pubs.acs.org/EF
1. INTRODUCTION
Biodiesel is dened as monoalkyl esters of vegetable oils or
animal fats. It is suitable as a replacement or complement for
conventional diesel fuel (petrodiesel) in a compression-ignition
(diesel) engine.1 The most common forms of biodiesel are
methyl esters of vegetable oils. The use of methyl esters oers
the advantage that the high viscosity of vegetable oils is reduced
by an order of magnitude to a value close to that of petrodiesel.
The produced biodiesel must meet a series of physical and
chemical specication parameters. The iodine value (IV) is one
of them, which indicates the degree of unsaturation of the fuel,
expressing its trend to oxidize. In industrial applications,
oxidation stability is an issue not only for biodiesel but also for
lubricants.2 It is well-known that the rate of autoxidation of
unsaturated fatty compounds depends upon the number and
position of the double bonds.3 The algal oil contains a high
amount of polyunsaturated fatty acids (PUFAs) compared to
seed oils; therefore, the oxidation stability of algal-derived
biodiesel is less.
In European Standard EN-14214, the IV has been included,
usually being set to a maximum of 120. The limitation of the IV
in biodiesel is currently one of the most discussed topics within
the dierent worldwide biodiesel specications. The higher the
IV, the more extensive the unsaturation degree, meaning a
higher number of double bonds in the biodiesel. The iodine
number is a measure for the number of double bonds in a
sample. It species the amount of iodine in grams that is
consumed by 100 g of the biodiesel sample under the given
conditions. The determination of the iodine number by redox
titration with a solution of sodium thiosulfate is described by
the American Oil Chemists Society (AOCS). Some other
methods are also reported in the literature48 for estimation of
IV in vegetable oils and animal fats.
Nuclear magnetic resonance (NMR) has become one of the
most promising methods to determine IV of vegetable oils and
animal fats.911 There is no single method that has been
reported for the estimation of IV that can apply for all types of
biodiesel and especially for algal biodiesel. The traditional
2012 American Chemical Society
2. EXPERIMENTAL SECTION
2.1. Samples. Biodiesel samples were obtained from extracted
vegetable oil through the transesterication reaction using methanol as
the alcohol source. Algae samples (Scenedesmus, Chlorella, and
Spirulina) were provided by the Department of Agricultural and
Biological Engineering, University of Illinois at UrbanaChampaign
(UIUC), Urbana, IL, to the R&D Center of IOC, Ltd.
2.2. Extraction of Oil and Biodiesel Synthesis. Oils were
extracted from the dierent seeds by Soxhlet extraction using
petroleum ether (bp 6080 C) at 80 C for 20 h.12 The oil
extracted seeds were again subjected to Soxhlet extraction under
identical conditions for an extra 5 h to ensure complete oil extraction.
The sample recovered after the extraction was monitored by thin-layer
chromatography (TLC) using a mixed solvent system of petroleum
ether (85 mL), diethyl ether (13.5 mL), and glacial acetic acid (1.5
mL).
Algal oil was extracted from the solid algal sample by the Bligh and
Dyer method.13 The extracted oils from seeds and algae were
converted into biodiesel through the transesterication reaction using
methanol as the alcohol source.14
2.3. NMR Spectroscopic Studies. All of the 1H NMR spectra
were recorded on a Bruker ACP-300 MHz NMR spectrometer. The
concentration of the sample used was 510% (w/w) in CDCl3 for 1H
NMR, containing tetramethylsilane (TMS) as an internal reference per
the following experimental conditions: spectral width, 3600 Hz (0.0
12.0 ppm); spectral size, 16 K; digital resolution, 0.2197 ppm/point;
90 pulse, 18 s; relaxation delay, 10 s; and number of scans, 64.
Received: June 14, 2012
Revised: September 22, 2012
Published: October 2, 2012
7005
Article
r = 15/3,
% ME = (R r )/E 100
(1)
The present study used the number of double bonds against the
area per hydrogen. The total number of double bonds (DBs) is
calculated by the olenic hydrogen number (O).
number of double bonds (DBs) = O/2
(2)
r=5
(3)
r = 15/3,
7006
r=5
dx.doi.org/10.1021/ef300991n | Energy Fuels 2012, 26, 70057008
Article
MW = 351.24
IV = 114.2
IV by the
traditional method
IV by
H NMR
% ME by
1
H NMR
91.0
118.6
125.0
132.0
114.0
89.9
120
132
137.4
111.6
97.3
98.2
98.1
97.6
97.4
10.0
91.4
49.0
115.4
106.4
121.0
260.4
11.4
89.1
50.6
114.2
109
125
260.4
98.8
97.1
97.6
96.8
97.1
97.4
100.0
Article
biodiesel samples
1
2
3
4
5
Jatropha 1
soybean 1
sunower
coconut
Jatropha 2
2.4
2.2
0.8
35.1
2.4
4. CONCLUSION
The results of the IVs obtained by 1H NMR showed good
correlation with the traditional AOCS method. Additionally,
the 1H NMR method can also be used to calculate the average
MW of the fatty acid methyl esters and the yield of methyl
esters produced in the transesterication reaction. The 1H
NMR method is rapid, environmentally friendly, and useful for
the evaluation of biodiesel samples obtained by the methylic
route. The 1H NMR method does not depend upon the nature
of biodiesel feedstock. It is applicable to all methyl biodiesel
samples obtained from dierent raw materials, including algal
oils.
AUTHOR INFORMATION
Corresponding Author
*E-mail: kumarr88@indianoil.in.
Notes
ACKNOWLEDGMENTS
The authors are thankful to the management of the R&D
Center, IOC, Ltd., Faridabad, India, for allowing the present
work to be published. The authors acknowledge the Department of Agricultural and Biological Engineering, UIUC,
Urbana, IL, for providing the algae samples and Dr. Dheer
Singh for synthesis of biodiesel from algal and vegetable oils.
REFERENCES