Chapter 4: Fuels

Fuel: “Fuel is a combustible substance containing carbon as a main constituent, which on

proper burning gives large amount of heat. Which can be used economically for domestic and
industrial purposes”

Or

“Material used for production of energy/heat are known as fuel”

ℎ𝑖𝑔ℎ 𝑡𝑒𝑚𝑝
Fuel + O2 → Combustion products + Heat

As most of the fuels contain carbon and hydrogen, the combustion involves the oxidation of
carbon to carbon dioxide and hydrogen to water. Sulphur, if present, is oxidized to sulphur
dioxide while the mineral matter forms the ash.

Fuels like coal, crude oil, natural gas known as fossil fuels found under earth crust.

Chemical fuels: The fossil fuels, wood, vegetable oils etc. which produce heat on burning are
known as chemical fuels.

Classification of Fuels

Classification of fuels on the basis of physical state and occurrence:

Natural/ Primary fuels: which are found in nature.

Artificial/ Secondary/ Derived fuels: which are derived from primary fuels by further
chemical processing.

Solid fuel (e.g.,

wood, coal)

Liquid fuel (e.g.,

Based on
crude petroleum,
Physical State
natural gasoline)

Gaseous fuel (e.g.,

Classifications natural gas)
of Fuels
Primary or natural
fuels (e.g., wood,
coal)
Based on
occurrence Secondary or
prepared fuels (e.g.,
charcoal, petroleum
coke).

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Classification of fuels on the basis of chemical reactions involved in combustion:

Characteristics of an Ideal Fuel

 The calorific value of a fuel should be as high as possible, so that its use become
economical.
 The ignition temperature of the fuel should be moderate. It should not be too high or too
low.
 It should not undergo spontaneous combustion as it can cause fire hazards.
 The rate of combustion of the fuel should be moderate and controllable.
 The products formed during combustion of a fuel should be harmless, non-toxic and non-
polluting.
 Low ash (non-combustible) matter.
 The fuel should be easy to transport, cheap and require less space for storage.
 The fuel should burn in air with efficiency, without smoke.
 Moisture content of the fuel should be low.

Calorific Values

The heat released by burning fuel is measured in terms of calorific value.

“It is defined as the total quantity of heat liberated by complete combustion of unit mass (or
volume) of the fuel at STP.”

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Types of calorific values (1) Gross calorific value (G.C.V.)

(2) Net calorific value (N.C.V.)

Higher or Gross Calorific Value (G.C.V.)

All fuels contain some hydrogen which on combustion gets converted into steam. If the products
of combustion are condensed to the room temperature, the latent heat of condensation (of water
2450 J/gm or 587 cal/gm) of steam also gets included in the measured heat.

Thus during the study of calorific value of a fuel, we get some heat directly by combustion of
fuel and in addition we get certain amount of heat by cooling the products of combustion to
15°C.

Definition

Gross calorific value of a fuel can be defined as “the total amount of heat produced, when unit
mass/volume of the fuel has been burnt completely in an insulating container and the
products of combustion have been cooled to room temperature"

The G.C.V. is of only theoretical importance because in actual practice, we do not have any
provision of cooling the products of combustion during combustion of a fuel in an engine,
furnace or any other fuel burning device and the product gases leaves with some heat.

Lower or Net Calorific Value (N.C.V.)

A fuel containing hydrogen produces steam, on combustion. Out of the total heat produced in
combustion of the fuel, the water takes away a considerable portion of the heat for evaporation
and actually less heat is available for heating.

There is no any furnace, engine or device designed to collect the heat being taken away by the
water vapours. Therefore practically we get lower calorific value than the theoretically expected.

Definition

Net calorific value is defined as the “amount of heat obtained practically on complete
combustion of unit mass or volume of fuel at STP and the products of combustion are allowed
to escape with some heat.”

The N.C.V. and G.C.V. are related as under,

NCV = GCV – Latent heat of water vapour formed

= GCV – (Mass of steam * latent heat of steam)

= GCV – [(9*Mass of hydrogen)*latent heat of steam]

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This is based on the fact that 1 part of H by mass gives 9 parts of H2O, and latent heat of steam is
587 kcal/kg. If mass of hydrogen is expressed as %H, then, mass of hydrogen per gram of fuel
will be H/100

Where ‘h’ is the percentage of hydrogen in the fuel.

It should be noted that the unit of latent heat of water and unit of G.C.V., N.C.V. should be same.

Units of calorific value:

1 cal/gm =1 kcal/kg = 4.18 kJ /kg

system Calorific value

Solid / liquid fuel Gaseous fuel
CGS cal/gm cal/litre
MKS kcal/kg kcal/m3
S.I. joules/kg joules/m3

Determination of G.C.V. of Solid or Non-volatile Liquid Fuels by Bomb Calorimeter

The experimental determination of calorific value is done by using apparatus called as

calorimeters.

Principle of Bomb Calorimeter:

Total heat liberated by complete combustion of known amount of heat is absorbed by the known
mass of water in calorimeter. From the rise in temperature of water the calorific value of the fuel
can be determined.

