Fuel 88 (2009) 786–791

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

Theoretical study of the transesterification of triglycerides to biodiesel fuel

Yusuke Asakuma a,*, Kouji Maeda a, Hidetoshi Kuramochi b, Keisuke Fukui a
a
Department of Mechanical and Systems Engineering, University of Hyogo, 2167 Shosha Himeji, Hyogo 671-2280, Japan
b
Research Center for Material Cycles and Waste Management, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan

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

Article history: The transesterification of various triglycerides was considered in terms of the activation energy obtained
Received 9 July 2008 from quantum computational chemistry. According to these values, the effect upon the reactivity of the
Received in revised form 30 October 2008 structure of the triglyceride is not particularly large. Moreover, the transesterification reaction is com-
Accepted 30 October 2008
pleted via a transition state, in which ring formation consisting of the carbon of the carboxyl and alkoxy
Available online 28 November 2008
groups appears, even if a long-chain alcohol is used as a reactant. Finally, an ideal reaction pathway, in
which the ester bond at the center of the triglyceride is transesterified before peripheral ester bonds,
Keywords:
was shown by an activation energy analysis and electrostatic potential (ESP) distribution.
Transesterification
Biodiesel fuel
Ó 2008 Published by Elsevier Ltd.
Electrostatic potential

1. Introduction tion can be rather complex. A typical transesterification of a tri-

Biodiesel is becoming increasingly important as an alternative
fuel for diesel engines due to diminishing petroleum reserves
and as part of the effort to save the global environment. Biodiesel
is made from renewable biological sources such as vegetable oils
and animal fats consisting of the simple alkyl esters of fatty acids,
and is considered to contribute much less to global warming than
fossil fuels [1].
Transesterification is a process of reacting a triglyceride such as
vegetable oil with an alcohol, usually methanol, in the presence of
an alkaline catalyst to produce fatty acid esters and glycerol. An
alkaline-catalyzed transesterification process is normally adopted
for biodiesel production because alkaline metal alkoxides and
hydroxides are more effective than acid catalysts. Sodium and
potassium methoxide are much more effective catalyst for the
base-catalyzed transesterification of triglycerides. A number of
researchers have demonstrated the importance of variables such
as reaction rate and selectivity of catalyst to the transesterification,
and we have studied the solubility properties of a mixture of tri-
glyceride and methanol in a vapor–liquid–liquid three phases
equilibrium [2].
The properties of the biodiesel fuel are strongly influenced by
the structure and concentration of the fatty acid esters, which de-
pend on the source, such as palm, soybean, corn or sunflower. Nor-
mally, the triglyceride consists of one glycerol and various types of
fatty acid esters [3,4], which vary in carbon chain length and in
number of unsaturated bonds. Therefore, a transesterification reac-
* Corresponding author. Tel./fax: +81 792 67 4847.
E-mail address: asakuma@eng.u-hyogo.ac.jp (Y. Asakuma).
glyceride is shown in Fig. 1, consisting of consecutive reversible
reactions, where R1, R2 and R3 represent long-chain alkyl groups
[5–8]. The triglyceride is converted stepwise to a diglyceride, a
monoglyceride and finally, to glycerol by removal of an alkyl in
each step, as shown in Fig. 2 [9,10]. Moreover, the transesterifica-
tion reaction is carried out by the addition of methanol, ethanol,
mixtures of methanol/ethanol and another alcohol [11,12], and
many different fatty acid esters are produced. Accordingly, we
thought that systematic theoretical estimations of the transesteri-
fication would be essential to clarify the transesterification path-
ways and the complex transesterification mechanism of various
types of oils. Our interest in this study was focused on the transe-
sterification mechanism. Quantum computational chemistry was
used to analyze the mechanism in a first attempt. In this study, var-
ious types of behavior such as the effect of the length of the alkyl
group, R, and the number of unsaturated bonds on the reactivity,
and the pathway from triglyceride to diglyceride and monoglycer-
ide, were considered by means of activation energy and electro-
static potential (ESP) distribution obtained from a quantum
orbital method.
2. Calculation
Fig. 1 shows the transesterification reaction of a triglyceride
such as vegetable oil or animal fat. The meaning of the numbers
1, 2, and 3 in Fig. 1 is the position of the carboxyl group, either
in the center (2) or on the outside (1 and 3). The triglyceride is split
into its components via transesterification catalyzed by the addi-
tion of a base. Transesterification is the process of exchanging
the alkoxy group of an ester compound for another alkoxy group

0016-2361/$ - see front matter Ó 2008 Published by Elsevier Ltd.

doi:10.1016/j.fuel.2008.10.045
 Y. Asakuma et al. / Fuel 88 (2009) 786–791 787

Table 1
Characteristics of fatty acids.

