Fuel 140 (2015) 724730

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

Determination of the kinetics of biodiesel saponication in alcoholic

hydroxide solutions
Valentine C. Eze, Adam P. Harvey, Anh N. Phan
School of Chemical Engineering & Advanced Materials (CEAM), Newcastle University, NE1 7RU, UK

h i g h l i g h t s
 Quantitatively investigated kinetics of fatty acid alkyl esters saponication in alcoholic hydroxides.
 FAME saponication occurred 57 times more rapidly in ethanol than in methanol.
 Found actual saponication rate constants for the methanolKOH and ethanolKOH.
 Found activation energies for the FAME saponication in the alcoholic hydroxides.
 Provided useful data in understanding/modelling base-catalysed transesterication reactions.

a r t i c l e

i n f o

Article history:
Received 8 July 2013
Received in revised form 18 September
2014
Accepted 1 October 2014
Available online 18 October 2014
Keywords:
Kinetics
Transesterication
FAME Saponication
Rate constants
Hydroxide-alkoxide equillibrium

a b s t r a c t
The research focused mainly on kinetics of the side reactions occurring during homogeneous basecatalysed transesterication processes, which were not studied previously. The rates of fatty acid methyl
esters (FAME) saponication with sodium and potassium hydroxides were investigated in methanol and
ethanol (commonly used in biodiesel production) at temperatures of 40, 50 and 60 C. The effect of water
on the rate of FAME saponication in the alcoholic hydroxide solutions was also studied (at 60 C). The
apparent rate constants of FAME saponication were strongly inuenced by the types of alcohol, but little
affected by variation of the metal hydroxides. The apparent rate constants for FAME saponication using
the ethanol hydroxides were 57 times higher than for methanol hydroxides. This was due to the lower
acidity of ethanol, leading to a higher concentration of hydroxide ions in the ethanolhydroxide solutions. The rate constant of the FAME saponication increased with temperature. For example, it was
1.31 L mol1 min1 at 40 C, but 3.08 and 5.63 L mol1 min1 at 50 and 60 C in the methanolNaOH solution. Arrhenius activation energies for the FAME saponication in the alcoholic hydroxides were in the
range of 60.364.0 kJ mol1. It was found that the FAME saponication rate in ethanolhydroxides was
3.5 times higher than that in methanolhydroxides in the presence of water. This indicates that use of
methanol should be preferred over ethanol in alkali-catalysed transesterication, as the amount of soap
produced by saponication of triglycerides and alkyl esters will be lower.
Crown Copyright 2014 Published by Elsevier Ltd. All rights reserved.

MG ROH $ AE GL

1. Introduction
Transesterication of triglycerides with alcohols with/without
catalyst is one method for producing biodiesel, a renewable alternative to diesel. It proceeds via three reversible stepwise reactions
[1,2] as follows

TA ROH $ AE DG

DG ROH $ AE MG

Corresponding author. Tel.: +44 0191 208 5212.

E-mail address: anh.phan@ncl.ac.uk (A.N. Phan).
http://dx.doi.org/10.1016/j.fuel.2014.10.001
0016-2361/Crown Copyright 2014 Published by Elsevier Ltd. All rights reserved.

Overall reaction:

TG 3ROH $ 3AE GL

(TG: triglyceride; DG: diglyceride; MG: monoglyceride; GL:

glycerol; ROH: alcohol; AE: alkyl esters).
In alkali-catalysed homogeneous transesterications, hydroxides and methoxides of sodium and potassium are commonly used.
In a hydroxide-catalysed transesterication process, alongside
three main transesterication steps (Eqs. (1)(3)), there can also
be saponication of the oil (TG) and the alkyl esters (AE) (Eqs. (6)
and (7)) to form soap. This occurs alongside the main reactions
due to the existence of the hydroxide-alkoxide equilibrium (Eq.

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V.C. Eze et al. / Fuel 140 (2015) 724730

CH3 CH2 OH + KOH CH3 CH2 OK + H2 O

(5)). This equilibrium shifts towards the formation of hydroxide

when the water content is increased. The formation of soap leads
to emulsication, which renders the downstream separation of
glycerol very difcult. The deleterious effect of water means that
in practice transesterication is limited to very dry (<0.5 wt% moisture) vegetable oils.
K eq

ROH OH $ RO H2 O

TG 3OH ! 3Soap GL

AE OH ! Soap ROH

Fig. 2. EthanolKOH reaction.

