Kinetics of Iodide-Catalyzed Decomposition of
Hydrogen Peroxide in a Continuous-Stirred Tank
Reactor
Jared Audie Dwight O. Miguel
Bicol University, Legazpi City, Philippines; jaredaudiedwight.miguel@bicol-u.edu.ph
Abstract – The catalytic decomposition of hydrogen
peroxide provides a range of reaction mechanism
possibilities of varying complexity. This is because of the
variety of catalysts, such as catalase in biological
processes and inorganic metals for industrial
applications that will increase the rate of decomposition
and the methods that can be used to monitor the
reaction. In this paper, the kinetics of the decomposition
of hydrogen peroxide using iodide catalyst under acidic
condition is analyzed using thiosulfate ion as the time
rate indicator. The experimental data were used in the
differential analyses and linear regressions using MS
Excel. The analyses involved variation of iodide and
hydrogen peroxide initial concentrations, and estimation
of pseudo rate coefficient. Results suggested that the
reaction can be approximated as a first order reaction
however the non-integral value obtained for reaction
order suggested that it is a non-elementary reaction. A
designed continuous-stirred tank reactor was considered
in calculating the theoretical yield of the reaction. Using
a 0.5-L reactor tank and 1.0M initial concentration of
hydrogen peroxide, the conversion is 40% which is
relatively low. Higher conversion of up to 90% can be
achieved by using a 20-L reactor tank.The conversion
can be increased if either the initial concentration of the
reactant is increased.
Index Terms: Continuous-stirred tank reactor, initial rate,
iodide-catalyzed, order, reaction order
INTRODUCTION
Oxidants are ubiquitous in atmospheric processes and
biochemical systems, one of the most common that occur in
the environment being hydrogen peroxide. In many living
organisms, hydrogen peroxide can also be present as a
product of metabolism that must be broken down because
appreciable amount of peroxide is toxic to the organisms. It
is damaging to cells because it attacks unsaturated fatty acids
found in cell membranes, hence as an adaptive mechanism,
cells produce a powerful catalyst, called catalase, that
decomposes H2O2. The rate of decomposition is increased by
the intra-cellular enzyme catalase. It is a catalyst, rather than
just another reactant, because it reacts both as an electron
donor and as an electron acceptor. As an interesting contrast,
a similar increase in the rate of decomposition of hydrogen
peroxide can be achieved using an inorganic catalyst such as
manganese (IV) oxide, lead (lV) oxide or oxides of iron.
There are many other compounds that decompose hydrogen
peroxide such as iodide ion under acidic conditions. If the
solution is relatively acidic (with a pH is less than about 3)
the rate of reaction is independent of the pH. The
decomposition is characterized by the stoichiometric
reaction :
+¿+ H 2 O2 →I 2+ 2 H 2 O ¿
2 I −¿+2 H ¿
As with a lot of kinetics, the concentration of reactants or
products at any instant is difficult to measure directly, so in
this study the rate will be determined indirectly. A
convenient test using starch indicator for the presence of the
iodine in the products is suggested in most experiments.
Starch reacts with iodine to form a blue/black colored
complex. Unfortunately as soon as any iodine is produced it
will react to make the complex and the solution will turn
blue-black instantaneously. Thus, using starch as an
indicator by itself would not be of much help. It confirms
that some amount of I2 is being formed, but it presents
nothing about the kinetics of the decomposition reaction -
the rate which indicates how long it takes to produce a given
quantity of I2.
The problem in measuring the kinetics of the reaction
can be resolved by introducing a side reaction involving
thiosulfate ions that will remove the initial I 2 that is produced
by our main reaction. This will prevent the solution from
turning black long enough so that time measurements can be
made. The following side reaction will be used:
−¿+ S 4 O6
2−¿¿
¿
I 2+ 2 S2 O 32−¿ →2 I ¿
Thiosulfate ion, reacts with I2 which prevents the
solution from turning blue-black. A carefully measured the
amount of thiosulfate (a small amount that will run out fairly
quickly) will be used to know exactly how much iodine it
will take to react with this thiosulfate. Once the small
amount thiosulfate has completely reacted, I 2 will start to
build up in the solution. As soon as the thiosulfate runs out, 2 150 25 15 5 25 275 25
I2 will react with the starch and the solution will turn blue- 3 150 25 20 5 25 275 25
black. By putting in this time delay, the rate at which I 2 is 4 150 25 25 5 25 275 25
being formed can be calculated. H2O2 initial concentration variation
1 100 25 25 5 25 200 100
In this paper, the results of the experiment and the 2 100 25 25 5 25 225 75
calculated reaction kinetics data served as the baseline in 3 100 25 25 5 25 250 50
choosing a reactor that will meet the reaction conditions. A 4 150 25 25 5 25 275 25
continuous stirred tank reactor (CSTR) is considered since it
is normally used for a homogeneous liquid-phase reaction.
Determination of the order of the reaction
In the laboratory, it may also be used for a gas-phase
reaction for experimental measurements, particularly for a Assume that the rate of the reaction under acidic conditions
catalysed reaction. Therefore, a CSTR is proposed for this is given by,
reaction. It is characterized by running it at steady state with
continuous flow of reactants and products. Additionally, the r =k ¿ ¿
feed assumes a uniform composition throughout the reactor,
exit stream has the same composition as in the tank. where k is the rate coefficient,¿ is the iodide concentration,
[ H 2 O2 ] is the hydrogen peroxide concentration and a and
METHODOLOGY
b are the order of the reaction with respect to iodide and
Laboratory scale experimental data is considered to generate hydrogen peroxide, respectively. Suppose that we measured
a differential analysis of the rate of the reaction between the rate using some baseline concentrations of iodide and
iodide and hydrogen peroxide in an acidic environment hydrogen peroxide, ¿ and ¿ respectively. The baseline rate is
which is the basis of the design of a continuous-stirred tank denoted by r 0.
reactor. In order to achieve this, the laboratory data
presented in the experiment conducted by Sweeney, et. al. The ratio between the new rate and the baseline rate is
(2014) is used. The following table presents the reagents given by the following equation
used and the corresponding specifications.
r
TABLE I =¿ ¿ ¿
REAGENTS USED IN THE PRE-EXPERIMENT r0

