DE LA SALLE UNIVERSITY

Gokongwei College of Engineering

Chemical Engineering Department

ENGINEERING THERMODYNAMICS LABORATORY

(LBYCHED) AY 2016-2017 3rd Term

FINAL LABORATORY REPORT

EXPERIMENT NO. # 9
Bomb Calorimetry and Properties of Solid Fuels

Group No. 4 Section EA3

NAME SIGNATURE CRITERIA SCORE
1. Chua-Unsu, Audrey Gayle Content
Alexis Y. (50%)
Presentation
2. Dee, Perry C. (25%)
Relevance
3. Nebres, Angela E. (25%)

26 July 2017 2 August 2017

DATE OF PERFORMANCE DATE OF SUBMISSION

DR. KATHLEEN B. AVISO

INSTRUCTOR

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 I. Objectives

A. Analysis and Heating Value of Solid Fuels

This part of the experiment aims to determine the proximate analysis and heating value of coal.

B. Bomb Calorimetry and Heat of Combustion

This portion of the experiment had the following objectives:

1. To determine the heat capacity of the bomb calorimeter under constant volume.
2. To determine the heat of combustion of benzoic acid using the bomb calorimeter.

II. Theory

A. Analysis and Heating Value of Solid Fuels

Coal is one of the commonly used valuable sources of energy for steam or electric
generation. It is a sedimentary rock that consists mostly of carbon and is formed from organic
matter of land-based plants that were buried millions of years ago, having pressure applied to the
organic matter. Aside from carbon, it also contains hydrogen, nitrogen, sulfur, and ash. Coal’s
quality is determined by its carbon content. It is divided into four ranks, from least to most carbon
content - lignite, sub-bituminous, bituminous, and anthracite. Higher levels of carbon produce
more heat when the coal is burned. Based on carbon content, the highest rank of coal would be
graphite, however it is hard to ignite ("Coal Properties - Coal - Alberta's Energy Heritage", n.d.;
"Properties of Coal", n.d.).

The two methods of analyzing coal are ultimate analysis and proximate analysis. The
former takes into account all the elements (either solid or gaseous) in the coal, while the latter is
only concerned in determining the percentages of fixed carbon, volatile matter, moisture, and ash
(Properties of Coal, n.d.).

B. Bomb Calorimetry and Heat of Combustion

Chemical reactions are accompanied by enthalpy changes; particularly of interest for this
experiment is the combustion reaction. The standard enthalpy of combustion would refer to the

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standard enthalpy for the complete oxidation of an organic compound containing C, H, and O
atoms to CO2 gas and liquid H2O and to N2 gas if it also has N atoms (Atkins & de Paula, 2010).

The study of the transfer of energy as heat during the physical and chemical processes is known
as calorimetry and the device used to measure the energy transferred as heat is referred to as the
calorimeter (Atkins & de Paula, 2010). The measurement done in the determination of the heat of
combustion is performed at a constant volume, and not at constant pressure. In determining the
heat of combustion of certain fuels and pure organic substances, a commercial bomb calorimeter
(Fig. 1) is used. It contains a combustion bomb which is made of corrosion-resistant metal, and
holds the sample of interest. This bomb is charged with oxygen gas after the sample and wire are
placed in the bomb, and is then placed in a bucket containing a specified quantity of water. The
temperature rise brought about by the combustion can be seen from the thermometer whose bulb
is in contact with the water. (Crockford & Nowell, 1956).

Figure 2. A bomb calorimeter set up (Chang, 2010)

As stated earlier, the sample inside the bomb calorimeter combusts and heats the bomb, also
warming the water around it when the electrical current is passed through the wires. The observed
temperature rise is recorded as a function of time and has a typical calorimeter curve, also known
as a thermogram, as shown in Fig. 2. Since the temperature rise due to the chemical reaction is
commonly nonlinear, the initial and final slopes of the thermogram may be different and an
extrapolation can be done. The difference of the two extrapolated lines at an intermediate time
during the reaction is the net temperature rise (ΔTc). However, the definite location of the
intermediate time is dependent on the calorimeter and the reaction under study. A usual criterion

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used in estimating the time is done by locating the ΔT at the point wherein the shaded areas in the
thermogram are equal. It is said that when the temperature is approximately 0.63ΔT, the shaded
areas are equal. Also, the temperature rise (ΔT) of the reaction can be measured from the difference
between the initial temperature (Ti) and the final temperature (Tf) from the thermogram (Worrell,
Vesilind, & Ludwig, n.d.).

Figure 2. Temperature-time plot from a bomb calorimeter (Worrell, Vesilind, & Ludwig, n.d.)