Construction of Bomb Calorimeter

A Bomb calorimeter consists of,

a) Bomb Pot:
 It is a cylindrical, strong stainless steel pot having a lid. The lid can be fitted air tight to
Bomb pot by screwing.
 There are two electrodes fitted through the lid and there is an oxygen inlet valve at its
center.
 These electrodes are attached to 6 V DC battery to start combustion.

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  One of the electrodes is provided with a ring to hold the crucible containing fuel. There is
a thin resistance wire tied to the electrodes in loop form and the loop touches the fuel.
 A known amount of fuel is burnt in the Bomb pot in the presence of high pressure
oxygen.

b) Calorimeter:
 There is a stainless steel or copper calorimeter in which the Bomb pot is kept. It contains
a known volume of water and the water is kept circulating around the Bomb pot with the
help of a stirrer.
 A Beckman thermometer or digital thermometer is kept in the water of calorimeter,
which can record the rise in temperature of water due to absorbing heat generated in
burning of fuel in Bomb pot.

c) Water and Air Jackets

 The calorimeter is surrounded by air jacket and water jacket to avoid heat losses due to
radiation.

Bomb calorimeter

Working of Bomb Calorimeter

 A known mass of fuel is taken in a crucible. Keep the crucible in the ring of the electrode.
Tie the resistance wire between electrodes such that it touches to the fuel.
 Add about 10 ml of distilled water at the bottom of Bomb pot and fix the lid tightly to
Bomb by screwing.
 Fill the Bomb with oxygen at the pressure about 25 kg/cm2.
 Place the Bomb in calorimeter. Add known volume of water in the calorimeter so that the
Bomb gets immersed in the water.
 Place the calorimeter in the water jacket over the plastic studs. Keep the thermometer and
stirrer in the water of calorimeter.

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  Put the plastic cover on the top and make electrical connections from battery to
electrodes.
 Operate the stirrer for 5 minutes and note the initial temperature of water.
 Pass the current for about 5-10 seconds to heat the wire so that it ignites the fuel. The fuel
burns completely and heat is liberated.
 The heat liberated on combustion is absorbed by the water in the calorimeter. Stirring of
water in calorimeter is continued for uniform distribution of heat and the maximum
temperature reached is noted.
 The water equivalent of the calorimeter is determined in the separate experiment using a
standard fuel whose calorific value is already known. E.g. benzoic acid

(As the heat evolved during combustion is also transferred to the apparatus which is in contact
with water, it is essential to know the heat utilized to raise the temperature of instrument,
measured in terms of water. This is known as water equivalent)

Calculations:

Let, Mass of fuel in gm = x gm

Mass of water in calorimeter = W gm

Water equivalent of calorimeter set = w gm

Gross Calorific value of fuel = L calories/gm

Rise in temperature of water = (t 2 – t1) ᵒC

From the principle of conservation of energy, total heat liberated by combustion of fuel = Heat
absorbed by water and by the calorimeter apparatus.

x.GCV = [S.W(t 2-t1) + S.w (t2-t1)] ; x.GCV = [S.(W+w)(t 2-t1)]

S = specific heat or heat capacity of water at constant pressure is 1 cal/gm (kcal/kg)

GCV = (W+w)(t2-t1)/x cal/gm or GCV = 4.18 (W+w)(t2-t1)/x J/gm (kJ/kg)

Corrections

(i) Fuse wire correction (f): The heat liberated includes the heat given out by ignition of the
fuse wire used. This heat however small should be deduced from the heat liberated.

(ii) Acid correction (a): Fuels containing sulphur and nitrogen are oxidized under high pressure
and temperature of ignition to produce sulphur oxides and nitrogen oxides. This dissolve in the
water present in the calorimeter and form sulphuric acid and nitric acid. Formation of these acids
is an exothermic reaction and the heat evolved should be subtracted.

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 S + O2 → SO2 + ½ O2 → SO3

SO3 + H2O → H2SO4 + heat

N + O2 → NO2 → NO2 + 2H2O → 2HNO3 +H2 + heat

(iii) Cooling correction: Time taken to cool the water from maximum temperature to room
temperature is noted. From the rate of cooling (dt /min) and actual time for cooling (t min), the
cooling correction dt x t is added to rise in temperature.

After applying all the above corrections, the gross calorific value is given by

(𝐖 + 𝐰)(𝐭𝟐 − 𝐭𝟏 + 𝐭. 𝐝𝐭) − (𝐚 + 𝐟)
𝐋(𝐆𝐂𝐕) = 𝐜𝐚𝐥/𝐠
𝐗

NCV = GCV – [0.09 x H x 587] cal/gm

Ex. 0.072 gm of a fuel containing 80% Carbon, when burnt in a bomb calorimeter, increased the
temperature of water from 27.3°C to 29.1°C. If the calorimeter contains 250 gm of water and its
water equivalent is 150 gm, calculate GCV of the fuel.

Ans: Rise in temperature (t 2 – t1) = 29.1 – 27.3 = 1.8°C

Mass of fuel = m = 0.072 gm
Water equivalent of calorimeter = 150 gm = w
Mass of water in calorimeter = 250 gm = W

= 10,000 cal/gm. …Ans.