No Abbr. Chemical structure CH3-(R)-CO2H Common name

1 C4:0 -(CH2)2- Butyric
2 C8:0 -(CH2)6- Caprylic
3 C12:0 -(CH2)10- Lauric
4 C18:0 -(CH2)16- Stearic
5 C18:1(9) -(CH2)7CH@CH(CH2)7- Oleic
Fig. 1. Overall reaction of triglyceride transesterification. 6 C18:2(9,12) -(CH2)3(CH2CH@CH)2(CH2)7- Linoleic
7 C18:3(9,12,15) -(CH2CH@CH)3(CH2)7- Linolenic

saturated or unsaturated, long, unbranched, aliphatic chain. In the

Fig. 2. Three different pathways of transesterification.
of a different alcohol. The fatty acid monoalkyl ester can be used as
biodiesel fuel (BDF) in diesel engines. There are various types of oil,
and their physical characteristics are decided by the alkyl group, a
same way, the characteristics (density, viscosity, boiling point, va-
por pressure, flash point, etc.) of a fatty acid ester used as BDF de-
pend on the alkyl and alkenyl functional groups R1, R2 and R3,
which can vary in the number of carbon atoms and double bonds.
After the ester linkage of triglyceride is cut by an alkoxy group un-
der basic conditions, three fatty acid esters and glycerol (glycerin)
are produced via a transesterification reaction. When the carbonyl
is attacked by the alkoxy group, this reaction proceeds through a
tetrahedral intermediate or transition state [13]. The characteris-
tics of these reactions are best considered by evaluation of the acti-
vation energy [13,14].
It is first necessary to calculate the optimized size of the
ground state and transition state for the transesterification be-
cause each state has different energy. In this study, ab-initio
molecular orbital was chosen because semi-empirical calculation
[15] might be insufficient for evaluation of electronic structure.
The quantum data of each state is derived using Gaussian soft-
ware (Gaussian R 03W Ver. 6, Gaussian, Inc.) [13,14]. The struc-
tures of ground state molecules (triglyceride, alkoxyl group and
fatty acid ester) and the transition state of the transesterification
reaction were simulated. The activation energy of the transeste-
rification reaction was obtained from optimized structures calcu-
lated under minimum energy configurations from the initial
approximate coordinates of the atoms. The basis set used in this
calculation was HF/STO-3G [16].
The various fatty acids used in this calculation are listed in
Table 1. The effects of chain lengths (x) and double bonds (y) on

Fig. 3. Ring formation involving methanol at the transition state in transesterification. (Blue circle shows the ring formed by the attachment of methoxy) (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article.).
788 Y. Asakuma et al. / Fuel 88 (2009) 786–791

Fig. 4. Electric charge and electrostatic potential distribution of triglyceride transesterification.

85 85
Activation energy [kcal/mol]

Activation energy [kcal/mol]

80 80

75 75
4 8 12 18 0 1 2 3
Carbon chain length of fatty acid The number of double bonds in fatty acid

Fig. 5. Relationship between fatty acid size and activation energy. Fig. 6. Relationship between the number of double bonds and activation energy.
 Y. Asakuma et al. / Fuel 88 (2009) 786–791 789

reactivity are considered comparing, for instance, No. 1–No. 4, or
No. 4–No. 7. In this case, methanol is used as the reactant. Sepa-
rately, ethanol, 1-propanol and 1-butanol were used as reactants
[11,12] in order to investigate the effect of the reactant. Finally,
the main reaction pathway is predicted. The triglyceride has three
ester bonds which are transesterified one by one as shown in Fig. 2.
The activation energy obtained from this calculation can show
which ester bonds are easier to transesterify initially, and which
are main pathways.
3. Results and discussion
Every transesterification proceeds via the transition state. The
alkoxy group attacks the carbon of the carboxyl group, and a polyg-
onal ring with a tetrahedral intermediate carbon and an alkoxy
group is formed [13,14]. For methoxy, the shape of the ring is pen-
tagonal, as shown in Figs. 3 and 4 (a and b) show electric charge
and the ESP distribution around the ester bond of the triglyceride.
Electrons of the carboxyl carbon are pulled by the neighbor oxygen

Ethoxy
Tetra hedral intermediate Hexagonal ring formation

R1
R3

R2
H
C
(a) Ethanol O

Proxy
Tetra hedral intermediate Heptagonal ring formation

R3
R1

R2

(b) 1-Propanol

Butoxy
Te trahedral intermediate
Octagonal ring formation

R1 R3

R2

(c) 2-Butanol

Fig. 7. Ring formation involving ethanol at the transition state in transesterification. (Blue circle shows the ring formed by the attachment of the alkoxy group).
790 Y. Asakuma et al. / Fuel 88 (2009) 786–791

90 120
Activation energy [kcal/mol]

(a) 1-2-3
(b) 1-3-2
(c) 2-1-3

Activation energy [kcal/mol]

80
Ave.
100

70

60 80
MeOH EtOH PrOH BtOH
Solvent

Fig. 8. Activation energy by various types of alkoxy groups.

atoms because of their higher electronegativity. Electric charge of 60

E1 E2 E3
the carbon becomes the highest in the triglyceride molecule. In the
same way, the charge of oxygen atoms shows the lowest value. Fig. 9. Activation energy of the transesterification pathway.
ESP is closely related with electric charge and so ESP values of oxy-

Fig. 10. Electrostatic potential distribution of triglyceride, diglyceride and monoglyceride.

