Fuel 238 (2019) 198–207

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Study of the kinetic and thermodynamic parameters of the oxidative T

degradation process of biodiesel by the action of antioxidants using the
Rancimat and PetroOXY methods
Leanne Silva de Sousaa,b, Marco Aurélio Suller Garciaa, Ellen Cristina Pereira Santosa,
Jurandy do Nascimento Silvac, Adriano Gomes de Castroa, Carla Verônica Rodarte de Mouraa,
⁎
Edmilson Miranda de Mouraa,
a
Departamento de Química, Universidade Federal do Piauí, Teresina 64049-550, PI, Brazil
b
Instituto Federal do Piauí, Valença do Piauí 64300-000, PI, Brazil
c
Instituto Federal do Piauí, Teresina – Zona Sul 64018-000, PI, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: The addition of antioxidants to biodiesel, as well as the elimination of conditions favoring the initiation of the
Antioxidants oxidation reaction, can inhibit or retard the oxidative process. In this work, we present a comparative study of
Biodiesel the antioxidant activity of extracts of bilberry (BE), oregano (EO), and basil (BAE), quercetin (QC) and pyrogallol
Kinetic and thermodynamic parameters (PY) in biodiesel derived from soybean oil. The oxidation stability of the samples was studied using the Rancimat
and PetroOXY methods under 90, 100, 110, 120, 130 and 140 °C. Among the extracts, the highest total phenolic
contents were found in the oregano extract, followed by the basil and bilberry extracts. The apparent activation
energy for the consumption of the antioxidants was determined by the Arrhenius equation. The substrates were
ranked in the descending order of PY (81.39 kJ mol−1) > QC (77.73 kJ/mol) > BE (63.85 kJ/mol) > BAE
(62.02 kJ/mol) > OE (52.04 kJ/mol) for the Rancimat method and PY (79.64 kJ/mol) > QC (68.92 kJ/
mol) > BE (45.31 kJ/mol) > OE (44.48 kJ/mol) > BAE (41.98 kJ/mol) for the PetroOXY method. Parameters
such as enthalpy, entropy, and Gibbs free energy indicated a non-spontaneous endothermic process, as expected
for antioxidant samples. The shelf-life of the samples was predicted as: PY > QC > BE > BAE > OE and
PY > QC > OE > BE > BAE for Rancimat and PetroOXY methods, respectively. Considering the sensibility
and the analysis time, both methods meet the necessary requirements for the stability evaluation of biodiesel
samples.

1. Introduction highly susceptible to oxidative degradation, promoting its deterioration

While the world watches a massive increase in industry and trans-
port, which require a large amount of energy to grow, an opposite si-
tuation is observed for the carbon-based fossil energy sources. The
petroleum fuel has been depleting day by day, driving efforts in di-
versifying energy resources, such as solar and wind energies and bio-
mass-derived fuels [1–5]. Within this scenario, biodiesel production
and commercialization have increased since the last decade due to its
promising characteristics, like renewable feedstock sources (vegetable
oils, animal fats, and waste cooking oils), lower toxicity, biodegrad-
ability, and absence of sulfur and aromatics [6–8]. However, the pro-
duced biodiesel must be resistant against oxidation and the presence of
unsaturated methyl esters of linolenic, linoleic and oleic acids makes it
[9,10].
Although non-edible oils have been largely investigated over the
past few years as alternative sources [11], soybean oil is still largely
used as a substrate for biodiesel production [12]. However, its major
chemical composition is comprised of unsaturated fatty acids, making it
not suitable for industrial purposes without any sort of modification as
its deterioration results in loss of fuel quality [13,14].
The application of antioxidants is the most accepted procedure for
improving the stability of biodiesel [15]. The efficiency of such com-
pounds depends upon many factors; among them, chemical structures
and appropriate interaction with the substrate [16]. Thus, bioactive
compounds from vegetables (steroids, carotenoids, phytosterols, ter-
penes, reducing sugar, phenolic content, and cardiac glycosides) usually

⁎
Corresponding author.
E-mail address: mmoura@ufpi.edu (E.M. de Moura).

