J. R. Santos / Chem 26.

1 (2019) Page |1

Chemical Kinetics: Iodine Clock Reaction

John Rebo Santos

Department of Mining, Metallurgical, and Materials Engineering
College of Engineering, University of the Philippines, Diliman
Quezon City 1101, Philippines
[email protected]

Abstract - The formation of iodine (I2) from persulfate starch solution in beaker B) were prepared. The
(S2O82-) and iodide (I-) ions was observed in the measurements are shown on table 3 of the appendix.
experiment to determine the effects of the reactant
concentration, temperature and presence of catalyst on On the second part, four sets of 50-mL beakers A and B
with the same concentrations of reactants were prepared.
the reaction rate. In the first part of the experiment, five
The first three sets were conducted at different temperatures.
runs with two beakers each were prepared. The beakers In Set 1, the beakers were cooled in an ice bath and were
in each run had varying concentrations of reactants mixed when the temperature reached 5 oC. Set 2 was
S2O82- and I-. Then, four sets of equal reactant already performed in the first part of the experiment (Run 2)
concentrations were prepared. Three were subjected to at room temperature (27.5 oC). In Set 3, the beakers were
varying temperatures (5 oC, 27.5 oC and 50 oC) while heated in a water bath and were mixed at a temperature of
CuSO4, a catalyst, was added to the fourth set. For each 50 oC. In Set 4, four drops of 0.01 M CuSO4 were added to
beaker A - also performed at 27.5 oC.
run and set, time was recorded from the mixing of the
contents in beaker A and beaker B to the appearance of For each run and set, time was recorded immediately after
blue in the resulting mixture. By the initial rates method, the contents of beaker A were poured into beaker B until the
a rate law of R=1.17x10-2[S2O8 2-][I-] was obtained. Using mixture has turned blue.
calculations based on the Arrhenius equation, an
III. RESULTS AND DISCUSSION
activation energy of 65.71 kJ/mol and Arrhenius
The primary reaction in the experiment was the formation of
constant of 3.43x109 were determined. It was observed
iodine from persulfate and iodide ions (1). In order to
that the reaction rates increased as the temperature went measure the rate of reaction, a small known quantity of
up and the reaction with the presence of CuSO 4 as a thiosulfate was added. As it was formed, the iodine
catalyst also had a relatively higher reaction rate. produced in the first reaction was reduced back to iodide by
the thiosulfate in a second reaction (2).
I. INTRODUCTION
Chemical reactions happen everywhere. These can be S2O8 2- + 2 I- → 2 SO4 2- + I2 (1)
described by the rate of reaction - the change in
concentration of reactant or product per unit of time. [1] 2 S2O3 2- + I2 → 2 I- + S4O6 2- (2)
Understanding reaction rates have both biological and
industrial significance. For example, chemists need to know When all the thiosulfate (S2O32-) has been consumed, free
and maintain a desired rate of reaction in manufacturing iodine (I2) began to appear in the solution. The time it took
medicines or commercial products. [2] to produce enough iodine to consume all the thiosulfate was
recorded in order to determine the rate of the first reaction.
Clock reactions are self-indicating reactions in which
nothing seems to happen for a while and then a change The rate law is an equation that can be used to predict the
suddenly becomes visible. [3] The Iodine Clock Reaction relationship between the rate of reaction and the
Experiment was conducted in two parts. First, five runs were concentration of reactants. [4] In the form of rate law for this
prepared - each with different concentrations of reactants in experiment (3), k is the rate constant, m is the partial
two beakers that were to be mixed to start the reaction. The reaction order with respect to [S2O82-] and n is the partial
same was done on the second part but with the reaction order with respect to [I-].
concentrations held constant and the temperature varied in
three setups. One set of reaction was done in the presence of R = k[S2 O8 2− ]m [I − ]n (3)
a catalyst.
Meanwhile, the Arrhenius equation (4) was used to
After the reactions were timed, the objective was to determine the activation energy where A is the Arrhenius
investigate the influence of reactant concentration, constant, Ea is the activation energy (J mol-1), R is the ideal
temperature and presence of catalyst to the rate of reaction gas constant (8.314 J mol-1 K-1), and T is the temperature
between persulfate and iodide ions to form iodine. (K).
−Ea
II. METHODOLOGY k = Ae RT (4)
The experiment was divided into two parts. On the first part,
five runs of two 50-mL beakers A and B containing varying KI, K2S2O8 and Na2S2O3 were the source of reactants S2O82-,
concentrations of solutions (KI and KCl in beaker A; I- and S2O32-, respectively. KCl and K2SO4 were added to
K2S2O8, K2SO4, Na2S2O3 and 3 drops of 2.5% (w/v) fresh maintain the total volume and ionic strength of the solutions
 J. R. Santos / Chem 26.1 (2019) Page |2

