Chemical energy sources

FUEL

A fuel is defined as naturally occurring or artificially manufactured

combustible carbonaceous material which on proper burning serves
particularly as source of heat and light and also in few cases as a source of
raw material.

Classification of fuels Fuels are classified into a two types.

Based on their origin they are classified into

a) Primary Fuels: There are naturally occurring fuels which serves as

source of energy without any chemical processing.
Ex: Wood, Coal, Crude oil, Natural gas, Peat, Lignite, Anthracite..

b) Secondary Fuels: - They are derived from primary fuels & serves as
source of energy only after subjecting to chemical processing.
Ex: Charcoal, Coke, produser gas, Petrol, Diesel etc.,

Bases on their physical state fuel are classified into a)

Solid
b) Liquid
c) Gaseous fuels.

SOLID LIQUID GASEOUS

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

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

Calorific value is of two types as follows:-

1) Higher calorific value. (HCV) or Gross calorific value. (GCV)
2) Lower calorific value. (LCV) or Net calorific value. (NCV)

1) HCV: - It is the amount of heat liberated when a unit mass of fuels

burnt completely in the presence of air or oxygen and the products of

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 combustion are cooled to room temperature. Here it includes the heat
liberated during combustion and the latent heat of steam. Hence its
value is always higher than lower calorific value.

2) LCV: - It is amount of heat liberated when a unit mass of fuel is

burnt completely in the presence of air or oxygen and the product of
combustion are let off completely into air. It does not include the latent
heat of steam. Therefore it is always lesser than HCV.

NCV = HCV Latent heat of steam.

= HCV 0.09X % H2 X 587 KJ/Kg

In SI system the units of calorific values for solid fuels are

expressed in KJ/Kg and for gaseous and liquid are expressed in J/m3.

Bomb Calorimeteric Method

A small quantity of a fuel is weighed accurately (M Kg) and is placed in the

Bomb. The bomb is placed in known amount water taken in a copper
calorimeter. The initial temp of water is noted as a t10C with the help of
thermometer. Oxygen gas is pumped under pressure 20 to 25 atm through the
O2 valve provided.

The fuel is ignited by passing electric current through the wires

provided. As the fuel undergoes combustion and liberates heat, which is
absorbed by surrounding water. The water is stirred continuously to

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distribute the heat uniformly and the final temp attained by water is
noted t20C. & gross calorific value of the fuel is calculated as follows:-

Calculation:
Mass of the fuel = M Kg.
Initial temp of the water = t10C Final
temp of the water = t20C Change in
temp = t = (t2 t1)0 C
Specific heat of water = S
Water equivalent of calorimeter = W Kg.

GCV = W x S x t J/Kg or
M
GCV = (W+w) x S x t kJ /Kg
M

NCV = GCV 0.09 x %H2 x 587 cal/g

Petroleum Cracking Fluidized Bed Catalytic Cracking Method

Cracking is a process that involves breaking of C-C and C-H bonds in the
chains of high boiling hydrocarbons of high molecular weight, to yield
simpler, low boiling hydrocarbons of lower molecular weight.

To
fractionatin
Fuel

Riser
Air

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

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heavy oil) is preheated to 5000C and forced into the cracking chamber along
with the catalyst by a steam blast where a floating

Catalyst becomes inactive after cracking process. It is sent to

catalyst activation chamber and it is activated by burning carbon
deposited on the catalyst by air blast at 6000C. The catalyst can be used
again and the process is continuous.
Reformation Of Petroleum
It is a process of bringing structural modifications in the strait
chain hydrocarbons (with lower octane number) to increase the octane
number and thereby improving the anti-knocking characteristics of
petrol.
Reforming is a chemical process, which involves modification of the
structure of molecules without much change in the molecular masses.
Reformation of petroleum involves the following reforming reactions:
1) Isomerisation.
2) Dehydrogenation.
3) Cyclisation & dehydrogenation and
4) Hydro cracking.
1) Isomerisation: -
It is a process of converting the straight chain hydrocarbon
compound of lower octane number into a branched chain hydrocarbon
compound of higher octane number.

2) Cyclisation: Straight chain hydrocarbons undergo cyclisation

producing cyclic hydrocarbons which have higher octane number.

