Kinetic Studies on

Saponification of Ethyl
Acetate Using an Innovative
Conductivity-Monitoring
Instrument with a Pulsating
Sensor
KUHELI DAS, P. SAHOO, M. SAI BABA, N. MURALI, P. SWAMINATHAN
Electronics and Instrumentation Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India
Received 24 February 2010; revised 16 June 2011; accepted 3 July 2011
DOI 10.1002/kin.20597
Published online in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: An innovative conductometric measurement technique using a nonconventional

but high-performance (high-precision, high-resolution, rapid response features for online
graphic display) in house–built pulsating conductivity monitoring instrument has been de-
ployed to study the kinetic behavior during the reaction of ethyl acetate and NaOH. A laboratory-
made constant temperature reaction bath with the facility of continuous stirring of solution
for homogeneous mixing was used to carry out experiments at desired solution temperatures.
Rate constants of the saponification reaction in the temperature range at various tempera-
tures (30–55◦ C) were determined, and the results were compared with the reported values.
Although the reported data exhibit wide scatter, our data are in agreement with some of the
literature data. From these data, thermodynamic parameters such as activation energy, acti-
vation enthalpy, activation entropy, and activation free energy have been evaluated. With the
introduction of this novel conductometric measurement technique, the determination of rate
constants at various solution temperatures becomes much simpler and faster.  C 2011 Wiley

Periodicals, Inc. Int J Chem Kinet 1–9, 2011

INTRODUCTION primary objective of this activity is to develop a suit-

able methodology to use the oscillatory reaction as a
In our laboratory, we have taken up a project to study platform for rapid chemical assay. Before augmenting
the effect of temperature on oscillatory chemical reac- the pulsating sensor to study the kinetics of the os-
tions using our in house–built pulsating sensors. The cillatory reaction, we preferred to study the kinetics
of a well-known nonoscillatory reaction using a pul-
sating sensor to verify the reliability of our measure-
Correspondence to: P. Sahoo; e-mail: [email protected]. ment technique for kinetic investigation of an unknown

c 2011 Wiley Periodicals, Inc. system. Hence, we chose one of the most popular
2 DAS ET AL.

