Fuels and Combustion

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Sub Topics
⚫ Fuels –Introduction, definition, classification, calorific value, Gross and
Net, theoretical calculation.
⚫ Solid fuel- Coal- classification ,Analysis- Proximate and ultimate
⚫ Carbonisation process-Metallurgical coke-Manufacture of coke by Otto
Hoffmann process.
⚫ Liquid fuel-Petroleum processing and fractions-manufacture of synthetic
petrol by Bergius process. Knocking in SI and CI engines. Octane and
cetane number
⚫ Gaseous fuels - CNG, LPG, Water gas and a producer gas.
⚫ Power alcohol and Biodiesel
⚫ Combustion- Introduction and theoretical calculation of air.- Problems
⚫ Ignition Temperature and explosive range. Flue gas analysis by Orsat
method.

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INTRODUCTION

⚫ Fuels –Introduction, definition, classification, calorific value, Gross and

Net, theoretical calculation.
⚫
⚫ A fuel is a combustible substance containing carbon as the main
constituent which on proper burning gives large amount of heat that can
be used economically for domestic and industrial purposes. During the
process of combustion of a fuel, the atoms of carbon, hydrogen, etc
combine with oxygen with simultaneous liberation of heat. The
calorific value of a fuel depends mainly on the two elements.
⚫ C + O2 CO2 + 94 kcals.
⚫ 2H2 + O2 2H2 O + 68.5 kcals.
⚫
⚫ So, carbon compounds have been used for many centuries as the source
of heat and energy.
⚫ The main source of fuel is coal and petroleum. These are stored fuels
available in earth's crust and are generally called fossil fuels because
they were formed from the fossilised remains of plants and animals.

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Classification of Fuels
⚫ 1. Primary fuels which occur in nature as such, e.g. coal, petroleum and
natural gas.
⚫ 2. Secondary fuels which are derived from the primary fuels, e.g. coke,
gasoline, coal gas, etc.
⚫ Both primary and secondary fuels may be further classified based upon their
physical state as
⚫ (i) solid fuels (ii) liquid fuels and (iii) gaseous fuels.
CALORIFIC VALUE
⚫ Calorific value of a fuel is "the total quantity of heat liberated, when a
unit mass (or volume) of the fuel is burnt completely."
Units of heat :
(1) 'Calorie' is the amount of heat required to raise the temperature of one
gram of water through one degree Centigrade (15-16°C).
(2) "Kilocalorie" is equal to 1,000 calories. It may be defined as 'the quantity
of heat required to raise the temperature of one kilogram of water through
one degree Centigrade. Thus: 1 kcal = 1,000 cal
(3) "British Thermal unit" (B.T.U.) is defined as "the quantity of heat
required to raise the temperature of one pound of water through one degree
Fahrenheit (60-61°F). This is the English system unit.
1 B.T.U. = 252 cal = 0.252 kcal 1 kcal = 3.968 B.T.U.
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 HCV and LCV

Higher or gross calorific value:

⚫ Usually, all fuels contain some hydrogen and when the calorific value of
hydrogen-containing fuel is determined experimentally, the hydrogen is
converted into steam. If the products of combustion are condensed to the
room temperature (15°C or 60°F), the latent heat of condensation of steam
also gets included in the measured heat, which is then called "higher or
gross calorific value". So, gross or higher calorific value (HCV) is "the total
amount of heat produced, when unit mass/volume of the fuel has been burnt
completely and the products of combustion have been cooled to room
temperature"(i.e., 15°C or 60°F ).
Lower or net calorific value (LCV)
⚫ In actual use of any fuel, the water vapour and moisture, etc., are not
condensed and escape as such along-with hot combustion gases. Hence, a
lesser amount of heat is available. So, net or lower calorific value (LCV) is
"the net heat produced, when unit mass /volume of the fuel is burnt
completely and the products are permitted to escape".
⚫ Net calorific value= Gross calorific value - Latent heat of condensation of
water vapour produced
⚫ = GCV - Mass of hydrogen per unit weight of the
fuel burnt x 9 x Latent heat of condensation of water vapour

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⚫ Dulong's formula for calorific value from the chemical
composition of fuel is :

⚫ HCV = 1/100 [8,080 C + 34,500 (H – O/8)+ 2,240 S] kcal/kg

⚫ where C, H, O, and S are the percentages of carbon, hydrogen,

oxygen and sulphur in the fuel respectively. In this formula, oxygen
is assumed to be present in combination with hydrogen as water,
and

⚫ LCV = [ HCV - 9H/100 x 587] kcal/kg = [HCV - 0.09 H x 587]

kcal/kg

⚫ 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.