Ex. A sample of coal containing 5% H2 when allowed to undergo combustion in Bomb

Calorimeter, the following data were obtained.
Weight of coal burnt = 0.95 gm
Weight of water taken = 700 gm
Water equivalent of bomb calorimeter = 2000 gm
Rise in temperature = 2.48°C
Cooling correction = 0.02°C
fuse wire correction = 10 cal
acid correction = 60 cal
Calculate Gross and Net Colorific Value of Coal.

Ans: Water equivalent = w = 2000 gm, water in calorimeter =W = 700 gm, mass of fuel burnt =
m = 0.95, t2 – t1 C= 2.48°C, h = 5%, acid correction = a = 60 cal, fuse wire correction = f = 10
cal, cooling correction = t.dc = 0.02°C

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 ∴ GCV = 6946.31 Cal/gm

NCV = GCV – 0.09 h × Latent Heat

= 6946.31 – 0.09 × 5 × 587

= 6682.16 cal/gm

= 6682.16 × 4.18

= 27931.45 Joules/gm

Determination of G.C.V. of volatile Liquid/ Gaseous Fuels by Boy’s Gas Calorimeter

Principle of Boy’s Calorimeter:

A gaseous fuel is burnt at a known constant rate in the calorimeter under such conditions that
entire amount of heat produced is absorbed by circulating water.

Construction of Boy’s Calorimeter:

Gas burner: There is a gas burner in which a known volume of gas is burnt at a known pressure.
The gas is burnt at the rate of 3 to 4 litre per minute.

Combustion chamber (chimney): Around the burner there is a combustion chamber which has
a copper tubing coiled inside as well as outside of it. Water enters from top of the outer coil,
moves to bottom of chimney and then goes up through the inner coil to the exit at top.

Thermometers: There are two thermometers to measure temperatures of inlet (t1) water and
outlet (t2) water.

Insulating cover: The assembly is covered with an insulator to detach combustion chamber
from atmosphere. There is a hole on top for exhaust gas, water inlet and condensed steam comes
out from bottom outlet.

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 Boy’s gas calorimeter

Working of Boy’s Calorimeter

For initial warm up period, circulation of water and burning of gaseous fuel are continued at
constant rate for about 15 minutes.

The rate of fuel burning and water circulation are controlled so that the exit water leaves the
apparatus nearly at constant pressure.

After the steady conditions are reached, simultaneously note the following:

a) Volume of gas burnt at given temperature and pressure in certain time period.

b) Quantity of water passed through coil during this period.

c) Mass of water condensed from product gas during the period.

d)The steady rise in temperature of water (t2 – t1) °C.

Calculations:

First convert the volume of gas burnt to volume of gas at STP. Let this STP volume be V m3.

Let, W = mass of cooling water used in the period of observation, in kg.

Let m = mass of water condensate in kg.

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L = G.C.V. of the fuel.

Heat produced by combustion of fuel = heat absorbed by cooling water

V x L = S. W (t2 – t1); specific heat of water = 1kcal/kg

VL = W (t2 – t1); L = W (t2 – t1) / V kcal/ m3 or L = 4.18 W (t2 – t1) / V kJ/ m3

Mass of the steam condensed per m3 of gas = m/V kg

Latent heat of steam per m3 of gas = m x 587/V kcal

NCV/ LCV = [GCV – m x 587/ V] kcal/ m3

Ex. Observations in the Boy’s gas calorimeter experiment on a gaseous fuel are given below;
Find the G.C.V. and N.C.V. of the fuel, Volume of gas burnt (STP) = 0.08 m3
Mass of cooling water used = 29.5 kg
Rise in temperature of circulating water = 9.1°C
Mass of steam condensed = 0.04 kg.

Ans: volume of gas burnt = V = 0.08 m3, mass of cooling water = W = 29.5 kg, rise in
temperature = (t2 – t1) = 9.1°C, mass of steam condensed = m = 0.04 kg.

GCV = 29.5 x 9.1 / 0.08 = 3355.6 kcal/ m3

NCV = L – m/V 587 = 3355.6 – 0.04/0.08 x 587 = 3062.1 kcal/ m3

Ex. In Boy’s gas calorimeter’s experiment when 0.1m3 of a fuel gas is burnt during which 25 kg
of water is circulated. Temperature of incoming water and outgoing water is 20°C and 33°C
respectively. Weight of steam condensed is 250 gm. Calculate gross calorific value and net
calorific value, if heat liberated in condensing water vapour and cooling the condensate is 586
kcal/kg.

Ans: Volume of gas burnt = 0.1 m3 = V

Mass water circulated = W = 25 kg

Steady rise in temperature = (t 2 – t1) = 33 – 20 = 13°C

Weight of steam condensed = m = 250 gm = 0.25 kg

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GCV = 25 x 13 / 0.1 = 3250 kcal/ m3

NCV = L – m/V 587 = 3250 – 0.25/0.1 x 586 = 3250 – 1465 = 1785 kcal/ m3

Coal

Coal is highly carbonaceous matter formed from vegetable matter buried in geomorphic
changes, under pressure, by action of aerobic and anaerobic bacteria for a long time.