reactions—the saponification reaction of ethyl acetate lowing our own measurement technique. Moreover,
and sodium hydroxide—for the kinetic study. there is always a need for continuous evolution of
The hydrolysis of ethyl acetate is one of the most a simplified method for a kinetic study of any re-
well-known reactions in chemistry, and it is represented action in a more convenient way. A brief descrip-
as a model example of the second-order reaction in the tion of this unique approach of rapid online conduc-
literature dealing with chemical kinetics [1,2]. This tivity measurement using our in house–built pulsat-
reaction has been studied by several investigators at ing sensor with special attention given to its use in
different temperatures using a variety of measurement the kinetic study and comparison of our results with
techniques [3–9]. Daniels et al. [3] and Smith and the literature data reported by several investigators
Levenson [4] adopted a volumetric titration method [4,7–9,14] are presented in this paper.
independently, in which the composition of reacting
mixture was followed by an analysis of sample aliquots
withdrawn from the reaction vessel at definite time in- PRINCIPLE OF CONDUCTIVITY
tervals. The precision of the method is limited by the MEASUREMENT
withdrawal of appropriate volume of sample at a fixed
duration in addition to errors associated with titration For the kinetic study using a conductometric measure-
using a color indicator. The second technique reported ment approach, a high-performance (high precision,
by Walker [5] depends on conductometric measure- high sensitivity, and very fast response) conductivity
ments to determine the composition at any given time. meter is the best choice. Fortunately, in our labora-
This conductometric technique avoids periodic with- tory, such type of a conductivity-monitoring unit has
drawal of samples for analysis. The measurements already been developed and is used for many miscella-
were carried out manually. However, the reliability of neous applications [15–18]. The working principle and
results fully depends upon the response time and re- the design of this conductivity meter are entirely dif-
producibility in a conductivity measurement. Another ferent from the conventional conductivity monitoring
technique reported by Stead et al. [6] uses a continu- instruments available in the market. The conductivity
ous flow system, where the reactants are fed contin- meter is designed in such a way that the conductivity
uously at constant temperature into a stirred vessel. cell forms a part of a specially designed logic gate os-
The method uses of a large volume of solution. Jensen cillator (LGO) circuit. Once the cell is disconnected
et al. [7] used high-frequency titrimetry. The method from the rest of the electronics, it will not act as an
does not need any external indicator or introduction of oscillator. This conductivity sensor is operated at 5 V
any electrodes into the reaction vessel. Although the DC with very low power consumption. When it is pow-
authors have taken precaution to introduce a calibra- ered, the oscillator oscillates between two logic states
tion technique for the nonlinearity of the instrument (max: 1, min: 0). The output of the sensor is a train
performance, it involves a number of manual opera- of rectangular pulses of 5-V amplitude from which the
tions in methodology as compared with the proposed pulse frequency can be determined. The frequency of
method. Shui-yuan et al. and Ge-li et al. [10,11] used the LGO changes with the change in the ionic conduc-
acidometry and microcalorimetry techniques, respec- tivity of the solution taken in the cell. This frequency is
tively, to determine rate constant of saponification of directly related to the conductivity of the solution. Prior
ester. However, these latest techniques are not as sim- to the deployment of a conductivity probe for a particu-
ple as the proposed technique. Zhanjun et al. [12] and lar application, it is calibrated using a series of standard
Yong-Tao et al. [13] focused their attention on online KCl solutions to establish a relationship between fre-
data acquisition using a conductometric technique to quency and conductivity of solution following a multi-
make the methodology much simpler. However, the point calibration technique developed in-house. From
conventional conductivity sensors used by these au- the calibration plot, a polynomial equation (either in
thors are not as precise as the innovative sensors used second degree or in third degree) is generated, the co-
in the present work. efficients of which are loaded in the software to give
Although various studies have been conducted by a direct display of conductivity during measurement.
several investigators, there is significant scatter in data In the present case, the instrument is designed in such
on the rate constant and activation energy in the saponi- a way that with a change in the conductivity of the
fication reaction of ethyl acetate and sodium hydroxide solution by 1 μS cm−1 , there is a change of about
[4,7–9]. While augmenting our new measurement ap- 20 Hz in pulse frequency. Even in some specific ap-
proach for such a study, we analyzed these results and plications such as online radiation dosimetry, assay of
independently determined the rate constant of this re- boron in heavy water, and assay of the heavy water
action and the related thermodynamic parameters fol- content in a mixture of light water and heavy water,

