Engineering Chemistry Notes

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Engineering chemistry
Engineering Chemistry
Sub. Code : 14CHE22

Hours/ week : 04
Total Hours : 50 Exam.
14CHE22
I.A.Marks:25
Exam.Hours: 03
Marks : 100
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Module-1
Electrochemistry and Battery Technology
Electrochemistry: Introduction, Derivation of Nernst equation for electrode potential.
Typesofelectrodes: metal-metal ion, metal-metal salt ion, gas, amalgam, redox & ion selective.
Reference electrodes: Introduction; construction, working and applications of calomel and
Ag/AgClelectrodes. Measurement of standard electrode potential using calomel electrode.
Constructionand working of glass electrode, determination of pH using glass electrode.
Concentration cells:Electrode & Electrolyte, numerical problems on electrolyte concentration
cells.
Battery
Technology:
Introduction,
classification
primary,
secondary
and
reservebatteries.Characteristics - cell potential, current, capacity, electricity storage density,
energyefficiency,cycle life and shelf life. Construction, working and applications of Zinc-Air,
Nickel- metalhydride batteries. Lithium batteries: Introduction, Li-MnO2 and Li-ion batteries.
Fuel Cells: Introduction, difference between conventional cell and fuel cell, limitations
&advantages.Classification of fuel cells based on temperature, fuel and electrolyte; construction
&working of methanol-oxygen fuel cell with H2SO4 electrolyte.
10 hours
Module-2
Corrosion and Metal Finishing:
Corrosion: Introduction, electrochemical theory of corrosion, galvanic series.
Factorsaffectingthe rate of corrosion: ratio of anodic to cathodic areas, polarization of anodic &
cathodic regions,nature of metal, nature of corrosion product, nature of medium pH,
conductivity, andtemperature. Types of corrosion- Differential metal , differential
aeration(Pitting and waterline) and stress (caustic embrittlement in boilers).Corrosion control:
Design and selection ofmaterials, inorganic coatings-Anodizing of Al and phosphating, metal
coatings-Galvanizationand Tinning. Cathodic protection (sacrificial anodic and impressed
current methods).
Metal
Finishing:
Introduction,
Technological
importance.
Electroplating:
Introduction,principles governing-Polarization, decomposition potential and overvoltage. Factors
influencingthe nature of electro deposit-current density, concentration of metal salt, metal ion &
electrolyte;pH, temperature & throwing power of plating bath, additives-complexing agents,
brighteners,levellers, structure modifiers & wetting agents. Electroplating of chromium and gold
(acidiccyanide bath). Electro less plating: Introduction, distinction between electroplating and
electroless plating, electro less plating of copper & manufacture of double sided Printed Circuit
Boardwith copper. 10 hours
Module-3
Fuels and Solar Energy:
Fuels: Introduction, classification, calorific value- gross and net calorific values, determinationof
calorific value of fuel using bomb calorimeter, numerical problems Cracking: Introduction,
fluidized catalytic cracking, synthesis of petrol by Fishcher-Tropsch process, reformation of
petrol, octane and cetane numbers. Gasoline and diesel knocking and their mechanism,
antiknocking agents, unleaded petrol, power alcohol, biodiesel & biogas.
Department of Chemistry/SJBIT
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Solar Energy: Introduction, utilization and conversion, photovoltaic cells-importance,

construction and working. Design: modules, panels & arrays. Advantages & disadvantages of PV
cells. Silicon-physical & chemical properties relevant to photovoltaics, production of solar grade
silicon(union carbide process), doping of silicon-diffusion technique (n&p types) andpurification
of silicon(zone refining).
10 hours
Module-4
Polymers:
Introduction, types of polymerization: addition and condensation, mechanism of
polymerizationfreeradical mechanism taking vinyl chloride as an example. Molecular weight of
polymers:number average and weight average, numerical problems. Glass transition temperature
(Tg):Factors influencing Tg-Flexibility, inter molecular forces, molecular mass, branching &
crosslinking, and stereo regularity. Significance of Tg. Structure property relationship:
crystallinity,tensile strength, elasticity, plastic deformation & chemical resistivity. Synthesis,
properties andapplications of PMMA (plexi glass), Teflon, Polyurethane and polycarbonate.
Elastomers:Introduction, synthesis, properties and applications of Silicone rubber. Adhesives:
Introduction,synthesis, properties and applications of epoxy resin. Polymer Composites:
Introduction,synthesis, properties and applications of kevlar and carbon fiber. Conducting
polymers:Introduction, mechanism of conduction in Polyaniline and applications of conducting
polyaniline.
10 hours
Module-5
Water Technology and Nanomaterials:
Water Technology: Introduction, sources and impurities of water; boiler feed water, boiler
troubles with disadvantages -scale and sludge formation, priming and foaming, boiler
corrosion(due to dissolved O2, CO2 and MgCl2). Determination of DO, BOD and COD,
numerical problems. Sewage treatment: Primary, secondary (activated sludge method) and
tertiary methods. Softening of water by ion exchange process. Desalination of sea water by
reverse osmosis & electrodialysis (ion selective)..
Nano Materials: Introduction, properties (size dependent). Synthesis-bottom up approach
(solgel,precipitation, gas condensation, chemical vapour condensation, hydro thermal &
thermolysisprocesses). Nano scale materials-nano crystals & clusters, nano crystalline,
fullerenes, carbonnano tubes, nano wires, nano rods, dendrimers & nano composites. 10 hours
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Index Sheet
Page number
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Module-2:Corrosion And Metal Finishing:
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Module-1: Electrochemistry And Battery Technology:
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Content
22-39
40-63
Module-4:Polymers:
64-78
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Module-3:Fuels And Solar Energy:
7 9 -9 9
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Module-5:Water Technology And Nanomaterials:
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MODULE-1
ELECTRODE POTENTIAL AND CELLS
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Electrode Potential and Cells :

Introduction: Derivation of Nernst equation for electrode potential. Types of
electrodes: Metal-Metal ion, Metal-Metal salt ion, gas, Amalgam ,redox and ion
selective, Reference electrodes: Introduction, construction, working and
applications of calomel electrode and Ag AgCl electrode, Measurement of
standard electrode potential using calomel electrode. Construction and working of
Glass electrode, Determination of pH of a solution using glass electrode,
concentration cells, E lec tr od e a nd e le ct rol y te. Numerical problems on electrolyte
concentration cells.
5 Hours
Contents :
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Introduction, Derivation of Nernst equation for electrode potential. Types

of electrodes: Metal-Metal ion, Metal-Metal salt ion, gas, Amalgam, redox
and ion selective .
Measurement of standard electrodepotential using calomel electrode.

Construction and working of Glass electrode
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Reference electrodes: Introduction, construction, working and applications

of calomel electrode and Ag AgCl electrode
Determination of pH of a solution using g lass electrode, concentration
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cells, Ele ct ro de a nd ele ct roly t e

Numerical problems on electrolyte concentration cells.
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ELECTROCHEMICAL CELL
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GALVANIC CELL
It is a device, which converts chemical energy into electrical energy with redox reaction at the
respective electrodes.
ELECTROLYTIC CELL: The device, which converts electrical energy to chemical energy,
is called electrolytic cell.
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ELECTROLYTIC CELL
GALVANIC CELL
It requires external electric source
It doesnot requires external electric source
Redox reaction are non spontaneous
Redox reaction are spontaneous
Cathode is negative electrode
Cathode is positive electrode
Anode is positive electrode
Anode is negative electrode
DANIEL CELL
Daniel cell consists of zinc electrode dipped in a solution of zinc nitrate and copper electrode
dipped copper nitrte solution. The two electrodes are externally connected by a wire through
volt meter and internally through salt bridge .The U tube is filled with KCl solution and the
ends are plugged with material as shown in fig. The salt bridge maintains electrically neutral of
both compartments and eliminated liquid junction potential.
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Fig.Daniell cell
When the circuit is completed the following reaction takes place.
At zinc electrode, Zn goes into the solution as Zn+2 ions liberating electrons.
Zn
Zn+2 + 2e
Oxidation half reaction
+2
At copper electrode Cu ions in electrolytic solution gets reduced to cu by gaining electrons
from Z
electrode and deposition of metallic Cu on Cu electrode takes place
Cu+2 + 2e
Cu
Reduction half reaction
The overall reaction is given by
Zn + Cu+2
Zn+2 + Cu
The electrons liberated at Zn half cell builds up an electrical potential difference between the
electrode measured using the volt meter. By convention the electrode at which oxidation
occurs is anode and where reduction occurs is cathode. Therefore, in above Daniel cell, the
zinc is anode and copper is cathode.
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ELECTROCHEMICAL CONVENSIONS
1.REPRESENTATION OF ELECTRODE
It oxidation reaction takes place at anode, then the electrode is represented as M/Mn+
It reduction reaction takes place at the cathode then the electrode is represented as Mn+/M
The vertical lines indicated the contact between metal electrodes and metal ions.
2.REPRESENTATION OF CELL
The following points have to be noted to represent an electrochemical cell
a> Anode is always written to LHS.
b> Cathode of the cell is written to RHS of the anode.
c> The 2 vertical lines denotes the salt bridge and interface between the 2 electrodes.
Cell notation is given by
M / Mn+ // Mn+ /M
Ex. Zn(s) / Zn+2 // Cu+2 / Cu(s)
3.CALCULATION OF EMF OF THE CELL
According to electrochemical application
Ecell =Ecathode Eanode.
If the EMF value is + ve then the reaction is spontaneous & if it is ve the reaction is
nonspontaneous.
SINGLE ELECTRODE POTENTIAL (E)
Single electrode potential is defined as the potential developed at the interface between the
metal an electrolytic solution, when it is contact with solution of its own ions.
STANDARD ELECTRODE POTENTIAL (E0)
It is the potential measured, when the electrode is in contact with solution of unit
concentration at 298K.
If the electrode involves gas, then gas is at 1 atm pressure.
EMF OF THE CELL (Ecell )
The potential difference between the two electrodes of the galvanic cell which causes the flow
of current from one electrode(higher potential) to the other(lower potential) is know as EMF
of the cell.
MEASUREMENT OF ELECTRODE POTENTIAL
The potential of any metal electrode is measured using Standard Hydrogen Electrode
[SHE]
whose potential is zero and it involves the following steps.
1.CONSTRUCTION OF THE CELL ASSEMBLY
The electrode is coupled with SHE through salt bridge as shown in figure. The emf is
measured using electronic voltmeter.
For example: To measure the electrode potential of zinc electrode, it is combined with SHE
and the cell notation is given by
Zn(s)/ Zn2+ // H+(1M) / H2(g)/Pt
2.ASSINGING THE SIGN ON THE ELECTRODE
The anode and the cathode of the cell can be identified by connecting the electrodes to the
appropriate terminals of the voltmeter. The emf is measured only when Zn electrode is
connected to the ve terminal and h ydrogen electrode to +ve terminal of the voltmeter.
Then the emf value observed is 0.76V .
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3CALCULATION OF ELECTRODE POTENTIAL

E0cell= Ecathode-Eanode
0.76v= ESHE E0zn2+/Zn
0.76 = 0 V E0zn2+/Zn
Therefore E0zn2+/Zn = - 0.76 V
Z
Similarly the electrode potential is determined for other metal electrodes.
n
Nernst equation:
/Z
It relates electrode potential and concentration of the electrolyte species
E
Consider the following0 reversible electrode reaction
z
Mn+ +ne
M ---------------1
n
The decrease in free energy (-2+ G) represents the maximum amount of work that can be
obtained
/Z
i.e. - G = Wmax
-----------------2
n
The max. work done is given by
n
Wmax.=No. of Coulombs x Energy available/Coulomb-----3
Wmax = nF xE
-----------------------4
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where n-No. of electrons,F-Faraday value ,E-Electrode potential

Equating equations 2&4
- G = nFE
----------------------5
0
0
Under standard conditions - G = -nFE
----------------------6
According to thermodynamic equation
- G = - G0 - RT ln Kc
--------------------------7
Where R-gas constant,T-temperature,Kc-equilibrium constant
Kc for forward reaction of equation no. 1 is
Kc= [M] / [Mn+] = 1/ [Mn+] since[M]=1
Substitute the values of - G , - G0 & Kc in equation 7
nFE= nFE0 -RT ln 1/ [Mn+]
----------------------------------8
Convert ln to log10 by multiplying with 2.303 and divide the equation through out by nF
E = E0 - 2.303RT/ nF log 1/ [Mn+] --------------------------------9
Substitute the values of R,F and temperature at 250 C
E = E0 0.0591/n log1/[Mn+] or
E = E0 +0.0591/n log [Mn+] --------------------------------------10
Nernst equation for Ecell for the following reaction at 250C is
aA+bB
cC+dD
o
Ecell = E cell +0.0591/n log[A]a][B]b/ [C]c [D]d
Calomel Electrode: It is a metal-metal salt ion electrode.It consists of a glass tube having
a side tube on each side.Mercury(Hg) is placed at the bottom of the tube and it is covered
by a paste of Hg2Cl2 with Hg.A solution of KCl is introduced above the paste through side
tube.
A platinum wire sealed in to the glass tube is dipped in to mercury which gives the external
electric contact.
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Fig.Saturated Calomel electrode

Working: It acts as anode or cathode depending on nature of the other electrode.
When it acts as anode,the electrode representation is
2Hg + 2 ClHg2Cl2 + 2e
When it acts as cathode the electrode reaction is
Hg2Cl2 + 2e
2Hg + 2 ClThe net reversible electrode reaction is
Hg2Cl2 + 2e
2Hg + 2 ClAcording to Nernst equation electrode potential is
E = E0 - 0.0591 log [Cl-] at 298K
The electrode potential is decided by the concentration of chloride ions.
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Uses:It is used as secondary reference electrode to measure electrode potential

Used as reference electrode in potentiometric determination
Used as reference electrode in pH determination .
Advantages: Easy to construct,electrode potential is reproducible, and stable for long
period,cell potential does not vary with temperature.
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Silver Silver chloride electrode: It is prepared by coating a thin layer of AgCl electrolytically
on to a silver wire.This wire when placed in a solution of potassium chloride develops a
definite potential depending on the concentration of the electrolyte used.
Fig. Silver silver chloride electrode
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Electrode representation: Ag(s)/AgCl(s) / ClElectrode reaction:

AgCl(s) + e
Ag(s) + Cl0
Electrode potential is given by
E = E - 0.0591 log [Cl-] at 298K
The electrode potential depends on concentration of chloride ions and for the saturated KCl
the potential is 0.199 V
Uses:
Used as secondary reference electrode to measure electrode potential
Reference electrode in ion selective electrode
Used to determine potential distribution uniformit y.
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Ion selective electrodes:The electrodes that are able to respond to certain specific ions only
their by developing a potential with respect to that ions and ignoring all other ions in a
solution are called ion selective electrodes.
Ex. Glass electrode ,Crystalline membrane electrode , Solid state membrane electrode.
Uses:1.Used to determine concentration of cations like H+,K+,Na+,Mn2+,Cu2+,Mg2+ Etc.
2.Anions like F-,CN-,and halides.
3.Used to determine the pH of the solution
4.Used to determine concentration of gas using gas sensing electrode.
Glass electrode principle:The potential developed across the membrane is a function of the
concentration of the analyte and reference solution.When the concentration of the reference
solution is kept constant the potential developed at the membrane is the linear function of
conc. of analyte solution.
Glass electrode Construction:It consists of a glass membrane made up of special t ype of
glass (22%Na2O, 6%CaO and 72%SiO2)of lower melting point and high electrical
conductance.The glass bulb is filled with a solution of constant pH(0.1M HCl)& Ag-AgCl
electrode is inserted which serves as internal reference electrode and also as external electric
contact.
Fig. Glass electrode

Electrode representation: Ag(s)/AgCl(s) /0.1M HCl/glass membrane.
The membrane undergoes an ion exchange reaction as follows.
H+ + Na+GlNa+ + H+GlAdvantages:i.It can be used in oxidizing and reducing environments ii. Accurate results are
obtained between pH range 1-9,iii.Electrode does not poisoned.
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Limitations: i. Ordinary potentiometers cannot be used ii. It can be used up to pH 13 but

becomes sensitive to Na+ ions above pH 9 resulting alkaline error, iii. It does not function
properly in pure alcohol and some organic solvents.
Determination of pH:
To determine the pH of a given solution the glass electrode is dipped in a solution whose
pH need to be determined. It is combined with saturated calomel electrode as shown in fig.
The cell assembly is given by
Hg(l)/ Hg2Cl2 (s)/Cl-//Unknown pH solution/Glass membrane/0.1M HCl)/AgCl(s)/ Ag(s)
The EMF of the cell is given by Ecell = EG - E sat.calomel electrode -------------1
The boundary potential established due to exchange of H+ with glass membrane is mainly
responsible for glass electrode potential EG and given by
EG = Eb + EAg/AgCl +EAsy ----------2
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Fig.Determination of pH
EAg/AgCl is internal reference electrode potential, Eb boundary potential and EAsy is

as ymmetric potential observed when Concentration C1 = C2
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The boundary potential is given by Nernst equation at membrane

Eb = E1 E2 -------3
Since E1= Const. + 0.0591 log C1
E2= Const. + 0.0591 log C2
Therefore Eb = 0.0591 log C1 - 0.0591 log C2 since n=1
Eb = L + 0.0591 log C1 -------------4, where constant L= - 0.0591 log C2
,since C2=(H+)=const.
Eb = L + 0.0591 log(H+) since C1=(H+)
Eb = L 0.0591pH -----------5, where pH = -log(H+)
Therefore EG = L 0.0591pH + EAg/AgCl +EAsy -------6
Combine all constant values in the above equation,ie. L= L + EAg/AgCl +EAsy
EG = L 0.0591pH -----------7
Therefore equation 1 becomes
Ecell = L 0.0591pH - E sat.calomel electrode
or
pH = L - E sat.calomel electrode - Ecell -----------8
0.0591
or pH = K- Ecell ---------9
0.0591
where K = L - E sat.calomel electrode which is constant
To evaluate K the electrode assembly is dipped in a standard buffer solution and pH meter
is calibrated to the pH of the buffer solution.
PH(b) = K- Ecell(b) ---------10
0.0591
Next the electrode assembly is dipped in a solution of unknown pH and pH(u) is given by
PH(u) = K- Ecell(u) ---------11
0.0591
Subtract equation 10 from 11,
PH(u) = PH(b) - Ecell(u) + Ecell(b)
---------12
.0,0591
Concentration Cells: It is an electrochemical cell that generates electrical energy when
two electrodes of same metal are in contact with solution of its own ions of different
concentration.
Consider the following concentration cell represented by
Cu(s) /Cu2+ (C1) // Cu2+ (C2) /Cu(s)
Where C1 and C2 are molar concentrations of the Cu2+ ions in the two half cells.
Fig.Concentration cell
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By electrochemical convention if C1<C2, the left electrode is anode and right electrode is
cathode.The cell reactions are
At anode Cu(s)
Cu2+ (C1) +2e
2+
At cathode Cu (C2) +2e
Cu(s)
The net cell reaction is Cu2+ (C2)
Cu2+ (C1)
The voltage of the cell exists as long as C1<C2
The EMF of the concentration cell is given by
Ecell = E0 Cathode - E0 Anode
Therefore Ecell =[ E0 Cu2+/Cu + 0.0591/2 log C2] [E0 Cu2+/Cu +0.0591/2 log C1]
or Ecell= 0.0591/2 log C2/C1 Where E0 Cu2+/Cu - E0 Cu2+/Cu = 0
In general the EMF of the concentration cell is given by
0.0591 log C2
Ecell=
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C1
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Types of electrodes
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From the above equation following conclusions may be drawn

i.When C1 = C2 the concentration cell does not generate electrical energy
ii.When C2/C1 > 1, log C2/C1 is positive and Ecell is positive
iii.Higher the ratio of C2/C1 higher is the cell potential.
Metal-metal ion electrodes
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Many electrode reactions involve only ionic species, such as Fe2+ and Fe3+. If neither of the
electroactive species is a metal, some other metal must serve as a conduit for the supply or
removal of electrons from the system. In order to avoid complications that would arise from
electrode reactions involving this metal, a relatively inert substance such as platinum is
commonly used. Such a half cell would be represented as
Pt(s) | Fe3+(aq), Fe2+(aq) || ...
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and the half-cell reaction would be
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Fe2+(aq) Fe3+ (aq) + e
The reaction occurs at the surface of the electrode (Fig 4 above). The electroactive ion diffuses to
the electrode surface and adsorbs (attaches) to it by van der Waals and coulombic forces. In
doing so, the waters of hydration that are normally attached to any ionic species must be
displaced. This process is always endothermic, sometimes to such an extent that only a small
fraction of the ions be able to contact the surface closely enough to undergo electron transfer,
and the reaction will be slow. The actual electron-transfer occurs by quantum-mechanical
tunnelling.
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Gas electrodes
Some electrode reactions involve a gaseous species such as H2, O2, or Cl2. Such reactions must
also be carried out on the surface of an electrochemically inert conductor such as platinum. A
typical reaction of considerable commercial importance is
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Cl(aq) Cl2(g) + e
Similar reactions involving the oxidation of Br2 or I2 also take place at platinum surfaces.
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Metalmetalsalt ion electrodes
The half cell would be represented as

... || Cl (aq) | AgCl (s) | Ag (s)
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A typical electrode of this kind consists of a silver wire covered with a thin coating of silver
chloride, which is insoluble in water. The electrode reaction consists in the oxidation and
reduction of the silver:
AgCl(s) + e Ag(s) + Cl(aq)
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Although the usefulness of such an electrode may not be immediately apparent, this kind of
electrode finds very wide application in electrochemical measurements, as we shall see later.
Ion selective electrodes:
The electrodes that are able to respond to certain specific ions only their
by developing a potential with respect to that ions and ignoring all other ions in a solution
are called ion selective electrodes.
Ex. Glass electrode ,Crystalline membrane electrode , Solid state membrane electrode.
Uses:1.Used to determine concentration of cations like H+,K+,Na+,Mn2+,Cu2+,Mg2+ Etc.
2.Anions like F-,CN-,and halides.
3.Used to determine the pH of the solution
4.Used to determine concentration of gas using gas sensing electrode.
Redox electrode:
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"An inert electrode (e.g., platinum, gold, carbon) the potential of which is controlled by a
redox reaction in solution. This is somewhat of a misnomer since all electrodes involve
oxidation/reduction. The distinction is that in the case of a redox electrode both oxidized and
reduced species are dissolved in the solution surrounding the electrode.
Amalgam electrode:It is formed by placing the metal-amalgam in contact with a solution of

metal ion
It is represented by M(Hg)/Mn+(aq)
Eg;Ag-amalgam electrode.
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BATTERY TECHNOLOGY:
Contents:
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Introduction,classification primary, secondary and reserve batteries

charecteristics: cell potential, current, capacity, electricity storage
density,energy efficiency, cycle life and shelf life. Construction, working and
applications of Zn air, Ni metal hydride batteries, Lithium
batteries,Introduction Li MnO2 and Li-ion batteries.
Fuel cells I n t r o d u c t i o n , Differences conventional cell and fuel cell,
Limitations and Advantages.Classification of fuel cells based on temperature
fuel and electrolyte. Construction and working of CH3OH O2 fuel cells with
H2SO4 as electrolyte.
5Hours
Introduction,classification primary, secondary and reserve batteries

cell
potential,
current,
capacity,
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characteristics:
electricity
storage
density,energy efficiency, cycle life, and shelf life Construction.