Ex. CH3 CH2 CH2 CH2 CH2-CH3

n- Hexane Cyclo hexane

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

CH3 CH2 CH2 CH2 CH2-CH3

n- Hexane Cyclo hexane Benzene

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

ELECTROCHEMICAL CELLS

Electrochemical energy systems involve the study of interconversion of chemical energy to

electrical energy and vice versa.
A cell consists of two electrodes; each electrode (or metallic conductor) in contact with an
electrolyte (or ionic conductor) comprises an electrode compartment.
If the electrolytes are different, the electrode compartments may be coupled through a salt
bridge.(agar jelly saturated with potassium chloride or ammonium nitrate) to connect the
electrode compartments.
It provides an electrical contact between the two electrodes.
Electrochemical cells
Electro chemical cell is device it convert electrical energy into chemical energy or chemical
energy into electrical energy through redox reaction.
Classification of electro chemical cells

Electrolytic cell Galvanic cell

The cell converts electrical energy into The cell converts chemical energy.
Chemical energy in to electrical energy
A non-spontaneous reaction is driven by Electric current is generated due to
The external source of current Spontaneous redox reaction
Example: Electrolytic bath Example; Daniel cell

Classification of Electrolytic cell;

GALVANIC CELLS(VOLTAIC CELL)

Primary cell Secondary cell Concentration

Primary cells: In case of certain cells generating definite amount of electrical energy, if
electrical energy slightly greater than this is applied in the opposites direction (reverse
direction), the cell reaction is not reversed. Such cells are called primary cells or
irreversible cells. Example: Dry cell.

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Secondary cells: In the case of secondary cells, the cell reactions producing electrical energy
can be reversed by applying external current in the opposite direction. These are also called
reversible cells.
Example: Lead acid battery, Nickel-cadmium battery
Concentration Cells:
It is a type of galvanic cell, consists of two identical electrodes in contact with its salt
solution of different concentration.
The cell potential is due to difference in the concentrations of the metal ions, hence
called concentration cell.
The electrode with lesser concentration of metal ions behaves as anode and with higher
concentration of metal ions acts as cathode.
Oxidation occurs at lower concentration and reduction occurs at higher concentration of
electrolyte. The driving force of these cells is the difference in concentration. & no net
chemical reaction in the concentration cell.
Example; Cu concentration cell. Fe concentration cell.

CONSTRUCTION OF GALVANIC CELL:

Galvanic cells are the devices in which free energy change accompanying redox
reactions, is converted into electrical energy. Ex: Daniel Cell

It consists of Zn rod dipped in ZnSO4 and a copper rod dipped in CuSO4. The electrodes are
connected externally through a metallic wire. The electrodes are connected internally by
means of a salt bridge.

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Zn dissolves as zinc ions in the solution and the electrons left behind on the metal, flow through
the connecting wire to the Cu electrode.
Zn Zn2+ + 2e- (oxidation at anode)
These electrons are used by Cu2+ ions in the solution and reduction occurs.
Cu2+ + 2e- Cu ( reduction at cathode)
The flow of electrons from the Zn electrode to the Cu electrode provides a source of electricity.

SINGLE ELECTRODE POTENTIAL

The tendency of an electrode to either lose or gain electrons when it is in contact with the
solution of its own ions.
Single electrode potential is also known as half cell potential.
The electrode potential may be termed as oxidation potential or reduction potential, when
oxidation or reduction takes place respectively at the electrode with respect to Standard
Hydrogen Electrode (SHE) as a reference electrode

ORIGIN OF ELECTRODE POTENTIAL

Let us consider a metal in contact with a solution of its own ions.
According to Nernst equation, whenever a metal rod is dipped in its solution, two distinct
tendencies will appear.
Tendency-1:
The metal atoms (Zn) have a tendency to go into the solution in the form of ions leaving
behind electrons on the surface.
Zn ----- Zn2+ + 2e {Oxidation of metal (Zn) }
So, the metallic surface becomes negatively charged. Because of this, the positive ions (Zn2+)
present in the solution accumulate around the metal.
Tendency 2
Simultaneously, another tendency would also appear. The metal ions ( Zn2+) in the solution
tend to get deposited on the surface, thus rendering the metal positive.
Zn2+ +2e ---- Zn (Reduction reaction)
As the two tendencies appear simultaneously, there exists an equilibrium between the two
tendencies.
Therefore, Zn Zn2+ + 2e
Thus, an electrical double layer called Helmohltz electrical double (HED) layer is established at
the metal-solution interface. This resultant potential difference between the metal and the
solution is termed as the electrode potential.
Thus, electrode potential is defined as the potential that exists between the metal or gas and its
ions in solution at their equilibrium, when they are in contact with each other.

