Fuel 90 (2011) 773–778

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Fuel
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Evaluation of the oxidative stability of corn biodiesel

M.B. Dantas a, A.R. Albuquerque a, A.K. Barros b, M.G. Rodrigues Filho c, N.R. Antoniosi Filho d,
F.S.M. Sinfrônio e, R. Rosenhaim a, L.E.B. Soledade f, I.M.G. Santos a, A.G. Souza a,⇑
a
Departamento de Química, CCEN, Universidade Federal da Paraíba, João Pessoa, PB, Brazil
b
Departamento de Física, Universidade Federal do Maranhão, São Luís, MA, Brazil
c
Coordenação de Química, CCEN, Universidade Estadual do Piauí, Teresina, PI, Brazil
d
Departamento de Química, Universidade Federal de Goiás, Goiânia,GO, Brazil
e
Pró-Reitoria de Pesquisa e Pós-Graduação, Universidade Federal do Maranhão, São Luís, MA, Brazil
f
Universidade Federal do Maranhão, Campus de Pinheiro, Pinheiro, MA, Brazil

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

Article history: The main factors responsible for the oxidative processes of biodiesel are oxygen, metal traces, high tem-
Received 30 November 2009 perature and the amount of unsaturated fatty acids. The biodiesel quality is harmed by the oxidation
Received in revised form 14 September products, which are corrosive to engine chambers and may lead to clogging of the injection pumps
2010
and filters, besides increasing the biodiesel viscosity. Thus, this work aimed at investigating the oxidative
Accepted 16 September 2010
Available online 10 November 2010
stability of corn biodiesel, obtained by base-catalyzed transesterification reaction, using the ethanol
route. As-synthesized, stored and heated biodiesel samples were characterized by peroxide value, iodine
value and dynamic viscosity. UV/Vis absorption was used to evaluate the oxidative degradation of biodie-
Keywords:
Biodiesel
sel, by means of the 232 and 272 nm absorption peaks, ascribed to double bonds and carbonyl groups,
Oxidative stability respectively. The TG and PDSC thermal analysis techniques were also employed to analyze the oxidative
UV/VIS stability. The oxidative decomposition was confirmed by the increase of the dynamic viscosities. PDSC
Thermal analyses curves showed that the oxidation onset temperature was reduced as the sample was exposed to degra-
dation factors during heating and storage. Such results were in agreement with the peroxide and iodine
values, as well as with dynamic viscosity values.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction petroleum-based fuels [7,8]. However, biodiesel is more suscepti-

Corn oil has been used in the production of biodiesel along with
other oil sources, such as soybean, physic nut, cotton and castor
oils [1–4]. All of them have been under investigation in order to
improve the productive biodiesel chain. Modifying the alcohol
moiety is another possibility for inherently improving the fuel
properties of biodiesel [5]. The most frequently employed are the
short chain alcohols, such as methanol, ethanol, propanol and
butanol. Ethyl esters are the most likely esters other than methyl
to possess some commercial significance and are the most com-
mon form of biodiesel in Brazil [6]. Moreover, the fuel is obtained
from biomass and, thus the whole process becomes totally inde-
pendent of petroleum.
A serious problem associated with the use of petroleum fuels
including diesel oil is the increase in the pollutant emissions. Bio-
diesel appears as a renewable natural fuel that inflicts minimal
harm to the environment and can be applied as an alternative to
⇑ Corresponding author. Tel./fax: +55 83 3216 7441.
E-mail address: agouveia@quimica.ufpb.br (A.G. Souza).
ble to auto-oxidation than fossil fuels [7].
The oxidative stability of biodiesel is affected by numerous fac-
tors during its commercialization. As the parent vegetable oil, bio-
diesel is vulnerable to the oxidation of its unsaturated fatty acid
esters [8,9]. Ultraviolet irradiation, metal contamination, humidity,
pigments, some enzymes and heating can alter biodiesel, deterio-
rating its fuel performance when exposed to oxygen [10,11]. Both
oxygen content and exposition time play an important role in the
formation of undesired compounds, which can corrode the engines
or clog the filters and injection systems of the engines [12]. Thus,
oxidative stability has to be considered as an essential characteris-
tic in the control of the biodiesel properties [10,13,14].
The oxidative stability determination is quite often based on the
methodology of accelerated tests, originally proposed by Hadorn
and Zurcher [15] for the monitoring of the rancidity of edible oils,
known as the Rancimat method. This test is based on the increase
of the conductivity of deionized water contained in a reservoir,
which retains the volatile acids liberated during the propagative
oxidation of fatty materials. The European standard EN 14112
establishes that the oxidative stability of biodiesel should be deter-
mined at 110 °C by the Rancimat method, requiring a minimum
value of 6 h for the induction period [16].