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Solid fuel

COAL
⚫ Coal is regarded as a fossil fuel produced from large accumulations of
vegetable debris due to partial decay and alteration by the action of heat
and pressure over millions of years. Coal is a highly carbonaceous matter
that has been formed as a result of alteration of vegetable matter (e.g.,
plants) under certain favourable conditions. It is chiefly composed of C, H,
N, and 0, besides non-combustible inorganic matter.
Classification of Coal
⚫ Coals are classified on the basis of their rank. Rank is defined as the degree
or extent of maturation and is therefore a qualitative measure of carbon
contents. Peat, lignite and sub-bituminous coals are referred as low rank
coals while bituminous coals and anthracites are classed as high rank. In
European terminology, the lignite and sub-bituminous coals are called soft
coals while bituminous coals and anthracite coals are termed as hard coals.
In North American terminology, the coal series is written as
⚫ Wood peat lignite bituminous
anthracite.

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Analysis of Coal

⚫ In order to assess the quality of coal the following two types of analysis
are made.

⚫ 1. Proximate Analysis It includes the determination of moisture,

volatile matter, ash and fixed carbon. This gives quick and valuable
information regarding commercial classification and determination of
suitability for a particular industrial use.

⚫ 2. Ultimate Analysis It includes the determination of carbon, hydrogen,

nitrogen, sulphur and oxygen in coal. Since it is used
⚫ For the determination of elements present in the coal, it is also called
elemental analysis. This analysis gives exact results and are useful in
calculating the calorific value of coal using Dulong's formula.

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Proximate analysis
⚫ (1) Moisture: About 1 g of finely powered air-dried coal sample is weighed in
a crucible. The crucible is placed inside an electric hot air-oven, maintained at
105° - 110°C. The crucible is allowed to remain in oven for 1 hour and then
taken out, cooled in a desiccator and weighed. Loss in weight is reported as
moisture (on percentage-basis).

⚫ Percentage of moisture = Loss in weight x 100

Wt. of coal taken
⚫ (2) Volatile matter: The dried sample of coal left in the crucible in (1) is then
covered with a lid and placed in an electric furnace (muffle furnace),
maintained at 925°± 20°C. The crucible is taken out of the oven after 7 minutes
of heating. The crucible is cooled first in air, then inside a desiccator and
weighed again. Loss in weight is reported as volatile matter on
percentage-basis.
Percentage of volatile matter=
Loss in weight due to removal of volatile matter x 100
Wt. of coal sample taken

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⚫ (3) Ash: The residual coal in the crucible in (2) is then heated without
lid in a muffle furnace at 700 ± 50° C for 1/2 hour. The crucible is then
taken out, cooled first in air, then in desiccator and weighed.

⚫ Heating, cooling and weighing is repeated, till a constant weight is

obtained. The residue is reported as ash on percentage-basis.

⚫ Percentage of ash = Wt. of ash left x 100

⚫ Wt. of coal taken

(4) Fixed carbon: Percentage of fixed carbon = 100 - % of (moisture +

volatile matter + ash)
⚫ high percentage of rued carbon is desirable.

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Importance of proximate analysis

⚫ Proximate analysis provides following valuable informations in assessing

the quality of coal:

⚫ (1) Moisture: Moisture lowers the effective calorific value of coal.

Moreover, it quenches the fire in the furnace. Hence, lesser the moisture
content, better the quality of coal as a fuel. However, presence of moisture,
up to 10%, produces a more uniform fuel-bed and less of "fly-ash".

⚫ (2) Volatile matter: A high volatile matter containing coal burns with a long
flame, high smoke and has low calorific value. Hence, lesser the volatile
matter, better the rank of the coal. Higher volatile content in coal is
undesirable.

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⚫ A high volatile matter content means that high-proportion of fuel will
be distilled and burned as a gas or vapour. The volatile matter present in
the coal may be combustible gases (such as methane, hydrogen, carbon
monoxide and other hydrocarbons) or non-combustible gases (like CO2
and N2). Volatile matter content is of special significance in coal gas
manufacture and in carbonization plants, particularly when by-product
recovery is the main object. Thus, high-volatile matter containing coals
do not cake well; whereas medium-volatile matter content coals are
capable of yielding hard and strong coke on carbonization.
⚫ (3) Ash is a useless, non-combustible matter, which reduces the
calorific value of coal. Moreover, ash causes the hindrance to the flow
of air and heat, thereby lowering the temperature. Also, it often causes.
trouble during firing by forming clinker), which block the inters paces
of the grate. This in-turn causes obstruction to air supply; thereby the
burning of coal becomes irregular. Hence, lower the ash content, better
the quality of coal. The presence of ash also increases transporting,
handling and storage costs. The presence of ash also causes early wear
of furnace walls, burning of apparatus and feeding mechanism.
⚫ (4) Fixed carbon: Higher the percentage of fixed carbon, greater is its
calorific and better the quality coal. Greater the percentage of fixed
carbon, smaller is the percentage of volatile matter. This also represents
the quantity of carbon (in coal) that can be burnt by a primary current
of air drawn through the hot bed of a fuel.

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Ultimate analysis
Carbon and hydrogen: About 1-2 g of accurately weighed coal sample is
burnt in a current of oxygen in a combustion apparatus. C and H of the
coal are converted into CO2 and H2O respectively. The gaseous products
of combustion are absorbed respectively in KOH and CaCl2 tubes of
known weights. The increase in weights of these are then determined.

