(QP-1)

APJ ABDUL KALAM TECHNOLOGICAL UNIVERSITY

Second Semester B. Tech Degree Examination July 2021 (2019 scheme)
Course Code: CYT100
Course Name: ENGINEERING CHEMISTRY

Max. Marks: 100 (2019 Scheme) Duration:3 Hours

PART A M
Answer all questions, each carries 3 marks
1 What is galvanic series? How it is different from electrochemical series? (3)
(OR)
How is galvanic series advantageous over electrochemical series in corrosion
chemistry?

A Galvanic series is the study of the corrosion of metals and alloys in a given environment.
The electrochemical series is the study of chemical reactivity of metals. Electrochemical
series is useful in providing the data regarding the chemical reactivity of metals and may
not be able to provide the sufficient information in predicting the corrosion behavior of
metal in given environment. Galvanic series and electrochemical series differ in
that galvanic series explains the order of nobility of metals and semimetals, whereas
electrochemical series depicts the order of standard electrode potentials of chemical
elements.
Galvanic series

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2 Why full charging is not allowed in Li-ion cell? (3)

A In a lithium-ion battery, overcharging can create unstable conditions inside the battery,
increase pressure, and cause thermal runaway. That is the reason full charging is not
allowed in Li-ion cell.
3 CHCl3 gives a singlet at 7.26 ppm, while CH3Cl shows a singlet at 3.06 ppm in the (3)
1H NMR spectrum. Give reason?

A In CHCl3, there are 3 chlorine atoms and results more deshielding and eventually results
the singlet at 7.26 ppm, while CH3Cl contains one chlorine atom and results less shielding
and shows a singlet at 3.06 ppm.
4 Explain the reason for broadening of UV-Visible (electronic) spectrum. (3)

This is because a number of vibrational energy levels are available at each electronic
A
energy level, and transitions can occur to and from the different vibrational levels. This
results in peak broadening
5 Write any three applications of TGA. (3)
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A Three applications of TGA are given below:

1) Stability of sample at elevated temperature.

2) Identification of substances, and their purity determinations.
3) Decomposition mechanisms of polymers, inorganic salts etc.
6 Explain terms retention time (tR) and relative peak area (RPA) in GC. (3)

A Retention time (Rt):

1. Retention time (Rt) is a measure of the time taken for a solute to pass through a
chromatography column.

2. It is calculated as the time from injection to detection.

3. The Rt for a compound is not fixed.

4. It depends on factors like temperature, column length etc.

Relative peak area (RPA) in GC:

The peak area is proportional to the amount of the component, so if a 100 ppm
concentration has a count of 1000, a 700 count means a 70 ppm concentration. with
qualitative analysis, one could say that a standard sample is also required for quantitative
analysis.
7 Draw the Fischer projection formulae for the meso form of the following and (3)
convert it into Saw-Horse structure, C6H5-CH(Cl)-CH(Cl)-C6H5.

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8 Write the synthesis of polypyrole? (3)

A
Polypyrole is synthesized by the Oxidative Polymerization of Pyrrole. For
polymerization of pyrole, water is the ideal solvent and ferric chloride is the best
oxidizing agent and doping agent. The reaction of pyrole with aqueous ferric chloride is
very fast and the product is a black powder. Polymerization occurs through the formation
of pi-radical cation.

The reaction for the synthesis of polypyrole is given below:

9 Which buffer is used in EDTA method? What is its role in titration? (3)

A Eriochrome Black-T (EBT) indicator is used in EDTA method.

EBT role in titration:
When Eriochrome Black-T (EBT) indicator is added to the hard water sample, it forms
wine red colour, unstable complex at pH=10 with Ca2+ and Mg2+ ions. When this solution

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 is titrated against EDTA solution, the colour of the complex changes from wine red to
deep blue which indicates the end point.
10 Explain break point chorination? (3)

A Break point of chlorination is defined as the chlorination of water to such degree that
living organisms as well as other organic impurities in water are eliminated. It involves
the addition of sufficient chlorine dosage to oxidize organic matter, reducing substances,
and free ammonia in raw water, leaving behind only free chlorine with disinfecting action
against pathogenic bacteria. This phenomenon is known as Free-residual chlorination.
Figure shows break point chlorination:

PART-B
Answer one full question from each module, each question carries 14 marks
Module-1
11 [a] Derive the Nernst equation for the cell EMF of Daniel Cell. (8)

A The Nernst equation is given by,

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E = Electrode potential.
Eo = Standard electrode potential.
R = Gas constant = 8.314 JK-1 Mol-1.
T = Temperature in Ok.
F = One Faraday i.e. 96500 columbs.
[M] = Concentration of electrode, which is unity always.
[Mn+] = Concentration of electrolyte.

Derivation of Nernst equation for the cell EMF of Daniel Cell

Daniel Cell is represented as Zn/Zn2+ //Cu2+/Cu
Ecell = Ecathode-Eanode = E Cu-E Zn
Eocell = Eocathode-Eoanode
E Cu = Eocu- RT/nF ln 1/Cu2+
E zn = Eozn- RT/nF ln 1/Zn2+
Therefore
Ecell = Ecathode-Eanode = E Cu-E Zn
= Eocu- RT/nF ln 1/Cu2+ - Eozn + RT/nF ln 1/Zn2+
= {Eo Cu-Eo Zn} - RT/nF{ ln 1/Cu2+ - Eozn - RT/nF ln 1/Zn2+}

Ecell = Eocell- RT/nF ln Zn2+/Cu2+

This is called Nernst equation derivation for Daniel Cell.
b) How is electroless nickel plating done? Write the reactions involved. Give any (6)
two applications of it?

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A Electroless nickel plating is used to deposit a layer of nickel on a substrate without the
use of electrical energy. In the first stage, the object to be plated are pretreated with SnCl 2
in acid medium followed by treatment with PdCl2 solution. The pretreated object is
immersed in the plating bath containing nickel salt and reducing agent like sodium
hypophosphite for a certain time so that following reactions will occur and nickel gets
coated over the object.
Reactions:
At Cathode
Ni2+ + 2e ⇌ Ni; Eo = -0.26V
At Anode
H2PO2- + H2O ⇌ H2PO3- + 2H+ + 2e; Eo = -0.499V
Overall reaction (1) + (2)
Ni2+ + H2PO2- + H2O ⇌ H2PO3- + 2H+ + Ni
As H+ ions are released in the reaction, pH of the solution decreases. To maintain constant
pH, buffer solutions are generally used. This gives a uniform fine-grained plating.
Applications:
1) In Aerospace components: For wear resistance, corrosion protection, chemical
resistivity and lubricity on valves, pistons, engine shafts, engine amounts,
compressor blades etc.
2) In packaging and handling machinery:
(OR)
12 a) With the help of electrochemical equations, show that rusting of iron is more (8)
severe in oxygen rich acidic medium than alkaline medium.

