J. Phys. Chem.

A 2010, 114, 6521–6526 6521

Non-Triiodide Based Autoinhibition by Iodide Ion in the Trithionate-Iodine Reaction

György Csekő and Attila K. Horváth*

Department of Inorganic Chemistry, UniVersity of Pécs, Ifjúság útja 6., H-7624 Pécs, Hungary
ReceiVed: March 24, 2010; ReVised Manuscript ReceiVed: May 3, 2010

The trithionate-iodine reaction has been studied spectrophotometrically in a slightly acidic medium at 25.0
( 0.1 °C in acetate/acetic acid buffer monitoring the absorbance at 468 nm at the isosbestic point of the
iodine-triiodide ion system in the absence and presence of initially added iodide ion at I ) 0.5 M ionic
strength adjusted by sodium perchlorate. The stoichiometry of the reaction was found to be S3O62- + 4I2 +
6H2O f 3SO42- + 8I- + 12H+. It is also shown that the consumption of iodine is inhibited by iodide ion,
but it cannot be simply explained via the fast equilibrium formation of triiodide ion. A five-step kinetic
model with four fitted and fixed kinetic parameters is proposed and discussed in detail, on the basis of which
all the most important characteristics of the measured kinetic curves are adequately explained.

Introduction from the initiating fast equilibrium between tetrathionate and

Although trithionate is thought to be at least as stable as
tetrathionate in aqueous solutions, its oxidation by simple
inorganic halogen-containing oxyanions are considerably less
known. The reactions of the corresponding tetrathionate by
iodine and chlorite, for example, have fascinating kinetics
because they are autoinhibited by iodide ion1,2 and are auto-
catalytic with respect to hydrogen ion and hypochlorous acid
as well as self-inhibited by chlorite ion, respectively.3 Moreover,
the tetrathionate-chlorite reaction has recently become the
subject of studying different types of spatiotemporal phenomena
in connection with front propagation such as lateral instability4–6
and spatial bistability.7,8 Although the stoichiometry and kinetics
of the reaction are rather complex,3,9,10 a simple stoichiometric
equation along with a relatively simple rate equation was
suggested to interpret the different spatiotemporal behaviors
found experimentally.11 Our latest results, however, just showed
that the formerly measured front velocity-concentration data
pairs can be explained semiquantitatively with slightly modified
stoichiometric and rate equations that also reflect to the
complexity of the reaction.12 The complete quantitative descrip-
tion was not possible because it is well-known13 that tetrathion-
ate is subject to decompose in alkaline solution into trithionate,
sulfite, and thiosulfate. Unfortunately, no information has been
available yet in the literature about the kinetics and mechanism
of the trithionate-chlorite reaction. Moreover, systematic search
among the articles published with the subject of trithionate has
revealed the complete knowledge of only few oxidation reac-
tions of trithionate. Since little is known about the redox
reactions of trithionate but one may expect some analogies
between that of the tetrathionate and trithionate due to their
similar chemical structure, exploration of a less complex redox
reaction of trithionate seems to be more preferable for a start
to understand the chemistry of trithionate gradually. The reaction
of iodine with trithionate may therefore be a good candidate
since on the one hand the reaction can easily be followed by
UV-vis spectroscopy and on the other hand the kinetics of the
corresponding tetrathionate-iodine reaction is well-known.1,2 It
was clearly demonstrated that the iodide inhibition mainly arose
* To whom correspondence should be addressed: E-mail: horvatha@
gamma.ttk.pte.hu.