⚫ Increase in weight of KOH tube x 12 x 100

Percentage of C = Weight of coal sample taken x 44

⚫ Increase in weight of CaCl2 tube x 2 x 100

Percentage of H = Weight of coal sample taken x 18

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 Significance of ultimate analysis

⚫ (1) Carbon and hydrogen: Greater the percentage of carbon and hydrogen
better is the coal in quality and calorific value. However, hydrogen is
mostly associated with the volatile matter and hence, it affects the use to
which the coal is put. Also higher percentage of carbon in coal reduces the
size of combustion chamber required. The amount of carbon, the major
combustible consti1fent of coal, depends on the type of coal and its
percentage increases with rank from lignite to anthracite. Thus, percentage
of carbon forms the basis of classification of coal.

⚫ (2) Nitrogen has no calorific value and hence, its presence in coal is
undesirable; thus, a good quality coal should have very little nitrogen
content.

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Nitrogen: About 1 g of accurately weighed powdered 'coal is heated with
concentrated H2SO4 along-with K2S04(catalyst) in a long-necked flask(called
Kjeldahl's flask). After the solution becomes clear, it is treated with excess of
KOH and the liberated ammonia is distilled over and absorbed in a known
volume of standard acid solution. The unused acid is then determined by back
titration with standard NaOH solution. From the volume of acid used by
ammonia liberated, the percentage of N in coal is calculated as follows:
Volume of acid used x Normality x 1.4
⚫ Percentage of N = Weight of coal taken

Sulphur is determined from the washings obtained from the known mass of coal,
used in a bomb calorimeter for determination of a calorific value. During this
determination, S is converted into sulphate. The washings are treated with
barium chloride solution, when barium sulphate is precipitated. This precipitate
is filtered, washed and heated to constant weight.

⚫ Weight of BaSO4 obtained x 32 x 100

Percentage of S = Weight of coal sample taken in bomb x 233

Ash determination is carried out as in proximate analysis.

Oxygen: It is obtained by difference.
⚫ Percentage of O = 100 - Percentage of (C + H + S + N + ash)

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⚫ (3) Sulphur, although contributes to the heating value of coal, yet on
combustion produces acids (S02 and S03), which have harmful effects of
corroding the equipments and also cause atmospheric pollution. Sulphur is,
usually, present to the extent of 0.5 to 3.0% and derived from ores like iron
pyrites, gypsum, etc., mines along-with the coal.
⚫ Presence of sulphur is highly undesirable in coal to be, used for making
coke for iron industry, since it is transferred to the iron metal and badly
affects the quality and properties of steel. Moreover, oxides of sulphur
(formed as combustion products) pollute the atmosphere and leads to
corrosion.

⚫ (4) Oxygen content decreases the calorific value of coal. High

oxygen-content coals are characterized by high inherent moisture, low
calorific value, and low coking power. Moreover, oxygen is in combined
form with hydrogen in coal and thus, hydrogen available for combustion is
lesser than actual one. An increase in 1% oxygen content decreases the
calorific value by about 1. 7% and hence, oxygen is undesirable. Thus, a
good quality coal should have low percentage of oxygen

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⚫ (5) Cost: Coke should be cheap and easily available near the site of the
metallurgical plant, so that the transportation cost is low.

⚫ (6) Combustibility: Coke should burn easily. The combustibility of coke

depends upon the nature of the coal, carbonization temperature and
reaction temperature. Cokes obtained from strongly coking coals are not as
combustible as those derived from weakly caking and non-caking coals. At
a given temperature, cokes obtained by high-temperature carbonization
process are less combustible compared to those obtained by
low-temperature carbonization. However, at high combustion temperatures
(800° - 900°C), all cokes appears to be equally reactive. At about 1,000°C,
it appears that the rate of combustion depends only on the rate of
oxygen/air supply.
⚫ (7) Calorific value: The calorific value of coke should be high.
⚫ (8) Low ash, S and P contents to avoid the incorporation of these in the
metal to be extracted.

⚫ (9) Reactivity to steam: Reactivity towards steam increases with the

reaction temperature and varies inversely with carbonizing temperature at
which the coke was produces. Moreover, coke derived from non-caking
coals are more reactive to steam than those derived from taking coals.

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 Liquid Fuels
The important liquid fuels are petroleum, petroleum products, tar,
alcohols. These are naturally found under the sea surface. Liquid fuels are
also obtained synthetically from' hydrogenation of coat. Liquid fuels find
extensive use in domestic and industrial fields.
Petroleum
⚫ Petroleum or crude oil is a dark greenish brown or black coloured viscous
oil found deep in earth's crust. The oil is usually floating over a brine
solution and above the oil, natural gas is present. Crude oil containing
mixture of paraffinic, olefinic and aromatic hydrocarbons with minor
amounts of organic compounds like N, 0 and S. The average composition of
crude oil is C =80 - 87 %, H =11-15%, S = 0.1 -3.5%, (N +O) =0.1- 0.5%.
a) Classification of petroleum
⚫ Petroleum is classified into three types based on variation of chemical
nature of crude oil found in the earth.
⚫ i) Paraffinic-base type crude oil: It contains saturated hydrocarbons from
CH4 to C35H72 and little amount of naphthalenes and aromatics.
⚫ ii) Asphaltic-base type crude oil: It contains mainly cycloparaffins or
naphthalenes with smaller amount of paraffins and aromatic hydrocarbons.
⚫ iii) Mixed-base type crude oil : It contains both paraffinic and asphaltic
hydrocarbons and are generally in the form of semi-solid waxes.
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 Knocking
⚫ Knocking is a kind of explosion due to rapid pressure rise occurring in an IC
engine.