A Rusting is an oxidation reaction. when acidic substances come in contact with metals,
such as iron or steel, it forms rust. Rust is the result of corroding steel

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 after the iron particles, have been exposed to oxygen and moisture. When steel is exposed
to water, the iron particles become oxidized and produces Fe 2+.
Electrochemical equation: 4Fe + 3O2 + 6H2O -----> 4Fe(OH)3.
The reaction 4Fe + 3O2 + 6H2O -----> 4Fe(OH)3 takes place in the acidic medium and Fe
is converted into Fe2+. Alkalis are compounds that have OH- ions in them, they liberate
hydroxide ions on dissociation. The alkalis are generally bases and they react with acids
to neutralize the solutions to produce water. The hydroxyl ions are consuming the protons
or H+ to form water. Thus, the reaction medium doesn’t have any hydronium ions left
and the oxidation reaction of iron cannt proceed. Hence, we say that an alkaline medium
prevents the rusting of iron because of non-availability of H+ ions which reduces the
oxidation of Fe to Fe2+ ions.
Module-II
13 Draw the molecular orbital energy diagram of 1) Ethene, ii) 1,3-butadiene iii) 1, 3, (8)
5 hexatriene and iv) benzene to explain their UV-Vis absorption.

A 1) Ethene:

The unsaturated hydrocarbons containing double or triple bonds show this type of
transition. For example, C=C of ethylene molecule gives an absorption maximum at 169
nm. Ethene has 2 π-molecular orbitals (ᴪ1, ᴪ2) formed by linear combination of 2 atomic
orbitals. Here ᴪ1is bonding molecular orbital and ᴪ2 is antibonding orbital. In the ground
state the two π electrons occupy bonding molecular orbital. Here the transition takes
place from HOMO ᴪ1 to LUMO ᴪ2.

ii) 1,3-butadiene:

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1,3-butadiene gives an absorption maximum at 217 nm. There are 2 double bonds in
conjugation. 1,3-butadiene has 4 π-molecular orbitals (ᴪ1, ᴪ2, ᴪ3 and ᴪ4) formed by
linear combination of 4 atomic orbitals. Here ᴪ1, ᴪ2 are bonding molecular orbital and
ᴪ3, ᴪ4 are antibonding orbital. In the ground state the four π electrons occupy bonding
molecular orbital ᴪ1, ᴪ2. Here the transition takes place from HOMO ᴪ2 to LUMO ᴪ3
with λ max = 217 nm.

1, 3, 5 hexatriene:

1, 3, 5 hexatriene gives an absorption maximum at 247 nm. There are 3 double bonds in
conjugation. 1, 3, 5 hexatriene has 6 π-molecular orbitals (ᴪ1, ᴪ2, ᴪ3 and ᴪ4, ᴪ5, ᴪ6)
formed by linear combination of 6 atomic orbitals. Here ᴪ1, ᴪ2, ᴪ3 are bonding molecular
orbitals and ᴪ4, ᴪ5, ᴪ6 are antibonding orbital. In the ground state the six π electrons
occupy bonding molecular orbitals ᴪ1, ᴪ2, ᴪ3. Here the transition takes place from
HOMO ᴪ3 to LUMO ᴪ4 with λ max = 247.

Benzene:

Benzene gives an absorption maximum at 255 nm. There are 3 double bonds in
conjugation. Benzene has 6 π-molecular orbitals (ᴪ1, ᴪ2, ᴪ3 and ᴪ4, ᴪ5, ᴪ6) formed by
linear combination of 6 atomic orbitals. Here ᴪ1, ᴪ2, ᴪ3 are bonding molecular orbitals
and ᴪ4, ᴪ5, ᴪ6 are antibonding orbital. In the ground state the six π electrons occupy
bonding molecular orbitals ᴪ1, ᴪ2, ᴪ3. Here the transition takes place from HOMO to
LUMO with λ max = 255 nm. Here ᴪ2, ᴪ3 and ᴪ4, ᴪ5 are degenerate orbitals.

Molecular orbital energy diagrams of 1) Ethene, ii) 1,3-butadiene iii) 1, 3, 5

hexatriene and iv) benzene are shown below:

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 [b] Discuss the principal of IR spectroscopy. Arrive the expression for vibrational (6)
energy states of a diatomic molecule. Draw the potential energy diagram.

Principle:
A
Infrared spectroscopy involves the transitions between the vibrational energy levels of a
molecule on the absorption of radiations falling in the spectral range of 500 cm-1 (infra-
red region).
Derivation of vibrational energy states of a diatomic molecule. Draw the potential
energy diagram.

During the vibration of a molecule, if there occurs a change in dipole moment, hence will
lead to the generation of an oscillating electrical field. Now if the frequency of this
oscillating electric field is equal to the frequency of fluctuating electric field of radiation
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(oscillating in a plane perpendicular to the direction of propagation of electromagnetic
radiation), there occurs the phenomenon of resonance and hence energy can be
transferred from the radiation to the molecule or vice versa. This will lead to the
generation of absorption IR-spectra or emission IR-spectra respectively.

Vibrational energy states of diatomic molecule are given by

Evib = [V+1/2] x hVo

Where V is the vibration quantum number and has the values of 0,1,2,3-----

Vo is the fundamental vibrational frequency of such a molecule behaving like a

simple harmonic oscillator is given by eq [1],

Vo = 1/2π(k/µ)1/2……(1)

k is the force constant.

µ is the reduced mass of a diatomic molecule [µ = m1m2/m1+m2]

multiplying Plank’s constant “h”(on both sides)

Equation (1) becomes hVo = h/2π(k/µ)1/2

[however hVo = hc𝜈̅ ]

Therefore, hc𝜈̅ = h/2π(k/µ)1/2

cancelling “h” on both sides;

c𝜈̅ = 1/2π(k/µ)1/2
(OR)

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 or K = 4𝜈̅ 2π2c2[m1m2/m1+m2]

Figure of Potential energy diagram

(OR)
14 a) Explain the origin of spin-spin splitting and draw the splitting pattern in (8)
CH3-CH2-CH2-Cl?

A Spin-Spin splitting results from the interaction of the nuclear spin of the hydrogen atoms
on an adjacent carbon atoms. In general, sets of hydrogen atoms on nonequivalent
neighboring carbon atoms couple with each other.
In 2-chloropropane, there are 2 types of protons a, b. a type is having 3 protons and
give signal (triplet) at 1.49 ppm while b type having two protons gives signal (quartet)
at 3.51 ppm.

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 NMR spectrum of 2-chloropropane
b) An organic compound C3H6O contains a carbonyl group. How will its NMR (6)
spectrum decide whether it is an aldehyde or a ketone?

A In acetone, all protons are in same kind of environment and give only one peak.

NMR spectrum of acetone (ketone)

In propionaldehyde, there are three types of protons a, b, c. a type having 3 protons. b
type having 2 protons and c type having 1 proton. The NMR spectrum contains 3 peaks.

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 one triplet at 1 ppm, multiplet at 2.5 ppm and triplet at 9.5 ppm. Therefore, if the nmr
spectrum contains 3 peaks it is an aldehyde and if the nmr spectrum contains 1 peak it is
ketone.
Module-III
15 a) Discuss the principle and procedure in column chromatography. Explain (10)
how TLC is useful in checking the purity of each fraction.

A Principle: Column chromatography is a chromatographic separation technique in which

the stationary phase is a solid or a liquid. Usually, stationary phase in column
chromatography is silica, alumina, calcium carbonate, calcium phosphate, magnesia,
starch etc. Mobile phase used is a single solvent or a mixture of solvents like benzene,
cyclohexane. chloroform, carbon tetrachloride, carbon sulphide, ethyl alcohol, acetic
acid and ethyl acetate
Figure 1 shows Column chromatography.

