Thermochimica Acta 672 (2019) 43–52

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Dielectric properties and kinetic analysis of nonisothermal decomposition of T

ionic liquids derived from organic acid
Bojan Jankovića, , Nebojša Manićb, Richard Buchnerc, Iwona Płowaś-Korusd, Ana B. Pereiroe,
⁎

Eliseo Amado-Gonzálezf,
⁎

a
University of Belgrade, Institute of Nuclear Sciences “Vinča”, Department of Physical Chemistry, Mike Petrovića Alasa 12-14, P.O. Box 522, 11001 Belgrade, Serbia
b
University of Belgrade, Faculty of Mechanical Engineering, Fuel and Combustion Laboratory, Kraljice Marije 16, P.O. Box 35, 11120 Belgrade, Serbia
c
Institut für Physikalische und Theoretische Chemie, Universität Regensburg, Universitätsstr. 31, D-93040 Regensburg, Germany
d
Institute of Molecular Physics, Polish Academy of Sciences, M. Smoluchowskiego 17, 60-179 Poznan, Poland
e
Alternative Fluids for Green Chemistry Unit, LAQV, REQUIMTE, Department of Chemistry Faculdad de Ciências e Tecnologia, FCT/UNL, Universidade Nova de Lisboa,
Campus da Caparica, 2829-516 Caparica, Portugal
f
Faculty of Basic Sciences, University of Pamplona, Biofuels Lab-IBEAR, Pamplona, Colombia

ARTICLE INFO ABSTRACT

Keywords: Dielectric relaxation spectra of three representatives of the class of hydroxyethylammonium carboxylate protic
Dielectric spectroscopy ionic liquids (PILs), namely 2-hydroxyethylammonium formate [2-HEAF], 2-hydroxyethylammonium propio-
Ionic liquids nate [2-HEAP] and 2-hydroxyethylammonium butanoate [2-HEAB], were recorded over a wide frequency range
Isoconversional analysis (0.05 ≤ ν(GHz) ≤ 50) at 25 °C. The thermal decomposition kinetics of these ionic liquids derived from organic
Thermal stability
acids was studied by thermogravimetry (TG) using nonisothermal experiments. For the purpose of kinetic
Anion chain length
Steric impediment
analysis, the thermal behavior of the samples was studied in the temperature interval from ambient temperature
up to 420 °C at different heating rates (5, 10, 15 and 20 °C min−1). Isoconversional kinetic analysis was per-
formed using Friedman’s (FR) differential method and the integral Kissinger–Akahira–Sunose (KAS) method. The
dependence of the apparent activation energy (E) on the conversion fraction (α) for the investigated decom-
position processes was analyzed. It was found that the molecular structure of the involved anion significantly
influences the dielectric properties of the studied PILs. It was also established that a change in the anion structure
drastically affects the shape of the thermo-analytical curves. Among the considered PILs [2-HEAF] has the
highest thermal stability. However, considering kinetic properties, certain deviations were observed and referred
to hydrogen bonding development and steric impediment effects.

1. Introduction
Protic (produced through the combination of a Brӧnsted acid and
Brӧnsted base) ionic liquids (PILs) form a class of ionic liquids (ILs), i.e.,
salts with melting points below 100 °C. PILs are the subset of ILs that
are prepared by stoichiometric Brӧnsted neutralization [1,2]. A key
feature of PILs is that they have an available proton on the cation. By
convention, the rest of the ILs can be classified as aprotic ILs (AILs),
although there are some other subsets that are similar to the PILs such
as Brӧnsted acidic ILs, which are functionalized such that they have an
available proton, typically on the anion.
Due to favorable physical chemistry properties of ILs, like no
flammability, thermal stability and low vapor pressure, and the multi-
tude of potential applications the interest in Ionic liquids (ILs) has in-
creased exponentially [3–6]. Although PILs have a wide potential for
industrial uses as an alternative for organic solvents [7], their future
applications will depend on the understanding of the relation between
molecular-level structure, cooperative dynamics, and macroscopic
properties like thermal and electrochemical stability, a wide electro-
chemical window, and a good ionic conductivity [8,9]. The effects of
symmetry and hydrophobicity on alkyl ammonium formates (AAFs)
were studied by different methods [10–13]. To investigate cooperative
dynamics, the dielectric spectra of ethylammonium formate (EAF) and
n-butylammonium formate (BuAF) at room temperature were recorded
[14–16]. Also, the influence of cation size and H-bond donor sites on
PILs dynamics were previously studied [17] but a systematic analysis of
the effect of cation substitution on dielectric and transportation prop-
erties of AAFs is still lacking. Nowadays, thermogravimetric analysis
(TGA) is used to determine the thermal stability and decay kinetics of
ionic liquids. There are two versions of TGA analysis: 1) in a

⁎
Corresponding authors.
E-mail addresses: bojanjan@ffh.bg.ac.rs (B. Janković), eamado@unipamplona.edu.co (E. Amado-González).

