Chemistry Notes Vtu

Sri Shridevi Charitable Trust( R )
SHRIDEVI INSTITUTE OF ENGINEERING

AND TECHNOLOGY, TUMKUR-572106

ENGINEERING CHEMISTRY ENGINEERING CHEMISTRY ENGINEERING CHEMISTRY ENGINEERING CHEMISTRY
CLASS NOTES CLASS NOTES CLASS NOTES CLASS NOTES

1. Dr. CHANDRASEKHAR. N

H.O.D of chemistry

2. Miss. SUJATHA.K
3. Miss. SHWETHA S. RAO

NAME :____________________
USN :____________________
BRANCH : ____________________
SECTION : ____________________

SHRIDEVI INSTITUTE OF ENGINEERING AND TECHNOLOGY.
ENGINEERING CHEMISTRY DEPARTMENT, S.I.E.T., TUMKUR. 1

CONTENTS

UNIT TITLE
PAGE
NO
I CHEMICAL ENERGY SOURCES 04-24
II
ELECTROCHEMICAL ENERGY
SYSTEMS
25-43
III
CONVERSION AND STORAGE OF
ELECTROCHEMICAL ENERGY
44-56
IV CORROSION SCIENCE 57-71
V METAL FINISHING 72-84
VI
LIQUID CRYSTALS AND THEIR
APPLICATIONS
85-98
VII HIGH POLYMERS 99-115
VIII WATER TECHNOLOGY 116-132
IX MODEL QUESTION PAPER 133-140

Syllabus Syllabus Syllabus Syllabus
PART A
Unit - I
Electrode Potential and Cells
Introduction, Differentiation between galvanic and electrolytic cells,
Construction of galvanic cell, EMF of a cell , Origin of single electrode
potential, Sign convention and cell notation, Standard electrode
potential, Derivation of Nernst equation for single electrode potential.
Types of electrodes: Reference electrodes Primary and secondary ,
Limitations of standard hydrogen electrode, Construction and working of
calomel electrode and Ag AgCl electrode, Measurement of single
electrode potential, Numerical problems on electrode potential and EMF
of a cell, Ion selective electrode: Glass electrode Construction ,
Determination of pH of a solution using glass electrode.

7 Hours

Unit - II
Batteries and Fuel Cells
Basic concepts, Battery characteristics, primary, secondary, reserve
batteries and super capacitors with examples.
Classical batteries: Construction, working and applications of Zn MnO2
battery, Lead acid storage battery and Ni Cd battery.
Modern batteries: Construction and working and applications of Zn air,
Ni metal hydride and Li MnO2 batteries
Fuel cells Differences between battery and fuel cell, construction and
working of H2 O2 and
CH3OH O2 fuel cells

6 Hours
Unit - III
Corrosion and its control
Electrochemical theory of corrosion, Galvanic series, Types of corrosion-
Differential metal corrosion, Differential aeration corrosion(Pitting and
water line corrosion) , Stress corrosion (caustic embrittlement in boilers),
Factors affecting the rate of corrosion.
Corrosion control: Inorganic coatings Anodizing and phosphating,
Organic coating painting,
Metal coatings Galvanizing and Tinning, Corrosion inhibitors, Cathodic
protection.

7 Hours
Unit IV


Metal Finishing
Technological importance, Theory of electroplating, Significance of
Polarization, Decomposition potential and Overvoltage in electroplating.
Effect of plating variables on the nature of electrodeposit. Electroplating
process, Electroplating of Copper and Chromium.
Distinction between electroplating and electrolessplating,
Electolessplating of copper and nickel.

6 Hours
PART B
Unit - V
Chemical fuels and Photovoltaic cells
Introduction, Classification of chemical fuels, Calorific value High and
Low calorific values, Determination of calorific value solid or liquid fuel
using Bomb calorimeter, Gaseous fuel using Buoys calorimeter,
Numerical problems.
Petroleum Cracking by fluidized catalytic cracking process,
Reformation of petrol, Octane and Cetane numbers. Knocking
mechanism and harmful effects. Antiknocking agents TEL, Catalytic
converters Principle and working, Unleaded petrol, Power alcohol and
Biodiesel.
Photovoltaic cells Production of solar grade silicon, Doping of silicon,
Construction and working of photovoltaic cell, Advantages.

7 Hours
Unit - VI
The Phase rule and Instrumental methods of analysis
Statement of Gibbs phase rule and explanation of the terms involved,
Phase diagram of one component system water system, Condensed
phase rule , Phase diagram of two component system- Eutectic Pb Ag
system and Fe C system. Application Desilverization of lead.

Instrumental methods of analysis- Theory , Instrumentation and
applications of Colorimetry, Potentiometry , Conductometry and Flame
photometry.

6 Hours
Unit - VII
Polymers
Types of polymerization Addition and Condensation, Mechanism of
polymerization Free radical mechanism taking ethylene as example.

Glass transition temperature ( Tg) . Structure property relationship.
Types of plastics Thermosetting and thermoplastics. Compounding
resins to plastics, Manufacture of plastics by compression and injection
moulding, extrusion method.
Synthesis and applications of Teflon, PMMA, Polyurethane and Phenol
formaldehyde resins.
Elastomers: Deficiencies of natural rubber, Vulcanization of rubber.
Synthesis and applications of Neoprene and Butyl rubber, Silicone
rubbers.
Adhesives: Synthesis and applications of epoxy resins.
Polymer composites - Synthesis and applications of Kevlar and Carbon
fibers.
Conducting polymers Definition, Mechanism of conduction in
Polyacetylene and Polyaniline.

7 Hours
Unit - VIII
Water Chemistry
Impurities in water, Water analysis Determination of different
constituents in water Hardness, alkalinity, chloride , fluoride , nitrate ,
sulphate and dissolved oxygen by Winklers method. Numerical problems
on hardness and alkalinity.
Sewage BOD and COD, Numerical problems, Sewage treatment.
Desalination of water Reverse Osmosis and Electrodialysis

6 Hours

Text Books
1. A text book of Engineering Chemistry P.C. Jain and Monica Jain
Dhanpatrai Publications,
New Delhi.
2. Chemistry In Engineering and Technology ( Vol. 1 &2) J.C.
Kuriacose and J. Rajaram.

Reference Books
1. Principles of Physical Chemistry B.R. Puri , L.R.Sharma & M.S.
Pathania, S. Nagin chand and Co.
2. Text Book of Polymer Science F.W. Billmeyer John Wiley & Sons.
3. Corrosion Engineering M.G. Fontana Mc. Graw Hill Publications.
4. Environmental Chemistry Stanley E. Manahan , Lewis Publishers.
5. Polymer Science V.R. Gowariker , Wiley Eastern Ltd.


UNIT UNIT UNIT UNIT I II I
CHEMICAL ENERGY SOURCES:
FUELS

1.1 Define a fuel. Explain the classification of fuels with examples.
5 Marks

A fuel is defined as naturally occurring or artificially
manufactured combustible carbonaceous material which serves
particularly as source of heat and light and also in few cases as a source
of raw material.
Classification of fuels Fuels are classified into a two types.
1) Based on their origin they are classified into
a) Primary fuels
b) Secondary fuels.
a) Primary Fuels: There are naturally occurring fuels which serves as
source of energy without any chemical processing.
Ex: Wood, Coal, Crude oil, Natural gas, Peat, Lignite, Anthracite..
b) Secondary Fuels: - They are derived from primary fuels & serves as
source of energy only after subjecting to chemical processing.
Ex: Charcoal, Coke, produsergas, Petrol, Diesel etc.,
2) Bases on their physical state fuel are classified into
a) Solid
b) Liquid
c) Gaseous fuels.

SOLID

LIQUID

GASEOUS

Primary Fuels
Wood, Coal,
Peat, Anthracite
Crude oil Natural gas.
Secondary Fuels Coke, Charcoal
Petrol, Gasoline,
Diesel
LPG,
produsergas,
Coal gas.

1.2 Define Calorific Value. Explain the types 04 Marks
Calorific value is defined as the amount of heat liberated when a
unit mass of fuel is burnt completely in presence of air or oxygen.

Calorific value is of two types as follows:-
1) Higher calorific value. (HCV) or Gross calorific value. (GCV)
2) Lower calorific value. (LCV) or Net calorific value. (NCV)

1) HCV: - It is the amount of heat liberated when a unit mass of fuels
burnt completely in the presence of air or oxygen and the products
of combustion are cooled to room temperature. Here it includes the
heat liberated during combustion and the latent heat of steam.
Hence its value is always higher than lower calorific value.

2) LCV: - It is amount of heat liberated when a unit mass of fuel is
burnt completely in the presence of air or oxygen and the product
of combustion are let off completely into air. It does not include the
latent heat of steam. Therefore it is always lesser than HCV.

NCV = HCV Latent heat of steam.
= HCV 0.09X % H2 X 587 cal/g

1.3. Mention the SI units of calorific value. 2 Marks
In SI system the units of calorific values for solid fuels are
expressed in J/Kg and for gaseous and liquid are expressed in J/m
3
.

1.4. Explain the determination of calorific value of solid fuel
using Bomb calorimetric method. 6 Marks

A small quantity of a fuel is weighed accurately (M Kg) and is
placed in the Bomb. The bomb is placed in known amount water taken in
a copper calorimeter. The initial temp of water is noted as a t1
0
C with the
help of thermometer. Oxygen gas is pumped under pressure 20 to 25
atm through the O2 valve provided.

The fuel is ignited by passing electric current through the wires
provided. As the fuel undergoes combustion and liberates heat, which is
absorbed by surrounding water. The water is stirred continuously to
distribute the heat uniformly and the final temp attained by water is
noted t2
0
C. & gross calorific value of the fuel is calculated as follows:-

Calculation:

Mass of the fuel = M Kg.
Initial temp of the water = t1
0
C
Final temp of the water = t2
0
C
Change in temp = t = (t2 t1)
0
C
Specific heat of water = S
Water equivalent of calorimeter = W Kg.

GCV = W x S x t J/Kg or
M
GCV = (W+w) x S x t J /Kg
M
NCV = GCV 0.09 x %H2 x 587 cal/g

PROBLEMS:
1) Calculate calorific value coal samples from the following data.
6 Marks

Mass of the coal = 1g.
Water equivalent of calorimeter = 2 Kg.
Specific heat of water = 4.187 J/Kg/c.
Rise of temperature = 4.8
0
C.

Solution: GCV = W x S x t J/Kg
M
= 2 x 4.187 x 4.8
0.001
= 40195.2 KJ/Kg.

2) A coal sample with 93% carbon, 5% of Hydrogen and 2% Ash is
subjected to combustion in a bomb calorimeter. Calculate GCV and NCV
Given that. 6 Marks
Mass of the coal sample = 0.95g
Mass of water in copper calorimeter = 2000g.
Water equivalent wt of calorimeter = 700g.
Rise in temp = 2.8
0
C
Latent heat of = 587 cal/g.
Specific heat of water = 1 cal/g/
0
C

GCV = (W+w) x S x t
M
= (2000+700) x 10
-3
kg x 1 cal/g/
0
C x 2.8
0
C x 4.184
0.95 x 10
-3
kg

= 33295.83 J/kg.

NCV = GCV 0.09 x %H2 x 587x4.184 J/kg.
= 33295.83 J/kg 0.09 x 5 x 587 x4.184 J/kg.
= 32190.62 J/kg

3) When 0.84g of coal was burnt completely in Bomb calorimeter the
increase in temp of 2655 grams of water was 1.85
0
C if the water
equivalent calorimeter is 156g Calculate GCV.

GCV = (W+w) x S x t
M
= (2655+156) x 1.85 x 10-3 x 4.187
0.84 x 10-3
= 25921.26 J/Kg

4) Calculate GCV and NCV of a fuel from the following data.
Mass of fuel=0.75g, W=350g. t =3.02
0
C, Mass of water = 1150,
% H2=2.8. 6 Marks

GCV = (W+w) x t x S
M
= (1150+350) x10
-
x
3
3.02 x 4.184
0.75 x 10
-3

GCV = 25271. 36 KJ/Kg

NCV = GCV 0.09 x H x 587 x 4.184

= 25271.36 0.09 x 2.8 x 587 x 4.184

NCV = 24652.44 KJ/Kg

5) Calculate calorific value of a fuel sample of a coal form the following
data. Mass of the coal is 0.6g. Water equivalent wt of calorimeter is
2200g. Specific value 4.187 Kg/KJ/C rise in temperature = 6.52
0
C.
3 Marks
GCV = (W1+W2) x S x t
M
= (2200) x 10-3 x 4.184 x 6.52
0.6 x 10-3

= 100025.49 KJ/Kg.

6) Calculate GCV and NCV of a fuel from the following data.
Mass of fuel =0.83g, W=3500g. , W = 385 g, t1 =29.2
0
C, t2 = 26.50C, % H2
= 0.7 and S = 4.2 kj/kg/c
6 Marks
GCV = (W+w) x t x S
M
= (3.5 + 0.385) x (29.2 26.5) x 4.2
0.83 x 10
-3

GCV = 53079.39 KJ/Kg

NCV = GCV 0.09 x H x 587 x 4.184

= 53079.39 0.09 x 0.7 x 587 x 4.2

NCV = 52924.07 KJ/Kg


1.5 Explain the determination of calorific value of gaseous fuel
using Buoys calorimetric method.

Buoys Calorimeter

The calorific value of a gaseous fuel is determined by burning known
volume of gas in steady flow calorimeter. Water is allowed to pass
through the tubes surrounding the combustion chamber till the
temperatures measured by the thermometers T1 & T2 are the same. The
gaseous fuel under steady is introduced into the burner through the gas
inlet at a steady rate recorded by the gas meter. The gas is burnt in the
combustion chamber and the combustion products are passed over the
tubes through which water flows at a constant rate of 6-10 cm
3
/ sec.
When a temperature of the apparatus reaches a constant value (i.e when
T2 shows a constant reading the heat released by the combustion of the
fuel in an certain interval of time will be equal to the heat absorbed by
water during the same interval of time. Calorific value Q is given by the
equation

Q = mass of water x rise in temp. x specific heat
Volume of gas burnt

The rise in temperature should be of the order of about 20 K. Vapors
cooled by circulating water are further cooled in condenser tubes to
condense water form during the combustion of hydrogen and
hydrocarbons in the fuel. Amount of condense water collected in the

measuring cylinder for the volume of gas burnt could be made use of for
calculating the net calorific value.
Observations and calculations:
i) Volume of gas burnt at NTP in time t = V m
3

ii) Weight of cooling water circulated in time t= W kg
iii) Steady temperature of the inflow water = t1
0
C
iv) Steady temperature of the outflow water = t2
0
C
v) Rise in temperature = (t2-t1)
0
C
vi) Weight of water produced from steam condensation = m kg

Heat released by the combustion of
V cm3 of gas fuel = Heat absorbed by water
HCV x V = W (t2-t1)
Higher calorific value of the fuel = W (t2-t1) k cal /m
3

V
= W (t2-t1) 4.187 kJ/m
3

V
m x 587
Latent heat of steam = k cal m3
V
W (t2-t1) 4.187 m x 587 x 4.187
Lower (net) calorific value of fuel = -
V V

=------------- kJ/m
3

Numericals:
1)Calculate gross and net calorific value of a gaseous fuel from the
following data obtained from boys experiment:

i) Volume of gaseous fuel burnt at STP ----- = 0.09 m
3

ii) Weight of water used for cooling ----- = 25.0 kg
iii) Temperature of inlet water ----- = 25.0
0
C
iv) Temperature of outlet water ----- = 40.0
0
C
v) Weight of water produced by steam condensation ---- = 0.02 kg
vi) Latent heat of steam ----- = 587 k cal kg

Solution:
W x (t2-t1)
Higher calorific value of the given gaseous sample = x 4.187
V


= 25 x (40-25) x 4.187

0.09
= 17445.8 kJ m3

0.02 x 587 x 4.187
Heat released in condensing steam =
0.09

Net calorific value = 546.17 kJ m3
= HCV latent heat of steam
= 17445.8 546.17
= 16899.63 kJ m3

2)Calculate the gross and net calorific value of a gaseous fuel at STP from
the following data
Volume of gas burnt =0.02m
3

Temperature of the gas =293 K
Mass of water passing through calorimeter =4.5 kg
Rise in temp =18.5 K
Absolute pressure of gas =101990 N/m
2

Specific heat of water =4.18J/g/K
Amount of water collected =7.5 cm
3

Latent heat of steam at 288K =2.454 kJm
3

Solution:
i)Heat absorbed by cold water
=mass of water x specific heat x rise in temp
=4.5 kg x 4.18 J/g/K x 18.5 K
=4500 g x 4.18 J/g/K x 18.5 K
=348000 J or 348 kJ
ii)Reduce the volume of the gas to that at STP using combined gas law
P1V1 P2V2
=
T1 T2
101990 N/m
2
x 0.02 m
3
101325 N/m
2
x V

=
293 K 273 K

V=0.0188 m
3

iii) Calorific value, Q=Heat absorbed by cold water

Volume of gas

=348/0.0188
= 18510 k J/m
3

iv) Net Q:
Water condensed during combustion = 7.5cm3 = 7.5 gram
Latent heat of steam at 288 K = 2.454 kJ/g
Therefore heat to be deducted from gross calorific value
7.5 g x 2.454 kJ/g
= 0188 m3

= 979 kJ/m3

Therfore Net Q = 18510 -979 = 17531 kJ/m3

1.6 What is Petroleum cracking? Explain the Fluidized bed catalytic
cracking method.
6 Marks
Cracking is a process that involves breaking of C-C and C-H bonds
in the chains of high boiling hydrocarbons of high molecular weight, to
yield simpler, low boiling hydrocarbons of molecular weight.

Fluidized bed catalytic cracking method.

The catalyst such as alumina or zeolyte is finely powered and
mixed with steam and it is pumped to cracking chamber. The feedstock

(gas oil, heavy oil) is preheated to 500
0
C and forced into the cracking
chamber along with the catalyst by a steam blast where a floating
turbulent bed forms.
In cracking chamber the higher molecular weight hydrocarbons are
broken down into simpler fragments. The products are withdrawn and
sent to fractionating column for separation.
The catalyst becomes inactive after cracking process. It is sent to
catalyst activation chamber and it is activated by burning carbon
deposited on the catalyst by air blast at 600
0
C. The catalyst can be used
again and the process is continuous.

1.7 What is Reformation of Petroleum? Explain the Reformation of
Petrol
6 Marks
It is a process of bringing structural modifications in the strait
chain hydrocarbons (with lower octane number) to increase the octane
number and thereby improving the anti-knocking characteristics of
petrol.
Reforming is a chemical process, which involves modification of the
structure of molecules without much change in the molecular masses.
Reformation of petroleum involves the following reforming reactions:
1) Isomerisation.
2) Dehydrogenation.
3) Cyclisation & dehydrogenation and
4) Hydro cracking.
1) Isomerisation: -
It is a process of converting the straight chain hydrocarbon
compound of lower octane number into a branched chain hydrocarbon
compound of higher octane number.

2) Cyclisation: Straight chain hydrocarbons undergo cyclisation
producing cyclic hydrocarbons which have higher octane number.

Ex. CH3 CH2 CH2 CH2 CH2-CH3

n- Hexane Cyclo hexane

3) Cyclisation and dehydrogenation: Straight chain hydrocarbons
undergo cyclisation to form cyclic compounds, which further undergoes
dehydrogenation to form aromatic compounds.

Ex. CH3 CH2 CH2 CH2 CH2-CH3

n- Hexane Cyclo hexane Benzene

4) Hydro cracking: -Straight chain hydrocarbons undergo hydro
cracking in presence of hydrogen and platinum catalyst producing low
molecular weight gaseous fractions which are removed to improve the
octane number.

1.8 What is Knocking? Explain the Mechanism of Knocking
6 Marks
The explosive combustion of petrol and air mixture produces shock
waves in I.C. engine, which hit the walls of the cylinder and piston
producing a rattling sound is known as knocking.

Mechanism of Knocking

Beyond a particular compression ratio the petrol mixture suddenly
burns into flame. The rate of flame propagation increases from 20 to
25m/s to 2500m/s, which propagates very fast, producing a rattling
sound. The activated peroxide molecules decomposes to give number of
gases products which produces thermal shock waves which hit the walls
of the cylinder and piston causing a rattling sound which is known as
knocking.
The reactions of normal and explosive combustion of fuel can be
given as follows taking ethane as an example


1.9 Define octane number.
2 Marks
Octane number is defined as the percentage of isooctane present in
a standard mixture of isooctane and n-heptane, which knocks at the
same compression ratio as the petrol being tested.
Isooctane is the branched chain hydrocarbon has least knocking
rate, hence its octane number is arbitrarily fixed as 100. N-heptane a
straight chain hydrocarbon has highest tendency to knock hence its
octane number is fixed as zero. Octane number of petrol is 80 means it
contains 80% by volume isooctane and 20% by volume n- heptane.

1.10 Define Cetane number.
2 Marks
It is defined as the percentage of cetane present in standard
mixture of a cetane and Alfa- methylnaphthalene, which knocks at the
same compression ratio as the diesel fuel being tested.

1.11 What are Antiknocking agents? Explain Leaded & Unleaded
Petrol
5 Marks
These are the substances added to petrol in order to prevent
knocking in I.C. Engines.

Ex: TEL Tetra Ethyl led.
TML Tetra Methyl led.
MTBE Methyl Tertiary Butyl Ether.

Leaded Petrol:
The petrol containing TEL or TML as anti knocking agents is
called leaded petrol. TEL or TML are the very good anti knocking agents
but has some disadvantages as follows.

a) After combustion lead is deposited as lead oxide on piston
and engine walls it leads to mechanical damage.
b) Lead is a poisonous air pollutant.
c) It spoils the catalyst used in catalytic converter.

Unleaded Petrol:
The petrol, which contains antiknocking agent other than lead, is
known as unleaded petrol.
Ex: MTBE is used, as an antiknocking agent in place of TEL or
TML and the petrol is known as unleaded petrol.

1.12 Explain working and principle of Catalytic converter
Principle: Use of catalytic converter in the internal combustion engines
of automobiles helps in cleaning up the exhaust emissions. Such
converters built into the automobile engines promote oxidation-reduction
cycles and ensure complete combustion of CO, NOx and HC.
Working: The following fig illustrates the action of catalytic converters:
use of catalytic converters in 2 stages helps in the elimination of
pollutants from exhaust gases before they are discharged into the
atmosphere

REDUCTION STAGE I AIR OXIDATION

STAGE II

HC,CO,NO
From exhaust
gases
Released to atmosphere

N2
CO2
H2O
Pt-H=Platinum hydrogen compound
Pt-O= Platinum Oxygen compound
HC=Hydrocarbon, CO=Carbon monoxide
NO=Nitrogen oxide, N=Nitrogen
NH3=Ammonia
Flow chart of Catalytic converters for treating auto missions

i)In the first converter, nitrogen oxides are reduced to nitrogen and
ammonia in the presence of finely divided catalyst Pt
ii)In the second converter, air is introduced to provide an oxidizing
atmosphere for complete oxidation of CO & HC into CO2 and H2O in the
presence of Pt catalyst

1.13 Explain the manufacture of Synthetic petrol by Bergius
Process?
6 Marks
Coal is considered as black diamond because of its high utility value. The
principal elements present in coal are carbon and hydrogen. It is
Pt-H+NO Pt-
O+N2+NH3
Pt-O+HC+CO Pt-
H+CO2+H2O

therefore coal can be converted into liquid hydrocarbons from which
much demand and needed petrol can be obtained.

The synthetic petrol can be manufactured by the following
methods.
1) Direct hydrogenation of coal. (Bergius process)
2) Direct hydrogenation of coal. (Fischer-Tropsch process)

Bergius process: (Direct conversion of coal)
In this method the lignite is grinded into a fine powder. This powder is
mixed with heavy oil & made into a paste. Iron oxide or nickel is added
as catalyst. The mixture is pumped into a reactor. The temperature of the
reactor is maintained about 500-550
0
C & a pressure is maintained
about 250 atmospheres. H2 gas is passed through the reactor. Lignite
under goes hydrogenation to form a mixture of hydrocarbons. These
mixture of hydrocarbons are passed through a fractionating column to
for separation to obtain synthetic petrol.

2) Fischer-Tropsch process: (Indirect conversion of coal)
This method involves the following steps
a) Production of water gas: Water gas (CO+H2) is obtained by passing
steam over white hot coal.

C + H2O (g) CO + H2 (water gas)
b) Production of synthesis gas
the water gas obtained above is freed from dust, H2S and organic Sulfur
compounds and blended with hydrogen to form synthesis gas (CO + 2H2).
c) Hydrogenation of carbon monoxide: the Synthesis gas (CO + 2H2) is
compressed to 5-10 atm pressure and admitted into a catalytic reactor.

containing the catalyst (mixture of cobalt (100 parts), thoria (5 parts) and
magnesia (8 parts)). The reactor is heated to about 250
0
C.
Hydrogenation, reactions takes place to form saturated and unsaturated.
These mixture of saturated and unsaturated hydrocarbons are passed
through a fractionating column to for separation to obtain synthetic
petrol.

1.14 What is Power alcohol? Explain the advantages
4 Marks
A mixture of ethyl alcohol and gasoline blend, which can be used
as fuel in internal combustion engine, is known as power alcohol or
gasohol.
Absolute alcohol is mixed with ether, benzene etc compounds and
one volume of this is mixed with four volumes of petrol and is used as a
fuel.

Advantages:
The power out put is good.
It has better antiknock property.
Ethanol is biodegradable; hence it is environmental friendly fuel.
The use of ethanol in alcohol increases the oxygen content of the
fuels and promotes more and complete combustion of
hydrocarbons in gasoline.
It reduces carbon monoxide emission.

1.15 Bio diesel:
Biodiesel refers to a vegetable oil- or animal fat-based diesel fuel
consisting of long-chain alkyl (methyl, propyl or ethyl) esters. Biodiesel is
typically made by chemically reacting lipids (e.g., vegetable oil, animal fat
(tallow)) with an alcohol.
Biodiesel is meant to be used in standard diesel engines and is thus
distinct from the vegetable and waste oils used to fuel converted diesel
engines. Biodiesel can be used alone, or blended with petrodiesel.


