Laboratory Experiment

Cite This: J. Chem. Educ. XXXX, XXX, XXX−XXX pubs.acs.org/jchemeduc

Introducing Students to Thermogravimetry Coupled with Fourier

Transform Infrared Spectroscopy
Marisol Fernández Rojas, Angélica M. Giorgi Pérez, María F. Agudelo Hernández,
and Luz A. Carreño Díaz*
School of Chemistry, Universidad Industrial de Santander, Street 9, 27, Bucaramanga 678, Colombia
*
S Supporting Information

ABSTRACT: Thermogravimetry coupled with Fourier transform

infrared spectroscopy (TG-FTIR) is a useful technique for the
thermal and structural characterization of materials at academic and
research levels. This paper describes an experiment for chemistry
students to understand the use of TG-FTIR for advanced
qualitative and quantitative thermal analysis using a natural
compound as a sample. In the classroom, students learned about
the fundamental principle of thermal analysis, TG-FTIR
instrumentation, and different applications of this coupled
technique for materials characterization. In the laboratory, students
received a description of each part of the TG-FTIR system, as well
as how to tune the system and to develop a method. The primary
objective of the experiment was to guide them in the interpretation
of results including thermograms, infrared spectra, DSC, and Gram Schmidt (GS) curves. For this, students prepared and
analyzed cellulose fibers extracted from pineapple leaves and a mixture of them with sodium hydroxide (NaOH) and
monoethanolamine (MEA). Students were initially instructed to study the TG, DSC, and Gram Schmidt curves and to identify
the temperatures at which the most significant mass changes occurred. Then, they focused on analyzing the infrared spectra
obtained at each temperature range. This practice allowed them to identify the gases emitted during fiber decomposition and the
volatile character of the MEA as well as to corroborate the MEA presence in the fiber/MEA mixture. This procedure can be
adapted to guide students in the analysis of pure substances and mixtures.
KEYWORDS: Upper-Division Undergraduate, Analytical Chemistry, Laboratory Instruction, Hands-On Learning/Manipulatives,
IR Spectroscopy, Thermal Analysis, Fourier Transform Techniques

