UNIT-II: ENERGY TECHNOLOGY

Chemical Fuels
Fuel: A fuel is the substance which on combustion produces a
large amount of heat.

As most of the fuels contain carbon or carbon and

hydrogen, the combustion involves the oxidation of carbon to
carbon dioxide and hydrogen to water. Sulphur, if present, is
oxidized to sulphur dioxide while the mineral matter forms the
ash.
Fuels like coal, crude oil, natural gas known as fossil fuels found
under earth crust.
Chemical fuels: The fossil fuels, wood, vegetable oils etc. which
produce heat on burning are known as chemical fuels.
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.
Physical state Primary fuels Secondary fuels

Solid Liquid Wood, coal Charcoal, coke

Gas Petroleum Petrol, diesel, kerosene

Natural Gas LPG

Importance of hydrocarbons as fuels:
Fossil fuels contain mainly hydrocarbons. These hydrocarbons are
important sources of energy in daily life. Hydrocarbons are used as energy
sources in cooking, lighting, automobiles, production of electricity in
thermal power plants etc. These hydrocarbon fuels meet 80% of the
world’s energy demand. Thus hydrocarbons are important sources of
energy
Characteristics of a Good/ideal fuel:
While selecting an ideal fuel for domestic or industrial purpose we
should keep in mind that the fuel selected must possess the
following characteristic properties.
1. It should possess high calorific value.
2. It should have proper ignition temperature. The
ignition temperature of the fuel should neither be too
low nor too high.
3. It should not produce poisonous products during
combustion. In other words, it should not cause
pollution on combustion.
4. It should have moderate rate of combustion.
5. Combustion should be easily controllable i.e.,
combustion of fuel should be easy to start or stop as
and when required.
6. It should not leave behind much ash on combustion.
7. It should be easily available in plenty.
8. It should have low moisture content.
9. It should be cheap.

Knocking of IC Engine:
Knocking in Petrol Engines:
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”.
Knocking is the rattling noise or metallic sound produced in an internal
combustion engine due to uneven combustion (detonation) of fuel and air
mixture.
The reasons for Knocking are
(1) Very high compression ratio causes preignition.
Compression ratio is the ratio of the volume of the fuel and air
mixture (V1) at the end of suction stroke to the volume of the
mixture (V2) at the end of compression stroke.
Compression ratio (CR) = V1/V2
The value (CR) will always be greater one. Power output of IC
engine increases continuously with increase in compression ratio.
The compression ration corresponding to maximum power output
is known as highest useful compression ratio (HUCR).
Very high compression ratio means that the fuel and air are
compressed to a maximum extent, leads to increase in the
temperature of the cylinder. Hot spots are formed inside. When the
fuel and air mixture are compressed hot spots ignites the fuel even
before spark plug produces spark. This phenomenon is called
preignition which leads to knocking.

(2) Peroxide formation leads to self-Ignition

A. Under Normal Conditions there is a slow oxidation of the
fuel.
 Normal combustion takes place due to the chain reaction. The
overall reaction may be represented as

B. Under Knocking Conditions, the rate of combustion is very

high. It involves following steps.
1. Oxygen combines with hydrocarbon molecule forming
peroxides.

2. The peroxides decompose readily to give a

number of gaseous products. For example,

Fast reaction leads to rapid increase of pressure. This results in

knocking.
(3) Chemical Structure of the Fuel:
Knocking tendency decreases with the increase in compactness of
the molecule and increases with the increase in the length of
hydrocarbon chain.
Ex., i) 2, 2-dimethyl pentane knocks lesser than 2-methyl
hexane
ii) n-butane knocks lesser than n-hexane.
The tendency to knock has been found to decrease in the
order
n-alkane > mono substituted alkanes > cycloalkane > alkenes >
Polysubstituted alkanes >aromatic compounds.
Octane Number:
Graham Edger proposed an arbitrary scale for expressing the
knocking characteristics of gasoline in combustion engine as
octane number in 1972 on the basis of antiknock properties.
It has been found that n-heptane, CH3-CH2-CH2-CH2-CH2-CH2-
CH3, knocks very badly and hence, its antiknock value has been
arbitrarily given zero. On the other hand, isooctane (2, 2, 4 –
trimethylpentane) gives very little knocking, so its antiknock value
is given as 100.
Thus, Octane number (or rating) of a gasoline (or any other
internal combustion engine fuel) is the percentage of isooctane in a
mixture of isooctane and n-heptane, which matches the fuel under
test in knocking characteristics.
Reference Fuels Chemical Structure Octane
Isooctane numbe
(2,2,4 –trimethylpentane) r
100