10.1021/jp102661k  2010 American Chemical Society
Published on Web 05/20/2010
iodine despite the fact that trihalide ion is usually a less reactive
species than the corresponding halogen molecule. The initiating
equilibrium between the reactants resulted in the formation of
S4O6I- and I- as a formal I+ transfer from iodine molecule to
one of the inner sulfur atom of tetrathionate.1,2 The aim of our
paper is, if it exists, to seek a general analogy between the redox
reactions of tetrathionate and trithionate, as well as to unravel
the kinetics and mechanism of the trithionate-iodine reaction,
comparing it to that of the corresponding tetrathionate-iodine
reaction.
Experimental Section
Materials and Buffers. The sodium trithionate was first
prepared by the reaction of sodium thiosulfate with hydrogen
peroxide as described previously.14 Unfortunately, the purity of
the sodium trithionate was found to be less than 97%, therefore
the relatively unpure solid substance was redissolved in a small
amount of water, which resulted in an almost saturated solution.
The sodium trithionate was then recrystallized by addition of
ice cold absolute ethanol (at 0-2 °C). The volume of the ethanol
added was approximately the same as that of the saturated
solution. The purity of the crystallyzed sodium trithionate was
checked by the following method. Known amount of sodium
trithionate was dissolved in pure distilled water followed by
addition of bromine solution in excess. The reaction mixture
was left to stand for at least five minutes, which was proven to
be enough to oxidize trithionate into sulfate completely. The
excess of bromine was then removed by boiling the solution
for a couple of minutes. The H+ liberated by the oxidation
(S3O62- + 4Br2 + 6H2O f 3SO42- + 8Br- + 12H+) was
determined by titrating the sample against standard sodium
hydroxide solution. The validity of this stoichiometric equation
was checked in separate experiments. The purity of the sodium
trithionate was found to be better than 99.5%. Detailed
investigations of the trithionate-bromine reaction are going to
be carried out in our lab, and the results will be published later
elsewhere. All the other chemicals (iodine, potassium iodide,
acetic acid, sodium acetate, and sodium perchlorate) were of
the highest purity commercially available and were used without
further purification. The stock solutions were freshly prepared
each day from double-distilled and twice ion-exchanged water.
6522 J. Phys. Chem. A, Vol. 114, No. 23, 2010
Figure 1. Measured (symbols) and calculated (solid lines) absorbance-time curves at pH ) 4.55, [S3O62-]0 ) 0.278 mM and [I2]0 ) 0.58 mM
in the presence of initially added iodide ion. [I-]0/mM ) 0.0 (b), 0.1 (0), 0.3 ((), 0.7 (∆), 1.0 (9).
The pH of the solutions was regulated between 4.25 and 5.25
by acetic acid/acetate buffer taking the pKa of acetic acid as
4.55.15 The acetate concentration was always kept constant at
0.1 M and the pH was adjusted by the necessary amount of
acetic acid. The ionic strength was set to 0.5 M by adding the
necessary amount of sodium perchlorate. The temperature of
the reaction vessel was maintained at 25.0 ( 0.1 °C. The initial
concentrations of the reactants for all the 63 kinetic runs are
collected in Table S1 of the Supporting Information.
Methods and Instrumentation. The reaction was followed
by a Zeiss S10 diode array spectrophotometer in the visible
range without using the deuterium lamp. The reaction has been
carried out in a standard quartz cuvette equipped with magnetic
stirrer and Teflon cap having 1 cm optical path. The buffer
components, the reactants iodine, and iodide (if necessary) were
delivered from a pipet first. The spectrum of the solution was