■ INTRODUCTION
The use of thermal analysis techniques such as thermogravim-
etry (TG) and differential scanning calorimetry (DSC) is
essential in the characterization of a wide range of materials.
These allow the determination of moisture and volatile content;
thermal stability; melting, crystallization, and glass transition
temperatures; specific heat and enthalpy; and the composition
of a multicomponent system. Besides this, it is possible to study
the kinetic decomposition, and the effect of reactive and
corrosive atmospheres on materials.1 The thermogravimetric
analysis (TGA) system coupled online to a Fourier transform
infrared spectroscopy (FTIR) allows for the identification of
the evolved gas during the loss of matter. It is a useful
complement for a better interpretation of decomposition and
volatilization processes and has been reported for the
characterization of a wide range of materials including
polymers, ceramics, catalyst, drugs, biomass, biofuels, cellulose,
and coal, among others.2−4 In this Journal were reported
experiments involving an introduction to the TGA5 and TGA-
DSC6 analysis, as well as a combined TGA/FTIR study without
direct coupling.7 However, no experiment using a TG-FTIR
coupled system has been published. TG-FTIR is one of the
© XXXX American Chemical Society and
Division of Chemical Education, Inc.
techniques included in the theory and laboratory courses for
upper-division undergraduate chemistry students at Universi-
dad Industrial de Santander. This practical session aimed to
give the students a hands-on experience in qualitative and
quantitative TG-FTIR analysis; likewise, we encouraged
students to apply the acquired knowledge about the TG and
FTIR techniques and verified the advantages of their coupling.
This laboratory experiment reports a two-session learning
experience performed by 12 students in the Laboratory of
Analytical Chemistry course. In the first 4 h, students extracted
the cellulose fibers from pineapple leaves and modified them by
alkaline treatment and monoethanolamine immobilization.
These fibers were selected as study samples as they decompose
almost entirely when heated to 600 °C, generating a sufficient
amount of gases to be detected by FTIR. In the second
afternoon session, they analyzed the samples. Students received
the explanation about the description of the TG-FTIR system
and the operation instructions; then, they were guided in the
Received: November 9, 2017
Revised: April 12, 2018
A DOI: 10.1021/acs.jchemed.7b00826
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education
Figure 1. Cellulose fiber extraction from pineapple leaves: (a) pineapple leaves, (b) vegetal material removal, (c) fiber extraction, and (d) raw fibers.
Figure 2. Cellulose fiber treatment: (a) fibers in NaOH solution 5% for 1 h, (b) fibers obtained after alkaline treatment, and (c) fibers after MEA
immobilization.
interpretation of TG thermograms and the infrared spectra of
evolved gases. They evaluate the thermal behavior of fiber and
the influence of their modifications.
■
MATERIALS AND METHODS
Materials
We collected pineapple leaves (Ananas comosus MD2) in a
marketplace in Bucaramanga, Colombia. León Laboratories
Ltd. supplied the sodium hydroxide (NaOH), and Merck
supplied the monoethanolamine (MEA) for synthesis. All of
the laboratory materials used as well as the reagents and sample
amounts are specified in the Supporting Information.
Pineapple Leaves Fiber Extraction, Alkaline Treatment, and
Immobilization of Monoethanolamine (MEA)
Six groups of two students each (12 students) received several
pineapple leaves (Figure 1a); they washed and manually
removed the covering vegetal material with a knife, as shown in
Figure 1b. Once exposed, fibers were obtained by pulling them
from the matrix (Figure 1c,d). They were then washed and
immersed in distilled water and then sonicated in an ultrasonic
bath for 15 min at a frequency of 50 Hz at room temperature.
B DOI: 10.1021/acs.jchemed.7b00826
Laboratory Experiment
Fibers were dried at 60 °C for 30 min in an oven and were
labeled as raw fibers (RF). Then, the students immersed clean
untreated fibers in 5% NaOH solution for 1 h, to remove traces
of vegetal material (Figure 2a). They washed the treated fibers
with distilled water and dried them for 1 h in an oven at 60 °C.
Fibers obtained for each group were labeled as alkali fibers
(AF) (Figure 2b). Finally, students distributed AF fibers within
a Petri dish to get a film of approximately 2 mm thick and
added an aqueous solution of MEA at 40% until all the AF was
thoroughly soaked (Figure 2c) (approximately 0.3 mL of
solution per gram of fiber). They labeled samples as AF-MEA.
TG-FTIR Analysis
Under lecturer and instrument technician supervision, students
performed thermogravimetric analyses of RF, AF, MEA, and
AF-MEA using a Netzsch Simultaneous Thermal Analyzer
(STA) 449 F5 Jupiter, which can measure TG and DSC
simultaneously. Students weighed around 5 mg of each sample
in a Pt/Rh (80/20) crucible sample container. Samples were
heated from 35 to 600 °C at a heating rate of 20 °C/min, using
nitrogen as an inert atmospheric and protection gas with flow
rates of 40 and 60 mL/min, respectively. The STA instrument
is coupled to a TGA-IR module of a Bruker Tensor II
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education
Figure 3. TG, DSC thermograms, and Gram Schmidt curves of (a) RF, (b) AF, (c) MEA, and (d) AF-MEA.
spectrometer through a transfer line at 230 °C. This module
has an MCT (mercury−cadmium−telluride) detector and a
stainless-steel light pipe gas cell at 200 °C. It has a single-pass
beam cell with an optical path length of 123 mm. IR spectra of
the evolved gas were recorded with a resolution of 4 cm−1 every
15 s with an average of 32 scans per sample in the range 4000−
650 cm−1 throughout the heating process. Students learned to
use Netzsch Proteus-Thermal Analysis 6.1.0 software to analyze
curves obtained from the STA. FTIR spectra were analyzed
using the Bruker OPUS 7.5 software; the baseline correction
was performed using a concave rubber band algorithm
computed with 10 iterations on 64 points. A specific TG-IR
operative guide, as well as the procedure guide given to
students, is included in the Supporting Information. Examples
of infrared spectra analysis using libraries are also found there.
■ HAZARDS
The students handled the solutions of NaOH and MEA with
personal protective equipment. Before the laboratory session,
they were required to consult the risks of exposure to these
substances. NaOH causes eye and skin burns, irritation by
inhalation, intoxication, and internal burns by ingestion. MEA is
harmful by inhalation, causes injuries, and is irritating to eyes,
the respiratory system, and skin.
C DOI: 10.1021/acs.jchemed.7b00826
Laboratory Experiment
■ RESULTS AND DISCUSSION
Thermal Analysis
In the second 4 h laboratory session, students analyzed the
thermal behavior of samples from thermograms. A data analysis
guide given to the students are included in the Supporting
Information. The TG-FTIR system provided the TGA, DSC,
and Gram Schmidt (GS) curves shown in Figure 3 as an
example. Students determined the thermal stability of RF, AF,
MEA, and AF-MEA from TGA curves. They associated the
stage of highest mass loss with the Gram Schmidt (GS) peak.
This peak is related to the amount of evolved gases detected
with an FTIR spectrometer since the GS curve reflects the sum
of IR absorbance at all wavenumbers as a function of
time.2Students spotted endothermic or exothermic events
from DSC curves. They found endothermic events associated
with a loss of mass. They plotted the first derivative of the TG
curve (DTG) for each sample (Figure 4) to identify more
efficiently the stages of mass loss as well as the initial and final
temperatures of each stage through the DTG peaks.2
Students analyzed TG, DTG, DSC, and GS curves based on
previously read TG-IR research articles3,8 and completed Table
1, which summarizes the thermoanalytical data. In this table,
students reported three stages of mass loss for RF and AF. An
initial mass loss below 120 °C due to water evaporation was
always greater for RF than for AF confirming the hydrophobic
surface character after alkali treatment. The second stage
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Laboratory Experiment