https://doi.org/10.1016/j.tca.2018.12.013
Received 16 October 2018; Received in revised form 11 December 2018; Accepted 13 December 2018
Available online 15 December 2018
0040-6031/ © 2018 Elsevier B.V. All rights reserved.
B. Janković et al. Thermochimica Acta 672 (2019) 43–52

temperature-ramped or scanning TGA experiment, the mass loss of the
sample is recorded as a function of temperature with constant heating
rate; and 2) in isothermal TGA experiments the mass loss of the sample
is recorded as a function of time, while the sample temperature is
maintained constant. TGA is a very useful and effective technique
providing quick quantitative access to kinetics parameters. Among
these parameters, the effective (apparent) activation energy (E) and the
pre-exponential (frequency) factor (A) are considered to be most re-
levant as they give significant information about the reactivity of the
studied system. The current work focuses on the thermal properties and
kinetic behavior of ionic liquids synthesized from organic acids, em-
phasizing the effect of the anion. As a model, the cation 2-hydroxy-
ethylammonium was selected, and the anion changed from formate to
propanoate to butanoate. To the best of our knowledge, no systematic
analysis of the anion effect on the thermal stability and accordingly the
decomposition mechanism of hydroxy-ethylammonium carboxylate
protic ionic liquids have been reported yet. Model-free (isoconver-
sional) analysis methods were utilized for determination of effective
(apparent) activation energies (E), and the pre-exponential factors (A)
of thermally induced events. Moreover, the isoconversional approach
was used in order to predict possible reaction steps and reactive species
participating in the thermal decomposition process.
Therefore, the main goal of this study was to evaluate the effect of
the chain length of the anion of the hydroxyethylammonium carbox-
ylate protic ionic liquids (PILs) on the kinetic behavior. Besides, the
dielectric properties and the influence of the chain length of the anion
on them were also analyzed.
2. Experimental
2.1. Synthesis and characterization
The PILs were synthesized by a Brønsted-Lowry titration between
ethanolamine and the corresponding organic acid (see Table 1) as
previously described [18,19]. Neat PILs were obtained after eliminating
the excess of the acid by evaporation and washing. To ensure the ab-
sence of water and volatile substances’ contents, all PILs were dried
under a 3 × 10−2 Torr vacuum with a continuous stirring for at least
48 h. Water content was verified by volumetric Karl-Fischer titration
(titroline KF, Schott instruments) to be 6 × 10−4 in mass fraction.
All isolated ionic liquids were completely characterized by 1H NMR
in order to check their final purities. The 1H NMR spectra were carried
out on a Bruker AVANCE 400 spectrometer operated at room tem-
perature with 16 scans. All spectra were acquired using DMSO or D2O
for field-frequency lock and NMR internal standard. 1H NMR spectra
certify the structures and the purity of the obtained ILs was higher than
97%. The analysis of 1H NMR gave the next results: [2-HEAF], δH
(400 MHz; DMSO) 8.41 (1H, s, H-COO-); 5.97-4.37 (3H, broad signal,
NH3+); 3.57 (2H, t, NH3+-CH2-); 2.83 (2H, t, -CH2-OH) (Fig. S1 of
Supporting Information); [2-HEAP]: δH (400 MHz; D2O) 3.72 (2H, t,
CH2-OH); 3.04 (2H, t, NH3+-CH2); 2.09 (2H, q, CH3-CH2-COO-); 0.96
(3H, t, CH3-CH2-), (Fig. S2 of Supporting Information); [2-HEAB]: δH
(400 MHz; D2O) 3.74 (2H, t, -CH2-OH); 3.06 (2H, t, NH3+-CH2-); 2.07
(2H, t, -CH2-COO-); 1.48 (2H, q, CH3-CH2-CH2-); 0.81 (3H, t, CH3-CH2-
), (Fig. S3 of Supporting Information.
In the calibration of the dielectric cell, the analytical grade liquids,
mercury, N,N-dimethylacetamide (Sigma-Aldrich, > 99.8%), benzoni-
trile (Sigma-Aldrich, > 99.9%), and 1-butanol (99.8%), required for
calibration of the dielectric measurements, were kept over activated 4 Å
molecular sieve to avoid moisture uptake.
2.2. Dielectric relaxation spectroscopy
Dielectric measurements in the frequency range of 0.05 ≤ ν(GHz)
≤ 50 were determined in reflection mode with an Agilent E83564B
Vector-Network-Analyzer (VNA) setup combining the data recorded
with 20 GHz and 50-GHz reflection probe-heads [20]. The VNA was
calibrated with air, purified mercury and N,N-dimethylacetamide as the
open, short and load, standards, respectively. The acquired raw data
spectra were corrected with a complex Padé approximant using 1-bu-
tanol and benzonitrile as secondary standards [21]. The polarization
(macroscopic dipole moment per volume) is expressed in terms of a
generalized frequency-dependent complex permittivity as:
η*(ν) = ε’ (ν) - i[ε’’(ν) + κ/(2πνε0)] (1)
where ε’(ν) is the relative permittivity at frequency ν, ε’’(ν) is the di-
electric loss, κ the DC conductivity and ε0 the vacuum permittivity. All
experiments were carried out at 25 °C with a temperature uncertainty of
0.10 °C. Small amounts of water were added to 2-HEAP and 2-HEAB to
obtain viscous liquids. For all samples used in the dielectric experiments
the water content was determined by Karl-Fischer titration (Table 2).
2.3. Thermal decomposition
The simultaneous TGA-DTA (thermogravimetric analysis - differ-
ential thermal analysis) curves for PILs samples were obtained in a
TGA-DTA simultaneous SDT-Q600 module, controlled by a
ThermoAdvantage® software (release 4.2.1) both from TA Instruments
(TA Instruments, 159 Lukens Dr, Newcastle, DE 19720, USA). The
studies were conducted with PIL sample masses of about of 15 ± 1 mg
within the thermo balance in korund pans under (99.9995 vol. %) ni-
trogen (N2) flow (with gas flow rate of φ = 50 mL•min-1) in a tem-
perature range from ambient up to 420 °C, at the heating rates of β = 5,
10, 15 and 20 °C min−1 in a linear heating regime.
Before thermal measurements, the following calibrations were
performed: calibration of mass; calibration of TGA signal, calibration of
the DTA base line, temperature calibration; the calibration of tem-
perature signal (as a standard, the eletrochemically pure metals (zinc

