by lime-soda process, free Na2CO3is usually present in small portion in the soft
water which decomposes to give sodium hydroxide and carbon dioxide at high pressure of theboilers.
3. Byaddingtanninorlignintoboilerwaterwhichblocksthehaircracksandpitsthat
arepresentonthesurfaceoftheboilerplatethuspreventingtheinfiltrationofcaustic sodasolution.
4. The addition of sodium sulphate to boiler water blocks the hair cracks and pits present on the surface
of the boiler plate, thereby preventing caustic soda infiltration intothem.
5. The sodium sulphate is added to boiler water so that theratio
The sodium sulphate is added to boiler water so that the ratio [Na2 SO4 ) concentration]/[NaOH
concentration]
15 What is the interrelation of units of hardness? (Jun 2015 [R13]) Level-4 CO2
Ans 1ppm= 1mg/L= 0.1oFr= 0.07oCl= 0.02m.eq./L
1 Cl= 1.43 Fr=
o o 14.3ppm= 14.3mg/L= 0.286m.eq./L
16 Write the specifications of portable water. (Jun 2015 [R13]),]),(Jan 2020 Level-3 CO2
SNIST [R18])
Ans Potable Water
The water which is safe for drinking is called Potable water. The
essentialrequirementsofsuchwaterwhicharerecommendedbythe US Public Healthare:
1. Water should be clear andodourless.
2. It should be pleasant totaste.
3. It should be perfectlycool.
4. Its turbidity should not exceed 10 NTU (National TurbidityUnits).
5. It should be free from objectionable minerals such as lead, arsenic, chromium and
manganesesalts.
6. It should be free from objectionable dissolved gases likeH2S.
7. pH should be in the range of 7.0 –8.5.
8. Total hardness should be less than500ppm.
9. Total dissolved solids should be less than500ppm.
0. It should be free from disease producing micro-organisms.
17 What is Calgon? Write the reaction involved in Calgon conditioning? Level-2 CO2
(May 2019 [R18])
Ans Calgon conditioning: Sodium hexa meta phosphate Na2[Na4(PO3)6]or
(NaPO3)6iscalledcalgon.Thisformssolublecomplexcompoundswith CaSO4 which
Na2[Na4(PO3)6] ⇌ 2 Na+ + [Na4P6O18]2-
Calgon
Soluble complex ion
18 What is the significance of breakpoint chlorination in the treatment of Level-2 CO2

municipal water? (May 2019 [R18])
Ans Break point chlorination:When chlorine is added to water, it is used
for oxidation of a.) reducing substances, b.) Organic matter, c.) free ammonia in raw
water, leaving behind mainly free chlorine which helps in the destruction of pathogenic
bacteria. The amount of chlorine
required to kill bacteria and to remove organic matter is called Break
point chlorination.The water sample is treated with chlorine and estimated for the
residual chlorine in water and a graph is plotted as shown below which gives the break
point chlorination.
It is seen from the figure, that initially all the chlorine is consumed and there is
no residual chlorine. This is due to the complete oxidation of reducing substances
present in water by chlorine. As amount of chlorine dosage is increased, there is steady
increase in the amount of residual chlorine. This stage corresponds to the formation of
chloro-organic compounds without oxidizingthem.
Next,whenthedosageoftheappliedchlorineishighenough,oxidation of organic
compounds and chloramines sets in and accordingly free residual chlorine also
decreases and reaches a dip when the oxidative destruction is complete. Here after,
the amount of chlorine added is not used in any reaction and the residual chlorine
keepsincreasing.
So, for effectively killing the microorganisms, sufficient chlorine has to be added and
this is indicated by the dip in the plot. Addition of chlorine in such dosages is known as
break-point or free-residual
chlorination.
Advantages:
1. It ensures complete destruction of organic compounds which give colour,
unpleasant taste and badodour.
2. It also ensures complete destruction of disease producing micro-organisms.
It prevents the growth of any weeds inwater.
19 What is caustic embrittlement? (May/June 2019 [ R18]),(Jan2020 Level-1 CO2

AGI[R18])
the softening process by lime-soda process, free Na2CO3is usually present in small portion in the soft
water which decomposes to give sodium hydroxide and carbon dioxide at high pressure of theboilers.
Na2CO3 + H2O 2 NaOH +CO2

3. Byaddingtanninorlignintoboilerwaterwhichblocksthehaircracksandpitsthat
arepresentonthesurfaceoftheboilerplatethuspreventingtheinfiltrationofcaustic sodasolution.
4. The addition of sodium sulphate to boiler water blocks the hair cracks and pits present on the surface
of the boiler plate, thereby preventing caustic soda infiltration intothem.
The sodium sulphate is added to boiler water so that the ratio
The sodium sulphate is added to boiler water so that the ratio [Na2 SO4 ) concentration]/[NaOH
concentration]
20 How is potable water disinfected by ozonation (May/June 2019 [ R18]) Level-1 CO2
Ans Ozonization:Ozoneisanexcellentandefficientdisinfectant.Itdestroys
effectively all types of bacteria present in water and makes the water absolutely safe
for consumption. It leaves behind noodour.
Ozone is highly unstable and breaks down, liberating nascent oxygen.
O3 O2 +[O]
The nascent oxygen so produced, being a very strong oxidizing agent, destroys the
pathogenic germs. It also removes both colour and odour present in water through
oxidation of organic matter. It makes the
treated water safer, tasty and pleasant. Ozone treatment of water is too
expensive to be used for large quantity of water supply.
21 What is meant by Reverse osmosis process? Write the advantages of this Level-3 CO2
process(May /June 2019 [ R16])
Ans A pressure higher than the osmotic pressure is applied on the solution, the solvent will
flow from the solution into the pure solvent through SPM. Since the flow of solvent is in
the reverse direction to that observed in the usual osmosis, the process is called reverse
osmosis.
Thus, in reverse osmosis method pure solvent, water is separated from its contaminants
rather than removing contaminants from the water. This membrane filtration is often
called as “super-filtration” or
“hyper-filtration”.
Method: In the reverse osmosis process pressure of the order 15-40 Kg/cm2 is applied to
the sea water or impure water to force its pure
water out through SPM, leaving behind the dissolved salts or solids both ionic as well
as non-ionic.
The membrane consists of very thin films of cellulose acetate, affixed to either
side of a perforated tube. However, more recently superior membranes made of
polymethacrylate and polyamide polymers have come into use.

1.Process is simple. 2.Involves no phase
change. 3.Requires low energy.
4.It deals with the problem of removing colloidal silica which is not removed by
othermethod–demineralization.
Life time of SPM (cellulose acetate) is quite high, 2 years and can be replaced within
minutes, thereby providing nearly uninterrupted water supply.
22 Explain calgon conditioning. Write the chemical reaction

involved.(Dec/Jan 2020 GNITC [R18]) Level-3 CO2
Ans Calgon conditioning: Sodium hexa meta phosphate Na2[Na4(PO3)6]or

(NaPO3)6iscalledcalgon.Thisformssolublecomplexcompoundswith CaSO4 which
Na2[Na4(PO3)6] ⇌ 2 Na+ + [Na4P6O18]2-
Calgon
Soluble complex ion
23 Give the specifications of potable water. (Dec/Jan 2020 GNITC [R18]) Level-2 CO2
Ans Potable Water
The water which is safe for drinking is called Potable
water.Theessentialrequirementsofsuchwaterwhichare recommended by the US
Public Healthare:
Water should be clear and odourless. 1.It should be
pleasant to taste.
3. ts turbidity should not exceed 10 NTU (National Turbidity Units).
4. It should be free from objectionable minerals such as lead, arsenic,
chromium and manganesesalts.
5. ItshouldbefreefromobjectionabledissolvedgaseslikeH2S. 6.pH should be in the
range of 7.0 –8.5.
7.Total hardness should be less than 500ppm.
8.Totaldissolvedsolidsshouldbelessthan500ppm.
9.It should be free from disease producingmicro-organisms.
24 Define Temporary and permanent hardness of water? How it is caused?

(Dec/Jan 2020[R18]) Level-2 CO2

Temporary hardness is caused by the presence of
dissolvedbicarbonateofcalciumandmagnesium.This hardness can be removed
by boiling of water, when bicarbonatesareconvertedintoinsolublecarbonates.
Calcium bicarbonate
Permanent Hardness/Non-carbonate hardness/Non- alkaline hardness
Permanent hardness is caused by the dissolved salts of calcium and
magnesium, other than bicarbonates. They are chlorides, sulphates, nitrates,
etc. Unlike temporary
hardness,permanenthardnesscannotberemovedbyboiling. Removal of this
hardness requires certain special chemical treatmentmethods.
25 Outline the specifications of potable water. (Dec/Jan 2020[R18])(Jan

2020SNIST[R18] Level-3 CO2
Ans Potable Water

Public Healthare:
11. Water should be clear andodourless.
12. It should be pleasant totaste.
Itsturbidityshouldnotexceed10NTU(NationalTurbidity Units).
15. Itshouldbefreefromobjectionablemineralssuchaslead, arsenic, chromium
and manganesesalts.
16. It should be free from objectionable dissolved gases like H2S.
17. pH should be in the range of 7.0 –8.5.
18. Total hardness should be less than 500ppm.
0. It should be free from disease producing micro-organisms.
26 Explain the process of a colloidal conditioning of boiler feed water.( Jun

2019SNIST[R18] Level-3 CO2
Ans Colloidal conditioning:The scale formation in low pressure

boilers is prevented by the addition of kerosene, tannin, agar- agar, etc. which
get coated over the scale forming precipitates. These form loose, non-sticky
deposits that can be removed by blow down. This type of treatment is called
colloidal conditioning.
27 Why calgon conditioning is better than Phosphate conditioning.( Aug

2019 SNIST [R18]),NOV2020GNITC[R18] Level-4 CO2
Ans In calgon Conditioning, the added calgon forms soluble complex compound with CaSo4,
thereby it prevents the scale and sludge formation in water. this soluble complex does not
cause any problem in boilers. Hence calgon conditioning is better thanphosphate
conditioning.
PART–B
1 Write a note on disinfection of water. ( May 2019 [ R16]) Level-3 CO2
15 What is disinfection of water? Explain the chlorination method.(May/June 2017 Level-2 CO2
[R16])
27 Explain disinfection by chlorination? (May 2016[R13]).(May/June 2019 [ R18]) Level-2 CO2
51 Explain disinfection of water by chlorination. (Dec/Jan 2020[R18]),(Jan 2020 Level-3 CO2
AGI[18])
21 Explain the different methods of disinfection of potable water. (Aug /sep2017- Level-2 CO2
[R15]) Level-2 CO2
Ans DisinfectionandSterilization:Waterafterpassingthrough
sedimentation, coagulation and filtration operations still
containsasmallpercentageofpathogenicbacteria.So,water for drinking
purposes must be freed from disease producing bacteria and viruses. The
process of destruction of bacteria and viruses in water is called disinfection.
The chemicals which are used to destroy the bacteria and viruses are called
the disinfectants.
Disinfection refers to the process of killing disease causing bacteria alone, while
sterilization refers to the destruction of all living organisms present in water.
(Though not correct, the two terms are usedsynonymously).
The disinfection of water can be carried out by following
methods:
Boiling: Boiling of water for 15–20 minutes kills all types of
bacteria present in water. This method is commonly used in hospitals and for
house-hold purpose. Since the method is expensive, it is not used for
municipal water supply.
Additionofbleachingpowder:Insmallwater-works,about
1kg of bleaching powder per 1,000 kilolitres of water is mixed and water
allowed to stand undisturbed for several hours. The chemical action produces
hypochlorous acid which is a powerful germicide.
CaOCl2 + H2O Ca(OH)2 + Cl2 Cl2 +
H2O HOCl +HCl
(Hypochlorous acid)
Limitations:
1. Excess of bleaching powder gives a bad taste andsmell towater.
2. Bleaching powder introduces calcium in water, thereby making it
morehard.
Chlorination:Among the common disinfectants, chlorine is
the most widely used disinfectant in municipal water treatment. The high
popularity of chlorine is due to the following reasons:
5. It is readily available either in the liquid or in the gaseousform.
6. It has powerful bactericidalproperty.
7. It does not introduce any impurities inwater.
8. It iseconomical.
Mechanismofchlorination:When chlorine is added to water, it produces two
species, namely, ionized hydrochloric acid and unionized hypochlorous acid at
lower pH values of 6.5.
Cl2 + H2O HOCl + H+ + Cl- (pH6.5)
Hypochlorous acid is found to be a powerful bactericidal. Gleen and Stumpf,
reported that the death of pathogenic bacteria is due to the reaction of unionized
hypochlorous acid with the enzymes in the cells of the micro-organisms which
are essential for theirmetabolism.
At higher pH value of 8, hypochlorous acid undergoes appreciable ionization
and exists as hypochlorite ion (OCl-) and H+ ion. Hypochlorite ion is a weak
bactericidal because it cannot deactivate the enzymes in the cells of the micro-
organisms. Therefore, chlorine is a powerful disinfectant at lower pH values.
HOCl ⇌ H+ + OCl-
Limitations:
4. High residual chlorine produces unpleasant taste and odour.
5. Excess chlorine present in water attacks mucous membrane and
causesirritation.
6. Chlorine produces toxic compounds such asCHCl3,
CCl4, etc. by reacting with organic pollutantspresent
in water. The long term consumption of such water may damage liver,
kidney, etc.
Breakpointchlorination:Whenchlorineisaddedtowater,it
is used for oxidation of a.) reducing substances, b.) Organic matter, c.) free
ammonia in raw water, leaving behind mainly free chlorine which helps in the
destruction of pathogenic
bacteria.Theamountofchlorinerequiredtokillbacteriaand
toremoveorganicmatteriscalledBreakpointchlorination.
Thewatersampleistreatedwithchlorineandestimatedfor the residual chlorine
in water and a graph is plotted as
shownbelowwhichgivesthebreakpointchlorination.
It is seen from the figure, that initially all the chlorine is consumed and there
is no residual chlorine. This is due to the complete oxidation of reducing
substances present in
waterbychlorine.Asamountofchlorinedosageisincreased, there is steady
increase in the amount of residualchlorine.
This stage corresponds to the formation of chloro-organic compounds without
oxidizing them. Next, when the dosage of the applied chlorine is high enough,
oxidation of organic compounds and chloramines sets in and accordingly free
residual chlorine also decreases and reaches a dip when the oxidative
destruction is complete. Here after, the amount of chlorine added is not used in
any reaction and the residual chlorine keeps increasing. So, for effectively
killing the microorganisms, sufficient chlorine has to be added and this is
indicated by the dip in the plot. Addition of chlorine in such dosages is known
as break-point or free-residual chlorination.
Advantages:
1. It ensures complete destruction of organic compounds which give colour,
unpleasant taste and badodour.
2. It also ensures complete destruction of disease producing micro-organisms.
3. It prevents the growth of any weeds in water. Dechlorination: Over-
chlorination after the breakpoint produces unpleasant taste and odour
inwater.
Dechlorination of such water can be achieved by either passing water through a
bed of molecular carbon or by adding activated carbon to water and removing
it by filtration after the reaction period. The excess chlorine can also be
removed by adding small quantities of substances like SO2 or Na2SO3.
SO2 + Cl2 + 2H2O H2SO4 + 2HCl
Na2SO3 + Cl2 +H2O Na2SO4 + 2HCl
Ozonization:Ozoneisanexcellentandefficientdisinfectant.
Itdestroyseffectivelyalltypesofbacteriapresentinwaterand makes the water
absolutely safe for consumption. It leaves behind noodour.
O3 O2 +[O]
The nascent oxygen so produced, being a very strong oxidizing agent, destroys
the pathogenic germs. It also removes both colour and odour present in water
through oxidation of organic matter. It makes the treated water safer, tasty and
pleasant. Ozone treatment of water is too expensive to be used for large quantity
of watersupply.
Addition of chloramines: When chlorine and ammoniaare
mixed in the ratio 2:1 by volume, a compound chloramine is formed.
Cl2+ NH3 ClNH2 + HCl
Chloramine is much more lasting than chlorine alone and consequently, it is
a better bactericidal than chlorine alone.
ClNH2 + H2O HOCl +NH3
It imparts good taste to water.
2 Give the steps involved in the treatment of domestic water. (Dec 2018 Level-4 CO2
[R18]), Oct/Nov2020 JNTUH[R18]),Nov2020GNITC[R18])
9 What is potable water? What are the steps taken to obtain pure drinking water. Level-1 CO2
(Dec 2018 [R16])
12 Describe various steps involved in domestic water treatment (May 2018 [R15], Level-2 CO2
May 2018 [R13
18 What of parameters for potable water? (Dec2017 [R13 Level-1 CO2
19 Explain principle and method of purification of domestic water by reverse Level-2 CO2
osmosis and also write its significance.(Dec2017 [R13])
28 What are the specifications of potable water? Write the steps involved in the Level-2 CO2
treatment of potable water.(May/June 2019 [ R16])
30 What are the specifications of potable water? (May 2016[R13]) (May 2019 Level-1 CO2
[ R18])
31 What is potable water? What are the various parameters for the quality of water? Level-3 CO2
Explain their significance. (Oct 2016 [R13])
34 Summarize the steps involved in the treatment of potable water. (Dec 2018 Level-4 CO2
GNITC [R18])
Ans Potable Water
Public Healthare:
1.Water should be clear and odourless. 2.It should be
pleasant to taste.
4. Its turbidity should not exceed 10 NTU (National Turbidity Units).
5. It should be free from objectionable minerals such as lead, arsenic,
chromium and manganesesalts.
ItshouldbefreefromobjectionabledissolvedgaseslikeH2S.
7.pH should be in the range of 7.0 – 8.5. 8.Total hardness
should be less than 500ppm.
10. It should be free from disease producing micro-organisms.Treatment of water
for domestic purposes(Municipal watersupply)
In general, water treatment for municipal supply or
domestic use consists of the following stages:
1. Screening
2. Sedimentation
3. Coagulation
4. Filtration
5. Disinfection andSterilization
1. Screening:Therawwaterobtainedfromrivers,reservoirs and lakes is passed
through steel screens, having large number of holes. The screening removes
solid floating materials such as dead fish and animals, bits of wood, weeds
and other debris present inwater.
2. Sedimentation:Sedimentationisaprocessofremoving
suspended impurities by allowing water to remain
undisturbedinbigtanks.Mostoftheparticlessettledown at the bottom of the
tank due to gravitational force.
Theretentionperiodinthesedimentationtankrangesfrom2to
8hours.Theclearsupernantwateristhendrawnfromtank with the help of
pumps. Periodically the accumulation of sediments is removed. In this
process, about 75% of the suspended impurities areremoved.
3. Sedimentation with coagulation: Finely dividedsilica,
clay and organic matter do not settle down easily and cannot be removed
by mere sedimentation. Most of these
areincolloidalformandareusuallynegativelychargedand hence do not
aggregate due to mutual repulsions. Such impurities are commonly
removed by chemically (coagulant) assistedsedimentation.
In this method, certain chemicals are added which produce ions of
appropriate electrical charge that neutralize the oppositely charged colloidal
particles and facilitate their aggregation. When sufficiently dense particles
are formed, they settle down. This process is known as flocculation. The
coagulants are generally added in the solution form. For proper mixing of
coagulants with water, mixers are employed. Properly mixed water is then
sedimented
The following are most commonly used coagulants:

Alum[K2SO4.Al2(SO4)3.24H2O]–Itisthemostwidelyusedin
watertreatmentplants.Alumreactsinwaterinthepresence
of alkalinity of water. If natural alkalinity is not present,
sufficient lime or Na2CO3 is also added.
Al2(SO4)3+ 3Ca(HCO3)2 2 Al(OH)3↓ + 3 CaSO4 + 6CO2↑
(coagulant) (calciumbicarbonate Aluminiumhydroxide
presentinwater) (Flocculantppt.)
Sodium aluminate (NaAlO2) – It is obtained from bauxite refineries in the form of
a thick solution. This can be used very
easily for treating water having no alkalinity. pH range for best results is 5.5 –
8.0.
NaAlO2 + 2H2O Al(OH)3↓ +NaOH
(Gelatinous Floc)
The aluminium hydroxide floc causes sedimentation. The sodium
hydroxide thus produced, precipitates magnesium salts as Mg(OH)2.
MgSO4 + 2NaOH Mg(OH)2 +Na2SO4
CopperasorFerroussulphate[FeSO4.7H2O]–Itiscommonly
usedforcoagulationpurposes.ItgivesgoodresultsabovepH
value of 8.5. Copperas reacts in water in the presence of slight alkalinity. If
alkalinity is not present, sufficient lime is also added.
FeSO4 +2Mg(HCO3)2 Fe(OH)2↓ + MgCO3 +MgSO4
+ 3 CO2 + H2O
(coagulant) (Magnesium bicarbonate present in water)
4 Fe(OH)2↓ + O2 +2H2O 4Fe(OH)3↓
(Dissolvedoxygen) Ferric hydroxide(Heavy
floc)
Fe(OH)3 is in the form of heavy floc, which causes quick sedimentation.
4.Filtration:Itisaprocessofremovalofsuspendedmatter
from water by passing it through the porous medium or bed. When water
percolates through the pores of filter bed, the suspended particles are retained
by the bed. The filtered
wateracquiresahighlevelofclarity.Thetwotypesoffilters used in water
treatment are gravity filters or sand filters and pressure filters. Usually, sand
filters areemployed.
Sand filters/Gravity filters: In these filters, water flows
through the filter bed by gravity. There are two types of gravity filters – slow
sand filters and rapid sand filters.
Slow sand filters: It is made up of a concrete tank having a
drainage system at the bottom. Above the under drain, there are three layers of
filter beds. A thick top layer of fine sandplaced over coarse sand layer
andgravel.
When the water percolates through the bed of fine sand, all the suspended
matter and some of the bacteria are retained by the sand bed and the filtered
water gets collected at the bottom in the drain system. The fine sand bed
acts as the filter, while the coarse sand and gravel beds act as the support
for the fine sand bed.
The rate of filtration decreases with time due to clogging of space between
the sand particles. After long use, the sand bed gets exhausted. Therefore,
the exhausted sand layer at the top is replaced by fresh fine sand. The
exhausted sand is
washed with water, dried and may be reused.
Rapidsandfilters:Theworkingprincipleofrapidsandfilters
is very much similar to that of slow sand filters except that rapid sand filters are
provided with reverse wash system.
The water is filtered through the filter bed for some time until the rate of
filtration becomes slower. At this stage, filtration is stopped and a portion of the
filtered water is forced through the reverse direction of filtration. This reverse
process washes off the deposited suspended matter in the sand filter bed. The
cleaned filter bed is once again ready forfiltration
DisinfectionandSterilization:Waterafterpassingthrough sedimentation,
coagulation and filtration operations still contains a small percentage of
pathogenic bacteria. So, water for drinking purposes must be freed from disease
producing bacteria and viruses. The process of destruction of bacteria and
viruses in water is called disinfection. The chemicals which are used to destroy
the bacteria and viruses are called thedisinfectants.
Disinfection refers to the process of killing disease causing bacteria alone, while
sterilization refers to the destruction of all living organisms present in water.
(Though not correct, the two terms are usedsynonymously).
The disinfection of water can be carried out by following methods:
Boiling: Boiling of water for 15–20 minutes kills all types of
bacteria present in water. This method is commonly used in hospitals and for
house-hold purpose. Since the method is expensive, it is not used for
municipal water supply.
Additionofbleachingpowder:Insmallwater-works,about
1kg of bleaching powder per 1,000 kilolitres of water is mixed and water
allowed to stand undisturbed for several hours. The chemical action produces
hypochlorous acid which is a powerful germicide.
CaOCl2 + H2O Ca(OH)2 + Cl2 Cl2 +
H2O HOCl +HCl
(Hypochlorous acid)
Limitations:
Excess of bleaching powder gives a bad taste and smell to water.
Bleaching powder introduces calcium in water, thereby making it more hard.
Chlorination:Among the common disinfectants, chlorine is
the most widely used disinfectant in municipal water treatment. The high
popularity of chlorine is due to the following reasons:
Itisreadilyavailableeitherintheliquidorinthegaseousform. It has powerful
bactericidalproperty.
It does not introduce any impurities in water. It is economical.
Mechanism of chlorination: When chlorine is added to
water, it produces two species, namely, ionized hydrochloric acid and
unionized hypochlorous acid at lower pH values of 6.5.
Cl2 + H2O HOCl + H+ + Cl- (pH6.5)
Hypochlorous acid is found to be a powerful bactericidal. Gleen and Stumpf,
reported that the death of pathogenic bacteria is due to the reaction of unionized
hypochlorous acid with the enzymes in the cells of the micro-organisms which
are essential for theirmetabolism.
At higher pH value of 8, hypochlorous acid undergoes appreciable ionization
and exists as hypochlorite ion (OCl-) and H+ ion. Hypochlorite ion is a weak
bactericidal because it cannot deactivate the enzymes in the cells of the micro-
organisms. Therefore, chlorine is a powerful disinfectant at lower pH values.
HOCl ⇌ H+ + OCl-
Limitations:
High residual chlorine produces unpleasant taste and odour. Excess chlorine
present in water attacks mucous membrane and causes irritation.
ChlorineproducestoxiccompoundssuchasCHCl3,CCl4,etc.
byreactingwithorganicpollutantspresentinwater.Thelong term consumption of
such water may damage liver, kidney, etc.
Breakpointchlorination:Whenchlorineisaddedtowater,it
is used for oxidation of a.) reducing substances, b.) Organic matter, c.) free
ammonia in raw water, leaving behind mainly free chlorine which helps in the
destruction of pathogenic
bacteria.Theamountofchlorinerequiredtokillbacteriaand
toremoveorganicmatteriscalledBreakpointchlorination.
Thewatersampleistreatedwithchlorineandestimatedfor the residual chlorine
in water and a graph is plotted as
shownbelowwhichgivesthebreakpointchlorination.
It is seen from the figure, that initially all the chlorine is consumed and
there is no residual chlorine. This is due to the complete oxidation of
reducing substances present in
water by chlorine. As amount of chlorine dosage isincreased,
there is steady increase in the amount of residual chlorine. This stage
corresponds to the formation of chloro-organic compounds without oxidizing
them. Next, when the dosage of the applied chlorine is high enough, oxidation
of organic compounds and chloramines sets in and accordingly free residual
chlorine also decreases and reaches a dip when the oxidative destruction is
complete. Here after, the amount of chlorine added is not used in any reaction
and the residual chlorine keeps increasing. So, for effectively killing the
microorganisms, sufficient chlorine has to be added and this is indicated by the
dip in the plot. Addition of chlorine in such dosages is known as break-point or
free-residual chlorination.
Advantages:
It ensures complete destruction of organic compounds which give colour,
unpleasant taste and bad odour.
It also ensures complete destruction of disease producing micro-organisms.
It prevents the growth of any weeds in water. Dechlorination: Over-chlorination
after the break point produces unpleasant taste and odour in water.
Dechlorination of such water can be achieved by either passing water through a
bed of molecular carbon or by adding activated carbon to water and removing
it by filtration after the reaction period. The excess chlorine can also be
removed by adding small quantities of substances like SO2 or Na2SO3.
SO2 + Cl2 + 2H2O H2SO4 + 2 HCl Na2SO3 + Cl2 +H2O
Na2SO4 + 2HCl
Ozonization:Ozoneisanexcellentandefficientdisinfectant.
Itdestroyseffectivelyalltypesofbacteriapresentinwaterand makes the water
absolutely safe for consumption. It leaves behind noodour.
O3 O2 +[O]
The nascent oxygen so produced, being a very strong oxidizing agent, destroys
the pathogenic germs. It also removes both colour and odour present in water
through oxidation of organic matter. It makes the treated water safer,
tasty and pleasant. Ozone treatment of water is too expensive
to be used for large quantity of water supply.
Addition of chloramines: When chlorine and ammoniaare
mixed in the ratio 2:1 by volume, a compound chloramine is formed.
Cl2+ NH3 ClNH2 + HCl
Chloramine is much more lasting than chlorine alone and consequently, it is

a better bactericidal than chlorine alone.
ClNH2 + H2O HOCl +NH3
It imparts good taste to water.
3 What is the principle involved in complexometric method in estimation Level-1 CO2

of hardness of water. (Dec 2018 [R18])
5 Discuss the principle involved in the estimation of hardness of water by Level-2 CO2
complexometric titration using EDTA. (April 2018 [R16])
16 Explain the principle involved in the estimation of hardness of water by EDTA Level-2 CO2
method (Dec2017 [R13
26 Explain the principle involved in complexomteric (EDTA) method for the Level-2 CO2
determination of hardness of water. (May 2016[R15]),(May/June 2019 [
R18]),(May 2016[R13]), (Aug 2019 SNIST [R18])
50 Discuss complex metric method for estimation of hard water. (Dec/Jan Level-3 CO2
2020[R18])
Ans Estimation of hardness by EDTA Method
Ethylene diamine tetra acetic acid (EDTA) is a strong complexing
agent whose formula is -
As such this is not very soluble in water and hence EDTA is used in the
form of its soluble disodium salt in complexometric titrations.
This sodium salt yields the anion which forms complex ions with Ca+2 and
Mg+2 (Metal-EDTA Complex)
Where M = Ca or Mg
In order to determine the equivalence point (i.e., just completion of metal-
EDTA complex formation), indicator Eriochrome black-T (EBT) or
Solochrome black-T is employed, which form an unstable wine-red complex
with Ca+2 and Mg+2 ions. This indicator is effective at a pH≈10. So the water
sample to be titrated is buffered (using NH4OH- NH4Cl solution) to a pH value
of 10 and a few drops of EBT indicator are added. The indicator forms a wine-
red unstable
complex.
𝐩𝐇 ~ 𝟏𝟎
𝐌 𝟐+ + 𝐄𝐁𝐓→[𝐌−𝐄𝐁𝐓]𝐜𝐨𝐦𝐩𝐥𝐞𝐱
(Ca++orMg++ ofHardwater) Winered
In the course of the titration of water sample against EDTA, it first combines
with free metal ions to give very stable and colourless metal-EDTA complex.
After all the free metal ions are reacted upon by EDTA, the next drop of EDTA
solution added displaces the indicator from [M-EBT] complex since the stability of
[M-EDTA] is greater than the stability of [M-EBT].
[𝐌−𝐄𝐁𝐓]𝐜𝐨𝐦𝐩𝐥𝐞𝐱+ 𝐄𝐃𝐓𝐀→[𝐌−𝐄𝐃𝐓𝐀]𝐜𝐨𝐦𝐩𝐥𝐞𝐱
+𝐄𝐁𝐓
Wine red
Blue
Thus, at the end point there is change in colour from
wine red to blue.
Various steps involved in the method are -
1. Preparation of standard water sample: One gram ofpure
CaCO3 is dissolved in a minimum quantity of HCl and the solution is
evaporated to dryness over a hot water bath. The residue left behind is
dissolved in distilled water and the solution is made up to one litre. Each ml
of this solutioncontains 1 mg of CaCO3 equivalent hardness (1 ppm).
2. PreparationofEDTASolution:3.7gmofdisodiumsaltof
EDTA is dissolved in distilled water and made up to one litre.
3. Preparation of Indicator:0.5 gm of Eriochrome black-T is
dissolved in 100 ml of ethanol.
4. Preparation of buffer solution (pH≈10): 67.5 gm of Ammonium chloride is
added to 570 ml of ammonia and made up to one litre with distilledwater.
5. StandardizationofEDTASolution:Rinseandfillupthe
burette with EDTA solution. Pipette out 50 ml of standard hard water into a
250 ml conical flask. Add 10 ml of buffer solution and 2-3 drops of indicator.
Titrate the solution against EDTA until the wine red colour changes to
blue.Let the volume of EDTA consumed be V1 ml.
6. Determination of total hardness of water: Titrate 50ml
of water sample against EDTA as per procedure in step 5. Let the volume of
EDTA consumed be V2 ml.
7. Determination of permanent hardness of water:Take
250 ml of the water sample in a 500 ml beaker and boil it till the volume is
reduced to about 50 ml. Any bicarbonate of calcium and magnesium present
would have now gotdecomposed to CaCO3 and Mg(OH)2. Filter and wash the
precipitate with distilled water and quantitatively collect the filtrate and
washings in a 250 ml volumetric flask and make up the volume to 250 ml
with distilled water. Titrate 50 ml of the water sample against EDTA as in
step 5. Let the volume used be V3ml.
Calculations:
50 ml of standard hard water = V1 ml of EDTA V1 ml of EDTA =
50 mg of CaCO3 (∵
1mlofstandardsolutioncontains1mgofCaCO3 )
50
1 ml ofEDTA= mg of CaCO3 equivalenthardness.
V1
Now 50 ml of given hard water (before boiling) = V2 ml of EDTA
50
V2 ml of EDTA = ( ) × V2 mg of CaCO3 equivalent.
V1
50 1000
∴ One litre of hard water = ( ) × V2 × ( ) mg of CaCO3
V1 𝟓𝟎
eq.
V2
=( ) × 1000 mg of CaCO3 equivalent
V1
= (V2) × 1000 ppm
V1
This is the total hardness of water.
50 ml of hard water (after boiling) = V3 ml of EDTA
= (V3 ) × 50 mg of CaCO3 equivalent.
V1
One litre of boiled water = ( 50) ×V3 × ( 1000) mg of CaCO3
V1 𝟓𝟎
equivalent
= (V3 ) × 1000 mg of CaCO3 equivalent
V1
= (V3 ) × 1000 ppm.
V1
This is the permanent hardness of water. Temporary hardness of
water = Total hardness–
permanent hardness
= 1000 [(V2 ) – (V3 )] ppm.
V1
(V2 –VV31)
=1000 ppm.
V1
Advantages of EDTA method
This method is definitely preferable to the other methods, because of the
1. Greateraccuracy,
2. Convenience and
More rapidprocedure.
4 Differentiate between scales and sludges. (Dec 2018 [R18]) Level-4 CO2
10 Write the names of three sludge forming and three scale forming compounds. Level-3 CO2
(Dec 2018 [R16])
23 Define scales and sludge’s. What are the causes, effects and preventive method Level-1 CO2
of these? (Dec2016 [R16]) , Jan 2019 CVR [R18 ])
39 Write in detail an account on Scale and Sludge formation in boilers? (May 2019 [ Level-3 CO2
R16])
46 Differentiate scales and sludges. How do you prevent boiler corrosion? (Dec/Jan Level-2 CO2
2020 GNITC [R18])
Ans Scale and Sludge formation
Boilers are employed for the generation of steam in power
plants,wherewateriscontinuouslyheatedtoproducesteam.
Asmoreandmorewaterisremovedintheformofsteam,the boiler water gets
concentrated with dissolved salts and progressively reaches the saturation
point. At this point, the dissolvedsaltsareprecipitatedoutandslowlysettleonthe
inner walls of the boiler. The precipitation takes place in two ways:
1) In the form of soft, loose and slimy deposits formed
comparativelyinthecolderportionsofboilerwhichiscalled
“Sludge” and
2) In the form of hard deposits that stick very firmly on the inner walls of the
boiler which is called“Scale”.
Sludgeformation:Sludgesaresoft,loose,slimyandnon- sticky precipitates
produced due to the higher concentration of dissolvedsalts.
Reasons for the formation of sludges: The dissolved salts

whose solubility is more in hot water and less in cold water produce sludges.
Eg: MgCO3, MgCl2, CaCl2 and MgSO4.
e sludges were formed at comparatively colder portions of the boiler and get
collected where rate of flow of water is low.
Disadvantages of sludges:
1. Sludges are bad conductors of heat and results in the wastage of heat
andfuel.
2. Sometimes sludges were entrapped in the scale and gets deposited as scale
which causes more loss of efficiency of boiler.
3. Excessivesludgeformationleadstothesettlingofsludgein slow circulation
areas such as pipe connections, plug openings, gauge-glass connections
leading to the choking of pipes.
Prevention of sludge formation:
1. By using well softenedwater.
2. By frequently carrying out blow downoperation.
(Note: Blow down operation = drawing off a portion of concentrated water)
Scaleformation:Scalesarehard,stickydepositsformedon the inner walls of the

boiler. Scale cannot be removed mechanically by abrasion. These are the main
sources of boilertroubles.
Reasons for the formation of scales:

2.
Decomposition of Ca(HCO3)2 : Due to hightemperature
and pressure present in the boilers, the Ca(HCO 3)2 salt
decomposestoCaCO3↓,aninsolublesalt,formsscaleinlow
pressure boilers.
∆
Ca(HCO3)2 → CaCO3↓ + CO2↑ +H2O
CaCO3 is soluble in high pressure boilers.
CaCO3 + H2O Ca(OH)2 +CO2↑
Soluble
3.
DepositionofCaSO4:CaSO4 ismoresolubleincoldwater.Its solubility decreases
as the temperature of theboiler
increasesandprecipitatesouttoproducehardscaleonthe
surfaceoftheboiler.ThesolubilityofCaSO4is3200ppmat
15oC,reducesto27ppmat320oCandcompletelyinsoluble in super-heated
water in high pressure boilers. This is the main reason for the formation of
scales in high pressure boilers. CaSO4 scale is very hard, highly adherent
and difficult toremove.
4.
Hydrolysis of magnesium salts: Dissolvedmagnesium
salts undergo hydrolysis at high temperature forming magnesium
hydroxide precipitate, which form soft type scale.
MgCl2 + 2H2O Mg(OH)2↓ + 2HCl
5.
Presenceofsilica:SiO2presenteveninsmallquantities, deposits as calcium
silicate (CaSiO3) or Magnesiumsilicate
(MgSiO3). The deposits form hard scale which are verydifficult to remove.
Disadvantages of scale formation:
1. Wastage of fuel: Scales are bad conductors of heat due to
which the flow of heat from boiler to inside water is decreased, hence
excessive heating is required which increases the fuel consumption causing
wastage of fuel. The wastageoffuelincreaseswithincreaseinthethicknessof
the scale as shown below:
ess of scale (mm)
0.325
0.625
1.25
2.50
stage of fuel
10%
15%
50%
80%
2. Loweringtheboilersafety:Duetoscaleformationover heating of boiler is done to
maintain the constant supply of steam. Due to overheating the boiler material
becomes softer and weaker, which can causes distortion of boiler. Thus the
boiler safety islowered.
3. Decreaseinefficiency:Scalesdepositedinthevalvesand
condensers of the boiler cause choking which results indecrease in efficiency
of the boiler.
4. Danger of explosion: Because of the formation ofthe
scales, the boiler plate faces higher temperature outside and lesser
temperature inside. Due to uneven heattransfer
cracksaredevelopedinthelayerscales.Waterpasses
throughthecracksandcomeincontactwithboilerplate
having high temperature. This causes formation of large amount of steam
suddenly developing sudden high pressure. This causes the explosion of
theboiler.
Removal of Scales:
1. If the scale formed is soft, it can be removed by a scrapper, wire brush,etc.
2. Bygivingthermalshocks,donebyheatingtheboilertohigh temperature and
suddenly cooling with cold water, if the scale is brittle innature.
3. If the scale is very adherent and hard, chemical treatment must begiven.
Eg: CaCO3 scale is removed by washing with 5-10% HCl and CaSO4 scale is
removed by washing the boiler plate with EDTA solution.
Frequent “blow down operation” can remove the scales which are
looselyadhering.
6 Explain the process of reverse osmosis. How is it useful in softening of

water? (April 2018 [R16]), (May 2017[ R13]) ,(Dec 2017 [ R13]), (Jan Level-2 CO2
2019 CVR [R18 ]),(Jan 2020 AGI[18]), 2020GNITC[R18])
48 Explain a method for desalination of brackish water. (Dec/Jan 2020[R18]) Level-3 CO2
Ans Reverse Osmosis
When two solutions of unequal concentrations are separated by a semi-
permeable membrane/SPM (which selectively does not permit the passage of
dissolved solute particles, i.e., molecules, ions, etc.), flow of solvent takes place
from dilute to concentrated sides, due to osmosis. If however, a pressure higher
than the osmotic pressure is applied on the solution, the solvent will flow from
the solution into the pure solvent through SPM. Since the flow of solvent is in
the reverse direction to that observed in the usual osmosis, the process is called
reverse osmosis. Thus, in
reverseosmosismethodpuresolvent,waterisseparatedfrom
its contaminants rather than removing contaminants from the water. This
membrane filtration is often called as“super- filtration” or“hyper-filtration”.
Method:In the reverse osmosis process pressure of the order
15-40 Kg/cm2 is applied to the sea water or impure water to force its pure water
out through SPM, leaving behind the dissolved salts or solids both ionic as well
asnon-ionic.
The membrane consists of very thin films of cellulose acetate, affixed to
either side of a perforated tube. However, more recently superior membranes
made of polymethacrylate
and polyamide polymers have come into use.
e. Process issimple.
f. Involves no phasechange.
g. Requires lowenergy.
h. It deals with the problem of removing colloidal silica which is not removed
by othermethod–demineralization.
Life time of SPM (cellulose acetate) is quite high, 2 years and can be replaced
within minutes, thereby providing nearly uninterrupted watersupply.
7 Discuss the Ion exchange process of softening hard water. (Dec 2018 Level-2 CO2
[R16]),(Jan 2020 AGI[18]), Nov2020GNITC[R18])
11 Explain Ion exchange process for the softening of water (May 2018 Level-2 CO2
[R15],May/June 2017 [R16], May 2019 [ R18],.May/June 2019 [ R18],
May/June 2019 [ R18])
38 Why is ion exchange process preferred for the softening of water for use in Level-3 CO2
boilers? (May 2019 [ R16])
43 Explain the principle, process, advantages and limitations of ion exchange Level-2 CO2
method of softening of water.( May/June 2019 [ R16])
47 How ion-exchange process carried out? How the exhausted resins are Level-2 CO2
regenerated.(Dec/Jan 2020 GNITC [R18]),(June 2019 SNIST[R18])
Ans Ion – exchange Process
This is alternatively known as deionization or demineralization since all the
cations and anions are completely removed in this process. The resins used for
this purpose are organic, cross linked insoluble polymers carrying some
functional groups which are responsible for the ion- exchanging properties.
Resins containing acidic functional groups such as –COOH and –SO3H etc. are
capable of exchanging their H+ ions with other cations which come into contact
with them and hence they are termed as Cation exchangers. Resins containing
basic functional groups such as –NH2, =NH, etc. as hydroxides or
hydrochlorides are capable of exchanging their anions with other ions in water
and therefore are known as anionexchangers.
1. Cation exchange resins (RH+) are mainly Styrene-divinyl benzene copolymers
which on sulphonation or carboxylation acquire capability to exchange their
hydrogen ions with other cations in water. They can besimply
represented as R- H+ where R- represents the insoluble
polymeric matrix. Their exchange reactions with other cations are shown
below:
2R- H+ + Ca+2 R2Ca + 2H+
2R H
- + + Mg +2 R2Mg + 2H+
2. Anion exchange resins (R′OH-) are Styrene-divinyl benzene or amine–
formaldehyde copolymers which carry amino or quaternary ammonium
groups. After treatment with NaOH solution, these become capable of
exchanging their OH-with other anions in water. They can be simply
represented as R+ OH- where R+ represents the insoluble organic matrix. Their
exchange reactions with other anions can be represented as follows:
R+OH- + Cl- RCl +OH-
2R+OH- + SO4-2 R2SO4 + 2OH-
2R OH
+ - + CO3 -2 R2CO3 + 2OH-
R OH
+ - + HCO3- RHCO3 + OH-
Process: The hard water is first passed through thecation
exchange column when all the cations like Ca+2, Mg+2, etc.
areremovedandanequivalentamountofH+isreleasedfrom the resin to water.
Subsequently, this water is passed
throughtheanionexchangecolumnwhenalltheanionslike Cl-,SO4-
2,etc.areremovedandanequivalentamountofOH-
is released from this column
to water. The H+ and OH- released respectively from cation exchanger and
anion exchanger combine to givewater.
H+ + OH- H 2O
Thus, water flowing out of the anion exchange column is free from all
the cations and anions and becomes ion-free or deionized or demineralized.
Regeneration:
When the cation exchangers and anion exchangers are fully saturated by
the absorption of cations and anions respectively from water, they lose their
exchanging capacity and become “exhausted”. The exhausted cation exchange
column is regenerated by passing a solution of dilute HCl or H2SO4 through it.
R2Ca + 2H+ 2 RH +Ca+2
The column is washed with deionized water and the washings containing
Na , Cl- and SO4-2 are drained.
+
The exhausted anion exchange

columnisregeneratedbypassingadilutesolutionofsodiumhydroxidethroughit.R2S
O4 +2OH- 2ROH +SO4-2
The column is drained with deionized water andthe
washing containing Cl-, SO4-2, etc. are drained. The regenerated exchanger
can be used again. The residual
hardness of water in this process is 0-2 ppm.
Advantages:
1. The process can be used to soften highly acidic or alkaline waters.
2. It produces water of very low hardness. So it is very good for treating water
for use in high-pressureboilers.
Disadvantages:
1. The equipment is costly and more expensive chemicals are needed.
If the water contains turbidity, then the output of the
processisreduced.Theturbiditymustbebelow10ppm
8 What is caustic embrittlement? (Dec 2018 [R16]) Level-1 CO2

