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 Calorific Value
Two types of calorific value 1.GCV/ HCV :-

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A known quantity of fuel is burnt in a closed combustion chamber and

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combustible gases are not allowed to escape and cooled to temp 15

in
0C.

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2. NCV / LCV :- of
A known quantity of fuel is burnt in an open chamber where
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combustible gases are allowed to escape.

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So we can state that GCV is greater than NCV

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GCV > NCV

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 HCV and LCV
Higher or gross calorific value:

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Usually, all fuels contain some hydrogen and when the calorific value

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of hydrogen-containing fuel is determined experimentally, the
hydrogen is converted into steam. If the products of combustion are

g,
condensed to the room temperature (15°C or 60°F), the latent heat

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of condensation of steam also gets included in the measured heat,

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which is then called "higher or gross calorific value". So, gross or

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higher calorific value (HCV) is "the total amount of heat produced,

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when unit mass/volume of the fuel has been burnt completely and

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the products of combustion have been cooled to room
temperature"(i.e., 15°C or 60°F ).
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Lower or net calorific value (LCV)

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In actual use of any fuel, the water vapour and moisture, etc., are not
condensed and escape as such along-with hot combustion gases.
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Hence, a lesser amount of heat is available. So, net or lower calorific

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value (LCV) is "the net heat produced, when unit mass

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/volume of the fuel is burnt completely and the products are

permitted to escape".
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Net calorific value= Gross calorific value - Latent heat of

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condensation of water vapour produced

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= GCV - Mass of hydrogen per unit weight of

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the fuel burnt x 9 x Latent heat of condensation of water vapour

 Relation between GCV and NCV
GCV /HCV and NCV/LCV can be related as, NCV = GCV -Latent

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heat of water vapour formed

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g,
= GCV – (Mass of steam X Latent heat of steam)

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= GCV = [( 9 X Mass of hydrogen) X Latent heat of steam

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[ As 18 parts of water are formed by 2 parts of hydrogen Therefore,

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mass of steam will be 9 times mass of hydrogen].
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H2 + 1/2 O2 H2O
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2 parts 18 parts
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Latent heat of steam = 587cal/gm

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If mass of hydrogen is expressed as % H, then, mass of hydrogen per gram

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of fuel will be H/100.

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NCV = GCV- [ 9 X H/100 X 587] NCV = GCV – 0.09 X H X 587 cal/gm

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 Determination of calorific value

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Three types of fuel are present namely solid, liquid and gaseous.

Pu
g,
1. Solid and liquid fuels :- Bomb Calorimeter

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2. Gaseous fuels :- Boy’s Calorimeter.

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 Calculation of Bomb Calorimeter
x= mass of fuel

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W = mass of water in copper calorimeter w = Water equivalent of calorimeter

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g,
t1 = Initial temp of water t2 = Final temp of water L= GCV /HCV

in
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Heat liberated = Heat absorbed by water Heat liberated= x. L

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Heat absorbed = M X Cp X (t2-t1)

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en
( M= mass of water, Cp= specific heat of water = 1cal/g)
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GCV = (W+w)(t2-t1)/x cal/gm

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GCV = 4.187 (W+w) (t2-t1)/x J/gm or kJ/Kg

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 Corrections in calculations
Mainly three corrections:-

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1.Fused wire correction ( tf) :- Magnesium wire burns or ignite

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by producing additional heat so it can be subtracted from formula.

g,
in
2.Acid correction ( ta) :- Fuel is a hydrocarbon which also

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contains S, N in its composition. During combustion reaction sulfur

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and nitrogen get converted to sulphuric acid and nitric acid rep.

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Formation of these acids is exothermic process producing additional
of
heat. So it is subtracted from formula.
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S + 2H + 2O2 H2SO4 + heat

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2N + 2H + 3O2
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2HNO3 + heat
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 Correction formula

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3. Cooling correction ( tc):- The heat liberated by combustion of fuel

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should be transferred completely to water. By the time temp reaches to
maximum in the Bomb calorimeter expt.cooling begins. Because of

g,
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cooling actual rise in temp is lowered. So it is added in formula.