SOLAR ENERGY

1.16 What is solar energy? Mention the advantages &
disadvantages of solar energy. 4 Marks
The radiations reaching earth from the sun and converting them in to
different useful forms of energy is called solar energy.
The utilization of solar energy is of two types Direct solar power and
indirect solar power.

Advantages:
The Solar power is pollution free.
It can operated with little maintenance or intervention after initial
setup.
The Solar power is becoming more and more economical as costs
associated with production decreases, and the technology becomes
more effective in energy conversion.
The Solar power can be viewed as a local resource because of
original climatic variances.

Disadvantages:
The Solar power is only practical in certain areas with a favorable
climate and latitude. That is, areas near the tropics and which are
relatively cloud free.
The Solar power is not available at night.
The Solar power decreases during cloudy.
The Solar power must be converted into some other form of energy
to be stored.
Solar cell technologies produce DC power which must be converted
to the AC power.

1.17 What are photovoltaic cells? 2 Marks
Photovoltaic cells or Solar cells are the semiconductor devices
which converts sunlight into direct current electricity on illumination.

1.18 Explain the working of photovoltaic cells?
6 Marks
The Solar cells or Photovoltaic cells are made out of
semiconductors which have the capacity to absorb light. When n-type
and p-type semiconductor are bought together a semiconductor diode is
formed. The semiconductor diode separates and collects the carriers and
conducts the generated electrical current preferentially in a specific
direction.

A typical silicon photovoltaic cell is composed of a thin wafer
consisting of an ultra thin layer of phosphorus doped. (n-type) silicon on
top of boron doped (p-type) silicon. Hence a p-n junction is formed. A
metallic grid forms one of the electrical current contacts of the diode and
allows light to fall on the semiconductor between the grid lines. An
antireflective layer between the grid lines increases the amount of light
transmitted to the semiconductor. The cells other electrical contacts is
formed by a metallic layer on the back of the solar cell.
When light radiation falls on the p-n junction diode, electron hole
pairs are generated by the absorption of the radiation. The electrons are
drifted to and collected at the n-type end and the holes are drifted to p-
type end. When these two ends are electrically connected through a
conductor, there is a flow of current between the two ends through the
external circuit. Thus photoelectric current is produced.

1.19 Explain the Importance of Photovoltaic cells: 6 Marks
The conventional energy exhaustible and depleting. Where as Solar
energy being ultimate, inexhaustible and renewable energy. There
the photovoltaic cells are important means to utilize this
continuous energy source.
The Photovoltaic cells can serve for both off-grid and on-grid
applications. It can be used for off-grid professional devices and
supply systems such as telecommunication equipment, solar home
systems, etc.
The Photovoltaic energy conversion environmental friendly as there
is no harmful emission of pollutants.

Use of or production of solar energy doesnt produce noise
pollution.
The electricity obtained from solar energy is useful in minimizing
global warming due to carbon dioxide.
Photovoltaics can be used as roof integrated systems, providing
power and also serving as optical shading elements for the space
below and preventing overheating in the summer.
Photovoltaic cells provide power for spacecraft and satellites.
Developments in the field of photovoltaic cells will boost the
semiconductor industry and storage battery industries.

Silicon:
The most common material used for solar cells is crystalline silicon, with
multicrystalline silicon is most used. Silicon is the second member in the
group IV A in the periodic table. It never occurs free in the nature, but
occurs as oxides and silicates.
The solar cells are made out of three primary categories of crystalline
silicon as follow.
i) Single crystalline or mono crystalline wafers.
ii) Poly or multi crystalline wafers.
iii) Ribbon silicon-drawn from molten silicon, having a multicrystalline
structure.

1.20 Explain the Physical properties of Silicon relevant to
Photovoltaic 6 Marks
i) Silicon is a semiconductor with a band gap of 1.12 eV at 25
0
C.
ii) Silicon crystallizes into a diamond cubic structure at atmospheric
pressure.
iii) Usually metals expand on heating and contract on cooling but silicon
Contracts on melting and expands during solidification.
iv) Silicon can be made into semiconductor by adding impurities.
(Providing either free electrons or holes). Impurities from VA group are
n-dopants and impurities from IIIA group are p-dopants.
v) Silicon has relatively high refractive index which limits the optical
applications of silicon. There fore it is coated with antireflective
agent.
vi) Silicon is brittle even when alloyed with small quantities of impurities.
vii) Shaping for photovoltaic applications require sawing and grinding.

1.21 Explain the Chemical properties of silicon relevant to
Photovoltaic 6 Marks

i) Silicon is stable in the tetravalent state and has a strong affinity for
oxygen, forming stable oxides and silicates. Elemental silicon readily
oxidizes, forming a thin protective film of silica (SiO2).
ii) Silicon and carbon from a strong Si-C bond and stable products.
Silicon carbide also finds various applications in photovoltaics and
electrons. Primary uses exploit the abrasive properties of SiC for wafering
silicon crystals. Silicon forms hydrides, and monosilane (SiH4) is a key
chemical compound for the production of amorphous silicon and the
purification of silicon to semiconductor grade.
iii) The chemical reactivity of silicon with chlorine is also very important.
Trichlorosilane and tetrachlorosilane are both the intermediates and the
by-products of the purification processes in upgrading metallurgical
grade silicon to semiconductor grade, as these compounds are volatile at
low temperature and can be decomposed to elemental silicon at higher
temperature. Other chlorosilanes or halogenosilanes are also used in
chemical vapor deposition applications. Silicon and germanium are
isomorphism and mutually soluble in all proportions.

1.22 Explain the production of semiconductor grade silicon?
6 Marks
Production of semiconductor grade silicon involves the following three
stages.
i) Production of metallurgical grade silicon (Carbo thermic reduction
of silica)
Metallurgical grade silicon of purity of 98.5% Si is produced in
submerged electrical arc furnace. The furnace consists of a crucible filled
with quartz and carbon (metallurgical coke or coal). Silicon is formed as
follows.

SiO2 + 2C(s) Si (I) +2CO (g)
Silicon is formed as molten state and is tapped from the bottom of the
furnace. The carbon monoxide further oxidized to carbon dioxide and
released into the atmosphere.
ii) Refining of silicon:
The crude silicon obtained in the above method is taken in a large ladle
and treated SiO2 and lime/limestone (CaO/CaCO3). The less noble
elements than silica such as Al, Ca and Mg are oxidized as their oxides.


iii) Production of semiconductor grade silicon
The metallurgical grade silicon obtained in the above process is further
processed in four stages to get semiconductor grade silicon or
polysilicon.
1. Synthesis of silicon hydride.
2. Purification of the hydride.
3. Decomposition to elemental silicon.
4. Removal of byproducts.
The metallurgical grade silicon is treated with dry HCl gas at 300
0
C to
form trichlorosilane & a small amount of tetrachlorosilane. The mixture
is distilled to get pure trichlorosilane.

The tetrachloro silane (SiCl4) is reduced with hydrogen at 1000
0
in a
reactor to get tri chloro silane (HSiCl3).

The tri chloro silane is then passed through fixed bed columns
containing quaternary ammonium ion exchange resins catalysts.

The products obtained in the above process are separated by distillation.
Tetrachlorosilane & trichlorosilane are again recycled to the
hydrogenation reactor & the exchange resin respectively. Silicon hydride
or silane is further purified by distillation & passed into a reactor
containing heated silicon seed rods. Silane gets pyrolysed to form
polysilicon (semiconductor grade silicon)

1.23 Explain the Doping of Silicon
6 Marks
The process of incorporating the desirable impurities in the crystals of
semiconductors to get desirable extrinsic semiconductor properties as
known as doping techniques.


Doping of Silicon can be carried out as follows.

i) Doping during crystal formation

Doping can be carried out at the crystal formation stage itself, by adding
calculated amount of dopants into the melt. When silicon is deposited on
to the surface of silicon rod by vapor decomposition, doping can be
accomplished by simultaneously depositing a dopant with the
semiconductor material. This can be done by mixing the reaction mixture
gas feed with vapors of suitable compounds of the dopant. For example,
calculated amount of PH3 is mixed with the gas feed to get n-type doping
and BH3 for p-type doping.

ii) Diffusion technique:

In this technique, a region of semiconductor material is incorporated
with dopant atoms by the diffusion of impurity atoms into the crystal of
the material without actually melting it. By this technique, the extent of
impurity penetration can be controlled to a very small thickness of the
material. For example, a n-type silicon can be obtained by heating a
silicon wafer below its melting point in an atmosphere of n-type
impurities such as phosphorus. The impurity atoms considered on the
surface of the wafer diffuses into the crystal. Similarly p-type silicon can
be obtained by heating in an atmosphere of p-type dopants. The extent of
diffusion can be regulated by controlling the temperature and the
concentration of the impurity atoms.

iii) Ion Implantation technique:

In this technique, the semiconductor is impacted with an ion beam of
impurity ions. This results in the implantation of some dopants atoms
into the semiconductor crystal. Extent of implantation is controlled by
the energy of the ion beam.


Objective type questions:

1) Bomb-calorimeter is used for determining the calorific value of
a) Solid fuel b) liquid fuel
c) Gaseous fuel d) both solid fuel & liquid fuel

2) Octane number is related to the petroleum product
a) Diesel b) Kerosene c) Petrol d) Lubricating oil

3) The process by which the higher hydrocarbons are broken into
lower hydrocarbons by the application of heat by
a) Combustion b) Cracking c) Sparking d) jetting

4) Quality of Diesel fuel is determined by
a) Octane rating b) Percentage of Carbon
c) Length of Hydrocarbon chain d) Cetane number

5) The tendency of Knocking is high in
a) Aromatics b) Olefins
c) Straight chain hydrocarbons d) Cycloparaffins
6) A device in which electricity is produced using Solar energy is
called
a) Fuel cell b) Voltaic cell c) Photovoltaic cell d) Concentration
cell

7) Knocking is due to
a) Slow combustion b) Instantaneous explosive combustion
c) Incomplete combustion d) All

8) Which of the following is the primary fuel
a) Producer gas b) Coal gas c) Petroleum d) Water gas

9) HCV is always ----------- than NCV

a) Less b) More c) Equal d) Not related

10) Main constituent present in photovoltaic cells are
a) Silicon b) Sand c) Carbon d) Iron

11) Unit of Calorific Value is
a) g/cc b) Cal/ml c) kJ d) kJ/Kg

12) The Knocking tendency of Hydrocarbon decreases in the following
order
a) Straight chain> Cyclo alkanes > Aromatic > Branched Chain
b) Straight Chain > Branched Chain > Cyclo Alkanes > Aromatic
c) Aromatic > Cyclo Alkanes > Branched Chain > Straight Chain
d) Cyclo Alkanes > Aromatic > Branched Chain > Straight Chain

13) The catalyst employed in the fluidized catalytic cracking is
a) Al2O3 + SiO2 b) Fe2O3+ SiO2
c) ZrO2 + SiO2 d) TiO2 + SiO2

14) In photovoltaic cells solar energy is utilized to transform
a) Solar energy into light and heat energy
b) Solar energy into electrical energy
c) Solar energy into electrical chemical energy
d) All the above

15) In Fischer- tropsch process of preparation of synthetic petrol -------
-is used as raw material
a) CO+H2 b) CO2+H2 c) CO+H2O d) CO2+H2O


REVIEW QUESTIONS
1. Define a fuel. Explain the classification of fuels with examples.
2. Define calorific Value. Explain the types of calorific value.
3. Mention the SI units of calorific value.
4. Describe the Bomb calorimetric method of determination of calorific
Value of solid fuel.
5. What is petroleum cracking? Explain the process of fluidized bed
Catalytic cracking method
6. What is reformation of Petroleum? Give the reactions involved in
reforming.
7. What is Knocking? Explain its Mechanism
8. Define octane number.
09. Define cetane number.
10. What are anti knocking agents? Explain leaded and unleaded petrol.
11. What is synthetic petrol? Explain the production of synthetic petrol
12. What is power alcohol? Give its advantages as fuel.
13. What are photovoltaic cells?
14. Explain how a photovoltaic cell works?
15 Explain the Chemical properties of silicon relevant to Photovoltaic
16 Explain the Physical properties of Silicon relevant to Photovoltaic
17. Explain the production of semiconductor grade silicon
18. Explain the Doping of Silicon?


UNIT UNIT UNIT UNIT II II II II

ELECTRO CHEMICAL ENERGY SYSTEMS

ELECTRODE POTENTIAL AND CELLS

2.1 What is an electrochemical cell Explain the classification with
examples 5 Marks
An electrochemical cell is a device, which is used to convert
chemical energy into electrical energy and vise versa.
These electrochemical cells are classified into two types as follows.
1) Galvanic or Voltaic cells: These are the electrochemical cells, which
converts chemical energy into electrical energy.
Ex. Daniel cell, Dry cell, etc.
2) Electrolytic cell: These are the electrochemical cells, which are used
to convert electrical energy into chemical energy.
Ex: Lead acid battery, Nickel cadmium battery etc.,
Galvanic or Voltaic cells:
Galvanic or Voltaic cells are again classified into three types as follows

a) Primary cells: These are the cells which serve as a source of energy
only as long as the active chemical species are present in the cell.
The cell reactions are irreversible. These are designed for only single
discharge and cannot be charged again.
Ex: Dry Cell, Zn Hgo cell, Zn-Ag2o cell etc.

b) Secondary cells: These cells are chargeable and can be used again
and again. The cell reactions are reversible and are often called as
reversible cells. During discharging the cells acts like voltaic cell
converting chemical energy into electrical energy. During charging the
cell acts like electrolytic cell by converting electric energy into chemical
energy, hence these batteries are called as storage battery.
Ex: Lead acid Battery, Ni-cd cells. Lithium ion cells etc.

c) Concentration of cells:
These are the electrochemical cells consisting of same metal
electrodes dipped in same metal ionic solution in both the half cells but
are different in the concentration of the metal ions.
Ex: copper concentration cell, Zinc concentration cell

2.2 Explain the construction and working of Daniel cell
6 Marks

The Daniel cell consisting of two half cells in which zinc and copper
electrodes are immersed in zinc Sulphate and copper Sulphate solution
respectively. The two half cells are internally connected by a salt bridge
and externally by a metallic wire. The zinc electrode undergoes oxidation
and looses electron. The electron liberated migrates to another half cell.

Oxidation
Zn (s) Zn
2 +
+ 2e
-

In the other half-cell the cupric ions accepts the electrons,
undergoes reduction, and get deposited on copper electrode as copper
atoms.

Reduction
Cu
++
(aq) + 2e
-
Cu (s)

Due to the above simultaneous oxidation and reduction reactions the
Daniel cell generates electrical current, which is indicated by voltmeter or
ammeter. The Daniel cell can be represented as

Zn (s) /Zn
2+
(aq) //Cu
2+
(aq) /Cu.

2.3 Mention the Cell notations and Cell Conventions
Cell notations 4 Marks
/ Single vertical line represents phase boundary between the metal
and its solution.

// Double vertical line represents salt bridge.

Arrow mark indicates the direction of flow of electrons.

Cell Conventions

i) The half cell which undergoes oxidation is always written towards left
side of the salt bridge.

ii) The half cell which undergoes reduction is always written towards
right side of the salt bridge.

iii) If the direction of arrow mark indicates from left to right. The
electrons flow from anode to cathode and the cell reactions are
spontaneous and if the direction of arrow mark indicates from right to
left, then electrons flow from cathode to anode. Then cell reactions are
non spontaneous.

iv) The term electrode potential always refers to the reduction potential.

2.4 Define Single electrode Potential. 2 Marks
It is defined as the potential developed at the interphase between
the metal and the solution, when a metal is dipped in a solution
containing its own ions. It is represented as E

2.5 Explain the origin of electrode Potential: 6 Marks
When a metal is dipped in a solution containing its own ions, the
metal may undergo oxidation by loosing electrons or the metal ions may
undergo reduction and get depositing metal atoms on the metal surface.
Consider a metal M is dipped in a solution containing its ions M
n+.

The tendency of metal to pass in to solution (oxidation) can be
represented as,
M M
n+
+ ne
-

Simultaneously the metal ions from the solution tend to deposit on
the metal as metal atoms (reduction)
M
n+
+ ne
-
M

The above two opposite tendencies will results in equilibrium as follows

M
n+
+ ne
-
M

When a metal undergoes oxidation it loses positive ions into
solution leaving behind a layer of negative charges on its surfaces. This
layer attracts positive changes and forms an electric double layer (EDL)
because of the formation of EDL electrode potential arises.

When metal ions undergo reduction depositing metal atoms on the
metallic surfaces the metal surface becomes positively charged. The
accumulated positive charge on the metal surface attracts a layer of ve
charges and forms an electrical double layer or Helmotz EDL which
causes the origin of electrode potential.

2.6 Explain the measurement of electrode potential 4 Marks

The electrode potentials of any metal electrodes can be determined
by using reference electrodes like standard hydrogen electrode. (SHE).
The SHE is coupled with the electrode whose electrode potential is
to be determined and the electrode potential of the electrode is
determined by fixing the electrode potential and SHE as zero [at all
temperatures]
Example: Consider the determination of Single electrode potential
of Zinc electrode using Standard Hydrogen electrode.
To determine the Single electrode potential of Zinc electrode it is
coupled with Standard Hydrogen electrode as follows


The electrode potential of Zinc electrode can be calculated as
E cell = E cathode E anode
E cell = E SHE E Zn
0.76 = 0 - E Zn
E Zn = -0.76 V

The electrode potentials can also be determined by using
secondary reference electrode such as calomel electrode and Ag / Agcl
electrode.

2.7 Define electron motive force. (EMF) 2 Marks

It is defined as the potential difference between the two electrodes
of a galvanic cell which causes the flow of current from an electrode with
higher reduction potential to the electrode with lower reduction potential.
It is denoted as E cell.
E cell = E right E left.
E cell = E cathode E anode.

Problems:
1) Calculate emf of a cell constructed by combining Cu & Zn electrodes
dipping in their respective ionic solutions. The standard electrode
potential of Cu and Zn are 0.34 V and 0.76 V respectively at 298K.
= Ecu Ezn
= 0.34 (-0.76) = 1.1volt

2.8 Define Standard electrode potential. 2 Marks

It is defined as potential developed at the interface between the
metal and the solution. When a metal is dipped in a solution containing
its own ions of unit ion concentration and at 298K. [If the electrodes
involve gases then it is one atmospheric pressure] It is denoted as E
0

2.9 Derive Nernst Equation for single electrode 6 Marks

In 1889 Nernst derived a quantitative relationship between the
electrode potential and the concentrations of metal ions are involved.
The maximum work available from a reversible chemical process is
equal to the maximum amount of electrical energy that can be obtained;
it shows decrease in free energy.
Wmax = W ele
Wmax = - G.
The amount of electrical energy available from a cell is equal to the
product of no of coulombs and volts (energy).
Electrical energy = Volts x coulombs
The number of coulombs of current is the product of number of
moles of electrons that flow and Faradays constants. Number of volts or
energy is the E
W max = W ele = - n x F x E.
(No. of moles of electrons) x(Faradays constant) x (No.of volts or
energy).


Where,
E = Electrode potential
E
0
= standard electrode potential
n = no. of electrons
[M
n+
] = Concentration of metal ions
R = Universal gas constant
T = Temperature(In Kelvin).


Problems:

1) Calculate the emf of the cell Fe / Fe
++
(0.01) // Ag
+
(0.1) /Ag at 298K if
standard electrode potentials of Fe and Ag electrodes are 0.42 and 0.8
V respectively.
6 Marks
E
0
cell = E
0
cathode E
0
anode
= E0 Ag
+
/Ag E
0
Fe
++
/ Fe
= 0.8 ( 0.42)
= 1.22 V.

= E0cell + 0.0591 log10 [Ag
+
]
2

n [Fe
++
]
= 1.22 + 0.0591 log10 (0.1)
2

2 (0.01)
= 1.22 + 0.02955 log 1
= 1.22 V.

2) A cell is constructed by coupling Zn electrode dipped in 0.5 M ZnSO4
and
Ni electrode dipped in 0.05 M NiSO4. Write the cell representation, cell
reaction. Calculate the EMF of cell, given that reduction potentials of Zn
and Ni as 0.76 and 0.25 volt respectively.
6 Marks
Cell representation: Zn / ZnSO4(0.5M ) // NiSO4 ( 0.05M ) / Ni.
Cell reactions: Zn (S) + Ni
++
(aq) Zn
++
(aq) + Ni (S)

E
0
cell = E
0
cathode E
0
anode
= E
0
Ni
++
/Ni E
0
Zn
++
/Zn
= 0.25 ( 0.76)
= 0.51 V.


= E
0
cell + 0.0591 log10 [Ni
++
]
n [Zn
++
]
= 0.51 + 0.0591 log10 (0.05)
2 (0.5)
= 0.51 + 0.02955 log 0.1
= 0.4805 V.
3) Calculate the potential of Ag Zn cell at 298 K if the concentrations of
Ag
+
and Zn
++
are 5.2 x 10
6
M and 1.3 x 10
3
M respectively. E
0
of the cell
at 298K is 1.5 V. Calculate the change in free energy G for the
reduction of 1 mole Ag
+
. 1 faraday = 96.5 k J/ V / mole.
6 Marks
Cell reaction: 2Ag
+
(aq) + Zn (S) Zn
++
(aq) + Ag (S)

= E
0
cell + 0.0591 log10 [Ag
+
]
2

n [Zn
++
]
= 1.5 + 0.0591 log10 (5.2 x 10
6
)
2

2 (1.3 x 10
3
)
= 1.5 + 0.02955 log (20 x 10
9
)
= 1.2729 V.
For the reduction of 2 moles of Ag
+
ions, 2 electrons are required
For the reduction of 1 mole of Ag
+
ions, 1 electron is required
G = n F E cell.
= 1 x 96.5 x 1.2729
= 122.83 K J / mol

4) A cell is constructed by coupling Ni electrode dipped in 0.01 M NiSO4
and Pb electrode dipped in 0.5 M PbSO4. Write the cell representation,
cell reactions. Calculate the EMF of cell, given that reduction potentials
of Ni and Pb are 0.24 and 0.13 volt respectively.
6 Marks
Cell representation: Ni / Ni
++
(0.01 M) // Pb
++
(0.5M) / Pb.

Cell reactions: At anode Ni Ni
++
+ 2e
-

At cathode Pb
++
+ 2e
-
Pb

Net cell reaction: Ni (S) + Pb
++
(aq) Ni
++
(aq) + Pb (S)

E
0
cell = E
0
cathode E
0
anode
= E0 Pb
++
/Pb E
0
Ni
++
/Ni
= 0.13 ( 0.24)
= 0.11 V.

= E
0
cell + 0.0591 log10 [Pb
++
]
n [Ni
++
]
= 0.11 + 0.0591 log10 (0.5)
2 (0.01)
= 0.11 + 0.02955 log 50
= 0.1602 V.
2.10 What are concentrations cells? Explain with an example
6 Marks
These are the galvanic cells consisting of same metal electrodes
dipped in same metal ionic solution in both the half cells but are
different in the concentration of the metal ions.

Ex: Consider the following concentration cell constructed by dipping two
copper electrodes in CuSO4 solutions of M2 molar and M1 molar where
M2M > M1M.

The two half-cell are internally connected by a salt bridge and
externally connected by a metallic wire through voltmeter or ammeter.


The electrode, which is dipped in less ionic concentrations
solutions (M1) act as anode and undergoes oxidation. The electrode,
which is dipped in more ionic concentration (M2) act as cathode and
undergoes reduction.

At anode : Cu (S) Cu
2+
(M1) + 2e
-

At cathode : Cu
2+
(M2) + 2e
-
Cu (S)
_____________________________________________________
NCR Cu
2+
(M2) Cu
2+
(M1)

E

of cell = E

cathode E

anode.
E cell = [ E
o
+ 0.0591 log (M2) ] [E
o
+ 0.0591 log (M1)]
n n

Where, (M2) > (M1)

Problems:
1. Calculate emf of the following concentration cell at 25
0
C
Ni (S) / Ni
++
( 0.01M) // Ni
++
( 0.1M) / Ni (S)
4 Marks
Where, (M2) > (M1)

E cell = 0.0591 log (0.1)
n (0.01)

= 0.02955V

2. Calculate emf of the following concentration cell at 25
0
C
Cu (S) / Cu
++
(0.05M) // Cu
++
(5M) / Cu (S)
4 Marks
Where, (M2) > (M1)

E cell = 0.0591 log (5)
n (0.05)

= 0.0591V

2.11 Mention the different types of single electrodes
4 Marks
i) Metal-Metal ion electrode
These electrodes consists of a metal dipped in a solution of its own
ions.
Example: Zn/Zn
++
Cu/Cu
++
Ag/Ag
+

ii) Metal-Metal salt electrode

These electrodes consists of a metal in contact with a its salt
Example: Calomel electrode (Hg/Hg2Cl2/Cl
-
)
Silver Silver Chloride electrode(Ag/AgCl/Cl
-
)
Lead Lead sulphate electrode(Pb/PbSO4/SO4
-
)


iii) Gas electrode
Example: H2 electrode (H2/Pt/H
+
)
Chlorine electrode (Pt/Cl2/Cl
-
)

iv) Amalgam electrode
Example:Lead amalgam electrode(Pb-Hg/Pb
+
)

v) Oxidation Reduction electrode
Example: Pt/Fe
2+
, Fe
3+

Pt/Ce
3+
, Ce
4+

Pt/Sn
2+
, Sn
4+
vi) Ion selective electrode
Example: Glass electrode

2.12 What are Reference Electrodes? Mention the types with
Examples 3 Marks

These are the standard electrodes with reference to these, the electrode
potentials of any other electrode can be determined.
The Reference Electrodes can be classified in to two types
i) Primary reference electrodes Ex: Standard hydrogen electrode
ii) Secondary reference electrodes Ex: Calomel and Ag/Agcl electrodes
2.13 Explain the construction, working and limitations of standard
hydrogen electrode 6 Marks

The standard hydrogen electrode consists of platinised platinum foil
fused to the glass tube. Mercury is placed at the bottom of the tube and

a copper wire is used for electrical connections. The platinum foil is
immersed in a solution containing unit molar hydrogen ions. Pure
hydrogen gas is bubbled about the electrode through the H2 gas inlet at
1atm pressure.
The electrode is represented as Pt/H2 (g)/H
+
If the concentration of H
+
is 1M, H2 gas bubbled at 1atm pressure and at
temperature 298k, then the electrode is called standard hydrogen
electrode. And the electrode potential is arbitrarily fixed as zero.
The electrode reactions is

Limitations of SHE
i) The construction of SHE is difficult.
ii) It is very difficult to maintain the concentration of H
+
as 1M and
pressure H2 gas at 1atm
iii) Platinum electrode is poisoned by the impurities of the gas
iv) It can not be used in the presence of oxidizing agents.