because these can influence the rate coefficient (k) of ionic Figure 2 below shows that the plot of ln(rate) and ln [I -] is
reactions. [3] To make the appearance of I2 more visible, directly proportional. The line of best fit in the figure is y =
starch solution was added, which forms a dark blue complex 1.12x - 8.03 with linearity value R2 equal to 0.967. Since the
with it. slope is equal to 1.12 ≈ 1, the partial reaction order n is also
one (first order).
The known [S2O32-] = 8.0x10-4M - the limiting reactant in
the second chemical reaction (2) - and the recorded time -10
were used to solve for the initial rates. This is summarized -5 -4 -3 -2 -1 0

ln(rate)
in the formula for rate of reaction (5). -11

d[ I2 ] 1 d[ S2 O3 2− ] -12
rate = dt
=− 2 dt
(5)
-13
ln[I-]
Table 1 below shows the initial rates of reactions of the five
runs with varying reactant concentrations.
Fig. 2. ln(rate) vs. ln [I -] plot
Table 1. Initial rates of reactions with varying initial reactant
concentrations Given the rates of the reactions, the concentrations of
Run [S2O82-] [I-] Initial Rate reactants and the reaction orders, k was computed for each
(M) (M) (M s-1) run. The mean k was accounted for in the rate law (8) with
1 0.02 0.08 1.75x10-5 an overall reaction order of 2.
2 0.02 0.04 1.03x10-5 R = 1.17x10−2 M −1 s −1 [S2 O8 2− ][I − ] (8)
-6
3 0.02 0.02 3.69x10
Table 2 below shows that for Sets 1, 2 and 3, as the
4 0.03 0.04 8.66x10-6 temperature goes up, the initial rate and rate constant also
increase. Meanwhile, Set 4 had a relatively high initial rate
5 0.04 0.04 2.89x10-5 due to the addition of the catalyst CuSO4. The initial rates
were calculated using the rate formula (5). Change in
The rate law was expressed in linear form (6) where ln(rate) temperature affects the rate constant k [1], so the new rate
is the y-variable, ln [S2O8 2-] is the x-variable, partial constants needed to be calculated. By using the rate law (8)
reaction order m is the slope and lnk[I-]n is the y-intercept. and the calculated initial rates, the corresponding rate
By the initial rates method, ln(rate) vs. ln [S2O8 2-] was constant of each set was determined.
plotted linearly. Three points used were from Runs 2, 4, and Table 2. Initial rates of reactions with varying temperatures and presence of
5 wherein [I-] is conveniently held constant. catalyst
Set Temperature Initial Rate Rate
ln(rate) = m ln[S2 O8 2− ] + lnk[I − ]n (6) (K) (M s-1) constant
(M-1 s-1)
Figure 1 below shows that the plot of ln(rate) and ln [S2O8 2- 1 274.65 8.82x10-7 1.10x10-3
] is directly proportional. The line of best fit in the figure is
y = 1.36x - 6.37 with linearity value R2, which shows how 2 300.65 1.03x10-5 1.29x10-2
close the data are to their fitted regression line [5], equal to 3 323.15 6.65 x10-5 8.31x10-2
0.529. Since the slope is equal to 1.36 ≈ 1, the partial
reaction order m is one (first order). 4* 300.65 1.90 x10-5 2.37x10-2
*set 4 contains the catalyst and is not accounted for in the ln
-10 k vs. 1/T plot
-5 -4 -3 -2 - 1 -10.5 0
ln(rate)

-11 Figure 3 below is a graphical representation of the direct

relationship between temperature and rate constant.
-11.5
-12
ln[s2o82-] 0.1
rate constant