Table 1
Chemical name, source, purification method and purity.
Chemical name Source Purification method Purity (mass fraction %) Mass water content

Etanolamine Sigma Aldrich, CAS No 141-35-5 No further purification ≥ 98.0

Formic Acid Carlo Erba, CAS No 64-18-6 No further purification 99
Propionic Acid Alfa Aesar, CAS No 79-09-4 No further purification 99
Butiric Acid Alfa, CAS No 107-92-6 No further purification 99
[2-HEAF]a Synthesis/ yellow liquid Evaporation and washing > 98 < 500 ppm

b
[2-HEAP] Synthesis/yellow solid Evaporation and washing > 97 < 500 ppm

[2-HEAB]c Synthesis/yellow solid Evaporation and washing > 99 < 500 ppm

a
2-Hydroxyethylammonium formate.
b
2-Hydroxyethylammonium propanoate.
c
2-Hydroxyethylammonium butanoate.

44
B. Janković et al. Thermochimica Acta 672 (2019) 43–52

Table 2
Water content, DC conductivity, κ, static permittivity, ε, relaxation strength, S,
relaxation time, τ, asymmetry parameter, β, high-frequency permittivity, ε∞, of
the investigated IL samples. Also indicated is the minimum frequency, νmin, of
the data used in the fit.
IL Water κ (S m−1) ε S τ (ns) β ε∞ νmin (MHz)
content
(w%)

2-HEAF 1.0 0.30 47.1 41.8 1.1 0.58 5.2 80

2-HEAF 0.0 61.0a
2-HEAP 1.9 0.06 19.1 14.7 2.2 0.46 4.4 50

2-HEAB 2.2 0.04 15.3 11.2 1.9 0.46 4.1 50

35.0b

a
Ref. [15].
b
Ref. [32].
Fig. 1. Relative permittivity, ε’(ν), of 2-HEAF ( ), 2-HEAP ( ) and 2-HEAB ( )
and corresponding fits (lines) with the Cole-Davidson model.
and tin (performed at 2 °C min-1 scanning, from Tm = -100 °C to Tm
= + 50 °C; (m) – melting point))), as well as the calibration of “dual
sample weight” signal. i AR E
ln = ln ,
A DTA measures the temperature difference between the sample T 2, i g( ) E i
RT , i (4)
and a reference pan as a function of time and temperature. The DTA
where from the linear plot of ln(βi/Tα,i2)
versus 1/Tα,i obtained at the
construction enables the heat transfer by purge gas and irradiation. The
several thermo-analytical curves, the E can be estimated, while A can be
TA Instruments SDT-Q600 is capable of measuring both heat flow and
calculated from the intercept of the straight line, if the exact form of the
mass change as a function of time/temperature at a controlled rate and
integral reaction model function g(α) is known [26].
in a controlled atmosphere. The simultaneous measurement allows for
The merit of such kinetic isoconversional procedures is that they
an accurate determination of heat changes during phase change, as well
provide a way to get kinetic parameters with ignoring completely the
as the heat of reaction for endothermic and exothermic processes. The
reaction mechanisms. Consequently, they are often called model-free.
whole equipment is calibrated with recommendation of TA
These methods are based on the isoconversional principle, where the
Instruments. Measurements conducted at every heating rate were re-
reaction rate at fixed conversion fraction depends only on the tem-
peated twice for improving the quality of repeatability.
perature [27].

3. Kinetic study 4. Results and discussion

3.1. Isoconversional (model-free) approach 4.1. Dielectric spectroscopy results and analysis

The mass loss versus temperature at constant heating rate can be For [2-HEAP] and [2-HEAB] the spectrum of the relative permit-
expressed by the dimensionless quantity known as the conversion tivity, ε’(ν), (Fig. 1) is reasonably smooth over the entire covered fre-
fraction (α): quency range. However, due to the small but not negligible DC con-
ductivity of the samples (Table 2) and the limited performance of the
(mo mT )
= , probe-heads at frequencies < 200 MHz, the corresponding dielectric
(mo mf ) (2) loss, ε’’ shows significant oscillations at low frequencies (Fig. 2). For [2-
HEAF] ε'(ν) (Fig. 1) was reasonably smooth between 0.08 and 50 GHz
where mo, mT, and mf are the initial sample mass, the sample mass at
but ε”(ν) showed unphysical oscillations below 280 MHz (Fig. 2) for the
time t, and the final sample mass, respectively.
same reasons as 2-HEAP and 2-HEAB.
The methods for the prediction of apparent activation energies and
The obtained dielectric spectra are well fitted by a Cole-Davidson
pre-exponential factors used in thermal decomposition kinetics assume
(CD) equation (Fig. 3):
that the reaction model f(α) in the rate-law equation is independent on
the heating rates [22]. According to Friedman’s isoconversional dif-
ferential (FR) method, the change of the conversion fraction with time
is given by:

d d E
ln i ln = ln [A f ( )]i ,
dT ,i dt ,i RT , i (3)

where E and A are the apparent activation energy and the pre-ex-
ponential factor, respectively, at the constant value of conversion
fraction (α); f(α) is the differential form of reaction model function,
while Tα,i is the temperature at considered heating rate βi; (dα/dt)α,i is
the reaction rate at α = const., and at the heating rate βi. The E can be
estimated from the slope of the linear plot of ln(dα/dt)α,i versus 1/Tα,i,
at constant α value and i-th heating rate. The pre-exponential factor (A)
can be calculated, if the exact form of f(α) function is known [23].
The integral Kissinger-Akahira-Sunose (KAS) method [24,25] was
developed from the Coats and Redfern approximation of temperature Fig. 2. Dielectric loss, ε’’(ν), of 2-HEAF ( ), 2-HEAP ( ) and 2-HEAB ( ) and
integral and expressed as: corresponding fits (lines) with the Cole-Davidson model.