The process of formation of coal from plant matter is called as coalification.

The sequential stages involved in the conversion include peat, lignite, bituminous coal and
anthracite coal. This progressive transformation of wood to anthracite results in the decrease in
moisture content, hydrogen, oxygen, nitrogen, sulphur, volatile matter with corresponding
increase in carbon content, calorific value and hardness.

Analysis of Coal

Two types of analysis: Proximate and Ultimate

Proximate Analysis of Coal

Proximate analysis is the study or analysis of coal sample in which

(i) Moisture % (ii) Volatile matter % (iii) Ash % (iv) Fixed carbon %,
are found out.

Moisture %

(a)Principle: All moisture in coal escapes on heating coal at 110°C for 1 hour.

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(b)Method: A known weight of powdered and air dried coal sample is taken in a crucible and it is
placed in an electric hot oven for 1 hour at 110°C. Then the coal is cooled in a desiccator and
weighed. If the initial weight of the coal is m gm and final weight is m1 gm. The loss in weight
(m – m1) corresponds to moisture in coal.

Volatile Matter (V.M.) %

(a)Principle: At 925°C, coal molecules undergo thermal degradation to produce volatile matter.

(b)Method: Moisture free coal left in the crucible in first experiment (m1) is covered with a lid
loosely. Then it is heated at 925°C in a muffle furnace for 7 minutes. The crucible is taken out
and cooled in a desiccator. Then it is weighed (m2 gm.). The loss in weight (m1 – m2) is due to
loss of volatile matter present in the coal sample. (Volatile matter in coal during burning of coal,
escapes without combustion, in the form of smoke).

The volatile matter % can also be determined by taking the fresh weight of the air dried coal but
the loss in weight at 925°C, will be due to loss of moisture and volatile matter. If w is the weight
of air dried coal and w1 is the mass of coal left at 925°C heating, then

Ash %

(a)Principle: Inorganic matter in the coal gets oxidized to form metal oxides and silica, which is
non-combustible and left as ash.

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(b)Method: The residual coal in the above experiments is heated and burnt in an open crucible at
above 750°C for half hour. The coal gets burnt. The ash left in crucible is cooled in a desiccator
and weighed (m3 gm).

Fixed carbon %

Fixed carbon % = 100 – (% Moisture + % V. M. + % ash)

Significance (Importance of Proximate Analysis)

1. Moisture

 Moisture is evaporated during burning of coal and in doing so, it uses some part of the
liberated heat. Thus, it reduces calorific vale.
 It increases ignition point of coal.
 It adds to handling, storage and transportation cost by its weight.
 Hence, a coal with lower moisture % is of better quality.

2. Volatile Matter

 Volatile matter is not originally present in the coal but it is formed and escapes during
combustion process. It decreases calorific value of coal.
 It elongates flame and decreases flame temperature.
 It forms smoke and pollutes air.
 Hence, a coal with lesser V.M. is better quality coal.
 However, the coals containing 15-25% of V.M. on carbonization give coke oven gas
which is the source of various organic aromatic chemicals.

3. Ash

 Ash reduces calorific value of coal as ash is non-burning part in coal. It contains SiO2,
Al2O3, CaO, MgO, etc.
 Ash involves additional cost for its disposal.
 Ash fuses to form clinker at high temperature, obstructing the air supply to coal burning
in furnace.
 It increases transportation, handling and storage cost on account of its weight.
 Hence, lesser the ash %, better is the quality of coal.

4. Fixed Carbon

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  Carbon is the burning part in coal. Fixed carbon represents the quantity of carbon in coal
that can be burnt by primary current of air. Thus higher the FC%, higher is calorific
value. Hence a good quality coal contains high FC%

Ultimate Analysis of Coal

Definition: The analysis of coal in which percentages of C, H, N, S, O and ash are found out, is
known as ultimate analysis.

Estimation of Carbon and Hydrogen in coal (by combustion method)

(a) Method for determination :

 A known weight of powdered and air dried coal sample is burnt in the presence of pure
oxygen, in a combustion apparatus. C and H are converted to CO2 and H2O vapours
respectively.
 The gaseous products are allowed to pass through first preweighed U-tube containing
anhydrous CaCl2 or magnesium per chlorate (absorbing H2O vapours) and then through
the KOH solution in a preweighed U-tube (absorption of CO2).
 The increase in weight of U-tube containing anhydrous CaCl2 corresponds to weight of
H2O formed and increase in weight of U-tube containing KOH solution corresponds to
CO2 formed, by combusting the coal sample.

(b) Reactions :

(c) Formulae for calculation :

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 Combustion apparatus

Estimation of Sulphur

 Sulphur is determined from the washings obtained from the known mass of coal, used in
a bomb calorimeter for determination of calorific value.
 During this determination, sulphur is converted into its sulphate. The washings are treated
with barium chloride solution, barium sulphate is precipitated. The precipitate is filtered,
washed and dried.

