Module I

ENERGY SOURCES

Dr. Bhavna Vyas

 Introduction
Definition of Fuel: Any carbon containing material, which on

combustion gives large amount of heat that can be utilised

domestically or industrially.

Or

Fuel is a material used to produce energy or heat that can be

used domestically or industrially.

Chemically carbon containing fuel can be represented as carbon

bonded to hydrogen by covalent bond (C-H). There may be

presence of nitrogen, sulphur, oxygen along with hydrogen in a

fuel.
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 Classification
Fuels can be classified based on occurrence, state of fuel and
based on chemical reaction.

• Classification based on occurrence:

o Natural (Primary fuel): Wood, Coal , Crude oil

o Artificial or Synthetic fuel (Secondary fuel): Charcoal,

Petrol, Diesel

• Classification based on state of fuel:

o Solid: Coal, Wood, coke

o Liquid: Crude oil or petroleum, Petrol, Diesel

o Gaseous: Natural gas, CNG, LPG

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 Classification
Classification of fuel based on chemical reaction

1. Based on combustion reaction

a) In presence of excess of oxygen: Fossile fuel, wood

b) In presence of sufficient oxygen: IC engine fuel like diesel,

petrol

c) In absence of oxygen: rocket fuel

2. Based on spontaneous oxidation reduction reaction: Fuel cell

e.g. Hydrogen, ethanol, hydrocarbon

3. Based on nuclear reaction

a) Nuclear Fusion: deuterium, tritium, hydrogen

b) Nuclear Fission: U235, P239

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Sr. Criteria Solid Fuel Liquid Gaseous
No. Fuel Fuel
1 Calorific Value (C.V.) Low Higher Highest
2 Ignition Point (I.P.) Very high Moderate Very low
3 Cost Very cheap costly Costly
4 Noncombustible matter High Negligible Nil
(ash)
5 Rate of Combustion Not Controllabl Controllable
controllable e
6 Transportation Laborious but Easy Easy but risk
hazard free (piping) of hazard
7 Air requirement fro Large excess Small Just
complete combustion excess sufficient
8 Use in I.C. engine Cannot be Convenien Can be used
used t
9 Volatile matter Large Negligible Nil
10 Space for storage Small Smaller Very large
11 Moisture High Nil Nil
12 Smoke (pollution) Considerable Lower Nil
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13 Thermal efficiency Low High High
 Solid Fuels: Coal
Coal: highly carbonaceous material, regarded as a fossil fuel
produced from the vegetable debris under conditions of
high temperature and pressure over million of
years.
The process of conversion of wood into coal is known as
coalification.
Coalification is a very slow process and takes millions of years
for formation.
• Main constitute of coal is C atom – mostly sp2 hybridized
• Atoms like H,O,N,S are covalently bonded to C atom
• Coal molecules are huge with indefinite number of carbon
atom.
• Coal contains water and minerals
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© Bhavna M. Vyas 6
 Solid Fuels: Coal
• Complex mixture of organic and inorganic materials, primarily composed
of carbon along with various other elements like hydrogen nitrogen,
sulphur etc.

• Coal is formed when the plant and animal debris under the earth crust are
subjected to conditions of high temperature and pressure over millions of
years. Hence, regarded as a fossil fuel.

• Process of formation of coal is called as Coalification.

• Mainly comprises of carbon, hydrogen, nitrogen and oxygen along with

non-combustible matter. Composition of coal varies according to the
coalification, based on its carbon content, energy content & other content.

• Different types of coal in increasing order of alteration are Peat, Lignite

(brown coal immature), Bituminous and Anthracite (mature).

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 Analysis of Coal
To fix price and use of coal
To calculate CV of coal
To calculate air and oxygen requirement for complete
combustion of coal
Analysis of coal: 1) Proximate analysis
2) Ultimate analysis

% of M , VM, and Ash

PROXIMATE

To get % of CARBON
Analysis of
coal
% of C , H , N , S and Ash

ULTIMATE

To get % of Oxygen
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 Analysis of Coal

Analysis of Coal
The results of analysis are generally reported in the following ways:
 As received basis
 Air dried basis
 Moisture free basis (oven dried)
 Moisture and ash free basis

Proximate Analysis:
Determination of % Moisture, % Volatile Matter, % Ash and %
Fixed Carbon.

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 Proximate Analysis of Coal
1) % Moisture

Air-dried coal sample Porcelain crucible,

110ºC Electric oven Time: 1 hr
Initial weight of coal = w g,
Final weight is w1 gm (Moisture free coal)
Loss in weight of the coal sample = w-w1

Loss in weight of the sample or weight of moisture

% Moisture = ∗ 100
Weight of coal sample taken

(W – W1)
% Moisture = ∗ 100
𝑊

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 Proximate Analysis of Coal
1) % Moisture

 A coal sample weighing 1 gm, looses 0.09 gm weight on

heating at 110 0 C for 1 hour calculate % moisture.

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 Proximate Analysis of Coal
1) % Moisture
Significance
 Excess of moisture is undesirable in coal
 Moisture lowers the heating value of coal and takes away
appreciable amount of the liberated heat in the form of latent heat
of vaporisation. For every percent of moisture present 1% of heat
is lost.
 Moisture increases ignition temperature.
 Moisture also increases the transport costs.
 Excessive surface moisture may cause difficulty in handling the
coal.
 Prescence of excessive moisture quenches fire in the furnace.
 Hence lesser the moisture content better is the quality of coal
as a fuel. However, presence of about 5-10% moisture is desirable
as it produces a uniform fuel bed and less of “fly ash”.
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 Proximate Analysis of Coal
2) % Volatile Matter (VM)
The volatile matter in coal consists of a complex mixture of gaseous and liquid
products resulting from the thermal decomposition of the coal. Volatile matter
does not include moisture of coal. It consists mainly of combustible gases such
as H2, CO, CH4 and other hydrocarbons.