Construction, working and applications of Zn air
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Construction, working and applications of Ni metal hydride batteries

Introduction Li MnO2 and Li-ion batteries.
Fuel cells I n t r o d u c t i o n , Differences conventional cell and fuel cell
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Classification of fuel cells based on temperature fuel and electrolyte
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Construction and working of CH3OH O2 fuel cells with H2SO4 as
electrolyte.
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DEFINITION: A battery is a device that consists of one or more cells connected in series
or parallel to supply the necessary current.
Cell: It is a device that consists of only two electrodes that generate electrical energy.
Classification:
1) Primary cells: In this type electrical energy can be obtained at the expense of chemical
energy only as long as the active materials are present. These batteries cannot be recharged
and reused eg: Zn-MnO2
2) Secondary cells: In this type of batteries once used can be recharged by passing current
through it . The redox reaction gets reversed during recharging. Here electrical energy is
stored in the form of chemical energy and utilized for supplying current whenever needed.
Therefore secondary batteries are also known as storage batteries. Eg.Pb-acid , Ni-Cd
3) Reserve batteries: The batteries which are stored in an inactive state and made ready for
use while activating them before use are known as reserve batteries. In this t ype one of the
component is separated from the rest of the battery . Usually the electrolyte is the component
that is isolated . The electrolyte eliminates the self discharge of battery prior to use. These
are used for long term storage . Ex. Ag-MnO2
BATTERY CHARACTERISTICS
Batteries are designed to a particular application based on their performance characteristics.
Voltage: the voltage available depends on EMF of the cell and EMF in turn depends on
free energy change.Consider the equation
Ecell=E0 cell -2.303 RT/nF log Q
0
Where E cell =E0 cathode-E0 anode ,Q is the reaction quotient ie. [products]/[reactant]
From the above equation we can conclude that
a) If the difference in std.electrode potential is more ,EMF of the cell is also higher
b) as the temperature increases the EMF of the cell decreases
c) as the value of Q increases ie, when current is drawn from the cell the cell reaction
proceeds and EMF of the cell decreases.
To derive maximum voltage in addition to above the electrode reaction must be fast to
reduce the overpotentials and the resistance of the cell must be low
Current: It is the measure of the rate at which a battery is discharging .For efficient working
of the cell there must be a large quantity of electroactive species which help in rapid
electron transfer.
Capacity :It is the total amount of a electric current involved in the electro chemical
reaction and expressed in a term of coulombs or ampere hour(Ah). It depends on a size of
a battery and given by
C=WnF/M where W is the mass& M is the molar mass of active materials .
CYCLE LIFE: It is the number of charge or discharge process that are possible before
failure occurs . Primary batteries are designed for single discharge but secondary batteries
is chargeable. The c ycle life of a storage must be high.
It depends on chemical composition, morphological changes and distribution of active
materials in the cell
Energy efficiency: it is given by
%energy efficiency =
energy released on discharge x 100
energy required for charging
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It depends on rate of charge or discharge,current efficiency of the electrode process and the
overpotential during charge and discharge reactions as well as the battery resistance.
Shelf life: The duration of storage under specified conditions at the end of which a cell or
battery still retains the ability to give a specified performance is called shelf life.It must be
good for storage cells.Good shelf life for batteries is expected when there is no self discharge
or corrosion of current collectors causing loss of performance
Energy storage density : It is the measure of charge per unit weight stored in the
battery.ie.it is the capacity per unit weight.
Power density : The ratio of power available from a battery to its weight (W/Kg).It
decreases during discharge.
Zinc-Air Battery:
This is a t ype of metal air battery which uses ox ygen directly from atmosphere to produce
Electrochemical Energy. A loose granulated powder of zinc is mixed with
electrolyte(30%KOH) acts as anode material. The outer metal acts as cathode of the battery
which is filled with small amount of catalyst and carbon to optimize the evolution of oxygen
in alkaline solution and for better reduction. The two electrodes are separated by plastic
gasket as insulator. As the electrode is compact, high energy densities are obtained.
Battery Notation: Zn | KOH | air ,C
The Cell Reactions:
2 Zn + 4 OH2ZnO + 2 H2O + 4eat Anode
O2 + 2 H2O + 4 e
4 OH
at Cathode
Over all Reaction:
2Zn + O2
2ZnO
-1
It has energy density of about 100W h Kg three times that of Lead acid battery or twice that
of Ni- Cd Battery.
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Advantages:High energy density,long shelf life,low cost ,no ecological problem.

Uses: It finds applications in military radio receivers,Power source for hearing aids,medical
devices,remote communications etc.
Nickel- Metal Hydride (Ni-MH) battery:
It .is similar to Ni-Cd cell. Instead of Cadmium metal h ydride battery uses h ydrogen
adsorbed on a metal alloy for the anode active materialAnode active materials such as VH2,
ZrH2 and TiH2 are used .The active material at the cathode is NiO(OH) .
The metal alloy is capable of undergoing a reversible reaction as the battery is charged or
discharged. The cathode cell can is filled with NiO (OH) and anode is highly porous
structured with a Ni wire gauge in to which hydrogen storage alloy is coated. The two
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electrodes are separated with an insulator material at the top and the active materials by an
aqueous solution of KOH soaked with absorbent material which acts as electrolyte.
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Fig . Nickel Metal Hydride battery

The battery Representation:
MH | KOH | Ni (OH)2 , NiO(OH)
The Cell Reactions:
MH + 2OHH2O + M + 2eAnode
2NiO(OH) + 2H2O + 2e
Ni (OH)2 + 2OHCathode
Over all Reaction:
MH + 2NiO (OH)
Ni (OH) 2 +M
Potential values varies from 1.25V to 1.35V
Uses:It is used in Computers, Cellular Phones ,camcorders, electric vehicles.
Advantages:High capacity,long c ycle life,shelf life,less environmental problems.
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Li MnO2 Batteries:
Li MnO2 cell is one of the most widely used batteries It consists of Li anode and MnO2 as
cathode. Lithium halide in organic solvent solution is used as electrolyte. The MnO2 pellet
and anode disc are separated by polypropylene separator pasted with electrolyte.The cell is
sealed with can serving as the cathode terminal and cap as the anode terminal.
Fig.Li-MnO2 Cell
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Lithium-ion battery: During the charge and discharge processes, lithium ions are
inserted or extracted from interstitial space between atomic layers within the active
material of the battery.
Simply, the Li-ion is transfers between anode and cathode through lithium
Electrolyte. Since neither the anode nor the cathode materials essentially change, the
operation is safer than that of a Lithium metal battery.
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Cell Reactions:
Li
Li+ + eAnode
IV
+
III
Mn + Li +e
LiMn O2
Cathode
Overall Reaction:
Mn IVO2 + Li
LiMn III O2
In the above cell reaction Mn reduces from +4 oxidation state to +3 oxidation state.Lithium
ion enters in to the MnO2 crystal lattice.
The voltage of the cell is up to 4V depending on the cathode used
Uses:It is mainly used in applications watches, calculators, cameras, lighting equipments
and long time memory backups.
Advantages:High current density due to low atomic mass of lithium
Operates between wide range of temperature(-40to 700 C)
Low self discharge rate and shelf life is high.
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Construction
Li-ion cell has a four-layer structure.
A positive electrode made with Lithium Cobalt Oxide
has a current collector
made of thin aluminum foil - cathode
A negative electrode made with specialty carbon has a
current collector of thin
copper foil anode.A separator is a fine porous polymer film.
An electrolyte made with lithium salt in an organic solvent.
The electrolytes are selected in such a way that there should be an effective transport
of Li-ion to the cathode during discharge.
The type of conductivity of electrolyte is ionic in nature rather than electronic.
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Working
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The traditional batteries are based on galvanic action but Lithium ion secondary
battery depends on an "intercalation" mechanism.
This involves the insertion of lithium ions into the crystalline lattice of the host
electrode without changing its crystal structure.
These electrodes have two key properties. One is the open crystal structure, which
allow the insertion or extraction of lithium ions and the second is the ability to accept
compensating electrons at the same time. Such electrodes are called intercalation
hosts.
The chemical reaction that takes place inside the battery is as follows, during charge
and discharge operation:
During discharge current flows through external circuit and light glows
During charging, no the electrons flows in the opposite direction.
During charging, lithium in positive electrode material is ionized and moves from
layer to layer and inserted into the negative electrode.
During discharge Li ions are dissociated from the anode and migrate across the
electrolyte and are inserted into the crystal structure of the host compound of cathode.
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Advantages :
They have high energy density than other rechargeable batteries
They are less weight
They produce high voltage out about 4 V as compared with other batteries.
They have improved safety, i.e. more resistance to overcharge.
Disadvantage:
They are expensive
They are not available in standard cell types.
Applications:
The Li-ion batteries are used in cameras, calculators
They are used in cardiac pacemakers and other implantable device
They are used in telecommunication equipment, instruments, portable radios and TVs,
pagers
They are used to operate laptop computers and mobile phones and aerospace
application
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FUEL CELLS
Definition: It is an electrochemical device that continuously transform free energy change
of redox reactions of a fuel to electrical energy at the electrodes.
A Fuel cell is represented as follows
Fuel/Electrode , Electrolyte , Electrode/Oxidant
At anode
Fuel
Oxidation product + ne
At Cathode
Oxidant + ne
Reduction products
Advantages :
1. High efficiency of the energy conversion process .
2. Recharging of fuel cell not required .
3. Absence of harmful waste products .
4. Silent operation .
Methanol oxygen fuel cell :
It consists of two porous carbon electrodes .Anode is coated with platinum
catalyst and cathode with silver catalyst .The electrolyte is an aqueous solution of KOH
.The Methane gas is continuously supplied at the anode and oxygen is supplied at the
cathode . As the Methane gas diffuses through anode it is adsorbed on the electrode surface
and reacts with Hydroxyl ions to form water . At the cathode Ox ygen diffusing through the
electrodes is adsorbed and reduced and
get reduced to hydroxyl ions .
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Fig. Methanol ox ygen fuel cell
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The electrodes reactions are

At anode, CH3OH + 6OHCO2 + 5H2O +6e
At cathode,3/2 O2 + 3 H2O +6e
6OHNet cell reaction CH3OH + 3/2O2
CO2 +2 H2O
CLASSIFICATION OF FUEL CELLS
Direct fuel cells:In this t ype products of cell reactions are discarded
Regenerative fuel cells: In this t ype products are regenerated using thermal or electrical or
photochemical process.
Indirect fuel cells: In this type fuel of the cell is obtained from organic fuel
Based on temperature
Low temperature fuel cell (25-100oC)
Intermediate temperature fuel cell (100- 500oC)
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High temperature fuel cell (500-1000oC)

Very high temperature fuel cell (above 1000oC)
Based on Type of fuel used
Solid fuel cell Eg.Coal
Liquid fuel cell Eg.Alcohols
Gaseous fuel cell Eg. H2
Based on Type of electrolyte used
Alkaline fuel cell : These cells uses aqueous solutions of alkali as electrolyte . Oxygen
reduction is more rapid in alkaline electrolytes than acid electrolytes . In this type if the
final product of oxidation is carbon dioxide, it forms carbonates . For this reason it is not
suitable for carbon containing fuels.They work at 80oC and and allow the use of wide range
of electrode catalysts.
CO2 + 2OHCO3- + H2O
Phosphoric acid fuel cells: These cells uses 98% phosphoric acid and operates at 160oC
220oC .At lower temperatures phosphoric acid is a poor ionic conductor . Teflon bonded gas
diffusion electrodes are used. Platinum particles dispersed on carbon acts as catalyst at both
anode and cathode. The phosphoric acid electrolyte is absorbed into a solid matrix of SiC.
Advantages : 1. Low volatility of phosphoric acid above 150oC
2. Simple construction since it uses SiC, Teflon & Carbon.
3. Excellent thermal chemical & electrochemical stability.
Solid oxide fuel cell: In this type the electrolyte is a solid ,nonporous metal oxide like
Zirconia (ZrO2)doped with Yttrium Oxide. This cell operates at 650oC 1000oC where ionic
conduction takes place by the migration of ox ygen ions(O22- )across the electrolyte through
the vacant lattice sites. The anode is of Co or Ni on ZrO2 & cathode is Strontium doped with
LaMnO3.
Advantages : 1. High operational temperature avoids expensive catalyst.
2. High tolerance to impurities.
3. No liquids are used in the cell.
Molten Carbonate Fuel cell: It consists of porous anode made up of Ni, a porous cathode
made up of NiO2 & molten carbonate as electrolyte .The electrolyte consists of 40%
LiAlO2,28% K2CO3 & 32%Li2CO3.It operate between 600-650oC.
At anode H2 + CO32CO2 + H2O + 2e
At cathode O2 + 2CO2 + 4e
2CO32These fuel cells have efficiency greater than 55%.
Solid polymer electrolyte fuel cell: It is similar to H2-O2 fuel cell. Instead of KOH
pol ymer membrane in solid form is used as electrolyte for ionic conduction. Polymer
membrane used is fluorocarbon pol ymer back bone similar to Teflon, to which sulphonic
acid groups are attached. It operates at 80oC. The porous Carbon electrodes with platinum
catalyst are used.
Bio-Chemical fuel cell: In this t ype the electrode reactions are promoted by biological
processes. They should be operated between 0-40oC & pH 7.0 which is suitable for
sustaining life of an organism.
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MO D UL E - 2
CORROSION AND METAL FINISHING
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Corrosion : Introduction, electrochemical theory of corrosion, galvanic series.

Factors affecting the rate of corrosion: ratio of anodic to cathodic areas,
polarization of anodic & cathodic regions, nature of metal, nature of corrosion
product, nature of medium pH, conductivity, and temperature. Types of
corrosion- Differential metal , differential aeration(Pitting and waterline) and stress
(caustic embrittlement in boilers).Corrosion control: Design and selection of
materials, inorganic coatings-Anodizing of Al and phosphating, metal coatingsGalvanization and Tinning. Cathodic protection (sacrificial anodic and impressed
current methods).
5 Hours
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Contents:
Introduction, electrochemical theory of corrosion, galvanic series.
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Factors affecting the rate of corrosion
ratio of anodic to cathodic areas, polarization of anodic & cathodic regions,

nature of metal, nature of corrosion product
nature of medium pH,
conductivity, and temperature.
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Types of corrosion- Differential metal , differential aeration(Pitting and

waterline) and stress (caustic embrittlement in boilers).
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Corrosion control: Design and selection of materials
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inorganic coatings-Anodizing of Al and phosphating,

metal coatings-Galvanization and Tinning.
Cathodic protection (sacrificial anodic and impressed current methods).
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CORROSION AND ITS CONTROL
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Definition
The destruction or deterioration of metal by surrounding environment through chemical
or electrochemical attack is known as corrosion.
Ex.Formation of reddish brown scale on iron due to formation of Fe2O3
Green scale on copper vessel due to CuCO3&Cu(OH)2
Dry corrosion is direct chemical attack in the absence of moisture by dry gases like
SO2,CO2,Cl2,H2S etc.
Wet corrosion is common in nature & occurs by electrochemical attack on the metal with
the moisture and ox ygen present in the atmosphere.
Electrochemical theory of corrosion.
When an iron rod is exposed to the environment the following electrochemical changes
takes place,
i)Formation of anodic cathodic areas,at anode oxidation takes place producing electrons
and metal ion(Mn+).At cathode electrons are taken up by reduction reaction
ii)Corrosion takes place at the anode.
iii)Reduction of water and ox ygen in the atmosphere to OH- occurs at cathodic area.
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Consider the metal like iron exposed to the corrosive environment the reactions that occur
are as follows, Anodic reaction : Oxidation takes place resulting corrosion of metal
Fe
Fe2+ + 2e
Cathodic reaction: At cathode reduction reaction takes place depending upon the nature of
electrolyte.The different possible reduction reaction are
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i.If the solution is aerated and neutral oxygen and water are reduced to OH- ions
O2 + 2H2O + 4e
4OHii. If the solution is deaerated and neutral cathodic reaction involves liberation of H2 gas
and
OH- ions
2H2O + 2e
H2 + 2OHiii. If the solution is deaerated and acidic cathodic reaction involves liberation of H2 gas
2H+ +2e
H2
2+
Corrosion of iron produses Fe at anode and OH- at cathode.These ions diffuse towards
cathode and form Fe(OH)2 near cathode.In oxidizing environment it is oxidized to ferric
oxide and the yellow rust hydrated ferric oxide.
2 Fe2+ + 4OH2 Fe(OH)2
4Fe(OH)2 + O2 + 2H2O
2Fe2O3. 3H2O
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Factors influencing the rate of corrosion

Nature of metal
The metals with lower electrode potential(higher up in series)are more reactive than with
metal of higher potential.The more reactive metals are more susceptible for corrosion.
Thus the tendency of a metal to under go corrosion decreases with increase in electrode
potential. For example K,Na,Mg,Zn etc. with low electrode potential values are more
susceptible to corrosion.The noble metals Ag,Au,Pt etc. with high electrode potential
values are less susceptible to corrosion.
Hydrogen over voltage
The metal with low hydrogen over voltage on its surface is more susceptible for corrosion
when cathodic reaction is hydrogen evolution.When the h ydrogen over voltage is low
hydrogen gas is liberated easily and thus the cathodic reaction is faster.This will also
makes the anodic reaction faster and hence intence corrosion takes place.When the
hydrogen over voltage is high cathodic reaction is slower and corrosion also becomes slow.
Nature of corrosion product
The corrosion product is usually the oxide layer formed on metal surface determines the
corrosion rate. If the layer formed is stoichiometric,highly insoluble,and non-porous with
low electronic conductivity then the la yer formed prevents further corrosion.The thin layer
formed acts as a barrier between fresh metal surface and the corrosion environment. On
the other hand if the corrosion product formed is non-stoichiometric, soluble, porous and
non-uniform then the la yer formed can not control corrosion.
Metals like Al,Cr,Ti etc. forms thin oxide la yer in corrosive environment on their surface
and become passive to corrosion.
Anode and cathode areas
The rate of corrosion greatly influenced by the relative sizes of anode and cathodic areas.If
the metal has smaller anodic area compared to large cathodic area intence corrosin takes
place at anode. Since all the electrons liberated at small anode area are rapidly consumed
by the large cathode area.If the cathode is smaller the consumption of electrons will be
slower and corrosion will become slower.
For example when tin is coated on iron in such a way that some pin holes are left results in
small anode area and large cathode area.Since tin is cathodic to iron corrosion occurs at the
small anode area exposed.on the other hand when zinc coated on iron leaving behind small
pin holes results large anodic and small cathodic ares.Since zinc is anodic to iron corrosion
of iron will not occur.
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Temperature :With the increase in temperature the reaction as well as diffusion rate
increases there by corrosion rate is generally enhanced.In the case of corrosion resistant
passive metals the rise in temperature reduces passivity and leads to an increase in
corrosion.
pH: Generally acidic media are more corrosion than alkaline and neutral media. However
some metals like Al,Zn etc. undergoes fast corrosion in highly alkaline medium.
Polarisation of A n o d i c & C a t h o d i c r e g i o n s :
The potential difference between the anode and cathode causes electrochemical
corrosion,but corrosion is controlled due to polarisation of anode or cathode.
As soon as the corrosion current begins to flow,certain irreversible factors that tends to
oppose the direction of current flow occur adjacent to electrodes referred as polarisation.
In anode polarisation as the corrosion reaction progress,the rate of dissolution of metal as
metal ion is decreased due to an increase in the concentration of ions of the dissolved
metal in the vicinity of the electrode.Because of anode polarisation the anode reaction
becomes slower and over all corrosion rate decreases.
In cathode polarisation , it retards the cathodic reaction. This is due to chemical
polarisation of cathode,i.e ,hindering the combination of cathode reactant with the
electron.For the corrosion to take place both anodic and cathodic reaction should take place
simultaneously. If one of the reaction is slower corrosion rate also slow.When the potential
of polarized electrodes are plotted against current or current density in the corrosion circuit
polarisation curves called Evans diagrams are obtained as follows.
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In the above curves the polarisation curve posses a steeper slope for the electrode which
is polarized to the greater extent.
Types of corrosion:
Diffrential metal corrosion(Galvanic corrosion)
When two dissimilar metals are electrically connected and exposed to corrosive
environment the metal with lower electrode potential (higher up in electrochemical
series) undergoes corrosion.For example when zinc and copper are electrically connected
in presence of electrolyte the zinc metal with low electrode potential acts as anodic
area; gets corroded as shown in figure,where as copper which is higher electrode
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potential become cathode.

