CHEMICAL KINETICS: THE IODINE CLOCK REACTION

JOHN JOSEPH CHUA

DEPARTMENT OF FOOD SCIENCE AND NUTRITION, COLLEGE OF HOME ECONOMICS
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 26 FEBRUARY 2015
DATE PERFORMED: 12 FEBRUARY 2015

ABSTRACT
This paper aims to describe the kinetics of the Iodine Clock Reaction by observing the effects of the
concentration of the reactants, I- and S2O82-, exposing of the setup at room temperature, 5C and
60C, and addition of catalyst of the reaction, CuSO4. The said objectives are attained by the
integration of the authors current knowledge regarding the study of Chemical Kinetics and the
Iodine Clock Reaction experiment, which serves as an application of this knowledge. Through the
method of initial rates, dependence of the reaction rate to the concentration of the reactants is
].
actualized, resulting in the differential rate law of
= [
[ ].
, with the rate
constant approximately at 144.65

. Through varying temperatures of the setups, it is

deduced that ln k is inversely proportional to the reciprocal of the temperature in Kelvin. The
activation energy and constant A computed are 4.89 10
and 5.34 10 respectively.
Addition of the catalyst reduced the activation energy to 4.35 10 which made the reaction
faster.

INTRODUCTION

Chemical Kinetics concerns how rates of

chemical reactions are measured, how they
can be predicted, and how reaction-rate
data are used to deduce probable reaction
mechanisms [1]. This study uses the rate
law in determining the speed of the reaction
and the effects of increased concentrations
of reactants, temperature, and presence of
catalysts to it [4].
The Iodine Clock refers to a group of
reactions which involve the mixing of two
colorless solutions to produce a solution
which remains colorless for a precise
amount of time, then suddenly changes to a
deep purple-blue color [2]. Through the
known reaction,
S2O82- + 2I- 2SO42- + I2

(1)

the rate of formation of I2 can be identified.

Knowing the rate of formation of I2, the rate
of disappearance of the reactants, which can
be in the form of the differential rate law,
can be given.

[ ]

] [ ]

[ ]

(2)

The rate law may be written with respect to

the change of concentration of the reactant
or product over change in time or as
presented in (2), wherein k is the rate
constant and x and y are powers of [S2082-]
and [I-] respectively which define the order
of the reaction. The method to be used in
identifying the kinetics of the reaction being
studied is the initial rate method, which is
done by varying the concentrations of one
reactant while keeping the other constant
[1].
However,
in
the
experiment,
the
identification of I2 is not described by the
chemical equation 1. Upon addition of
NaS2O3, I2 formed from reaction (1) is
immediately used up as S2O3- ions react
with I2 to form S4O6- and 2I-.
2

+2

(3)

The
constant
addition
of
known
concentration of the clock chemical, NaS2O3,
completes the clock reaction. As the
consuming of I2 by S2O3- is the much faster
reaction, the conversion of I2 to I- is
basically instantaneous [2]. When the I2
from reaction (1) has already been
consumed by the present S2O3-, a time delay
is obtained, sharpening the color
development of the solution. Starch
indicates the presence of Iodine by a deep
purple-blue color. Time delay until the
appearance of the deep purple-blue
complex is inversely proportional to the
rate of the reaction; consequently, color
development is directly related to the rate.
Addition of S2O3- ions acts as a reducing
agent which instantaneously reacts with the
produced I2 so that the concentration of I2
does not reach the visible level until all the
reducing agent is consumed [2]. Therefore,
the rate of the reaction 1 is determined by
the appearance of free I2, which is detected
through the formation of the deep purpleblue complex due to starch.
The experiment aims to identify the rate of
the iodine clock reaction in varying
concentrations of reagents in a constant
room temperature, varying temperatures
under the same concentrations and the
effect of the addition of a catalyst. To
accomplish these objectives, the reagents
and their respective concentrations in
figure 1 are prepared.
Figure 1. Reagents to be used and their respective
concentrations

Reagent

Concentration

Potassium Iodide, KI
Potassium Chloride, KCl
Potassium Persulfate, K2S2O8
Potassium Sulfate, K2SO4
Sodium Thiosulfate, Na2S2O3
Copper (II) Sulfate, CuSO4
Starch Solution

0.2 M
0.2 M
0.1 M
0.1 M
4.0 mM
1.0 M
1%

Aliquots from the prepared solutions are

extracted.
Essentially,

number of moles is removed from the stock

solutions, depending on the volume of the
aliquot. Five repetitions of the experiment
with varying volumes of the reagents are
done, volumes of which are indicated in

figure 2. There are two beakers per run,

labelled A and B, which contain the
reagents. It is shown in figure 2 that for
Runs 2, 4 and 5 the volumes of KI are kept
constant; on the other hand, for Runs 1, 2
and 3, the volumes of K2S2O8 are also kept
constant. These measurements are used in
accordance with the initial rate method:
keeping the concentration of one reactant
constant while varying the other. The
method is used to identify whether the
reagent which concentration is varied has a
direct effect on the rate of the reaction,
considering the rate in (2).
Figure 2. Volumes of Reagents per beaker, per run
Beaker A (in
Beaker B* (in mL)
mL)
KI
KCl
K2S2O8 K2SO4 Na2S2O3
Run