always recorded before injection of the trithionate solution to
precisely determine the initial concentration of iodine. Then,
the reaction was started with the addition of the necessary
amount of trithionate solution from a fast delivery pipet. The
spectra of the reacting solution at the wavelength range of
400-700 nm was acquired up to approximately 9000 s.
To confirm the purity of the sodium trithionate and to check
the sulfur-containing end products of the reaction, Raman
spectroscopy was also carried out by a NXR FT-Raman
spectrometer.
Data Treatment. MRA studies have shown16 that the only
absorbing species in the visible range are iodine and triiodide
ion. Therefore, the simultaneous evaluation of the kinetic curves
was carried out at the isosbestic point of I2-I3- system at 468
nm by the program package ZiTa.17 The molar absorbance of
both species was found to be 750 M-1 cm-1 at this wavelength.
Originally each kinetic run contained more than 400 absorbance-
time data pairs, therefore it was necessary to reduce the number
of time points (40-50) to avoid unnecessary time-consuming
calculations. The essence of this method has already been
described elsewhere.10 To obtain the kinetic model and the rate
coefficients, absolute fitting procedure has been chosen to
minimize the average deviation between the measured and
calculated absorbance. Altogether, almost 2700 experimental
points from the 63 kinetic series were used for the simultaneous
evaluation. Our quantitative criterion for an acceptable fit was
Csekő and Horváth
that the average deviation for the absolute fit approached 0.004,
which is close to the experimentally achievable limit of error.
Results
Stoichiometry. The stoichiometry of the reaction was estab-
lished by standard iodometry as well as by Raman spectroscopy.
Raman spectroscopy clearly showed that no sulfur-containing
product formed via the reaction besides sulfate. After the reaction
completed in excess of iodine the iodometric titration indicated
that the strict stoichiometry of the reaction can be described by
the following equation
S3O62- + 4I2 + 6H2O f 3SO42- + 8I- + 12H+
(1)
This result was also confirmed by VIS-spectroscopy from the
end of the kinetic measurements in excess of iodine because
the consumed iodine-trithionate ratio calculated from the ab-
sorbance loss at 468 nm was found to be 4.0 ( 0.1. Since sulfate
ion is the only sulfur containing end-product of the reaction
that was supported by the Raman measurements (see: Figure
S1 of the Supporting Information), eq 1 has to be also valid
strictly in trithionate excess.
Preliminary Observations. The most important character-
istics and results of the preliminary individual curve fitting on
the kinetic curves can be summarized as follows.
(1) No pH dependence of the kinetic curves can be observed
within the pH range studied (see: Figures S3 and S4 of the
Supporting Information). This feature is not unique among the
polythionate-iodine reactions because it was already noticed
in the tetrathionate-iodine system as well.1,2
(2) Figure 1 shows the effect of initially added iodide ion
on the decay of the total amount of iodine. It is easily seen that
the increase of initial iodide concentration significantly retards
the consumption of total amount of iodine. Our preliminary
calculations demonstrated that eq 1, being treated as a simple
second order chemical process (the kinetic order of both
reactants is one) along with the fast equilibrium formation of
triiodide ion, is not sufficient to interpret quantitatively the
observed iodide inhibition. For the sake of completeness, the
calculations yielded an unacceptably high 0.050 absorbance unit
Non-Triiodide Based Autoinhibition by Iodide Ion J. Phys. Chem. A, Vol. 114, No. 23, 2010 6523

