Non renewable energy sources

Chemical Fuels
A chemical fuel is a substance, which on combustion in air or oxygen produces heat energy, which is used in
domestic and industrial purpose conveniently and economically”.

FUEL + O2 Combustion
PRODUCTS + HEAT
More heat energy content Lesser heat energy content

Classification of chemical fuels

1. Based on their 2. Based on their physical states

origin
a) Primary fuels a) Solid
b) Secondary fuels b) Liquid
c) Gaseous
Classification based on their origin
Classification based on physical state
 Calorific value
The total quantity of heat is liberated, when a unit mass or volume of the fuel is burnt
completely in air or O2.

Units of heat Calorific value has been classified in two ways

For solid or liquid
a.Calorie (Cal/g) (C.G.S-system)
b.Kilocal orie (Kcal/Kg) (M.K.S-system)
c.British thermal unit (BTU) (F.P.S-system)
1 BTU=252 cal=0.252 kcal
For gaseous fuel
J/cm3 or KJ/m3
1.Higher (HCV) or Gross Calorific Value (GCV)
The total amount of heat is produced, when a
unit mass or volume of the fuel has been burnt
completely and the products of combustion have
been cooled to room temperature.
2.Lower (LCV) or Net Calorific Value (NCV)
The total amount of heat is produced, when a
unit mass or volume of the fuel has been burnt
completely and the products are permitted to escape.
Determination of calorific value of solid fuel using Bomb calorimeter

Bomb calorimeter 1. Construction

2. Working
3. Observations
• Weight of the fuel = m g
• Weight of water in the calorimeter = W1g
• Water equivalent of the calorimeter, stirrer,
thermometer and bomb =W2g
• Initial temperature of water in calorimeter =
t10C
• Final temperature of water in calorimeter = t20C
 4. Calculations
(i)Determination of higher calorific value (HCV)
• Heat gained by water = W1 (t2-t1) S Cal.
• Heat gained by calorimeter, stirrer, thermometer and bomb =
W2 (t2-t1) S Cal.
• (Weight of apparatus X Specific heat)
• Total heat gained = W1 (t2-t1) S + W2 (t2-t1) S
• = (W1+W2) S (t2-t1) Cal.
• Total heat liberated by fuel = m.C
• Now, heat liberated by fuel = total heat gained

• m.C = (W1+W2) S (t2-t1)

 
• Higher calorific value = C =(W1+W2) S (t2-t1) Cal/g.
m
(ii)Determination of lower calorific value (LCV)
•  LCV=HCV- Latent heat of water vapour formed.
• HCV- 0.09H% X Latent heat of steam
• HCV- 0.09H% X 587 X 4.187 Cal/g.
 Petroleum Cracking
The breaking of long chain, higher molecular weight of hydrocarbons into smaller chain, lower molecular weight of hydrocarbons. It is known as cracking.

C10H22 (Decane) cracking C5H12(n-pentane) + C5H10(pentene)

Breaking up hydrocarbons can be done in two ways

Thermal Cracking Catalytic Cracking

700 C
450 C
THERMAL VS CATALYTIC CRACKING
FLUIDISED BED OR MOVING BED CATALYTIC CRACKING
 Fluidized (moving) bed
catalytic cracking
• Construction
• Working
The conditions of cracking process
• Feed: Heavy oil fraction mixed with steam
• Catalyst: Alumino Silicate (12.5% Al2O3
+87.5% SiO2)
• Time: 3-4 Seconds
• Percentage Cracking: 70%
• Temperature: 5000C
 ADVANTAGES & DISADVANTAGES OF FUIDISED CATALYTIC CRACKING
• Fuel after cracking has higher %
of branched chain
• Fuel after cracking has higher %
of aromatics
• Highly controlled process
• No wastage of catalyst
• Rapid mixing of fuel and catalyst
may lead to non uniform
residence time
• Agglomeration of fine particles
• Fine particles of catalyst may be
carried away during pressurized
flow
• Erosion of pipes
REFINING PROCESS
 Reforming of petroleum
Reforming is a process of bringing about structural modifications of straight chain gasoline into branched and aromatic compounds. It
is used to improving anti-knocking characteristics. It is carried out either thermally or in the presence of catalyst.

2. Isomerisation CH3
The reaction conditions
CH3-(CH2)4-CH3 → CH3-CH-CH2-CH2-CH3
Feed stocks: pre-processed gasoline
n-Hexane 2-Methyl pentane
Catalyst: Platinum supported on alumino-silica.
3. Dehydrogenation
Temperature: 4600C
Pressure: 35-50 atm.
The main reactions during catalytic reforming process
are Methyl cyclohexane toluene
1.Hydrocracking 4. Dehydrocyclization
CH3 CH3
CH3-(CH2)8-CH3 Pt, H2 2 CH3-(CH2)3-CH3
H3C CH3
n-decane n-pentane
-H2
- 3H2
Gasoline Knocking and its mechanism
Knocking is the rattling noise or metallic sound produced in an internal combustion engine due to uneven combustion of the fuel and air mixture.

