SONOCHEMISTRY

ELSEVIER

Ultrasonics Sonochemistry 5 (1998) 7 12

Ultrasound assisted PTC catalyzed saponification of

vegetable oils using aqueous alkali
B.S. Bhatkhande, S.D. Samant *
Organic Chemistry Laboratory, Chemistry Division, UniversityDepartment of Chemical Technology, N.M. Parikh Marg, Matunga,
Mumbai-400019, India
Received 1 May 1997; received in revised form 16 September 1997

Abstract

A few vegetable oils were saponified using aqueous KOH and different PTCs at room temperature in the presence of ultrasound.
The extent of saponification was studied using the saponification value as a reference. Optimizations of various parameters such
as time, selection of PTC, quantity of PTC, quantity of KOH and quantity of water were carried out using soyabean oil as a
sample oil under sonication with stirring. To study the effect of ultrasound, the saponification was also carried out at 35_+2C
under different conditions, namely stirring, sonication, stirring and sonication, and heating at 100C. It was found that the
heterogeneous liquid-liquid phase saponification of different vegetable oils using aq. KOH/CTAB was remarkably accelerated at
35 +2C in the presence of ultrasound along with stirring. 1998 Elsevier Science B.V. All rights reserved.

Keywords: Vegetable oils; Phase transfer catalyst; Alkaline saponification; Ultrasound

1. Introduction

Saponification of oils and fats is a commercially

important heterogeneous unit process which is not only
used for the preparation of soaps, but also for the
preparation of commercially important fatty acid salts.
In recent years we have witnessed the development of
novel synthetic methodologies to circumvent the problems associated with classical heterogeneous thermal
reactions. Among these techniques are turbulenceinduced saponification of ethyl palmitate [1], enzyme
catalyzed hydrolysis of animal fats [2], high pressure
hydrolysis of fats [3], superheated steam hydrolysis of
fats [4] and the hydrolysis of oils using hydrodynamic
cavitation [5].
The use of ultrasound in organic synthesis has distinct
advantages, such as reduction in steps of the synthesis
facilitating one pot synthesis, reduction in time of the
reaction, allowing use of laboratory grade reactants and
reagents, and the reduction in the reaction temperature.
Excellent reviews are available on the use of this versatile
technique in Synthetic Organic Chemistry [6]. With this
background one may anticipate the success of the appli* Corresponding author. Tel: 91 22 414 56 16; fax: 91 22 414 56 14;
e-mail: ssd@udct.ernet.in

1350-4177/98/$19.00 1998 Elsevier Science B.V. All rights reserved.

PII: S 1350-4177 (97) 00044-8

cation of ultrasound in the hydrolysis of oils and fats.

To our knowledge, there are only two references on the
use of ultrasound in this area. Both of these references
describe the use of aqueous ethanolic alkali and phase
transfer catalyst ( P T C ) for the hydrolysis of wool wax
and oils [7]. As wool wax or oil forms a homogeneous
solution in 50% ethanol, the reaction becomes a homogeneous reaction in which the exact role of PTC in
conjunction with ultrasound seems to be complex.
This paper is a part of our study in the area of
sonochemical liquid-liquid ( L - L ) heterogeneous reactions [8]. Here, we would like to report our observations
on the saponification of a few commercially important
vegetable oils in aqueous alkaline solution using phase
transfer catalysts (PTCs) in the presence of ultrasound,
wherein we would like to describe the specific importance
of the PTC and ultrasound.
Soyabean oil was taken as a model oil and its saponification was studied in detail. Optimizations of various
parameters, such as selection and quantity of PTC,
quantity of KOH, and quantity of water were carried
out. The PTCs used were polyethylene glycol-200
(PEG-200), polyethylene glycol-400 (PEG-400), sodium
lauryl sulfate (SLS), cetyl trimethyl ammonium bromide
(CTAB), tetrabutyl ammonium bromide (TBAB). The
effect of stirring and heating at 100C was compared

B.S. Bhatkhande, S.D. Samant/Ultras'onics Sonochemistrv 5 (1998) 7 12

with that of mere sonication, and sonication with

stirring.

2. Experimental

1. Chemicals
The following commercial grade vegetable oils were
used: soyabean oil (saponification value, 190), castor oil
(saponification value, 189), sesame oil (saponification
value, 192), sunflower oil (saponification value, 190),
linseed oil (saponification value, 190). K O H and PTCs
used were of analytical grade. Saponification values o f
the above oils were determined by the standard AOCS
method [9].

