of reaction increase.

The opposite will occur

at low temperatures[2].

INTRODUCTION
Chemical Kinetics is the branch of
chemistry which deals with the rates of

Two

methods

of

determining

the

CHEMICAL KINETICS: THE IODINE CLOCK

REACTION
LORENZO M. ZARATE
NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY, COLLEGE OF
SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES

ABSTRACT
Many processes carried out in everyday situations revolve around
chemical reactions. These reactions proceed in different rates. To determine these rates
and describe the kinetics of a reaction, an experimental setup must be conducted. In
this study, the experiment done was the Iodine Clock Experiment.
Solutions of potassium iodide, potassium chloride, potassium persulfate, sodium
thiosulfate, and starch were mixed in beakers in various proportions and conditions and
were made to react. The time it took for the mixture to turn blue was recorded. The data
obtained was used to determine the rates of the reaction, and eventually the orders and
rate constants for the reactions.
Using the Initial Rates Method (IRM) and the Graphical Method (GM), the orders
of the reaction were determined. The orders of the reaction with respect to the
chemical reactions. It deals with the changes kinetics of reactions will be observed: the
in concentration of reactants (a decrease), orInitial Rates Method, which relates the
products (an increase) as a function of time[1]. concentrations of the reactants to the orders
and rates of reaction, and the Graphical
Multiple factors determine how fast aMethod, which makes use of plot lines to
reaction goes, and one of the most common isdetermine the rates and orders of reactions.
concentration. Once the concentration of aIn this experiment, the concept of chemical
reactant in a solution increases, more of its kinetics will be observed through the Iodine
molecules will collide with others in theClock Reaction.
mixture and will therefore have a larger
probability that the molecules that collide
The Iodine Clock Experiment was
will react. The opposite of this will occur at discovered in 1886 by a Swiss chemist named
low concentrations. Another factor is theHans Heinrich Landolt. The experiment
temperature temperature is directlyinvolves two colorless solutions forming a
proportional to the kinetic energy of a blue mixture after a certain amount of time [3].
system. If a reaction occurs in a system with These solutions are mixed together, and the
a high-temperature, the molecules of onetime it takes for the solution to turn
reactant will collide with the molecules of the completely blue are taken and recorded.
other more frequently, and thus the
probability that the molecules colliding are
Since many industrial and natural
reactive is increased. This will make the rate processes rely on chemical reactions, there
are times when chemical reactions are

manipulated to better suit the needs of the

Two additional sets of run 2 were
people using these materials or carrying out prepared (these runs will be referred to as
these processes. There are processes that sets 2 and 3) to test for the effect of
would be better slowed down, such as rust temperature in the rate of reaction. Beaker B
formation, while there are processes that are of set 2 was heated on a hot plate to 60oC
better off sped up. The factors that influence while beaker B of set 3 was put in an ice bath
how fast a reaction is carried out must beand cooled to 18oC. The contents of beaker A
understood since these factors may bewere poured into beaker B for both sets, and
utilized to make industrial and natural the time it took for the mixtures to turn blue
processes more efficient than they alreadywas measured.
are[2].
To test the effect of a catalyst on the
This experiment aims to determine therate of reaction, a fourth set of run 2 was
rates of the reaction mechanism that involvesprepared. The contents of beaker A were
the following reactions:
poured into beaker B, and four drops of
copper (II) sulfate were added to the mixture
S2O82- + 2I- 2SO42- + I2
(1)
immediately. The time it took for the mixture
2S2O32- + I2 S4O62- + 2I(2)
to turn blue was taken and recorded.
Measuring the rate at which the S2O32The data including the concentrations
disappears in equation 2 will determine the of the persulfate, thiosulfate and iodide ions,
rate of formation of I2, and therefore willand the recorded time were recorded in the
describe the kinetics of the reaction.
data sheet. The data including the reaction
temperature and recorded time were
recorded in the data sheet as well. These
METHODOLOGY
values were used to determine the reaction
Before the experiment was done, freshrate, the rate constant, the orders of
solutions of 0.2 M potassium iodide (KI), 0.2reaction, and the equations of the lines of the
M potassium chloride (KCl), 0.1 M potassium plots with respect to the various parameters
persulfate (K2S2O8), 0.1 M potassium sulfatemanipulated in the experiment.
(K2SO4), 0.1 M sodium thiosulfate (Na 2S2O3),
4 mM copper (II) sulfate (CuSO4), and 1%RESULTS AND DISCUSSION
starch were prepared by class.
The time for the mixtures to turn
To test the effect of persulfate andcompletely blue in all setups was taken.
iodide concentrations on the rate of reaction,These recorded times (measured in seconds)
the solutions were mixed in two beakerswere used to determine the rate of reaction
labeled A and B in different proportions through the equation
referred to in Table 1. The contents of beaker
A were poured into beaker B and the time it
took for the mixture to turn completely blue
was taken and recorded. This step was done
five times, for each of the runs.
(3)