0016-2361/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.09.014
774 M.B. Dantas et al. / Fuel 90 (2011) 773–778
Alternatively the oxidation process can also be evaluated by
thermoanalytical techniques, such as Thermogravimetric Analysis
(TG), Differential Scanning Calorimetry (DSC) and Pressurized Dif-
ferential Scanning Calorimetry (PDSC) [17,18].
PDSC measures the liberation of energy during the oxidation
reactions, instead of measuring the oxidation products with the
analyses being carried out directly in the sample. It is a powerful
tool for the high precision determination of the thermodynamic
properties, showing significant applicability for oils, lubricants
and polymers. Furthermore, PDSC analyses reach temperature
ranges not often detected by conventional oxidative techniques,
such as the Rancimat test. This technique differs from the Ranci-
mat, as it is a rapid method and contains an extra variable, the
pressure, having thus the possibility to increase the number of oxy-
gen moles present in the environment and speeding up the reac-
tion, besides using minor amounts of sample, without losing
accuracy [1,17–19].
PDSC is efficient in its dynamic mode, in which the oxidation
temperature of the sample is determined and in the isothermal
mode, when the onset oxidation time of the sample is determined.
In both modes the sudden energy liberation is measured in relation
to the heat flow baseline, corresponding to the temperature or time
of oxidative induction [20].
Along with titrimetric analyses, UV/Vis has been applied for the
study of biodiesel oxidation [21]. It allows measuring the absorp-
tion due to the formation of dienes, trienes and peroxides in bio-
diesel, resulting from oxidative processes.
Therefore, this work aims at studying the oxidative stability of the
corn biodiesel, obtained by the ethanol route, during its long-term
storage and heating (150 °C). For this purpose, thermal analysis tech-
niques, such as TG and PDSC were employed in conjunction with UV/
Vis spectroscopy, physico-chemical parameters and viscosity.
2. Experimental
2.1. Synthesis and storage of biodiesel
Refined edible corn oil (Bunge Salada), ethanol (Merck, 99.5%)
and potassium hydroxide (Merck) were used for synthesis of
biodiesel.
The biodiesel was obtained by means of the transesterification
reaction, using 1:6 oil:ethanol molar ratio and potassium hydrox-
ide (1% mass ratio) as a homogeneous basic catalyst [1]. Initially
potassium ethoxide was prepared by mixing 30 g of ethanol with
1 g of KOH for each 100 g of oil in beaker, under stirring up to
the complete dissolution of KOH. Next potassium ethoxide was
added to corn oil, placing the beaker on a plate featuring magnetic
stirring, in order that the transesterification reaction occurs at
room temperature. The reaction reaches equilibrium (steady state)
within 80 min. Taking into account the concept of chemical equi-
librium, the formation of fatty acid esters is favored by increasing
the alcohol/oil molar ratio. After the separation of ester/glycerin
phases, the biodiesel was washed with distilled water and dried
with anhydrous Na2SO4 (Vetec) [22].
After transesterification, the as-synthesized corn biodiesel (B0)