The depletion of metal hydroxide in a saponication mixture

containing alcohol where carboxylic acid esters were saponied
using 0.10.5 M NaOH prepared in approximately 9:1 (v/v) of CH2Cl2/methanol was reported [7]. The presence of sodium methoxide
formed by the reaction of NaOH with methanol lead to the transesterication of the original esters to form methyl ester [7]. However, the authors explained these results due to hydroxide ions
assisted bimolecular collisions of methanol and the original
esters.
Furthermore, the magnitudes of activation energies for alkyl
esters saponication indicate that the differences in the desolvation energies of the OH in aqueous/protic and aprotic solvents
was not entirely responsible for the higher rates of alkyl esters
saponication in dipolar aprotic co-solvents. For instance, the
Arrhenius activation energies of 41.4063.18 kJ mol1 [3,5,6,11]
for alkyl esters saponication in aqueous/protic medium were
too small to account for the desolvation energy of 423.4 kJ mol1
[9] required for the desolvation of OH in the aqueous medium.
The values of the activation energies for alky esters saponication
suggest that the direct collision of desolvated OH ions is
implausible.
Although extensive research on the kinetics of alkaline hydrolysis of esters has been done, no study has been carried out on the
kinetics of fatty acid alkyl esters saponication in alcohol hydroxides. Such investigation is essential to understanding the competitive saponication of biodiesel produced during alkali-catalysed
homogeneous transesterication. As methanol and ethanol are
commonly used for the biodiesel production, kinetic studies of
saponication of fatty acid alkyl esters (biodiesel) in these alcoholic media provide fundamental in choosing alcohol and/or operating conditions to achieve high yield and quality product. In this
study, the kinetics of fatty acid methyl esters (FAME) saponication in both methanolhydroxide and ethanolhydroxide solutions
of NaOH and KOH at a temperature range of 4060 C were investigated. These conditions are similar to those used in commercial
homogeneously catalysed biodiesel processes. The effect of water
on the rate of the FAME saponication in the alcoholic NaOH and
KOH solutions was also studied.

Saponication of alkyl esters can occur in aqueous hydroxide

solutions [3], mixtures of water and soluble organic solvents, such
as dimethyl sulphoxide (DMSO) [4], ethanol [5,6] and mixtures of
protic solvents, e.g. methanol and dichloromethane [7]. It has been
reported that saponication of carboxylic acid esters in hydroxide
solutions is a bimolecular reaction, which is rst order for ester and
hydroxide ions [3,8]. Hydroxide ions attack the carbonyl to form a
tetrahedral intermediate, which then decomposes to the products
(Fig. 1a). However, recent studies [7,9] found that the reactions
did not occur via simple bimolecular collisions, but rather required
a molecule of water to form the tetrahedral intermediate. This indicates that a water molecule stabilises the transition-state complex
through hydrogen bonding (Fig. 1b). Such hydrogen bonding could
also be provided by other protic solvents such as simple alcohols.
The rate of saponication of alkyl esters was strongly dependent on steric and electronic interactions of the esters and metal
hydroxides with the solvent [7]. Such interactions determine the
rate of saponication in various solvent environments. For
instance, the hydroxide anions are highly solvated because of the
electronic charge in a predominantly aqueous and protic solvent
environment. The solvation of the OH anions reduces the rate of
direct collisions between the anions and the alkyl ester molecules
in the solution [10]. This phenomenon was used to explain the
higher rate of saponication of esters in 0.5 M KOH prepared in
8090% (v/v) DMSO in water than that of 0.5 M KOH prepared in
8090% (v/v) ethanol in water [4]. 63.5% of the ester was saponied
in a 0.5 M KOH solution prepared in 83.5% (v/v) aqueous DMSO,
whereas only 9.2% was saponied in a 0.5 M KOH prepared in
83.5% (v/v) aqueous ethanol after 3 min at the same conditions.
However, the differences in the rates of saponication of the esters
in 0.5 M KOH prepared in 83.5% (v/v) aqueous DMSO and 0.5 M
KOH prepared in 83.5% (v/v) aqueous ethanol were not entirely
due to the reduction in the desolvation energy of the OH in the
aqueous DMSO solution. The authors did not take into account
the reactions of the KOH with ethanol to form potassium ethoxide
(Fig. 2), which reduces the amount of KOH in the solutions and
consequently lowering the rate of saponication.

2.1. Materials
Rened RSO (Henry Colbeck, UK) used in production of the
FAME contained approximately 98.7 wt% triglycerides, 0.03 wt%

OH

(a)

2. Materials and methods

OR'

O
(b)

OR'

OH

OR'

O-

+ R'OH

OR'
+

O
H

C
O

O
-

H
O

O- + R'OH + H2O

O
H

Fig. 1. Saponication of alkyl esters (a) reaction mechanism for alkyl esters saponication; (b) bimolecular collision by solvated hydroxide ions to form H-bond stabilised
tetrahedral intermediate.

