Chemical Engineering and Processing 39 (2000) 141 – 148

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Batch and semibatch reactor performance for an exothermic

reaction
M.D. Grau a, J.M. Nougués b, L. Puigjaner b,*
a
Mining Engineering and Natural Resources Department, Escola Uni6ersitàtia Politècnica de Manresa, Uni6ersitat Politècnica de Catalunya,
61 -73 -08240, Manresa, Spain
b
Chemical Engineering Department, Escola Tècnica Superior d’Enginyers Industrials de Barcelona, Uni6ersitat Politècnica de Catalunya,
647 -08028 Barcelona, Spain
Received 19 October 1998; received in revised form 10 February 1999; accepted 19 February 1999

Abstract

In this work, a study of a batch and semibatch reactor has been carried out based on a very exothermic reaction between
thiosulfate and hydrogen peroxide. The experiments were carried out in a glass-jacketed reactor of 5 l, provided with different
sensors and a data acquisition system. Thermal and kinetic studies were carried out previously using an adiabatic batch reactor.
Then, these results have been used for experiments in semibatch mode of operation with heat transfer. Several experiments have
been carried out at different operating conditions (addition flow, initial temperature, initial concentration of reagents…). In batch
and adiabatic mode of operation, experimental measures of the reaction mass temperature provided concentration profiles of
reagents and products which have been compared to those determined by simulation. In semibatch mode of operation,
temperature profiles have also been simulated and validated with experimental results. An algorithm describing the mathematical
model has been developed and implemented in a software module written in FORTRAN 77 language. With this mathematical
model it has been possible to obtain concentration and heat profiles for the semibatch mode of operation. © 2000 Elsevier Science
S.A. All rights reserved.

Keywords: Batch; Thiosulfate; Hydrogen peroxide

1. Introduction
Batch processes play a very important role in the
chemical process industry, being their main applications
in the production of specialty chemicals, polymers, or
bioproducts. These processes are characterized not only
by small scale flexible production and high added value
products, but also by reaction systems that may be
quite complex and not entirely known. For this reason,
batch reactors are also very much used in studies of
reaction kinetics and thermal effects modelling. Semi-
batch mode of operation can be used to have a better
control of the reaction, and is particularly important
for highly exothermic processes where safety is of high
* Corresponding author. Tel.: +34-934016678;
934017150.
concern.
Studies with adiabatic reactors have been reported by
several authors using the thiosulfate–peroxide reaction.
Most of them have studied the influence of different
initial reagent concentrations, and started the reaction
at 273 K, in order to obtain the kinetic equation in an
adiabatic batch reactor. For example Root and Schmitz
[1] and Vetjasa and Schmitz [2] studied the reaction in
a batch reactor and used the data obtained for the
study of steady state multiplicity in a loop reactor and
a stirred tank reactor (CSTR), respectively. Similar
work was made by Chang and Schmitz [3]. Guha et al.
[4] reported also a study of transient behavior of an
adiabatic CSTR.
On the other hand, Ausikaitis and Engel [5] and Lin
and Wu [6] studied the stability and performance of an
adiabatic controlled cycled stirred tank reactor
fax: +34- (CCTR). Also, Lo and Cholette [7] studied optimum
performance of an adiabatic MT reactor.

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PII: S 0 2 5 5 - 2 7 0 1 ( 9 9 ) 0 0 0 1 5 - X
142 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148