for the average deviation if the iodide inhibition is treated TABLE 1: Fitted and Fixed Rate Coefficients of the
exclusively with the formation of triiodide. The nontriiodide- Proposed Kinetic Modela
based inhibitory effect of iodide ion was already justified step rate equation parameter
experimentally in the tetrathionate-iodine reaction as well.1,2 -
(R1) kR1[I2][I ] 5.7 × 10 M-1 s-1
9

(3) The iodide inhibitory feature of the reaction made it (-R1) k-R1[I-3] 8.5 × 106 s-1
possible to fit eq 1 with the following rate equation (R2) kR2[I2] 5.52 × 10-2 s-1
′
kR2[HOI][H+][I-] 1.023 × 1011 M-2 s-1
(-R2) k-R2[I2]/[H+] 1.98 × 10-3 Ms-1
′
k-R2[HOI][I-] 3.67 × 109 M-1 s-1
(R3) kR3[S3O2-6 ][I2] 103 M-1 s-1
[S3O2-
6 ][I2] (-R3) k-R3[S3O6I-][I-] 107 M-1 s-1
V1 ) kapp (2) kR4[S3O6I-] 24.7 ( 2.4 s-1
[I-] (R4)
(-R4) k-R4[S3O6][I-] 4.28 ( 0.51 M-1 s-1
(R5) kR5[S3O6] (1.37 ( 0.09) × 10-3 s-1
(R6) kR6[SOI][I2] (6.95 ( 1.01) × 103 M-1 s-1
(R7) kR7[HSO- 3 ][I2] 3.1 × 109 M-1 s-1
individually for most of the kinetic curves. The surprising result
of our calculations was that with kapp ) (8.24 ( 1.50) × 10-4 a
No error indicates that the value in question was fixed during
s-1 all the measured 63 kinetic curves could be fitted with an the fitting procedure.
almost acceptable average deviation of 0.0059 absorbance unit
(see: Figures S5 and S6 of the Supporting Information). I2 + I- h I-
3 (R1)
However, careful inspection of the individually fitted kinetic
curves has revealed that systematic deviation could be noticed
between the measured and calculated absorbance-time series, I2 + H2O h HOI + I- + H+ (R2)
especially at large trithionate excess, high iodide concentrations,
and relatively high reactant concentrations as well. More - -
precisely, it meant that eq 2 was not able to describe almost 6 + I2 h S3O6I + I
S3O2- (R3)
one-third of the measured kinetic traces properly. We therefore
concluded that eq 1 along with the rate equation indicated by S3O6I- h S3O6 + I- (R4)
eq 2 is not enough for sound description of the kinetic curves
simultaneously, although it may serve as a solid starting point
to create the final kinetic model. S3O6 + 3H2O f 3HSO-
3 + 3H
+
(R5)
(4) In case of the remaining 20 kinetic curves (at higher initial
iodine concentrations) we found that the following rate equation S3O6I- + I2 + 4H2O f 2HSO- -
3 + SO4 + 3I + 6H
2- +

works adequately: (R6)

2- 2
[S3O6 ][I2]
V1 ) (3)
ka + kb[I-]
with ka ) (1.51 ( 0.60) × 10-4 M2 s and kb ) (4.82 ( 1.74)
× 10-2 M s. It should be emphasized that the second-order
dependence of the rate equation on the concentration of iodine
was found to be a necessary condition to fit those kinetic traces.
Proposed Kinetic Model. Since the simple stoichiometric
equation (eq 1) along with its rate equation (eq 2) was not able
to fit the measured kinetic characteristics adequately, we have
chosen the following set of species that most likely participate
as a reactive intermediate. This group consists of S2O3OH-,
S2O3I-, S3O6I-, S3O6, HSO3-, as well as HOI. Considering the
possible mono- and bimolecular reactions among the reactants
and the intermediates, we started the fitting procedure with 32
different chemically different steps. During the fitting procedure
the steps, the rate coefficients of which became insensitive to
the average deviation, were omitted step by step. This method
has been applied successfully in several cases of our previous
work.2,10,18 After long but straightforward systematic reduction,
the following model has emerged.
CH3COOH h H+ + CH3COO- (E1)
HSO- -
3 + I2 + H2O f SO4 + 2I + 3H
2- +
(R7)
The rapid de- and reprotonation process E1 was taken into
account with known equilibrium constant to follow the slight
change in pH during the reaction. This acid dissociation
equilibrium may be regarded as an auxiliary process necessary
for the detailed calculation, but it is not central part of the
proposed model. Table 1 contains the fitted and fixed kinetic
parameters used in the simultaneous evaluation of the kinetic
curves. The average deviation was found to be 0.0042 absor-
bance unit (AU). The final results of the proposed kinetic model
are illustrated in Figures 1-4.
Discussion
Step R1 is the rapid equilibrium formation of triiodide ion
investigated a couple of decades ago by several authors.19,20 The
rate coefficients of the forward and reverse reactions were set
to kR1 ) 5.7 × 109 M-1 s-1 and k-R1 ) 8.5 × 106 s-1,
respectively to give log βI3- ) 2.83, where βI3- is the formation
constant of triiodide ion.15
Step R2 is the well-known hydrolysis of iodine in aqueous
solution. The rate coefficients of the forward and reverse
reactions including the hydroxide-driven hydrolysis were de-
termined previously, therefore we used these values as fixed
parameters through the fitting procedure.21–23
Step R3 is the fast initiating equilibrium formation of S3O6I-
explained by a formal I+ transfer from iodine molecule to
6524 J. Phys. Chem. A, Vol. 114, No. 23, 2010 Csekő and Horváth

Figure 2. Measured (symbols) and calculated (solid lines) absorbance-time curves at pH ) 4.55 and [I2]0 ) 0.57 mM in absence of initially
added iodide ion. [S3O62-]0/mM ) 0.155 (b), 0.10333 (0), 0.0775 (2), 0.062 ()), 0.05166 (9).