The rate of this t ype of corrosion depends on difference in potential. Higher the
difference in potential faster is the rate of corrosion.
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Ex.:1)Steel pipe connected to copper
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2)Tin coating on copper vessel 3) Zinc coating on mild steel
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Differential aeration corrosion

It occurs when a metal surface is exposed todifferent air / oxygen concentration. The
metal part exposed to less ox ygen concentration acts as anodic area and corrodes where
as the higher ox ygenated area is protected from corrosion(Cathode).For example when an
iron strip is partiallyi mmersed in aerated solution of sodium chloride as shown in
figure.The metal part inside electrolyte get corroded due to anodic reaction and the more
oxygenated area of the metal(cathode) is protectedEx.:Nail inside the wall corrodes,
Window frame inside wall corrodes
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Water-line corrosion
It is observed in water storage tanks,ship water lifting pipes etc. For example in water
storage tank the metal Tank part inside water level exposed only to dissolved ox ygen get
orroded(anode) while the part above water line is exposed to higher ox ygen concentration
is protected(cathode).
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Pitting corrosion :
It occurs when small particles of dust,water drop on metal surface or breakdown of
protective film. A t ypical pitting corrosion is illustrated as shown in figure.The metal
portion covered by dust act as anode due to less ox ygenated and undergoes corrosion
beneath the dust forming a pit.The metal part free from dust exposed to higher ox ygen
concentration become cathode and protected from corrosion.The corrosion rate is higher in
this case due to small anode area and large cathode area.All the electrons liberated at
anode(pit) are absorbed by large cathode area for reduction reaction.
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Stress corrosion
It is observed in metals under stress due to the mechanical operations such as welding
,bending ,pressing, riveting etc.In this case corrosive agents are specific and selective
such as KOH or NaOH for mild steel, traces of ammonia for brass, solution of metal
chlorides for stainless steel.
Stress corrosion is explained on the basis of electrochemical theory. In a corrosive
environment the stressed portion act as anode under goes corrosion and stress free part
become cathode.
The metal which is bended as shown in figure has a stress at the bent region.At the
stressed part the metal atoms are always at higher energy levels as compare to the one free
from stress.The stressed part of the metal therefore become more reactive and undergoes
corrosion
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Example of stress corrosion:
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Caustic embrittlement
It is observed in mild steel boilers.The boiler water contains small portion of sodium
carbonate added during softening purpose.In boilers this breaks up to give sodium
hydroxide and carbon dioxide and makes water alkaline.
Na2CO3 + H2O
2 NaOH + CO2
Due to crack developed at stressed portion the alkaline boiler water enters in to minute hair
cracks by capillary action.The water get evaporated leaving behind NaOH at cracks.As the
concentration of NaOH increases it attacks the mild steel and dissolves the iron as sodium
ferrate which decomposes to magnetite.
3 Na2FeO2 + 4 H2O
6 NaOH + Fe3O4 + H2
The regenerated NaOH further enhances the corrosion.It is prevented by adding sodium
sulphate, tannin, lignin etc. which blocks the cracks and prevents the infiltration of alkali.
Corrosion control
Design and Selection of materials
Avoid the contact of dissimilar metals in the presence of a corroding media
When two dissimilar metals are to be in contact ,the anodic material should have as
large area as possible compared to cathode.
If two dissimilar metals are in contact have to be used they should be as close as
possible to each other in electrochemical series.
Whenever the direct joining of dissimilar metals,is unavoidable ,an insulating
material may be placed between them to avoid direct contact.
Sharp corners and recesses should be avoided
The equipment should be supported on legs to allow free circulation of air as shown
in figure
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Inorganic coating : Anodizing o f A l :

The process of formation of a film of metal oxide on the surface of a metal by
electrochemical oxidation is known as anodizing.
The aluminium article to be anodized is degreased followed by electropolishing to remove
impurities present on the metal surface.It is connected to positive terminal i.e. made as
anode and steel or copper is made as cathode.
Bath composition:
Electrolyte: 5-10 % Chromic acid/10% H2SO4/Oxalic acid
Temperature: 350 C
Current density: 10-20 mA/cm2
Electrode reaction:
Anode
2Al(s) + 3 H2O(l)
Al2O3 + 6H+ (aq)+ 6e
Cathode
6H(a+q) + 6e
3 H2(g)
Finally the object is treated with nickel or cobalt acetate followed by boiling water
treatment to improve corrosion resistance.
Uses:Used for soap boxes, Tiffin carriers ,window frames etc.
Phosphating :
It is a process of converting surface metal atoms into their Phosphate by chemical or
electrochemical process. Phosphating offers improved corrosion resistance and also
imparts the surface a good paint adhesion quantity. Phosphating bath contains free
phosphate ions, a metal phosphate (Fe,Mn,Zn) & an accelerator. The pH is about is 1.8 to
3.2. and temp is 350C. The reaction involves the dissolution of metal or metal ions, metal
ions reacting with the phosphate ions to form a metal phosphate & deposition of metal
phosphate on the surface of the metal. It is used in refrigerators, washing machines car
bodies to provide better paint adhesion in addition to improve corrosion resistance.
Metal coating
Deposition of a protective metal over the surface of a base metal is called metal coating.It
is divided in to two types:anodic and cathodic coating
Anodic coating(Galvanization)
Galvanization is a process of coating a base metal surface with zinc metal by hot dipping
process.It involves the following steps:
The metal surface is washed with organic solvents to remove grease and oil
Rust and other deposits are removed by washing with dilute H2SO4
Finally the article is washed with water and dried
The article is then dipped in a bath of molten zinc maintained at 425-4300C and
covered with NH4Cl flux to prevent the oxidation of molten zinc.
The excess zinc on surface is removed by passing through a pair of hot rollers,which
wipes out excess of zinc coating and produces a thin coating.
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Uses It is used to protect iron from corrosion in the form of roofing sheets,fencing
wire,buckets,bolts, nuts, nails ,screws, pipes etc.
They are not used for preparing and storing food stuffs,since zinc dissolves in dilute acids
producind toxic zinc compounds.
Tinning :
It is produced by coating a base metal with a more noble metal which is cathodic.Tinning is
the most commonly used cathodic coating on steel surfaces by hot dipping process and
involves the following steps
The metal surface is washed with organic solvents to remove grease and oil
Rust and other deposits are removed by washing with dilute H2SO4
Finally the article is washed with water and dried
The clean and dry sheet is passed through molten zinc chloride flux which helps
the molten metal to adhere on the metal surface
Then it is passed through a tank containing molten tin
Finally passed through series of rollers immersed in palm oil .The rollers wipes
out excess of tin deposits and produces a continuous , thin coating of tin.the oil
prevents the oxidation of the tin coated surface
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It protects against corrosion only if it covers the steel surface completely.Since tin is
cathodic to iron even if small crack is formed intense corrosion takes place due to small
anode and large cathode areas.
Uses:It is used for storing food stuffs such as jam,,instant food,milk products etc.
CATHODIC PROTECTION:
Cathodic protection is a method of protecting a metal or alloy from corrosion by
converting base metal completely into cathodic and no part of it is allowed to act as anode.
The principle of cathodic protection is to reverse the flow of electrons during corrosion.
This can be achieved by providing electrons from external sources that the specimen
always remains cathodic. The electrons can be provided by two methods.
Sacrificial anodic method:
In this method the more reactive metals(sacrificial anodes) like Zn, Mg which provide
electrons connected to the metal structure to be protected.The base metal will become
cathodic &more reactive metal become anode, preferentiallycorrosion occurs at anode.
The sacrificial anode which gets corroded, has to be replaced to protect base metal
continuously.
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Example: A Mg block connected to a buried oil storage tank.
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IMPRESSED CURRENT METHOD:

In this method the electrons for cathodic protection are supplied by a source of direct
current .The specimen to be protected should be made ve otherwise it corrodes. This is
used in buried oil pipe lines, water storage tanks.
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METALFINISHING:
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Contents:
Introduction, Technological importance.
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Introduction,Technologicalimportance.Electroplating:introduction,principles
governing-Polarization, decomposition potential and overvoltage. Factors
influencing the nature of electro deposit-current density, concentration of
metal salt, metal ion & electrolyte;pH, temperature & throwing power of
plating bath, additives-complexing agents, brighteners,levellers, structure
modifiers & wetting agents. Electroplating of chromium and gold
(acidiccyanide bath). Electro less plating: Introduction, distinction between
electroplating and electroless plating, electro less plating of copper &
manufacture of double sided Printed Circuit Boardwith copper.
5 Hours
Electroplating: Introduction, principles governing
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Polarization, decomposition potential and overvoltage.
Factors influencing
the nature of electro deposit-current density,
concentration of metal salt, metal ion & electrolyte;
pH, temperature & throwing power of plating bath,
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additives-complexing agents, brighteners,levellers, structure modifiers &

wetting agents.
Electroplating of chromium and gold (acidiccyanide bath).
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Electro less plating: Introduction, distinction between electroplating and

electro less plating,
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electro less plating of copper & manufacture of double sided Printed Circuit
Board
with copper.
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Definition: It is defined as a process carried out in order to modify the surface properties of
a metal by deposition of a la yer of another metal, polymer or by formation of oxide layer.
Technological importance of metal finishing:
It is the addition of certain properties to the materials to increase the utility of the
material.
These include
to increase corrosion resistance
to improved wear resistance
to impart electrical and thermal conducting surface
imparting thermal resistance
imparting hardness
to offer the surface thermal or optical reflectivity
manufacture
of
electrical
and
electronic
components
such
as
PCBs,capacitors,contacts
electroforming process
electropolishing,electrochemical etching
The important techniques of metal finishing are electroplating and electro less plating
Electroplating:It is a process of electrolytic deposition of metal,alloy or composite on the
base metal by means of electrolysis.
The three factors governing the electrolysis are polarisation,decomposition potential and
over voltage.
Polarisation:It is defined as the departure of the electrode potential (increase or decrease)
due to inadequate supply of species from the bulk of solution to the electrode surface.
The electrode potential is given by the Nernst equation
E = Eo + 0.0591/n log [Mn+]
Where E-electrode potential, Eo standard electrode potential and [Mn+] is the metal ion
concentration.In presence of electric current metal ion concentration decreases due to
deposition of metal.When the diffusion rate of metal ion is slow the variation in electrode
potential is observed.At that stage the electrode is said to be polarized.
Factors depending on polarisation are
i.Nature of electrode (size&shape) ii.Concentration of electrolyte and its conductance
iii.Temperature iv.Products formed at electrode v.Rate of stirring of the electrolyte. To
decrease the polarisation effect the electrode surface must be large and low concentration
of electrolyte with high conductance.
Decomposition potential:The minimum external voltage applied in order to cause
continuous electrolysis of an electrolyte is called decomposition potential. It is measured
using an el ect rol yt i c cell .
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Determination of decomposition potential :

The cell consists of two platinum electrodes immersed in the electrolyte.The voltage is
varied by moving the contact C along the wire AB and the current passing through the cell
is measured with ammeter.When dilute solution of acid or base is taken in the cell,at low
voltage i.e. Less than 1.7 V no reaction is found to occur because the inert platinum
electrodes are converted in to active hydrogen and oxygen gas electrodes.The secondary cell
formed produces back emf
opposing the applied emf.When the voltage is increased above 1.7V sudden evolution of H2
and O2 gas takes place at the respective electrodes.The abrupt increase in current also
observed at this point.The decomposition potential is calculated by plotting current versus
applied voltage as shown in the graph.
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The intersection of these two straight lines gives the decompositon potential mathematically
Eback emf = Ecathode - Eanode
The decompositon potential values enables the
i.Calculation of emf required for continuous electrolysis
ii.used in separation of metal ion mixture by electrolysis
Over voltage: The excess voltage that has to be applied above the theoretical decomposition
potential to start the continuous electrolysis is called Over voltage.
ED = Ecathode - Eanode + , where -over voltage
The factors influences the over voltage are
i.Electrode surface ii.Current density iii. Temperature iv. Rate of stirring of the electrolyte
v.Nature of substance discharged.
For example the reversible electrode potential of ox ygen gas with smooth platinum electrode
surface under standard condition is 1.23 V . But actual gas evolution takes place at a
potential of 1.68V.This excess 0.45 V is the over voltage of ox ygen on smooth platinum
surface.
The knowledge of over voltage is used in the electrolysis for deposition of metals.Higher the
electrode potential cations will be easily discharged at the electrode surface.
Electroplating process:
It is a process of electrolytic deposition of metal,alloy or composite on the base metal by
means of electrolysis. The deposits are Single metals such as Sn,Cu,Ni,Cr,Ag,Au,Pt etc.
Alloys like Cu-Zn,Cu-Sn,Sn-Ni,Ni-Co,Ni-Cr etc.
Composites such as metals containing solids like WC,SiC
The principal components of electroplating are
1.An electroplating bath containing conducting salt,metal to be plated in soluble
form,complexing agent,additives,buffering agent.
2.Cathode i.e. the article to be plated
3.Anode:Coating metal itself or inert electrode
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4.An inert container to hold all above components.

The object to be plated is made as cathode and the possible reactions at cathode is
Mn+ + ne
M
The dissolution of metal at anode takes place.If the inert anode is used the ox ygen evolution
takes place and metal ions are added in the form of metal salt.
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M
Mn+ + ne
The electrolysis conditions are maintained in such a way that current efficiencies of both
reactions are same.For successful electroplating pretreatment of object,careful selection of
anod with proper plating bath solution,current density and other electrolysis conditions are
necessary.
Factors influencing the nature of electrodeposit:
Current density : It is the current per unit area of the electreode surface(mA/cm2)
At low current densities surface diffusion is fast compared to electron transfer and
adatoms find most favorable position resulting in well formed deposit.
As the current density increased surface diffusion is slowed down compared to electron
transfer and adatom may not reach most favorable position resulting in less ordered deposit.
At very high current density (below limiting value) mass transport predominates in
solution resulting in bad deposit with rough and powdery texture which is poorly adherent to
surface.
When current density is increased beyond limiting current burnt and spongy appearance
of deposit takes place.This is due to depletion of H+ ions at the cathode and formation of
metal hydroxide also takes place. There fore optimum current density should be applied to
get good deposit.
Plating bath:
Metal salt and electrolyte concentration:The metal salt concentration is kept high to
decrease the mass transfer otherwise the quality of plating is adversely affected.Electrolytes
are also added to increase the conductivity of the plating bath.They also have the role of
controlling the pH of bath solution particularly if the evolution of H2 or O2 at cathode or
anode.H2SO4 is added to prevent h ydrolysis of salt.Boric acid is used as buffering agent.
Complexing agents : These are added to convert free metal ions in to complexing ions to
get fine grained and more adherent deposit.They are also added for the following reasons
To prevent the reaction of cathode metal and plating ions
To prevent passivation of anode and increase in current efficiency
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To improve throwing power of plating bath

To increase the stability of slightly soluble metal salts
To make potential of plating Mn+ more -ve to carry out plating at lower potential.
The most common complexing agents are cyanides,h ydroxides,sulphamates,citrates,
tartarates etc.
Organic additives :A wide range of organic compounds are added in low concentration to
modify the structure,morphology and properties of the deposit.The common additives are
a)Brightners :These are added to get bright and light reflecting deposit.The reflection takes
place only when grain size of deposit is lower than the wave length of the incident
light.Brightners used to produce microscopically fine deposit parallel to substrate surface.
Ex.Aromatic suphones or sulphonates and compounds containing C= N,N=C=S, or >C=O
groups.
b)Levellers:Substrate surface may contain dislocations where plating takes place faster
resulting uneven thickness.When levelers are used they absorb at such regions where rapid
deposition takes place and prevent rate of electron transfer.ex.Sodium allyl sulphonates.
c)Stress relievers or structural modifiers:An electroplating process involves internal
stress.If the stress level is high cracking takes place. Stress relievers reduces the formation of
internal stress by modifying the structure of the deposit.Ex.Saccharin
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d)Wetting agents:In electroplating hydrogen gas evolved at cathode and these gas bubbles
adhere to the cathode surface.The gas may try to escape when the plating is over and makes
the deposit porous and brittle.Wetting agents added detach adsorbed h ydrogen gas on the
cathode surface and improve the adhesion of the deposit. Ex.Sodium lauryl sulphate.
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PH: At low pH value , hydrogen gas evolution takes place causing deposit brittle and burnt.
At higher pH deposits of insoluble metal h ydroxides takes place.Hence optimum pH is
maintained by using suitable buffers.
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Temperture:At slightly higher temperature good deposit takes place due to increase in the
surface diffusion of ions.But at high temperature decomposition of organic additives,
corrosion of equipment and hydrogen evolution may takes place.Hance optimum
temperature is used(30 to60o C)
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Throwing power:The ability of the plating bath to give uniform and even deposit on the
entire surface of cathode of irregular shape.
It is determined by Haring blum cell.It consists of insulating container filled with electrolyte
whose throwing power is to be determined. Anode is placed at the center and two cathodes
(C1&C2)are placed at different distances d1& d2(d1>d2) as shown in the fig.
Electroplating is carried out for sufficient time and weights w1&w2 deposited on cathodes
C1&C2 are determined.
The weight of deposit (w1) on cathode C1 is less because of its lower over potential .
It is calculated by the equation
% Of TP =100(x-y) /(x+y-2)
where x= d1/d2 & y=w2/w1
Determination of throwing power
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Electro-plating of chromium:
Ba t h
: Cr2O3 250 g + 2.5 g H2SO4(100:1)
Temperature
: 45-55 C
Current density : 100-200 mA/Cm2.
Current efficiency: 10-15%
Anode
: Insoluble anode Pb-Sb or Pb-Sn coated with PbO2
Cathode
: Object to be plated.
At anode:
CrO3 + H2O
H2 C rO4
2 H2CrO4
H2Cr2O7 + H2O
Cr2O7 -2 + 2H+ +H2O
Cr2O7 -2 + 14 H+ + 6e
2Cr+3 + 7 H2O
+3
Cr
+ 3e
Cr
At Cathode: 2 H2O
O2 + 4H+ + 4e
Sulphuric acids acts as catalyst in converting Cr(VI) to Cr(III) by complex anodic
reaction. To maintain the concentration of Cr(III) ions insoluble anodes like Pb-Sb,
P bSn, alloys are used covered PbO2 which oxidize Cr(III) to Cr(VI)& controls the
concentration of Cr(III) ions.
1) Cr metal passivates strongly in acid sulphate medium.
2) It gives Cr(III)ions on dissolution.In presence large Cr(III) ions a block Cr deposit is
obtained .
3)Difference in efficiency of anode and cathode(anode -100% cathode -20%).
Uses: Used in decorative and corrosive resistant finish. Decorative & durable finish like
cycles ,automobiles ,furniture, house hold fittings, surgical and dental instruments, others
like optical instruments ,machine tools, electronics parts, piston rings, cylinder liners of
diesel engines& aircrafts cylinders.
Electro plating of gold (alkanie cyanide bath) :
Gold plating baths are divided in to three types based on pH range
i.Alkaline cyanide bath(pH 10 to 13)
ii.Neutral cyanide bath(pH 6 to 9)
iii.Acid cyanide bath (pH 3.5to 5.0)
The alkaline cyanide bath composition is
Ba t h
: pot. Gold cyanide 12-15gL-1, Citric acid, Cobalt
PH
:3.6-4.5
Temperature
:40-65oC
Current densit y
: 86-252 mAcm-2
Additives : Citrate Buffer , Sodium allyl sulphonate as leveler
Anode
:Platimised titanium , gold,or graphite
Cathode
: object to be plated
C h em cal as o rp t i o n o f [ A u (C N 2 )] - C o m p l ex
[ Au (C N2 )] (Au C N) (a d ) + C N The chemical desorption and crystallization make up the final step
(Au C N) (a d ) + e (Au 0 C N )- (a d )
0
(Au C N ) (a d )
A u l at t i c e + C N The equilibrium depend on the crystal orientation of the substrate and presence of
i m p u ri t i es s u c h a s n i ck el t h at c an af f ect t h e n u cl e at i o n r at e an d h ar d n es s o f t h e g o l d .
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Uses:
Used in decorative purposes like jewellary,watch case ,pen points etc
Electrical industry like PCB, contacts
Electronic industry like transistors, integrated circuit parts
Reactors and Heat exchangers in the conductor tube because of good corrosion
resistance.
Electroless plating: It is defined as deposition of metal or alloy from metal salt solution on
to a electrilytically active surface by controlled chemical reduction of Mn+ ions by suitable
reducing agents without using electrical energy .
Advantages:
1) Does not require electrical power source.
2) Semiconductors & insulators like plastic can be coated.
3) Good throwing power, hence uniform coating is achieved on article of irregular shape.
4) Plating is harder than electro-plating.
5) Deposits have unique chemical, mechanical and magnetic properties.
6) Levelers are not used.
Distinction between Electro-plating and electro less-plating
Driving force
Anode reaction
separate anode
article to be plated
pure metal or definite alloy

not satisfactory
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Nature of deposit
Throwing power
M + ne
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Cathode reaction
Site of anode
reaction
Site of cathode
reaction
n+
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Electro-plating
power supply
M
Mn+ + ne
Or H2O
O2 + H+ + e -
applicable only toconductors
R
Oxidized product+ne
n+
M + ne
M
article to be plated
article to be plated with
Catalyticallyactivesurface
Metal contaminated with O/R
species
good
applicable both for conductors and
non Conductors
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Application
Eelectro less -plating

auto-catalytic redox reaction
Electroless plating of copper

Pretreatment and activation of surface:The surface is treated to remove grease and other
impurities.In case of insulators ,the surface is activated by dipping in stannous chloride and
then in palladium chloride.The surface is dried.
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Plating bath:
Ba t h
Reducing agent
Buffer
Complexing agent
pH
Temoerature
: Copper sulphate 12 g per litre