Porcelain crucible with lid having vent, Muffle furnace, 925º C for 7 min.

Initial weight of coal = w1 g,

Final weight is w2 gm (Moisture free coal)
Loss in weight of the coal sample = w1 – w2

Loss in weight of the sample or weight of volatile matter

% Volatile Matter = ∗ 100
Weight of coal sample taken

(W1 – W2)
% Volatile Matter = ∗ 100
𝑊
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 Proximate Analysis of Coal
2) % Volatile Matter (VM)
a) 1.0 gm of a coal sample is heated to remove all moisutre. Then
the residual coal looses 0.21 gm weight when heated in muffles
furnace at 950 0C. Calculate % volatile matter.
b) A coal contains 10 % moisture and 1 gm of coal looses 0.3 gm
weight on heating at 925 0C in the absence of air. Calculate %
volatile matter.
For fresh coal sample

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 Proximate Analysis of Coal
2) %Volatile Matter (VM)
Significance
 A high percent volatile matter indicates that a large proportion of fuel is burnt as a gas or
vapor or may escape unburnt.
 For efficient use of fuel, the outgoing combustible gases (volatile matter) have to be
burned by supplying secondary air. This requires a large combustion space.
 The high volatile matter content coal produce long flames, high smoke and relatively
low heating values.
 The high volatile coals do not cake well whereas medium-volatile coals containing 20-
30% of volatile matter are capable of forming hard and strong coke on carbonization.
 Coals containing less than 14% of volatile matter do not cake at all and are thus not
suitable for manufacturing coke.
 Hence, lesser the volatile matter content, better is the quality of coal. However, high
volatile matter content is desirable in coal gas manufacture because volatile matter in coal
denotes the proportion of the coal which will be converted into gas and star products by
heat.
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 Proximate Analysis of Coal
3) % Ash
Ash is the non-combustible, useless matter that is left behind when all
the combustible substances have burnt off from coal. Ash usually consist
of silica, alumina, iron oxide and small quantities of lime, magnesia etc.
Open silica crucible, 750º C for half hour in muffle furnace
Heating, Cooling and Weighing is continued till constant weight of ash

weight of ash formed

% Ash = ∗ 100
Weight of coal sample taken

W3
% Ash =
∗ 100
𝑊
1 gm of coal sample is ignited at 750 0C in a muffle furnace the
residue weighed is 0.15 gm. Calculate the % ash

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 Proximate Analysis of Coal
3) % Ash
Significance
 High percentage of ash is undesirable as it reduces the calorific
value of the fuel.
 Presence of ash increases the transporting, handling and storage
cost. It also involves additional cost of ash disposal.
 Fused ash lumps (clinkers) block the interspaces of the grate on
which coal is being burnt. This causes obstruction in air supply.
Hence, burning of coal becomes irregular.
 Hence, lower the ash content better the quality of the coal.

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 Proximate Analysis of Coal

4) % Fixed Carbon
Fixed carbon content increases from low ranking coals
such as lignite to high ranking coals such as anthracite.

% Fixed Carbon = 100 – (% Moisture + % Volatile Matter + % Ash)

Significance

Higher the percentage of fixed carbon greater is its calorific

value and better is the quality of coal.

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 Proximate Analysis of Coal
Numericals:

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 Significance of Proximate Analysis
Moisture
• decreases calorific value, increases ignition temperature
• Lower the % moisture, better the quality of coal .
Volatile matter
• Decreases calorific value, increases pollution, elongates
flame
• Lesser the % V.M., better the quality of coal.
• 25- 30 % volatile matter content is desirable or suitable for
making hard and strong coke .
Ash
• Reduces calorific value, disposal is a problem, fuses to from
clinker that blocks air supply
• Lesser the % ash, better the quality of coal .

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 Combustion
• Fuel can be represented as C-H i.e. hydrocarbons

• Combustion is a chemical process in which the carbon and

hydrogen from fuel reacts with oxygen to produce CO2 and
H2O along with liberation of heat.

C-H + O2 CO2 + H2O ∆ H = – 97 kcal.

• As in case of combustion there is a production of water

molecule along with heat, some part of heat produced is
taken away by water molecule.

• This amount of heat taken away by water molecule is called

as latent heat (587 cal/g).

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 Combustion Numericals
• To ensure complete combustion of a fuel, it is essential that

appropriate amount of oxygen and air is supplied. If the

amount of oxygen and air supplied is insufficient, complete

combustion will not take place and too much excess should

also not be supplied.

• Hence in any industrial and metallurgical processes it is

essential to calculate the minimum amount of oxygen and air

required for the complete combustion of the fuel used.

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 Combustion Numericals
Calculation of air required for the combustion

• Weight of each constituent present per kilogram of the fuel is

calculated from the percentage composition of the fuel.

Let the weight of carbon, hydrogen, oxygen, and sulphur in

one kg of the fuel be C kg, H kg, O kg and S kg, respectively.

• The quantity of oxygen required for the combustion of C kg of

carbon, H kg of hydrogen, S kg of sulphur can be calculated

with the help of the reactions.

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 Combustion Numericals
Combustion of carbon
C + O2 → CO2
12 kg 32 kg (12 kg of carbon requires 32 kg of oxygen)
C kg of carbon requires (32/12) C kg or 2.67 C kg of oxygen
Combustion of hydrogen
H2 + (1/2)O2 → H2O
2 kg 16 kg (2 kg of hydrogen requires 16 kg of oxygen)
H kg of hydrogen requires (16/2)×H kg or 8 H kg of oxygen

Combustion of sulphur
S + O2 → SO2
32 kg of sulphur requires 32 kg of oxygen.
S kg of sulphur requires (32/32)× S kg or 1 S kg of oxygen.
The other constituents present in fuel do not require oxygen.

