Eur. J. Lipid Sci. Technol.

2008, 110, 341–346 341

Research Paper
Studies on the kinetics of in situ epoxidation of vegetable oils

Chuanshang Cai, Honghai Dai, Rongsheng Chen, Caixia Su, Xiaoya Xu, Shi Zhang, Liting Yang

School of Chemistry and Environment, South China Normal University, Guangzhou, China

In the present work, the kinetics of the epoxidation of soybean oil (SBO) by peroxyacetic acid (PAA)
generated in situ in the presence of sulfuric acid as the catalyst was studied at various temperatures (45, 65
and 75 7C). It was found that epoxidation with almost complete conversion of unsaturated carbon and
negligible oxirane cleavage can be attained by the in situ technique. The rate constant for epoxidation of
SBO was found to be of the order of 10–6 mol–1s–1 and the activation energy of epoxidation is 43.11 kJ/mol.
Some thermodynamic parameters: enthalpy, entropy and free activation energy of 40.63 kJ/mol,
–208.80 J/mol and 102.88 kJ/mol, respectively, were obtained for the epoxidation of SBO. The kinetic and
thermodynamic parameters of epoxidation obtained from this study indicate that an increase in the pro-
cess temperature would increase the rate of epoxide formation. The epoxidation of corn oil and sunflower
oil were also investigated under the same conditions. The results show that the reaction rate is in the order
of soybean oil . corn oil . sunflower oil.

Keywords: Epoxidation / Kinetics / Peroxyacetic acid / Vegetable oil

Received: April 12, 2007; accepted: November 22, 2007
DOI 10.1002/ejlt.200700104

Supporting Information for this article is available from the author or on the WWW under
http://www.wiley-vch.de/contents/jc_2114/2008/200700104_s.pdf

1 Introduction
Epoxides of all kinds of plant oils are well known commercially
because of the many important reactions they undergo.
Epoxidation of long-chain olefins and of unsaturated fatty
acid derivatives such as soybean oil (SBO) and other plant oils
is carried out on the industrial scale [1]. Today, one of the
most important epoxidized vegetable oils is epoxidized soy-
bean oil (ESO), and its worldwide production is about
200,000 t/year [2]. Fatty epoxides are used directly as plasti-
cizers which are compatible with polyvinyl chloride (PVC),
and as stabilizers for PVC resins to improve flexibility, elasti-
city, and toughness and to impart the stability of polymers to-
wards heat and UV radiation. Due to high reactivity of the
oxirane ring, epoxides also act as a raw materials for a variety
of chemicals, such as alcohols, glycols, alkanolamines, car-
bonyl compounds, olefinic compounds and polymers like
polyesters, polyurethanes (PU), and epoxy resins.
Correspondence: Liting Yang, School of Chemistry and Environment,
South China Normal University, Guangzhou 510631, China.
E-mail: yanglt63@yahoo.com.cn, yanglt@scnu.edu.cn
Fax: +86 20 39310187
Especially, the oil was characterized for its hydroxyl values
and fatty acid composition. The modified oils had higher hy-
droxyl values and lower unsaturated acids than regular
unmodified oils. The modified soy-based vegetable oil polyols
could be incorporated as a replacement for conventional
polyols, reacting with isocyanates (TDI and MDI), to pro-
duce flexible slabstock PU foams, elastomers, and coatings.
SBO is highly hydrophobic; so an excellent weather stability of
the derived PU can be expected; then, the thermal and oxida-
tive stabilities of the SBO-based PU are comparable with those
of the polypropyleneoxide-based PU [3–6].
As energy demands increase and fossil fuel reserves are
limited, there has been a growing interest in the utilization of
renewable resources as an alternative to petroleum-based
polymers. Consequently, much attention has been focused on
the development of polymeric materials from vegetable oils, a
sustainable resource [7, 8]. Vegetable oil, which is readily
available and is a comparatively inexpensive material, can be
used to synthesize various types of polymers.
There are four known technologies to produce epoxides
from olefinic types of molecules: (a) epoxidation with percar-
boxylic acids [9], the most widely used in the industry, which
can be catalyzed by acids or by enzymes [1, 10]; (b) epoxida-
tion with organic and inorganic peroxides, which includes