CH3-CH2-CH2-CH2-CH2-CH2-CH3 0
n-heptane

Ex: If a sample of petrol gives as much knocking as the mixture of

65% isooctane and 35% n-heptane, then the octane number of
petrol is 65.
Anti-Knocking Agents
The octane rating of gasoline samples can be increased by the
addition of certain organometallic compounds called anti-knocking
agents and the process is called “doping”.
1) An extensively used anti-knocking agent is tetraethyl lead
 Pb(C2H5)4 0.5ml/litre. (but it causes air pollution by Pb.)
2) Addition of alkylate fraction to petrol i.e. branched chain
alkane of higher mol. wt.
3) Addition of benzene, toluene, xylene (BTX) to petrol.
4) Addition of methyl t-butyl ether (MTBE) or ethyl t-butyl
ether.
5) Adjusting suitable compression ratio
Quality of Petrol can be Improved by Adding:
1. Antioxidant to improve oxidation resistance.
2. Octane no. improvers like MTBE.
3. Freezing point depressant like ethanol, glycol to minimize
ice formation in fuel line in cold regions.
4. Detergents like fatty amines to clean fuel line and
carburetor.
Knocking in Diesel Engines
It works on the principle of compression ignition. Air is drawn into
the cylinder and compressed to a pressure of 3.5 X 10-3 kgm-2.
During compression cylinder gets heated around 350 °C. Then
diesel is introduced in the form of spray which is spontaneously get
ignited and burns producing pressure on the piston. It takes some
time for the fuel to get ignited. The time interval between the fuel
injection and ignition is called ignition delay. It will be
milliseconds.
The shorter ignition delay leads to burning of the fuel at the rate
which it is injected. Whereas longer ignition delay results in
accumulation of the fuel in the engine and this causes an explosive
combustion when ignited. As a result the diesel engine knocks.
Cetane Number of Diesel
Cetane Number is a measurement of the combustion quality of
diesel fuel during compression ignition. It is a significant
expression of the quality of a diesel fuel. Cetane number is a
measure of a fuel's ignition delay, the time period between the start
of injection and the first identifiable pressure increase during
combustion of the fuel. In a particular diesel engine, higher cetane
fuels will have shorter ignition delay periods than lower cetane
fuels.
The suitability of a diesel fuel is determined by its cetane value
which is the percentage of n-hexadecane in a mixture of n-
hexadecane and 2-methyl naphthalene, which has the same
ignition characteristics as the diesel sample.
Reference Fuels Chemical Structure Cetane
Number

α-methyl Naphthelene

CH3-(CH2)14-CH3
Cetane(Hexadecane) 100

Relative order of cetane no. values

n-alkanes > cycloalkanes > alkenes > branched alkanes >
Aromatics
How to increase Cetane No.
Alkyl nitrates (principally 2-ethylhexyl nitrate) and di-tert-butyl
peroxide are used as additives to raise the cetane no.
• Antioxidant to improve oxidation resistance during storage.
• Lubricity additives for lubrication of fuel injection system.
• Detergents to clean fuel line and carburetor.
Power Alcohol
When ethyl alcohol is used as fuel in internal combustion engine, it
is called as power alcohol. It contains 25% of alcohol and 75%
petrol.
Advantages of Power Alcohol:
(i) Ethyl alcohol has good antiknocking property and its
octane number is 90, while the octane number of petrol
 is about 65. Therefore addition of ethyl alcohol to petrol
increases its octane number.
(ii) Alcohol has property of absorbing any traces of water if
present in petrol.
(iii) If a specially designed engine with higher
compression ratio is used, then the disadvantage of
lower C.V. of ethyl alcohol can be overcome.
(iv) Ethyl alcohol contains ‘O’ atoms, which help for
complete combustion of power alcohol and the polluting
emissions of CO, hydrocarbon, particulates are reduced
largely.
(v) Use of ethyl alcohol in petrol reduces our dependence
on foreign countries for petrol and saves foreign
currency considerably.
(vi) Power alcohol is cheaper than petrol.
Disadvantages of Power Alcohol:
(i) Ethyl alcohol has C.V. 7000 cal/gm much lower than
C.V. of petrol 11500 cal/gm. Use of power alcohol
reduces power output upto 35%.
(ii) Ethyl alcohol has high surface tension and its
atomisation, especially at lower temperatures, is difficult
causing starting trouble.
(iii) Ethyl alcohol may undergo oxidation to form acetic
acid, which corrodes engine parts.
(iv) Ethyl alcohol obtained by fermentation process
directly cannot be mixed with petrol but it has to be dehydrated
first.
(v) As ethyl alcohol contains ‘O’ atoms, the amount of air
required for complete combustion of power alcohol is lesser and
therefore carburettor and engine needs to be adjusted or modified,
when only ethyl alcohol is used as fuel.
Biodiesel
Chemically biodiesel is the mixture of methyl esters of long chain
carboxylic acids. It is eco-friendly fuel obtained from renewable
sources like vegetable oils and animal fats. Common vegetable
(edible and Non-edible) oils used are Soyabean oil, palm oil,
peanut oil, cotton seed oil, corn oil, pongamial oil, Jatropha oil etc.
Vegetable oils are the triglycerides, which have high viscosity,
flash point and low heating value. Hence they cannot be used as
such in diesel engine. Triglycerides are need to be converted into
biodiesel by a process is called Transesterification.
During the transesterification, the triglyceride is treated with
methanol or ethanol in the presence of a base like KOH/NaOH,
forms methyl or ethyl esters of fatty acids (biodiesel)
Conditions: Temperature: 55-60 C, Catalyst-KOH/NaOH, Reaction
time-1-8 hrs.

