Engineering Chemistry (CYT-101)

Branch/Semester: All L T P
branches I/II Semester
B.Tech.
Type: Core 2 1 0

Lecture Plan Course Content

Unit 1 Water and its treatment: Introduction, Hardness, type of Hardness, Units of
hardness, disadvantages of hard water and methods of estimation of hardness.
Removal of Hardness (Softening Methods): Lime Soda process, Permutit or Zeolite
process and Deionization or Demineralization process.
Municipal Water Supply: Requisites of Drinking water, Purification of water by
various methods, Detailed study of methods of Disinfection.

Unit 2 Lubricants: Introduction of lubricants and lubrication. Types of mechanism of

lubrication, Uses and properties of lubricants viz. Viscosity & Viscosity index.
 Engineering Chemistry (CYT-101)
Unit 3 Fuels and Combustion: Classification and Properties of fuels, Calorific value,
Petroleum refining and fractional distillation of crude petroleum, Cracking, Synthetic
petrol, Knocking, Anti-knocking agents, Octane and Cetane number, Gaseous fuels,
hydrogen gas.
Unit 4 New Engineering Materials: Organic/hybrid photovoltaic materials, Conducting
polymers, Introduction to nanotechnology and nanomaterials (fullerenes and
quantum dots).
Unit 5 Corrosion : Introduction, theory of corrosion, galvanic and differential aeration
corrosion, control of corrosion by protective coating, inhibitors, cathodic and anodic
protection, stress corrosion, hydrogen embrittlement.

Unit 6 Advanced electrochemical systems: Introduction to energy storage devices, Li-ion

batteries, redox flow batteries, fuel cells, H2-O2 fuel cells.

Unit 7 Spectroscopy: Introduction, classification, and applications, Ultra-violet Visible, Infra-

Red, and Nuclear Magnetic Resonance Spectroscopy.
 Engineering Chemistry (CYT-101)
References 1. Engineering Chemistry: A Text book by P.C. Jain. Dhanpat Rai & Sons.
2. Engineering Chemistry: Fundamentals and Applications by Shikha Agarwal,
Cambridge university press
3. Solid State Chemistry and its Applications by Anthony R. West, Wiley 2014
4. Modern Batteries by C.A. Vincent and B. Scrosati, Elsevier 1997.
5. Spectroscopy of organic compounds, by P.S. Kalsi, New Age International (P) Ltd.
6. Fundamentals of molecular spectroscopy by Colin Banwell and Elaine McCash,
Tata McGraw Hill Education Pvt. Ltd.

Marking Scheme
Mid Term Exam 30
End Term Exam
Internal Assessment
50
20
75%
Total 100
 Fuel
A Fuel is a substance that produces useful energy either through combustion or through nuclear reaction.
An important property of a fuel is that the energy is released in a controlled manner and can be harnessed
economically for domestic and industrial use.
Examples: Wood, coal, charcoal, petrol, diesel, kerosene, producer gas, oil gas etc.
Based on nature by which heat is released

1. Chemical fuel 2. Nuclear fuel

A fuel which releases energy through combustion A fuel which releases energy through fission or fusion of nuclei
Examples: Coal, Petrol, Diesel, CNG, LPG etc. Examples: Plutonium, Tritium, Uranium etc.
Nuclear fuel releases much higher energy as compared to chemical
fuel
Fuel + O2 Products + Heat

C + O2 Products + 94 kcals The main source of fuel is coal and petroleum

These are stored fuels available in earth’s crust and
2H2 + O2 2H2O + 68.5 kcals generally called fossil fuels because they were formed
from the fossilized remains of plants and animals.
 Classification of Fuels
Based on Occurrence

1. Primary fuels/Natural Fuels 2. Secondary fuels/Derived Fuels

Found to occur in nature and are used as such either without derived from primary fuels by further chemical processing
processing or after being processed to a certain extent, which Examples: charcoal, kerosene, producer gas, water gas etc.
does not alter the chemical constituent of the fuel
Examples: Coal, wood, Peat, lignite, natural gas etc.

Based on State of Aggregation

1. Solid 3. Gas
Fuel whose physical state is solid Fuel whose physical state is gas
Examples: Coal, wood, Peat, lignite etc. Examples: Natural gas, Coal gas, water gas etc.