2.13 Explain the construction and working of Calomel electrode

6 Marks

Calomel electrode consisting of a glass container at the bottom of
which mercury is placed above which a layer of mercury and mercurous
chloride (called calomel) is placed with 3/4
th
of bottle is filled with
saturated KCl solution. Electrode potential of the cell depends on the
concentration of KCl used. The calomel electrode can be represented as.
Hg (l) / Hg2 Cl2 (S) / Saturated KCl.

The calomel electrode acts as both anode and cathode depending
upon the other electrode used. The platinum wire is used for electrical
connections. Salt bridge is used to couple with other half cell.
When it acts as anode the electrode reactions is,

Hg2Cl2 + 2e
-
2Hg + 2Cl
-

When it acts as cathode the electrode reaction is
Hg2Cl2 + 2e
-
2Hg + 2Cl
-

Advantages of Calomel Electrode:
It is simple to construct.
The electrode potential is reproducible and stable.
It is used as a reference electrode.

2.13. Explain the construction and working of Silver-Silver chloride
electrode.
6 Marks
Ag/AgCl electrode is a metal metal salt electrode. It consists of
narrow glass tube at the bottom of which agar is placed above which
saturated solution of KCl is placed. The silver wire is used for electrical
connections and it is coated electrolytically with AgCl. The cell can be
represented as.
Ag(s) / AgCl (s) / Saturated KCl.
Electrode acts as both anode and cathode depending on the other
electrode used. When it acts as anode the electrode reaction is
Ag + Cl
-
Ag Cl + e
-
When it acts as cathode the electrode reaction is
AgCl + e
-
Ag + Cl
-
.


2.14. What are Ion Selective Electrodes? Explain the Glass electrode
6 Marks
These are the electrodes, which responds to specific ions only and
develops a potential against that ions while ignoring the other ions
present in the solution.
Ex: Glass electrode.

Glass electrode is a pH sensitive electrode widely used for pH
determinations. It is consisting of a long glass tube at the bottom of

which a thin and delicate glass bulb, which made up of special type of
glass (12 % Ba2O, 6% of Cao, 72% of SiO2) with low melting point and
high electrical conductance is used. The glass bulb is filled with 0.1.M
Hcl and Ag Agcl is used as a internal reference electrode. A platinum
wire is used for electrical contant. The glass electrode can be represented
as Ag/AgCl(s) /0.1M (HCl) / Glass.

2.15 Explain the determination of PH using glass electrode.
6 Marks
To determine pH of unknown solution the glass electrode is
combined with secondary reference electrode such as calomel electrode
and the glass - calomel electrode assembly is dipped in the solution
whose pH is to be determined. The two electrodes are connected to
potentiometer or pH meter.

The combined electrodes can be represented as.
Hg(l) / Hg2 Cl2 (S) / Saturated KCl //solution of unknown pH
/glass/0.1M Hcl/Ag/AgCl(s)

The emf of the above cell is given by
E cell = E calomel E glass
E glass = E calomel E cell
The potential of E glass is given by
E glass = - RT/nf ln [a2/a1]
= RT/nf ln [a1/ a2]


Where a1 = Concentration of [H
+
] ions in glass bulb
a2 = Concentration of [H
+
] ions in unknown solution
E glass = RT/nf ln a1 RT/nf ln [a2]
E glass = Constant RT/nf ln [a2 ]
(Because an [H+] ion in glass bulb is constant)
E glass = Constant 0.0591 log [H
+
]
E glass = Constant + 0.0591pH
pH = E glass Constant
0.0591
pH = E calomel E cell - Constant
0.0591

pH = 0.242 E cell - Constant
0.0591

1. _____ Converts chemical energy into electrical
a) Galvanic cell b) Daniel cell c) Dry cell d) all

2. In the anodic chamber ----------- reaction takes place
a) Oxidation b) Reduction c) Addition d) Substitution

3. In the cathodic chamber ----------- reaction takes place
a) Oxidation b) Reduction c) Addition d) Substitution

4. Origin of electrode potential is explained in
a) Nernst theory b) Helmholtz double layer theory
c) galvanic theory d) Electrochemical theory

5. In two half cells, the one which is having high negative value acts as
a) anode b) Cathode c) Dry cell d) None

6. EMF of a concentration cell depends on
a) [M1] & [M2] b) No. of charges c) temperature d) All of the above

7. Calomel electrode potential is dependent of
a) Cl
-
concentration b) Hg2Cl2 c) Temperature d) None

8. Glass electrode is an example for
a) Reference electrode b) Ion selective electrode
c) Primary electrode d) None

9. Standard electrode potential is nothing but single electrode potential at
a) Unit concentration b) 1 atm. pressure c) 298 K d) All of the above


10. Potential of standard hydrogen electrode is taken as
a) 1V b) 0 V c) 10 V d) None

11) Metal rod dipped in a solution of its ion. Its electrode potential is
independent of
a) Temperature of the solution b) Conc. Of the solution
c) Area of the metal exposed d) Nature of the metal

12. Double vertical line (||) represents
a) Solid liquid interphase b) Salt bridge
c) solid - solid or Liquid - liquid interphase d) None

13. In the pH determination of a solution---------- electrode is used along
with glass electrode
a) Ag-Agcl electrode b) Calomel electrode
c) Ion selective electrode d) None.

14. A chemical change that occurs when electric current is passed
through an electrolyte is
a) Conduction b) Dissociation c) Ionization d) Electrolysis

15. Daniel cell is a combination of standard electrodes of
a) Cu & Ag b) Zn & Cd c) Zn & Cu d) Cu & Cd


REVIEW QUESTIONS

1. What is an electrochemical cell? Explain the types with examples.
2. What are galvanic cells? Explain with example
3. Mention the cell notations and conventions
4. Define single electrode Potential. Explain the origin of electrode
Potential
5. Explain the measurement of electrode potential
6. Define electron motive force. (EMF)
7. Define standard electrode potential. Derive the Nernst equation for
single electrode potential.
8. What are Concentration of cells? Explain with an example.
9. What are Reference Electrodes? Mention the types with examples.
10. Explain Calomel electrode. Mention its advantages.
11. Explain Silver-Silver chloride electrode
12. What are Ion Selective Electrodes? Explain the Glass electrode
13. Explain the determination of PH using glass electrode.


UNIT UNIT UNIT UNIT III III III III

CONVERTION AND STORAGE OF ELECTROCHEMICAL
ENERGY

BATTERY TECHNOLOGY

3.1 What is a Battery? Explain the classification with examples.
6 Marks
Battery is a collection of cells connected either in series or in
parallel to get required amount of energy.

Classification of Batteries
Batteries are classified into three types as follows.
a) Primary
b) Secondary
c) Reserved.

a) Primary Batteries: These are the batteries which serve as a source of
energy only as long as the active chemical species are present in the
battery or in the cell. The cell reactions are irreversible. These are
designed for only single discharge and cannot be charged again.
Ex: Dry Cell, Zn Hgo cell, Zn-Ag2o cell etc.,

b) Secondary Batteries: These batteries are chargeable and can be used
again and again. The cell reactions are reversible and are often called
reversible batteries. During discharging the cell acts like voltaic cell
converting chemical energy into electrical energy. During charging the
cell acts like electrolytic cell by converting electric energy into chemical
energy, hence these batteries are called as storage battery.
Ex: Lead acid Battery, Ni-cd battery etc.

c) Reserved Batteries: The batteries which can be stored in an active
state and made ready for use by activating them prior to the
applications (usage) are called as reserved batteries. The key
components of the batteries such as electrolyte etc., is separated from
the battery. And the battery is stored for a longer time. The electrolyte
if filled before its usage. The advantages of the reserved batteries are,

Batteries can be stored for a longer period.
To prevent corrosion at contact points during storage.
Self-discharging reactions during storage can be eliminated or avoided.
They can be used whenever they are required.

Ex: Mg water activated batteries (Mg- Agcl & Mg cucl), Zn-Ag2O
Batteries etc.

What are Super capacitors ?
An Electric double-layer capacitor, also known as supercapacitor,
supercondenser, pseudocapacitor, electrochemical double layer capacitor
(EDLC), or ultracapacitor, is an electrochemical capacitor that has an
unusually high energy density when compared to common capacitors.

3.2 Explain the Characteristics of a battery.
8 Marks
A good battery must have the following characteristics.
a) Voltage: The voltage of a battery depends on the energy change in the
overall cell reaction and the nature of cell reaction. To obtain maximum
voltage from a cell.

i) The potential difference between the electrodes must be high.
ii) The resistance of the cell must be low.
iii) Electrode reactions must be fast to reduce the over potential.

b) Capacity (C): The capacity of a battery is the charge or the amount of
electric current that can be obtained from a battery. It is charge in
ampere hours (Ah). The capacity of a battery depends on
i) Size of a battery
ii) Discharge conditions

The capacity of a battery is to be determined by

Where,
C Capacity of battery (in Ah)
W Weight of the active material
n number of electrons.
F Faradays constant.
M Molar mass.

c) Energy density: Energy density is the ratio of energy available from a
battery to its weight or volume

Energy density = Energy available from a battery
Weight or volume of cell.

d) Power density: It is the ratio of power available from a battery to its
weight or volume during discharge power density decreases.

Power density = Power available from a cell
Weight or volume of cell.

e) Energy efficiency: The battery should have high-energy efficiency.
The percent energy efficiency can be calculated as.

Percentage of Energy efficiency = Energy released on discharge X 100
Energy required for charging.
f) Cycle Life: Primary batteries are designed for single discharge and
secondary batteries can be chargeable again and again. The number of
charge and discharge cycles that are possible in secondary batteries,
before failure occurs is called cycle life. The cycle life of batteries must be
high. The factors which decrease the cycle life are:

a) Corrosion at the contact point.
b) Leakage of the current.
c) Shortening between electrode due to irregular crystal growth and
change in morphology
d) Shedding of the active material from the battery.

g) Shelf life: The duration of storage under specified conditions at the
end of which a cell or a battery retains its ability to work or to produce
energy is called shelf life. A good battery should have more shelf life. It
depends on self-discharge reactions and corrosion at contact points.

3.3 Explain the construction and working of Lead acid battery.
Mention the electrode reactions and advantages
6 Marks
Lead acid battery consisting of two flat grids of spongy lead filled with
lead (Pb) and lead oxide (PbO2), which acts as anode and cathode
respectively. Several such anode and cathode pairs are immersed in 5 M
or 37% H2SO4 of specific gravity 1.25 g/cm
3

The battery is encased in plastic or glass container. Each pair of anode
and cathode produces a voltage of 2v.

Due to the formation of water in the cell reactions during discharging the
acid gets diluted when its specific gravity falls below 1.25 g/cm3 the
battery needs charging.

During charging lead and lead oxide is again deposited on anode and
cathode respectively and charging reaction is.

Applications:
1) Lad acid battery is used for starting motors
2) Used in UPS Systems and research centers etc.
3) Used in marketing areas etc.
4) Used in security and alarm systems.

3.4 Explain the construction and working of Nickel-Cadmium
Battery. Mention the electrode reactions and advantages
6 Marks
Ni-Cd Battery consisting of anode and cathode compartments. The Anode
compartments consisting of 78% cadmium, 18% Iron, 1% Nickel and
cathode compartment consisting of 80% of Nickel oxy hydroxide, 18% of
graphite & traces of Barium and cobalt. 6MKOH is used as electrolyte.

The graphite increases the conductivity, Barium, and cobalt compound
increases the efficiency of the active materials and cycle life.

Applications:
1) Used in electronic devices such as earphones, security and alarm
systems.
2) Used in pocket calculators, emergency lights.

3.5 Explain the construction and working of Zinc -air battery.
6 Marks

Zinc air battery consisting of anode containing granules of zinc
mixed with 20%NaOH electrolyte. Cathode can contains a porous
carbon plate which provides site for the reduction reaction and do not
involves in the reaction. Carbon is catalytically activated to absorb
oxygen gas. The anode and cathode compartments are separated by a
separator and both are encased in plastic or ebonite insulator. The
reactions are as follows.


Advantages:
i) High energy density.
ii) Low cost and compact
iii) Does not produce harmful products.

Applications: Used in Military radio receivers, transmitters, hearing
aids.

3.6 Explain the construction and working of Nickel - metal hydride
battery.
6 Marks

Nickel Metal hydride battery is made up of anode containing metal
hydride such as ZrH2, VH2 and TiH2 with hydrogen storage metal alloy
such as La Ni5 or TiNi.Cathode consisting of nickel oxy hydroxide both
the compartments are separated by polypropylene. KOH used as
electrolyte. Cell reactions are as follows.

Applications: Used in electric vehicles, laptops, cellular phones etc.

Advantages: i) Resistance to chemical oxidation
ii) High energy storage capacity.


3.7 What are Lithium cells? Explain the construction and working
of Lithium cells? Mention the advantages
Lithium cells 3 Marks
Lithium cells are most popularly used cells, which are available in
various configurations such as button type, bobbin type, spiral wound
prescematic, rectangle etc configuration. The cells have the following
advantages.

These are light in weight.
High energy density
More cycle life.
Ex: Li MnO2 cell

Li MnO2 cell 6 Marks

Lithium manganese dioxide cell consisting of anode can containing
lithium and the cathode can consisting of specially heat-treated
manganese dioxide (MnO2). Both anode and cathode are seperated by a
separator made up of polypropylene impregnated with the
electrolyte.(metal salt such as LiCl, LiBr, LiAlCl4 which are mixed in a
organic solvent such as 1,2 dimethoxy ethane, and propylene carbonate.)
The cell delivers an emf of 3V. The cell reactions are as follows:-

During the all reactions Mn IV stage reduced to Mn III stage.
Uses: Li MnO2 cells are used in Safety and Security Devices, Calculator,
watches, automatic camera, memory batteries, cellular phones etc.,

3.8 What are Fuel Cells? Explain the Classification of Fuel cells
based on temperature
5 Marks

Fuel cells are the galvanic cells in which chemical energy of fuel is
directly converted into electrical energy.

Classification of Fuel cells

These are classified into three types as follows.
1] Low temp fuel cells: Which operates at the temp range about 75
o
C
and contains water base electrolytes.

2] Moderate temp fuel cells: Which operates at the temp range about
600
o
C and contains salt electrolyte.

3) High temp fuel cells: Which operates at the temp range about 1000
o
C
and contains ceramics as electrolyte.

Difference between battery and fuel cell
Battery Fuel cell
1. A battery stores the chemical
reactants, usually metal
compounds once used up you
must recharge or throw away
the battery

1.A fuel cell creates
electricity through
reactants stored
externally

3.9 Explain the construction and working of H2 O2 fuel cell.
6 Marks


Hydrogen - oxygen fuel cells consisting of two porous graphite
electrodes, which is impregnated with an electro catalyst such as finely,
divided Pt Co - Ru or Pt-Ni-Ru. Concentrated KOH is used as an
electrolyte. A wick is placed to maintain water balance. Hydrogen gas
and oxygen gas are continuously supplied to the anode and cathode
respectively. The hydrogen undergoes combustion generating electric
current. The cell delivers an emf of 1.23v. The cell reactions are as
follows.

Uses: The H2-O2 cells are used in Space vehicles, military and mobile
power systems.

3.10 Explain the construction and working of Methanol Oxygen
fuel cell.

6 Marks

It consists of two electrodes made up of platinum in between the
electrodes H2SO4 is placed as a electrolyte. Methanol and H2SO4 is
supplied at the anode and pure oxygen gas is supplied at the cathode.
The ethanol is oxidized to CO2 & H2O with the liberation of electrical
energy. The cell delivers an emf of 1.20v. The cell reactions are as
follows.

Uses:
1) Used in Military applications.
2) Used for large scale power production stations.

3.11 Explain the Classification of fuel cells based on the electrolyte
6 Marks
Fuel cells are classified into the following types based on the type of
electrolyte used.
1) Alkaline fuel cells.
2) Phosphoric acid fuel cell.
3) Molten carbonate fuel cell.
4) Solid oxide fuel cell.
5) Solid polymer electrolyte fuel cell.

1) Alkaline fuel cells: These fuel cells containing alkali such as KOH or
NaOH as electrolyte. Hydrogen is used as fuel and oxygen gas is used
as an oxidant. The cell operates at a temp of 80
0
C.
Uses: These are used in emergency lights and portable power
generations, space applications, military applications etc.,

2) Phosphoric acid fuel cells: These fuels cells consisting of 98%
phosphoric acid, 2% water as electrolyte, O2 is used as oxidant.
Hydrogen LPG, NPG etc are used as fuels. These operate at a temp
190 to 200
O
C . Platinum alloys such as platinum- cobalt- chromium,
are used as electro catalyst.
Uses: These cells are used to provide light and heat in large buildings.

3) Molten carbonate fuel cells: These fuel cells consisting of molten
carbonates such as lithium carbonate 26.2% and potassium
carbonate (K2CO3) 23% and lithium. Aluminum carbonate as
electrolyte. The anode is made up of nickel and cathode made up of
nickel oxide. Operating temperature is 650
0
C.
Uses: These are used in chemical industries such as aluminum
Cloroalkali industries.

4) Solid oxide fuel cells: These contains ZrO2, Y2O3 are solid
electrolytes. Cathode is made up of porous strontium doped with
LaMnO3 or In2O3 and SnO2. Anode is made up of cobalt, nickel, or
ZrO2. Operating temperature is 1000
0
C.
Uses: These cells are used in KW power plants, water heating etc,

5) Solid Polymer Electrolyte: These contain ion exchange membrane
as solid electrolyte for ionic conduction nafionR membranes which
are chemically and electrochemically stable at 200
0
C are used
.Operating temperature of the cell is 80
0
C. The electrodes are made
up of platinum and noble metals are used as electro catalysts.
Uses: Used in the manned Gemini terrestrial orbital missions.

Objective questions:
01. Battery is a
a) Collection of cells connected in series b) Collection of cells
connected in parallel c) Both a & b d) none

02. Which of the following is a primary battery
a) Li-MnO2 battery b) Lead acid battery c) Nicd battery d) None

03. Which of the following is a secondary battery

a) Zn-MnO2 battery b) Li-MnO2 battery
c) Lead acid battery d) Zn-HgO battery

04. In which battery a key component is separated from the rest of the
battery prior to activation.
a) primary battery b) Secondary battery
c) Reserve battery d) None

05. The reaction the takes place at anode of the battery is
a) Reduction b) Oxidation c) Neutralization d) Addition

06. Voltage of a battery can be expressed as
a) Ohms b) Volts c) Both a & b d) None

07. The electrolyte used in the lead acid battery is
a) KOH b) NaOH c) HCl d) H2SO4

08.The electrolyte used in the Zinc air battery is

09.The electrolyte used in the Ni-MH battery is

10.The electrolyte used in the Li-MNO2 battery is
a) KOH b) NaOH c) HCl d) LiCl

11. In Ni-MH battery the anode is
a) Ni b) Cd c) ZrH2 d) All

12. In Li-ion battery the anode is
a) Ni b) Cd c) ZrH2 d) Li

13. The electrolyte used in alkaline fuel cells
a) NaOH b) H3PO4 c) K2CO3 d) ZrO2

14.The electrolyte used in Phosphoric acid fuel cells

15. The electrolyte used in Molten carbonet fuel cells


REVIEW QUESTIONS

1 What is a Battery? Explain the classification of Batteries with examples
2. Explain any 4 characteristics of a battery.
3. Explain the construction and working of Lead acid battery.
Mention the electrode reactions and advantages
4. Explain the construction and working of Nickel-Cadmium
Battery. Mention the electrode reactions and advantages

5. Explain the construction, working and application of Zinc -air battery.
6. Explain the construction, working and application of Nickel metal
hydride battery.
7. What are lithium cells? Explain the construction, working and
application of lithium cell.
8. What are Fuel Cells? Explain the classification of fuel cells based on
temperature.
9. Describe the construction and working of H2 O2 fuel cell.
10. Describe the construction and working of methanol Oxygen fuel
cell.
11. Explain the classification of fuel cells based on the electrolyte used.

UNIT UNIT UNIT UNIT IV IV IV IV

CORROSION SCIENCE

4.1 Define corrosion
2Marks
Corrosion is defined as the destruction or deterioration of a metal
or its alloy and consequent loss of metal, caused due to direct chemical
action or electrochemical reactions with its environment.

4.2 Explain the electrochemical theory of corrosion
6 Marks
According to electrochemical theory, corrosion of metals occurs
due to the following changes, when they are exposed to the environment.
1) A large number of minute galvanic cells are formed which acts as
anodic and cathodic areas.
2) At anode the metal undergoes oxidation and electrons are liberated
which migrates towards cathodic region
3) Oxygen of the atmosphere undergoes reduction at cathodic area in the
presence of moisture forming hydroxyl ions at the cathode

Anodic reactions: At anode the metal undergoes oxidation-liberating
electrons
M M
n+
+

ne
-

Metal Metal ions
Ex: when iron is exposed to the environment it undergoes
oxidation as
Fe Fe
2+
+ 2e
_
Cathodic reactions: The electrons released at anode migrates to
the cathodic area and reduces oxygen to hydroxyl ions.

The different cathodic reactions are,
a) In acidic medium: In acidic medium and in the absence of
oxygen, hydrogen ions are reduced to hydrogen gas
2H
+
+ 2e
-
H2
b) In alkaline and in the absence of O2. If the solution is alkaline
and in the absence of oxygen the cathodic reaction is,
2 H2O + 2e
-
2OH
-
+ H2
c) In neutral and aerated medium: when the solution is neutral and
aerated, hydroxyl ions are formed as follows.
2 H2O + O2 + 4e
-
4OH
-
d) Formation of corrosion product: The hydroxyl ions migrate
towards anode and reacts with metal ions (M
n+
ions) and forms corrosion
product. In the case of iron OH- reacts with Fe
2+
ions and forms an
insoluble hydrated ferric oxide known as brown rust.
2Fe
++
+ 4OH
-
2Fe (OH) 2
2Fe (OH) 2+ O2 + 2H 2O 2 (Fe 2O 3. 3H 2O) rust.
4.3 What is Galvanic series ?
The arrangement of elements in the order of their standard reduction
potential is reffered to as emf or electrochemical series. Such a
arrangement of few elements given in the table.

M
n+
/ M E
0
(v) M
n+
/ M E
0
(v)
Li
+
/Li -3.05 Cd
2+
/Cd -0.40
K
+
/K -2.93 Sn
2+
/Sn -0.14
Ba
2+
/Ba -2.90 Pb
2+
/Pb -0.13
Ca
2+
/Ca -2.87 H
+
/H2 0.00
Na
+
/Na -2.71 Cu
2+
/Cu 0.34
Mg
2+
/Mg -2.37 Ag
+
/Ag 0.80
Al
3+
/Al -1.66 Hg
2+
/Hg 0.85
Zn
2+
/Zn -0.76 Pt
2+
/Pt 1.20
Fe
2+
/Fe -0.44 Au
3+
/Au 1.38

1)A negative value indicates oxidation tendency and a positive value
indicates reduction tendency with respect to hydrogen.

2)The metal with lower electrode potential are more reactive and as the
electrode otential increases, the reactivity decreases and metals with
higher electrode potentials are more noble.
3)Metals with lower electrode potentials have the tendency to replace
metals with higher electrode potential from their solutions for example,
Zn displaces Cu, Cu displaces Ag
4)Metals with negative electrode potentials can liberate hydrogen from
acidic solutions
4.4 Explain the different types of corrosion.
6 Marks
The corrosion can be mainly classified as follows
1. Differential metal corrosion.
2. Differential aeration corrosion
3. Stress corrosion and
4. Grain boundary corrosion
1. Differential metal corrosion.
This type corrosion occurs when two different metals are in
contact with each other due to the formation of galvanic cell. The metal
having less standard reduction potential value under goes oxidation and
liberates electrons, which migrates to the cathode. The other metal
having high SRP value acts as cathode and reduction reaction takes
places on its surface forming OH- ions or any one kind of reduction
reactions. The rate of corrosion depends on the potential difference
between the two metals. If the difference is more corrosion occurs faster
and vice versa. The anodic metal undergoes corrosion and cathodic metal
is unaffected .The reactions that occurs are
At anode M M
n+
+ ne
-

At cathode Depending on the nature of corrosion environment the
cathodic reaction are as fallows
i) 2H
+
+ 2e
-
H2 (in acidic environment)
ii) H2O + O2 + 4e
-
OH
-
(in neutral environment)
iii) 2H2O + 2e
-
2OH
-
+ H2 (in alkaline environment)
Example: Iron metal in contact with Copper metal, Brass tap in contact
with Iron pipe etc.