17 What is caustic embrittlement? Write the causes of it and explain the preventive Level-3 CO2
methods (Dec2017 [R13] ,May 2016 [R 15], May/June 2019 [ R16])
29 Write notes on caustic embrittlement? (May 2016[R13]) Level-3 CO2
Ans Caustic Embrittlement
Caustic embrittlement is a term used for the appearance
of cracks inside the boiler particularly at those places which are under stress
such as riveted joints due to the high
concentrationofalkalileadingtothefailureoftheboiler.The
crackshaveappearanceofbrittlefracturehencethefailureis called
causticembrittlement.
Reasons for the formation of caustic embrittlement:
The boiler feed water containing carbonates and bicarbonates of alkali
metals, sodium hydroxide and a small quantity of silica or sodium silicate is
purified by lime soda process. During the softening process by lime-soda
process, free Na2CO3is usually present in small portion in the soft water which
decomposes to give sodium hydroxide and carbon dioxide at high pressure of
the boilers.
The precipitation of NaOH makes the boiler water alkaline or ‘caustic’. The
NaOH containing water flows into the small pits and minute hair-cracks present
on the inner walls of the boiler. As the water evaporates, the concentration of
caustic soda increases progressively creating a concentration cell as given below
thus dissolving the iron of the boiler as sodium ferrate.
atbends, ncentrated luteNaOH n at plane vetsandjoints
NaOHsolution solution surfaces
Anode
Cathode
This causes the cracking of the boiler particularly at stressed parts like bends,
joints, rivets, etc. causing the failure of the boiler. The iron at plane surfaces
surrounded by dilute NaOH becomes cathodic while the iron at bends, rivets and
joints is surrounded by highly concentrated NaOH becomes anodic which is
consequently decayed orcorroded.
Prevention of Caustic embrittlement:
1.The pH of the feed water should be carefully adjusted to 8-9
2.Byusingsodiumphosphateassofteningreagentinsteadof
sodium carbonate.
3. By adding tannin or lignin to boiler water which blocks the hair cracks and
pits that are present on the surface of the boiler plate thus preventing the
infiltration of caustic soda solution.
4. The addition of sodium sulphate to boiler water blocks the hair cracks and pits
present on the surface of the boiler plate, thereby preventing caustic soda
infiltration intothem.
Thesodiumsulphateisaddedtoboilerwatersothatthe ratio
[Na2SO4 concentration] [NaOH concentration]
is kept as 1:1, 2:1 and 3:1 in boilers working at pressures up to 10, 20 and
above 20 atmospheres respectively.
Disadvantages of caustic embrittlement:
The cracking or weakening of boiler metal causes failure of the boiler.
13 Write about boiler corrosion. (May 2018 [R13], June 2015 [ R13]), Level-3 CO2
Oct/Nov2020 GNITC[R18])
Ans Boiler Corrosion:
The decay of boiler material by chemical or electrochemical ttack of its
environment is called boiler corrosion. The main easons for boiler corrosion are
as follows:
a.) Dissolved oxygen.
b.) Dissolved carbon dioxide. c.) Acids from
dissolved salts
a.)Dissolvedoxygen:Amongthedissolvedgasesoxygenisthe
most corroding impurity. At room temperature water contains 8ml of
dissolved oxygen perlitre.
Disadvantages of dissolved oxygen: At high temperature,
oxygen attacks the boiler plate creating serious corrosion problem.
2 Fe + 2H2O + O2 2Fe(OH)2↓
4 Fe(OH)2 + O2
2[Fe2O3.2H2O]
Rust
Removal of dissolved oxygen:
1. Addition of sodium sulphite or sodium sulphideremoves O2 by converting
O2 to sodiumsulphate.
2Na2SO3 + O2 2 Na2SO4Na2S + 2O2
Na2SO4
2. Additionofhydrazine(NH 2NH2)isanidealreagent added to boiler to
remove dissolved oxygen asH2O.

NH2NH2 + O2 N2 + 2H2O
N2 is harmless to boilers. Hence hydrazine
removesdissolvedoxygenwithoutincreasingthe concentration of
dissolvedsolids.
3. Mechanical deaeration is another method of degasification. Water is
sprayed through a perforated plate, fitted in the degasification tower,
heatedfrom
sides and connected to vacuum pump as shown in the
figure. High temperature, low pressure and large exposed surface
reduce dissolved oxygen and other gases in water.
b.)Dissolved carbon dioxide: Dissolved carbon dioxide has a
slowcorrosiveeffectonthematerialsofboilerplate.Source
ofcarbondioxideintowateristheboilerfeedwaterwhich contains
bicarbonates. Under the high temperature and pressure, maintained in the
boiler the bicarbonates decompose to produce carbondioxide.
∆
Ca(HCO3)2 → ∆ CaCO3 + CO2↑ + H2O Mg(HCO3)2
→ Mg(OH)2 + 2CO2↑
The disadvantage of the carbon dioxide is slow corrosive effect on boiler
plates by producing carbonic acid.
CO2 + H2O H2CO3
Removal of Carbon dioxide is carried out by two ways:
 by the addition of calculated quantity ofammonia
2 NH4OH + CO2 (NH4)2CO3 +H2O
 by mechanical de-aerationprocess
c.) Acids : Presence of acids in boiler water is another main reason for
boilercorrosion.
1. Sources of acid production are dissolved magnesium salts which
undergo hydrolysis to produceacids.
MgCl2 + 2H2O Mg(OH)2 + 2HCl
2. Disadvantages of the acid production is that the acids react with iron of
the boiler plate in a chain reaction to produce decay of themetal.
Fe + 2HCl FeCl2 + H2↑
FeCl2 + 2H2O Fe(OH)2 + 2HCl
2 Fe(OH)2 + H2O +½O2 Fe2O3.3H2O
Rust
Consequently even a small amount of MgCl2 can cause corrosion to a
largeextent.
20 What is calgon conditioning? Explain.(Dec2017 [R13]) Level-1 CO2
Ans Calgon conditioning: Sodium hexa metaphosphate

Na2[Na4(PO3)6]or(NaPO3)6iscalledcalgon.Thisformssoluble complex compounds
with CaSO4 which causes no boiler troubles.
Na2[Na4(PO3)6] ⇌ 2 Na+ + [Na4P6O18]2-
Calgon
Soluble complex ion
25 Write a short note each on Calgon and Phosphate conditioning of boiler feed Level-3 CO2
water.(Dec2016 [R16]), NOV2020GNITC[R18])
Ans 1. Phosphate conditioning: The scale formation dueto

permanent hardness causing calcium salts is avoided bycomplexation with
sodium phosphate in high pressure boilers. The complex formed is soft, non-
adherent and easilyremovable.
3 CaCl2 +2Na3PO4 Ca3(PO4)2 + 6 NaCl
3 MgCl2 +2Na3PO4 Mg3(PO4)2 + 6NaCl
TheCaandMgphosphatecomplexeswereremovedbyblow downoperation.
The three phosphates employed for conditioning are:
 NaH2PO4 - sodium dihydrogen phosphate(acidic)
 Na2HPO4 - disodium hydrogen phosphate (weaklyalkaline)
 Na3PO4 - trisodium phosphate(alkaline)
Trisodium phosphate is the most preferred reagent because it not only
forms complex with Ca2+ and Mg2+ ions, but also maintains the pH of water
between 9-10, where the calcium and magnesium ions undergo
complexation.
If the alkalinity of boiler water is sufficient then disodium phosphate is
selected for conditioning. If the alkalinity of the boiler water is very high,
then sodium dihydrogen phosphate is selected for the treatment to reduce the
alkalinity of the water.
2. Calgon conditioning: Sodium hexa meta phosphate
Na2[Na4(PO3)6] or (NaPO3)6 is called calgon. This forms soluble complex
compounds with CaSO4 which causes no boiler troubles.
Na2[Na4(PO3)6] ⇌ 2 Na+ + [Na4P6O18]2-
Calgon
Soluble complex ion
22 Explain the various internal treatment methods of boiler water. (Aug /sep2017- Level-3 CO2
[R15]) (Dec 2018 GNITC [R18])
45 What is the internal conditioning of water? How calgon, phosphate and colloidal Level-2 CO2
minerals helps in conditioning of boiler water.(Dec/Jan 2020 GNITC [R18])
Ans Internal Treatment/Conditioning of Water
The softening of water carried out inside the boiler is called conditioning or
internal treatment of water. In this
processthehardnesscausingdissolvedsaltswereprohibited
-
1. Bycomplexingthehardnesscausingsolublesaltbyadding appropriate
reagents.
2. By precipitating the scale forming impurities in the form of sludge which can
be removed by blow downoperation.
3. By converting the scale forming salts into compounds
whichstayin'dissolvedform'anddonotcauseanytrouble to the boilers.
All internal treatment methods must be followed by blow down operation so
that accumulated sludges are removed. Important internal conditioning
methods are:
3. Colloidal conditioning: The scale formation in low
pressure boilers is prevented by the addition of kerosene, tannin, agar-agar,
etc. which get coated over the scale forming precipitates. These form loose,
non-sticky deposits that can be removed by blow down. This type of
treatment is called colloidal conditioning.
4. Phosphate conditioning: The scale formation dueto
permanent hardness causing calcium salts is avoided bycomplexation with
sodium phosphate in high pressure boilers. The complex formed is soft, non-
adherent and easilyremovable.
3 CaCl2 +2Na3PO4 Ca3(PO4)2 + 6 NaCl
3 MgCl2 +2Na3PO4 Mg3(PO4)2 + 6NaCl
TheCaandMgphosphatecomplexeswereremovedbyblow downoperation.
The three phosphates employed for conditioning are:
 NaH2PO4 - sodium dihydrogen phosphate(acidic)
 Na2HPO4 - disodium hydrogen phosphate (weaklyalkaline)
 Na3PO4 - trisodium phosphate(alkaline)
Trisodium phosphate is the most preferred reagent because it not only
forms complex with Ca2+ and Mg2+ ions, but also maintains the pH of water
between 9-10, where the calcium and magnesium ions undergo
complexation.
If the alkalinity of boiler water is sufficient then disodium phosphate is
selected for conditioning. If the alkalinity of the boiler water is very high,
then sodium dihydrogen phosphate is selected for the treatment to reduce the
alkalinity of the water.
5.Calgon conditioning: Sodium hexa meta phosphate
Na2[Na4(PO3)6] or (NaPO3)6 is called calgon. Thisforms
soluble complex compounds with CaSO4 which causes no boiler troubles.
Na2[Na4(PO3)6] ⇌ 2 Na+ + [Na4P6O18]2-
Calgon
Soluble complex ion
41 What is hardness of water? Give the various units of hardness of water. Level-4 CO2
(May/June 2019 [ R18])
Ans Units of Hardness (Units and Inter-conversions of
Units)
The units normally used to express hardness are parts per million (ppm) or
milligrams per litre (mg/L) of CaCO3 equivalents.
5. Parts per million (ppm) is the parts of CaCO3 equivalent hardness per 106
parts ofwater.
i.e. 1 ppm = 1 part of CaCO3 eq. hardness in 106 parts of water.
6. Milligrams per litre (mg/L) is the number of milligrams of CaCO3 equivalent
hardness present per litre ofwater.Thus,
1 mg/L = 1 mg of CaCO3 equivalent hardness per 1 litre of water.
But 1 litre of water weighs 1 Kg.
1Kg=1000g=1000×1000mg=10 mg. 6
∴ 1 mg/l = 1 mg of CaCO3 equivalents per 106 mg of water 1 part of CaCO3

equivalents per 106 parts ofwater
7. Clarke’s degree (oCl) is number of grains (1/7000 lb)/(65 mg) of CaCO3
equivalent hardness per gallon (10 lb)/(4.546 lit) of water. Or it is parts of
CaCO3 equivalent hardness per 70,000 parts of water.Thus,
1o Clarke = 1 grain of CaCO3 equivalent hardness per gallon of water.
(or)
1o Clarke = 1 part of CaCO3 equivalent hardness per 70,000 parts of
water
4.
Degree French (oFr) is the parts of CaCO3equivalent hardness per 105
parts of water.Thus,
1oFr = 1 part of CaCO3 hardness equivalent per 105 parts of water.
5.
Milliequivalentperlitre(m.eq/L)isthenumberofmilli equivalents of hardness
present per litre.Thus,
1m.eq/L=1m.eq.ofCaCO3perlitreofwater.
= 10-3 × 50 g of CaCO3 per litre.
= 50 mg of CaCO3 equivalent per litre.
= 50 mg/L CaCO3 equivalent = 50 ppm.
Relationship between various units of hardness
m= 1mg/L= 0.1oFr= 0.07oCl= 0.02m.eq./
/L= 1ppm= 0.1 Fr=
o 0.07oCl= 0.02m.eq./
= 1.43oFr= 14.3ppm= 14.3mg/L= 0.286m.eq.
= 10ppm= 10mg/L= 0.7 Cl=
o 0.2m.eq./Leq./L= 50mg/L=
50ppm= 5oFr= 3.5oCl
42 One litre of water from an underground reservoir in Tirupati Town in
Andhra Pradesh showed the following analysis for it’s contents.
Mg(HCO3)2=42mg, Ca(HCO3)2= 146mg, CaC12= 71mg ,NaOH=
40mg, MgSO4=48mg , Organic impurities =100mg. Calculate Level-5 CO2
temporary, permanent and total hardness of this sample of water in
Degree French and Clark.
( May 2019 [ R16])
Solution:
14 A sample of water contains following dissolved salts per liter. Ca
(HCO3)2= 16.2mg, Mg (HCO3)2=14.6mg, CaC12=1.1mg and Level-5 CO2
MgSO4=12mg. Calculate the total, permanent and temporary hardness of
water? (May 2017 [ R16]),(Jan 2020 AGI[18])
3 A sample of water contains0.438gof Mg(HCO3)2,38mg ofMgCl2 2.4mg
of Ca(HCO3)2 and13.6mg of caso4per liter .what is its Temporary and permanent Level-3 CO2
hardness.( April 2018 [R16])
44 calculate Temporary and permanent hardness of water containing
Mg(HCO3)2=7.3mg/L,
Level-3 CO2
Ca(HCO3)2=16.2mg/L,mgcl2=9.5mg/L,CaSO4=13.6mg/L. (Dec/Jan
2020 GNITC [R18])
52 A sample of hard water contains the following dissolved salts per liter.
NaCl =58.5mg/L, Ca(HCO3)2= 16.4mg/L, Mg(HCO3)2= 14.6mg/L,
CaC12= 111mg/L, MgSO4= 12mg/L,CaSO4 =13.6mg/L. Calculate Level-5 CO2
temporary, permanent and total hardness of water in ppm and Degree
French.( May/June 2019 [ R16])
Unit-3
PART–A
1 Why small anodic area undergo intense corrosion? (May/June 2019 [ Level-4 CO3
R18])
Ans If the metal has smaller the anodic area and larger the cathodic area exposed to
corrosive atmosphere, more intense and faster is the corrosion occurring at anodic area because
at anode oxidation takes place and electrons are liberated. At the cathode these electrons are
consumed. This process makes the anodic reaction to takesplace at its
maximum rate thus increasing the corrosion rate.
2 Why coating of Zn on (iron) Fe is called sacrificial anode, explain. (Dec Level-2 CO3
2018 [R18])
Ans As zinc is an active metal, it serves as a sacrificial anode, so that even if
the coating is scratched, the exposed steel will still be protected by the remaining zinc
3 Why do electrochemical cells stop working after some time? (Dec 2018 Level-2 CO3
[R16])
Ans Electrochemical cells stop working after some time because, When one compound of in the
anode of the electrochemical cell is oxidized, those electrons serve to reduce the compound on
the cathode side. When the material at anode does not have electrons to loose, the reaction stops
and cell stops working.
4 Write a short note on calomel electrode.(Dec 2018 [R16]) Level-3 CO3

Ans It is a secondary reference electrode. It acts as reduction electrode. A paste of mercurous
chloride, Hg2Cl2 (commercially known as calomel) and
mercuryisusedinthiselectrode.KClsolutionactsaselectrolyte.Depending upon the concentration of
electrolyte, the cell potentialvaries.
0.1M KCl | Hg2Cl2 (s) | Hg, pt 0.3338 V
1.0M KCl | Hg2Cl2 (s) | Hg, pt 0.2800 V Saturated KCl | Hg2Cl2 (s) | Hg, pt 0.2422V
5 Write the cell notation for calomel electrode.(May 2018 [R15]) Level-3 CO3
Ans Cell representation: Pt, H2 (1atm) │ H+( 1M) ║ KCl (saturated) │
Hg2Cl2, Hg
6 What is the reason for pitting corrosion to occur? (May 2018 [R15]), Level- C
3 O
3
Ans It is formed due to formation of cracks on the surface of a metal. Metal undergo
corrosion due to presence of external impurities, such as sand ,dust, water drop etc, on
the surface of metals leads to pitting corrosion.(pitting means crack, pit, hole, cavity)
7 Write cell notation for calomel electrode. What is the reason for pitting Level- C
corrosion to occur? (May 2018 [R13]) 3 O
3
+
Ans Cell representation: Pt, H2 (1atm) │ H ( 1M) ║ KCl (saturated) │ Hg2Cl2, Hg
8 Differentiate between primary and secondary cell. (May 2017 [R16], May/June 2019 Level- C
[ R16]), Oct/Nov2020 JNTUH[R18]) 4 O
3
Ans S. PRIMARY CELLS SECONDARY CELLS
No.
These are non-rechargeable and are 1.Secondarybatteriesarerechargeableandaremeantfor a multi
meant for a single use and meant to be cycleuse.
1 discarded after use.
2 Cell reaction is not reversible 2.Cell reaction can be reversed
3 Cannot be rechargeable 3.Can be rechargeable
4 Less expensive 4.Expensive
Can be used as long as the materials 5.Can be used again and again by recharging the cell
5 are active in their composition
Example: Lechlanche’s cell, Lithium 6.Lead acid cell, Nickel-cadmium cell
6 cells
9 Write the Nernst equation and mention its importance? (May 2017 Level- C
[R16]),(Jan2020 SNIST [R18]), Oct/Nov2020 GNITC[R18]) 3 O
3
Ans Nernst’s equation: The relation between Cell reaction, emf and the concentration of an
electrolyte is given by a famous scientist, known as Nernst’s equation. It is a thermodynamic
equation.
Nernst equation E= E0 + 2.303RTlog [Mn+]

nF
Where E° = Standard EMF of the cell for 1 M solution at 298 K; E = electrode
potential of the metal;
R = Gas constant (8.314JK-1mol-1) T = Kelvin
temperature (298K)
n = number of electrons involved in the cell reaction;
F = Faraday of electricity (96500)
n+
[M ] = activity of metal ions in the solution is taken equal to their molarities
Importance:
1. Nernst equation is used to determining ionconcentration
2. It is also used in solubility products and potentio-metrictitrations.
It is also used in pHmeasurements.
10 Write the Principle involved in pitting corrosion? (Dec 2017 [R13]) CO