2. Liquid
Fuel whose physical state is liquid
Examples: Kerosene, Petrol, Diesel etc.
 Fuel
Chemical Fuel Nuclear Fuel

Primary Fuel or Secondary Fuel or

Natural Fuel Derived Fuel

Solid Gas Solid Gas

Wood, Peat, Natural Gas Coke. Charcoal Coal Gas, Water Gas,
Lignite, Coal Biogas
Liquid Liquid
Crude Oil Kerosene, Petrol,
(Petroleum) Diesel
 Characteristics of a Good Fuel
1. High Calorific Value: A good fuel should posses high calorific value because calorific value determines
the efficiency of the fuel. Higher the calorific value, greater is the heat liberated per unit mass or volume.
2. Ignition Temperature: It is the lowest temperature to which a fuel must be preheated so that it starts
burning smoothly. An ideal fuel should have moderate ignition temperature. Low ignition temperature can
cause fire hazards, making storage and transportation difficult. Fuel with low ignition temperature can burn
spontaneously leading to explosion. High ignition temperature, on the other hand, makes it difficult to kindle
(ignite) the fuel.
3. Moisture Content: Moisture content should be low because the presence of moisture lowers the
calorific value of the fuel
4. Non-combustible Matter: Non-combustible matter that left behind after combustion e.g. Ash, clinker.
Good fuel should have low amount of non-combustible matter because it reduces the calorific value of the fuel
and also require additional money investment for storage, handling and disposal of the waste products
produced.
5. Velocity of Combustion: If the velocity of combustion is low, then a part of the liberated heat may get
radiated instead of raising the temperature; hence, the required high temperature may not be attained. On the
other hand, if the velocity of combustion is very high then the rate of combustion might become
uncontrollable. For a continuous supply of heat, fuel must burn with a moderate rate.
 Characteristics of a Good Fuel
6. Combustion Products: The product obtained during combustion of the fuel should be harmless and
non-polluting. Harmful gases such as CO, SO2, H2S, PH3 and PbBr2 should not be produced, and also the
amount of smoke produced should be less.
7. Cost of the fuel: A good fuel should be readily available at a low cost.
8. Storage and Transportation: A good fuel should be easy to handle, store and transport at low cost.
9. Size: In case of solid fuels, the size should be uniform so that combustion is regular.
10. Combustion should be controllable: If The combustion process should be controllable, that is it
can be started or stopped when required.
 Comparison of solid, liquid and gaseous fuel
S.No. Solid Fuel Liquid Fuel Gaseous Fuel
1. Cheap and easily available Costlier than solid fuel except in Costly, because except natural gas
the countries of origin all other gaseous fuels are derived
from solid and liquid fuels
2. Convenient to store without Great care must to be taken to Very large storage tanks are
any risk of spontaneous store them in closed containers needed. Storing gaseous fuel
explosion require extra care as they are highly
inflammable
3. Large space is required Storage space is less compared They must be stored in leak proof
with solid and gaseous fuels containers

4. They are easy to transport They can be easily transported They are also transported through
through pipelines pipelines

5. They posses moderate ignition Combustion takes place readily Combustion is fast and can be
temperature. Combustion is and can be easily be controlled or controlled and stopped easily
slow but it cannot be stopped by reducing or stopping
controlled easily the fuel supply
 Comparison of solid, liquid and gaseous fuel
S.No. Solid Fuel Liquid Fuel Gaseous Fuel
6. Ash is produced and its Ash is not produced, however Neither ash nor smoke is
disposal is a big problem. fuels with high carbon and produced
Smoke is also produced aromatic contents may produce
smoke
7. They cannot be used in Used in internal combustion Used in internal combustion
internal combustion engine engine (petrol, diesel) engines (CNG, LPG)

8. They have low thermal Their thermal efficiency is higher Their thermal efficiency is the
efficiency than solid fuels highest

9. Their calorific value is lowest Their calorific value is higher than Their calorific value is the highest
solid fuels

10. Least risk of fire hazards Risk of fire hazards is high Highest risk of fire hazards
 Calorific Value
It is defined as the total amount of heat liberated when a unit mass or volume of the fuel is burnt completely.

Units of Heat
1. Calorie: It is defined as the amount of heat required to raise the temperature of 1 g of water by 1 Cͦ (from
15 C
ͦ to 16 C
ͦ )
1 calorie = 4.185 joules = 4.185 x 107 ergs
2. Kilocalorie: It is defined as the amount of heat required to raise the temperature of 1 kg of water by 1 Cͦ
(from 15 C
ͦ to 16 C
ͦ )
1 kcal = 1000 cal
3. British Thermal Unit (BTU): It is defined as the amount of heat required to raise the temperature of 1
pound (lb) of water by 1 Fͦ (from 60 Fͦ to 61 Fͦ )
1 BTU = 252 cal = 0.252 kcal = 1054.6 Joule = 1054.6 x 107 ergs
4. Centigrade Heat Unit (CHU): It is defined as the amount of heat required to raise the temperature of
1 pound (lb) of water by 1 C
ͦ (from 15 C
ͦ to 16 C
ͦ )
1 kcal = 3.968 BTU = 2.2 CHU
 Units of Calorific Value
The units of calorific value for solid, liquid and gaseous fuels are given below.

System Solid / Liquid fuels Gaseous fuels

CGS cal / g cal / cm3
MKS kcal / kg kcal /m3
BTU BTU / lb BTU / ft3
These units can be interconverted as follows.