C2H6 + 31/2 O2 → 2CO2 + 3H2O

C2H6 + O2 → CH3-O-O-CH3
CH3-O-O-CH3 → CH3CHO + H2O
CH3CHO + 1/2 O2 → HCHO + CO2 + H2O
HCHO + O2 → H2O + CO2
 Octane Number
The percentage of iso-octane in the mixture of iso-octane and n-heptane which are tested anti-
knocking qualities under similar experimental conditions. It is known as octane number

The octane number changes with the change in the

structure of the hydrocarbons as follows
1. CH3 – CH2 – CH2 – CH2 – CH2 – CH2 – CH3 Straight chain alkanes< branched chain
alkanes<alkenes<cycloalkanes<aromatics.
( n – heptanes , octane number = 0)

Types of gasoline
2.
Third grade gasoline- O.C.no<74
Regular grade gasoline-O.C.no-74.
Premium gasoline-O.C.no-81 and above
Aviation gasoline-O.C.no-100
 Cetane Number

The percentage of cetane in the mixture of cetane and α-methyl naphthalene which are tested
ignition quality under the similar experimental conditions. It is known as cetane number

1.CH3-(CH2)14-CH3
Cetane (C.NO=100) Types of cetane numbers
High speed-C.no-45
medium speed-C.no-35
2. low speed diesel -C.no-25

α-methyl naphthalene (C.NO= 0)

 Anti-knocking agents
The substances added (about 0.5-1.5 ml/liter) to gasoline for controlling the knocking in Internal
combustion engines are called anti-knocking agents.
 

Examples
1. Tetra ethyl lead [TEL-Pb(C2H5)4]
2. Tetra methyl lead [TML-Pb(CH3)4]
.
3. Diethyl telluride - Te(C2H5)2 Pb(C2H5)4 + 1/2O2 → pbO + 4 C2H5
UNLEADEDPETROL
The substances added to gasoline for controlling the knocking in Internal combustion engines, but free
from lead.

Examples
1.Methyl tertiary butyl ether (MTBE)
2.Ethyl tertiary butyl ether (ETBE)
3.Methanol
4.Ethanol
 Disadvantages of non renewable energy

• Once a non renewable energy source is used up it cannot be replaced

again.
• Non renewable energy source are highly polluting sources and increase
the greenhouse gasses.
• The non renewable energy source are responsible for all kinds of non-
biodegradable material accumulation.
• The exposure to non renewable energy sources has increased the level of
pollution.
• The rise in temperature due to greenhouse gas accumulation
• Zero carbon fuel burned with oxygen
• Used in fuel cells or internal combustion engines
 Production methods 
Methane pyrolysis - Low cost one step method

Partial oxidation - Fuel-air or fuel-oxygen mixture is partially combusted

Steam methane reforming - high-temperature steam (700°C–1,000°C) is used to produce

hydrogen from a methane

Electrolysis - The electrons flow through an external circuit and the

hydrogen ions selectively move across the Polymer electrolyte membrane
to the cathode.
 
 Hydrogen storage materials
.

Challenges in storage of hydrogen –

• H2 can be stored as liquid or gas.

• Storing it as liquid takes less space than storing it as a gas at normal temperature and pressure. On
liquefaction, it can be maintained as a liquid in pressurized and thermally insulated containers. However,
liquid H2 density is very low compared to other liquid fuels and liquefaction requires application of
critical pressure and cooling down to temperatures below 33 degrees Kelvin.
Chemical storage –
1. Metal hydrides- Metal powders absorb hydrogen to form hydrides. Metal hydrides are the most safest way to store flammable

hydrogen at room temperature. Ex- MgH2, NaAlH4, LiAlH4, LiH, LaNi5H6, TiFeH2, ammonia borane, and palladium hydride

Step 1 - H2 sticks to metal surface, break down into hydrogen atoms (H) and then penetrate into the interior of the metal crystal

forming "metal hydride“ with release of heat.

Step 2 – Since MH less stable than H 2, Hydrogen atoms migrate to the surface of the metal hydride, combine into H 2 and flow away

as hydrogen gas. The metal atoms contract to form the original metal crystal structure absorbing heat.
2. Organic hydrogen carriers - Hydrogen and energy-rich aromatic and cyclic aliphatic organic molecules are produced by cyclic
catalytic hydrogenation and dehydrogenation of the unsaturated organic molecule at a location that has access to a source of
renewable hydrogen. When solar energy is available, solar cells produce electricity to run the hydrogenation unit.