: Formaldeh yde 8 g per litre
: NaOH 15 g/litre & Rochelle salt 14 g/litre
: EDTA 20 g /litre
: 11
0
: 25 C
2 HCOO + 2 H2O + H2 + 2e
Cu
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Double sided
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Reactions
At anode
2 HCHO + 4 OH
At cathode Cu2+ + 2e
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Printed circuit board Uses: Used in printed circuit board,plating on nonconductors,plating

through hole connections.
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MODULE-3
FUELS AND SOLAR ENERGY
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Fuels: Introduction, classification, calorific

value-gross and net calorific
values,determination of calorific value of fuel using bomb calorimeter,numerical
problems.Cracking: Introduction,fluidized catalytic cracking,synthesis of petrol by
Fishcher-Tropsch process,reformation of petrol,octane and cetane number.Gasoline
anddiesel.Knocking and their mechanism, antiknocking agents, unleaded petrol,
poweralcohol,biodiesel and biogas.
5Hours
Introduction, classification.
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Content :
Calorific value-gross and net calorific values,determination of calorific

value of fuel using bomb calorimeter,numerical problems.
Cracking: Introduction,fluidized catalytic cracking,synthesis of petrol by

Fishcher-Tropsch process,reformation of petrol.
Gasoline and diesel .Knocking and their mechanism,antiknocking

agents,unleaded petrol,.
power alcohol,biodiesel and biogas.
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octane and cetane number.
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Fuels
Secondary fuels
Charcoal, coke
Petrol,diesel,kerosene
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Primary fuels
Wood, coal
Petroleum
Natural Gas
LPG
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Physical state
Solid
Liquid
Gas
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Introduction and classification:

Definition of a chemical fuel: A chemical fuel is a substance, which produces a
significant amount of heat enegy and light energy when burnt in air or ox ygen
Classification of chemical fuels: Chemical fuels are classified as primary and secondary
fuels.
Fuels, which occur in nature, are called primary fuels. Fuels, which are derived
from primary fuels, are called secondary fuels. Chemical fuels are further classified as
solids, liquids and gases. A complete classification of fuels with examples is shown in the
following table.
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Calorific value-gross and net calorific values, determination of calorific value of fuel
using bomb calorimeter, numerical problems:
Definition of calorific value of a fuel [Gross calorific value]: It is defined as the
amount of heat liberated when unit quantity (1 kg or 1 m3 ) of a fuel is completely burnt
in air or oxygen and the products of combustion are cooled to room temperature.
Definition of net calorific value: It is defined as the amount of heat released when unit
quantity of a fuel is completely burnt in air or oxygen and the products of combustion are
let off into the atmosphere .
S. I. unit of calorific value: For solids, calorific value is expressed in J kg-1 (Joules per kg).
For gaseous fuels it is expressed in J m-3 (Joules / m3).
Determination of calorific value of a solid fuel using Bomb Calorimeter:
Principle: A known mass of the solid sample is burnt in excess ox ygen. The surrounding
water and the calorimeter absorbs the heat liberated. Thus the heat liberated by the fuel is
equal to the heat absorbed by the water and the calorimeter.
Construction: The bomb calorimeter consists of a stainless steel vessel with an
airtight lid. This vessel is called bomb. The bomb has an inlet valve for providing
oxygen atmosphere inside the bomb and an electrical ignition coil for starting of
combustion of fuel. The bomb is placed in an insulated copper calorimeter. The
calorimeter has a mechanical stirrer for dissipation of heat and a thermometer for
reading the temperature.
Working: A known mass of the solid fuel is placed in a crucible. The crucible is placed
inside the bomb. The lid is closed tightly. The bomb is placed inside a copper
calorimeter. A known mass of water is taken in the calorimeter. The bomb is filled with
ox ygen at a pressure of 25-30 atm. The temperature t1 in the thermometer is noted. On
passing an electric current through the ignition coil, the fuel gets ignited. The fuel
burns liberating heat. The water is continuously stirred using the stirrer. The maximum
temperature attained by the water, t2 , is noted.
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Oxygen
Stirrer
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Wires for ignition

Thermometer
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Sample
Observation and calculations:
(w1 + w2 ) s t
m
J kg-1
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Gross calorific value =
w
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where
w = w1 + w2
= mass of water in the calorimeter, in kg + water equivalent of the calorimeter, in kg
s = specific heat of water, in J kg-1 oC-1
t = t2-t1 = rise in temperature, in oC
m = mass of the fuel, in kg
(Note: If the mass of fuel is given in grams, convert that into kg. For example, 0.2 g = 0.2
10-3
kg. If specific heat of water is given in J kg-1 oC-1, calorific value will be in J kg-1. If the
specific
heat is given in kJ kg-1 oC-1, then the calorific value will be in kJ kg-1.)
(Note: Specific heat of water is the amount of heat energy required to increase the
temperature of
one kg of water by one degree C.)
Problem 1. Calculate the calorific value of a sample of coal from the following data:
Mass of Coal = 0.6 g
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m = 0.6 g = 0.6 10-3 kg

w1 + w2 = 2200 g = 2.2 kg
s = 4.187 kJ kg-1 oC-1 = 4.187 103 J kg-1 oC-1
t = 6.52o C
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Given:
(w1 + w2 ) s t
J kg-1
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Mass of water + water equivalent of calorimeter = 2200 g

Specific heat of water = 4.187 kJ kg-1 oC-1
Rise in temperature = 6.52 oC
Solution:
(Note: In solving the problem, follow the steps given below:
1. Write the given quantities and convert them into appropriate units.
2. Write the equation.
3. Substitute the values.
4. Simplify using calculator if necessary.
5. Write the answer.
6. Write the units.)
2.2 4.187 10 3 6.52

0.6 10 -3
1.001 108 J kg-1
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Problem 2. A 0.85 g of coal sample (carbon 90 %, H2 5%, and ash 5% ) was

subjected to
combustion in a bomb calorimeter. Mass of water taken in the calorimeter was 2000 g
and the
water equivalent of calorimeter was 600 g. The rise in temperature was 3.5 oC.
Calculate the
gross and net calorific value of the sample. (Given, specific heat of water = 4.187 kJ
kg-1 oC-1
and latent heat of steam = 2454 kJ kg-1 )
Solution: Given
m = 0.85 g = 0.85 10-3 kg

% of hydrogen = 5%
w1 = 2000 g = 2 kg
w2 = 600 g = 0.6 kg
t = 3.5 oC
s = 4.187 kJ kg-1 oC-1 = 4.187 103 J kg-1 oC-1
L = 2454 kJ kg-1 = 2454 103 J kg-1
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(w1 + w2 ) s t
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(2 + 0.6 ) 4.187 10 3 3.5
0.85 10 -3
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a) Gross C.V. =
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= 4.4825 107 J kg-1
100 kg of coal contains 5 kg of H2 (given).

1 kg of coal contains
5 1
100
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b) Calculation of Net C.V.:
= 0.05 kg of H2
0.05 kg of H2 produces
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W.k.t. 2 kg of H2 produces 18 kg of steam (from the equation

H2 + 1/2O2
H2O
1 8 0 .0 5
= 0.45 kg of steam.
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Heat released when 1 kg of steam condenses = 2454 103 J (given).
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Heat released when 0.45 kg of steam condenses =
2454 103 0.45

1
= 1.104 106 J
= 0.1104 107 J
= Q2
= 4.4825 107 - 0.1104 107

= 4.3721 107 J kg-1
(Note: Latent heat of steam is the amount of heat energy liberated when one kg of
steam is
converted into one kg liquid water.)
3. On burning 0.75g of a solid fuel in a bomb calorimeter the temperature of 2.5kg of
water is
increased from 240C to 280C the water equivalent of calorimeter and latent heat of
steam are
0.485 Kg and 4.2X587 KJ/Kg, specific heat of water is 4.0KJ/Kg/0C
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Net C.V. = Q1 - Q2
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2.985 X 4 X 4.2 X 103

J / Kg = 6.66 X 10 7 J / Kg
0.75 X 10 -3
100g of coal contains 2.5g of H2
We know that
2 Kg of H2 produces 18 Kg of steam
0.025 X 18
= 0.225 Kg Steam
2
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0.025 Kg of H2 produces =
100
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Given
(w1 + w2 ) s t
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a) Gross C.V. =
m = 0.75 g = 0.75 10-3 kg

w1+W2 = (2.5+0.485) kg = 2.985 kg
t = t2-t1=28-24=4 oC
s = 4.2 kJ kg-1 oC-1 = 4.2 103 J kg-1 oC-1
L = 2454 kJ kg-1 = 2454 103 J kg-1
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Solution: Given
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Given, Heat released when 1Kg of steam releases =(4.2X 587) KJ/Kg=2465.4X103J/Kg
So
heat
released
when
0.225
Kg
of
steam
released,
Latent
Heat
2465.4 X 103 X 0.255
=
= 0.05547 X 10 7 J / Kg
1
NCV = [GCV-Latent heat of steam] = [6.66 X 107 0.05547 X 107] J/ Kg
= 6.60 X 107 J/Kg
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5. On burning 0.96g of a solid fuel in bomb calorimeter the temperature of 3500g of

H2O increased by 2.70C water equivalent of colorimeter and latent heat of steam are 385
g and 587 cal/g respectively. If the fuel contains 5% H2 calculate its gross and net calorific
value.
Given:
m=0.96g=0.96X10-3Kg
W1=3500g=3500X10-3Kg
W2=385g= 385X10-3Kg
t=2.70C
Latent heat =587 cal/g = 587X4.18X103 J/Kg
S= 4.187X103J/Kg/0C
(w1 + w2 ) s t
J / Kg
m
(3500 X10 -3 + 385 X10 -3 ) 4.187 10 3 2.7

0.96 10 -3
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14CHE22

5 1
100
= 0.05 kg of H2
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W.k.t. 2 kg of H2 produces 18 kg of steam (from the equation H2 + O2 H2O)

1 8 0 .0 5
= 0.45 kg of steam.
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6. calculate the grass and net calorific value of coal sample from the fallowing
data
obtained from bomb calorimeter requirement
Weight of coal sample taken = 0.085 Kg
Weight of water taken in the colorimeter= 1.4Kg
Water equivalent of colorimeter=0.47Kg
Initial temperature t1 = 250C
Final temperature= t2= 27.3 0C
Percentage of H2 in coal sample = 5%
Latent heat of steam = 587 X4.2KJ/Kg=587X4.2X103 J/Kg
Specific heat of water = 4.187 KJ/Kg = 4.187 X 103 J/Kg
(w1 + w2 ) s t
J / Kg
1.87 4.187 10 3 2.3

0. 0 8 5
Solve
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w
w
5 1
100
= 0.05 kg of H2
W.k.t. 2 kg of H2 produces 18 kg of steam (from the equation H2 + O2 H2O)
1 8 0 .0 5
= 0.45 kg of steam.
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CRACKING :
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Definition of cracking: Cracking is defined as the process of converting high molecular

weight hydrocarbons into lower molecular weight hydrocarbons.
C7H16 + C7H14
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Fluidized bed catalytic cracking:

Principle: In fluidized bed catalytic cracking, the powder catalyst is kept agitated by gas
streams (cracking fuel) so that the catalyst can be handled like a fluid system. This also
results in a good contact between the catalyst surface and the reactant.
Construction: A schematic diagram of fluidized bed catalytic cracking method is shown
in the
following figure.
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Optimum conditions:
Catalyst used: y- type zeolite activated with a rare earth oxide(Al2O3+ SiO2)
Temperature: 5500 C
Working: The feed stock vapours are passed into cracking chamber. The reactants
undergo cracking in the presence of catalyst. The products are passed to a fractionating
column. Spent catalyst from the cracking chamber is continuously transported into
the regeneration chamber through an air stream. The carbon deposited on catalyst
particles is burnt off in regeneration Chamber. The regenerated catalyst is transported
back into the cracking chamber
together with feed stock.
Fischer Tropsch Process:
The FischerTropsch process involves a series of chemical reactions that produce a variety of
hydrocarbons, ideally with to the formula (CnH(2n+2)). The more useful reactions produce alkanes
as follows:
(2n + 1) H2 + n CO CnH(2n+2) + n H2O
where n is typically 10-20. The formation of methane (n = 1) is unwanted. Most of the alkanes
produced tend to be straight-chain, suitable as diesel fuel. In addition to alkane formation,
competing reactions give small amounts of alkenes, as well as alcohols and other oxygenated
hydrocarbonsThe FischerTropsch process involves a series of chemical reactions that produce a
variety of hydrocarbons, ideally with to the formula (CnH(2n+2)). The more useful reactions
produce alkanes as follows:
(2n + 1) H2 + n CO CnH(2n+2) + n H2O
where n is typically 10-20. The formation of methane (n = 1) is unwanted. Most of the
alkanes produced tend to be straight-chain, suitable as diesel fuel. In addition to alkane
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formation, competing reactions give small amounts of alkenes, as well as alcohols and other
oxygenated hydrocarbons.
The Fischer-Tropsch process:
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The Fischer-Tropsch process is a catalyzed chemical reaction in which carbon dioxide, carbon
monoxide and methane are converted into liquid hydrocarbons of various forms. Typical
catalysts used are based on iron and cobalt.
The principal purpose of this process is to produce a synthetic petroleum substitute.
CH4+1/2O22H2+CO
(2n + 1) H2 + n CO CnH(2n+2) + n H2O
The mixture of carbon monoxide and hydrogen is called synthesis gas or syngas. The resulting
hydrocarbon products are refined to produce the desired synthetic fuel.
The carbon dioxide and carbon monoxide is generated by partial oxidation of coal and woodbased fuels. The utility of the process is primarily in its role in producing fluid hydrocarbons or
hydrogen from a solid feedstock, such as coal or solid carbon-containing wastes of various types.
Non-oxidative pyrolysis of the solid material produces syngas which can be used directly as a
fuel without being taken through Fischer-Tropsch transformations. If liquid petroleum-like fuel,
lubricant, or wax is required, the Fischer-Tropsch process can be applied. Finally, if hydrogen
production is to be maximized, the water gas shift reaction can be performed, generating only
carbon dioxide and hydrogen and leaving no hydrocarbons in the product stream. Fortunately
shifts from liquid to gaseous fuels are relatively easy to make.
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REFORMATION
Definition of reformation of petrol: Conversion of straight chain hydrocarbons in

petrol into branched chain, cyclic and aromatic hydrocarbons, resulting in upgradation of
petrol is known as reformation .
How reformation improves the quality of petrol?
The octane number for straight chain h ydrocarbons is low. For branched chain,
cyclic and aromatic hydrocarbons, the octane number is high. Thus reformation
converts the low octane number petrol into high octane number petrol.
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H3C CH2 CH2 CH2 CH2
CH2 CH3
CH
CH2
CH3
CH2
CH2
CH3
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n-Heptane
H3 C
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Reformation reaction conditions:

Reactant (feed stock) : Gasoline obtained by fractionation of petroleum + H2
Catalyst : Platinum supported on alumina (Pt / Al2O3 )
Temperature : about 500 oC
Pressure : 15-50 atm.
Reformation reactions:
The main reformation reactions are:1) Isomerization, 2) Dehydrogenation and
3) Cyclization and dehydrogenation.
1) Isomerization:
Example: n Heptane 5 - Methyl hexane
2-Methyl-h exan e
2) Dehydrogenation:
C yclo hexane Benzene + Hydrogen
C6H6 + 3H2
Benzene
C6H12
Example:
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Cycloh exane
3) Cyclization and dehydrogenation

C6H6 + 3H2
Benzene
C6H12
Cyclohexane
Octane number is the percentage by volume of isooctane present in a mixture of

isooctane and n heptane which has the same knocking characteristic as the petrol under
test.
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Octane Number
The resistance to knocking offered by petrols is expressed in terms of an arbitrary scale
called octane number
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The octane value of isooctane is arbitrarily taken as 100 and that of n heptane as zero.
Different standard mixtures ( 90:10; 80:20, 75:25 etc) of isooctane and nheptane are
prepared and the compression ratio of each of these is determined under standard
conditions.
The compression ratio of the fuel under test is determined under the same conditions.
Suppose the compression ratio of the fuel is same as that of 80 :20 mixture, the octane
number of the fuel is 80.
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Cetane Number:
The resistance to knocking offered by diesels is expressed in terms of an arbitrary scale

called cetane number
It is the percentage by volume of cetane present in a mixture of cetane and D- methyl
naphthalene which has the same knocking characteristic as the diesel under test.
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Knocking in petrol engines:
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In petrol engines, the mixture of petrol and air is drawn in to the cylinder. The fuel-air
mixture is compressed by the piston and is ignited by an electric spark.
As the flame front travels in the combustion chamber, rapidly expanding combustion
products compress the remaining unburnt fuel and raise its temperature. If the flame front
travels rapidly at an optimum speed, the combustion of unburnt fuel takes place smoothly.
On the other hand, if the flame front travels too slowly, the entire last portion of fuel
mixture may get heated up beyond its ignition temperature and undergo instantaneous
explosive combustion. This result in emission of a characteristic rattling sound called
knocking.
Definition of knocking: Knocking may be defined as the production of a shock wave in
an IC engine as a result of an explosive combustion of fuel-air mixture, leading to a
rattling sound.
Knocking in IC Engines
x The power output and efficiency of an IC engine depends on the Compression ratio
which is the ratio of the volume of the cylinder at the end of the suction stroke to the
volume of the cylinder at the end of the compression stroke.
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Compression ratio =
Volume of cylinder at end of compression stroke
Under ideal conditions, in an IC engine the petrol-air mixture drawn into the cylinder of
the engine undergoes compression and then ignited.
The hydrocarbons in petrol undergo complete combustion and the flame propagates
smoothly.
Sometimes, due to deposits of carbon on the walls of the cylinder the hydrocarbons in
petrol form peroxy compounds.
The accumulated peroxides decompose suddenly and burst into flames producing shock
waves.
The shock wave hits the walls of the engine and the piston with a rattling sound.
This is knocking.
The reactions that take place in an IC engine are given below (taking ethane as an
example for the hydrocarbon present in petrol):
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Volume of cylinder at end of suction stroke
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Under ideal conditions

C2H6
+ 7/2 O2
2 CO2
+ 3H2O
CH3 O-O- CH3
CH3CHO + H2O
CH3CHO + 3/2 O2
HCHO + CO2 + H2O
HCHO + O2
H2O + CO2
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CH3 O-O- CH3

(Dimethyl peroxide)
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+ O2
Note that the overall reaction is the same under both the conditions. One molecule of
ethane reacts with 7/2 molecules of oxygen forming carbon dioxide and water with the
release of energy.
Under ideal conditions, the energy is released at a uniform rate.
Under knocking conditions, the energy is released slowly at first followed by a lag
(formation of peroxides) and finally the energy is released at a very fast rate
(decomposition of peroxides)
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Under knocking conditions
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Ill effects of knocking

1. Decreases life of engine
2. Causes Piston wrap
3.Consumption of fuel is more
Antiknocking agent:
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Antiknocking agent is a chemical substance added to petrol to improve the antiknocking

property of the petrol. For example, tetra ethyl lead (TEL). Addition of TEL to petrol
increases the octane number of petrol. TEL is normally used along with ethylene
dibromide or ethylene dichloride. [Formula of tetra ethyl lead = (C2H5)4Pb ]
Unleaded petrol: Unleaded petrol is the petrol where tetra ethyl lead (TEL) is not used
as an antiknocking agent. Addition of TEL to petrol leads to release of PbBr2 and
PbCl2 into the atmosphere through automobile exhaust. This results in air pollution.
To prevent air pollution, unleaded petrol is preferred. In unleaded petrol, methyl-t-butyl
ether (MTBE) and ethyl-t-butyl ether (ETBE) are used as antiknocking agents.
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POWER ALCOHOL
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This is alcohol-blended petrol.

