Determination of Calorific Value: Bomb Calorimeter

A practice problem:
❖ On burning 0.83 g of a solid fuel in a bomb calorimeter, the temperature of 350 g of water increased from
26.5 oC to 29.2 oC. In another experiment in the same calorimeter 0.5 g of naphthalene (HCV = 9,688 kcal/kg)
was burnt and temperature was increased form 25.5 oC to 29.2 oC. Latent heat of evaporation of water is
587.0 cal/g and the fuel contains 0.7 % hydrogen, calculate its gross and net calorific value.
 Bomb Calorimetric Corrections
❑ Precision in bomb calorimetry is dependent
upon a repeatable set of operating conditions.
➢ Those factors which cannot be held constant
will require corrections to compensate for their
effects. Any differences between the
combustion as it takes place in the bomb in
relation to the process in a power plant or other
application must also be taken into account
❑ There are three major corrections:
● Fuse wire correction
● Acid correction
● Cooling correction
❑ Fuse wire correction
➢ Together with the sample, part of the ignition or
fuse wire is also burned. The heat generated by
burning of the fuse wire is also gets included in the
gross calorific value and this value must be
subtracted from observed value to get correct HCV
➢ A correction term, ∆Qwire, the heat released by the
combustion of the wire must be introduced
➢ ∆Qwire is obtained by measuring the length of the
fuse wire before and after combustion and
multiplying the difference by a conversion factor
qwire, valid at standard temperature
∆Qwire = qwire × (L0 – L)
L0 = fuse wire length before combustion
L = fuse wire length after combustion
 Bomb Calorimetric Corrections
❑ Acid correction
➢ Combustion in the bomb takes place in an
atmosphere of pure oxygen at high temperature
and pressure. Fuels containing S and N gets
oxidized under high pressure & temperature of
ignition producing H2SO4 & HNO3
S + O2 → SO2
2 SO2 + O2 + 2 H2O → 2 H2SO4 ΔH = - 144 kcal/mol
2 N2 + 5 O2 + 2 H2O → 4 HNO3 ΔH = - 57.2 kcal/mol
➢ These side reactions, being exothermic, generate
an appreciable amount of heat which can’t be
credited to the sample
➢ This heat liberated gets included into the overall
HCV. Hence, the heats of formation of H2SO4 and ➢
HNO3 should be subtracted from the heat
liberated
➢ The correction term for the formation of
sulphuric and nitric acid is obtained by titrating
the aqueous residues in the bomb with a
standardized NaOH solution
→ For 1 ml of 0.1 N H2SO4 formed: 3.6 calories should be
subtracted
→ For 1 ml of 0.1 N HNO3 formed: 1.43 calories should be
subtracted
→ When H2SO4 is determined by precipitation as BaSO4:
For 1 mg of S is 2.25 cal should be subtracted
❑ Cooling correction
➢ For an adiabatic calorimeter, the heat loss to the water
jacket is negligible. Cooling correction isn’t necessary
➢ For an isothermal/static calorimeter, the heat loss occurs
due to the radiation through the dewar. Highest
temperature recorded be slightly less than the actual.
This loss is corrected with an empirical radiative
correction (RC). The rate of cooling of the calorimeter
from maximum temperature to room temperature is
noted. From this rate of cooling (i.e., dt/min) and the
actual time taken for cooling (X min), correction (dt × X) is
called cooling correction and is added to the (t2 - t1) term.
 Bomb Calorimetric Corrections

𝑾 + 𝒘 𝒕𝟐 − 𝒕𝟏 + 𝒕𝒆𝒎𝒑. 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏 − 𝑨𝒄𝒊𝒅 + 𝒇𝒖𝒆𝒍 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏

𝑯𝑪𝑽 =
𝑴𝒂𝒔𝒔 𝒐𝒇𝒕𝒉𝒆 𝒇𝒖𝒆𝒍 (𝒎)

NCV = HCV – (0.09 × H × latent heat of steam) cal/g

❖ A sample of coal contains C = 93 %; H = 6 % and ash = 1 %. The following data were obtained when the above
coal was tested in bomb calorimeter. wt. of coal burnt = 0.92 g, Wt. of water taken = 550 g, water equivalent of
calorimeter = 2200 g, rise in temperature = 2.42 °C, fuse wire correction = 10.0 cal, acid correction = 50.0 cal.
Calculate gross and net calorific value of the coal. The latent heat of condensation of steam is 580 cal/g.

• Wt. of coal sample (m) = 0.92 g;
• wt. of water (W) =550 g;
• water equivalent of calorimeter (w) = 2,200 g;
• temperature rise (t2-t1) = 2.42 oC;
• acid correction = 50.0 cal;
• fuse wire correction = 10.0 cal;
• latent heat of steam = 580 cal/g;
• percentage of H =6%
GCV/HCV = (W + w) (t1 - t2) – [ acid + fuse corrections]
m
= {(550 + 2,200) × 2.42} – [50 + 10] cal = 7168.5 cal/g.
0.92g
 NCV = [HCV – 0.09 H × latent heat steam]
= (7168.5 – 0.09 × 6 × 580) cal/g = 6855.3 cal/g
 Determination of Calorific Value: Bomb Calorimeter
Problem 1 (7th Problem of DA)
➢ The temperature of 950 g of water increased from
25.5 °C to 28.5 °C on burning 0.75 g of solid fuel in a
bomb calorimeter. Water equivalent of the
calorimeter and the latent heat of steam are 400 g
and 587 cal/g. If the fuel contains 0.65% of
hydrogen, calculate its net calorific value.
❑ Problem 3 (9th Problem of DA)
➢ A sample of coal contains C = 90 %, H = 8.9 % and
ash = 3 %. On burning 1 g of coal in a bomb
calorimeter, the temperature of 2500 g water
increased 2.5 °C. Mean specific heat of the
apparatus is 0.098. Acid and fuse-wire corrections
are 50 cal and 10 cal respectively. Calculate gross
and net calorific value of coal sample. Given the
latent heat of water is 587 cal/g.
❑ Problem 2 (7th Problem of DA)
➢ A sample of coal contains C = 92%; H = 5% and
ash = 3%. The following data were obtained
when the above coal was tested in bomb
calorimeter.
Wt. of coal burnt = 0.95 g,
Wt. of water taken = 700 g,
Water equivalent of calorimeter = 2000 g,
Rise in temperature = 2.48 °C,
Fuse wire correction = 10.0 cal,
Acid correction = 60.0 cal and
Cooling correction = 0.02 °C.
Calculate gross and net calorific value of the coal,
assuming the latent heat of condensation of
steam as 580 cal/g.