Laboratory Experiment

Cite This: J. Chem. Educ. 2019, 96, 132−136 pubs.acs.org/jchemeduc

Integrated TGA, FTIR, and Computational Laboratory Experiment

Andrew T. Pemberton,† D. Brandon Magers,* and Daniel A. King*
Department of Chemistry and Biochemistry, Taylor University, Upland, Indiana 46989, United States
*
S Supporting Information

ABSTRACT: Thermogravimetric analysis (TGA), Fourier transform infrared spectros-

copy (FTIR), and computational chemistry are used in concert to evaluate the thermal
decomposition of calcium acetate monohydrate, Ca(C2H3O2)2·H2O, and to engage
students in high-level thinking as they synthesize results from several techniques.
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Students use TGA to generate and isolate the reaction intermediates and final product.
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Three common TGA transitions (the loss of water, the generation of a metal carbonate,
and the generation of a metal oxide) with very different reaction temperatures are
observed with this sample. The resulting four samples (starting material, two
intermediates, and final product) are then analyzed by FTIR. Students are able to
observe the progress of the reaction through a comparison of the IR spectra, via the
change of water, O−H, and C−H signals. The computational analysis of the vibrational
frequencies of carbonate is performed to demonstrate the concepts of predicting the
number of principal vibrational frequencies, vibrational degeneracy, and IR activity in addition to aiding in the identification of
the second decomposition intermediate, CaCO3. This integrated approach also encourages students to appreciate the strengths
and weaknesses of various techniques and recognize that often chemical analysis requires the use of multiple tools.
KEYWORDS: Upper-Division Undergraduate, Analytical Chemistry, Laboratory Instruction, Computer-Based Learning,
Hands-On Learning/Manipulatives, Inquiry-Based/Discovery Learning, Computational Chemistry, Instrumental Methods,
IR Spectroscopy, Quantum Chemistry, Thermal Analysis