https://doi.org/10.1016/j.fuel.2018.10.082
Received 28 August 2018; Received in revised form 8 October 2018; Accepted 11 October 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
L.S. de Sousa et al.
meet the necessary requirements. They tend to be very effective since
they break the chain propagation by donating hydrogen atoms to free
radicals, avoiding the oxidative reactions [17,18]. Many naturally oc-
curring compounds have shown the antioxidant effect and are the
target of wide study [19,20] as the learning of oxidation processes in
detail allows a reliable storage period to be specified for the biodiesel
without its degradation until the time of use.
Currently, there are few studies with antioxidant plant extracts as
additives to improve the oxidative stability of biodiesel, since herbs and
spices are a major source of natural antioxidants. Among them, basil is
a good antioxidant and part of a group of medicinal plants of great
economic interest. Its constituents may include essential oils, flavo-
noids, tannins, saponins, caffeic acid, ascorbic acid, and camphor [21].
Oregano is also known for its antioxidant properties. The most im-
portant components are γ-terpinene, cymene, sabinene, and carvacrol,
although its chemical composition may vary depending on the species,
climate, altitude, harvest time and stage of growth [22]. Bilberry may
present tannins, essential oils, and flavonoids and may also be very
interesting as an antioxidant [23]. Therefore, natural antioxidants have
been used to improve the oxidative stability of biodiesel as well as
synthetic ones; nevertheless, natural antioxidants present the advantage
of being easy to obtain and relatively low cost.
The study of oxidative stability at different temperatures allows the
determination of kinetic and thermodynamic parameters and can be
used to evaluate the effect of antioxidants that prevent the propagation
of oxidative processes [19]. As far as we can tell, there are just a few
comparative studies on the kinetics of biodiesel oxidation reactions
using the Rancimat and PetroOXY techniques. The Rancimat method,
accepted by standard EN 14214 for the analysis of the oxidative sta-
bility of biodiesel (EN 14112), determines the oxidative stability by
increasing the conductivity of the samples at atmospheric pressure.
Thus, only highly volatile oxidation products are detected, non-volatile
products such as gums remain in the sample and the results obtained
using this method provide an incomplete analysis [19,24,25]. The
PetroOXY method (ASTM D7545) detects an O2 pressure drop during
the oxidation process. Supporters of the methodology claim that Pet-
roOXY includes all oxidation products, both volatile and non-volatile,
providing a complete analysis of the stability of the oxidation sample,
differently from the standard EN 14112 [26–28]. Based on such ac-
celerated oxidation processes, it is also essential to perform the study of
the kinetics and thermodynamic parameters of the biodiesel.
In this work, we present a comparative study of the antioxidant
activity of extracts of bilberry (BE), oregano (EO), and basil (BAE),
quercetin (QC) and pyrogallol (PY) in biodiesel derived from soybean
oil using accelerated methods as Rancimat and PetroOXY. In addition,
we explore the kinetic and thermodynamic parameters of the oxidative
degradation process.
2. Experimental
All reagents used in this study were of analytical grade
(Sigma–Aldrich, Vertec, or Merck) and used without prior purification.
Vegetable oils used were purchased from a local market (Teresina-PI,
Brazil) and from the same manufacturing lot. For the studies, pyr-
ogallol, quercetin, and extracts of bilberry (Plectranthus barbatus), or-
egano (Origanum vulgare (L.)), and basil (Ocimum basilicum (L.)) were
used as antioxidants. The bilberry, oregano, and basil plants were
homegrown by the authors.
2.1. Biodiesel synthesis and oil composition determination
The biodiesel synthesis and purification were performed according
to the literature [14]. Total fatty acid methyl esters (FAME) were
analyzed by using GC (Shimadzu CG 2010 plus, Rtx-wax capillary
column, flame ionization detector (FID)). The sample (1 µL) was in-
jected using a column oven temperature program of 210 °C for 50 min,
199
Fuel 238 (2019) 198–207
the temperature of FID was 250 °C and the H2, air and carrier gas (N2/
air) flow were of 40, 400 and 25 mL min−1, respectively.
2.2. Extracts preparation
The plant extracts were prepared from leaves. The preparation in-
volves water cleaning and drying of the leaves in an oven at 60 °C for
7 days. In a typical procedure, fine powders were prepared by grinding
the leaves with a mechanical blender, followed by sifting through a 140
mesh sieve. Then, the solids were immersed in absolute ethanol for
5 days and shaken manually every 24 h before a 2-hour mechanical
stirring and filtration under vacuum. The filtrates were concentrated in
rotavapor at 40 °C for the extracts obtaining. The ethanolic extracts
were stored in amber bottles.
The bilberry, oregano, and basil extracts were freeze-dried using
Virtis 4KBTXL-75 (SP Scientific Series, USA) freeze dryer for 12 h at
−78 °C.
2.3. Phytochemical screening of the extracts
The ethanolic extracts of bilberry, basil and oregano were tested for
the presence of steroids, flavonoids, tannins, alkaloids, terpenes, sapo-
nins, reducing sugar, phenols, and cardiac glycosides [29,30]. The ex-
periments were performed 3 times each. The qualitative results are
expressed as (+) for the presence and (−) for the absence of the
phytochemicals. The color intensity or precipitate formation were used
as analytical responses for the tests.
2.4. Determination of total phenolic content
The total phenolic content was analyzed based on the
Folin–Ciocalteu colorimetric method [31]. The samples were solubi-
lized in distilled water containing DMSO (250 μg/mL). An aliquot of
0.5 mL of the extract was mixed with 8 mL of distilled water and 0.5 mL
of the Folin–Ciocalteu reagent (20 vol%). After 5-minute stirring, 1 mL
of 6% sodium carbonate was added and the mixture was allowed to
stand at 37 °C for 1 h. The absorbance of the mixture was measured at
720 nm. Standard calibration curve for gallic acid in concentrations of
1.5, 3.0, 6.0, 12.0, 24.0, 48.0 and 96.0 μg/mL (prepared in the same
manner of the samples) was obtained and results were expressed as mg
gallic acid equivalent (GAE) per gram of extract. The experiments were
performed 3 times each.
2.5. Accelerated oxidation methods
The study of the biodiesel oxidative stability with antioxidants was
performed following the methodology described in EN 14112 [14,32],
using the Rancimat equipment mod 743 from Metrohm and the Pet-
roOXY equipment ASTM D7545 from Petrotest [14,33]. The prepared
extracts, pyrogallol, and quercetin were added to biodiesel in a range of
500–3000 ppm (to evaluate any prooxidant effect) and analyzed in a
temperature range of 90–140 °C. Table 1 presents the designation of all
the samples and the specific concentration of each additive added.
2.6. Kinetic and thermodynamic parameters of biodiesel oxidation reactions
The determination of the reaction constant (k) at different tem-
peratures was performed by considering the reactions as pseudo-first
order, according to Eq. (1).
ln[concentration] = −kt + ln[concentration]crit (1)
The activation energy of the reactions was obtained using the
Arrhenius equation for the six temperatures studied (Eq. (2)).
k= A e( −Ea/RT)
or
L.S. de Sousa et al. Fuel 238 (2019) 198–207