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GCV (L) :-

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(W+w) (t2-t1 + cooling correction)- (Acid correction+Fuse wire
of
correction)
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cal/gm / X ( mass of fuel)

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NCV = GCV – 0.09 X H X 587 cal/gm

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 Numericals
1. Calculate the HCV (in kJ/kg) of 0.75 gm of a fuel containing 80% carbon, when burnt

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in a Bomb calorimeter increased the temperature of water from 27.3 to 29.70C. The

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calorimeter contains 250 gm of water and its water equivalent is 150 gm.

g,
Ans:- Weight of fuel = x = 0.75gm

in
er
Weight of water = W = 250 gm

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Water equivalent = w = 150 gm

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t1= 27.3 0C

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and t2= 29.7 0C
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lle

HCV (L) = (W+w) (t2-t1)/x cal/gm L =

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(250 + 150) (29.7-27.3) /0.75

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1280 cal/gm = 1280kcal/kg

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= 1280 X 4.187 kJ/kg

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= 5359.36 kJ/kg
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 2. 0.84 gm of a fuel on complete combustion in excess of oxygen
increased the temp. of water in calorimeter from 14.39 0C to 18.12 0C.
The mass of water in calorimeter was fiund to be 1350gm. Calculate higher

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calorific value of the fuel, if the water equivalent of calorimeter is 138 gm.

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(Ans- 6607.43 cal/gm)

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in
3. Complete combustion of 1.050 gm of fuel was carried out in a

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calorimeter in presence of excess of oxygen. The temp of 1500 gm of water

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of calorimeter raised from 25.7 to 27 0C. If the water equivalent of the

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calorimeter is 125gm, calculate the calorific value ( Ans- 2011.90 cal/gm)
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4. The determination of the calorific value of a coal sample gave the
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following data:-
lle

Weight of coal = 0.9gm

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Water equivalent of calorimeter = 440 gm Weight of water = 2500gm

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Rise in temp = 2.4 0C Cooling correction = 0.052 0C

Calculate GCV and NCV =?
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Coal contains 8% hydrogen with latent heat of steam= 600cal/gm

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( GCV= 7998.76 cal/gm, NCV = 7566.78 cal/gm)

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 5. 1.20 gm of a coal sample on analysis gave C= 90%, H=6%.
The ash content in the sample was 1%. The coal sample was burnt in
bomb calorimeter and following results were obtained.

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i) Weight of water taken in calorimeter = 500gm

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g,
ii) Initial temp of water = 24.2 0c

in
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iii) Final temp of water = 26.2 0C

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gi
iv) Fuse wire correction = 10 cal

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v) Acid correction = 50 cal
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vi) water equivalent of calorimeter = 2000 gm

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If latent heat of steam is 580 cal/gm. Calculate gross and net

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calorific value of the sample.

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GCV = 4116.66 cal/gm

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NCV = 3803.46 cal/gm

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 Boy’s Calorimeter:- Construction and working

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 A known volume of gas at known pressure can be burnt in it.

g,
 Burner is surrounded by a chimney or combustion chamber.

in
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 Combustion chamber has a copper tubing coiled inside as well as

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gi
outside it, water at a constant rate is passed through the coil.

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• Water enters from the top of the outer coil. It moves to the bottom of
of
the chimney and then goes up through the inner coil to the exit at top.
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lle

The thermometer T1 and T2 give the temperature of the incoming and

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• outgoing water resp.

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 During circulation of water through the coil, the circulating water

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absorbs heat formed by fuel after combustion.

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 Calculations
Volume of gas burnt = V m3.

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The quantity of water passing thr the coil = W kg Initial

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g,
temp = t1 0C

in
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Final temp = t2 0C

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gi
Mass of water condensed = m kg L= GCV/ HCV
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Heat produced = heat absorbed by water Heat produced by
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combustion of fuel = V X L
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Heat absorbed by circulating water = M X Cp X (t2-t1)

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= M X 1 X (t2-t1)
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Therefore, VL = W (t2-t1)
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GCV (L) = W(t2-t1) / V Kcal/m3

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 • GCV/HCV (L) = 4.187 [W(t2-t1)]/V KJ/m3

en
Mass of steam condensed per m3 of gas = m/V Kg

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Latent heat of steam per m3 of gas = mX 587/V Kcal

g,
in
er
Therefore,

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gi
NCV/LCV = [GCV- m X 587 / V ] Kcal/m3
en
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GCV (L) = W(t2-t1) / V Kcal/m3
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lle
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NCV/LCV = [GCV- m X 587 / V ] Kcal/m3

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 Numericals
1.The following data was obtained in a Boy’s Calorimeter expt:

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n
Pu
Volume of gas burnt =0.1 m3

g,
Mass of cooling water used = 28 Kg Temp of inlet water = 24.2 0C

in
Temp of outlet water = 32.4 0C

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Mass of steam condensed = 0.05 Kg Calculate GCV and NCV of the

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gas.