Total quantity of oxygen required for the complete combustion of 1 kg

of fuel = ((32/12) C + 8 H + S) kg.
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 Combustion Numericals
If oxygen is already present in the fuel, then, the quantity of oxygen to be

supplied from air = (Total oxygen required – O2 present in fuel)

or = ((32/12) C + 8 H + S – O) kg

So, minimum quantity of O2 or the theoretical amount of O2 required

for the complete combustion of 1 kg of a fuel

= ((32/12) C + 8 H + S – O) kg

As air contains 23% oxygen by weight,

Minimum weight of air theoretical amount of air required for

complete combustion = (100/23) ×(2.67 C + 8 H + S – O) kg.

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 Combustion Numericals
Calculation of volume of oxygen or air required

22.4 liters of any gas at NTP has a mass equal to its gram
molecular weight and air contains 21% oxygen by volume. Hence,
the volume of air required can also be calculated.

Calculation of quantity of flue gases

The gases coming out after combustion CO2, SO2, CO, O2,
N2 are called flue gases. The water vapours formed condense as
the gases cool down while the ash is excluded as it does not take
part in combustion. Therefore, water vapours and ash are not
included while calculating the percentage of dry combustion
products.
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 Combustion Numericals
Calculation of the flue gases when minimum amount of air is
supplied

All the O2 of air will be used in combustion of carbon and

sulphur while N2 in air remains unreacted.

Let 1 kg of fuel contain C kg of carbon and S kg of sulphur. The

weight of CO2 and SO2 thus formed by the combustion of fuel is
calculated as follows:

C + O2 → CO2

12 kg 44 kg 12 kg of carbon on combustion gives 44 kg of CO2

Therefore, C kg of carbon gives (44/12)×C kg of CO2.

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 Combustion Numericals
Calculation of the flue gases when minimum amount of air is
required

32 kg of sulphur on combustion gives 64 kg of sulphur dioxide.

S kg of sulphur gives (64/32)× S kg or 2 S kg of SO2.

Weight of N2 = (77/100)× weight of air supplied + weight of N2 per

kg of fuel.

Total weight of dry flue gases formed by the combustion of 1 kg of

fuel
= Weight of CO2 + weight of SO2 + weight of N2

The % composition by weight of each constituent can then be

calculated.
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 Combustion Numericals
Calculation of the flue gases when excess of air is supplied

(i) CO2 and SO2 are calculated as mentioned above.

(ii) N2 in flue gas = N2 of total air supplied + N2 present in the fuel.

(iii) When excess air is supplied, the flue gas will contain O2 of
excess air.

Hence, the total weight of flue gas per kg of the fuel (when excess air
is supplied) = weight of CO2 + weight of SO2 + weight of N2 (from
actual air supplied & from fuel if present) + weight of O2 (from excess
air)

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 Combustion Numericals
Important facts for combustion calculation
(i) Substances always combine in definite proportion.
C + O2 → CO2 + 97 kcal
12 kg 32 kg 44 kg
(ii) Composition of air: Air contains 79% nitrogen and 21%oxygen by
volume and 77% nitrogen and 23%oxygen by weight.
(iii) The average molecular weight of air is taken as 28.94 g mol−1

1 g mol of any gas at STP (0 °C and 760 mm pressure) occupies

22.4 L, that is weight of 22400 mL of a gas at STP is its molecular mass.

(iv) The mass of any gas can be converted into its volume by the gas law

PV = nRT where n is the number of moles of the gas.

(v) Minimum oxygen required for combustion

= Theoretical oxygen required − O2 present in fuel.

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 Combustion Numericals
Important facts for combustion calculation

(vi) Combustion seldom takes place efficiently with minimum weight of

oxygen or air. An excess of air has to be supplied for proper combustion.

𝐴𝑐𝑡𝑢𝑎𝑙 𝑎𝑖𝑟 𝑢𝑠𝑒𝑑 − 𝑀𝑖𝑛𝑖𝑚𝑢𝑚 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑖𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑

% 𝐸𝑥𝑐𝑒𝑠𝑠 𝐴𝑖𝑟 = × 100
𝑀𝑖𝑛𝑖𝑚𝑢𝑚 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑖𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑

(vii) Actual amount of air supplied is found out by taking excess air into
consideration.

(ix) To convert weight into volume and vice versa the Avogadro’s law is
used.

(xi) If excess air is used is used for combustion, then the dry flue gases will
contain CO2 + SO2 + N2 of the total air supplied + O2 from excess air.

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 Combustion Numericals
Combustion of gaseous fuel
CO, H2 and hydrocarbons such as CH4, C2H6, etc. are the main
constituents of common gaseous fuels. The quantity of O2 or air required in
such cases is measured by the volume according to the combustion
reactions of the constituents.

Combustion of carbon monoxide

2 CO + O2 → 2CO2
2 volume of CO combine with 1 volume of O2 to give 2 volume of CO2

Combustion of H2
• 2H2 + O2 → 2H2O
Here 2 volumes of H2 combines with 1 volume of O2

Combustion of CH4
• CH4+ 2O2 → CO2 + H2O
1 volume of methane reacts with 2 volumes of O2
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 Combustion Numericals
Combustion of gaseous fuel
C2H2 + 5/2 O2 → 2CO2 + H2O
1 vol 2.5 vol 2 vol

C3H8 + 5O2 → 3CO2 + 4H2O

1 vol 5 vol 3 vol

• The other constituents such as CO2 and N2 do not require any oxygen.

If the percentage composition of a gaseous fuel is known, then the

amount of O2 required for combustion can be calculated with the help of

the combustion equations. If the fuel already contains oxygen, then that

amount is subtracted from the total O2 required. As air contains 21% O2

by volume, the volume of air required can be calculated by multiplying

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with 100/21.
 Combustion Numericals
Combustion of gaseous fuel

• To determine the percentage composition of dry flue gases the volume of

CO2 is also calculated as above. N2 of the fuel comes out along with the

flue gases; hence, the total N2 in flue gases is ( N2 in fuel + N2 in air

supplied) for combustion. If excess air is supplied, then the volume of O2

present in the excess air is also taken into account.