Instrumentation and working

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 Procedure:
The mixture which is to be separated is dissolved in a suitable solvent and introduced at
the top of the column as shown in the fig.1 [A].
* The component with greater adsorption will be adsorbed at the top and the one with
lower adsorption will be adsorbed at the bottom in the fig.1 [B].
* The different components are separated by elution using more solvent in the fig.1 [C].
* Evaporation of the solvent from the different fractions collected in the test tube as
shown in in the fig.1 [D] gives the pure components.
(b) Sketch the Derivative TG graph of calcium oxalate monohydrate. (4)

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The thermogram of decomposition of pure hydrated calcium oxalate (CaC 2O4.H2O)
obtained by increasing the temperature at a rate of 50 0C /min is shown in the figure.
The different reactions taking place during heating are

CaC2O4.H2O  CaC2O4 + H2O (100-250 oC) {dehydration}

2CaC2O4  2CaCO3+ 2CO (400-500 oC) {decomposition}

CaCO3  CaO + CO2 (650-850 oC) {decomposition}

CaC2O4H2O is thermally stable up to 100 0C and water evaporates above 100 0C to form
anhydrous calcium oxalate (CaC2O4). The horizontal portion between 226-346 0C
indicates that anhydrous salt is thermally stable in this range. At slightly above 346 0C
the anhydrous calcium oxalate decomposes to give calcium carbonate. This process is
completed at about 420 0C. Calcium carbonate is not stable above 660 0C. Above 660 0C
it decomposes to CaO and CO2. This procedure is completed at 840 0C and above this
the horizontal portion denotes the stable CaO.
(OR)

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16 a) Explain the various chemical methods used for the synthesis of (10)
nanomaterials.

A There are three chemical methods used for the synthesis of nanomaterials.
a) Chemical reduction method
b) Hydrothermal method
c) Sol-gel method
Chemical reduction method
The chemical reduction of metal complexes to metallic nanoparticles is a very common
method of preparation. For this method of preparation various metal salts, (precursors),
reducing agents and polymeric stabilizers are used. Nano particles with a well-controlled
size and shape in colloid form is obtained by this method.

Procedure:
In this method,
(1) An inorganic metal salt is dissolved in water. In dissolved state, metals exist as
hydrated metal cations.
(2) These metal cations are reduced by using suitable reducing agents;
(3) Neutral metal particles undergo aggregation to form nano-particles;
(4) The obtained nano-particles are then stabilized by adding capping agents.

Hydrothermal method
In this method, a sealed vessel (bomb, autoclave etc.) is employed. In this sealed vessel,
solvents can be brought to temperature were above their boiling points by the increase in

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autogenous pressure resulting from heating. Performing a chemical reaction under such
condition is referred to as solvothermal synthesis. If the same process is done with water
as solvent is defined as hydrothermal processing.

 The synthesis method uses the solubility in water of almost all inorganic solvents
at elevated temperatures and pressures.

 As mentioned in the name, water at elevated temperatures plays an essential role

in the precursor material transformation.

 Temperature, water pressure and the time of reaction are, therefore, the three
principle parameters in hydrothermal processing.

Sol-Gel Technique:
Sol:It is a colloidal solution made of solid particles (few hundred nm in diameter)
suspended in a liquid phase.
Gel. The gel is a solid macromolecule immersed in a solvent.
Sol-gel process. It may be defined as the chemical transformation of a liquid (the sol)
into a gel state and with subsequent post treatment and transition into solid oxide
material.

The variety of steps of synthesis in the Sol-Gel Technique are given below:
(1) Formation of stable Sol solution by hydrolysis of metallic alkoxides or metal salts
(precursor)
(2) Transformation of Sol into gel by gelation process which involves
polycondensation or polyesterification reactions.
(3) Drying of the gel. For this, removal of solvent is achieved by heating in vacuum.
(4) Ageing and densification of the gel by annealing process. It involves heating the
gel to a suitable high temperature for a definite time period. Then the material is

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 slowly cooled to room temperature in several hours. In this stage, nanoparticles of
metals are produced.
(5) Sol-gel process is generally used for fabrication of coatings and films of various
nano-materials. In the coating process, the liquid coating system is poured over the
substrate to be coated. The Sol left on substrate forms a film of nanomaterial.
(6) Next stage after coating is gelation of coating by solvent evaporation and finally
annealing or calcination to obtain Thin-layer structure. The given figure
demonstrates various stages in sol gel process.
(7) The chemical reaction which takes place in the sol-gel metal alkoxides M(OR)2
during the hydrolysis and condensation is given by

M-O-R + H2O  M-O-H + R-O-H (Hydrolysis)

M-O-H + R-O-M  M-O-M + R-O-H (Condensation)

Figure 1. sol-gel procedure.

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 b) Explain the experimental procedure of TLC (4)

A
Thin layer chromatography (TLC) is chromatographic method used to separation,
purification and identification of components present mixture.
Instrumentation and working:

Experimental procedure of TLC:

In this method a glass plate coated with a material of adsorbent will constitute the
stationary phase.
The mixture to be separated is applied to one end of the plate and it is placed in the
solvent.
When the solvent moves upward, separation of mixture in to the components occurs.
When the solvent reaches near the top, it is removed and dried.
The different components are separated, isolated and detected by different detection
methods.
Module-IV

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17 a) How many optical isomers are possible for H3C-CH(OH)-CH(OH)-CHO? (8)
Draw the Fischer projection formulae of all the isomers. Which among them
are optically active?
A

Molecules having two asymmetric carbon atoms with different terminal groups are given

by formulae 2n:

Consider 2,3-dihydroxy butanaldehyde [CH3 -*CH(OH) -*CH(OH)-CHO] Here there

are two chiral carbon atoms.
Thererfore totally 22 = 4 isomers are expected.

b) What are OLEDS? Give the construction and working? (6)

A OLEDs are defined as thin film semiconductor devices activated by the

electroluminescent organic materials.
Construction: An OLED structure found to contain the five parts:
i. Glass substrate which supports the OLED.
ii. Anode made of indium tin oxide (ITO) which adds holes (or removes electrons)
when a current flows through the device.

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 iii. Conducting layer” made of polyaniline or poly (p-phenylene vinylene) that
transport holes from anode. This layer is also known as a hole transport layer
(HTL).
iv. Emissive layer made of polyfluorene polymer. It acts as an electron transport
layer (ETL);
v. A metallic cathode made of Al, Ca or Ag. It injects electrons when a current
flows through the device.

Working: As the voltage (or potential different) is applied across the anode and
cathode, the cathode receives electrons from the power source and anode loses electrons.
The added electrons make the emissive layer negatively charged (similar to the n-type
layer in a junction diode). Simultaneously, the conductive layer becomes positively
charged (similar to p-type material). Compared to electrons, holes are much more mobile
so they jump across the boundary from the conductive layer to the emissive layer. When
a hole meets an electron, the positive and negative charge cancel out and release a brief
burst of energy in the form of a quantum of light or a photon. This process is called
recombination. As long as the current keeps on flowing, the OLED produces continuous
light because recombination process occurs many times in a second.

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 Figure Operation of OLED

(OR)
18 a) What is meant by structural isomerism? What are the different types of (10)
structural isomerism in organic molecules? Explain with examples?

(a) Structural Isomerism:

Structural isomers are those isomers in which the atoms are completely arranged in a
different order with the same molecular formulas. These are the molecules having the
same kind of molecular formula with different connection depending upon the order they
are put together.

Chain Isomerism: Such compounds have the same molecular formulae but differ in the
order in which the carbon atoms are bonded to each other.

Examples are n-butane and isobutane:

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Positional Isomerism: Positional isomers have the same molecular formulae but differ
in the position of functional group on the carbon chain.

