CHEMICAL KINETICS: THE IODINE CLOCK

REACTION
W. YBAEZ1
1

NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY, COLLEGE OF SCIENCE

UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 15 FEBRUARY 2016
DATE PERFORMED: 9 FEBRUARY 2016

ABSTRACT
The visualization of the initial rate method for rate law determination and the effects of various factors
to the reaction rate in a laboratory setting is essential for the better understanding of concepts in
chemical kinetics. This experiment was designed to accomplish the aforementioned, specifically in the
reaction of I- and S2O82-. It involved the variation of reactant concentrations to determine the rate law.
It also included the adjustment of temperature and the addition of a catalyst to observe their effects on
the reaction rate. Through the experimentation, it was found out that the rate law of the reaction is
Rate = k[I-][ S2O82-], with k=6.7210-3 M-1s-1. It was also observed that increasing the reactant
concentrations, temperature and the addition of a catalyst increase the rate. Through subsequent
calculations, it was determined that Ea=24.44 kJ/mol and A= 154.69 M -1s-1.

2+2 I

2+ I 2 2 S 4 O 6

S 2 O3

RESULTS AND DISCUSSION

In the iodine clock reaction, the oxidation
of I- by S2O82- occurs as seen in Eqn. 1
below. To account for the rate, the rate of
change in concentration of either a
reactant or products must be measured.
This is done through the addition of S2O32and starch.

2+ I 2
2 SO 4
2+ 2 I
S2 O8

(1)

(2)

The reaction in (2) is much faster than the

one in (1) so the reduction of I2 back to I- is
essentially instantaneous; nothing is
observed in the macroscopic world. The
instant that S2O32-, the limiting reactant, is
exhausted, I2 is no longer reduced and the
dark blue starch-I2 complex turns the
solution from colorless to blue[1], as seen in
figure 1.

Page 1 of 5

Run 2 and 4
Run 2 and 5
Set-up 4 and 5
Mean

Figure 1. Starch-I2 solution

The rate is determined by the equation:

2
S2 O3

initial

[ I 2]
Rate=
=
t
as determined by the stoichiometric ratios
of I2 and S2O32- as seen in (3). After
computing for the rate of each reaction,
the rate law can now be determined either
by the initial rate method or by
constructing a line of regression[2].
The computation for the reaction orders of
the S2O82- and I- using the initial rate
method can be seen in Appendix B.i. It
involves the proportion of the rates and
reactant concentrations, holding one
concentration constant to find the order of
the other reactant. Table 1 shows the rate
order calculations in every two setup for
each reactant.

A line of regression is typically

constructed to model the relationship two
variables. It attempts to construct a
formula (of a line) that determines the
value of a certain variable by the value of
another. This is done by constructing a
scatterplot of the data to be model and
calculating the best-fit line for the data
by minimizing the sum of the squares of
the vertical deviations from each data
point to the line[3]. Regression lines and
scatterplots were constructed using the
application Graph.
First, the ln rate vs. ln[S2O82-] scatterplot
and regression line was constructed, as
seen in figure 2.

Figure 2 . ln rate vs. ln[S2O82-]

It was determined that the equation of the
regression line is

y=0.870 x8.810 (4)

Table 1. Experimental reaction orders

I- (S2O82- constant)
Run 1 and 2
1.06
Run 2 and 3
0.59
Run 1 and 3
0.84
Mean
0.84
2S2O8 (I constant)

0.29
0.91
1.79
1.00

with a coefficient of determination (r2)

value of 0.8127. This means that for every
unit increase in the ln[S2O82-], ln rate
increases by a factor of 0.870. Suffice to

Page 2 of 5

2
S2 O8

Rate=k

say, 0.870 is the reaction order of S2O82determined by the line of regression

technique. The r2 value means that 81.27%
of the variation in ln rate can be explained
by persulfate concentration and that the
equation has a strong fit to the data.
Next, the ln rate vs. ln[I-] scatterplot and
regression line was constructed, as seen in
figure 2.

rounding off the reaction orders for

simplification, although reaction orders
arent necessarily integers as what is
commonly thought to be. In a nutshell,
changes both the concentrations of iodide
and persulfate are directly proportional to
the rate of the reaction in a 1:1 effect, i.e.
doubling [S2O82-] or [I-] will also double
the reaction rate.
The proposed mechanism that is
consistent with the rate law previously
established is:

Figure 3. ln rate vs. ln[I-]

[ I S2 O8 ]( aq)

It was determined that the equation of the

regression line is:

2 slow

+ S2 O8(aq)

I (aq)

y=0.829 x9.366 (5)

with an r2 value of 0.9738. This means that
for every unit increase in the ln[I-], ln rate
increases by a factor of 0.829. Again,
suffice to say, 0.829 is the reaction order of
I- determined by the line of regression
technique. The r2 value means that 97.38%
of the variation in ln rate can be explained
by iodide concentration and that the
equation has a very strong fit to the data.
Taking into consideration data coming
from the two techniques, the rate law is
determined to be:

(7)

fast I 2(aq) +2 SO 4(aq)

I S 2 O8 ] (aq) + I (aq)
[

(8)

Since both reactants are first order, they

must appear only once in the rate
determining step. The first elementary
step being slow, determines the rate of the
multistep proposed reaction. Altogether,
this is consistent with the rate law that
was determined experimentally.
Using a manipulation of the rate law (5),
the value of the rate constant (k), can now

Page 3 of 5

be determined for each run through

substitution.