Level-3
3
Itisformedduetoformationofcracksonthesurfaceofametal.Metalundergocorrosion
duetopresenceofexternalimpurities,suchassand,dust,waterdropetc,onthesurface of
metals leads to pitting corrosion.(pitting means crack, pit, hole,cavity)
11 Give two differences between galvanic cell and electrolytic cell(Aug/Sep 2017 CO
[R15]) Level-4
3
Ans Sl. no. Galvanic cell Electrolytic cell
1 In this cell ,chemical energy is In this cell ,electrical energy is
converted into electrical energy converted chemical energy
2 In this cell, anode is - ve and cathode In this cell, anode is + ve andcat hode
is + ve is - ve
3 Salt bridge required Salt bridge not required
4 This process is reversible and This process is irreversible andn on
spontaneous spontaneous
5 EMF of the cell is positive EMF of the cell is negative
12 What is standard electrode potential? Give its units. (Dec 2016 [ R16], May/June CO
2019 [R18]) Level-1
3
Ans StandardElectrodepotential(E°):Itisthemeasureoftendencyofametallicelectrode
toloseorgainelectrons,whenitisincontactwithasolutionofitsownsaltofonemolar
concentration at 25°. It is measured inVolts
13 Explain the functioning of the dry cell with chemical reactions. (Dec 2016 [ R16]) CO
Level-2
3
Ans It is a primary cell. In this cell the chemical reactions are irreversible.
Cell reaction:
Atanode: Zn Zn+2 +2e-
Atcathode: NH4+ + MnO2 + 2e-MnO(OH)- + NH3 OverallReaction:
Zn + NH4+ + MnO2 Zn+2 + MnO(OH)- +NH3
In cathode reactions, Mn is reduced from +4 oxidation state to +3 oxidation state. The
liberationofNH3gas,whichdisruptsthecurrentflow,ispreventedbyareactionofNH3 with Zn+2
(fromZnCl2).
ZnCl2 (g) + 2 NH3 [Zn(NH3)2]Cl2(S)
14 Differentiate between primary and secondary cell. (May 2016 [R13]), CO
May 2019 [ R16]) Level-4
3
S.No. PRIMARY CELLS SECONDARY CELLS
These are non-rechargeable and are Secondary batteries are rechargeabl e
meant for a single use and meant to be and are meant for a multi cycleuse
1 discarded after use.
2 Cell reaction is not reversible Cell reaction can be reversed
3 Cannot be rechargeable Can be rechargeable
4 Less expensive Expensive
Can be used as long as the materials are Can be used again and againb y
5 active in their composition recharging the cell
Example: Lechlanche’s cell,Lithium Lead acid cell, Nickel-cadmiumcell
6 cells
15 What is the role of salt bridge in an electrolytic cell? (Oct.2016 [R13]) Level- C
3 O
3
Ans Salt bridge, in electrochemistry, is a laboratory device used to connect the oxidation and
reduction half-cells of a galvanic cell (voltaic cell), a type of electrochemical cell. It
maintains electrical neutrality within the internal circuit, preventing the cell from rapidly
running its reaction to equilibrium.
16 Why efficiency of fuel cells is greater than other energy devices. (June 2015[R13]) Level- C
4 O
3
Ans A device used to connect the oxidation and reductionhalf-cellsof a galvanic cell(voltaic cell) is
called salt bridge. It’s chemical composition is saturated KCl; gelatin, agar-agar gel. It acts as
semi permeable membrane between two half cells. It maintains electrical neutrality between the
two half cells. If salt bridge is not present, the solution in one half cell would accumulate negative
charge and the solution in the
other half cell would accumulate positive charge as the reaction proceeded, quickly preventing
further reaction, and hence production of electricity
17 Explain chemical theory of corrosion? (Jan2015 [R13]) Level- C
2 O
3
Dry or chemical theoryofcorrosion........Acid theory of corrosion Acid theorysuggests
that corrosion of a metal (iron) is due to the presence of acids around it. According to this theory, iron
is corroded by atmospheric carbon di-oxide, moisture and oxygen.
Dry (or) Chemical Corrosion :

This type of Corrosion occurs mainly through the direct
chemical action of atmospheric gasses (O2,
halogen, H2S, SO2. N2 or anhydrous inorganic liquid) with metal
surpasses in immediate proximity. Three types of chemical Corrosion
are as follows..
1. Oxidation Corrosion: This is carried out by the direct action of

oxygen low or high temperatures on metals in absence of
moisture at ordinary temperature metals or very slightly
attacked. The Exceptions are Alkali metals and Alkaline
earth metals. At high temperature all metals are oxidized.
The exception is Ag, Au and Pt.
2M 2Mn++ 2ne-(De- electronation)
(Metal ation)
nO2+2ne-  2nO2-(Electro-nation) (Oxide

ion)
2M+ nO2 2Mn+ + nO2- = 2MO (Metal oxide)
Mechanism: At the surface of metal oxidation occurs and the resulting

metal oxide scale forms a barrier which restricts further oxidation.
For oxidation to continue either the metal
must diffused outwards
through the scale to the surface or the oxygen must defuse inwards
through the scale to the underlying metal. Both the cases are
possible. But the outward diffusion of metal is generally more
rapid than inward
diffusion of oxygen since metal ion is appreciably smaller than the

oxygen ion and hence more mobile.
Metal + Oxygen Metal oxide
When oxidation starts, a thin layer of oxide is formed on the

metal surface and the nature of this film decides further action. If
the film is,
a)Stable,itbehaveshasaprotectivecoatinginnaturee.g.,theoxide films on Al, Pb,
Cu, Pt etc., are stable and therefore further oxidation corrosionofprohibited.
Metal oxide Metal + Oxygen
e.g., Ag, Au and Pt do not undergo oxidation Corrosion.

b) Volatilethatisoxidelayervolatilizesafterformationandassuchleavestheunderlying metal
surface exposed further attack. This causes continuous which is excessive. e.g. Molybdenum
oxide(MoO3)
c) Porous that is the oxide layer formed having pores or cracks. In this case the
Atmospheric oxygen passes through the pores or cracks of the underlying metal
surface. This causes continuous corrosion till complete conversion of metal
intoitsoxide
Unstable that is the oxide layer formed decomposes back into metal and oxygen. So,
Oxidation Corrosion is not possible.Metaloxide Metal +Oxygen

d) Volatilethatisoxidelayervolatilizesafterformationandassuchleavestheunderlying metal
surface exposed further attack. This causes continuous which is excessive. e.g. Molybdenum
oxide(MoO3)
Porous that is the oxide layer formed having pores or cracks. In this case the Atmospheric
oxygen passes through the pores or cracks of the underlying metal surface. This causes
continuous corrosion till complete conversion of metal into its oxide
18 Define battery? Write the applications of batteries? (Dec 2018 GNITC Level- C
[R18]) 1 O
3
Ans The term battery is generally used for two or more galvanic cells connected in series.
Thus a battery is a series of portable electrochemical cells which are capable of
generating electrical energy.
Applications:
1. Batteries are used in consumer electronic devices like calculators, transistor radios,
flash lights, quartz wall-clocks, walkman etc. and in small portable appliances where
small amount of current isneeded.
2. Laptops, cellular phones, electrical vehicles, Note PC -tabs, Portable electronic
apparatus etc.
19 Define standard electrode potentials? (May 2019 [ R18], May/June 2019 Level- C
[ R18]) 1 O
3
Ans The potential exhibited by single electrode at unit concentration of it’s metal ion at
250 C is called standard electrode potential. It is denoted with E0 volts
20 Why galvanized sheets are not advised in making utensils? (May 2019 Level- C
[ R18]) 3 O
3
Ans Galvanized metal containers are not considered safe for cooking or storage of food.
The galvanizing process creates a coating to the metal that prohibits rust. This coating
contains zinc, which can be toxic when consumed. Cooking utensils andstorage
containers are commonly not made of galvanized steel
21 Give the chemical reactions involved in the functioning of Hydrogen – Level- C
Oxygen fuel cell.(May/June 2019 [ R16]) 3 O
3
Ans Cell reactions:
A t Anode: 2H2(g) + 4OH-(aq)  4H2O +
4e−
AtCathode: O2 + 4H+ + 4e−4OH-(aq)
OverallReaction: 2H2(g) + O2

2H2O
22 Write the electrode reaction of calomel electrode. (Dec/Jan 2020 GNITC

Level- C
[R18])
3 O
3
Ans Hg2Cl2+2e- 2Hg + 2Cl-
And corresponding Nernst’s expression is;
E (Calomel)= E0(Calomel) + 0.0591 log [Mn+]
n
23 Tinned vessels are used for storing food, but not galvanized vessels. Give
Level- C
reason .(Dec/Jan 2020 GNITC [R18])
3 O
3
Ans Tinprotectstheparentmetalbyitsnoblecharacter.Aslongastinlayer isthere,nothing
willhappentosteelbecauseit doesnot undergo anyreactionastinprotectsthesteelby
cathodic nature. Galvanized metal containers are not considered safe for cooking or
storage food. The galvanizing process creates a coating to the metal that prohibitsrust.
This coating contains zinc, which can be toxic when consumed. Cooking utensilsand
storage containers are commonly not made of galvanized steel
24 Define single electrode potential.(Dec/Jan 2020[R18]) Level- C
(Dec/Jan 2020[R18]) 1 O
Ans The potential difference between the electrode and the electrolytic solution in which it 3
is immersed is called is called Single electrode potential.
25 Explain sacrificial anodic technique for prevention of corrosion. (Nov
2020GNITC[R18]) Level- C
3 O
3
Ans
In this method, the metal structure can be protected from

corrosion by connecting it with wire to a more anodic metal.
As this more active metal is sacrificed in the process of saving
metal from corrosion, it is known as sacrificial anode.
The metals which are commonly used as sacrificial anodes

are Mg, Zn, Al and their alloys. The important applications
of this method are
1. Protection of underground cables and pipelines from soilcorrosion.
2. Protection of sheets or rods into domestic water boilers ortanks.
26 Differentiate Galvanic series and Electrochemical series.( Aug 2019

Level- C
SNIST [R18]) 4 O
3
Ans
Electrochemical cell Electrolytic cell
(Galvanic Cell)
A Galvanic cell converts An electrolytic cell converts
chemical electrical energy into chemical energy.
energy into electrical energy.
Here, the redox reaction The redox reaction is not spontaneous
is spontaneous and electrical energy has to be
and is responsible for the supplied toinitiate the reaction.
production of
electrical energy.
The two half-cells are setup Both the electrodes are placed
In different containers, in a same container in the solution of moltenelectrolyt
being connected throughthe
salt bridge orporous
partition.
Here the anode is negative and Here, the anode is positive and
cathode is the positive electrode. cathode is the negative electrode.
The reaction at the anode is The reaction at the anode is
oxidation oxidation and that at the cathode is reduction.
and that at the cathode is
reduction.
The electrons aresupplied The external battery supplies
by the species getting the electrons. They enter
oxidized. They move through thecathode and
from anode to the cathode come out through theanode.
in the externalcircuit.
27 Classify the three different types of batteries with example.( Jan2020

AGI[R18]) C
O
3
Ans
Batteries are classified into two categories depending on
their recharging capabilities and the third category is
fuel cells.
a. Primarybatteries
b. SecondaryBatteries
c. Fuelcells
Primary batteries:These are non-rechargeable and are meant
for a single use and meant to be discarded after use.
Primary batteries are non-rechargeable and are less
expensive and are often used in ordinary gadgets like torch
lights, watches and toys. Commercially many kinds of
primary batteries are available but our discussion only on
Lechlanche’s cell, Alkaline cell and Lithium cell.
Secondary batteries:
Secondary batteries are rechargeable and are meant for a
multicycleuse.Aftereveryusetheelectrochemicalreaction
could be reversed by external application of voltage. The
cycleisreversedtillthecapacityfadesorlostduetoleakage or
internal short circuit. These cells are rechargeable and
reusable. A combination of all reversible electrochemical
cells gives secondary batteries. Many kinds of secondary
batteries are available in the market but we are restricting
our discussion to Lead-acid cell, Ni/Cd cells, Ni-Metal
hydride cell and Lithium ioncells.
S.No. PRIMARY CELLS SECONDARY CELLS
1 Secondary batteries are rechargeable and are These are non-rechargeable and are meant for
meant for a multi cycle use single use and meant to be discarded after use.
2 Cell reaction is not reversible Cell reaction can be reversed
3 Cannot be rechargeable Can be rechargeable
4 Less expensive Expensive
5 Can be used as long as the materials are active Can be used again and again by recharging the cell
in their composition
5 Example: Lechlanche’s cell, Lithium cells Lead acid cell, Nickel-cadmium cell
c. Fuel cells: A cell in which one or both of the reactants are not permanently contained in the
cell, but are continuously supplied from a source external to the cell and the reaction products
continuously removed is called a fuel cell. Unlike the metal anodes typically used in batteries,
the fuels in a fuel cell are usually gas or liquid, with oxygen as the oxidant. It generates
electricity inside a cell through reactions between a fuel and an oxidant, triggered in the
presence of an electrolyte. The reactantsflow into the cell, and the reaction products flow out of
it, while the electrolyte remains within it. Fuel cells can operate continuously as long as the
necessary reactant and oxidant flows are maintained.
Ex: Hydrogen – Oxygen fuel cells
PART–B
1 What is an Electrochemical cell? Explain the construction and reactions of Level-2 CO3
Calomel electrode? (May 2018 [ R16]), (Jan 2020 AGI[18])
Ans Electro chemical cells or voltaic cells or galvanic cells chemical
energy is converted to electrical energy. Daniel cell is an example
for the galvanic cell.
Standard Calomel Electrode –SCE: Calomel electrode is particularly very
simple to construct, free from surface sensitivity and accurate to use even in
a very normal laboratory.
The calomel electrode consists of an inner glass tube and an outer

jacket. In the inner glass tube a platinum wire is dipped into mercury
which rests on a paste of mercurous chloride, Hg 2Cl2 (commercially
known as calomel) and mercury. This paste is in contact with KCl
present in the outer jacket, through the glass frit plug fixed at the
bottom of inner glass tube. The calomel electrode comes in contact
with the experimental solution through a frit arranged to the outer
jacket. The potential of this electrode depends on the concentrationof
KCl taken in the outer jacket. Some of the most popularly used
concentrations of KCl and corresponding single electrode (reduction)
potentials on the hydrogen scale at 250C are givenbelow;
Saturated KCl | Hg2Cl2 (s) |Hg,pt 0.2415V
0.1M KCl | Hg2Cl2 (s) | Hg, pt 0.3338V
1.0M KCl | Hg2Cl2 (s) | Hg, pt 0.2800 KCl |

The corresponding electrode reaction is;Hg2Cl2+2e-
2Hg + 2Cl-
EHg2Cl2|Cl -=E0Hg2Cl2|Cl --2.303loga2Cl -
F
2 What is a fuel cell and mention its applications? Describe construction Level-3 CO3
and working principle of Hydrogen-Oxygen fuel cell. (May 2018 [
R13])]),(Jan 2020SNIST [R18]),(Jan 2020 AGI[18])
Ans In a fuel cell, an electrical energy is obtained without combustion from
oxygen and a gas that can be oxidized. A fuel cell converts the chemical
energy of the fuels directly to electricity.
Applications:
1. It is used as energy source in space shuttles e.g. Apollospacecraft.
2. Used in small- scale applications in submarines and other military
vehicles.
3. Suitable in places where environmental pollution and noiseare
objectionable.
4. Drinking water source in space crafts, submarines and other
militaryapplications.
Fuel Cells
Inafuelcell,anelectricalenergyisobtainedwithoutcombustionfrom
oxygenandagasthatcanbeoxidized.Afuelcellconvertsthechemical
energy of the fuels directly toelectricity.
Fuel cell came into discovery arena in early 1840. Sir William Grove
invented first fuel cell in 1839. For the very first time fuel cell wasused
commercially by NASA to launch space shuttles. Now a days fuel cells
are used as power backup for industries, commercial housing areas
even used in some vehicles, motorcycles, submarines, boats, including
forkliftsetc.
The important process in the fuel cell is Fuel + O2 Oxidation product
+ Electricity
Construction: Both anode and cathode consists porous graphite

electrodes impregnated with finely divided Pt/Pd. The electrolyte is
25% KOH held in asbestos matrix. The reactants (fuel + oxidant)
are constantly supplied from outside and the products are removed at
thesamerateastheyareformed.Theproductdischargediswaterand the
standard EMF of the cell is 0.8 V –1.0V.
The reactions that produce electricity happen at the electrodes. Every
fuel cell has two electrodes, one positive, called the anode, and one
negative, called the cathode. These are separated by an electrolyte
barrier.Fuelgoestotheanodeside,whileoxygen(orjustair)goestothe
cathode side. When both of these chemicals hit the electrolyte barrier,
they react, split off their electrons, and create an electric current. A
chemical catalyst speeds up the reactionshere
Anodic reaction:2H2 4H+ +
4e−Since electrons are lost at
anode it is known as
OxidationReaction.
Cathodic Reaction: O2 + 4H+ +
4e− 2H2O +Heat
Since electrons are gained at cathode it is known as Reduction
Reaction.
Cell reactions
Overall Reaction: 2H2(g)+ O2 2H2O
3 Describe mechanism of electrochemical corrosion by taking Rusting of Level-2 CO3

Iron as an example. (May 2018 [ R13]),(Aug 2019 SNIST [R18])
Ans
This type of Corrosion occurs where a conducting liquid is in contact with the
metal or when two dissimilar metals or alloys are dipped partially in a
solution.
Thiscorrosionoccursduetotheexistenceofseparateanodicandcathodicparts,
between which current flows through the conducting solution. At anodic area,
oxidation reaction occurs there by destroying the anodic metal either by
dissolution or formation of compounds. Hence corrosion always occurs at
anodicparts.
At Anode: M Mn+ + ne-
At cathodic part, reduction reaction (electro nation) occurs. It does not
affect the cathode, since most metals cannot be further reduced. At cathodic
part, the dissolved constituents in the
conductingmediumaccepttheelectronsformingions(OH-,O2-).Themetallic ions
formed at anodic part and the ions formed at cathodic part diffuse towards
each other through conducting medium and form a corrosion product
somewhere between anode andcathode.
Mechanism:
Electrochemical corrosion involves flow of electrons between anode
and cathode. The anodic reaction involves dissolution of metal
liberating free electrons.
M Mn+ + ne-
The cathodic reaction consumes electrons with either evolution of
hydrogen or absorption of oxygen which depends on the nature of
corrosive environment.
Evolution of hydrogen:This type of corrosion occurs in acidic

medium e.g., considering the metal Fe, anodic reaction is dissolution
of iron as ferrous ions with liberation of electrons.
Fe Fe2+ + 2e- ( Oxidation)

The electrons released flow through the metal from anode to cathode,
whereas H+ ions of acidic solution are eliminated as hydrogen gas.
2H++2e-H2
The
overall
reaction
is
Fe +
2H+
Fe2++
H2
This type
of corrosion causes displacement of hydrogen ions from the solution by
metal ions. All metals above hydrogen in electrochemical series have a
tendency to get dissolved in acidic solution with simultaneous evolution of
H2 gas. The anodes are large areas, whereas cathodes are small areas.
Absorptionofoxygen:Forexample,rustingofironinneutralaqueous
solutionofelectrolytesinpresenceofatmosphericoxygen.Usuallythe
surface of iron is coated with a thin film of iron oxide. If the film
develops cracks, anodic areas are created on the surface. While the
metal parts act ascathodes.
At anode: Fe Fe2+ + 2e- (Oxidation)
At cathode:
The released electrons flow from anode to cathode through iron metal.
½ O2 + H2O + 2e-2OH- (Reduction)
Fe2+ + 2OH-Fe(OH)2
If oxygen is in excess, ferrous hydroxide is easily oxidized to ferrichydroxide.
4Fe2+(OH)-2+ O 2+ 2H O 2
4Fe (OH) 3
The product called yellow rust corresponds to Fe2O3. xH2O

4 Define reference electrode? Explain the construction and working of
calomel electrode in the determination of pH of a solution. (Aug 2018 Level-2 CO3
GNITC PHARM[R16]) ,May 2018 [ R16]),May 2017 [R16], Dec 2016
[R16]),(Aug 2019 SNIST [R18])
Ans Refernce electrode:
The electrode which is used to find the potential of an electrode instead of
using standard hydrogen electrode is called reference electrode.
Thecalomelelectrodeconsistsofaninnerglasstube and
an outer jacket. In the inner glass tubea
platinumwireisdippedintomercurywhichrestson a
paste of mercurous chloride, Hg2Cl2 (commercially
known as calomel) and mercury. This paste is in
contact with KCl present in the outer jacket,
through the glass frit plug fixed at the bottom of
inner glass tube. The calomel electrode comes in
contact with the experimental solution through a
frit arranged to the outer jacket. The potential of
this electrode depends on the concentration of KCl
taken in the outer jacket. Some of the most
popularly used concentrations of KCl and
corresponding single electrode(reduction)
potentials on the hydrogen scale at 250C are given
below;
0.1M KCl | Hg2Cl2 (s) |Hg,pt 0.3338V

1.0M KCl | Hg2Cl2 (s) |Hg,pt 0.2800V
The corresponding electrode reaction is; Hg 2Cl2+2e

2 Hg + 2Cl-
E Hg2Cl2/Hg = E0 Hg2Cl2/Hg - 0.0 591 log [ci]-
5 Discuss the differences between Galvanizing and Tinning with neat Level-2 CO3
diagrams? (Dec 2017 [R13])
Ans
Galvanizing Tinning
1. Zinc is coating metal, used to 1 . Tin is coating metal, used to
protect to protectiron. protect to protect iron/steel.
2. Zinc is more electropositive than 2. Tin is more electropositive than
the base metal i.e zinc is anodic to the base metal. i.e Tin is cathodic to
iron. iron.
3. It can not be store acidicproducts.
3.Galvanized article cannot be used
to store acidic foodproducts.
6 What is Daniel cell? Give its cell notation, construction and cell reactions. Level-2 CO3
(April 2018 [R16])
Ans Anelectrochemicalcellisadevicewhichconvertschemicalenergyinto
electrical energy. The redox reaction is utilized for generation of
electrical energy. The electrochemical cells are commonly referred as
Voltaic or Galvaniccells.
Construction of Daniel cell / voltaic cell : It consists of Zinc electrode
dipped in ZnSO4 solution. Where oxidation takes place, known as
oxidation half-cell and copper electrode dipped in CuSO4 solution.
Wherereductiontakesplace,knownasreductionhalf-cell.Thesetwo
solutions are separated by a salt bridge (U- tube containing
concentrated solution of KCl or NH4NO3 in an agar-agar gel). Or
porous pot, it provides an electrical contact between twosolutions.
The following chemical reactions take place
AtAnode:Zn Zn2+ + 2e- (Oxidation Half Reaction)
At Cathode: Cu+2+2e- Cu (Reduction halfreaction)
Net cell reaction Zn +Cu2+ Zn2+ +Cu
7 Explain the construction, charging and discharging reactions of lithium-ion Level-2 CO3
cell. (April 2018 [R16]) , May 2018 [ R16]),(Aug 2019 SNIST [R18])
Ans
Lithium ion Cells:

Lithium metal batteries have some safety disadvantages, Lithium ion
batteries overcomes that problem. Lithium ion battery is a secondary
battery. The movement of lithium ions is responsible for charging and
discharging.
Lithium ion battery has the following 3 components.
1. A positive electrode (layers of lithium-metaloxide)
2. A negative electrode (Layers of porous carbon)anode
3. An electrolyte (Polymer gel)Separator
The negative electrode is made from layers of porous carbon(C)