726

V.C. Eze et al. / Fuel 140 (2015) 724730

moisture and 0.05 wt% free fatty acids. The measured oils viscosity
and density at 60 C were 25.5 mPas and 890 kg/m3 [12].
Fatty acid methyl esters (97.85 wt% purity), known as FAME,
were obtained via a continuous alkaline catalysed transesterication process at a molar ratio of methanol to rapeseed oil of 6:1,
reaction temperature of 60 C as described in previous studied
[12]. FAME consisted mainly of esters of oleic acid (63.2%), linoleic
acid (19.8%), linolenic acid (8.6%) and less than 10 wt% of others
(palmitic acid: 5.3%, stearic acid: 1.7% and icosenoic acid: 1.4%).
Sodium hydroxide (97% purity), potassium hydroxide (90%
purity), methanol (99.8% purity), hydrochloric acid (36.538.0%
purity), potassium hydrogen phthalate (99.5% purity) and other
analytical standard chemicals such as methyl heptadecanoate
(99.0% purity), methyl oleate (99.0% purity) were purchased from
SigmaAldrich. Ethanol (99.99% purity) was obtained from Fisher
Scientic.

0.25 mm diameter BPX70 CP wax capillary column. The oven temperature was set at 210 C (isothermal) while the injector and FID
detector temperatures were set at 250 and 260 C, respectively.
The amounts of FAME in the samples were quantied using the
British standard for quantication of FAME content (BS EN
14103: 2003). Errors in FAME analysis were 1.3%. The FAME
saponication experiments at 60 C using methanolKOH were
repeated three times for reproducibility (errors less than 1.6%).
Conversion of the FAME (0.012) to soap was calculated as follows:

FAME conversion to soap X: X

Wo  Wt
Wo

(wt: weight fraction of FAME in the sample; wo: weight fraction of

FAME at zero saponication).
3. Results and discussion

2.2. Experimental methods

FAME was dried in oven for 12 h at 105 C to remove all water.
The dried FAME was then saponied with 0.5 M NaOH (or KOH) in
alcoholic solutions using a 100 ml three-neck jacketed glass reactor connecting to a water condenser and a thermocouple for monitoring reaction temperature as shown in Fig. 3.
Approximately 75 ml of 0.5 M alcoholic hydroxide solution was
heated in the reactor to the desired temperature of 40, 50 or 60 C
by circulating hot water inside the jacket. As soon as the desired
temperature reached, 6 g of pre-heated FAME was transferred into
the reactor and mixed vigorously using a magnetic stirrer. The ratio
of FAME and hydroxide alcohol solution (w/v) in this study was
adapted from the saponication procedure of fats and oils [13].
The same procedure was also used to obtain the weight percentage
of FAME in alcohol solution in absence of hydroxide without
saponication (Wo).
About 0.5 ml of the reaction sample was collected using a
1000 lm micropipette at various time intervals for 60 min. The
sample was transferred into a pre-weighed 2 ml vial containing
0.5 ml HCl (0.5 M) to quench the reaction immediately. All the
samples were stored in a freezer for further analysis.
2.3. Analysis
FAME content in the sample collected during the experiments
were analysed using a 5890 Hewlett Packard Series II gas chromatography (GC) equipped with a 30 m length, 0.25 lm thickness and

Condenser

Sampling port
3-neck glass
jacketed reactor

Magnetic stirrer

Fig. 3. Experimental set-up for FAME saponication.

3.1. Effect of alcohols and alkali on the rates of the FAME

saponication
Fatty acid alkyl esters saponication is an undesired reaction
during alkali-catalysed transesterication, as it hinders the separation process, reduces yield and reduces the quality of the raw biodiesel product. As presented in Table 1, KOH has a stronger effect
on the saponication of FAME than NaOH in methanol solution.
For instance, at 60 C reaction temperature, the FAME conversion
was 0.06 for KOH, but was only 0.03 for NaOH after 2 min. The
nding in this study was similar to others [14], who reported that
saponication was much faster for KOH than for NaOH. The difference became smaller when the reaction time was above 30 min.
Generally, the effect of temperature and reaction time on the
saponication of FAME was similar for both metal hydroxides.
Increasing the reaction temperature increased the rate of conversion of FAME into soap, e.g. the conversion was 0.14 at 40 C but
0.34 at 60 C for methanolNaOH at 30 min reaction time.
Because of the similarity of KOH and NaOH as shown in the
Table 1, the following discussion only focuses on the effect of the
alcoholic hydroxides of the potassium solutions. As shown in
Fig. 4, the conversion of the FAME to soap at the reaction times
of 030 min was 4 times faster for ethanolhydroxide solutions
than for methanolhydroxide solutions for all tested reaction temperatures. For example, the FAME conversion was 0.1 for methanolKOH, but 0.43 for ethanolKOH at 50 C and 10 min reaction
time (Fig. 4(b)). At 60 C, the conversion was 0.36 for methanol
KOH but was 0.86 for ethanolKOH after 30 min reaction time
(Fig. 4(c)). This agreed well with other ndings which the amount
of soap formation in both ester-rich phase and glycerine-rich phase
was 3.5 times higher when using ethanol than when using methanol for alkaline catalysed transesterication [14]. Menegheti et al.
[17] obtained higher fatty acid alkyl esters conversion and lower
soap formation when using methanol than ethanol. The higher
rates of saponication in the ethanolhydroxide systems accounts
for the lower ester contents in the ethanolysis.
The higher conversions of the FAME to soap obtained for ethanolKOH in the Fig. 4 can be explained by the existence of more
hydroxide ions (OH) in the ethanolKOH than in the methanol
KOH due to the stronger acidity of methanol than ethanol (4.4 times
higher), which will be discussed later in detail (Section 3.3). As a
result, the formation of methoxide ions (CH3O) is more favourable
in a methanolKOH system, resulting in less free hydroxide ions
(OH) for the FAME saponication, than that of ethoxide ions
(C2H5O) in an ethanolKOH system. Therefore, the higher rates
of FAME saponication in the ethanolKOH solution was as a result
of higher amount of available hydroxide ions concentration in the
solution. This study provided a full explanation about the reduction