Examples are 2 methyl butane and pentane:

Functional Isomerism: They have the same molecular formulae but they have different
nature of functional group.

Examples are ethanol and dimethyl ether

Metamerism: This type of isomerism is due to unequal distribution of carbon atoms on

either side of the functional group. Such compounds are members of homologous series.

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Examples are diethyl ether and methyl propyl ether

Tautomerism: This isomerism is defined as dynamic equilibrium between two isomers

which are rapidly interconvertible into one other. One isomer is called enol form and
other isomer is called keto form. Indeed, we can say that keto form rapidly interchanged
to enol-form by exchange of hydrogen atom between oxygen atom and carbon atoms.
Keto form is more stable and exist in 99 % and enol form is less stable and exists in 0.001
%. Both forms exist as racemic mixture. This is also termed as keto-enol tautomerism.

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 b) Write the structure of ABS and its monomers. Also list any two applications (4)
of ABS?

A
Structure: In ABS, a long chain of polybutadiene is criss-crossed with shorter chains
of poly(styrene-co-acrylonitrile).

Uses: Keyboard, keycaps, household goods, consumer goods, buffer edging for furniture,
enclosures for electrical and electronic assemblies, drain-waste-vent (DMV) pipe system,
golf club head etc.

Module-V
19 a) Explain trickling filter and UASB processes in waste water treatment? (10)

A
TRICKLING FILTERS

Trickling filters are named as secondary aerobic treatment process. Trickling filter
consists of a rectangular or circular tank of about 2 m depth. The tank is filled with
crushed rock or large anthracite coal or graded clinkers. There is a drain at the bottom
to collect the treated effluent.

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 Figure Trickling Filter treatment

Working of trickling filters

Sewage is introduced to the top of filters by means of a rotating distributor. As the sewage
starts flowing downwards, through the filtrating media, microorganisms (present in
sewage) grow on the surface, aerobic oxidation takes place and sewage gets cleaned.
Finally, sewage can be collected through the bottom drain. The spraying mechanism
involves the saturation of the waste water with oxygen and supports to maintain aerobic
conditions. This results in the development of a gelatinous film containing
microorganisms.

UP FLOW ANAEROBIC SLUDGE BED (UASB) PROCESS

USAB method is a secondary anaerobic oxidation treatment method, based on the settle
ability of microbial flocs. UASB reactor consists of a rectangular tank with proper inlet
and outlet for feeding and collecting the effluent. There is mechanism for the collection
of fuels formed. In this process, the effluent is fed from the bottom of the reactor, so that
it passes upward through the sludge blanket. The sludge blanket is basically formed
granules of diameter 1 to 1.5 mm. As the waste water comes in contact with the granules,
anaerobic oxidation takes place and gases like methane are formed. The temperature is
maintained around 35 oC and the gases are collected through the gas collector domes
fitted to the top of the reactor. USAB process is the most preferred method of sewage

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 treatment in developing countries, due to its low capital cost and integrated control
mechanism.

Figure UASB process.

b) Discuss the procedure for the determination of DO in water? (4)

A
Estimation of Dissolved Oxygen A optimum amount of dissolved oxygen in water at
room temperature and pressure is about 8 mg/L. It is good for sustaining aquatic life.
Dissolved oxygen in water is determined by winklers method.

Procedure: 2 ml of Manganese sulphate solution and 2 ml of alkaline potassium iodide

solution are added to 250 mL of water sample. The bottle is stoppered and shaken well
for 10-15 minutes and allowed to stand for few minutes to settle the precipitate. Then 2-
3 ml of concentrated sulphuric acid is added, stoppered and shaken to dissolve the
precipitate. 100 ml of the solution is pipetted out from the bottle into a clean conical flask
and titrated against standard hypo solution using starch as indicator. End point is
disappearance of blue colour.

Calculation volume of hypo solution consumed = V1 ml

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 Normality of the dissolved oxygen = N1V1/100

Weight of dissolved oxygen per litre of water = V1xN1x8/100 g

= V1 X N1 X 8 X 106/100 X 1000 ppm

(OR)
20 a) Define reverse osmosis. Explain the method for the desalination of water (8)
using reverse osmosis. Give its advantages.
A
Definition of reverse osmosis: Reverse Osmosis is a process by which a solvent pass
through a porous membrane in the direction opposite to that for natural osmosis when
subjected to a hydrostatic pressure greater than the osmotic pressure.
Method for the desalination of water using reverse osmosis

When a semipermeable membrane separates two solutions of different concentrations,

the flow of solvent take place from less concentrated to a region of more concentrated
due to osmosis. The semipermeable membrane is cellulose acetate, polymethys
methacrylate and polyamide polymers. Semipermeable membrane can allow only solvent
(water) but not solute particles. If more pressure, which is higher than osmotic pressure,
is applied then reverse osmosis takes place, i.e., flow of solvent from higher
concentration to less concentration (Fig. 5.2). Using this principle drinking water is
obtained from brakish (sea water/saltish water). In this method, a pressure in the range
of 15-40 kg/cm2 is applied on the brakish water. The water molecules pass through the
membrane in the effluent stream which can be removed.

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 Figure Reverse osmosis

Advantages:
RO is Highly Effective at Removing Contaminants.
RO is Energy Efficient.
RO Provides Clean Water.
RO Will Save You Money.

b) Explain the ion exchange process in water treatment. How is it exhausted (6)
resin regenerated?
A
This is also known as De-mineralization process. Ion-exchange resins are insoluble,
cross-linked, long chain organic polymers. The functional groups attached to the chains
can exchange hardness producing cations and anions present in water.

Process: The process involves the following steps.

1.The first chamber is packed with cation exchange resin (RH+). When the hard water is
passed through a bed of cation exchange resin it exchanges hydrogen ions with Ca +2,
Mg+2, K+, Na+, etc. of hard water (fig.1)

RH+ + Mg+2  R2Mg+2 + 2H+

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 RH+ + Ca2+  R2Ca2+ + 2H+
Thus, hardness producing cations (Ca2+, Mg2+, etc.) are removed.

2. The second chamber is packed with anion exchange resin (R’OH-). The water coming
out of the first chamber contains H+, Cl-, SO42- and HCO3-.

R’OH- + Cl-  RCl- + OH-

2R’OH- + SO42+  R2SO42- + 2OH-
R’OH- + HCO3-  R’HCO3 - + OH-
Thus, hardness producing anions like Cl-, SO42- and HCO3- are removed (figure 1)
The H+ ions produced from first chamber combine with OH- ions produce from the
second chamber to form water
H+ + OH-  H2O
Hence, the water produced from ion-exchange process is completely free from all cations
and anions of salts.
Regeneration of Exhausted Resins:
The resin beds exhausted, when used for a long period and can be regenerated;
(a) The exhausted cation exchange resin can be regenerated by passing Dil. HCl.
R2Mg+2 + 2H+  RH+ + Mg+2
R2Ca2+ + 2H+  RH+ + Ca2+
(b) The exhausted anion exchange resin can be regenerated by passing Dil. NaOH.

RCl- + OH-  R’OH- + Cl-

R2SO42- + 2OH-  2R’OH- + SO42+

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 Figure 1. Demineralization of water

Advantages:

1. The soft water produced by this method is completely free from all salts and fit for
use in boilers.
2. It produces very low hardness nearly 2 ppm.
3. Highly acidic or alkaline water can be treated by this process.

