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I NTERNATIONAL J OURNAL OF C HEMICAL

R EACTOR E NGINEERING
Volume 7 2009 Article A18

Kinetics of Benzyl Butyrate Synthesis under


Solid-Liquid Phase Transfer Catalysis

Sonali Sengupta∗ Jayanta Kumar Basu†


Indian Institute of Technology, Kharagpur, India, sonalis.iitkgp@gmail.com

Indian Institute of Technology, Kharagpur, India, jkb@che.iitkgp.ernet.in
ISSN 1542-6580
Copyright 2009
c The Berkeley Electronic Press. All rights reserved.
Kinetics of Benzyl Butyrate Synthesis under
Solid-Liquid Phase Transfer Catalysis∗
Sonali Sengupta and Jayanta Kumar Basu

Abstract
The substitution reaction of benzyl chloride and sodium butyrate to form ben-
zyl butyrate, using tetrabutyl ammonium bromide as the phase transfer catalyst
(PTC) in a solid-liquid phase condition was studied. Benzyl chloride in solvent
toluene forms the organic phase whereas sodium butyrate remains in solid form.
A kinetic study of the system had been performed by varying different process
variables. Different phase transfer catalysts were employed to find out the most
effective catalyst. No conversion was found without catalyst.

Homogeneous solubilisation mechanism was followed to explain the kinetic model


and to interpret the experimental data.

KEYWORDS: phase transfer catalysis, solid-liquid phase, substitution reaction,


kinetic study


Please send correspondence to Sonali Sengupta, tel: +91-3222-283954, fax: +91-3222-282250,
email: sonalis@che.iitkgp.ernet.in.
Sengupta and Basu: Kinetics of Benzyl Butyrate Synthesis under S-L PTC 1

1. Introduction
The phenomenon of rate enhancement of a reaction between chemical species
located in different phases (immiscible liquids or solid and liquid) may occur by
addition of a small quantity of an agent, called the ‘phase transfer catalyst’ (Starks
et.al, 1994). These catalysts extract one of the reactants, most commonly an
anion, across the interface into the other phase so that reaction can proceed. These
catalysts are salts of ‘onium ions’ (e.g. tetra alkyl ammonium salts) or agents as
complex inorganic cations (e.g. crown ethers). The catalyst cation is not
consumed in the reaction although an anion exchange does occur. Since the
catalyst is often a quaternary ammonium salt (e.g., tetra butyl ammonium,
[C4H9]4N+), which may be called "quat" and is symbolized by Q+ and the ion pair
Q+X- (X- being the anion to be reacted). The importance of phase transfer
catalysis as a means of accelerating different reactions in heterogeneous systems
has been established since the early 1970’s.
A substantial amount of work has been done on liquid –liquid and solid –
liquid phase transfer catalysis. Yadav et. al (2003) studied the kinetics and
mechanism of liquid–liquid phase transfer catalysed reduction of p-nitroanisole to
p-anisidine. Yadav and Lande (2006) investigated the rate intensive and selective
etherification of vanillin with benzyl chloride under solid-liquid phase transfer
catalysis. The activation energy supported the fact that the overall rate of reaction
is not influenced by mass transfer resistance and it is an intrinsically kinetically
controlled reaction. Yang and Lin (2003) proposed a kinetic model describing the
behavior of interfacial catalysis for the reaction between benzyl bromide and
sodium benzoate in liquid–liquid system catalyzed by aliquat 336. The
experimental data were interpreted as a pseudo-first-order reaction. Wang et.al
(1994) investigated the substitution reaction of benzyl chloride and sodium
acetate using pyridine 1-oxide as the inverse phase-transfer catalyst in a two-
phase system. A larger reaction rate was observed for a more polar organic
solvent. Wang and Rajendran (2007) synthesized ethoxy-4-nitrobenzene using
benzyl triethyl ammonium chloride as a phase-transfer catalyst and under
ultrasound irradiation conditions. The use of phase-transfer catalysts and
ultrasound has been compared.
Kinetic study of synthesizing N-butylphthalimide under solid–liquid
phase-transfer catalysis conditions was carried out successfully by Wang, Chen
and Wang (2005). The reaction is greatly enhanced in the solid–liquid system
compared to the reaction in a liquid–liquid medium. A kinetic model is proposed
assuming a pseudo first-order reaction. The alkylation of 2-hydroxy acetophenone
with 1-bromopentane was studied by Yadav and Desai (2006) by using liquid–
liquid phase transfer catalysis with a variety of catalysts. Hundred percent
selectivity was obtained towards the formation of the product 2-pentyloxy