was stored in an amber glass container at room temperature for
12 months, being denominated BS. Artificial accelerated aging of
the biodiesel sample was carried out in a closed glass system under
air atmosphere (30 mL min 1), in which the B0 sample was heat
treated at 150 °C during 1 (BH1), 2 (BH2) and 6 (BH6) h.
2.2. Characterization of the biodiesel samples
The as-synthesized biodiesel sample (B0) were analyzed by gas
chromatography, acid number (ASTM D664), free glycerin (ASTM
D6584), total glycerin (ASTM D6584), water and sediment (ASTM
D2706), flash point (ASTM D93), specific mass (ASTM D4052), cop-
per corrosion (ASTM D130) and oxidative stability (EN 14112) by
the Rancimat method.
The physico-chemical analyses performed in the B0, BH1, BH2,
BH6 and BS samples were iodine value, peroxide value, dynamic
viscosity, thermogravimetric analyses, PDSC and UV/Vis
spectroscopy.
2.2.1. Gas chromatography
The gas chromatography analyses of as-synthesized (B0) were
made in a CG-FID VARIAN 3800 gas chromatograph, with split/
splitless injector.
2.2.2. Oxidative stability by Rancimat
The oxidative stability of B0 was determined according to the
standard EN 14112, using the Rancimat equipment (model 743,
Metrohm). In this method, 3 g of sample were heated at 110 °C un-
der constant air flow (10 L h 1).
2.2.3. Iodine value
For the determination of the iodine value, the Hübl’s methodol-
ogy was employed [23]. The sample was diluted in chloroform
(Merck, 99.4%), with the later addition of solutions of alcoholic io-
dine and mercuric chloride. The iodine excess was titrated with a
sodium thiosulfate (Vetec) solution with starch as indicator, until
the disappearing of the blue color.
2.2.4. Peroxide value
The peroxide value was determined according to the AOCS Cd 8-
53 standard [24]. The sample was dissolved in an acetic acid–chlo-
roform solution, with the addition of also a saturated solution of
potassium iodide and a 1% starch (Vetec) solution. The liberated io-
dine was titrated with a sodium thiosulfate (Vetec) solution, until
the disappearing of the bluish color.
2.2.5. Dynamic viscosity
The dynamic viscosities of the samples were determined in a
Brookfield equipment; model LV-DVII, coupled to a heat controller
at the temperature of 25 °C, using a small sample adaptor.
2.2.6. Thermogravimetric analyses
The non-isothermal thermogravimetric curves were obtained in
an equipment SDT 2960 (TA Instruments), in the 25–600 °C tem-
perature range, using a synthetic air atmosphere (100 mL min 1),
alumina crucibles, heating rate of 10 °C min 1 and a sample mass
of 10.0 mg [1].
2.2.7. PDSC
The PDSC curves (dynamic mode) were recorded in a DSC 2920
(TA Instrument) with pressure cell, using platinum crucible, heat-
ing rate of 10 °C min 1, 1400 kPa oxygen gas (99.5% purity and
constant volume), at the 25–150 °C temperature range and a sam-
ple mass of 10.0 mg [25].
2.2.8. UV/Vis absorption spectroscopy
The UV/Vis spectra were obtained in a Shimadzu UV-2550 spec-
trophotometer, using 1:1000 (in volume) dilution ratio in dichloro-
methane (Merck). All data were collected in the 200–400 nm
range. The deconvolution of UV–Vis spectra was performed using
the free Peak Fit software.
 M.B. Dantas et al. / Fuel 90 (2011) 773–778 775