■ INTRODUCTION
The traditional undergraduate chemistry curriculum is both
broad and deep. The breadth is reflected in the variety of
courses from among the principle subdisciplines of inorganic,
organic, physical, analytical, and biochemistry. From the math-
heavy theories of physical chemistry to the application focused
techniques of analytical chemistry, it will typically require four
years for students to explore all of these areas. The depth of the
chemistry curriculum is reflected in the amount of content
within the subdisciplines. The content is so rich that it is
common for universities to offer two-semester course
sequences in each of the subdisciplines. Consequently, the
challenge for undergraduate students is to master the detailed
content of the subdisciplines while somehow building
horizontal connections among them at the same time.1−6
Instrumental analysis (IA) is typically taught as an advanced
course within the Analytical Chemistry subdiscipline and, like
the other subdisciplines, is composed of its own jargon and
tools. When students are exposed to the most fundamental
information regarding chemical instruments, they will be
engaging in the first two levels of thinking within Bloom’s
Taxonomy: (1) Gathering Knowledge and (2) Comprehend-
ing and Confirming.7,8 This factual oriented portion of the
course is often reflected in objective test questions and
vocabulary. Then, when students are exposed to the uses of the
instruments and the interpretation of data, they will be
engaging in the next two levels of thinking: (3) Applying and
(4) Analyzing. However, it is difficult to engage IA students in
the two highest levels of thinking, (5) Synthesizing and (6)
© 2018 American Chemical Society and
Division of Chemical Education, Inc.
Evaluating, without placing the students into a context where
they must either interact with technique and theory at the
same time or apply multiple techniques at the same time.9,10 In
addition to achieving high-level cognitive involvement, this
approach has the advantage of modeling several crucial
characteristics of career work within the field of analytical
chemistry that might not otherwise find its way into the
curriculum:
(1) All methods have strengths and weaknesses, uses and
limitations.
(2) To fully answer your research question multiple
methods may be necessary.
(3) You may need the interpretation of one method’s data to
help you interpret the data from another.
Furthermore, the applications of instrumental techniques
and the theories behind them can often be strong points of
connection with the other subdisciplines. For example, the
high-performance liquid chromatography analysis of a
biochemical material can considerably fortify knowledge
acquired in both the analytical and biochemistry areas if the
students are provided time and incentive to engage the context
of the application within the structure of the course. Among
the common chemical instruments that would comprise the
undergraduate IA course curriculum, there are clear
Received: July 26, 2018
Revised: November 17, 2018
Published: November 29, 2018
132 DOI: 10.1021/acs.jchemed.8b00607
J. Chem. Educ. 2019, 96, 132−136
Journal of Chemical Education
applications in all of the subdisciplines, while the theory
behind them is often a strong point of connection to physical
chemistry.
In an effort to create a laboratory experience that would
achieve the primary goal of providing students with experience
using chemical instruments, and the secondary goal of
engaging content at the highest level of thinking, this paper
describes an integrated laboratory experiment that requires
students to use computational chemistry, thermogravimetric
analysis (TGA), and Fourier transform infrared spectroscopy
(FTIR) in concert to determine the identities of a compound
and its thermal decomposition intermediates and product.
Previous reports of such integrated approaches have shown
positive learning outcomes, some including TGA and
FTIR.11−17 This experiment requires students to have not
only a functional understanding of the three techniques, but
also an understanding of the techniques’ strengths and uses,
and how the set of data might be used together to corroborate
one another. The specific incorporation of computational
chemistry within this experiment also illustrates to the students
the growing and valued role that computational chemistry
(traditionally located within the Physical Chemistry subdisci-
pline) is playing within the field of modern analytical
chemistry.
Pedagogically, the Computational Chemistry section of this
laboratory experiment is particularly chosen to help introduce
concepts and principles of infrared spectroscopy. Students
should finish this exercise having met certain learning
outcomes, including being able to determine the number of
expected fundamental vibrational frequencies for a molecule
(3N − 6 or 3N − 5 for a linear molecule), understand the
concept of degenerate modes, and resolve whether a vibration
should be IR active or inactive by observing a change in dipole
moment in the vibration. The instrumental portion of this
experiment will not only improve students’ comfort level in
operating the TGA and FTIR, but also familiarize students
with the kind of information that can be gleaned from both
techniques. Students should be able to recognize several
common transitions within TGA traces of organic compounds
and should be able to interpret observed mass losses and
compare them to theoretical mass losses. Students should be
able to recognize a few key IR peaks and interpret the
significance of these functional group indicators in monitoring
a multistep process. The background information needed for
the students to understand these concepts while performing
the experiment is provided to them in the laboratory
instructions and prelab discussion by the instructor. Students
are required to record their data and their interpretation of
results in a lab notebook which would include balanced
chemical equations, hazards, and observations. The postlab
questions (included in the Supporting Information) require
students to specifically demonstrate their mastery of the
learning objectives.
