CHEMICAL KINETICS: THE IODINE CLOCK

REACTION
J. A. PUNZALAN1 and O. T. MALLAPRE2
1, 2
NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY, COLLEGE
OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 26 FEBRUARY 2015
DATE PERFORMED: 12 FEBRUARY 2015

ABSTRACT
The rate at which a particular chemical reaction progresses is expressed by
chemical kinetics. Chemical kinetics is the study of reaction rates, the changes in
concentrations of reactants (or products) as a function of time (Silberberg 686). The
experiment done aimed to determine the kinetics of the reaction involving the
persulfate (S2O82-) and iodide (I-) ions, whose reaction can be summarized as S 2O82+ 2I- 2S2O42- + I2. It is divided into two parts: the first one focusing on the effect of
reactant concentration gradients on the rate of reaction, and the second one basing
on the effect of temperature and presence of a catalyst on the reaction rate. The
significant values obtained for the first part of the experiment are the overall
reaction rate and the reaction order for S 2O82- and I-. These values are then used to
determine the rate law, which is

1 1

r rxn=5.78 1 0 M s

[S2O82-][I]. For the second

1

part, the important values obtained are the activation energy ( Ea =35.06 kJ mo l

and the Arrhenius constant ( A=8993 .88 M-1s-1). The present of a CuSO 4 catalyst
in the fourth setup of the second part of the experiment caused a significantly
faster reaction rate and larger rate constant than those of the other setups.

INTRODUCTION
Knowledge of chemical kinetics gives
one an idea of how fast or slow a
reaction between two or more
reagents will proceed before a
physical or chemical change occurs (a
change in composition of the reagents
involved). This rate of reaction is
affected by five factors, namely, the
concentration
of
reactants,
the

temperature of the system, the

presence of a catalyst, the nature and
phase of the reactants, and the
pressure applied on the system. In the
experiment performed, the first three
factors aforementioned and how they
affect the rate of reaction were
studied particularly for the reaction
between persulfate (S2O82-) and iodide
(I-) ions. The chemical reaction can be
written as S2O82- + 2I- 2S2O42- + I2.

The I2 formed will be reduced back to I by S2O32- ions as can be summarized in

this chemical equation: 2S2O32- + I2
S4O62- + 2I-. When all S2O32- is used up,
free I2 is formed. The molecular iodine
formed
is
detected
by
starch,
therefore making the solution turn
blue.
In the experiment, two elementary
reactions were undergone, but the
rate law is only based on the S 2O82- +
2I- 2S2O42- + I2 since it is the slow,
rate-determining step.
The effects of the said factors on the
reaction were used to describe the
kinetics of the reaction. In the first
part of the experiment, four runs were
performed using different persulfate
and iodide ion concentrations. In the
second part of the experiment, four
more sets of the second run used in
the first part of the experiment were
prepared,
and
this
time
were
subjected to different temperatures
and conditions: the first one in an ice
bath, the second one in a warm water
bath, and the third one in room
temperature. The fourth setup was
also subjected to room temperature,
but this time CuSO4 (a catalyst) was
also added to the solution.
The data recorded for the first part
were
used
to
determine
their
independent reaction rates, and then
the rate constant and rate law.
Given a sample reaction aA + bB cC
+ dD, the reaction rate can be
computed using the following formula:

r rxn=

[ A ]
( 1) ;
at

where rrxn is the rate of the reaction.

For the experiment, the equation can

be modified to be:

S 2 O3

r rxn=
The rate constant, on the other hand,
can be calculated using the following
formula:

B n

A m

r
k = rxn

where k is the rate constant, m and n

are the reaction orders for reactant A
and reaction B, respectively. These
reaction orders can be obtained using
the initial rates method.
Again, for the experiment performed,
the
above
equation
can
be
appropriated to be:

I ( 4 )
2 m

r
k = rxn

Lastly, the above equation can be

modified to get the rate law equation,
written below:

n (5)
I
2 m

r rxn =k

The Arrhenius constant, on the other

hand, can be attained using the
formula written as follows:
Ea

k =A e RT ( 9 ) ;

The overall rate constant can be

computed with the following formula:

k=

k 1+k 2 +k 3 ++ k n
(6 );
n

where k1, k2, k3, , kn are the rate

constants for each run and n is the
number of runs.
The data for the second part, on the
other hand, were used to plot the line
ln k vs. 1/T and to calculate the
activation
energy
and
Arrhenius
constant
for the
reaction. The
activation energy can be computed
using the following formula:

ln

k 2 Ea 1
1
=
( ) (7) ;
k1
R T2 T1

where R is the gas constant (8.314

J/mol K) and Ea is the activation
energy, the minimum amount of
energy required to initiate a chemical
reaction (Chang 583).
Alternatively, the activation energy
can be obtained from the following
linear equation

ln k =ln A

Ea
(8)
RT

by just multiplying the slope of the

equation of the graph of ln k vs. 1/T by
R (Silberberg 706).

