Fuel 97 (2012) 638–643

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Fuel
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Commercial antioxidants and thermal stability evaluations

Nataly A. Santos a,⇑, Angela M.T.M. Cordeiro b,c, Sarah S. Damasceno a, Rebeca T. Aguiar a, Raul Rosenhaim d,
José R. Carvalho Filho a, Ieda M.G. Santos a, Ary S. Maia a, Antonio G. Souza a
a
Departamento de Química, CCEN, Universidade Federal da Paraíba, 58059-9000 João Pessoa, Paraíba, Brazil
b
Departamento de Engenharia de Alimentos, CT, Universidade Federal da Paraíba, 58059-9000 João Pessoa, Paraíba, Brazil
c
Instituto Federal do Amazonas, 69020-120 Amazonas, Brazil
d
Departamento de Engenharia Química, CT, Universidade Federal da Paraíba 58059-9000, João Pessoa, Paraíba, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Synthetic and natural antioxidants are used in the biodiesel and food industries to increase product shelf
Received 28 October 2011 lives. Rancimat, which is regulated by EN 14112, is the official analytical method used to determine the
Received in revised form 27 January 2012 oxidation stability of biodiesel, oils and fats. It involves subjecting samples to a temperature of 110 °C for
Accepted 30 January 2012
prolonged periods. Some antioxidants decompose or volatilize below 110 °C, leading to false results. A
Available online 14 February 2012
TG/DTA technique with both dynamic and isothermal (110 °C) analysis methods was used to evaluate
the thermal stability of commercial antioxidants. Synthetic antioxidants exhibited thermal resistances
Keywords:
in the following order: PG > TBHQ > BHA > BHT. Initial thermal decomposition temperatures were lower
Antioxidants
Thermal analysis
than 110 °C, and BHT, BHA and TBHQ volatilized during the first few hours of the analysis. Natural anti-
Thermal stability oxidants are resistant to heat and displayed stabilities in the following order: a-tocopherol > caffeic
Oxidation stability acid > ferulic acid > gallic acid. Subjecting chelating agents to a temperature of 110 °C for prolonged peri-
ods resulted in the following order of thermal stabilities: ascorbic acid > citric acid > EDTA. The initial
thermal decomposition temperatures for both gallic acid and EDTA were lower than 110 °C.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction BHA, BHT, TBHQ and PG are the synthetic antioxidants that are
most commonly used in industry [8,9]. Among the most widely
Oils and fats with high contents of unsaturated fatty acids are used natural antioxidants are the tocopherols and phenolic acids
highly susceptible to oxidation. Exposure to air, heat, light or metal [10,11]. Citric acid and ethylenediaminetetraacetic acid (EDTA)
contaminants accelerates oxidative reactions [1,2]. The reaction salts are the main chelating agents used [8,12]. The same industrial
products are primarily aldehydes, ketones, acids, peroxides, and antioxidants used in oils and fats have also been studied and used
polymers that affect the physical and chemical properties of the for biodiesel fuels [13–17].
oils [2]. Biodiesels derived from such oils and fats are also prone Maia et al. [4] evaluated the stability of soybean biodiesel when
to oxidation [3]. The oxidation of biodiesels during storage affects fortified with either pure or mixed BHA, BHT and TBHQ by using a
the physical and chemical properties of the fuels and may cause centric simplex plan. The results showed that BHA and TBHQ gen-
engine malfunctions [4]. erally offered a higher degree of protection, both separately and in
Antioxidants are used to increase the oxidation induction peri- mixtures, with induction periods of up to 6 h at 110 °C.
od or decrease the rate of oxidation [1]. The actions of antioxidants Other researchers [18,19] have examined phenolic acids as
have been extensively studied [5–8], and they can be functionally potential replacements for synthetic antioxidants, which are
classified as primary, biological, or mixed antioxidants, synergists, widely used in lipidic food storage. Phenolic compounds are pow-
oxygen removers, or chelators [4,8]. Primary antioxidants promote erful antioxidants that can prevent the oxidative deterioration of
the removal or inactivation of free radicals in the initiation and polyunsaturated fatty acids. Among these compounds, caffeic and
propagation stages of the oxidation by donating hydrogen atoms ferulic acids are widely recognized as natural antioxidants [18,20].
to interrupt the chain reaction [3,4,8]. Synergists are substances The official analytical method used to determine the oxidative
with little or no antioxidant activity, but they may increase the stability of biodiesels, oils, and fats is the Rancimat EN 14112 stan-
activity of primary antioxidants when used in an appropriate dard, which measures the induction period (IP) [21]. The American
combination [8]. (ASTM D 6751-11b) [22] and European (EN 14214) [23] standards
specify 3 h and 6 h, respectively, as the minimum IP limits for
which biodiesel must resist oxidation.
⇑ Corresponding author. Tel./fax: +55 8332167441. Researchers have used the Rancimat method to optimize the
E-mail address: [email protected] (N.A. Santos). amounts of antioxidants necessary to achieve the limits specified