dcB
In this work, the method used is more similar to the = − 2·k·cA·cB (5)
dt
one presented by Cohen and Spencer [8]. As a previous
work [9], the kinetic equation can be derived from data dcP 1
= − ·k·cA·cB (6)
obtained in a series of runs in which the initial reagent dt 2
concentrations is held constant and the initial tempera-
ture is varied. Where, cP is the concentration of the products Na2S3O6
The objective of this work is to obtain the maximum and Na2SO4.
information about the reaction, by only measuring the The equation of Energy Balance is solely referred to
temperature of the mass reaction. The data of tempera- the reaction mass:
ture versus time obtained is used to determine the dT DHr·k·cA·cB
concentration evolution of reagents and products, rate =− (7)
dt r·Cp
of reaction, heat generated, etc. Then, the profiles ob-
tained experimentally are compared to those deter- It is possible to introduce a correction factor: (1 +o) in
mined by simulation. An algorithm describing the the denominator of Eq. (7) to take into account the
mathematical model (written in FORTRAN 77) has heat absorption effect of the reactor wall and stirrer.
been developed, using the thermodynamic and kinetic Lin and Wu [6] estimated o from the equation:
data obtained in the previous experiments. 2·rW·CPW·DrW
This information will be useful for the semibatch o= (8)
r·CP·rW
mode of operation, because of the exothermicity of the
reaction contemplated. Gygax [10] and Stoessel [11] In this work the ratio between the concentrations of
reported the importance of adiabatic determinations to reagents used is cA/cB = 2/3; therefore, H2O2 (B) is the
the study of potential runaway reactions. Hugo et al. limiting reagent.From Eqs. (5) and (7) it is obtained:
[12] determined the maximum temperature in a CSTR
DHr
and a SBR in case of breakdown of cooling and used dT= ·dc (9)
data obtained by adiabatic operation. 2·r·CP B
By integrating this equation, the following expression is
obtained:
2. The mathematical model
DHr
T− T0 = ·(c − cB0) (10)
For an adiabatic batch reactor the mathematical 2·r·CP B
model is made up by a set of differential equations Taking into account the relationship of cB with conver-
resulting from Mass and Energy Balances referred only sion Eq. (10) becomes:
to the reaction mixture, because there is not heat
transfer. DHr·cB0
T− T0 = − ·x (11)
The stoichiometry of the reaction studied is: 2·r·CP

Na2S2O3 + 2 H2O2 where the difference between initial and final tempera-
tures, when conversion is x= 1, is defined as DTad:
“ 1/2 Na2S3O6 + 1/2 Na2SO4 +2 H2O
DHr·cB0
The kinetic equation is first order with respect to two DTad = − (12)
2·r·CP
reagents: Na2S2O3 (A) and H2O2 (B).
and Eq. (11) can be rewritten as:
r= k·cA·cB (1)
T= T0 + DTad·x (13)
Considering constant density conditions, the equations
Parameter DTad is very useful to determine Maximal
corresponding to the Mass Balance are:
Temperature attainable by runaway of the desired Syn-
Total Mass Balance:
thetic Reaction (MTSR). Also, DTad gives a method to
d(r·V) obtain DHr from Eq. (12).
(2) Eq. (13) allows one to find the conversion at any
dt
instant using only one measure of temperature. Then,
dV concentrations of the reagents and products can be
=0 (3)
dt found:
Component Mass Balance: 1
cA = cA0 − cB0·x· (14)
dcA 2
= − k·cA·cB (4)
dt cB = cB0·(1−x) (15)
 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148 143