(Graphite).
Both the electrodes are dipped in a polymer gel electrolyte (Organic
solvent) and separated by a separator which is a perforated and allows
the Li+ ions to pass through.
Working: During charging, Li+ ions flow from the positive electrode (
LiCoO2) to the negative electrode (Graphite) through the electrolyte.
Electrons also from the positive electrode to the electrode. The
electrons and Li+ ions combine at the negative electrode and deposit
there as Li.
LiCoO2+C Li1-xCoO2 + CLix
Discharging: During discharging, the Li+ ions flow back through the
electrolyte form negative electrode to the positive electrode. Electrons
flow from the negative electrode to the positive electrode. The li+ ions
andelectronscombineatthepositiveelectrodeanddepositthereasLi.
Li1-xCoO2 +CLix LiCoO2 +C
Advantages: 1. Lithium ion batteries are high voltage and light weight
batteries.
3. It is smaller insize.
4. It produces 3 time the voltage of Ni-Cdbatteries.
5. It has none of the memory effect seen in Ni-Cdbatteries.
Applications: Laptops, cellular phones, electrical vehicles, Note PC -

tabs, Portable electronic Apparatus etc.
8 With neat diagram explain the principle, construction and applications of Level-3 CO3
Glass electrode.(April 2018 [R16])
Ans
Glass Electrode
They possess an ability to respond to only certain specific ions
therebydevelopingapotentialwithrespecttothatspeciesonlyin
agivenmixtureandignorealltheotherionstotally.Thepotential
developedbyionselectiveelectrodedependsontheconcentration of
specific ion ofinterest.
Eg: Glass electrode specific for H+ ions and pressed pallet ofAg2S
+ AgCl specific for Cl- ions.
Construction:
When two
solutions of
different pH
values are
separated by athin
glass membrane, a
potential
difference
develops between
the two surfaces of
the membrane.
This potential
difference
developed is
proportional tothe
difference in pH
value. The glass
membrane
functions as ion-
exchange resin. An
equilibrium is
established
between Na+ ions
of the glass andH+
ionsinthesolution.
o
The potentialofthe glasselectrodeisgivenby:EG =E G+0.0592pH
Where pH range of the test solution is 1-10.The glass electrode
consists of a thin walled glass tube containing AgCl coated Ag-
electrode or simply Pt-electrode in 0.1M HCl.
Cell representation of glass electrode is given by:

Ag │ AgCl(s) H+ (0.1M) │ Glass or Pt, HCl (0.1M)│ Glass
9 Describe the factors effecting rate of corrosion by nature of metal. (June

Level-2 CO3
2014 [R13], (May/June 2019 [ R18]),(June 2019,Jan2020 SNIST[R18]),
(Jan 2020 AGI[18]), Oct/Nov2020 JNTUH[R18])
Ans
Factors affecting corrosion

The rate and extent of corrosion depends on the nature of the metal and
nature of corrodingenvironment.
NATURE OF METAL:
Purity of metals : Impurities in a metal cause heterogeneity, which
decreases corrosion-resistance of the metal. Thus, the corrosion-
resistance of a given metal may be improved by increasing its purity.
Purification of metals like Al, Mg, etc., provides a coherent and
impervious protective oxide film on their surface, when exposed to
environment. However, corrosion-resistance of a purified metal depends
on the nature of corrosiveenvironment.
Position in galvanic series:when 2 metals or alloys are in electrical contact
inpresenceofanelectrolytethemoreactivemetal havinghigherposition in
the galvanic series undergoes corrosion. The greater is the difference in
position, the faster isthecorrosion.
Galvanic Series:it is used to provide sufficient information in predicting
the corrosion behavior in a particular set of environmental conditions.
Oxidation potential measurement of various metals and alloys has been
made using standard calomel electrode as the reference electrode and
immersing the metals and alloys in sea water. These are arranged in
decreasingorderofactivityandthisseriesisknownasthegalvanicseries.
Natureofsurface/oxidefilm:In aeratedatmosphere,allmetalsgetcovered
withathinsurfacefilmof metaloxides.Theratioofthevolumesofmetal
oxidestothemetalisknownasspecificvolumeratio.Greateristhisvalue lesser
is the oxidation corrosion rate. Specific volume ratios of Ni, Cr and W
are1.6,
2.0 and 3.6 respectively suggesting Tungsten hasleast
corrosion.Furtherthe corrosion depends onnatureof
oxidefilm. Metals like Al
have a firm oxidefilm in comparison
toFeandhenceAlin lesscorrosivemeansitfollowsPilling-Bed
worth Rule. The iron
oxide is porous in nature and this leads to extension of corrosion to
inner surface.
Nature of environment:
a. Temperature:As the temperature of environment is increased the

reaction rate is increased there by accelerating corrosion. The effect of
temperature on the corrosion rate is complicated because of the fact that it
affects the various factors in different ways. The rate of chemical reaction
increases, with rise in temperature but the solubility of gases, like oxygen
which affect corrosion, decreases. The temperature may affect the protective
coatings in different ways. In general, the rate of corrosion due to oxygen
or oxidizingagentsisdecreasedwithriseintemperaturebuttherateofhydrogen
type corrosion isincreased.
b. Effect of pH:In the corrosion reaction described H+ or OH- are also
involved.ThereforetheeffectofpHisobvious.It canbeeasilyseenfromthe
chemical equation for a reaction the direction in which it will shift
bychange
inconcentrationofH+orOH-.Asageneralrule,acidsaremorecorrosivethan
neutral or alkaline solutions. Exceptions to the rule are amphoteric metals,
aluminium, zinc and lead, which form anions as well as cations. In acid
solutions these react quickly like other metals but in alkaline solutions they
form complex ions and go intosolution.
c. Humidity of air:critical humidity is defined as the relative humidity
abovewhichtheatmospherecorrosionrateofmetalincreasessharply.The
value of critical humidity depends on nature of metal and
corrosionproducts. Corrosion of a metal is furnished in humid atmosphere
becausegases (CO2, O2) and vapours present in atmosphere furnish water
to the electrolyte essential to establish an electrochemical corrosion cell.
The oxidefilmonthe metalsurface
d. has the property to absorb moisture. In presence of this absorbed
moisture, corrosion rate is enhanced. Rain water may also wash away the
oxide film from the metal surface. This leads to enhanced atmospheric
attack. The exceptions are Cr,Al.
10 Explain the mechanism of oxidation corrosion. (June 2014 [R13]), Level-2 CO3
(Aug 2019 SNIST [R18]) , Oct/Nov2020 GNITC[R18])
Ans
Oxidation Corrosion:This is carried out by the direct action of
oxygen low or high temperatures on metals in absence of
moisture at ordinary temperature metals or very slightly
attacked. The Exceptions are Alkali metals and Alkaline earth
metals. At high temperature all metals are oxidized. The
exception is Ag, Au and Pt.
2M 2Mn++2ne- (De- electronation)
n
)
nO2+2ne- 2nO2-(Electro-nation) (Oxide

ion)
2M+nO2 2Mn+ + nO2- = 2MO(Metal
oxide)
Mechanism:At the surface of metal oxidation occurs and the
resulting metal oxide scale forms a barrier which restricts further
oxidation. For oxidation to continue either the metal must diffused
outwards
through the scale to the surface or the oxygen must
defuse inwards through the scale to the underlying
metal. Both the cases are possible. But the outward
diffusion of metal is generally more rapid than inward
diffusion of oxygen since metal ion is appreciably smaller
than the oxygen ion and hence more mobile.
Metal+Oxygen Metaloxide
When oxidation starts, a thin layer of oxide is formed on the metal

surface and the nature of this film decides further action. If the
film is,
a) Stable, it behaves has a protective
coating in nature e.g., the oxide films
on Al, Pb, Cu, Pt etc., are stable and
therefore further oxidation corrosion of
prohibited.
b) Unstablethat is the oxide layer formed decomposes back into
metal and oxygen. So, Oxidation Corrosion is not possible.
Metaloxide Metal +
Oxygene.g., Ag, Au and Pt do not undergo
oxidationCorrosion.
Unstable that is the oxide layer formed decomposes back into metal and
oxygen. So, Oxidation Corrosion is not possible
Metaloxide Metal +Oxygen
e.g., Ag, Au and Pt do not undergo oxidation Corrosion
a)Volatilethatisoxidelayervolatilizesafterformationandassuchleaves the
underlyingmetal surface exposed further attack. This causes
continuous which is excessive. e.g. Molybdenum oxide (MoO3)
Porous that is the oxide layer formed having pores or cracks. In this
case the Atmospheric oxygen passes through the pores or cracks of the
underlying metal surface. This causes continuous corrosion till complete
conversion of metal into its oxide.
11 What is Cathodic protection? What are the types of cathodic Level-2 CO3
protection? Explain them. (May 2017 [R13], May 2016[ R15])
Ans CATHODIC PROTECTION: The cathodic protection of metals is used to
control corrosion metals where it is impartibly to alter the nature of the corrosion
medium. The principle involved in this method is to protect metals and alloys
from corrosion by making them completely cathodic. Since there will not be any
anodic area on the metal, therefore corrosion does not occurs
The following are 2 types of cathodic protections.
Sacrificial anodic protection:In this method, the metal structure

canbeprotectedfromcorrosionbyconnecting it withwiretoamoreanodic
metal. As this more active metal is sacrificed inthe process of saving metal
from corrosion, it is known as sacrificial anode. The metals which are
commonly used as sacrificial anodes are Mg, Zn, Al and theiralloys.
The metals which are commonly used as sacrificial
anodes are Mg, Zn, Al and their alloys. The
important applications of this method are
3. Protection of underground cables and pipelines from soil corrosion.
Protection of sheets or rods into domestic water boilers or tanks
b. Impressed current cathodic protection:As the name implies, an impressed
current is applied to convert the corroding metal from anode to cathode. The applied
current is in opposite direction since to nullify the corrosion current. This can be
accomplished by applying sufficient amount of direct current source like battery or
rectifier to an anode like graphite, highsilica iron, stainless steel or platinum buried
in the soil or immersed in the corrosion medium. And connected to the corroding
metal structure which is to be protected as shown in the diagrambelow.
In impressed current cathodic protection, electrons are supplied from an external
cell, so that the object itself becomes cathodic and not oxidized. This
typeofcathodicprotectionhasbeenappliedtoburiedstructuressuchastanks and
pipelines, transmission line-towers, marine piers, laid-up ships etc. since, their
operating and maintenance costs are less, they are well suited for large structures
and long termoperations.
12 Define corrosion? Explain different types of corrosion? (Dec 2018 Level-2 CO3
GNITC[R18])
Ans Corrosion may be defined as “the destruction of a metallic material by

chemical, electrochemical, or metallurgical interaction between the
environment and the metal
Pitting corrosion:
Pitting corrosion is a localized accelerated attack, resulting in the formation of
cavities around which the metal is relatively un-attacked. Thus pitting corrosion
results in the formation of pinholes, pits and cavities in the metal.
Pittingisusuallytheresultofthebreakdownorcrackingoftheprotectivefilm on a metal at
specific points. This gives rise to the formation of small anodic
andlargecathodicareas.Inthecorrosive environmentthisproducescorrosion current.
The pitting corrosion may be due to following reasons:
1. Metal surface are nothomogeneous.

2. External environment is nothomogeneous.
3. Films are not perfectlyuniform.
4. Crystallography directions are not equal in thereactivity.
5. Environment is not uniform with respect to concentration.
Galvanic Corrosion:When two dissimilar metals are electrically connected
and exposed to an electrolyte, the metal higher in electrochemical series
undergoes corrosion. This type of corrosion is called galvanic corrosion.
e.g., Zinc (higher in electrochemical series) forms the anode and is attacked
and gets dissolved; whereas copper (lower in electrochemical series) acts as
cathode.
WaterlineCorrosion:Thissalsoknownasdifferentialoxygenconcentration
corrosion.
In general, when water is stored in a steel tank, it is observed that the
maximum amount of corrosion takes place along a line just beneath the
level ofthewatermeniscus.Theareaabovethewaterline(highlyoxygenated)acts
as cathodic and is not affected by corrosion. However, if the water is
relativelyfreefromacidity,lesscorrosionoccurs.Theproblemofwaterline
corrosion is a matter of concern for marine engineers. This type of
corrosion is prevented to a great extent by painting the sides of the ships by
antifoulingpaints.
13 What is an electro chemical cell? Explain the working principle of Zn-

Cu electro chemical cell .(May/June 2019 [ R16]), (June 2019 Level-2 CO3
SNIST[ R18]), Nov 2020GNITC[R18])
Ans An electrochemical cell is a device which converts chemical energy
into electrical energy. The redox reaction is utilized for generation of
electrical energy. The electrochemical cells are commonly referred as
Voltaic or Galvaniccells.
Construction of Daniel cell / voltaic cell: It consists of Zinc electrode
dipped in ZnSO4 solution. Where oxidation takes place, known as
oxidation half-cell and copper electrode dipped in CuSO4 solution.
Wherereductiontakesplace,knownasreductionhalf-cell.Thesetwo
solutions are separated by a salt bridge (U- tube containing
concentrated solution of KCl or NH 4NO3 in an agar-agar gel). Or
porous pot, it provides an electrical contact between twosolutions.
The following chemical reactions take place
AtAnode:Zn Zn2+ + 2e- (Oxidation Half Reaction)
At Cathode: Cu+2+2e- Cu (Reduction half reaction)
Net cell reaction Zn+ Cu2+ Zn2++Cu
14 Explain the mechanism of Electrochemicalcorrosion with suitable example. Level-2 CO3

(Dec 2015 [ R13]),(Jan 2020SNIST [R18]),( Jan 2020AGI[18]), Nov
2020GNITC[R18])
Ans 1. Wet corrosion/ electro chemical corrosion
This type of Corrosion occurs where a conducting liquid is in contact
with the metal or when two dissimilar metals or alloys are dipped
partially in a solution. This corrosion occurs due to the existence of
separate anodic and cathodic parts, between which current flows
through the conducting solution. At anodic area, oxidationreaction
occurs there by destroying the anodic metal either by dissolution or
formation of compounds. Hence corrosion always occurs at anodic
parts.
AtAnode: Fe Fe2++2e-
The cathodic reaction consumes electrons with either

evolution of hydrogen or absorption of oxygen which
depends on the nature of corrosive environment.
medium e.g., considering the metal Fe, anodic reaction is
dissolution of iron as ferrous ions with liberation of electrons.
Fe Fe2+ + 2e- ( Oxidation)
whereas H+ ions of acidic solution are eliminated as hydrogen
gas.
2H++2e- H2
The overall reaction is
Fe+2H+ Fe2++H2
This type of corrosion causes displacement of
hydrogen ions from the solution by metal ions. All metals
above hydrogen in electrochemical series have a tendency
to get dissolved in acidic solution with simultaneous
evolution of H2 gas. The anodes are large areas, whereas
cathodes are small areas
Absorption of oxygen: -For example, rusting
of iron in neutral aqueous solution of electrolytes in presence of

atmospheric oxygen. Usually the surface of iron is coated with a
thin film of iron oxide. If the film develops cracks, anodic areas
arecreatedonthesurface.Whilethemetalpartsactascathodes. It
Atanode:Fe Fe2+ + 2e-(Oxidation)
At cathode:
.
½ O2 + H2O + 2e- 2OH-
(Reduction)
Fe2++2OH- Fe(OH)2
4Fe2+(OH)- + O + 2H O 4Fe (OH)3
The product called yellow rust corresponds to Fe2O3. xH2O
15 What is electrochemical series? Explain its applications with suitable Level-3 CO3
examples. (May 2019[ R18] ,(May/June 2019 [ R18])
Ans
When the various electrodes (metals) are arranged in the order of
their increasing values of standard reduction potential on the
hydrogen scale, then the arrangement is called electrochemical
series. (or)
When the various electrodes (metals) are arranged in the order of their
decreasing values of standard oxidation potential on the hydrogen scale,
then the arrangement is called electrochemical series
Applications of electrochemical series:

1. Calculation of standard EMF of thecell.
2. Relative ease of oxidation (or)Reduction.
3. Displacement of one element by theother.
4. Hydrogen displacementbehavior.
5. Corrosion tendency of theelements
16 What is cathodic protection? Explain sacrificial anodic method? (May Level-3 CO3
2019[R18]), Nov 2020GNITC[R18])
Ans CATHODIC PROTECTION: The cathodic protection of metals is used to
control corrosion metals where it is impartibly to alter the nature of the corrosion
medium. The principle involved in this method is to protect metals and alloys
from corrosion by making them completely cathodic. Since there will not be any
anodic area on the metal, therefore corrosion does not occurs
Sacrificial anodic protection:In this method, the metal structure

canbeprotectedfromcorrosionbyconnecting it withwiretoamoreanodic
metal. As this more active metal is sacrificed inthe process of saving metal
from corrosion, it is known as sacrificial anode. The metals which are
commonly used as sacrificial anodes are Mg, Zn, Al and theiralloys.
ThemetalswhicharecommonlyusedassacrificialanodesareMg,Zn, Al
and their alloys. The important applications of this methodare
4. Protection of underground cables and pipelines from soil corrosion.
Protection of sheets or rods into domestic water boilers or tanks
17 How pH of a solution is determined by Glass electrode? Discuss. (May Level-2 CO3
2019 [R18]), Oct/Nov2020 GNITC[R18]),
Ans Determination of
pH of unknown
solution by Saturated Calomel electrode: Cell representation:
Construction:
When two
solutions of
different pH
values are separated by athin glass membrane, a potential
difference develops between the two surfaces of the
membrane.
This potential difference developed is
proportional tothe difference in pH value. The glass membrane
functions as ion- exchange resin. An equilibrium is
+ +
established between Na ions of the glass andH ionsinthesolution.
The potential of the glass electrode is given by
Ag │ AgCl(s) H+ (0.1M) │ Glass or Pt, HCl (0.1M)│ Glass
Determination of pH of a solution using Glass electrode:

The glass electrode is placed in the solution under test and is coupled with
saturated calomel electrode. The emf of the cell is measured from the emf,
the pH of the solution is calculated as follows:
Ecell = Eright – Eleft Ecell = Ecal – Eglass
Ecell = 0.2422 – [E0G + 0.0591 pH]
Ecell = 0.2422 – E0G - 0.0591 pH
pH =0.2422 – E0G- Ecell

0.0591
18 Write the detailed note on Electroless plating of Copper? (May 2019 [ Level-4 CO3
R18]),(Jan 2020 SNIST [R18])
Ans Pre-treatment of surface:
a. Fe, Co and Ni can be directly plated
b. Non-conductors, glass, plastics and ceramics are first activated in
SnCl2and HCl followed by drying in PdCl2 and HCl. On drying, the
Pd layer is formed on the surface.
Bath Composition:
Coating solution: CuSO4
Reducing agent: HCHO
Complexing agent: EDTA
Buffer: NaOH, and Rochelle salt (KNaC4H4O6·4H2O) pH = 11,
Temperature = 250C.
Process: The reduction of cupric ions to thin metallic Cu at controlled rate.
Cu+2 + 2HCHO + 2OH-Cu+2 + 2HCHO + 2H2O + H2
Applications: It is used in the preparation of PCBs (Printed circuit boards).
Thin layer of Cu is electroplated on PCBs made up of glass reinforced
rubbers.
Limitation: High cost of chemicals, slow coating rate and poor stability of
the solution.
19 Describe the construction and working of SCE? (May/June 2019 [ R18]) Level-2 CO3
Ans
Thecalomelelectrodeconsistsofaninnerglasstube
and an outer jacket. In the inner glass tube a
below;
0.1M KCl | Hg2Cl2 (s) |Hg,pt 0.3338V

1.0M KCl | Hg2Cl2 (s) |Hg,pt 0.2800V
The corresponding electrode reaction is; Hg2Cl2+2e
2 Hg + 2Cl-
EHg2Cl2/Hg = E0 Hg2Cl2/Hg -0.0591 log [ci]-
20 What is corrosion? Explain theory of chemical corrosion. (May/June
Level-2 CO3
2019 [R18])
Ans Corrosion may be defined as “the destruction of a metallic material by
chemical, electrochemical, or metallurgical interaction between the
environment and the metal
Corrosion (Oxidation)  Metal  Metallic compound +
Energy
Dry (or) Chemical Corrosion:

This type of Corrosion occurs mainly through the direct chemical action of
atmospheric gasses (O2, halogen, H2S, SO2. N2 or anhydrous inorganic
liquid)withmetalsurpassesinimmediateproximity.Threetypesofchemical
Corrosion are asfollows.
1. Oxidation Corrosion:This is carried out by the direct action of
oxygen low or high temperatures on metals in absence of moisture at
ordinarytemperaturemetalsorveryslightlyattacked.TheExceptionsare
Alkali metals and Alkaline earth metals. At high temperature all metals
are oxidized. The exception is Ag, Au andPt.
2M 2Mn+ + 2ne-(De- electro nation)
(Metal ion)
nO2+2ne-2nO2-(Electro-nation)
2M+ nO2 2Mn+ + nO2- = 2MO

(Metaloxide)
Mechanism:Atthesurfaceofmetaloxidationoccursandtheresultingmetal
oxide scale forms a barrier which restricts further oxidation. For oxidation to
continue either the metal must diffused outwards through the
scale to the surface or the oxygen must defuse inwards through the scale
to the underlying metal.
Both the cases are possible. But the outward diffusion of metal is generally
more rapid than inward
diffusionofoxygensincemetalionis appreciablysmallerthantheoxygen ion
and hence more mobile.
Metal +Oxygen Metal oxide
When oxidation starts, a thin layer of oxide is formed on the metal
surface and the nature of this film decides further action. If the filmis,
a) Stable, it behaves has a protective coating in nature e.g., the oxide
films on Al, Pb,Cu,
Pt etc., are stable and therefore further oxidation corrosion of prohibited.
b) Unstable that is the oxide layer formed decomposes back into metal and
oxygen. So, Oxidation Corrosion is notpossible.
Metal oxide Metal + Oxygen
c) Volatilethatisoxidelayervolatilizesafterformationandassuchleavesthe
underlying metal surface exposed further attack. This causes continuous
which is excessive. e.g. Molybdenum oxide(MoO3)
d) Porous that is the oxide layer formed having pores or cracks.In
this case the Atmospheric oxygen passes through the pores or cracks of the
underlying metal surface. This causes continuous corrosion till complete
conversion of metal into its oxide.
Pilling–BedworthRule:Ifvolumeofmetaloxideonthesurfaceofametal is
more than metal, the oxide film will beprotective.
For example: for Al2O3, Fe, Ni, Zn, W, Cr it will be non-protective if the
volume of oxide is less than the volume of metal.
The specific volume ratio of W is 3.6, Cr = 2, Ni = 1.6. Hence, the rate of
corrosion is very less in Tungsten. It is called Pilling – Bed worth rule.
21 Derive Nernst Equation. (May/June 2019 [ R18]) Level-3 CO3

Ans Nernstequation gives the relationship between electrod epotentials and
concentration of electrolytic solutions.