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 STANDARD ELECTRODE POTENTIAL
It is defined as the tendency of a metal to lose or to gain electrons, when the electrode is in
contact with its salt solution of unit concentration at 298K.
The standard electrode potentials (Eo) of a number of electrodes are determined with respect
to SHE and they are arranged in the increasing order of their electrode potential values a series
obtained is known as Electrochemical series. (cf. Table-1)

CELL NOTATION AND CONVENTIONS

Galvanic cells are represented with the help of symbols and formulae.
ZnZnSO4(aq) || CuSO4(aq) Cu
Conventions:
1. A galvanic cell consists of two electrodes and each of these are called half cells.
2. If oxidation occurs at an electrode it will be a negative electrode or oxidation
electrode, and if reduction occurs at an electrode, it will be a positive electrode
or reduction electrode.
3. While representing a galvanic cell, the oxidation electrode (anode) is written on
the LHS and the reduction electrode (cathode) on the RHS.
4. A vertical line (|) or a semicolon (;) is used to represent the interfaces across
which a potential difference exists .

DERIVATION OF NERNST EQUATION:

In 1889, Nernst derived a quantitative relationship between electrode potential
and concentration of the electrolyte species involved.
Nernst equation is useful in determining the magnitude of the electrode potential
of a metal. In order to derive the equation , the concept of free energy is used .
n+ -
Let us consider a reversible electrode reaction as M + ne M
----(1)
According to law of mass action,
[M] 1
K = --------- here [M] = 1 , = ----------- -------(2)
n+ n+
[M ] [M ]
Where K is equlibrium constant.
If G is the change in free energy of the system, it varies with temperature and the
concentration of reactants and products.
0
G = G + RT In K ------(3)
0
Where G is the change in free energy in standard condition.
If the electrode potential is E then the decrease in free energy G, due to transfer of one mole
of ions across the double layer will be nEF where F is Faraday constant and n is no. of electrons
involved in the electrode reaction.

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In a reversible reaction, the electrical energy is produced by decreasing the free energy of the
system.

i.e., G = - nEF and G0= - nE0F -------(4)

( where, G = free energy change, G0= standard free energy change, E=electrode potential;
E0=standard reduction potential n=number of electrons change; F is Faraday = 96,500C mol-1)

By substituting (2) and (4) in equation (3)

- n E F = - n Eo F + RT ln -------- ---------(5)

[Mn+]

RT 1
o
E = E - ------ ln ---------
n+
nF [M ]

2.303 RT 1
o
E = E - ------------- log -------
n+
nF [M ]
This equation is the Nernst Equation.
At 298 K, the Nernst Equation.

0.0591 1
o
E = E - ------- log ------ =E +
0 0.0591
n
[
log M n + ]
n+
n [M ]
The cell potential may be calculated using the relation

0 2.303RT [ M n + ]cathode
Ecell = E cell + log
nF [ M n + ] anode

REFERENCE ELECTRODES
Reference electrodes are the electrodes with reference to those, the electrode potential of any
electrode can be measured.

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Standard hydrogen electrode (SHE) is the primary reference electrode as the electrode
potential values of other electrodes are assigned with respect to it. For convenience, its
potential is taken as zero at298 K.
As on today, potential of electrodes known are on hydrogen scale. Hence, SHE is referred as
primary reference electrode.
NEED FOR DEVELOPING SECONDARY REFERENCE ELECTRODES
For the sake simplicity and to overcome the above difficulties, there was a need
for the development of secondary reference electrodes.
The potentials of these electrodes are known on the hydrogen scale and are used
in place of hydrogen electrode. These electrodes can be easily set up.
Secondary reference electrodes are those whose
Potentials are standardized using SHE.
Potentials are known at the conditions.
Presently two such electrodes are in common use.
Ex: Calomel electrode and Silver-silver electrode.
BATTERIES
A battery is a portable energy source with three basic components-an anode (the negative
part), a cathode (the positive part), and an electrolyte. As current is drawn from the battery,
electrons start to flow from the anode through the electrolyte, to the cathode.
The conversion of chemical energy into electrical energy is the basis for the functioning of a
galvanic cell or a battery. A cell designates a single unit, but a battery is an arrangement of two
or more cells either connected in series or parallel or both
It ranges from small button cells used in electric watches to the lead acid batteries used for
starting, lighting and ignition in vehicles with internal combustion engines
BASIC CONCEPTS:
The basic electro chemical unit in a battery is a galvanic cell . The components of such a cell are
shown in the figure. The term battery is often applicable to single cell.
The Battery has the following major components.
The anode :
It is a negative electrode at which oxidation of the species occur. The electrons liberated are
taken out of the compartment by an external connection.
The Cathode:
It is a positive electrode at which reduction of the species occur. The electrons reach this
electrode through the metallic wire for reduction reaction.
The Electrolyte:
The electrolyte is commonly a solution of acids, alkalis or salts having a high ionic conductivity.
Solid electrolytes with appreciable ionic conductivity are also used at the operating
temperature of the cell.
The Separator:
The material which electronically isolate anodes & cathodes in a battery to prevent internal
short circuiting are referred to as separators . They are permeable to the electrolyte so as to
maintain desired conductivity. Thus their main function is to transport ions from the anode
compartment to cathode compartment and vice versa.
Materials used most commonly as separators include fibrous forms of regenerated cellulose,
vinyl polymers, cellophane.

