Title: Bomb Calorimetry - Measuring Heats of Combustion

Name: Brandon Cox

Course: CHEMU541-01L

Experiment Due Date: 09/30/2021

Date of Submission: 09/30/2021

Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

Introduction

The purpose of this experiment is to calculate the molar enthalpy change when a sample

of naphthalene and biphenyl undergoes combustion. The chemical reaction for the combustion of

naphthalene can be found below in Equation (1) and (2).

C10H8 (s) + 12 O2 (g)  10 CO2 (g) + 4 H2O (l) ΔHcomb(naphthalene) (1)

29
C12H10 (s) + O (g)  12 CO2 (g) + 5 H2O (l) ΔHcomb(biphenyl) (2)
2 2

Bomb calorimetry is a particularly useful technique for accomplishing this goal because

the combustion occurs in a constant-volume container, making it possible for the energy to

transfer exclusively in the form of heat1. In turn, the heat transfer can be detected as a

temperature change in the system. This general relationship can be expressed in the form of

Equation (3), where ΔU is the change in internal energy, ΔT is the change in temperature, and Cv

is the heat capacity of the bomb calorimeter.

ΔU = −CvΔT (3)

Since Cv is an unknown value, it becomes necessary to run a calibration trial for this

experiment, where a sample of benzoic acid with a known mass can be combusted in the same

conditions as the naphthalene and biphenyl samples. The combustion of benzoic acid, which has

a known energy of combustion of -26.41 kJ/g1, can be found below in Equation (4).

15
C6H5COOH (s) + O (g)  7 CO2 (g) + 3 H2O (l) (4)
2 2

The last factor to consider for the experiment is the sliver of iron wire that attaches the

respective samples of benzoic acid or naphthalene to the terminals of the bomb. Once the bomb
Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

ignites, the iron wire burns up and contributes some energy to the system. As such, it is

important to include the ΔU value of the fuse wire1, -5.858 kJ/g, not only in the calibration of the

bomb calorimeter, but also in the determination of the specific energy for naphthalene and

biphenyl’s combustion. Upon calculating naphthalene and biphenyl’s specific energy of

combustion, the molar enthalpy change can be determined by using Equation (5), shown below

where ΔH is the molar enthalpy change, ΔUnaphthalene/biphenyl is the molar energy change, R is the

ideal gas constant, Δngas is the change in moles of gas, and T is the temperature of the reaction.

ΔH = ΔUnaphthalene/biphenyl + RTΔngas (5)

Materials and Methods

To begin, a fuse wire was cut to a length of 10 cm and weighed on an analytical balance.

A sample of benzoic acid was also weighed on an analytical balance, pressed into a pellet, and

then fused to the center of the wire using a direct current supply. Next, the wire was fastened to

the terminals of the bomb such that the benzoic acid pellet was aligned with the bomb’s pan.

Once the wire and pellet were in place, the bomb was reassembled and purged of any

atmospheric nitrogen. After the bomb had been purged, it was filled with 30 atm of oxygen gas.

The bomb was placed in the dry pail of the calorimeter, where it was connected to its ignition

wires and surrounded with 2 L of room-temperature water.

Finally, the lid of the calorimeter was closed, stirrer turned on, and a baseline temperature

of the water was established by recording the temperature reading of the digital thermometer

every 30 seconds. After 5 minutes of time-temperature readings, the bomb was ignited, and the

temperature of the water was recorded every 30 seconds for an additional 10 minutes. Once the

run was completed, the bomb was reopened and any excess wire that had not been consumed
Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

during the run was pulled off the terminals and weighed on an analytical balance. At this point,

all of the necessary data was recorded in order to solve for the calorimeter constant using

Equation (6), where mwire is the consumed mass of fuse wire, mBA is the mass of the benzoic acid

tablet, ΔUwire is the specific heat of combustion of the fuse wire, and ΔUBA is the specific heat of

combustion of the benzoic acid pellet.

massBA Δ U BA + masswire ΔU wire

Cv = (6)
ΔT

Once all the components needed to calculated the heat capacity for the bomb calorimeter

were gained, the entire experimental procedure was repeated with a naphthalene and biphenyl

pellet, which had been fabricated using a pellet press.

Results

1. Attach all T vs. time graphs. Choose a graph to discuss how ΔT was determined.

a. ΔT was calculated in Excel see Sheet: Benzoic Acid – Ours for the fuller image of

ΔT calculations. In brief, it involves splitting the data into three sections Top,

Middle, Bottom and integrating those sections of data results in values that can be

used in Equation (7) to calculate ΔT.

∆T ∆T
ΔT = (Tf – Ti) –
((( ) ( )) (( ) ( )))
∆t i
t d−t i −
∆t d
t f −t d (7)

Where ( ∆∆Tt ) is the initial (i) and final (f) drift rates, i.e. the slope of the
temperature vs. time curve at the time of ignition (ti) or at the time when the

change in temperature is approximately linear (tf). Ti is the temperature at ti, Tf is

the temperature at tf, and td being a specific time between ti and tf. The specific
Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

time of td is determined to be the point where the experimental T vs. time curve

and extrapolated Top and Bottom curve (the area under those curves).2

Heat Curve of Benzoic Acid (Ours) - Temp/Time

25.5

25

24.5
Temp (°C)

24

23.5

23
0 100 200 300 400 500 600 700 800 900

Time (s)

Table 1: Experimental Heat Curve of Benzoic Acid (Group 1)

Heat Curve of Benzoic Acid (Theirs) - Temp/Time

25.5

25

24.5
Temp (°C)

24

23.5

23

22.5
0 100 200 300 400 500 600 700 800

Time (s)