Separation:

As above two products are immiscible phases, we can

easily drain off the glycerine/glycerol by washing with water and
biodiesel can be collected.
Advantages of Biodiesel:
(i) Biodiesel is cheaper, as it is manufactured from cheap,
non-edible or waste oil or animal fats.
(ii) It has high cetane numbers 46 to 54 and high C.V of
about 40 kJ/gm.
(iii) It is regenerative and environment friendly.
(iv) It does not give out particulate and CO pollutants, as
Oxygen atoms in biodiesel help for complete
combustion.
(v) It has certain extent of lubricity, due to higher oiliness
of the esters.
(vi) Its use provides good market to vegetable oils and
reduces our dependence on diesel on foreign countries,
saving currency.
(vii) It is clean to use biodiesel in diesel engines.
Limitations of Biodiesel:
(i) Cloud and pour points of biodiesel are higher than
diesel and can cause problem in fuel flow line. So it
cannot be used in cold regions.
(ii) Biodiesel may have dissolving action rubber hoses,
gaskets.
(iii) There is shortage of vegetable oils and the starting
material if costly, the biodiesel will be costly.
 (iv) Biodiesel strongly adheres on metals and can become
gummy.
Rocket Fuels and Propellants
Rocket propellants consist of rocket engines powered by propellants. These
are used both in space vehicles as well as in offensive weapons such as
missiles. The propellants are chemical substances which on ignition provide
thrust for the rocket to move forward. These substances are called rocket
propellants. A propellant is a combination of an oxidiser and a fuel which
when ignited undergoes combustion to release large quantities of hot gases.
The passage of hot gases through the nozzle of the rocket motor provides the
necessary thrust for the rocket to move forward according to Newton's third
law of motion.
The function of a rocket propellant is similar to that of petrol in a motor car
except that in the later case, the oxygen needed for burning the fuel is taken
from the atmospheric air.
(1) Types of rocket propellants: Depending upon the physical state,
propellants can be classified as :
(i) Solid propellants: The solid propellants are mixtures of solid fuel and a
solid oxidiser. These are further divided into two classes,
(a) Composite propellants: These are solid propellants which use polymeric
binder such as polyurethane or polybutadiene as a fuel and a solid oxidiser
such as ammonium perchlorate, nitrate or chlorate. The performance of these
propellants can be increased by using some additives such as finely divided
magnesium or aluminium metal along with the fuel.
(b) Double base propellants: These are solid propellants which mainly use
nitroglycerine and nitrocellulose. The nitrocellulose gels in nitroglycerine set
in as a solid mass.
The main disadvantage of solid propellants is that these propellants once
ignited will continue burning with predetermined rate. These cannot be
regulated.
(ii) Liquid propellants: These consist of an oxidizer such as liquid oxygen,
nitrogen tetroxide (N2O4) or nitric acid and a fuel such as kerosene, alcohol,
hydrazine or liquid hydrogen. These are further classified as,
(a) Monopropellants: The propellants in which a single chemical compound
acts as fuel as well as oxidizer are called monopropellants. For example,
hydrazine, nitromethane, methyl nitrate, hydrogen peroxide, etc. Except
hydrazine, the other compounds contain both the oxidizer and the fuel
elements in the same molecule.
 (b) Bipropellants : These are propellants in which the fuel and oxidiser are
stored separately but are allowed to combine at the time of combustion. For
example, kerosene and liquid oxygen.
Hydrazine can act both as a monoliquid as well as a biliquid propellant.
Hydrazine (H2N−NH2) acts as a monoliquid propellant as it decomposes
exothermally into hot gaseous mixture of N2 and H2.
H2N−NH2→N2+2H2+heat
As a biliquid propellant with liquid oxygen as oxidiser,
H2N−NH2+O2→N2+2H2O+heat
Advantages of Biliquid Propellants over Solid Propellants
• The biliquid propellants give higher thrust than solid propellants.
• The thrust generated by liquid propellants can be controlled by
switching on and off the flow of propellants. On the other hand, the
thrust cannot be controlled in solid propellants.
(iii) Hybrid propellants: These are the propellants which consist of solid
fuel and a liquid oxidiser. For example, liquid N2O4 (liquid oxidiser) and
acrylic rubber (solid fuel).
(2) Examples of Propellants used in Different Rockets
(i) Saturn booster rocket of American space programme used a mixture of
kerosene and liquid oxygen as the propellant in the initial stage whereas liquid
oxygen and liquid hydrogen were used as propellant in high altitudes.
(ii) Russian rockets such as Proton used a liquid propellant consisting of
kerosene and liquid oxygen.
(iii) The Indian satellites SLV-3 and ASLV used composite solid propellants.
(iv) The rocket PLSV will use solid propellant in the first and third stages and
liquid propellant in second and fourth stages. The liquid propellant will
consist of N2O4 and unsymmetrical dimethyl hydrazine (UDMH) and
N2O4 and monomethyl hydrazine (MMH) respectively.