• Percentage composition of dry flue gases is then calculated. Dry flue

gases do not contain water vapour as they condense on cooling, hence,

H2O is not included in the calculation of the % composition of dry flue

gases.
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 Combustion Numericals

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 Combustion Numericals

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 Combustion Numericals

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 Combustion Numericals

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 Combustion Numericals

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 Combustion Numericals

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 Combustion Numericals

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 Alternative Fuels: Power Alcohol
Power Alcohol: When ethanol is blended with petrol

(about 20-25%) and is used as fuel for IC engines, it is

known as Power Alcohol.

Preparation of Ethanol:

 It can be obtained from Molasses which contains

sucrose. Sucrose is converted into Glucose and Fructose
by means of enzyme invertase from yeast at 300C

C12 H 22O11 + H2O ®C6 H12O6 +C6 H12O6

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 Alternative Fuels: Power Alcohol
Preparation of Ethanol:

 The enzyme Zymase (from yeast) converts glucose and

fructose into ethyl alcohol and CO2 by fermentation

C6 H12O6 ® 2C2 H5OH +CO2

 Fermented liquid (containing 18-20% of alcohol) is then

subjected to fractional distillation to give 90-95% alcohol
(also called as rectified spirit)

 For getting 100% alcohol (absolute alcohol) rectified

spirit is treated with lime
16-10-2024 and
© Bhavna M. Vyasdistilled 47
 Alternative Fuels: Power Alcohol
Advantages:
1) High Octane number (ON) about 90 as compared to
conventional petrol with ON:60-70 (provide better
antiknocking properties)
2) Ethanol renewable source of energy; reduces foreign
dependency
3) Reduced emission of harmful gases as alcohol blended
with petrol burns clean
4) Reduces the overheating of engine; extending engine life
5) Reduces deposition of Carbon and the gummy products
on internal parts of engine when alcohol is blended
6) Removes all traces of moisture in the petrol as Alcohol
capable to absorb
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 Alternative Fuels: Power Alcohol
Disadvantages:
1) Ethanol lowers the calorific value of petrol
2) Alcohol may get oxidized to acetic acid which may
cause corrosion of engine parts
3) Air required for complete combustion is less as as
ethanol contains Oxygen atoms; hence needed
modification of air inlet or operation of choke
4) Alcohol has high surface tension, hence difficult to
atomize, particularly at low temperatures, causes
starting trouble; hence carburetor needs special
arrangements in the vehicle
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 Alternative Fuels: Biodiesel
Biodiesel: Also called as Biofuel obtained from

renewable sources of energy such as vegetable oils or

animal oils by transesterification

 Mainly used as a fuel for diesel engines (compression

Ignition engine)

 Vegetable oils like sunflower oil, peanut oil, palm oil,

soyabean oil, rapeseed oil etc. used for biodiesel.
(Normally non edible vegetable oils are preferred)

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 Alternative Fuels: Biodiesel
Chemical Nature of Biodiesel:
 Vegetable oils are mainly triglycerides of fatty acids
(ester of glycerol and 3 fatty acids) with High Viscosity,
High Flash point and Low calorific value
 Vegetable oils can be converted into Biodiesel by the
process called Transesterification.
 Transesterification: Conversion of one type of ester to
other. In this process, animal/vegetable oils are heated
with excess of methanol in presence of catalysts like
sodium methoxide, potassium methoxide, NaOH/KOH.
Catalysts should be free from moisture (otherwise it
promotes the saponification
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and not transesterification)
© Bhavna M. Vyas 51
 Alternative Fuels: Biodiesel
Chemical Nature of Biodiesel:

R1, R2, R3 – fatty acid alkyl groups (same or different)

Biodiesel (FAME) may contain compound like:
Methyl Stearate (C17H35COOH CH3),
Methyl
16-10-2024Palmitate (C
15H31COOH
© Bhavna [Link]
Vyas
3) 52
 Alternative Fuels: Biodiesel
Chemical Nature of Biodiesel:
 Biodiesel (also called as B100) used as an alternative
fuel for diesel engine or it can be blended with
petroleum diesel
 Most commonly used blends are B5 (5% of Biodiesel
mixed with 95% of petroleum diesel) and B20
 Blended Biodiesel can be used directly into diesel engine
(designed for conventional diesel) while B100 needs
modification in engine
 Jatropa and Karanja oil seeds are used in India for
Biodiesel
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 Alternative Fuels: Biodiesel
Preparation of Biodiesel:
 Filtered non edible vegetable/animal oil(free from moisture)
taken in Reaction vessel and heated to about 1100C. About 2%
sodium methoxide (Na metal + Methanol) and 20% methanol
added to reaction vessel
 Mixture is refluxed at 60-700C for about 1 to 7 hours
depending on the type of oil used
 Mixture is cooled and mixed with water to dissolve glycerine
formed in the reaction
 Water insoluble Biodiesel phase is then separated from water
phase through a separating funnel
 Suitable antioxidants are added to avoid oxidation & increase
stability
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 Alternative Fuels: Biodiesel
Advantages:
1) Non conventional and renewable source of energy obtained
from domestic sources.
2) High Cetane Numbers 46 to 54 and high Calorific Value of
about 40 kJ/gm than that of conventional diesels
3) Clean fuel as Oxygen present in fuel helps for complete
combustion and thus no particulates/CO pollutants
4) Reduces dependency on foreign countries for diesel
5) Non toxic, free from Sulphur
6) Better Lubricity
7) Higher Flash point and thus safer for storage
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 Alternative Fuels: Biodiesel
Limitations:
1) Higher Cloud Point and Pour point than conventional
diesel (cause problem in fuel flow line, hence cannot be
used in cold countries)

