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Experiment 2 Chemical Kinetics, a Clock Reaction

Chem 102
March 3, 2009
Abstract
In this experiment, a set amount of sodium thiosulfate was used to interact with the I2 product
from the primary reaction. Thus, creating a clock reaction and paralleled the time it took for a color
change with the time to produce a necessary amount of I2. By using different mixtures of reactants and
measuring the time it would take for the solution to turn blue, which is a result of the I2 interacting with
the starch, the dependence of the reaction rate of concentration was demonstrated. With greater
concentration of the reactants, I-, BrO3-, and H+, in the reaction, the time it took for the color change
was faster. Along with concentration, the dependence of reaction rate on temperature was shown by a
faster reaction time when the reaction was performed at 40C in comparison to 0C. The use of
ammonium molybdate demonstrated the dependence of reaction rate on a catalyst by lowering the
activation energy and speeding up the reaction eleven folds. Therefore, the three separate parts of this
experiment validated how concentration, temperature, and a catalyst affect the reaction rate. The
individual orders for I-, BrO3-, and H+ are 1, 1, and 2 respectively. The overall order of the reaction is 4,
the average rate constant is 2929 1/M3s, and the activation energy is 45.3 kJ/mol.
Introduction
Chemical kinetics encompasses the study of reaction rates, how these rates change due to
conditions, and the molecular level activity that occurs in a reaction. The four common variables that
influence reaction rate are the concentration of the reactant, temperature, catalyst, and surface area. For
a reaction to occur, the molecules must collide and more collisions occur with increased thermal
energy to greater number of molecules present.
To further the understanding of chemical kinetics and the reaction rates dependence on
concentration, temperature, and the presence of a catalyst, this experiment focused on the primary
reaction between iodide, bromate, and hydrogen ions (1) and determining the reactions rate law (2):
6I-(aq) + BrO3-(aq) + 6H+(aq)
rate

3I2(aq)

k[I-]x[BrO3-]y[H+]z

+ Br-(aq) +

3H2O(1)

(1)
(2)

In this reaction, there are three reactants and different concentrations of each reactant were used in the
five different mixtures to obtain the orders, x, y and z. Hence, the rate constant k can then be
calculated. It is expected that the reaction occurs more quickly in the presence of greater concentration
of reactants.

In order to make sure that the same small amount of I2 product formed for each mixture
reaction, sodium thiosulfate was used to create a clock reaction (3) that occurred faster than the
primary reaction:
2S2O32-(aq)

I2(aq) +

2I-(aq) +

S4O62-(aq)

(3)

The addition of a set amount of sodium thiosulfate consumed a set amount of I2. Therefore, the blue
color, which is created by the interaction between I2 and starch, formed once the thiosulate was fully
consumed. From reactions (1) and (3), the relationship between bromate and thiosulfate was formed:

3 mol I 2
1 mol BrO 3-

2molS2O 2
3
[BrO 3- ] 1 [S 2 O 32- ]

1molI 2 accounts for


t
6
t

(4)

For the second part of this experiment, four different temperatures settings were used to show

the relationship between temperature and the reaction rate. Using the Arrhenius equation:
ln k

- Ea 1
ln A ; A is a constant; R = 8.314 J/molK
R T

(5)

the activation energy Ea can be calculated and it is expected that reactions occurring at a higher
temperature will have an increased average kinetic energy of the molecules, allowing more molecules
to overcome the activation energy barrier. Hence, the increase in temperature speeds up the reaction
rate. In addition, a decrease in temperature slows down the reaction. Lastly, the use of ammonium
molybdate, which is a catalyst to the reaction, will lower the activation energy and reaction occurs in a
shorter time span.
Experimental
For the first part of this experiment, the contents in reaction flask 2 were poured into the
reaction flask 1 (Table 1) and the time was taken to see how long it would take for the solution to turn
blue. The mixture was continuously swirled until it turned blue. Although it was recommended to use
three drops of starch, six drops of starch was used for each trial. The final temperature was also
recorded for each trial.