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 00CYT100121903 (QP-2)
APJ ABDUL KALAM TECHNOLOGICAL UNIVERSITY
First Semester B. Tech Degree Examination July 2021 (2019 scheme)
Course Code: CYT100
Course Name: ENGINEERING CHEMISTRY

Max. Marks: 100 (2019 Scheme) Duration:3

Hours
PART A M
Answer all questions, each carries 3 marks
1 Calculate the equilibrium constant for the following reaction at 25 oC: (3)
Fe(s) + Cu2+ = Fe2+ (aq) + Cu (s)
Given Eo Fe2+/Fe = -0.44 V, EoCu2+/Cu = 0.34 V

A Eo cell = E cathode-E anode

= 0.34 – (-0.43)
= 0.77
Eo cell = -0.059/2 logKc
0.77 = -0.059/2 logKc
logKc = 1.55/-0.055
Kc = 1.91 X 1026
2 Give the electrochemical reaction taking place when an iron nail is dipped (3)
dil.HCl. Eo Fe2+/Fe = -0.44 V, Eo Fe3+/Fe = -0.04 V, EoH+/H2 = 0 V.

When iron filings (Fe) are added to dilute hydrochloric acid (dil.HCl), ferrous
A
chloride (FeCl2) and hydrogen gas are formed.

Fe + 2HCl  FeCl2 + H2 (g)

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3 State and explain the law governing absorption of electromagnetic radiation (3)
by matter. Give any one limitation of this law.

A When a beam of monochromatic radiation is allowed to pass through a transparent

medium, the rate of decrease of intensity (-dI) with thickness of absorbing medium
(dx) is proportional to the intensity of incident radiation (I) as well as to the
concentration of the solution(C).
𝑑𝐼
− ∝ 𝐼𝐶
𝑑𝑥
I = Intensity of incident radiation
C = Concentration of the absorbing solution

One LIMITATION:

 When different types of molecules are in equilibrium with each other.

4 Which molecule will absorb at longest wavelength in UV? Explain. (3)

Molecule “a” will absorb at longest wave length in UV when compared to “b”. The
A
reason is conjugated double bonds in “a” and is absent in “b”.
5 What are the classifications of chromatography bases on physical state of (3)
mobile and stationary phases?

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 There are four main types of chromatography. on the basis of stationary phase,
physical nature there are the following types. These are Liquid Chromatography, Gas
Chromatography, Thin-Layer Chromatography and Paper Chromatography.
6 Explain the synthesis of nanoparticles by chemical reduction. (3)

Chemical reduction is the excellent method for the preparation of stable

A
nanoparticles. Chemical reduction method is used for the preparation of silver
nanoparticles in water or organic solvents. Silver nanoparticles can be prepared by
the reduction of AgNO3 with aniline in dilute aqueous solution containing
cetyltrimethylammonium bromide (CTAB). Aniline act as a reducing agent as well
as adsorbing agent in the preparation of silver nanoparticles.

7 Write the IUPAC name and assign R/S notation. (3)

A 3(S)-hydroxy, 4(S)-chloro pentane.

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8 Write the different types of copolymers formed by the monomers A and B. (3)

A Start with two monomers: A and B. These two monomers can be mixed in
following different ways to result copolymers:

(1) alternating copolymer, Here the two monomers are joined in an alternating
manner:

-A-B-A-B-A-B-A-

(2) random copolymer, Here the two monomers are joined in any fashion:

-A-B-A-A-A-B-B-B-A

(3) block polymer, here all of one type of monomers are grouped together (to form
a block), and all of other are grouped together (to form another block).

(4) graft copolymer, here chains of polymer made of monomers A are grafted onto
a polymer chain of monomer B.

9 Calculate the hardness of (i) 0.05 M AlCl3 and (ii) 0.04 N MgCl2 (3)

A Normality of AlCl3 = M X Charge of Al+3

= 0.05 X 3 = 0.15
Hardness of AlCl3 = N X Eq.wt of CaCO3

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 = 0.15 X 50 = 7.5 gm/L
= 7500 mg/L = 7500 ppm
Hardness of MgCl2 = N X Eq.wt of CaCO3
= 0.04 X 50 = 2 gm/L = 2000 mg/L
10 What is the significance of measuring BOD of waste water? (3)

A BOD test is a very valuable test in the analysis of sewage, industrial effluents and
waste waters. BOD is expressed in mg/liter or ppm. Sewage sample usually gives a
BOD value in between 100 to 150 mg/liter. Higher the BOD greater the pollution.
The BOD test consists of the measurement of dissolved oxygen of the sample, before
and after incubation at 20 oC for 5 days.
PART-B
Answer one full question from each module, each question carries 14 marks
Module-1
11 a) Explain the construction and working of a calomel electrode as a (8)
reference electrode. What is the variation in the potential of a calomel
electrode with change in chloride ion concentration?

A Calomel electrode:
Construction and working:
It is a secondary reference electrode, consists of a glass tube having a side tube on
each side as shown in fig 1. Mercury is placed at the bottom of this tube and is
connected to the other circuit by means of platinum wire sealed in a glass tube. The
surface of mercury is layered with a paste of mercurous chloride (calomel) and
mercury in potassium chloride solution. The electrolyte is also a solution of KCl.

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This electrode is connected with the help of side tube on the left through a salt bridge
with the other electrode, the potential of which is to be determined.

The potential of Calomel electrode depends upon the concentration of the potassium
chloride solution. It has been very accurately determined by connecting it to a
standard hydrogen electrode and the results are obtained for reduction potentials of
this electrode (Hg/Hg2Cl2) for different concentrations of KCl at 24 oC are given
below:
For 0.1 N KCl solution E = +0.3338 V
For 1.0 N KCl solution E = +0.2800 V
For saturated KCl solution E = +0.2422 V
The positive value indicates that when combined with standard hydrogen electrode,
reduction takes place at this electrode.

Figure 1: Calomel electrode

b) Why Mg corrodes in both acidic and alkaline oxygen deficient conditions? (6)
Mg2++ 2e  Mg, Eo = -2.36 V,
Fe2+ + 2e Fe, Eo = -0.44 V

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 H+ + e 1/2 H2, Eo = 0V

A Magnesium is more reactive than iron.

It oxidize more readily than iron. So the nail does not rust.

Thus means it oxidize more than copper it rusts faster than nail alone.

Magnesium and its alloys are highly susceptible to galvanic corrosion, because
magnesium has the lowest standard potential of all the engineering metals as
illustrated in table corrosion can also occur between two different phase.
OR
12 a) Write the construction, working and advantages of Li-ion cell. (8)

Lithium-ion cells (Rechargeable): Lithium-ion cells are also called as

A
Rechargeable batteries. These cells do not contain metallic lithium and use only
lithium ions instead hence they are called lithium-ion cells. Therefore, the cell’s
operation does not actually involve true oxidation and reduction. But it uses the
transport of Li+ ions through the electrolyte from one electrode to the other
accompanied by the transport of electrons through the external circuit to maintain
charge balance.

Advantages:
 Lightweight.
 Longest Life. ...
 More Usable Capacity. ...
 Constant Power. ...

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  Temperature Tolerant. ...
 Charging - Fast & Safe.