Figure 3. Measured (symbols) and calculated (solid lines) absorbance-time curves at [S3O62-]0 ) 0.085 mM, pH ) 4.55 and in absence of
initially added iodide ion. [I2]0/mM ) 0.0666 (b), 0.148 (0), 0.308 (@), 0.473 ()), 0.643 (9), 0.72 (O).

possibly the inner sulfur atom of trithionate. This equilibrium
is a complete analogy of the initiating equilibrium of the
corresponding tetrathionate-iodine reaction.1,2 Our calculation
indicated that this equilibrium must be shifted far to the left
and the equilibrium constant cannot be determined from our
experiments. If KR3 is set at any value less than 0.01, then exactly
the same average deviation can be calculated, which means that
we could set only an upper limit for KR3 with a sufficiently fast
forward and backward reactions. To provide a sufficiently low
level of [S3O6I-] during the calculation, we set KR3 ) 1 × 10-4
as a result of the ratio of kR3 and k-R3, being 103 M-1 s-1 and
107 M-1 s-1, respectively.
Step R4 indicates that S3O6I- is involved in another equi-
librium process in which cleavage of iodide ion results in a
formation of an intermediate S3O6. The rate coefficients of the
forward (kR4) and backward (k-R4) reactions can only be
calculated if KR3 is fixed at 10-4 as mentioned above. In this
case the rate coefficients of both the forward and reverse reaction
could be determined from our experiments as 24.7 ( 2.4 s-1
and 4.28 ( 0.51 M-1 s-1, respectively. It should be emphasized
again that the value of kR4 is in total correlation with that of
k-R3 as well as kR6, meaning that only their ratios (kR4/k-R3 and
kR6/k-R3) could be calculated. Therefore, neither their absolute
value nor the KR4 ) kR4/k-R4 equilibrium constant could be
determined from our experiments. The underlying chemistry
seems to be clear since it only means that S3O6I- must be a
short-lived intermediate and its fast conversions govern the
kinetics of the reaction. Further discussion about S3O6 will be
detailed later in the formal kinetics part.
Step R5 is the hydrolysis of S3O6 formed in step R4 and kR5
was determined to be (1.37 ( 0.09) × 10-3 s-1. This pathway
is responsible for governing the reaction at lower iodine and
initial iodide concentrations, that is, at larger trithionate excess.
It is also interesting to note that steps R3 and R4 may be
equilibrated in the initial phase of the reaction in such a way
that the concentration of S3O6 might be as high as 10-4 M, since
its lone pathway to decay its concentration is relatively slow.
The halftime of S3O6 calculated from kR5 is about 8 min meaning
that it may be accumulated in some extent during the first stage
of the reaction. Therefore, we tried to exchange this reaction
Non-Triiodide Based Autoinhibition by Iodide Ion J. Phys. Chem. A, Vol. 114, No. 23, 2010 6525

Figure 4. Measured (symbols) and calculated (solid lines) absorbance-time curves at constant [S3O62-]0/[I2]0 ≈ 1.0 ratio in absence of
initially added iodide ion at pH ) 4.55. [I2]0/mM ) 0.0737 (O), 0.157 (×), 0.238 (∆), 0.328 (+), 0.518 (b), 0.588 (0), 0.635 (2), 0.68 ()),
0.756 (9).

by many conceivable reaction steps with no success. Exclusion trithionate and iodine concentrations. At such experimental
of this reaction results in not even an unacceptably high average conditions the following rate law can be deduced:
deviation (0.0209 AU) but also systematic deviations between