Electrochemical Devices
Electrochemical cell is a device in which chemical energy is
converted into electrical energy or electrical energy into chemical
energy by oxidation-reduction reaction. The electrode where
oxidation occurs is called anode and the electrode where reduction
occurs is called cathode.
TYPES OF ELECTRODES:
(i) METAL-METAL ION ELECTRODE:
This type of electrode consists of a metal in contact with a solution
of its own ions.
Eg: 1. Zinc in a solution of zinc sulphate
2. Copper in a solution of copper sulphate.
(ii) METAL-METAL SALT ION ELECTRODE:
This type of electrode consists of a metal in contact with one of its
sparingly soluble salts and a solution of a soluble salt having a
common anion with the sparingly soluble salt.
Eg: 1. Calomel electrode Hg(l)| Hg2Cl2(s) |KCl
Or Pt, Hg(l), Hg2Cl2(s) |KCl (….M)
2. Silver-Silver chloride electrode Ag, AgCl (s) | KCl (….M)
(iii) METAL-GAS ELECTRODE:
A gas electrode consists of a particular gas flushed around an inert
electrode (Pt), which is dipped in a solution containing ions to which
the gas is reversible. The metal provides electrical contact and
facilitates the establishment of equilibrium between the gas and its
ions.Eg: SHE: Pt | H2 (1atm) | H+ (1M), Chloride electrode
[Pt/Cl2/Cl-]
(iv) OXIDATION-REDUCTION ELECTRODE:
This type of electrode consists of an inert electrode (Pt or Au)
immersed in a mixed solution containing both the oxidized and
reduced forms of a molecule or ion.
2+ 3+ 2+ 4+
Eg: Pt / Fe : Fe , Pt / Sn : Sn
(v) ION SELECTIVE ELECTRODE:
In ion selective electrode, a membrane is in contact with a solution,
with which it can exchange ions. These are the electrodes in which
certainly respond to specific ions and determine the potential.
Example-Glass electrode
REFERENCE ELECTRODE:
Reference electrodes are those whose potentials are known.
PRIMARY REFERENCE ELECTRODE [SHE]:
Hydrogen gas at a pressure of one atmosphere in equilibrium with
one molar hydrochloric acid in the presence of platinum is called
standard hydrogen electrode.
LIMITATIONS OF HYDROGEN ELECTRODE:
• It is difficult to maintain the pressure of hydrogen gas
uniformly at one atmosphere.
• It is difficult to maintain the hydrogen ion concentration 1M
throughout the experiment.
• Platinum foil is easily poisoned by the adsorption of
impurities present in the solution.
• The adsorptions of impurities on the platinum foil decrease
the adsorption of hydrogen and hence equilibrium between
hydrogen gas and hydrogen ions gets disturbed.
• Hydrogen electrode cannot be used in the presence of
oxidizing agent.
These limitations lead to the construction of secondary reference
electrode.

SECONDARY REFERENCE ELECTRODE:

Eg- (i) Calomel electrode, (ii) Ag-AgCl electrode

CALOMEL ELECTRODE:
The calomel electrode consists of a glass vessel containing a layer of
Hg over which is placed a paste of an Hg, Hg2Cl2 and KCl. Above
this there is a solution of KCl saturated with the Mercurous salt. A
platinum wire is fused in the glass tube for electrical connection. A
salt bridge is used to couple with other half-cell.

General representation
Pt, Hg(l), Hg2Cl2(s)/(………KCl)
When connected to an oxidation electrode, reduction occurs at
calomel electrode and acts as cathode
Hg22+ + 2e- 2Hg
Hg2Cl2 Hg22+ + 2Cl-
Net reaction at cathode Hg2Cl2 + 2e- 2Hg + 2Cl-
When act as anode, the electrode reaction is
2Hg Hg22+ + 2e-
Hg22+ + 2Cl- Hg2Cl2
Net reaction at anode 2Hg + 2Cl- Hg2Cl2 + 2e-
The net reversible electrode reaction is,
Hg2Cl2(s) + 2e- <=> 2Hg(l) + 2Cl-
Electrode potential, E = Eo – (2.303RT/2F)log[Cl-]2
= E 0 – (2.303RT/F)log[Cl-]
= E 0 – 0.0591 log[Cl-]at 298K
The potential of the calomel electrode depends on the concentration
of KCl used.
For saturated KCl, the potential is +0.241V, For 1N & 0.1N KCl the
values are 0.281V, +0.334V respectively.
2.6.6 USES:
The calomel electrode is simple to construct, the cell potential is
reproducible and stable over a long period and does not vary with
temperature. Hence it is commonly used as a secondary reference
electrode for potential measurements.
ION SELECTIVE ELECTRODE
Ion selective electrodes are the electrodes that respond to certain
specific ions present in solution in a mixture of ions and they
develop potential due to the presence of such ions by ignoring other
ions in the solutions.
For ex. Glass electrode responds to only H+ ions selective.
GLASS ELECTRODE:
Construction:
(i) A glass electrode consists of a
long glass flask having a very thin
walled bulb with a thin walled bulb
(0.01-0.03mm thickness).
The approximate composition of
this glass is
22% Na2O, 6% CaO and 72% SiO2
(iii) The bulb is filled with 0.1 N
HCl(internal solution)
(iv) Ag-AgCl electrode dipped in
the solution provides electrical
contact (internal reference
electrode. Cell Representation
Ag, AgCl(s)/O.1M HCl/Glass
membrane/Unknown solution
Working of a glass electrode
(i) The surface of the glass membrane on both side get hydrated
(ii) Hydrogen ions get absorbed on the hydrated surface.
(ii) The exchange of H+ ions for the low atomic weight alkali ions
takes place in the hydrated region.
H+[solution] + Na-Gl Membrane ⇆ Na+ + HGl Membrane
Expression for Glass Electrode potential