2. Differential aeration corrosion.
This type of corrosion occurs when a metal is exposed to different
concentrations of Oxygen. The part of metal which is more exposed to air
act as cathode and unaffected. The other part of the metal, which is less,
exposed to air act as anode and undergoes corrosion.
Example i) Water line corrosion:
It is differential aeration type of corrosion observed in water
storage tanks, ships, etc.During water line corrosion, the part of the
Metal below waterline is exposed to less Oxygen concentration act as
anode and undergoes corrosion than the other part which is more
exposed to atmospheric Oxygen which act as cathode.
At anode Fe Fe
++
+ 2e
_
At cathode 2Fe
++
+ 4OH
-
2Fe (OH) 2
2Fe (OH) 2+ O2 + 2H 2O 2(Fe 2O 3. 3H 2O) rust.

Example ii) Pitting corrosion:
Pitting corrosion occurs when small particle like dust, mud etc get
deposited on metals surface. The portion of metal covered by the dust or
other particles is less aerated and act as anode. The other portion of the
metal exposed to more oxygen of the environment act as cathodic region.
Corrosion takes place at the portion below dust and a small pit is
formed. Then the rate of corrosion increases due to small anodic area
and large cathodic area.


3. Stress corrosion.
Stress corrosion is seen in metals suffering from stress which may
result from mechanical operations such as design riveting, cold working,
welding, bending, pressing, quenching etc. In an corrosive environment
the stressed portion act as anode and undergoes corrosion. The other un
stressed part of the metal acts as cathode.
Example: Caustic embritlement in boilers or intercrystalling corrosion.
It is a form of stress corrosion that takes places in boilers
operating at high pressure between 10 to 20 atmospheres. The stressed
portion contains fine hair like cracks. Boiler water contains of alkali,
which enters into the cracks. The water evaporates leaving behind
caustic soda. An electrochemical cell is set up between the iron under
stress and iron in the main body. The iron surrounded by dilute NaOH
act as cathode and iron under stress act as anode and gets corroded
resulting in failure of boiler.

4.5 Explain the affect of factors on the rate of corrosion.
6 Marks
The main important factors, which affect on the rate of corrosion, are
a) Nature of the metal and
b) Nature of the environment

a) Nature of the metal: -

i) Nature of corrosion product:
If the nature of corrosion product forms, a protective layer on the
metal surface, it prevents the further corrosion of metal .If the corrosion
product is thin, invisible and doesnt form a protective layer it leads to
further corrosion of metal.
Example: In oxidizing environment metals like Al, Cr, Ti etc. forms
protective metal oxide films on their surfaces which prevents further
corrosion .Metals like Zn,Fe ,Mg ,etc .do not form protective layer and are
readily under goes corrosion .Therefore the rate of corrosion depends on
the nature of corrosion product.

ii) Electrode Potential of anode and cathode.
The rate of corrosion increases if the potential difference between
anode and cathode is high and vice versa. When two different metal with
large electrode potential difference (SRP values) under goes very fast
corrosion
Example: The potential difference between copper and iron is 0.78 V.
The potential difference between iron and tin is 0.3 V. In these two cases
iron undergoes fast corrosion when it is in contact with copper than
when it is in contact with tin.

iii) Anodic to cathodic areas:
If a metal has small anodic and large cathodic area the rate of
corrosion increases and vice versa. This is because when anode is small
the electrons liberated during oxidation are completely consumed on
large cathodic surface for the reduction reactions and rate of corrosion
increases.

b) Nature of the environment:

i) Temperature: Increases in temperature results in an increase in the
conductance of the aqueous medium and rate of corrosion also increases
and vice versa.

ii) PH:
In general at lower PH value the rate of corrosion is more at higher pH
value (more than pH = 10) the rate of corrosion ceases due to the
formation of protective coating of hydrous oxides on the metal. Corrosion
rate is maximum between PH 3 and 10 in presence of oxygen

iii) Anodic polarisation and cathodic polarization
The process where there is a variation of electrode Potential due to the
inadequate supply of species from the bulk of the solution to the
electrode is known as polarisation.
Anodic polarization: Increase in anodic polarization, decreases the rate
of corrosion. Due to the anodic polarization the tendency for oxidation
decreases.
Cathodic polarization: Increase in Cathodic polarization, decreases the
rate of corrosion. Due to the cathodic polarization the tendency for
reduction decreases. Due to inadequate Supply of electrons and
oxidation cannot continue. Therefore rate corrosion decreases.

4.6 Mention the corrosion control methods.
2 Marks
The important methods used to control corrosion are,
1. Design and selection of the materials.
2. Protective coatings.
a) Organic coatings paints and enamels.
b) Inorganic coatings
i) Metal coatings anodic and cathodic
ii) Surface conversion coatings anodizing, phosphating.
3) Corrosion inhibitors
4) Cathodic protection
5) Anodic protection.

4.7 What are Inorganic Coatings?
4 Marks
i) Metal coatings anodic and Cathodic
ii) Surface conversion coatings anodizing, phosphating.

i) Metal coatings
Deposition of protective metal over the surface of base metal (metal
to be procted from corrosion) is known as metallic coatings. It is divided
into Anodic and Cathodic metal coatings.

a) Anodic metal coatings:
Anodic metal coatings involve coating the base metal with more
active metals, which are anodic to the base metal.

Example: Galvanization

b) Cathodic coatings: Cathodic coatings involve coating a base metal
with more noble metals, which are cathodic to the base metal. Metals

such as Copper, Nickel, and Tin Silver etc are coated on Iron. One of the
disadvantage of Cathodic coatings is if coating ruptures it leads more
corrosion because of small anodic area and large cathodic area.
Example: Tinning
Surface conversion coatings

Surface conversion coatings are chemical conversion coatings. The
surface layer of the base metal is converted into a compound by chemical
or electrochemical reactions, which prevents the base metal form
corrosion. The coating can be done by chemical dip, spray or by
electrolytic method. The coating helps in the increased electrical
insulation, enhanced adherence for paints and prevention of corrosion.
Example: Anodizing , Phosphating

4.8 Explain the process of Galvanization
5 Marks
It is a process of coating the base metal surface with Zinc, tin,
lead, or aluminum metal.

Example: coating Zinc on Iron by hot dipping Method. It involves the
following steps.
The Iron metal surface is washed with organic solvents to remove oil,
grease etc content on the metal surface.
Then the metal is passed through dilute sulphuric acid to remove rust
and other depositions
Finally the metal is washed with water and dried.
The metal is then dipped in molten Zinc and passed through
Ammonium chloride and Zinc chloride flux to prevent oxidation of
Zinc.
The excess Zinc is removed by passing through the rollers or by
wiping.
Uses: Galvanisation is used for roofing sheats, buckets, bolts, nuts,
nails, pipes etc.

4.9 Explain the process of Tinning.
5 Marks
Tinning is a process of coating the base metal with Tin (Sn).It is
carried out by hot dipping method as fallows.
The base metal surface is washed with organic solvents to remove oil,
grease etc content on the metal surface.
Then the metal is passed through dilute sulphuric acid to remove rust
and other depositions
Finally the metal is washed with water and dried.

The metal is passed through Ammonium chloride and Zinc chloride flux
and then dipped in molten Tin
Finally it is dipped in palm oil to prevent oxidation of Tin.
The excess Tin is removed by passing through the rollers or by wiping.

Tinning is used for food storage articles.

4.10 What is Anodizing? Explain the process of Anodizing of
aluminum
6 Marks
Anodizing is a process of artificially converting protective passive
oxide film on the surface of metals such Al, Zn, Mg, Ti, Zr, Ta, Cr, etc by
electrochemical oxidation.
ANODIZING OF ALUMINUM.
Aluminum when it is made as cathode it allows the passage of
electrons but it ceases to conduct when made as anode. It exhibits
anodic passivity in the medium like chromic and sulphuric acids. This is
known as anodic oxidation or anodizing.

Process of anodizing aluminum.

Pretreatment: The article be anodized is degreased and followed by
electro polished
Aluminum is connected to positive terminal i.e., made as anode.
Steel or copper is made as cathode
The anode and cathode are dipped in electrolyte solution containing
5-10% chromic acid.
The temperature of the both is maintained at 35
o
c
Voltage is applied between 0-50V.
First ten minutes potential is increased to 0-40V.
After 20 minutes voltage is applied from 40-50V
The voltage is kept constant at 50 V for five minutes.

An opaque oxide layer of 2-8 micrometer thick aluminum oxide layer
is obtained. For higher thickness 10% H2SO4 is used as electrolyte.
Finally the object is treated with Ni or Cobalt acetate fallowed by boiling
water treatment to improve corrosion resistance.

Uses: Anodized articles are used as Tiffin carriers, soapboxes, household
utensils, window frames, etc.

4.11 Explain the process of Phosphating.
6 Marks
Phosphate coating is a process of converting the surface atoms of
the base metal into their phosphates by chemical or electrochemical
reaction between base metal and certain metal phosphates in aqueous
solution of phosphoric acid.
Phosphate coating is generally obtaining on steel, Al, and Zn.
The metal to be coated (base metal) is degreased, polished washed
and dried
It is dipped in a solution containing mixture of phosphoric acid,
metal phosphates such as Fe / Mn / Zn phosphates.
Accelerators such as copper salts, H2O2, nitrate etc.
pH of the bath is maintained between 3.2 7.8
Temperature is maintained about 35
O
C.
The metal ions dissolve and react with phosphate ions forming
metal phosphate.
The metal phosphates deposits on the surface of base metal.

Uses: - Phosphate coated metal widely used in automobile industry,
bolts, nuts, and refrigerators, washing machining, cars bodies etc.

4.12 Write a note on Organic coatings
4 Marks
Organic coatings are inert organic barriers applied on metallic
surface to protect metals from corrosion. A thin coat of paint or enamels
or lacquers is coated on the metal surfaces.

PAINTS:

Paint is a mixture of one or more pigments in organic medium
containing oil. This is mixed with volatile thinners and applied on metal
surface. The volatile thinner solvent evaporates leaving behind the paint
on metal surface.

Enamels: These are dispersions of pigment in varnishes these are
applied on metal surface to protect them from corrosion.

Uses: Organic coating are applied by different methods such as
brushing, spraying dipping roller coating etc. these organic coatings
protects the metals form corrosion and also increases the decorative ness
of the metal.

4.13 Explain corrosion inhibitors with suitable examples.
5 Marks
These are the substances added in small concentrations to a
corrosive environment to decrease the rate of corrosion. These slow down
the anodic or cathodic reactions.
Anodic inhibitors.
These inhibit the anodic oxidation reactions. The anodic inhibitors
include oxidizing agents such as sodium chromate, molybdates,
tungstates, chromates, nitrates etc. These prevent anodic reaction by
forming a protective layer on metal surface and prevent further anodic
reaction.
Cathodic inhibitors
These are the substance, which slow down the cathodic reaction.
The cathodic reactions involve liberation of hydrogen in acidic solution or
OH
-
ions in alkaline and neutral medium. The cathodic organic inhibitors
include amines, thiourea, sulphoxides etc. The two types of cathodic
inhibition reactions are liberation of hydrogen, absorption of oxygen and
formation of hydroxyl ions.
i) Inhibition of oxygen absorption
Removing oxygen from the corrosion media by using reducing
agents or oxygen scavengers such as hydrazine, sodium sulphite, etc can
control absorption of oxygen during cathodic reaction. Thus rate of
corrosion can be controlled.
O2 + NH2 - NH2 N2 + 2H2O.
2 Na2 SO3 + O2 2Na2 SO4

ii) Inhibition of Hydrogen liberation
Adding substances like thiourea can prevent the diffusion of H+
ions to the cathode, amine etc which forms protective film on cathode
and prevents the diffusion of H
+
ions. Increasing hydrogen over voltage
by adding AS2O3, Antimony or stats like sodium metal arsenate, can
prevent the evolution of hydrogen gas at cathode.

iii) Inhibition of hydroxyl ions (OH
-
)
Corrosion can be prevented by adding salts such as ZnSO4,
MgSO4, NiSO4, etc which migrates to cathode and reacts with hydroxyl
ions and reduces all OH
-
ions.
Zn
2 +
+ 2 OH
-
Zn (OH)2
Mg
2+
+ 2OH
-
Mg (OH)2
4.14 What is cathodic protection? Explain Sacrificial anodic
protection method and Impressed voltage method
6 Marks
Cathodic protection is a method in which the base metal to be
protected from corrosion is made to act as cathodic by attaching more
active anodic metal to it. The active anodic metal undergoes corrosion
and base metal is protected from corrosion the following methods are
used to protect metal from corrosion.
Example: a) Sacrificial anodic protection method
b) Impressed voltage method
a) Sacrificial anodic protection method.
In this method the more active metals like Zn, Mg, and Al etc are
attached to base metal. The anodic metals being more reactive undergoes
corrosion but base metal remains unaffected .The sacrificial anodes have
to be replaced from time to time after complete corrosion. The method is
used for protecting buried pipeline, ship hulls, industrial water tank steel
rods in RCC columns. Several hundred kilometers long zinc wire is
buried along oil pipe line in Alaska is an example for sacrificial anodic
protection method

b) Impressed voltage method.

In this method the base metal is connected to negative terminal of
the D.C source and made it cathode an inert anode consists of resin
bonded graphite rod, silicon - iron alloy (or) platinized Ti (or) Ta is
connected to positive terminal of the D.C source. The protected base
metal does not under goes corrosion.


4.15 Explain the Anodic Protection method.
6 Marks

In this method, the metal to be protected from corrosion is made
more anodic by passing external impressed current to make it more
anodic and it forms a thin oxide film which then protects the metal from
further corrosion .The metal part is connected to potentiostat for
maintaining constant potential having a reference electrode The auxiliary
electrode acts as cathode and base metal acts an anode after passing
current the metal from a passive layer which prevents further corrosion.
The advantage of the method is that it requires small current. A
drawback of this method is that it cannot be applied to the metals which
do not passivate.

Objective type questions
1. Rusting of iron is an example for
a) dry corrosion b) electrochemical corrosion
c) acid corrosion d) None

2. Differential metal corrosion is
a) galvanic corrosion b) Differential aeration corrosion
c) stress corrosion d) water line corrosion

3. Pitting corrosion can be explained on the basis of
a) relative areas of cathode and anode b) Differential aeration
c) centralized corrosion d) all of the above

4. Coating used for the iron container used for food package coated with
a) Zn b) Sn c) Pb d) Al

5. Waterline corrosion in steel tank is an example for
a) Differential metal corrosion b) Differential aeration corrosion
c) pitting corrosion d) stress corrosion

6. Caustic embrittlement in the boiler is an example of
a) pitting corrosion b) stress corrosion
c) water line corrosion d) Differential metal corrosion

7. Sacrificial anode method of protecting metal is an example of
a) anodic protection b) cathodic protection
c) metal coating d) organic coating

8. Corrosion can not take place in
a) acidic medium b) neutraql medium c) alkaline medium d) vacuum

9. When 2 metals are in contact with each other, metal which undergoes
corrosion has
a) less standard reduction potential b) high standard reduction
potential c) zero standard reduction potential d) high reduction
potential

10. In phosphating process, bath contains
a) iron phosphate b) zinc phosphate
c) manganese phosphate d) any one of the above

11. Galvanising is the process of coating iron with
a) Tin b) zinc c) copper d) nickel


12. Corrosion process is an example of
a) oxidation b) reduction c) Electrolysis d) both a & b

13. Rusting of iron takes place in
a) acid medium b) alkaline medium c) neutral medium d) all

14. In differential aeration corrosion, part of the metal which is more
exposed to air acts as
a) cathode b) anode c) insulator d) electrolyte

15. Which of the following is an cathodic inhibitor
a) thiourea b) sulphoxides c) hydrazine d) all


REVIEW QUESTIONS
1. Define corrosion? Explain electrochemical theory of corrosion.
2. Mention the different types of corrosion
3. Explain differential metal corrosion with suitable example.
4. Explain differential aeration corrosion with suitable example.
5. Explain stress corrosion with suitable example.
6. Explain 5 factors that affect on the rate of corrosion
7. Mention the Corrosion control methods:
8. What is galvanization? Explain the process of galvanization.
9. What is Tinning? Explain the process of Tinning
10. What is anodizing? Explain anodizing of Aluminium
11. What is Phosphating? Explain the process of Phosphating.
11. What is Phosphating? Explain the process of Phosphating.
12. What are organic coatings explain their role in preventing corrosion?
13. What are corrosion inhibitors? Explain anodic and catholic
inhibitors.
14. What is Cathodic protection explain with examples.
15. Explain the corrosion control by Anodic Protection method.


UNIT UNIT UNIT UNIT V VV V

METAL FINISHING

5.1 What is metal finishing? Mention the Technological importance
of metal finishing. 6 Marks
It is a process of modifying surface properties of metals by deposition
of a layer of another metal or polymer on its surface, by the formation of
an oxide film.
Technological importance of metal finishing.
The main technological importance of metal finishing include
1. Imparting the metal surface to higher corrosion resistance.
2. Imparting improved wear resistance.
3. Providing electrical and thermal conducting surface.
4. Imparting thermal resistance and hardness.
5. Providing optical and thermal reflectivity.
6. In the manufacture of electrical and electronic components such as
PCBs, capacitors contacts etc
7. In electro framing of articles, electrochemical machining, electro
polishing and electro chemical etching.
8. To increase the decorativeness of metal surface.
9. In electrotyping and to build up material or restoration.
10. To improve wear resistance or solder ability.

5.2 Explain the term Polarization. 3 Marks
The process where there is a variation of electrode Potential due to
the inadequate supply of species from the bulk of the solution to the
electrode is known as polarization.
When there is a passage of current, the metal ion concentration in
the vicinity of the electrode surface decreases due to the reduction of
some of the metal ions into metal atoms.
M
n+
+ ne
-
M
.
As a result there will be a change in the electrode potential, however
equilibrium is reestablished due to the diffusion of metal ions towards
the electrode.
If the diffusion is slow the electrode potential changes and the electrode
is said to be polarized. Polarized electrode uses more negative potential
than required in order to maintain given current.
Electrode polarization depends on several factors as follows:

Nature, size, shape, and composition of electrode.
Conductivity and concentration of electrolytic solution.
Temperature.
Products formed at the electrodes.
Rate of stirring of the electrolyte.

5.3 Explain the term decomposition potential.
3 Marks
It is defined as the minimum external voltage that must be applied in
order to bring about continuous electrolysis of an electrolyte.
Electrolysis of an electrolyte occurs only when applied voltage is above
certain value below which electrolysis do not occur. This can be
determined by an electrolytic cell, if dilute acid or bases are used as
electrolytes decomposition occurs when voltage is increased with sudden
evolution of H2 and O2 at the electrodes. It requires more than 1.7v. The
decomposition potential for Zn and iodine cell is experimentally found to
be 4.3volts. The decomposition potential is represented as ED.

ED = E cathode E anode

5.4 Explain the term over voltage.
3Marks
It is defined as excess voltage that has to be applies above theoretical
decomposition potential to bring the continuous electrolysis of an
electrolyte is known as over voltage.
The theoretical voltage required for the decomposition of aqueous
solution of an acid is equal to the emf of the reversible cell with hydrogen
and oxygen gases at one atmosphere. This is known to be about 1.23
volts at ordinary temperature with platinised platinum electrodes. It is
however found that the observed decomposition potential is always
higher than the theoretical value. Thus with platinum and lead
electrodes, a voltage of 1.7 and 2.2 is respectively required for the
electrolysis of dilute sulphuric acid as against a theoretical value of 1.23
volt. This difference between the observed and theoretical decomposition
potential is called over voltage.

Over voltage of an electrolyte depends on
i) Nature and physical state of the metal employed for the electrodes.
ii) Nature of the substance deposited.
iii) Current density
iv) Temperature.
v) Rate of stirring of electrolyte.


5.5 Explain the process of electroplating.
6Marks
It is a process of deposition of a metal by electrolysis, over the surface of
substrate. The substrate may be another metal, polymer, ceramic, or a
composite. The principal components of electroplating process are: -

1. Electroplating bath.
2. Cathode.
3. Anode.
4. Electroplating tank.
5. D.C. electrical power source.
6. Reactions at anode and cathode.
1) Electroplating bath: The plating bath contains solution for plating
process. It is normally a mixtures of metal ion solution, other
electrolytes, complexing agents and various organic additives added to
improve the nature of deposit.
2) Cathode: The substrate to be plated is made cathode and suspended
as separate bus bars. These cathode electrodes are placed in
electrolytic bath solution.

3) Anode: The metal which is to be plated on the other metal is made as
anode. Anode is used in the form of a rod, a plate or pellets. The anode
is enclosed inside an anode bag to retain impurities.

4) Electroplating tank: It is made of wood or steel. If steel tanks are
used these are thermally insulated with ceramic or polymeric
materials. The volume of tank may vary from 20-100 dm
3
.

5) D.C.Electrical Power Source: A D.C voltage of 8-12v & an operating
current density 1-200 mA/cm
2
is used for plating process. Motor
generators or d c rectifiers are used to provide current.

6) Reaction at anode and cathode: Electroplating is the process of
electrolytically depositing a layer of metal onto a surface. The anode
metal undergoes oxidation liberating metal ions & electrons. The
electrolytic bath containing metal ion undergoes reduction to metal
atoms and get deposited on the metal or substrate to be plated.

5.6 Explain the factors influencing on the nature of electro deposit.
6Marks
The various factors which influences on the nature of electro deposit are
as follows:-

1. Metal ion concentration.
2. Electrolytic concentration.
3. Complexing agents.
4. Organic additives.
5. Current density.
6. P
H

7. Temperature.
8. Throwing power of plating bath.

1. Metal ion concentration: For a good adherent deposit, the metal
ion concentration should be low. The low metal ion concentration
can be achieved by addition of compounds having common ion or
by the formation of complex compounds and ions.
2. Electrolyte concentration: Electrolytes are added in high
concentrations to increase the conductivity of the plating bath. The
electrolytes used do not participate in the electrode reactions.
3. Complexing agents: These are added to convert metal ions to
complex ions to keep metal ion concentration at optimal range. The
complexing agents are added when plating metal ions are known to react
with the cathode and to prevent passivation of anode and the anode
dissolves slowly. The complexing agents also increase throwing power.
Ex. Cyanides, hydroxides, sulphonates.

4. Organic additives: These are added to improve the nature
electrodeposit. They modify the structure, morphology, and properties of
the electrodeposit. The different organic additives used are as follows: -
a) Brighteners, b) Levelers, c) Structure modifiers, d) Wetting agents.

a) Brighteners: These are added to obtain a bright and microscopically
fine deposit. Ex. Sulphonates, & compounds containing C = O, N = C = S
etc

b) Levelers: Certain organic compounds are added as levelers in order to
get a level deposit. Sodium allyl sulphonates etc

c) Structure modifiers or stress relievers: These additives modify the
structure of the deposit and orientation in such a way as to alter the
deposit properties. Ex. Saccharin.

d) Wetting agents: Wetting agents are used to release hydrogen gas
bubbles from the surface. The wetting agents also improve the adhesion
of the deposit.

5) Current density: It is the current per unit area and expressed in
mA/cm
2
of the electrode surface. At low current density the discharge of
ions occurs slowly and deposits are coarsely crystalline and loosely held.
At higher current density hydrogen evolution occurs and deposits
are spongy, irregular and loosely held. Deposits may have a burnt
appearance.
For good deposit the current density should be optimum.

6) P
H
: If ph of the medium is low H2 has is evolved causing brittle and
burnt deposit. At higher P
H
values, deposits of metallic oxides or
hydroxides may form. Hence an optimum P
H
between 4 to 8 is employed.

7) Temperature: A good deposit formed at slightly higher temperatures.
At very high temperatures hydrogen evolution takes place at the cathode
forming a burnt deposit. Therefore moderate temperature between 35 to
60
0
C is used to get good deposit.

8) Throwing power of a plating bath: The ability of a plating bath to
give a uniform and even deposit on the entire surface of the object,
irrespective of its shape is known as throwing power.
Throwing power of plating bath can be determined by using Haring
blum cell.
Haring Blum cell consists of plating bath solution whos throwing power
is to be determined. Anode is placed at the center and two cathodes are
placed either side of the anode at a distance C1 & C2. Electroplating is
carried out and weight of electro deposit on the two cathodes is weighed.
The weight of electro deposit (W1) on cathode 1 which is placed far from
anode, is less than another cathode 2, which is very nearer to the anode.
Then throwing of plating bath is calculated from the equation,


100X (x - y)
% throwing power =
(x + y)-2

Where x = C1/C2 (When C1> C2)
y = W2/W1

5.7 Explain the process of surface preparation prior to the
electroplating process
4Marks
The object before subjecting to electroplating process, it is essential
to clean the surface of object. The following methods are used to clean
the metal surface.

i) Solvent cleaning: Organic solvents such as Trichloro ethylene and
methylene chloride are used to remove organic matter and grease on the
surface of cathode. Trichloro ethylene is used to remove paint varnishes,
films, resins etc. Perchloro ethylene is used to remove high melt waxes
and cleaning PCB. The above process is called solvent cleaning.

ii) Alkali cleaning:
After solvent cleaning the metal is cleaned with alkali solution. Alkali
cleaners such as soaps, detergents, sodium carbonate, sodiumhydorxide,
sodium phosphate etc are commonly used.

iii) Mechanical cleaning: The object is subjected for mechanical
cleaning to remove oxide scales, rust and other impurities on the metal
surface. The mechanical cleaning methods involves, cleaning with Bristle
brushes, mechanical polishing, grinding using polishing machines,
buffing and sand blasting.

iv) Pickling: In this method the oxides scales are removed by dipping the
base metal in a dilute acids. Pickling of steel involves dipping in dilute
HCl or dilutes H2SO4 to remove rust and other oxide scales.

v) Rinsing with water: After surface cleaning process the metallic
surface is thoroughly rinsed with water, dried and subjected for
electroplating process.

5.8 Explain the Electroplating process of chromium.
6 Marks
Plating bath Chromic acid and H2SO4 in 100:1 proportion.
Temperature 45-60
0
C.
Current Density 100-200mA/Cm
2
.
Anode Insoluble anodes Pb-Sb or Pb-Sn coated with
PbO2.
Cathode Object to be plated.

Chromium anodes are therefore not used in Cr plating for following
reason.
Chromium metal passivates strongly in acid sulphate medium &
Chromium anode gives rise to Cr (III) ions on dissolution. In
presence of large concentration of Cr (III) ions, a black Cr deposit is
obtained.

