ISSN 00360244, Russian Journal of Physical Chemistry A, 2011, Vol. 85, No. 13, pp. 2279–2282.

© Pleiades Publishing, Ltd., 2011.

CHEMICAL KINETICS
AND CATALYSIS

The Kinetics of Iodide Oxidation by Hydrogen Peroxide in Acid Solution1

M. C. Milenkovi c  and D. R. Stanisavljev
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 1216, P. O. Box 137, YU11001 Belgrade, Serbia
email: maja.milenkovic@gmail.com
Received December 23, 2010

Abstract—The kinetics of the complex reaction between I– and H2O2 in acid media was investigated. The
particular attention was focused on the determination of the rate constant of the reaction between HIO and
H2O2 involved in the investigated complex process. The examination of the whole kinetics was performed by
–
simultaneously monitoring the evolution of O2 pressure, I 3 and I– concentrations. We modeled the behavior
of experimentally followed components based on Liebhafsky’s research. Our preliminary results suggest a sig
nificantly higher rate constant (3.5 × 107 M–1 s–1) of the reaction between HIO and H2O2 as those proposed
in the literature.

Keywords: kinetics, iodide oxidation, complex reaction, hydrogen peroxide.

DOI: 10.1134/S0036024411130140

1
INTRODUCTION
The reactions of iodine are of environmental inter
est in the evaluation of the consequences of a nuclear
reactor accidents [1–3] as well as in marine chemistry
[4, 5]. Also, iodine has significant role in living organ
isms [6] and it is important component of several well
investigated chemical oscillators [7–11]. The first
investigations of the reaction between iodide and
hydrogen peroxide, as an important part of iodine
chemistry, is performed by Liebhafsky [12]. Although
it seems simple, this reaction takes place through a
–
series of observable intermediates (I2, I 3 )[13–16] and
short lived intermediates (such as HIO). Liebhafsky
observed complex kinetics of this reaction and found
that the rate constant for the ratedetermining step in
neutral solution is k 1' = 0.0115 M–1 s–1. More recently,
Hansen [17] has reexamined the same reaction in neu
tral solution. Using initial rates, he has determined
k '1 = 0.0173 M–1 s–1 in good agreement with Liebhaf
sky’s value. This rate constant, linearly depends of H+
concentration (k1 = 0.0115 + 0.175[H+]) [18] and
refers to the reaction (1) (see table).
The process (1) is the ratedetermining one and is
followed by much faster reaction (2).
The rate constant of reaction (2) was also calcu
lated by Liebhafsky [19] as k2 = 37 M–1 s–1. For the
determination of this constant, the rate and concen
trations of HIO and H2O2 should be known (ν2 =
k2[HIO][H2O2]). In his investigations, the rate ν2 was
1 The article is published in the original.
calculated from the rate of oxygen evolution. Due to
high reactivity and difficult experimental monitoring
of HIO, various authors [19–21] used convenient
approximations to simplify the determination of its
concentration. Liebhafsky assumed that the quantity
of reacted hydrogen peroxide can be determined
from the amount of evolved oxygen and that the
concentration of HIO can be calculated from the
equilibrium constant of iodine hydrolysis [HIO] =
Kh[I2]/([I][H+]). In the mixture initially containing
only of H2O2, I2 and H+ he further simplified calcula
tions of [HIO] assuming that: (a) the concentration of
iodide ions is solely determined by the solubility prod
uct constant of the precipitated TII, (b) iodine is
mostly determined by its solubility in water due to its
high excess relatively to added Tl+, (c) the triiodide
complex formation is neglected because of the low I–
concentration.
The process (2) was also investigated by Furrow
[20] as a part of the reaction between iodine and
hydrogen peroxide. He assumed that the whole system
is in a quasi steady state due to the small changes in I2
–
and I 3 concentrations determined spectrophotomet
rically. Furrow proposed as well that the I– concen
tration can be determined exclusively from the triio
dide equilibrium (4) and the concentration of HIO
from iodine hydrolysis reaction. He calculated the
value of 3 ± 2 M–1 s–1 for the rate constant of the reac
tion between HIO and H2O2. He has also mentioned
that a true steady state is never reached.
The determination of the concentration of I–, as
well as HIO, predominantly from the one equilibrium