2) Strongly adheres on some metals and can become

gummy

3) Not compatible with some rubber hoses and gaskets as

it’s dissolving action

4) Costly in the regions where there is shortage of

vegetable oils (costly starting material)
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HYDROGEN AS A FUTURE FUEL
o Its availability from fully renewable resources
( water and sunlight)
o It is nontoxic
o It’s a clean fuel
o It has high calorific value
o It is used as a rocket fuel
o Can be used as a fuel for vehicles
o In a fuel cell, directly Hydrogen gas or by using
CH3OH as H2 carrier which avoids the need to store
H under pressure, constant
2
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source of energy 57
 PROPERTIES OF HYDROGEN
• Colorless, odorless and insoluble in water
• Diatomic molecule in which two H atoms are joined by
strong covalent bond with bond energy 435.9 KJ/mole
• Density is 0.08987 gm/cc at 0° C and 1 atm.
Pressure, it is 14 times lighter than air
• It burns in air forming water and liberates a large
amount of energy. This reaction is often explosive
• It reacts with halogen, many metals, with N2
• Clean source of energy hence it can replace coal
and oil as major source of energy in future
• Liquid hydrogen is used as a fuel in space rockets
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 Production of Hydrogen
1) Industrial Method:
a) Steam reforming of Methane
/Natural gas
b) Steam reforming of coal/coke
2) Electrolysis of water
3) Lab scale: by acids or alkalies.
4) Solar Energy Method:
Water Splitting (Thermal Processes)
Photolysis of water using coordination
catalyst i.e. Photosensitizer, e.g. [Ru(bPy)3]+2
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 Production of Hydrogen
1) Steam Reforming of Methane:
3 Steps process
i) Steam reforming reaction: Methane with steam at
8000 C in presence of Ni catalyst to produce water gas
(CO+H2)

CH4 + H2O ® CO + 3H2

ii) Water Gas Shift reaction: At 3700 C in presence of
FeO catalyst to produce CO2 & H2 with steam

FeO,370 0 C
CO + H 2 ® CO2 + H 2
H 2O

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 Production of Hydrogen
iii) Removal of CO2 : Compression & liquefaction of
mixture (obtained from Water Gas Shift reaction) to
separate Hydrogen gas

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 Production of Hydrogen
1) Steam Reforming of coal/coke
3 Steps process
i) Steam reforming reaction: Coal/Coke with steam at
10000 C in presence of Ni/FeO catalyst to produce
water gas (CO+H2)

C + H 2O ® CO + H 2
ii) Water Gas Shift reaction: At 3700 C in presence of
FeO catalyst to produce CO2 & H2 with steam

FeO,370 0 C
CO + H 2 ® CO2 + H 2
H 2O

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 Production of Hydrogen
iii) Removal of CO2 : Compression & liquefaction of
mixture (obtained from Water Gas Shift reaction) to
separate Hydrogen gas

H2 obtained from coal is less & with impurities like

H2S, SO2 hence less preferred although cheap
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 Storage of Hydrogen
Difficulties:
• Decarburization
• Lightest gas (MW:2); Quantity stored less
• High cost of compression & energy
• Very low Boiling Point -252.60C, difficult to liquefy;
high cost of cooling &insulation
• Very low Ignition Temp., highly inflammable
• Mixture of 2:1H2-O2 highly explosive
• Storage in hydrides requires longer duration &
Decomposition requires high Temp
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 Storage of Hydrogen
Physical Storage:
• Compression – Tanks & cylinders at high pressure
• Liquefaction – Cryogenic storage
• Adsorption on Carbon nanomaterials – small size, porous
structure(pores of molecular dimension), low density,
high surface area
• Metal Organic framework (MOF) – crystalline, porous,
inorganic-organic hybrid materials

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 Applications of hydrogen
1) As a fuel in Internal combustion engine of vehicles
2) For preparation of ammonia (Haber’s process)
3) As a Rocket propellant
4) As a fuel for fuel cells
5) Used in industries:
annealing of metal,
cutting metals,
oxy-hydrogen flame for fabrication

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 Batteries
• Batteries are called as the store house of energy

• It is a simple device which stores chemical energy and converts

it into electrical energy through electrochemical reactions.

• A battery is a collection of one or more cells connected together

to provide a desired voltage or current.

• Commonly, a battery can refer to either a single cell or a

combination of cells that either generate electricity
spontaneously like a Voltaic or Galvanic cell or electrolytic
cells that require an external source of electricity to drive non
spontaneous reactions. Similar to Voltaic or Galvanic cell, a
battery also consists of an anode, a cathode and an electrolyte.
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 Components of Batteries
• Electrodes: The negative electrode where oxidation (loss of
electrons) occurs called as anode and the positive electrode
where reduction (gain of electrons) occurs called as cathode.
• Electrolyte: The medium usually an ionic solution or the
substance that allows the movement of ions between the
anode and cathode to facilitate the chemical reaction to
produce electrical energy.
• Separator: A barrier which prevent the contact between the
anode and cathode and still allow the flow of ions.
• External Circuit: It is a pathway through which electrons
flow from anode to cathode which generates the electric
current that can power devices.
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 Working of Batteries
Explained as follows with two types of cycles.

• Discharge Cycle: During the discharge, battery supplies

electric power. The anode undergoes oxidation releasing
electrons, while the cathode undergoes reduction, accepting
those electrons. The electrolyte facilitates the flow of ions,
balancing the charge within the cell.

• Recharge Cycle (for rechargeable batteries): During the

recharge, an external power source reverses the chemical
reactions. The electrons are forced back to the anode and ions
move in the opposite direction resulting in the restoring of
charge of the battery.

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 Types of Batteries
Primary batteries: These are non-rechargeable batteries. In

these batteries, the cell reaction is irreversible, i.e., the reaction

taking place in the forward direction cannot be reversed by the

application of external potential. Once the cell reaction has taken

place and the reactants have been converted into products, the

cell gets discharged and cannot be used again like Dry cells or

Leclanche cell. Common examples of primary batteries are

alkaline batteries and zinc-carbon batteries.