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2012.01.074
 N.A. Santos et al. / Fuel 97 (2012) 638–643 639

O O 2.2. Thermal analysis

OH OH OH
Non-isothermic thermogravimetric curves (TG) were obtained
on a Shimadzu Thermal Analyzer, Simultaneous DTA-TG, DTG
HO OH model H-60, in a synthetic air atmosphere at a heating rate of
O OH OH 20 °C min 1. Approximately 10 mg of sample was heated over a
BHA BHT TBHQ PG temperature range of 25–1000 °C. Differential thermal analysis
(DTA) curves were obtained simultaneously.
Fig. 1. Structure of synthetic antioxidants. Samples that showed mass variation before 110 °C using the
non-isothermal method were analyzed by the isothermal method.
The TG curves in the isothermal mode were obtained on a Shima-
by the international standards for commercialized products [4,14].
dzu Thermal Analyzer, Simultaneous DTA-TG, DTG model H-60, in
The oxidation process is accelerated by temperature and oxygen in
a synthetic air atmosphere, using approximately 10 mg of sample.
the air. In this method, the sample is heated to 110 °C, and air flow
The following heating schedule was used: an initial heating rate of
of 10 L h 1 is injected. Any oxidation products formed are sent to a
10 °C min 1 was maintained until the temperature reached 100 °C,
conductivity cell containing deionized water. The induction time is
followed by a rate of 2 °C min 1 until reaching 110 °C, at which
determined by the inflection point of the conductivity curve [24].
point the isotherm measurement was performed.
Some antioxidants volatilize or decompose at this temperature,
leading to a false IP [17,20]. The aims of this study were to analyze
the thermal profiles of commercial antioxidants, determine the ini- 3. Results and discussion
tial temperatures of decomposition and measure the time it takes
to decompose or vaporize these compounds at 110 °C. 3.1. Synthetic antioxidants

2. Materials and methods BHA, BHT, TBHQ and PG are the most commonly used synthetic
antioxidants in the biodiesel and food industries (Fig. 1). The struc-
2.1. Antioxidants tures of these phenolic compounds allow for the donation of
hydrogen atoms protons to free radicals, thus inhibiting the oxida-
TBHQ, BHT, BHA, PG, a-tocopherol, caffeic acid and ferulic acid tive process [25].
were obtained from Sigma–Aldrich. L-(+)-Ascorbic acid and gallic In the dynamic method, the thermogravimetric curves for BHA,
acid were obtained from VETEC. EDTA was obtained from F. Maia. BHT and TBHQ (Fig. 2a–c) indicated that mass loss is initiated at
Citric acid was obtained from Cargill. temperatures lower than 100 °C (Table 1), and each compound

10
(a) 100 (b) 100 TG 0
0
DTA
80 -10
Weight remained/%

TG
Weight remained/%

-10 80
DTA
-20
60 -20

DTA/μV
60
DTA/μV

-30
40 -30
40 BHT
-40
BHA -40
20 20
-50
-50
0 exo 0 exo -60
-60
0 100 200 300 400 500 0 200 400 600 800 1000
Temperature/% Temperature/°C

10
(c) 100
(d) 100 TG
30
TG 0 DTA 20
DTA
-10 80
Weight remained/%

80 10
Weight remained/%

-20
60 0
DTA/μV

60 -30
DTA/μV

PG -10
-40 40
40 -20
TBHQ -50
20
-60 -30
20
-70 0 -40
0 exo
exo -80 -50
-20
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature/% Temperature/°C

Fig. 2. TGA/DTA dynamic (a) BHA, (b) BHT, (c) TBHQ and (d) PG.
640 N.A. Santos et al. / Fuel 97 (2012) 638–643