The instrumental analysis course where this experiment has
been performed over the past three years typically has about 10
students, who generally have limited or no exposure to these
techniques. So by performing this experiment in groups of 3−
4, three small groups need to be guided through the lab. The
computation portion of the experiment takes approximately 30
min and can be done at a separate meeting time. The TGA and
FTIR portions of the lab will be performed in one full lab
session. The TGA experiment takes only a little more than an
hour if the longest run is completed for them (2 h if the
133
Laboratory Experiment
students perform all runs, details explained later), and the
FTIR takes approximately 1 h for all four samples. The three
groups will come to lab staggered by 1 h. Each group will
complete the exercise in 2 h in lab with approximately 1 h of
work to be done outside of lab in completing the post lab
report sheet. Performed in this manner, 4 h of instructional
time by the instructor is required to guide all three groups
through the TGA/FTIR lab session.
■ HAZARDS
For the TGA and FTIR portions of this experiment, students
should wear eye protection and exam gloves. Although the
compound used in this particular experiment is not hazardous,
students should learn how to perform such experiments in a
safe manner for future experiments when the samples may be
more hazardous. Additionally, TGA pans can be very hot, and
they should be handled with gloves or tweezers because they
can burn your skin and the oils from the skin can affect the
performance of the instrument. For the IR analysis, the pellet
press which uses many tons of pressure should never be
operated without eye protection. Oils from skin on a prepared
IR pellet can also affect the performance of this instrument.
■
RESULTS AND DISCUSSION
Computational Chemistry
Though the intricacies of computational chemistry are beyond
the scope of an undergraduate instrumental analysis course, the
use of computational chemistry tools as a black box is well
within the expected intellectual grasp. In practice, the
computational analysis of the starting material, Ca-
(C2H3O2)2·H2O, is much too complex, so the carbonate
anion was chosen for this experiment because it is relatively
simple computationally and it is an important species within
the decomposition pathway of most organic compounds.
Students computed an optimized geometry and harmonic
fundamental frequencies of carbonate using WebMO18 and
PSI4,19 a web-based interface and an open-source computa-
tional chemistry package, respectively. Default settings were
selected, and computations were carried out with the MP2
level of theory20 with a cc-pVTZ basis set.21 See method
details in Supporting Information. The computed vibrational
frequencies (Table 1) can be evaluated to some degree by the
students. Students see that there are six fundamental
vibrational frequencies, which follows the 3N − 6 guideline.
Most importantly, WebMO can visually display each vibra-
tional mode. Students observed each vibrational mode and
predicted which ones would be IR active based on a change in
Table 1. Comparison of Computed Harmonic Frequency
Values of CO32− and FTIR Vibrational Frequency Values of
CaCO3
Frequency, cm−1
Description Computeda Exptlb
In-plane bendc
645 713
Out-of-plane bend 898 875
Symmetric C−O stretch 1025
Asymmetric C−O stretchc 1446 1429
a
Computed harmonic CO32− frequencies, performed at the MP2 level
of theory with a cc pVTZ basis set. bFTIR CaCO3 vibrational
frequencies. cDoubly degenerate mode.
DOI: 10.1021/acs.jchemed.8b00607
J. Chem. Educ. 2019, 96, 132−136
Journal of Chemical Education
dipole moment. A sample video of one of the vibrational
modes is provided in the Supporting Information. A free anion
carbonate will have one IR inactive mode, ν1, corresponding to
the all-symmetric stretch of the C−O bonds. Students also
noted how multiple vibrations can be degenerate and thus
absorb at the same energy. Both ν3 and ν4 are doubly
degenerate, at 1025 and 1446 cm−1, respectively. It is worth
noting that, at the time of this paper, IR intensities are not
available in PSI4 and thus show as zero in the WebMO results
page. The students will compare these computational results
with the FTIR spectra produced for the thermal decom-
position intermediates and products to confirm to presence or
absence of carbonate in the samples.
Thermogravimetric Analysis
For the sake of time, an initial complete decomposition scan of
the calcium acetate monohydrate sample by TGA was
performed by the instructor ahead of time and the resulting
trace is provided the students upon arrival to the lab. This
experiment was carried out on a Q600 dual TGA/DSC (TA
Instruments). A representative decomposition trace, the
heating of sample from 20 to 800 °C at 20 °C/min, is
shown in Figure 1. See method details in Supporting
Figure 1. Thermogravimetric decomposition trace for calcium acetate
monohydrate.
Information. The trace clearly shows an initial mass loss near
4 min (100 °C), with the plateau extending to 15 min (400
°C) when there is a second mass loss. Finally, at approximately
30 min (600 °C) there is another mass loss event. The three
transitions correspond to loss of approximately 10%, 30%, and
40% of the initial sample weight, respectively. The final
product was removed from the TGA sample pan and set aside
for FTIR analysis. Students used this complete decomposition
trace to determine the approximate temperatures at which
subsequent runs should be stopped in order to generate and
isolate the two decomposition intermediates. Students ran the
second sample using the same method as before but stopped at
approximately 14 min (300 °C) to collect the first
intermediate. The product was removed from the pan and
set aside for FTIR analysis. Students ran the third sample as
before but stopped at approximately 26.5 min (550 °C) to
collect the second intermediate. The product was removed
from the pan and set aside for FTIR analysis.
Knowing only that the original sample was Ca(C2H3O2)2·
nH2O, and that what is likely a loss of water near 100 °C
134
Laboratory Experiment
corresponds to 9.9% of the original sample, students should be
