Calorific Value Analysis by Oxygen Bomb Calorimeter

GRACE LYN NIADAS Y.

Department of Chemical Engineering, College of Engineering and Architecture, Cebu Institute of Technology University, N. Bacalso Ave. Cebu City, 6000
Philippines

The calorific value of the fuel (coal) was obtained by combusting half of a gram of the fuel in
the oxygen bomb calorimeter which is at constant volume and zero work. The amount of the
fuel was accurately measured in the combustion capsule, and then the fuse wire was attached
in the bomb. After sealing the sample in the bomb it was flushed with oxygen and pressurize
to 35 atm and the bomb was placed into 2000 ml of distilled water. The temperature was
recorded at 30-second interval for 12 minutes, igniting the bomb in the first 5 minutes. With
the recorded rise of the temperature and its thermochemical corrections, the higher heating
value (calorific value) is determined by the heat liberated through complete combustion after
firing the bomb. The calorific value is useful in calculating heating values for fuels where
condensation of the reaction products is practical.

1. Introduction
The bomb calorimetry is used to determine the enthalpy of combustion, combH, for
hydrocarbons:
CxHYOz (s) + (2X+Y/2-Z)/2 O2 (g)

X CO2 (g) + Y H2O (l)

(Eq. 1)

The combustion reactions are usually exothermic, so combH is typically negative.

Since the bomb is made from stainless steel, the combustion reaction occurs at constant
volume and there is no work. Thus the change in the internal energy, U, for the calorimeter
is zero. Since the calorimeter is isolated from the rest of the universe, we can define the
reactants (sample and oxygen) to be the system.
The bomb calorimeter consists primarily of the sample, oxygen, the stainless steel
bomb and water. The Dewar prevents heat flow from the calorimeter to the rest of the
universe (see Eq. 2). Since the bomb is made from stainless steel, the combustion reaction
occurs at constant volume and there is no work (see Eq. 3).
qcalorimeter = 0
w calorimeter= p dV =0

(Eq. 2)
(Eq. 3)

Combustion is achieved by combining two key elements of combustion: a fuel and

oxygen, at an elevated temperature of an ignition temperature. The combustion process
involves the oxidation of constituents in the fuel. The heat calibrated is called heat of
combustion while the amount of heat corresponding to a unit mass of a fuel is called the
heating value. The Higher Heating Value (HHV) is used to distinguish cases in which water
in the combustion product is liquid while the Lower Heating Value (LHV) is gaseous.
The calorific value is defined as the quantity of heat produced by the complete
combustion of a specified mass of a particular fuel (it can be coal and diesel) which is
expressed in joules per kilogram. This value is determined by measuring the heat removed
when using the standard reference temperature. In addition to measuring the energy release of
one particular reaction, calorimetry is an important tool for determining the enthalpy of
formation for the compound under study. This information can be applied to any reaction
involving the compound.
2. Materials and Methods

Fig. 1 The
Bomb

Fig. 2 The Bomb with the Stirrer,

Water Jacket and Thermometer

The sample was prepared in a cylinder and charged with oxygen until its bomb
pressure rises to 35 atm. Then the calorimeter bucket was filled with 2000 grams of distilled
water and the bucket was set in the jacket together with the bomb by carefully lifting the
handle to the two holes in the side of the screw cap and lowering the bomb in the water with
its feet spanning the circular boss at the bottom of the bucket. After the ignition lead wires
were pushed into the terminal sockets on the top of the bomb, the jacket was covered with the
thermometer and the stirrer was turned and slipped into the pulley of the drive belts while
turning on its motor. The stirrer ran for 5 minutes to reach the equilibrium before measuring
its temperature. The temperature was then recorded for 5 minutes with a one-minute interval.
Then at the start of the 6 th minute, the bomb was fired by pressing the ignition button until the
indicator lights out. Any parts of the body should not be over the calorimeter when firing the
bomb for 30 seconds. The temperature will suddenly fluctuate few minutes after firing and
will slow down after reaching the stable maximum by the temperature rise curve. Accurate
time and temperature observations were recorded accurately to determine the calorific value
of the sample. After the rapid rise period, the temperature was adjusted and recorded until the
difference between successive readings has been constant to five minutes. After the last
temperature reading, the motor was stopped, the belt was removed and the cover was lifted
from the calorimeter. The bomb was also lifted out of the bucket while pulling out the
ignition wire. The knurled knob was opened slowly to release the gas pressure then the
cylinder was taken out and examined if soot or other evidence of incomplete combustion was
observed.