1 cal/g = 1 kcal/kg = 1.8 BTU/lb

1 kcal = 0.1077 BTU/ft3

1 BTU/ft3 = 9.3 kcal/m3

 Gross and Net Calorific Value
Gross Calorific Value (GCV): It is defined as the total amount of heat produced when a unit quantity
(mass or volume) of fuel is burnt completely in presence of oxygen and the products of combustion are cooled
to room temperature. It is also called Higher Calorific Value (HCV).
Mostly all fuels contain hydrogen. During combustion, the hydrogen present in the fuel is converted into
steam. When the combustion products are cooled to room temperature, the steam gets condensed into water
and heat that equals to the latent heat of vaporisation of steam is evolved. This heat gets included in the
measured heat, and so its value is higher; hence it is called Higher Calorific Value (HCV)
Net Calorific Value (NCV): It is defined as the total amount of heat produced when a unit quantity (mass
or volume) of fuel is burnt completely in presence of oxygen and the hot products of combustion are allowed
to escape. It is also called Low Calorific Value (LCV).
In actual practice, when a fuel is burnt water vapor escapes along with the hot combustion gases; hence, heat
available is lesser than the gross calorific value. Therefore, this is called Low Calorific Value (LCV).
LCV = HCV – Latent heat of water vapour formed
2H2 + O2 2H2O
4g 32 g 36 g
1g 8g 9g
LCV = HCV – Weight of hydrogen in unit mass/ volume of fuel X 9 X Latent heat of steam
 LCV = HCV – H % in fuel X 0.09 X Latent heat of steam
Question: 2 kg of a coal sample was burnt in a bomb calorimeter. The heat liberated was estimated and
found to be 14114 kcal. Calculate the calorific value of the coal sample.

Solution: Heat liberated on burning 2 kg coal = 14114 kcal

14114
Heat liberated on combustion of 1 kg coal = = 7057 kcal
2
Calorific value of coal = 7057 kcal / kg

Question: The gross calorific value of a fuel containing 8% hydrogen was found to be 9225.9 kcal/kg. Find out
its net calorific value if the latent heat of steam is 587 kcal/kg.
Solution: Gross calorific value of the fuel = 9225.9 kcal/kg
Hydrogen % in fuel = 8
NCV = GCV – H % in fuel X 0.09 X Latent heat of steam
NCV = 9225.9 – 8 X 0.09 X 587
= 9225.9 – 422.64
= 8803.26 kcal/kg
NCV = 8803.26 kcal/kg
 Determination of Calorific Value
Calorimeter: A calorimeter is a device that measures heat changes in a system and its surroundings.

The calorific value of solid and non-volatile liquid fuels is determined by bomb calorimeter, whereas the calorific value of
gaseous fuels is determined by Junkers calorimeter.

Principle: A known amount of fuel is burnt in excess of oxygen and the heat liberated is absorbed in a known amount of
water. This heat liberated is measured by noting the change in temperature.

Calorific value of the fuel is then calculated by applying the following principle:

Heat liberated by the fuel = Heat absorbed by water and calorimeter

 Bomb calorimeter
Battery
1. Stainless Steel Bomb: It consists of a long cylindrical
O2 Inlet valve container made up of stainless steel. It has a lid that is made
air tight with the help of screws. The lid is provided with two
holes for electrodes and has an oxygen inlet valve. A small
Stirrer ring is attached to one of the electrodes. This ring acts as a
support for nickel or stainless steel crucible in which the fuel
is burnt. Magnesium wire touching the fuel sample extends
across the electrodes. The steel bomb is lined inside with
platinum to resist corrosive action of HNO3 and H2SO4 vapors
formed because of burning of fuel and is designed to
withstand high pressure (25–50 atm).
Beckmann Crucible Insulating jacket
Thermometer 2. Copper Calorimeter: The bomb is placed in a copper
Copper
calorimeter containing a known amount of water. The
Fuel sample calorimeter
calorimeter is provided with an electrical stirrer and a
Air jacket Beckmann thermometer that can read accurate temperature
difference of up to 1/100th of a degree
Water
3. Air Jacket and Water Jacket: The copper calorimeter is
Mg fuse wire Stainless steel bomb surrounded by an air jacket and a water jacket to prevent loss
of heat owing to radiation.
 Working: A known amount of fuel (0.5–1 g) is taken in a clean crucible supported over the ring. A fine magnesium wire, touching the fuel sample, is then
stretched across the electrodes. About 10 mL of distilled water is introduced into the bomb to absorb vapors of sulphuric acid and nitric acid formed
during combustion, and the lid of the bomb is tightly screwed. The bomb is filled with oxygen at 25 atmospheric pressure and placed in the copper
calorimeter containing a known weight of water. The stirrer is started and the initial temperature of water is noted. The electrodes are then connected
to a 6-volt battery to complete the circuit. The sample burns and heat is liberated. This heat is absorbed by water. Maximum temperature shown by the
thermometer is recorded. Time taken to cool the water in the calorimeter from maximum temperature to room temperature is also noted. The gross
calorific value of the fuel is calculated as follows.
Corrections
Calculations: Let Fuse Wire Correction: The gross calorific value calculated above includes
Weight of fuel sample taken = x g the heat liberated by the ignition of Mg fuse wire; hence, this amount of
Weight of water in the calorimeter = W g heat has to be subtracted from the total value.
Water equivalent of calorimeter, = w g Acid Correction: Acid Correction During combustion, sulphur and nitrogen
stirrer, thermometer, bomb etc. present in the fuel get oxidized to H2SO4 and HNO3 , respectively:
Initial temperature of water = t1ᴼC S + O2 → SO2
Final temperature of water = t2ᴼC 2SO2 + O2 + 2H2O → 2H2SO4 ∆H = – 144000 cal
Higher calorific value of fuel = H calorie / g 2N2 + 5O2+ 2H2O → 4HNO3 ∆H = – 57160 cal
Heat liberated by burning of fuel = x × H Hence, the formation of acids is exothermic and this should be subtracted
Heat gained by water = W × ∆T × specific heat of water from the obtained value of GCV..
= W (t2– t1) × 1 cal Cooling Correction: Heating and cooling are simultaneous processes. As the
Heat gained by calorimeter = w (t2– t1) temperature rises above the room temperature, the loss of heat occurs due
Total heat gained = W (t2– t1) + w (t2– t1) to radiation and the highest temperature recorded will be slightly less than
= (W + w) (t2– t1) that obtained if there was no heat loss. A temperature correction (cooling
correction) is therefore necessary to get the correct rise in temperature.
Heat liberated by the fuel = Heat absorbed by water & calorimeter.
If the time taken for the water in the calorimeter to cool from maximum
x × H = (W + w) (t2– t1) temperature attained to room temperature is ‘y’ minutes and the rate of
(W + w) (t2– t1) cooling is dt/min, then the cooling correction is y × dt and this is to be added
𝐻=
𝑥 to the rise in temperature.
(W + w) (t2– t1 + cooling correction) − (Fuse wire + Acid correction)
𝑯=
𝒙
Question: 0.72 g of a fuel containing 80% carbon, when burnt in a Question: On burning 0.83 g of a solid fuel in a bomb calorimeter, the
bomb calorimeter, increased the temperature of water from 27.3 °C temperature of 3500 g of water increased from 26.5 °C to 29.2 °C.
to 29.1 °C. If the calorimeter contains 250 g of water and its water Water equivalent of calorimeter and latent heat of steam are 385.0 g
equivalent is 150 g, calculate the HCV of the fuel. Give your answer and 587.0 cal/g, respectively. If the fuel contains 0.7% hydrogen,
in kJ/kg. calculate its gross and net calorific values.
Solution: Weight of fuel sample taken (x) = 0.83 g
Solution: Weight of fuel sample taken (x) = 0.72 g Weight of water in the calorimeter (W) = 3500 g
Weight of water in the calorimeter (W) = 250 g Water equivalent of calorimeter (w) = 385 g
Water equivalent of calorimeter (w) = 150 g stirrer, thermometer, bomb etc.
stirrer, thermometer, bomb etc. Initial temperature of water t1 = 26.5ᴼC
Initial temperature of water t1 = 27.3ᴼC Final temperature of water t2 = 29.2ᴼC
Final temperature of water t2 = 29.1ᴼC latent heat of steam = 587 cal/g
Higher calorific value of fuel (H) = ? Cal / g Hydrogen percentage = 0.7
(W + w) (t2– t1) Gross calorific value of fuel (H) = ? cal / g
𝐻=
𝑥 (W + w) (t2– t1)
𝐻=
𝑥
(250 + 150) (29.1– 27.3)
𝐻=
0.72 (3500 + 385) (29.2– 26.5) (3885) (2.7)
𝐻= =
0.83 0.83
(400) (1.8)
=
0.72 GCV= 𝟏𝟐𝟔𝟑𝟕. 𝟗𝟓 = 𝟏𝟐𝟔𝟑𝟖 𝐜𝐚𝐥/𝐠
= 1000 𝑐𝑎𝑙/𝑔 NCV = GCV – H % in fuel X 0.09 X Latent heat of steam
= 1000 𝑋 4.18 𝐽/𝑔 NCV = 12638 – 0.7 X 0.09 X 587
𝐻 = 4180 𝐽/𝑔 = 12638 – 37
𝑯 = 𝟒𝟏𝟖𝟎 𝒌𝑱/𝒌𝒈 NCV = 12601 cal/g
Question: A coal sample contains: C = 93%; H = 6% and ash = 1%. The Question: A coal sample contains C = 92%, H = 5% and ash = 3%. When
following data were obtained this coal sample was tested in the laboratory for its calorific value in a
when the above coal was tested in a bomb calorimeter: bomb calorimeter, the following data were obtained
(i) Wt of coal burnt = 0.92 g Wt of coal burnt = 0.95 g, Wt of water taken = 700 g
(ii) Wt of water taken = 550 g Water equivalent of bomb and calorimeter = 2000 g
(iii) Water equivalent of bomb and calorimeter = 2200 g Rise in temperature = 2.48 °C, Fuse wire correction = 10.0 cal
(iv) Rise in temperature = 2.42 °C Acid correction = 60.0 cal, Cooling correction = 0.02 °C
(v) Fuse wire correction = 10.0 cal Calculate the gross and net calorific value of the coal sample in cal/g.
(vi) Acid correction = 50.0 cal Assume the latent heat of condensation of steam as 580 cal/g.
Calculate the gross calorific value of the coal.
Solution: Weight of fuel sample taken (x) = 0.95 g
Solution: Weight of fuel sample taken (x) = 0.92 g Weight of water in the calorimeter (W) = 700 g
Weight of water in the calorimeter (W) = 550 g Water equivalent of calorimeter (w) = 2000 g
Water equivalent of calorimeter (w) = 2200 g stirrer, thermometer, bomb etc.
stirrer, thermometer, bomb etc. rise in temperature Δ t = 2.48ᴼC
rise in temperature Δ t = 2.42ᴼC Higher calorific value of fuel (H) = ? Cal / g
Higher calorific value of fuel (H) = ? Cal / g (W + w) (t2– t1 + cooling correction) − (Fuse wire + Acid correction)
(W + w) (t2– t1 + cooling correction) − (Fuse wire + Acid correction) 𝐻=
𝐻= 𝑥
𝑥
(700 + 2000) (2.48+0.02)−(10.0 + 60.0)
(550 + 2200) (2.42)−(10.0 + 50.0) 𝐻=
𝐻= 0.95
0.92
(2700) (2.5)−(70) (6750)−(70) 6680
(2750) (2.42)−(60) (6655)−(60) = = =
= = 0.95 0.95 0.95
0.92 0.92
𝑮𝑪𝑽 = 𝟕𝟎𝟑𝟏. 𝟓𝟕 𝒄𝒂𝒍/𝒈
6595 NCV = GCV – H % in fuel X 0.09 X Latent heat of steam
=
0.92 NCV = 7031.57 – 5 X 0.09 X 580 = 7031.57 – 261
NCV = 6770.57 cal/g
𝑮𝑪𝑽 = 𝟕𝟏𝟔𝟖. 𝟒𝟕 𝒄𝒂𝒍/𝒈
 Junker’s calorimeter
Principle: A known volume of gas is burnt at known pressure in a small enclosed combustion chamber. The heat
liberated is absorbed by water flowing at constant rate through the water jacket. By knowing the initial and final
temperatures of water, the quantity of water and weight of water condensed, the calorific value can be determined.
1. Bunsen Burner: It is used for the combustion of gaseous fuel. It is clamped at the
bottom and can be pulled out or pushed into the chamber during combustion.