International Journal of Chemical Kinetics DOI 10.1002/kin

 KINETIC STUDIES ON SAPONIFICATION OF ETHYL ACETATE 3

where it was required to monitor a very minor shift in specific applications. The advantage of adopting this
the conductivity, were addressed by using our pulsating innovative conductivity measurement technique is that
conductivity monitoring technique with minor modifi- the primary signal from the sensor end is in a direct
cation in the design of probes and associated electron- digital form, i.e., the output is digital pulse frequency.
ics [18]. Because of these advantages, in the present Hence, it avoids additional instrumentation for analog-
work we applied this new type of the conductivity mon- to-digital conversion unlike conventional instrumenta-
itoring device (response time: <1 s, resolution: 0.1 μS tion. Since the primary signal is in a digital domain
cm−1 , relative standard deviation [RSD]: 0.5%) in the form, the signal loss during long distance transmis-
kinetic study. sion is practically nil and it possesses excellent noise
immunity. In the present application, the frequency
varies from 50 to 6255 Hz, which covers the conduc-
EXPERIMENTAL tivity range from ≤1 to 1000 μS cm−1 . In this kinetic
study, the pulse counting is done at every 1-s interval.
Chemicals Using our indigenously made data acquisition system,
the online data in graphic form are recorded and stored
All chemicals used for this work are of AR grade. for future use. The detailed instrumentation, calibra-
The stock solutions of NaOH (∼1 M) and glacial tion technique, and the performance of this innovative
acetic acid (∼1 M) were prepared using high-purity conductivity meter have been described in one of our
distilled water (Millipore water conductivity less than latest publications [19].
1 μS cm−1 ), whereas ethyl acetate (Fisher Scientific,
Mumbai, India; Qualigen, Mumbai, India; density:
0.898 g cm−3 ) was directly used as stock solution. Experimental Setup
Stock solution of NaOH was standardized against Initial kinetic studies were conducted at room temper-
freshly prepared standard oxalic acid. All working ature to determine the order of the reaction in saponifi-
standards used in this work were freshly prepared be- cation of ester. A fixed volume of desired solution was
fore continuing the experimental campaign. taken in a beaker in which the conductivity probe was
mounted vertically. A commercially available mag-
netic stirrer was used to mix the solution homoge-
Conductivity Monitoring Instrument
neously. A series of experiments were conducted at
A pulsating sensor based conductivity monitoring in- prevailing solution temperature to determine the order
strument [19] was used in the present study. A vertical- of the reaction.
type Teflon probe with a pair of platinum electrodes Further experiments were carried out at desired so-
(platinum rods with 0.5 mm diameter, 5 mm length, lution temperatures with the goal of determining the
5 mm gap between electrodes) fixed onto the bottom rate constant of the reaction at different temperatures.
of it was used for online monitoring of conductiv- An experimental facility was designed and made in our
ity shift during kinetic experiments. The conductivity laboratory to carry out the experiments at a fixed so-
probe was connected to the associated electronics of lution temperature. A high-precision constant temper-
LGO. The LGO was connected to a personal computer ature bath (Siskin Julabo VPC, which could maintain
(PC) via a power supply cum signal routing unit. In this temperature of ±0.1◦ C) was used for this application.
case, a fixed capacitor is used in the LGO, whereas the A microcontroller-based vertical-type stirrer using a dc
conductivity cell forms the resistivity part of the oscil- stepper motor was made in-house. Arrangement was
lator circuit. When the LGO is operated by 5 V DC, made to mount a beaker holder in the temperature bath.
a train of rectangular pulses are generated from which The reaction vessel containing solution was placed in-
the pulse frequency is determined. The train of pulses side it. The vertical stirrer was fixed in the reaction
is sent directly to the PC through its parallel port. The vessel to mix the solution homogeneously throughout
in house–developed software package converts pulses the experiment. The conductivity probe was also verti-
to frequency and then from frequency to the respective cally placed in the solution to monitor the conductivity
conductivity. The frequency value purely depends on of solution during the experiment. Figure 1 shows a
conductivity of solution for a fixed LGO circuit. Even schematic diagram of experimental setup.
for a fixed conductivity value, the frequency can be al-
tered by changing the capacitance part of the timing os-
Methodology
cillator. While doing so, one has to consider regarding
stability and uncertainty in measurement. Accordingly Twenty-five milliliter of distilled water was taken
the appropriate oscillator circuit can be designed for in the reaction vessel and kept in the constant

International Journal of Chemical Kinetics DOI 10.1002/kin

4 DAS ET AL.

Figure 1 Experimental setup for the kinetic study (1: con-

ductivity probe; 2: logic gate oscillator; 3: vertical stirrer;
4: reaction vessel; 5: speed control unit; 6: reaction vessel
holder; and 7: temperature bath).

