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An Alternative to Recycling: Measurement of Combustion

Enthalpies of Plastics via Bomb Calorimetry
Benjamin J. Knurr* and James F. Hauri*
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ABSTRACT: For the past century, humans have been increasingly dependent on plastics, but have
not developed adequate disposal practices. In this lab, students are asked whether burning plastic
for energy seems like a reasonable disposal technique. To answer the chemical aspects of this
question, students use bomb calorimetry to quantify the combustion energy of various plastics. The
students confirmed the quality of their data by comparing their results from this experiment with
Downloaded via BIU SANTE on April 17, 2020 at 13:30:59 (UTC).

current literature values for various plastic combustions. Their results also show that some plastics
contain comparable amounts of energy to that of current fossil fuel and biofuel sources and that the
energy content of the plastics vary predictably depending on the presence of oxygen in the polymer
structure. At the conclusion of the experiment, students will not only have learned the technique of
bomb calorimetry but will have also gained insight into whether burning plastic for energy makes
sense from a chemical energy perspective.

KEYWORDS: Upper-Division Undergraduate, Environmental Chemistry, Physical Chemistry, Laboratory Instruction, Discovery Learning,
Calorimetry, Consumer Chemistry

■ INTRODUCTION
Plastic
values as well as the energy content of competing fossil and
biofuels.
Bomb Calorimetry
Over the past hundred years, plastics have exploded both in
Bomb calorimetry is a commonly utilized technique for the
terms of applications and polymer types.1 Though this
determination of internal energy content of combustible
expansion has led to significant improvements in society, it
materials (e.g., solid fuels, liquid fuels, foods, etc.) and has
has also resulted in our being awash in used and waste plastics.
been employed in numerous teaching applications to determine
Plastics contribute to more than 10% of municipal solid waste
the internal energy or combustion energy of a substance.5,6,8 A
(MSW) in the United States.2 Despite the fact that six of the
bomb calorimeter is designed to create a well-controlled
plastics have special recycling codes (all others plastics are
explosion where the volume of the reaction vessel, the bomb,
lumped into recycling code “7” designated as other), only
does not change. The constant volume aspect of the experiment
poly(ethylene) terephthalate (PET, recycling code “1”) and
means that change in internal energy (ΔU) is measured, not
high density polyethylene (HDPE, recycling code “2”) have
change in enthalpy (ΔH). By experimenting with a bomb
recycling rates above 10% in the United States.3 Instead, 3/4 of
calorimeter, students experience a unique calorimeter and a
plastics are sent to landfills. Even if we increase our recycling
practical application of a constant volume thermodynamic
rates, there is a question of whether it is cost-effective to reuse
processes. However, at its core the technique is still classic
the polymers for new products. Currently, only a small amount
calorimetry for which the user measures the change in the
(13%) of MSW is burned for energy in the U.S., but this disposal
temperature of the surroundings to measure the energy change
method holds great promise for the future.4 Plastics are primarily of the system (qsys = −qsurr). The instrument used to obtain the
derived from fossil fuels and are mostly made up of data presented here was a plain jacket oxygen bomb calorimeter
hydrocarbons (Figure 1), thus it would be expected that they but there are other variations of bomb calorimeters.
would have a similar energy content to that of a fossil fuel. There
have been a number of proposed experiments that encourage
students to investigate alternate energy sources for a variety of Received: January 27, 2020
processes.5−7 In this experiment, students were asked whether Revised: April 2, 2020
burning recyclable plastics for energy makes sense from a
chemical energy perspective. To answer this question, students
directly measured the combustible energy content in several
types of plastics and compared these values both to literature
© XXXX American Chemical Society and
Division of Chemical Education, Inc. https://dx.doi.org/10.1021/acs.jchemed.0c00076
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Figure 1. Structures of the polymer subunits for the six recyclable
plastics and PLA (recycling code 7). Any plastic that is not a 1−6
recycling code is designated code 7.
The goals of this experiment are to accurately calibrate a bomb
calorimeter and then determine the energies of combustion for
different types of recyclable plastics. Comparisons will be made
between the energy content of the tested plastics and their
respective literature values to confirm the accuracy of the
experiment. Finally, comparisons can be made between the
combustion energies of the plastics studied and other fuel
sources such as coal, hydrocarbons, or biofuels.