For the general reduction reaction occurring at an electrode,
Mn+ + ne- ↔ M
NernstequationE= E0 + 2.303RTlog [Mn+]

nF
NernstequationE= E0 + 0.0591 log [Mn+]
n
NernstequationE= E0-0.0591 log [Mn+]

n
WhereE° =Standard EMFof thecellfor1M solution at
298 K;
E= electrodepotential ofthe metal;
R =Gas constant
(8.314JK-1mol-1)
T=Kelvin temperature (298K)
n=numberofelectrons
involved in the
cellreaction;
F=Faradayof
electricity (96500)
[Mn+]= activityof metal ions in thesolution is taken equal to
theirmolarities;
22 What is a battery? Explain the functioning of Li ion battery (May/June 2019

Level-3 CO3
[R18],(May 2019 [ R16]), Oct/Nov2020 JNTUH[R18])
Ans Battery:The term battery is generally used for two or more galvanic cells
connected in series. Thus a battery is a series of portable electrochemical
cells which are capable of generating electrical energy.
Lithium ion battery has the following 3 components.

1. A positive electrode (layers of lithium-metaloxide)
2. A negative electrode (Layers of porous carbon)anode
3. An electrolyte (Polymer gel)Separator
Construction: The positive electrode is typically made from a layers of

chemical compound called Lithium cobalt oxide (LiCoO2).
Thenegativeelectrodeismadefromlayersofporouscarbon(C)(Graphite).
Boththeelectrodesaredippedinapolymergelelectrolyte(Organicsolvent) and
separated by a separator, which is a perforated and allows the Li+ ions to
passthrough.
Working: During charging, Li+ ions flow from the positive electrode (
LiCoO2) to the negative electrode (Graphite) through the electrolyte.
Electronsalsofromthepositiveelectrodetotheelectrode.Theelectronsand Li+
ions combine at the negative electrode and deposit there asLi.
LiCoO2 + C Li1-xCoO2 + CLix
Discharging: During discharging, the Li+ ions flow back through the
electrolyte form negative electrode to the positive electrode. Electrons flow
from the negative electrode to the positive electrode. The li+ ions and
electrons combine at the positive electrode and deposit there as Li.
Li1-xCoO2 + CLixLiCoO2 + C
Advantages: 1. Lithium ion batteries are high voltage and light weight
batteries.
2. It is smaller insize.
3. It produces 3 time the voltage of Ni-Cdbatteries.
4. It has none of the memory effect seen in Ni-Cdbatteries.
23 ExplainhowtheGlasselectrodeisusedtodeterminethe PH of agiven
solution .What are the limitations of Glass electrode? (May/June 2019 Level-3 CO3
[ R16], May 2019 [ R16]) Oct/Nov2020GNITC [R18])
Ans Glass electrode is a type of specific ion electrode .It identifies protons
present in the given electrolytic solution
Glass electrode is one of the types of selective electrode. (ISE). It is also
known as specific ion electrode is made up of
glass tube ended with small glass bulb
sensitive to protons. The tube has strong and
thick walls and the bulb is made as thin as
possible. Inside of the electrode is usually
filled with buffered solution of chlorides in
which silver wire is covered with AgCl is
immersed. The pH of internal solution can
be varies. In this electrode, active part of
electrode is this glass bulb. The surface of
the glass is protonated by both internal and
external solution till equilibrium is achieved. Both sides of the glass are
changed by the absorbed protons. And this charge is responsible for
potential difference. This potential is directly proportional to the pH
difference between the solutions on both sides of the glass. Glass electrode
work in the pH range of 1-12 the glass electrode may be represented as
Ag, AgCl/ Hcl (0.1N) / glass / H+ (unknown)
For this, 2.303𝑅𝑇
Nernsteq’is Eg=E0g_ log[H+]
𝐹
= E0g+ 0.059 PH
To find the ph of given solution glass electrode is combined with
SCE Ecll = ESCE - Eglass
= 0.24- [E0g+ 0.059 PH]

= 0.24- E0g - 0.059 PH
pH = 0.24- E0g - Ecll/0.059
Limitations: This electrode only can be used for acidic electrolytes

Electrochemical series has wide range of applications. Illustrate your
24 answer. (Dec/Jan 2020 GNITC [R18]) Level-3 CO3
Ans
series. (or)
Significanceofelectrochemical series:
1. Calculation ofstandard EMFofthecell.
2. Relative easeof oxidation (or)Reduction.
3. Displacement of one element bytheother.
4. Hydrogendisplacementbehavior.
5. Corrosion tendencyof theelements.
25 Differentiate sacrificial anodic and impressed current cathodic

protection with suitable examples. (Dec/Jan 2020 GNITC [R18]), CO3
Level-4
(Jan2020 SNIST [R18])
Ans Sacrificial anodic Impressed current cathodic

protection Protection
1.construction is simple.No 1. Longer anode life
monitoring is required .Monitoring is required
2.Used for small structures 2 Can be used for any type of
structure.
3. Low cost 3.High cost
4.No external power required 4. External power required
5.Active metal acts as anode 5. Active metal acts as anode
26 What is glass electrode? Explain PH of an unknown solution determined
by using glass electrode? (Dec/Jan 2020 GNITC [R18]) Level-3 CO3
Ans Glass electrode is a type of specific ion electrode .It identifies protons
present in the given electrolytic solution
Glass electrode is one of the types of selective electrode. (ISE). It is also
known as specific ion electrode is made up of glass tube ended with small
glass bulb sensitive to protons. The tube has strong and thick walls and the
bulb is made as thin as possible. Inside of the electrode is usually filledwith
buffered solution of chlorides in which silver wire is covered with AgCl is
immersed.ThepHofinternalsolutioncanbevaries.Inthiselectrode,active part
of electrode is this glass bulb. The surface of the glass is protonated by both
internal and external solution till equilibrium is achieved. Both sides of the
glass are changed by the absorbed protons. And this charge is responsible
for potential difference. This potential is directly proportional to the pH
difference between the solutions on both sides of the glass. Glass electrode
work in the pH range of 1-12 the glass electrodemay be
represented as
Ag, AgCl/ Hcl (0.1N) / glass / H+ (unknown)
For this, 2.303𝑅𝑇
Nernsteq’is Eg=E0g_ log[H+]
𝐹
= E0g+ 0.059 PH
To find the ph of given solution glass electrode

is combined with SCE
Ecll = ESCE - Eglass
= 0.24- [E0g+ 0.059 PH]

= 0.24- E0g - 0.059 PH
pH = 0.24- E0g - Ecll/0.059
27 Write the construction and working of calomel electrode. (Dec/Jan

2020[R18]) Level-2 CO3
Ans
Thecalomelelectrodeconsistsofaninnerglasstube
and an outer jacket. In the inner glass tube a
below;
0.1M KCl | Hg2Cl2 (s) |Hg,pt 0.3338V

1.0M KCl | Hg2Cl2 (s) |Hg,pt 0.2800V
The corresponding electrode reaction is;Hg2Cl2+2e

2 Hg + 2Cl-
EHg2Cl2/Hg = E0 Hg2Cl2/Hg -0.0591 log [ci]-
28 Explain electrochemical theory of corrosion by taking rusting of iron as

an example(Dec/Jan 2020[R18]) Level-3 CO3
Ans
This type of Corrosion occurs where a conducting liquid is in contact with the
metal or when two dissimilar metals or alloys are dipped partially in a
solution.
Thiscorrosionoccursduetotheexistenceofseparateanodicandcathodicparts,
between which current flows through the conducting solution. At anodic area,
oxidation reaction occurs there by destroying the anodic metal either by
dissolution or formation of compounds. Hence corrosion always occurs at
anodicparts.
At Anode: M Mn+ + ne-
At cathodic part, reduction reaction (electro nation) occurs. It does not
affect the cathode, since most metals cannot be further reduced. At cathodic
part, the dissolved constituents in the
- 2-
conductingmediumaccepttheelectronsformingions(OH ,O ).Themetallic ions
formed at anodic part and the ions formed at cathodic part diffuse towards
each other through conducting medium and form a corrosion product
somewhere between anode andcathode.
Mechanism:
Electrochemical corrosion involves flow of electrons between anode
and cathode. The anodic reaction involves dissolution of metal
liberating free electrons.
M Mn+ + ne-
The cathodic reaction consumes electrons with either evolution of
hydrogen or absorption of oxygen which depends on the nature of
corrosive environment.

medium e.g., considering the metal Fe, anodic reaction is dissolution
of iron as ferrous ions with liberation of electrons.
Fe Fe2+ + 2e- ( Oxidation)

whereas H+ ions of acidic solution are eliminated as hydrogen gas.
2H++2e-H2
The overall reaction is
Fe + 2H+Fe2+ + H2
This type of corrosion causes displacement of hydrogen ions from the
solution by metal ions. All metals above hydrogen in electrochemical series
have a tendency to get dissolved in acidic solution with simultaneous
evolution of H2 gas. The anodes are large areas, whereas cathodes are small
areas.
Absorption of oxygen:For example, rusting of iron in neutral aqueous
solutionofelectrolytesinpresenceofatmosphericoxygen.Usuallythe
surface of iron is coated with a thin film of iron oxide. If the film
develops cracks, anodic areas are created on the surface. While the
metal parts act ascathodes.
At anode: Fe Fe2+ + 2e- (Oxidation)
At cathode:
The released electrons flow from anode to cathode through iron metal.
½ O2 + H2O + 2e-2OH- (Reduction)
Fe2+ + 2OH-Fe(OH)2
If oxygen is in excess, ferrous hydroxide is easily oxidized to ferric
hydroxide.
4Fe2+(OH)-2+ O 2+ 2H O
2
4Fe (OH) 3
The product called yellow rust corresponds to Fe2O3. xH2O.
29 Explain the principle and working of lead acid storage battery. (Dec/Jan
2020[R18]) Level-3 CO3
Ans OUT OF GNITC SYLLABUS
30 Explain galvanic and pitting corrosion. (Dec/Jan 2020[R18]) Level-3 CO3

Ans Galvanic Corrosion:When two dissimilar metals are electrically
connected and exposed to an electrolyte, the metal higher in
electrochemical series undergoes corrosion. This type of corrosion is called
galvanic corrosion. e.g., Zinc (higher in electrochemical series) forms the
anode and is attacked and gets dissolved; whereas copper (lower in
electrochemical series) acts ascathode.
Pitting corrosion:
Pitting corrosion is a localized accelerated attack, resulting in the formation
of cavities around which the metal is relatively un-attacked. Thus pitting
corrosion results in the formation of pinholes, pits and cavities in the metal.
Pittingisusuallytheresultofthebreakdownorcrackingoftheprotectivefilm on a
metal at specific points. This gives rise to the formation of small anodic
andlargecathodic areas.Inthecorrosiveenvironmentthisproducescorrosion
current.
The pitting corrosion may be due to following reasons:
1. Metal surface are nothomogeneous.

2. External environment is nothomogeneous.
3. Films are not perfectlyuniform.
4. Crystallography directions are not equal in thereactivity.
5. Environment is not uniform with respect toconcentration.
31 Summarize electrochemical series along with the characteristics of
metals present above and below hydrogen. Outline two applications of CO3
Level-2
the series with examples. .(Aug 2019 SNIST[R18])
Ans
series. (or)
Applications of electrochemical series:

1. Calculation ofstandard EMFofthecell.
2. Relative easeof oxidation (or)Reduction.
3. Displacement of one element bytheother.
4. Hydrogendisplacementbehavior.
5. Corrosion tendencyof theelements.
32 Calculate the emf of a concentration cell at 250C consisting of two zinc

electrodes immersed in solutions of Zn+2 ions of 0.1M and 0.01M CO3
Level-5
concentrations.(June 2019 SNIST[R18])
Ans OUT OF GNITC SYLLABUS
33 What do you understanding by Hot dipping? Discuss Galvanizing.( Aug
2019 SNIST[R18])(Jan 2020 AGI [18]). Level-2 CO3
Ans
Hot-dipping:Hot dipping process is applicable to the metals having higher
meltingpoint thanthecoating metal.Itconsistsofimmersingwellcleanedbase
metalinabathcontainingmoltencoatingmetal,andafluxlayer.Thefluxcleans
thesurfaceof thebasemetal and prevents the oxidation ofthemolten
coatingmetal.
Galvanizing:Galvanizing is a process in which the iron article is protected
from corrosion by coating it with a thin layer of zinc. In this process, at first
iron or steel is cleaned by pickling with dilute sulphuric acid solution (H2SO4)
at a temperature range of 60-900C for 15 to20 minutes.
Therefore, it removes scale, rust and other impurities present if any and then
washed well and dried. Then after, dipped in the bath molten zinc which is at
425-4500C. To prevent it from oxide formation, the surface of bath is covered
with a flux (NH4Cl). When the iron piece is taken out it is coated with a thin
layer of zinc. And to remove excess zinc, it is passed through a pair of hot
rollers; lastly, it is annealed at a temperature of 4500C and then cooled slowly.
Galvanizing is widely used for protecting iron exposed to the atmosphere, as
is the case with roofs, wire fences, pipes and articles fabricated from
galvanized sheets like buckets, tubes, etc., Galvanized ware is not used for
keeping eatables because of the solubility of zinc. The popularity of
galvanizing is due the low cost of zinc. Easy application and the
anodic protection offered by the zinc.
34 What is difference between electroplating and electro less plating? Write
about electro less plating on nickel. (Aug 2019 SNIST[R18]) Level-2 CO3
Ans Electrolessplating:
Pre-treatment of surface:
a. Fe, Co and Ni can be directlyplated
b. Non-conductors, glass, plastics and ceramics are first activated
inSnCl2and HCl followed by drying in PdCl2 and HCl. On drying,
the Pd layer is formed on thesurface.
Bath Composition:
Coating solution: CuSO4
Reducing agent: HCHO
Complexing agent: EDTA
Buffer: NaOH, and Rochelle salt (KNaC4H4O6·4H2O) pH = 11,
Temperature = 250C.
Process: The reduction of cupric ions to thin metallic Cu at controlled rate.
Cu+2 + 2HCHO + 2OH-Cu+2 + 2HCHO + 2H2O + H2
Applications: It is used in the preparation of PCBs (Printed circuit boards).
Thin layer of Cu is electroplated on PCBs made up of glass reinforced
rubbers.
ELECTROPLATING ELECTROLESSPLATING
1.coating of a metal on the 1.coating of a metal on the
surface of another metal by surface of another metal
passing electricity without passing electricity
2.electrodes are needed for 2.atalytically activated
electroplating surface is needed for
electrolessplating
3.Deposition cannot be 3. Deposition can be done
done on nonmetals such as on nonmetals such as
plastics ceramics plastics ceramics
4.Deposition of metal done 4. Deposition of metal
by electrochemical reaction . done by chemical reaction
What is galvanic corrosion?Give about corrosion controle methods. (Oct/Nov2020 JNTUH[R18])
Galvanic Corrosion:When two dissimilar metals are electrically connected and exposed to an electrolyte,
the metal higher in electrochemical series undergoes corrosion. This type of corrosion is called galvanic
corrosion. e.g., Zinc (higher in electrochemical series) forms the anode and is attacked and gets dissolved;
whereas copper (lower in electrochemical series) acts ascathode.
CATHODIC PROTECTION: The cathodic protection of metals is used to control corrosion metals
whereitisimpartiblytoalterthenatureofthecorrosionmedium.Theprincipleinvolvedinthismethod is to protect
metals and alloys from corrosion by making them completely cathodic. Since there will not be any anodic
area on the metal, therefore corrosion doesnot occurs.
a. Sacrificial anodicprotection
b. Impressed current cathodicprotection
A.Sacrificial anodicprotection:
In this method, the metal structure can be protected from corrosion by connecting it with wire to a
moreanodicmetal.Asthismoreactivemetalissacrificedintheprocessofsavingmetalfromcorrosion, it is known as
sacrificialanode.
The metals which are commonly used as sacrificial anodes are Mg, Zn, Al and their alloys. The important
applications of this method are
1. Protection of underground cables and pipelines from soilcorrosion.
2. Protection of sheets or rods into domestic water boilers ortanks.
a. Impressed current cathodic protection:As the name implies, an impressed current is applied to convert
the corroding metal from anode to cathode. The applied current is in opposite direction sinceto nullify the
corrosion current. This can be accomplished by applying sufficient amount of direct current source like
battery or rectifier to an anode like graphite, high silica iron, stainless steel or
platinumburiedinthesoilorimmersedinthecorrosionmedium. Andconnectedtothecorrodingmetal structure
which is to be protected as shown in the diagrambelow..
Inimpressedcurrentcathodic protection, electronsaresupplied fromanexternalcell,sothattheobject itself becomes
cathodic and not oxidized. This type of cathodic protect ion has been applied toburied
structures such as tanks and pipelines, transmission line-towers, marine piers, laid-up ships etc. since, their
operating and maintenance costs are less, they are well suited for large structures and long term operations.
8Unit-3B. Srinivas,
PART-A – ANSWERS
Unit-4
PART–A
1 SN1 reaction occurs with retention of configuration, why? (Jan 2019 Level-4 CO4
SNIST [A18]) Oct/Nov2020 GNITC[R18])
A In SN1 reactions, the rate of the reaction depends only on the concentration of the substrate and
is independent of concentration of nucleophile. It produces mirror image products.
The carbocation intermediate is formed in the reaction's rate determining step
is sp2hybridized carbon with trigonal planar molecular geometry. This allows two different
ways for the nucleophilic attack, one on either side of the planar molecule. If neither ways is
preferentially favored, these two ways occur equally, yielding inverted as well as retained
configuration of enantiomers (racemicmixture) if the reaction takes place at a
stereocenter. So, the percentages of product showing inversion and retention configuration
depends upon reactantsinvolved.
2 Write the structure and synthesis of paracetamol. (Jan 2019 CVR Level-3 CO4
[R18])
A Paracetamol is a non–narcotic or non-addictive analgesic compound.
Synthesis: 4-Aminophenol reacts with acetic anhydride to get paracetamol.
3 Why Markovnikov’s rule fails in the addition of HBr to propene in Level-4 CO4
presence of H2O2? (Dec 2018 [ R18])
A Addition of HBr to propene in presence of H2O2 forms n-bromo propane rather than isopropyl
bromide because in the presence of hydrogen peroxide the addition takes place by free radical
mechanism rather than ionic mechanism.
4 State and explain Saytzeff rule? (Dec 2018 GNITC [R18]) Level-1 CO4
A Saytzeff rule: It states that neutral substrates capable of forming double bond on either side of
the chain prefer to yield most substituted alkene i.e. the loss of –hydrogen occurs preferably
from the most substituted position.
According to this rule, major product is the most substituted alkene i.e., major product is
obtained by elimination of H+ from that β-carbon which has the least number of hydrogens.
Product of the reaction in this case is known as Saytzeff product
5 Write a short note on Hydro-boratian of olefins.(Dec 2018 GNITC Level-3 CO4

[R18])
A Borane (BH3) is unstable and exists in the form of diborane (B2H6). It is a colorless gas.
To stabilize boron hydride in the form of BH3, Lewis bases such as amines and ethers are used.
Addition of BH3 group to an alkene is called as Hydroboration of olefins.
6 What is SN1 reaction? (Jan-2017 GNITC B-Pharm[R16]) Level-1 CO4
A The SN1 reaction is a substitution reactionin organic chemistry. "SN" stands for
"nucleophilicsubstitution", and the "1" says that the rate-determining stepis unimolecular.
InSN1reactions,therateofthereactiondependsonlyontheconcentrationofthesubstrateand is
independent of concentration ofnucleophile.
SN1 reaction mechanism favours low temperature. It produces mirror image products.
Reaction: R-X + :Nu-R-Nu + X-
7 Write bayers (KMnO4) Oxidation with Example? (May 2016 Level-3 CO4
JNTUH PHARM [R15]
A The substance used for oxidation is called oxidizing agents.
Examples: KMnO4 and chromic acid (CrO3).
Oxidation of alcohols using KMnO4:
Alcohols when oxidized with acidified KMnO4 to form carbonyl compounds.
8 Explain Saytzeff rule, with an example? (May 2016 PHARM [R15] Level-2 CO4
A Saytzeff rule: It states that neutral substrates capable of forming double bond on either side of
the chain prefer to yield most substituted alkene i.e. the loss of –hydrogen occurs preferably
from the most substituted position.
According to this rule, major product is the most substituted alkene i.e., major product is
obtained by elimination of H+ from that β-carbon which has the least number of hydrogen.
Product of the reaction in this case is known as Saytzeff product.
9 Write the reaction involved in the addition of HBr to propene in the Level-3 CO4
presence of peroxide? (May 2019 [R18])
A Anti Markovnikov’s rule: In the presence of Peroxide, addition of HBr tounsymmetrical
alkene,thehydrogenatomofHBrbecomesbondedtothecarbonatomthathadtheleastnumber of
hydrogen atoms in the starting alkene. It is also called as Anti Markovnikov’srule.
Example: Addition of HBr to Propene
10 Explain Grignard addition on carbonyl compounds. (May/June 2019 Level-2 CO4
[ R18])
A Grignard additions on carbonyl compounds: Organo Magnesium Halide (R-Mg-X)
reagents are known as Grignard reagents .Formaldehyde react with Grignard reagent and it
form primary alcohol, other aldehydes form secondary alcohols .
11 SN2 reaction gives inverted configuration of product. Explain with an Level-3 CO4
example. (Dec/Jan 2020 GNITC [R18]),?(Jan 2020 SNIST [R18])
A SN2 reaction takesplace in a concerted(single step)manner.Unlike, here leaving group is still
intact with the substrate so nuceofile can not attack from the same side as the leaving
group.Hence nuleopjile attacks the substrate from theopposite side of the leaving group
leading to walden invertion at chiral centre
H3C-Cl + OH-  H3C-OH + Cl-
12 Define and give examples for electrophiles and nucleophiles. Level-1 CO4
(Dec/Jan 2020 GNITC [R18])
A ElectrophilesareatomsormolecUlesknowntobeelectrondeficientandthatcarryapartial(or fUlly)
positive charge and will seek an electron pair to form acovalent bond.
electrophilesarehydroniUmion(H3O+,fromBrønstedacids),borontriflUOride(BF3), alUminUm
chloride(AlCl3),
A nuCleophile is a chemical species that donates an electron pair to form a chemical bond
in relation to a reaction. All molecUles or ions with a free pair of electrons or at least one pi
bond can act as nUCleophiles. BecaUSe nUCleophiles donate electrons, they are by definition
Lewis bases.
Example of nUCleophiles are anions sUCh as Cl−, or a compoUnd with a lone pair of electrons
such as NH3 (ammonia
13 Explain electrophilic addition reaction with an example. (Dec/Jan Level-3 CO4
2020[R18]) OR
A
Electrophilic addition reactions: These reactions are brought about by electrophiles and
occurs in compounds containing “C=C” double and triple bonds.
Example:
Addition of HBr to Propene:
14 Differentiate addition and substitution reactions. Level-4 CO4