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 Types of Batteries
• Secondary batteries: These are rechargeable batteries. In
these batteries, the cell reaction is reversible. Once the forward
reaction occurs and the cell is discharged, it can be charged
again by applying external power source. Hence can be used
multiple times. Common examples include lithium-ion
batteries, nickel-cadmium (Ni-Cd) batteries, and lead-acid
batteries.

• Alkaline Batteries: Widely used in household devices. They

are primary batteries that use zinc and manganese dioxide as
electrodes.

• Lead-Acid Batteries: Used in automobiles for starting engines

and in backup power supplies. They are large, heavy, and
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rechargeable.
 Types of Batteries
• Lithium-ion Batteries: Popular in portable electronics and

electric vehicles. They have a high energy density and are

rechargeable.

• Nickel-Metal Hydride (NiMH) Batteries: Common in

rechargeable household batteries and hybrid vehicles. They

have a lower energy density compared to Li-ion but are safer.

• Flow Battery: H2 - O2 Fuel Cells

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 Lithium Ion Battery
Stanley Whittingham, John B. Goodenough and Akira

Yoshino shared the Nobel prize in Chemistry in 2019, for the

development of Lithium-ion battery

Type of rechargeable LiCoO2 and Graphite battery having high

energy density.

Lithium-ion battery uses the reversible intercalation of Li+ ions

into electronically conducting solids to store energy.

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 Lithium Ion Battery
Construction:

Lithium ion battery consists of the key components as anode,

cathode, electrolyte and separator.

• Anode (Negative Electrode): It is typically made of graphite (a

form of carbon). It functions as a kind of stable storage space

for lithium atoms and one lithium atom per six carbon atoms

is the most thermodynamically stable (LiC6). The anode stores

lithium ions when the battery is fully charged. During

discharge, lithium ions move from the anode to the cathode.

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 Lithium Ion Battery
Construction:

• Cathode (Positive Electrode): It is made from a lithium metal

oxide, such as lithium cobalt oxide (LiCoO₂), lithium iron
phosphate (LiFePO₄), or lithium manganese oxide (LiMn₂O₄).
The specific material determines the battery's characteristics,
such as energy density, safety, and lifespan. The most
commonly used is lithium cobalt oxide (LiCoO₂).

• Both the electrodes (anode and cathode) allow lithium ions

to move in and out of their structures with a process
called intercalation (insertion) or deintercalation
(extraction), respectively.

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 Lithium Ion Battery
Construction:

• Separator: It is a thin, porous membrane generally made up of

polyethylene (PE) and polypropylene (PP) that prevents physical
contact between the anode and cathode while allowing lithium
ions to pass through it. The separator is critical for the safety of
the battery, as it prevents short circuits.

• Current Collectors: The electrodes are separated from external

electronics with a piece of metal called a current collector.
Graphite and Cobalt oxides are not good at collecting or
distributing the electrons, hence a conductive copper layer is
added next to the graphite and a conductive aluminium layer
next to the cobalt oxide.
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 Lithium Ion Battery

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 Lithium Ion Battery
Working of Lithium-ion Batteries:

Discharge Cycle or Discharging: During the discharge, the

negative electrode is the anode (Graphite) and the positive
electrode is the cathode (lithium cobalt oxide) and the electrons
flow from the anode to the cathode through the external circuit.
Lithium is oxidised from Li to Li+ (0 to 1 oxidation state) in the
lithiated graphite anode.

Consequently, oxidation reaction occurs at anode to give

lithium ions with the release of electrons.
LiC6 → C6 + Li+ + e− at anode

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 Lithium Ion Battery
Working of Lithium-ion Batteries:
LiC6 → C6 + Li+ + e− at anode

• The lithium ions are small enough to be able to move through

a micro-permeable separator between the anode and
cathode. Lithium ions move through the electrolyte by
diffusion and electrons through the external circuit towards
the cathode where these electrons recombine with the cathodic
material. The electrolyte provides a conductive medium for
lithium ions but does not take part in the electrochemical
reaction. The electrolyte facilitates the flow of ions, balancing
the charge within the cell.

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 Lithium Ion Battery
Working of Lithium-ion Batteries:

• Cathode (Lithium cobalt oxide) undergoes reduction, accepting

these electrons. Migrated lithium ions from the anode are

incorporated into lithium cobalt oxide through the following

reaction, which reduces cobalt from Co4+ to Co3+ i.e. +4 to +3

oxidation state.

Li+ + CoO2 + e− → LiCoO2 at cathode

[Link]

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 Lithium Ion Battery
Working of Lithium-ion Batteries:

• Recharge Cycle or Charging: During the recharge, an

external power source reverses the chemical reactions.
Consequently, an external electric current drives lithium ions
from the cathode through the electrolyte into the anode. The
electrons flow through the external circuit to balance the
charge, and lithium ions are intercalated (inserted) into the
graphite layers of the anode. During charging, cobalt gets
oxidised from Co3+ to Co4+.

LiCoO2 → Li+ + CoO2 + e− at cathode

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 Lithium Ion Battery
Working of Lithium-ion Batteries:

• Recharge Cycle or Charging: During the recharge, an

external power source reverses the chemical reactions.
Consequently, an external electric current drives lithium ions
from the cathode through the electrolyte into the anode. The
electrons flow through the external circuit to balance the
charge, and lithium ions are intercalated (inserted) into the
graphite layers of the anode. During charging, cobalt gets
oxidised from Co3+ to Co4+.
LiCoO2 → Li+ + CoO2 + e− at cathode
C6 + Li+ + e− → LiC6 at anode

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 Lithium Ion Battery
Reactions of Lithium-ion Batteries:

LiCoO2 → Li+ + CoO2 + e− at cathode

C6 + Li+ + e− → LiC6 at anode

Net Reaction:

LiC6 + CoO2 ⇌ C6 +LiCoO2

Here, forward reaction indicates the discharging of

battery while backward reaction indicates the charging of

battery.