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com

342 C. Cai et al.
alkaline and nitrile hydrogen peroxide epoxidation as well as
transition metal-catalyzed epoxidation [11]; (c) epoxidation
with halohydrins, using hypohalous acids (HOX) and their
salts as reagents for the epoxidation of olefins with electron-
deficient double bonds [9]; and (d) epoxidation with molecu-
lar oxygen [9].
But of the ways of epoxidation of vegetable oils, the
available technologies that need to be explored are only (a)
and (b) as described above, which are clean and efficient,
namely epoxidation with percarboxylic acids and epoxdation
with organic and inorganic peroxides [12]. These technolo-
gies can be rendered cleaner by using heterogeneous cata-
lysts replacing traditional homogeneous ones [13]. Although
the cleanest epoxidation process is direct insertion of oxygen
from air into the olefinic bond in the absence of any catalyst
in the mixture, the conversion of a double bond to an oxi-
rane ring under this condition is far from application in the
industry. In the present work, we investigate the kinetics of
epoxidatin of three oils (SBO, corn oil and sunflower oil) by
PAA generated in situ and the relation between the extent of
epoxidation and temperature. The kinetic parameters and
some thermodynamic parameters, i.e. enthalpy, entropy and
free activation energy of the epoxidation of oils, were
obtained.
Partial epoxidation of oils will give unsaturated epoxidized
oils with different oxirane contents, which can generate poly-
ols with different OH values. These kinds of polyols react with
isocyanate and can produce series of PU for different appli-
cations.
2 Materials and methods
2.1 Materials
The refined SBO, corn oil and sunflower oil were kindly pro-
vided by Nanhai Oil Co. Ltd. Glacial acetic acid (99.5%),
sodium carbonate, sodium hydroxide, hydrogen peroxide
(30%) and sulfuric acid were of analytical reagent grade and
purchased from Guangzhou Chemical Reagent Co. They
were used as supplied.
2.2 Determination of fatty acid composition
The fatty acid composition of the oils was determined by gas
chromatography after methanolysis according to reference
[14]. A sample (0.1 g) was placed in a 50-mL reaction bottle
with a reflux condenser, and 0.75 g calcium methoxide dis-
persed in methanol (20 mL) was added. The bottle was
heated at 70 7C for 30 min. The products of the transester-
ification reaction were cooled and then analyzed using a
Hewlett Packard 6890 gas chromatograph equipped with a
mass selective detector HP 5973. The capillary column (30 m
long with 0.25 mm inside diameter) had an INNOWAX
phase. Helium was used as the carrier gas with a split ratio of
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 2008, 110, 341–346
100. The flow rate of the carrier gas was 1.2 mL/min. The gas
chromatograph injector temperature was 200 7C. The oven
temperature was held at 50 7C for 6 min and then pro-
grammed from 50 to 250 7C at 10 7C/min. The oil reference
standards, AOCS, from Sigma Chemicals were used as exter-
nal standards for quantitative analysis.
2.3 Epoxidation of SBO
Epoxidation of SBO was carried out in a 1000-mL four-
necked round-bottom flask equipped with a thermometer
sensor, a mechanical stirrer, a condenser, and an isobaric
funnel. The whole apparatus was kept in a water bath to
maintain the respective reaction temperature of 45, 65 and
75 6 1 7C. Thus, the temperature was measured inside the
reaction vessel. Of SBO, 150 g (0.172 mol) was placed in the
round-bottom flask. With agitation, PAA, prepared in situ by
reacting various mixtures of 35 g (0.58 mol) 99.5% glacial
acetic acid and 165 g (1.46 mol) 30% H2O2 in the presence of
small quantities of concentrated sulfuric acid for about 12 h,
was added slowly through an isobaric funnel. This precaution
was taken to prevent overheating of the system due to the
exothermic nature of epoxidation reactions. The stirring rate
was controlled so that the oil in the mixture was finely dis-
persed. The reaction was monitored by withdrawing aliquots
of the reaction mixture at various time intervals. The samples
were quenched inside the refrigerator to stop the epoxidation
reaction, and delaminated soon.
To purify the samples, the samples were poured into a
separator funnel. The aqueous layer was drawn off and the
oil layer was washed successively with warm dilute sodium
carbonate solution until the pH was neutral, and then
washed with saturated sodium chloride solution and dis-
tilled water, respectively. The solvent was removed using a
rotary evaporator, with the help of a water vacuum pump.
The oil phase was further dried above anhydrous magne-
sium sulfate and then filtered. The epoxy oxygen content
was measured according to a standard procedure for oils
and fats [15].
The epoxidation reactions of corn oil and sunflower oil
were carried out according to the same procedure as describe
above.
The infrared spectra were recorded on a Perkin-Elmer
Spectrum-1000 FT-IR spectrometer. Samples were prepared
as thin liquid films on a KBr or NaCl salt plate.
3 Results and discussion
The main compositions of SBO, corn oil and sunflower oil
were analyzed by gas chromatography after methanolysis
according to [14] and the results are shown in Table 1. As seen
from Table 1, the saturated acid contents of SBO, corn oil and
sunflower oil are 13.5, 12.9 and 12.7, respectively, and the
unsaturated acid contents are 86.1, 87.1 and 88.9, respec-
www.ejlst.com
Eur. J. Lipid Sci. Technol. 2008, 110, 341–346 Kinetics of in situ epoxidation of vegetable oils 343