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acetophenone and a theoretical analysis of the reaction was done to develop a


model.
Phase transfer catalysed reactions in liquid-liquid phase had been studied
by many scientists (Yang and Lin, 2003; Wang et. al, 1994; Yadav and Desai,
2006; Yadav and Jadhav, 2003; Wang and Yang, 1990). The major drawback of
liquid-liquid PTC is that the reactant anion becomes hydrated by water molecules
in the aqueous phase and does not become easily accessible by the quaternary
cation. Whereas, the solid-liquid PTC eliminates the chance of water hydration
and often increases the nucleophilicity of anionic species (Starks et. al, 1994;
Wang et. al, 2005).
Moreover it is easier to recover the catalyst in solid-liquid system, which
always resides in the organic phase unlike the liquid-liquid system, where the
catalyst becomes distributed between both the phases.
Organic esters are mostly used as solvents, plasticizers, perfumery and
flavouring agents and they have a huge application in pharmaceuticals,
agrochemicals and other fine chemicals. Benzyl butyrate is widely used in the
field of perfumery and personal care products. So it is worth to study the kinetics
of the synthesis reaction of benzyl butyrate and develop a kinetic model.
The objective of the present study was to investigate the reaction between
benzyl alcohol and sodium butyrate to benzyl butyrate. Different parameters were
varied to study the kinetics of the reaction. A model has been developed and fitted
to the experimental data.

2. Experimental Section

2.1 Materials

The chemicals benzyl chloride and toluene of A/R grade were procured from M/s
s. d. Fine Chemicals Pvt. Ltd. Mumbai, India. Sodium butyrate and pure benzyl
butyrate had been obtained as a gift sample from Krupa Scientific, Mumbai.
TBAB, TPAB, ETPB and TBAHS of pure grade were obtained as gift samples
from M/s. Dishman Pharmaceuticals and Chemicals Ltd., Ahmedabad, India.
These were used as received without any further purification.

2.2 Procedure

The reaction were studied in a 5 cm internal diameter, glass reactor of 250 cm3
capacity, equipped with a 4 bladed–turbine impeller and a reflux condenser. The
reactor was kept in a constant temperature bath whose temperature could be
maintained at a desired value by using a temperature controller with an accuracy
of ± 10C. The system was allowed to react with constant stirring and samples

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Sengupta and Basu: Kinetics of Benzyl Butyrate Synthesis under S-L PTC 3

were collected initially at 5 minutes interval and then at 15 minutes interval from
the organic phase. The main reaction product was benzyl butyrate which goes to
the organic phase; another product was sodium chloride which remains as solid.
The analysis of reactants and products were carried out using Chemito Model
8610 GC interfaced with a Shimadzu C-R6A Chromatopac data processor with
±1% variation. The column used was 10% SE-30 (diameter: 0.8mm, film
thickness: 0.25µm, length: 2 m) with Chromosorb W (80/100) for quantitative
analysis of the reactants and products.

3. Kinetic Model

The experimental work has been done to study the role of TBAB as a phase
transfer catalyst in catalyzing the reaction between benzyl chloride and sodium
butyrate which is shown in Figure1. Ordinarily the reaction is very slow or
negligible without the PTC, since benzyl chloride is soluble in organic phase
whereas sodium butyrate does not dissolve but remains as solid. This problem has
been tackled by the use of phase transfer catalyst which in this case is TBAB. The
catalyst takes the sodium butyrate from the solid phase to the organic phase where
the reaction takes place.