1
2
3
4
5

10
5
2.5
5
5

0
5
7.5
5
5

5
5
5
7.5
10

5
5
5
2.5
0

5
5
5
5
5

*Addition of 8 drops of starch

After preparation of the solutions and their

appropriate volumes, the contents of
Beaker B are added to Beaker A.
Immediately upon addition, the timer is
started. During the first appearance of the
blue shade in the solution, the timer is
stopped.
Two more setups of Run 2, Setup 2 and 3,
are prepared to determine the effect of
temperature and addition of a catalyst to
the reaction being studied. The beakers of
Setup 2 are heated to 60C then their
contents are combined. The beakers of
Setup 3 are cooled down to 5C; afterwards,
their contents are combined. The same
method of timing used during the first runs
is used for the current setups.
Using the Arrhenius equation (4), the values
for the activation energy, denoted as Ea, and
for the constant, A, can be computed
mathematically.
=

(4)

According to the collision theory, chemical

reactions
occur
through
molecular

Another setup of Run 2, labelled Setup 4, is

prepared. Immediately after combining the
contents of the beakers of the setup, 4 drops
of the catalyst of the reaction, CuSO4 is
added. Addition of this aqueous catalyst
implies a homogenous catalysis [1], as the
state of all the reagents is the same as the
catalyst used. The same method of timing
used during the first runs is used for the
current setup.
RESULTS AND DISCUSSION

The Iodine Clock Reaction experiment has

been done to show whether the
concentration of the reactants, S2O82- and I-,
temperature, and the catalyst CuSO4 have
an effect on the kinetics of the reaction,
which is shown through the differential rate
law.
Figure 3 is the graph of ln rate vs ln [S2O82-].
The values on the x-axis are acquired by
getting the natural logarithm of the ratio of
the product of the reagent concentration
and volume to the total solution volume.
The values on the y-axis are computed by
getting the natural logarithm of the
reciprocal of the time elapsed before the
first shade of blue appeared in the solution.
Using this technique, the slope of the best fit
line is the exponent of [S2O82-], or simply the
reaction order with respect to [S2O82-].

Figure 3. Effect of [S2O82-] to the Rate of Reaction

0
-5

-4

-3

-2

-1 -0.5 0
-1

ln Rate

-1.5
-2
-2.5
-3
-3.5
-4
ln [S2O82-]

The rate of reaction is expressed as the

reciprocal of the time elapsed as an
approximation to the true value, because
the concentration of I2 during the course of
the reactions is assumed to be constant.
This approximation is used for the further
computations of the rate of the reaction.
In figure 3, the equation of the best fit line is
= 1.0426 + 0.4702 with a coefficient of
determination, R2, equal to 1. The presented
equation suggests that the reaction order
with respect to S2O82- is 1.04. This implies
that the concentration of S2O82- is
approximately directly proportional to the
rate of the reaction.
The method used in identifying the relation
of the concentration of S2O82- to the rate is
also applied to I-. The data points and best
fit line are indicated in figure 4.
Figure 4. Effect of [I-] to the Rate of Reaction

0
-6

-4

-2

-1

-2
ln Rate

collisions. In order for these collisions to

happen, molecules must have enough
kinetic energy to permit bond breakage.
The minimum energy required to
accomplish bond breakage is activation
energy [1]. As the constant is the product of
collision frequency Zo and probability due
to orientation p, the value can generally
make visualizations regarding the number
of collisions during the reaction. In the light
of the collision theory, a higher value means
a faster chemical reaction. Activation
energy also takes its place in identifying the
kinetics of the reaction. Consequently, high
activation energy means that more energy
is needed to bring about collisions, resulting
in a slower reaction [1].

-3
-4
-5
ln [I-]

-6

The equation of the best fit line indicated on

figure 4 is = 1.3966 + 0.7095 wherein
the coefficient of determination is 0.9753.

Ideally, the attained reaction order values

should be whole numbers but errors are
taken into account. Random errors [3] such
as misreading of the pipette graduations
can reduce or increase moles of the reactant
can tamper with experiment results. The
use of a cellular phone timer can cause a
difference in the measured time, as time for
the user to push the required button to stop
the timing is also counted in the reaction
time, s. A theoretical error [3] is observed
during the usage of the reciprocal of s as
there is the assumption of a constant .
Although this is the case, it is possible to
have the reaction orders as Zero or a
fractional value, depending on the
environment and experimental values [1].
= [

[ ]

(5)