Table 2: Experimental Heat Curve of Benzoic Acid (Group 2)

Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

Heat Curve of Naphthalene (Ours) - Temp/Time

29

28

27
Temp (°C)

26

25

24

23

22
-100 100 300 500 700 900 1100 1300

Time (s)

Table 3: Experimental Heat Curve of Naphthalene (Group 1)

Heat Curve of Naphthalene (Theirs) - Temp/Time

26

25

24
Temp (°C)

23

22

21

20

19
0 100 200 300 400 500 600 700 800 900 1000 1100

Time (s)

Table 4: Experimental Heat Curve of Naphthalene (Group 2)

Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

Heat Curve of Biphenyl (Ours) - Temp/Time

25.5
25
24.5
24
Temp (°C)

23.5
23
22.5
22
21.5
0 100 200 300 400 500 600 700 800 900

Time (s)

Table 5: Experimental Heat Curve of Biphenyl (Group 1)

Heat Curve of Biphenyl (Theirs) - Temp/Time

25
24.5
24
23.5
Temp (°C)

23
22.5
22
21.5
21
0 100 200 300 400 500 600 700 800 900 1000 1100

Time (s)

Table 6: Experimental Heat Curve of Biphenyl (Group 2)

Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

2. From the benzoic acid data, what is the average heat capacity of the calorimeter?

kJ
a. C vavg=−10.71
C

3. What are the ΔUcomb and ΔHcomb of each run and the average values associated with them?

kJ kJ
a. Naphthalene: ΔU combavg=−5280.46 ; ΔH combavg=−5267
mol mol

kJ kJ
b. Biphenyl: ΔU combavg=−5419.42 ; ΔH combavg =−6504.25
mol mol

4. Compare the ΔHcomb with literature values and note % errors. What sources of error could

be contributing to these values, and how do they affect your results?

3 kJ
a. Naphthalene: ΔH comblit =−5150.09 ; % diff =−2.23 %
mol

4 kJ
b. Biphenyl: ΔH comblit =−6251.8 ; % diff =−3.96 %
mol

c. As observed from the NIST (literature) values which are obtained are with far

more accurate systems to monitor and control temperature of the system. There

must be some errors that occurred during this experiment which led to the

inaccuracy of our results. Some potential errors may have been due to the fact that

the process was not completely adiabatic. Heat is still capable of escaping through

the walls of the calorimeter, thus adding uncertainty to the recorded temperature

values. The amount of water surrounding the bomb is also a source of error. Even

a small amount of uncertainty in the amount of water measured could lead to error

in the experiment. For example, if 2001 mL was measured rather than the

expected 2000 mL, the water would require more energy to increase the

temperature. There also exist a multitude of smaller sources that contributed to

error propagation like weighing and transferring the samples.

Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

5. What computational methods were used to obtain your calculated values?

6. How do the experimental ΔHcomb of each compound and the ΔHcomb obtained from the

semi-empirical calculations differ from one another?

7. Semi-empirical calculations assume the substance is a gas. How will this contribute to

differences in the computationally determined ΔHcomb as compared to the experimental

ΔHcomb?

8. Compare the heats of formation calculated from the ΔHcomb of each compound with

literature values, and calculate % errors.

9. If biphenyl and naphthalene could be used as fuels, which would be the most efficient for

producing energy? How do they compare to other fuels such as methane, octane, coal or

ethanol?

Calculations

See Attached Excel File for Calculations

Conclusion and Future Work

Overall, the experimental results indicate that the specific energy of combustion for

naphthalene is –41.20 kJ/g and biphenyl is -42.28 kJ/g. Converting the specific energy to molar

energy of combustion yielded a value of -5280.46 kJ/mol for naphthalene and -5419.42 kJ/mol

for biphenyl. This molar energy was necessary for the calculation of ΔH, as shown in Equation

(5). Thus, the change in molar enthalpy of naphthalene was determined to be -5267 kJ/mol for

naphthalene and -6504.25 kJ/mol for biphenyl. In regards to experimental error, there were

multiple factors that could have affected the accuracy of the measurements. For instance, the

combined mass of the naphthalene and the wire which was recorded from the analytical balance

is not equivalent to the sum of the two separate values of the mass of naphthalene and the mass
Experiment 2: Bomb Calorimetry - Measuring Heats of Combustion Cox 1

of the wire. This would stand to reason that a small fraction of the naphthalene pellet flaked off

as it was being fused to the wire, thereby creating some error in the calculated value for ΔH. In

an effort to remedy this error, the design of the pellet press could be improved to better pack the

naphthalene mass into the pellet shape needed for the calorimetry run. Additionally, the ΔT value

may have been marginally inaccurate, given that there were not as many points after the ignition

that could have contributed to the plateau region of the graph. A simple solution to remove this

error would have been to take more data points after the ignition. Regardless, the ΔH value bears

close resemblance to the values present in literature3,4, so the error must be very minimal.

References

1
Gunn, Alaina. Bomb Calorimetry - Measuring Heats of Combustion. 2019.

2
“Bomb calorimetry: Finding Delta T using Kaleidagraph.” YouTube, uploaded by Steve

Davidowski, 17 March 2013, https://www.youtube.com/watch?v=1ghSLKWpWTQ&t.

3
Naphthalene, National Institute of Standards and Technology,

https://webbook.nist.gov/cgi/cbook.cgi?Name=naphthalene.

4
Benzoic Acid, National Institute of Standards and Technology,

https://webbook.nist.gov/cgi/cbook.cgi?ID=C65850&Type=HCOMBS.