temperature bath. After attaining a desired solution

temperature, 0.5 mL of 0.1 M NaOH and 0.5 mL of
0.1 M ethyl acetate (both reactants were maintained
at same the temperature prior to their addition) were
added to it and immediately real-time conductivity of Figure 2 Demonstration of response time of the pulsating-
solution was monitored for a fixed duration (500–1000 type conductivity-monitoring instrument (t1 : time in seconds
s) at every 1-s interval using our PC-based conductiv- when the reagent was added; t2 : time in seconds correspond-
ity monitoring unit. Immediately after the experiment, ing to 63% of an increase in signal).
the data acquisition can be terminated and saved for
further off-line processing.
To measure the conductivity of the solution at in- This shows that the shift in frequency per change in
finite time, instead of continuing this experiment for the conductivity of 1 μS cm−1 is about 20 Hz. The
a long period, a new approach was adopted. Twenty- precision in measurement is less than 0.7 Hz, and
five milliliters of distilled water was taken in a beaker the resolution of instrument used for the present ap-
at a constant temperature, and after attaining the tem- plication is about 0.1 μS cm−1 . However, resolution
perature 0.5 mL of 0.1 M acetic acid and 0.5 mL of can be further improved by slightly modifying the ge-
0.1 M NaOH were added to it. Thus sodium acetate, ometry of electrodes and the capacitive component of
which was formed as the product in the above reaction, instrumentation [19]. The response time, which is de-
attributed for the conductivity at infinite time (κ∞ at fined as the time required by the instrument to respond
constant temperature). 63% of a sudden change in signal, has been evaluated
from this figure. In this figure, the presence of a small
shoulder, which gives an apparent impression of noise
RESULTS AND DISCUSSION level, is not the noise level, but it is due to the actual
phenomenon of conductivity shift during the mixing
At the outset, we investigated the potential of our pul- of reagents before attaining the stable homogeneous
sating conductivity meter to assess its suitability for a value. This phenomenon is demonstrated in Fig. 3,
rapid kinetic measurement. Hence, we conducted ap- which is derived from Fig. 2. The time corresponding
propriate experiments to determine the response time, to the reagent addition and the time corresponding to
precision in measurement, and influence of reagent the stable conductivity value achieved after homoge-
mixing time on measurement. Figure 2 shows that with neous mixing are clearly indicated in this figure. From
the addition of 100 μL of 0.01 M KCl solution to this, it is clearly realized that the time of mixing to get
25 mL of dilute KCl solution with a fixed conductivity, a homogeneous solution is about 1.3 s, which includes
the pulse frequency shifts from 7.5 to 17.5 μS cm−1 . the time required for addition of reagent.

International Journal of Chemical Kinetics DOI 10.1002/kin

 KINETIC STUDIES ON SAPONIFICATION OF ETHYL ACETATE 5

Figure 3 Demonstration of kinetics of mixing of reagents Figure 4 Real-time plot of conductivity versus time for
(t1 : time in seconds when the reagent was added; t2 : time the saponification reaction at a constant solution temperature
in seconds corresponding to the steady value after homoge- (323.0 ± 0.1 K).
neous mixing).

response and high precision in measurement using

It is well known from the literature that the saponi- a pulsating conductivity sensor. The conductivity of
fication of ethyl acetate in the presence of a strong solution during the reaction at every 1-s interval is
base (NaOH) is a second-order reaction, in which both shown on the online plot. From this online plot using
the reactants are consumed to form sodium acetate and a cursor navigation, conductivity values of solution at
ethyl alcohol. each 100-s interval were extracted and are presented in
Table I. In each case, conductivity contributed by dis-
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH tilled water was deducted and corrected conductivity
values were tabulated. To determine the specific con-
In the present work, the concentration of each reac- ductance at infinite time instead of continuing mea-
tant in the bath has been taken as equimolar to avoid surement for a prolonged period as used convention-
the system to turn into an exponential decay after a ally, we adopted a new approach. At infinite time, both
long time. With the progress of the reaction, highly reactants, ethyl acetate and NaOH, are completely con-
conducting OH− ions (equivalent ionic conductance, verted to sodium acetate and ethyl alcohol as the reac-
λ0OH -: 199.2 S cm2 gequiv−1 [20]) in the solution were tion product. The conductivity of solution in the reac-
replaced by an identical number of less conducting tion vessel is governed by sodium acetate since ethyl
acetate ions (λ◦ CH3COO -: 41 S cm2 gequiv−1 [20]), re- alcohol will not contribute to conductivity change.
sulting in a continuous decrease in conductivity of so- Hence, the conductivity of a synthetic sodium acetate
lution. From the onset of reaction, the decrease in con- solution (prepared by using NaOH and acetic acid of
ductivity was continuously monitored online using a equimolar concentration, 1.92 mM) corresponding to
high-performance laboratory-made pulsating conduc- same molar concentration of either of the reactant (1.92
tivity meter. Figure 4 shows an online graphic view of mM in this case) refers to the conductivity at infinite
conductivity with respect to time during the saponi- time. Thus, this approach avoids having to carry out
fication reaction conducted at a constant temperature. measurement for a prolonged period (at least for 2 h).
Such a smooth online plot was generated due to fast From these data, as given in Table I, the rate constant at