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 Lithium Ion Battery
Advantages of Lithium-ion Batteries:
• High Energy Density: Lithium-ion batteries can store a large amount
of energy in a small and lightweight package, making them ideal for
portable devices like smartphones, wrist watches, laptops, and
electric vehicles. It is due to the relatively light weight and low density
of lithium.
• Long Cycle Life: These batteries can be recharged hundreds to
thousands of times before their capacity significantly degrades,
offering a long lifespan compared to other rechargeable batteries. It is
due to the small radii of lithium ions, which causes fewer disruptions
of the electrode structure during ion transfer.
• Low Self-Discharge: Lithium-ion batteries have a low self-discharge
rate, meaning they lose their charge slowly when not in use, making
them more reliable for long-term storage.
• No Memory Effect: Unlike some other rechargeable batteries (like
nickel-cadmium batteries), lithium-ion batteries do not suffer from
the memory effect, where partial discharge followed by recharging
reduces the usable capacity.

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 Lithium Ion Battery
Disadvantages of Lithium-ion Batteries:

• Safety Concerns: Lithium-ion batteries can overheat, leading to

thermal runaway, fires, or explosions if damaged, overcharged, or
exposed to high temperatures. However, modern batteries include
safety mechanisms to mitigate these risks.

• Cost: The materials and manufacturing processes involved in

lithium-ion batteries are relatively expensive, though costs have been
decreasing as technology advances.

• Limited Lifespan: Although they have a long cycle life, lithium-ion

batteries do eventually degrade over time, with capacity gradually
reducing after many charge-discharge cycles.

• Environmental Impact: The extraction of lithium and other

materials used in these batteries can have significant environmental
impacts, though recycling efforts are being developed to mitigate this.

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 Lithium Ion Battery
Applications of Lithium-ion Batteries:
• Consumer Electronics: Laptops, tablets, smartphones, cameras
and other portable devices such as smart wrist watches, fitness
trackers and other wearable devices offering long battery life in a
compact form.
• Electric Vehicles: Powering the electric cars, buses, bikes and
other vehicles.
• Power Tools: Power drills, saws and other battery operated tools.
• Implanted Medical devices: Portable medical equipment such as
pacemakers and defibrillators.
• Power storage: Used for solar and wind power storage.
• Aerospace technologies: Due to their light weight, they are used
in aerospace technologies such as satellites and space probes.

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 Fuel Cell
 Fuel cells represent the new generation of high efficiency,

environmentally friendly energy systems.

 Fuel cells are the direct generators of power which take chemical

substances from the external source and convert them into

electrical energy by electrochemical reaction.

 Consequently fuel cell is an electrochemical device that converts

chemical energy from a fuel into electrical energy through a

chemical reaction with oxygen or another oxidising agent.

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 Fuel Cell
 Fuel cells are different than the battery, as in battery the chemical

substances are an integral part of a storage battery whereas in fuel

cells chemical substances are fed into the cells whenever energy is

required. Fuel cells do not need recharge periodically, but instead

continue to produce electricity as long as fuel source is provided.

 Hence fuel cell is also called as Flow Battery.

 Fuel cells are clean, efficient, reliable and quiet source of power.

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 Fuel Cell
• Components of fuel cell:
• Electrodes: In fuel cells, the electrodes are generally used are inert
materials like graphite, platinum etc. but have catalytic properties. Two
types of electrodes:
• Anode (negative electrode): The anode is where the fuel, typically
hydrogen, is supplied. At the anode, the fuel undergoes oxidation,
releasing electrons and creating positively charged ions.
• Cathode (positive electrode): The cathode is where the oxidant, usually
oxygen from the air, is supplied. Here, the reduction reaction occurs,
where electrons from the external circuit combine with the oxidant and
the positively charged ions.
• Electrolyte: The electrolyte allows ions (but not electrons) to move
between the anode and cathode. The type of electrolyte used determines
the type of fuel cell and its operating temperature.
• Catalyst: Catalysts are often used at the anode and cathode to speed up
the chemical reactions. Platinum is a common catalyst in many fuel cells,
particularly those using hydrogen.
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 H2 - O2 Alkaline Fuel Cell

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 Fuel Cell
Working of fuel cell:
• A typical fuel cell works by passing hydrogen through the anode of a fuel
cell and oxygen through the cathode.
• At the anode site, a catalyst splits the hydrogen molecules into electrons
and protons.
Anodic Reaction: Oxidation of fuel (Hydrogen)
𝐻2 → 2𝐻 + + 2𝑒 − 𝑎𝑡 𝑎𝑛𝑜𝑑𝑒
• The protons pass through the porous electrolyte membrane, while the
electrons are forced through a circuit, generating an electric current and
excess heat.
• At the cathode, the protons, electrons, and oxygen combine to produce
water molecules.
Cathodic Reaction: Reduction of Oxygen
1
𝑂2 + 2𝐻 + + 2𝑒 − → 2𝐻2𝑂 𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒
2
Overall Reaction:
2𝐻2 + 𝑂2 → 2𝐻2 𝑂
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 Fuel Cell
Types of fuel cell:

Electrolyte plays very important role in fuel cells. Based on

the electrolyte used and the temperature of operation, fuel cells are
classified as:

• Alkaline H2 - O2 Fuel Cell

• Solid Oxide Fuel Cell

• Phosphoric Acid Fuel Cell

• Molten Carbonate Fuel Cell

• Phosphoric Acid Fuel Cell

• Polymer Electrolyte Fuel Cell

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 H2 - O2 Alkaline Fuel Cell
Construction: H2-O2 fuel cell consists of anode, cathode and

electrolyte . The electrodes used are anode and cathode which

consists of porous graphite (carbon) impregnated with finely divided

platinum or a 75/25 alloy of palladium(Pd) with silver(Ag) or nickel

(Ni), which acts as catalyst. Electrolyte used is alkali solution like

aqueous 25% (to 40%) KOH or NaOH, working at temperature

below 100oC. Hydrogen as a fuel is bubbled through the anode and

oxygen as an oxidant is passed through cathode.