2
S2 O 8

Rate
k=

rate, since k is part of the rate law and is

directly proportional to the rate. This is
because the molecules of the reactants
have higher KE (and higher chance) to
collide correctly to form products[5].
Then, the ln rate vs. ln[S2O82-] scatterplot
and regression line was constructed, as
seen in figure 2.

Table 2 shows the values of k in each run.

Theoretically, k-values of runs subjected to
room temperature (301.65 K) must show
little variation since k is not affected by
reactant concentration[4]. However, the kvalues for runs 3 and 4 were dissimilar by
inspection and were possible outliers. To
determine whether or not they are
outliers, the Grubbs Test was performed
on the data set (see Appendix B.iv for the
calculation). By the Grubbs Test, these
values must be accepted. The deviation of
the two k-values may be due to a random
error since the values occur on both sides
of the mean.

Figure 2 . ln k vs. 1/T

It was determined that the equation of the
regression line is

y=2939.98 x+5.04 (10)

with an r2 value of

that for every unit increase in the 1/T, ln k

increases by a factor of 0.870. The r 2 value
means that 87.04% of the variation in ln k
can be explained by the variation in
temperature and that the equation has a
strong fit to the data.

Table 2. k-values of different runs

Run
1
2
3

Temp (K)
301.65
301.65
301.65

k (M-1s-1)
6.9510-3
6.6410-3
8.8110-3

4
5
2.2

301.65
301.65
Mean
328.15

4.9810-3
6.2510-3
6.7210-3
2.2710-2

2.3

204.15

5.9210-3

0.8704 . This means

Establishing analogy between (10) and the

Arrhenius equation (11) below,

It can be also be observed that increasing

the temperature, also increases the value
of k. Transitively, increasing the
temperature also increases the reaction
Page 4 of 5

lnk=

Ea 1
+lnA (11)
R T

it can be seen that the slope of (10) equals

Ea/R (activation energy; ideal gas
constant). Therefore multiplying the slope
by R(-8.314 J/Kmol), we obtain Ea =
24.44 kJ/mol. Subsequently, the Arrhenius
constant, A, can also be calculated (

e 5.0414 ) equaling to 154.69 M-1s-1.

The determination of the Ea is important
since it gives the experimenter an idea on
[1]
how much energy is required for
molecules to react. It also paves an
alternative way of calculating the enthalpy
of the reaction by finding a way to
measure the Ea of the reverse reaction. It
also serves as a basis of comparison in
illustrating the effects of a catalyst in the
kinetics of a reaction. The Arrhenius [2]
constant, in congruence, gives us a
preview on the amount of collisions that
occur, so the lower the value of A the
slower the reaction[4].
[3]
Lastly, the effect of a catalyst, CuSO4, on
the reaction rate was determined.
Obviously, the CuSO4 sped the reaction
up, as archetypal of a catalyst. Using the [4]
Arrhenius equation (11), Ea for the run
involving the catalyst is equal to 21.09 kJ.
The catalyst speeds the reaction up by
providing an alternative mechanism for
[5]
the reaction with lower Ea[6].
The experimental results were consistent
with the hypotheses. Increasing reactant
concentration, temperature and the [6]
addition of a catalyst increases reaction
rate. The lowering of the Ea when the
catalyst was added is also consistent
theoretically.

Errors in the experiment may be generally

caused by the preparation of the reagents.
Reactant concentration must be highly
accurate to obtain accurate measures of
rates, k-values etc. A mistake/delay in
reading the temperature and time could
also cause errors.
REFERENCES
Chemistry Department. (2010). Chemical
Kinetics:
The
Iodine-Clock
Reaction.
Chemistry 102 Laboratory. Colgate
University. Retrieved February 13, 2016,
from
http://classes.colgate.edu/jchanatry/
chem102/Exp16calcsW.pdf
Analytical Chemistry Group. (2013).
Analytical Chemistry Lab Manual.
Quezon City: University of the Philippines
Institute of Chemistry
Triola, M. (2015). Essentials of Statistics.
(5th
Edition).
(pp.
503-510).
Massachusetts: Pearson Education Inc.
Silberberg, M. (2009). Chemistry: The
Molecular Nature of Matter and Change. (5th
Edition). (pp. 706-708). New York: The
McGraw-Hill Companies, Inc.
Brown, T., LeMay, H., Bursten, B., Murphy,
C., Woodward, P. (2012) Chemistry: The
Central Science. (12th Edition). (pp. 575
880). Illinois: Pearson Education, Inc.
Petrucci, R., Herring, F., Madura, J.,
Bissonnette, C. (2011). General Chemistry.
(10th Edition). (pp .637-368). Ontario:
Pearson Prentice Hall

Page 5 of 5