2.2. Sonication
For the sonication, a circular ultrasonic cleaner bath
was used. It was well characterized with respect to
pressure intensity profiles developed, when filled with
appropriate amount of water, using a pressure pulse
intensity measurement probe (PPIMP) developed in our
laboratory [10]. The bath (circular cross section with
diameter of 14.3 cm and height 20 cm) having frequency
35 +_3 kHz and power 120 W (Model Dakshin D2 (120),
from M/s Dakshin, Mumbai, India) was used.

2.3. Temperature control

It is known that the maximum cavitation in water
takes place at 3 5 C [ l 1]. Hence, the temperature of the
water in the ultrasonic cleaner was maintained at
35 2 C by adding crushed ice to the bath from time
to time and the water level inside the bath was kept
constant.

2.4. Reaction vessel

It is known that a flat bottom vessel is useful for
sonochemical reactions [12]. A flat bottom Erlenmeyer
flask of 250 ml capacity with a long neck was used for
the reactions.

2.5. Saponification of vegetable oil

Saponification of vegetable oils was carried at 35 ___2C
under stirring, sonication, and sonication and stirring.
Also it was carried out separately at 100C.

2.6. General proeedure of sonoehemical saponification of

vegetable oil
To the aqueous KOH solution (50 ml, 3%) taken in
a flat bottom Erlenmeyer flask (250 ml), a vegetable oil

( 1.0 g) and CTAB (0.30 g) were added and the reaction

mixture was stirred with an overhead stirrer (150 rpm)
and sonicated for 3 h.
For the nonsonicated reaction, the above reaction
mixture was only stirred at the desired temperature.

2.7. The extent of sapon(fication

For the determination of the extent of saponification,
blank experiments were carried out simultaneously,
keeping all the other quantities except oil the same. The
reaction mixture as well as a blank mixture were titrated
against 0.05 N HC1 using phenolphthalein indicator.
The extent of saponification was determined as follows
Blank titration reading=
Main titration reading =
Normality of H C 1 Equivalent wt. of KOH =
Weight of oil =
Saponification value found
out by classical method [9] =
Extent of saponification (%)=

A ml of 0.05 N aqueous HC1

B ml of 0.05 N aqueous HCl
0.05 N
56.10
Wg
X

( A - B ) x 0.05 x 56.10 x 100

WX X

3. Results
In the present study, soyabean oil was used as a
model oil and all the reaction parameters were optimized
with respect to this oil.

3.1. PTC
The hydrolysis of soyabean oil was carried out using
different PTCs, cationic, anionic and nonionic, in aqueous alkaline solution (3% K O H ) . The reaction mixture
was sonicated at 35 +2C with stirring for 180 min and
the extent of saponification was measured.
1.3 mmol of each PTC was used for 1.00 g of the oil
(Table 1). To establish the necessity of the PTC, the
results of the saponification without PTC under the
same experimental conditions were compared. The reaction was greatly accelerated in the presence of CTAB.

3.2. Time
The saponification of soyabean oil was carried out in
an aqueous K O H solution (3%, 50 ml) using CTAB,
under sonication and stirring at 35 + 2C. The extent of
saponification was continuously monitored at 30 min
intervals (Fig. 1 ). It was observed that after 180 min the
saponification was complete. Hence, for all the experiments, saponification was carried out for 180 min.

B.S. Bhatkhande, S.D. Samant / Ultrasonics Sonochemistry 5 (1998) 7 12

Table 1
Saponification of soyabean oil a in presence of different PTCs
Sr.No.

I.
2.
3.
4.
5.
6.

PTC b

Extent of saponification(%)c

No PTC
PEG-200
PEG-400
SLS
TBAB
CTAB

Stirring

Sonication

Sonication and stirring

Thermal

5
25
35
28
36
53

18
20
21
20
22
70

27
37
40
38
42
99

30
59
65
65
76
98

"Soyabean oil 1.00 g and aqueous K O H (3%, 50 mt ).

b| .3 mmol PTC per g oil.
CTime for each reaction (3 h).

dReaction temperature (100'C).

100

80

,--

60

e--

g 4o
~q

20

30

60

90

120

150

180

210

Time (rain)

Fig. 1. Optimization of time of the sonochemical saponification of soyabean oil using aq. K O H - C T A B system.