Gasohol is a blend of 10 85% of absolute ethanol and 90 15% of petrol by volume
and is used as a fuel in the United States. Absolute alcohol is used in the preparation of
Power alcohol to prevent phase separation.
Alcohol contains higher percentage of oxygen than MTBE and hence brings about
complete oxidation of petrol more effectively.
Therefore power alcohol has better antiknocking characteristics than unleaded petrol.
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Advantages of power alcohol
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x power output is high

x does not release CO, causes less pollution.
x alcohol is obtained from molasses, a agricultural product and hence renewable.
x biodegradable.
x
Biodiesel
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It is an alternative fuel to diesel > It is ecofriendly fuel obtained from renewable

sources like vegetables oils and animal fuels . Vegetable oils like soyabean oil, palm
oil,peanut oil are used to obtain biodiesel.
The trigl ycerides are needed to converted into biodiesel by a process caleed
transesterfication .During trans esterification,the triglyceride is treated with methanol or
ethanol in the presence of base to form methyl or ethyl ester of fatty acids
Trigl yceride +3CH30H
R1COOCH3+R2COOCH3+ R3COOCH3+ Gl ycerol
Before subjecting the oil for trans esterification process, free fatty acid of oils are to be
esterfied in the presence of an acid catalyst otherwise a semisolid soap will form
and it affects the performance of the engine as well as separation of glycerol from diesel
layer Where R1 ,R2, R3 are long chain fatty acids , Transesterification is carried
above the BP of alcohol around 55 -60.C for a period of 1 to 8 hours.The upper la yer of
methyl ester is washed with water and is purified further to remove excess of alcohol.
Adavantages
Non edible oil can be used

Eco friendly products are formed
Biproducts gl ycerol can be used for various process
It is completely degradable ,non toxic free fronm S compounds
Biogas
Biogas is produced by the breakdown of organic waste by bacteria without oxygen

(anaerobic digestion or fermentation). Biogas is a mixture of methane and carbon dioxide .
Biogas is a fuel used as an energy source for light, heat or movement
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It can also be captured from landfill sites where organic waste has been rotting under
the ground
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Biogas is made by fermenting organic waste in a biogas digester.
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Contents :
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SOLAR ENERGY
Solar Energy : i n t r o d u c t i o n , u t i l iz a t i o n a n d c o n v e r s i o n , p ho t o v o l t a i c c el l s i mp o r t a n c e , c o n s t r uc t i o n
and
w o rk i n g . d e s i g n : mo d u l e s , p a n e l s
and
a r r ay s . a d v a n t a ge s a n d d i s a d v a n t a g e s o f p v c e l l s . s i l i c on - p h y s ic a l a nd
c h e mi c a l p r o p e r t i e s r e l e v a n t t o p h o t ovo l t a i c s , p r o d u ct i o n of s o l a r g r a d e
s i l i c o n ( u n i o n c a r b id e p r o c e s s ) , d o p i n g of s i l i c o n - d i f f u s io n t ec h n i q u e ( n a n d
p t y pe s ) a n d p u ri f i ca t i o n o f s i li c o n ( z o ne r e f i n i n g ).
5 Hours
I n t r o d u c t i o n , u ti l i za t i o n a n d c o n v er s i on .
P h o t o v o l t a i c c e l l s - imp o r t a n c e , c o n s t r u ct i o n a n d w o r k i n g .
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D e s i g n : mo d u l e s , p a n e l s a n d a r r ay s . A dv a n t a g e s a n d d i s a dv a n t a g es
of PV cells.
S i l i c o n - p hy s i c al
and
c h e mi c a l
properties
r el e v a n t
to
p h o t o v o l t a i c s , pr o d uc t i o n o f s o l a r g ra d e s i l i c o n ( u n i o n c a r b i d e
process).
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D o p i n g o f s i l ic o n - di f f u s i o n t e c h ni q u e (n a n d p ty p e s ) ,.
P u r i f i c a t i o n o f S i l i c o n ( Zo n e r e f i n i n g ) .
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I n t r od u c ti o n :
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Light striking certain substances causes the surface of the material to emit electrons. It is as if
light somehow kicks electrons right out of atoms. Light striking other substances causes the
material to accept electrons. It is the combination of these two substances that can be made use
of to cause electrons to flow through a conductor.This is the so called photo-electric effect.
Photovoltaic means sunlight converted into a flow of electrons (electricity). Photovoltaic
devices, or solar cells, are like generators that work in sunlight. They make electricity without
waste, noise or pollution. They produce electricity without combustion. A solar cell is a solid
state device in which there are no moving parts (except for photons and electrons) so nothing
wears out.The fuel is "photons". These can be thought of as "packets of sunlight" that carry a
phenomenal amount of energy to earth at a prodigious rate. The Solar Panels of today make use
of this abundant energy by using silicon crystals with small amounts of impurity added. This
process of adding minute amounts of different elements into an otherwise pure crystal is called
"doping". By having two thin layers of doped material bonded against one another, an electric
current can be induced when exposed to light.
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Solar energy-based water production and recycling;

Power electronics for more-electric aircrafts;
Power drive trains for electric vehicles;
Fuel-cell electric buses;
Solid-state lighting for green buildings.
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The bulk of energy consumption in the world is in the utilization for lighting, cooling,
transportation, industrial applications, water production and consumer applications. All these
will benefit from improved efficiency in the energy conversion process. In lighting, dischargearc lamps can be improved by more energy-efficient ballasts while in the long run, solid-state
lighting systems based on LED and electroluminescence can deliver even better efficiencies.
Better design of variable-speed motor drives is the key to more energy-efficient air-conditioning
and refrigeration. Vast amount of electrical energy is required in modern electric railways and
also increasingly in automotives as vehicles are moving towards greener hybrid designs.
Research into more energy-efficient power converters, electric motors and power integrated
circuits can greatly benefit the transportation sector. Manufacturers of switch-mode power
supplies used in data storage, computing and telecommunication equipment are always in search
of more energy-efficient power semiconductor devices and converter topologies. Clean water
production is another vital process which consumes vast amount of energy, and energy efficiency
in this process is very important. Our current research areas in Efficient Energy Conversion and
Utilization are:
Research in solid-state lighting for green bulding
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Research in solar energy based water production and recycling

Photovoltaic Cells:
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Photovoltaic cells are semiconductor device which convert solar energy into electrical
energy. (Photovoltaic cell is based on the principle of photoelectric effect).
Solar cells :The combination of p & n types of semiconductors is called semi conductor
diodes. These diodes when exposed to magnetic radiation (sunlight) electricity is generated
. such devices are called as photovoltaic cell or solar cell.
Working of Photovoltaic Cell:
A typical silicon photovoltaic cell is composed of a thin water consisting of an ultra thin
layer of phosphorous doped (n-t ype) silicon on top of boron doped (p-t ype) silicon.
Sunlight
Antireflective layer
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n-Type layer
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P- Type layer
Hence
Metallic layer
a p-n junction
is formed
between the two.
A metallic grid forms one of the electrical contacts of the diode and allows light to
fall on the semiconductor between the grid lines.
An antireflective layer between the grid lines increase the amount of light
transmitted to the semiconductor.
The cells other electrical contact is formed by a metallic layer on the back of
the solar cell.
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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 and collected at the 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 and available for use.
Importance of Photoelectric cell
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Photovoltaic cell provides enormous amount of energy from sun which is

unlimited, inexhaustible and renewable.
Photovoltaic cells can serve for both off grid and on grid application.
Photovoltaic cell produces no pollution so it is environment friendl y.
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Photovoltaic cell energy conversion is highly modular. This is important with respect
to the development of electricity supply systems in man y rural and remote areas, where
grid extension is economically not feasible.
It provides power for space craft and satellite.
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.
Developments in the field of Photovoltaic cells will boost the semiconductor
industry and storage battery industries.
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Design:modules,panels and arrays:Sunlight has an energy content of 1 kW (1,000 watts)

per square metre. The typical Solar Panel today achieves between 10% (amorphous solar
panels) and 18% (poly/mono-crystalline solar panels) conversion. The theoretical maximum
efficiency of a silicon cell is about 21%. Using a more costly technology 31% conversion
has been achieved.
What to expect from a Solar Panel
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A single 190 watt solar panel (24V) should produce about 5.5 amps under sunny conditions.
Each day of reasonable sunshine you should expect about 26 amp-hours from one such panel
(based on solar radiation data for north coast NSW). You need to take into account the number of
consecutive days when you may not see much sun, and allow for this by having a large enough
solar array and battery bank to tide you over through such periods. Photovoltaic cells are
connected electrically in series and/or parallel circuits to produce higher voltages, currents and
power levels. Photovoltaic modules consist of PV cell circuits sealed in an environmentally
protective laminate, and are the fundamental building blocks of PV systems.
Photovoltaic panels include one or more PV modules assembled as a pre-wired, field-installable

unit. A photovoltaic array is the complete power-generating unit, consisting of any number of PV
modules and panels.
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The performance of PV modules and arrays are generally rated according to their maximum DC
power output (watts) under Standard Test Conditions (STC). Standard Test Conditions are
defined by a module (cell) operating temperature of 25o C (77o F), and incident solar irradiance
level of 1000 W/m2 and under Air Mass 1.5 spectral distribution. Since these conditions are not
always typical of how PV modules and arrays operate in the field, actual performance is usually
85 to 90 percent of the STC rating.
Figure 1. Photovoltaic cells, modules, panels and arrays.
Advantages of PV cells :
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Todays photovoltaic modules are extremely safe and reliable products, with minimal failure
rates and projected service lifetimes of 20 to 30 years. Most major manufacturers offer
warranties of 20 or more years for maintaining a high percentage of initial rated power output.
When selecting PV modules, look for the product listing (UL), qualification testing and warranty
information in the module manufacturers specifications.
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Fuel source is vast and essentially infinite.

No emissions, no combustion or radioactive residues for disposal. Does not
contribute to global change or pollution.
Low operating cost (no fuel).
No moving parts and so no wear and tear.
High reliability in modules.
No recharging
They do not corrode.
Can be integrated into new or existing building structures.
High public acceptance and excellent record.
Disadvantages of PV cells:
Sun light is a diffuse, i.c., it is relatively low density energy.

High installation cost.
Poor reliability of auxiliary elements including storage.
Energy can be produced only during the day time.
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Physical properties of silicon relative to photovoltaics:

Physical properties of silicon are as follow:
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Silicon is a semiconductor with band gap of 1.2eV at 25oC.

At atmospheric pressure, silicon crystallizes to diamond cube like structure.
Silicon contracts when melted and expand when solidify.
High refractive index limits the optical applications of silicon.
The absorption and transmission properties in the 0.4-0.5 m wavelength
spectra are important in the performance of photovoltaic cells.
Chemical properties relevant to photovoltaics:
Silicon is stable in the tetravalent and has a strong affinity for ox ygen,
formingstable oxides and silicates.
Silicon and carbon form a strong Si-C bond and stable products.
Silicon forms h ydrides, and monosilane (SiH4) is key chemical compound
for the production of Amphrous silicon and the purification of silicon to semiconductor
grade.
Silicon forms trichlorosilane and tetrachlorosilane with chlorine, whi ch
are the intermediates and the by-products of the purification process in metallurgical
grade silicon to semiconductor grade.
Production of solar grade silicon:
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Solar grade silicon has impurities in the ppb level is required for polysilicon
used in semiconductor industry. It can be prepared by using two methods.
Essential silicon is made by the reduction of silica with carbon.At high temperature
silica is reduced to elemental silica. SiO2+ 2C
Si+2CO
CO is further oxidized to CO2 & reduced to atmosphere the silica is in molten state.
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Refining: O2 is passed through molten silicon mixed with a flux of silica.Al, Ca, Mg
are oxidized to respective oxides. These oxides combines with silica forming a slag
of silicates.The slag is removed and refined melt is poured into moulds where
silica is solidifies.This is called Metallurgical grade silica.
4Al+3SiO2
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2Ca+ SiO2
2Mg+ SiO2
3Si+2Al2O3
Si +2 CaO
Si +2MgO
To get semiconductors grade silicon metallurgical grade Si is treated with dry HCl gas at
3000C .
Si + 3HCl
SiHCl3 + H2
Tri chloro silane
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Si + 4HCl
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SiCl4+ 2Cl2
Tetra chloro silane
The mix is treated to get pure tri chloro silane

HSiCl3+ HCl
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SiCl4+ H2
The Union Carbide process:

This process involves the following steps:
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The h ydrogenation of tetrachlorosilane through a bed of metallurgical silicon is carried out

in a fluidized bed reactor
3SiCl4 + 2H2 + Si
4SiHCl3
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The trichlorosilane is separated by distillation while the unreacted tetrachlorosilane is

recycled back to the h ydrogenation reactor.
The purified trichlorosilane is passed through a fixed bed column filled with
quaternary ammonium ion exchange resin acting as catalyst. Trichlorosilane
gets converted into dichlorosilane.
2SiHCl3
SiH2Cl2 + SiCl4
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The products are separated by distillation, tetrachlorosilane is rec ycled to the h ydrogen
reactor and dichlorosilane is passed through a second fixed bed column filled
with quaternary ammonium ion exchange resin. Dichlorosilane is converted into silane.
3SiH2Cl2
SiH4 + 2SiHCl3
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The above products are separated by distillation and trichlorosilane is recycled to the first
bed column. Silane is further purified by distillation and then p yrolized to produce
polysilicon onto heated silicon seed rods mounted in a metal bell-jar reactor
Si H 4
2H2 + Si
Doping of Silicon by Diffusion Technique (n and p type):
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In this technique, a region of a semi conductor material is incorporated with dopant

atoms by the different impurity atom 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 walfer below its melting point in an atmosphere of n-type impurity
such as Phosphorus. The impurity atoms condense on the surface of the walfer diffuse
into the crystal. P-t ype silicon can be obtained by heating a silicon walfer below its
melting point in an atmosphere of P-t ype impurity such as Boran. The extent of diffusion is
regulate by temperature and concentration of the impurity atom.
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n-doping
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The 5-valent dopant has an outer electron more than the silicon atoms. Four outer electrons
combine with ever one silicon atom, while the fifth electron is free to move and serves as charge
carrier. This free electron requires much less energy to be lifted from the valence band into the
conduction band, than the electrons which cause the intrinsic conductivity of silicon. The dopant,
which emits an electron, is known as an electron donor (donare, lat. = to give).
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The dopants are positively charged by the loss of negative charge carriers and are built into the
lattice, only the negative electrons can move. Doped semimetals whose conductivity is based on
free (negative) electrons are n-type or n-doped. Due to the higher number of free electrons those
are also named as majority charge carriers, while free mobile holes are named as the minority
charge carriers.
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n-doping with phosphorus
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Arsenic is used as an alternative to phosphorus, because its diffusion coefficient is lower. This
means that the dopant diffusion during subsequent processes is less than that of phosphorus and
thus the arsenic remains at the position where it was introduced into the lattice originally.
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p-doping: In contrast to the free electron due to doping with phosphorus, the 3-valent dopant
effect is exactly the opposite. The 3-valent dopants can catch an additional outer electron, thus
leaving a hole in the valence band of silicon atoms. Therefore the electrons in the valence band
become mobile. The holes move in the opposite direction to the movement of the electrons. The
necessary energy to lift an electron into the energy level of indium as a dopant, is only 1 % of the
energy which is needed to raise a valence electron of silicon into the conduction band.
With the inclusion of an electron, the dopant is negatively charged, such dopants are called
acceptors (acceptare, lat. = to add). Again, the dopant is fixed in the crystal lattice, only the
positive charges can move. Due to positive holes these semiconductors are called p-conductive
or p-doped. Analog to n-doped semiconductors, the holes are the majority charge carriers, free
electrons are the minority charge carriers.
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p-doping with boron
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Doped semiconductors are electrically neutral. The terms n- and p-type doped do only refer to
the majority charge carriers. Each positive or negative charge carrier belongs to a fixed negative
or positive charged dopant.N- and p-doped semiconductors behave approximately equal in
relation to the current flow. With increasing amount of dopants, the number of charge carriers
increases in the semiconductor crystal. Here it requires only a very small amount of dopants.
Weakly doped silicon crystals contain only 1 impurity per 1,000,000,000 silicon atoms, high
doped semiconductors for example contain 1 foreign atom per 1,000 silicon atoms.
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Purification of Si (Zone refining)The liquid zones are formed by heating (and by cooling the
adjacent solids). Many practical heating methods have been used: electrical resistance coils,
induction heating, electric arc, and electron beam, radiant energy, plasmas (ionized gases), solar
heating, lasers, and peltier heating and cooling (produced by an electric current flowing across
the junction between two different materials). For organic compounds resistance-heated coils of
wire are most common, although radiant heating has been used. If a compound or element is
liquid at room temperature, the operation is conventionally done in a refrigerator.
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Clamp
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Si rod
R F coil
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Moving direction
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The usual container is one that will not contaminate the material. Glass, Vycor (heat- and
chemical-resistant glass), fused silica, molybdenum, tantalum, and graphite have all been used. If
zone refining is done vertically, a transparent container is helpful, but good work has been done
using opaque containers such as stainless steel. If the container is a horizontal, semicircular
cross-section boat, it can be opaque, because the liquid zone is readily distinguished from the
solid. If a filled container, horizontal or vertical, is used, care must be taken to prevent cracking
either by change in volume during freezing (or melting) or by differential thermal contraction (if
the charge sticks to the containing wall). Various solutions have been found for these problems.
Contamination of the charge by the container is a problem in all purification work, but a unique
solution was found for zone refining, namely,float zoning, invented by a U.S. scientist to
produce ultrapureSi. This semiconducting element is even more useful than germanium for most
transistor applications. In float zoning, a vertical silicon rod is held by end clamps, and a short
molten zone is produced by induction heating (producing heat from electric currents induced by
an alternative magnetic field) and moved along the rod. The liquid is held in place by its surface
tension, which theoretically limits the stable zone height. Various ingenious induction-heating
procedures have been devised for stabilizing zones of greater height. Nearly perfect single
crystals of ultrapure silicon have been produced commercially by such means.Substances that
melt at high temperatures also have high surface tension, enabling them to be ultrapurified by
float zoning. Examples are tungsten, molybdenum, tantalum, and Be. A half-inch bar of
beryllium, normally a very hard and brittle metal, has been easily bent 360 by hand after float
zoning in a high vacuum using an electron beam to produce the molten zone. Other important
factors, however, must be considered in applying zone-melting techniques. These include
stirring, natural convection, and the handling of vaporous substances.
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MODULE-4
HIGH POLYMERS
Introduction types of polymerization: addition and condensation mechanism of
polymerization-free radical mechanism taking vinyl chloride as an example
.molecular weight of polymers :number average and weight average ,numerical
problems. Glass transition temperature (Tg): Factors influencing Tg-Flexibility,
inter molecular forces, molecular mass branching and cross linking. And stereo
regularity. Significance of Tg. Structure property relationship: crystallinity. Tensile
strength, elasticity , plastic deformation and chemical resistivity ,Synthesis,
properties and applications of PMMA (plexi glass), Teflon polyurethane and
polyurethane. Elastomers: Introduction, synthesis, properties and applications of
silicone rubber. Adhesives: Introduction, synthesis, properties and applications of
epoxy resin. Polymer composites Introduction, synthesis properties and applications
of Kevlar and carbon fiber. Conducting polymers: Introduction, mechanism of
conducting in polyaniline and applications of conducting polyaniline.
10 Hours
Contents:
Introduction types of polymerization
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Addition Mechanism Of Polymerization-Free Radical Mechanism

Molecular weight of polymers :number average and weight average
Glass transition temperature (Tg)
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Molecular Mass Branching And Cross Linking

Synthesis, properties and applications of PMMA
Elastomers: Introduction, synthesis, properties and applications of silicone
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rubber
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Adhesives: Introduction, synthesis, properties and applications of epoxy resin
Polymer composites
Synthesis Properties And Applications Of Kevlar And Carbon Fiber
Conducting polymers: Introduction, mechanism of conducting in polyaniline
Applications Of Conducting Polyaniline.
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Types Polymerization Process
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Polymer:
A polymer is a large molecule, made up of small and simple molecules joined together
chemically through covalent bond to form one giant macromolecule.
Monomer: A monomer is defined as a simple molecule with two or more bonding sites through
which it forms covalent linkage with other monomer molecules to form the macromolecule.
Functionality: The functionality of a monomer is defined as the number of bonding sites present
in a molecule of a monomer.
Example:
All double bonded compounds like CH2=CH2 are bifunctional, i.e. have a functionality of
two
Similarly glycols (OH-CH2-CH2-OH), adipic acid (HOOC-(CH2)4-COOH) bifunctional
Phenols have their 2,4,6 positions as active sites, hence they are trifunctional.
Degree of Polymerization: The number of times the unit is repeated in a chain is called as
Degree of Polymerization. High polymers have a high degree of polymerization and hence large
molecular masses.
Molecular weight of a polymer = Molecular weight of repeating unit u Degree of Polymerization
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Addition Polymerization or Chain Polymerization:

The polymerization reaction in which a rapid self-addition of several bifunctional monomers to
each other, takes place by chain reaction without the elimination of any by-product is called
Addition or Chain polymerization
The product has the same elemental composition as the monomer compounds containing reactive
double bonds, like alkenes undergo chain polymerization. Addition polymerization is initiated
using small amounts of substances called initiators
n [CH2 = CH2] o -CH2 CH2-CH2 [ CH2-CH2]n CH2 CH2-CH2
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Condensation Polymerization OR Step polymerization:

A polymerization reaction in which a bi- or poly functional monomer undergoes intermolecular
condensation with another bifunctional monomer having a suitable functional group resulting in
continuous elimination of by-products (of small molecules like H2O, HCl, NH3 etc) is called
condensation or step polymerization.
These reactions are normally catalyzed by acids or alkali
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Ex: n HOOC(CH2)4 COOH + n 2HN(CH2)6NH2

CO n +2n H2O
Adipic Acid
Hexamethylene diamine
HN(CH2)6NHOC(CH2)4
Nylon 66
Mechanism of Addition or Chain Polymerization

Compounds containing reactive double bonds undergo a chain polymerization reaction. Chain
polymerization consists of 3 major steps, viz. a. Initiation b. Propagation c. Termination. The
first step of the process of polymer chain growth can be brought about by either a free radical or
an ion (cation or an anion) or a complex formation between the monomer and a catalyst and
accordingly follow different mechanisms.
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Free Radical mechanism:

The first step in this mechanism involves the production of highly reactive species called free
radicals by the hemolytic decomposition of the compounds called `initiators
Some typical compounds used as initiators are: Azo compounds, Peroxides, Peracids
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Initiation:
The initiators are thermally unstable. In presence of thermal energy it dissociates in to diradical
[C6H5COO]2
2 C6H5COOx
2 C6H5x +CO2
The free radical of the initiator, attacks the double bond in the monomer molecule as
C6H5x + CH2 = CHCl
o R CH2 - CxHCl
Now, the monomer unit linked to the free radical of the initiator through a sigma bond and the
free radical site is shifted from the initiator to the monomer unit
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Propagation:
In this step, the radical site at the first monomer unit attacks the double bond of a fresh monomer
unit results in linking up of second monomer to the first and transfer of the radical site to the
second
R CH2 - CxHCl + CH2 = CHCl o
R CH2 CHCl CH2 - CxHCl
The new free radical attacks another molecule of monomer, adds it on and transfers the radical
site to it, this proceeds in quick succession leading to a growing chain of polymer
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R CH2 CHCl CH2 -CxHCl + CH2 = CHCl o R CH2 CHCl CH2 -CHCl CH2 Cx
HCl
R CH2CHCl CH2 -CHCl CH2Cx HCl + CH2 = CHCl o R [CH2 CHCl]3 CH2 Cx
HCl
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R [CH2 HCl]n-1 CH2 Cx HCl + CH2 = CHCl o R [CH2 CHCl]n CH2 Cx HCl
Termination:
The propagation lasts till the chain growth is stopped by the free-radical site being killed by a
termination step.The process of termination results in deactivated chain of polymer, which is
called as dead polymer chain. Depending on the conditions, termination may take place in two
different ways
(i) Termination by coupling:
Combination of one polymer free radical with another polymer free radical or an initiator free
radical to form a dead polymer as
R [CH2 CHCl]m CH2 Cx HCl + R [CH2 CHCl]n CH2 Cx HCl o
R [CH2 CHCl]m CH2 CHCl CH2 CHCl [CH2 CHCl]n R