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V.C. Eze et al. / Fuel 140 (2015) 724730

Table 1
Effect of sodium hydroxide and potassium hydroxide in methanol on the conversion of FAME into soap at temperatures of 40 C, 50 C and 60 C.
Temperature, C

Conversion of FAME into soap (X)

0.5 M NaOH solution prepared in 99.8% methanol

0.5 M KOH solution prepared in 99.8% methanol

Reaction time (min)

60 C

50 C

40 C

60 C

50 C

40 C

0
0.5
2
5
10
20
30
40
50
60

0.00
0.01
0.03
0.10
0.16
0.26
0.34
0.40
0.47
0.53

0.00
0.00
0.04
0.04
0.12
0.19
0.26
0.30
0.34
0.38

0.00
0.00
0.02
0.04
0.07
0.11
0.14
0.17
0.20
0.23

0.00
0.01
0.06
0.14
0.20
0.30
0.36
0.42
0.50
0.53

0.00
0.01
0.04
0.06
0.14
0.20
0.27
0.32
0.38
0.40

0.00
0.00
0.01
0.05
0.08
0.10
0.16
0.19
0.22
0.24

1.0

(a) 40oC

1.0

Methanol solution
Ethanol solution

0.6
0.4

0.6
0.4
0.2

0.2
0.0

Methanol solution
Ethanol solution

0.8

Soap formation

Soap formation

0.8

(b) 50oC

10

20

30

40

50

0.0

60

10

Reaction time (mins)

1.0

(c) 60oC

30

40

50

60

Methanol solution
Ethanol solution

0.8

Soap formation

20

Reaction time (mins)

0.6
0.4
0.2
0.0

10

20

30

40

50

60

Reaction time (mins)

Fig. 4. FAME saponication in 0.5 M alcoholKOH solutions at a molar ratio of FAME to KOH of 1:1.85 and reaction temperatures of (a) 40 C, (b) 50 C and (c) 60 C.

of fatty acid alkyl esters in alkali-catalysed biodiesel production

with methanol [12,15,16] and with ethanol [14,17] at greater
reaction times, particularly at high catalyst concentrations.
Previously this has been either explained qualitatively
[12,14,16,17] or wrongly attributed to increased reverse transesterication [15].
Menegheti et al. [17] and Mendow et al. [14] also observed that
more soap formation and consequently less yield of fatty acid alkyl
esters was obtained in the ethanolysis of sunower oil than the
methanolysis. An explanation for the increase in saponication
rate was due to higher solubility of the hydroxide catalyst in the
oil-ethyl esters phase than in the oil-methyl esters phase [14].
However, the results in this study indicate that the higher rate of
saponication in ethanol than that in methanol is due to higher
amount of hydroxide ions (OH). This suggests that the choice of
alcohol for homogeneous alkali-catalysed biodiesel process must

be restricted to short chain alcohols. The longer chain (higher

molecular weight) alcohols such as propanol and butanol contain
even more mole fractions of hydroxide ions in the alcoholic
hydroxide solution, which accelerate saponication reactions of
the biodiesel. Therefore, in order to minimise saponication reactions, methanol must be chosen in homogeneous alkali-catalysed
transesterication. In addition, fatty acid methyl esters have lower
viscosity than other alkyl esters produced from ethanol and longer
chain alcohols [18].
3.2. Kinetics of fatty acid methyl esters (FAME) saponication in the
alcoholic bases
Kinetic studies of the fatty acid alkyl esters saponication in
association with biodiesel production have not been reported in
literature. The aim of this section is to explain quantitatively the