Reagents r
Acetate buffer solution 0.5 M, pH 3.0
=¿ ¿
r0
Sodium thiosulfate 0.02 M
Potassium iodide 0.3 M In this case linear regression can be used to determine an
Hydrogen peroxide 6% v/v experimental value. By taking the natural logarithms of both
Starch solution 1.00 g/25.0 mL water
sides of equation,

The variation of the initial concentration of the reactants

was employed in the initial method of determining the order
ln ( rr )=a ln¿
0
and rate constants of the reactions. The experimental
solutions are presented in Table II. Therefore if we measure the reaction rate at some
concentration of iodide and then make several more
TABLE II measurements at differing concentrations of iodide and plot
EXPERIMENTAL SOLUTIONS FOR VARYING KI AND H2O2 INITIAL
CONCENTRATIONS
ln ⁡(r /r 0 ) as a function of ln ⁡¿ the slope will be equal to a ,
the order of the reaction with respect to the iodide
KI initial concentration variation concentration. Similar reasoning is applied to measure the
Sa H2O Buffe KI Na2S2 order of the reaction with respect to the hydrogen
Starch H2O H2O2
mp (mL r (m O3
le ) (mL) L)
(mL)
(mL)
(mL) (mL) peroxide concentration.
1 150 25 10 5 25 275 25
 r /r 0 , were also obtained.
ln ( rr )=b ln¿
0
The ratios of the measured rates,
Taking the natural logarithms, ln ⁡¿ as the independent
variable and ln ⁡(r /r 0 ) as the dependent variable, a linear
Estimation of the pseudo rate coefficient regression was performed. The plot is shown in Figure I.
The pseudo rate coefficient with respect to iodide and
another pseudo rate coefficient with respect to hydrogen
peroxide are to be estimated. To estimate a pseudo rate
coefficient with respect to iodide, use the data where the
iodide was varied and the hydrogen peroxide concentration
was kept constant. Under these conditions, let
k ' =k [ H 2 O2 ]b , and the expression for the reaction rate
becomes:

r =k ' ¿

If the measured reaction rate, r , is plotted as a function of ¿

FIGURE I
then k ' can be determined from the slope.

To estimate a pseudo rate coefficient with respect to

hydrogen peroxide, use the data were the hydrogen peroxide
was varied and the iodide concentration was kept constant.
Define this pseudo rate coefficient k '' =k ¿ and the
expression for the reaction rate becomes,
r =k ' ' [ H 2 O2 ] b
If the measured reaction rate, r , is plotted as a function of
[ H 2 O2 ]b then k ' ' can be determined from the slope.
Design of the CSTR
For the reactor sizing, the Levenspiel approach is used by
plotting the rate function and conversion.
F A0 X A
V=
−r A
RESULTS AND DISCUSSION
PLOT OF ln ⁡¿ VERSUS ln ( rr )
0
The order of the reaction with respect to iodide
concentration was represented by the slope of the curve
generated with a shared variance, R2 of 0.9938 which means
that the data fitted satisfactorily. The order with respect to
iodide is 0.6735 which indicates that the reaction is clearly
non-elementary.
Variation of H 2 O2 initial concentration
In this part of the experiment, the concentration of KI
was held constant. Using solution 4 as the baseline solution
(see Table 2), the ratios, [ H 2 O 2 ] /¿, for the solutions A,B, C
and D were calculated. The ratios of the measured rates,
r /r 0 , were also obtained. Taking the natural logarithms,
ln ⁡¿ as the independent variable and ln ⁡(r /r 0 ) as the
dependent variable, a linear regression was performed. The
plot is shown in Figure II.

The rate constant and order of the reaction were calculated

using the experimental data with the aid of MS Excel. This
section discusses the effect of variation of iodide and
hydrogen peroxide initial concentrations, and estimation of
pseudo rate coefficient.