A Addition Reactions:
A reaction in which the substrate and the reagent add up to form

a product is called Addition reaction. This reactions generally
takes place in compounds containing multiple bonds.
Substitution Reactions: In these types of reactions, an atom or

group replaces another atom or group present in acompound,
without causing a change in the stricture of thatcompound.
Hydrolysis of an alkylbromide:
(H3C)3C-Br + :OH-(H3C)3C-OH + :Br-
PART–B
1 What is oxidation ?Give the mechanism of oxidation of alcohols with Level-3 CO4
CrO3 .(Jan 2019 SNIST [A18])
A Oxidation :
Oxidation involves loss of electrons or increasing oxidation
state.Oxidation takes place with loss of hydrogen (dehydrogenation) or
addition of oxygen. The substance used for oxidation is called oxidizing
agents.
2 What is unimolecular elimination? Give an example. .(Jan 2019 SNIST Level-3 CO4
[A18])
A An E1 (unimolecular elimination) elimination reaction is a type of
organic reaction in which two substituents are removed from
a molecule in two-steps, two-step mechanism elimination is
known as the E1 reaction.
Dehydro halogenation of Alkyl-halides: Alkyl halides undergo Dehydro halogenation
formation of unsaturated hydrocarbons like alkene and alkynes.
Step1: In this stage leaving group (Cl-) breaks
away along with the bond electrons. This is
rate determination step and slow step.
Step2: In this step, the carbon loses a proton to from alkene,

it is fast step.
3 Differentiate SN1 & SN2 reactions? (Jan 2019 SNIST [A18]) Level-4 CO4
A SN1 SN2
Two : One :
(1)R:X→ R+ +X- R:X+ Nu- → RNu+ X-
Steps (2)R+ + Nu- →RNu
Rate =K [RX] (1st order) =K[RX][:Nu-] (2ndorder)
TS of slow step
Stereochemistry Inversion and racemization Inversion (backside attack)

Molecularity Unimolecular Bimolecular
Reactivity structure 3o>2o>1o>CH3 CH3>1o>2o>3o

of R Determining Stability ofR+ Steric hindrance in R group RI>
Factor Nature of X RI> RBr> RCl> RF RBr> RCl> RF
Solvent effect on rate Rate increases in polar solvent with Nu- there is a large rate
increase in polar aprotic solvents.
Effect of nucleophile No effect as it does not appear in the Ratedependson nucleophilicity I-
rate expression. >Br- >Cl-;RS- >RO-
Catalysis Lewisacid, eg. Ag+, AlCl3, ZnCl2 None
Competitive reaction Elimination, rearrangement Elimination
4 Explain SN1 mechanism by taking suitable example? (Jan 2019 CVR Level-2 CO4
[R18])
A
Unimolecular Nucleophilic substitution Reaction Mechanism (SN1): In SN1 reactions, the rate of the
reaction depends only on the concentration of the substrate and is independent of concentration of
nucleophile.
SN1 reaction mechanism favours low temperature. It produces

mirror image products.
Mechanism: It follows first order kinetics and it is two step mechanism.
Step1: The first step is the slow and it is the rate determining step
Rate = k[RX]
R-X R+ + X-
Step2: The second step is fast, involves the attack of the nucleophile
on the carbocation.
Eg. R+ + :Nu- R-Nu
Eg. Nucleophilic substitution on t-butyl chloride:
5 Write a note on elimination reactions with examples? (Jan 2019 CVR Level-3 CO4
[R18])
A Elimination reactions:
Thereactionsinwhichtwogroupsareeliminatedfromamoleculeneitherbeingreplacedby another
group are called eliminationreactions.
Elimination reactions are two types:

1.E1- elimination reaction
2.E2- elimination reaction
E1- elimination reaction:
An E1 elimination reaction is a type of organic reaction in

which two substituents are removed from a molecule in two-
steps, two-step mechanism elimination is known as the E1
reaction.
Dehydro halogenation of Alkyl-halides: Alkyl halides undergo Dehydro halogenation
E2- elimination reaction:
An E2 elimination reaction is a type of organic reaction in

which two substituents are removed from a molecule in one-
step, one-step mechanism elimination is known as the E2
reaction.
6 Give the synthesis and pharmaceutical applications of Aspirin. (Jan Level-6 CO4
2019 CVR [R18])
A Synthesis:-
Salicylic acid react with acetic-anhydride in presence of conc.H 2SO4 or H3PO4, it acts as catalyst to
produce aspirin, co-product is acetic acid.
Pharmaceutical Applications:-
 Aspirin is an effective analgesic (painreliever)
 Antipyretic- free from pyrogens or feverreducer
 Anti-inflammatory drug, it prevents aggregation of platelets and it can prevent strokes.
It is also used in the treatment of rheumatoid arthritis and osteoarthritis
7 What are SN1 and SN2 reactions? Write the mechanism with suitable Level-3 CO4
examples? Give their stereochemistry. (Dec 2018 [R18]), Nov
2020GNITC[R18])
A unimolecular nucleophilic substitution reaction mechanism(SN1): In SN1 reactions, the rate
of the reaction depends only on the concentration of the substrate and is independent of
concentration of nucleophile.
SN1reaction mechanism favours low temperature. It produces mirror image products.
Mechanism:- It follows first order kinetics and it is two step mechanism.
Step 1: The first step is slow and it is the rate determining step.
Rate=k[RX]
R-X R+ + X-
Step 2:- The second step is fast, involves the attack of nucleophile on the carbocation.
Streochemistry of SN1 reaction:-

The carbocation intermediate is formed in the reaction's rate determining step is
an sp2hybridized carbon with trigonal planar molecular geometry. This allows two different
avenues for the nucleophilic attack, one on either side of the planar molecule. If neither avenue is
preferentially favored, these two avenues occur equally, yielding a racemicmixture of
enantiomers if the reaction takes place at a stereocenter.
Bimolecular nucleopholic substitution reaction mechanism (SN 2):- In SN2 reactions, the rate
of reaction depends on the concentration of the substrate and also concentration of nucleophile.
It is a single step reaction.
Rate of the reaction = k[R-X] [:Nu-]
2
SN reaction example:-
Methyl chloride in aqueous NaOH solution .
H3C-Cl + OH-  H3C-OH +Cl-
Substrate Nucleophile Product leavinggroup
Rate ɑ [H3C-Br] [OH-]
Mechanism
Stereochemistry of SN2Reactions
In this path, the nucleophile attacks the carbon atom from the side opposite to that of the leaving
group to form the transition state (TS).
In this state carbon atom is SP2 hybridized.
The three (3) Hydrogen atoms and carbon lie in one plane with C-OH and c-Cl bonds lying
perpendicular to the plane.
Thetransitionstate(TS) subsequentlycollapsetoformtheproducts.Theenergyrequired to break
the C-Cl bond is compensated by the energy released during the making of the C-OH bond.
Since purely SN2 reactions show 100% inversion in stereochemical configuration, it is clear that
these Reactions occur through a backside attack
8 What are Elimination reactions? Explain Dehydro halogenations of Level-2 CO4

alkyl halides with suitable examples? (Dec 2018 [R18])
A Elimination reactions :The reactions in which two groups are eliminated from a molecule neither
being replaced by another group are called elimination reactions.
Dehydro halogenation of alkyl-halides:
Alkyl halides undergo dehydro halogenation formation of unsaturated hydrocarbons like alkene
and alkynes.
away along bond electrons.
This is rate determination step and slow step.

it is fast step.
9 Explain the mechanism of SN1 and SN2 reactions with one example? Level-2 CO4
(Dec 2018 GNITC [R18])
A Unimolecular nucleophilic substitution reaction mechanism(SN1): In SN1 reactions, the rate
Rate=k[RX]
R-X R+ + X-
Bimolecular nucleopholic substitution reaction mechanism (SN 2):- In SN2 reactions, the rate
of reaction depends on the concentration of the substrate and also concentration of nucleophile. It
is a single step reaction.
SN2 reaction example:-

Methyl chloride in aqueous NaOH solution .
H3C-Cl + OH- H3C-OH +Cl-
Mechanism
 Inthispath,thenucleophileattacksthecarbonatomfromthesideoppositetothatof the
leaving group to form the transition state(TS).
 In this state carbon atom is SP2hybridized.
 The three (3) Hydrogen atoms and carbon lie in one plane with C-OH and c-Cl
bonds lying perpendicular to theplane.
 The transition state (TS) subsequently collapse to form theproducts.
 The energy required to break the C-Cl bond is compensated by the energyreleased
during the making of the C-OHbond.
10 State and explain Markovnikov’s rule and Anti Markovnikov’s? Why Level-2 CO4
the rule does fails? (Dec 2018 GNITC [R18])
A Markovnikov’s rule: when an unsymmetrical alkene reacts with a ‘HX’ to give alkyl halide, the
hydrogen adds to the carbon of the alkene that has the more number of hydrogen substituents,
and the halogen to the carbon of the alkene with the fewer number of hydrogen substituents. It
rule is known as Markovnikov’s rule.
Anti Markovnikov’s rule: In the presence of Peroxide, addition of
HBr tounsymmetrical alkene, the hydrogen atom of HBr
becomes bonded to the carbon atom that had the least
number of hydrogen atoms in the starting alkene. It rule is
known as Anti Markovnikov’s rule.
Addition of HBr to propene in presence of H2O2 forms 1-bromo propane rather than 2 bromo
propane because in the presence of hydrogen peroxide the addition takes place by free radical
11 Explain the preparation method and mention its pharmaceutical Level-6 CO4
applications of Aspirin? (Dec 2018 GNITC [R18]), Nov
2020GNITC[R18])
A Structure:
Preparation : Salicylic acid react with aetic anhydrie

presence of conc. H2SO4, produce aspirin, co product is
acetic acid
Pharmaceutical applications:
Aspirin is an effective analgesic (pain reliever)
Antipyretic – free from pyrogens or fever
reducerAnti-inflammatory drug, it prevents
aggregation of platelets and it can prevent strokes. It
is also used in the treatment of rheumatoid arthritis
and osteoarthritis.
12 What is kharasch effect? Explain with an example? (Jan2017 GNITC Level-2 CO4
PHARM-R-16]
A Kharash Effect or also also popUlarly named as anti markownikoff's rUle is the effect
when alkenes react with hydrogen halides asymmetrically in the presence of
peroxides(mostlyofbenzenes).IthappensonlywiththeadditionofHBr.Thereaction
proceeds via free radical mechanism
Ex:
13 Explain the reaction when a hydrogen halide reacts with alkenes? (Jan Level-2 CO4
2017 GNITC PHARM[R16])
A
Hydrogen halide reacts with alkenes is example for Electrophilic addition
Electrophilic addition reactions: These reactions are brought about by electrophiles
and occurs in compounds containing “C=C” double and triple bonds
Example:
14 Explain Saytzeff rule with example. (Jan 2017 GNITC PHARM[R16]), Level-2 CO4
Nov 2020GNITC[R18])
A
Saytzeff rule: It states that neutral substrates capable of forming double bond on either side of the
–hydrogen occurs preferably
fromthe most substitutedposition.
Accordingtothisrule,majorproductisthemostsubstitutedalkene i.e.,
major product is obtained by elimination of H+ from that β-
carbon which has the least number of hydrogen. Product of the
reaction in this case is known as Saytzeffproduct.
15 Explain the factors that play role in SN1 and SN2? (May 2016 PHARM Level-2 CO4
[R15] )
A Since SN1 reaction is first order reaction so the factors that affect SN1 reaction are:
Rate is directly proportional to [alkyl halide]
1. weak nucleophile with low concentration isrequired

2. Better leaving group is required for thereaction
3. Formation of carbocation should bestable
4. Alkyl halide is stericallyhindered
5. Polar protic solvent with high dielectric constant isrequired.
Now the SN2 reactions are those reactions which follows 2nd order kinetics in this only
transition state form no formation of intermidate takes place and factors that affect SN2 reactions
are
Rate is directly proportional to [alkyl halide] [conc. Of nucleophile]
1. Stability of transitionstate
2. Better leaving group isrequired
3. Nucleophile attack should bestrong
4. Solvent medium isrequired
5. Catalyst is required which tells the rate ofreaction
16 Explain briefly walden-invertion with an example? (May 2016 PHARM Level-2 CO4
[R15] )
A SN2 reaction takesplace in a concerted(single step)manner.Unlike, here leaving group is still
intact with the substrate so nuceofile can not attack from the same side as the leaving
group.Hence nuleopjile attacks the substrate from theopposite side of the leaving group leading
to walden invertion at chiral centre
H3C-Cl + OH-  H3C-OH + Cl-
17 Explain the Markovnikov’s rule with suitable example. Why this rule
failed during the addition of HBr in presence of a peroxide? (May 2019[ Level-2 CO4
R18])
Markovnikov’s rule: when an unsymmetrical alkene reacts with a

‘HX’ to give alkyl halide, the hydrogen adds to the carbon of the
alkene that has the more number of hydrogen substituents, and the
halogen to the carbon of the alkene with the fewer number of
hydrogen substituents. It rule is known as Markovnikov’s rule.
Mechanim:
Addition of HBr to propene in presence of H2O2 forms n-bromo propane rather than isopropyl
bromide because in the presence of hydrogen peroxide the addition takes place by free radical
18 Write the synthetic methods for paracetamol and aspirin. Give their
pharmaceutical applications? (May 2019[ R18]) Level-6 CO4
Synthesis: 4-Aminophenol is reacts with acetic anhydride produce

A paracetamol.
It is a common pain killer used to treat aches and

pain. It also acts as anti-pyretic ie, it reduces fever.
It is used to ease mild to moderate pain from head-aches, muscle and joint pains etc.
Synthesis of aspirin: Salicylic acid react with acetic-anhydride in presence of conc. H2SO4 or
H3PO4, it is acts as catalyst to produce aspirin, co product is acetic acid.
Aspirin is an effective analgesic (pain reliever)
Antipyretic – free from pyrogens or fever reducer
Anti-inflammatory drug, it prevents aggregation of platelets and it can prevent
strokes. It is also used in the treatment of rheumatoid arthritis and osteoarthritis.
19 Explain the mechanism of Dehydro halogenations of alkyl Level-2 CO4
halides.(May/June 2019 [ R18])
A Dehydro halogenation of Alkyl-halides: Alkyl halides undergo Dehydro halogenation
away along with the bond electrons. This is
rate determination step and slow step.

it is fast step.
20 Explain the mechanism of SN1 and SN2 reactions? Level-2 CO4

(May 2019 [R18],May/June 2019 [ R18])
A unimolecular nucleophilic substitution reaction mechanism(SN1): In SN1 reactions, the rate
Rate=k[RX]
R-X R+ + X-
Mechanism:
Bimolecular Nucleophilic substitution Reaction Mechanism (SN 2): In SN2 reactions, the rate of the
reaction depends on the concentration of the substrate and also concentration of nucleophile. It is single
stepreaction.
It is second order reaction.

Rate is dependent on concentration and strength of thenucleophile.
Transition state is formed which is SP 2 hybridized planar structure
No carbocation formation takes place in thisreaction
Rate of reaction depends on 10> 20> 30 substrates
Walden inversion product formation takes place in this reaction.
SN2 Reaction – Example:
Methyl Chloride in aqueous NaOH solution
H3C-Cl + OH- H3C-OH + Cl-


Mechanism:
21 Discuss reduction of carbonyl compounds using LiAlH4. (May/June Level-2 CO4
2019 [ R18])
A LAH is a powerful, versatile and non-selective reducing agent. LAH can reduce aldehydes to primary
alcohols, ketones to secondary alcohols.
Mechanism: Reduction of Aldehydes using LiAlH4
23 State and explain saytzeff’s rule with suitable examples.(Dec/Jan 2020 Level-3 CO4
GNITC [R18]) Oct/Nov2020 GNITC[R18])
A Saytzeffrule:Itstatesthatneutralsubstratescapableofformingdoublebondoneithersideofthe chain
prefer to yield most substituted alkene i.e. the loss of –hydrogen occurs preferably from the
most substitutedposition.
According to this rule, major product is the most substituted alkene i.e., major product is obtained
by elimination of H+ from that β-carbon which has the least number of hydrogen. Product of the
reaction in this case is known as Saytzeff product.
24 KMNO4 is powerful oxidizing agent. Illustrate the reactions with Level-3 CO4
suitable examples.(Dec/Jan 2020 GNITC [R18])
A KMNO4 is powerful oxidizing agent
25 Explain the mechanism of reduction of carbonyl compounds to Level-2 CO4

alcohols using LiALH4. (Dec/Jan 2020[R18])
A LAH is a powerful, versatile and non-selective reducing agent.
Mechanism: Reduction of Aldehydes using LiAlH4
26 Explain markownikov’s rule with the help of an example. (Dec/Jan Level-3 CO4
2020[R18]), Oct/Nov2020 JNTUH[R18])
A Markovnikov’s rule: when an unsymmetrical alkene reacts with a ‘HX’ to give alkyl halide, the
hydrogen adds to the carbon of the alkene that has the more number of hydrogen substituents,
and the halogen to the carbon of the alkene with the fewer number of hydrogen substituents. It
rule is known as Markovnikov’s rule.
Mechanism:
27 Discuss the mechanism involved in oxidation of alcohols using KMnO4 Level-3 CO4
(Dec/Jan 2020[R18]).(May/June 2019 [ R18])
The substance used for oxidation is called oxidizing agents.
Oxidation of alcohols using KMnO4:
Alcohols when oxidized with acidified KMnO4 to form carbonyl compounds.
Primary Alcohols
Secondary Alcohols
30 How do you prepare 1-Bromo propane from propene?.Explain the Level-3 CO4
mechanism. (Oct/Nov2020 GNITC[R18])
Addition of HBr to propene in presence of H2O2 forms 1-bromo propane
,in the presence of hydrogen peroxide the addition takes place by free
radical
Addition of HBr to alkenein the presence of Peroxide, , the hydrogen
atom of HBr becomes bonded to the carbon atom that had the
least number of hydrogen atoms in the starting alkene. It rule is
known as Anti Markovnikov’s rule.
PART-B
1 What is electronic spectroscopy? Explain about different types of Level-2
electronic excitation? (Dec 2018 GNITC [R18]) Oct/Nov2020 GNITC[R18])
Types of electronic excitations or transitions:
According to the molecular orbital theory, when a molecule is excited by the

absorption of energy (Uv or Visible light), its electrons are promoted from a bonding
to an antibonding orbital.
They are four (4) types.