 Y. Asakuma et al. / Fuel 88 (2009) 786–791
gen and carboxyl carbon of the triglyceride become negative and po-
sitive, respectively. On the other hands, negative ESP distribution of
the methoxy oxygen concentrates around the oxygen atom as
shown in Fig. 4c. Accordingly, the pentagonal ring is formed by
two forces, electrostatic force between the oxygen atom of the meth-
oxy and the carboxyl carbon, hydrogen bond between the hydrogen
atom of the methoxy and the carbonyl oxygen. This ring appeared in
every calculation of the optimum structure for the components
listed in Table 1, and this tetrahedral structure is therefore defined
as a transition state. Moreover, a larger ring was formed for the tran-
sition state if a longer-chain alcohol was used as a reactant. The
importance of the ring formation in the transition state was reported
for another transesterification reaction [13,14].
3.1. Effect of chain length of triglyceride on activation energy
The transesterification of a triglyceride with exclusively straight
chains was considered because saturated fatty acids form straight
chains. Fig. 5 shows the relationship between the chain length of
the triglyceride and the activation energy. Because of the similar
activation energy values for all of the transesterification reactions
in this calculation, the decomposition behavior seems to be similar,
even if the triglyceride chain length is different. This differs from
other researchers who have shown that the reaction rate of triglyc-
erides with larger fatty acids is slower [17]. This might be caused
by a mixture property because the cosolvent of triglycerides with
varying fatty acid sizes and methanol shows differences in a va-
por–liquid–liquid three phase equilibrium [3,18].
3.2. Effect of the number of double bonds in the fatty acid on activation
energy
Fig. 6 shows the relationship between the number of double
bonds and activation energy. Clearly, there is no significant differ-
ence. Moreover, no difference between cis and trans configurations
was found in this calculation.
3.3. Effect of reactant on activation energy
A larger transition state ring is formed when a longer-chain
alcohol is used as a reactant, as shown in Fig. 7. The appropriate-
sized ring (hexagonal, heptagonal or octagonal) formed by ethanol,
1-propanol or 1-butanol should be more stable than the pentago-
nal ring produced for methanol. As expected, when a larger ring
is formed by the longer-chain alcohol, smaller activation energy
is obtained, as shown in Fig. 8. This means that the larger ring is
more stable because torsion and bond angles in the ring are mod-
erate. Ethanol and longer-chain alcohols such as 1-propanol and 1-
butanol can be used to produce ethyl and alkyl ester biodiesel.
However, methanol is most commonly used to produce methyl es-
ters as it is the cheapest alcohol available, and the methyl ester
fatty acid is generally superior in terms of physical properties such
as kinetic viscosity and flash point as a diesel fuel [18,19].
3.4. Transesterification reaction of triglyceride
Fig. 9 shows the activation energy of each of the three stages of
transesterification. According to the activation energy values, path-
way (c) is ideal because the total activation energy of pathway (c) is
lower than the others. This means that transesterification of a center
ester bond is performed in preference to outside ester bonds. More-
over, transesterification reactions of diglycerides and monoglyce-
rides (DE2 and DE3), which have larger activation energies, are
more difficult than for triglycerides (DE1). The ESP distribution of
791
triglyceride, diglyceride and monoglyceride are shown in Fig. 10
when outside ester bond was initially removed. Positive ESP distri-
bution appears at the position of transesterification in the case of
diglyceride and monoglyceride. Because the positive charge pre-
vents the methoxy with negative charge from attacking the carboxyl
carbon, activation energy of diglyceride and monoglyceride about
the transesterification becomes higher than triglyceride. This
behavior corresponds to experimental data wherein transesterifica-
tion is incomplete, and a small portion of monoglyceride and diglyc-
eride remains in the end [9,10].
4. Conclusions
The activation energies of transesterification reactions of various
triglycerides were calculated by Gaussian software to clarify the
mechanism. The values show that the effects of the structure of
the triglyceride on the reactivity are not particularly large. More-
over, formation of the fatty acid alkyl ester by the addition of an alk-
oxy group was considered by the activation energy. Ring formation
involving the carbon of the carboxyl group and the alkoxy group at
the transition state is essential for the transesterification reaction.
Finally, the transesterification reaction was analyzed in detail. Ide-
ally, the center ester bond in the triglyceride is transesterified before
the outside ester bonds. Transesterification of monoglycerides and
diglycerides is more difficult than for triglycerides by activation en-
ergy and ESP obtained from quantum computational chemistry.
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