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V.C. Eze et al. / Fuel 140 (2015) 724730

reduction in fatty acid alkyl esters in homogeneously alkalicatalysed biodiesel production at various reaction times and
catalyst concentrations.
The saponication rate of FAME in an alcoholic hydroxide solution was analysed based on bimolecular collisions of the metal
hydroxide and FAME, with FAME as the limiting reactant [3,8,9].
The saponication rate of FAME in alcoholic hydroxide solution
can be written as:

dX ME
kbdt
1  X ME hB  X ME

Integrating Eq. (9):



1
hB  X ME
0
kbt k t
 ln
hB  1MEo
hB 1  X ME

10

Eq. (10) could be simplied as:

0

A  lnB k t
where k = kb is the apparent saponication rate constant (L mol1
min1), k is actual saponication rate constant (L mol1 min1), b
is mole fraction of unreacted metal hydroxide in the alcoholic
hydroxide solutions, ME is Fatty acid methyl esters, [ME]o is initial
concentration of FAME, (mol/L), XME is conversion of FAME to soap,
hB is the ratio of the initial concentration of alcoholic hydroxide
solutions to FAME.
The apparent rate constants for the saponication of FAME at
temperatures of 40, 50 and 60 C were determined using Eq. (10)
and the experimental data obtained from Table 1 and Fig. 4. The
correlation coefcients (R2) of all the plots used to estimate the rate
constants were more than 0.99. There was a linear relationship
between the saponication rate constants and temperature for all
the tested temperatures. As shown in Table 2, the apparent rate
constants (k0 ) increased approximately a factor of 2 for every
10 C increase in the temperature, e.g. it increased from
0.0536 L mol1 min1 at 40 C to 0.114 L mol1 min1 at 50 C and
0.2152 L mol1 min1 at 60 C for the ethanolpotassium hydroxide solution. This indicates that the saponication of the fatty acid
alkyl esters is an endothermic reaction. The difference in the apparent FAME saponication rate constants between NaOH and KOH
was small, e.g. the apparent rate constant was 0.105 L mol1 min1
for the ethanolNaOH and 0.114 L mol1 min1 for ethanolKOH at
50 C reaction temperature (8% difference), but signicant between
methanol and ethanol. The apparent rate constant for FAME saponication was 57 times higher for the ethanolhydroxide than for
the methanolhydroxide. This was due to more hydroxide ions
available in the ethanolhydroxide solution than in the methanolhydroxide solution as explained above.

R0 OH  OH
R0 O H2 O

The amount of hydroxide ions available for the saponication of

FAME is a fraction of the original hydroxide dissolved in the alcohol. Caldin and Long [19] reported that the hydroxide ion fraction
available in the 0.5 M ethanolsodium hydroxide at 25 C was
0.037. This hydroxide ion fraction was assumed to be same for
the 0.5 M ethanolpotassium hydroxide at the same condition. In
this study, the hydroxide ion fraction of 0.037 was used to estimate
the actual rate constants for the FAME saponication in the ethanolhydroxides. The actual rate constants of the FAME saponication in the methanolhydroxides were calculated based on the
relative acidity of ethanol and methanol, e.g. methanol was 4.4
times more acidic than ethanol at 26 C [21]. The estimated relative apparent saponication rate constants of ethanolhydroxides
to methanolhydroxides were 5.396, 5.423 and 6.938 at 40, 50
and 60 C, respectively. These corresponded to 0.0069, 0.0068
and 0.0053, mole fractions hydroxide ions in the methanol
hydroxide solutions at 40, 50 and 60 C. Table 3 shows the actual
rate constants of the FAME saponication in the alcoholic hydroxide solutions using these hydroxide ions fractions.
The actual FAME saponication rate constants (k) were independent of both alcohol and metal hydroxide but depended on
temperatures as shown in Table 3. The Arrhenius activation energies of the FAME saponication ranged from 60 to 64 kJ mol1,
within the range reported in the literature for alkyl esters saponication [3,5,6].
The actual saponication rate constants for the ethyl acetate,
ethyl propanoate and ethyl laurate esters in the Table 4 were calculated using the data from Caldin and Long [19] for sodium
hydroxideethoxidewater solution and the apparent rate constant for the saponication in 85 wt% aqueous ethanol [5,6]. As
listed in Table 4, the alkyl ester saponication rate constants are
strongly dependent upon the carboxylic acid chain length. The
saponication rates constants at 50 C (55 C) were 8.07 L mol1
min1 for acetic acid ester, 4.10 L mol1 min1 for propanoic acid
ester and 3.17 L mol1 min1 for lauric acid ester.
3.4. Effect of water in the alcoholic hydroxide solutions on FAME
saponication

When a metal hydroxide is dissolved in an alcoholic solution,

there exists an equilibrium between hydroxide and ethoxide ions
as shown below:

Anhydrous ethanol (99.99% purity) and methanol (99.8% purity)

were used in order to determine the effect of alkaline catalysts on
the saponication of FAME during transesterication, and to evaluate the effect of water on the saponication. The results for the
FAME saponication at a reaction temperature of 60 C using alcoholic hydroxide solutions containing 010% (v/v) of water in the
alcohols, are presented in the Figs. 5 and 6.
Figs. 5 and 6 clearly show that water accelerates the rates of
FAME saponication. For instance, at 2 min reaction time, the
FAME conversions to soap in the methanolhydroxides increased
rapidly from 0.03 to 0.10, 0.17 and then to 0.21 for the methanolNaOH; and from 0.06 to 0.13, 0.19 and to 0.26 for the methanolKOH when the water content rose from 0% to 2, 4 and 10 vol%
(Fig. 5). The rapid increase in the FAME conversion to soap in the

Table 2
Apparent rate constants (k0 ) for the methyl esters saponication in 0.5 M alcoholic
hydroxide solutions at various temperatures (L mol1 min1).

Table 3
Actual rate constants (k) and activation energy (Ea) for the saponication of FAME in
0.5 M alcoholic hydroxide solutions at various temperatures (L mol1 min1).

3.3. The hydroxidealkoxide equilibrium for the alcoholic solutions of

the NaOH and KOH

Solution

MethanolNaOH
MethanolKOH [20]
EthanolNaOH
EthanolKOH

k0 (L mol1 min1)

Solution

40 C

50 C

60 C

0.0090
0.0099
0.0484
0.0536

0.0208
0.0195
0.1050
0.1140

0.0300
0.0316
0.2120
0.2152

MethanolNaOH
MethanolKOH [20]
EthanolNaOH
EthanolKOH

k (L mol1 min1)
40 C

50 C

60 C

1.313
1.444
1.308
1.449

3.078
2.921
2.838
3.081

5.626
5.926
5.723
5.816

Activation energy (kJ mol1)

61.73
61.16
64.01
60.26

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V.C. Eze et al. / Fuel 140 (2015) 724730

Table 4
Comparison of the kinetic parameters for the FAME saponication with that reported in the literature for other alkyl esters.
k (L mol1 min1)
40 C

50 C

3.88
1.98
1.57 @ 45 C
1.44
1.31
1.31
1.45

8.07
4.10
3.17 @ 55 C
2.92
3.08
2.84
3.08

presence of water is due to the reaction of the water with alkoxide

ions in the hydroxidealkoxide equilibrium (Eq. (4)), producing
more hydroxide ions, by Le Chateliers principle. The rate of the
FAME saponication in methanolhydroxide (Fig. 5) was again
below that of the ethanolhydroxide shown in Fig. 6, because
methanol has a higher acidity than ethanol [21], resulting in fewer
hydroxide ions being available for saponication. As shown in
Table 5, the apparent rate constants of the FAME saponication
increased with increasing water content, e.g. from 0.03 to
0.399 L mol1 min1 for methanolNaOH and from 0.212 to
1.494 L mol1 min1 for the ethanolNaOH, when the water content rose from 0 to 10 vol%. This corresponds to an increase in
the apparent rate constants by factors of 3.7% and 12.7% per unit
increase in the vol% water in the alcohol for the methanolNaOH
and ethanolNaOH, respectively. The deleterious effects of water
on alkali-catalysed homogeneous transesterication can be fully
inferred from this study. The increased hydroxide ions concentration in the presence of water leads to the saponication of both
glycerides and fatty acid alkyl esters (biodiesel). Soap formation
due to the saponication of glyceride and biodiesel reduces the
biodiesel yield, and causes emulsication, which adversely affects
glycerol separation unit operations in the downstream processing
[22,23]. To minimise such reactions, anhydrous reactants must
be used for the reactions. Some studies suggest that reactants that
contain some moisture (less than 0.3 wt%) can be used in the basecatalysed homogeneous transesterication [24], such process
achieves less biodiesel conversions due to the increased triglyceride and biodiesel saponication in the presence of water.
The actual rate constants (k) for the FAME saponication were
expected to be similar at the xed reaction temperature of 60 C.
The increases in the apparent rate constants (k0 ) when increased
water content in Table 5 are plainly due to the increase in the mole

FAME conversion to soap

References

61.50
61.50
63.18
61.16
61.73
64.01
60.26

Smith and Levenson [6]

Smith and Levenson [6]
Levenson and Smith [5]
Eze et al. [20]
This study
This study
This study

0.8

0.6

0.4

Ethanol-NaOH solution
0% (v/v)
2% (v/v)
4% (v/v)
10% (v/v)

0.2

0.0

10

15

0.8

20

25

30

35

30

35

Time (mins)
1.0

0.8

0.6

0.4

Ethanol-KOH solution
0% (v/v)
2% (v/v)
4% (v/v)
10% (v/v)

0.2

1.0

0.0

10

15

20

25

Time (mins)

0.6

Fig. 6. Effect of water level on FAME saponication in 0.5 M solutions of ethanol

NaOH and ethanolKOH at a molar ratio of FAME to hydroxide of 1:1.85, 60 C.