2. Gasometer: It measures the volume of the gas burning per unit time. It is
attached with a manometer fitted with a thermometer to record the pressure
and temperature of the gas before burning.

3. Pressure Governor: It regulates the supply of a gaseous fuel at constant pressure.

4. Gas Calorimeter: It consists of a vertical cylindrical combustion chamber where

combustion of gaseous fuel is carried out. The combustion chamber is
surrounded by an annular water space where water is made to circulate. Loss of
heat by radiation and convection is prevented by an outer jacket, which is
chromium-plated. Moreover, the outer jacket contains air that is a very good heat
insulator. There are openings at appropriate places where thermometers are
placed for measuring the temperature of the inlet and outlet water..
Working: A known volume of gas is burnt at a constant rate in a Question: The following data were obtained in a Junker’s calorimeter
combustion chamber in the presence of excess air. All the heat produced is experiment:
absorbed by water circulating in the annular space around the combustion Volume of gas used = 0.1 m3 at STP, Wt of water heated = 25 kg
chamber. Temperature of inlet water = 20 °C, Temperature of outlet water = 33 °C
Calculations: Let Weight of steam condensed = 0.025 kg
The volume of gaseous fuel burnt at a given temperature and pressure in Calculate the higher and lower calorific value per m3 at STP. Take the heat
a certain time = V m3 liberated in condensing water vapours and cooling the condensate as 580
Weight of water circulated through the coils in time t = W g kcal/kg.
Temperature of inlet water = t1ᴼC Solution: Volume of fuel sample used (V) = 0.1 m3 at STP
Temperature of outlet water = t2ᴼC Weight of water in the circulating coil (W) = 25 kg
Weight of steam condensed in time t in a graduated cylinder = m kg Temperature of inlet water ( t1 ) = 20ᴼC
Higher calorific value of fuel = H kcal / m3 Temperature of outlet water ( t2) = 33ᴼC
Heat produced by the combustion of fuel = V × H Weight of steam condensed = 0.025 kg
Heat absorbed by circulating water = W (t2– t1) Higher calorific value of fuel (H) = ? kcal / m3
W (t2– t1)
Heat liberated by the fuel = Heat absorbed by circulating water. 𝐻= kcal/m3
𝑉
V × H = W (t2– t1)
(25) (33−20)
W (t2– t1) 𝐻=
𝐻= kcal/m3 0.1
𝑉
(25) (13) 325
Weight of steam condensed in a certain time (t) by the combustion of = =
V m3 of the fuel = m kg 0.1 0.1
𝐺𝐶𝑉 = 3250 𝑘𝑐𝑎𝑙/𝑚3
𝑚
Mass of H2O condensed per m3 of the fuel = kg NCV or LCV = 𝐻 −
𝑚 𝑋 580
kcal/m3
𝑉
𝑉
𝑚 𝑋 587 0.025 𝑋 580
Heat released by per m3 of the fuel = kcal = 3250 − kcal/m3
𝑉 0.1
NCV = 3105 𝑘𝑐𝑎𝑙/𝑚3
𝑚 𝑋 587
NCV or LCV = 𝐻 − kcal/m3
𝑉
 Theoretical calculation of calorific value of a fuel
Dulong's assumed that the heat evolved comes from the combustion of carbon, hydrogen and sulphur present in the fuel,
and the calorific value of the fuel is the sum of the calorific values of these constituents.