For all samples, the GS signal peak coincided with the region of
highest mass loss, showing a good correlation between this and
the evolved gases detected with the FTIR spectrometer.
Additionally, AF-MEA exhibited an increase in the GS signal
at 158 °C due to MEA evaporation.
Evolved Gas Analysis
Once the thermal behavior was understood, students identified
more clearly what happens during RF, AF, MEA, and AF-MEA
mass loss through the analysis of the evolved gases. Students
were instructed to analyze the three-dimensional FTIR plot (as
Figure 5) which presents all the FTIR spectra obtained as a

Figure 4. TG and DTG curves of RF, AF, and AF-MEA.

between 250 and 389 °C corresponds to cellulose, hemi-

cellulose, lignin, and noncellulosic polysaccharide decomposi-
tion.3 It has been demonstrated that alkaline treatment of
natural fibers disrupts hydrogen bonding in the network
structure, increases fiber crystallinity degree, and removes
noncellulosic constituents in the amorphous region such as
lignin, wax, and oils. Consequently, the higher crystalline
structure gave AF a better thermal degradation resistance. The
last mass loss starting at 390 °C is attributed to the
carbonization process.3,8,9
Thermograms of MEA showed one stage of mass loss from
the beginning of the heating until 175 °C due to volatilization.
This behavior was consistent with what others have reported
for this substance.10 For AF-MEA, students observed a mass
loss between 140 and 233 °C corresponding to MEA
evaporation in addition to the other stages of degradation
identified for RF and AF. The AF-MEA thermal stability is
decreased slightly relative to AF. In the DSC curves, AF-MEA
and MEA exhibited a peak corresponding to an endothermic
process in the temperature range of highest mass loss which is
attributed to bonds breaking and evaporation, respectively,
whereas for RF and AF these peaks were not entirely defined.
Figure 5. Three-dimensional FTIR spectra of evolved gas during AF
decomposition.
function of temperature or time. They used these figures to
select an FTIR spectrum at a specific temperature or for
monitoring a particular signal through the temperature and
relate it to the stages of mass loss found in the thermal analysis
(see Table 1). For RF and AF, they selected the most visible
FTIR spectrum from those collected for the mass loss stage
beginning at 295° as well as the spectra recorded at the
temperatures of GS maximum, i.e., 350 and 480 °C (Figure 6).
For MEA and AF-MEA, the students selected FTIR spectra at
which MEA loss mass was observed (Figure 7).
For the RF FTIR spectra of evolved gas at 295 °C, the
students assigned the signals as follows at υ (cm−1): 3735 and

