In the Laboratory

Kinetics and Mechanism of Iodide Oxidation by Iron(III):

A Clock Reaction Approach
Jurica Bauer and Vladislav Tomišić*
Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102 a, 10000 Zagreb, Croatia;
*vtomisic@chem.pmf.hr

Petar B. A. Vrkljan
XVIII Gymnasium, Zagreb, Croatia

Clock reactions are commonly used as demonstrations by
chemical educators owing to their visual appeal (1). Recently,
however, clock reactions have been used to illustrate chemical
kinetics (2–4). Oxidation of iodide by iron(III) ions in an acidic
medium is a reaction that can easily be transformed into a clock
reaction. Thiosulfate is used as a limiting reagent and starch as
an indicator for I3− ions. Chemical changes in this clock reaction
can be presented by the following equations (1, p 51–55):
extent of reaction 2 at the time Δ t is small, and consequently the
quotient Δ[Fe3+]/Δ t can be taken as a satisfactory approximation
of the initial reaction rate. However, if the initial thiosulfate
concentration is too low, the time period Δ t is short and cannot
be measured accurately. Therefore, both of these considerations
must be taken into account in the experimental design.
Suppose that the dependence of the initial reaction rate on
iron(III) and iodide ion concentrations can be expressed as

Fe3(aq)  S2O32(aq) [Fe(S2O3)](aq) (1) x y S 2O3 2 

v0  k Fe 3  I  0 (6)
0 0 %t

2Fe3(aq)  3 I (aq) 2Fe2(aq)  I3(aq) (2)
where x is the reaction order with respect to Fe3+ and y is the
 2
I3 (aq)  2 S2O3 (aq)

3I (aq)  S4O6 (aq) 2
(3) reaction order with respect to I−. If the initial concentration
of only one reactant is varied while the initial concentrations
of the other participants are kept unchanged, it is possible to
2I3(aq)  starch starch—I5  I(aq) (4)
determine the order of reaction with respect to the reactant
whose concentration is being varied.
The complex [Fe(S2O3)]+ is purple and the starch–pentaiodide
complex is blue. The reaction is started by mixing a colorless
acidic solution of iron(III) nitrate with a colorless solution The Experiment
containing sodium thiosulfate, potassium iodide, and starch.
The experiments are conducted using a thermostated
The solution immediately turns purple. The color gradually fades
cell placed on a magnetic stirrer (Figure 1). A total of 55 mL
until the solution becomes colorless. At that very moment, the
of solution A (containing Na2S2O3, KI, KNO3, and starch)
solution suddenly turns dark blue.
is placed in the cell and 5 mL of solution B [containing
The exercise presented here is conducted in an undergradu-
Fe(NO3)3 and HNO3] is placed in the syringe. Solution A
ate physical chemistry laboratory course. The course is based on
individual or group work of students. The aim of the exercise is
to examine the kinetics of iodide oxidation by iron(III) ions (eq
2), that is, the dependence of reaction rate on reactant concen-
trations and to gain insight into the reaction mechanism.
The kinetics of a reaction transformed into a clock reaction
is easily investigated by the initial rates method. The time elapsed
from the mixing of the two solutions to a sudden color change
is measured (2–4). From the stoichiometry of the reactions, one
can deduce the following expression for the initial reaction rate
of the oxidation of iodide by iron(III) ions:

% Fe 3  S 2O3 2 
v0 {   0 (5)
%t %t
where Δ[Fe3+] is the change in the concentration of iron(III)
ions in the initial period of the reaction. If Δ t is the time mea- thermostat
sured, then Δ[Fe3+] is the decrease in iron(III) ion concentration
from the moment of mixing to the moment of complete thiosul-
fate (the limiting reagent) consumption. The relationship in eq 5
holds if the initial concentration of thiosulfate is sufficiently low magnetic stirrer
compared to that of iron(III) and iodide ions. In this case the Figure 1. The apparatus used for the monitoring of reaction kinetics.

© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 8  August 2008  •  Journal of Chemical Education 1123
 In the Laboratory

18
is stirred by a magnet. Solution B is injected into solution
16 A and a stop watch is started at that point. Time is recorded
at the moment the solution suddenly turns dark blue. The
14
experiment is conducted three times for each concentration.
12 The temperature is set at 25.0 ± 0.1 °C. The ionic strength is
set to 1.0 mol L‒1 by KNO3 and HNO3 to keep it constant
10 during the course of reaction.
%t / s

8
Hazards
6

4
Concentrated nitric acid is both a strong acid and a power-
ful oxidizing agent. Contact with the skin can result in severe
2 burns. The vapor irritates the respiratory system, eyes, and other
0
mucous membranes. Iron(III) nitrate and potassium nitrate are
0 1 2 3 4 5 6 7 strong oxidizing agents and skin irritants. Contact with com-
[S2O32ź]0 / (10ź4 mol/L) bustible materials can cause fire. Sodium thiosulfate may cause
irritation to skin, eyes, and respiratory tract.
Figure 2. Dependence of Δt on initial thiosulfate concentration:
[Fe(NO3)3]0 = 6.5 mmol L−1, [KI]0 = 20.0 mmol L−1, • experimental,
— calculated by means of eq 7. Results and Discussion
The first experiment involves examination of the effect of
thiosulfate concentration on the reaction rate. The initial thio-
25
sulfate concentration is varied while the initial concentrations
of other participants are kept unchanged. The data obtained
are submitted to linear regression analysis according to eq 6.
20 The typical results are given in Figure 2 and by the following
equation:

mol L
(7)
%t / s

4 2 1
15
%t s  0. 20  2. 32 t 10
S 2O3 0

10 Δ t is found to be approximately proportional to the initial thio-

sulfate concentration. This result must be interpreted carefully.
It confirms eq 6, but it also states that the reaction rate does
5 not in fact depend on thiosulfate concentration; thiosulfate
is merely the limiting reagent in the clock reaction. The initial
7 8 9 10 11 12 13 14 15 16 thiosulfate concentration determines Δ t but it does not deter-
[Iź]0 / (10ź3 mol/L) mine the reaction rate.
Figure 3. Dependence of Δt on initial iodide concentration:
To determine the reaction order with respect to iodide, a
[Fe(NO 3) 3] 0 = 8.5 mmol L −1, [Na 2S 2O 3] 0 = 0.2 mmol L −1, • set of experiments is performed in which the initial iodide con-
experimental, — calculated by means of eq 8. centration is varied while the initial concentrations of all other
participants are kept unchanged. The data obtained are submit-
ted to linear (ln Δ t vs ln [I−]0) or nonlinear regression analysis
according to eq 6. The typical results of nonlinear regression
18 analysis are given in Figure 3 and by the equation:

\ mol L
^
1. 98
16 %t s  1. 54 t 10 3 I  1 (8)
0
14

Therefore, the reaction is second order with respect to iodide.

%t / s

12
Finally, the students have to determine the reaction order
with respect to iron(III) ions. The data obtained in an experi-
10
ment analogous to those previously described, are submitted
8
to linear (ln Δ t vs ln [Fe3+]0) or nonlinear regression analysis
according to eq 6. The typical results of nonlinear regression
6 analysis are given in Figure 4 and by the following equation:

\ Fe mol L
^
4 5 6 7 8 9 10 11 12 13 1. 10
3
3á
[Fe ]0 / (10 ź3
mol/L) %t s  5. 01 t 10 2 1 (9)
0
Figure 4. Dependence of Δt on initial iron(III) ion concentration: [KI]0
= 0.013 mol L−1, [Na2S2O3]0 = 0.25 mmol L−1, • experimental, — According to eq 9, the reaction is first order with respect to
calculated by means of eq 9. iron(III) ions.