able to calculate that the sample is monohydrated. The water
loss is in excellent agreement with the theoretical mass loss of
10.2%. Therefore, students should be able to determine that
the starting material is Ca(C2H3O2)2·H2O, and the first
intermediate ought to be the anhydrous calcium acetate,
Ca(C2H3O2)2. Then, knowing that the next to last transition
for organics tends to be the formation of the metal carbonate,
with a little prodding students ought to be able to predict that
the second intermediate is likely to be CaCO3. This can be
further supported by comparing the observed mass loss
between the starting material and the second intermediate of
42.5% and the theoretical weight loss of 43.2%. Finally,
students should predict that the final product will be the metal
oxide, calcium oxide in this case. The observed weight loss
between the starting material and the final product was 67.9%,
which agrees quite nicely with the theoretical mass loss
between calcium acetate monohydrate and calcium oxide,
68.2%. Chemical reactions for each decomposition step are
shown below.
Ca(C2H3O2 )2 ·H 2O(s) → Ca(C2H3O2 )2 (s) + H 2O(g)
Ca(C2H3O2 )2 (s) + 4O2 (g)
→ CaCO3(s) + 3CO2 (g) + 3H 2O(g)
CaCO3(s) → CaO(s) + CO2 (g)
Fourier Transform Infrared Spectroscopy
At this point, the students should be pretty confident in the
identity of each of the four materials, Ca(C2H3O2)2·H2O,
Ca(C2H3O2)2, CaCO3, and CaO. For further corroboration of
their findings, the starting material and the three samples
isolated from the TGA (two intermediates and the final
product) were analyzed by FTIR (Nicolet 6700) at a
resolution of 2 cm−1. Samples were prepared as pellets in a
1/10 ratio with KBr. See method details in Supporting
Information. Sample spectra are shown in Figure 2. Although
the thorough interpretation of an IR spectra can be
complicated and particularly so for decomposition intermedi-
ates which are not likely to be pure, students are well-equipped
to use the IR spectra to help evaluate their determinations
made from the TGA data. Therefore, students only need to be
able to recognize key IR transitions relevant to the comparison
of the four materials. For example, students should recognize
the very broad signal characteristic of the OH stretch (3300
cm−1), which is indicative of the presence of water or alcohol
in the starting material. To evaluate the first transition, the IR
spectrum of the starting material is compared with that of the
first intermediate. The characteristic water signal dramatically
decreases during the first transition which should confirm to
them the loss of water. The rest of the spectrum remains
primarily unchanged during this transition. The removal of the
water reveals more discrete signals from 3000 to 3600 cm−1
indicative of O−H vibrations from an alcohol or carboxylate as
well as CH vibrations that were previously covered up. The
presence of a carbonyl signal, CO, at approximately 1600−
1700 cm−1, may help to confirm the presence of the
carboxylate.
When comparing intermediates 1 and 2, students should
notice that there are no more CH or OH signals, or fine
fingerprint region signals indicative of organics. Additionally,
the CO vibration previously observed in the 1600−1700
DOI: 10.1021/acs.jchemed.8b00607
J. Chem. Educ. 2019, 96, 132−136
Journal of Chemical Education
Figure 2. FTIR spectra of the starting material (solid), first intermediate (small dashes), second intermediate (medium dashes), and final product
(large dashes) are shown.
cm−1 range is now gone, leaving a prominent signal at about
1400 cm−1. Students will not likely know that this strong signal
at 1400 cm−1 is indicative of carbonates prior to this
experiment, but at this point the computational results can
be used to complement their identification of the calcium
carbonate as the second intermediate. The IR spectra of the
final product is rather empty, and its most important
characteristic is its decrease in significant IR signals. They
should observe that the carbonate signal, if not entirely gone, is
now significantly diminished. This should strengthen their
confidence in their determinations.
■
CONCLUSIONS
This experiment has proven to be an effective method for not
only providing students with hands-on experience performing
computational, thermogravimetric, and FTIR analyses, but also
engaging students in high-level thinking practices of
application, analysis, synthesis, and evaluation. Throughout
this experiment students must analyze the results from several
techniques while synthesizing them into a coherent evaluation
of a decomposition reaction. Using the TGA as a means to
generate and isolate thermal decomposition intermediates for
subsequent analysis by FTIR requires students to be able to
interpret a TGA trace and to intentionally alter operational
settings to stop their two subsequent runs at the desired
temperatures. Common TGA transitions (the loss of water, the
135
Laboratory Experiment
production of a metal carbonate, and then the production of a
metal oxide) with large gaps in reaction temperatures make
Ca(C2H3O2)2·H2O an ideal choice for this experiment. While
comparing the FTIR spectra of the starting material, two
intermediates, and final product, students are encouraged to
look for signals that indicate changes in functional groups
among the samples. As identifications are proposed, students
can compare observed decreases in the weight percent from
the TGA to theoretical mass losses to support their theories.
The inclusion of the computational analysis of carbonate is a
great way to incorporate the vibrational spectroscopy concepts
of the number of principle vibrational frequencies, degeneracy,
and IR activity, as the specific computational results aid in the
interpretation of the FTIR spectrum of the second
intermediate, CaCO3.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available on the ACS
Publications website at DOI: 10.1021/acs.jchemed.8b00607.
Method details (PDF, DOCX)
Student instructions (PDF, DOCX)
Postlab questions (PDF, DOCX)
Video of carbonate vibration (MPG)
DOI: 10.1021/acs.jchemed.8b00607
J. Chem. Educ. 2019, 96, 132−136
Journal of Chemical Education

