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Engineering Chemistry

Determination of Calorific value


1. Bomb calorimeter
2. Boys calorimeter

1. Determination of calorific value of solid and non volatile liquid fuels: It


is determined by bomb calorimeter.
Principle: A known amount of the fuel is burnt in excess of oxygen and heat
liberated is transferred to a known amount of water. The calorific value of
the fuel is then determined by applying the principle of calorimeter i.e.
Heat gained = Heat lost

Construction:

Working

Calculation
• A known mass of the fuel sample is burnt completely in excess of
oxygen.
• The liberated heat is absorbed by water and calorimeter.

Beckmann 6v battery
thermometer Oxygen
valve
Stirrer

Electrodes

Cu calorimeter

Mg fuse
wires Stainless steel bomb
Stainless steel
crucible

Air jacket Fuel


Bomb Calorimeter
Water jacket
• The heat lost by burning fuel is the heat gained by water and
calorimeter.
• The calorific value of the fuel is calculated from the measured
data.
Beckmann 6v battery
thermometer Oxygen
valve
Stirrer

Electrodes

Cu calorimeter

Mg fuse
wires Stainless steel bomb
Stainless steel
crucible

Air jacket Fuel


Bomb Calorimeter
Water jacket
Calculations
Let weight of the fuel sample taken = x gm
Weight of water taken in the calorimeter = W gm
Water equivalent of the Calorimeter, stirrer, bomb, thermometer etc. = w gm
Initial temperature of water = t1oC
Final temperature of water = t2oC
Higher or gross calorific value of the fuel = C cal/gm
Heat gained by water = W x Dt x specific heat of water
= W (t2-t1) x 1 cal
Heat gained by Calorimeter = w (t2-t1) cal
Heat liberated by the fuel = x C cal
Heat liberated by the fuel = Heat gained by water and calorimeter
x C = (W+w) (t2-t1) cal
C = (W+w)(t2-t1) cal/g = GCV
x
Water Equivalent
• In a reaction the quantity of heat that raises
the temperature of some substance by some
amount, the same quantity of heat can
simultaneously raise the same temperature of
a certain mass of water. The mass of water is
then termed as water equivalent.
Net Calorific value:
Let percentage of hydrogen in the fuel = H
mass of water produced from 1 gm of the fuel = 9H/100 gm
Heat liberated during condensation of steam
= 0.09H  587 cal
Net (Lower calorific value) = GCV-Latent heat of water formed
= GCV-0.09H  587 cal/gm

Corrections: For accurate results the following corrections will have to be


incorporated:
(a) Acid Correction (tA): During combustion, sulphur and nitrogen present in
the fuel are oxidized to their corresponding acids under high pressure and
temperature.

S + O2 SO2

2SO2 + O2 + 2H2O 2 H2SO4 + Heat; Δ H = - 144,000 cal

2N2 + 5O2 + 2H2O 4 HNO3 + Heat; Δ H = - 57,160 cal


The amount of H2SO4 and HNO3 is analyzed by washings of bomb by titration while H2SO4
is determined by precipitation as BaSO4.
For each ml of 0.1 N H2SO4 formed, 3.6 calories should be subtracted.
For each ml of 0.1 N HNO3 formed, 1.43 calories must be subtracted.
(B) Cooling correction (tc): As the temperature rises above the room temperature, the loss
of heat does occur due to radiation, and the highest temperature recorded will be slightly
less than that obtained. A temperature correction is therefore necessary to get the correct
rise in temperature.
If the time taken for the water in the calorimeter to cool down from the maximum
temperature attained, to the room temperature is x minutes and the rate of cooling is
dto/min, then the cooling correction = x  dt. This should be added to the observed rise in
temperature.
(C) Fuse wire correction(tf): As metal wire is used for ignition, the heat generated by
burning of metal wire is also included in the gross calorific value. Hence this amount of heat
has to be subtracted from the total value.
(D) Cotton thread correction (tt): The correction for the cotton thread used for firing the
charge is calculated from the weight of the dry cotton thread actually used. Hence this
amount of heat has to be subtracted from the total value.
Therefore, Gross calorific value
GCV =(W+w)(t2 - t1+ tc] - [tA+ tF + tt]
Mass of the fuel.
2. Determination of calorific value of gases and volatile liquid fuels:

It is determined by Boy’s calorimeter.

Principle: principle involved in this method is to burn the gas at a known


constant rate in a vessel under such conditions that the entire amount of heat
produced is absorbed by water which is also flowing at a constant rate.

Construction:

Working

Calculations
Boy’s Calorimeter
• A known volume of gaseous fuel sample is burnt in the combustion chamber
of a Boy’s calorimeter.
• The released heat is quantitatively absorbed by cooling water, circulated
through copper coils surrounding the combustion chamber.

Boy’s Calorimeter
• The mass of cooling water and its rise in temperature are noted.
• The mass of water produced by condensation of steam is calculated.
• The calorific value of the fuel sample is then calculated from these data.

Boy’s Calorimeter
Calculations:
Let W = wt of cooling water passed in time t
V = volume of gas burnt at S.T.P. in time t
t1 = temperature of the incoming water
t2 = temperature of the outgoing water
m = weight of steam condensed in time t in a graduated cylinder
θ = HCV of fuel

Heat absorbed by circulating water = W (t2-t1)


Heat produced by combustion of fuel = V θ

Assuming no heat loss


V θ = W (t2-t1)
HCV = θ = W (t2-t1)/ V Kcal/m3

Weight of total H2O condensed for ‘V’ m3 of gas = m Kg


Weight of H2O condensed per m3 of gas = m/V Kg
Latent heat of steam per m3 of gas = m/V × 587 Kcal

Net calorific value = [gross calorific value – m/V × 587] Kcal/m 3


Theoretical calculation of Calorific value of a Fuel:
The calorific value of a fuel can be calculated if the percentages of the
constituent elements are known.

Substrate Calorific
value
Carbon 8080
Hydrogen 34500
Sulphur 2240
Dulong’s formula for calculating the calorific value
is given as:
Gross calorific Value (HCV)
1 O
 [8080C  34,500( H  )  2,240S ]kcal / kg
100 8

Net Calorific value (LCV)


9H
 [ HCV   587]kcal / kg
100
 [ HCV  0.09 H  587]kcal / kg
If oxygen is also present, it combines with hydrogen to form H 2O. Thus
the hydrogen in the combined form is not available for combustion and
is called fixed hydrogen.

Amount of hydrogen available for combustion


= Total mass of hydrogen-hydrogen combined with oxygen.

H2 + ½ O2 H 2O
1g 8g 9g

Therefore, mass of hydrogen available for combustion


= Total mass of hydrogen-1/8 mass of oxygen in fuel
= H-O/8
Since air has 23% oxygen by weight and 21% oxygen by volume

Weight of air required = Net oxygen × 100/23 kg

Volume of air required = Net oxygen × 100/21 m3