45
B. Janković et al.
Fig. 3. Cole-Cole plot, ε’’ = f(ε’(ν)), of 2-HEAF ( ), 2-HEAP ( ) and 2-HEAB (
) and corresponding fits (lines) with the Cole-Davidson model.
S decomposition temperature range. It should be noted that the shapes of
*( ) = +
(1 + i2 ) (5)
where ε∞ is the high-frequency permittivity, S the relaxation strength, τ
the relaxation time and β the asymmetry parameter of the relaxation.
The static permittivity is given as ε = ε∞ + S. Note that in the fitting
procedure the DC conductivity, κ, was also treated as an adjustable
parameter because of the fringing-field error of the probeheads [28]
and thus may differ by up to 20% from the true value. The fit para-
meters are summarized in the Table 2.
Due to the high viscosity of all studied ILs their dynamics is very
slow with relaxation times of ∼1 to 2 ns. Accordingly the loss peak is
around 100 MHz (Fig. 1) and thus in a frequency range affected by
considerable systematic errors (the oscillations of ε’’(ν)). Also, ε’(ν) is
still far from its low-frequency plateau which makes determination of
the static permittivity, ε = limν→0ε’(ν), rather unreliable. With ε ≈ 47
the static permittivity of 2-HEAF is very large. It exceeds the value of
ethylammonium formate (ε = 34.14) and is comparable to that of
ethanolammonium nitrate (ε = 43.94) [29]. On the other hand, the
static permittivity of 2-HEAB (ε = 15.3) is rather small for a protic ionic
liquid and comparable to values for imidazolium ILs (∼ 10–20) [30]
but also for butylammonium formate (∼ 19.64) [31]. A theoretical
estimate of the static permittivity of 2-HEAB (ε = 38.5) differs con-
siderably from the experimental value of ε = 15.3 [32]. Interestingly,
the static permittivity for 2-HEAF, 2-HEAP and 2-HEAB decreases lin-
early with an increasing number of carbon atoms (R2 = 0.9507, Fig. 4).
A similar behaviour was observed for the series 2-hydro-
xyethylammonium acetate [2-HEAAc] and [2-HEAF] from Ref. [15]
and [2-HEAB] from Ref [32]. but with a considerable offset between the
present static permittivity of [2-HEAF] and the value given in Ref. [15].
Fig. 4. The static permittivity (ε) of the analysed PILs decreases roughly line-
arly (R2 = 0.9507) with increasing number of carbon atoms ( ). This is also the
case for literature data ( ) of 2-hydroxyethylammonium acetate [2-HEAAc]
and [2-HEAF], Ref. [15], and [2-HEAB], Ref. [32], but with a considerable
offset.
46
Thermochimica Acta 672 (2019) 43–52
Almost certainly, this discrepancy reflects the difficulty in obtaining
pure samples.
4.2. Thermal behavior
Thermal analysis of the hydroxyethylammonium-based ILs provided
the information on the thermal stabilities of studied ILs. The stability of
ILs depends upon three major factors: a) the strength of inter-molecular
interaction, b) on the possibility of back proton transfer because of
equilibrium, and c) the amount of the moisture present in ILs. Fig. 5
(a–c) and (d–f) shows TG (thermogravimetry) and DTG (derivative
thermogravimetry) curves obtained under the inert (nitrogen (N2)) at-
mosphere for [2-HEAF], [2-HEAP] and [2-HEAB] samples, respectively.
It can be seen from TGA curves (Fig. 5 (a–c)) and from Table 3 that
studied ILs exhibit different thermal stability in monitored thermal
TGA curves at various heating rates for [2-HEAF] are visibly different
from the other two ILs samples (this can be seen from Fig. 6, which
provides a comparative visual representation of the TGA curve shapes
for studied systems at a single heating rate (10 °C min-1); in considered
cases, the onset decomposition temperatures lie below 150 °C, and these
values were generally defined as where there was 10% mass loss using
TGA measurements).This also may suggests on the different mechanism
of decomposition and thermal behavior in the case of [2-HEAF] in
comparison with [2-HEAP] and [2-HEAB] samples.
It is evident that the anionic change in the ILs structure, drastically
affects the appearance of thermo-analytical curves, which can also be
seen on the basis of the shapes of corresponding DTG curves (Fig. 5
(d–f)). All samples show two main decomposition peaks, however, the