{ }
the measured and calculated absorbance-time curves especially
at high initial trithionate concentrations. If, however, kR5 is 1 d[I2] kR6 kR6
- ) kR3 1 + [I2][I-] + [I ] /
supposed to be a fast reaction (kR5 > 102 s-1) then the average 4 dt kR5KR4 kR4 2

{
deviation was found to be 0.0081 AU, but systematic deviation kR6 kR6
can still be observed between the measured and calculated 1+ [I2][I-] + [I ] +
kinetic curves (see: Figure S7 of the Supporting Information). kR5KR4 kR4 2
These facts together serve as an indirect evidence for the
necessity of the inclusion of step R5, therefore we concluded
this step to be necessary for detailed and sound description of
k-R3 -
kR4
[I ] +
k-R3 - 2
kR5KR4 }
[I ] [S3O62-][I2] (5)

the kinetic curves.

Step R6 is a process of fast oxidation of S3O6I- by iodine.
As mentioned above, the absolute value of this rate coefficient
cannot be determined from our experiments, only the ratio of
kR6/k-R3. Since k-R3 was fixed at 107 M-1 s-1, our calculation
has provided a value of (6.95 ( 1.01) × 103 M-1 s-1 for kR6.
This pathway determines the kinetics at higher initial iodine
concentrations. It is interesting to note that we have also tried
to replace step R6 by the following equation:
The second and the third terms in the nominator of the right-
hand side of eq 5 is negligible because the conditions of [I2] ,
(kR4)/(kR6) ) 0.00355 M and [I2][I-] , (KR5kR4)/(kR6) ) 1.14 ×
10-6 M2 are fulfilled in most of the kinetic traces measured.
Moreover [I-] . (kR4)/(k-R3) ) 2.47 × 10-6 M is also valid as
a result of the relatively rapidly established iodine hydrolysis
represented by eq R2. It allows us to simplify eq 5 as