where A is the Arrhenius constant, the

product of collision frequency and the
steric factor (which is always less than
1), a quantity which reflects the
fraction
of
collisions
occurring
(Zumdahl 568).
The Arrhenius constant can also be
obtained from equation (8).
Graphing the line ln k vs. 1/T using the
Microsoft Excel software allows us to
get the regression factor r2, a quantity
which tells about the linearity of the
graph. This allows the verification of
the correctness of the reaction order
assigned. If the r2 value computed is
close to 1, then the reaction values
assigned are correct.
METHODOLOGY
The reagents to be prepared prior to
and for use in the experiment are 500
mL volumes of 0.2 M KI, 0.2 M KCl, 0.2
M, 0.1 M K2S2O8, 0.1 M K2SO4, 4.0 mM
Na2S2O3; 20 mL of 1% fresh boiling
starch; and 5 mL of 1 M CuSO4.
For the first part of the experiment, all
runs
were
performed
in
room
temperature.
Two
beakers
were
produced for each run, each labelled
as beaker A and B. The reagent
volumes (in mL) for each run is
presented in the following table.
Table 1. The different runs for the
effect of concentration of iodide and
persulfate ions on the reaction rate.

Beaker A

1
2
3
4
5

0.2
M
KI

0.2
M
KCl

10
5
2.5
5
5

0
5
7.5
5
5

Beaker B (+20 drops

fresh boiling starch)
0.1
0.1 M
4.0
M
K2SO4 mM

K2S2
O8
5
5
5
7.5
10

Na2S2
O3
5
5
5
2.5
0

5
5
5
5
5

The contents of beaker A for each run

was poured into beaker B. The
reaction was immediately timed. Once
the mixture turned blue, the timer was
stopped. The time elapsed for each
run was recorded as the reaction time.
For the second part of the experiment,
two more sets of run 2 in the first part
were prepared. Beakers A and B for
the first set prepared were then
heated in a water bath until the
temperature reached 50 0C. The
contents of beaker A was poured into
beaker B and the reaction was timed
until the solution turned blue. Beakers
A and B for the second set prepared,
on the other hand, were then
subjected to an ice bath until the
temperature has reached 5 0C. The
contents of beaker A was poured into
beaker B and the reaction was timed
until the solution turned blue. The
reaction time for the third run for the
second part of the experiment was
just copied from that of run 2 in the
first part of the experiment. Lastly, for
the fourth set prepared, the contents
of beaker A was poured into beaker B.
Afterwards, 4 drops CuSO4 was added
to the solution and the reaction was
timed until the solution turned blue.
RESULTS AND DISCUSSION

The data obtained for the first part of

the experiment is presented in the
following table:
Table 2. The data obtained for the
effects of reactant concentration on
reaction rate

[S2O82
]M

[I-]
M

0.02

0.0
8

[S2O32]
M
8 x 10-

trxns

rrxn,
M/s

55

7.27
x10-

2
3

0.02
0.02

0.0
4
0.0
2

8 x 10-

80

8 x 104

16
1

5x
10-6
2.48
x106

0.03

0.0
4

8 x 10-

59

6.78
x106

0.04

0.0
4

8 x 10-

40

1x
10-5

The reaction rate was calculated using

equation 2. Using the first run, the
reaction rate was calculated as:

S 2 O3

r rxn=

r rxn=

8 x 104
2(55)
r rxn=

7.27x10-6

when the equation used is with

respect to the rate of disappearance of
S2O32-.
The linearity of the graph of ln

r rxn

vs. ln [S2O82-] was checked to

determine whether the reaction is first

order in S2O82-. This was done using

Excel for runs 2, 4, and 5 for the first
part of the experiment. The data used
and the trend line pertinent to the
data points was presented below.
0
-12.5 -12 -11.5 -11
-1
-2

ln [persulfate]

Graph 2. The graph of ln

vs. ln

[I-].
For Graph 2, the equation of the trend
line is y = 1.2525x + 12.205. The r2
value obtained is equal to 0.9704,
which is also close to 1. That leads to
the inference that the reaction is first
order in I-.