With the experimental data shown on

figures 3 and 4, it can be deduced that the
differential rate law equation of the Iodine
Clock Reaction is as indicated on (5). The
most plausible way of easily explaining the
effect of the concentrations of the reactants
to the rate of the reaction is by saying that
the concentrations of S2O82- and I- are
approximately directly proportional to the
rate of the reaction.
The proposed mechanism for the reaction is
(

](

](
(

(6)

+2

(7)

wherein reaction (6) the rate law

determining reaction as it is slow. Assigning
and " to the rate constants of (6) and (7)
respectively, the overall rate constant is the
product of the mentioned constants. The
reaction (7) occurs very fast and it
immediately consumes the produced
complex at reaction (6). This signifies that
the differential rate law of reaction (7) is
insignificant, thus, for this study, " is given
an arbitrary value of 1 to ensure that the
insignificance of the reaction. Therefore, the
rate constant k is 144.65 M s , which is
equal to the median value of all the rate

constants of the five runs of the experimentin simpler terms, the experimental overall
rate constant.
To determine the effect of temperature to
the rate of reaction, the concentration of the
reactants is made constant in each run of
every setup. A graph as shown in figure 5
indicates ln k versus ln .
Figure 5. Effect of Temperature to the Rate of Reaction

ln k

According to this equation, the reaction

order of I- is equal to 1.3996.

8
7
6
5
4
3
2
1
0
0.0025

0.003

0.0035
ln 1/T

0.004

The computed values on the axes are based

on the linear form of the Arrhenius
equation (8).
ln

+ ln
=

(5)

The values on the y-axis are the natural

logarithms of the rate constant, k. The rate
constant is computed by getting the ratio of
the rate (which is the reciprocal of the
reaction time, in s) to the product of the
concentrations of the reactants raised to
their respective powers. It is established
from figure 5 there are different k values in
different temperatures.
The values on the x-axis are the natural
logarithms of the reciprocal of the different
temperatures to which the setup is exposed.
To reiterate, these computations are done
in this way to go in accordance with the
linear form of the Arrhenius equation.
In the best fit line of the graph of figure 5,
the equation is:
= 5883.9 + 24.702 (9)

with a coefficient of determination of 1. The

graph indicates that the values of ln k vary
inversely as ln . The equation (9) indicates
that the activation energy, Ea, is equal to
4.89 10
and = 5.34 10 . Ea is
computed by equating the slope of the line
to
, wherein R is the gas constant
8.314 . The constant A is calculated by
making the y-intercept of the equation the
power raised to Eulers number, e.
The rate of reaction when the catalyst
CuSO4 is added is 2.44 10

. Using
the Arrhenius equation, the Ea is equal to
4.35 10
which is roughly 89% of the
activation energy of the reaction setup
without the catalyst. This finding indicates
that the catalyst generated a different
pathway that lessens the activation energy
needed by the reaction without the catalyst
[5].
SUMMARY AND CONCLUSIONS

The kinetics of Iodine Clock Reaction is

dependent of the concentration of the
reactants by roughly first order, or
specifically with the differential rate
].
law
= [
[ ] .
.
The
overall reaction order is approximately 2. It
is also dependent on the temperature as it
is deduced that in the case of this reaction,
increasing the temperature increases the
rate constant k, which also implies that
there is a speeding up of the reaction.
Addition of the catalyst to the reaction
CuSO4 caused an alternative mechanism
that lowers the activation energy needed
thus speeds up the reaction.
It is evident with the reaction orders in
fraction form that there are errors in the
experiment, which may be caused by
random errors such as misreading of all
kinds of graduations in the used glassware,
neglecting error propagation in the usage of
glassware, and the varying reaction times
due to different scenarios where the one
who takes the time bases the end time on
different shades of blue. Theoretical errors
are also evident due to assumptions in the
reaction rate and rate constant of the faster
reaction in the reaction mechanism.

Better expertise in glassware usage,

instrument usage, using an instrument that
is made to measure extent of time, and
calculating for the actual values by avoiding
assumptions are the recommendations to
make this study and experiment a lot more
accurate.
REFERENCES

[1] Petrucci, R., et. al., 2011. General

ChemistryPrinciples
And
Modern
Applications. Toronto, Ontario: Pearson
Canada,
Inc.603-604,609-611,613,622623,626-628
[2] Bertrand, G. (n.d.). The Iodine Clock
Reaction:
a
Simulated
Experiment.
Retrieved 24 2, 2015, from Missouri
University of Science and Technology:
http://web.mst.edu/~gbert/IClock/IClock.
html
[3] Types of Errors. (n.d.). Retrieved
February 24, 2015, from New Mexico State
University:
http://www.physics.nmsu.edu/research/la
b110g/html/ERRORS.html
[4] Zumdahl, S., & Zumdahl, S. (2010).
Chemistry, 8th Edition. Boston: Cengage
Learning. 540
[5] Lower, S. (2011, September 29).
Collision and Activation: The Arrhenius
Law. Retrieved February 24, 2015, from
General Chemistry Virtual Textbook:
http://www.chem1.com/acad/webtext/dy
namics/dynamics-3.html