Applications:

a) Decorative chromium provides a durable finish on cycles,
automobiles, furnitures, air craft and surgical instruments etc.

b) Hard Chromium is used in cutting tools, piston rings, cylinder
liners, crankshafts of marine & aero engines, bearings etc.

c) Black Chromium is used in optical instruments, machine tools &
electronic parts.

d) It is also used for non-glase finishes on automobiles, & as an
efficient coating for solar energy collectors.

5.9 Explain the Electroplating process of copper 6 Marks
Electroplating of copper
Sulphate bath Cyanide bath
Plating bath solution 200-250 g CuSO4, 50-
75 g H2SO4, per L of
bath solution
40-50 g CuCN, 20-30g
KCN, 10 g K 2CO3 per
L
Operating temperature 20-40
0
C 40-70
0
C
Current density 20-50 mA/cm
2
10-40 mA/cm
2

Addition agents Gelatin, dextrin,
sulphur containing
brighteners, sulphonic
acids
Sodium thiosulphate
Current efficiency(%) 95-99 60-90

Anode Phosphorous
containing rolled Cu
O2 free high
conductivity Cu
Cathode object to be coated
pretreated
object to be coated
pretreated
Applications In PCR boards In Cr plating, PCR
boards

5.10 What is Electro less plating? 2 Marks
Electro less plating is the controlled autocatalytic deposition of a
continuous film of a metal from its salt solution on a catalytically active
surface by a suitable reducing agent without using electrical energy.

Metal ions + reducing agent Metal + oxidized product.

5.11 Distinction between electroplating and Electroless plating
4 Marks
Electroplating

Electro less plating

1. Require electrical power
source and accessories.

1. Does not require
electrical power source and
accessories.

2. Deposition cant be made
on non-conductors such as
plastics, ceramics etc.

2. Deposition can be made
on non-conductors such as
plastics, ceramics etc.

3. requires Levelers 3. Does not require Levelers

4. Plating baths dont have
excellent throwing power.

4. Plating baths have
excellent throwing power.

5.12 Explain the Electro less plating process of Nickel.
6 Marks
Plating bath solution: A solution of NiCl2 20g /litre,
Reducing agent: Sodium hypophosphate 20g/litre
Buffer: Sodium Acetate 10g/lt
Complexing agent: Sodium Succinate.
P
H
: 4.5
Temperature: 93
0
C


Anodic reaction: H2PO2
-
+ H2O H2PO3
-
+ 2H
+
+ 2e
-

Cathodic reactions: Ni
2+
+ 2e
-
Ni.
Overall reaction: Ni
2+
+ H2PO2
-
+ H2O Ni + H2PO3
-
+ 2H
+
.

Uses:

i)Used to plate on industrial components such as pumps and valves,
shafts, gears, reaction vessels and other tools.

ii) To coat on steel, plastic, PCBs etc.

5.13 Explain the Electro less plating process of copper.
6 Marks
Electroless plating of copper on PCBs is carried out as follows.

Plating bath Solution: CuSO4..5 H2O (12 g per dm
3
), NaOH (15 g per/L
Rochelle salt (14 g per dm
3
), EDTA (15 g per dm
3
)
Reducing Agent: Formaldehyde (8 g per dm
3
)
Complexing agent: EDTA Solution.
P
H
: 11 - 12
Temperature: 25
0
C
Electrode Reactions:
At Anode: 2HCHO + 4OH
-
2HCOO
-
+ 2H2O + H2 + 2e
-

At Cathode: Cu
2+
+ 2e

Cu.
Overall reactions: 4OH
-
+Cu
2+
+ 2HCHO
-
Cu + 2HCOO
-
+ 2H2O +H2

APPLICATIONS:

Widely used for moralizing (PCBs) printed circuit boards.
For producing through hole connections.
For plating on non-conductors.
As an undercoat for electroplating.
For decorative plating on plastics.


Objective Type Questions:

1) In the electroplating process the over voltage potential depends on
a) Electrolyte b) Temperature c) Current density d) All

2) In chromium plating anode is
a) Soluble Chromium anodes b) Insoluble anodes
c) Inert anodes d) both b & c

3) Autocatalytic reaction method of plating is also known as
a) Electroplating b) Electrolysis plating
c) Electro less plating d) electro refining

4) For a electrolytic mixture containing Zn
2
+ , Cu
2+
, Ag
+
the ion which
is going to be discharge first is
a) Zn
2+
b) Cu
2+
c) Ag
+
d) None

5) Conductors and insulators can be plated by
a) Electroplating b) Electro less plating
c) Electro polishing d) None

6) The phenomenon in which the back EMF produced due to the
products of Electrolysis is
a) Electroplating b) Electro less plating
c) Polarization d) None

7) When the metal structure to plated is irregular the process employed
is
a) Electroplating b) Electro polishing
c) Electro less plating d) None

8) Addition of Complexing agent to the plating bath is to
a) Increase the rate of electro deposition b) increase the metal ion
concentration c) Decrease the metal ion concentration d) None

9) Over voltage depends on
a)current density b) Temperature
c) Nature of the substance deposited d) All

10) For good deposition throwing power of a plating bath has to be
a) Low b) High c) Zero d) No effect


11) For a good deposition, metal ion concentration should be
a) low b) high c) zero d) none

12) Organic additives are added to bath solution to get
a) bright deposit b) level deposit c) fine deposit d) all

13)In electroplating of copper, anode is
a) insoluble b) coated with PbO2 c) both a & b d) copper

14) In electrolesss plating process,
a) levelers are not required b) current desity is not required
c) reducing agent is required d) all

15) In electro less plating process of copper, plating bath contains
a) CusO4 b) EDTA c) HCHO d) All


REVIEW QUESTIONS

1. What is metal finishing? Mention the Technological importance
of metal finishing
2. Explain the term Polarisation. Mention the factors that affect
Polarisation
3. Explain the term decomposition potential.
4. Explain the term over voltage. Mention the factors that affect over
voltage
5. Explain the process of electroplating
6. Explain the factors influencing on the nature of electro deposit.
7. Explain the methods of cleaning a metal surface prior to
Electroplating.
8. Explain electroplating of chromium.
9. Explain the electroplating of Gold
10. What is Electroless plating? Mention the advantages of Electroless
plating over electro plating.
11. Distinction between electroplating and Electroless plating
12. Explain electroless plating of Nickel
13. Explain electroless plating of copper.

UNIT UNIT UNIT UNIT V VV VI II I
PHASE RULE
6.1 what is phase diagram? 2 mark
A single graph depicting the overall relationships among the
various phases (solid, liquid and vapour phases) of a substance is known
as a phase diagram. A phase diagram summarizes the conditions at
which a substance exists as a solid, liquid or gas.
Phase diagrams are of considerable commercial and industrial
significance, particularly for semiconductors, ceramics, steels, polymers,
composites and alloys. They are also the basis of separation procedures
in the petroleum industry and cosmetic preparations.

6.2 what is Gibbs Phase Rule? Explain the terms. 4 Marks
The number of degrees of freedom (F) of a heterogeneous system at
equilibrium at a definite temperature and pressure is related to the
number of components (C) and of phases (P) by the phase rule equation,
P + F = C + 2 or F = C - P + 2
Where P=No of phases in the system
C= No of Components of the system
F= No of degrees of freedom or variables of the system(T,P and
Composition or concentration)

6.3 Define PHASE . 2 Marks
A phase is defined as any homogeneous physically distinct and
mechanically separable part of a system which is separated from other
parts of the system by definite boundary lines.
Eg. 1) A mixture of Ice, liquid water and water vapour is a two-phase
system.
2) Two miscible liquids -is one phase system. e.g. Ethanol and
water is a one phase system.
3) Two immiscible liquids- is two phase system.e.g. Chloroform and
water constitutes a two-phase system. Ether and water constitutes
a two-phase system.
4) An aqueous solution of a solid substance such as sodium
chloride or sugar is a one-phase system.
5) All gases mixture freely to form a homogeneous mixture.
Therefore, any mixtures of gases, say oxygen and nitrogen is a one-
phase system
6)Decomposition of calcium carbonate to calcium oxide and CO2 is
a three phase system with two solid phases and one gaseous
phase.
CaCO3(s) CaO(s) + CO2(g)

6.4 Define COMPONENT : (C) 4 Marks
It is the smallest (least) number of independent chemical constituents by
means of which the composition of each phase present in the particular
system can be expressed, either directly by formula or in the form of a
chemical equation.
i) One component :-
1) Water system has three phases i.e. Ice(s) Water(l) Water
vapour(g)
The composition of all the three phases is expressed in terms of one
chemical constituent, H2O. Thus water system is a one component
system.

2) Sulphur has four phases : i) rhombic ii) monoclinic iii) liquid and
iv) sulphur vapour.
The composition of all these phases can be expressed by one
chemical individual,
S(sulphur). Thus sulphur system has one component only.
3) A mixture of gases Nitrogen and Oxygen is a one phase two component
system.
4) Two miscible liquids is one phase two component system.
5) Two immiscible liquids- is two phase two component system.
6) An aqueous solution of a solid substance such as sodium chloride is a
one-phase two component system.
7) A saturated solution of a solid substance such as sodium chloride is a
two-phase two component system.
8) Dissociation of ammonium chloride in a closed vessel is a two-phase
one component system.
NH4Cl(s) NH3(g) + HCl(g)
The composition of both NH3 and HCl can be expressed in terms of
NH4Cl vapour.

ii) Two component :-
8) Decomposition of calcium carbonate.
CaCO3(s) CaO(s) + CO2(g)
It has three phases; solid CaCO3, solid CaO and gaseous CO2. The
composition of all the phases can be expressed in terms of any two (of
three) chemical substances in equilibrium.
9)Dissociation of copper sulphate is a two component system.
CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g)
Components are CuSO4 and H2O
10)Dissociation of ammonium chloride in a open vessel is a two-phase
two component system.
NH4Cl(s) x NH3(g) +y HCl(g)
The Components are NH4Cl and NH3 in excess or HCl in excess

6.5 Define DEGREES OF FREEDOM OR VARIANCE (F): 3 Marks
The number of degrees of freedom of a system is the minimum number of
independently variable factors, such as temperature, pressure and
composition which need to be fixed in order that the condition of a
system at equilibrium may be completely defined.
Eg. 1) Thus, the state of a pure gas can be specified by two variables,
pressure and temperature or pressure and volume. This means that a
pure gas has two degrees of freedom.
2) A system consisting of boiling water.
In this system, water (l) and steam (g) are in equilibrium and does not
have a composition variable since both water and steam contain
molecules of the same fixed formula, H2O. To define the system, it is
necessary to specify only the steam pressure because the temperature of
boiling is automatically fixed (or vice versa). Application of the phase rule
to the system gives,
P + F = C + 2; F = C- P+2: F = 1-2+2 = 1 i.e. either pressure or
temperature but not both.
A system with F = 1 is referred to as univariant or monovariant.
3) Ice(s) Water (l) Water vapour (g)
In the above system all the three phases are present in equilibrium.
All the three phases co-exist only at one particular temperature and
pressure. If variables like T or P is altered one of the phase disappears.
A system with F = 0 is known as invariant.
A system with F = 1 is referred to as univariant.
A system with F = 2 is called bivariant.

6.6 Calculate the number of components and degrees of freedom in
the following equilibria.
i). Na2SO4.10H2O (s) Na2SO4 (s) + 10H2O (g)
P = 3; C = 2; F = C-P +2 = 2-3 +2 =1
ii).N2 (g) + O2 (g) 2NO (g)
P = 1; C = 2; F = C-P +2 = 2-1 +2 =3
iii) N2O4 (g) 2NO2 (g)
P = 1; C = 1; F = C-P +2 = 1-1 +2 =2
iv) NH4Cl(s) NH3(g) + HCl(g), when pNH3 = pHCl
P =2; C = 2; F = C-P +2 = 1-2 +2 =1
v) Fe(s) + H2O(g) FeO (s)+ H2(g)
P= 3; C=3; F= C-P +2 = 3-3+2 = 2

6.7 Derive phase rule. 6 Marks
Gibbs phase rule is derived from the thermodynamic result
Consider a system with component number C is existing altogether in P
number of phases in equilibrium.
Total number of variables may be calculated as,

One variable Temperature- same for all phases.
One variable pressure - same for all phases .
Another variable concentration or composition is independent
variable.
For a system of one phase, the independent concentration variable in
respect of C components is C-1.
(The concentration variable is left over value).
For a system of P phases it is P (C-1) concentration or composition
terms must be specified in order to define the composition completely.
In addition to composition or concentration, the temperature and
pressure of the system which are the same in all phases must be known.
Therefore, the total number of independent variables which must be
specified is P (C-1)+2.
According to thermodynamics for a system in equilibrium at constant
temperature and pressure, the chemical potential () of any given
component has the same value in every phase.
In a system of phases at equilibrium, the total quantity of material in any
phase does not matter, it is the composition of the phase that is
important.( Eg., In a saturated solution of a pure solid, the composition
of the solution is independent of the total quantity of solution and
undissolved solid).
The chemical potential of any component is the same in all phases at
equilibrium according to equations:
1(a) = 1(b) = -------- = 1(P)
2(a) = 2(b) = -------- = 2(P)
C(a) = C(b) = -------- = C(P) for C components in P phases.

For one component this give rise to (P-1) restrictions for the P number of
phases.
For C component this give rise to C (P-1) restrictions for the P number of
phases.
(Chemical potential is a function of temperature, pressure and
concentration or composition.)
The number of variables remaining undetermined for the system at
equilibrium is given by
F=Total number of independent variables specified-The number of
variables defined.
F= [P(C-1) + 2] - [C(P-1)] = C-P + 2
In order to define the system completely, the number of variables must
be arbitrarily fixed and hence it must be equal to F.
Therefore, F = C-P + 2.

6.8 Explain the application of phase rule to one
component system 6 Marks
THE WATER SYSTEM:
Consider water system Ice (s) Water (l) Water vapour(g)
Water can exist in three possible phases, namely, solid ice, liquid water
and water vapour. Hence there can be three forms of equilibria,
1. Ice(s) Liquid water(l)
2. Ice(s) Water vapour(g)
3. Water(l) Water vapour(g)
The phase diagram or P-T graph for water system is obtained by plotting
the pressure against temperature. It consists of
i) Three areas, namely, COA, COB and AOB.
ii) Three curves, OA, OB and OC.
iii) One triple point,O.
A
A'
O
C
B
Ice
Water
Water vapor
0.006
atm
1 atm
0
100
Temperature
P
r
e
s
s
u
r
e
0.01
( C)
o

Curves:
In the phase diagram, the curve OA represents the vapour pressure
curve of liquid water. Along this curve two phases co-exist.
Water (l) Water vapour (g)
The point N on the curve OA indicates the B.P. of water is 100
o
C at 1
atms.pressure. Keeping pressure constant at 1 atms. rise in temperature
behind 100
o
C brings about a change in the phase from water to water
vapour along the line NH. And decrease in temperature below 100
o
C
reverse is the phase change. The curve OA terminates at A which is the
critical point (Critical pressure = 218 atms.pr. & Critical temperature =
374
o
C). Behind the critical point water phase merge into vapour phase.

The curve OB is known as sublimation curve and it shows the variation
of vapour pressure with temperature for the solid ice. The vapour

pressure increases with increase in temperature. Along this curve two
phases exist in equilibrium.
Ice (s) Water vapour (g)
The point B is a natural limit at -273
o
C, behind this point vapour phase
merge into ice.
The dotted curve OA
|

which is the continuous extension of OA is
obtained for water below
0
o
C. Liquid water may be cooled below its freezing point without
solidifying. This is called super cooling. The dotted curve OA
|
represents
the super cooled state of water. This curve represents a meta-stable
system.

The curve OC represents the melting curve of ice or freezing curve of
water. Along this curve two phases exist in equilibrium.
Ice (s) Water (l)
The slope of OC towards the pressure axis shows that the melting point
of ice is decreases by increase in pressure. It may be seen from the phase
diagram that the point M on the curve OC represents the freezing point
(0
o
C temperature & 1 atms.pr). Any increase in pressure on ice keeping
temperature constant ice melts into water along MK.

Along the curves OA, OB and OC two phases exist in equilibrium and the
number of component of the system is one. By applying the phase rule,
F = C - P + 2
F = 1 - 2- + 2
F = 1
It means that only one variable, either pressure or temperature is
sufficient to define the system. It implies that pressure is not freely
variable, if the temperature is set.
Thus each system is univariant.

Areas:
The phase diagram can be divided into three areas, COB, COA and AOB.
Each area contains one pure phase only as mentioned here under.
Area Phase
COB Ice
COA WATER
AOB Water vapour
Application of phase rule gives (P = 1; C = 1),
F = C-P+2; F = 1-1+2; F = 2
Thus each area of phase diagram represents a bivariant system. Both
the variables (temperature and pressure) can be varied independently
without changing the number of phases.
Thus each system namely ice, water & water vapour is bivariant system.

The phase rule predicts that both the variables T & P are necessary to
locate any point G in an area.

Triple point:
The three curves OA, OB & OC meet at point O, the point O is
called triple point. The triple point shows the conditions under which all
the three phases solid, liquid and vapour can exist in equilibrium.
Ice(s) Water (l) Water vapour (g)
At the triple point, P = 3, C =1 and F= C-P+2 = 1-3+2 = 0.

All the variables are fixed for this system at this point. If any of the
variables is altered, the equilibrium will be disturbed and one of the
phases will disappear. The triple point is fixed for water system. It occurs
at 0.01
o
C & 0.006 atms.pressure.
Thus the system is zero variant or invariant.
Application of phase rule to two component system

6.9 Explain Lead silver system: 6 Marks

Lead-silver system is a two component system. It is a solid / liquid
system.
Lead-silver system is a condensed system. A system in which only solid
and liquid phases are present with gaseous phase being absent is called
a condensed system. The degrees of freedom in such a case is calculated
by a reduced phase rule equation,
F = C-P+1.
The phase diagram for lead-silver system is obtained by plotting
temperature on Y-axis and
% composition on X-axis.

0% Pb 0 % Ag
Composition (%)
2.6% Ag
Solid Ag + Eutectic
Solid Pb
+ Eutectic
100 % Pb 100%Ag
Liquid +
Solid Pb
Liquid + Solid Ag
E
B
C D
303
961
Liquid Melt
327
A
T
e
m
p
e
r
a
t
u
r
e

(

C
)
o

The various features of the phase diagram or P-T graph are illustrated
here under.
The phase diagram consists of curves, areas and eutectic point.

Curves (OA & OB)
Pure lead melts at 327
o
C and the addition of silver lowers its freezing
point along AO. This is called freezing point curve for the lead. Along AO
the melting point of lead gradually falls on the addition of Ag till lowest
point O (303
o
C) is reached where liquid melt gets saturated with respect
to Ag and the melting point of Pb does not fall further. On cooling further
whole mass (Eutectic composition) crystallize out. Pure silver melts at
961
o
C and the addition of lead lowers its freezing point along BO and is
called freezing point curve of silver. This curve indicates that the melting
point of Ag falls gradually on adding Pb, along BO till the lowest point O
(303
o
C) is reached Where liquid melt gets saturated with respect to pb
and m.p. of Ag does not fall further .On cooling further whole mass
(eutectic composition) crystalize out.
The phase diagram has the following two curves.
Curve OA - Along this curve, solid lead and liquid mixture of Pb + Ag co-
exist i.e. P = 2.
Curve OB- Along this curve solid silver and liquid mixture of Ag +Pb co-
exist i.e. P = 2.
Applying reduced phase rule,
F = C-P+1
= 2-2+1
= 1

The systems solid Pb / liquid mixture of Pb + Ag and solid Ag / liquid
mixture of Ag +Pb are univariant systems. For a point on the line change
in either T or % composition changes the phase. On the other hand along
any of the line one variable T or % C is specified and the other is fixed
automatically.
Areas :
There are three areas in the phase diagram, namely, AOB, AOC and
BOD. The phases present in each of these are,
AOB - 1 (liquid melt)
AOC - 2 (solid Pb + liquid mixture of Pb + Ag)
BOD - 2 (solid Ag + liquid mixture of Ag +Pb)
Area AOB: By applying phase rule, we have
F = C-P+1 = 2-1+1 = 2.
It is necessary to specify the temperature as well as the % composition in
order to define any point in this area. This system (liquid melt) is a
bivariant system. Both T & % C are needed to locate any point in this
area AOB. Within this area when two variables are altered no change in
phase.

Area AOC and BOD: In the areas AOC and BOD, P = 2, C = 2
F = C-P+1 = 2-2+1 = 1.

The composition of each phase is fixed, each being a pure component
and so only one variable is the temperature. These systems have one
degree of freedom. These are invariant systems. To locate any point in
these areas either T or %C is needed.

Ex: If an alloy of Ag & Pb of %composition Z is heated to a point U &
cooled and no solid separates till it reaches a point V on the line BO. At V
pure Ag separates out which will be in equilibrium with the liquid melt of
Ag+Pb. If it is cooled further to a point Z more silver separates out along
VX. The %composition of the liquid melt at Z will be same as that at
point X on the line BO.
If T is known, the %C of the liquid melt in the areas AOC & BOD can be
known or vice-versa.

6.10 What is Eutectic point ? 2 Marks
At the point O, where the curves AO and BO meet, both the solids Pb and
Ag are in equilibrium with the liquid melt and is called the eutectic point.
The point O is the lowest temperature at which any liquid mixture of
silver and lead will freeze and consequently represent the lowest melting
point of any mixture of solid lead and solid silver.
At eutectic point,
F = C-P+1 = 2-3+1 = 0

This is a invariant system or Zero variant system
The variables, both temperature (303
o
C) and composition (97.4% Pb and
2.6% Ag) are fixed.
The eutectic mixture, although has a definite melting point, is not to be
regarded as a compound. A mixture containing two components which
are not miscible in the solid state is called a eutectic mixture. The
eutectic composition is 2.6% Ag & 97.4% Pb. The eutectic temperature is
303
o
C.

6.11 What is meant by Desilverisation of lead by
Pattinsons process? 4 Marks

The phase diagram of Pb-Ag has a special significance in the
desilverisation of lead. The argentiferrous lead contains a very small
percentage of silver (0.1%). The argentiferrous lead is first heated well
above the melting point of lead so that the system consists only of a
liquid phase which is represented by the point, p in the figure. The liquid
melt is allowed to cool. The temperature of the melt falls along pp. As the
temperature corresponding to p is reached on the curve AC, lead will
begin to solidify and the liquid will contain relatively higher silver.

.
Y
P'
P
A
327
Liquid Melt
961
303
D
C
B
E
Liquid + Solid Ag
Liquid +
Solid Pb
100 % Pb 100%Ag
Solid Pb
+
Eutectic
Solid Ag + Eutectic
2.6% Ag
% Ag 0% Pb
T
e
m
p
e
r
a
t
u
r
e

(

C
)
o

Lead continues to separate out and is removed constantly by means of
ladles. The melt continues to be richer and richer in silver until the point
Y is reached when the percentage of silver rises to 2.6. Thus the original

argentiferrous lead which contains 0.1% silver now contains about 2.6%
silver. The process of raising the relative proportion of silver in
argentiferrous lead is known as Pattinsons process

Instrumental Methods of Analysis.

6.12 What is Instrumental Methods of Analysis . 3 Marks

It is one of the quantitative analysis methods of a compound.
An instrument is used for chemical analysis, converts the property of a
substance which is under investigation in to form that can be readily
measured. The measured quantity is related to the quantity or quality of
the sample
The analysis may contain different steps such as generation of
signals, transformation of signals, amplification and presentation of
signals by displaying on a recorder or read out.

6.13 What are the advantages of Instrumental methods?
2 Marks
1. These methods are faster than chemical methods.
2. These methods requires only small quantities of the sample
3. Easy when a large number of samples have to be analyzed
4. These methods are Accurate.
5. The analytical process can be automated

6.14 Explain the instrumentation and theory of Potentiometric
Titrations.
8 Marks
Instrumentation.
Potentiometer consists of a reference electrode, an indicator
electrode & a potential measuring device. The indicator electrode
responds rapidly to the changes in the concentration of the analyte i.e.
the solution under study. A simple arrangement of Potentiometric
titration is depicted in diagram. A is a reference electrode, B is the
indicator electrode & C is a mechanical stirrer. The solution to be titrated
is taken in the beaker.

A known volume of analyte is taken & its potential is
determined. The titrant is added in increment of 1ml & the emf is
measured each time. At the approach of equivalence point, the emf tends
to increase rapidly. At this point, small increments, say, 0.1ml of titrant
are added. A few readings are taken beyond the end point. Thus the
changes in potential at different volumes of titrant are recorded.


Theory: Redox titrations can be carried out potentiometrically using
platinum- calomel electrode combination in a manner similar to acid-
base neutralizations. For the reaction.

Reduced from oxidized form + n electrons

The potential is given by Nernst equation.

Where E
o
is the standard potential of the system. The potential of the
system is thus controlled by the ratio of the concentration of the oxidized
to that of the reduced species in the vicinity of the end point of the
titration. This may be followed potentiometrically and a change of
potential against volume (titration curve) is characterized by a sudden
change of potential at the equivalence point. The sudden change in the
potential at the equivalence point is explained as follows. The reaction
that takes place in the determination of Fe
2+
is
Fe
2+
Fe
3+
+ e
Cr2O7
2-
+ 14H
+
+ 6e 2Cr
3+
+ 7H2O
Prior to the equivalence point the potential is determined by the
Fe
3+
/Fe
2+
system and the potential is given by the equation.