-3
-4
-5

ln rrxn

Graph 1. The graph of ln

r rxn

The rate constant can be obtained

using equation (4), with the reaction
orders for S2O82- and I- both being equal
to one. Data from run 2 was used in
the calculation below.

vs. ln

2-

[S2O8 ].
The trend line for graph 1 has an
equation of y = 0.9883x + 8.1884, as
given by Excel. It also has an r2 value
of 0.9721, which is close to 1. With
that, it can be inferred that the
reaction is first order in S2O82-.
The linearity of the graph of ln

r rxn

vs. ln [I-] was checked to determine

whether the reaction is first order in I-.
This was done using Excel for runs 1,
2, and 3 for the first part of the
experiment. The data used and the
trend line obtained from the data
points is shown in the following graph.
-13

r rxn

-12.5

-12

0
-11.5
-1
-2

ln [iodide]

-3
-4
-5

ln rrxn

I
2 m

r
k = rxn

k=

5 106 M
s ( 0.02 M )( 0.04 M )

k =6.25 103 M 1 s1
After plugging in the rate constants for
each run obtained and I- in equation
(6), the overall rate constant was
computed as:

k=

k 1+ k 2 +k 3 + k 4 +k 5
5
k =5.78 1 03 M 1 s1

Finally, using equation (5), the overall

rate law can be summarized as:

r rxn=5.78 1 03 M 1 s1 [S2O82-][I-].

The obtained reaction order value of 1

for both

2
S 2 O8

and I indicates that

when the concentration of either

reactant increases by a certain factor,
the rate of reaction increases by a
factor equal to that of the reactants
increase.
The data recorded in the second part
of the experiment is summarized in
the following table.
Table 3. The data obtained for the
effects of temperature and catalyst on
reaction rate.

Set
1
Set
2
Set
3
Set
4

T,
K
29
9
32
3
27
8
29
9

trxn,
s
80

rrxn, Ms-1

25

1.6 x 10-

5 x 10-6

k,
M-1s-1
6.28 x
10-3
2.0 x 10-2

20
7
7

1.9 x 106

5.7 x 105

2.42 x
10-3
7.14 x
10-2

The reaction rates were obtained

using equation (2) and the rate
constants
were
obtained
using
equation (4).
ln k vs. 1/T was then graphed and
checked for linearity. This was done
using the first 3 sets for the second
part of the experiment. The data
points and the trend line observed
from the data points is shown below.

ln k

0
-10
-2
-3
-4
-5
-6
-7

1/T

Graph 3. The graph of 1/T vs. ln k.

As given by Excel, the equation of the
trend line for Graph 3 is y = -4216.7x
+ 9.1043. The trend line also has an r2
value of 0.9961, which is very close to
1.
The activation energy was obtained by
multiplying the slope of the graph by
R. x is substituted for 1/T and y is
substituted for ln k in equation (8) as
shown below.

ln k =ln A
y ln A

Ea
RT

Ea
x
R

Going back to the equation of the

trend line, it can be inferred that

Ea
=4216.7ln A=9.1043
R
Therefore,

Ea =4216.7 R
Ea = 35059 J
Ea =35.06 kJ mo l1
and

ln A=9.1043

[1] Silberberg, M. Chemistry: The

Molecular Nature of Matter and
Change. 2010. New York: McGraw-Hill.
686, 706.

A=8993 .88 M-1s-1

Set 4 gave out a significantly larger
reaction rate and greater rate
constant than all other sets. This
signals that the presence of a catalyst
such as CuSO4 accelerates the
formation of reactants and elevates
the amount of products that can be
formed for a certain amount of time.
SUMMARY AND CONCLUSIONS
The linearity of the graphs of ln
vs. ln [S2O82-] and ln

r rxn

r rxn

vs. ln [I-]

give sufficient basis to conclude that

the
reaction
between
persulfate
(S2O82-) and iodide (I-) ions is first order
in both ions. After obtaining the rate
constants for each run, the overall
rate constant was computed as the
mean of the rate constants for each
run, and has a value of 5.78 x 10 -3 M1 -1
s . The rate law can then be
summarized
as
3

1 1

r rxn=5.78 1 0 M s

[S2O82-][I-].

The equation of the trend line of the

graph of 1/T vs. ln k was used to
determine the activation energy and
Arrhenius constant, whose values are
computed

as

35.06 kJ mo l1 ,

and

8993 .88 M-1s-1, respectively.

The presence of a catalyst increases
both the reaction rates and rate
constants, which signals that it speeds
up the formation of products.
REFERENCES

[2] Chang, R. Chemistry. 2010. New

York: McGraw-Hill. 583.
[3] Zumdahl, S. and Zumdahl, S.
Chemistry. 2010. Belmont: Brooks
Cole. 568.

APPENDICES
Equations Used in Calculations

r rxn=

[ A ]
at

B n
A m

r rxn
k=
k=

k 1+ k 2 +k 3 ++k n
n
ln k =ln A

Data Sheet (Next Page)

Ea
RT