Working, Equations and Diagram

In Lithium-ion batteries, there is no true oxidation and reduction. But it uses the
transport of Li+ ions through the electrolyte from one electrode to the other
accompanied by the transport of electrons through the external circuit to maintain
charge balance. It was discovered that Li+ ions are able to slip between two layers of
atoms in certain crystals such as graphite and LiCoO 2, when the cell is constructed,
it is in its uncharged state with no Li+ ions between the layers of carbon atoms in the
graphite. When the cell is discharged, Lithium ions leave LiCoO2 and travel through
the electrolyte to the graphite (C6).
Initial charging

LiCoO2 + graphite (C6) → Li1-x CoO2 + Lix C6

When the cell spontaneously discharges to provide electrical power, Li+ ions move
back through the electrolyte to the cobalt oxide while the electrons move through
external circuit from the graphite electrode to the cobalt oxide electrode. If we
represent amount of Li+ transferring by “y”

the discharge reaction

Li1-x CoO2 + Lix C6 → Li1-x+y CoO2 + Lix-y C6

Thus, the charging and discharging cycle simply sweep Li+ ions back and forth
between the electrodes with electrons flowing through external circuit to keep the
charge balance.

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 Figure 1.6 Lithium-ion cell. (a) During the charging cycle, an external voltage forces
electrons through the external circuit and causes lithium ions to travel from the
LiCoO2 electrode to the graphite electrode. (b) During the discharge, the lithium ions
spontaneously migrate back to the LiCoO2 electrode and electrons flow through the
external circuit to balance the charge.
b) What are the products of electrolysis at cathode and anode when NaCl (6)
solution is electrolyzed using Cu electrodes.
Na+ + e-  Na, E0= -2.71 V,
Cu2+ + 2e Cu, E0 = 0.34 V,
Cl2 + 2e  2Cl-; E0 = + 1.36 V
H+ + e  ½ H2, E = -0.41 V (at PH = 7)
O2 + 2H2O + 4e  4OH-, E = 0.82 V (at PH = 7)

A The products of electrolysis of sodium chloride are sodium hydroxide, hydrogen

gas, produced at cathode and chlorine gas at anode.
Module-II

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13 (a) Predict the number of signals, their relative positions ad splitting (8)
pattern in the nmr spectrum of the following
1) benzaldehyde 2) C6H5CH3

1) benzaldehyde: In benzaldehyde, C6H5CHO there are three environments a,

A
b, c. a, b, c type of protons will give signal at 10.1 ppm, 8.1 ppm, 7.2 ppm
respectively. a type of protons is highly deshielded due to carbonyl group.

NMR spectrum of C6H5CHO

In C6H5CH3, there are two types of protons and two types will result two signals in
NMR spectrum. In NMR spectrum of C6H5CH3 there is 1 signal at 7 ppm due to
phenyl protons and another peak at 2.34 ppm due to methyl group.

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 NMR spectrum of C6H5CH3
(b) Compare the strengths of C-H bond and C=O bond if the absorption (6)
frequencies are 3000 cm-1 and 1700 cm-1 respectively.

A Absorption frequency increases with bond strength. Therefore C-H bond has
absorption frequency at 3000 cm-1 and C=O bond has absorption frequency at 1700
cm-1. The strengths of C-H bond is greater than the C=O bond.
OR
14 (a)Give the instrumentation of UV spectrophotometer and explain the (8)
components in it. Comment on the role of conjugation in the wavelength of
absorption with the help of examples.

A Principle:
It involves the transitions of electrons within a molecule or ion from a lower to a
higher electronic energy level or vice-versa by the absorption or emission of
radiations falling in the UV-visible range of electromagnetic spectrum.

Instrumentation:
The essential parts of a UV-Visible Spectrophotometer are as follows.
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 a) Radiation source:
The wavelength in UV-Visible Spectrophotometers extends from 200 nm to
about 780 nm. Hydrogen lamps in the range 200 to 370 nm and a tungsten
filament lamp in the range 325 to 750 nm were used as radiation sources.
b) Monochromator/filter
The filter unit consists of an entrance slit, a dispersing element and exit slit.
The dispersing element us generally a prism or grating.
c) Sample holder/cells
The light beam from the source is divided into two identical parallel beams of
equal intensity. These beams are allowed to pass through the sample cell and
reference cell containing the solvent. Sample holder is made of quartz cell.
d) Photodector:
This unit detects and converts radiant energy into electrical signal.
e) Recording system:
The two beams, one emerging from the sample cell and the other from the
reference cell, are then led to the detector system. The detectors convert the
transmitted radiation into electrical energy.

Figure 1. Schematic diagram for UV-visible spectrophotometer:

Advantages of (UV-Visible spectroscopy):
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 1. Determination of unknown compounds.
2. Detecting the impurities in organic compounds.
Comment on the role of conjugation.
1, 3 butadiene have greater absorption maxima (λ = 217 nm) than C2H4 (λ = 167
nm). presence of conjugation in 1, 3 butadiene results more absorbance and absence
of conjugation in C2H4 results less absorbance.
b. Briefly explain the principle involved in MRI. Mention any two (6)
applications

MRI is called Magnetic resonance imaging. It is a medical imaging technique used

A
in radiology to address the health issues of the body. The technique is widely used in
hospitals for medical diagnosis.

Principle: magnetic resonance imaging employs nuclear resonance protons to

produce proton density maps of the human body. Thus, MRI can be utilized to
differentiate between healthy and diseased tissues of the body. It is based on the fact
that the protons present within water, lipids, fats etc. resonate at a given frequency.
Since human body contains about 75 % water (H2O) having two hydrogens. In a
diseased condition of body part, the distribution of water, fats, lipids etc. varies and
hence by using MRI, one can detect the diseased parts of the body.

Working: Magnetic field is applied across the body part for taking the MRI image.
The protons in various regions of body resonate at different frequencies and the
intensity of signal is proportional to the number of protons at that magnetic field. The
body part is then rotated into a different orientation and another projection is made.
Finally, the data obtained from different projections are combined by a computer to
get a three-dimensional image of the body part.

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 Applications:

1. For investing the functioning of myocardium, heart etc.

2. For identifying the regions of excessive fat deposition.

3. For estimating fluorine concentration in body parts.

Module-III
15 (a) Discuss in detail the instrumentation of TG and DTA with neat sketch (8)

(TGA): Instrumentation of TGA

A The main components of TGA apparatus are shown in the form of block diagram in
Fig.1 are Analytical thermo balance, furnance, environmental control equipment and
recorder

(a) Analytical thermobalance is used for the measurement of mass with

reproducibility of the order of ± 10 micrograms.
(b) Furnance linked with microprocessor-controlled power source generally
programmed to increase the temperature linearly at a predetermined rate of 0.5-
25 oC/min from room temperature to 1200 oC.
(c) Environment control equipment for providing inert atmosphere for the sample
whenever desired.
(d) A recorder that gives a graph of m as function of T.

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 Figure 1 Block diagram of TGA apparatus.
Working
For TGA the sample is introduced in a crucible, and is continuously heated by the
power source, the Power source, the weight change of the sample at different
temperatures is recorded.

Instrumentation, working of DTA:

The instrumentation of DTA is similar to TGA, however the only difference is that
reference holder is placed along with sample holder in DTA. The main components
of DTA instrumentation are shown in fig 2

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 Figure 2 Block diagram of DTA apparatus.

Sample holder - To take the sample.