⚫ In a petrol engine, a mixture of gasoline vapour and air at 1: 17 ratio is

used as fuel. This mixture is compressed and ignited by an electric spark.
The products of oxidation reaction (combustion) increases the pressure and
pushes the piston down the cylinder. If the combustion proceeds in a regular
way, there is no problem in knocking. But in some cases, the rate of
combustion (oxidation) will not be uniform due to unwanted chemical
constituents of gasoline. The rate of ignition of the fuel gradually increases
and the final portion of the fuel-air mixture gets ignited instantaneously
producing an explosive sound known as "Knocking". Knocking property of
the fuel reduces the efficiency of engine. So a good gasoline should resist
knocking.

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⚫ Chemical structure and knocking
⚫ The knocking tendency of fuel hydrocarbons mainly depends on
their chemical structures. The knocking tendency decreases in the
following order.
⚫ Straight chain paraffins> Branched chain paraffins> Cycloparaffins
> Olefins > Aromatics.

⚫ Improvement of antiknock characteristics

⚫ The octane number of fuel can be improved by
⚫ (i) blending petrol of high octane number with petrol of low octane
number, so that the octane number of the latter can be improved.
(ii) the addition of anti-knock agents like Tetra-Ethyl Lead (TEL).

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Anti-Knocking agent

⚫ LEADED PETROL (ANTI-KNOCK AGENT)

⚫ The anti-knock properties of a gasoline can be improved by the

addition of suitable additives. Tetraethyl lead (TEL) or (C2H5)4
Pb is an important additive added to petrol. Thus the petrol
containing tetra ethyl lead is called leaded petrol.

⚫ TEL reduces the knocking tendency of hydrocarbon. Knocking

follows a free radical mechanism, leading to a chain growth which
results in an explosion. If the chains are terminated before their
growth, knocking will cease. TEL decomposes thermally to form
ethyl free radicals which combine with the growing free radicals of
knocking process and thus the chain growth is stopped.

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⚫ Disadvantages of using TEL
⚫ When the leaded petrol is used as a fuel, the TEL is converted to
lead oxide and metallic lead. This lead deposits on the spark plug
and on cylinder walls which is harmful to engine life. To avoid this,
small amount of ethylene dibromide is added along with TEL. This
ethylene dibromide reacts with Pb and PbO to give volatile lead
bromide, which goes out along with exhaust gases.
⚫ But this creates atmospheric pollution. So nowadays aromatic
phosphates are used instead of TEL
⚫ (iii) Nowadays aromatic phosphates are used as antiknock agent
because it avoids lead pollution.

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OCTANE NUMBER (or) OCTANE RATING

⚫ Octane number is introduced to express the knocking characteristics

of petrol. It has been found that n-heptane knocks very badly and
hence, its anti-knock value has been given zero. On the other hand,
iso-octane gives very little knocking and so, its anti-knock value has
been given 100.

⚫ Thus octane number is defined as 'the percentage of iso-octane

present in a mixture of iso-octane and n-heptane.‘

⚫ Iso-octane (Octane number = 100)

⚫ CH3 – CH2 – CH2 – CH2 – CH2 – CH2 - CH3
⚫ n - heptane (Octane number = 0)

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CETANE NUMBER (or) CETANE RATING

⚫ Cetane number is introduced to express the knocking characteristics of

diesel. Cetane has a very short ignition lag and hence its cetane number is
taken as 100. On the other hand 2-methyl naphthalene has a long ignition
lag and hence its cetane number is taken as zero.
⚫ CH3 – (CH2)14 – CH3
⚫ n-cetane (hexa decane)
CH3

⚫ cetane number = 100

⚫ 2-methyl naphthalene (cetane number = 0)

⚫ Thus the cetane number is defined as "the percentage of hexa decane
present in a mixture of hexa decane and 2-methyl napthalene, which has
the same ignition lag as the fuel under test".
⚫ The cetane number decreases in the following order.
⚫ n-alkanes > Cycloalkanes > alkenes >branched alkanes >aromatics
⚫ The cetane number of a diesel oil can be increased by adding additives
called dopes.
⚫ Important dopes: Ethyl nitrate, Iso-amyl nitrate.
⚫