Table 1
Chemical composition of the ethanol corn biodiesel (B0) and corn oil (literature data).

Fatty chain This work/wt.% [26]/wt.% [27]/wt.%

Caprylic (C8:0) 0.06 – –
Lauric (C12:0) 0.01 – –
Myristic (C14:0) 0.04 0 –
Palmitic (C16:0) 2.58 12 11.8
Stearic (C18:0) 1.66 2 2.0
Oleic (C18:1) 13.00 25 24.8
Linoleic (C18:2) 77.18 60 61.3
Linolenic (C18:3) 0.66 Traces 0.0
Others 4.80 – 0.3

3. Results and discussion

The biodiesel samples B0 were analyzed by gas chromatogra-

phy, in order to assess the conversion of the triglycerides into their
ethyl esters. Table 1 presents these results, as well as theoretical
biodiesel compositions, based on the fatty acid compositions of
corn oil available in the literature [26,27]. The results, as expected
by the corn oil composition, indicated the prevalence of the ethyl
linoleates (77.18 wt.%), a value higher than those found in the lit-
erature. The second richest ester in the biodiesel is ethyl oleate,
with 13 wt.%.
In Table 2, are shown the physico-chemical properties of biodie-
sel B0, as well as the limits established by the standards EN 14214
[28] and ASTM D6751 [29]. The tests acid number and total glyc-
erin displayed values slightly higher than those set up by EN and
ASTM. The oxidative stability was determined by the method EN
14112, the method Rancimat, showing a figure of 2.89 h, smaller
than the lower limits of 3 h and 6 h from ASTM and EN,
respectively.
The TG/DTG data (Fig. 1 and Table 3) showed two main mass
loss steps for the B0 sample and three for BS, BH1 and BH2, with
all the samples possibly yielding keto-aldehyde compounds and
polymeric products. In all samples the first mass loss step was
attributed to volatilization (mainly ethyl linoleate) and peroxide
decomposition reactions. It was noticed that the more the sample
was oxidized before the Thermogravimetric Analysis; the lower
was the onset temperature of the first mass loss step. This was
due to the volatilization of the aldehydes and ketones previously
formed (step 4 of Fig. 2).
For the BH6 (Fig. 1b), four steps were observed, being the first
one related to oxidation and decomposition reactions and the last
three steps related to the subsequent polymerization and combus-
tion reactions. That thermal behavior was confirmed by the abrupt
increase on the BH6 absolute viscosity (Table 4).
The PDSC curves (Fig. 3) demonstrate that the onset oxidative
temperatures were reduced from 131 °C (B0) to 115 °C (BS),
103 °C (BH1) and 95 °C (BH6). According to Knothe et al. [30], the
oxidation temperature of a biodiesel is inversely proportional to
the amount of bis-allylic hydrogens; in other words, the higher
Fig. 1. TG/DTG curves for (a) as-synthesized (B0) and long-term stored (BS) and (b)
samples of thermally treated corn biodiesel, obtained by the ethanol route (BH1, BH2
and BH6).
the amount of linoleic acid in natura, the more easily biodiesel is
oxidized.
However, the oxidation temperature is also very sensitive to the
amount of peroxides existing before the DSC analysis [31].
Although in the previously heat treated samples the amount of
bis-allylic hydrogen is low (high conjugation), the amount of pre-
existing peroxides is high (rise of the peroxide value for the previ-
ously heat treated samples), leading to a more rapid mass loss (no-
ticed in the TG) and diminishment of the onset oxidation
temperature (noticed in PDSC). Such results are in agreement with
the peroxide and iodine values, as well as with the dynamic viscos-
ity values presented in Table 4.
According to Table 4 and Fig. 4, the dynamic viscosity of biodie-
sel raised considerably as consequence of the thermal stress at
150 °C, being barely modified during the long-term storage at
room temperature. It was reported that viscosities of mineral lubri-
cant oils increase when submitted to thermal stress, due to the for-
mation of carbonyl compounds, which interact with hydrogen
bonds [32,33]. Similarly, the biodiesel rheology can also be ex-
plained by this kind of interaction.

Table 2
Physico-chemical properties of ethanol corn biodiesel (B0), as compared with the EN and ASTM specification limits.