0.1 M Hcl

Ag-AgCl electrode

H+ Ion Solution

Glass electrode

Let us consider the glass electrode dipped in a solution of

concentration C2 with respect to H+ ion. If C1 is the concentration of
the solution inside, then the boundary potential is given by
Eb= E1 - E2, where E1 and E2 are the potentials of the solution
outside and inside respectively.
According to Nernst, boundary potential is given by

If C2 = C1, then the potential differences across the membrane shall

be zero. But it doesn’t happen so. There is some residual potential
measured across the boundary which is due to the following
(i) Anatomy of glass electrode shown that it contains, Ag-AgCl
electrode as a reference electrode. It will also develop potential (E int
ref) and can’t be neglected.
(ii) Whatever be the care taken in the manufacture of glass
membrane, strain of the inside and outside of the electrode bulb and
unevenness of the membrane can’t be avoided. The potential that
arises due to this called Asymmetric potential (Eassy pot)
So, the glass electrode potential Eb can be given as fallows

Where C2= [H+], concentration of unknown solution. In the above

equation, the first 3 terms are constants for a given glass electrode.
They are replaced by another constant called Eog .

At 298k,

Here, n= 1, F= 96,500 C, R= 8.314 J/K/Mol.

The value, E 0 g is constant for a given glass electrode, on a particular
day. Hence before determining the pH of any given solution E 0 g
value shall be determined using solution of known concentration of
H+.
ADVANTAGES:
• It is simple to operate.
• It is not poisoned easily.
• It can be used both in oxidizing and reducing agents.
• The equilibrium between the two solutions is reached
quickly.
• Only a few drops of the liquid are enough to determine the
pH.
• It provides accurate results.
 • It can be used in solution with pH values ranging from 0 to
10.
DISADVANTAGES:
• Glass electrode cannot be used in presence of fluoride ions.
• It cannot be employed in pure ethyl alcohol, acetic acid and
gelatin.
• The bulb is too fragile, so the glass electrode has to be used
with utmost care.
• Glass electrode cannot be used when pH of the solution is
above 10, as it introduces alkaline error. As the electrodes
become selective to Na+ ion also.
DETERMINATION OF A pH OF A SOLUTION USING A
GLASS ELECTRODE:
The experimental activity has two stages:
(i) Determination of 𝐄𝟎 g
The given glass electrode is washed with distilled water and the
bulb is carefully wiped off using cotton. It is then dipped in a
solution of known pH. The electrode is coupled with saturated
Calomel electrode (SCE) using a salt bridge.

The cell assembly is represented as,

Pt, Hg| Hg2Cl2|Cl-||Solution of known pH|glass|0.1M
HCl|AgCl, Ag
The cell is connected to VTVM (Vacuum tube voltmeter) and the
emf measure (E known).
Eknown= Eg - ESCE
At 298 K, ESCE = 0.2412
Eg= Eknown + ESCE
But, Eg = E 0 g - 0.0591pH
As the pH is known E 0 g = Eg + 0.0591pH
(ii) Determination of the given pH of the solution
The glass electrode is removed, washed with distilled water and
wiped off using cotton, it is dipped in the solution of unknown pH
and coupled with SCE using salt bridge. The cell is connected to
VTVM (Vacuum tube voltmeter) and the emf measure (Eknown).
The cell assembly is represented as,
Pt, Hg| Hg2Cl2|Cl-||Solution of unknown pH|glass|0.1M
HCl|AgCl, Ag
Eunknown= Eg - ESCE
Eg= Eunknown + ESCE
But, Eg = Eog-0.0591pH
pH can be calculated suing the equation

Problems:
1. A galvanic cell consisting of Cu versus H2 electrode was used to
determine the pH of an unknown solution which was placed in H2
electrode compartment and PH2 = 1atm. Concentration of Cu2+ was
1M and emf of cell at 25◦C was found to be 0.48V. Calculate the pH
of this unknown solution. Reduction potential of copper electrode is
+0.34V.