Table 1 3.2. Phytochemical screening and total phenolic content assay

Additives for biodiesel.
Samples Additive concentration Synthetic or natural antioxidants have been applied to prevent the
oxidation of biodiesel [36]. Thus, the protective effects of quercetin and
B100 Biodiesel without antioxidant pyrogallol against oxidative degradation of the soybean-derived fuel
B100 + PY 500 Biodiesel + 500 ppm of Pyrogallol
were studied for comparison with the extracts prepared. Since the an-
B100 + PY 1000 Biodiesel + 1000 ppm of pyrogallol
B100 + PY 1500 Biodiesel + 1500 ppm of pyrogallol
tioxidant activity of some compounds is believed to be mainly due to
B100 + PY 2000 Biodiesel + 2000 ppm of pyrogallol their redox properties [37], and that phenols have scavenging ability
B100 + PY 2500 Biodiesel + 2500 ppm of pyrogallol due to their hydroxyl groups [38], the preliminary phytochemical
B100 + PY 3000 Biodiesel + 3000 ppm of pyrogallol screening of ethanolic extracts of bilberry, oregano, and basil aimed at
B100 + QC 500 Biodiesel + 500 ppm of quercetin
detecting the main classes of secondary metabolites, such as steroids,
B100 + QC 1000 Biodiesel + 1000 ppm of quercetin
B100 + QC 1500 Biodiesel + 1500 ppm of quercetin flavonoids, tannins, alkaloids, terpenes, saponins, reducing sugar,
B100 + QC 2000 Biodiesel + 2000 ppm of quercetin phenols, and cardiac glycosides. Such procedure was of vital im-
B100 + QC 2500 Biodiesel + 2500 ppm of quercetin portance for the studies performed herein since it showed whether the
B100 + QC 3000 Biodiesel + 3000 ppm of quercetin
extracts contained compounds able to act as antioxidants or not. For
B100 + BE 500 Biodiesel + 500 ppm of extracts of bilberry
B100 + BE 1000 Biodiesel + 1000 ppm of extracts of bilberry
this purpose, the color intensity or precipitate formation were used as
B100 + BE 1500 Biodiesel + 1500 ppm of extracts of bilberry analytical responses for the tests performed.
B100 + BE 2000 Biodiesel + 2000 ppm of extracts of bilberry As expected, the extracts presented chemical phenotypic variations,
B100 + BE 2500 Biodiesel + 2500 ppm of extracts of bilberry which are attributed to the effect of the taxonomic variety, genetic
B100 + BE 3000 Biodiesel + 3000 ppm of extracts of bilberry
variability, environment, and other factors [39]. Since the analytical
B100 + OE 500 Biodiesel + 500 ppm of extracts of oregano
B100 + OE 1000 Biodiesel + 1000 ppm of extracts of oregano sensitivity of the testes is limited, it is well-known that some secondary
B100 + OE 1500 Biodiesel + 1500 ppm of extracts of oregano metabolites may be not detected, due to their very low concentration;
B100 + OE 2000 Biodiesel + 2000 ppm of extracts of oregano the preliminary phytochemical screening clearly showed that bilberry
B100 + OE 2500 Biodiesel + 2500 ppm of extracts of oregano and oregano extracts presented higher varieties of phytochemical
B100 + OE 3000 Biodiesel + 3000 ppm of extracts of oregano
B100 + BAE 500 Biodiesel + 500 ppm of extracts of basil
components (Table 2), within the analysis conditions performed.
B100 + BAE 1000 Biodiesel + 1000 ppm of extracts of basil However, the three extracts met the requirements to be studied as an-
B100 + BAE 1500 Biodiesel + 1500 ppm of extracts of basil tioxidants for biodiesel maintenance.
B100 + BAE 2000 Biodiesel + 2000 ppm of extracts of basil Since the phytochemical screening is just qualitative, for a more
B100 + BAE 2500 Biodiesel + 2500 ppm of extracts of basil
accurate analysis of the most important compounds that may act as
B100 + BAE 3000 Biodiesel + 3000 ppm of extracts of basil
antioxidants, the total phenolic content of the additives was carried out
using the method of Folin-Ciocalteu. Such data were expressed as µg/g
ln k = ln A − (Ea/R)(1/T) (2) of the Gallic Acid Equivalent (GAE), as displayed in Table 3. Quercetin
and pyrogallol served as positive controls for the tests since they are
where A is the pre-exponential factor, Ea is the activation energy (kJ expected to present the higher total phenolic content.
mol−1), R is the molar gas constant (8.314510 J K−1 mol−1), and T is Oregano extract showed the highest total phenol content when
the absolute temperature in Kelvin. compared to other plant extracts. According to the values obtained, the
Enthalpy (ΔH*) and entropy (ΔS*) of the activated states were de- total phenol content of the investigated compounds can be ranged in
termined by the regression of ln (k/T) versus 1/T (Eq. (3)), which is the following order: pyrogallol > quercetin > oregano extract >
derived from the theory of the activated complex and expressed by basil extract > bilberry extract.
Eyring equation.

k= (kB/h)TeΔS∗ /R e−(ΔH∗ /RT)