Dead heavy Polymer
Since this process involves coupling of two lone electrons, it is called `termination by coupling.
(ii) Termination by Disproportionation:
In this case, one H atom from one growing chain is abstracted by the other (second) growing
chain so that two dead polymers, one saturated and one unsaturated are formed
R [CH2 CHCl]m CH2 Cx HCl + R [CH2 CHCl]n CH2 Cx HCl o
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R [CH2 CHCl]m CH2 CH2Cl + R [CH2 CHCl]n CH = CHCl

This type of termination results in formation of two molecules of shorter chain length.
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Glass transition temperature (Tg)

The temperature at which the polymer abruptly transforms from glassy state to rubbery state is
known as glass transition temperature. The rotation about the inter unit bonds in the polymer is
effectively frozen at Tg and below Tg.
Glassy state
Viscoelastic state
Viscofluid State
(Hard and brittle) Tg
(Rubbery)
Tm
(Polymer melt)
Factors influencing glass transition temperature.
Melting temp.(Tm)
1100C
1400C
1800C
2100C
2400C
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Glass transition temp.(Tg)

-1100C
-900C
-180C
870C
1000C
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Polymeric material
Polyethylene(LDPE)
Polyethylene(HDPE)
Polypropylene
PVC
Polystyrene
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Chain flexibility:A free rotation about the inter unit bonds in polymer chain imparts flexibility
to
the polymer. The polymer having simplest chemical structure has lowest Tg like
polyethylene. The presence of double bond, aromatic or bulky side group hinder the freedom of
rotation and restricts the chain mobility thereby increases Tg value.
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Presence of plasticizers: Addition of plasticizer to the polymer reduces the Tg, since plasticizer
imparts flexibility to the polymer.
Molecular mass: Tg decreases as the molecular weight of a polymer decreases. This is because
there are more chain ends in low molecular weight polymer. Increase in molecular weight, free
rotation of molecules is restricted and Tg increases. It is not significantly affected if the degree of
polymerization is above 250.
Branching and cross linking: A small amount of branching will lowers the Tg .On the other
hand a high density of branching brings the polymer chain closer and reduces the chain
mobility resulting an increase in Tg. Cross linked polymers have higher Tg due to presence of
strong covalent bond throughout the structure.
Intermolecular forces: Due to presence of large number of polar groups in the polymer chain
leads to strong intermolecular forces of attraction which restrict the chain mobility. This leads to
increase in Tg. For example polypropylene is -180C and nylon 66 is 570C. In nylon 66 the
hydrogen bonding takes place between individual polymer chains at NH and CO groups of
the polymer chain.
Stereoregularity of the polymer: In Syndiotactic polymers, the substituent group present
alternatively one above and another below the plane have higher Tg than atactic which in turn
has higher Tg than its isotactic. Isotactic polymers have all substituent groups on one side where
as atactic polymers have random arrangement of substituent groups.
Crystallinity: Higher the crystallinity larger is the Tg value of polymer.In crystalline polymer
the chains are lined up parallel to each other and are held by strong cohesive forces. This leads to
higher Tg.
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Significance of Tg:
It is used to evaluate the flexibility of a polymer and predict its response to mechanical
stress.
It is useful in choosing proper temperature range during processing operations.
Coefficient of thermal expansion, heat capacity, refractive index, electrical properties etc.
at Tg determine the usefulness of a polymer over a temperature range.
Structure Property Relationship
The properties of a polymer such as strength, elasticity, chemical resistivity etc depend greatly
on the structure aspects of polymers such as, molecular weight, crystallinity, nature of polymer
chains, stereo regularity of the molecule, presence of polar groups etc.
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Strength: It is measured by magnitude and distribution of the attraction forces between the
molecules, viz., I) primary or chemical bond forces ii) secondary or intermolecular forces.
In straight chain and branched chain polymers the individual chains are held together by weak
intermolecular forces of attraction, the strength of which increases with the chain length or
molecular weight as shown in fig by plotting DP against Tensile strength. High molecular weight
polymers accounts for high softening point and tensile strength. Therefore high molecular weight
polymers are tougher and more heat resistant. The intermolecular forces increased by the
presence of polar groups like carboxyl, hydroxyl, chlorine, fluorine etc.
Strength of straight chain polymers also depends on the slipping power of one molecule over the
other. Shape of the polymer molecules greatly affects the resistance to slip. For example in
polyethylene limited restriction to movement of one molecule over other whereas in PVC,
movement is much more restricted between molecules due to the presence of large lumps of Cl
atoms. Therefore PVC is stronger and tough compare to polyethylene.
In cross linked polymers all structural units are linked by strong covalent force. Therefore they
are more strong and tough since the movement of intermolecular chains is restricted.
-500
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Tensile stress
PVC
PE
PS
Degree of
polymerization
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Degree of
polymerization
-1000
-500
Tensile stress
Crystallinity: The arrangement of the polymer with respect to each other results in crystalline
and amorphous state. In amorphous state molecules are arranged in random position and in
crystalline state chains can be aligned in orderly arrangement.
Crystallization imparts a denser packing of molecules, thereby increasing the intermolecular
forces of attraction. This accounts for higher and sharper softening point, greater rigidity and
strength, and greater density as compared to that of amorphous polymer.
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The degree of crystallinity determines several factors such as stiffness, yield point, modulus,
hardness, permeability, optical property and heat capacity.
Crystalline regions occur when linear polymer chains without branching and no bulky side
groups are orderly arranged parallel and close to each other. High degree of crystallinity makes
the polymer to exhibit high tensile strength and high impact strength.
Linear polyethylene is highly crystalline because the atoms will become closer approach and it
decreases with branching. On the other hand a polymer with bulky side groups prevents closer
approach. Crystallinity decreases by copolymerization because it lowers the structural symmetry.
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Introducing cross linking at suitable molecular positions. Cross links provided at constant
interval will hold the molecules and not allow them to slip past each other on stretching.
Avoiding bulky side groups such as aromatic and cyclic structures on the repeat units
Inter chain cohesive forces should be low. This is achieved by avoiding polar groups in
repeat units.
Introducing more nonpolar groups on the chain so that the chain dont separate on
stretching
To get an elastic material any factor that introduces crystallinity should be avoided.
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Elasticity: This is a property similar to spring the polymer elongates on applying force and
regains its shape on release of force. It is characterized by recoverance of original shape after a
deforming stress is released. For a polymer to show elasticity the individual chains should not
break on prolonged stretching. The elasticity increases by
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Chemical Resistance: The chemical nature of monomeric units and their molecular
arrangement determines the chemical resistance of polymers.
Usually chemical attack causes softening, swelling and loss of strength of material.
A polymer is generally more soluble in a structurally similar solvent.
For e.g polymers containing polar groups like OH or COOH are usually attacked
by polar solvents like water, alcohols and ketones but are nearly resistant to non
polar solvents like benzene, toluene, CCl4 etc.
But polymers having non-polar groups such as methyl (-CH3) and phenyl (-C6H5) are
swollen or even dissolved in non polar solvents but resistant to polar solvents like
water, ethyl alcohol etc.
Polymers which are more aliphatic character are more soluble in aliphatic solvents
where as those of aromatic character are more soluble in aromatic solvents.
For a given polymer, swelling character decreases with increase in molecular weight.
Chemical resistance increases with increase in the degree of crystallinity, due to denser
packing of chain molecules which makes penetration of solvent more difficult.
Polymers containing unsaturation such as poly isoprene (rubber) and poly butadiene are
easily attacked by oxygen or ozone and undergo oxidative degradation.
Polymers such as poly alkenes, PVC ,poly fluorocarbon have high degree of chemical
resistance.
Plastic deformation: It is found in thermoplastics, whose structure is deformed to plastic
stage on application of heat or pressure or both. The linear polymers without cross linking or
branched structure show the greatest degree of plastic deformation. Under pressure polymers
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deform at high temperature because at high temperature the Van der Waals forces acting
between different molecules become more and more weak.
On cooling they become rigid in the moulded shape, because plasticity of the material
decreases with fall of temperature. So plasticity is reversible in linear polymers.
In cross linked polymers deformation does not occur on heating, because only primary
covalent bonds are present throughout the structure and no slip between the molecules can
occur. Therefore in thermosetting polymers plasticity does not increase with increase in
temperature.
CH3
O +HCN
CH3
CH3
OH Hydrolysis CH2 C
CH3 OH CH2 C
H2SO4
CN
COOH
COOCH3
Acetone cayanohydrin
Methyl Acrylic Acid Methyl
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Acetone
methacrylate
CH3
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Polymethyl methacrylate(PMMA): (Plexiglass)

CH3
CH3
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Elastic deformation: The elastic deformation arises from the fact that polymers consists of
very long chain molecules, having free rotating groups. Since polymers contain both
crystalline and amorphous regions the elongation increases proportionately to the load and
reacts instantaneously on withdrawal of the load.
The deformation depends upon the degree of crystallinity, degree of cross linking and
glass transition temperature.
nCH2
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Monomer : Methyl methacrylate

Temperature:1000 C
Initiator
:Acetyl peroxide or Hydrogen peroxide
Polymerization process:
CH3
CH3
CH2
COOCH3
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COOCH3
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Properties: Amorphous, High resistance to sunlight, High optical transparency,Softening point

130 to 140 0 C, Above 65 0 C it becomes like a rubber structure
Good mechanical properties and resistance to many chemicals but soluble in organic solvents
like esters
Low scratch resistance compare to glass
Uses: Lenses, artificial eye, dentures bone (artificial teeth), paints, TV screens, attractive sign
boards, used in buildings for decorative purposes.
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Poly Tetra Fluro Ethylene (PTFE)or Teflon

Monomer : Tetra fluro Ethylene(CF2 = CF2)
Pressure : High pressure
Initiator
: Oxygen or Hydrogen peroxide
Polymerisation process:
o
-CF2 CF2-CF2 [ CF2-CF2]n CF2 CF2-CF2
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n [CF2 = CF2]
Properties:
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Linear and no branches, presence of highly electronegative F atoms and regular configuration
results strong attractive forces. Because of these strong attractive forces it is extreme toughness,
high softening point(about 3600C)and high chemical resistance except molten alkali and hot
fluorine solution. Mechanical properties unchanged over wide temperature range. Resistant to
strong acids.
Uses: Used as insulating material, gaskets, tank linings, chemical carrying pipes, insulator for
motor generators, transformers and capacitors. Lubricant, coating material for weapons to
prevent corrosion
Polyurethane polymers: Polyurethanes are characterized by the presence of urethane linkage,
[-NHCOO-] in their repeat units. They resemble polyamides in their structure, with the presence
of one more O making the chain more flexible. They are linear polymers with the structure
represented by:
[ - C N (R) N C O (R) O -]n

O H
H O
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Polyurethanes are prepared by the addition polymerization reaction between alkyl di-isocyanate
with diol. During addition the H atom of the OH group gets attached to N-atom to form NH CO
group as follows:
n O = C = N (R) N = C = O + n HO (R) OH
tert. Amine
Alkyl di isocyanate
diol
HO - R - O - [ - C N (R) N C O (R) O -]n H

O H
H O
Poly urethane
Ex.Perlon urethane
n HO [CH2)4 OH + n O = C = N [CH2)6 N = C = O
- O - [ - C N [CH2)6 N
C O [CH2)4 O -]n - H

O H
HO
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CH3
H-O
C
CH3
Bisphenol A
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Properties:
Polyurethanes are spongy, transparent linear thermoplastics
They have low melting point and high degree of flexibility
They are resistant to water, oil, and corrosive chemicals.
Applications:
Due to their resistance to oil , grease and corrosive chemicals, polyurethanes are used in
tire treading and industrial wheels.
Polyurethane fibers are used in light -weight water repellant garment like swim suits.
Polyurethanes are abrasion resistant and hence they are used as floor coating of
gymnasium, dance floors, etc
Polyurethane foams (U foams) are used in cushions for furniture and car upholsteries.
The abrasion resistance and superior adhesion properties of polyurethane adhesives have
enabled the advancement of recording densities in the form of magnetic binders for
various forms of recording media from audio/video tapes, computer disc, and even
prepaid cards and transportation tickets.
Due to polyurethanes electrical insulation characteristics, they are also used extensively
in wire coatings and optical fiber cables
Polycarbonates:
Polycarbonates are condensation polymers - polyesters of phenols and carbonic acid, HO CO
OH. They contain [ - O CO O - ] linkage.
Preparation:
They are prepared by condensing Bisphenol A with diphenyl carbonate involving elimination of
phenol in presence of tert.amine catalyst
+
O-H
C6H5
C6H5
Diphenyl carbonate
CH3
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C
O
CH3
C6H5
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Polycarbonate
They are also prepared by condensation reaction of phosgene and sodium salt of Bisphenol A.
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CH3
NaO C6H5 C C6H5 ONa + n Cl C Cl
CH3
O
Sodium salt of Bisphenol A
Phosgene
CH3
o>-O C6H5 C C6H5 OC@n +2NaCl
CH3
O
Polycarbonate
Properties:
Polycarbonate is a transparent thermoplastic.
Polycarbonate has a high melting point, around 2650C
It has a high tensile strength and impact resistance
It is resistant to water and many organic compounds but alkalis slowly hydrolyze it.
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Applications:
The great commercial success of polycarbonate is due to its unique combination of properties
extreme toughness, outstanding transparency, excellent compatibility with several polymers, and
high heat distortion resistance.
It finds application in making many useful articles such as safety goggles, safety shields,
Telephone parts and automobile light lenses etc
Polycarbonates are clear thermoplastic polymers which are mainly used as molding compounds.
CD-ROMs and baby bottles are well known examples of their use.
Used as insulator in electronic and electrical industries
Adhesives:
It is defined as the non metallic polymeric binding materials, which firmly hold two
similar or different materials such as metals glasses etc. by surface attraction.
Some natural adhesives are gum and glue while synthetic adhesives are phenol
formaldehyde resin, urea formaldehyde resin, epoxies etc
Synthetic adhesives are far superior to natural adhesives in their adhesive capacity.
Each type of adhesive is useful for bonding only a select group of materials, eg. Epoxy
resins are good adhesives for metals, wood, glass, concrete, ceramics and leather while
phenol- formaldehyde is used for rubber.
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Epoxy Resins [Araldite]
R-CH - CH -
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O
Epoxy resins are basically poly ethers and containing epoxy group:
Epoxy resins are combination 2, 2-bis (4-hydroxyphenyl) propane (I) (Bisphenol) and
epichlorohydrin in presence of alkaline catalyst at 60o C. It is made by condensation
polymerization.
The reactive epoxide and hydroxyl groups give a three dimensional cross linked structure.
Melting point between 145-155oC.
Properties:
Due to presence of stable ether linkage they are highly resistant to water, various solvents,
alkalis, acids.
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They are further cured with polyamines, polyamides etc. there by increasing toughness and
heat resistance.
Epoxy resins are thermosetting materials as opposed to thermoplastic materials.
The epoxy resins have excellent adhesion quality for various surfaces
They have very good electrical insulating property.
They are flexible due to the presence of reactive groups(OH and Epoxide) which are
widely spaced
Applications:
Epoxy resins find a large number of uses due to their remarkable chemical resistance and good
adhesion.
Epoxy resins are excellent structural adhesives for many surfaces like glass, metals, wood
etc
They are used as surface coatings for skid-resistant surfaces for highways
Mould made from epoxy resins are employed for production of components of aircrafts
and automobiles
Epoxy resins are applied over cotton, rayon and bleached fabrics to impart creaseresistance and shrinkage control
They are one of the principal constituents of fiber -reinforced plastics
They are used as laminating materials for electrical equipments.
Elastomers:
They are high polymers which undergo very large elongation (500 to 1000%) under stress and
regain original size on release of stress.
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Natural Rubber (NR)

Natural rubber is obtained in the form of latex from rubber trees.
Natural rubber is a highly soft and elastic material. It is a poly isoprene, obtained from the and its
structure is
Monomer, isoprene (2 -methyl 1, 3 butadiene), CH2 C CH CH2
CH3
-[ CH2 C CH CH2 - ]n
|
CH3
(n 5000)
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Silicone rubber:
They contain Silicon-Oxygen structure, which has organic radicals attached to silicon atom.
Silicon on reaction with alkyl halide in presence of Grignard reagent produces mono methyl and
dimethyl silicon chlorides. Further they form very long chain polymers as below
CH3Cl
+ Si
CH3SiCl3 and (CH3)2SiCl2
Methyl Chloride Silicon
CH3
|
Hydrolysis
n Cl Si Cl
CH3SiCl3
|
H2O; -HCl
CH3
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Cross linked silicone rubbers are obtained by mixing linear dimethyl silicone polymers with
fillers and curing agents like peroxides. Peroxide causes the formation of cross link through
methyl groups of adjacent chains. Bi and tri functional silicon halides also results in the
formation highly cross linked silicon
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Properties: Resistance to sunlight, dilute acids and alkalis. Flexible in the temperature range of
90-2500C. Cross linked silicones are thermosetting, good electrical insulating properties and heat
resistance.
Uses: Used as sealing material in aircraft engines, manufacture of tires for fighter aircrafts. Used
in making lubricants, paints, protective coatings for fabric finishing and water proofing. Used as
insulators.
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Number average molecular weight (Mn)

It is measured by colligative properties- Relative lowering of vapor pressure, Elevation of boiling
point, Depression of freezing point and Osmotic pressure.
It is defined as the ratio of total mass of all molecules in a polymer sample to the total number of
polymer molecules in the mixture.
Mn = w/n Where w= nM n-number of molecules, M-molecular mass of repeating unit
ni M i
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n1M1+n2M2+n3M3+niMi
Mn =
=
n1+n2+n3+ni
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Weight average molecular weight (Mw)

It is obtained by light scattering and ultracentrifugation techniques. It is also expressed in the
similar form. In a mixture, if w is mass and M is the molecular mass of each species then Mw is
given by
wiMi
since n=w/M or w=nM
wi
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w1M1+w2M2+w3M3+wiMi
Mw =
=
w1+w2+w3+wi
w
w
n1M21+n2M22+n3M23+niM2i niM2i
Mn =
=
n1M1+n2M2+n3M3+niMi
ni M i
Mw of a polymer is either equal or greater than its Mn, hence Mw/Mn1 This ratio is called
distribution ratio, which is a measure of polydispersity of polymers.
POLYMER COMPOSITES:
Combination of two or more structurally different components combine to form a new class of
material suitable for structural applications is referred as composite material. When one of the
component is a polymer, the resulting composite is called a polymer composite.
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Fiber reinforced composites are strong and light weight. They are stronger than steel with less
weight and hence they can be used in automobiles to achieve fuel efficiency and less pollution.
They finds higher strength per unit weight, low cost of fabrication and resistant to corrosion.
Polymeric composites are produced by suitably bonding a fiber material with polymer resin
matrix and curing the same under pressure and heat. Alternate layers of resin and fiber are laid
in a similar sequence to get the desired thickness. The polymer matrixes generally used are
epoxy resin, Phenolic resins, silicone resins, melanine resins etc. The fibers used are glass fiber,
carbon fiber and Kevlar.
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Kevlar(Aramid): It is synthesized from the monomers 1,4-phenylene diamine(para phenylene

diamine) and terephthaloyl chloride through a condensation reaction with the liberation of HCl
as byproduct.1,4-phenylene diamine terephthaloyl chloride
Kevlar or Poly(para-phenylene
terephthalamide)
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It is high strength due to presence of inter chain hydrogen bonds formed between carbonyl group
and NH group. Additional strength is achieved from aromatic staking interactions between
adjacent strands. Kevlar is a synthetic fiber stronger than steel.
Molecular structure of Kevlar, dashed line indicates hydrogen bonding
Properties: High tensile strength, high chemical inertness, very low coefficient of thermal
expansion, flame resistance, high impact resistance, low weight.
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Uses: used as inner lining for tires to prevent punctures, used in table tennis, tennis, badminton
and squash racquets, cricket bats, hockey sticks, used in personal armor such as helmets, ballistic
face masks, bullet proof vests etc. It is often used in the field of cryogenics for its low thermal
conductivity and high strength. Used in boat hulls, helicopter blades etc.
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Carbon fiber: Alternatively graphite fiber or carbon fiber is a material consisting of fibers about
5-10m in diameter and composed of mostly of carbon atoms.
Carbon fibers are synthesized by acrylonitrile which contains highly polar nitrile group. The
initiation is carried out by peroxides, persulphates, azo compounds.
-CH2-CH- CH2-CH- CH2-CH- CH2-CHI
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CN
CN
CN n
CN
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n CH2=CH heat
I
CN
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Acrylonitrile
Poly Acrylonitrile
Poly Acrylonitrile on heating carefully and slowly, the polymer cyclises through the cyano
groups to form a polycyclic chain. The resulting solid is heated gradually to expel hydrogen and
rings become aromatic. Then it is slowly roasted at 400-6000C to remove more hydrogen which
makes the adjacent chains joins together. Then the temperature gradually increased to 20000C to
get wider ribbon like mass. The temperature 20000C is maintained till all the nitrogen is expelled
leaving behind pure carbon fiber in graphite form.
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Properties: High stiffness, high tensile strength, low weight, high chemical resistance, high
temperature tolerance and low thermal expansion.
Uses: Used in aerospace, civil engineering, sports equipments, wind turbine, fishing rods,
racquet frames, golf clubs, classical guitar strings etc.
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Conducting polymers: An organic polymer with delocalised 3-electron system, having

electrical conductance of the same order of a conductor is called conducting polymer.
This is one of the simplest chain polymers it possesses conjugated double bond.
Conducting polymers are obtained generally by doping (Doping is either the addition of
electrons (reduction reaction) or the removal of electrons (oxidation reaction) from an
organic polymer with conjugated backbone (consisting of alternating double and single
carbon-carbon bonds
In a conjugated system, as the electrons are only loosely bound, electron flow may be
possible. However as the polymers are covalently bonded the electrons are localized and
do not take part in conductivity. Hence the material needs to be doped for electron flow to
occur. Once doping has occurred, the electrons in the pi-bonds are able to "jump" around
the polymer chain. As the electrons are moving along the molecule, electric current
occurs.
Polyaniline: Distilled 0.2M aniline dissolved in pre cooled 1M HCl solution and maintained at
50C. Calculated amount of 0.5M(NH4)2S2O8(oxidizing dopant) dissolved in 1M HCl is added
slowly to above prepared solution. Since the polymerization reaction is exothermic, to maintain
temperature of 0 to 50C the reaction vessel is placed in ice bath. After the complete addition of
(NH4)2S2O8 the mixture is stirred for about two hours. Polyaniline finally precipitates in the
green form. The dark green precipitate was washed with 1M HCl until the green color
disappears. Polyaniline in undoped state is a semiconductor with conductivity 10-8S/cm.
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Different oxidation states of polyaniline are
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y=1 Leuco emeraldine

y=0.5 Emaraldine base
y=0 Pernigraniline
Emaraldine base consisting of equal proportions of amine(-NH-) and imine(=N-) sites. On
protonic acid doping, imine sites are protonated by acids to form bipolaron bands.
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Applications: Used as electrode material for commercial rechargeable batteries, used as

conductive tracks on printed circuit boards, used in light emitting diodes, in fuel cells as the
electro catalytic materials, used as sensors and biosensors in glucose sensing for medical
applications and amine sensing for environmental and food safety applications.
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MODULE-5
WATER TECHNOLOGY AND NANOMATERIALS
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Water Technology: Introduction, sources and impurities of water; boiler feed water,
boiler troubles with disadvantages -scale and sludge formation, priming and
foaming, boiler corrosion(due to dissolved O2, CO2 and MgCl2). Determination of
DO, BOD and COD, numerical problems. Sewage treatment: Primary, secondary
(activated sludge method) and tertiary methods. Softening of water by ion exchange
process. Desalination of sea water by reverse osmosis & electrodialysis (ion
selective).
5 Hours
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Contents :
Introduction:Water Technology;Sources of water & impurities in

water.
Boiler feed water, boiler troubles with disadvantages -scale and sludge
formation.
Priming and foaming, boiler corrosion(due to dissolved O2, CO2 and