Ru
n

1
2
3
4
5

Table 1. Volumes (in mL) of solutions for

where t = the time it took for the solution to
runs 1 through 5 in Beakers A and B
turn completely blue. This equation was used
since the moment which determines the step
Beaker
Beaker B (+3 dps starch)
is the moment when the thiosulfate ion runs
A
out in the solution. When the S 2O32- ions run
KC
Na2S2O
KI
K2S2O8 K2SO4
out, free, I2 (no longer reduced to I-) starts
l
3
forming in the solution, which in turn, reacts
10
0
5
5
5
with the starch, forming the blue complex.
5
5
5
5
5
The in the rate equation comes from the
2.5 7.5
5
5
5
stoichiometric ratio between the iodine and
5
5
7.5
2.5
5
5
5
10
0
5

the thiosulfate in reaction (2), where one I 2

molecule must have been generated for every
2 ions of S2O32- initially present in the
solution[4].

(4)

where k is the rate constant, [S2O82-] and [I-]

were the respective concentrations of the
The reaction orders with respect to
persulfate and iodide ions. The rate constant
the reagents were also calculated. This was
was determined by manipulating (4) into an
done using the Initial Rates Method (IRM),
equation that solves for the rate constant,
where experimental setups would be carried
defined by:
out and based on the data gathered, a ratio of
two runs was used to determine the orders of
reactions with respect to the reagent being
tested. These calculations were done thrice
with respect to each reactant in the reaction,
and the calculated values were then
(5)
averaged. The average value for the order of
reaction
with
respect
to
S2O82- was
The rate constant was calculated for
determined to be 0.6437027338, while the runs 1 to 5 of the experiment using the
value for the order of reaction with respect to derived form of (4). The average rate
I- was computed to be 0.9390466657. The constant (kave) was also determined and was
overall order, which is the sum of the found out to be 1.489580597x10-3 M-1s-1.
individual orders with respect to the These values are shown in Table 3.
reactants, is 1.5827493995. The calculated
orders of reaction with respect to I - and S2O82-Table 3. Values of rate and rate constant
are shown in Table 2.
using the Initial Rates Method

Table 2. Calculated orders of reaction with

respect to I- and S2O82-

Runs
2&4
2&5
4&5

Order
wrt S2O82(x)
0.791305
87
0.661198
09
0.477821
47

Order
wrt I- (y)

xave

Run

Rate
(M/s)

9.30x10-6

6.45x10-6

2.53x10-6

8.89x10-6

1.02x10-5

yave

Average

Rate constant
(1/Ms)
1.221572264x103

1.644488506x103

1.223187764x103

1.728254778x103

1.649473663x103

1.493395395x103

0.64 0.939
37
0
0.52793
1&2
156
0.93904
1&3
666
1.35016
2&3
178
After the orders of reaction were
calculated, the rate law for the reaction was
determined, and the rate constants for all
runs of the experiment were computed. The
rate law for the reaction is

The orders of reaction were then

determined through the Graphical Method
(GM), which observes the relationship
between concentration and rate. It was
determined that as the concentration of S2O82in the mixture increased, so did the rate of
reaction. The line that relates the rate of the
reaction and the concentration of the
persulfate ion is defined by the equation

(6)

where x is ln[S2O82-] and y is ln(rate of Figure 2. Effect of concentration of iodide ion on the rate of reaction
reaction).