3.3. Oxidative stability of the samples
ou:
The biodiesel produced (B100), had an induction period of 3.77 h in
ln(k/ T ) = (−ΔH∗/R)(1/T) + {ln(kB/h) + (ΔS∗/R)} (3) the Rancimat test at a temperature of 110 °C (Table S1). This value is
outside the limit established by the standard EN 14112, that is 8 h.
where kB is the Boltzmann’s constant (1,381 × 10−23 J K−1), h is the
When using the PetroOXY technique, the induction period obtained for
Plank constant (1,841 × 10−37 Jh), T is the absolute temperature (K),
the B100 was 0.76 h in the same range temperature (Table S2). This
ΔH* is the enthalpy of activation, and ΔS* is the entropy of activation.
difference in the induction periods, using different techniques, for the
Gibbs Free energy was obtained from the relation between entropy,
B100 sample, may be explained by the aging conditions, which are ex-
enthalpy, and temperature (Eq. (4)).
tremely different. The PetroOXY method determines the oxidative
Δ G= Δ H− TΔS (4)
Table 2
Phytochemical components of the ethanolic extracts of bilberry, oregano, and
3. Results and discussion basil.
Phytochemical components Bilberry Oregano Basil
3.1. Characterization of soybean-derived biodiesel
Reducing sugar + + +
Steroids − − −
Gas chromatography technique was used to characterize the bio- Phenols + + +
diesel produced from the soybean oil purchased. Such information is Flavonoids + + +
important since the composition of the oil may differ according to the Cardiac glycosides + + +
variety and growing conditions [34], which affect the chromatography Saponins − + −
Tannins + + +
profile of the fatty esters obtained. Linoleic (C18:2), oleic (C18:1),
Terpenes + + +
palmitic (C16:0), stearic and linolenic (C18:3) acids represented 56.6, Alkaloids + − −
23.6, 10.8, 3.4 and 5.7% of the total oil, respectively, which is in ac-
cordance with the literature [14,19,35]. + = presence; − = absence.

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L.S. de Sousa et al. Fuel 238 (2019) 198–207

Table 3 oxidation products are detected. While the Rancimat method detects
Total phenolic content of selected additives. only the highly volatile products of oxidation. The variation of the in-
Antioxidants µg GAE/mg dry extract IC 95% duction periods found by the two methods can be explained by the
variation of pressure and temperature used in the methodologies.
Pyrogallol (PY) 626.1 ± 2.02 608.0–644.3 [24,26,28].
Quercetin (QC) 571.1 ± 1.01 562.1–580.2
The low induction period values obtained in both techniques make
Bilberry extract (BE) 68.29 ± 1.01 59.20–77.37
Oregano extract (OE) 231.1 ± 5.04 185.8–276.5
the biofuel (B100) highly prone to oxidation by exposure to air during
Basil extract (BAE) 99.00 ± 4.04 62.66–135.3 storage. The addition of antioxidants, in this case, is necessary to reach
the minimum limit of oxidative stability, required by the standard that
± standard deviation of the mean, n = 3. Confidence interval of 95% (IC 95%). governing the commercialization of biodiesel. Therefore, to evaluate
the addition of antioxidants as well as the kinetics of delayed oxidation
stability of biodiesel faster than the Rancimat method. of biodiesel, the period of induction under different temperatures (90,
In addition to the faster analysis in the PetroOXY method, all 100, 110, 120, 130 and 140 °C) and concentrations of different

45 25
90 °C a) PY 90 °C b) QC 90 °C
100 40 100 °C
c) BE
100 °C 100 °C
110 °C 110 °C
35 120 °C 20 110 °C
120 °C 120 °C
80 130 °C
130 °C 130 °C
30 140 °C
140 ºC
Induction Period (h)

Induction Period (h)

140 °C
Induction Period (h)

15
60 25

20
40 10
15

10
20 5
5

0 0
0
0 500 1000 1500 2000 2500 3000 0 500 1000 1500 2000 2500 3000
0 500 1000 1500 2000 2500 3000
Concentration (ppm) Concentration (ppm) Concentration (ppm)

55
25 d) OE 90 °C
90 °C e) BAE 90 °C f) PY
100 °C 100 °C 50
20 C
110 °C 110 °C
45 110 °C
20 120 °C 120 °C
130 °C 130 °C 40 120 °C
140 °C 15 140 °C 130 °C
Induction Period (h)

Induction Period (h)

Induction Period (h)

35 140 °C
15
30
10 25
10
20

5 15
5
10
5
0 0
0
0 500 1000 1500 2000 2500 3000 0 500 1000 1500 2000 2500 3000
0 500 1000 1500 2000 2500 3000
Concentration (ppm) Concentration (ppm)
Concentration (ppm)

8 9
25 90 °C h) BE i) OE
90 °C g) QC 90 °C
7 100 °C 8 100 °C
100 °C
110 °C 110 °C
110 °C 7
20 6 120 °C
120 °C 120 °C
130 °C
130 °C 6 130 °C
Induction Period (h)

5 140 °C
Induction Period (h)

140 °C 140 °C
Induction Period (h)

15 5
4
4
10 3
3
2
2
5
1
1

0 0
0
0 500 1000 1500 2000 2500 3000 0 500 1000 1500 2000 2500 3000
0 500 1000 1500 2000 2500 3000
Concentration (ppm) Concentration (ppm)
Concentration (ppm)

8 90 °C j) BAE
100 °C
7 110 °C
120 °C
6
130 °C
Induction Period (h)

140 °C
5

0 500 1000 1500 2000 2500 3000

Concentration (ppm)

Fig. 1. Concentration effect on the oxidative stability of the biodiesel using Rancimat (a, b, c, d, e) and PetroOXY (f, g, h, i, j) tests under the range of 90–140 °C.