Table 1 OH
Values obtained from dynamic and isothermal TG curves.
OH
Antioxidants Dynamics Isothermal (110 °C) O
O
Steps Temperature (°C) Dm (%) Time (min) Dm (%)
OH
BHA 1st 85–239 100 155 100
OH
BHT 1st 71–235 100 90 100
TBHQ 1st 98–272 100 1500 100 Tocopherol Gallic acid
PG 1st 184–388 81 – –
2nd 388–549 19 O O

HO HO

Table 2 OH OH
Values obtained from DTA curves. OH O
Antioxidants Transition Process Temperature (°C)
Caffeic acid Ferulic acid
BHA 1st Endo 68
2nd Endo 222 Fig. 4. Structure of antioxidants.
BHT 1st Endo 78
2nd Endo 214
TBHQ 1st Endo 136
2nd Endo 250
PG 1st Endo 152 100 TGA 0
2nd Endo 314
DTA
3rd Exo 504 -10
80

Weight remained/% -20

DTA/μV
60

100 -30
40
BHA
80
Weight remained/%

BHT 20 -40
α -tocopherol exo
TBHQ
60 0 -50

40 0 200 400 600 800 1000

Temperature/°C
20
Fig. 5. Curves TG/DTA dynamics of a-tocopherol.

0
These results show that BHT and BHA should volatilize during
0 500 1000 1500 2000 the early hours of analysis for accelerated tests such as the Ranci-
Time/min mat method at 110 °C, as emphasized by Karavalakis and Stournas
[16]. Thus, we suggest modifying the method so that it can be per-
Fig. 3. Isothermal TG curves of BHA, BHT and TBHQ.
formed at lower temperatures. Another possibility would be the
use of the P-DSC and petroOxy methods, in which the tests are con-
showed a single-step thermal decomposition. The complete evap- ducted under increased pressures [26,27]. These methods have al-
oration/decomposition of these three antioxidants was observed ready been discussed in the literature as faster alternatives to the
at 250 °C. Due to its chemical structure, the antioxidant PG had a Rancimat method, and in the case of the P-DSC method, smaller
distinct thermal profile, exhibiting greater thermal resistance, an amounts of the samples are required [28,29].
initial decomposition temperature of 184 °C and a two-step An additional problem is encountered when using these antiox-
decomposition. idants in frying oils. Because of their volatility, these antioxidants
The DTA curves (Fig. 2a–c) for BHA, BHT and TBHQ showed two do not guarantee the right levels of protection when the oils are
endothermic transitions. The first is due to fusion of the antioxi- subjected to the thermal stress of frying [8]. The safety of these
dants and does not involve a mass variation. The second transition synthetic antioxidants has also been questioned because of their
is due to volatilization and/or decomposition (Table 2). The curve toxic and carcinogenic effects in animals and humans. TBHQ, for
for PG (Fig. 2d) also shows these two endothermic transitions, example, is not permitted in Canada or the European Economic
but these are followed by an exothermic transition due to the com- Community because of its role in hemoglobin count reductions
bustion of the compound at higher temperatures. and basal cell hyperplasia [8]. The volatility and instability of syn-
Fig. 3 shows the thermal profile at 110 °C for BHA, BHT and thetic antioxidants at high temperatures has driven the industry to
TBHQ. The times required for the complete vaporization of BHT, examine natural antioxidants as an alternative [1].
BHA and TBHQ were 90 min, 155 min and 1500 min, respectively
(Table 1). The heat resistance decreases in the order PG > TBHQ > 3.2. Natural antioxidants
BHA > BHT, which corroborates the Rancimat data obtained for
antioxidant protection using an accelerated oxidation method, as The most widely used natural antioxidants are the tocopherols,
seen in the literature [4,14]. This shows the necessity of knowing phenolic acids and plant extracts (Fig. 4).
the thermal profile of an antioxidant when using accelerated meth- The thermogravimetric profile for a-tocopherol (Fig. 5) shows
ods, which can lead to unreliable results under some analytical an initial loss of mass at a temperature of 199 °C and exhibits three
conditions. stages of mass variation. The first and most significant stage should
 N.A. Santos et al. / Fuel 97 (2012) 638–643 641

(a) (b) 100

100 TGA 0
DTA
80
Weight remained/%

Weight remained/%
-20 95
60

DTA/μV
-40
40 90

exo -60
20
85
-80
0
Gallic acid Gallic acid
-20 -100 80
0 200 400 600 800 1000 0 100 200 300 400 500 600 700
Temperature/°C Time/min

Fig. 6. Gallic acid (a) TGA/DTA dynamic and (b) isothermal TG curve.