Chang (2010) notes that during the time of measuring the temperature increase, one can assume
that there is no heat or mass lost to the surroundings due to the distinctive design of the calorimeter.
Consequently, the bomb and water wherein it is submerged can be treated as an isolated system,
and that throughout the process, no heat enters or leaves the system. Thus, the heat change of the
system is zero (Eq. 1). The heat capacity of the calorimeter and the temperature rise must be
determined in order to calculate the heat change of the calorimeter (Eq. 3).

𝑞𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑞𝑐𝑎𝑙 + 𝑞𝑟𝑥𝑛 = 0 (1)

𝑞𝑐𝑎𝑙 = −𝑞𝑟𝑥𝑛 (2)

where qcal is the heat change of the calorimeter and qrxn is the heat change of reaction.

𝑞𝑐𝑎𝑙 = 𝐶𝑐𝑎𝑙 ∆T (3)

where Ccal is the heat capacity of the calorimeter and ΔT is the temperature increase during the
reaction.

Worrell, Vesilind, and Ludwig (n.d.) elaborate that since every calorimeter is different, it should
be standardized by a material for which its heat of combustion is known. The commonly used

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 material for standardization is benzoic acid, which is specifically formed into a pellet for this
purpose. The benzoic acid pellet is combusted in a bomb calorimeter, and with the determined
temperature rise (ΔT) from the thermogram, the heat capacity of the calorimeter is obtained (Eq.
4). In addition, the heat from the combustion of the ignition wire is also accounted for in order to
have accurate analyses (Eq. 5).

𝑈𝑀𝑏 (4)
𝐶𝑐𝑎𝑙 =
∆𝑇

6318𝑀𝑏 + 𝑞𝑤 𝑀𝑤 (5)
𝐶𝑐𝑎𝑙 =
∆𝑇

where Ccal is the heat capacity of the calorimeter in cal/°C, U is the heat of combustion of benzoic
acid in cal/g °C, Mb is the mass of benzoic acid pellet in g, ΔT is the temperature rise from
thermogram in °C, qw is the heat of combustion of the ignition wire in cal/g, and Mw is the mass
of ignition wire used in g. In Eq. 5, the heat of combustion of benzoic acid (6318 cal/g) is directly
substituted.

III. Set-up

i. Actual Set-up
A. Analysis and Heating Value of Solid Fuels

Figure 3.1. Meker burner with iron stand, Figure 3.2. Dessicator with silica gel at the
clay triangle, and crucible. bottom.

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B. Bomb Calorimetry and Heat of Combustion

Figure 3.3. Isochoric tank. Figure 3.4. Parr ignition unit.

ii. Engineering Drawing

A. Analysis and Heating Value of Solid Fuels

Figure 3.5. Meker burner set-up

B. Bomb Calorimetry and Heat of Combustion

Figure 3.6. Schematic diagram of bomb calorimeter (“Bomb Calorimeter”, n.d.).

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IV. Summary of Procedures

A. Analysis and Heating Value of Solid Fuels

The amount of moisture, volatile matter, and ash in activated carbon was determined by
heating a 1g sample and cooling. Inside a crucible, 1g of activated carbon was weighed and
heated using a Meker burner (shown in Fig. 3.1). The sample was allowed to burn for one
minute, then cooled inside the dessicator shown in Fig. 3.2. After cooling the activated carbon,
it was weighed. The weight lost after burning is the amount of moisture in the sample. This
was then burned for seven minutes, then cooled and weighed. The difference in the weight is
the degree of volatility of the sample. Finally, the activated carbon was burned until only ash
remained.

B. Bomb Calorimetry and Heat of Combustion

A 1g pellet of benzoic acid was placed inside the dish of the cover of the bomb calorimeter.
A 10-cm piece of ignition wire was measured the put in contact with the pellet. Approximately
1mL of water was placed inside the bomb calorimeter, then covered and sealed tightly. The
bomb was then pressurized with 35atm of oxygen. Afterwards, the bomb was placed inside a
constant volume tank (shown in Fig. 3.3) filled with 2L of water. The tank was covered and
the stirrer was connected to the motor using a rubber band. The temperature inside the tank
was allowed to stabilize for five minutes before firing the Parr ignition unit (shown in Fig. 3.4).
After firing, the temperature inside the tank was measured every fifteen seconds until three
constant temperature readings were obtained. Finally, the bomb calorimeter was removed from
the tank and opened, and the amount of unburned wire was measured.