The measure of the variation of the temperature with 3. Experimental set-up

time permits also to determine the Arrhenius equation.
The Eq. (7) can give the rate constant at each instant: The experimental set-up is shown in Fig. 1. A glass-
jacketed reactor of 0.005 m3 is used to carry out the
(dT/dt)·r·CP
k= (16) reaction. The reactor is provided with temperature, pH,
( −DHr)·cA·cB and conductivity sensors connected on-line with the
Taking into account that the Arrhenius expression is: data-logging system. Dosing equipment, temperature
control, and variable stirring is also available. Tempera-
k = k0·e − Ea/R·T (17)
tures are measured using Pt-100 temperature sensors.
from recorded temperature – time curve, the derivative The analog signals from the sensors are fed to a
dT/dt can be calculated and using the values obtained measuring and control unit provided with A/D and
with the Eq. (16) ln k is calculated. Therefore, with a D/A converters and a power interface. The data acqui-
single experiment it is possible to obtain k0 and Ea/R, sition units are connected to the data processor by a
and represent these values in a ln k versus 1/T plot at standard IEEE-488 interface (IEC Bus). A process con-
each instant. It is also possible to obtain reaction rate trol engineering software support the data manage-
using Eq. (1) and the heat generated by the following ment. All physically available analog inputs and
expression: outputs as well as all virtual channels are automatically
monitored and process values are stored. The process
Qr = − V·DHr·cA·cB (18)
values can be transmitted using three different mediae.
The information provided by these variables will be It is also possible to obtain on-line configured curves on
essential in the follow-up and performance measure- the display screen. The display period is determined by
ment of the reaction. the configured interval. A D-Base Software Adapter
For semibatch mode of operation and with heat was used to convert the compressed data form of the
transfer, Eqs. (3)–(5) and (7) become: history file (on the hard disk) into D-Base III Plus file
format. The adapter operates off-line, i.e. process value
dV
=F0 (19) recording must have been already terminated, and the
dt program must be quit. Then these D-Base files can be
d(V·cA) converted to Lotus 1-2-3 or Excel spreadsheet, and use
= − V·k·cA·cB (20)
dt a familiar environment for data acquisition application.
d(V·cB)
=F0·cB0 − 2·V·k·cA·cB (21)
dt 4. Experimental procedure
dT F0·(T0a − T) DHr·k·cA·cB QM
= − − (22)
dt V r·Cp V·r·CP The first step to carry out the experiments has con-
sisted of isolating the chemical reactor, and the annular
where QM is the heat exchanged with the wall. In this
space of the jacket has been evacuated in order to
mathematical model the equations of the energy bal-
approach adiabatic conditions.
ance for wall and for jacket have also been enclosed.
Because a batch mode of operation has been chosen,
two different kind of experiments have been planned,
depending on the way the reagents are introduced into
the reactor:
1. Solution of Na2S2O3 is introduced in the reactor and
then H2O2 is introduced;
2. The two reagents are introduced simultaneously in
the reactor.
All the experiments have been carried out with the
same initial concentrations of reagents: cA0 = 0.6 M and
cB0 = 0.9 M. Reagent concentrations at the inlet of
batch reactor are half of those indicated above, because
the volume of the two solutions is the same. Experi-
ments (A) and (B) have been carried out at four differ-
ent initial temperatures (Table 1).
For the semibatch mode of operation, the jacket was
filled with water at a temperature of 293 K, circulating
at a flow of 1.37×10 − 5 m3 s − 1. Three sets of experi-
Fig. 1. Pilot plant and data acquisition. ments have been executed as is shown in the Table 3. In
144 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148

Table 1 5. Results and discussion

Summary of batch reactor experiments

Run Initial temperature Final temperature −DHr(kJ Figs. 2 and 3 show the experimentally recorded tem-
(K) (K) kmol−1) perature versus time curve obtained for experiments (A)
and (B), respectively. With these measures it is possible
1A 288.37 317.76 5.722 E5
to determine all variables related in Eqs. (12)–(18).
2A 293.47 321.57 5.471 E5
3A 298.23 326.37 5.478 E5 As a previous work [9], the thermodynamic and
4A 307.12 335.08 5.443 E5 kinetic data are calculated. First, DHr is calculated from
1B 293.07 322.34 5.698 E5 Eq. (13), taking into account the correction factor of
2B 297.66 327.19 5.749 E5
Eq. (8). Thus, an estimated value of o= 0.0478 is ob-
3B 303.41 333.17 5.794 E5
4B 306.90 336.00 5.665 E5 tained. It is assumed that the density and heat capacity
of reacting fluids are the same as those of water. The
results of the calculation of DHr are indicated in Table
Table 2 1.
Arrhenius values of the bibliography
Most of the experiments (A) give values of DHr lower
Authors k0 (m3 kmol−1 s−1) Ea/R (K) than those of experiments (B). This can be due to the
different method used to carry out the mixing of the
Cohen and Spencer [8] 6.85 E11 9200 two reagents. Chang and Schmitz [3] and Lo and
Lo and Cholette [7] 2.13 E10 8238
Cholette [7] reported the importance of the type of the
Lin and Wu [6] 2.00 E10 8238
reagent employed and the ratio of the reagents’ concen-
tration. This also means the necessity to measure values
Table 3 of kinetic constants for our experiments.
Operation conditions for semibatch reactor