Table 1. Comparative Thermoanalytical Dataa from TG, DTG, and GS Curves

Thermogravimetry
Sample Trange, °C Weight, % DSC Endothermic Effect,d °C DTGe Peak, °C Gram Schmidt Maximum, °C
Raw fibers 60−100 5.67 ± 0.17 347 ± 3.20 347 ± 3.20 342 ± 3.70
250−389 58.55 ± 1.76
380−541 5.66 ± 0.17
Residue, 600 °C 35.41 ± 1.06
Alkali fibers 60−100 3.39 ± 0.10 356 ± 4.34 349 ± 3.14 350 ± 3.14
267−391 57.79 ± 1.74
391−541 7.59 ± 0.23
Residue, 600 °C 34.46 ± 1.03
MEAb 50−175 100.00 173 ± 2.08 173 ± 2.08 173 ± 2.08
AF-MEAc 60−100 5.95 ± 0.18 320 ± 4.16 315 ± 2.84 158 ± 1.27
140−233 4.71 ± 0.14 320 ± 2.56
233−368 46.82 ± 1.40
368−573 10.45 ± 0.31
Residue, 600 °C 39.97 ± 1.20

a
Data reported in this table correspond to the average obtained by all groups. bMEA: monoethanolamine. cAF-MEA: alkali fibers treated with an
aqueous solution of MEA. dEndothermic events in the differential scanning calorimetry curves associated with a loss of mass. eFirst derivative of the
thermogravimetric curve.

D DOI: 10.1021/acs.jchemed.7b00826
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Journal of Chemical Education
Figure 6. FTIR spectra of evolved gas from (a) RF and (b) AF at noncellulosic (295 °C) and cellulose decomposition (350 °C), and carbonization
(480 °C). Variation of the main infrared bands with temperature during (c) RF and (d) AF decomposition.
Figure 7. FTIR spectra of evolved gases from MEA at several
temperatures and for AF-MEA at the first GS maximum.
3649 (antisymmetric (asy) and symmetric (sy) stretch (s)
H2O), 3567 (OH s of acetic (aa) and formic acids (fa)), 2828
(CH2 s formaldehyde), 2359 (asy s CO2), 2178 and 2110
(CO), 1796 (CO s aa), 1774 (CO s fa), 1750 (CO s
formaldehyde), around 1500 (products of lignin decomposi-
tion), 1269 (OH bend aa), 1177 (CO s aa), 1105 (CO s
fa), 1033 (CO s methanol).3,11 These gases have been
reported to be emitted mainly during xylan, lignin, hemi-
E DOI: 10.1021/acs.jchemed.7b00826
Laboratory Experiment
cellulose, and other noncellulosic polysaccharide decomposi-
tion, between 200 and 300 °C.3,11,12 When these spectra were
compared with those obtained from the evolved gases from AF
at the same temperature, a decrease was observed in the
intensity of the signals corresponding to acetic and formic acids.
Signals corresponding to H2O and products of lignin
decomposition also decreased. This indicated xylan and lignin
removal due to alkali treatment.
Spectra recorded at 350 °C for RF and AF were similar, and
students assigned the observed signals to CO2, CO, H2O,
formaldehyde, methanol, and formic acid. It has been reported
that these gases are emitted mainly during the decomposition
of cellulose between 300 and 400 °C.3 This assignment was in
agreement with the GS peak observed at around 350 °C since
cellulose is the main component of RF and AF and was
detected at a higher amount in the infrared spectrometer. At
480 °C during the carbonization process, the CO2 peak for AF
showed less intensity than that for RF, whereas the peak at
3015 cm−1 corresponding to CH4 showed a higher intensity for
AF than for RF. Students selected some of the most important
signals of evolved gas infrared spectra of the RF and AF, to see
their evolution with temperature (Figure 6c,d). The absorbance
of AF signals between 200 and 300 °C was lower than for RF.
This decrease allowed them to confirm the removal of
noncellulosic compounds due to alkali treatment. Between
300 and 400 °C, an opposite behavior was observed, and they
related it to the higher cellulose content of AF.
J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Laboratory Experiment