Physical storage  
• Carbon nano tubes – Hydrogen absorption may be physisorption making use of van der Waals interaction between carbon materials and
hydrogen molecules or every carbon atom can be utilized as interaction site for chemisorption. The hydrogen storage capacities of CNTs are
mainly depend on its structure, pretreatments, geometry, structural defects, operating pressure, temperature, etc. Minimum surface area required for
the adsorption of 1 mol of hydrogen is 85.917 m2mol−1
• Graphene - Large surface area (2630 m2/g), porous nature, lightweight, and high chemical and thermal stability (melting point ~ 4510 K) along
with the possibility of economical and scalable production, graphene-based solid-state porous materials have shown promising applications in
efficient hydrogen storage. Minimum surface area required for the adsorption of 1 mol of hydrogen is 1315 m2mol−1of a singlegraphene sheet.
 Renewable energy sources

Photovoltaic cell
 why silicon in photovoltaics ?

• Provides an organized structure that makes conversion of light into

electricity common semiconductor material as SiO2
• Non toxic
• Ecofriendly
• high efficiency,
• low cost,
• long lifetime
• Electrical endurance up to 125 C
 FREE ENERGY CHANGE

Electrode reactions occur in the presence of active materials in a battery.

Free energy of the redox system decreases.

− ∆ 𝑮=𝒏𝑭𝑬
 Capacity of a battery
Total quantity of electricity involved in the electrochemical reaction
In Amphere hour or coloumb

𝑸=𝒙𝒏𝑭
x= number of moles of reactants
n=number of electrons transferred
F= faraday’s constant

Mc = Molecular mass
 POWER
W=VxI

Expressed in watts
V = Cell voltage
I = Cell current
POWER DENSITY
Power / mass is power density expressed in W/Kg
 CYCLE LIFE
Charge / Discharge cycles

Expressed in years

SHELF LIFE
The duration of storage under specified conditions at the end of
which a cell or a battery still retains the ability to give a specified performance
 Battery Technology
A Battery is a combination of two or more galvanic cells arranged in series or parallel.
Classification
i) Primary Battery: Acts as source of electricity without being previously charged up by an electrical current from an external source

Example - Dry cell, Zn-MnO2, Zinc-air, Li-MnO2 battery, etc.

ii) Secondary battery: Can be recharged by passing current through it

Example – Lead-acid battery, Ni-Cd battery, Ni-MH battery, Li-ion battery, etc.
iii) Reserve Battery:
The battery which may be stored in an inactive state and made ready for use by activating them prior to applications.
Key component i.e., electrolyte is separated from the rest of the battery and is added just before it is needed.

Example : Magnesium-water activated batteries, zinc-silver oxide batteries, etc.

COMPONENTS OF BATTERIES

Anode is the negative or reducing electrode that releases electrons

to the external circuit and oxidizes during and electrochemical
reaction.

Cathode is the positive or oxidizing electrode that acquires

electrons from the external circuit and is reduced during the
electrochemical reaction.

Electrolyte is the medium that provides the ion transport

mechanism between the cathode and anode of a cell. Electrolytes
are often thought of as liquids, such as water or other solvents, with
dissolved salts, acids, or alkalis that are required for ionic conduction

Separator  keeps the two electrodes apart to prevent electrical

short circuits while also allowing the transport of ionic charge
carriers that are needed to close the circuit during the passage of
current in an electrochemical cell.
ZINC AIR BATTERY

Anode

(E0 = － 1.25
V)
Cathode
 Nickel–metal hydride battery (1.35V)

A nickel metal hydride battery, abbreviated NiMH or Ni–MH, is a type of rechargeable battery.

Applications
Cell phones, laptops, automobiles and space crafts.

Anode MH + OH- M + H2O + e-

Cathode NiO(OH) + H2O + e- Ni(OH)2 + OH-

Overall MH + NiO(OH) M + Ni(OH)2

 Li ion battery

Discharge

Anode C6 Li Li +
+ e-

Cathode + MO2 LiMO2

 Li-ion Battery
Advantages of Li-battery:
i) High voltage: Lithium batteries have voltages up to about 4 V, depending on the cathode material , ii) highly stable iii) wide
operating temperature (ie. from -40oC to +70oC) iv) Flat discharge Characteristics v) High specific energy and energy density:

Construction Reactions
Anode (-ve electrode): Lithiated carbon At anode
Cathode (+ve electrode): Lithiated metal oxide LiMO2(M=Co, Mn, Ni) Discharge
Electrolyte : LiPF6 in dimethyl carbonate and ethylene carbonate. LiC6 6C + Li + e
Separator: polyolefine/polypropylene. Charge
At cathode
Discharge
Li + e +MO2 LiMO2
Charge

Applications
It is used in cell phones, laptops, automobiles, defense and
aerospace applications.
Fuel cells
GENERAL REPRESENTATION OF FUEL CELL
CLASSIFICATION BASED ON ELECTROLYTE
METHANOL OXYGEN FUEL CELL
POWER ALCOHOL
Ethyl alcohol blended petrol used in the internal combustion engines is called
power alcohol.