2279
2280 MILENKOVIC , STANISAVLJEV

The model (1)–(4) proposed by Liebhafsky

(1) H+ + I– + H2O2 HIO + H2O k1 = 0.0115 + 0.175[H+] M–1 s–1 [18]
(2) HIO +H2O2 H + I– + O2 +H2O
+ k2 to be simulated
(3) –
I +HIO +H + I2 + H2O k3 = 3.6 × 109 M–1 s–1 [20]
k–3 = 0.0018/[H+] M s–1
–
(4) I2 + I– I3 k4 = 6.2 × 109 M–1 s1 [22]
k–4 = 8.5 × 106 s–1

(although they participate in the more than one fast
equilibrium) is an oversimplification which may intro
duce large uncertainties. According to this, we per
formed additional investigations of the reaction
involving HIO and H2O2 in the acidic media consider
ing all reactions proposed by Liebhafsky but without
any simplifications. The reactions are summarized in
the model consisting of four major processes with the
rate constants taken from different literature data (see
table).
In our numerical simulations only k2 is optimized
for the best possible agreement with experimental
data.
EXPERIMENTAL
The experimental setup is designed for simulta
–
neous monitoring of three reaction species: I–, I 3 and
O2 which enables more reliable correlation between
experimental data and investigated model.
The experiments were carried out in the closed,
well sealed reaction glass vessel at room temperature.
The free volume over the reaction mixture (occupied
by evolved oxygen during the process) was (64.01 ±
Fiber optic
probe Pressure
sensor
Working
I electrode
Reference
electrode Thermometer
Ag/AgCl
Solution
0.8 ml. The volume of the reaction solution was 90 ml.
Ports for I– ion sensitive electrode (Metrohm
6.0502.160), reference electrode Ag/AgCl (Metrohm
6.0726.100), pressure sensor (Freescale MPX2010 DP
pressure sensor “Merni istrumenti Budimir and Co.”)
and quartz fiber optic probe (Hellma 662.000UV,
Z.12) were carefully sealed to prevent leaking of gas
eous oxygen. Evolution of oxygen was monitored by
recording the potential of pressure sensor. The iodide
concentration was monitored by recording the poten
tial of iodide ionsensitive electrode versus double
junction Ag/AgCl reference electrode. Interior vol
ume of the reference Ag/AgCl electrode was filled
with 3 mol/dm3 KCl and the outer electrolyte was a
saturated solution of K2SO4. The formation of triio
dide complex was determined at 351 nm by quartz
fiber optic probe interfaced to the Agilent 8453
UV/VIS spectrophotometer. The experimental
setup is shown in Fig. 1.
All solutions are prepared in deionized water of
resistivity 18 MΩ cm and all chemicals were of p.a.
grade, hydrogen peroxide and potassium iodide from
Merck, sulfuric acid from Fluka. The experiment
was monitored for 500 seconds. To prevent oxygen
supersaturation the reaction solution was stirred
with the magnetic stirrer at 800 rpm. The initial
composition of the reaction mixture was: [H2O2]0 =
1.07 × 10–2 mol/dm3, [KI]0 = 1.035 × 10–3 mol/dm3
and [H2SO4]0 = 4.35 × 10–2 mol/dm3.
The calibration curve for pressure sensor was estab
lished using water manometer. Iodide sensitive elec
trode was calibrated with iodide standard solutions
made in sulfuric acid (of the same concentration as in
experiments). Linear dependence of absorbance for
different triiodide concentrations were checked by
making standard triiodide solutions from iodine and
iodide in sulfuric acid. The actual concentration of tri
iodide was calculated taking into account well known
equilibrium constant for the triiodide formation [23].
Before any experiment, tight sealing of all junctions
was carefully checked by constant sensor reading of
pressurized vessel.

RESULTS AND DISCUSSION

Magnet
The time dependencies of concentrations of iodide
and triiodide and oxygen pressure during the experi
Fig. 1. The experimental setup. ment are shown in Fig. 2. Due to the efficient stirring,

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 85 No. 13 2011

 THE KINETICS OF IODIDE OXIDATION BY HYDROGEN PEROXIDE 2281

(a) (a)
10
[I−] × 104, mol dm−3

[I−] × 104, mol dm−3

10
2
2
8 8
1 1

6 6

(b)
[I−3] × 105, mol dm−3

4 4 1

[I−3] × 105, mol dm−3

1 (b)

2
2 2
2

0
(c) 0
1
(c)
4 1
P(O2) × 10−2, Pa

4
P(O2) × 10−2, Pa

2
2
2
2
0
0 200 400 0
t, s
0 200 400
t, s
Fig. 2. The experimental results (1) and simulations (2): Fig. 3. The experimental results (1) and simulations (2):
(a) iodide concentration, (b) triiodide concentration and (a) iodide concentration, (b) triiodide concentration and
(c) oxygen pressure, for the value of k2 suggested by Lieb (c) oxygen pressure, for the value of k2 (3.5 × 107 M–1 s–1)
hafsky (37 M–1 s–1). optimized in this work.