Test Units Value EN 14214 limit [28] ASTM D6751 limit [29]
1
Acid number mg KOH g 0.8 max. 0.5 max. 0.5
Free glycerin % 0.015 max. 0.02 max. 0.02
Total glycerin % mass 0.27 max. 0.25 max. 0.24
Water and sediment % vol 0.044 – max. 0.050
Flash point °C 169 min. 120 min. 130
Specific mass at 20 °C kg m 3 876.1 860–900 at 15 °C –
Copper corrosion 3 h at 50 °C – 1 max. 1 max. 3
Oxidative stability at 110 °C h 2.89 min. 6 min. 3
776 M.B. Dantas et al. / Fuel 90 (2011) 773–778

Table 3 center, full width at half maximum (FWHM) and analytic area of
Thermogravimetry data for corn biodiesel, obtained by the ethanol route, after storing each band, are summarized in Table 5.
and thermal treatment at 150 °C.
According to literature, for linoleic acid the conjugated dienes
Sample Steps Temperature range (°C) Mass loss (%) absorb at 232 nm, due to p ? p* transitions. The secondary oxida-
B0 1 159–376 95.1 tion products, particularly a-diketones or unsaturated ketones,
2 411–519 3.5 display an absorption peak at 272 nm, also attributed to p ? p*
BS 1 122–294 92.7 transitions [35–38].
2 294–363 4.8
3 364–544 1.9
In the present work, such absorption bands of linoleic acid ester
BH1 1 114–307 87.7 were detected, although minor shifts were noticed, moreover for
2 307–391 8.7 the higher wavelength band. The first band was called band 1
3 411–577 4.0 and the higher wavelength one, band 2. The intensities of both
BH2 1 118–301 91.2
bands grew as the heat treatment time increased. The different
2 301–390 7.3
3 453–560 2.1
BH6 1 116–383 89.7
2 383–432 9.8 Table 4
3 432–471 3.3 Physico-chemical properties of as-synthesized, stored and heated biodiesels.
4 471–565 3.8
Parameter B0 Bs BH1 BH2 BH6
Peroxide value (meq kg 1 oil) 15.30 89.92 90.05 29.65 22.83
Dynamic viscosity (mPa s) 6.03 6.18 6.64 7.12 12.10
The iodine values of the biodiesel samples decreased with the Iodine value (mg I2 100 g 1) 128.00 92.35 113.00 86.00 75.00
heat treatment time at 150 °C, Table 4 and Fig. 4. The value for
BS was lower than B0, indicating that the biodiesel was degraded
during the long room temperature storage. Comparing room tem-
perature storage (BS sample) with heat treatment at 150 °C (BH
samples), iodine values indicated that the 12 month storage at
room temperature corresponded to 1–2 h of heat stress at 150 °C.
As a general rule, the peroxide values considerably increased
during the long-term storage and after the heat treatment process,
for short periods of time (BH1), indicating the prevalence of the
propagation step. In addition, the reduction of the peroxide value
as a function of the time of heat treatment can be attributed to
the termination reaction step, resulting in peroxide decomposition
[34]. Correspondingly, the iodine values reduced in magnitude for
both storage systems, evidencing the oxidative degradation of the
samples. The values presented in Table 4 and Fig. 4 were in agree-
ment with such general rule.
Fig. 5 displays the UV/Vis spectra of all the samples. The spec-
trum of each sample was deconvolved, as exemplified in Fig. 6 Fig. 3. PDSC curves for the as-synthesized corn biodiesel, obtained by the ethanol
for the sample B0. The results obtained, in terms of amplitude, route (B0) and after storage (BS) and thermal treatment (BH1 and BH6).

Fig. 2. Reaction scheme for the double bond conjugation in linoleic acid [36].
 M.B. Dantas et al. / Fuel 90 (2011) 773–778 777

Fig. 6. Deconvolution of the UV/Vis spectrum of the B0 sample, related to the

untreated sample.
Fig. 4. Influence of the heat treatment time on the dynamic viscosity and iodine
values of the biodiesel samples.