Table 1. Main fatty acid composition of oils. decreased during the initial 8 h. The reaction at lower tem-
perature showed a lower rate, but gave a more stable oxirane
Fatty acids [wt-%] ring (for epoxidation at 45 7C). These results suggested that
Palmitic Stearic Oleic Linoleic Linolenic the optimum level of epoxidation could be obtained in a
(16:0) (18:0) (18:1) (18:2) (18:3) shorter time at moderate reaction temperatures ranging from
65 to 75 7C, at which the rate of epoxide degradation was
Soybean oil 10.5 3.0 23.1 56.5 6.5 relatively low. Consequently, only the initial stage of the reac-
Corn oil 11.6 1.3 30.6 55.8 0.7 tion was taken into account for the kinetic study. The extents
Sunflower oil 9.2 3.5 20.4 68.1 0.4
of epoxidation of corn oil and sunflower oil by PAA generated
in situ at various temperatures are shown in Figs. A-1 and A-2
(see Supporting Information on the WWW).
tively. But the contents of oleic, linoleic and linolenic acids in SBO and the purified sample spread on an NaCl plate
the three oils are very different. were analyzed using FT-IR to check whether SBO was con-
verted to ESO. The FT-IR spectra of SBO and ESO are
3.1 Oxidation of vegetable oils described in Fig. 3.
In the FT-IR spectrum of SBO, the characteristic peak at
The oxidation of oils was carried out according to the Mate- 3009 cm–1 was attributed to the C–H stretching of the SBO
rials and methods section at 75 7C and the results are shown in C=C–H. The peak at 3009 cm–1 disappeared after the epox-
Fig. 1. As can be seen from Fig. 1, the reaction rate of SBO is idation reaction. As Fig. 3 shows, obviously, the peak at
the fastest and gives the highest oxirane ring content. This 3009 cm–1 had disappeared almost completely at 65 and 75 7C
may be due to the different acid contents of oleic, linoleic and after 6 h, indicating that almost all the C=C had taken part in
linolenic in the oil. As is seen from Table 1, the linolenic acid the epoxidation reaction. The C=O double bonds at 1725 cm–1
content in SBO is 6.5; linolenic acid has three double bonds in (C=O stretching vibrations) remained unaltered after the
the chain, thus having higher reactivity. epoxidation reaction. The presence of new peaks in the FT-IR
The extent of epoxidation of SBO by PAA generated in spectrum of ESO at 823 and 833 cm–1, attributed to the epoxy
situ at various temperatures is shown in Fig. 2. The results group, corroborated the conclusion relative to the success of
indicated that increasing the temperature shows a favorable the epoxidation reaction of SBO. The other new peak at
effect on the extent of SBO by PAA generated in situ. The 3463 cm–1 was attributed to the hydroxyl O–H stretching,
initial increase in the extent of epoxidation of SBO with reac- indicating that the epoxy group has been opened; then, the
tion time reached maximum values (for epoxidation at 75 7C), intensity of the 3463 cm–1 band indicated the extent of hy-
and then decreased with further increases in reaction time. droxyl of ESO. Consequently, this obviously shows that the
The decreased extent of epoxidation at 75 7C was very reaction temperature was higher, and the epoxy group had
obvious, while the extent of epoxidation at 65 7C hardly been opened partially.