International Journal of Chemical Kinetics DOI 10.1002/kin

6 DAS ET AL.

Table I Data for the Computation of Rate Constant in the Saponification Reaction at a Constant Temperature
Specific Conductance, Specific Conductance
Time, t (s) κsoln. (μS/cm) (Corrected), κt (μS/cm) (κ0 − κt ) = A (κt − κ∞ ) = B A/B
0 721.6 720.2 0 438.1 0
100.3 678.9 677.5 42.7 395.4 0.11
200.7 646.9 645.5 74.7 363.4 0.21
300.2 619.8 618.4 101.8 336.3 0.30
400.5 599.4 598.0 122.2 315.9 0.39
500.9 582.5 581.1 139.1 299.0 0.47
600.4 567.8 566.4 153.8 284.3 0.54
700.7 554.9 553.5 166.7 271.4 0.61
800.2 545.2 543.8 176.4 261.7 0.67
900.6 535.4 534.0 186.2 251.9 0.74
1001 526.1 524.7 195.5 242.6 0.81
Composition of bath solution: [ethyl acetate]0 = 1.92e–3 M; [NaOH]0 = 1.92e–3 M.
Bath temperature: 323 K.
Specific conductance of distilled water at solution temp: 1.40 S cm−1 .
κt : specific conductance of solution at t, S cm−1 = (κsoln − 1.40).
κ0 : specific conductance at t = 0 (here κ0 = 721.6 − 1.4 = 720.2 (S cm−1 ).
κ∞ = specific conductance at t = ∞. (κ∞ = 283.5 − 1.4 = 282.1 (S cm−1 ).

a constant solution temperature was determined using Figure 5 shows the plots of (κ0 − κt )/(κt − κ∞ ) at
the relation cited in the literature [21,22]. We also ver- different solution temperatures in a typical experimen-
ified this real-time conductivity plot with the calcu- tal campaign. The slope of each plot was used for
lated conductivity values using the rate constant at this the determination of the rate constant. It is observed
temperature determined in the present work. To do so, that in some cases the plots show the presence of in-
we used the initial concentration of reagents, initial tercepts (about 0.03–0.035) instead of showing zero,
solution conductivity, conductivity at infinite time as as predicted theoretically. The presence of such small
used in this experimental run as the input parameters. intercepts is attributed possibly to difficulty in exact
The data points corresponding to the calculated con- determination of the κ0 value at elevated temperature.
ductivity values at every 50-s interval are placed in the Since the saponification reaction is a relatively fast re-
experimental plot. Both experimental and calculated action, and the reaction becomes still faster at elevated
values agreed well. temperature, it might have been difficult to detect the
exact conductivity of solution before the onset of the re-
action even if a number of precautions have been taken
for faster addition of reactant, counting time, rapid ho-
mogeneous mixing, and a uniform stirring rate, etc.
The presence of such a small value of intercept was
not observed in two experiments conducted at rela-
tively lower temperature. Moreover, as we are able to
get highly reliable data in conductivity during the re-
action, data acquisition for a period of 500 s will be
sufficient to get information about the rate constant.
Thus, the proposed technique is quite faster than the
other measurement techniques reported by earlier in-
vestigators.
To ensure the reliability in the determination of rate
constants at different constant solution temperatures,
we conducted seven measurement campaigns at each
Figure 5 Plot of (κ0 − κt )/( κt − κα ) against time for the solution temperature. The rate constant at each temper-
determination of rate constants of the reaction at differ- ature computed from the respective slope is presented
ent solution temperatures. [EtAc]0 : 1.923 mM; [NaOH]0 : in Table II. The uncertainty in the determination of
1.923 mM. slopes from seven independent measurements and the