3.3. Quantity of CTAB

In order to fix the quantity of CTAB, the saponification of soyabean oil was carried out in aqueous K O H
(3%, 50 ml ) using an increasing quantity of CTAB under
sonication and stirring at 35 _+2C (Fig. 2). It was found
that the extent of saponification increased with the
amount of CTAB. The saponification was found to
increase drastically above 0.25 g of CTAB per gram of
oil. It was found to be almost complete when 0.30 g of
CTAB was used.

3.4. Aqueous alkali

It was noted that, being a heterogeneous reaction, for
the sonication to be effective, it was essential to take
the oil and water in optimum ratio. Hence, using a fixed
quantity of K O H (1.5g), soyabean oil (1.00g) was
saponified with increasing amount of water (Fig. 3).
From Fig. 3, it is clear that 50 ml of water per gram of
soyabean oil was optimum for the saponification. As

the rate of saponification depended upon the concentration of KOH, the amount of K O H was gradually
increased, maintaining the ratio of (soyabean oil: water)
as 1:50 (Fig. 4). The optimum quantity of K O H was
found to be 1.5 g per gram of oil (3% aq. solution,
50 ml ).

3.5. Effect of sonication

To study the effect of sonication in the saponification
of different oils, 1.00 g of an oil was suspended in
aqueous K O H (50ml, 3%) with CTAB (0.30g).The
reaction mixture was sonicated for 180 rain with stirring
( 150 rpm).
To bring out the importance of sonication in comparison with mere stirring, as well as with heating, each
stirred reaction (150 rpm) was carried out without sonication at 35+2C. Similarly, the reaction was also
carried out at 100C with stirring ( 150 rpm), but without
sonication.
In the case of castor oil, sunflower oil and sesame oil,

B.S. Bhatkhande, S.D. Samant / Ultrasonics Sonochemistry 5 (1998) 7 12

10

100

80

c
o

60

~ 4o
m

20

--

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

Quantity o f C T A B (g)

Fig. 2. Optimization of the quantity of the CTAB in the sonochemical saponification of soyabean oil using aq. KOH-CTAB system.
100

80

60

8. 4o

20

0 -o

i
10

I
20

[
30

40

50

60

Q u a n t i t y of w a t e r (ml)

Fig. 3. Optimization of the quantity of the water in the sonochemical saponification of soyabean oil using aq. KOH-CTAB system.
it was found that 0.3 g of CTAB was insufficient to give
complete saponification. By increasing the quantity of
the PTC to 0.4 g the saponification was found to be
complete. Using the optimized conditions, different vegetable oils were saponified under different conditions
(Table 2).

4. Discussion
4.1. Concentration of alkali
One of the important factors accelerating a L-L
heterogeneous reaction is the thorough dispersion of the
minor phase in the major phase. For complete mixing,
the ratio of the two phases should be optimum, In the
present study we found that the emulsification of an oil

in the water phase was satisfactory at 2% concentration

of the oil. The results of saponification were also satisfactory at this concentration.
It is possible that in the presence of sonic cavitation
in an aqueous solution, the saponification may take
place with the water alone. However, when the quantity
of the alkali was gradually increased, we found that the
rate of saponification also increased gradually. In the
absence of alkali, mere sonication did not effect saponification. The optimum quantity of K O H was found to
be 1.5 g per gram of the oil used.

4.2. Role of PTC

In the L-L heterogeneous saponification of soyabean
oil using aqueous alkali, the presence of alkali led to
poor emulsion under sonication as compared to the

B.S. Bhatkhande, S.D. Samant /' Ultrasonics Sonochemistry 5 (1998) 7 12

I1

100

8O

5o

~.

4o

2o

0,25

0.5

0.75

1.25

1.5

Quantity of KOH (g)

Fig. 4. Optimization of the quantity of K O H in the sonochemical saponification of soyabean oil using aq. KOH-CTAB system.

Table 2
Saponification of different vegetable oils under different experimental conditions
Sr. No.

Oil ~

Extent of saponification (%)b

Stirring

Sonication

Stirring and sonication

Thermal ~

1.
2.
3.

Soybean a
Linseed d
Sesame c

53
38
33

70
60
50

99
98
83

98
98
85

4.
5.