Figure 1. Oxirane content of three oils versus reaction

time at 75 7C.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com

344 C. Cai et al.
Figure 2. Extent of epoxidation of SBO at different temperatures.
Figure 3. FT-IR spectra: Spectra of SBO and ESO prepared at
various temperatures, reacting for 6 h.
3.2 Kinetics of epoxidation
The in situ epoxidation reaction generally takes place in two
steps: (i) formation of a peroxy acid and (ii) reaction of the
peroxy acid with the unsaturation [16].
(i) Formation of a peroxy acid:
RCOOH þ H 2 O2 , RCOOOH þ H 2 O
(ii) Epoxidation
RCOOOH 1 R1CH=CHR2 ? R1CHOCHR2 1 RCOOH
If the first step is considered to be rate determining and the
concentration of the peroxy acid is assumed to be constant
throughout the reaction, then the rate of epoxidation will be
given by the following expression [17]:
d½EP

¼ kf½H 2 O2
0  ½EP
g  ½RCOOH
0 (1)
dt
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 2008, 110, 341–346
Figure 4. Kinetics of in situ epoxidation of SBO by PAA.
where the subscript 0 denotes the initial concentrations and
EP denotes the epoxides.
Hence
Lnf½H 2 O2
0  ½EP
g ¼ k½RCOOH
0  t þ Ln½H 2 O2
0 (2)
According to Eq. (2), the plot of {[H2O2]0 – [EP]} vs. time
should yield straight lines for those reactions with negligible
degradation of oxirane. Deviations from linearity were
observed for the reaction with substantial ring opening. In
such cases, rate constants were obtained with the initial slopes.
Figure 4 shows the kinetic plots for in situ epoxidation of SBO
at different temperatures, and Figs. A-3 and A-4 show the
kinetic plots for in situ epoxidation of corn oil and sunflower
oil at different temperatures, respectively.
The rate constants obtained for the reaction were of the
order 10–6 mol–1s–1 (Table 2). The values of the rate con-
stant showed the expected dependence on temperature, as
an increase in the reaction temperature from 45 to 75 7C
was accompanied by an about fourfold increase in the value
of the rate constant of epoxidation. Because the epoxidation
reagent (PAA) had been formed and mixed with SBO to
prepare ESO, the rate of the epoxidation of SBO by
PAA was very fast. Consequently, the rate constant of
epoxidation was bigger than the one in references [13, 18].
Table 2. Rate constants of SBO epoxidation at various tempera-
tures.
Temperature [7C] Rate constant of epoxidation
K6106 [mol–1s–1]
45 7.4
55 11.4
65 18.0
75 29.6
www.ejlst.com
Eur. J. Lipid Sci. Technol. 2008, 110, 341–346 Kinetics of in situ epoxidation of vegetable oils 345

where k is the rate constant; R the gas constant, T is the abso-

lute temperature, N the Avogadro constant, and h is Planck’s
constant.

DF ¼ DH  T DS (5)

The average values of the thermodynamic parameters were

calculated using the equations above and the results are shown
in Table 3.

4 Conclusions

The results from this study show that the epoxidation of SBO
by PAA generated in situ can be carried out at moderate tem-
peratures with minimum epoxide degradation. The kinetic
and thermodynamic parameters of the epoxidation obtained
Figure 5. Activation energy, Ea, for the epoxidation of SBO by PAA. indicate that an increase in the process temperature would
increase the rate of epoxide formation and would be useful for
The kinetic data for the in situ epoxidation of SBO by PAA the scaled-up production of ESO using the in situ technique.
gave a good Arrhenius plot (Fig. 5), from which the activation The activation energy of the reaction follows the sequence
energy, E, of epoxidation was determined to be 43.11 kJ/mol. SBO , corn oil , sunflower oil.
Figures A-5 and A-6 also show the Arrhenius plots of corn oil
and sunflower oil. The activation energy values for in situ
epoxidation of corn oil and sunflower oil were obtained
according to the same process as above, and the results are
Acknowledgment
shown in Table 3. As can be seen from Table 3, the activation
This work was supported by the Natural Science Foundation of
energy of the oils follows the sequence ESoybean oil , ECorn oil ,
Guangdong Province (No. 06025028).
ESunflower oil, and this result may be due to the different fatty
acid compositions of the oils. A higher linolenic acid content
gives a lower activation energy.
Conflict of interest statement

The authors have declared no conflict of interest.