■
Laboratory Experiment

AUTHOR INFORMATION (16) Björk, E. M. Synthesizing and Characterizing Mesoporous Silica

SBA-15: A Hands-On Laboratory Experiment for Undergraduates
Corresponding Authors Using Various Instrumental Techniques. J. Chem. Educ. 2017, 94 (1),
*E-mail: brmagers@taylor.edu. 91−94.
*E-mail: dnking@taylor.edu. (17) Jefferson, A.; Phillips, D. N. Teaching Polymer Science to
Third-Year Undergraduate Chemistry Students. J. Chem. Educ. 1999,
ORCID 76 (2), 232−235.
Andrew T. Pemberton: 0000-0001-9089-5861 (18) Schmidt, J. R.; Polik, W. F. WebMO, 17.0.; WebMO LLC:
Holland, MI, 2017.
D. Brandon Magers: 0000-0001-6002-0183 (19) Parrish, R. M.; Burns, L. A.; Smith, D. G. A.; Simmonett, A. C.;
Daniel A. King: 0000-0002-5993-0814 DePrince, A. E.; Hohenstein, E. G.; Bozkaya, U.; Sokolov, A. Y.; Di
Present Address Remigio, R.; Richard, R. M.; et al. Psi4 1.1: An Open-Source
† Electronic Structure Program Emphasizing Automation, Advanced
Department of Chemistry, Washington State University, Libraries, and Interoperability. J. Chem. Theory Comput. 2017, 13,
Pullman, Washington 99164, United States. 3185−3197.
Notes (20) Møller, C.; Plesset, M. S. Note on an Approximation Treatment
for Many-Electron Systems. Phys. Rev. 1934, 46, 618−622.
The authors declare no competing financial interest. (21) Dunning, T. H. Gaussian Basis Sets for Use in Correlated

■ REFERENCES
(1) Levy, S. T.; Wilensky, U. Crossing Levels and Representations:
Molecular Calculations. I. The Atoms Boron through Neon and
Hydrogen. J. Chem. Phys. 1989, 90 (2), 1007−1023.