Constituent Higher Calorific Value

Carbon (C) 8080 kcal / kg
Hydrogen (H) 34500 kcal / kg
Sulphur (S) 2240 kcal / kg
If oxygen is also present, it combines with hydrogen to form H2O. Thus, the hydrogen in combined form is not available for
combustion and is called fixed hydrogen.
Amount of hydrogen available for combustion = Total mass of hydrogen – Hydrogen combined with oxygen.

2H2 + O2 2H2O
4g 32 g 36 g
1g 8g 9g
that is 8 parts of oxygen combines with 1 part of hydrogen to form water or for every 8 parts of oxygen, 1 part of hydrogen
gets fixed.
 Theoretical calculation of calorific value of a fuel
If the fuel contains O mass of oxygen then
1 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛 𝑖𝑛 𝑓𝑢𝑒𝑙
𝐹𝑖𝑥𝑒𝑑 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 = ×𝑂 =
8 8
𝑂
Amount of hydrogen available for combustion = H −
8

Dulong's formula for calculating calorific value is given as

1 𝑂
𝐺𝑟𝑜𝑠𝑠 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐻𝐶𝑉) = 8080 𝐶 + 34500 H − + 2240 𝑆 𝑘𝑐𝑎𝑙/𝑘𝑔
100 8

9𝐻
𝑁𝑒𝑡 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐿𝐶𝑉) = 𝐻𝐶𝑉 − × 587 𝑘𝑐𝑎𝑙/𝑘𝑔
100
Question: Calculate the gross and net calorific values of coal having the following composition:
Carbon =85%; hydrogen = 8%; sulphur = 1%; nitrogen = 2%; ash = 4%
Latent heat of steam = 587 cal/g.
Solution:
% 𝑂𝑥𝑦𝑔𝑒𝑛 = 100 − % 𝐶 + 𝐻 + 𝑆 + 𝑁 + 𝐴𝑠ℎ

% 𝑂𝑥𝑦𝑔𝑒𝑛 = 100 − % 85 + 8 + 1 + 2 + 4

% 𝑂𝑥𝑦𝑔𝑒𝑛 = 100 − 100 = 0

1 𝑂
𝐺𝑟𝑜𝑠𝑠 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐻𝐶𝑉) = 8080 𝐶 + 34500 H − + 2240 𝑆 𝑘𝑐𝑎𝑙/𝑘𝑔
100 8

1 0
𝐺𝑟𝑜𝑠𝑠 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐻𝐶𝑉) = 8080 (85) + 34500 8 − + 2240 (1) 𝑘𝑐𝑎𝑙/𝑘𝑔
100 8
1 1
= 686800 + 276000 + 2240 = 965040 = 9650.4 𝑘𝑐𝑎𝑙/𝑘𝑔
100 100
9𝐻
𝑁𝑒𝑡 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐿𝐶𝑉) = 𝐻𝐶𝑉 − × 587 𝑘𝑐𝑎𝑙/𝑘𝑔
100

9 8
𝑁𝑒𝑡 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 𝐿𝐶𝑉 = 9650.4 − × 587 = 9227.76 𝑘𝑐𝑎𝑙/𝑘𝑔
100
Question: A boiler is fired with a coal with composition: C = 75%, H = 9%, S = 2%, O = 4%, N = 3%, ash = 7%. Calculate gross and net calorific
value of 1 kg of coal sample.
Latent heat of steam = 587 kcal/kg.
Solution:
1 𝑂
𝐺𝑟𝑜𝑠𝑠 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐻𝐶𝑉) = 8080 𝐶 + 34500 H − + 2240 𝑆 𝑘𝑐𝑎𝑙/𝑘𝑔
100 8