3.3 Thermodynamics of epoxidation of vegetable oils

The enthalpy of activation, DH, was calculated using the fol-

lowing equation [19]: References
DH ¼ E  RT (3) [1] L. A. Rios, P. Weckes, H. Schuster, W. F. Hoelderich: Meso-
porous and amorphous Ti-silicas on the epoxidation of vege-
The average energy of activation, DS, and the free energy of tables oils. J Catal. 2005, 232, 19–26.
activation, DF, were obtained using the relationship [20]: [2] M. R. Klaas, S. Warwel: Complete and partial epoxidation of
plant oils by lipase-catalysed perhydrolysis. Ind Crops Prod.
Table 3. Kinetic parameters for in situ epoxidation of vegetable 1999, 9, 125–132.
oils. [3] A. Guo, I. Javni, Z. S. Petrovic: Rigid polyurethane foams based
on soybean oil. J Appl Polym Sci. 2000, 77, 467–473.
E R2 DH DS DF [4] A. Guo, Y. Cho, Z. S. Petrovic: Structure and properties of
[kJ/mol] [kJ/mol] [J/mol] [kJ/mol] halogenated and non halogenated soy based polyols. J Polym Sci
A Polym Chem. 2000, 38, 3900–3910.
Soybean oil 43.11 6 0.33 0.9987 40.63 –208.80 102.88 [5] Z. S. Petrovic, A. Guo, W. Zhuang: Structure and properties of
Corn oil 74.22 6 0.50 0.9980 71.74 –120.01 110.00 polyurethanes based on halogenated and nonhalogenated soy
Sunflower oil 85.21 6 0.42 0.9986 82.73 –83.17 110.01 based polyols. J Polym Sci A Polym Chem. 2000, 38, 4062–
4069.
[6] I. Javni, Z. S. Petrovic, A. Guo, R. Fuller: Thermal stability of
RT DS=R E=RT polyurethanes based on vegetable oils. J Appl Polym Sci. 2000,
k¼ e e (4) 77, 1723–1734.
Nh

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com

346 C. Cai et al.
[7] S. Ahmad, F. Naqvi, K. L. Verma, S. Yadav: Studies on a
newly developed linseed oil-based alumina-filled poly-
esteramide anticorrosive coating. J Appl Polym Sci. 1999, 72,
1679–1687.
[8] S. Ahmad, S. M. Ashraf, F. Naqvi, A. Hasnat, S. Yadav: A
polyesteramide from Pongamia glabra oil for biologically safe
anticorrosive coating. Prog Org Coat. 2003, 47, 95–102.
[9] S. Guenter, R. Rieth, K. T. Rowbottom (Eds.): Sixth Ull-
manns Encyclopedia of Industrial Chemistry. Vol. 12. Wiley-
VCH Verlag, Weinheim (Germany) 2003, pp. 269–284.
[10] S. Warwel, M. R. Klaas: Chemo-enzymatic epoxidation of
unsaturated carboxylic acids. J Mol Cat B Enzym. 1995, 1,
29–35.
[11] K. B. Sharpless, S. S. Woodard, M. G. Finn: On the mechan-
ism of titanium-tartrate catalyzed asymmetric epoxidation.
Pure Appl Chem. 1983, 55, 1823–1836.
[12] V. V. Goud, A. V. Patwardhan, N. C. Pradhan: Studies on the
epoxidation of mahua oil (Madhumica indica) by hydrogen
peroxide. Bioresour Technol. 2006, 97, 1365–1371.
[13] A. Campanella, M. A. Baltanas, M. C. Capel-Sanchez, J. M.
Campos-Martin, J. L. G. Fierro: Soybean oil epoxidation with
hydrogen peroxide using an amorphous Ti/SiO2 catalyst.
Green Chem. 2004, 6, 330–334.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 2008, 110, 341–346
[14] S. Gryglewicz, K. Grabas, G. Gryglewicz: Use of vegetable
oils and fatty acid methyl esters in the production of spherical
activated carbons. Bioresour Technol. 2000, 75, 213–218.
[15] M. He, X. Wang, J. Liu: Epoxidation of vegetable oils cata-
lyzed by heteropoly acids. Chinese J Appl Chem. 1998, 15,
117–118.
[16] B. Rangaraja, A. Harvey, E. A. Grulke, P. D. Culman: Kinetic
parameters of a two-phase model for in situ epoxidation of
soybean oil. J Am Oil Chem Soc. 1995, 72, 1161–1169.
[17] L. H. Gan, S. H. Goh, K. S. Ooi: Kinetics studies of epox-
idation and oxirane cleavage of palm olein methyl esters. J Am
Oil Chem Soc. 1992, 69, 347–351.
[18] F. E. Okieimen, O. I. Bakare, C. O. Okieimen: Studies on the
epoxidation of rubber seed oil. J Ind Crops Prod. 2002, 15,
139–144.
[19] F. A. Zaher, M. H. El-Mallah, M. A. El-Hefnawy: Kinetics of
oxirane cleavage in epoxidised soybean oil. J Am Oil Chem
Soc. 1989, 66, 698–700.
[20] A. A. Frost, R. G. Pearson: Kinetics and Mechanism. 2nd Edn.
John Wiley, New York, NY (USA) 1961.
www.ejlst.com