shape of DTG curves and the position of the first peak only differ in the
case of [2-HEAF], while DTG curves for [2-HEAP] and [2-HEAB] show
similar characteristics (Fig. 5 (d–f) and Fig. 6). It should be noted that a
strong inter-molecular interaction may increases the decomposition
temperature due to the strong electrostatic interaction between the
cation and anion. Therefore, it takes more energy for breaking the
chemical bonds. These qualities are especially emphasized for behavior
of the onset temperature (Tonset). The Tonset values and other char-
acteristic decomposition temperatures and thermal features (including
endset temperatures (Tendset), peaks temperatures (Tpeak) as well as total
mass losses (Δmtotal loss)) for studied systems are listed in Table 3.
From the presented results, considering all heating rates, the order
of Tonset values is as follows: [2-HEAF]Tonset < [2-HEAP]Tonset < [2-
HEAB]Tonset. The decrease in water content value from [2-HEAB] to [2-
HEAF] (Table 2) influences on the lowering Tonset independently on
the heating rate [33,34]. In addition, the purity of ILs definitely affects
the thermal decomposition, as in the case of hydroxyethylammonium
ionic liquids which have tendency to adsorb the moisture. The Tpeak1
quantity (Table 3) is probably associated with anion chain length, and
this temperature has the trends to increase with increases of the chain
length, but at the higher heating rates (especially above 10 °C min-1)
can show variation depending on the reactivity of observed system
[35]. The protic ionic liquids which have carboxylate anions, especially
formiate, may have lower Tonset and Tpeak1 values at the lower heating
rate, due to the eventual participation in condensation reactions [36].
Taking into account the above-mentioned, the chain lengths affect the
thermal performance of studied ILs. The longer chain length results in
greater van der Waals forces. Since that the ionic liquids are ionic
compounds it could also reduce the inter-molecular electrostatic in-
teraction, which causes an overall decrease interaction and lower
thermal stability [37]. Considering this issue, the density of a given
material may influence on the chain length, since it is apparent that the
density decreases slowly as the chain length increases. This observation
was identified in the case of alkylammonium cations, alkylimidazolium
cations, or alkylcarboxylate anions [36].
Taking into account that the same cation is present, the thermal
stability dictates the doped anion in the considered samples. Due to
B. Janković et al.
Fig. 5. TGA (a – c) and DTG (d – f) curves of thermal decomposition process of [2-HEAF], [2-HEAP] and [2-HEAB] samples, in an inert (nitrogen) atmosphere at the
various heating rates (5, 10, 15 and 20 °C min−1).
these results, it can be concluded that anions play an important role in
thermal mechanism of hydroxyl-ethyl-ammonium-based ILs. In that
light, as the main fact, the stability of actual ILs was generally con-
trolled by the anion. These results are in agreement with others re-
porting that the thermal stability of ILs is largely determined by the
coordinating ability of the anion [38]. The thermal stability and de-
composition can be directly correlated to electrostatic force between
the anion and cation. Since that OH group in a carboxylic acid is weakly
acidic, the dissociation constant of acid/anion is defined as the Ka
47
Thermochimica Acta 672 (2019) 43–52
values. The exponential numbers of the dissociation constant was
converted into a normal range by taking their negative logarithm (de-
fined by pKa), that represents the strength of acidity. The lower pKa
value is a stronger acidic in nature. Strong acid is able to form a strong
chemical bonding with the cation. Hence it needs more energy to break
the chemical bonding. The stronger acidity of the anion exhibits a
higher thermal stability. Among these three anions, the formiate anion
has a lower pKa value (pKa = 3.75), than the others anions, propionate
(pKa = 4.85) and butanoate (pKa = 4.82) [39], and as a result [2-
B. Janković et al. Thermochimica Acta 672 (2019) 43–52