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COMPRESSED NATURAL GAS

⚫ Natural Gas is obtained from wells dug in the oil bearing regions. When
natural gas occurs along with petroleum in oil wells, it is called as ‘wet
gas’ and contains gaseous hydro carbons from C1 to C4. The wet gas is
then suitably treated to remove propane, propene, butane and butane, which
is used as LPG.When the natural gas is compressed, it is called
Compressed Natural Gas (CNG). The primary component present in CNG
is methane. It is mainly derived from natural gas.
⚫ The natural gas can either be stored in a tank of a vehicle as compressed
natural gas (CNG) at 3,000 or 3,600 psi or as liquified natural gas (LNG) at
typically 20-150 psi. A suitably designed natural gas engine may have a
higher output compared with a petrol engine because the octane number of
natural gas is higher than that of petrol.
⚫ Compressed natural gas vehicles require a greater amount of space for fuel
storage than convention gasoline power vehicles. Since it is a compressed
gas, rather than a liquid like gasoline, CNG takes up more space for each
GGE (Gallon of Gas Equivalent). This makes it difficult to design smaller
vehicles that look and operate like the vehicles that people are accustomed
to.

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⚫ CNG is often confused with liquefied natural gas (LNG). While both are
stored forms of natural gas, the key difference is that CNG is in
compressed form, while LNG is in liquefied form. CNG has a lower cost of
production and storage compared to LNG as it does not require an
expensive cooling process and cryogenic tanks. CNG requires a much
larger volume to store the same mass of natural gas and the use of very
high pressures (3000 to 4000 lbf/in², or 205 to 275 bar).
⚫ CNG has been made mandatory for all public transport in the Indian capital
city of New Delhi.

⚫ Properties
⚫ l. CNG is; the cheapest, cleanest and least environmentally impacting
alternative fuel.
⚫ 2. Vehicles powered by CNG produce less carbon monoxide and
hydrocarbon (HC) emission.
⚫ 3. It is less expensive than petrol and diesel.
⚫ 4. The ignition temperature of CNG is about 550°C. CNG requires more air
for ignition.

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 Various Reactions

⚫ The reactions of producer gas production can be divided into four zones as
follows.
⚫ (i) Ash Zone
⚫ This is the lowest zone consists mainly of ash. The incoming air and steam
mixture is preheated in this zone.
⚫ (ii) Combustion or Oxidation Zone
⚫ This is the zone next to ash zone. Here the coke is oxidised to CO and CO2.
Both the reactions are exothermic. Hence, the temperature of the bed reaches
around 1,100°C.
⚫ C +O2 CO exothermic H + 95 k cal
⚫ C + 1/2O2 CO2 exothermic H + 29 k cal
⚫

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(iii) Reduction Zone
⚫ This is the middle zone. Here both CO2 and steam combine with
red hot coke and liberate H2 and CO. The reduction reactions are
endothermic and the temperature in the zone is about 1000°C. If no
steam is supplied, the temperature of the producer raise and this
may fuse the ash and refractory lining.
⚫ C + CO2 2CO endothermic – 36 k cal
⚫ C + H2O CO + H2 endothermic – 29 k cal

⚫ iv) Distillation or Drying Zone

⚫ In this zone (400 - 800°C) the down coming coal is heated by the
outgoing gases. The heat given by the gases and the heat coming out
from the reduction zone will distill the fuel.
⚫ Uses
⚫ 1. It is used as a reducing agent in metallurgical operations.
⚫ 2. It is also used for heating muffle furnaces, open-hearth furnaces
etc.

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Manufacture

⚫ The reactions of water gas production involves the following two

steps.
⚫ Step 1
⚫ In the first step, steam is passed through the red hot coke, where CO
& H2 gases are produced. The reaction is endothermic. Hence, the
temperature of the coke bed falls.
⚫ C + H2O CO + H2 endothermic – 29 k cal
⚫ Step 2
⚫ In the second step, in order to raise the temperature of the
coke bed to 1000 C , the steam supply is temporarily cut off and air
is blown in. The reaction is exothermic.
⚫ C +O2 CO2 exothermic H + 95 k cal
⚫ 2C + O2 2CO exothermic H + 59 k cal
⚫ Thus the steam – run and air blow are repeated alternatively to
maintain proper temperature.
⚫ Uses.
⚫ It is used for the production of H2 and in the synthesis of ammonia.
It is also used as a source of and illuminating gas and fuel gas.

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Power alcohol

⚫ When ethyl alcohol is used as fuel in internal combustion engine, it

is called as "power alcohol". Generally ehty alcohol is used as its
5-25% mixture with petrol.
Advantages of power alcohol:
⚫ Ethyl alcohol has good antiknocking property and its octane number
is 90, while the octane number of petrol is about is 65. Therefore,
addition of ehtyl alcohol increases the octane number of petrol.
Alcohol has property of absobing any traces of water if present in
petrol.
If specially designed engine with higher compression ratio is used,
then disadvantage of lower Calorific value of ethyl alcohol can be
overcome.
ethyl alcohol contains 'O' atoms, which helps 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 considerably.
-Power alcohol is cheaper than petrol.