201
L.S. de Sousa et al. Fuel 238 (2019) 198–207

-6,0 -6,0 -6,0

a) PY b) QC 90 °C
c) BE
90 °C 90 °C
100 °C 100 °C 100 °C
110 °C 110 °C
-6,5 110 °C -6,5 -6,5
120 °C 120 °C
120 °C
130 °C 130 °C
130 °C 140 °C 140 °C
140 °C
ln [C] (ppm)

ln [C] (ppm)
-7,0

ln [C] (ppm)
-7,0 -7,0

-7,5 -7,5 -7,5

-8,0 -8,0
-8,0

0 20 40 60 80 100 0 10 20 30 40
0 5 10 15 20
Induction Period (h) Induction Period (h)
Induction Period (h)

-6,0 -6,0
-6,0
d) OE e) BAE f) PY
90 °C 90 °C
100 °C 90 °C
100 °C
110 °C 100 °C
-6,5 -6,5 110 °C
120 °C -6,5 110 °C
120 °C
130 °C 120 °C
130 °C
140 °C 130 °C
140 °C
140 °C
ln [C] (ppm)

ln [C] (ppm)

-7,0 -7,0

ln [C] (ppm)
-7,0

-7,5 -7,5
-7,5

-8,0 -8,0
-8,0

0 5 10 15 20 0 5 10 15 20
0 5 10 15 20 25 30 35 40 45
Induction Period (h) Induction Period (h) Induction Period (h)

-6,0 -6,0
-6,0
g) QC i) OE
90 °C h) BE
90 °C 90 °C
100 °C
100 °C 100 °C
110 °C
-6,5 110 °C -6,5 110 °C
120 °C -6,5
130 °C 120 °C 120 °C
140 °C 130 °C 130 °C
140 °C 140 °C
ln [C] (ppm)

-7,0

ln [C] (ppm)
ln [C] (ppm)

-7,0 -7,0

-7,5
-7,5 -7,5

-8,0
-8,0 -8,0

0 2 4 6 8 10 12 14 16 18 20
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6
Induction Period (h)
Induction Period (h) Induction Period (h)

-6,0
j) BAE
90 °C
100 °C
-6,5
110 °C
120 °C
130 °C
140 °C
ln [C] (ppm)

-7,0

-7,5

-8,0

0 1 2 3 4 5 6
Induction Period (h)

Fig. 2. Natural logarithm of the initial antioxidant concentration versus induction time for Rancimat (a, b, c, d, e) and PetroOXY (f, g, h, i, j) tests at the range of
90–140 °C.

antioxidants (500, 100, 1500, 2000, 2500 and 3000 ppm) was studied. the biofuel, since the induction periods were higher than the control
Such a range of concentrations was chosen in order to observe any sample (B100), even at the lowest concentration used (500 ppm); the
prooxidant effects of the extracts. In addition, we did not mean to es- same trend was observed for both acceleration techniques. The anti-
tablish or correlate any synergies among the compounds with anti- oxidant efficiency of quercetin and pyrogallol corresponds to the low
oxidant effects on the extracts or already available naturally on the critical antioxidant concentration used in this study. The study showed
biodiesel (although we believe, if existing, such natural antioxidants are that the higher the compound concentration used, the better the oxi-
in a very low concentration or were extracted from the biodiesel during dation stability, showing that there were no prooxidant effects or that,
the washing steps), we wanted to present a general antioxidant char- at least, the antioxidant effects presented are more expressive. In con-
acteristic. Tables S1 and S2 show the results obtained when the Ran- trast, higher temperatures adversely affected the induction periods,
cimat and PetroOXY techniques were used, respectively. In general, we since more severe conditions can degrade both the biodiesel and the
can highlight that antioxidants had a positive impact on the stability of antioxidant, which is in agreement with the literature [16]. The highest

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L.S. de Sousa et al. Fuel 238 (2019) 198–207

Table 4
Reaction constant k (h−1), critical concentration Ccr (ppm), and coefficient of determination (R2) for consumption of selected antioxidants at the range of 90–140 °C
for Rancimata and PetroOXYb tests.
PY QC BE OE BAE

T k Ccr R2 k Ccr R2 k Ccr R2 k Ccr R2 k Ccr R2

90 °Ca 0.0424 34.8133 0.9707 0.1360 10.4856 0.9581 0.3196 4.4371 0.9073 0.3659 2.0960 0.9133 0.3288 5.0531 0.9346
100 °Ca 0.0671 87.3567 0.9668 0.1662 73.6998 0.9589 0.5733 3.8190 0.9795 0.5351 3.4212 0.9526 0.5733 3.7810 0.9795
110 °Ca 0.2849 2.4843 0.9293 0.3907 23.8075 0.9230 0.5980 56.8263 0.9472 0.5762 42.5211 0.9479 0.5896 57.3974 0.9578
120 °Ca 0.5422 3.2544 0.9799 0.7125 14.1540 0.9109 1.6468 16.4446 0.9395 0.8546 79.0436 0.9122 1.1484 48.9109 0.9131
130 °Ca 0.6601 35.1632 0.9106 1.0844 41.2644 0.9149 2.3711 82.2695 0.9150 1.8706 99.4843 0.9485 2.3711 80.6404 0.9150
140 °Ca 0.8533 34.4670 0.9863 3.0602 32.1367 0.9893 3.9650 56.2609 0.9193 2.9951 64.7154 0.9384 4.0147 35.5166 0.9366
90 °Cb 0.1753 2.8864 0.9152 0.2970 7.9248 0.9839 1.6567 2.7456 0.9166 2.1035 33.7844 0.9654 2.1141 31.8170 0.9691
100 °Cb 0.2446 37.3376 0.9097 0.5184 25.5337 0.9649 3.3891 2.0544 0.9501 2.2115 5.4195 0.9131 3.0224 1.0093 0.9373
110 °Cb 0.3353 38.8613 0.9279 1.2175 27.9383 0.9234 3.3985 41.2644 0.9321 3.5629 7.4633 0.9478 3.1874 44.7012 0.9224
120 °Cb 0.6601 68.0335 0.9106 2.0399 83.0963 0.9311 4.4769 66.0288 0.9548 3.5914 90.0171 0.9034 3.4805 103.5443 0.9193
130 °Cb 2.4556 7.2427 0.9737 2.9935 151.4113 0.9003 5.3109 190.5663 0.9047 4.5708 217.0222 0.9361 5.4231 225.8791 0.9222
140 °Cb 3.3783 7.1707 0.9172 4.3196 129.0200 0.9505 15.4198 61.5592 0.9351 16.9332 25.0281 0.9746 15.9048 45.1504 0.9627

a) 3 b)
1

1
ln (k)
ln (k)