Experiment F0×106 (m3 s−1) cA0 (M) cB0 (M)

1 1.75 0.8 1.2

2 3.12 0.8 1.2
3 4.67 0.8 1.2
4 5.74 0.8 1.2
5 6.58 0.8 1.2
6 7.58 0.8 1.2
7 1.75 1.6 2.4
8 3.12 1.6 2.4
9 4.67 1.6 2.4

Table 4
Experiments with different addition temperature

Experiment F0×106 (m3 s−1) T0 (K) Fig. 2. Experimental temperature profiles for experiments A.

1 1.75 292.3
3 4.67 293.1
6 7.58 293.5
10 1.75 277.7
11 4.67 283.9
12 7.58 282.4

the first case, initial concentrations were: cA0 =0.8 M

and cB0 =1.2 M. The reagent B (H2O2) was added
continuously at different flow for each experiment. In
the second case, the conditions were similar but initial
concentrations were: cA0 =1.6 M and cB0 =2.4 M. An-
other variable changed was the addition in temperature
of H2O2 as is indicated in the Table 4. Fig. 3. Experimental temperature profiles for experiments B.
 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148
Fig. 4. Comparison of experimental and simulated temperatures and
conversions. (Experimental data are taken every 10 s, but are repre-
sented every 30 s).
Fig. 5. Comparison of experimental and simulated results of temper-
ature versus conversion.
Fig. 6. Experimental and simulated (Eqs. (1)–(7)) concentration
profiles. (Experimental data are taken every 10 s, but are represented
every 30 s).
The following results are referred only to experiments
(B), because the reagents are introduced simulta-
145
neously. Using Eqs. (16) and (17), a value of k0 =8.13
E11 m3 kmol.s and a value of Ea/R=9156 K were
obtained. These kinetic data are consistent with those
obtained by other investigators as can be seen in Table
2.
The following results are referred to experiment 1 B,
in order to compare experimental and simulated results
(they are only referred to experiment 1 B in order for
the figures to be clearer). The algorithm built on the
mathematical model has been implemented in a soft-
ware module written in FORTRAN 77 language. Simu-
lation runs have been conducted following the same
conditions used in the experiments carried out.
Fig. 4 shows the temperature rise. Simulated temper-
ature is obtained by Eq. (7), but it is necessary to
introduce a time delay:
dTH T− TH
= (23)
dt D
The relationship between temperature and conversion
according to the Eq. (13) is represented in Fig. 5.
Fig. 6 shows experimental and simulated concentra-
tions of reagents and products. Experimental concen-
trations have been obtained using Eqs. (13)–(15) and
simulated results have been obtained using Eqs. (1)–(7)
and Eq. (17).
Some differences can be seen among these represen-
tations, but the final concentrations take the same
values at the same time. At 270 s, H2O2 is consumed
and Na2S2O3 and products are 0.1 and 0.15 M, respec-
tively. This can be explained because of the different
methods used: the simulated concentrations are calcu-
lated using differential equations, and the Arrhenius
expression is for the main reaction (written above)
between Na2S2O3 and H2O2 (Eqs. (1)–(7)), on the other
hand experimental concentrations are not found by
direct measure but calculated from the temperature
measures, using Eqs. (13)–(15).
Fig. 7. Experimental and simulated (Eqs. (13) – (15)) concentration
profiles. (Experimental data are taken every 10 s, but are represented
every 30 s).
146 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148
Fig. 8. Experimental evolution of heat generated and conversion
versus time for adiabatic reactor.
Fig. 9. Evolution of addition flow of H2O2 for semibatch experi-
ments. (Experimental data are taken every 10 s, but are represented
every 60 s).
Fig. 10. Experimental temperature profiles for semibatch experiments
with different addition flow. (Experimental data are taken every 10 s,
but are represented every 60 s).
Fig. 7 shows the experimental and simulated concen-
tration profile, but in this case simulated concentrations
are calculated by the same method as experimental
values, using Eqs. (13)–(15). Now the results are more
similar to the ones obtained with the experiments.
Finally Fig. 8 indicates the relationship between heat
generated and conversion. At 90 s, the rate of reaction
and heat generated is maximum, reaching about 40%
conversion.
For the semibatch experiments, Fig. 9 shows the
evolution of flow for the six different experiments with
the temperature profile indicated in Fig. 10. In this
case, initial concentration of reactants are 0.8 and 1.2
M, as is indicated in Table 3. Fig. 11 permits to
compare the temperature evolution for three different
addition flow with different initial concentration. Ex-
periments 1 and 7, 2 and 8, and 3 and 9 had the same
operation conditions, but the influence of initial con-
centration can be seen. The temperature goes on rising
when the addition flow is stopped, but for the more
concentrated solution, the decreasing of temperature
Fig. 11. Comparison of temperature profiles for experiments with
different initial concentration. (Experimental data are taken every 10
s, but are represented every 60 s).
Fig. 12. Comparison of temperature profiles for experiments with
different addition temperatures. (Experimental data are taken every
10 s, but are represented every 60 s).
 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148 147