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⚫ Disadvantages of power alcohol:

⚫ Ethyl alcohol has calorific value 7000cal/gm much lower than

calorific value of petrol 11500cal/gm. Use of power alcohol reduces
power output upto 35%.

⚫ Ethyl alcohol has high surface tension and its atomisation,

especially at lower temperature, is difficult causing starting trouble.

⚫ Ethyl alcohol may undergo oxidation reaction to form acetic acid,

which corrodes engine parts.

⚫ As ethyl alcohol contains 'O' atoms, the amount of air require for
complete combustion of power alochol is lesser and therefore
carburettor and engine need to be modified, when only ethyl alcohol
is used as fuel.

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 Production of ethanol

⚫ The basic steps for large scale production of ethanol are: microbial
(yeastThe basic steps for large scale production of ethanol are: microbial
(yeast) fermentationThe basic steps for large scale production of ethanol
are: microbial (yeast) fermentation of sugars, distillationThe basic steps for
large scale production of ethanol are: microbial (yeast) fermentation of
sugars, distillation, dehydrationThe basic steps for large scale production
of ethanol are: microbial (yeast) fermentation of sugars, distillation,
dehydration (requirements vary, see Ethanol fuel mixtures, below), and
denaturingThe basic steps for large scale production of ethanol are:
microbial (yeast) fermentation of sugars, distillation, dehydration
(requirements vary, see Ethanol fuel mixtures, below), and denaturing.
Prior to fermentation, some crops require saccharificationThe basic steps
for large scale production of ethanol are: microbial (yeast) fermentation of
sugars, distillation, dehydration (requirements vary, see Ethanol fuel
mixtures, below), and denaturing. Prior to fermentation, some crops require
saccharification or hydrolysisThe basic steps for large scale production of
ethanol are: microbial (yeast) fermentation of sugars, distillation,
dehydration (requirements vary, see Ethanol fuel mixtures, below), and
denaturing. Prior to fermentation, some crops require saccharification or
hydrolysis of carbohydrates such as cellulose and starch into sugars.
Saccharification of cellulose is called cellulolysis . Enzymes are used to
convert starch into sugar.
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⚫ With increasing attention being paid to saving energy, many methods have
been proposed that avoid distillation altogether for dehydration. Of these
methods, a third method has emerged and has been adopted by the majority
of modern ethanol plants. This new process uses molecular sieves to remove
water from fuel ethanol.
⚫ In this process, ethanol vapor under pressure passes through a bed of
molecular sieve beads. The bead's pores are sized to allow absorption of
water while excluding ethanol. After a period of time, the bed is regenerated
under vacuum or in the flow of inert atmosphere (e.g. N2) to remove the
absorbed water. Two beds are often used so that one is available to absorb
water while the other is being regenerated. This dehydration technology can
account for energy saving of 3,000 btus/gallon (840 kJ/L) compared to
earlier azeotropic distillation.

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Biodiesel

⚫ A fuel derived from organic oils, such as vegetable oil, rather than
petroleum. Biodiesel's use and production are increasing. It's
typically used for aircraft, vehicles and as heating oil.
⚫ Transesterification
⚫ Animal and plant fats and oils are composed of triglyceridesAnimal
and plant fats and oils are composed of triglycerides, which are
estersAnimal and plant fats and oils are composed of triglycerides,
which are esters containing three free fatty acidsAnimal and plant
fats and oils are composed of triglycerides, which are esters
containing three free fatty acids and the trihydric alcohol,
glycerolAnimal and plant fats and oils are composed of
triglycerides, which are esters containing three free fatty acids and
the trihydric alcohol, glycerol. In the transesterification process, the
alcohol is deprotonatedAnimal and plant fats and oils are
composed of triglycerides, which are esters containing three free
fatty acids and the trihydric alcohol, glycerol. In the
transesterification process, the alcohol is deprotonated with a base
to make it a stronger nucleophileAnimal and plant fats and oils are
composed of triglycerides, which are esters containing three free
fatty acids and the trihydric alcohol, glycerol. In the
transesterification process, the alcohol is deprotonated with a base
to make it a stronger nucleophile. Commonly, ethanol or methanol
are used. As can be seen, the reaction has no other inputs than the
triglyceride and the alcohol. Under normal conditions, this reaction 34
⚫ Almost all biodiesel is produced from virgin vegetable oils using the
base-catalyzed technique as it is the most economical process for treating virgin
vegetable oils, requiring only low temperatures and pressures and producing
over 98% conversion yield (provided the starting oil is low in moisture and free
fatty acids). However, biodiesel produced from other sources or by other
methods may require acid catalysis, which is much slower.

35
Theoretical calculation of calorific value

⚫ 1. Elements always combine in definite proportions to give. the products.