S oxidation SO2 oxidation SO3 H2O in bomb H2SO4 BaCl2 BaSO4 ppt
Calorimeter

32 X wt. of BaSO4 formed X 100

%S =
233 X wt. of coal sample taken

Estimation of Nitrogen
Principle:
N in coal gets converted to ammonium sulphate, by action of hot concentrated H2SO4 and then
on treatment with alkali solution, equivalent amount of NH 3 is liberated.

Method:

 A known weight of powdered and air dried coal is heated with concentrated H 2SO4 along
with K2SO4 catalyst in a long necked Kjeldahl flask.
 After the contents become clear, it is treated with alkali solution in a round bottom flask.
The ammonia (basic gas) liberated is absorbed in a known volume of standard acid
solution.
 The unused acid is determined by back titration with NaOH solution.
 For determining the amount of acid neutralized by ammonia, a blank titration is carried
out. In this the same quantity of acid as used to absorb ammonia is titrated against the
same standard NaOH.

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From the amount of acid neutralized by NH3, the amount of NH3 liberated and hence the amount
of nitrogen present in coal can be calculated.

i)Weight of coal = W gm.

ii)V2 ml = (Blank titration reading).

iii)V1 ml = (Back titration reading, after passing NH3)

iv)Volume of the acid consumed by NH3 = (V2 – V1) ml.

v)N = normality of standard acid used or standard base used for back titration.

Formula:

Estimation of nitrogen in coal

Estimation of Ash
Ash is determined in the same way as carried out in proximate analysis.

Estimation of Oxygen
It is obtained by the difference

% of O = 100 - % of (C + H + S + N + ash)
Significance (Importance of Ultimate Analysis)
Carbon and hydrogen: the quality and calorific value of coal is directly related to the
percentage of carbon and hydrogen. Calorific value of hydrogen is four times greater than that of
carbon. So, it greatly reflects in calorific value of coal. However hydrogen is mostly linked with

16
volatile matter and therefore is a deciding factor in designing combustion chamber. Higher the %
C and H, better the quality of coal.

Sulphur: although, sulphur contributes to calorific value, yet on combustion it produces acidic
oxides leading to corrosion of equipment and atmospheric pollution (causing acidic rains). Hence
lesser the % S, better the quality of coal.
Nitrogen: Nitrogen has no calorific value hence its presence in coal is undesirable. Hence lesser
the % N, better the quality of coal.
Ash: ash reduces the calorific value of coal. It also increases transportation, handling cost. Hence
lesser the % Ash, better the quality of coal.
Oxygen: higher oxygen in coal is characterized by higher inherent moisture leading to low
calorific value and low caking property. Hence lesser the % O, better the quality of coal.

Ex. 0.25 gm of a coal sample on burning in a combustion chamber in the current of pure oxygen
was found to increase weight of U-tube with anhydrous CaCl2 by 0.075 gm and of KOH U-tube
by 0.52gm. Find C and H percentages in coal.

Ans: Weight of coal = w = 0.25 gm

Increase in weight of U - tube containing CaCl2 = Weight of moisture formed = 0.075 gm

Increase in weight of KOH U-tube = Weight of CO2 formed = 0.52 gm

C % = 12 x increase in weight of KOH U-tube x 100 = [(12 x 0.52) / (44 x 0.25)] x 100 =
56.72%

44 x weight of coal

H % = 2 x increase in weight of CaCl2 U-tube x 100 = [(2 x 0.075) / (18 x 0.25)] x 100 = 3.33%

18 x weight of coal

Ex. One gram of coal sample was burnt in oxygen. Carbon Dioxide was absorbed in KOH and
water vapour in CaCl2. The increase in weight of KOH and CaCl2 was 3.157 and 0.504 gm
respectively. Determine % C and % H in the sample.
(C % = 86.1, H% = 5.6)

Ans: Weight of CO2 absorbed in KOH = 3.157 gm

Weight of H2O absorbed in CaCl2 = 0.504 gm

Weight of coal burnt = 1.0 gm

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Ex. 1.0 gm of coal sample was completely combusted in bomb calorimeter. The solution from
the bomb pot on treatment with BaCl2 solution formed a precipitate of BaSO4. After washing and
drying the weight of BaSO4 precipitate was found to be 0.3 gm. Calculate % of Sulphur in coal.

Ans: Weight of coal burnt = 1.0 gm

Weight of BaSO4 precipitate formed = 0.3 gm

S % = 32 x Weight of BaSO4 precipitate x 100 = [(32 x 0.3) / (233 x 1.0)] x 100 = 4.12 %

233 x weight of coal

Ex. 1.56 gm of the coal was kjeldahlized and NH3 gas thus evolved was absorbed in 50 ml 0.1 N
HCl. After absorption, the residual acid required 6.25 ml of 0.1 N NaOH for neutralization.
Calculate % N.

Ans: Weight of coal = 1.56 gm, amount of base required for back titration of acid = 6.25 ml,
blank titration reading = 50 ml, normality of acid or base = 0.1 N.