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2.Following observation was observed in case of Boy’s calorimeter.
ge

Volume of gas burnt =0.08 m3 Mass of cooling water = 30 Kg

lle

Rise in temp = 8.2 0C

co

Mass of steam condensed = 0.04 Kg Clculate GCV and NCV.

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 Numericals
3.The temp of 950 gm of water increased from 25.5 0C to 28.5 0C on

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burning 0.70 gm of a solid fuel in a Bomb Calorimeter.Water

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equivalent of calorimeter and latent heat of steam are 400gm and

g,
587 cal/gm resp. If the fuel contains 0.65% of hydrogen, calculate

in
NCV.

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ne
4.In an actual determination of calorific value of fuel by Bomb

gi
en
calorimeter, following data were obtained.
of
weight of silica crucible with nichrome fuse = 3.4 gm
ge
lle

weight of crucible, nichrome fuse and fuel = 4.31 gm water

co

equivalent of calorimeter = 750 gm

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Quantity of water taken in calorimeter = 1750 gm Rise in temp of

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water = 2.96 0C
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Calculate gross calorific value of fuel.

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 Solid fuel
• The decay of plant materials deposited in earth’s crust million of

e
n
years ago resulted in the formation of coal.

Pu
g,
• Coal mainly contains C, H and O along with N, S and non

in
combustible organic matter.

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• Coal is highly carbonaceous matter that has resulted from

gi
alteration of vegetable matter under favourable conditions.
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• The plants were converted to coal under combined effect of high
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pressure, temp and bacteria, this process is called as

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coalification.
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• Formation of coal is a slow process.

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Temperature Time
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Moisture 105 -110 0C 1 hour

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Ash 725-750 0C 30 min

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Volatile matter 925-975 0C 7 min

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 Proximate analysis
(1) Moisture: About 1 g of finely powered air-dried coal sample is weighed in a

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crucible. The crucible is placed inside an electric hot air-oven, maintained at 105°

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- 110°C. The crucible is allowed to remain in oven for 1 hour and then taken out,

Pu
cooled in a desiccator and weighed. Loss in weight is reported as moisture (on

g,
percentage-basis).

in
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Loss in weight x 100
Percentage of moisture =

gi
Wt. of coal taken

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(2) Volatile matter: The dried sample of coal left in the crucible in (1) is then
lle

covered with a lid and placed in an electric furnace (muffle furnace), maintained
co

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.
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Loss in weight is reported as volatile matter on percentage-basis.

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Percentage of volatile matter=

Loss in weight due to removal of volatile matter x 100
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Wt. of coal sample take

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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

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air, then in desiccator and weighed.

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Pu
Heating, cooling and weighing is repeated, till a constant weight is obtained. The

g,
residue is reported as ash on percentage-basis.

in
er
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Percentage of ash = Wt. of ash left x 100 Wt. of coal taken

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

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matter + ash)
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high percentage of carbon is desirable.

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 Importance of proximate analysis

n e
Pu
Proximate analysis provides following valuable informations in assessing the

g,
quality of coal:

in
er
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1)Moisture: Moisture lowers the effective calorific value of coal. Moreover, it

gi
quenches the fire in the furnace. Hence, lesser the moisture content, better the
en
quality of coal as a fuel. However, presence of moisture, increases weight of
of
fuel by that increases cost for storage and transportation.
ge
lle
co

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
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matter, better the rank of the coal. Higher volatile content in coal is
hw

undesirable. It requires large furnace for combustion as it burns with a long

flame.
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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

e
content

n
Pu
is of special significance in coal gas manufacture and in carbonization plants,
particularly when by-product recovery is the main object. Thus, high-volatile

g,
matter

in
containing coals do not cake well; whereas medium-volatile matter content coals

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are capable of yielding hard and strong coke on carbonization.