Variation of iodide initial concentration

Using solution 4 as the baseline solution (see Table 2),

the ratios, ¿ ¿, for the solutions 1, 2, 3 and 4 were calculated.
 The shared variance of 0.9995 showed that the data fitted
satisfactorily. The value of the rate constant was determined
using the value of the y-intercept of the line. Taking the
antilog of the value and dividing it by the concentration of
0.71
L
KI, the rate constant is equal to 0.45415 ( )
mol
min−1.
Therefore the rate equation of the reaction is:

0.71
L
−r =0.45415 ( )
mol
min−1 ¿ ¿

Reactor sizing

The design of the reactor is based on the conventional

reactor tank with installed stirrer inside and connected to
FIGURE II
tubes where the feed flows from the top of the tank and the
PLOT OF ln ⁡¿ VERSUS ln ⁡(r /r 0 )
product flows through the tube connected to the bottom part
of the tank.
The order of the reaction with respect to H 2 O 2 was found
to be 1.0355 as indicated by the slope of the line as shown in
Figure II. A shared variance of 0.9995 indicates that the date
fitted well. The reaction order can be considered as a first
order reaction with respect to H 2 O 2 . However, considering
the overall reaction order, from that of KI, the reaction is
still concluded to be non-elementary.

Estimation of pseudo rate coefficient

The rate constant was determined using the pseudo

estimation. From the baseline solution D, the rate in terms of
moles of hydrogen peroxide per minute and [ H 2 O 2 ]b were
calculated. To linearize, the natural logarithms of the values
were obtained and tabulated. The values were plotted,
b
ln ⁡(rate) as the dependent variable and ln ⁡( [ H 2 O2 ] ) as
the independent variable. The graph is presented in Figure FIGURE IV
III. SCHEMATIC DIAGRAM OF THE PROTOTYPE CONTINUOUSLY-STIRRED TANK
REACTOR FOR THE IODIDE -CATALYZED DECOMPOSITION OF HYDROGEN
PEROXIDE

A small CSTR was constructed with a reactor volume of

0.5 L and total feed flow rates of 4 mL/s (2 mL/s in each
reactant). Using the established rate equation, the conversion
of in the reactor can be calculated at varying initial feed
concentrations in the inflow. The initial concentrations of KI
and H2O2 are set as equimolar. The volume of a CSTR can
be represented as the shaded areas in the Levenspiel plot
shown in Figure 5. For an initial concentration of 1.0 M for
each reactant, the corresponding conversion is about 40%.
FIGURE III To achieve higher conversion, say 90%, from Figure 6, the
DETERMINING THE RATE CONSTANT OF THE REACTION
required reactor volume is 20 L which is very large for a
laboratory scale reactor.
In a practical sense, the 40% conversion is relatively low.
The conversion can be increased if either the initial
concentration of the reactant is increased or the flow rate is
decreased (so as to promote increased reaction time). On the
other hand, a series of CSTR can be proposed. However, the
economics of this reactor must be primarily considered in
decision making.
FIGURE V
PLOT OF THE FAO/R VERSUS CONVERSION X
The view of the curve is intensified by lowering the
maximum and minimum values in the axes.
FIGURE V
PLOT OF THE FAO/R VERSUS CONVERSION X. THE CURVE IS EXTENDED UP
TO THE CONVERSION OF 1.0
CONCLUSION
The kinetic data obtained such as the rate constant and
the respective order of the reaction are generally
satisfactorily based on the shared variance values shown in
the plots. In addition, more statistical tool can be used other
than shared variance to support the results and validate
further. The rate equation was successfully established,
however, additional statistical analyses or comparison with
other experimental studies would increase the confidence of
the results if the results are consistent. The proposed small
single CSTR for the reaction yields a relatively low
conversion. It is expected that low reactor volume will result
to low conversion. The parameters residence time and space
time must also be considered in designing a reactor.
Operating parameters involving temperature, pressure and
the likes can also be varied. These must be taken in to
consideration when selecting the type of material and
specifying energy requirements.
RECOMMENDATION
There are lots of interesting reactions that can be a
subject for a kinetic study. In designing a reactor, it is
advised to use software that can provide interactive visual
and numerical simulation of data. Furthermore, a more
comprehensive and in-depth knowledge in reaction kinetics
and heat and mass transfer principles are highly necessary to
design an operational and safe reactor.
ACKNOWLEDGEMENT
The author would like to express deep gratitude to Engr.
Junel B. Borbo for the insights and supplementary materials
to work on, which aid in understanding the topics in ChE
127 - Chemical Reactions Engineering. Through this
material, I was able to determine and analyze the kinetic data
of a specific reaction via experimentation and numerical
analysis; and to apply the results in designing a simple
reactor.
 REFERENCES Sweeney, W., Lee, J., Abid, N., and DeMeo, S. (2014). Efficient Method
for the Determination of the Activation Energy of the Iodide-Catalyzed
Helfferich, F.G. (2004). Kinetics of multi-step reactions. 2nd edition. Decomposition of Hydrogen Peroxide. Journal of Chemical Education, 91
Volume 40. 309-345. (8), 1216-1219.
Levenspiel, O. (1999). Chemical reaction engineering. 3rd edition. New
York: John & Wiley, Inc. Jared Audie Dwight O. Miguel, Student, Department of
Chemical Engineering, Bicol University.