% N = [(blank titration reading – back titration reading) x normality x 1.4] / initial weight of coal

= [(50-6.25) x 0.1 x 1.4] / 1.56 = 3.92 %

Ex. 2.4 gm of coal sample was weighed in silica crucible. After heating for one hour at 110°C,
the residue weighed as 2.25 gm. The crucible was then covered with a vented lid and strongly
heated for exactly 7 minutes at 950°C. The residue weighed as 1.42 gm. The crucible was further
heated without lid until a constant weight was obtained. The last residue was found to be 0.22
gm. Calculate the % results of the above analysis.

Ans: W = weight of coal = 2.4 gm

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Petroleum or Crude Oil

 Petroleum is a dark, greenish brown, viscous liquid that is found underground.

 It comprises hydrocarbons such as Straight paraffins or cyclo-paraffins such as methane,
ethane, propane, butane, iso-butane, pentane, hexane. Olefins such as ethylene, butene,
isobutene and acetylene, butadienes. Aromatics such as benzene, naphthalene,
cyclohexane, methyl cyclopentane. Some organic compounds containing nitrogen,
oxygen and sulphur.
 It is an important primary liquid fuel. It is a dark greenish-brown viscous oil found deep
in the earth’s crust.
 It is formed millions of years ago by anaerobic decay of debris of plants and animals
(which are buried due to volcanoes) under the influence of high temperature and pressure.
 Mining of petroleum is done by drilling holes in the earth’s crust. Through the holes,
pipes are sunk up to oil bearing rocks.
 Usually crude oil gushes out itself because of pressure of natural gas or it may be
mechanically pumped out using air lift pumps. The oil then is conveyed to refinery
through pipelines.

Composition of crude oil

Elemental composition

Element Percent range

Carbon 80 to 87%
Hydrogen 11 to 15%
Nitrogen 0.1 To 3.0%
Oxygen 0.1 To 0.5%

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 Sulfur 0.1 to 3.0%
Metals < 0.1%

Refining of petroleum

Refining or fractionation is the process of separation of various fractions from crude oil, on the
basis of fractional distillation along with separation of impurities. The crude oil contains a large
number of hydrocarbons but by the process of refining, they are divided into few groups of
molecular weights or boiling point ranges.

The refining consists of-

(i) Removal of water (by Cottrell’s process): crude oil obtained from oil well is in form of
stable emulsion of oil and salt water. First the emulsified water along with salts dissolved, is
removed by passing the crude oil between highly charged electrodes. The colloidal water
droplets unite on positive electrode to form large drops which separate from oil.

(ii) Removal of sulphur: Then the crude oil is treated with hot CuO. It results in the formation
of copper sulphate precipitate which is removed by filtration.

(iii) Fractional Distillation: The principle of fractional distillation is that the vapours of higher
boiling point compounds first get condensed into liquid, during the stepwise cooling. Various
useful fractions like petrol, diesel, kerosene etc. are obtained by fractionation.

(b) Portion of fractionating tower

(a) Fractionating tower

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Working

 The crude oil is heated at about 400°C in a furnace to convert it into vapours. Asphalt or
coke is left as residue. The vapours enter into the fractionating column at the bottom
which is a tall, cylindrical tower in which number of horizontal stainless steel trays are
fixed at short distance.
 Each tray is provided with bubble cup which is covered with a loose cap. The vapours
travel upwards through the bubble cups and gradually get cooled. The vapours of organic
compounds with higher b.p. get condensed in bubble cups and the liquid deposits on the
trays.
 The uncondensed vapours rise up and get condensed turn by turn on upper bubble trays.
There is vigorous bubbling action on each tray. In case, large part of the vapours get
condensed on a tray, then the extra liquid flows down to higher temperature lower trays
and gets evaporated.
 From some bubble trays, the fractions like petrol, diesel, kerosene, naphtha, heavy oil etc.
are taken out. Finally a small part of vapours comes out as uncondensed gases from the
top which are liquefied (LPG).
 Heavy oil fraction can be further fractionated to get lubricating oils, Vaseline, wax. The
petrol obtained from refinery is called as straight run petrol but is not a good quality
petrol.
 It is possible to convert any higher boiling fraction into petrol or LPG by the process
known as cracking.
 Fractions of Petroleum refining

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Gaseous Fuels

Gaseous fuels have high calorific value, burn clean without smoke or ash. Their combustion can
be easily controlled.

Highly inflammable hence special care is required for their storage.

Compressed Natural Gas (CNG):

Compressed natural gas is derived from ‘dry’ natural gas. CNG is natural gas compressed to a
high pressure of about 1000 atmospheres. A steel cylinder containing 15 kg of CNG contains
about 2 x 104 L or 20 m3 of natural gas at 1 atmospheric pressure. Its main constituent of CNG is
methane.

Composition: CH4 = 88 %, C2 to C4 hydrocarbons = 10 %, CO = 0.5 to 1%

Properties:

 CNG is comparatively much less pollution causing as it produces less CO, ozone and
hydrocarbons during combustion.
 During its combustion, no sulphur and nitrogen gases are evolved.
 No carbon particles are ejected during combustion.
 It is less expensive than petrol and diesel.
 The ignition temperature of CNG is 550 0C.
 CNG is a better fuel than petrol/diesel for automobiles.
 CNG mixes better with air than liquid fuels.