International Journal of Chemical Kinetics DOI 10.1002/kin

 KINETIC STUDIES ON SAPONIFICATION OF ETHYL ACETATE 7

Table II Rate Constants of the Saponification Reaction at Different Temperatures

Temperature, T (K) Slopea Rate Constant, k a (L mol−1 s−1 )
303 3.11e–04 ± 2.80e–06 1.62e–01 (%RSD: 0.9)
311.7 5.11e–04 ± 5.62e–06 2.66e–01 (%RSD: 1.1)
313.3 5.38e–04 ± 5.16e–06 2.80e–01 (%RSD: 0.96)
317.5 6.66e–04 ± 5.86e–06 3.46e–01 (%RSD: 0.88)
323 8.40e–04 ± 9.41e–06 4.37e–01 (%RSD: 1.12)
328.5 1.16e–03 ± 1.28e–05 6.03e–01 (%RSD : 1.1)
a
Precision in measurement is calculated based on seven independent experimental results.

uncertainty in the determination of rate constants are et al. [8], Jensen et al. [7], and Warder [14]. The value
also indicated in this table. Results from the above reported by Smith et al. [4] is about 30% lower than
experimental campaigns show excellent agreement. our value. They also reported a very high value of
Using these data for rate constants at different tem- activation energy (61.4 kJ mol−1 ) [4] with respect to
peratures, the activation energy was determined and is the value reported in this work. Such a large deviation
presented in Table III. The other thermodynamic pa- in the values on the rate constant as well as activation
rameters in the saponification reaction of ethyl acetate energy can be attributed to errors associated with a vol-
and sodium hydroxide such as activation enthalpy, ac- umetric titration technique by withdrawal of aliquots of
tivation entropy, and free energy of activation were the sample at a periodic interval (off-line techniques).
computed using the data for rate constants at different Recently, Schneider and Stoessel [9] used the com-
temperatures following the Eyring equation [22], and mercial microcalorimeter integrated with a microreac-
they are shown in Table III. In the Eyring equation, tor for kinetic investigation in the flowing system. In
delta Cp# is considered to be very small and the re- their study, they used 0.8 M ethyl acetate and 1.0 M
action is considered to be 100% completion. It shows NaOH and conducted the experiments at five different
excellent agreement in these thermodynamic parame- temperatures ranging form 30 to 70◦ C. They obtained
ters with RSD varying from 0.9% to 1.4%. the value of activation energy, 46.5 kJ mole−1 , which
The rate constant at 30◦ C and activation energy was about 10% higher than the present value. The au-
for the saponification reaction, as obtained from the thors have taken a number of precautions, such as (i)
present work, were compared with the data reported by good mass transfer using a small radius of microchan-
earlier investigators in Table IV. This table shows sig- nel, (ii) homogeneous mixing of reactants by designing
nificant scatter in the data for both the reaction rate and the microreactor as a plug-flow reactor for a continu-
activation energy reported [4,7–9,14]. In the present ous operation at steady state, and (iii) selection of a
work, the rate constant at 30◦ C is 0.16 L mol−1 s. It calorimeter with high thermal sensitivity to carry out
is in agreement with the values reported by Tsujikawa the experiment. The measurement is based on the heat

Table III Thermodynamic Parameters in Saponification Reaction

Serial Number of Activation Energy Activation Enthalpy Activation Entropy G(298 K)
Experimental Campaign (kJ mol−1 ) (kJ mol−1 ) (J mol−1 K−1 ) (kJ mol−1 )
1 42.1 39.1 −131.1 78.2
2 40.7 38.1 −128.5 76.4
3 41.5 38.1 −133.2 77.8
4 40.8 38.2 −131.3 77.3
5 41.8 39.1 −130.9 78.2
6 41.2 38.5 −131.9 77.8
7 42.0 39.3 −130.3 78.2

Activation energy: 41.4 ± 0.6 kJ mol−1 .