The potential of the solution will be around 0.75V (since the contribution
to the potential by the second term is negligible). At the equivalence point
the potential is determined by both E
and E
o
is given by

E
0
Fe
2+
+ E
0
Cr2O7
2-
0.75V + 1.33V
Ecell = = = 1.04 V
2 2
Beyond the equivalence point the potential is determined by Cr2O7
2-
/
Cr
3+
system given by the equation.
0.0591 [Cr2O7
2-
]
Ecell = Ecr2 = E
0
Cr2O7
2-
/ Cr
3+
+ log
6 [Cr
3+
]


0.0591 [Cr2O7
2-
]
= 1.33V + log
6 [Cr
3+
]

Thus an abrupt increase in the potential of the solution in the vicinity of
the equivalence point is observed. This makes the equivalence point in
the experiment, the potential of the cell is determined with reference to
saturated calomel electrode.
PROCEDURE:
Pipette out 25 cm
3
of ferrous ammonium sulphate solution into a
beaker. Add one test tube full of dilute sulphuric acid. Immerse the
electrode assembly into the solution in the beaker and connect the
electrodes to a potentiometer. Measure the potential. Fill the burette with
potassium dichromate solution. Add 0.5 cm
3
of K2Cr2O7 to the beaker.
Blow the solution carefully using a glass tube and measure the potential
after 15 seconds. Continue the procedure till potential shows a tendency
to increase rapidly. Determine the end point by differential method i.e.,
by plotting
E against volume (V) as shown in the figure.
V
Calculate the normality of the ferrous ammonium sulphate solution and
determine the amount of iron in the given solution.

Advantages.
1. Turbid, fluorescent, opaque or colored solutions can be titrated.
2. Mixture of solutions or very dilute solutions can be titrated.
3. The results are more accurate because the actual end point is
determined graphically.


6.15 Explain the instrumentation and theory of Conductometric
estimation. 8 Marks

Theory and Instrumentation.
Measurement of conductance can be employed to determine the end
point in acid-base titrations. In conduct metric titrations there is a
sudden increase in conductance of the solution at equivalence point. The
principle underlying conductometric titrations is the substitutions of ions
by other ions of different mobility. Therefore, the conductance of a
solution depends on the number and mobility of ions. The equivalence
point is determined graphically by plotting conductance (ordinate)
against titer values (abscissa). From the equivalence point the
concentration of analyte can be determined.
Conductometer consists of a conductivity cell& a conductance
measuring device. The cell has 2 platinum electrodes placed at unit
distance apart. The assembly responds rapidly to the changes in the
concentration of the analyte. The simple arrangement of conductometric
titration is represented as follows.

Advantages of conductometric titrations
1) Mixture of acids can be titrated more accurately.
2) Colored solutions can be titrated.
3) Very weak acids such as H3 PO3, phenol, which cannot be titrated
potentiometrically in aqua solutions can be titrated conduct metric.


Applications
a) Titration of strong acid v/s strong base

Conduct metric titration may be applied for the determination of acid
present in a. In the titration of a mixture of a weak acid (CH3 COOH) and
strong acid (HCl) with a strong base (NaOH), the conductance decreases
upon adding NaOH to acid mixture owing to the substitution of highly
mobile H
+
ions of HCl replaced i.e., the strong acid is neutralized.
Continued the addition of NaOH raises the conductance moderately, as
the weak acid (CH3COOH) is converted into its salt (CH3COONa).
Further, addition of NaOH raises the conductance steeply due to the
presence of OH
-
ions (mobility: 198 ohm
-1
). The titration curves in the
graph given determine the location of the equivalence points.

Estimation of HCL
Pipette out 25 cm
3
of the given acid into a clean 100 cm
3
beaker.
Dip the conductivity cell in the solution and note down the conductance
of the solution i.e., when the volume of NaOH added is zero. Now added
standard NaOH solution from the burette in increments of 0.5 cm
3
. After
each addition, stir the solution gently and note down the conductance.
As the titration proceeds, the conductance first gradually decreases and
then rises sharply. Continue until the conductance is more or less same
as it was in the beginning. Plot a graph of conductance on y- axis versus
volume of NaOH on X- axis to get two straight lines. The point of
intersection of the two lines gives the volume of NaOH required to
neutralize only HCl. (after drawing a perpendicular lines to x- axis).

CALCULATION: Estimation of HCL

Volume of NaOH required to neutralize HCI V1 = cm
3

Normality of HCL = Normality of NaOH x volume of NaOH
25 cm
3

= 0.5 x --------
25

= -------N
Therefore, the weight of HCL/dm
3
= Normality x Eq. wt. of HCL (36.5)

= ..x 36.5

= ..g/ dm
3

6.16 Explain the Colorimetric estimation of copper.
8 Marks
PRINCIPLE: When a monochromatic light of intensity I0 is incident on a
transparent medium, apart Ia of it is absorbed, apart Ir is reflected and
the remaining part It is transmitted.
Io = Ia + Ir + It
For a glass- air interface Ir is negligible. Therefore,
Io = Ia + It
It/Io = T called the transmittance log 1/T = log Io/It is called the
absorbance or optical density A. The relation between absorbance A,
concentration c (Expressed in mol/liter)
And path length 1 (expressed in cm) is given by Beer Lamberts law.
A = log Io/It = Ct
Where C is the molar extinction coefficient, t is the path length. is a
constant for a given substance at a given wavelength. If t- the path
length is kept constant, then A C. hence a plot of absorbance against
concentration gives a straight line.
A series of standard solutions of copper is treated with ammonia to get
blue cuprammonium complex and is diluted to a definite volume. The
absorbance of each of these solutions is measured at 620 nm since the
complex shows maximum absorbance at this wavelength. The
absorbance values are plotted against volume of copper sulphate (cm3) to
get a calibration curve.
A known volume of the test solution is treated with strong ammonia
and diluted to the same volume as above. The absorbance of this
solution at 620 nm is measured and its concentration is determined from
the calibration curve.

PROCEDURE:
Transfer the given copper sulphate solution (stock solution) to a burette
and draw out 2.5, 5.0, 7.5, 10.0 and 12.5 cm
3
of the solution into 25 cm
3

volumetric flasks. Add 2.5 cm
3
of ammonia solution to each of them and
dilute up to the mark with ion exchange water. Stopper the flasks and
mix the solutions well. To the test solution given in a 25 cm
3
volumetric
flask, add 2.5 cm
3
ammonia solutions and then dilute up to the mark.
Mix well, prepare a blank solution by diluting 2.5 cm
3
of ammonia
solution in a 25 cm
3
volumetric flask up to the mark with ion exchange
water and mix well. Measure the absorbance of the solutions against
blank at 620 nm using photoelectric colorimeter. Tabulate the reading.
Draw a calibration curve by plotting optical density (OD) against volume
of copper sulphate (cm
3
). Using the calibration curve find out the
concentration of copper in the test solution and calculate the amount of
copper in 25 cm
3
of the given solution.

Applications.
A colometric method may frequently be applied where no satisfactory
gravimetric or titrimetric procedure exists i.e., for certain biological
substances. .. .

6.17Explain the instrumentation and theory of Flame photometric
Estimation
Principle: Sodium, Potassium, Calcium and Lithium and other common
elements impart characteristic colors with the Bunsen flame. The
intensity of the colored flame varies with the amount element introduced.
This forms the basis of the flame photometry. When a solution
containing a compound of the metal to be investigated is aspirated into a
flame,
The following process occurs.
i) Solvent evaporates leaving behind a solid residue.
ii) Vaporizations of the solid coupled with dissociation into its
constituents atoms which are initially in the ground state.

iii) Some gaseous atoms get excited by the thermal energy of the
flame to higher energy levels.
The excited atoms which are unstable quickly emit photons and return to
lower energy state i.e, ground state. Flame photometry involves the
measurement of emitted radiation.
The relation ship between ground state and excited state populations is
given by the Boltzmann equation
N1/N0 = (g1/g0) e
E/KT

N1= Number of atoms in the excited state; N0 = Number of atoms present
in the ground state.
g1/g0 = Ratio of statistical weight weights for ground and excited states;
E = Energy of excitation = hv
K = The Boltzman constant; T = Absolute Temperature.
From the above equation, it is evident that the ratio N1/N0 is dependent
upon both the excitation energy E and the temperature T. An increase in
temperature and a decrease in E will both result in a higher value for
the ratio N1/N0.
Instrumentation of flame photometry:
Air, at a given pressure is passed into an atomizer and the suction
thus produced draws solution of the sample into the atomizer where it
joins the air stream in the form of a fine mist and passes into the burner
system. Here the air meets the fuel gas supplied under pressure in a
small mixing chamber and the mixture is burnt in the burner. The
radiations resulting from the flame pass through an optical filter which
permits only the radiations characteristic of the element under the
investigation to pass through the photocell. The output from the
photocell is measured on a digital read-out system.
A calibration curve has to be plotted, first using solution of known
concentrations. This is done by aspirating into the flame known
concentrations of the element to be determined, measuring the respective
readings and plotting them against the respective concentrations of the
standard solutions used.

Estimation of sodium:
Procedure:
1. Transfer 2, 4, 6, 8, 10 ml of standard NaCl solution in to 50 ml
standard volumetric
flasks and dilute up to the mark with distilled water.
2. Set the instrument to read Zero by placing te distilled water in the
suction capillary of
the instrument. (Using sodium filter (598 nm))
3. Read the flame emission intensity 2, 4, 6, 8, 10 solutions by placing
solutions in the
suction capillary of the instrument. (Rinse with distilled water between
each reading)
4. Dilute the given test solution up to the mark and shake well and read
the flame
emission intensity solution as above.
5. Draw a calibration curve by plotting the emission intensity (Y-axis)
and volume of
NaCl solution (X-axis).
6. From the calibration curve, find out the volume of the given test
solution and from
which calculate the amount of Na in the water sample.

1) Phase rule is the basis of separation procedures in the
a)petroleum industry and cosmetic preparations.
b) Cotton industry & Rayon industry
c) Pharmaceutical industry
d) None of the above

2) At the point O, where the two curves meet in the phase diagram.
a) Eutectic point b) Triple point c) Double point d) All

3) The argentiferrous lead contains a very small percentage of
a) Gold b) Diamond c) copper d) silver

4) Condensed system consists of
a) only solid and liquid phases b) only liquid and gaseous phase
c) only Solid and gaseous phases d) Solid, liquid & Gaseous phase

5) super cooling is
a) Liquid water may be cooled below its freezing point without
solidifying.
b) solid water may be heated to evaporation.
c) Liquid water may be cooled to freezing point for solidification.
d) All of the above.

6) The triple point for water system occurs at
a)) 0.001 0C & 0.006 atms.pressure b) 0.01
o
C & 0.006 atms.pressure
c) 1
o
C & 0.006 atms.pressure d) b) 0.01
o
C & 0.006 atms.pressure

7) In the estimation of FAS by potentiometry the indicator electrode used
is
a) Silver Silver Chloride electrode b) Platinum electrode
c) Calomel electrode d) Glass electrode

8) Measurement of optical density using monochromatic light in
calorimery involves
a) IR range b) Visible range
c) UV range d) All

9 Ion selective electrode used in the determination of pH is
a) Silver Silver Chloride electrode b) None of the above
c) Calomel electrode d) Glass electrode

10) Instrumental methods of analysis are widely adopted when compare
to classical methods of analysis because
a) The methods are much faster b) Applicable at concentrations
c) the analytical process can be automated d) All

11) Colorimetry involves measurement of absorbance using
monochromatic light in the
a) UV range b) IR range c) Visible range d) All

12) Flame photometry is suitable for the detection of
a) Li b) Cu c) Fe d) Zn

13) For photometric titrations the analyte should
a) Have different oxidation state b) Conduct electricity
c) Ionize d) All

14) For potentiometric titration, the analyte should
a) have different oxidation states b) conduct electricity c) ionize d) all

REVIEW QUESTIONS
1. what is phase diagram?
2. what is Gibbs Phase Rule? Explain the terms.
3. Define Phase.
4. Define Component.
5. Define Degrees of freedom OR variance.
6. Derive phase rule.
7. Explain the application of phase rule to one
component system
8. Explain Lead silver system:
9. What is Eutectic point ?
10. What is meant by Desilverisation of lead by Pattinsons process?
11 What is Instrumental Methods of Analysis ?
12 Explain the instrumentation and theory of Potentiometric
Titrations.
13 Explain the instrumentation and theory of Conductometric
estimation.
14 Explain the Colorimetric estimation of copper.
15.Explain the instrumentation and theory of Flame photometer

UNIT UNIT UNIT UNIT VII VII VII VII

HIGH POLYMERS

7.1 What are Polymers? Explain the Classification of polymers with
examples 5 Marks
Polymers are the high molecular weight compounds obtained by
repeated union of simple molecules. (Monomers).

Ex: Starch, Polyvinyl chloride, Polyethylene, Nylon 6, 6 and etc.

Classification of polymers.

Polymers are classified into two types as follows:
i) Natural Polymers.
ii) Synthetic (artificial) polymers.
i) Natural polymers: These are the polymers obtained naturally by
plants and animals.
Ex: Silk, wool, natural rubber, protein, starch, cellulose, etc.

ii) Synthetic Polymers: These are artificially prepared polymers also
known as man made polymers.
Ex: PVC, Nylon 6.6, Polythene, Phenol, Formaldehyde, Resin etc.,

7.2 What are Monomers? Give examples
2 Marks
Monomer is a simple repetitive unit which when joined together in
large numbers which give rise to a polymer. These are the building
blocks of Polymer
Ex: Vinyl chloride, ethene, propylene etc.

7.3 What is Polymerization? Explain the types with examples
5 Marks
Polymerization is a process of chemical union of large number of
monomers to form a polymer. During polymerization the monomers are
linked through covalent leakages to give raise to polymer.
Based on the type of polymerization reaction, it is classified into
two types as follows.

i) Addition Polymerization
ii) Condensation Polymerization

i) Addition Polymerization: It is process in which the monomers
undergo simple addition reactions to give raise to a polymer without
eliminating by products. Alkenes and substituted alkenes readily
undergo addition polymerization reactions.
Ex: When large number of ethene molecules undergoes addition
polymerization reactions, polyethylene polymer is obtained.

ii) Condensation Polymerization:- It is a process in which the
monomers undergoes intermolecular condensation reactions to form a
polymer with the elimination of simple molecules like water, HCl,
ammonia, phenol etc.,
Ex: When adepic acid and hexamithylene diamine undergoes
condensation polymerization reaction to form Nylon 6,6 polymer.

n.NH2(CH2)6-NH2+ n.HOOC(CH2)4COOH
Hexa methylene di amine Adipic acid

(NH (CH2)6- NH -OC (CH2)4 CO-)n + n H2O
Nylon 6,6

7.4 What is degree of polemerization (DP). 2 Marks

Degree of polymerization is a number, which indicates the number
of repetitive units (monomers) present in the polymer. By knowing the
value of DP, the molecular weight of the polymer can be calculated.

[Molecular wt of the polymer] = DP x Molecular wt of each monomer.
DP is represented as n.

Ex: (CH2 CH2) n
Polythene
Here n is the DP.

i) Calculate the molecular weight of the polythene polymer given DP is
100.
Molecular weight of the polythene = DP X Molecular weight of
Polethene
= 100 X 28

= 2800.

7.5 Explain the free radical mechanism addition polymerization by

taking ethylene as example
6 Marks
The free radical mechanism polymerization of ethylene involves the
following three steps
i) Initiation
ii) Propagation
iii) Termination

i) Initiation: When the initiators are heated or exposed to sunlight, they
undergo hemolytic decomposition forming highly reactive species known
as free radicals. The free radical attacks the double bond of the monomer
and initiates the chain reaction.
Example: when dibenzoyl peroxide initiators are heated or exposed to
sunlight, they produces phenyl free radicals, which attacks the ethylene
monomer and converts it into reactive monomer. the reactive monomer
again reacts with another monomer and chain growth is initiated.

(C6H5COO) 2 2 C6H5* + 2CO2
Dibenzoyl peroxide phenyl free radical

CH2=CH2 + C6H5* C6H5 - CH2 - CH2*
Ethylene Reactive monomer
Monomer

ii) Propagation: The reactive monomer again reacts with another
unsaturated monomer and converts it into reactive monomer and growth
of the polymer chain continues.

C6H5 - CH2 - CH2* + CH2=CH2 C6H5 - CH2 - CH2 - CH2 - CH2*
Reactive monomer Ethylene growing polymer chain

iii) Termination: Termination growing polymer chain occurs by any one
of the following reaction.

a) Coupling of two growing polymer chain
When two growing polymer chains react with each other
termination occurs due to the formation of a dead polymer chain.

C6H5 - CH2 - CH2 - CH2 - CH2* + *CH2 - CH2 - CH2 - CH2 C6H5
growing polymer chain growing polymer chain

C6H5 - CH2 - CH2 - CH2 - CH2 CH2 - CH2 - CH2 - CH2 C6H5
Dead polymer chain

b) Coupling of one growing polymer chain with free radical
When one growing polymer chains reacts with a free radical,
termination occurs due to the formation of a dead polymer chain.
C6H5 -CH2 - CH2 - CH2 - CH2* + C6H5* C6H5 - CH2 - CH2 - CH2 -CH2- C6H5
Growing polymer chain Dead polymer chain

7.6 Explain the Methods of polymerization.
6 Marks
Polymerization is brought about by the following methods.
i) Bulk polymerization.
ii) Solution polymerization.
iii) Suspension polymerization.
iv) Emulsion polymerization.

i) Bulk polymerization: This method is used for liquid monomers. The
initiators are dissolved in the liquid monomers and form a homogeneous
phase. Heating or exposing to the sunlight initiates the polymerization
reaction. The reaction is exothermic and viscosity of medium increases
as the reaction proceeds. The reaction mixture is stirred constantly to
dissipate the heat liberated.

Advantages:
The method is simple.
The products dont require purification or isolation.
The products have high optical clarity.
The purity of the products is high

Disadvantages
Agitation becomes difficult due to viscosity build up
The heat control is more difficult

Applications: The method is used for making polymers such as PVC,
PMMA, and PS etc.

ii) Solution polymerization: This method is used for monomers &
initiators dissolved in a suitable inert solvent. The inert solvent reduces
the viscosity build up during the reaction progress & facilitates heat &
mass transfer. In this method the obtained polymer can be easily
separated from the solvent by evaporating the solution or it can be
directly used for coating & adhesive purposes.

Advantages:

Viscosity produced in the reaction is negligible.
Better heat transfer can be achieved.
In solution face the polymer can be directly used as paintings,
coating, & adhesive. Purposes
This method is used for preparation of polythene, pvc,
polyacrylonitrile, etc.,

iii) Suspension Polymerization Method (Pearl Polymerization
method):
In this method water in soluble monomers are suspended in water
as tiny droplets by continuously agitating (shaking). Initiators are soluble
in monomers. Monomers and initiator forms heterogeneous mixture with
the water. Polymerization is initiator by heating or exposing to radiation.
The polymerization takes place within the tiny droplets the polymer is
obtained as spherical pearls or beads hence it is also called as pearl
polymerization methods. Since the product is insoluble in water. It can
be easily separated just by filtration & the product needs no further
purification.

Advantages:
Viscosity build up is negligible
High purity product is obtained.
Isolation of the product is easy and it does not require any
purification.

Uses: This method is used for preparing PVC, PVA (Polyvinyl acetate),
styrene, divinyl benzene (ion exchanger)

iv) Emulsion Polymerization method: In this method the monomers &
water soluble initiators forms the emulsion with water. The surfactants
such as soap, detergents, etc are add which hold the monomers &
initiators (H2O2 or per sulphate) in the form of a micelles. Polymerization
takes place inside the micelle on exposing to heat or radiation. Filtration
& deemulsifying agents can isolate the obtained polymer.

Advantages:
The rate of polymerization is high
Viscosity build up is negligible
High purity product is obtained
Isolation is easy.
This method is used to prepare PVC, adhesive etc.,

7.7 What is Glass transition temperature? Mention the factors
which affecting the Tg of a polymer 6 Marks
When an amorphous polymer is heated, it gets converted from
hard brittle state (glassy state) to a soft flexible state (rubbery state). The
temperature at which a polymer transforms from a hard glassy state to
soft rubbery state is called glass transition temperature.

Glass State viscoelastic state Viscofluid state
(Hard & brittle) (Rubbery) (Polymer melt)
Tg Tm
Significance of Tg :
It is used as a measure for evaluating the flexibility of a polymer
and the type of response the polymeric material would exhibit to
Tg is very useful in choosing the right processing temperature for
fabrication (moulding, calendaring and extrusion )
Tg is very useful in determining the coefficient of thermal
expansion, heat resistant, refractive index, electrical property, etc.,
Factors affecting glass transition temperature

1. Chain Flexibility: Linear polymer chains have high degree of freedom
for rotation ie., more chain flexibility and low Tg.
Aromatic or cyclic groups on the back bone of carbon atoms hinder the
freedom of rotation ie., chain flexibility decreases and causes an increase
in Tg.
2. Cross-linking and branching: A small amount of branching will tend
to lower Tg and a high density of branching reduces chain mobility and
elevates the Tg.
The cross linking brings the polymer chain closer, lowers free
volume and restricts molecular motion and hence rises Tg.
3. Intermolecular forces: The presence of large number of polar groups
in the molecules lead to strong intermolecular cohesive forces which
restrict the segmental motion. As a result Tg increases.
4. Molecular mass: Higher the molecular mass more is the restriction in
the molecular freedom. However, Tg is not significantly affected by
molecular masses if the degree of polymerization is above 25o;
5. Presence of plasticizers: Addition of plasticizers reduces the Tg vale;
for example, addition of di-isooctyl phthalate to pvc reduces its Tg from
80
o
C to below room temperature.
5. Stereo regularity of the polymer: A syndiotactic polymer has a
higher Tg than atactic polymer, which in turn has higher Tg than its
isotactic stereoisomer.

7.8 Explain relationship between structure and property of a polymer

6 Marks
A polymer should have the following property, which depends
mainly on the structure of the polymers.
1. Tensile strength : A polymer should have more tensile strength it
depends on
a. Molecular weight of the polymer: Low molecular weight polymers
are soft gummy, & less resistant to heat. But high molecular weights of
the polymers are tough & resistant to heat.
b. Structure of the polymer: Cross linked & branched polymers are
stronger than linear less branched polymers

2. Crystalinity: A polymer would have high degree of crystalinity, which
have more melting point more tensile strength & resistance to heat. The
degree of crystalinity depends on
a. Structure of polymers: Linear polymers without bulky groups &
hydrogen bounding are more crystalline than branched & polymers have
bulky groups.
Ex: HDPE High density polyethylene has high degree crystalinity than
polyvinylactetate.
b. Configuration of the polymer: Isotactic Polymers are more crystalline
than atactic polymers.
Ex; Isotactic polyvinyl chloride is more crystalline than Atactic polyvinyl
Chloride (random arrangements of groups)

Isotactic Polystyrene Atactic Polystyrene

c. It also depends on polar groups & hydrogen bonding for those
Polymers having polar groups & hydrogen bonding have high degree of
crystaslinity.

3. Elasticity: A polymers should have good elastic property. The
elasticity is due to uncoiling & recoiling of the molecular chain on the
application of force. It should not break on prolonged stretching. The
elasticity of a polymer can be improved.
a. By introducing cross linkages at suitable positions.
b. Avoiding side group such as aromatic and cyclic structures.
c. By introducing more non polar groups on the chain so that
the chain does not separate on stretching.
d. By introducing internal plasticizers during polymerization.

4. Chemical. Resistance: Polymer should have more resistivity to
chemical attack and should not become soft, swelling, or loosing its
strength. The chemical resitivity of a polymer depends on mainly.
a. Presence of polar & non polar groups in the polymer chain:
Presence of polar groups such as OH, -COOH, are less resistance to
chemical attack. But non-polar groups such as CH3, -C6H5, NHCO, etc.,
are not usually attacked by chemicals.
Ex: PVC, ABS, PS, etc., have high resistance towards chemicals.
b. Degree of crystalinity & Molecular mass: Chemical resistance
increases with increase in degree of crystalinity because crystalline
regions make the penetration of chemicals or solvent more difficult.
Higher the degree of crystalinity higher is the chemical resistance.

7.9 What are resins? Give examples 2 Marks
Resins are linear, low molecular weight polymeric materials. These
further undergo polymerization and cross linking during curing to form
hard and rigid three dimensional networks. These resins are used as
coatings, adhesives and molding powders.
Ex: Epoxy resin
Phenol-formaldehyde resin
Urea - formaldehyde resin
Polyester resin

7.10 What are plastics? Give examples 2 Marks
Plastics are linear, high molecular weight polymeric materials, which can
be molded by the application of heat and pressure. During the process of
molding, these become hard but retain plasticity.
Ex: Polyethylene
Polystyrene
Poly vinyl chloride etc.

7.11 Explain compounding of resin. 6 Marks
The process of mechanical mixing of various additives to resins and
converting resins in to plastics is called as compounding of resin. The
important additives used in compounding are as follows
i) Fillers
ii) Plasticizers
iii) Stabilizers
iv) Colorants

i) Fillers: These are organic or inorganic compounds added during
compounding to increase the bulk of the polymer. The fillers also
enhance the tensile strength, impact resistance and abrasion resistance.
Ex: Wood, mica, clay, silica, talk, fabric scraps, glass fibers, carbon

black, polyesters etc,

ii) Plasticizers
Plasticizers are the substances, which are added during compounding to
increase the plasticity of a polymer. These decrease the Tg and helps in
converting a hard, brittle polymer into a soft, flexible polymer.
Ex: Tricrysyl phosphate, Tri phenyl phosphate, dioctyl phthalate, fatty
acids etc,

iii) Stabilizers
Polymers have tendency to undergo degradation by air and light. The
Stabilizers are added to minimize the degradation of polymers.
Ex: Phenyl salicylate, aryl and alkyl phosphates, tri phenyl phosphates.

iv) Colorants
These are added to impart required color to the polymer. These increases
the attractive and decorativeness of a polymer. The colorants include
organic and inorganic pigments.
Ex: Titanium oxide, lead chromate, BaSo4, carbon black, azo dyes etc,

7.12 Plastic Manufacturing Methods
Plastics are made into shapes in many ways:
1. EXTRUSION
Hot molten plastic is squeezed through a nozzle to make long lengths of
special shapes like pipes, spouting and wallboard joining strips. It is also
used to make large thick sheets of plastic for fabrication.
2. BLOW EXTRUSION (Fig 1)
This is used for making plastic films and bags. While it is still hot, an
extruded tube is blown up like a balloon, with compressed air. This
stretches the plastic and makes it thin. The balloon is made long enough
to allow the plastic to cool. The end of the balloon is pinched together by
rollers, to hold the air in and make it flat. The flat tube is then wound on
to a big roll. You can see continuous rolls of plastic bags in a fruit shop.