1124 Journal of Chemical Education  •  Vol. 85  No. 8  August 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education 
 In the Laboratory

On the basis of the above results, the rate law (eq 6) can The experiment has also been simplified and used as a high
be written as school students’ miniproject in teaching chemical kinetics in the
2 classroom (five six-student groups, 90 minutes period). Students
v  k Fe 3  I (10)
By comparing eq 10 with eqs 7–9, the rate coefficient values
can easily be obtained from each set of experiments: k = 16.6 L2
mol‒2 s‒1; 15.3 L2 mol‒2 s‒1; 29.5 L2 mol‒2 s‒1, respectively.
It should be noted that there is another redox reaction
taking place in the system investigated, namely the oxidation
of thiosulfate to tetrathionate by iron(III) ions (5, 6). How-
ever, according to the experimental results described above
(independency of reaction rate on thiosulfate concentration
and obtained partial reaction orders with respect to Fe3+ and
I−), any significant influence of this reaction on the kinetics of
the reaction studied can be ruled out.
The goal of kinetic studies is gaining insight into the reac-
tion mechanism. Based on the data collected in the study as well
as on “chemical intuition and imagination”, the students may
propose the following possible mechanism:
K1

are first familiarized with clock reactions and the initial rates
method, then guided through the miniproject to devise experi-
ments to determine the reaction orders, obtain the rate law, and
possibly discuss the reaction mechanism.
Acknowledgment
This work was supported by the Ministry of Science,
Education and Sports of the Republic of Croatia (Project No.
119-1191342-2960).
Literature
1. Shakhashiri, B. Z. Chemical Demonstrations; The University of
Wisconsin Press; Madison, WI, 1992; Vol. 4, pp 3–86.
2. Creary, X.; Morris, K. M. J. Chem. Educ. 1999, 76, 530–531.
3. Vitz, E. J. Chem. Educ. 2007, 84, 1156–1157.
4. Copper, C. L.; Koubek, E. J. Chem. Educ. 1998, 75, 87–89.
5. Schmid, H. Z. Phys. Chem. A 1930, 148, 321–336.
Fe3(aq)  I (aq) [FeI ]2(aq) 6. Holluta, J.; Martini, A. Z. Anorg. Allg. Chem. 1924, 140,
k2 206–226.
[FeI ]2(aq)  I(aq) Fe2(aq)  I2(aq) (11) 7. Gershgoren, E.; Banin, U.; Ruhman, S. J. Phys. Chem. A 1998,
k3 102, 9–16.
2I2(aq) I3(aq)  I (aq)

Alternatively, the mechanism may be offered to the students,
and they should be able to show that it is in accordance with
the experimental results.
The existence of the species I2− (7–9) as well as of the reac-
tion proposed in the last step of the mechanism (10–12) is well
known from the literature. A similar mechanism for the reaction
investigated was proposed earlier (13). However, the clock reac-
tion method described herein is experimentally simpler than the
titrimetric analysis used in ref 13.
8. Benjamin, I.; Barbara, P. F.; Gertner, B. J.; Hynes, J. T. J. Phys.
Chem. 1995, 99, 7557–7567.
9. Walhout, P. K.; Alfano, J. C.; Thakur, K. A. M.; Barbara, P. F. J.
Phys. Chem. 1995, 99, 7568–7580.
10. Nord, G.; Pedersen, B.; Farver, O. Inorg. Chem. 1978, 17,
2233–2242.
11. Langmuir, M. E.; Hayon, E. J. Phys. Chem. 1967, 71,
3808–3814.
12. Hubbard, C. D; Jones, J. G.; McKnight, J. J. Chem. Soc., Dalton
Trans. 2000, 3143–3148.
13. Fudge, A. J.; Sykes, K. W. J. Chem. Soc. 1952, 119–124

Conclusion Supporting JCE Online Material

http://www.jce.divched.org/Journal/Issues/2008/Aug/abs1123.html
A simple method for studying the kinetics of a chemical
reaction is described. If the studied reaction can be transformed Abstract and keywords
into a clock reaction, valuable information can easily be obtained
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by means of the initial rates method. By studying the kinetics us-
ing the clock reaction method students can experience the initial Links to cited JCE articles
rates method first hand. In that way they can determine the rate
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law as well as the reaction rate coefficient. An important feature
of the work presented here is that it shows the significance of Student handouts
reaction orders in deducing possible reaction mechanisms. Instructor notes

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