Ecell = E 0 copper - E 0 hydrogen

0.48 V = 0.34 – (-0.0592 V) pH
pH = (0.48 - 0.34) V/ (0.0592) V = 2.365
2. The emf of the following cell at 25◦C is
Pt,H2(1 atm)| H+ (test solution) || KCl sat. solution| Hg2Cl2 | Hg
Calculate the pH of the unknown solution, Ecell = 0.2415
Ecell = 0.445 V (given)
E 0 cell = E 0 right - E 0 left
= 0.2415 – 0 = 0.2415 V
Using the relation
Ecell = Eright - Eleft
0.445 = 0.2415 – (-0.0591 x pH)
pH = 0.2035/0.0591 = 3.44

3.While determining the pH of a solution, the quinhydrone

electrode, H+, Q, QH2 was in conjuction with a saturated calomel
electrode, as represented below:
Hg,Hg2Cl2(s);KCl (salt.soln.) || H+ (unknown); Q,QH2, Pt
The emf of the cell was found to be 0.2640 volt at 25◦C. Calculate
the pH of the solution at this temperature. Ecalomel = +0.2422 volt at
25◦C and E 0 (H+, Q, QH2) = +0.6996 V
The emf of the cell is given by
Ecell = Eright - Eleft
0.2640 = 0.6996 – 0.0591 pH – 0.2422 (at 25◦C)
pH = (0.6996 – 0.2422 – 0.2640)/ 0.591 = 3.27
BATTERY TECHNOLOGY:

CELL:
A cell designates a single unit. The conversion of chemical energy
into electrical energy is a function of cells or batteries.
BATTERY:
A Battery is an electrochemical cell or often several electrochemical
cells connected in series that can be used as a source of direct
electric current at a constant voltage.
Uses:
Batteries are used in calculators, watches and pacemakers for heart
hearing aids, computers, car engines, standby power supplies,
emergency lightning in hospitals, electroplating industrial tractions
and military and space applications.
Batteries have revolutionized the telecommunication system and are
ushering a new era of transportation with the possible replacement
of petrol driven automobiles by the electrical powered ones. In
modern days portability of electronic equipment’s in the form of
handsets has been made possible by batteries.
Note: The size of the batteries ranges from a fraction of a cubic
centimeter to several cubic decimeters.
Components of Battery:
The cell consists of three major components.
(i) Anode:
The anode selected with the following properties in mind; efficiency
as a reducing agent, high columbic output (Ah/g) good conductivity
, stability ease of fabrication and low cost .
(ii) Cathode:
The cathode must be an efficient oxidizing agent, be stable when in
contact with the electrolyte, and have a useful working voltage.
(iii) Electrolyte:
The electrolyte must have good ionic conductivity but not be
electrically conductive. This would cause internal short circuiting.
Electrolyte should be non-reactive with the electrode materials.
OPERATION OF A BATTERY DURING DISCHARGE AND
CHARGE.

DURING DISCHARGING:
The Battery acts as voltaic cell i.e. oxidation takes place at the
negative electrode (anode) and reduction takes place at the positive
electrode (cathode).
DURING CHARGING:
The Battery acts as an electrolytic cell. The current flow is reversed
and oxidation takes place at the positive electrode (anode) and
reduction takes place at the negative electrode (cathode).
COMMERCIAL CELLS:
A useful commercial cell should meet the following basic
requirements.
• Portability.
• Should be compact and lightweight.
• Should provide economically priced, continuous electric
supply.
• Should be capable of recharging.
• Should have long shelf life.
LITHIUM ION BATTERY
Lithium Primary battery
Ex: Li-MnO2-Battery
Anode: Li
Cathode-MnO2(heat treated)
Electrolyte-Lithium salt like LiCl, LiBr, LiAlCl4 in mixed organic
solvent like 1, 2-dimethoxy ethane and Propylene carbonate
Reactions:
At anode
Li → Li + + e-
At cathode
Li + + MnO2 + e- --> MnO2(Li+)
_________________________________________
Li + MnO2 --> MnO2(Li+)
LiCoO2 battery (Secondary battery)

Lithium Cobalt is a mature, proven, industry-standard battery

technology that provides long cycle life and very high energy
density. The polymer design makes the cells inherently safer than
"canned" construction cells that can leak acidic electrolyte fluid
under abusive conditions. The cell voltage is typically 3.7 Volts.
Positive electrode: Lithiated form of a transition metal oxide
(lithium cobalt oxide-LiCoO2 or lithium manganese oxide LiMn2O4)
Negative electrode: Carbon (C) usually graphite (C6)
Electrolyte: solid lithium-salt electrolytes (LiPF6, LiBF4, or LiClO4)
and organic solvents (ether)
Figure of LiCOO2 battery with mechanism of lithium ion motion
Chemical reactions (During discharging)
At anode

LiXC6 →Li+ + Xe- + 6C

At cathode
Li 1-X CoO2 + XLi+ + Xe- → LiCoC6

Overall reaction
LiXC6 + Li 1-X CoO2 → Li1-xCoO2 + 6C

In the above reaction x can be 1 or 0

With discharge the Co is oxidized from Co3+ to Co4+.
The reverse process occurs when the battery is being charged.
The chemical reaction that takes place inside the battery is as
follows, during charge and discharge operation:
FUEL CELLS
Fuel cell is an electrochemical device, which can continuously
convert the chemical energy of a reducing agent and an oxidant fuel
stored externally by a process involving an essentially invariant
electrode electrolyte system.
Fuel cell consists of two electrodes and an electrolyte. However, the
fuel and the oxidizing agents are continuously and separately
supplied to the two electrodes of the cell, at which they undergo
reactions. These cells are capable of supplying current as long as
they are supplied with the reactants.