■
DESCRIPTION OF EXPERIMENT
This experiment was performed in a physical chemistry
laboratory. At the time that this experiment was carried out,
the lecture portion of the course was focused on changes to
internal energy and enthalpy. A bomb calorimeter setup can be
competently operated by one or two students. Groups of three
can work but one member may find themselves with little to do.
Groups larger than three should probably be avoided so that all
group members can be actively involved in the experiment. Due
to the cost of a single bomb calorimeter setup ($5,000 − $10,000
depending on the configuration) it is suggested that this
experiment be carried out in a round robin fashion (i.e., multiple
experiments that different student groups rotate through over
B https://dx.doi.org/10.1021/acs.jchemed.0c00076
Laboratory Experiment
multiple weeks). Four different groups, using two bomb
calorimeter setups, performed separate calibrations and data
collection to acquire the data presented over the course of 3
weeks.
Depending on the number of samples students are required to
combust, their laboratory capabilities, and the duration of the
lab/class period, this experiment can take multiple laboratory
periods. It was observed here that a competent group of junior
and senior science majors were consistently able to complete the
benzoic acid calibration combustion and two other sample
combustions during a single 3 h laboratory period. Groups
would then usually finish a remaining trial within about 30−40
min of the next laboratory period, at which time the next group
could begin the experiment. However, if each group is only
required to calibrate the calorimeter and then combust two
samples, it is reasonable to complete the entire experiment in
one 3 h lab period. A single combustion trial can take 30 to 70
min depending on the capabilities and competencies of the
experimenters.
■ LEARNING OBJECTIVES
In this experiment, students are asked to use their chemistry
skills to answer an applied environmental chemistry question,
thus there are really two learning objectives. First, the students
need to learn the chemical principles associated with bomb
calorimetry, such as the thermodynamics of a constant volume
combustion process for which the measured value is ΔU. While
this is still a calorimeter experiment, because of the unique
experimental conditions, enthalpy is not the measured value
(unlike in many solution, or thermos, calorimeters where ΔH is
measured directly). Additionally, most bomb calorimeters are
well insulated resulting in little energy exchange with the
surroundings of the calorimeter. This aspect of the experiment
can both help ensure good results and give students some basis
for what a nearly “isolated system” is. In addition to learning how
to operate the calorimeter, the students need to use the
combustion energy data to answer the larger question of
whether some plastics should be burned for energy. The
students need to compare their data with literature values of
combustion energy data of other fuel sources in order to put the
combustion of plastics into the greater context of MSW. By
having the students work on a larger applied question, the
students can better understand that the data generation is only
one step of the overall scientific process.
■
METHODS
While there is no preliminary setup required by students, it is
highly advised that students read and familiarize themselves with
the calorimeter setup and the procedure before coming to lab in
order to complete the entire experiment within a 3-h period. The
experiment can be broken into two major parts: Calibration with
Benzoic Acid and Sample Combustion. Both parts of the
experiment follow the same general procedure and are outlined
below. Detailed information is given in the Supporting
Information.
Calibration
The first combustion that needs to be performed is that of a
standard substance (benzoic acid in this experiment) with an
accurately determined ΔcH. Approximately 1.0 g of benzoic acid
was compressed into a small pellet, massed after compression,
and then placed in the sample cup. The rest of the bomb
calorimeter was assembled and prepared according to the user
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manual (see Supporting Information or the user manual for your Table 1. Plastic Combustion Results from the Student
specific calorimeter for further information). Gathered Data and Literature Plastic Combustion Dataa
Once the calorimeter was assembled and the internal
Combustion
temperature was equilibrated, the ignition unit was connected, Plastic Type Energy (kJ/g) Source of Plastic
and the bomb was ignited. The temperature was recorded, using
Student Data
a thermometer precise to 0.01 °C, at roughly 30 s intervals until
1 (PET) −21.0 ± 0.5 Fresh raspberry container
the temperature remained constant. The equilibration was
2 (HDPE) −46.8 ± 0.5 Gallon milk jug
considered complete when the temperature remained steady for 4 (LDPE) −45.6 ± 0.5 Disposable plastic bag
a few minutes. The bomb was then disassembled to determine if 5 (PP) −46.6 ± 0.5 Rigid take-out food container