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FUEL CELLS
Fuel cell is defined as a galvanic cell in which electrical energy is directly derived by the
combustion of chemical fuels supplied continuously
A fuel cell differs from a conventional battery in the following aspects
In a fuel cell, the reactants are fed from outside the cell & do not form an integral part as in a
battery.
Unlike batteries, fuel cells do not store energy.
Reactants are constantly supplied and the products are constantly removed from a fuel cell.
Like any other electrochemical cell, the fuel cell has two electrodes and an electrolyte .
However, the fuel & the oxidizing agents are continuously & separately supplied to 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.
A fuel cell essentially consists of the following arrangement.
Fuel /electrode/electrolyte/electrode /oxidant
At the anode, fuel under goes oxidation
Fuel oxidation product + n e-
At the cathode, the oxidant gets reduced

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 -
Oxidant + n e Reduction products.
The fuel cell has following advantages:
Their power efficiency is high.
Silent operation.
They are eco friendly , since the products of the overall reactions are not toxic & hence no
pollution problems.
No need of charging.
They can produce direct currents for long periods at a low cost.
Limitation:
Cost of power is high as a result of the cost of the electrodes.
Power out put is moderate.
Fuels, in the form of gases and oxygen need to be stored in tanks under high pressure .
To have an appreciable voltage, a battery fuel cells must be available
Based on the type of electrolytes used, fuel cells are classified into the following types.
Alkaline fuel cells: (AFCS)
0
These operate at 80 C. & Electrolyte: alkali
At anode: hydrogen, At cathode: oxygen
Advantages:
Hydrogen and oxygen are cheap.
Since the electrolyte is an alkali, any type of electrode can be used.
When started at room temperature has low efficiency but on operation gets
warmed up and gives optimum efficiency.
Applications: It is used in portable & emergency power generation equipments.
Phosphoric acid fuel cells (PAFCs):
0
These operate at 200 C.
At anode: hydrogen or pure LPG and at cathode: air
Electrolyte: Phosphoric acid adsorbed on a solid..
Electrodes are made of Teflon.
Uses: To supply light and heat in large buildings.
Molten carbonate fuel cells (MCFCs):
0
These operate at 600 C.
At anode: hydrogen and at cathode : Oxygen
Electrolyte - LiAlO2 + Li2CO3 + K2CO3
Uses: It finds applications in Aluminum industries.
Reactions
2
At anode H2 + CO3 CO2 + H2O + 2e
2
At cathode 1/2 O2 + CO2 + 2e CO3
Ni electrodes with a small amount of Cr are used.
Solid polymer electrolyte cells(SPECS):
0
These operate up to 200 C
Anode: hydrogen and Cathode: Oxygen

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 Electrolyte: ion exchange membrane- Nafion R
Anode and cathode are made of platinum electrodes.
Uses: Used in space vehicles.
Solid oxide fuel cells(SOFCs):
0
These operate at 1000 C & Electrolyte: ZrO2 Y2O3
Anode: Ni on ZrO2 & Cathode: Strontium doped LaMnO2
Advantage: does not corrode
Uses: In locomotives since large amount of heat is evolved
CONSTRUCTION, WORKING AND APPLICATIONS OF METHANOL-OXYGEN FUEL CELL

1.23 V e
e
Anode Cathode
H2 O2

Porous graphite
electrode coated with
platinum
electrocatalyst
Polystyrene sulphonic
It has an anodic compartment & cathodic compartments. Both contain graphite
electrodes impregnated with Pt-Ru-Co.
acid ion exchange
O +HO
H2 Hydrogen is bubbled through the anodic compartment
2 2
Oxygen is bubbled through the cathodic compartment.
Electrolyte is concentrated KOH solution.
Wicks for maintaining
water balance
Reactions:
-
At anode : H2 + 2OH 2H2O + 2e
-
At cathode : 1/2 O2 + H2O + 2e 2OH
Net reaction: H2 + O2 = H2O

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