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V. Data
A. Analysis and Heating Value of Solid Fuels

Table 5.1. Proximate Analysis of Fuel

Combustion Properties

Time (s) Weight of Crucible (g) Weight of Crucible + Content (g) Content (g)

0 44.76 45.80 1.04

60 44.76 45.46 0.34

420 44.76 45.13 0.33

Infinity 44.76 44.74 0.39

B. Bomb Calorimetry and Heat of Combustion

Table 5.2. Properties of Calorimetry

Weight of Benzoic Acid 1g

Pressure 35 atm

Wire, Initial 10 cm

Wire, Final 7.5 cm

Wire, Heat of Combustion 1400 cal/g

2.3 cal/cm

Table 5.3. Temperature Rise during Combustion

Time (s) Temperature (oC)

Pre-Period

0 27.08

60 27.08

120 27.08

180 27.08

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240 27.09

300 27.09

Rise-Period

15 27.09

30 27.14

45 27.36

100 27.56

115 27.78

130 27.90

145 28.02

200 28.12

215 28.20

230 28.23

245 28.27

300 28.30

315 28.33

330 28.35

345 28.36

400 28.38

415 28.39

430 28.40

445 28.42

500 28.42

515 28.43

530 28.44

545 28.44

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 600 28.45

Post-Period

615 28.46

630 28.46

645 28.46

VI. Results and Analysis

A. Analysis and Heating Value of Solid Fuels

In the first heating of the carbon sample, 0.34 g of moisture was evaporated. This was heated
for exactly 60 seconds as excess heating would have amounted to burning the volatile matter. In
conjunction to the second heating, a total of 0.33 g of volatile matter was measured. Subsequent
final heating to time equals infinity yielded a residue of 0.39 g of ash. Addition of the three
combustion products, gives a total of 1.06 g of carbon. It can be observed that the amount of
obtained combustion products is not equivalent to the original weighed 1 g of reagent. The most
prominent error from this part came from immediate weighing of sample without letting the sample
cool completely. This is because a heated object will weigh slightly more than a cooled object due
to the gravitational force of the stress energy of the body, of which includes the mass and kinetic
energy of the body (Heile, 2013).

B. Bomb Calorimetry and Heat of Combustion

According to the literature, the equivalent energy of the bomb calorimeter is 5000 J/K. This
will be used in the calculation of the heat of combustion of Benzoic Acid.

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 28.8

28.6

28.4

28.2
y = 0.4169ln(x) + 25.857
Temperature (oC)

28 R² = 0.958

27.8

27.6

27.4

27.2

27

26.8
0 100 200 300 400 500 600 700
Time (s)

Figure 6.1. Temperature vs. Time of the Combustion of Benzoic Acid

In the thermogram in Fig. 6.1, the figure is to be split into three phases, namely: pre, rise, and
post period. In the first part of the experiment, the calorimeter was first set to achieve equilibrium
with its surroundings reaching a temperature of 27.09oC. Upon stabilization, the reaction was then
immediately simulated which led to a rise-period where the gradual increase in slope can be
observed. In the latter part of the experiment, a gradual decrease in change can be observed as the
temperature stagnated to a reading of 28.46oC, which is the post-period of the thermogram. From
this, the change in temperature is calculated taking into account 63% of the change in temperature
of the rise period. In this case, the change in temperature is 0.8568oC.

The heat of combustion of the calorimeter was calculated to be 4187.7306J. A correction factor
for the wire was applied to the solution.

Comparing this with the theoretical value of 6000J, an error of 30.20% was obtained. This high
percentage error can be attributed to the presence of impurities within the calorimeter during
combustion. Another form of error may be due to heat losses towards the surrounding
environment.

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VII. Individual Observations

Name Observation

Chua-Unsu, Audrey After igniting the bomb calorimeter, the temperature inside the
tank increased slowly and minutely. It was observed that the
thermometer used was appropriate and that a less accurate
thermometer would not be able to show the rise in temperature.

Dee, Perry The proximate analysis of coal was obtained through the
continuous burning of carbon. I noticed that measuring a heated
crucible containing the sample weight of the residue would lead to
an increase in weight reading. Thus, cooling is needed in order for
a more accurate reading.

Nebres, Angela The temperature inside the calorimeter began to rise after ignition
and it stabilized after a few minutes. Also, the length of the wire
shortened by around 2.5cm and moisture and ash were seen inside
the calorimeter after the whole combustion process.

VIII. Conclusion and Recommendations

A. Analysis and Heating Value of Solid Fuels

It can be seen that the proximate analysis of carbon contained very minimal deviation from the
original 1g of sample. This deviation occurred simply due to improper weighing procedures.
Because the sample was not given the chance to cool completely, an increase in weight was
observed. However, it can be said that obtaining the proximate analysis of each component can be
measured easily. It is recommended that for future experiments, proper cooling procedures be done
when weighing the moisture, volatile matter, and ash content of the carbon sample.