MgCl2).
Determination of DO, BOD and COD, numerical problems.
Sewage treatment: Primary, secondary (activated sludge method) and
tertiary methods.
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Softening of water by ion exchange process.
Desalination of sea water by reverse osmosis & electrodialysis (ion selective).
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WATER TECHNOLOGY
Sources of Water: The sources of water classified as follows
Underground water
Spring water
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Rain water, River water, Lake water, Sea water
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Surface water
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Sources water
Well water
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1) Rain water: Purest form of water contains many dissolved gases and suspended solid
particles .
2) River water: Contains dissolved minerals of soil such as chlorides, sulphates,
bicarbonates of sodium, calcium, Mg, Fe etc. It is also contains the organic matter, small
particles of soil and sand in suspension.
3) Lake water: It contains less dissolved minerals but high quality of organic matters.
4) Sea water: It is the most impure form of natural water. It contains dissolved salts such
as NaCl, sulphates of sodium, bicarbonates of K, Mg & Ca, and bromides of K& Mg.
Under ground water: clear in appearance but contains many dissolved salts and organic
matter.
Impurities in water:The water found in nature is never pure which contains large number
of impurities in varying amount. These impurities mainly depend upon its source and are
classified into four different t ypes.
1) Dissolved gases; these includes dissolved oxygen, CO2,SO2,NH3,(NO)x, all of which
derived from atmosphere.
2) Dissolved solids; these includes salts like bicarbonates, Chlorides and Sulphates of Ca, Mg,
& Na. in addition to that small amount of nitrates, nitrites, silicates, ammonia and ferrous salt
etc.
3) Suspended impurities: Suspended impurities are the dispersed solids which can be removed
by filtration or settling
Suspended impurities are of two t ypes;
i) inorganic impurities: clay, silica, oxides of Fe & Mg etc.
ii) organic impurities: wood, pieces, dead animal matter, leaf, fish, bacteria, algae, protozoa
etc.
4) organic matter: organic compounds derived form the decay of vegetable and animal matter
including bacteria may be present in water. Water also gets contaminated with sewage and
excretal matter. Consequently the pathogenic bacteria and microorganism are the main causes
for water born diseases.
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Chemical Analysis of Water: determination of various constituent present in water in

order to ascertain the quality of water as per WHO slandered and there by utility of water is
increased is known as water analysis.
The different constituents generally determined are hardness of water, alkalinity, chlorides,
nitrates, sulphates, fluorides, dissolved oxygen etc.
Boiler feed water is water used to supply ("feed") a boiler to generate steam or hot water. At
thermal power stations the feed water is usually stored, pre-heated and conditioned in a feed
water tank and supplied to the boiler by a boiler feed water pump. water treatment was not so
much of an issue, as temperatures and pressures were so low that high amounts of scale and rust
would not form to such a high amount, especially if the boiler was cleaned and/or blown down.
It was general practice though, to install zinc plates and/or alkaline chemicals to reduce corrosion
within the boiler. Many tests had been preformed to try and determine the cause and possible
protection from corrosion in boilers using distilled water, various chemicals, and sacrificial
metals. In modern boilers though, treatment of boiler feed water is extremely critical, as many
problems can result from the use of untreated water in extreme pressure and temperature
environments; this includes lower efficiency in terms of heat transfer, overheating, damage, and
high costs of cleaning.The feedwater must be specially treated to avoid problems in the boiler
and downstream systems. Untreated boiler feed water can cause corrosion and fouling.
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Boiler corrosion: Corrosive compounds, especially O2 and CO2 must be removed, usually by
use of a deaerator. Residual amounts can be removed chemically, by use of oxygen scavengers.
Additionally, feed water is typically alkalized to a pH of 9.0 or higher, to reduce oxidation and to
support the formation of a stable layer of magnetite on the water-side surface of the boiler,
protecting the material underneath from further corrosion. This is usually done by dosing
alkaline agents into the feed water, such as sodium hydroxide (caustic soda) or ammonia.
Corrosion in boilers is due to the presence of dissolved oxygen, dissolve carbon
dioxide,dissolved salts.
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Boiler feed water Boiler feedwater is water used to supply ("feed") a boiler to generate hot
water. At tthermal power station the feedwater is usually stored, pre-heated and conditioned in a
feed water tank and supplied to the boiler by a boiler feed pump.
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Scale is caused by impurities being precipitated out of the water directly on heat transfer surfaces
or by suspended matter in water settling out on the metal and becoming hard and adherent.
Evaporation in a boiler causes impurities to concentrate. This interferes with heat transfers and
may cause hot spots. Leading to local overheating. Scaling mechanism is the exceeding of the
solubility limits of mineral substances due to elevated temperature and solids concentration at the
tube/water interface.
The deposition of crystalline precipitates on the walls of the boiler interferes with heat transfer
and may cause hot spots, leading to local overheating. The less heat they conduct, the more
dangerous they are.
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Boiler sludge is a deposit that forms when suspended materials present in the boiler water settle
on, or adhere to, hot boiler tubes or other surfaces. Sludge typically consists primarily of
compounds such as hydroxyapatite (also known as calcium hydroxyl phosphate) or serpentine
(magnesium silicate). Metal oxides are normally the result of condensate corrosion but may also
come from the makeup water or feedwater system corrosion. Metal oxides can form a hard
tenacious deposit on tube surfaces which restricts heat transfer. Metal oxides can also be
absorbed onto sludge particles and become part of the sludge. Metal oxides are typically iron
oxide but may include copper or other metallic components.ChemTreats boiler scale and
deposition control treatment programs are designed to prevent and control crystallization
resulting in deposit formation, as well as provide deposit dispersion and sludge conditioning.
Common feed water contaminants that can form boiler deposits include Ca,Mg,Fe and silica.
Scale is formed by salts that have limited solubility but are not totally insoluble in boiler water.
These salts reach the deposit site in a soluble form and precipitate.
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Foaming -Boiler water carry-over is the contamination of the steam with boiler-water solids.
Bubbles or froth actually build up on the surface of the boiler water and pass out with the steam.
This is called foaming and it is caused by high concentration of any solids in the boiler water. It
is generally believed, however, that specific substances such as alkalis, oils, fats, greases, certain
types of organic matter and suspended solids are particularly conducive to foaming. In theory
suspended solids collect in the surface film surrounding a steam bubble and make it tougher. The
steam bubble therefore resists breaking and builds up foam. It is believed that the finer the
suspended particles the greater their collection in the bubble.
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Priming is the carryover of varying amounts of droplets of water in the steam (foam and mist),
which lowers the energy efficiency of the steam and leads to the deposit of salt crystals on the
super heaters and in the turbines. Priming may be caused by improper construction of boiler,
excessive ratings, or sudden fluctuations in steam demand. Priming is sometimes aggravated by
impure in boiled fed water. Some mechanical entrainment of minute drops of boiler water in the
steam always occurs. When this boiler water carryover is excessive, steam-carried solids produce
turbine blade deposits. The accumulations have a composition similar to that of the dissolved
solids in the boiler water. Priming is common cause of high levels of boiler water carryover.
These conditions often lead to super heater tube failures as well. Priming is related to the
viscosity of the water and its tendency to foam. These properties are governed by alkalinity, the
presence of certain organic substances and by total salinity. The degree of priming also depends
on the design of the boiler and its steaming rate. The most common measure to prevent foaming
and priming is to maintain the concentration of solids in the boiler water at reasonably low
levels. Avoiding high water levels, excessive boiler loads, and sudden load changes also helps.
Very often contaminated condensate returned to the boiler system causes carry-over problems. In
these cases the condensate should be temporarily wasted until the source of contamination is
found and eliminated. The use of chemicalanti foaming and anti priming agents , mixtures of
surface-active agents that modify the surface tension of a liquid, remove foam and prevent the
carry-over of fine water particles in the stream, can be very effective in preventing carry-over
due to high concentrations of impurities in the boiler-water.
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Corrosion in boilers:
Corrosion is the reversion of a metal to its ore form. Iron, for example, reverts to ironoxide as the
result of corrosion. The process of corrosion, however is a complex electro chemical reaction and
it takes many forms. Corrosion may produce general attach over a large metal surface or it may
result in pinpoint penetration of metal. Corrosion is a relevant problem caused by water in
boilers. Corrosion can be of widely varying origin and nature due to the action of dissolved
oxygen, to corrosion currents set up as a result of heterogeneities on metal surfaces, or to the
iron. While basic corrosion in boilers may be primarily due to reaction of the metal with oxygen,
other factors such as stresses, acid conditions, and specific chemical corrodents may have an
important influence and produce different forms of attack. It is necessary to consider the quantity
of the various harmful substances that can be allowed in the boiler water without risk of damage
to the boiler. Corrosion may occur in the feed-water system as a result of low pH water and the
presence of dissolved oxygen and carbon dioxide. Starting form these figures, and allowing the
amount that can be blown down, the permitted concentration in the make-up water is thus
defined. Starting form these figures, and allowing the amount that can be blown down, the
permitted concentration in the make-up water is thus defined. Corrosion is caused principally by
complex oxide-slag with low melting points. High temperature corrosion can proceed only if the
corroding deposit is in the liquid phase and the liquid is in direct contact with the metal. Deposits
also promote the transport of oxygen to the metal surface.
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Cracking in boiler metal may occur by two different mechanisms. In the first mechanism, cyclic
stresses are created by rapid heating and cooling and are concentrated at points where corrosion
has roughened or pitted the metal surface. This is usually associated with improper corrosion
prevention. The second type of corrosion fatigue cracking occurs in boilers with properly treated
water. In these cases corrosion fatigue is probably a misnomer. These cracks often originate
where a dense protective oxide film covers the metal surfaces and cracking occurs from the
action of applied cyclic stresses. Corrosion fatigue cracks are usually thick, blunt and cross the
metal grains. They usually start at internal tube surfaces and are most often circumferential on
the tube.
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DETERMINATION OF DISSOLVED OXYGEN PRESENT IN A

GIVEN SAMPLE OF WATER BY WINKLERS OR IODOMETRIC METHOD
Theory :
The principle involved in the determination of dissolved oxygen is that the
divalent manganese solution along with a strong alkali are added to water sample. The DO
present in water sample oxidises divalent manganese to tetravalent manganese. The basic
manganic oxide formed acts as ox ygen carrier to enable the dissolved ox ygen in molecular
form to take part in the reaction. Upon acidification, tetravalent manganese reverts to
divalent state with the liberation of nascent oxygen, which oxidises KI to I2. The
liberated iodine is titrated against standard sodium thiosulphate solution using starch as
indicator.
MnSO4 + 2KOH o Mn(OH)2 + K2SO4
2Mn(OH)2 + O2 o 2MnO(OH)2 (Basic manganic oxide)
MnO(OH)2 + H2SO4 o MnSO4 + 2H2O + [O]
2KI + H2SO4 + [O] o K2SO4 + H2O + I2
I2 + 2Na2S2O3 o Na2S4O6 + 2NaI
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Procedure : Pipette out 300 cm3 of water sample into a clean glass stoppered bottle.
Add 3 cm3 of manganous sulphate solution followed by 3 cm3 of alkaline potassium iodide
solution. Stopper the bottle and shake well and allow the precipitate to settle down.
Now add 1 cm3 of concentrated sulphuric acid slowly and mix well until the
precipitate dissolves completely. Pipette out 50 cm3 of this solution into a clean conical
flask and slowly titrate against 0.02N sodium thiosulphate solution using 2 cm3 starch
indicator near the end point. Repeat the titration to get concordant readings.
of dissolved oxygen :
: Na2S2O3 solution
: 50 cm3 oxygen solution
: Starch solution near the end point
: Disappearance of blue colour
Trail 1
Trail 2
Trail 3
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Burette Reading
Final Reading
Initial Reading
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Part B : Determination
Burette
Conical flask
Indicator
End point
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OBSERVATION AND CALCULATION
Volume of Na2S2O3
run down in cm3
Normality x Volume of ox ygen solution = Normality x Volume of Na2S2O3

Normality x Volume of Na2S2O3
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Normality of ox ygen solution=
NxV
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---a
50
Weight of dissolved oxygen/dm3 = Normality x Equivalent weight of ox ygen
= a x 8.0 =
g ---b
= b x 1000 mg
=
RESULT: The weight of dissolved ox ygen in the given water sample =
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Volume of oxygen solution
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WATER POLLUTION
Discharge of certain foreign substance into water that affects the physical, biological and
chemical properties of water which in turn decreases the utility of water is known as water
pollution . The matter which is responsible for these unhealthy changes in water is known as
water pollutants .
Eg. Pd, Hg, CN, As, Cu, acids alkalis pesticides, insecticides, fungicides, animal matter, human
excreta, radio active wastes etc.
The contaminated in water is called sewage water or effluent.
Depends on the sources of water Pollutant, sewage water is classified into two t ype
1. Domestic Sewage
2. Industrial sewage
Domestic sewage: It is waste discharge away from residence, Institutes, Hospitals etc.
These include certain organic wastes, pathogenic bacteria, plant materials Pesticides, detergents
and other materials. Domestic sewage causes water born diseases like dysentery, cholera
typhoid, and hookworm infection.
Industrial sewage: The water released by industries contains Pd, Hg, CN, As, Cu, acids,
alkalis, pesticides, detergents, insecticides, fungicides, soap, phenol etc. The industrial sewage
also causes several environmental problems. The sewage can be render harmless by suitable
treatments. The organic waste present in water undergoes degradation and breakdown into
simple molecules by bacteria. The bacterial degradation is of two t ypes;
1. Aerobic degradation or oxidation: Brought about by bacteria in presence of air and
dissolve ox ygen of water. Aerobic oxidation produces simpler compounds like water and CO2.
2. Anaerobic degradation or oxidation: Brought about by bacteria in absence of air and
produces harmful product such as NH3, H2S, H2S, CH4 etc.
Biological Oxygen demand (BOD) BOD is defined as the amount oxygen required by
microorganism to oxidize all organic matter present in one litre of waste water at 20oC over a
period of 5 days
Determination: To determine BOD a known volume of sample sewage is diluted with equal
volume of fresh water contains nutrient for bacterial growth, whose dissolve ox ygen can be
determined . The solution is kept in a closed bottle at 20oC over a period of 5 days. After 5 days
the unused oxygen contents in water is determined. The difference between ox ygen contents in
fresh water and unused oxygen contents in water is determined. The difference between ox ygen
contents in fresh water and unused oxygen in solution gives the BOD value.
Chemical Oxygen Demand (COD): It is defined as the amount of ox ygen consumed in the
chemical oxidation of organic and inorganic impurities present in one litre of waste water by
using acidified K2Cr2O7 solution in presence of silver sulphate and mercuric sulphate as
catalyst.
3CH2 O + 16 H++ 2Cr2O72-
4 Cr3+ + 3 CO2 + 11H2O
Determination :
Principal: The method consists of in adding excess standard solution of acidified K2Cr2O7 to
known volume of effluent sample and back titrating the excess of K2Cr2O7 against a standard
solution of FAS.
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Procedure: Pipette out 25 ml of waste water sample into a clean conical flask and 10ml of 0.25
N K2Cr2O7, 30 ml of 6N H2SO4, 1g Ag2SO4 and 1g of HgSO4 reflux the mixture for two hours,
cool and titrate against FAS using ferroin indicator till to get reddish brown colour. Let the
titer value be a cm3. Perform a blank titration in similar way except using waste water sample.
Let the blank titer value be b cm3 .
CALCULATION
Volume of K2Cr2O7 consumed for the sample = (b-a) cm3
1000 cm3 of 1N FAS solution = 1 equivalent of ox ygen = 8 g of ox ygen (or 8 x 103 mg of O2)
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8 x 103 x (b-a) x N of FAS

(b- a) cm3 of ......N FAS solution =
= ......... X.mg of oxygen/
1000 x 1
25cm3 of waste water
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25 cm3 of water sample consumed X mg of O2

.X x 1000
1000 cm3 of waste water sample contains =
25
mg
3
dm
COD of waste water sample = ........................................ mg of O2 per dm3
of
ox ygen
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Water treatment or sewage treatment

Removal of harmful contamination from waste water completely or partially is known as water
treatment or sewage treatment.
The treatment of sewage water is carried out by three different stages.
1. Primary treatment
2. Secondary treatment
3. tertiary treatment
Primary treatment: The removal of coarse solid in the sewage water is affected by means of
narrow rocks, screens, grit chambers, and skimmed tank etc. The water is then passed into
sedimentation tank where it is allowed to settle. The non settled impurities are removed by
adding coagulant such as potash alum
Secondary treatment or activated sludge method: The waste water after primary treatment is
allowed to flow into a large tank where biological treatment is carried out. Here the water is
spra yed with activated sludge, the microorganism present in sludge form a thin la yer on water
and break down all organic impurities into simpler compounds. The air is passed from the
centre of tank vigorously in order bring effective aerobic oxidation. The residual water is
chlorinated to kill bacteria and then treated with potash alum to settle the impurities. The water
is then filter and discharge into drainage.
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Tertiary treatment: The water even after secondary treatment contains phosphate, heavy
metal ions, colloidal impurities, coloring matter etc. Hence the water is subjected to tertiary
treatment. The tertiary treatment includes the treatment with lime to remove phosphates,
treatment with S2- to remove heavy metal ions as insoluble sulphides, treatment with activated
charcoal to absorb coloring matter and then potash alum to remove colloidal impurities and
then discharge to drainage.
Portable water: Water that is fit for human consumption and meets the microbiological and
chemical standards of quality to prevent water born diseases and health risk from toxic
chemicals is known as portable water.
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Desalination of water: The process of partial or complete removal of NaCl salt from highly
saline water such as sea water is known as desalination.
Desalination can be carried out by different techniques which are
1. Flash evaporation
2. Electro dialysis
3. Reverse osmosis
Electro dialysis: An electro dialysis unit consists of a series of alternative cation and anion
permeable membrane which permits only respective ions. The anode is placed near anode
permeable membrane while cathode is placed near cation permeable membrane as shown in fig.
The suitable emf is applied across the electrodes that depend on the level of salt in saline water.
Under the influence of emf Na+ ions move towards the cathode through cation permeable
membrane where as Cl move towards anode through anion permeable membrane. The net
result is the depletion of salt in AC compartment and increase of salt concentration in CA
compartment. The fresh water obtained from AC compartment.
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C l-
Na+
Cl
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Reverse Osmosis: Osmosis is the process where the solvent molecules naturally diffuse from
lower concentration region to higher concentration region through semi permeable membrane
due to osmotic pressure (Po). This natural process may be reserved by applying pressure on
brine side higher than that of somatic pressure, when fresh water tends to flow from brine to
fresh water region as shown in fig.
Br in e
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Fresh
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NANOMATERIALS
Contents :
Introduction, Properties (Size Dependent).
Precipitation
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Gas Condensation
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Synthesis-Bottom Up Approach By Solgel,
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Nano Materials: Introduction, properties (size dependent). Synthesis-bottom up

approach (solgel, precipitation, gas condensation,chemical vapour condensation,
hydrothermal & thermolysis processes). Nano scale materials-nano crystals &
clusters, nano crystalline, fullerenes, carbon nano tubes, nano wires, nano rods,
dendrimers & nano composites.
5 Hours
Chemical Vapour Condensation
Hydro Thermal & Thermolysis Processes
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Nano scale materials-nano crystals & clusters
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Nano Crystalline And Fullerenes,

Carbon Nano Tubes, Nano Wires, Nano Rods
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Dendrimers & Nano Composites.
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Nanomaterial is a term used to explain an intentionally made nanomaterial. A nanomaterial is

an object that has at least one dimension in the nanometer scale. Nanomaterials are categorised
according to their dimensions. For example a nanomaterial with three dimensions and less than
100nm are nanoparticles, quantum dots etc. nanomaterials with two dimensions and less than
100nm, are nanotubes, fibres, and nanowires. Nanomaterials with one dimension and less than
100nm are thin fibres, layers and surface coatings.
1. Introduction
Nanomaterials are cornerstones of nanoscience and nanotechnology. Nanostructure science and
technology is a broad and interdisciplinary area of research and development activity that has
been growing explosively worldwide in the past few years. It has the potential for
revolutionizing the ways in which materials and products are created and the range and nature of
functionalities that can be accessed. It is already having a significant commercial impact, which
will assuredly increase in the future.
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Fig. 1. Evolution of science and technology and the future
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What are nanomaterials?