3. INJECTION MOULDING
Hot molten plastic is squeezed into a mould to make lots of objects all
the same. They can be very small like a washer or quite large, like a bowl
or a clothes basket. Lots of everyday articles are made this way.
4. BLOW MOULDING (Fig 2)
A little bit of hot soft plastic is squeezed into the end of a mould.
Compressed air is used to blow a big bubble inside the plastic. The
plastic swells out like a balloon until it fills up the whole mould. Many
bottles, toys and money boxes are made this way.

5. ROTATIONAL MOULDING
Plastic powder is scooped into a mould. The mould is rotated over a big
gas burner. As the mould gets hot, the plastic melts and sticks to the
mould. This method is used for making big hollow things like water
tanks and barrels.
6. COMPRESSION MOULDING
This is used for thermoset resins. Dry powder is put in a mould which is
squeezed and heated until the plastic is cured. This is used for making
ashtrays, cups and plates, and some electrical switches.
7. REACTION INJECTION MOULDING

Two chemicals are mixed together and squirted into a mould. The
chemicals react together. This is how they make car bumpers, some
disposable cups and plates, and the meat trays you get from
supermarkets.

7.13 Give the manufacture and applications of Teflon. 4 Marks
Teflon is the trade name of poly tetra fluro ethylene. The monomers
for the preparation of Teflon are tetra fluro ethylene Teflon is prepared by
emulsion polymerization method using ammonium persulfate as
initiators under pressure.
persulfate initiators
n. CF2=CF2 (-CF2-CF2-) n
Tetrafloroethylene Polytetrafloroethylene

Properties:
a. It has density about 2.3 gram/cm
3

b. It has high melting point 320
0
C
c. It has nonstick property & slippery over wide range of temperature.
d. It has got good electric insulating property.

Uses:
It is used for insulating motors, cables, and generators transformers,
capacitors.
Used for nonstick cooking utensils
Used for gaskets, belts pump and valves packing etc.
Used as a dry lubricant.

7.14 Give the manufacture and applications of Poly methyl
methacrylate PMMA (Plexi Glass) 4 Marks

Plexi glass is the trade name of polymethyl methacrylate. The
monomers used for the preparation of plexi glass are methyl
methacrylate. Plexi glass is prepared by emulsion polymerization method
at 60 to 70c in presence of trace of H2O2 or Acetyl peroxide as initiator.


Properties:
i. Plexi glass is a white transparent thermoplastic
ii. It has got high optical clarity
iii. It is resistant to chemical action
Applications:
i. It is used in the preparation of aircraft windows.
ii. Attractive sign boards.
iii. Manufacturing of transparent moulded articles & tubes.
iv. Lenses for automobiles, artificial eyes etc.,

7.15 Give the manufacture and applications of Polyurethanes.
4 Marks
Ployurethanes are produced by the polymerization of disocyanate
and diol or triol (or the addition reaction between 2, 4-tolylene
diisocyanate with glycol). In the production of polyurethanes foams,
glycol, toylene diisocyanate, catalyst tertiary amines), water and
surfactants are mixed together and heated.

Properties:
i. These can be obtained in the form of foams, fibers, Elastomers,
Coatings etc.
ii. The foams are available in both rigid & flexible forms.
Uses:
i. Flexible foams are used for cushions in automobiles & furniture.
ii. Rigid foams are used to reinforce hallow structural units.
iii. Fibers of Polyurethanes are used in lightweight garments and swim
suits because of their stretching property.
iv. These are used to coat gymnasium floor and dance floor.
v. These are used in tyre treads and industrial wheels.

7.16 Give the manufacture and applications of Phenol Formaldehyde
Resins.
6 Marks
Phenol formaldehyde resins are prepared from condensation
reaction between phenol & formaldehyde. Commercially these are
available into two forms nova lacks & resols..

i) Nova lacks.

These are phenol formaldehyde resins obtained by condensation of
phenol & formaldehyde in presence of acid as catalyst when phenol to
formaldehyde ratio is greater than one

Properties:
i. Nova lacks are linear polymers.
ii. These have got good electric insulating property
Uses:
i. Used for sealing metal holders to the glass bulbs.
ii. Bounding sheets of paper, wood, card boards etc.,
ii) Resol Resins.

These are phenol formaldehyde resins obtained by the
condensation of phenol & formaldehyde. In presence of alkali as catalyst
when phenol to formaldehyde ratio is less than one.

Properties.
i. These are cross linked polymers
ii. These are non conductor of electricity
iii. Resols can be converted into bakelite by adding additives
such as wood, dies etc.,

Uses.
i) Resol in the form of bakelite is used for the preparation of electrical
fittings such as switches plugs, sockets, etc.
ii) It is also used for preparing telephone out parts etc.

7.17 What are elastomers? Give examples. 2 Marks
These are the high polymers which undergoes very long elongation
when they are subjected to an external force and readily regains their
original shape when stress is released ( when external force is removed).
Ex: Rubber.

7.18 Mention the advantages of Synthetic Rubbers over natural
rubber. 5 Marks
i. These are more resistance to heat & cold ( nitrile rubber)
ii. These are not easily attacked by sunlight & air ( neoprene and nitrile
rubber)
iii. These have high abrasion and high tensile strength.
iv. Rubber property is retained at high temperatures (ex: silicon rubbers-
90
0
- 316
0
c)
v. Do not age easily (ex; Polyurethane rubber)
vi. Do not swell and can hold organic solvent better than natural rubber
(ex; polysulphide rubber)
vii. Hold more air and water at high pressures (ex; butyl rubber)

7.19 What is Vulcanization of rubber
Vulcanization or vulcanisation is a chemical process for converting
rubber or related polymers into more durable materials via the addition
of sulfur or other equivalent "curatives". These additives modify the
polymer by forming crosslinks (bridges) between individual polymer
chains.
[1]
The vulcanized material is less sticky and has superior
mechanical properties

7.20 Give the manufacture and applications of Neoprene rubber
4 Marks

Poly propylene (Neoprene) is produced by the polymerization of
chloroprene units by Emulsion polymerization method.

Uses: It is used for hoses, tubes for carrying oils and chemicals, gloves,
coated fabric, cables, belts, shoe heels, solid tyres,

7.21 Give the manufacture and applications of Butyl rubber.
4 Marks
Butyl rubber is prepared by copolymerization of isoprene (2-methyl 1,3
Butadiene) Isobutylene by emulsion polymerization method at 90
0
C.

Uses.
i. Butyl rubber is widely used for preparation of inner tubes for
tiers.
ii.It is also used for insulating high voltage wires & cables.

7.22 Silicone rubber:
Synthesis: Silicone rubber is a rubber-like material composed of silicone
itself a polymer containing silicon together with carbon, hydrogen,
and oxygen. During manufacture heat is required to vulcanize (set or
cure) the silicone into its rubber-like form. This is normally carried out in
a two stage process at the point of manufacture into the desired shape,
and then in a prolonged post-cure process. It can also be injection
molded.


Properties: Silicone rubber is generally non-reactive, stable, and
resistant to extreme environments and temperatures from -55C to
+300C while still maintaining its useful properties. Due to these
properties and its ease of manufacturing and shaping, silicone rubber
can be found in a wide variety of products, including: automotive
applications; cooking, baking, and food storage products

7.23 What are Adhesives? Give examples
2 Marks
Adhesives are the polymeric non metallic compounds which can
hold firmly two materials together by surface attachment.
Ex: Epoxy resin

7.24 Give the manufacture and applications of Epoxy Resin. 4 Marks
Araldite or Epon are the trade names of epoxy resin. It is prepared by
condensation polymerization of Bis phenol A & Epichloro hydrin.

USES.
i. It can be used to bind cardboard, boats, glass for laminating
purposes.
ii.Used in shrinkage proof garments.

7.25 Polymer composite:
Polymer composite is any material made of more than one component.
Polymer composites are composites made from polymers, or from
polymers along with other kinds of materials.

7.26 Kevlar fibers:
Kevlar is synthesized in solution from the monomers 1,4-phenylene-
diamine (para-phenylenediamine) and terephthaloyl chloride in a
condensation reaction yielding hydrochloric acid as a byproduct. The
result has liquid-crystalline behavior, and mechanical drawing orients
the polymer chains in the fiber's direction. Hexamethylphosphoramide
(HMPA) was the solvent initially used for the polymerization, but for
safety reasons, DuPont replaced it by a solution of N-methyl-pyrrolidone
and calcium chloride


7.27 what are Carbon fibers?
Carbon fiber (carbon fibre), alternatively graphite fiber, carbon graphite
or CF, is a material consisting of extremely thin fibers about 0.005
0.010 mm in diameter and composed mostly of carbon atoms
A common method of manufacture involves heating the spun PAN
filaments to approximately 300 C in air, which breaks many of the
hydrogen bonds and oxidizes the material. The oxidized PAN is then
placed into a furnace having an inert atmosphere of a gas such as argon,
and heated to approximately 2000 C, which induces graphitization of
the material, changing the molecular bond structure. When heated in the
correct conditions, these chains bond side-to-side (ladder polymers),
forming narrow graphene sheets which eventually merge to form a single,
columnar filament. The result is usually 9395% carbon.

7.28 7.28 What are Conducting polymers? Give examples 2 Marks
These are the organic polymers having the conductivity band
similar to that of conductors with highly delocalized Pi electron system.
Ex: Polyaniline, Polypyrole, Polythiopene, Polyacetylene, etc
Conducting polymers are obtained by doping an oxidizing or
reducing agent into organic polymers. With the carbon backbone
consisting of alternate double bond & single bonds doping results in
delocalization of electrons responsible for conduction.

7.29 Explain the mechanism of conduction in Poly acetylene.
6 Marks
The electron is removed from the top of the valence band of
Polyacetylene creating a vacancy or hole. The Polyacetylene molecule,
now positively charged, is called a radical cation, or polaron. The lone
electron of the double bond, from which can electron was removed, can
move easily. Therefore, the electron successively moves along the
polymer chain.This are called delocalization of electrons. The positive
charge, on the other hand, is fixed by electrostatic attraction to the
iodide ion; when I2 added as dopant which does not move so readily. If

Polyacetylene is heavily doped (heavily oxidized), polarons form pairs
called Solitons.
The Solitons are delocalized over 12 carbon atoms. Due to the
formation of Solitons, a new localized electronic state appears in the
middle of the energy gap. When doping is high, several charged solution
band. This band can later merge with edges of valence & conduction
bands thus exhibiting conductivity.

7.30 Mention the structure & applications of conducting poly
Aniline
4 Marks

i) Used as conducting tracks on PCBs (Printed Circuit Boards)
ii) Used as electrode materials for rechargeable batteries
iii) Used in humidity sensors.
iv) Used in electrochemical transducers.
v) Used in biosensors.
vi) Used in artificial nerves and optical computers etc.
vii) Used in smart windows which absorb sunlight.

7.31 Explain the mechanism of conduction in Poly aniline 6 Marks

Partial oxidation
Ammoniumperoxy
di sulphate (NH2 S2 O8)

Base form of
polyaniline

Protonation
Aq. HCl ( 1 M)

Protonic acid doping:
The synthesis of conducting polyaniline is a typical example of this type
of doping technique. In this technique current carrying charged species
(-/+) are created by the protonation of imine nitrogen.
Polyaniline is partially oxidized, first using a suitable oxidizing
agent into a base form of aniline which contains alternating reduced and
oxidized forms of aniline polymer backbone. This base form of aniline
when treated with aqueous HCl (1M) undergoes protonation of imine
nitrogen atom, creating current carrying charged sites (+ve) in the
polymer backbone. These charges are compensated by anions (Cl
-
) of the
doping agent, giving the corresponding salt.
This type of protonic acid doping of polyaniline results in an
increase of conductivity by approximately 09-10 orders of magnitude.

Applications:
Conducting polymers are highly promising materials to be used in
electric and electronic applications, some of the applications are.
1) As electrode material for commercial rechargeable batteries, for higher
power to weight ratio (coin type of batteries)
2) As conductive tracks of on printed circuit boards

3) As sensors: Humidity sensor, Gas sensor, Biosensor for glucose,
Galactose etc.
4) In electro chromic display windows.
5) In information storage device.
6) As film membranes for gas separations.
7) In light emitting diodes.
8) In fuel cells as the electro catalytic materials.

Objective type questions.
1) Tetrafluro ethylene is the monomer of
a) Nylon 66 b) neoprene c) Teflon d) PVC

2) Phenol-formaldehyde resin is commercially
a) PVC b) Bakelite c) Elastomer d) Nylon

3) Sulfur is used particularly in
a) Manufacture of Buna-S b) Compounding of plastics
c) Corrosion control d) Vulcanization of raw rubber

4) Isoprene is a monomer of
a) Natural rubber b) Synthetic rubber c) starch d) PVC

5) A polymer with higher Tg value is
a) PVC b) polyethylene c) Polypropylene d) polystyrene

6) The polymer which can be used as synthetic adhesive is
a) Neoprene b) Buna-S c) Epoxy resin d) Polystyrene

7) Co-polymer of Isoprene and Isobutylene is known as
a) Butyl rubber b) Buna-S c) PTFE d) Polyurethane

8) Which of the following polymer is used as a substitute for glass
a) Teflon b) polyurethane c) PMMA d) PVC

9) The monomer phenol is
a) Mono-functional b) Bi-functional c) Tri-functional
d) Poly-functional

10) Neoprene is obtained by the polymerization of
a) Styrene b) Propylene c) Chloroprene d) Isosoprene

11) Suspension polymerization is also known as ____ polymerization
a) bulk b) pearl c) addition d) degree

12) Glass transition is dependent on
a) chain felxibbility b) molecular mass c) branching d) all

13) Polar groups in a polymer offer _____ resistance to chemical attack.
a) More b) less c) maximum d) no

14) Fillers are added to resins to
a) enhance tensile strength b) resist abrasion
c) increase bulk density d) all

15) An example for conducting polymer is
a) poly aniline b) poly thiophene c) poly acetylene d) all


REVIEW QUESTIONS

1. What are polymers? Give the classification of polymers with examples.
2. What are monomers? Give examples.
3. What is Polymerization? Explain the types with examples.
4. What is degree of polymerization (DP)? Mention its importance.
5. Explain the free radical mechanism for the polymerization of ethylene.
6. Explain the methods of polymerization.
7. What is Glass transition temperature? Mention its significant. Discuss
factors affecting the glass transition temperature?
8. Explain the relationship between structure and property of a polymer?
9. What are plastics and resins? Give examples
10. Explain the compounding of resin.
11. Explain the manufacture of Teflon & Mention its properties & uses?
12. Explain the manufacture, properties, & uses of Poly methyl
methacrylate?
13. Explain the manufacture, properties & uses of Poly urethanes?
14. Explain the manufacture, properties & uses of Phenol
Formaldehyde Resin?
15. What are Elastomers? Mention the advantages of synthetic rubbers
Over natural rubbers?
16. Explain the manufacture, properties & uses of Neoprene rubber
17. Explain the manufacture, & uses of Butyl rubber?
18. What are adhesives? Explain the manufacture and uses of Epoxy
Resin?
19 What are conducting polymers? Give Examples
20 Explain the Mechanism of conduction in polyacetylene
21 Write the Structure of conducting poly aniline and mention its
applications.


UNIT UNIT UNIT UNIT VIII VIII VIII VIII
WATER TECHNOLOGY

8.01 Discuss the different types of Impurities present in natural
water with examples. 6 Marks
Impurities in water may be broadly classified into four categories:
i) Dissolved impurities
ii) Suspended impurities
iii) Dissolved gases &
iv) Organic matter.

i) Dissolved impurities.
The soluble salt impurities present in water include salts of Ca,
Mg, Na in various soluble salt forms oxides of Mn, Fe, Pb & Ar may also
present in water.

ii) Suspended impurities.
Suspended impurities are the dispersion of solid particles,
which can be removed by filtration or settling.
They are of 2 types:-
Inorganic: Includes clay silica, oxides of Fe & Mn etc.
Organic: Includes wood pieces, disintegrated particles of dead
animals, leaf, fishes, Bacteria, Algae, and Protozoa etc.

iii) Dissolved gases.
Most water contain dissolved gases such as O2,CO2,SO2
,
NH3 &
oxides of N all of which are derived from atmosphere.

iv) Organic matter.
Organic compounds derived from the decay of vegetables &
animal matter including bacteria, water also gets contaminated with
sewage & human excreted matter etc.

8.02 What is water analysis 2Marks

Analysis of water involves determination of various constituents
present in water in order to ascertain the quality of water & thereby the
utility of water.

8.03. Explain the method of Determining the Total Hardness of
Water.
8 Marks
Principle: Hardness of water is due to the presence of calcium and
magnesium salts in water. Ethylene diamine tetra acetic acid (EDTA)
forms complexes with a large number of cat ions including Ca
++
and Mg
++
ions. Accordingly it is possible to determine the total hardness of water
using EDTA reagents.

The di sodium EDTA molecule (H2Y) has two easily replaceable hydrogen
atoms and the resulting ion after ionization may be represented as H2Y
2-
.
The later forms complexes with metal ions as fallows.
M
2+
+ H2Y
2-
MY
2-
+ 2H
+
. (1)
Where M
2+
is Ca
2+
and Mg
2+
in water. Reaction (1) can be carried out
quantitatively at a P
H
of 10 using Erichrome black-T indicator. Since the
reaction involves the liberations of H
+
ions a buffer mixture has to be
used to maintain a P
H
of 10. The buffer mixture used in the titration is
NH3 NH4 Cl. The hardness of water is usually expressed in terms of
ppm (Parts per million) of CaCO3. Since EDTA (free acid) is sparingly
soluble, its disodium salt, Na2H2Y, is used for preparing the reagent.
Procedure:

Part A: Preparation of a Standard EDTA Solution Weigh accurately the
given EDTA crystals using an electronic weighing balance. Note the
weight, transfer the crystals carefully into a funnel placed over a 250 cm
3

volumetric flask and note down the empty weight of the weighing bottle.
Add few drops of ammonia and pour ion exchange water through the
funnel allowing all the crystals to run down into the flask. Wash the
funnel with ion exchange water and remove the funnel. Dissolve the
crystals by swirling the flask gently. Add some more water if needed.

Dilute the solution up to the mark with ion exchange water, Stopper the
flask and mix the solution thoroughly by inverting the flask several times
so that a homogeneous solution results. Calculate the morality of EDTA.

Part B: Determination of total hardness of a sample of water
Pipette out 25 cm
3
of the given water sample into a clean conical flask.
Add 5 cm
3
of NH3 NH4 Cl buffer and a pinch of Erichrome black T
indicator. Titrate against standard EDTA solution till the color of the
solution changes from wine red to clear blue. Repeat the titration for
concordant values.

Calculations:
Volume of EDTA consumed =.cm
3

1000 cm
3
1 M EDTA = 100 g CaCO3 (Molecular mass of CaCO3 = 100)

cm3 of .M EDTA = ..cm3 x M x 100 g of CaCO3

1000 x 1

25 cm
3
of the water sample contains g of CaCO3

Total hardness of the given water sample = ..g x 10
6
ppm of CaCO3
25

= pm of CaCO3

Result: The Hardness of the given water sample = ppm of
CaCO3

8.04. What is meant by Alkalinity?
4 Marks
Alkalinity in water arises due to the substances that can cause the
formation of hydroxyl ions & in turn can react with strong acids.
Substances that cause the alkalinity in water are of three types.
Hydroxides (NaOH, Ca(OH) etc)
Carbonates (Na2CO3, CaCO3, etc)
Bicarbonates (NaHCO3, Ca (HCO3)2etc.)
When a sample of alkaline water is treated with a strong acid such as
HCL, the following reactions occur.


A) (i) For estimation of alkalinity in a water sample phenolphthalein and
methyl orange end points were found to be 30ml and 45ml respectively.
The readings indicate the presence of:
a) OH
-
and CO3
2-

b) CO3
2-
and HCO3
-

c) OH
-
and HCO3
-

d) Only HCO3
-

Answer:- Alkalinity of water is calculated by titration, By reacting water
sample with NaOH using phenolphthalein and methyl orange indicator.
The reaction water sample may be represented as

NaOH + NaHCO3Na2CO3 + 2H2O
The alkalinity in the sample can be combination can be represented as
Aph = Ah + 0.5 Ac ------- (1)
At = Am.o = Ah +Ac + Ab------ (2)
Where Aph= Alkalinity of phenolphthalein, Am.o =Alkalinity of methyl
orange, Ah= Alkalinity of Hydrodroxide, Ac= Alkalinity of Carbonate, Ab=
Alkalinity of Bicarbonate.

a) OH
-
and CO3
2-
In this case carbonate is absent

i.e, Aph = Ah + 0.5 Ac
Am.o = Ah +Ac

Ah= Aph - 0.5 Ac
Therefore Am.o = Ah +Ac
= Aph - 0.5 Ac + Ac
Am.o = Aph + 0.5 Ac

b) CO3
2-
and HCO3
-
in this case hydroxide alkalinity is absent
I.e., from equation (1)
Aph = 0.5 Ac
Am.o = Ab +Ac

c) OH
-
and HCO3
-
in this case carbonate alkalinity is absent
Aph = Ah
Am.o = Ah + Ab

d) Only HCO3
-
in this case both carbonate and carbonate are absent
Aph=0
Am.o = Ab


8.05 Explain the method of Determining the Alkalinity in water
6 Marks
Principle: Alkalinity is determined by titrating a known volume of
water sample with indicator against a strong acid.
Two types of alkalinity can be evaluated based on the indicator
used.
Alkalinity when methyl orange is used.
When methyl orange is used as indicator, only after all the three
reactions, the color change observed & that indicate the end point.
Total alkalinity = Alkalinity due to hydroxyls + Alkalinity due to Carbonates +
Alkalinity due to bicarbonates.

when phenolphthalein is used , only after the two reactions (I&II) before
the III reaction occur, the color change observed & that indicate the end
point.

Alkalinity with phenolphthalein = Alkalinity due to hydroxyls + 1/2
Alkalinity due to Carbonates.

Procedure.
Pipette out 100ml water sample into a clean conical flask. Add
two drops of Methyl Orange indicator. Titrate against standard (say
0.02N) HCL till the color of the solution changes sharply from yellow to
orange. Let the volume of HCL consumed be Xml.
To another 100ml sample of water, add two drops of Phenolphthalein.
Titrate against standard (say 0.02N)HCL till the color of the solution
changes sharply from pink to colorless. Let the volume of HCL consumed
be Yml.

Calculations.
a) Alkalinity due to methyl orange.
1000ml of 1N HCl is equivalent to 50 g of CaCO3 (50 being the
equivalent weight of CaCO3).
1ml of 1 N HCL is equivalent to 50/1000 g of CaCO3
Xml of 0.02 N HCL is equivalent to 50XxX 0.02/1000 g of CaCO3
10
6
ml of water sample contains 50XxX0.02X10
6
/1000X100 g of CaCO3
= Xg of CaCO3

i.e. Alkalinity of methyl orange = 10X PPM of CaCO3 equivalent

b) Alkalinity due to Phenolphthalein.

This is also in similar way that is
Alkalinity of Phenolphthalein is 50 x Y x 0.02X10
6
/ 1000X100
= 10 Y PPm CaCO3

8.06 Explain the method of determining the Chloride content in
water 6 Marks
Procedure:
Transfer 100cm
3
of water sample into a clean conical flask.
Add about 1 cm
3
of K2CrO4 indicator solution & titrate against standard
(say 0.02N) AgNO3 solution until a reddish brown color persists in the
white precipitate. Record the volume of AgNO3 consumed (Let a cm
3
).
Perform a blank titration taking 100 cm
3
of distilled water. The volume of
AgNO3 consumed Let b cm
3.

Calculation:
Volume of AgNO3 required for chlorine estimation = (a-b) cm
3
= V
1000ml of 1 N AgNO3 = 35.45g/Cl
-
1 ml of 1N AgNO3 = 0.03545g/Cl
-
V ml of 0.02 N AgNO3 = 0.03545 X V X 0.02 g/Cl
-

Cl
-
content in the sample = 0.03545 X V X 0.02 grams /Cl
-

100
Cl
-
content in the sample = 0.03545 X V X 0.02 X 1000 mg/Cl
-

100

8.07 Explain the method of determining the Fluoride content in
water. 6 Marks

SPADNS METHOD.( Sodium 2-(p-sulphophenylazo)-1,8-dihydroxy-3,6
naphthalene disulphonate).

Principle:
Under acidic conditions, fluorides react with Zirconium
SPANDNS solution & the color of SPADNS reagent gets bleached.
Bleaching is a function of fluoride ions & is directly proportional to the
concentration of fluoride ions.

Procedure:
1. Prepare a blank solution by adding 10ml SPANDNS solution in to 100
ml standard volumetric flask and add a solution HCl (7ml conc. HCl

diluted to 10ml) and make up to the mark. Use this blank solution to
set zero in the colorimeter at 570nm.
2. Prepare a series of standard Sodium fluoride (NaF) solutions in the
concentration range of 0.0-2.0mg/l.
3. Add 1 drop of NaAsO2 solution (0.5%) to remove any residual chlorine
to each of the standard solutions.
4. Add 10ml of Zirconyl- SPANDNS reagent to each flask and dilute to
100ml with distilled water. Mix well & read the optical density of
bleached color at 570 nm in the colorimeter.
5. Take suitable aliquot of water sample as test solution, add 1 drop of
NaAsO2 solution (0.5%) to remove any residual chlorine. Add 10ml of
Zirconyl- SPANDNS reagent and dilute to 100ml with distilled water.
6. Read the optical density of bleached color at 570 nm in the
colorimeter.
7. Draw a calibration curve by plotting concentration versus absorbance
and calculate the concentration of Fluoride ion.