the surface of the solution exhibits stochastic fluctua
tions which are reflected on the reading of the sensitive
pressure sensor (Fig. 2c). Oxygen pressure, iodide and
triiodide concentration obtained in numerical simula
tions using proposed model (1)–(4) are also presented
in Fig. 2 for better comparison with experiment. Sim
ulations are performed with the EZ Solve program
[24]. All rate constants are taken from table. If k2 is
Liebhafsky’s value 37 M–1 s–1 [19], investigated model
(1)–(4) relatively well simulates iodide and triiodide
concentrations (Figs. 2a and 2b), but oxygen is not
evolved in full measure even after 500 s (see Fig. 2c).
From Fig. 2c it is clearly evident that the rate constant
for the formation of oxygen (Eq. (2)) should be con
siderably higher than the proposed value of 37 M–1 s–1
or oxygen is produced by reaction different from Eq. (2)
indicating that model (1)–(4) should be extended.
To get better simulations of experimental results k2
is optimized. The best agreement is obtained for k2 =
3.5 × 107 M–1 s–1 (see Fig. 3). Despite of the high val
ues for k2, the production of oxygen is still low com
pared with the experiment (see Fig. 3c). Although bet
ter evolution of oxygen is obtained, further develop
ment of model is needed.
It is obvious (Figs. 2 and 3) that using the same
model (1)–(4) but without any tentative simplifica
tions, the rate constant of the reaction (2) should be
much higher from the value proposed in the literature
by Liebhhafsky (k2 = 37 M–1 s–1) [19], Furrow (k2 =
3 M–1 s–1) [20], and Schmitz (k2 = 23 M–1 s–1) [21].
Related with this problem, we believe that one reason
for the large discrepancies between the values of k2
estimated in our work and previous papers stems from

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 85 No. 13 2011

2282 MILENKOVIC , STANISAVLJEV
oversimplifications in the calculations of I–, HIO, I2
concentrations. The second serious reason can arise
from the incomplete model considered in mentioned
papers.
Our results indicate that usual kinetic assumptions,
associated with the establishment of preequilibrium or
stationary states, may lead to incorrect conclusions.
Additional sources of uncertainty may arise from
numerical calculations based on low number of exper
imentally monitored parameters. This can be illus
trated by Fig. 2. Although iodide and triiodide con
centrations can be well fitted with the rate constants
existing in literature (Figs. 2a, 2b), oxygen curves
(Fig. 2c) apparently suggest that modifications of the
model (1)–(4) are necessary. Another fact, which also
indicates the necessity of extending the model, is the
different slopes of experimental and simulated curves.
The different slopes could be potentially reconciled by
extending the existing model as is already mentioned.
Even the results of Liebhafsky himself [19] suggest
the possibility of a much higher rate constant for reac
tion between HIO and H2O2 (process (2)). In alkaline
solution, he proposed for the reaction:
IO– + H2O2 I– + O2 + H2O (5)
the rate constant of 3.3 ×109 M–1 s–1.Recent research
[25] suggests that reaction (5) is not elementary one
and the rate constant of the rate determining step, for
oxygen formation in basic media, can be estimated as
5.8 × 107 mol dm–3 s–1. This value is too high com
pared to the corresponding process in acidic media,
i.e. 37 M–1 s–1 by Liebhafsky [19], 3 M–1 s–1 by Furrow
[20], 23 M–2 s–1 by Schmitz [21]. Taking into account
that the standard reduction potential for this reaction
is much lower than for the corresponding reaction in
the acidic medium, it is possible to expect significantly
higher value for the acidic analog [26].
Our preliminary results support further investiga
tions of this complex process which plays important
role of iodine chemistry in various area of technologi
cal and scientific interest.
CONCLUSIONS
In this work we simulated three experimentally fol
lowed components of the reaction between I– and
H2O2 with the model (1)–(4), frequently considered
in the literature. As shown, experimental and simula
tion results are in good agreement only for a very high
value of the rate constant in great discrepancy from lit
erature data. It is an indication that the existing reac
tion model should be extended for better understand
ing of this complicate process.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
ACKNOWLEDGMENTS
The present investigations are partially supported
by the Ministry of Science and Environmental Protec
tion of the Republic of Serbia, project no. 142025.
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Vol. 85 No. 13 2011