Fig. 7. Evolution of the amplitude of the absorbance peaks, as a function of the heat
treatment time.

Fig. 5. UV/Vis spectra of as-synthesized, stored and heated samples of corn

biodiesel, obtained by the ethanol route.
auto-oxidation mechanism occurred after 2 h. The increase of the
absorbance of the 232 nm band apparently did not agree with
Table 5 the concomitant decrease of iodine value, with the decrease of
Deconvolution of the UV/Vis spectra of the samples. the heat treatment time (Fig. 5). However, this might be due to
Samples B0 BS BH1 BH2 BH6
the conjugation between the two double bonds of linoleic acid,
which took place upon oxidation [36], as depicted in Fig. 2. It
Peak 1
Center (nm) 226 230 229 230 232
should be stressed that the conjugated dienes did not react with io-
Amplitude (a.u.) 0.55 1.87 1.20 2.15 2.93 dine under the conditions prevailing in the iodine test.
Area (a.u.) 29.2 72.4 62.4 89.5 118.2
FWHM (nm) 50.1 36.4 48.7 39.1 38.0
4. Conclusions
Peak 2
Center (nm) 279 280 282 279 279
Corn biodiesel, obtained by the ethanol route, was submitted to
Amplitude (a.u.) 0.16 0.15 0.29 0.49 0.80
Area (a.u.) 4.4 3.1 8.0 15.1 23.3 oxidative degradation, by long time storage at room temperature
FWHM (nm) 25.9 19.7 26.0 28.8 27.3 and by heat treatment at 150 °C. The degradation was found to
r2 0.9970 0.9928 0.9954 0.9918 0.9910 be more pronounced under heating conditions.
Amplitude 3.44 12.47 4.14 4.39 3.67 The profile of TG curve of non-oxidized biodiesel (B0) showed
(Peak1/Peak2) the same tendency observed in literature, while for the oxidized
samples the initial temperature was reduced and the number of
mass loss steps increased. The increase of the number of steps is
consistent with the formation of secondary oxidation products.
intensities of these bands were particularly interesting, once they Both calorimetric data and physico-chemical parameters demon-
allowed evaluating the oxidation stages, based on the amplitude strated that biodiesel stability is reduced with long-term storage
ratios of these two peaks. Initially the amplitude ratio between and more drastically when it is submitted to a heat stress. This
peak 1 and peak 2 was relatively low, corresponding to the onset work demonstrated that UV–Vis spectrometry technique is an
of the oxidation process. As the oxidation process continued, such important tool for monitoring the oxidative stability of biofuels,
ratio increased along with the peroxide content, reaching a maxi- since the amplitude of the absorption bands at 232 and 272 nm
mum at about 2 h of heat treatment. At high oxidation times the respond to the oxidative degradation of this class of products.
ratio decreased corresponding to higher amounts of secondary oxi- The physico-chemical parameters (viscosity, iodine value and
dation products, Fig. 2. peroxide value) were successfully related to the different oxidation
The results of the deconvolved bands, as a function of heat steps and supported the quantitative analysis performed by
treatment time, Fig. 7, pointed out that a step change in the lipid UV–Vis spectrometry.
778 M.B. Dantas et al. / Fuel 90 (2011) 773–778
The utilization of the techniques focused in the present work
aimed at an integrated analysis of the influence of the initial
oxidation stage (different values of peroxide reached by the ther-
mal pre-treatment) of biodiesel on the thermogravimetric (TG),
thermo-oxidative (PDSC), spectroscopic (UV–Vis) and rheological
(dynamic viscosity) behaviors. Each different technique supplies
information of different oxidative events in the oxidation process,
differently of the volatile formation, which only occurs in the last
oxidation stages, as is the case of the Rancimat method. Further-
more, all the techniques that were applied in the present work
are of low operational cost and rapid execution.
Acknowledgements
The authors acknowledge the Brazilian agencies CNPq, CAPES
and FINEP the financial support.
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