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 H2 - O2 Alkaline Fuel Cell
Electrodes:
Anode (negative electrode): The anode is where the fuel (Hydrogen) is
supplied. Made up of porous graphite (carbon) impregnated with finely
divided platinum or a 75/25 alloy of palladium(Pd) with silver(Ag) or nickel
(Ni), which acts as catalyst. At the anode, the hydrogen undergoes oxidation,
releasing electrons and creating positively charged hydrogen ions.
Cathode (positive electrode): The cathode is where the oxidant(Oxygen),
from the air, is supplied. Similar to anode, it is also made up of porous
graphite (carbon) impregnated with finely divided platinum or a 75/25 alloy
of palladium(Pd) with silver(Ag) or nickel (Ni), which acts as catalyst. Here,
the reduction reaction occurs, where electrons from the external circuit
combine with the oxygen and the positively charged hydrogen ions.
Electrolyte: The electrolyte in AFC is an aqueous alkali solution like aqueous
25% (to 40%) KOH or NaOH, operating at temperature below 100oC. It
allows hydroxide ions (but not electrons) to move between the anode and
cathode. Consequently, it is responsible for conducting hydroxide ions (OH⁻) from the
cathode to the anode during the reaction.

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 H2 - O2 Alkaline Fuel Cell
Diagram

[Link]

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 H2 - O2 Alkaline Fuel Cell
Working of Alkaline Fuel Cell

Fuel (H₂) is introduced at anode & O2 /Air is supplied at the cathode.

Anodic Reaction: Hydrogen is oxidized, splitting into protons (H⁺)

and electrons (e⁻). Hydrogen reacts with hydroxide ions from the
electrolyte to form water and release the electrons.

2H2+4OH−→4H2O+4e−

Cathodic Reaction: Oxygen is reduced by combining with water and

electrons to form hydroxide ions. The reaction is:

O2+2H2O+4e−→4OH−

Net Reaction: 2H2 + O2 → 2H2O

Water is the only byproduct, and electricity is generated as
electrons flow through the external circuit.
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 H2 - O2 Fuel Cell
Applications Fuel Cell

Transportation: Fuel cell vehicles (FCVs) are a type of electric vehicle

that employs fuel cell technology to generate electricity onboard.

Fuel cell vehicles (FCVs) offer an alternative to conventional internal

combustion engine vehicles by producing zero-emission power.

Hydrogen-powered FCVs boast

longer ranges and shorter

refuelling times compared

to electric vehicles, making

them a promising contender

for a cleaner future on the roads.

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 H2 - O2 Fuel Cell
2. Energy Generation
Alternative to Electricity
Can be deployed as distributed power sources, providing
electricity to homes, businesses, and even remote areas. Additionally,
fuel cells can be integrated into existing power grids, offering stability
during peak demand periods.

Backup Power
Fuel cells are well-suited for backup power applications. They
offer a reliable energy source during grid failures and emergencies,
ensuring essential services continue without interruption.

Portable and Remote Power

Portable fuel cells power a range of devices, from laptops and
smartphones to camping equipment. Moreover, in remote and off-grid
areas, fuel cells provide a sustainable energy solution, supporting
communities without access to traditional power infrastructure.

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 H2 - O2 Fuel Cell
3. Aerospace Industry

• Fuel cells have found applications in the aerospace sector, powering

unmanned aerial vehicles (UAVs) and space missions. Their high
energy density and lightweight nature make them ideal for aircraft
where every kilogram counts.

4. Spacecraft Power Systems

• Fuel cells have been used in space missions to generate electricity for
spacecraft. For example, fuel cells have been used on space shuttles
and space stations to provide power and water for crew members.

5. Marines Systems

• Fuel cells have been used in sub-marines to generate electricity.

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 H2 - O2 Fuel Cell
Advantages of Fuel Cell

[Link] Benefits

Fuel cells stand out for their environmental advantages, producing

only water and heat as byproducts. This minimal impact on air quality
makes them a key player in combatting climate change and reducing
greenhouse gas emissions.

2. High Efficiency

Fuel cells are highly efficient, converting a significantly higher

percentage of energy stored in fuel to electricity compared to traditional
combustion engines. This efficiency leads to reduced fuel consumption and
increased overall sustainability.

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 H2 - O2 Fuel Cell
Advantages of Fuel Cell

3. Versatility

Fuel cells come in various shapes and sizes, offering versatility in

their applications. From powering vehicles to generating electricity for
stationary use, fuel cells cater to a wide range of needs.

4. Reliability

Fuel cells boast high reliability due to their minimal moving parts
and lower maintenance requirements. This characteristic makes them a
dependable source of power in critical situations.

5. Noise Reduction

Compared to traditional engines, the fuel cells operate quietly,

reducing noise pollution in both urban and remote areas. This aspect is
particularly advantageous for transportation modes, promoting a more
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pleasant and serene environment.© Bhavna M. Vyas 101
 H2 - O2 Fuel Cell
Disadvantages of Fuel Cell

• Cost: Fuel cells, especially those using platinum catalysts, can be

expensive.

• Hydrogen Infrastructure: Hydrogen fuel cells require hydrogen,

which is not yet widely available. Storing and transporting
hydrogen also presents

• challenges.

• Durability: Some types of fuel cells have shorter lifespans and

may degrade faster than conventional power generation systems.

• Electrode gets poisoned easily

• Fuel and oxygen supplied must be pure and free from CO2

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 REFERENCES
• Engineering Chemistry
Jain & Jain (Dhanpat Rai Publishing)
• A text book of Engineering Chemistry
Dr. S. S. Dara & Dr. S. S. Umare
• Engineering Chemistry
B. Sivasankar
• Engineering Chemistry
O. G. Palanna
• Engineering Chemistry
Wiley India

16-10-2024 103M. Vyas

© Bhavna
 Thank You

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