O O
CH2Cl
O + NaCl
+ NaO CH2CH2CH3

Benzyle chloride Sodium butyrate Benzyl butyrate Sodium chloride

Figure 1. Reaction scheme

The reaction path in solid-liquid PTC condition for this system may be
shown in Figure 2. The solid sodium butyrate is assumed to be partially soluble in
the organic phase (Step1) and the transport of solid is enhanced by the action of
phase transfer catalyst in the bulk of the liquid phase by the intermediate ion-
exchange reaction (Step2) with the quaternary ions to form the quaternary-
butyrate in toluene phase. Then the reaction between benzyl chloride and
quaternary-butyrate is taking place. The product is formed in the organic phase by
Step 3, where the quaternary compound is released back to the organic phase
following the natural catalytic phenomena. The sodium chloride in the organic
phase formed in the reaction is crystallized out as solid and this will be at
equilibria with sodium chloride at the solid phase (Step 4).

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Solid-phase Liquid film Bulk liquid-phase

k1
MYS MYL Step- 1
k2 k3
MYL + QX QY + MXL Step- 2
k4
k5
QY + RX RY + QX Step- 3
k6
MXS MXL Step- 4
k7

Figure 2. Reaction pathway of solid-liquid phase transfer catalysis

The rate equation is derived based on the homogeneous reaction


mechanism for bimolecular reaction. Steps 1, 2 and 4 are assumed to be
maintained at equilibria, while step 3 is the rate determining step. In absence of
mass transfer effect for homogeneous reaction the rate of the reaction may be
written as,

dC RX
− rA = − = k 5 CQY C RX (1)
dt

and in terms of conversion of RX

dX A
− rA = −C RX 0 = k 5 CQY C RX 0 (1 − X A ) (2)
dt

The concentration of QY in organic -phase is obtained from the equilibrium


constants as

CMY S
CQY = K ′K ′′K ′′′ CQX = K R CQX (3)
CMX S
Where, K R = K ′K ′′K ′′′CMYS / CMX S

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Sengupta and Basu: Kinetics of Benzyl Butyrate Synthesis under S-L PTC 5

Initial concentration of quaternary salt C Q0 may be considered as constant and is


given by

C Q0 = C QX + C QY and C QY is given by

K R C Q0
C QY = (4)
1 + KR

dX A KR
− C RX 0 = k5 CQ C RX 0 (1 − X A ) (5)
dt 1+ KR 0

where XA is the conversion of benzyl chloride to benzyl butyrate


and

K ′K ′′K ′′′( M − X A ) initial moles of MY in organic phase


KR = where M = (6)
XA initial moles of RX in organic phase

Combining Equations (5) and (6) and on integration for the limit t = 0, XA = 0
to t = t, XA = XA, it results

XA
X A + K ′K ′′K ′′′( M − X A ) t


0
K ′K ′′K ′′′(1 − X A )( M − X A )
dX A = ∫ C Q0 k ′dt
0
(7)

M M − XA
ln − N ln(1 − X A ) = k ′CQ0 t (8)
M −1 M

⎛ 1 − K ′K ′′K ′′′ + K ′K ′′K ′′′M ⎞


Where, N = ⎜ ⎟ and k ′ = k5 K ′K ′′K ′′′ (9)
⎝ M −1 ⎠

From Equation (8),

M M − XA
ln
M −1 M t
= k ′CQ0 +N (10)
ln(1 − X A ) ln(1 − X A )

k' is the apparent rate constant and may be obtained from the slope of the plot of
Equation (10).

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4. Experimental Results

4.1 Effect of different catalysts

Different PT catalysts had been employed to test the efficacy of the catalysts for
this system. In this purpose various phase transfer agents such as TBAB, TBAHS,
TPAB and ETPB were evaluated on the basis of conversion at 50 0C and at 700
rpm under otherwise similar conditions. The order of reactivity was: TBAB>
TBAHS> TPAB> ETPB. No conversion was found without catalyst (Figure 3). It
has been seen that TBAB worked as the best catalyst among the lot with respect
to conversion to the product benzyl butyrate.

70

60

50
Conversion, %

40

30

20

10

0
0 20 40 60 80
Time (min)

ETPB TPAB TBAB TBAHS

Figure 3. Effect of different catalysts


Sodium butyrate: 0.0166 mol, benzyl chloride: 0.05 mol,
catalyst : 0.0015mol, speed of agitation: 700 rpm, temperature:
50 0C, volume of organic phase: 40ml., time: 60 min.