ne
(3) Ash is a useless, non-combustible matter, which reduces the calorific value

gi
of coal. Moreover, ash causes the hindrance to the flow of air and heat, thereby

en
lowering the temperature. Also, it often causes. trouble during firing by forming
of
clinker), which block the inters paces of the grate. This in-turn causes obstruction
to
ge

air supply; thereby the burning of coal becomes irregular. Hence, lower the ash
lle

content, better the quality of coal. The presence of ash also increases transporting,
co

handling and storage costs. The presence of ash also causes early wear of furnace
walls, burning of apparatus and feeding mechanism.
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hw

(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
nc

percentage of volatile matter. This also represents the quantity of carbon (in coal)
hi

that can be burnt by a primary current of air drawn through the hot bed of a fuel.
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 Numericals
1. A sample of coal on analysis gave the following results:

n e
Pu
1 gm of an air dried sample, on heating for an hour at 110 0C in a silica
crucible, left a dry residue of 0.98 gm. The crucible was covered with

g,
in
a vented lid and the heating was continued for another 7 min at 950

er
0C, when a residue of 0.85 gm was obtained. The crucible was then

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heated strongly in air until a constant weight was realized. The final

gi
en
residue weighed 0.15 gm. Calculate the proximate analysis result on
of
i)
ge
lle

Ans:- Weight of coal = 1 gm

co

Weight of moisture = 1-0.98 = 0.02 gm

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hw

Weight of volatile matter = 0.98-0.85 = 0.13 gm Weight of ash =

nc

0.15 gm
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 • % moisture = Weight of moisture / weight of coal X 100
= 0.02/1 X 100

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n
=2%

Pu
• % VM = Weight of VM / weight of coal X 100

g,
in
er
= 0.13/1 X 100

ne
= 13 %

gi
en
% Ash = Weight of ash / weight of coal X 100
of
= 0.15 /1 X 100
ge

= 15 %
lle
co

Fixed carbon content = 100 – (%M + %VM + %Ash)

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= 100- (2 +13 + 15 )
hw

= 100 – 30
nc
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= 70%
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 Numericals
2. 1.20 gm of coal sample was heated in a silica crucible in an electric

e
oven at 110 0C for 1 hr. The weight of the residue was

n
Pu
1.15 gm. The residue was then ignited to a constant weight of

g,
0.90 gm. In an another expt. 1.20 gm of the same coal sample was

in
heated in a silica crucible covered with a lid at 950 0C for exactly 7

er
ne
min. The weight of the residue was 0.85 gm. Calculate the %

gi
moisture, volatile matter, ash and fixed carbon.

en
[Ans:- %M=4.16, % VM=27.50 ,% Ash= 7.50, % FC=60.84]
of
ge

3. A coal sample was analyzed as follows:

lle
co

Exactly 1.5 gm was weighed into a silica crucible. After heating for 1 hr
at 110 0C, the residue weighed is 1.435 gm. The crucible next was
ad

covered with a lid and strongly heated for exact 7 min.at 950 0C. The
hw

residue weighed 1.027 gm. The crucible was then heated without
nc

cover, until a constant weight was obtained. The last residue was
hi
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found to be 0.117 gm.

pr

Calculate the % results of the above analysis. [Ans:- %M=4.33,

m

%VM= 27.2, % Ash= 7.8, % FC=60.66]

Pi
 Ultimate analysis
1. Determination of % C and H :-

e
n
Pu
This is usually done through single expt based on combustion in
excess of pure oxygen.

g,
in
er
2. Determination of % N:-

ne
This is done by Kjeldahl’s method where a known weight of given

gi
en
sample is heated with conc. H2SO4 in presence of catalyst K2SO4.
of
3. Determination of % S:-
ge
lle

This is dne by heating a known quantity of cola sample with BaCl2.

co
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 Combustion Method

e
n
Pu
Carbon and hydrogen:
About 1-2 g of accurately weighed coal sample is burnt in a

g,
in
current of oxygen in a combustion apparatus. C and H of the coal are

er
converted into CO2 and H2O respectively. The gaseous products of

ne
combustion are absorbed respectively in KOH and CaCl2 tubes of

gi
en
known weights. The increase in weights of these are then determined.
of
ge
lle

Increase in weight of KOH tube x 12 x 100

co

Percentage of C = Weight of coal sample taken x 44

ad
hw

Increase in weight of CaCl2 tube x 2 x 100

nc

Percentage of H = Weight of coal sample taken x 18

hi
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 Significance of ultimate analysis

ne
Pu
Carbon and hydrogen:

g,
Greater the percentage of carbon and hydrogen better is the coal

in
in quality and calorific value.