0.4
0% (v/v)
2% (v/v)
4% (v/v)
10% (v/v)

0.2

0.0

Ea (kJ mol1)

1.0

FAME conversion to soap

Ethyl acetate and 0.05 M NaOH in aqueous ethanol

Ethyl propanoate and 0.05 M NaOH in aqueous ethanol
Ethyl laurate and 0.05 M NaOH in aqueous ethanol
FAME and 0.5 M methanolKOH
FAME and 0.5 M methanolNaOH
FAME and 0.5 M ethanolNaOH
FAME and 0.5 M ethanolKOH

FAME conversion to soap

Alkyl esters and the saponication media

10

20

30

40

50

60

70

Time (mins)
Fig. 5. Effect of water level on FAME saponication in 0.5 M solutions of methanol
NaOH at a molar ratio FAME to hydroxide of 1:1.85, 60 C.

fractions (b) of the hydroxides (k0 = kb). The actual rate constants
for the fatty acids alkyl esters saponication at the various water
contents, calculated using the hydroxidealkoxide equilibrium in
the Eq. (4), were consistent with the values in the Table 3. For
instance, the actual rate constants for the FAME saponication
were 5.808 L mol1 min1 at 2% (v/v) water, 5.942 L mol1 min1
at 4% (v/v) water and 5.598 L mol1 min1 at 10% (v/v) water, for
the saponication of FAME in 0.5 M NaOHmethanol solutions
containing various levels of water.

730

V.C. Eze et al. / Fuel 140 (2015) 724730

Table 5
Apparent rate constants (k0 ) for fatty acid alkyl saponication at 60 C using alcoholic hydroxide solutions with various vol% water concentrations in the alcohols (L mol1 min1).
Alkyl esters in alcoholic solutions

FAME in 0.5 M NaOHmethanol

FAME in 0.5 M KOHmethanol [20]
FAME in 0.5 M NaOHethanol
FAME in 0.5 M KOHethanol
Ethyl laurate in 0.05 M NaOHethanol [5]
a

k0 (L mol1 min1)
0% (v/v)

2% (v/v)

4% (v/v)

10% (v/v)

0.0300
0.0316
0.2120
0.2152

0.116
0.104
0.517
0.464

0.198
0.175
0.768
0.647

0.399
0.344
1.494
1.340
1.122a

Calculated for 12 vol% water and 55 C reaction temperature.

4. Conclusion

References

The kinetics of fatty acid methyl esters (FAME) saponication

with sodium and potassium hydroxides (NaOH and KOH) in methanol and ethanol solutions were studied over the range 4060 C.
This is similar to the range used in commercial biodiesel production. This study provides for a clear understanding of the saponication side reactions occurring in homogeneous base-catalysed
transesterication processes.
FAME saponication occurred 57 times more rapidly in ethanolhydroxide than in methanolhydroxide solutions. This was
attributed to the greater availability hydroxide ions in the ethanolhydroxide solution than in the methanolhydroxide solution,
as a result of the lower acidity of the ethanol. However, the actual
rate constants for the FAME saponication in the 2 alcoholic
hydroxides were similar. For instance, the apparent FAME saponication rate constants at 60 C were 0.032 L mol1 min1 for the
methanolKOH and 0.215 L mol1 min1 for the ethanolKOH;
whereas the estimated actual saponication rate constants were
5.93 L mol1 min1 and 5.82 L mol1 min1, for the methanol
KOH and ethanolKOH, respectively. Arrhenius activation energies
for the FAME saponication in the alcoholic hydroxides were in the
range 60.2664.01 kJ mol1. This is the rst time that thorough and
quantitative investigation has been carried out on the kinetics of
fatty acid alkyl esters saponication in alcoholic hydroxides.
Hence, these kinetic studies provide useful data in understanding
and modelling homogeneous base-catalysed transesterication
reactions. Previously, only qualitative explanations were given to
account for the saponication side reactions during the basecatalysed transesterication processes. Based on the ndings in
this study, it is recommended that methanol should be chosen in
preference to ethanol in homogeneous base-catalysed transesterications, to increase the yield and purity of biodiesel produced, as
its use results in signicantly lower rates of saponication.
In base-catalysed transesterication processes, triglyceride and
biodiesel saponication occurs in the presence of water, which
may lead to emulsication. Anhydrous reactants are, therefore, recommended for homogenous alkali-catalysed biodiesel production.
The increased rates of FAME saponication with increasing
water content of the alcohol can be used for rapid quantitative
determinations of saponication values of esters. Furthermore,
the trend of increasing hydroxide ion concentration, and therefore
saponication rate, with increasing alcohol chain length suggests
that longer chain alcohols, such as propanol, may be used for rapid,
quantitative determinations of the saponication values of esters
and vegetable oils.