Table 3
Values obtained curves TG/DTA.

Antioxidants TG – dynamic DTA

Steps Temperature (°C) Dm (%) Transition Process Temperature (°C)
a-tocopherol 1st 199–432 99 1st Endo 371
2nd 432–800 1 2nd Endo 561
3rd Endo 707
Gallic acid 1st 68–123 9 1st Endo 102
2nd 213–311 34 2nd Endo 268
3rd 311–375 25 3rd Endo 766
4th 375–996 32
Ferulic acid 1st Endo 177
1st 147–268 75 2nd Endo 240
2nd 268–407 12 3rd Endo 348
3rd 407–492 11 4th Endo 386
4th 492–606 2 5th Endo 471
6th Exo 553
Caffeic acid 1st 170–246 30 1st Endo 222
2nd 246–394 39 2nd Endo 312
3rd 394–570 31 3rd Endo 368
4th Exo 535

Table 4
Values obtained curves TG/DTA.

Antioxidants TG – dynamic DTA

Steps Temperature (°C) Dm (%) Transition Process Temperature (°C)
Citric acid 1st 148–310 92 1st Endo 162
2nd 310–750 8 2nd Endo 221
3rd Endo 459
4th Endo 685
Ascorbic acid 1st 186–248 40 1st Endo 195
2nd 248–466 30 2nd Exo 224
3rd 466–653 30 3rd Exo 537
4th Endo 616
EDTA 1st Endo 188
1st 90–215 10 2nd Endo 256
2nd 237–330 23 3rd Endo 332
3rd 330–441 27 4th Exo 387
4th 441–759 12 5th Exo 427
5th 759–1000 3 6th Exo 636
7th Exo 858
8th Exo 876

be associated with the endothermic processes of decomposition 3.3. Phenolic acids

and/or volatilization of the sample, as shown in the differential
thermal analysis curve. This antioxidant is thermally resistant The phenolic acids are structurally characterized by the pres-
and can be used in accelerated oxidation tests. ence of a benzene ring, a terminal carboxylic acid, and one or more
642 N.A. Santos et al. / Fuel 97 (2012) 638–643

(a) 100 100 (b) 120

TG 100 TG
exo DTA 80 exo DTA
80 80
Weight remained/%

80

Weight remaneid/%
60

40

DTA/μV
60

DTA/μV
60 40
20 Ferulic Acid
40 40
0 0

20 -20 20
-40
Caffeic acid -40
0 0
-60 -80
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature/°C Temperature/°C

Fig. 7. Curves TG/DTA dynamics of caffeic acid (a) and ferulic acid (b).

HO OH
Gallic acid (Fig. 6a) had an initial thermal decomposition tem-
N perature of 68 °C, at which point 9% of the mass was lost (Table
O OH HO H O O 3). In the isothermal mode at 110 °C (Fig. 6b), the time required
O O O O
for the gallic acid to lose 9% of its mass was 13 min, after which
HO O N
HO OH HO the mass remained stable for 10 h. This first mass-loss event is
OH HO
OH attributed to the water content according to Galvez et al. [30].
O OH
These authors also argued that gallic acid undergoes a facile ther-
Citric acid Ascorbic acid EDTA
mal decarboxylation to produce pyrogallol. Thus, the second event,
Fig. 8. Structure of chelating agents. at 213 °C, corresponds to the liberation of carbon dioxide upon
heating. The third event, at 316 °C, probably corresponds to the
hydroxy or methoxy groups, all of which confer anti-oxidative further loss of hydroxyl groups. Finally, the fourth peak corre-
properties [8]. sponds to the residual decomposition of gallic acid [30].

20
40
(a) 100 (b)
TG 100 TG
0
DTA DTA
80 20
Weight remained/%

80
Weight remained/%

exo -20

60 ascorbic acid
DTA/μV

60 0
-40

DTA/μV
40 40
-60 -20
exo
20 -80 20
Citric acid -40
0 -100 0
-60
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature/°C Temperature/°C
100
(c) 100 TG (d)
DTA 50 100
Weight remained/%

80 98
Weight remained/%

EDTA 0
EDTA
96
DTA/μV

60 -50
94
exo
-100 92
40
90
-150
20
88
-200
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature/% Time/min

Fig. 9. Curves TG/DTA dynamic (a) citric acid, (b) ascorbic acid, (c) EDTA. Isothermal TG curve (d) EDTA.
 N.A. Santos et al. / Fuel 97 (2012) 638–643 643

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