Table 3 and DTG curves show the possible temperature decomposition zones
Thermal results from nonisothermal scans at various heating rates in an ni- where the appropriate reactions take place, such as the follows: a) for
trogen atmosphere. [2-HEAF] ― I) up to 125 °C (mass loss ∼ 10.45% (at 5 °C min-1)), II)
5 °C min−1 125–200 °C (mass loss ∼ 40.29% (at 5 °C min-1)), and III) 200–245 °C
Sample Tonset (oC) Tendset (oC) Tpeak1 (oC) Tpeak2 (oC) Δmtotal loss (mass loss ∼ 49.11% (at 5 °C min-1)), b) for [2-HEAP] ― I) up to 185 °C
(%) (mass loss ∼ 94.55% (at 5 °C min-1)), II) 185–205 °C (mass loss ∼
[2-HEAF] 51.12 243.12 164.31 234.10 99.85
5.00% (at 5 °C min-1)), and finally c) for [2-HEAB] ― I) up to 190 °C
[2-HEAP] 66.12 204.04 172.73 198.56 99.63
[2-HEAB] 88.15 210.67 173.53 200.61 99.90 (mass loss ∼ 93.52% (at 5 °C min-1)), II) 190–210 °C (mass loss ∼
10 °C min−1 6.09% (at 5 °C min-1)). From these results, it can be seen that three
Sample Tonset (°C) Tendset (°C) Tpeak1 (°C) Tpeak2 (°C) Δmtotal loss reaction zones can be identified in the case of [2-HEAF] decomposition,
(%) while for [2-HEAP] and [2-HEAB], only two reaction zones exist, but
[2-HEAF] 64.55 261.26 175.98 247.05 99.62
with different thermal properties in comparison with [2-HEAF]. Con-
[2-HEAP] 70.70 214.72 179.24 207.64 99.66
[2-HEAB] 90.52 220.84 182.53 213.55 98.98 sidering two members, [2-HEAP] and [2-HEAB], the decomposition
15 °C min−1 reactions should have very similar kinetic characteristics. If we consider
Sample Tonset (°C) Tendset (°C) Tpeak1 (°C) Tpeak2 (°C) Δmtotal loss a thermal decomposition process at a fixed heating rate (10 °C min-1)
(%)
(Table 3), the temperature Tpeak2 which characterizes reactions that
[2-HEAF] 75.03 270.75 187.54 258.72 98.90
[2-HEAP] 79.10 221.73 186.93 215.33 99.13 occur in the high temperature zone for [2-HEAF] is greater than the
[2-HEAB] 93.28 247.75 190.33 223.93 99.59 Tpeak2 values attached to the [2-HEAP] and [2-HEAB]. On the other
20 °C min−1 hand, Tpeak2 values for the last-mentioned members are very close to
Sample Tonset (°C) Tendset (°C) Tpeak1 (°C) Tpeak2 (°C) Δmtotal loss each other, which further confirm the above facts. The residual mass
(%)
loss exhibits some variation with the change of the heating rate
[2-HEAF] 81.17 276.56 194.82 268.62 99.72
[2-HEAP] 84.39 226.19 190.88 219.17 98.37 (Table 3). Fig. 7 (a – c) shows DTA curves together with heat effects
[2-HEAB] 109.97 264.10 203.18 245.86 99.61 during thermal decomposition process for [2-HEAF], [2-HEAP] and [2-
HEAB], respectively.
DTA curves (Fig. 7) show significant differences between [2-HEAF],
in comparison with other PILs. Up to 100 °C, the two PILs [2-HEAP] and
[2-HEAB] exhibit conspicuous endothermic peak in comparison with
[2-HEAF], which can be correlated with higher water content.
For [2-HEAF], the two endothermic decomposition effects can be
detected in reaction temperature zones which overlaps with those
found in DTG curves, with different thermal “intensity” effects (con-
sidering separately; (Fig.7 a)). However, in the case of [2-HEAP] and
[2-HEAB] samples, the one, central, endothermic peak can be identi-
fied, where broadness increases with an increase in the heating rate
(Fig. 7 b–c). At all observed heating rates, the actual DTA peak is
characterized with the appearance of “inclination” on the sides of the
higher temperatures, indicated by the arrow and labeled with “ad” in
Fig. 7 (b–c). This phenomenon is directly related to the appearance of
the second (less pronounced) peak (“Peak 2″) in the DTG curves (Fig. 5
e–f). The endothermic effects follow the changes detected in DTG
curves, and all transformations can be related to the existence of var-
Fig. 6. The comparative TGA curves of [2-HEAF] (full line —), [2-HEAP] (full
line ) and [2-HEAB] (full line ) at a single heating rate of β = 10 °C min−1. ious decomposition reactions, which can take the variety of contribu-
tions in complex decomposition mechanisms of these protic ILs. It can
be noted that reaction of protic ammonium salts may results in for-
HEAF] exhibits higher thermal stability than other members
mation of amide structure and water was detected in studied protic ILs
Based on the DTG curves (see Fig. 5 (d–f)), it is worthy to note that
bearing an organic anion. Such condensation reaction shows tendency
the most stable IL [2-HEAF] showed two peaks with completely dif-
to generate the impurities in protic ILs during their storage. This as-
ferent profiles from the rest of ILs. The first DTG peaks for [2-HEAP]
sumption was made earlier in the discussion. In general, from presented
and [2-HEAB] samples are positioned at temperatures as sharp and
thermo-analytical observations, especially thermogravimetry (TG), the
quite elongated, unlike the ones present for the [2-HEAF] that arises in
data obtained from this technique allows getting the information only
similar temperature range, as more diffused and shallower. For the
about the mass loss of protic ILs. The chemical reactions, which do not
second DTG peak, we have a completely different situation. Namely,
relate to formation of evaporable products, are not detectable with this
the second DTG peak attributed to [2-HEAF] is much more pronounced
technique.
with high intensity in comparison with DTG peaks related to [2-HEAP]
and [2-HEAB] ILs (Fig. 5 (d–f)). The positions of these peaks are linked
4.3. Isoconversional analysis
with the values of Tpeak1 and Tpeak2 listed in Table 3. These tem-
peratures characterize the main decomposition stages for all studied
On Fig. 8 the dependence of the effective activation energy values
ILs, but, we should emphasize that the number of thermally induced
on the conversion fractions during progression of investigated process
reactions in these stages can be different from one to the other IL
in the α range of α = 0.05 (5.0%) – 0.95 (95.0%) for [2-HEAF], [2-
sample. This can also cause the different kinetic behavior among them,
HEAP] and [2-HEAB] ILs is shown. It is estimated using the Friedman’s
conditioning a different kinetic mechanism of the entire decomposition
(FR) and Kissinger-Akahira-Sunose (KAS) model-free methods. For all
process. On the other hand, an increase in the heating rate, the Tpeak
established FR and KAS plots, the very good correlation was obtained
shifts towards right. This movement of the DTG curve with increase of
(R2 > 0.9955). The error data results related to E were introduced in
the heating rate from lower to higher temperature is assigned to de-
Fig. 8. The isoconversional kinetic analysis was carried out in ac-
layed decomposition which dispenses more heat into the sample for a
cordance with the ICTAC Kinetics Committee recommendations
short time interval. Taking into account all these considerations, TGA
[40,41].