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 B. Bomb Calorimetry and Heat of Combustion

The heat of combustion of the bomb calorimeter was calculated to be 4187.7307 J. This
deviated from the supposed theoretical heat of combustion of 6000J. Possible errors that occurred
were due to insufficient insulation of the bomb calorimeter which effectively lead to heat losses
towards the immediate surroundings.

IX. Answers in Guide Questions

A. Analysis and Heating Value of Solid Fuels

1. What does bituminous coal refer to?

Bituminous coal is the second highest rank of coal, next to anthracite. This is the most
abundant and commonly used coal for electricity generation. It consists of 77 to 87% carbon
("What are the different types of coal? | American Geosciences Institute", n.d.; King, n.d.).

2. What are the constituents of coal?

Coal is composed of carbon, hydrogen, oxygen, nitrogen, ash, and sulfur (Chemical
and Mineral Composition of Coal, n.d.).

3. What are the important by-products from distillation or carbonization of bituminous coal?

These are bitumen and coke. Bitumen or tar is a black viscous material used for road
surfacing. Coke (fuel) is used to make iron ("coke | coal product", n.d.; "Properties of
Coal", n.d.).

4. What are the different types of coal?

Coal is classified according to its carbon content. The four major types of coal are, from
the most to least carbon content, anthracite, bituminous, subbituminous, and lignite. Aside
from these, there is also peat and graphite. Peat is a precursor to coal and when subjected to
great pressure and heat, turns into coal. On the other hand, graphite is technically the highest
rank of coal but is used as lead and powder for lubricant instead because of the difficulty in
igniting it ("What are the different types of coal? | American Geosciences Institute", n.d.;
"Properties of Coal", n.d.).

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 B. Bomb Calorimetry and Heat of Combustion

No guide questions for this section

Appendix

I. Sample Calculations
A. Analysis and Heating Value of Solid Fuels
𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 (𝑔) = 𝑆𝑎𝑚𝑝𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 ℎ𝑒𝑎𝑡𝑖𝑛𝑔 − 𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑆𝑎𝑚𝑝𝑙𝑒
= 45.80 − 45.46
𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 = 0.34 𝑔
B. Bomb Calorimetry and Heat of Combustion

𝑄 = 𝐸∆𝑇𝑐 − 𝐿(𝐶𝑓)

= 5000 (0.8568) − 10 (9.62964)

𝑄 = 4187.7306 𝐽

II. References
Atkins, P. W., & de Paula, J. (2010). Physical Chemistry, 9th ed. New York: Oxford University
Press.
Bomb Calorimeter. (n.d.). Retrieved from http://www.transtutors.com/homework-
help/engineering-chemistry/fuels/bomb-calorimeter-construction.aspx
Chang, R. (2010). Chemistry (10th ed.). New York: mcGraw-Hill Companies, Inc.
Coal Properties - Coal - Alberta's Energy Heritage. History.alberta.ca. Retrieved 29 July 2017,
from http://history.alberta.ca/energyheritage/coal/early-coal-history-to-1900/global-coal-
formation/coal-properties.aspx#page-1
coke | coal product. Encyclopedia Britannica. Retrieved 29 July 2017, from
https://www.britannica.com/technology/coke
Crockford, H. D., & Nowell, J. W. (1956). Laboratory Manual of Physical Chemistry. New York:
John Wiley & Sons, Inc.
Chemical and Mineral Composition of Coal (n.d.). Kentucky Foundation. Retrieved 29 July 2017,
from http://www.coaleducation.org/q&a/what_are_the_chemical.htm

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Heile, F. (2013, April 21). Is a Hot Object Heavier Than a Cold One? | HuffPost. Retrieved from
http://www.huffingtonpost.com/quora/is-a-hot-object-heavier-t_b_2717229.html
King, H. Coal: Anthracite, Bituminous, Coke, Pictures, Formation, Uses. Geology.com. Retrieved
29 July 2017, from http://geology.com/rocks/coal.shtml
Properties of Coal. Pittdixon.go-plus.net. Retrieved 29 July 2017, from http://www.pittdixon.go-
plus.net/coal/coal.htm
Properties of Coal. Retrieved from
https://www.researchgate.net/file.PostFileLoader.html?id=55101748d5a3f291118b45de
&assetKey=AS%3A273741534171138%401442276475492.
What are the different types of coal? | American Geosciences Institute. Americangeosciences.org.
Retrieved 29 July 2017, from https://www.americangeosciences.org/critical-
issues/faq/what-are-the-different-types-of-coal
Worrell, W., Vesilind, P., & Ludwig, C. (n.d.). Solid waste engineering (3rd ed.). Boston: Cengage
Learning.

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