d[S3O62-] 1 d[I2]
S3O6I- + 3H2O f 3HSO3- + I- + 3H+ (4) - )- )
dt 4 dt
1
This change, however, would result in a relatively small kR3 [S O 2-][I2] (6)
k-R3 - k-R3 - 2 3 6
increase in the average deviation from 0.0042 to 0.0054 [I ] + [I ]
absorbance unit, but at the highest initial iodine concentrations kR4 kR5KR4
systematic deviations could be encountered between the mea-
sured and calculated kinetic curves. Thus, it is concluded that
Step R6 cannot be replaced by eq 4. since the first three terms in the denominator of eq 5 are also
Step R7 is the well-known fast reaction between hydrogen negligible. After some algebraic manipulation the following
sulfite and iodine. This reaction was thoroughly studied by Yiin equation can be obtained:
and Margerum,24 and even the rate coefficient of this process
was determined to be 3.1 × 109 M-1 s-1. Therefore, we have
fixed kR18 at this value. d[S3O2-
6 ] 1 d[I2] kR5kR4 [S3O62-][I2]
- )- ) KR3
Formal Kinetics. As one may easily notice S3O6I- and HSO-3 dt 4 dt kR5 + k-R4[I-] [I-]
are short-lived intermediates, therefore steady-state approxima- (7)
tion may be applied with no restrictions to derive a formal rate
equation. However, for S3O6 the steady-state approximation is
held only at high initial iodide concentrations or at low initial Comparing eq 2 to eq 7 reveals that
6526 J. Phys. Chem. A, Vol. 114, No. 23, 2010
KR3kR5kR4
kapp ) -
(8)
kR5 + k-R4[I ]
that is, the apparent rate coefficient obtained by the individual
curve fitting method must depend on the actual concentration
of iodide ion. This feature of the apparent rate coefficient is
also well-established in the corresponding tetrathionate-iodine
reaction.1,2 Substitution of the corresponding rate coefficients
into eq 8 and taking into consideration that the average iodide
concentration during most of the kinetic runs is approximately
6 × 10-4 M, one can calculate 8.59 × 10-4 s-1 for kapp, which
is in complete coincidence with the fact that most of the kinetic
runs may be evaluated by eq 2 found in the preliminary studies.
This expression also provides a smooth understanding why the
individual rate coefficient of equilibrium R3 cannot be deter-
mined from these experiments. If the value of KR3 is fixed at a
relatively small value to maintain the concentration of S3O6I-
at a sufficiently low level than the values of kR4, k-R4, and kR5
can straightforwardly be determined. To check it, we have
undertaken an additional simultaneous curve fitting by the
proposed model not including step R6 only on those kinetic
curves, where the initial iodine concentration was lower than 6
× 10-4 M. This condition meant that only 43 kinetic curves
were used for parameter estimation. As expected, the remaining
three parameters are also capable of good description of the
selected kinetic curves with almost the same average deviation
(0.0043 AU). It is therefore concluded that under such experi-
mental conditions the value of kR6 cannot be calculated. The
underlying chemistry seems to be clear since at low iodine
concentrations the main pathway is Step R5 to produce sulfate
and iodide eventually. It, however, raises an important question
about the determination of kR6 by nonlinear parameter estimation
under present circumstances. As already mentioned previously,
not all the kinetic runs can be evaluated properly by eq 2. It is
easily seen that the second term of the nominator as well as
that of the denominator of eq 5 becomes no longer negligible
with an increase of the initial iodine concentration. It straight-
forwardly introduces the dependence of kapp on kR6, which
provides a solid base to determine the value of kR6 under our
experimental conditions by the remaining 20 kinetic curves
having high initial iodine concentrations. Thus, we concluded
that the 63 kinetic curves carry enough experimental information
to evaluate the parameters kR4, k-R4, kR5, and kR6 if KR3 is fixed.
Finally, it should also be noted that the formal rate equation
derived above is not valid at larger reactant concentrations
because one of the intermediates may be accumulated (S3O6)
in an appreciable amount in the early stage of the reaction.
Therefore, proper explanation of the necessity of the second-
order dependence of iodine in the rate equation is not possible
via simplification of eq 5, although mathematically it can easily
be deduced if the first term of the nominator in eq 5 is neglected
compared to the terms depending on the concentration of iodine.
Conclusion
The work presented here may be considered as the first
reliable attempt to unravel the kinetics and mechanism of the
trithionate-iodine reaction. It was experimentally demonstrated
that the reaction is autoinhibitory with respect to iodide ion,
and this effect cannot be solely attributed to the formation of
triiodide ion, which is less reactive toward the substrate than
iodine. The nontriiodide-based inhibition of iodide ion is not a
Csekő and Horváth
unique feature; it rather seems to be a general phenomenon
among the oxidation of polythionates by iodine that is based
on a formal I+ transfer from iodine molecule to (one of) the
inner sulfur of polytionates as an initiating equilibrium that was
previously established in the tetrathionate-iodine reaction as
well.1,2 The continuation of elucidation of this type of reaction
provides a better understanding and insight into the nature of
the sulfur-chain breaking reactions of polythionates that may
also be helpful as a guide in unraveling the more complex
oxidation reactions of these compounds. A better insight into
the mechanism of these reactions would thus result in an easier
and model-based comprehensive explanation of the wide variety
of the nonlinear dynamical phenomena appearing in a reaction4–6,12
having rather complex kinetics.
Acknowledgment. This work was supported by the Hungar-
ian Research Fund (OTKA) Grant No. K68172. A. K. H. is
grateful for the financial support of the János Bolyai Research
Scholarship of the Hungarian Academy of Sciences.
Supporting Information Available: Table containing the
condition of each kinetic run and figures containing the
measured and fitted data are found in the Supporting Informa-
tion. This material is available free of charge via the Internet at
http://pubs.acs.org.
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(4) Horváth, D.; Tóth, A. J. Chem. Phys. 1997, 108, 1447–1451.
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