* Transitions: It is a high energy process, -bonds are very strong. The
organic compounds in which all the valence shell electrons are involved in the
formation of “” bonds. Such transitions requires short wavelength <200m.
Example: saturated hydrocarbons methane, propane absorption occurs near 150 m.
n* Transitions: This type of transition takes place in saturated compounds
containing one hetero atom with unshared pair of electrons (n e-s).
Example: saturated halides, alcohols, ethers, aldehydes, ketones and amines etc.
Comparatively -*to n-* is required less energy.
In saturated alkyl halides, the energy required for such a transition decreases with
increases in the size of halogen atom or decreases in the electronegativity of the
atom.
Note:comparen* transition in H3C-Cl (169 nm) and H3C-I (258 nm), due to the
greater electronegativity of ‘Cl’ atom, ‘n’ electrons on Chlorine atom are
comparatively difficult to excite.
*Transitions: This type of transition occurs in the unsaturated centers of

the molecule.
Compounds containing double and triple bonds and also in aromatics.
The excitation of ‘’ electrons requires smaller energy and hence transition of this
type occurs at longer wavelength.
Examples:alkenes (ethane, propene), alkynes (ethyne, propyne)
Unconjugated alkenes absorbs around 170-190 nm
Conjugated compounds absorbs around 180 nm.
n* Transitions: In this type transition, an electrons of unshared electron pair on

hetero atom gets excited to *antibonding orbital.
It is requires least amount of energy out of all the transitions.
Examples: aldehydes and ketones
2 What is the selection rules employed in uv visible spectroscopy? Give Level-4

applications of fluorescence in medicine. (Jan 2019 SNIST [A18]),
SELECTION RULES:Dipole moment ( =d)
The most fundamental requirement for infrared (IR) activity is that a vibration must
cause change in the dipole moment of themolecule.
Examples: HCl, CO – Polar (IRactive)
H2, N2– Nonpolar (IR inactive)
Exception: CO2 is non polar still IR active, this is due to asymmetric stretching of
CO2 occurs a change in dipole moment and active.
Example: CO2 various vibrations
The molecules which exhibits harmonic oscillations can be identified in IR
spectroscopy.
The harmonic oscillations (vibrations) can be represented as ΔV= ±
The intensity of fundamental absorption depends upon the differences between the
dipole-moments of the molecule in the ground state and the vibrational excited state.
Greater the difference more is the intensity of absorption.
Since most molecules are in the vibrational level at room temperature V=0. Most
transitions occur from V=0 to V=1.
Force constant:It is defined as the applied force if the displacement in the spring is
unity.
Force constant which ultimately refers to Hooke's law. It states that the force (F)
needed to extend or compress a spring by somedistance.
3 What are various electronic transitions? Give a brief note with suitable Level-2
exmple. (Dec 2018 [R18])


* Transitions: It is a high energy process, -bonds are very strong. The
organic compounds in which all the valence shell electrons are involved in the
formation of “” bonds. Such transitions requires short wavelength <200m.
Example: saturated hydrocarbons methane, propane absorption occurs near 150 m.
n* Transitions: This type of transition takes place in saturated compounds
containing one hetero atom with unshared pair of electrons (n e-s).
Example: saturated halides, alcohols, ethers, aldehydes, ketones and amines etc.
Comparatively -*to n-* is required less energy.
In saturated alkyl halides, the energy required for such a transition decreases with
increases in the size of halogen atom or decreases in the electronegativity of the
atom.
Note:comparen* transition in H3C-Cl (169 nm) and H3C-I (258 nm), due to the
greater electronegativity of ‘Cl’ atom, ‘n’ electrons on Chlorine atom are
comparatively difficult to excite.
*Transitions: This type of transition occurs in the unsaturated centers of

the molecule.
Compounds containing double and triple bonds and also in aromatics.
The excitation of ‘’ electrons requires smaller energy and hence transition of this
type occurs at longer wavelength.
Examples:alkenes (ethane, propene), alkynes (ethyne, propyne)
Unconjugated alkenes absorbs around 170-190 nm
Conjugated compounds absorbs around 180 nm.
n* Transitions: In this type transition, an electrons of unshared electron pair on

hetero atom gets excited to *antibonding orbital.
It is requires least amount of energy out of all the transitions.
Examples: aldehydes and ketones
4 Write the basic principle of IR spectroscopy? Give various molecular Level-3

vibrations in the technique.(Dec 2018 [R18]),(Jan 2020 AGI[18]) Nov
2020GNITC[R18])
Introduction: The region from 4000 to 12500cm-1is known as near IR region and
from 667 to 50cm-1is called far IRregion.
Near IR region extends from 12500 to 4000cm-1 frequency region. In this region
overtones and combination bandsappears.
The region between 4000 – 667 cm-1 covers fundamental vibrations.
This region is highly useful for an organic chemist.
Almost all functional groups absorbs in this region.
Molecules shows pure rotational motion in this region
Molecular vibrations: A molecule may be regarded as a system of balls

(atoms)andsprings(bonds),whenitabsorbsIRradiationitvibratesresulting in
bond deformation, the bond deformation may be stretching andbending.
Vibrations fall into the two main categories of stretching and bending.
Stretching: In this type of vibrations, the distance between the two atoms
increases, but the atom remains in the same bond axis Or Change in inter-
atomic distance along bond axis.
Stretching vibrations are two (2) types:
Symmetric stretching vibration & asymmetric stretching vibration
a. Symmetric stretching vibration: In this type, the movement of atoms with

respect to a central atom in a molecule is in the samedirection.
b. Asymmetricstretchingvibration:Inthistype,oneatomapproachesthecentral atom
while the other departs fromit.
Bending vibrations:In this type of vibrations, the

positions of atoms changes with respect to the original bond
axis.
There are four (4) types of bending vibration.
Rocking: In this type, the two atoms are move in the
same direction.
Scissoring: In this type, two atoms approaches each other.
Wagging: Two atoms move up and below the plane with
respect to the central atom.
Twisting: In this type, one atom moves up and other atom moves down to the plane
of central atom.
5 What are the selection rules in IR spectroscopy? Give any two Level-4
applications of IR spectroscopy? (Dec 2018 [R18])
SELECTION RULES:Dipole moment ( =d)
The most fundamental requirement for infrared (IR) activity is that a vibration must
cause change in the dipole moment of themolecule.
Examples: HCl, CO – Polar (IRactive)
H2, N2– Nonpolar (IR inactive)
Exception: CO2 is non polar still IR active, this is due to asymmetric stretching of
CO2 occurs a change in dipole moment and active.
Example: CO2 various vibrations
The molecules which exhibits harmonic oscillations can be identified in IR
spectroscopy.
The harmonic oscillations (vibrations) can be represented as ΔV= ±
The intensity of fundamental absorption depends upon the differences between the
dipole-moments of the molecule in the ground state and the vibrational excited state.
Greater the difference more is the intensity of absorption.
Since most molecules are in the vibrational level at room temperature V=0. Most
transitions occur from V=0 to V=1.
Force constant:It is defined as the applied force if the displacement in the spring is
unity.
Force constant which ultimately refers to Hooke's law. It states that the force (F)
needed to extend or compress a spring by somedistance.
ApplicationsofIRSpectroscopy:Infraredspectroscopyiswidelyused inIndustryas well
as in research. It is a simple and reliable technique for measurement, quality
controlanddynamicmeasurement.Itisalsoemployedinforensicanalysisinciviland
criminalanalysis.
Some of the major applications of IR spectroscopy are as follows:
1. Identification of functional group and structureelucidation
2. Identification ofsubstances
3. Studying the progress of thereaction
4. Detection ofimpurities
5. Quantitativeanalysis
Identification of the functional group and structure elucidation: Entire IRregion
is divided into group frequency region and fingerprint region. Range of group
frequency is 4000-1500cm-1 while that of finger print region is 1500-400cm-1
6 Level-1
What is the principle involved in NMR spectroscopy? (Dec 2018 [R18]), Nov
2020GNITC[R18])
. NMR Spectroscopy&Principle of H-NMR spectroscopy:

Nuclear Magnetic Resonance (NMR): This spectroscopy is an analytical chemistry
technique used in quality control and research for determining the content and purity
of a sample as well as its molecular structure. For example, NMR can quantitatively
analyze mixtures containing known compounds.
Nuclear magnetic resonance (NMR) is a powerful tool for investigating nuclear
structure of atoms and molecules. In NMR, radio frequency waves induce transitions
between magnetic energy levels of nuclei of a molecule. The magnetic energy levels
are created by keeping the nuclei in a magnetic field.
Thenucleusofhydrogen(proton)spinsaboutitsownaxis.Duetoitspositivecharges, the
spinning proton generates a magnetic moment and behaves like a tiny bar magnet. If
the proton is placed in a strong magnetic field, the two energy levels become
separate. But, in the absence of external magnetic field the energy levels areequal.
1. Low energy level: It, corresponds to m1 = +1/2, is due to parallel to the
direction of magneticfield.
2. A transition from the low energy state to the high energy state can be abtained
by providing an energy between the two states,E.
If the nucleus lies in the upper energy state, E2, that will come to lower energy state,
E1, by emitting energy corresponding to E.
The frequency absorbed or emitted by a nucleus in moving from one energy level to
another is directly proportional to the applied magnetic field and gives the NMR
spectrum. Thus, NMR spectrum is plotted between absorption signal at the detector
and the strength of the magnetic field H+.
7 Level-2
Explain (NMR) chemical shifts? (Dec 2018 GNITC [R18])
Chemicalshift:InNMRspectroscopy,thechemicalshiftistheresonantfrequencyof a
nucleus relative to a standard in a magnetic field. Often the position and number of
chemical shifts are diagnostic of the structure of a molecule. Chemical shift are also
used to describe signals in other forms of spectroscopy such as photo emission
spectroscopy.
The position of the NMR signal is determined by the electronic environment of the
proton. The separation in the position of the signal of different types of protons from
that of a standard is called chemical shift.
Chemical shift is the difference between the resonance frequency of the observed
proton and TMS (Tetra methyl Silane). TMS is the common reference compound in
NMR, its =0.
Theexistenceofchemicalshift isduetothescreeningeffectofelectrons.Theposition of
NMR signal gives an idea about the kinds of protons (like aliphatic, aromatic,
primary, secondary). Different kinds of protons in different electronic environments
gives different peaks in NMR. This difference is represented by chemical shift.
 = (H0 (reference) – H0 (sample)/ H0 (reference)) x 106
Chemicalshielding:Thehighelectrondensityataroundanucleusshieldsthenucleus from
the external magnetic field. The net magnetic field felt by the nucleus, in a
molecule,willbelessthantheapplied(external)magneticfieldandthenucleusissaid
to be shielded. This, the NMR signals are up-field (lower (ppm) values) in the NMR
spectrum.
Chemical De-shielding: The low electron density at around a nucleus shields the
nucleus from the external magnetic field. The net magnetic field felt by the nucleus,
in a molecule, will be more than the applied (external) magnetic field and the
nucleus is said to be deshielded. This, the NMR signals are low/down-field (higher 
(ppm) values) in the NMR spectrum.
Chemical shifts of some common organic protons:
-CH3 = 0-3 ppm

-CC-H = 2-3 ppm
X-C-H = 3-5 ppm
-C=C-H = 5-6 ppm
C6H6(Benzene) = 7-8 ppm
R-CHO = 9-10ppm
R-COOH = 11-12ppm
8 What are different types of bending vibrations?(Dec 2018 Level-4
GNITC [R18])

axis.
same direction.
of central atom.
9 Explain the different types of electronic transitions.(Dec 2018 GNITC Level-2

[R18])
Fallow the 3rd question……answer
10 Describe various modes of electronic transitions when a molecule absorbs Level-2

UV-Visible region. (May 2019 [ R18])
Fallow the 3rd question…..answer
11 Explain the principle involved in NMR spectroscopy? (May 2019 [ R18], Level-2
(May/June 2019 [ R18])
Fallow the 6th question answer
12 Level-2
Write a note on Chemical shift? (May 2019 [ R18])
Chemicalshift:InNMRspectroscopy,thechemicalshiftistheresonantfrequencyof a
nucleus relative to a standard in a magnetic field. Often the position and number of
chemical shifts are diagnostic of the structure of a molecule. Chemical shift are also
used to describe signals in other forms of spectroscopy such as photo emission
spectroscopy.
The position of the NMR signal is determined by the electronic environment of the
proton. The separation in the position of the signal of different types of protons from
that of a standard is called chemical shift.
Chemical shift is the difference between the resonance frequency of the observed
proton and TMS (Tetra methyl Silane). TMS is the common reference compound in
NMR, its =0.
Theexistenceofchemicalshift isduetothescreeningeffectofelectrons.Theposition of
NMR signal gives an idea about the kinds of protons (like aliphatic, aromatic,
primary, secondary). Different kinds of protons in different electronic environments
gives different peaks in NMR. This difference is represented by chemical shift.
 = (H0 (reference) – H0 (sample)/ H0 (reference)) x 106
13 Level-4
Give an account of various fundamental vibrations. (May 2019 [ R18])
Molecular rotations: Rotational transitions are of little use to the spectro-

scopist.Rotationallevelsarequantized,andabsorptionofIRbygasesyields line
spectra. However, in liquids or solids, these lines broaden into a continuum
due to molecular collisions and otherinteractions.
Molecular vibrations: A molecule may be regarded as a system of balls

(atoms)andsprings(bonds),whenitabsorbsIRradiationitvibratesresulting in
bond deformation, the bond deformation may be stretching andbending.
Vibrations fall into the two main categories of stretching and bending.
Stretching: In this type of vibrations, the distance between the two atoms
increases, but the atom remains in the same bond axis Or Change in inter-
atomic distance along bond axis.
Stretching vibrations are two (2) types:
Symmetric stretching vibration & asymmetric stretching vibration
a. Symmetric stretching vibration: In this type, the movement of atoms with

respect to a central atom in a molecule is in the same direction.
b.Asymmetric stretching vibration: In this type, one atom approaches the central
atom while the other departs fromit.

axis.
same direction.
of central atom.
What is meant by shielding and Deshielding of a proton nucleus?

Level-1
14 (May/June 2019 [ R18])
Chemicalshielding:Thehighelectrondensityataroundanucleusshieldsthenucleus from
the external magnetic field. The net magnetic field felt by the nucleus, in a
molecule,willbelessthantheapplied(external)magneticfieldandthenucleusissaid to be
shielded. This, the NMR signals are up-field (lower (ppm) values) in the NMR
spectrum.
Chemical De-shielding: The low electron density at around a nucleus shields the
nucleus from the external magnetic field. The net magnetic field felt by the nucleus,
in a molecule, will be more than the applied (external) magnetic field and the nucleus
is said to be deshielded. This, the NMR signals are low/down-field (higher  (ppm)
values) in the NMR spectrum.
Explain the principle of UV spectroscopy. (May/June 2019 [ R18]),(Jan

Level-2
15 2020 AGI[18])
Principles of electronic spectroscopy:

UV-Visible spectroscopy is called electronic spectroscopy.
UV-Visible region of the complete electromagnetic spectrum extends from 150 to
800nm or m.
But 200-800nm is considered for analysis.
In the region below 200 nm, oxygen and nitrogen present in air absorb strongly.
Therefore,thisregioncanbeconsideredonlyaftertheevacuationofthecompletepath
lengths and is known as far/vacuum UVregion.
Principle: UV-visible spectra arises due to the absorption of ultraviolet (UV) or
Visible radiation by the sample resulting in electronic transition with the molecule or
ion.
Therelationshipbetweenenergyabsorbedinanelectronictransition(E),thefrequency (),
wave length (), and wave number () ̅ of radiation producing thetransition.
E = h = hc/ = hc ̅
C= velocity of lights
̅= wave number

E = energy absorbed during electronic transition in a molecule or ion from lower
energy state (E1) or ground to higher energy state (E2).
Therefore, the energy absorbed is given by
E = E2-E1 = h
The wavelength corresponding to such transition is = hc/E
16 Explain the applications of IR spectroscopy. (May/June 2019 [ R18]), Level-3

Oct/Nov2020 GNITC[R18])
ApplicationsofIRSpectroscopy:InfraredspectroscopyiswidelyusedinIndustryas well
as in research. It is a simple and reliable technique for measurement, quality
controlanddynamicmeasurement.Itisalsoemployedinforensicanalysisinciviland
criminalanalysis.
Some of the major applications of IR spectroscopy are as follows:
1. Identification of functional group and structureelucidation
2. Identification ofsubstances
3. Studying the progress of thereaction
4. Detection ofimpurities
5. Quantitativeanalysis
Identification of the functional group and structure elucidation: Entire IR region

is divided into group frequency region and fingerprint region. Range of group
frequency is 4000-1500cm-1 while that of finger print region is 1500-400cm-1
Ingroupfrequencyregion,thepeakscorrespondingto differentfunctionalgroupscan
be observed. According to corresponding peaks, functional group can be determined.
Identification of substances:Frequencies of various group vibrations / frequency region
and in fingerprint region of substances.
Studying the progress of the reaction: progress of 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 group and /or the rate of appearance of the characteristic absorption band of
the product is observed.
Detectionofimpurities:IRspectrumofthetestsampletobedeterminediscompared with
the standard compound. If any additional peaks are observed in I.R. spectrum, then it
is due to impurities present in thecompound.
Quantitativeanalysis:Thequantityofthesubstancecanbedeterminedeither inpure form
or as a mixture of two or more compounds. In these characteristics peak
corresponding to the drug substance is chosen and log10/lt of peaks for standard and
test sample is compared. This is called base line technique to determine the quantity
of thesubstance.
16 Write about applications of UV-VIS spectroscopy in quantitative

analysis.OCT/NOV2020JNTUH[R18]
Applications of UV-Visible spectroscopy:

1. Detection of functional groups- UV spectroscopy is used to detect the presence or
absence of chromophore in the compound. This is technique is not useful for the detection of
chromophore in complex compounds. The absence of a band at a particular band can be seen
as an evidence for the
absenceofaparticulargroup.Ifthespectrumofacompoundcomesouttobetransparent above200
nm than it confirms the absence of –
a) Conjugation b) A carbonyl group c) Benzene or aromatic compound d) Bromo or iodo atoms

2. Detection of extent of conjugation- The extent of conjugation in the polyenes can be
detected with the help of UV spectroscopy. With the increase in double bonds the
absorption shifts towards
thelongerwavelength.Ifthedoublebondisincreasedby8inthepolyenesthenthatpolyeneappears
visible to the human eye as the absorption comes in the visible
region.
3. Identification of an unknown compound- An unknown compound can be identified

with the help of UV spectroscopy. The spectrum of unknown compound is compared with
the spectrum of a reference compound and if both the spectrums coincide then it confirms
the identification of the unknown
substance.
4. Determinationofconfigurationsofgeometricalisomers-It isobservedthat cis-

alkenesabsorb atdifferentwavelengththanthetrans-
alkenes.Thetwoisomerscanbedistinguishedwitheachother when one of the isomers has non-
coplanar structure due to steric hindrances. The cis-isomersuffers distortion and
absorbs at lower wavelength as compared to trans-isomer.
5. Determination of the purity of a substance - Purity of a substance can also be

determined with
thehelpofUVspectroscopy.Theabsorptionofthesamplesolutioniscomparedwiththeabsorption
of the reference solution. The intensity of the absorption can be used for the relative
calculation of the purity of the samplesubstance.
17 Why methane does not absorb IR energy. (May/June 2019 [ R18]) Level-3 CO5
InanyhomonucleardiatomicthereisnoIRabsorptionbecausethese
molecules have no intrinsic dipole or one caused byvibrations. A
similar effect occurs in methane, the way the molecule vibrates
develops oscillating dipoles and these interact with the radiation and
so absorb energy.
What are different electronic excitations in UV
spectroscopy.(May/June Level-4 CO5
18
2019 [R18])
Fallow the 3rd question answer
How many types of electronic transitions are observed in UV-VIS

region? Explain by giving suitable examples. (Dec/Jan 2020 Level-3 CO5
19
GNITC [R18])
Fallow the 3rd question answer

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GURU NANAK INSTITUTIONS TECHNICAL CAMPUS

Academic Year : 2020-21

9 Give an account of LCAO. (Dec 2018 [R18]) Level-3 CO1

Ans Atomic orbitals Molecular orbitals

orbitals (AO’s). ψ(Mob) = ψ(A) + ψ(B) ψ(Mob) = bonding molecular orbital

4 Explain the crystal field splitting of d- orbitals by the ligands in

Salient features of CFT:

Crystal field splitting in octahedralcomplexes:

M (g)+e– M– (g) (anionformation)

The Radius of Sodium in Its Three Known Oxidation

Na+ Na0 Na−

Electron 1s22s22p6 1s22s22p63s 1s22s

Radius (pm) 102 154 202

(kJ mol-1). 1 eV per atom = 96.64 kJ mol-1 = 23.05 k cal mol-1

Factors affecting Ionization Energy:

Bond order (BO) = ½ [Number of bonding orbital electrons - Number of anti-bonding

Bond order (BO) ) = ½ [10-4]=3

The crystal field splitting in tetrahedral complexes is shown as

Dyz = dzx < dz2 < dxy < dx2-y2

16 What is LCAO? Explain (Dec/Jan 2020 GNITC [R18]) .Level-2 CO1

Salient features of CFT:

19 Write an account on π molecular orbitals of butadiene (Dec/Jan 2020

Pi – molecular orbitals of Butadiene:

Bond order (BO) = ½ [Number of bonding orbital electrons - Number of anti-bonding

A Pi – molecular orbitals of Butadiene:

Crystal field splitting in octahedralcomplexes:

energyoft2orbitalisraisedand“e”setorbitalsis lowered fromthe center.The “g”

The crystal field splitting in tetrahedral complexes is shown as

1. The pH of the feed water should be carefully adjusted to8-9.

9 Calgon Treatment prevents scale formation in Boilers. Give Level-2 CO2

13 What you understand by Reverse osmosis..(Oct 2016 [R13]) Level-2 CO2

Advantages of reverse osmosis:

18 What is the significance of breakpoint chlorination in the treatment of Level-2 CO2

19 What is caustic embrittlement? (May/June 2019 [ R18]),(Jan2020 Level-1 CO2

1. The pH of the feed water should be carefully adjusted to8-9.

Advantages of reverse osmosis:

22 Explain calgon conditioning. Write the chemical reaction

Ans Calgon conditioning: Sodium hexa meta phosphate Na2[Na4(PO3)6]or

24 Define Temporary and permanent hardness of water? How it is caused?

Ans Temporary Hardness/Carbonate hardness/Alkaline hardness

25 Outline the specifications of potable water. (Dec/Jan 2020[R18])(Jan

Ans Potable Water

26 Explain the process of a colloidal conditioning of boiler feed water.( Jun

Ans Colloidal conditioning:The scale formation in low pressure

27 Why calgon conditioning is better than Phosphate conditioning.( Aug

The following are most commonly used coagulants:

Chloramine is much more lasting than chlorine alone and consequently, it is

3 What is the principle involved in complexometric method in estimation Level-1 CO2

Reasons for the formation of sludges: The dissolved salts

Scaleformation:Scalesarehard,stickydepositsformedon the inner walls of the

Reasons for the formation of scales:

6 Explain the process of reverse osmosis. How is it useful in softening of

The exhausted anion exchange

8 What is caustic embrittlement? (Dec 2018 [R16]) Level-1 CO2

[Na2SO4 concentration] [NaOH concentration]

remove dissolved oxygen asH2O.

Ans Calgon conditioning: Sodium hexa metaphosphate

Ans 1. Phosphate conditioning: The scale formation dueto

∴ 1 mg/l = 1 mg of CaCO3 equivalents per 106 mg of water 1 part of CaCO3

4 Write a short note on calomel electrode.(Dec 2018 [R16]) Level-3 CO3

Nernst equation E= E0 + 2.303RTlog [Mn+]

10 Write the Principle involved in pitting corrosion? (Dec 2017 [R13]) CO

Dry (or) Chemical Corrosion :