Students analyzed spectra recorded for evolved gases from
MEA between 60 and 150 °C (see Figure 7). These are very
similar; however, the spectrum obtained at 120 °C looks
clearer. Students identified and assigned the signals at υ (cm−1):
3671 and 3580 (OH s), 3420 (NH2), 2934 and 2882 (CH2 asy
and sy s), 1623 (NH2 scissors), 1387 (C−H deformation
vibration), 1231 (CH2 wagging), 1035 (CO s), and 781 (NH2
wagging).11 These spectra corresponded to characteristic gas
phase spectrum of MEA in the NIST database library;13
therefore, this was a confirmation that mass loss was due to
MEA volatilization. For AF-MEA at 160 °C (Figure 7),
students observed only the signals of higher intensity of MEA,
due to the low amount of MEA that was actually immobilized
(approximately 4% according to TG). AF-MEA and AF spectra
recorded at higher temperatures were very similar.
and lignin. TG-FTIR analysis of volatile products. Thermochim. Acta
2014, 581, 70−86.
(4) Risoluti, R.; Fabiano, M. A.; Gullifa, G.; Vecchio Ciprioti, S.;
Materazzi, S. FTIR-evolved gas analysis in recent thermoanalytical
investigations. Appl. Spectrosc. Rev. 2017, 52 (1), 39−72.
(5) Burrows, H. D.; Ellis, H. a; Odilora, C. a. The Dehydro-
chlorination of PVC: An Introductory Experiment in Gravimetric
Analysis. J. Chem. Educ. 1995, 72 (5), 448.
(6) 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.
(7) Williams, K. R. Analysis of Ethylene-Vinyl Acetate Copolymers: A
Combined TGA/FTIR Experiment. J. Chem. Educ. 1994, 71 (8), A195.
(8) Wang, S.; Liu, Q.; Luo, Z.; Wen, L.; Cen, K. Mechanism study on
cellulose pyrolysis using thermogravimetric analysis coupled with
infrared spectroscopy. Front. Energy Power Eng. China 2007, 1 (4),

■
CONCLUSION
Chemistry students learned about TG-FTIR analysis, identify-
ing mass loss stages and products of decomposition or
volatilization. Students recognized the importance of the
thermal characterization of materials and how the coupled
system allowed a more detailed characterization of the material.
This experiment applies primarily to students interested in
developing their careers in applied engineering or materials
science and technology. With this kind of practical experiment,
the students acquired a better understanding of the analytical
techniques and a better understanding of the results.
413−419.
(9) Li, X.; Tabil, L. G.; Panigrahi, S. Chemical Treatments of Natural
Fiber for Use in Natural Fiber-Reinforced Composites: A Review. J.
Polym. Environ. 2007, 15 (1), 25−33.
(10) De Á vila, S. G.; Logli, M. A.; Matos, J. R. Kinetic study of the
thermal decomposition of monoethanolamine (MEA), diethanolamine
(DEA), triethanolamine (TEA) and methyldiethanolamine (MDEA).
Int. J. Greenhouse Gas Control 2015, 42, 666−671.
(11) Shimanouchi, T. Tables of molecular vibrational frequencies.
Consolidated volume II. J. Phys. Chem. Ref. Data 1977, 6 (3), 993−
1102.
(12) Shimanouchi, T. Tables of Molecular Vibrational Frequencies:
Consolidated Vol. I; National Standard Reference Data System,

■
National Bureau of Standards, Series 39; U.S. National Bureau of
Standards: Washington, DC, 1972. https://nvlpubs.nist.gov/nistpubs/
ASSOCIATED CONTENT Legacy/NSRDS/nbsnsrds39.pdf (accessed Apr 2018).
*
S Supporting Information (13) National Institute of Standards and Technology, U.S. Depart-
ment of Commerce. NIST Chemistry WebBook, SRD 69, entry for
The Supporting Information is available on the ACS “Monoethanolamine”. https://webbook.nist.gov/cgi/cbook.cgi?ID=
Publications website at DOI: 10.1021/acs.jchemed.7b00826. C141435&Type=IR-SPEC&Index=0# (accessed Apr 2018).
Instructor notes (PDF, DOC)
Student handout (PDF, DOC)

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: lcarreno@uis.edu.co.
ORCID
Marisol Fernández Rojas: 0000-0003-0219-4227
Luz A. Carreño Díaz: 0000-0002-4952-0053
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
The authors thank the Universidad Industrial de Santander, the
Vice-rectorate for Research and Extension, and the Laboratory
of Instrumental Chemical Analysis of Chemistry School, for
making the resources and the equipment available for the
analyses.

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Denner, T. A novel direct coupling of simultaneous thermal analysis
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Anal. Calorim. 2013, 113 (3), 1091−1102.
(3) Benítez-Guerrero, M.; López-Beceiro, J.; Sánchez-Jiménez, P. E.;
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F DOI: 10.1021/acs.jchemed.7b00826
J. Chem. Educ. XXXX, XXX, XXX−XXX