For example 12 gm of carbon combines with 32 gm of oxygen to give 44
gm of CO2
⚫ C + O2 CO2
⚫ 12 32 44
⚫ Similarly, 4gm of hydrogen combines with 32gm of oxygen to give 36gm
of H2O.
⚫ 2 H2(g) + O(g) 2H2O(g)
⚫ 4 32 36
2. At STP (273 K, l atm) one mole of all gases occupy a volume of
22.4litres. Hence at S.T.P. 22.4 liters of CO2 will have a weight of 44gm,
its molecular weight.
⚫ 3. Air contains 21 % of oxygen by volume and 23 % of oxygen by weight,
Hence 1 m3 of oxygen will be supplied by
⚫ 1 x l00 = 4.76m3 of air
⚫ 21

36
⚫ Similarly 1 kg of oxygen will be supplied by lxl00 = 4.3 5 kg of air.
⚫ 23
⚫ 4. Molecular weight of air is 28.94mol-1.
⚫ 5. Minimum oxygen required = (Theoretical O2 required) - (O2
present in fuels).
⚫ 6. The mass of flue gas is calculated by balancing the carbon in the
fuel and the carbon in the flue gas.
⚫ 7. Minimum O2 required is calculated on the basis of complete
combustion of fuel. If as a result incomplete combustion or CO is
formed then O2 is calculated for the conversion of CO to CO2.
⚫ 8. If the fuel contains both O2 and H2, the amount of hydrogen and
oxygen may be present in the form of as H2O, which is a
non-combustible substance. The remaining available hydrogen takes
part in the combustion reaction.
⚫ 2 H2(g) + O(g) 2H20

37
⚫ 32 gm of oxygen combines with 4gm of hydrogen, Hence 1 part of
hydrogen combines with 8 parts of oxygen.

⚫ Hence, theoretical amount of oxygen required for complete combustion of

1 kg of fuel is given by the equation,
⚫ {32/12 x C + 8[H – O/8] + S} kg

C, Hand S are masses of carbon. Hydrogen and sulphur respectively per

kg of the fuel. Since 1 kg of air-contains 23%of oxygen by weight, the
amount of air required theoretically to burn 1 kg of fuel completely is given
by equation.
⚫ 100/23 {32/12 x C + 8[H – O/8] + S} Kg

38
⚫ According to Dulong's formula for the theoretical calculation of calorific
value is,
⚫ 1/100 [8080C + 34500 (H – O/8) + 2240S] Kcal/kg
⚫ Where C, H, O and S represent the % of the corresponding elements in the
fuel. It is based on the assumption that the calorific value orc, Hand S are
found to be 8080, 34500 and 2240 kcal, when 1 kg of the fuel is burnt
completely.
⚫ However, all the oxygen in the fuel is assumed to be present in combination
with hydrogen in the ratio H:O as 1:8 by weight. So the surplus hydrogen
available for combustion is' H - 0 .
8
⚫ NCV (or) LCV = [HCV – 9/100H x 587] kcal.kg

39
Theoretical calculation of minimum air requirement for combustion of
a fuel

⚫ Combustion is the process of burning any combustible substance in

the presence of oxygen, which liberates energy in the form of heat
and light. For efficient combustion, it is essential that the fuel must
be brought into intimate contact with sufficient quantity of air or
oxygen.
⚫ The combustible substance usually present in fuels, which enter into
the combustion, are mainly C, H, S and O. But N, CO2 and ash are
incombustible matters present in the fuel, .do not take any oxygen
during combustion.
⚫ For the complete combustion of a given quantity of fuel can be
calculated by considering the following point. Substances always
combine in definite proportions, which are determined by the
molecular weights of the substances.

40
⚫ i) Combustion of carbon
⚫ C + O2 CO2
12 32 44 (by weight)
⚫ 12 parts by weight-of carbon requires 32 parts by weight of oxygen for
complete combustion. 'C' parts by weight of carbon requires == 32 C /12
== 2.67 C
⚫ (H- 0/8) parts by weight of hydrogen requires = (H - O/8) X 32
⚫ 4
⚫ = 8 (H- O/8)
⚫ ii) Combustion of hydrogen
⚫ . When oxygen is present in the fuel, it always combines with hydrogen.
The combined hydrogen does not take part in combustion reaction.
Therefore, the quantity of combined hydrogen must be deduced from the
total hydrogen in the fuel.
⚫ 2H2 + O2 2H2O
⚫ 2 2 36 (by weight)

41
⚫ 4 parts by weight of H2 requires 32 parts by weight O2 (or) 2 parts by
volume of H2 require 1 part by volume of O2
⚫ There fore ‘H’ parts by weight of hydrogen require 32x H parts by weight
of O2. 4
⚫

⚫ iii) Combustion of carbon monoxide

⚫ CO + ½ O CO2
⚫
⚫ 28 16 (by weight)
⚫
⚫ 1 0.5 (by volume)
⚫ 1 volume of CO requires 0.5 volume of oxygen.