Fuel cell may be represented as:

Fuel/electrode/electrolyte/electrode/oxidant

At the anode fuel undergoes oxidation and at the cathode oxidant

undergoes reduction.
Differences between a battery and a fuel cell:
Sl Battery Fuel cell
No
1 These are the energy storage These are energy conversion
devices devices
2 Secondary batteries are Fuel cells are not chargeable.
rechargeable
3 The reactants and products In fuel cells, there is a
form integral part of the continuous supply of fuel ,
batteries oxidant
4 Products remain in the cell Products are continuously
removed from the cell
ADVANTAGES:
• Savings in fossil fuels due to the high efficiency of
electrochemical energy conversion.
• Low pollution level, no noxious exhaust gases formed.
Low noise level.
• Low maintenance, exchangeable parts.
• No need of charging.
 Theoretically, the efficiency can be 100%. In practice, the
efficiency is 50-80% which is high compared to
conventional methods.
DISADVANTAGES:
• The electrodes used are Pt, Ag or alloys of noble metal
which are costly.
• High price of clean hydrogen.
Direct Methanol- Oxygen Fuel Cell

Construction:
Fuel: Methanol
Oxidant: oxygen
Anode:
Porous nickel
impregnated with
pt/pd
Cathode:
Porous nickel
impregnated with Ag
Electrolyte: H2SO4
EMF OFFERED 1.186V

Mechanism
Fuel cell is fed with methanol and water at anode site. After the
injection of methanol, it passes through anode catalyst (Pt/Rh) and
membrane, then splits in to carbon dioxide and proton with
liberation of electron. Carbon dioxide escapes from the system and
the electron will move in the external circuit. This electron reacts
with oxygen at cathode in presence of cathode catalyst(Ag) to
produce water as useful biproduct.
Anodic reactions
CH3OH + H2O → CO2 + 6H + + 6e-

Cathodic reactions

3/2 O2 + 6H+ + 6e- → 3H2O

Overall reaction is

CH3OH + 3/2 O2 → CO2 + 2H2O

Alkali electrolyte are not preferred in advanced methanol fuel cell
because, liberated CO2 during reaction is converted into carbonate in
presence of an alkali and would have an adverse effect on working
of the cell. Hence, design of methanol-oxygen fuel cell in acid
medium is attempted electrodes made of Pt-Ru-Ni and Pt-Ru-Ni
alloys are used.

• Energy density (15 times higher than Lithium-ion

batteries) and power density are high, Energy
Methanol-Oxygen Fuel Cell
efficiency is low.
Fuel: Methanol
• Sensitive to CO2 – if alkali is used this leads to the
Oxidant: oxygen
formation of carbonates spoiling the quality of
electrodes, hence sulphuric acid is used.
• CO2 formed blocks the porosities as carbonates and
efficiency of the cell is decreased.

CO2 + 2OH- CO3-2 + H2O

Green Fuel:
Demand for green fuel technologies are rising given their potential to
accelerate the transition to more sustainable forms of energy while still
supporting current energy models with all their regional variations.
Amongst all green fuels hydrogen is considered to be the best alternative.
Hydrogen is a zero-emissions source of fuel for trains, buses and cars. It
can be used as a feedstock gas for industries such as chemical, refining and
steel. In addition, it is a source of heat and power for buildings, and can
buffer energy generated from renewable sources.
Hydrogen Production
Over the last decades, an increasing interest has been devoted to the
generation of hydrogen from solar-powered water splitting devices as a
direct approach to generate a clean and sustainable energy vector. Among
the different alternatives, a direct photocatalytic process is the most
straightforward, where a light absorber is able to produce hydrogen and
oxygen under light irradiation without an external bias.

Photocatalytic water splitting:

The photocatalytic generation of solar fuels by suitable photocatalytic
materials suspended in water is certainly one of the most attractive and
challenging pathways for decarbonizing current energy systems. From the
outside, it seems as a simple approach combining water, solar light, and a
semiconductor. However, each of these components plays a key role in the
overall efficiency of the reaction, and mostly, many factors including
thermodynamic, kinetic, and other requirements hold back this technology
from its maximum potential.
Photocatalyst
Photocatalyst must be semiconductor. The minimum requirement is to
generate electrons-hole pairs due to irradiation, normally by a UV-vis
source. But it must also have a suitable crystalline phase, which ensures
the formation of the electron-hole pairs and does not favour its
recombination.

The
ideal
water splitting electrode should be
• Efficient light absorber
• Charge Separator
• Charge Conductor
Photocatalytic water splitting is an artificial photosynthesis process
with photocatalysis in a photoelectrochemical cell used for the dissociation
of water into its constituent parts, hydrogen and oxygen, using light.