Uses:

 CNG is used as automobile fuel.

 It can be used as Industrial fuel.
 Used for production of carbon black and hydrogen.

Hydrogen gas as a future fuel.

Hydrogen is often considered as a future fuel because-

It is nontoxic and clean burning, it has high calorific value as compared to fossil fuels, it is most
abundant element on earth.

Production of Hydrogen: hydrogen can be produced from electrolysis of water, by water

splitting using solar energy. However the most efficient method is the steam reforming of
hydrocarbons and coke (coal and steam method, coal gasification)

Steam reforming of Hydrocarbons (methane).

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It is the process of reacting steam with hydrocarbons in the presence of a catalyst at high
temperature to obtain hydrogen and carbon oxides.

Feed = Sulphur free natural gas (CH4), naphtha, petroleum fraction

Catalyst = Ni or FeO (reforming), FeO (for shift reaction)

Temperature = 800°C (reforming), 370°C (shift reaction)

Pressure = lesser than 1 atmosphere.

(i) Steam reforming :

CH4 + H2O CO + 3 H2

In shift reaction, more steam is mixed with (CO + H2) mixture to get higher % H2 mixture.

(ii) Shift reaction : This reaction produces more hydrogen by passing steam in the
mixture of CO and H2, in the presence of FeO catalyst at 370 °C

CO + H2O ⇌ CO2 + H2

Then the (CO2 + H2) mixture is compressed and cooled to get liquid CO2 and H2 gas. The
alternate way to remove CO2 from mixture is scrubbing the (CO2 + H2) mixture with alkali
solution or a solvent which can be recycled after evaporating out CO2.

Steam reforming of coke (coal and steam).

Coke is obtained by carbonization of coal. Hydrogen can be produced by passing steam over red
hot coke. Coal on heating with superheated steam in presence of Ni catalyst produces water gas
at 1000oC.

The water gas is then converted into CO2 and H2 by shift reaction in presence of FeO catalyst at
3700C.

C + H2 O Ni CO+H2 FeO catalyst, 3700C CO2+2H2

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Then the (CO2 + H2) mixture is compressed and cooled to get liquid CO2 and H2 gas. The
alternate way to remove CO2 from mixture is scrubbing the (CO2 + H2) mixture with alkali
solution or a solvent which can be recycled after evaporating out CO 2. H2 obtained is less &
associated with impurity of H2S, SO2. This method is less preferred although cheap.

Thermal decomposition of hydrocarbons.

CnH2n+2 nC + (2n+2)H2

In thermal cracking of natural gas or hydrocarbons of petroleum fractions at 800-900°C H2 is

obtained as a by-product. It is further purified by;

1. Liquification process
2. Diffusing H2 gas through thin and low porosity Pd films at 300 °C

Electrolysis.

Electrolysis of acidified water or ammonia can produce Hydrogen at cathode at higher purity
(99.9 %).
Cathode (Fe), anode (Ni), Conditions 2V, 80 °C

2H2O 2H2 + O2

2NH3 N2 +3H2

It is not preferred because, it is costly

Storage and Transportation of H2

Hydrogen is stored in different ways i.e. high pressure storage, cryogenic storage and storage in
chemical compounds (which release H2 on heating.) The storage in chemicals and cryogenic
storage are compact storages.

Physical storage

 In form of compressed H2.

 In form of liquefied H2.
 By adsorption on porous carbon material.

Chemical storage

 In form of metal hydrides.

 In form of sodium alanates.

Difficulties in storage and transportation of hydrogen:

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  Hydrogen is the lightest gas. 2 gm of H2 occupy a volume of 22.4 lit at STP. Hence, it has
to be stored in cylinders in compressed form the cost of compression is high.
 High pressure H2 storage in steel cylinders leads to decarburisation because of which
steel becomes brittle.
 Hydrogen gas on cooling at -252.6 ᵒC can be converted to its liquid form. Liquid H2 is
stored and transported in cryogenic tanks. Also, cost of cooling is very high.
 Hydrogen gas is highly inflammable.
 Chemical storage of hydrogen is a slow process and its recovery is also slow.

Uses of Hydrogen as a fuel:

 H2 can be used as a rocket fuel.

 It can be used as a fuel in internal combustion engine which is more efficient, less
polluting and safer than fossil fuel.
 It is also the best fuel for fuel cells, which are used as emergency source of electricity for
various purposes and also for automobiles.
 Hydrogen gas can be used as domestic fuel such as in water heaters.
 It has wide applications in industries such as; in fertilizer industries, for annealing of
metals, for cutting of metals, heating of furnaces, etc.

Alternative fuel:

Power Alcohol

When ethyl alcohol is used as fuel in internal combustion engine, around 5-25% with petrol, it is
called as power alcohol.

Alcohol is considered as an excellent alternative motor fuel for petrol engines, as it contains
oxygen which contributes to combustion.