48
B. Janković et al.
Fig. 7. DTA (a – c) curves of thermal decomposition process of [2-HEAF], [2-
HEAP] and [2-HEAB] samples, in an inert (nitrogen) atmosphere at the various
heating rates (5, 10, 15 and 20 °C min−1).
The main features demonstrated by these results can be summarized
as follow:
a) [2-HEAF] – Considering both methods (Fig. 8 a) – b)), these
methods give very similar trends of the effective activation energy
variations on α. The minor differences in the values of effective acti-
vation energy obtained by these methods are the consequence of some
limitations of these methods or error during interpretation of the data.
Both graphical imaging shows complex dependence of the effective
activation energy during the course of the process, with wider ranging
of E values in its variations with α. From E ― profiles presented in
Fig. 8 a) – b), it can be observed that constant E value (the case of a
single reaction) does not exists, so, these profiles indicate that the
49
Thermochimica Acta 672 (2019) 43–52
decomposition mechanism is a function of conversion fraction. Rapid
rise of E values from 32.0 to 88.0 kJ mol-1 occurs in α range of
0.05 < α < 0.19 which corresponds to temperatures up to 125 °C. In
this region, increases of E value at very beginning of the process up to
approximately α = 0.06 with the E ∼ 40.0 kJ mol-1 corresponds to the
water evaporation, taking into account the molar heat (or enthalpy) of
water vaporization (∼ ΔHvap = 44.0 kJ mol-1). Further increasing of E
value up to α ≈ 0.19 can be attributed to destabilization of the ex-
tensive hydrogen bonding which stabilizes the both the cation and
anion in considered IL, which requires additional input energy. The
additional energy needed here may reduce the formation of the neutral
moieties due to the retro-transfer of the proton [42]. Namely, this si-
tuation was characterized primarily by hydrogen bonding between
oxygen atoms in formate anion and hydrogen atom in the hydroxyl
group of 2-hydroxyethylammonium [2-HEA] cation, together with a
very strong interaction between HN hydrogen atoms in the cation and
oxygen atoms in the anion. The strong interaction between hydrogen
atoms bonded to nitrogen (designated by HN) in the cation and the
oxygen atoms in formate (designated by OF) (HN-OF cation-anion in-
teractions) leads to moderate property, related to degree of ionicity for
interacting pair. The first interaction is much weaker than the other,
which requires a lower E value with a rise in temperature to approxi-
mately α ≈ 0.40 (Fig. 8a) for the FR method). This phenomenon leads
to the appearance of the “Peak 1” (with lower intensity) in the DTG
curve (Fig. 8 d). Further increasing of the temperature and the con-
version progression leads to structural/geometric pre-orientation which
is the cause of this other interaction. This type of interaction leads to
very large interaction energies leading to a sharp rise in the E values at
higher α values (above α = 0.42, and up to α ≈ 0.80). The last-men-
tioned interaction is responsible for the appearance of the sharp “Peak
2” in the corresponding DTG curve (Fig. 8 d). The last process stage,
evolving through α passing above α = 0.80 and decreasing of the E
value, corresponds to the residual end-products, with gradually forming
of the char-like structure. The much lower E value and its declining for
this stage is not a surprise, considering the small number of C atoms,
compared to other studied members of ILs.
b) [2-HEAP] – In the case of [2-HEAP] decomposition, the E = E(α)
dependency (Fig. 8 c) – d)) is somewhat different from the one in the
case of [2-HEAF]. The higher E value identified for [2-HEAP] in com-
parison with [2-HEAF] at the beginning of the process is the result of
higher water content in the sample and its more severe release. With an
increasing of α, the E value continues to increase until to α = 0.65 with
E = 120.0 kJ mol-1 (considering FR method (Fig. 8 c)) at temperature
about 178 °C which corresponds to the main peak on the DTG curve
(“Peak 1”) (Fig. 5 e). The decomposition starts immediately after the
sample has lost the water. On the other hand, the dense may increases
in the case where we have the same cation but anion with higher ali-
phatic chain. This also requires more energy to break the links in the
carbon chain (Fig. 8 c)). Consequently, in actual case, the propionate
anion-based IL is denser than the formiate anion-based IL with 2-hy-
droxyethylammonium cation. The similar situation was identified in the
case of nitrate anion-based IL (compared with formate anion-based IL)
with alkylammonium cation [43,44]. It should also be considered and
ion-water interaction which depends to a great extent on the steric ef-
fects. In addition, the ion-pair interactions can decrease with increasing
the size of anion within the same cation groups [45]. So, for the [2-
HEAP], the last-mentioned phenomenon is more pronounced than in
the case of [2-HEAF] which may leads to gradually decreasing of E
values that occurs in the later stage of the process (Fig. 8 c)). Reduced
intensity of these interactions due to an increase in the size of the anion
may be a consequence of the appearance of the second (the sharper but
smaller in intensity potency) peak (“Peak 2”) in the DTG curves of [2-
HEAP] thermal decomposition (Fig. 5 e). The abruptly increase in the E
values above α = 0.90 against those noticed in [2-HEAF] can be at-
tributed to the formation of the richer carbonaceous matrix, due to the
presence of a much higher number of C atoms. This corresponds to a
B. Janković et al.
Fig. 8. Isoconversional dependencies of the apparent activation energies on conversion fraction during decomposition process of [2-HEAF], [2-HEAP] and [2-HEAB]
obtained by the Friedman (FR) and Kissinger-Akahira-Sunose (KAS) methods.
more straightforward (flatter) part of the DTG curves above 250 °C that
are presented in Fig. 8 e.
c) [2-HEAB] – In the case of [2-HEAB] decomposition process, we
have a more interesting situation. From the curve dependency of E = E
(α), it can be observed that E exhibits quite “uneven” variation with α
(Fig. 8 e) – f)). This is more expressed in the case of the application of
the differential Friedman’s (FR) isoconversional method. As the chain
length of the anion increases, the acceptor number (AN) [46] value
decreases, indicating a greater acidity. In our case, the [2-HEAB] takes