-1

0
PY PY
-2
QC QC
BE -1 BE
OE OE
-3
BAE BAE
-2
2,40 2,45 2,50 2,55 2,60 2,65 2,70 2,75 2,80 2,40 2,45 2,50 2,55 2,60 2,65 2,70 2,75 2,80
-1 -1
1000/T (K ) 1000/T (K )

Fig. 3. Temperature dependence of k for the antioxidants consumption for (a) Rancimat and (b) PetroOXY tests.

-3,0
-4,5 a) b)
-3,5
-5,0
-4,0
-5,5
-4,5
-6,0
-5,0
-6,5
ln (k/T)
ln (k/T)

-5,5
-7,0
-6,0
-7,5
PY -6,5 PY
-8,0
QC QC
-8,5 BE -7,0 BE
OE OE
-9,0 -7,5
BAE BAE
-9,5 -8,0
2,40 2,45 2,50 2,55 2,60 2,65 2,70 2,75 2,80 2,40 2,45 2,50 2,55 2,60 2,65 2,70 2,75 2,80
-1 -1
1000/T (K ) 1000/T (K )

Fig. 4. Temperature dependence of the ln k/T to biodiesel using (a) Rancimat and (b) PetroOXY tests.

values of induction period at 110 °C were obtained with pyrogallol, as
shown in Fig. 1a and f, for the Rancimat and PetroOXY tests, respec-
tively. At 110 °C, using the lowest concentration (500 ppm), the in-
duction period was 3 times greater than the requirement of suitability
for that specific purpose. The quercetin also showed a similar trend,
that is, for the concentration range used, the antioxidant presented
periods of induction above the required except at the concentration of
500 ppm, where it presented induction period of 7.91, a value very
close to the established by the standard. The extracts of oregano, basil
and bilberry were able to increase the oxidative stability of biodiesel
(B100) for the Rancimat (Fig. 1a, b, c, d, e) and PetroOXY tests (Fig. 1f,
g, h, i, j). Although the oxidative stability of the extracts of bilberry,
oregano, and basil did not reach the minimum limit predicted by the
legislation, a significant increase in the induction period was observed
in relation to the control sample, highlighting the value obtained by the
samples in the presence of the oregano extract that, in the highest

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L.S. de Sousa et al. Fuel 238 (2019) 198–207