4.2 Effect of speed of agitation

To ascertain the influence of resistance to the mass transfer on the reaction, the
stirrer speed was varied in the range of 200–1000 rpm and also without stirring
under otherwise similar conditions. It was observed that without stirring there was
no conversion but the conversion of benzyl chloride is highly influenced by the

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Sengupta and Basu: Kinetics of Benzyl Butyrate Synthesis under S-L PTC 7

speed of agitation at or below 500 rpm; i.e., the dissolution of sodium butyrate in
the organic solvent toluene limits the reaction rate. The conversion was found to
be practically the same at 700 and 1000 rpm (Figure 4). Further increase in the
speed of agitation beyond 700 rpm had practically no effect on the conversion.
This is revealed by the Figure 5 which shows that the initial rates are increasing
from 200 to 500 rpm while it is zero at zero rpm and a plateau forms from 700
rpm onwards and this plateau confirms the absence of mass transfer at and after
700 rpm. The dissolution of sodium butyrate increases and the reaction is almost
taking place homogeneously in the organic phase. Thus, a speed of agitation of
700 rpm was employed to get a maximum rate and for assessing the effect of
other variables on the rate of reaction.

70

60

50
Conversion, %

40

30

20

10

0
0 20 40 60 80
Time (min)
300 500 700 1000

Figure 4. Effect of speed of agitation


Sodium butyrate: 0.0166 mole, benzyl chloride: 0.05 mole,
TBAB : 0.0015 moles, temperature: 50 0C, volume of organic
phase : 40 ml., time: 60 min.

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0.007

0.006
initial rate ,Kmol/dm3.min

0.005

0.004

0.003

0.002

0.001

0
0 200 400 600 800 1000 1200

Speed of agitation, rpm

Figure 5. Plot of initial rate against speed of agitation

4.3 Effect of mole ratio

The effect of mole ratio of benzyl chloride (RX) to sodium butyrate (MYS) on
conversion was studied from 1:1 to 1:3, keeping the total volume of the organic
phase constant with toluene (Figure 6). The figure reveals that the maximum
conversion of the reaction was observed at the mole ratio 1:2. So the further
experiments were conducted keeping mole ratio 1:2. As the mole ratio increases,
the concentration of quaternary component of butyrate (CQY) increases and the
reaction rate increases as per Equation (2) but not significantly. At a mole ratio
1:2, CQY reaches a maximum saturation concentration in the solvent. Further
increase in mole ratio does not affect in enhancement of the reaction.

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Sengupta and Basu: Kinetics of Benzyl Butyrate Synthesis under S-L PTC 9

70

60

50
conversion, %

40

30

20

10

0
0 20 40 60 80
Time (min)
1:1 1:2 1:3

Figure 6. Effect of mole ratio of benzyl chloride to sodium butyrate


TBAB :0.0015 moles, speed of agitation: 700 rpm, temperature: 50 0C,
volume of organic phase: 40 ml., time :60 min.

4.4 Effect of catalyst amount

The catalyst amount was varied from 1.5 × 10-3 to 3.0 × 10-3 moles under
otherwise similar conditions (Figure 7). It was observed that the reaction rates had
been significantly enhanced as the concentration of the catalyst TBAB was
increased. In homogeneous reaction, the availability of both the reactants in the
toluene phase is important. From Figure 1, it was clear that the transport of QY is
influenced by the quaternary ions. So the concentration of PT catalyst has a
significant role on the conversion of reaction. It was observed that after 40
minutes of reaction the change of reactant concentration is low as the reaction
proceeds and the conversion does not increase much and approaches to the
maximum value.

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70

60

50
Conversion, %

40

30

20

10

0
0 10 20 30 40 50 60 70

Time (min)
0.0015 0.002 0.0025 0.003

Figure 7. Effect of catalyst loading


Sodium butyrate: 0.0166 mol, benzyl chloride: 0.05 mol,
temperature: 50 0C, speed of agitation : 700 rpm, volume of
organic phase : 40 ml., time: 60 min.