Reference holder - To take the reference.
 Temperature sensing device (thermometer) - To note the temperature of the
sample.
 Temperature sensing device (thermometer TR) - To note the temperature of
the reference.
 Environment control equipment - For providing inert atmosphere inside the
furnace.
 Thermal insulation system - To hinder loss of heat.
 Amplifier - To amplify the signals.
 Recorder - To record the signal and to graph the thermogram

Working
The sample is introduced in one chamber and the inert reference material like Al2O3
in the other chamber. The furnace is heated, the difference in temperature between
the sample (S) and the reference (R). T= TS-TR is continuously measured as a
function of the reference sample temperature (TR).
(b) Discuss the various detectors used in GC and HPLC (6)

A Gas chromatography – flame ionization detectors (FID)

The FID is the most common detector used in gas chromatography. The FID is
sensitive of detecting compounds that contain carbon atoms (C), which accounts for
almost all organic compounds.

HPLC: UV detector
Ultraviolet absorption (UV) detector is currently the most widely used detector for
HPLC.

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 OR
16 (a) Briefly explain the principle, instrumentation and application of SEM. (8)

Principle
A
SEM is scanning electron microscope shown in figure 1. It is a powerful tool used
for the surface characterization of materials. In this method the sample surface is
scanned with a focused accelerated beam of electrons which interacts with atoms in
the sample, producing various signals that contain information about the surface.
This examination provides information about topography (surface features.),
morphology (shape and size of the particles), composition and crystallographic
information.
Instrumentation

Figure 1. Scanning Electron Microscope.

The block diagram of SEM consists of the following parts.

(i) Electron gun – It is the source of electron (Example tungsten wire).
(ii) Condenser lens – Compresses the electrons to a narrow beam.

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 (iii) Aperture – It controls the diameter of the electron beam.
(iv) Objective lens- It focuses the electron beam to the sample.
(v) Sample chamber – This chamber keeps the sample.
(vi) Detector – To detect the signals.
(vii) Amplifier –To amplify the signals.
(viii) Display – To show the SEM image obtained.
Working
In this process a beam of energetic electrons is produced in an electron gun, and
it is passed through a series of electromagnetic lenses (like condenser lens aperture
and objective lens). Coming out radiations are detected, amplified and recorded to
get SEM image.
Applications
1. Used to characterize nanomaterial size and behaviors.
2. Used for forensic investigations.
3. It is a very essential research tool in life science, biology, gemology, and
metallurgy.
(b) Differentiate between TGA and DTA (6)

A TGA DTA

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 1. It is a thermal analytical technique in 1. It is a thermo analytic technique,
which the physical and chemical used for the identification of
properties of materials are studied as a different materials like clays,
function of temperature. minerals cements etc.
2. It is a technique where by the mass of a 2. In this method the temperature
substance is recorded continuously as the of the sample and a thermally inert
temperature. reference material are measured as
3. This method is used to study several a function of temperature.
physical and chemical changes that is 3. This method is used to study
followed by a mass change. every chemical and physical
changes that occurs with or
without a change in weight.

Module-IV
17 (a) Draw and explain the conformational isomerism in ethane and butane. (10)
Draw the energy profile diagram. Which conformer is more stable in each
case?

A Conformation of ethane:
The conformations of ethane (CH3-CH3) generated from the rotation of back -CH3
about a C-C sigma bond while keeping front -CH3 fixed. According to Newman’s
projection formula front carbon atom is shown at the center of the circle with the
three C-H bonds placed at projection of 120o. The back carbon atom C-H bonds are
shown over the circle which is also placed at projection angle of 120 o. In eclipsed
conformation the dihedral angle between the C-H bond of front and back carbon atom
is zero, where as in staggered conformation it is 60o.There is a 12 kJ/mol barrier
between staggered and eclipsed conformations. The most stable (low energy)

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conformation is the staggered conformer, so that -C-H bond repulsion between the
two-CH3 groups is minimum. The least stable (high energy) conformation is the
eclipsed conformer. Figure 1 shows Conformation of ethane.

Figure 1: Conformation of ethane

Conformations of butane
Figure 2 shows conformation of butane. The structure D in fig 2 has the highest
energy with zero dihedral angle. The structure D is called fully eclipsed
conformation, it has high torsional strain energy because of bulky -CH3 groups are
close to each other. When the front carbon of structure D is rotated through 60o
(while keeping back carbon fixed) in clockwise or anti clock wise direction structure
B is obtained, it is called skew or Gauche form. The Gauche form is stable by an
energy of 14.2 kJ/mol from fully eclipsed form D. When the front carbon atom of
structure D is turned though 120o, in clock wise or anti clock wise direction another
eclipsed form is obtained, called eclipsed form (structure C). When structure D is
turned through an angle of 180 oC in clockwise or anti clock wise direction fully
staggered form A is obtained. It is also called Anti-form, it is the lowest energy form
and more stable among all conformers. Figure 2 shows conformation of butane

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 Figure 2: Conformation of butane
(b) Explain the classification of conducting polymers. (4)

A Conducting polymers can be classifies as follows.

OR
18 (a) What is meant by conformational isomerism? Draw the cis and trans (8)
isomers of 1,4-dimethyl cyclohexane. In each case, mention the more stable
conformer.

A Conformational analysis:
The different special arrangement of atoms that results from the rotation of group
about a C-C sigma bond is defined as conformational isomers. The energy difference
between two extreme conformations is very small, thus rapid inter conversions takes
place at room temperature. It is impossible to separate one conformer from the other,

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 low energy conformer is more populated than high energy conformer at room
temperature.
The cis and trans isomers of 1,4-dimethyl cyclohexane
1, 4-dimethyl cyclohexane has two conformers (1a,4a) and (1e,4e). They inter
convert each other by flipping. (1a,4a) and (1e,4e). They inter convert each other by
flipping. (1a,4a) from each axial methyl group has two Gauche interactions with the
ring CH2 groups, thus there are 4 gauche interactions, whereas (1e,4e) form has no
Gauche interaction. Thus (1e,4e) conformer is more stable in (trans) 1,4- dimethyl
cyclohexane.

Figure shows conformations of 1,4-dimethyl cyclohexane.

(b) Brief out the basic principle, construction and working of OLED (6)

A OLEDs are defined as thin film semiconductor devices activated by the

electroluminescent organic materials.
Construction: An OLED structure found to contain the five parts:
i. Glass substrate which supports the OLED.

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 ii. Anode made of indium tin oxide (ITO) which adds holes (or removes
electrons) when a current flows through the device.
iii. Conducting layer” made of polyaniline or poly (p-phenylene vinylene) that
transport holes from anode. This layer is also known as a hole transport layer
(HTL).
iv. Emissive layer made of polyfluorene polymer. It acts as an electron
transport layer (ETL);
v. A metallic cathode made of Al, Ca or Ag. It injects electrons when a current
flows through the device.

Working: As the voltage (or potential different) is applied across the anode and
cathode, the cathode receives electrons from the power source and anode loses
electrons. The added electrons make the emissive layer negatively charged (similar
to the n-type layer in a junction diode). Simultaneously, the conductive layer
becomes positively charged (similar to p-type material). Compared to electrons,
holes are much more mobile so they jump across the boundary from the conductive
layer to the emissive layer. When a hole meets an electron, the positive and negative
charge cancel out and release a brief burst of energy in the form of a quantum of light
or a photon. This process is called recombination. As long as the current keeps on
flowing, the OLED produces continuous light because recombination process occurs
many times in a second.

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 Figure Operation of OLED
Module-V
19 (a) Describe the various steps involved in sewage treatment? (10)

Sewage treatment involves the following steps.

A
1. Screening or preliminary process: It involves the removal of large and coarse
solids, inorganic impurities, suspended and floating contaminants in sewage.
This involves in passing the sewage through bar screens and mesh screens.