Water splitting electrodes work much like the leaves of the plants
during photo synthesis. They absorb energy from the sunlight and
use it to generate charge carriers. Negatively charged electrons and
positively charged holes. These charges are delivered to water and
water molecules swipe electron away to form hydrogen gas and
whereas holes strip the molecules of electron to form oxygen gas.
Hydrogen Storage:
Hydrogen energy storage is an area of growing interest due to the
greater storage capacity offered by hydrogen over batteries, as well
as the benefits offered by the renewable generation afforded by
hydrogen as a fuel.
Hydrogen can be stored either as a gas or as a liquid. Hydrogen gas
storage typically requires the use of high pressure tanks (350-700
bar or 5000-10,000 psi), while liquid hydrogen storage requires
cryogenic temperatures to prevent it boiling back into a gas (which
occurs at −252.8°C). Hydrogen can also be stored on the surface of
(adsorption) or within solid materials (absorption).
How is it Stored?
Hydrogen can be stored in three different ways:
1. As a gas under high pressures
2. In liquid form under cryogenic temperatures
3. On the surface of or within solid and liquid materials
Application in fuel Cell:
Hydrogen fuel cells combine hydrogen and oxygen, creating nothing
but pure water as exhaust. By converting the chemical energy stored
in the gasses into electrical energy, the energy can be harnessed to
power electric drive motors, temporary storage batteries, or a variety
of other end applications. Hydrogen fuel cell electric vehicles
(HFCEVs) may not have received the public hype of battery electric
vehicles (BEVs), but the technology isn’t just for personal use. In
fact, current storage and logistic challenges currently mean that
hydrogen is often better suited for larger scale commercial
applications such as heavy-duty trucking.
Hydrogen fuel is readily available and efficiently produced as a
petroleum byproduct or through electrolysis using energy generated
by renewable sources. As a liquid or pressurized gas, it’s relatively
easy to transport and quick to refuel, bypassing the long charge
times required by today’s batteries.
Especially as hydrogen production continues to move to renewable
sources, electrolyzers and fuel cells represent a promising option for
powerful, efficient, 100% clean energy storage and distribution
around the world.
Solar Energy
Introduction
Solar energy is a renewable energy and it inexhaustible. The
earth is receiving approximately 1.8×1011 MW of energy which is
thousands times larger than the requirement of energy for present
consumption. Thus solar energy is the only energy that fulfils all our
present and future energy needs if we utilize properly. Solar energy
can be directly converted in to heat energy or electricity. A solar
cell, or photovoltaic cell, is an electrical device that converts the
energy of light directly into electricity by the photovoltaic effect
The solar cells are broadly classified as i) Inorganic solar cells, ii)
Organic/polymer solar cells iii) Dye sensitized solar cells (DSSC).
Amongst them inorganic solar cells are currently in global market.
The amorphous silicon solar cells are classified under inorganic
solar cells.
Advantages of Solar Cells
➢ Solar cell is renewable energy which can be continuously
drawn from the sun.
➢ It is economic friendly energy because once it installed there
will be minimum maintenance charges for small usage.
➢ Solar energy is environment friendly and green energy
because it doesn’t produce any greenhouse gasses and no
pollutants.
➢ It doesn’t involve any combustion reaction or radioactive
residue hence no pollution
Disadvantages of Solar Cells
➢ Space utilization: Solar cells required large area for
installation
➢ It requires high investment cost for a big power plant
➢ During the rainy season power production is less hence grid
maintenance will be difficult.
➢ Solar energy is produced only in the day time hence storage
will be a big challenge
Dye Sensitized Solar Cells
Photovoltaic effect is a process in which conversion of
sunlight directly in to electrical energy. The process of light
dependent voltage between two electrodes in an electrode system
was first discovered by Henry Becquerel in the year of 1839. In
1954 first silicon solar cell was discovered the initial efficiency was
found to be 6%. The discovery of DSSC was started in 60s by
German scientists Gerischer and Tributsch. Later Michel Gretzel a
Swiss scientist introduced porous electrode consists of Nano TiO2
for construction of DSSC, which helped to increase the efficiency of
solar cells up to 7%. This discovery of DSSC is a pioneer in the field
of photovoltaics, thereafter vast research is going on in the field.
Device Fabrication
It consists of two electrodes cathode and anode generally
cathode is made of graphite or platinum. Anode is made of
transparent conducting oxide such as Indium tin oxide. Anode is
coated with a layer of nano porous materials (TiO2 of ZnO). Further
these nano porous materials are coated with light absorbing
organic/inorganic dye molecules. Here the nano porous materials
acts as photo-sensitizer also it provides road way for electrons. A
triiodide electrolyte system is employed in between the electrodes,
which helps in electron transfer process.
 Dye sensitised solar cells mechanism of working.
Mechanism of Working
When light photon strikes the solar cell it passes through
ITO layer and it reaches the dye molecule. Once the photon hits the
dye molecule, dye undergoes excitation with the liberation of
electron, which travels through the network TiO2 nanoparticles and
finally it reaches to cathode. The cell is completely filled with
Triiodide electrolyte. The electron from the cathode directly reduces
the triiodide molecule to three iodide molecules. Further this iodide
molecule reaches the dye molecule oxidizes to form triiodide again
with the liberation of electrons, which can be easily absorbed by dye
molecules. And similar cycle continues whenever sunlight falls on
the solar cells.
Note:
In DSSC TiO2 nano particles are used as conducting media for
electrons, because they have a unique property of welding together
and to form a good network for the electron to travel through
Selection of dye molecule is an important criteria, because dye with
different color can absorb different wavelength of light hence they
produce different amount of energy.

N3 ruthenium dye used in DSSC