in Fig. 13 for the two extreme addition flows of H2O2

(experiment 1 and 6). Fig. 14 shows the concentration
profiles obtained by simulation for these extreme cases.
Final concentration for thiosulfate is 0.1 M (in excess)
and for products 0.15 M. When the flow is greater, the
reaction is developed more quickly, but the accumula-
tion of H2O2 (CB6) is more important. Finally, Fig. 15
indicates the heat generated by the reaction (Qr) and
the heat removed by the fluid circulating in the jacket
(QM). When the flow rate of addition is high there is an
important difference between Qr and QM, and it is clear
that the jacket is not able to remove the reaction heat.

6. Conclusions
Fig. 13. Experimental and simulated temperature profiles for experi-
ments 1 and 6.
An adiabatic batch reactor has been modelled for a
very exothermic reaction between thiosulfate and hy-
drogen peroxide. Experimental results show a good
agreement with the results obtained by simulation. Sub-
stantial information has been obtained by measuring
only the variation of temperature inside the reactor.
The experimental results obtained in adiabatic opera-
tion have been very useful in work realised in semibatch
mode of operation using the same reaction. Because the
heat transfer is insufficient to remove heat generated by
reaction, in further work it will be interesting to control
the temperature of reaction by adding H2O2 with vari-
able and controlled flow, in order to study safety
aspects.

Fig. 14. Concentration profiles of reactants and products for experi- Acknowledgements
ments 1 and 6.
Financial support received from CIRIT is thankfully
acknowledged (Project QFN95-4702).

Appendix A. Nomenclature

cA Concentration of Na2S2O3 kmol m−3

cA0 Initial concentration of kmol m−3
Na2S2O3
cB Concentration of H2O2 kmol m−3
cB0 Initial concentration of H2O2 kmol m−3
cP Concentration of products kmol m−3
CP Heat capacity of reactants kJ kg−1 K−1
CPW Heat capacity of wallk J.kg−1 K−1
D Time delay s
Ea Activation energy kJ kmol−1
Fig. 15. Heat evolution for experiments 1 and 6. F0 Addition flow m3 s−1
k Rate constant m3 kmol−1
begins before. Fig. 12 shows the influence of addition s−1
temperature of H2O2. This influence is more important k0 Specific rate constant m3 kmol−1
when the addition flow is greater. s−1
With these experiments in semibatch reactor, the Qr Heat generated kJ s−1
mathematical model has been validated as can be seen QM Heat removed kJ s−1
148 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148

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[4] B.K. Guha, G. Narsimhan, J.B. Agnew, An experimental study
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T0 Initial temperature K 146 – 152.
T0a Temperature of H2O2 added K [5] J. Ausikaitis, A.J. Engel, Steady state multiplicity and stability in
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r Density of reacting mass kg m−3 [9] M.D. Grau, L. Puigjaner, Internal report No. EUPM388, UPC,
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rW Wall density kg m−3
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