2. Sedimentation or Settling process: The suspended organic and inorganic

impurities is removed by this process. Sedimentation is done in large
sedimentation tanks. The suspended particles settle down due to gravity.
Sedimentation is accelerated by coagulants like alum, FeSO 4 etc. The settled
solids called raw sludge are removed mechanically. This process helps to
reduce about 50 % of the whole BOD.

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 3. Secondary treatment process: The secondary treatment process involves the
biological oxidation of organic compounds at aerobic or anaerobic conditions.

Method 1: TRICKLING FILTERS

Trickling filters are named as secondary aerobic treatment process. Trickling filter
consists of a rectangular or circular tank of about 2 m depth. The tank is filled with
crushed rock or graded clinkers. There is a drain at the bottom to collect the treated
effluent.

Figure represents Trickling Filter treatment

Working of trickling filters

Sewage is introduced to the top of filters by means of a rotating distributor. As the

sewage starts flowing downwards, through the filtrating media, microorganisms
(present in sewage) grow on the surface, aerobic oxidation takes place and sewage
gets cleaned. Finally, sewage can be collected through the bottom drain. The spraying
mechanism involves the saturation of the waste water with oxygen and supports to
maintain aerobic conditions. This results in the development of a gelatinous film
containing microorganisms.

Method 2: UP FLOW ANAEROBIC SLUDGE BED (UASB) PROCESS

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 UASB reactor consists of a rectangular tank with proper inlet and outlet for feeding
and collecting the effluent. There is mechanism for the collection of fuels formed. In
this process, the effluent is fed from the bottom of the reactor, so that it passes upward
through the sludge blanket. The sludge blanket is basically formed granules of
diameter 1 to 1.5 mm. As the waste water comes in contact with the granules,
anaerobic oxidation takes place and gases like methane are formed. The temperature
is maintained around 35 oC and the gases are collected through the gas collector
domes fitted to the top of the reactor. USAB process is the most preferred method of
sewage treatment in developing countries, due to its low capital cost and integrated
control mechanism.

Figure represents UASB process

(b) Write any four disadvantages of hard water? (4)

Domestic use:
A
(a) Washing and Bathing: Hard water does not form lather easily with soap. As a
result, a large amount of soap is wasted.

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 (b) Drinking: Hard water causes bad effects on our digestive system. Sometimes,
stone formation takes place in kidneys.

(c) cooking: the boiling point of water is increased due to the presence of salts. Hence,
more fuel and time are required for cooking.

Industrial use:

(a) Textile industry: Hard water consumes more soap. Precipitates of calcium and
magnesium soaps adhere to the fabrics and results damage.

OR
20 (a) Write the principle and procedure of estimation of permanent and (8)
temporary hardness of water by complexometric titration.

Principle Disodium salt of Ethylenediaminetetraacetic acid (EDTA) forms stable

A
complex with Ca+2 and Mg+2 ions in aqueous solution. The amount of EDTA
consumed in the reaction gives the amount of calcium and magnesium.

Structure of EDTA

Since EDTA is insoluble in water, the disodium salt of EDTA is used as complex
agent with Ca2+ and Mg2+ions.

Structure of EDTA (Disodium salt)

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When Eriochrome Black-T (EBT) indicator is added to the hard water sample, it
forms wine red colour, unstable complex at pH=10 with Ca2+ and Mg2+ ions. When
this solution is titrated against EDTA solution, the colour of the complex changes
from wine red to deep blue which indicates the end point i.e., EDTA formed stable
complex with ca2+ Mg2+ ions.

M2+ + EBT M-EBT [Unstable complex (wine red)]

M-EBT + EDTA  M-EDTA + EBT [stable complex blue]

Solutions used in the experiment

EDTA solution

Standard hard water

EBT Indicator

Buffer solution.

Procedure:

Standardization of EDTA solution: The burette is rinsed and filled with EDTA
solution. 50 ml of standard hard water is pipetted out into a clean conical flask. 5 ml
of ammonical buffer and few drops of EBT indicator are added and then titrated
against EDTA solution until the wine red colour changes to deep blue colour which
the end point.

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 Let the volume of EDTA used be V1 ml.

Estimation of Total hardness: 50 ml of a given sample of hard water is pipetted out

into a clean conical flask. 5ml of ammonical buffer and few drops of EBT indicator
are added and then titrated against EDTA solution until the wine red colour changes
to deep blue colour. Let the volume of EDTA used be V 2 ml.

Estimation of permanent Hardness: 250 ml of the hard water sample is taken in a

beaker and evaporated to nearly 50 ml (when all the bicarbonates are decomposed to
insoluble CaCO3 and Mg(OH)2.Filter and wash and make up the filtrate to 250 ml
with distilled water. 50 ml of made up solution is pipetted out into a conical flask. 5
ml of ammonical buffer and few drops of EBT are added and then titrated against
EDTA until the wine red colour red changes to deep blue. Let the volume of EDTA
used be V3 ml.

Calculations: It involves 3 steps

Step 1: Standardisation of EDTA

1 ml of standard hard water = 1 mg of CaCO3

50 ml of standard hard water = V1 mL of EDTA

50 mg of CaCO3 eq. = V1 mL of EDTA

1 mL of EDTA = 50/V1 mg of CaCO3 eq.

Step 2: Estimation of Total Hardness

50 ml of given hard water = V2 mL of EDTA

= V2 X 50/V1 mg of CaCO3 eq.

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1 mL of hard water = V2/50 X 50/V1 mg of CaCO3 eq.

1 mL of given hard water = V2/V1 mg of CaCO3 eq.

1 litre of given hard water = V2/V1 X 1000 mg of CaCO3 eq.

Total Hardness = V2/V1 X 1000 mg/L

Step 3: Estimation of Permanent Hardness

50 ml of boiled water = V3 mL of EDTA

= V3 X 50/V1 mg of CaCO3 eq.

1 mL of boiled water = V3/50 X 50/V1 mg of CaCO3 eq.

1 mL of boiled water = V3/V1 mg of CaCO3 eq.

1 liter of boiled water = V3/V1 X 1000 mg of CaCO3 eq.

Permanent Hardness = V3/V1 X 1000 mg/L

Temporary Hardness

Temporary Hardness = Total hardness-permanent hardness

= V2/V1 X 1000 - V3/V1 X 1000

Temporary Hardness = 1000[V2-V3/V1] ppm

Result:
Total Hardness = V2/V1 X 1000 mg/L
Permanent Hardness = V3/V1 X 1000 mg/L
Temporary Hardness = 1000[V2-V3/V1] ppm or mg/L

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 (b) 50 mL sewage water sample after reaction with 20 mL of K 2Cr2O7 required (6)
12.4 mL of 0.2 N ferrous ammonium sulphate solution. For blank titration 20
mL K2Cr2O7 required 20.4 mL of 0.2 N ferrous ammonium sulphate solution.
Calculate the COD of the sample.

Volume of FAS (ferrous ammonium sulphate) required

A
for blank solution = VB = 20.4 mL
Volume of FAS (ferrous ammonium sulphate) required
for sewage estimation = VE = 12.4 mL
VB- VE = 20.4 - 12.4 = 8 mL
Normality of FAS = 0.2 N
COD = 8 X N X (VB- VE) X 1000 /Volume of sewage mg/L
COD = 8 X 0.2 X 8 X 1000 /50 mg/L
= 256 mg/L

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