8.08 Explain the method of Determining the Nitrate in water.
6 Marks
Principle:
Nitrate reacts with phenol disulphonic acid (PDA) to produce a
nitro derivative, which in alkaline solution develops a yellow color. The
color produced follows Beers law & is proportional of NO3
-
present in the
sample. The concentration of NO3
-
is determined using a colorimeter or
spectrophotometer.

Procedure.
1. Prepare a standard nitrate (KNO3) solution in the 5-500 mg/L

2. Transfer 2.5, 5.0, 7.5, 10,1 2.5 cm
3
of standard nitrate (KNO3)
solutions to separate beakers & evaporate to dryness on a hot
plate.

3. To each beaker add 2 cm
3
of PDA & dissolve the residue.
4. Add 10 cm
3
of conc. NH3 to each beaker & dilute with distilled
water in 100 cm
3
standard volumetric flasks.
5. Take 25 cm
3
of the given water sample in a beaker & evaporate to
dryness on a hot plate. Add 10 cm
3
of conc. NH3 dilute up to 100
cm
3
in a standard volumetric flask.
6. Prepare a blank solution excluding the water sample.
7. Measure the absorbance at 410 nm wavelength using a Photo
colorimeter.
8. Draw a calibration curve by plotting absorbance against the conc.
of NO3
-
and find out the conc. of NO3
-
ions present

in the given
water sample.

8.09 Explain the method of determining the Sulphate content in
Water by colorimetric method. 8Marks
1. Prepare a standard sulphate solution by dissolving 1.479 g of
anhydrous sodium sulphate in distilled water & dilute to
1000ml to get 100 mg /ml of SO4 ion.
2. Transfer 2.5, 5.0, 7.5, 10, 12.5 cm
3
of standard sulphate
solutions to separate 250 ml conical flasks.
3. Add 5 ml of conditioning reagent. (50 ml of glycerol+30 ml of
con. HCl+300 ml of dil H2O+100 ml of C2H5 OH+75 g NaCl)to
each conical flasks.

4. Add BaCl2 crystals with constant stirring till to get a white
precipitate.
5. After 20 minutes, measure the absorbance of BaSO4
precipitate using a colorimeter/spectrophotometer at 420nm.
6. Transfer an aliquot of water sample to a 250ml conical flask
& dilute to 100ml & repeat the steps through 3 to 5.
7. Prepare a blank solution excluding the sample.
8. Draw a calibration curve of absorption versus conc. of SO4
ions and Calculate mg SO4/L.

8.10 Explain the method of determining sulphate content in water
by gravimetric method. 6 Marks
Principle: The sulphate ions in the sample are precipitated by the
addition of barium chloride solution to water sample acidified with
hydrochloric acid & kept near the boiling point.

Procedure
1 Transfer 200ml of water sample to a beaker
2 Add conc. Hydrochloric acid drop wise till to become just acidic.
& add three drops in excess.
3 Boil the sample to reduce the volume to 50ml.
4 Add hot barium chloride solution (10 %) slowly with constant
stirring until all the sulphate is precipitated.

5 Digest at its boiling temperatures for a few hours.
6 Filter through a gooch crucible & wash the precipitate with hot
distilled water until the washings are free from chlorides.
7 Dry the precipitate & weigh barium sulphate.

Calculation:
Weight of BaSO4 be W g
233.3 g BaSO4 contains 96.0g of SO4
2-
W g of BaSO4 contains 96.3 X W g of SO4
2-
= mg

233.3
Sulphate = m X 1000 mg/L
200

8.11. Define biological oxygen demand 2Marks

BOD is defined as the amount of oxygen in mg required for the
complete oxidation of biologically oxidisable matter present in a liter of
sewage effluent by a by micro organisms over a period of five days.

8.12. Define COD.
2Marks
COD is defined as the amount of oxygen in mg required for the complete
chemical oxidation of total oxidisable matter present in a liter of sewage
effluent by a suitable oxidizing agent such as potassium di chromate.
Problems
1) In a COD experiment 30 cm
3
of an effluent sample required 9.8 cm
3
of
0.001 M potassium di chromate for oxidation. Calculate the COD of the
sample.
6 Marks
i) 1000 cm
3
of 1M K2Cr2O7 solution contains 294 g of K2Cr2O7

9.8 cm
3
of 0.001 M K2Cr2O7 solution contains 294 X 9.8 X 0.001
1000 X 1
= 2.8812 mg
ii) K2Cr2O7 + H2SO4 K2SO4 + Cr2 (SO4)3 + 4H2O + 3[O]


294 g of K2Cr2O7 = 48 g of oxygen.

2.8812 mg of K2Cr2O7 = 48 X 2.8812 = 0.4704 mg of oxygen
294
iii) COD of the effluent sample = 0.4704 X 1000

30
= 15.68 mg of oxygen / dm
3

2) In a COD experiment, 25 cm
3
of an effluent sample required 8.3 cm
3
of
0.001 M potassium di chromate for oxidation. Calculate the COD of the
sample. 6 Marks

i) 1000 cm
3
of 1M K2Cr2O7 solution contains 294 g of K2Cr2O7

8.3 cm
3
of 0.001 M K2Cr2O7 solution contains 294 X 8.3 X 0.001
1000 X 1

= 0.3983 mg

ii) K2Cr2O7 + H2SO4 H2SO4 + Cr2 (SO4)3 + 4H2O + 3[O]

294 g of K2Cr2O7 = 48 g of oxygen.

0.3983 mg of K2Cr2O7 = 48 X 0.3983 = 0.4704 mg of oxygen
294
iii) COD of the effluent sample = 0.4704 X 1000

25
= 15.93 mg of oxygen /dm
3

8.13 Explain the Sewage Treatment. 6 Marks
The treatment of domestic sewage is carried out in 2 or 3 stages.
a) Primary treatment.
b) Secondary treatment.
c) Tertiary treatment.
a) Primary Treatment.

The removal of course solids in the sewage water is
effected by means of racks, screens, grid chambers & skimming
tanks. Then the water is passed into a sedimentation tank where it is
allowed to settle. The non-settle able solids are removed by
coagulation by treatment with coagulating agents like alum, ferric
chloride or lime.

b) Secondary treatment.( Activated sludge process ).
The waste water after the primary treatment is allowed to
flow into large tanks where biological treatment is carried out.
Activated sludge containing microorganisms is sprayed over the water.
The microorganisms present in the sludge form a thin layer & thrive
on the organic wastes in the sewage. Air is passed vigorously passed
from the center of the tank in order to bring good contact between the
organic wastes & bacteria in presence of air & sunlight. Under these
conditions, aerobic oxidation of organic matter occurs. The sludge
formed is removed by settling or filtration. A part of the sludge is
reused & the rest is used as fertilizer. The residual water is
chlorinated to remove bacteria & finally discharged into running water
or used for watering plants. The activated sludge process operates at
90-95percent efficiency of BOD treatment. If the treated water
contains a high concentration of phosphates, heavy metal ions,
colloidal impurities & non-degradable organic compounds, the water
is subjected to tertiary treatment.
c) Tertiary treatment.
The process includes
a) Treatment with lime for the removal of phosphates as insoluble
calcium phosphate
b) Treatment with S
2-
ions for the removal of heavy metal ions as
insoluble sulphides
c) Treatment with activated charcoal to adsorb remaining organic
compounds &

d) Treatment with alum to remove the colloidal impurities not
removed in the previous treatments to further reduce the BOD
level.
8.14 Define Potable water 2 Marks
Water that fit for human consumption & meets the stringent
microbiological & chemical standards of quality to prevent waterborne
diseases & health risks from toxic chemicals is called potable water.
8.15 Define Desalination and explain the methods of desalination.
6 Marks
The process of partial or complete demineralization of highly saline
water such as the sea water is referred to desalination.
Methods of desalination.
Reverse Osmosis.

A reverse osmosis unit consists of a membrane, a vessel & a high
pressure pump. The membranes are generally made up of cellulose
acetate or nylon and are usually fabricated in a cylindrical shape.
Electrodialysis.
Principle: Passage of an electric current through a solution of salt
results in migration of cations towards the cathode & anions towards the
anode. The use of semi permeable cation or anion exchange membrane
in an electrolytic vessel permits the passage of only cations or anions
respectively in the solution. An electrodialyzer consists of a chamber
carrying a series of compartments fitted with closely spaced alternate
cation (C) & anion (A) exchange semi permeable membranes between the
electrodes. An electrodialyzer unit will have 200 to 1000 compartments.
The feed water is taken in the dialyzer & the electrodes are connected to
a source of an electric current.


The anions pass through the anion permeable membrane towards
the anode. However, these ions do not pass through the next membrane
which is permeable only to cations. Similarly the cations moving in the
other direction will pass through the cation exchange membrane but not
the next. These anions & cations collect in the alternate chambers; the
water in these is enriched with salt while that in the other compartments
is desalinated. Micro porous sieves provided near the electrodes prevent
the reentry of any deposit, which might have been formed on the
electrodes, into the feed water. The enriched & desalinated waters are
withdrawn separately. The former is rejected & the desalinated water is
recycled to further reduce the salt content.
8.16 What are Hazardous chemicals? Explain the ill effects of
Hazardous chemicals 6 Marks
Chemicals which are combustible ,Oxidizers, explosives, flammable,
pyrophoric, unstable, water reactive, carcinogens, toxicagents,
reproductive toxins, irritants, corrosives, hepatotoxins, nephrotoxins,
neurotoxins the release of which may substantially endanger the public
health, public welfare or the environment are called hazardous
chemicals.
Hazardous
chemical
Source Ill effects
Cadmium Mining wastes, effluents
from plating industries
Renal failure,Bone disease called
itai-itai,high BP,Kidney
damage,destruction of RBC
Chromium Plating wastes Carcinogenic
Lead Discharges from Severe dysfunction of

mining,metallurgical
operations,plumbing, lead
acid batteries
Kidneys,reproductive systems &
lever,impairement of central &
peripheral nervous systems.
Mercury

Mineral processing
operations,organomercury
fungicides,discarded
batteries,amalgams,toothfi
llings.
Neurological damage including
paralysis,depression &
irritability,blindness,insnity,chro
mosomes breakage & birth
defects.
Arsenic
Radioactive
wastes
Erosion of natural
deposits,runoff from
otchards,runoff from glass
& electronics production
wastes.
Skin damage,prolems with
circulatory systems, increased
risk of getting cancer.
Pesticides Agricultural practices Headache, dizziness. Large
quantities may damage central
nervous system.
Cyanide Exists in water as HCN,
metal cleaning &
electroplating
60-90 mg is a fatal dose to living
beings.

Objective Questions:
1) The indicator used for the estimation of total hardness of a given water
sample by EDTA method is
a) Starch b) EBT c) Ferroin d) Methyl orange

2) Temporary hardness of water is caused due to the presence of
a) Calcium carbonate b) Calcium chloride
c) Magnesium bi carbonate d) None

3) The method used for desalination of water is
a) zeolite process b) Lime soda process c) Ion exchange process
d) Distillation

4) The indicator used in the determination of chloride content of water
sample by Mohrs method.
a) Phenolphthalein b) K2Cr2O4 c) Starch d) Ferroin

5) Permanent hardness of water is caused due to the presence of
a) Calcium carbonate b) Calcium chloride
c) Magnesium bi carbonate d) All


6) Winkler methods is used to determine
a) COD b) BOD c) DO d) Both D & C

7) Which of the following alkalinity is not present in water is
a) CO3
2-
and HCO
3-
b) CO3
2-
and OH
-
c) OH
-
only d) HCO3
-
and OH
-

8) Secondary treatment of sewage involves
a) Biological treatment b) Physical treatment C) Chemical treatment
d) All

9) In reverse osmosis the solute particle moves
a) From High to low concentration b) low to high concentration
c) Does not move d) both a & b

10) The ill effect o chromium is
a) Headache b) fatal b) Birth defect c) Cancer

11) In alkaline condition, nitrate ion reacts with phenol disulphoneic acid
to give
a) Yellow colour b) white colour c) green colour d) brouwn colour

12) In SPADNS method of estimating fluoride ion concentration,
wavelength used is
a) 410 nm b) 500 nm c) 570 nm c) 570 nm c) 570 nm c) 570 nm d) 620 nm

13) Sulphate ion is precipitated by the addition of
a) barium sulphate b) barium nitrate
c) barium chloride d) barium phosphate

14) Impurities present in natural water is
a) dissolved b) suspended c) organic d) all

15) Indicator used in the determination of alkalinity of water is
a) Phenolphthalein b) starch c) EBT d) methyl orange


REVIEW QUESTIONS
1. Discuss the different types of Impurities present in natural
with examples
2. What is water analysis?
3. Explain the method of Determining the Total Hardness of
Water
4. What is meant by Alkalinity?
5. Explain the method of Determining the Alkalinity in water
6. Explain the method of determining the Chloride content in
water
7. Explain the method of determining the Fluoride content in
water.
8. Explain the method of Determining the Nitrate in water.
9. Explain the method of determining the Sulphate content in
water by colorimetric method
10.Explain the method of determining sulphate content in water by
gravimetric method.
11.Define biological oxygen demand
12.Define COD.
13.Explain the Sewage Treatment
14.Define Potable water
15.Define Desalination and explain the methods of desalination.
16.What are Hazardous chemicals? Explain the ill effects of
Hazardous chemicals


I/II Semester B.E. Degree Examination, Dec.06/Jan.07
Common to all Branches
Engineering Chemistry
Time: 3 hrs Max. Marks: 100
Note: Answer any five full questions, choosing at
Least two questions from each Part A and Part B

Part A
1. a. Distinguish between gross and net calorific value of a fuel.
(04 Marks)
b. What is meant by cracking of petroleum? Explain fluidized bed
catalytic cracking. (07 Marks)
c. On burning 0.96 grams of a solid fuel in Bomb calorimeter, the
temperature of 3,500 grams of water increased by 2.7C. Water
equivalent of calorimeter and latent heat of steam are 385 grams
and 587 cals/gram respectively. If the fuel contains 5% H2, calculate
its gross and net calorific values. (06 Marks)
d. Write a note on power alcohol. (03 Marks)

2 a. Define electrode potential and derive Nernst equation for electrode
Potential. (05 Marks)
b. What are the advantages of secondary reference electrodes? Explain
the construction and working of Ag/AgCl electrode. (06 Marks)
c. What are electrochemical cells? Distinguish primary cells from
secondary cells with examples. (05 Marks)
d. What are concentration cells? Calculate cell potential of the following
cell at 298 k. Ag /Ag+ (0.001 M)// Ag+ (0.50 M) / Ag What will be
cell potential, when the concentration of silver ions in the above
cell is changed from 0.OO1M to 0.0005 M, at same temperature?
(04 Marks)
3. a. How does a fuel cell differ from battery? Explain the construction

and working of Nickel metal hydride battery. (08 Marks)
b. Explain the construction, working and application of H fuel cell,
with cell reaction. (06 Marks)
c. Give the classification of batteries with examples. (06 Marks)

4. a. Explain stress corrosion with examples. (04 Marks)
b. What are corrosion inhibitors? Explain how corrosion is controlled
by using anodic and cathodic inhibitors? (07 Marks)
c. Write a brief note on the effect of following factors on the rate of
corrosion i) Nature of metal ii) Hydrogen over voltage iii)
Relative areas of anode and cathode. (09 Marks)

PART B

5. a. What is electroplating? Give the technological importance of metal
finishing. (04 Marks)
b. Explain the following factors influencing the nature of deposit:
i) Complexing agents ii) Brighteners iii) Levellers and iv) wetting
agents. (08 Marks)
c. Discuss the electroless plating of copper on PCB. (04 Marks)
d. Write a note on over voltage governing the metal finishing(04 Marks)

6. a. Explain the following with examples
i) Thermotropic liquid crystal and ii) Lyotropic liquid crystal(06 Marks)
b. What is homologues series? Explain the liquid crystalline behaviour
of homologues of MBBA. (06 Marks)
c. Discuss the instrumentation and applications of conductometric
estimation. (08 Marks)

7. a. What are adhesives? Explain the synthesis and applications of
epoxy resin. (06 Marks)
b. What are elastomers? Mention the advantages of synthetic
elastomers. (04 Marks)
c. Give the synthesis and applications of butyl rubber. (04 Marks)
d. Discuss the mechanism of conductance in Polyacetylene. (06 Marks)

8. a. What is potable water? Discuss the purification of water by reverse
osmosis process. (05 Marks)
b. Explain the method of determining sulphate content in water by
gravimetric method. (05 Marks)
c. Explain the determination of dissolved oxygen by Winkler method.
Give the involved. (06 Marks)
d. Describe the secondary treatment of sewage by activated sludge

process. (04 Marks)

First Second Semester B.E. Degree Examination, July 2007
Common to All Branches
Time: 3 hrs.] [Max. Marks: l00
Note: Answer any FIVE full questions, choosing at least TWO questions
from each part.
PART A

1. a. Describe Fischer-Tropsch method of synthesis of petrol. (06 Marks)
b. Explain the process of doping of silicon. (05 Marks)
c. What is cracking? Explain fluidized catalytic cracking. (05 Marks)
d. Discuss the mechanism of knocking. (04 Marks)

2. a. Explain the origin of single electrode potential. Derive Nernst
equation for electrode potential. (07 Marks)
b. what are reference electrodes? Mention the limitations of primary
reference electrode and advantages of secondary reference
electrodes. (04 Marks)
C. Write a note on calomel electrode. (04 Marks)
d. Represent the cell formed by the coupling of two copper electrodes
immersed in cupric sulphate solutions. Concentration of cupric ions
in one electrode system is 100 times more concentrated than the
other. Write the cell reaction and calculate the potential at 300 K.
(05 Marks)
3 a. Define fuel cell. How does it differ from a conventional galvanic cell?
(04Marks)
b. Explain the following fuel cells:
i) Molten carbonate ii) Solid polymer electrolyte. (06 Marks)
c. Explain the following battery characteristics:
I) Cycle life ii) Shelf life iii) Energy efficiency. (06 Marks)
d. Describe the construction and working of zinc-air battery(03 Marks)


4 a. Define corrosion. Explain electrochemical theory of corrosion,
taking iron as a example. (08 Marks)
b. Explain differential metal corrosion with suitable example
(06 Marks)
c. What is cathodic protection? Explain corrosion control by sacrificial
anode method. (06 Marks)

PART B

5. a. What is electro less plating? Mention its advantages. (04 Marks)
b. Discuss the following factors influencing the nature of deposit:
1) Throwing power ii) pH of the electrolytic bath and
iii)Temperature. (06 Marks)
c. Discuss the electroplating of gold and mention its applications.
(05 Marks)
d. Explain electrolessplating of copper and its applications. (05 Marks)

6 a. Distinguish between Thermotropic and Lyotropic liquid crystals with
examples (06 Marks)
b. Explain the working of a liquid crystal in display systems.(06 Marks)
c. What are the advantages of instrumental methods? (03 Marks)
d. Explain the estimation of amount of strong acid in a given solution
conductmetrically. (05 Marks)

7 a. Define polymerization. Explain solution and suspension
polymerization techniques. (05 Marks)
b. Give the synthesis properties and uses of: i) Teflon ii) Butyl
rubber. (10 Marks)
c. What are conducting polymers? Give the structure of polyaniline and
mention its applications. (05 Marks)

8 a. Discuss the types of impurities present in natural water. (04 Marks)
b. Explain the determination of hardness of water by complexometeric
method. (06 Marks)
c. Explain the electodialysis method of desalination of water.(04 Marks)
d.Discuss determination of chloride by Argentometric method.
(06 Marks)


First/Second Semester B.E. Degree Examination, Dec. 07 / Jan. 08
Time: 3 hrs Max. Marks: l0O
Note: Answer any five full questions, choosing at least two questions
from each part.
Part A

1. a. Describe the Bomb calorimetric method of determination of calorific
value of a solid fuel. (06 Marks)
b. What is reforming of petroleum? Give any three reactions involved in
reforming. (05 Marks)
c. What is power alcohol? Give its advantages as a fuel. (04 Marks)
d. What is a photo voltaic cell? Explain its working. (05 Marks)

2. a. What are ion selective electrodes? Explain the measurement of p of
a solution using glass electrode. (07 Marks)
b. Explain the origin of single electrode potential. (05 Marks)
c. Describe the construction and working of a calomel electrode.
(04 Marks)
d. Calculate the emf of the cell Fe/Fe
2+
(0.01 M)// Ag+ (0.1 M)/ Ag at
298 K, if standard electrode potential of Fe and Ag electrodes are
0.42 V and 0.8 V respectively. (04 Marks)

3 a. Explain the construction and working of lead acid battery along with
the reactions involved during charging and discharging. Mention its
applications. (08 Marks)
b. Explain the construction, working and applications of Nickel
metalhydride battery. (06 Marks)
c. Explain the construction and working of the hydrogen oxygen fuel
cell. (06 Marks)

4 a. Explain the differential aeration corrosion with a suitable example.
(O8 Marks)
b. How do the following factors affect the rate of corrosion?
i) Nature of corrosion product. ii) Temperature. iii) PH. (09 Marks)
c. Write notes on: i) Galvanizing ii Tinning (06 Marks)

Part B

5. a. What is electroplating? Explain how the following factors influence
the nature of electrodeposit: i) Metal ion concentration. ii Wetting
agents. (05 Marks)
b. Discuss the electro plating of chromium. (05 Marks)
c. Mention the technological importance of metal finishing. (05 Marks)
d. Explain electroless plating of Nickel and its applications. (O8 Marks)

6 a. Discuss the instrumentation and applications of colorimetric
estimation. (08Marks)
b. What are liquid crystals? Explain the molecular ordering in the
following liquid crystal phases: i) Nematic crystal phase ii) Chiral
Nematic phase iii) Smectic phase. (08 Marks)
c. Distinguish between thermotropic and lyotrophic liquid crystals with
examples. (04 Marks)

7 a. What are polymers? Explain the free radical mechanism of addition
polymerization, taking ethylene as an example. (06 Marks)
b. What is glass transition temperature? Mention its significance.
Discuss any two factors affecting glass transition temperature.
(06 Marks)
c. Explain the manufacture of the following polymers and mention their
uses:
i) Phenol-formaldehyde ii) Polymethyl methacrylate. (08 Marks)

8 a. Discuss the different types of impurities present in natural water
with examples. (04 Marks)
b. Write a note on reverse osmosis. (05 Marks)
c. Explain the method of determining sulphate content in water by
gravimetric method. (06 Marks)

d. Calculate the COD of the effluent sample, when 25 cm of the effluent
requires 8.3 c of 0.001 M K for complete oxidation. (05 Marks)

First and Second Semester B.E. Degree Examination, June/July 08
Time: 3 hrs. Max. Marks: 100
Note: Answer any FIVE full questions, choosing at least two
questions from each part.
Part-A
1. a. Describe the experimental determination of calorific value of a
solid the using Bomb calorimeter. (06 Marks)
b. What is synthetic petrol? Describe the Bergius method of
synthesis of petrol. (05 Marks)
c. Write a note on reforming of petrol. (04 Marks)
d. Explain construction and working of silicon photovoltaic cell.
(05 Marks)

2. a. What are reference electrodes? Explain the construction and
working of alomel electrode. (08 Marks)
b. Calculate the standard electrode potential of Cu
2+
/Cu if its
electrode potential at 25 C is O.296V when [ is 0.015 M).
(03 Marks)
c. What are ion-selective electrodes? Explain the measurement of
pH of a solution using glass electrode. (07 Marks)
d. Derive Nearnst equation on electrode potential. (08 Marks)

3. a. Explain the following battery characteristics:
i) Energy efficiency ii) Current capacity iii) Cycle life. (06 Marks)
b. Describe the construction and working of Lead acid battery.
(08 Marks)
c. Describe the construction and working of H 02 fuel cell.
(06 Marks)

4. a. Discuss the effect of following on the rate of corrosion. (08 Marks)

I) Nature of the metal; ii) Nature of the corrosion product;
iii) pH iv) area effect.
b. Explain differential aeration corrosion with suitable example.
(06 Marks)
c. What is cathodic protection? How a metal is cathodically
protected by sacrificial anode method. (06 Marks)

Part B

5 a. Define polarization, decomposition potential and over voltage.
Mention their significance with reference to electrode position.
(08 Marks)
b. How do the following affect the nature of electroplating?
i) Current density ii) temperature iii) pH iv) organic additives.
(08 Marks)
c. What is electro less plating? Mention any two advantages.
(04 Marks)

6 a. What are liquid crystals? Distinguish between thermotropic and
lyotropic liquid crystals with examples. (06 Marks)
b. Explain the working of liquid crystals in display systems.
(06 Marks)
c. What are the advantages of conductometric titrations over
conventional titrations? (03 Marks)
d. Explain the determination of concentration of an unknown
solution by colorimetric method. (05 Marks)

7. a. Define polymerization. Explain different types of polymerization
processes with suitable examples. (05 Marks)
b. Give synthesis and uses of the following polymers
i) Teflon ii)Neoprene (06 Marks)
c. Write a note on compounding of resins. (04 Marks)
d. Write preparation, properties and uses of epoxy resins. (05 Marks)

8. a. Explain temporary and permanent hardness of water. (04 Marks)
b. Define B.O.D and C.O.D and mention various steps involved in
sewage treatment. (04 Marks)
c. Describe the argentometric method of estimation of chloride

content of a water sample. (04 Marks)
d. What is potable water? Describe the electrodialysis process of
desalination of water. (08 Marks)

Chemistry Notes Vtu

Diunggah oleh

Informasi Dokumen

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Chemistry Notes Vtu

Diunggah oleh

Hak Cipta:

Format Tersedia

Sri Shridevi Charitable Trust( R )

SHRIDEVI INSTITUTE OF ENGINEERING

Anda mungkin juga menyukai