Activation enthalpy: 38.6 ± 0.5 kJ mol−1 .
Activation entropy: −131.0 ± 1.4 J mol−1 K−1 .
Free energy of activation (298 K): 77.7 ± 0.7 kJ mol−1 .

International Journal of Chemical Kinetics DOI 10.1002/kin

8 DAS ET AL.

Table IV Comparison of Results

Rate Constants Activation Energy Technique
Investigators at 30◦ C (L mol−1 s) (kJ mol−1 ) Adopted
Smith et al. [4] 0.11 61.4 Volumetric titration
Jensen et al. [7] 0.15 – High-frequency titrimetry
Tsujikawa et al. [8] 0.16a 48.4 Conductivity measurement
Schneider and Stoessel [9] 0.19a 46.1 Microcalorimetry
Warder [14] 0.14 – –
Present work 0.16 41.4 Pulsating conductivity sensor
a
Data computed from the corresponding plots available in the literature.

changes during the reaction. In our work, the direct led us to evaluate thermodynamic parameters for the
online conductivity measurement of solution imme- saponification reaction. The values are in good agree-
diately after the onset of reaction is recorded, which ment with the recent data based on the microcalorimet-
provides kinetic information of the entire process. In ric technique. It will be extremely useful for researchers
view of simplicity in instrumentation and measurement and the students to use this novel measurement tech-
technique, the conductivity approach using the pulsat- nique for the kinetic study in any other system, which
ing sensor seems to be a better approach for the kinetic needs a precise measurement of conductivity.
study. Our reported value on activation energy is about
10% lower than the values reported by Tsujikawa et al.
and Schneider and Stoessel, as shown in Table IV. The authors are extremely grateful to Mr. S. A. V. Satya
The values for activation energy and other related Murty, Director, Electronics and Instrumentation Group, In-
dira Gandhi Centre for Atomic Research, Kalpakkam, India,
thermodynamic parameters are based on seven inde-
for his wholehearted support and constant encouragement
pendent campaigns carried out in this laboratory using throughout this work. We highly appreciate the contribution
the pulsating sensor, which show an excellent agree- of Mr. R. Ananthanarayanan, Mr. M. P. Rajiniganth, and Mr.
ment. This was possible due to augmentation of a high- K. Praveen in development of software and designing of the
performance pulsating conductivity monitoring system vertical stirrer used in this work. We are also thankful to Mr.
along with the in house–built experimental facility spe- M. Manogaran for providing necessary assistance throughout
cially designed for carrying out the kinetic study at a this work.
desired temperature. The high precision in conduc-
tivity measurement of extremely dilute solution using
BIBLIOGRAPHY
this innovative approach could permit us to carry out
all kinetic experiments successfully using reactants at a
1. Glasstone, S. Textbook of Physical Chemistry, 2nd ed.;
millimolar concentration level. Fast response and rapid McMillan: New Delhi, India, 1984; p. 1058.
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possible to complete an experimental campaign for the McMillan: New Delhi, India, 2004; Vol. 5, p. 116.
measurement of the rate constant within a short dura- 3. Daniels, F.; Matthews, J.; Williams, J. Experimental
tion (even in 500 s). This minimized the error associ- Physical Chemistry; McGraw-Hill: New York, 1941;
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International Journal of Chemical Kinetics DOI 10.1002/kin

 KINETIC STUDIES ON SAPONIFICATION OF ETHYL ACETATE 9

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International Journal of Chemical Kinetics DOI 10.1002/kin