The fuse wire was removed and its length was subtracted from its initial length of 10
cm. If evidence was found, the cylinder was washed with distilled water and collected in a
beaker. The washing was titrated with standard 0.075N (recommended) sodium carbonate
solution using the methyl orange indicator until its color turned pale yellow which indicates
the endpoint of the washings.

3. Results and Discussion

Table A.1 Temperature vs. Time Variation
Before Firing (min)

After Firing (sec)

15

30

45

60

75

19.88

19.88

19.88

19.88

19.88

19.88

20.32

20.4

20.7

20.76

After Firing (sec)

90

105

120

135

150

165

180

195

210

225

20.9

21.58

21.64

21.74

21.8

21.84

21.88

21.9

21.92

21.94

After Firing (sec)

240

255

270

285

300

315

330

345

360

21.96

21.96

21.96

21.98

21.98

21.98

21.98

21.98

21.98

Table A.2 for Fuel: Coal

Mass of
fuel, m

R1

R2

ta

tc

C1

C2

C3

1.0 g

2426
cal/g

5.00
min

6.88
min

9.5
min

0
0
C/mi C/mi
n
n

19.88
C

21.98
C

1.4
ml

0.1
4

15.41

Graph A.1 Diesel Temperature Rise Curve

22.5
22
21.5
21
TEMPEARATURE - DEG. C.

20.5
20
19.5
19
18.5
TIME - MINUTES

1.0g of coal was used as fuel .After the cylinder was taken out in the bomb, the
evidence of incomplete combustion was very small that it was rendered negligible, thus no
titration was done in the experiment. From Table A.2 W is the energy equivalent of the
calorimeter in calories per degree Celsius and determined under standardization test
procedure. The time of firing was recorded at 5.00 min (a), the time when the temperature
reaches 60% of the total rise was 6.5 min (b), and the time at the beginning of the period in
which the temperature starts to stabilize was 15.41 min. R1 and R2 are the rate of which the
temperature was rising 5-minute before firing and after time. C1, C2 and C3 are
thermochemical correction where C1 and C2 are the titration used in the washing and C3 as
the correction in calories for heat of combustion of fuse wire. 10 cm of the fuse wire was
recorded and since the fuse wire used is nickel-chromium, it was multiplied with 2.3. With

the data gathered and using the equation below (Eq. 4), the higher heating value of diesel
computed is 8347.96 cal/g.
Gross HeatingValue of Combustion ( HHV )=

W ( t )C 1C 2C 3
m

(Eq. 4)

4. Conclusion
The oxygen bomb calorimeter can determine the specific calorific value of a certain
amount of fuel. Its primary function is to access the gross calorific value which is the gross
heat of combustion of a material. The bomb calorimeter can determine the potential
maximum heat released by a fuel while undergoing complete combustion. Because the
process is adiabatic in which there is no heat exchange between the surroundings and the
system, the heating value of the sample was determined by recording its temperature before
and after firing the bomb and titrating the washings if there is an evidence of incomplete
combustion left in the washings of the fuel used. The calorific values are used to determine
how efficient and effective fuels are in energy generation. These values can also be seen in
the nutrition where they are used to determine how much energy can be derived from the
food.

Reference
http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
What Are Calorific Values?www.wisegeek.com
http://www.quora.com/What-is-the-difference-between-coking-coal-and-thermal-coal-Whatis-the-Gross-Calorific-Value-of-coking-coal
http://www.science.oregonstate.edu/~gablek/CH362/calorim1.htm