The

slope

of

the

line

-10.5
-4.5 -4 -3.5 -3 -2.5-11 -2
-11.5
ln rate
-12
-12.5
-13
-13.5

(the

coefficient of x) is the order of the reaction.

Figure 1. Effect of concentration of persulfate ion on the rate of reaction
-11.2
-4 -3.8 -3.6 -3.4 -3.2 -3
-11.4
ln rate

ln [I-]

-11.6
-11.8

Figure 2 shows the linear relationship

between the natural logarithms of the
concentrations of the iodide ion and the rate
of reaction. The linearity, defined by r2, was
computed to be approximately 0.940. The
order of the reaction with respect to the
iodide ion, the slope of (7), is 0.9387579967.

-12
ln[S2O82-]

Figure 1 shows the linear relationship

The rate law for the reaction in terms
between the natural logarithms of the
of
the
GM
results was then determined to be
concentration of the persulfate ion and the
rate of reaction. The linearity of the data,
defined by r2, was determined and the value
obtained was approximately 0.986. The order
(8)
of the reaction with respect to the persulfate
ion, the slope of (6), was determined to bewhile the rate constants were obtainable
0.6767744177.
through the formula
As the concentration of I- in the
mixture increased, the rate of reaction also
increased. The line that relates the rate of
the reaction with the concentration of iodide
ions is defined by the equation

(9)
Table 4 below shows a summary of
the results obtained by using the Graphical
Method.

(7)

Table 4. Values of rate and rate constant

where x is ln[I-] and y is ln(rate of reaction).using the Graphical Method
Rate
Rate constant
Similar to (6), the slope of the line in (7) is
Run
(M/s)
(1/Ms)
the order of the reaction.
1
9.30x10-6
1.39922728x10-3
2
6.45x10-6
1.85922164x10-3
1.397198492x103
2.53x10-6
3
4

8.89x10-6

1.02x10-5
Average

1.948208891x103

1.840243726x103

1.688820006x103

have to react[5]. This means that the

In the table above, the rate constantsmolecules in the system must have at least
were determined using the derived form ofthis amount of energy for them to react at
(8). The average rate constant (k ave) for thegiven conditions. This energy is related to the
runs using the Graphical Method was found rate constant in an expression known as the
to be approximately 1.69x10-3 /Ms.
Arrhenius equation, defined by
In one part of the experiment, two set(10)
ups were placed in temperatures higher (and
lower) than the room temperature. The setup
with the higher temperature had a rate thatwhere A is the Arrhenius constant, Ea is the
was significantly higher than that of the roomactivation energy, k is the rate constant, R is
temperature reaction, while the setup withthe universal gas constant (8.314 J/mol-K),
the lower temperature had a rate that was and T is the temperature of the system,
lower. This means that there is a relationship expressed in Kelvin. The above equation may
between the temperature and the rate of also be expressed in a linear equation defined
reaction such that an increase of temperatureby:
would increase the rate while a decrease of
temperature of the system would merit a
decrease in the rate of the reaction.
(11)
In the part of the experiment whereIn this equation, the manipulated factor is the
temperature was the manipulated factor, thetemperature of the system.
rates were calculated via (3) and the rate
constants were calculated via (5). TheTable 5. Values of the rate constant and
average rate constant was not computed temperature for sets 1 to 3 of run 2
since the three k values for the three sets
Run 2
Rate
Temperatur
were used as plot points in a graph relating
constant
e (K)
the rate constants and temperature.
(1/Ms)
Set 1
1.64x10-3
300.15
Copper (II) sulfate (CuSO4) was added
Set 2
1.46x10-2
333.15
into the mixture in the last part of the
-4
Set
3
6.54x10
291.15
experiment. This reagent was used as a
catalyst used to speed up the reaction.
The value of the calculated activation
What it really does is it provides another
energy
derived from (11) is 58463.88853
pathway for the reaction to occur which
J/mol.
This
means that for the reaction to
requires less activation energy, thus allowing
occur,
there
must be this much energy
the system to reach the activation energy
present
in
the
system for the reaction to
faster and carrying out the reaction faster.
occur. The value of the Arrhenius constant
Sodium thiosulfate (Na2S2O3) was(the number of collisions, also known as the
added in beaker B in all runs of the frequency factor, the product of collision
that is
experiment. This reagent was added to the frequency and collision probability [6]
specific
for
each
and
every
reaction
) was
solution to provide the thiosulfate ion
also
obtained,
and
was
computed
to
have
a
necessary to reduce I2 formed in the first step
7
2
value
of
2.20x10
.
The
linearity,
defined
by
r
,
of the reaction mechanism back to I .
was computed to be approximately 0.996.
The presence of starch in the reaction
mixture caused the change in color from
colorless to blue. The excess I2 in (2) reacted
with the starch to form a blue complex, which
indicated that the reaction was carried out.
The activation energy of a reaction is
the minimum energy the molecules must