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ne
However, hydrogen is mostly associated with the volatile matter

gi
and hence, it affects the use to which the coal is put. Also higher
en
percentage of carbon in coal reduces the size of combustion
of
chamber required. The amount of carbon, the major combustible
ge

constituent of coal, depends on the type of coal and its percentage

lle

increases with rank from lignite to anthracite. Thus, percentage

co

of carbon forms the basis of classification of coal.

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hw
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hi
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Pi
 • Calculation of % C :-
C + O2 CO2

e
n
(12 ) (44)

Pu
g,
Let ‘a’ gm be the increase in weight of KOH U-tube =amount of

in
CO2 formed.

er
ne
As 44 gm of CO2 corresponds to 12 gm of carbon. Therefore, ‘a’

gi
en
gm of CO2 corresponds to= 12 X a / 44 gm of Carbon
of
If ‘W’ is the weight of coal, then
ge
lle

Therefore, W gm coal contains = 12 X a /44 gm of Carbon

co

Therefore, 100 gm coal contains 12/44 X a/W X 100 gm of C

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hw

Therefore, % C = 12/44 X a/W X 100

nc
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% C = 12/44 X weight of CO2/weight of coal X 100

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 Calculation of % H

e
H2 + ½ O2 H2O

n
Pu
(2) (18)

g,
in
Let ‘b’ gm be the increase in the weight of CaCl2 U-tube= amount of

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water formed.

ne
gi
As 18 gm of water corresponds to 2 gm of hydrogen
en
of
Therefore, ‘b’ gm of water corresponds = 2 X b/18 gm H If ‘W’ is the
ge

weight of coal,
lle
co

Therefore, ‘W’ gm of coal contains 2 X b/18 gm of H Therefore,

ad

100 gm of coal contains 2/18 X b/ W X 100

hw
nc

% H = 2/18 X Increase in weight of CaCl2/ weight of coal X 100

hi
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% H = 2/18 X weight of H2O / weight of coal X 100

pr
m
Pi
 Numericals
1.1.3 gm of coal sample was burnt in oxygen. Carbon dioxide was

en
absorbed in KOH and water vapour in CaCl2. The increase in weight

Pu
of KOH and CaCl2 was 2.876 and 0.403 gm resp. Determine % C and

g,
in
% H in the sample.

er
ne
[Ans:- % C = 60.33 and % H = 3.44]

gi
en
of
2.0.20 gm of coal sample on complete combustion in presence of
ge

continuous oxygen supply increased weight of u-tube CaCl2 by

lle

0.10 gm and u-tube containing KOH by 0.52 gm. Calculate % C and

co

% H present in coal.
ad
hw

[ Ans :- % C =70.90 and % H = 5.55]

nc
hi
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m
Pi
 Determination of Nitrogen

en
(2) Nitrogen :-

Pu
About 1 g of accurately weighed powdered 'coal is heated with

g,
in
concentrated H2SO4 along-with K2S04 (catalyst) in a long-necked

er
ne
flask (called Kjeldahl's flask).

gi
2N + 6H + H2SO4 (NH4)2SO4
en
After the solution becomes clear, it is
of
ge

treated with excess of KOH and the liberated ammonia is

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distilled over and absorbed in a known volume of standard acid

co

solution. The
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unused acid is then determined by back titration with standard

nc

NaOH solution. From the volume of acid used by ammonia

hi

liberated, (NH4)2SO4 + 2 NaOH 2 NH3 + Na2SO4

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pr
m
Pi
 The percentage of N in coal is calculated as follows:

Volume of acid used x Normality x 1.4

e
Percentage of N

n
Pu
Weight of coal taken
=

g,
in
It has no calorific value and hence, its presence in coal is

er
undesirable; thus, a good quality coal should have very little nitrogen

ne
content.

gi
en
of
ge
lle
co
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nc
hi
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 Calculations of N
Let ‘W’ gm be the weight of coal.