The Connected Chemistry (CC1) Curriculum. J. Sci. Educ. Technol.

2009, 18 (3), 224−242.
(2) Bruck, L. B.; Towns, M.; Bretz, S. L. Faculty Perspectives of
Undergraduate Chemistry Laboratory: Goals and Obstacles to
Success. J. Chem. Educ. 2010, 87 (12), 1416−1424.
(3) Schaller, C. P.; Graham, K. J.; Johnson, B. J.; Fazal, M. A.; Jones,
T. N.; McIntee, E. J.; Jakubowski, H. V. Developing and
Implementing a Reorganized Undergraduate Chemistry Curriculum
Based on the Foundational Chemistry Topics of Structure, Reactivity,
and Quantitation. J. Chem. Educ. 2014, 91 (3), 321−328.
(4) Talanquer, V. Chemistry Education: Ten Facets To Shape Us. J.
Chem. Educ. 2013, 90 (7), 832−838.
(5) Levy, S. T.; Wilensky, U. Students’ Learning with the Connected
Chemistry (CC1) Curriculum: Navigating the Complexities of the
Particulate World. J. Sci. Educ. Technol. 2009, 18 (3), 243−254.
(6) Bretz, S. L.; Fay, M.; Bruck, L. B.; Towns, M. H. What Faculty
Interviews Reveal about Meaningful Learning in the Undergraduate
Chemistry Laboratory. J. Chem. Educ. 2013, 90 (3), 281−288.
(7) Krathwohl, D. R. A Revision of Bloom’s Taxonomy: An
Overview. Theory Pract. 2002, 41 (4), 212−218.
(8) Seddon, G. M. The Properties of Bloom’s Taxonomy of
Educational Objectives for the Cognitive Domain. Rev. Educ. Res.
1978, 48 (2), 303−323.
(9) Domin, D. S. A Content Analysis of General Chemistry
Laboratory Manuals for Evidence of Higher-Order Cognitive Tasks. J.
Chem. Educ. 1999, 76 (1), 109−111.
(10) Crowe, A.; Dirks, C.; Wenderoth, M. P. Biology in Bloom:
Implementing Bloom’s Taxonomy to Enhance Student Learning in
Biology. CBELife Sci. Educ. 2008, 7 (4), 368−381.
(11) Williams, K. R. Analysis of Ethylene-Vinyl Acetate Copolymers:
A Combined TGA/FTIR Experiment. J. Chem. Educ. 1994, 71 (8),
A195−A198.
(12) Williams, K. R.; Young, V. Y.; Killian, B. J. Coulometric
Titration of Ethylenediaminetetraacetate (EDTA) with Spectropho-
tometric Endpoint Detection: An Experiment for the Instrumental
Analysis Laboratory. J. Chem. Educ. 2011, 88 (3), 315−316.
(13) Luna Vera, F.; Guancha Chalapud, M.; Castillo Viveros, I.;
Vásquez Medina, E. A. From Eggshells to Quicklime: Using
Carbonate Cycle as an Integrating Concept To Introduce Students
to Materials Analysis by TGA and FTIR. J. Chem. Educ. 2018, 95 (4),
625−630.
(14) Harris, J. D.; Rusch, A. W. Identifying Hydrated Salts Using
Simultaneous Thermogravimetric Analysis and Differential Scanning
Calorimetry. J. Chem. Educ. 2013, 90 (2), 235−238.
(15) Hutchison, A. R.; Krepps, M. K.; Atwood, D. A.; Otieno, T.
Synthesis and Spectral and Thermal Properties of Pyrazine-Bridged
Coordination Polymers of Copper(II) Nitrate: An Experiment for
Advanced Undergraduates. J. Chem. Educ. 2002, 79 (11), 1355−1357.

136 DOI: 10.1021/acs.jchemed.8b00607

J. Chem. Educ. 2019, 96, 132−136