the last place (see the previous discussion). This could be due to the
50
Thermochimica Acta 672 (2019) 43–52
very pronounced steric hindrance of the cation-anion interactions on
increasing the chain length, as for the studied [2-HEAB]. It should be
noted the fact, it is possible that the density value decreases as the chain
length of the anion increases, leading to increase in the steric hindrance
as the chains become more voluminous. On the other hand, it was
showed [47] that in hydroxylammonium-based ILs with a fixed cation,
the ultrasonic sound velocity increases with an increase with carbon
chain length for anions, which can be attributed to the increase in
spatial distance between the molecules due to the steric hindrance.
The addition of the eCH2 group to the anion chain may causes
B. Janković et al.
increases in the compaction of the considered mixture. However, the
further extension of the chains may leads to the opposite effect, even if
it is quite moderate. In this respect, [2-HEAB] is quite sensitive and this
sensitivity is expressed through its thermal behavior and the marked
variation of the effective activation energy with process progression
(Fig. 8 e). Beyond α = 0.65 going to higher α values, the shape of E = E
(α) dependency for [2-HEAB] (Fig. 8 e) is almost identical to that for [2-
HEAP] (Fig. 8 c). The only significantly difference in this region con-
sidering [2-HEAB] and [2-HEAP], is in the magnitude of the variation
of E values between them, and which can be seen from a more “dif-
fused” second peak (“Peak 2”) in the DTG curves for [2-HEAB] thermal
decomposition (Fig. 5 f). At some lower temperatures and α < 0.65,
the [2-HEAB] exhibits a more intensive variation in comparison to [2-
HEAP] (Fig. 8 e) and c)). On this “uneasy” E behavior for [2-HEAB]
comparing to the [2-HEAP], the tremendous impact has the following
fact: the E values show the significant dependence not only on the
conversion fraction (α), but also from the temperature (T) (the strong
simultaneous dependence), and consequently on the value of the used
heating rate. This is particularly true at the highest heating rates, where
a certain “deviation” in the shape of the DTG curve attributed to the
first peak appears clearly (Fig. 5 f). To the best of our knowledge, these
effects are not recorded in the open literature.
Some kinetic property variations among tested IL members arise
from the several reasons: 1) different reactivity of ILs, when transition
occurs from the low-temperature to high-temperature reaction zone,
where the difference may be attributed to variations of experimental
conditions, especially reaction temperatures, which were higher by ∼
100 °C (Table 3) leading to faster chemical reactions which take place
during decomposition, 2) strong steric effects present in the case of [2-
HEAB], where steric impediment inhibits ending decompositions reac-
tions in pre-final stage, leading to a significant drop in the E values
(Fig. 8 e), for α > 0.65), 3) the presence of ethyl radical may increases
the thermal stability of [2-HEAP], due to the steric impediment, and 4)
during thermally induced process of [2-HEAF], it can be assumed that
[2-HEA+] and formate compete for the same interacting sites for hy-
drogen bonding developments. In this sense, the interaction between
cation and anion in [2-HEAF], may proceeds through both, the hy-
droxyl and ammonium sites. Such changes are clearly reflected on their
kinetic properties through the dependence of the effective activation
energy on the conversion fraction (Fig. 8). The causes behind con-
sidered variations are most likely tied to various physico-chemical
properties of the compounds, namely structural effects, bond strengths,
and electronegativity of the ions, as well as the liquid-phase properties
of the reactants and products, such as the dielectric constants, con-
ductivity, and the influence of hydrogen bonding. However, it is clear
from deduced parameters that there exist some notable similarities and
dissimilarities.
5. Conclusion
The nonisothermal decomposition of studied PILs was studied in
nitrogen (inert) atmosphere at various heating rates. The kinetic ana-
lysis of decomposition processes was performed using differential and
integral isoconversional (model-free) approaches.
For the considered PILs, it was found that the value of ε decreases
significantly with increasing carbon-chain length in the anion, i.e. in
the order: [2-HEAF] > [2-HEAP] > [2-HEAB], the onset temperature
(Tonset) criterion and the shape of the thermogravimetric (TG) curves,
follows the order: [2-HEAF] < [2-HEAP] < [2-HEAB]. Besides the ef-
fective activation energies during decomposition process (from a ki-
netic point of view), varies following the order of thermal decomposi-
tion resistance as [2-HEAB] < [2-HEAF] < [2-HEAP].
These results suggest that the 2-hydroxyethylammonium cation and
formate anion compete for the same interacting sites for the hydrogen
bonding developments. Consequently, the interaction between cation
and anion of [2-HEAF] can proceeds through both, the hydroxyl and
51
Thermochimica Acta 672 (2019) 43–52
ammonium sites. Such changes can lead to the significant differences in
the formation of effective activation energy versus conversion fraction
dependencies in the analyzed PILs. It was established that causes which
stand behind identified variations are closely related to various che-
mical properties of the investigated PILs. On conclusion, the established
results suggest that the dielectric properties and kinetic behavior of
studied PILs can be connected through their skeletal formula, including
impact of carbon chain lengths in the anions.
Acknowledgements
The authors would like to thank to the Ministry of Education,
Science and Technological Development of the Republic of Serbia under
the Projects 172015 (B. Janković) and III42010 (N. Manić)). A.B.
Pereiro would like to thank the financial support from FCT/MCTES
(Portugal), through Investigador FCT 2014 (IF/00190/2014) and the
Associate Laboratory for Green Chemistry LAQV, which is financed by
national funds from FCT/MEC (UID/QUI/50006/2013) and co-financed
by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-
FEDER-007265). Eliseo Amado-González thanks the financial support
of University of Pamplona, Internal Project 2-2017.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.tca.2018.12.013.
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