4.5 Effect of temperature

Temperature of the reaction was varied from 50 to 80 0C under otherwise similar


reaction conditions (Figure 8) to see its effect. It was found that the conversion
was increased substantially with increase in temperature. The kinetic model
[Equation (10)] was tested by transforming the rate data into the model
parameters and fitted by least square method. Figure 9 shows a well-correlated fit
of the data at different temperatures. The values of apparent rate constant (k′)
calculated from the slopes at different temperatures were used to fit with the
Arrhenius equation (Figure10). The correlation coefficient of the Arrhenius plot
was 0.9833. The apparent activation energy and frequency factor were found to be
18.5 kJ/mol and 8.1308 ×104 respectively.

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Sengupta and Basu: Kinetics of Benzyl Butyrate Synthesis under S-L PTC 11

80

70

60
Conversion, %
50

40

30

20

10

0
0 10 20 30 40 50 60 70

Time (min)
50C 60C 70C 80C

Figure 8. Effect of temperature


Sodium butyrate: 0.0166 mol, Benzyl chloride: 0.05 mol,
TBAB: 0.0015 mol, speed of agitation: 700 rpm, volume of organic phase:40 ml,
time: 60 min.

0.95
[M/{(M-1)ln(1-XA)}]ln(1-XA/M)

0.9

0.85

0.8

0.75

0.7

0.65

0.6
-85 -65 -45 -25 -5
t/ln(1-XA)

50C 60C 70C 80C

Figure 9. Fitting of rate data at different temperatures

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12 International Journal of Chemical Reactor Engineering Vol. 7 [2009], Article A18

5.4

5.2

5
ln k'

4.8

4.6

4.4

4.2
0.0028 0.0029 0.0029 0.003 0.003 0.0031 0.0031 0.0032
1/T, K-1

Figure 10. Arrhenius plot

5. Conclusion
The reaction of sodium butyrate and benzyl chloride was studied under solid-
liquid PTC by using TBAB as phase transfer catalyst. Benzyl chloride in toluene
was considered as the organic phase and sodium butyrate as the solid phase. The
products obtained were benzyl butyrate which was the major product and sodium
chloride which went into the solid phase. The effects of different parameters on
the conversion were also studied. A kinetic model was proposed which was well-
fitted with the experimental data in absence of mass transfer effects. The reaction
is intrinsically kinetically controlled. The activation energy was calculated based
on apparent rate constant.

Notation

CMX concentration of sodium chloride (mol ml-1)


CMY concentration of sodium butyrate (mol ml-1)
CQ concentration of quaternary salt(mol ml-1)
CQY concentration of quaternary-butyrate (mol ml-1)
CRX concentration of (mol ml-1)

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Sengupta and Basu: Kinetics of Benzyl Butyrate Synthesis under S-L PTC 13

k1, k2 rate constants (min-1)


k3 k4, k5 rate constants (mol-1 ml min-1)
k6, k7 rate constants (min-1)
k′ apparent rate constant (mol-1 ml min-1)
K′ , K′′, K′′′ reaction equilibrium constants (–)
KR constant defined in Equation (7)
M ratio of intial moles of sodium butyrate to initial
moles of benzyl chloride (−)
N constant defined in Equation (12)
-rA rate of disappearance of A (mol ml-1 min-1)
t time(min)
XA fractional conversion (–)

Abbreviations

MYS sodium butyrate in the solid phase


MYL sodium butyrate in the organic phase
MXL sodium chloride in the organic phase
MXS sodium chloride in the solid phase
Q+ quaternary ion
QX quaternary chloride
QY quaternary-butyrate
RX benzyl chloride
RY benzyl butyrate
ETPB ethyl triphenyl phosphonium bromide
TBAB tetra-n-butyl ammonium bromide
TBAHS tetra-n-butyl ammonium hydrogen sulfate
TPAB tetra-n-propyl ammonium bromide

Subscripts

A limiting reactant (benzyl chloride)


L liquid organic phase
o initial condition
S solid phase

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Published by The Berkeley Electronic Press, 2009

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