1 4
𝐺𝑟𝑜𝑠𝑠 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐻𝐶𝑉) = 8080 (75) + 34500 9 − + 2240 (2) 𝑘𝑐𝑎𝑙/𝑘𝑔
100 8
1 1
= 606000 + 293250 + 4480 = 903730 = 9037.3 𝑘𝑐𝑎𝑙/𝑘𝑔
100 100
9𝐻
𝑁𝑒𝑡 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 (𝐿𝐶𝑉) = 𝐻𝐶𝑉 − × 587 𝑘𝑐𝑎𝑙/𝑘𝑔
100

9 9
𝑁𝑒𝑡 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 𝐿𝐶𝑉 = 9037.3 − × 587 = 8561.83 𝑘𝑐𝑎𝑙/𝑘𝑔
100
 Liquid Fuels
Use of liquid fuels in internal combustion engines makes them very important fuels
Petroleum or crude oil
Petra means rock oleum means oil
It is a greenish-brown viscus oil found deep inside the earth’s crust and is a mixture of hydrocarbons such as straight chain
paraffins, cycloparaffins or naphthalene, olefines and aromatics along with small amount of organic compounds containing
oxygen, nitrogen and sulphur.
Average composition of crude petroleum
Elements Carbon Hydrogen Sulphur Nitrogen Oxygen
Percentage 75.5-87.1% 11.5-14.8% 0.1-3.5% 0.4-0.9% 0.1-0.9%
Classification of petroleum based on its composition

1. Paraffinic base petroleum 3. Mixed base petroleum

Mainly composed of straight chain saturated hydrocarbons Both type of paraffins and asphaltic hydrocarbons are
From CH4 to C35H72 along with small amount of naphthenes present
and aromatic hydrocarbon.
2. Naphthenic or asphaltic base petroleum
Mainly composed of cycloparaffins or naphthene along with smaller amount of paraffines
and aromatic hydrocarbons,
Mining of Petroleum Refining of Petroleum
Crude oil coming out from the oil well is a mixture
of solid, liquid and gaseous hydrocarbons
containing sand and water in suspension. The
process of removing unwanted impurities and
separating petroleum into useful fractions with
different boiling range is called refining of
petroleum

1. Separation of water (demulsification)

The crude oil from the well is an extremely stable emulsion of
oil and salt water. The demulsification is achieved by Cotrell’s
process. The crude oil is allowed to flow between two highly
charged electrodes where colloidal water droplets coalesce to
form large drops which separate out from the oil.
2. Removal of harmful impurities
The NaCl and MgCl2 corrode the refining equipment's. These
are removed by modern techniques like electrical desalting
and dehydration.
Harmful sulphur compounds are removed by treating the
crude oil with copper oxide. Sulphur reacts with copper oxide
forming copper sulphide, which is removed by filtration.
3. Fractional distillation
The crude oil is heated to 400 °C in an iron
retort whereby all the volatile constituents,
except asphalt or coke are evaporated. The
vapors are then passed into a fractionating
column, which is a tall cylindrical tower. The
tower is hot towards the lower end and
comparatively cooler at the upper end. It
consists of a number of horizontal stainless
steel trays at short distances. These trays are
provided with individual chimneys which are
covered with a loose cap. As the vapors go up,
fractional condensation occurs at different
heights of the column. Higher boiling fractions
condense first, while lower boiling fractions
condense later
S.No. Fraction name Boiling Approximate Uses
Temperature composition

1. Uncondensed gases Below 30 °C C1-C4 Used as domestic fuel

2. Petroleum ether 30-70 °C C5-C7 Solvents for fats, essential oils, used in dry
cleaning
3. Gasoline or petrol or motor spirit 70- 120 °C C5-C9 As a motor fuel for IC engines, as a solvent
and in drycleaning
4. Naphtha or solvent sprit 120 -180 °C C9-C10 As a solvent for paints and varnishes and in
dry cleaning
5. Kerosene oil 180-250 °C C10-C16 Fuel for stoves, jet engine fuel and for
preparing oil gas used in Laboratories
6. Diesel oil 250-320 °C C15-C18 Diesel engine fuel
7. Heavy oil 320-400 °C C17-C30 Fuel for ships, in metallurgical furnaces and in
Heavy oil on vacuum distillation gives conversion to gasoline by cracking
i. Lubricating oil ----- As lubricants
ii. Petroleum jelly (vaseline) C20-C28 Used in cosmetics and medicines
iii. Greases
iv. Paraffin wax In candles, boot polish, wax paper
8. Residue: It may be either > 400 °C C50 and above
i. Asphalt (if the crude oil is asphaltic)
ii. Petroleum coke
The crude oil obtained on fractionation yields approximately 20–30% gasoline, 30–35% middle oils and 20–25% heavy oils.
among all these fractions, gasoline (also called straight run petrol) is in maximum demand because of its use as fuel in the
automobile industry. Hence, there is a need to convert the middle oil and heavy oil fractions into a more useful fraction gasoline

Cracking
Cracking is defined as the process of converting high-molecular-weight bigger hydrocarbons into low-molecular-weight smaller
hydrocarbons by the application of heat, with or without a catalyst.