Table 5 The Arrhenius equation (Eq. (2)) was used to describe the tem-
Thermodynamics parameters for biodiesel with additives and determination perature dependence of k and the activation energy (Ea) for the anti-
coefficients (R2) using Rancimata and PetroOXYb tests. oxidants as a function of the slope of the lines (Ea/R) obtained. Fig. 3a
B100 + Antioxidants ΔH* (kJ ΔS* (J mol−1 R2 ΔG* at 25 °C (kJ shows that the ln k versus 1/T obtained using the Rancimat test follows
mol−1) K−1) mol−1) a linear relationship over the temperature range studied, with R2 being
0.9109, 0.9599, 0.9539, 0.9052, and 0.9378 for pyrogallol, quercetin,
PYa 78.15 −125.04 0.9035 115.43
bilberry extract, oregano extract, and basil extract, respectively. The
QCa 74.49 −128.20 0.9566 112.71
BEa 60.61 −157.97 0.9492 107.71 PetroOXY test presented R2 of 0.9131, 0.9823, 0.8121, 0.7040, and
OEa 48.80 −190.14 0.8941 105.49 0.7218 for the same order before Fig. 3b. One may notice, however,
BAEa 58.86 −163.12 0.9316 107.49 that the proportion of the variance is much higher for this test. The Ea
PYb 76.40 −121.63 0.9065 112.66
was ranked in the following order: pyrogallol (81.39 kJ/mol) >
QCb 66.93 −142.42 0.8847 109.39
BEb 42.15 −194.21 0.7880 100.05
quercetin (77.73 kJ/mol) > bilberry extract (63.85 kJ/mol) > basil
OEb 41.24 −197.12 0.6696 100.01 extract (62.02 kJ/mol) > oregano extract (52.04 kJ/mol), for Ran-
BAEb 38.74 −203.11 0.6869 99.30 cimat test (Fig. 3a), and pyrogallol (79.64 kJ/mol) > quercetin
(68.92 kJ/mol) > bilberry extract (45.31 kJ/mol) > oregano extract
(44.48 kJ/mol) > basil extract (41.98 kJ/mol), for PetroOXY test
concentration (3000 ppm), presented an induction period of 7.67 h, a (Fig. 3b). Therefore, the activation energies found for the consumption
value very close to the limit established by standard EN 14112. The of the antioxidants were consistent with the literature [40].
extract of basil and bilberry presented an induction period of 6.94 h and The entropy of activation (ΔS*) and enthalpy (ΔH*) were de-
6.92 h, respectively, for the Rancimat technique. For the PetroOXY termined by the regression of ln (k/T) versus (1/T) by the Eyring
technique, the same antioxidant efficiency sequence was maintained, equation. The superscript “*” notation refers to the activation complex
that is, oregano extract > basil extract > bilberry extract, at a tem- or transition state. From the graphs (Fig. 4), information for ln (kB/
perature of 110 °C (Table S2). It is worth noting that the objective of the h) + (ΔS/R) and (−ΔH/R) were obtained, which resulted in the en-
use of ethanol as a solvent in the extractions was due to the fact that this tropy of activation and enthalpy, respectively. From Eq. (4), the free
solvent extracted polar substances from the plants, mainly the phenolic activation energy (ΔG*) was also obtained. Such values are displayed in
compounds that are antioxidants [38,39]. The efficiency of the extracts Table 5. Again, as observed for the natural logarithm of the initial an-
in increasing the oxidative stability of biodiesel is associated with the tioxidant concentration versus induction time (Fig. 2), the Rancimat
presence of secondary metabolites such as phenols, flavonoids, tannins, test presented coefficients of determinations for the extracts higher than
terpenes, alkaloids as well as total phenolic content (Tables 2 and 3). 0.9.
This shows that they can be used in future works in possible synergisms It is important to point out that the negative values of the entropy of
with other antioxidants in order to increase the value of the oxidative activation obtained in both techniques showed that the oxidation of
stability, thus meeting the specification [25]. Thus, the general trend biodiesel containing pyrogallol, quercetin, basil, oregano and bilberry
observed for the antioxidant efficiency was the same for both accel- extracts provided transition state structures more ordered than the re-
eration techniques: bilberry extract < basil extract < oregano ex- actants in the ground state. Such data suggest an association me-
tract < quercetin < pyrogallol. chanism, in which the reactant species joined to each other to form the
The consumption of the antioxidants presents pseudo-first-order transition states. Positive ΔH* and ΔG* values indicate endothermic
reaction kinetics [16,17,24] (Eq. (1)) as all the compounds fit for the processes and high energy levels in the transition states, respectively
natural logarithm of concentration versus induction period (h) in the [16,24,41]. The positive free energy values obtained for both systems
range of 90–140 °C, as seen in Fig. 2. The coefficients of determination also suggest that the antioxidants are promoting the position of equi-
(R2) exceeded 0.9072 and 0.9002 for Rancimat and PetroOXY tests, librium in the reverse side of the natural oxidation reactions (they are
respectively (Table 4). The results suggest that the PetroOXY method is not spontaneous), corroborating the oxidation effect of the samples
a good alternative to measure the oxidation stability of biodiesel sam- applied to the studies herein performed.
ples, given its faster determination and the good linear correlation
found between the methods, as shown in the literature [27,28]. As 3.4. Shelf-life prediction
expected, the higher the temperature, the faster the rate of consumption
of the antioxidants and lower the induction periods, which is clearly Fig. 5 shows the temperature dependence of the induction period,
observed by the reaction constants (k) obtained for higher tempera- with the natural logarithm of the induction period (ln IP) as a function
tures. Such data state the strong dependence of the biodiesel oxidation of the temperature (in °C), for the biodiesel with or without the anti-
and the temperature range considered [16,40]. The total phenolic oxidants, for both acceleration techniques. High linear relationships
content of pyrogallol and quercetin confers to them higher oxidative were obtained for both techniques, according to the coefficients of
stability and, consequently, lower k values (Table 4). determination displayed in Table 6. The results were obtained in hours
The antioxidant efficiency of pyrogallol was the highest obtained in and in months. A 10 °C rise meaningfully decreased the induction time
the studies performed herein; however, such antioxidant presented the of the samples. It is worth mentioning that the concentration and an-
higher reaction constants increasing in the temperature range con- tioxidant nature highly affected the induction times with the tem-
sidered using the Rancimat test. From 100 to 110 °C, k value increased 4 perature increasing. The sample B100 + PY 2000 presented the longer
times, as seen in the literature [16,17,19,24], and the total augmenta- shelf life of the set (5296.90 h, 7.26 months) at room temperature
tion observed was 20 times, from 90 to 140 °C. Although quercetin (25 °C) for the Rancimat test. For the PetroOXY test, the sample
presented a similar increase in the range, the most expressive k mod- B100 + PY 3000 presented the longer shelf life (2491.88 h,
ification (k three times higher) was observed from 130 to 140 °C. The 3.46 months). As mentioned before, the antioxidant with the highest
PetroOXY test also corroborated that both antioxidants are very sensi- total phenolic content may present the best efficiency. Once again, the
tive to the temperature changing: at 140 °C, it was noticeable that the k data for the shelf life validated such information and attested pyrogallol
values were 14 and 19 times higher than the observed at 90 °C for as the best antioxidant in the concentration range used for the studies
quercetin and pyrogallol, respectively. The plant extracts presented a k developed. Quercetin also presented a high total phenolic content,
increasing of 12 times in the temperature range considered. Although showing the second longer shelf life and the second best performance as
their k values increasing were lower than the observed for pyrogallol an antioxidant. For the Rancimat test, the longer shelf life was with a
and quercetin, the tests also presented the same trend, as expected. 2000 ppm concentration; for the PetroOXY test, 500 ppm. This last

204
L.S. de Sousa et al. Fuel 238 (2019) 198–207

4
a) PY b) QC 3 c) BE
5 Blank Blank
Blank
500 ppm 500 ppm 500 ppm
1000 ppm 3 1000 ppm 1000 ppm
4
1500 ppm 1500 ppm 1500 ppm
2
2000 ppm 2000 ppm 2000 ppm
2500 ppm 2500 ppm 2500 ppm
3 2
3000 ppm 3000 ppm 3000 ppm

ln (IP)
ln (IP)

ln (IP)
1
2
1

1
0
0
0

-1
-1 -1 90 100 110 120 130 140
90 100 110 120 130 140 90 100 110 120 130 140
Temperature (°C)
Temperature (°C) Temperature (°C)