Figure 3. Plot of ln k vs 1/T for sets 1-3

0
2.90E-03 3.00E-03 3.10E-03 3.20E-03 3.30E-03 3.40E-03 3.50E-03
-1
-2
-3
-4
-5
-6
-7
-8

SUMMARY AND CONCLUSIONS

The experiment aimed to describe the

kinetics of the Iodine Clock Reaction. When
the rates were calculated through the initial
rates method, the computed values behaved
as they should have where an increase in
concentration of reactant would merit an
increase in rate. This was the same with
respect
to
both
reactants.
For
the
temperature, where a graphical method of
determination was used, the result was the
Figure 3 shows the linear relationshipsame in such a way that as the temperature
between the reciprocal of the temperature increased (1/T in (11) would decrease), the
and the natural logarithm of the rate rate would also increase, given that the
concentrations are left constant.
constant. The equation of the line is
Though both the initial rates method
and the graphical method yielded positive
When the temperature is high, itsresults, the graphical method was found to be
reciprocal is low, and it corresponds to an lnmore reliable, albeit more tedious, since it
k value that is high via (11), which implies a provided more accurate data. Any major
difference, however, in any calculated result
high rate constant.
may be caused by human error in calculation.
The series of reactions involved in this It is recommended that conventional rules in
experiment was a reaction mechanism. Out of calculations be set in order to avoid
the the proposed reaction mechanismssignificant differences in yielded results.
(12)

presented in the points to discuss (refer to

The experiment served its purpose in
the Appendix), the proposed reaction
helping
understand the concept of chemical
mechanism that is the most consistent with
kinetics,
and based on the results obtained by
the rate law of the reactions used in the
experiment
was
the
third
proposedprevious studies, the data that this
mechanism. This is because the reactantsexperiment yielded were valid and were
present in the rate-determining step (theaccepted.
slow reaction) of the proposed mechanism
are identical to those used in this experiment.REFERENCES
Thus, when their rate laws are determined,
the expression obtained that computes for [1] Martin S. Silberberg. Chemistry: The
Molecular Nature of Matter and Change, 5th
the rate would be the same as well.
Ed. McGraw Hill Companies, Inc. 2009. 685.
When
compared
with
previous[2] The Iodine Clock Reaction (n.d.).
December
11,
2013,
from
experimental results, the data obtained inRetrieved
this experiment would seem inaccurate, since Weebly.com:
the values obtained were somewhat different http://msmcgregor.weebly.com/uploads/6/7/3
from the results of previous experiments, /8/6738691/ch12labreport.pdf
however it is precise in that it is still able to [3] University of Sydney. Iodine Clock. First
determine what was asked in the experimentYear Chemistry. 2012. E4-4.
and the study was able to serve its purpose [4] Chemical Kinetics: The Iodine Clock
to determine how fast or slow a chemical Reaction (n.d.). Retrieved December 8, 2013
from
Colgate
University:
reaction may go in a mechanism.
http://classes.colgate.edu/jchanatry/
chem102/Exp16calcsW.pdf

[5] Martin S. Silberberg. Chemistry: The [6] Martin S. Silberberg. Chemistry: The
Molecular Nature of Matter and Change, 5thMolecular Nature of Matter and Change, 5th
Ed. McGraw Hill Companies, Inc. 2009. 706. Ed. McGraw Hill Companies, Inc. 2009. G-7.