1. Thermal Cracking 2. Catalytic Cracking

When the heavy oils are subjected to high temperature and It is carried out in the presence of a catalyst at a much
pressure in the absence of catalyst, it is called thermal lower temperature and pressure. The catalyst used is
cracking. The bigger hydrocarbons breakdown to give usually a mixture of silica and alumina (hydrated
smaller molecules of paraffins, olefins and some hydrogen. aluminium silicate) or zeolites in the form of beads or
This process may be carried out either in liquid phase or in pellets
vapour phase.
i) Liquid phase thermal cracking By this method any type of ii) Vapour phase thermal cracking This method is suitable for
oil (residue, fuel oil or gasoline) can be cracked. The charge oils which can be readily vaporised. The oil is first vaporised
is kept in liquid form by applying high pressure of the range and then cracked at about 600–650 °C and under a low
of 100 kg/cm2 at a suitable temperature of 475–530 °C. The pressure of 10–20 kg/cm2. It time than the liquid phase
cracked products are separated in a fractionating column. method. Petrol obtained from requires less vapour phase
The octane rating of the product is 65–70. cracking has better antiknock properties, but poorer stability
than the petrol obtained from liquid–phase cracking.
 Characteristics Liquid phase thermal cracking Vapour phase thermal cracking
Cracking Temperature 475 – 530 °C 600 – 650 °C
Pressure 100 kg / cm2 10 – 20 kg / cm2
Octane rating of petrol 65 -70 greater than 70
Type of oil used for cracking Any heavy oil can be cracked Oil should be readily vapourised

Catalytic Cracking
i) Fixed bed catalytic cracking: The vapours of the oil are
preheated in a pre-heater to a temperature of 420–450°C. It is then
passed through a catalytic chamber containing either silica-alumina gel
(SiO2 , Al2O3) or bauxite mixed with clay and zirconium oxide
maintained at 425°C–450°C and 1.5 kg/cm2 pressure. Cracking of heavy
oil vapours takes place and 30–40% of the charge is converted into
gasoline and about 3–4% carbon is formed which gets adsorbed on the
catalyst bed. The cracked vapours then pass through a cooler where
some gases are condensed along with gasoline and uncondensed gases
move on. The gasoline containing some dissolved gases is then sent to a
‘stabilizer’ where the dissolved gases are removed and pure gasoline is
obtained.
After 8–10 h, the catalyst stops functioning because of the deposition
of black layer of carbon formed during cracking. This is re-activated by
burning off the deposited carbon. During the reactivation of the
catalyst, the vapors of heavy oil are diverted through another standby
catalytic chamber so that the reaction proceeds continuously.
ii) Moving bed catalytic cracking: This is also known as fluidized
bed catalytic cracking. The feed oil is preheated. It is then mixed with
powdered catalyst and the mixture of preheated heavy oil and powdered
catalyst goes in a reactor maintained at 500 °C. Cracking of heavy oil
takes place. Near the top of the reactor there is a centrifugal separator
(called cyclone) which allows the cracked vapours to pass on to the
fractionating column but retains the catalyst powder. The catalyst
powder gradually becomes heavier, due to coating with carbon formed
and settles at the bottom. This is called spent catalyst and is forced by a
blast of air to the regenerator maintained at 600 °C. In regenerator,
carbon is burnt off and the catalyst is reactivated. The regenerated
catalyst then flows through a standpipe to get mixed with fresh charge.
The cyclone at the top of the regenerator allows the flue gases (e.g., CO2)
to escape retaining the catalyst particles. .

Advantages of catalytic cracking over thermal cracking:

1. The yield of gasoline is higher. About 70% of the raw material by 6. The process is faster.
weight is converted into gasoline. The yield of gaseous products (by- 7. Action of catalysts is selective, hence cracking of only high-boiling
product gases such as alkanes and alkenes) is about 12–15% and hydrocarbons takes place.
only 4–6% of the raw material is converted into coke. 8. The quality of gasoline produced is better because
2. Production cost is low as high temperatures and pressures are not i. The product contains very little amount of undesirable sulphur as
needed (pressure 1–5 kg/cm2. the major portion of it escapes out as H2S during cracking.
3. No external fuel is required for cracking since the heat required is ii. The gasoline obtained by cracking contains low percentage of
obtained by burning the carbon deposited on the catalyst itself olefins and higher percentage of isoparaffin and aromatic
during regeneration process. hydrocarbons. This increases the antiknock properties of gasoline.
4. Process can be controlled to obtain desired products. Gasoline formed by catalytic cracking has an octane number of 80.
5. The percentage of gum or gum-forming compounds is very low. Decomposition of aromatics removes only side chains but the
aromatic ring is not broken.