n e
Pu
Let N of HCl be used as the std acid titrated against NaOH for blank
and back titration.

g,
in
er
Let V1 be the back titration reading and V2 be the blank titration

ne
reading.

gi
en
Therefore, (V2-V1) ml= vol of acid consumed by liberated NH3. 1
of
equivalent of HCl = 1 equivalent of NH3
ge
lle

1 equivalent of NH3 = 1 equivalent of N Therefore 1 equivalent of

co

HCl= 1 equivalent of N 1000 ml 1N HCl = 14 gm of N

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Therefore, (V2-V1) ml N HCl = (V2-V1) X N X14 / 1000

nc

W gm coal contains = (V2-V1) X N X14 / 1000

hi
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m
Pi
 100 gm of coal contains = (V2-V1) X N X14 / 1000 X 100/W
gm of N

n e
% N = (V2-V1) X N X 1.4 / W

Pu
g,
% N = ( Blank titration – Back titration) X Normality X 1.4

in
er
ne
weight of coal

gi
en
of
ge

% N = Volume of acid X Normality X 1.4 / weight of coal

lle
co
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hw
nc
hi
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m
Pi
 Numericals
1.5 gm of a sample of coal was used for nitrogen estimation by

ne
Kjeldahl’s method. The ammonia obtained was absorbed in 30 ml

Pu
N/10 sulfuric acid. To neutralize the remaining acid, 15 ml of

g,
in
0.1 N NaOH was required. Determine % N.

er
ne
[Ans:- 1.4 %]

gi
en
of
1.2 gm of coal sample in Kjeldahl’s expt. Liberated ammonia which
ge

was absorbed in sulfuric acid. The resultant solution required 10 ml

lle

of 0.1 N NaOH for complete neutralization. The blank titration

co

reading was 50 ml. Calculate % of N in coal.

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[ans:- 4.66%]
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nc
hi
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m
Pi
 • 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

ne
from ores like iron pyrites, gypsum, etc., mines along-with the coal.

Pu
• Presence of sulphur is highly undesirable in coal to be, used for

g,
in
making coke for iron industry, since it is transferred to the iron metal

er
and badly affects the quality and properties of steel. Moreover, oxides

ne
of sulphur (formed as combustion products) pollute the atmosphere

gi
and leads to corrosion.

en
• It is determined from the washings obtained from the known mass of
of
coal, used in a bomb calorimeter for determination of a calorific value.
During this determination, S is converted into sulphate. The
ge

washings are treated with barium chloride solution, when barium

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sulphate is precipitated. This precipitate is filtered, washed and heated

co

to constant weight.
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Weight of BaSO4 obtained x 32 x 100

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

hi
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Pi
 ‘W’ be the weight of coal m be the weight of BaSO4
1 mole of BaSO4 = 1 mole of S 233 gm of BaSO4 = 32 gm of S

e
Therefore m gm of BaSO4 = m X 32 / 233 gm of S

n
Pu
W gm of coal contains m X 32 / 233 gm of S Therefore 100 gm

g,
in
of coal contains

er
ne
32/233 X m/W X 100 gm of S

gi
en
of
% S = 32/233 X weight of BaSO4 / Weight of coal X 100
ge
lle

Eschka Method for determination of sulfur.

co
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hi
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Pi
 Numericals
1.1 gm of coal of coal sample was completely combusted in a

en
Bomb Calorimeter. The solution from Bomb pot on treatment with

Pu
BaCl2 solution formed a precipitate of BaSO4. After washing and

g,
drying the weight of BaSO4 ppt was found to be 0.3gm. Calculate

in
er
% S in the given coal sample.

ne
gi
[ Ans- 4.12%]

en
of
ge

2.2.50 gm of coal in qualitative analysis gave 0.23 gm of BaSO4.

lle

Claculate % of sulfur in coal.

co

[Ans- 1.26%]
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m
Pi
 (4) Oxygen content decreases the calorific value of coal. High
oxygen-content coals are characterized by high inherent moisture,

e
low calorific value, and low coking power. Moreover, oxygen is in

n
combined form with hydrogen in coal and thus, hydrogen available

Pu
for combustion is lesser than actual one. An increase in 1% oxygen

g,
content decreases the calorific value by about 1. 7% and hence,

in
er
ne
gi
oxygen is undesirable. Thus, a good quality coal percentage of

en
oxygen. of
Oxygen: It is obtained by difference.
ge
lle
co
ad

Percentage of O = 100 - Percentage of (C + H + S + N+ash)

hw
nc
hi
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m
Pi
 • Q. 1.56 gm of coal was Kjeldahl’ed and NH3 gas thus evolved was
absorbed in 50 ml 0.1 N HCl. After absorbtion the residual acid
required 6.25 ml of 0.1 N NaOH for neutralization. 2.60 gm of coal

e
n
sample in a quantitative analysis gave 0.1755 gm of BaSO4.