42
⚫ iv) Combustion of sulphur
⚫ S + O2 SO2
⚫ 32 32 (by weight)
⚫ 1 1 (by volume)
⚫ 1 volume of 'S' requires 1 volume of oxygen.
⚫ v) Combustion of methane
⚫ CH4 + 2O2 CO2 + 2 H20
⚫ 16 64 (by weight)
⚫ 1 2 (by volume)

43
⚫ Problems For the calculation of Calorific value
⚫ Calculate the gross and net calorific values of a coal sample having the
following composition C = 80%; H = 7%;O = 3%; S = 3.5%; N = 2.5%
and ash 4.4%
⚫ Solution
⚫ (I) G.C.V = 1/100[8080*%C+34500(%H - %O/8)+2240*%S] kcal/kg
⚫ = 1/100[8080*80+34500(7 - 3/8)+2240*3.5] kcal/kg
⚫ = 8828.0 kcal/kg
⚫ ,,
⚫ (II) N.C.V = G.C.V – [0.09H*587] kcal/kg
⚫
⚫ = 8828 – [0.09*7*587] kcal/kg
⚫ = 8458.2 k cal/kg

44
 Flue Gas Analysis (Orsat's method)

⚫ The mixture of gases such as CO2, O2, CO, etc., coming out from the
combustion chamber is called flue gases. The analysis of a flue gas would
give idea about the complete or incomplete combustion process. If the flue
gases contain considerable amount of CO, it indicates that incomplete
combustion and it contain a considerable amount of oxygen indicates,
complete combustion. The analysis of flue gas is carried out by using
Orsat's apparatus.
⚫ Description of Orsat's Apparatus
⚫ It consists of a horizontal tube, having 3 way stopcock. At one end of this
tube, U-tube containing fused CaCl2 is connected. The other end of this
tube is connected with a graduated burette. The burette is surrounded by a
water-jacket to keep the temperature of gas constant. The lower end of the
burette is connected to a water reservoir by means of a rubber tube. The
level of water in the burette can be raised or lowered by raising or lowering
the reservoir. The horizontal tube is also connected with three different
absorption bulbs I, II and III for absorbing CO2, O2 , CO.

45
⚫ Bulb- I : It contains 'potassium hydroxide' solution, and it absorbs only
CO2
⚫ Bulb - II: It contains 'alkaline pyrogallol' solution, and it absorbs only
CO2 and O2
⚫ Bulb.:III : It contains 'ammoniacal cuprous chloride' solution, and it
absorbs only CO2, O2 and CO.
⚫ Working
⚫ The 3-way stopcock is opened to the atmosphere and the reservoir is
raised, till the burette is completely filled with water and air is excluded
from the burette. The 3-way stopcock is now connected to the flue gas
supply, the flue gas is sucked into the burette, and the volume of flue gas
is adjusted to 100 cc by raising and lowering the reservoir. Then the
3-way stop cock is closed.

46
⚫ a) Absorption of CO2 .
⚫ The stopper of the bulb-1 containing KOH solution is opened and all the
gas is passed into the bulb-1 by raising the level of water in the burette.
The gas enters into the bulb-I, where CO2 present in the flue gas is
absorbed by KOH. The gas is again sent to the burette. This process is
repeated several times to ensure complete absorption of CO2.The decrease
in volume of the flue gas in the burette indicates the volume of CO2 in 100
cc of the flue gas.
b) Absorption of O2
⚫ Stopcock of bulb-I is closed and stopcock of bulb-II is opened. The gas is
again sent into the absorption bulb-II, where O2 present in the flue gas is
absorbed by alkaline pyrogallol (925 g of pyrogallol + 200g of KOH in 500
ml distilled water). The decrease in volume of the flue gas in the burette
indicates the volume of O2.
c) Absorption of CO
⚫ Now stopcock of bulb-II is closed and stopcock of bulb-Ill is opened. The
remaining gas is sent into the absorption bulb-III, where CO present in the
flue gas is absorbed by ammoniacal cuprous chloride (100 g CuCl2 + 125
mL liquor ammonia + 375 mL distilled water). The decrease in volume of
the flue gas in the burette indicates the volume of CO. The remaining gas
in the burette after the absorption of CO2, O2 and CO is taken as nitrogen.

47
Orsat’s apparatus

48
TEXT BOOKS AND REFERENCES

⚫ Vairam S, Kalyani P and SubaRamesh.,“Engineering Chemistry”.,

Wiley India PvtLtd.,NewDelhi., 2011
⚫ DaraS.S,UmareS.S.“Engineering Chemistry”, S. Chand & Company
Ltd., New Delhi , 2010
⚫ Kannan P. and Ravikrishnan A., “Engineering Chemistry”, Sri
Krishna Hi-tech Publishing Company Pvt. Ltd. Chennai, 2009
⚫ Ashima Srivastava and Janhavi N N., “Concepts of Engineering
Chemistry”, ACME Learning Private Limited., New Delhi., 2010.
⚫ RenuBapna and Renu Gupta., “Engineering Chemistry”, Macmillan
India Publisher Ltd., 2010.
⚫ Pahari A and Chauhan B., “Engineering Chemistry”., Firewall
Media., New Delhi., 2010
⚫ P.C.Jain and Monica Jain, “Engineering Chemistry”, Dhanpat Rai
Pub. Co., New Delhi

49