the pellet completely combusted (if not the experiment must be 6 (PS, hard) −41.7 ± 0.4 Rigid disposable drink cup
repeated), and the mass of the remaining fuse wire. The final and 6 (PS, soft)b −51 ± 1 Styrofoam take-out food container
initial temperatures of the calorimeter, the mass of the benzoic 7 (PLA) −18.8 ± 0.3 Compostable single use drink cup
acid pellet, and the mass of the combusted portion of the fuse mystery −46.3 ± 0.4 Air packaging material with no
wire were then used to determine Ccal of the calorimeter. The plasticc recycling code listed
necessary calculations are discussed in detail in the Supporting Literature Data
Information. 1 (PET) −23 ± 1 11
Plastic Fuel Samples 2 (HDPE) −47 ± 1 11
4 (LDPE) −47 ± 1 11
The sample procedure is nearly identical to the benzoic acid 5 (PP) −45 ± 2 11
calibration. The only difference concerns sample preparation. 6 (PS) −43 ± 1 11
The mass of the plastic sample should generally be between 0.5 7 (PLA) −19 ± 2 12
and 1.0 g depending on the density of the plastic, but different a
The uncertainty in the student data was calculated based on the
methods may be used to get the sample into a useable shape. For precision of the equipment used (see Supporting Information for
hard plastics, they can likely be either cut or broken into pieces details). Uncertainty in the literature values are from the standard
that can fit into the sample cup. More malleable plastics and deviation of the values reported in the reference listed. bPS, soft
plastic bag material (usually LDPE or HDPE) can be required the liquid combustion technique to be measured. cMystery
compressed in a pellet press to fit them in the sample cup. plastic was acquired from an air packaging material and is speculated
The only sample type that was found to be difficult to combust to be a form of PE.
was soft Styrofoam (e.g., soft polystyrene) which does not
compress well and can be ejected from the sample cup and lose why energies of combustion of PET and PLA are substantially
contact with the fuse wire while priming the bomb with oxygen. lower than the other plastics.
There are procedures used in liquid fuel combustion that can be Looking at the structures of the four high energy plastics, they
employed to detonate foam-like plastics but these are more observed that all four follow a pattern of repeating ethane units
involved.9 albeit with different hydrocarbon functional groups protruding
Ultimately, the general guidelines are that the plastic sample from the primary chain (see Figure 1). Since the structures
needs to fit in the sample cup, maintain contact with the fuse consist of only carbon and hydrogen, it is reasonable to expect
wire during preparation of the bomb, and upon combustion that they would have similar energies of combustion. The higher
result in a 1.5 to 5 °C increase in calorimeter temperature after degree of unsaturation present in the PS subunit ultimately gives
detonation. Some plastic samples can be draped over the fuse rise to the slightly lower energy of combustion compared to
wire and still combust completely. HDPE/LDPE and PP.

■ HAZARDS
Students should not combust plastics containing chlorine (PVC,
saran wrap, etc.) due to concerns with dioxin formation.10 For
most bomb calorimeter setups, the ignition module usually
involves either spade terminals or banana plugs to connect the
electrodes. Care should be taken to not electrocute oneself by
creating a circuit through any part of the user’s body when
pressing the ignition switch.
The other two plastics tested (PET and PLA) have only about
19 kJ/g energy of combustion which can be attributed to the
presence of oxygen in these two polymers. Students can use this
observation to recommend that plastics that contain oxygen are
not as suitable for use in energy combustion applications as
those that are exclusively composed of carbon and hydrogen.
This will likely not be an expected result of students but is clearly
elucidated in the data.
One plastic tested was from an air-filled shipping packing

■
RESULTS AND DISCUSSION
Students working in groups collected data over several weeks
and then processed it as outlined in the instructor handouts. The
calculations can be involved depending on what equations are
presented to the students, but qsys = −qsurr is the backbone of the
calculation. This relationship is rewritten as qfuel + qwire = −qCal,
and the energy of combustion for the fuel can be calculated (see
Supporting Information for details on analyzing the results).
The resulting data (see Table 1) clearly separates into two
groups of plastics: those with energies around 20 kJ/g (PET and
PLA) and those in the 40−50 kJ/g range (HDPE, LDPE, PP,
and PS). This split gave the students the opportunity to consider
C https://dx.doi.org/10.1021/acs.jchemed.0c00076
material that did not bear a recycling code and was called the
“mystery plastic”. On the basis of the energy of combustion, the
plastic was determined to be a type of PE. Students speculated
that since plastic bags are usually HDPE or LDPE and the
combustion energy of the mystery plastic matched both of those,
it was a likely candidate for the identity of the mystery plastic.