Castor
Sunfloweff

51
40

80
71

98
97

98
98

a1.00 g oil and aqueous K O H ( 3%,50 ml ).

bTime for each reaction (3 h).
CReaction temperature (100"C).
d0.8 mmol of CTAB per g of oil.
el .0 mmol of CTAB per g of oil.
Note: In case of sesame oil, castor oil and sunflower oil when 0.8 mmol of CTAB per g of oil was used under sonication and stirring: the extent
of saponification was found to be 67, 73 and 83%, respectively.

emulsion of oil in water under sonication. This may be

due to the increased difference in the density of oil and
the aqueous alkaline solution, resulting in poor mass
transfer. The O H - anion is of relatively low polarizability (a hard anion) and is difficult to extract into a nonpolar medium. Thus, the presence of a PTC is of prime
importance in this reaction.
When different PTCs were compared for the saponification reaction, we found that only CTAB could effect
the saponification satisfactory. Though TBAB was
slightly better than the remaining PTCs, it was much
inferior to CTAB. In the present reaction the main
function of the PTC was to transport O H - ions into
organic phase. Obviously cationic surfactants are best
suited for this purpose. It is known that for the transport
of O H - ions, TBAB is inferior to CTAB in a nonsonicated reaction due to steric crowding at the quaternary
nitrogen atom in the TBAB [13]. Moreover, for an oil
having linear hydrocarbon chains, CTAB is better suited

than TBAB. Thus, under sonication also CTAB served

as a best catalyst. It is interesting to note that the
optimum concentration of CTAB was approximately six
fold excess of the critical micellar concentration ( C M C )
of the CTAB which is 1 mmol.
In a liquid-solid nonaqueous heterogeneous reaction
involving hydroxide ion transfer, PEGs are excellent
catalysts. In the present reaction PEGs did not serve as
effective PTCs. Moreover, SLS was also found to be
poor in the same reaction. In each case, though the
reaction using a PTC showed a betterment over the
reaction in the absence of a PTC, in the presence of
sonication, the reactivity profile of these PTCs, other
than CTAB, did not change much. This indicated that
PEG-200, PEG-400, SLS, and TBAB more or less acted
as surfactants rather than as phase transfer catalysts.
From Table 2, it can be seen that the other vegetable
oils more or less followed the same trend as followed
by soyabean oil. In all cases, sonication with stirring

12

B.S. Bhatkhande, S.D. Samant / Ultrasonics Sonochemistry 5 (1998) 7-12

was found to be much superior as compared to any one

of them alone. Individually also, sonication was found
to be better than stirring. Using a combination of PTC
and ultrasound, saponification comparable to thermal
saponification (at 100C) was observed, but at a considerably lower temperature (35 _+2C).

[3]
[4]
[5]
[6]
[7]

Acknowledgements
One of the authors (BSB) is grateful to the University
Grant Commission, New Delhi, India for the award of
a Research Fellowship.

[8]
[9]
[I0]
[11]

References
[1] J. Fang, P. Joos, Colloids Surf. A 83 (1994) 63.
[2] M. Virto, I. Agud, S. Montero, A. Blanw, R. Solozabal, J. Las-

[12]
[13]

cary, M. Llama, J. Serra, L. Landeta, M. deRenobales, Enzyme

Microb. Technol. 16 (1994) 61.
X. Huang, Riyong Huaxue Gongye 5 (1992) 260.
M. Deibert, Energy Res. Abstr. 18 (1993) Abstr. 3541 (C.A, 121:
2079300.
A. Pandit, J. Joshi, Chemical Engineering Science 48 (1993) 3442.
T.J. Mason, J.P. Lorimer, Sonochemistry: Theory, Applications
and Uses of Ultrasound in Chemistry, Ellis Horwood, UK, 1988.
(a) R. Davidson, A. Safdar, J. Spencer, B. Robinson, Ultrasonics
25 (1987) $35; (b) B. Robinson, A. Safdar, R. Davidson, Saponification of Fats, UK Patent Application No. 8602316, 1986.
S.R. Soudagar, S.D. Samant, Ultrasonic Sonochemistry 2 (1)
(1995) S15.
Official and tentative methods of the American Oil Chemist's Society, Method No. Cd-3-25.
S.R. Soudagar, S.D. Samant, Ultrasonic Sonochemistry 2 (I)
(1995) $49.
T.J. Mason, Practical Sonochemistry: Users Guide to Applications in Chemistry and Chemical Engineering, Ellis Horwood,
UK, 1990, p. 57.
B. N iemczewski, Ultrasonics 18 (1980) 107.
C.M. Starks, C.L. Liotta, M. Halpern, Phase-transfer Catalysis,
Fundamental Applications an Industrial Perspectives, Chapman
and Hall, USA, 1994, p. 129.