Pu
Calculate % N and % S?

g,
in
• Wt of coal =1.56gm

er
ne
• V2= Blank titration =50 ml V1 = Back titration = 6.25

gi
• Volume of acid consumed = 50-6.25 =43.75
en
% N = (V2-V1) X 0.1 X 1.4 /1.56
of
• = 3.926
ge
lle

•
co

Wt of coal =2.60 gm BaSO4 wt =0.1755

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% S = 32/233 X BaSO4 / wt of coal X100

nc

= 32/233 X 0.1755 /2.60 X 100

hi

= 0.927 %
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m
Pi
 Liquid Fuels
The important liquid fuels are petroleum, petroleum products, tar, alcohols.

e
These are naturally found under the sea surface. Liquid fuels are also

n
Pu
obtained synthetically from' hydrogenation of coat. Liquid fuels find
extensive use in domestic and industrial fields.

g,
in
er
ne
Petroleum

gi
Petroleum or crude oil is a dark greenish brown or black coloured viscous
en
oil found deep in earth's crust. The oil is usually floating over a brine
of
solution and above the oil, natural gas is present. Crude oil containing
ge

mixture of paraffinic, olefinic and aromatic hydrocarbons with minor

lle

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-
co

0.5%.
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hi
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 a) Classification of petroleum
Petroleum is classified into three types based on variation of chemical

ne
nature of crude oil found in the earth.

Pu
g,
i)Paraffinic-base type crude oil: It contains saturated hydrocarbons

in
from CH4 to C35H72 and little amount of naphthalenes and aromatics.

er
ne
ii)Asphaltic-base type crude oil: It contains mainly cycloparaffins or

gi
naphthalenes with smaller amount of paraffins and aromatic

en
hydrocarbons. of
iii)Mixed-base type crude oil : It contains both paraffinic and asphaltic
ge

hydrocarbons and are generally in the form of semi-solid waxes.

lle
co
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hi
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m
Pi
 Mining and Refining of Petroleum
The crude oil obtained from the earth crust contains water, sulphur and

e
some unwanted impurities. After removal of water, sulphur and these

n
Pu
impurities, the crude oil is separated into various useful fractions by
fractional distillation and finally conveI1ed into desired specific

g,
products having different boiling points. The process is called "Refining

in
er
of Petroleum" and the refining plants are called "Oil refineries". The process

ne
of refining involves the following steps.

gi
Step -I: Separation of water (Cottrell's process)
en
The crude oil from the oil well is an extremely stable emulsion of oil and salt
of
water. The crude oil is allowed to flow between two highly
ge

charged electrodes, where colloidal water droplets coalesce to form

lle
co

large drops, which is then separated out from the oil.

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Step - II: Removal of harmful impurities

hw

a)The presence of NaCI and MgCI in the crude oil can corrode the
nc

refining equipment, hence these salts are removed by electrical

hi

desalting and dehydration methods.

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b) The sulphur compounds present in the crude oil is removed by treating oil
pr

with copper oxide, which results in the formation of copper sulphide (solid),
m

which is then removed by filtration.

Pi
 Fractional distillation
Step - III: Fractional distillation

ne
Pu
The crude oil is then heated to about 400°C in an iron retort, whereby
all volatile substances (except asphalt or coke) are evaporated. The

g,
in
hot vapors are then passed up a fractionating column, which is a tall

er
cylindrical tower containing a number of horizontal stainless steel

ne
trays at short distances. Each tray is provided with small chimney

gi
en
covered with a loose cap. (Figure )
of
ge

When the vapours of the oil go up in the fractionating column, they

lle

become gradually cooler and get condensed at different heights of

co

column. The fractions having higher boiling points condense at lower

ad

trays whereas the fractions having lower boiling points condense at

hw

higher trays. The gasoline obtained by the fractional distillation is

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called straight --run gasoline. Various fractions obtained at different

hi

trays are given in table.