Nanoscale materials are defined as a set of substances where at least one dimension is less than
approximately 100 nanometers. A nanometer is one millionth of a millimeter - approximately
100,000 times smaller than the diameter of a human hair. Nanomaterials are of interest because
at this scale unique optical, magnetic, electrical, and other properties emerge. These emergent
properties have the potential for great impacts in electronics, medicine, and other fields.
Advances in Nanomaterials: The history of nanomaterials began immediately after the big bang
when Nanostructures were formed in the early meteorites. Nature later evolved many other
Nanostructures like seashells, skeletons etc. Nano scaled smoke particles were formed during the
use of fire by early humans. The scientific story of nanomaterials however began much later.
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Classification of Nanomaterials
Nanomaterials have extremely small size which having at least one dimension 100 nm or less.
Nanomaterials can be nanoscale in one dimension (eg. surface films), two dimensions (eg.
strands or fibres), or three dimensions (eg. particles). They can exist in single, fused, aggregated
or agglomerated forms with spherical, tubular, and irregular shapes. Common types of
nanomaterials include nanotubes, dendrimers, quantum dots and fullerenes. Nanomaterials have
applications in the field of nano technology, and displays different physical chemical
characteristics from normal chemicals (i.e., silver nano, carbon nanotube, fullerene,
photocatalyst, carbon nano, silica).
According to Siegel, Nanostructured materials are classified as Zero dimensional,
one dimensional, two dimensional, three dimensional nanostructures.
Nanomaterials are materials which are characterized by an ultra fine grain size (< 50 nm) or by a
dimensionality limited to 50 nm. Nanomaterials can be created with various modulation
dimensionalities as defined by Richard W. Siegel: zero (atomic clusters, filaments and cluster
assemblies), one (multilayers), two (ultrafine-grained overlayers or buried layers), and three
(nanophase materials consisting of equiaxed nanometer sized grains) as shown in the above
figure 3.
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Nanomaterial - synthesis and processing

Nanomaterials deal with very fine structures: a nanometer is a billionth of a meter. This indeed
allows us to think in both the bottom up or the top down approaches (Fig. 5) to synthesize
nanomaterials, i.e. either to assemble atoms together or to dis-assemble (break, or dissociate)
bulk solids into finer pieces until they are constituted of only a few atoms.
This domain is a pure example of interdisciplinary work encompassing physics, chemistry, and
engineering upto medicine.
In principle we can classify the wet chemical synthesis of nanomaterials into two broad groups:
1. The top down method: where single crystals are etched in an aqueous solution for producing
nanomaterials, For example, the synthesis of porous silicon by electrochemical etching.
2. The bottom up method: consisting of sol-gel method, precipitation etc. where materials
containing the desired precursors are mixed in a controlled fashion to form a colloidal solution.
Sol-gel process
The sol-gel process, involves the evolution of inorganic networks through the formation of a
colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase
(gel). The precursors for synthesizing these colloids consist usually of a metal or metalloid
element surrounded by various reactive ligands. The starting material is processed to form a
dispersible oxide and forms a sol in contact with water or dilute acid. Removal of the liquid from
the sol yields the gel, and the sol/gel transition controls the particle size and shape. Calcination of
the gel produces the oxide.
Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors such
as Si(OEt) 4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel chemistry
based on the hydrolysis and condensation of metal alkoxides
M(OR)z can be described as follows:
MOR + H2O MOH + ROH (hydrolysis)
MOH + ROM M-O-M + ROH (condensation)
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Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is

widely employed to prepare oxide materials. The sol-gel process can be characterized by
a series of distinct steps.
Fig. 7. Schematic representation of sol-gel process of synthesis of nanomaterials.
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1. Formation of different stable solutions of the alkoxide or solvated metal precursor.

2. Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by a
polycondensation reaction that results in a dramatic increase in the viscocity of the solution.
3. Aging of the gel (Syneresis), during which the polycondensation reactions continue until the
gel transforms into a solid mass, accompanied by contraction of the gel network and expulsion of
solvent from gel pores. The aging process of gels can exceed 7 days and is critical to the
prevention of cracks in gels that have been cast.
4. Drying of the gel, when water and other volatile liquids are removed from the gel network.
This process is complicated due to fundamental changes in the structure of the gel. The drying
process has itself been broken into four distinct steps: (i) the constant rate period, (ii) the critical
point, (iii) the falling rate period, (iv) the second falling rate period. If isolated by thermal
evaporation, the resulting monolith is termed a xerogel. If the solvent (such as water) is extracted
under supercritical or near super critical conditions, the product is an aerogel.
5. Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing the
gel against rehydration. This is normally achieved by calcining the monolith at temperatures up
to 8000C.
6. Densification and decomposition of the gels at high temperatures (T>8000C). The pores of the
gel network are collapsed, and remaining organic species are volatilized. The typical steps that
are involved in sol-gel processing are shown in the schematic diagram below.
The interest in this synthesis method arises due to the possibility of synthesizing nonmetallic
inorganic materials like glasses, glass ceramics or ceramic materials at very low temperatures
compared to the high temperature process required by melting glass or firing ceramics.
The major difficulties to overcome in developing a successful bottom-up approach is controlling
the growth of the particles and then stopping the newly formed particles from agglomerating.
Other technical issues are ensuring the reactions are complete so that no unwanted reactant is left
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on the product and completely removing any growth aids that may have been used in the process.
Also production rates of nano powders are very low by this process. The main advantage is one
can get mono sized nano particles by any bottom up approach.
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Precipitation is the creation of a solid in a solution or inside another solid during a chemical
reaction or by diffusion in a solid. When the reaction occurs in a liquid solution, the solid formed
is called the precipitate. The chemical that causes the solid to form is called the precipitant.
Without sufficient force of gravity (settling) to bring the solid particles together, the precipitate
remains in suspension. After sedimentation, especially when using a centrifuge to press it into a
compact mass, the precipitate may be referred to as a pellet.
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The precipitate-free liquid remaining above the solid is called the supernate or supernatant.
Powders derived from precipitation have also historically been known as flowers. Precipitation
may occur if the concentration of a compound exceeds its solubility (such as when mixing
solvents or changing their temperature).
Precipitation may occur rapidly from a supersaturated solution. In solids, precipitation occurs if
the concentration of one solid is above the solubility limit in the host solid, due to e.g. rapid
quenching or ion implantation, and the temperature is high enough that diffusion can lead to
segregation into precipitates. Precipitation in solids is routinely used to synthesize nanoclusters.
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An important stage of the precipitation process is the onset of nucleation. The creation of a
hypothetical solid particle includes the formation of an interface, which requires some energy
based on the relative surface energy of the solid and the solution. If this energy is not available,
and no suitable nucleation surface is available, super saturation occurs.
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Chemical Vapor condensation
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One of the outstanding strides in plasma processing for nanoparticles synthesis is the
developed process of the vapor condensation. The precursor material is put into the working
chamber with a stable arc.
The chamber is filled by reactive gas that becomes ionized; then molecular clusters are formed
and cooled to produce nanoparticles.
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Hydrothermal: Hydrothermal synthesis includes the various techniques of crystallizing

substances from high-temperature aqueous solutions at high vapor pressures; also termed
"hydrothermal method".
The term "hydrothermal" is of geologic origin. Geochemists and mineralogists have studied
hydrothermal phase equilibria since the beginning of the twentieth century. Hydrothermal
synthesis can be defined as a method of synthesis of single crystals that depends on the solubility
of minerals in hot water under high pressure. The crystal growth is performed in an apparatus
consisting of a steel pressure vessel called an autoclave, in which a nutrient is supplied along
with water. A temperature gradient is maintained between the opposite ends of the growth
chamber. At the hotter end the nutrient solute dissolves, while at the cooler end it is deposited on
a seed crystal, growing the desired crystal.
Possible advantages of the hydrothermal method over other types of crystal growth include the
ability to create crystalline phases which are not stable at the melting point. Also, materials
which have a high vapour pressure near their melting points can also be grown by the
hydrothermal method. The method is also particularly suitable for the growth of large goodquality crystals while maintaining good control over their composition. Disadvantages of the
method include the need of expensive autoclaves, and the impossibility of observing the crystal
as it grows.
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Chemical reactions: Micro porous crystals, super ionic conductors, metal oxides, ceramics,
zeolites, carbonaceous materials, magnetic materials, phosphers, plus nanoparticles, gels, thin
films, helical/chiral structures.
Advantages
Most material can be made soluble in a proper solvent by heating and pressurizing the system
close to its critical point;
Significant improvement in the chemical activity of the reactant, and in producing materials that
cannot be obtained via solid-state reaction;
Products of intermediate state, metastable state and specific phase may be easily produced >
novel products of metastable state and other specific condensed state.
Disadvantages
Expensive autoclaves;
Safety issues during the reaction;
Could not monitor and observe the reaction.
Difficult to control morphology, size, size distribution
Not for all materials
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Mechanism
Usually follows a liquid nucleation model;
Different from solid-state reaction mechanism in terms of diffusion of atoms/ions among
reactants
Enhanced solubility solubility of water increases with T, but alkaline solubility increases much
greater with T high pH.
USES : A large number of compounds belonging to practically all classes have been synthesized
under hydrothermal conditions: elements, simple and complex oxides, tungstates, molybdates,
carbonates, silicates, germanates etc. Hydrothermal synthesis is commonly used to grow
synthetic quartz, gems and other single crystals with commercial value. Some of the crystals that
have been efficiently grown are emeralds,rubies, quartz, alexandrite and others. The method has
proved to be extremely efficient both in the search for new compounds with specific physical
properties and in the systematic physicochemical investigation of intricate multicomponent
systems at elevated temperatures and pressures.
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Fullerene:
A fullerene is any molecule composed entirely of carbon, in the form of a hollow sphere,
ellipsoid, tube, and many other shapes. Spherical fullerenes are also called buckyballs, and they
resemble the balls used in football (soccer). Cylindrical ones are called carbon nanotubes or
buckytubes. Fullerenes are similar in structure to graphite, which is composed of stacked
graphene sheets of linked hexagonal rings; but they may also contain pentagonal (or sometimes
heptagonal) rings. The first fullerene molecule to be discovered, and the family's namesake,
buckminsterfullerene (C60).The structure was also identified some five years earlier by Sumio
Iijima, from an electron microscope image, where it formed the core of a "bucky onion."
Fullerenes have since been found to occur in nature. More recently, fullerenes have been
detected in outer space. "Its possible that buckyballs from outer space provided seeds for life on
Earth."
The discovery of fullerenes greatly expanded the number of known carbon allotropes,
which until recently were limited to graphite, diamond, and amorphous carbon such as soot and
charcoal. Buckyballs and buckytubes have been the subject of intense research, both for their
unique chemistry and for their technological applications, especially in materials science,
electronics, and nano technology. Minute quantities of the fullerenes, in the form of C60, C70, C76,
C82 and C84 molecules, are produced in nature, hidden in soot and formed by lightning discharges
in the atmosphere.
Types of fullerene
Buckyball clusters: smallest member is C20 (unsaturated version of dodecahedrane) and the
most common is C60;
Nanotubes: hollow tubes of very small dimensions, having single or multiple walls; potential
applications in electronics industry;
Megatubes: larger in diameter than nanotubes and prepared with walls of different thickness;
potentially used for the transport of a variety of molecules of different sizes;
polymers: chain, two-dimensional and three-dimensional polymers are formed under highpressure high-temperature conditions; single-strand polymers are formed using the Atom
Transfer Radical Addition Polymerization (ATRAP) route;
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nano"onions": spherical particles based on multiple carbon layers surrounding a buckyball

core; proposed for lubricants;
linked "ball-and-chain" dimers: two buckyballs linked by a carbon chain; fullerene rings.
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What is a nanotube?
A hollow nanowire, typically with a wall thickness on the order of molecular dimensions
The smallest (and most interesting) nanotube is the single-walled carbon nanotube (SWNT)
consisting of a single graphenesheet rolled up into a tube.
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Scanning Tunneling Micrograph of a single-walled carbon nanotube and corresponding model

(Dekker)
Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Nanotubes
have been constructed with length-to-diameter ratio of upto 132,000,000:1significantly larger
than for any other material. These cylindrical carbonmolecules have unusual properties, which
are valuable for nanotechnology, electronics, optics and other fields of materials science and
technology. In particular, owing to their extraordinary thermal conductivity and mechanical and
electrical properties, carbon nanotubes find applications as additives to various structural
materials. For instance, nanotubes form a tiny portion of the material(s) in some (primarily
carbon fiber) baseball bats, golf clubs, or car parts.
Nanotubes are members of the fullerene structural family. Their name is derived from their long,
hollow structure with the walls formed by one-atom-thick sheets of carbon, called graphene.
These sheets are rolled at specific and discrete ("chiral") angles, and the combination of the
rolling angle and radius decides the nanotube properties; for example, whether the individual
nanotube shell is a metal or semiconductor. Nanotubes are categorized as single-walled
nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). Individual nanotubes naturally align
themselves into "ropes" held together by van der Waals forces, more specifically, pi-stacking.
Applied quantum chemistry, specifically, orbital hybridization best describes chemical bonding
in nanotubes. The chemical bonding of nanotubes is composed entirely of sp2 bonds, similar to
those of graphite. These bonds, which are stronger than the sp3 bonds found in alkanes and
diamond, provide nanotubes with their unique strength.
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What is a nanowire?
Any solid material in the form of wire with diameter smaller than about 100 nm
Transmission electron micrograph of an InP/InAs nanowire .
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Dendrimers: There are a new class of polymeric materials. They are highly branched,
monodisperse macromolecules. The structure of these materials has a great impact on thei
physical and chemical properties. As a result of their unique behaviour dendrimers are suitable
for a wide range of biomedical and industrial applications. The paper gives a concise review of
dendrimers physico-chemical properties and their possible use in various areas of research,
technology and treatment.
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Polymer chemistry and technology have traditionally focused on linear polymers, which are
widely in use. Linear macromolecules only occasionally contain some smaller or longer
branches. In the recent past it has been found that the properties of highly branched
macromolecules can be very different from conventional polymers. The structure of these
materials has also a great impact on their applications. These hyper branched molecules were
called dendrimers. The term originates from dendron meaning a tree in Greek. At the same
time, Newkomes group independently reported synthesis of similar macromolecules. They
called them arborols from the Latin word arbor also meaning a tree. The term cascade
molecule is also used, but dendrimer is the best established one.
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SYNTHESIS
Dendrimers are generally prepared using either a divergent method or a convergent one. There is
a fundamental difference between these two construction concepts. In the divergent methods,
dendrimer grows outwards from a multifunctional core molecule. The core molecule reacts with
monomer molecules containing one reactive and two dormant groups giving the first generation
dendrimer. Then the new periphery of the molecule is activated for reactions with more
monomers. The process is repeated for several generations and a dendrimer is built layer after
layer. The divergent approach is successful for the production of large quantities of dendrimers.
Problems occur from side reactions and incomplete reactions of the end groups that lead to
structure defects. To prevent side reactions and to force reactions to completion large excess of
reagents is required. It causes some difficulties in the purification of the final product.
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The convergent methods were developed as a response to the weaknesses of the divergent
synthesis. In the convergent approach, the dendrimer is constructed stepwise, starting from the
end groups and progressing inwards. When the growing branched polymeric arms, called
dendrons, are large enough, they are attached to a multifunctional core molecule . The
convergent growth method has several advantages. It is relatively easy to purify the desired
product and the occurrence of defects in the final structure is minimised. It becomes possible to
introduce subtle engineering into the dendritic structure by precise placement of functional
groups at the periphery of the macromolecule. The convergent approach does not allow the
formation of high generations because steric problems occur in the reactions of the dendrons and
the core molecule. The first synthesised dendrimers were polyamidoamines (PAMAMs). They
are also known as starburst dendrimers. The term In the presence of methanol it reacts with
methyl acrylate and then ethylene diamine is added:
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NH3 + 3CH2CHCOOCH3 N(CH2CH2COOCH3)3 (1)

N(CH2CH2COOCH3)3 + 3NH2CH2CH2NH2 N(CH2CH2CONHCH2CH2NH2)3 +3CH3OH (2)
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At the end of each branch there is a free amino group that can react with two methyl acrylate
monomers and two ethylene diamine molecules. Each complete reaction sequence results in a
new dendrimer generation. The half- generations PAMAM dendrimers (e.g., 0.5, 1.5, 2.5)
possess anionic surfaces of carboxylate groups. The number of reactive surface sites is doubled
with every generation. The mass increases more than twice.
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APPLICATIONS:
There are now more than fifty families of dendrimers, each with unique properties, since the
surface, interior and core can be tailored to different sorts of applications. Many potential
applications of dendrimers are based on their unparalleled molecular uniformity, multifunctional
surface and presence of internal cavities. These specific properties make dendrimers suitable for
a variety of high technology uses including biomedical and industrial applications. Dendrimers
have been applied in invitro diagnostics. It has introduced a new method in cardiac testing.
Proteins present in a blood sample bind to immunoglobulins which are fixed by dendrimers to a
sheet of glass. The result shows if there is any heart muscle damage. This method significantly
reduces the waiting time for the blood test results (to about 8 min). When a randomly organised
solution of immunoglobulins is used the test lasts up to 40 min. Conjugates of dendrimer and
antibody improve also precision and sensitivity of the test.
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Nanocomposite:
A nanocomposite is a multiphase solid material where one of the phases has one, two or three
dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances
between the different phases that make up the material. In the broadest sense this definition can
include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid
combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to
dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical,
electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the
component materials. Size limits for these effects have been proposed, <5 nm for catalytic
activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes,
and <100 nm for achieving super paramagnetism, mechanical strengthening or restricting matrix
dislocation movement.
Nanocomposites are found in nature, for example in the structure of the abalone shell
and bone. The use of nanoparticle-rich materials long predates the understanding of the physical
and chemical nature of these materials.Investigated the origin of the depth of colour and the
resistance to acids and bio-corrosion of Maya blue paint, attributing it to a nanoparticle
mechanism. From nanoscale organo-clays have been used to control flow of polymer solutions
(e.g. as paint viscosifiers) or the constitution of gels (e.g. as a thickening substance in cosmetics,
keeping the preparations in homogeneous form). The polymer/clay composites were the topic of
textbooks, although the term "nanocomposites" was not in common use.
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In mechanical terms, nanocomposites differ from conventional composite materials due

to the exceptionally high surface to volume ratio of the reinforcing phase and/or its exceptionally
high aspect ratio. The reinforcing material can be made up of particles (e.g. minerals), sheets
(e.g. exfoliated clay stacks) or fibres (e.g. carbon nanotubes or electrospun fibres). The area of
the interface between the matrix and reinforcement phase(s) is typically an order of magnitude
greater than for conventional composite materials. The matrix material properties are
significantly affected in the vicinity of the reinforcement. polymer nanocomposites, properties
related to local chemistry, degree of thermoset cure, polymer chain mobility, polymer chain
conformation, degree of polymer chain ordering or crystallinity can all vary significantly and
continuously from the interface with the reinforcement into the bulk of the matrix.
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This large amount of reinforcement surface area means that a relatively small amount of
nanoscale reinforcement can have an observable effect on the macroscale properties of the
composite. For example, adding carbon nanotubes improves the electrical and thermal
conductivity. Other kinds of nanoparticulates may result in enhanced optical properties,
dielectric properties, heat resistance or mechanical properties such as stiffness, strength and
resistance to wear and damage. In general, the nano reinforcement is dispersed into the matrix
during processing. The percentage by weight (called mass fraction) of the nanoparticulates
introduced can remain very low (on the order of 0.5% to 5%) due to the low filler percolation
threshold, especially for the most commonly used non-spherical, high aspect ratio fillers (e.g.
nanometer-thin platelets, such as clays, or nanometer-diameter cylinders, such as carbon
nanotubes).
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Sub. Code : 14CHE22

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Solar Energy: Introduction, utilization and conversion, photovoltaic cells-importance,

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Module-2:Corrosion And Metal Finishing:

Module-1: Electrochemistry And Battery Technology:

Module-3:Fuels And Solar Energy:

Module-5:Water Technology And Nanomaterials:

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Electrode Potential and Cells :

Introduction, Derivation of Nernst equation for electrode potential. Types

Measurement of standard electrodepotential using calomel electrode.

Reference electrodes: Introduction, construction, working and applications

Determination of pH of a solution using g lass electrode, concentration

cells, Ele ct ro de a nd ele ct roly t e

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3CALCULATION OF ELECTRODE POTENTIAL

where n-No. of electrons,F-Faraday value ,E-Electrode potential

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Fig.Saturated Calomel electrode

Uses:It is used as secondary reference electrode to measure electrode potential

Fig. Silver silver chloride electrode

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Electrode representation: Ag(s)/AgCl(s) / ClElectrode reaction:

Fig. Glass electrode

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Limitations: i. Ordinary potentiometers cannot be used ii. It can be used up to pH 13 but

EAg/AgCl is internal reference electrode potential, Eb boundary potential and EAsy is

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The boundary potential is given by Nernst equation at membrane

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From the above equation following conclusions may be drawn

Metal-metal ion electrodes

and the half-cell reaction would be

Fe2+(aq) Fe3+ (aq) + e

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Metalmetalsalt ion electrodes

The half cell would be represented as

Amalgam electrode:It is formed by placing the metal-amalgam in contact with a solution of

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Introduction,classification primary, secondary and reserve batteries

Introduction,classification primary, secondary and reserve batteries

density,energy efficiency, cycle life, and shelf life Construction.

Construction, working and applications of Ni metal hydride batteries

Classification of fuel cells based on temperature fuel and electrolyte

Construction and working of CH3OH O2 fuel cells with H2SO4 as

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