[1] Bambase ME, Nakamura N, Tanaka J, Matsumura M. Kinetics of hydroxidecatalyzed methanolysis of crude sunower oil for the production of fuel-grade
methyl esters. J Chem Technol Biotechnol 2007;82:27380.
[2] Darnoko D, Cheryan M. Kinetics of palm oil transesterication in a batch
reactor. J Am Oil Chem Soc 2000;77:12637.
[3] Das K, Sahoo P, Sai Baba M, Murali N, Swaminathan P. Kinetic studies on
saponication of ethyl acetate using an innovative conductivity-monitoring
instrument with a pulsating sensor. Int J of Chem Kinet 2011;43:64856.
[4] Vinson JA, Fritz JS, Kingsbury CA. Quantitative determination of esters by
saponication in dimethyl sulphoxide. Talanta 1966;13:16737.
[5] Levenson HS, Smith HA. Kinetics of the saponication of the ethyl esters of
several phenyl substituted aliphatic acids. J Am Chem Soc 1940:23247.
[6] Smith HA, Levenson HS. Kinetics of the saponication of the ethyl esters of
normal aliphatic acids. J Am Chem Soc 1939;61:11725.
[7] Theodorou V, Skobridis K, Tzakos AG, Ragoussis V. A simple method for the
alkaline hydrolysis of esters. Tetrahedron Lett 2007;48:82303.
[8] Price CC, Michel RH. Rates of saponication of substituted ethyl 2-naphthoates.
J Am Chem Soc 1952;74:36527.
[9] Mata-Segreda JF. Hydroxide as general base in the saponication of ethyl
acetate. J Am Chem Soc 2002;124:225962.
[10] Matta MS, Toenjes AA. Solvation effects on the alkaline hydrolysis of some
p-nitrophenyl esters. J Am Chem Soc 1985;107:75916.
[11] Schneider MA, Stoessel F. Determination of the kinetic parameters of fast
exothermal reactions using a novel microreactor-based calorimeter. Chem Eng
J 2005;115:7383.
[12] Phan AN, Harvey AP, Eze V. Rapid production of biodiesel in mesoscale
oscillatory bafed reactors. Chem Eng Technol 2012;35:121420.
[13] Firestone D. Ofcial methods and recommended practices of the American Oil
Chemists Society. 5th ed. Champaign, Illinois: AOCS Press; 1998.
[14] Mendow G, Veizaga NS, Querini CA. Ethyl ester production by homogeneous
alkaline transesterication: inuence of the catalyst. Bioresource Technol
2011;102:638591.
[15] Darnoko D, Cheryan M. Continuous production of palm methyl esters. J Am Oil
Chem Soc 2000;77:126972.
[16] Keera ST, El Sabagh SM, Taman AR. Transesterication of vegetable oil to
biodiesel fuel using alkaline catalyst. Fuel 2011;90:427.
[17] Meneghetti SMP, Meneghetti MR, Wolf CR, Silva EC, Lima GES, de Lira Silva L,
et al. Biodiesel from castor oil: a comparison of ethanolysis versus
methanolysis. Energ Fuels 2006;20:22625.
[18] Knothe G. Analyzing biodiesel: standards and other methods. J Am Oil Chem
Soc 2006;83:82333.
[19] Caldin EF, Long G. The equilibrium between ethoxide and hydroxide ions in
ethanol and in ethanolwater mixtures. J Chem Soc 1954:373742.
[20] Eze VC, Phan AN, Harvey AP. A more robust model of the biodiesel reaction,
allowing identication of process conditions for signicantly enhanced rate
and water tolerance. Bioresource Technol 2014;156:22231.
[21] Reeve W, Erikson CM, Aluotto PF. A new method for the determination of the
relative acidities of alcohols in alcoholic solutions: the nucleophilicities and
competitive reactivities of alkoxides and phenoxides. Can J Chem
1979;57:274754.
[22] Demirbas A. Biodiesel production from vegetable oils via catalytic and noncatalytic supercritical methanol transesterication methods. Prog Energ
Combust 2005;31:46687.
[23] Demirbas A. Progress and recent trends in biodiesel fuels. Energ Convers
Manage 2009;50:1434.
[24] Freedman B, Pryde EH, Mounts TL. Variables affecting the yields of fatty esters
from transesteried vegetable oils. J Am Oil ChemSoc 1984;61:163843.