Production of ethyl alcohol: In India, ethyl alcohol is obtained from molasses which contains
sucrose. Sucrose is converted into glucose and fructose by means of enzyme invertase from yeast
at 30ᵒC. The enzyme zymase (from yeast) converts glucose and fructose into ethyl alcohol and
carbon dioxide by fermentation.

C12H22O11 + H2O C6H12O6 + C6H12O6

sucrose invertase glucose fructose
from molasses
Zymase

2C2H5OH + 2CO2
(18-20% alcohol)

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Fermented liquid (containing 18-20% alcohol) is then subjected to fractional distillation to give
rectified spirit (90-95% alcohol). For getting 100% alcohol (absolute alcohol) rectified spirit is
treated with lime and distilled.

Advantages of Power Alcohol:

 Ethyl alcohol has good antiknocking property and its octane number is 90, while the
octane number of petrol is about 60-70. Therefore addition of ethyl alcohol to petrol,
increases its octane number.
 Alcohol has property of absorbing any traces of water if present in petrol.
 Ethyl alcohol contains ‘O’ atoms, which help for complete combustion of power alcohol
and the polluting emissions of CO, hydrocarbon, particulates are reduced largely.
 Use of ethyl alcohol in petrol reduces our dependence on foreign countries for petrol and
saves foreign currency considerably.
 Ethanol is renewable source of energy.
 Deposition of carbon and the gummy products on internal parts of engine, is reduced
when alcohol is used as a fuel.

Disadvantages of Power Alcohol:

 Ethyl alcohol has calorific value of 7000 cal/gm much lower than calorific value of
petrol 11500 cal/gm.
 Ethyl alcohol has high surface tension and its atomization, especially at lower
temperatures, is difficult causing starting trouble.
 Ethyl alcohol may undergo oxidation to form acetic acid, which corrodes engine parts.
 Ethyl alcohol obtained by fermentation process directly cannot be mixed with petrol but
it has to be dehydrated first.
 As ethyl alcohol contains ‘O’ atoms, the amount of air required for complete combustion
of power alcohol is lesser and therefore carburettor and engine needs to be adjusted or
modified, when only ethyl alcohol is used as fuel

Biodiesel

 Biodiesel is a biofuel obtained from renewable sources of energy such as vegetable oils
or animal fats by transesterification.
 Chemically biodiesel is the mixture of methyl esters of long chain carboxylic acids.
Biodiesel is obtained by transesterification of vegetable oil or animal fats with methyl
alcohol using catalyst sodium methoxide. (Transesterification is the process of converting
one ester to another ester). During the reaction we get water soluble glycerol and a small
amount of sodium soaps. The water soluble part is easily separated by washing the
mixture with water and biodiesel is left behind.
 Vegetable oils like soyabean oil, palm oil, sunflower oil, cottonseed oil, etc. can be used
for the preparation of biodiesel. Normally non edible vegetable oils are preferred.

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Reaction for Biodiesel Formation:
CH2 – COOR1 R1COOCH3 CH2OH
CH3ONa +
CH - COOR2 + 3 CH3OH R2COOCH3 + CHOH
+
CH2 - COOR3 R3COOCH3 CH2OH

Oil Methanol Biodiesel Glycerol

Compounds present in biodiesel are like,

methyl palmitate H 3C - (CH2)14 - COOCH3

methyl stearate H3C - (CH2)16 - COOCH3

methyl oleate H3C - (CH2)7 - CH = CH - (CH2)7 - COOCH3

methyl linoleate H3C - (CH2)5 - (CH = CH)2 - (CH2)7 - COOCH36

Preparation of biodiesel:

 Filtered, cheap, non-edible vegetable oil or animal fat oil is taken in reaction vessel and
heated to about 100ᵒC to remove moisture if any.
 About 2% sodium methoxide and 20% methanol is added to the reaction vessel.
 The mixture is refluxed at 60-70ᵒC for about 1-7 hours, depending on the type of oil used.
 Mixture is cooled and mixed with water to remove water soluble glycerol and soap if
formed.
 The water insoluble biodiesel is separated using separating funnel and suitable
antioxidants are added to it to avoid oxidation and increase stability.

Advantages of Biodiesel:

 Biodiesel is cheaper, as it is manufactured from cheap, nonedible or waste oil or animal

fats.
 It has high cetane numbers 46 to 54 and high Calorific value of about 40 kJ/liter.
 It is regenerative and environment friendly.
 It does not give out particulate and CO pollutants, as O atoms in biodiesel help for
complete combustion.
 It has certain extent of lubricity, due to higher oiliness of the esters.
 Its use provides good market to vegetable oils and reduces our dependence on diesel on
foreign countries, saving currency.
 It is clean to use biodiesel in diesel engines.
 Its B5, B20, B100 blends can be used. B100 blend requires engine modification.

Limitations of Biodiesel:

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 Cloud and pour points of biodiesel are higher than diesel and can cause problem in fuel
flow line. So it cannot be used in cold regions.
 Biodiesel may have dissolving action on rubber hoses, gaskets.
 Biodiesel is not compatible with some metals and can become gummy.

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