3 d) OE 3 e) BAE 4 f) PY
Blank Blank
Blank 500 ppm 500
500 ppm 1000 ppm 3 1000
1000 ppm 1500 ppm 1500
2 2 2000
1500 ppm 2000 ppm
2000 ppm 2 2500
2500 ppm
2500 ppm 3000 ppm 3000
3000 ppm
ln (IP)

ln (IP)

ln (IP)
1
1 1

0 0 -1

-2
-1 -1
90 100 110 120 130 140 90 100 110 120 130 140 90 100 110 120 130 140
Temperature (°C) Temperature (°C) Temperature (°C)

2 2
g) QC h) BE i) OE
3 Blank Blank Blank
500 ppm 500 ppm 500 ppm
1000 ppm 1 1000 ppm 1 1000 ppm
2 1500 ppm 1500 ppm 1500 ppm
2000 ppm 2000 ppm 2000 ppm
2500 ppm 2500 ppm 2500 ppm
1 3000 ppm 0 3000 ppm 3000 ppm
0
ln (IP)

ln (IP)
ln (IP)

0
-1 -1
-1

-2 -2
-2

90 100 110 120 130 140 90 100 110 120 130 140 90 100 110 120 130 140
Temperature (°C) Temperature (°C) Temperature (°C)

2
j) BAE
Blank
500 ppm
1 1000 ppm
1500 ppm
2000 ppm
2500 ppm
0 3000 ppm
ln (IP)

-1

-2

90 100 110 120 130 140

Temperature (°C)

Fig. 5. Natural logarithm of the induction period as a function of temperature (90–140 °C) for biodiesel containing different concentrations of antioxidants using the
Rancimat (a, b, c, d, e) and PetroOXY (f, g, h, i, j) techniques.

result was quite contradictory when compared to the Rancimat tech-
nique, given that the best shelf life was obtained with the lowest con-
centration of the antioxidant. The same trend was observed for the
samples containing bilberry, oregano, and basil extracts. Such data
suggested a relationship between the high sensitivity of the PetroOXY
technique and the antioxidants structures. Thus, particular PetroOXY
technique specifications may affect the results. However, undoubtedly,
more studies will be necessary to clearly explain the tendency observed.
Keeping in mind such difference, the data revealed that the sample
B100 + BE 1000 presented the longer shelf life (1267.83 h, 1.76 months)
for Rancimat test and the sample B100 + OE 500 (366.09 h,
0.51 months) for the PetroOXY test, among the obtained extracts. The
basil extract presented the lowest values of shelf life in the PetroOXY
technique, and the B100 + BAE 3000 sample presented the lowest per-
formance: 197.53 h, which is equivalent to 0.27 months (Table 6). At
concentrations higher than 500 ppm, the shelf life of the basil, oregano,
and bilberry extracts seemed to be independent of the antioxidant
concentration for Rancimat and PetroOXY tests. In general, a longer
shelf life of soybean-derived biodiesel is expected with antioxidant
concentration increasing. Thus, according to the data presented in
Tables 4 and 6, lower reaction constants of antioxidants led to the
longer shelf life of the antioxidant-added biodiesel. The shelf life of
these antioxidants are as follows: PY > QC > BE > BAE > OE, by
the values obtained in the technique Rancimat and PY > QC >

205
L.S. de Sousa et al. Fuel 238 (2019) 198–207

Table 6 system, to retard or inhibit the oxidation process. The use of extracts
Shelf life for the samples at 25 °C and different antioxidant concentrations for holds great protection potential for biodiesel and may be interesting for
Rancimat and PetroOXY tests. the industry mainly since they have the advantage of being from natural
Samples Rancimat (a) PetroOXY (b) and renewable sources, easy to obtain and low cost.
The shelf life observed was contradictory in both techniques, what
Induction time Hours Months R2 Hours Months R2 can be explained by the different test conditions, as well as different
measurement principles, temperatures and partial oxygen pressures of
B100 1034.24 1.42 0.9922 422.15 0.59 0.9766
B100-PY-500 2318.37 3.17 0.9784 1691.81 2.35 0.9759 both methods. Although such approach is not conclusive, it shows a
B100-PY-1000 4648.38 6.37 0.9911 1702.11 2.36 0.9860 trend that needs to be further investigated in the future.
B100-PY-1500 5072.45 6.95 0.9886 1914.19 2.66 0.9856
B100-PY-2000 5296.90 7.26 0.9840 2153.77 2.99 0.9851
Acknowledgments
B100-PY-2500 4971.74 6.81 0.9840 2359.70 3.28 0.9855
B100-PY-3000 4846.50 6.64 0.9826 2491.88 3.46 0.9833
B100-Q-500 1722.34 2.36 0.9745 1795.71 2.49 0.9792 The authors acknowledge financial support from CAPES and CNPq.
B100-QC-1000 2281.44 3.17 0.9855 1654.01 2.30 0.9762
B100-QC-1500 2523.64 3.50 0.9906 1577.44 2.19 0.9739 Appendix A. Supplementary data
B100-QC-2000 2808.92 3.90 0.9884 1588.62 2.21 0.9737
B100-QC-2500 2517.18 3.50 0.9863 1422.80 1.98 0.9760
B100-QC-3000 2673.17 3.71 0.9855 1401.16 1.95 0.9761 Supplementary data to this article can be found online at https://
B100-BE-500 1149.76 1.60 0.9904 352.65 0.49 0.9873 doi.org/10.1016/j.fuel.2018.10.082.
B100-BE-1000 1267.83 1.76 0.9878 308.21 0.43 0.9907
B100-BE-1500 1197.95 1.66 0.9961 260.20 0.37 0.9914
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