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Pi
Pi
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en
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in
g,
Pu
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 Combustion
• C + O2 CO2 + heat

en
Pu
• C + ½ O2 CO + heat

g,
• S + O2 SO2 + heat

in
er
• H2 + ½ O2 H2O + heat

ne
gi
• CH4 + 2O2 CO2 +2H2O + heat
en
of
• C2H6 + 7/2 O2 2 CO2 + 3 H2O + heat
ge

• C3H8 + 5O2
lle

3 CO2 + 4H2O + heat

co

• C4H10 + 13/2 O2 4CO2 + 5H2O + heat

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hi
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Pi
 Combustion calculations
• 1. Mass

en
proportion:-

Pu
C + O2 CO2

g,
Volume 1 mole 1 mole 1 mole

in
er
Mass 12 32 44

ne
gi
2H2 en
+ O2 2 H2O
of
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2 moles 1 mole 2 moles

lle
co

mass 2 X 2=4 32 2 X 18
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=36
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Pi
 Combustion Numericals
Combustion of carbon monoxide

e
CO + ½ O CO2

n
Pu
28 16 44 (by weight)

g,
in
1 0.5 (by volume)

er
1 volume of CO requires 0.5 volume of oxygen.

ne
gi
en
Combustion of sulphur of
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S+ O2 SO2
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32 32 (by weight)
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1 1 (by volume)
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1 volume of 'S' requires 1 volume of oxygen.

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v) Combustion of methane
hi

CH4 2O2 CO2 + 2

iC

+ H20
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16 64 (by weight)
m
Pi

1 2 (by volume)
 Formulae

e
1.Air contains 21 % oxygen by volume and 23 % oxygen by mass.

n
Pu
2. Quantity of air = Oxygen quantity in Kg X 100 / 23 Kg

g,
in
3. Volume of air = volume of oxygen in m3 X 100 / 21 m3

er
ne
4. Excess air = In order to have complete combustion of fuel excess

gi
air is supplied.
en
of
5. Quantity of air actually supplied =
ge

Theoretical quantity of air X ( 100 + % excess air)

lle
co

100
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hi
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Pi
 Numericals
1. Calculate the volume of air required for complete combution of 1 m3 of

ne
gaseous fuel having CO =15%, CH4=36%, H2=46%, N2 =3%.

Pu
g,
Solution:- CO=0.15 m3, CH4 = 0.36 m3, H2 = 0.46 m3, N2 = 0.03 m3

in
er
ne
a)CO+ ½ O2 CO2 1 vol ½ vol

gi
0.15 X ½ = 0.075
en
of
b)CH4 + 2O2 CO2 + 2 H2O 1 vol 2 vol
ge

0.36 X 2 = 0.72
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C) H2 + ½ O2 H2O 0.46 X ½ = 0.23

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1 vol ½ vol
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hi
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 Volume of air required = Volume of O2 X 100/21
= 1.025 X 100/21

e
n
= 4.881 m3

Pu
g,
in
er
2. Calculate weight of air required for the complete combustion of 5 Kg

ne
of carbon.

gi
en
Solution:- of
Mass of carbon = 5 Kg
ge
lle

C + O2 CO2 12 32
co

For burning 12 kg of carbon, oxygen required is 32 Kg. Therefore For

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burning 5 Kg of carbon = ?
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hi

Oxygen required = 32/12 X 5 = 13.33 Kg

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Pi
 Theoretical amount of oxygen required = 13.33 Kg Weight of air
required = weight of oxygen X 100/23

en
= 13.33 X 100/23

Pu
= 57.97 Kg

g,
in
er
ne
3.Analysis of fuel gave C=90%, H= 3.5 %, O=3 %, S= 0.5 %,

gi
en
H2O=0.1%, N= 0.5 % and remaining ash. Calculate the minimum
of
weight of air required for complete combustion of 1Kg of fuel.
ge

4.The percentage analysis by volume of gaseous fuel is CH4=14%,

lle

H2=32%, N2=40% and O2= 14%. If 25% excess air is used for
co

complete combustion calculate volume of air in litre actually supplied

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per m3 of gaseous fuel.

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