Even with a reasonable explanation for the data groupings,
students were concerned about the accuracy of their work. This
anxiety about the quality of their work generated a discussion
about the ways chemists can corroborate their results. The
students were guided toward literature values (shown in Table
1) that both confirm the measured values of the individual
plastics and validate the duality in energies of combustion. In
general, if adequate data were collected, the calculated final
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results did not deviate substantially from the results found in the
literature. If there are large deviations, students should examine
their calculations first as there is likely a computational error
rather than an egregious systematic error present in the
experiment.
Following a comparison between the student’s measured
values and the literature combustion values of the various
plastics (see Table 1) it is abundantly clear that the student
results agree with those present in the literature. Not only does
this agreement validate the experimental technique but it can
help simplify student analysis by indicating to what their
calculated energies of combustion should be close.
Once the students were satisfied with their data, they could
consider whether burning plastic for energy would be acceptable
from a chemical energy perspective. Again, the students were
guided to consider literature values (Table 2) in order to
Table 2. Literature Combustion Values for Common Fossil
Fuels and Biodiesel Fuels That Can Be Compared to Plastic
Combustion Values. Uncertainties Were Given for Both
Diesel Fuels and Were Calculated from Standard Deviations
of the Data Presented for Coal and Both Oils
Fuel Type Combustion Energy (kJ/g) Source of Data
Biodiesel −41.2 ± 0.2 7
Diesel −47.0 ± 0.2 7
−30 ± 6
U.S. Coal 13
Shale oil −43 ± 3 13
Fuel oil −45 ± 1 13
contextualize their results. When comparing the combustion
data from Table 1 to the combustion energies of commonly used
fuels in Table 2, plastics clearly contain similar amounts of
combustible energy. Additionally, most plastics contain more
combustible energy than US coal (on a kJ/g basis). Even the
lower energy content polymers, PET and PLA, have nearly as
much combustible energy as low-grade coal. Similar to the
presence of oxygen decreasing the energy of combustion, the
higher amount of hydrogen in the more saturated hydrocarbons
increases the internal energy of combustion of a fuel on a per
gram basis. Thus, students can extrapolate this comparison to
consider that the increase in carbon to hydrogen ratio will
decrease the combustion energy per gram of PS compared to PE
just like it would in coal versus crude oil.
The combustion energies of plastics are very similar to the
liquid fuels, diesels and oils, and students can consider the many
similarities in the structures of the plastics and the fossil fuels.
The primary similarities concern the long hydrocarbon chain
backbone of the plastics and the liquid fuels. There is not one
structure for most petroleum oils and diesel fuels, but they are all
generally large hydrocarbon chains of about C12H24 for diesel
and similarly long chained alkyl esters for biodiesel. There is
some oxygen present in the liquid fuels, e.g. biodiesel, but it is a
small portion of the rest of the molecule. The large size of the
fuel molecules means that they are similar to the large polymeric
chains present in plastics, thus it is not necessarily surprising that
both hydrocarbon plastics and liquid fuels exhibit similar
energies of combustion.
Students generally enjoyed both the combustion aspect of,
and the practical environmental themes approached by this
experiment. This experiment exposes students to some
fundamental truths about hydrocarbon fuels and poses some
interesting questions about the potential future of MSW both in
D https://dx.doi.org/10.1021/acs.jchemed.0c00076
Laboratory Experiment
our country and possibly the world. This lab can be extended to
combust other plastics and could even possibly be used to
identify an unknown plastic as was done with the “mystery
plastic” tested by students here.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available at https://pubs.ac-
s.org/doi/10.1021/acs.jchemed.0c00076.
Student procedure (PDF, DOCX)
Instructor information (PDF, DOCX)
■
AUTHOR INFORMATION
Corresponding Authors
Benjamin J. Knurr − Assumption College, Worcester,
Massachusetts 01609, United States; orcid.org/0000-0003-
1812-8558; Email: bj.knurr@assumption.edu
James F. Hauri − Assumption College, Worcester, Massachusetts
01609, United States; Email: jhauri@assumption.edu
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jchemed.0c00076
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We would like to thank the undergraduate physical chemistry
class that performed these experiments and Prof. Brian Niece for
helpful discussions.
■
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