0.05
Fig. 1. ln(rate) vs. ln [S2O8 2-] plot
0
Similarly, the rate law was expressed in linear form (7) 260 280 300 320 340
where ln(rate) is the y-variable, ln[I-] is the x-variable, -0.05
partial reaction order n is the slope and lnk[S 2O8 2-]m is the Temperature (K)
y-intercept. ln(rate) vs. ln [I-] was plotted linearly using
three points from Runs 1, 2, and 3, which have the same Fig. 3. Temperature vs. Rate constant plot
[S2O8 2-].
Since the temperature was varied, the Arrhenius equation
was instead used for the second part of the experiment. The
ln(rate) = n ln[I − ] + lnk[S2 O8 2− ]m (7)
Arrhenius equation was expressed in linear form (9) where
 J. R. Santos / Chem 26.1 (2019) Page |3

lnk is the y-variable, 1/T is the x-variable, -Ea/RT is the

slope and lnA is the y-intercept. REFERENCES
[1] Silberberg, M. 2007. Principles of General Chemistry, 1st
Ea 1 edition. McGraw-Hills Company Inc. pp. 498-500.
lnk = − ( )+
R T
lnA (9)
[2] Frostburg, A. (n.d.). Everyday Kinetics. Retrieved 4
February 2019 from
Figure 4 below shows the plot of ln k and 1/T is inversely http://antoine.frostburg.edu/chem/senese/101/kinetics/faq/ev
proportional. The line of best fit in the figure is y = -7903x + eryday-kinetics.shtml
21.96 with linearity value R2 equal to 0.9999. Since the [3] Cartwright, H. 2006. Kinetics of the Persulfate-iodide
slope is equal to -7903, and R = 8.314 J mol-1K- 1, Ea was Clock Reaction (PDF). 2nd/3rd Year Physical Chemistry
computed to be 65.71 kJ mol-1. Now, since the y-intercept = Practical Course. Oxford University. Retrieved 4 February
21.957 = lnA, A was computed to be 3.43x109 M-1s-1. 2019
These lead to the Arrhenius equation of the reaction (10). [4] Petrucci, R. et al. 2011. General Chemistry: Principles
−65710 K and Modern Applications, 10th edition. Pearson Canada Inc.
k = 3.43M −1 s −1 x109 e 8.314 T (10) pp 608-610.
[5] Kelbert, M. and Suhov, Y. Probability and Statistics by
0 Example. 2005. Cambridge University Press. pp. 289.
0.003 0.0032 0.0034 0.0036 0.0038
APPENDICES
ln k

-5 Table 3. Volume of Chemicals in each solution

Run Beaker A Beaker B

-10
1/T +3 drops of 2.5% (w/v) starch
0.2 M 0.2 M 0.1 M 0.1 M 4mM
Fig. 4. ln k vs. 1/T plot KI KCl K2S2O8 K2SO4 Na2S2O3
(mL) (mL) (mL) (mL) (mL)
Set 2 and Set 4 of Run 2 had similar conditions. The 1 10 0 5 5 5
concentrations of their reactants as well as the temperature 2 5 5 5 5 5
of their solutions were the same. However, the presence of 3 2.5 7.5 5 5 5
CuSO4 in Set 4 resulted in its higher reaction rate. This is 4 5 5 7.5 2.5 5
because CuSO4 is a catalyst. A catalyst lowers the activation 5 5 5 10 0 5
energy required for the reaction to proceed. [1]

IV. CONCLUSION Table 4. Reaction time of each run and set

The experiment has shown that the persulfate-iodide Run Reaction Time (s)
reaction has an overall reaction order of 2. This means that
if [S2O8 2-] is multiplied by a constant and [I-] is multiplied 1 22.81
by another constant, the reaction rate is changed by a factor 2 (set 1) 453.53
equal to the product of the two constants. Moreover, it was 2 (set 2) 38.77
observed that the reaction rate constant increased with the
2 (set 3) 6.02
temperature, raising the reaction rate with it. Moreover, the
addition of CuSO4 as a catalyst proved to have raised the 2 (set 4) 21.12
reaction rate as well. 3 108.34
4 46.19
In order to record the time with high accuracy, it is advised
that a video of the reaction is taken. 5 13.84