Table 1: Volume of reagents for Mixtures 1 to 5


Reaction Flask 1(250 mL)
Mix 0.010 M 0.0010 M H2O
KI
Na2S2O3
1
10 mL
10 mL
10 mL
2
20 mL
10 mL
0 mL
3
10 mL
10 mL
0 mL
4
10 mL
10 mL
0 mL
5
8 mL
10 mL
12 mL

Reaction Flask 2 (125mL)


0.040 M 0.10 M Starch
KBrO3
HC1
10 mL
10 mL 3 drops
10 mL
10 mL 3 drops
20 mL
10 mL 3 drops
10 mL
20 mL 3 drops
5 mL
15 mL 3 drops

For the second part, mixture 1 reaction was completed in the four different temperature
settings, 40, 20, 10 and 0 C. To ensure constant temperature from the beginning to end of the reaction,
the flasks were kept in the necessary temperature water or ice baths. Time was also taken to see how
long it would take for the solution to turn blue.
For the third part, mixture 1 was used and the addition of ammonium molybdate, the catalyst.
The catalysts function is to lower the activation energy and create new elementary steps to the reaction
and transition states. Overall, it speeds up the reaction. One drop of 0.5 M (NH 4)2MoO4 was added to
the reagents in reaction flask 2, which was later mixed in with reaction flask 1. The reaction times for
with and without the catalyst were both recorded.

Results and Discussion


In Table 2, the reaction time varies with the reactant concentrations of iodide, bromate, and
hydrogen ions for the different mixtures. As the iodide ion concentration doubles in mix 2, the time of
the reaction halves, when compared to mix 1. As the bromate ion concentration doubles in mix 3, the
time of the reaction decreases, when compared to mix 1. As the hydrogen ion concentration doubles in
mix 4, there is a three fold decrease in reaction time, when compared to mix 1. In mix 5, the reaction
has the least reactant concentration and it took the longest for the solution to turn blue.

Table 2: Reaction time and rates for Mixtures 1 to 5


Mix Time
(s)
1
2
3
4
5

160
82
99
46
210

Rate
-[BrO3-]/t
= 3.33 x 10-5 (mol/L)/t
2.083E-7
4.065E-7
3.367E-7
7.246E-7
1.587E-7

Reactant concentration
(mol/L)
[I-]
[BrO3-]
[H+]
0.0020 0.008
0.002
0.0040 0.008
0.002
0.0020 0.016
0.002
0.0020 0.008
0.004
0.0016 0.004
0.003

Temp
)C)
20.8-21
20.8-21
20.8-21
20.8-21
20.8-21

From chemical kinetics, a higher reactant concentration results in more molecules likely to
collide and interact with each other and allowing the reaction to occur more quickly. Therefore,
mixtures 2, 3, and 4 have greater number of collisions between the sodium thiosulfate and iodine and
allowing the clock reaction to occur quickly and allowing the iodine to react with the starch to turn the
solution blue.
When the reactants for mix 1 were heated to 40C and later mixed, it took 60 seconds for the
reaction to occur (Table 3). At higher temperatures, the increased thermal energy allows the molecules
to collide more often and react. In contrast, the colder temperatures of 10C and 1.8C resulted in longer
reaction times, 406 and 660 seconds, respectively. Hence, the trend shows that the decrease in
temperature results in a longer reaction time and smaller rate value. According to the lecture notes, a 10
Celsius increases correlates with a doubling or tripling of the reaction rate. When comparing the
reaction rates for 10 and 1.8 C, there is a 1.6 fold difference and when comparing 10C to 20C, there is
a 2.5 fold change in the rate. By comparing these results to a theoretical concept, there is variability in
the change of rate as the temperature increases in 10 C increments.
Table 3: Reaction and rates for Mix 1 at 40, 20, 10, 1.8 C
Mixture
1A
1B
1C
1D

Time
(s)
60
160
406
660

Rate = -[BrO3-]/t
(mol/L-s)
5.56E-7
2.08E-7
8.21E-8
5.05E-8

Temp
( C)
40
20.8
10
1.8

Calculated k
(1/M3s)
8680.56
3255.21
1282.84
789.141

In Figure 1, the trend line for the ln k vs 1/T graph shows that the slope is -5526 K and the
activation energy derived from this trend line is 46 kJ/mol. From the data in Table 3, the calculated
slope for these points is -5446 K and the activation energy Ea is 45 kJ/mol.
Figure 1: Graph lnk vs 1/T (y=-5526x +26.761), includes Table 3 data

Since the rate constant k increases with temperature, the rate of reaction will increase at any give
reactant concentration. This clock reaction experiment shows an Arreneius behavior and the high Ea
indicates a strong temperature dependence of the rate constant. When comparing the calculated slope
and Ea to the trend line slope and derived Ea, the values are pretty close. From online literature
sources, the Ea for an iodine clock reaction is 53kJ/mol, which is higher than what was calculated in
the experiment. Since only four temperature settings were used, a more accurate Ea could be derived
by conducting the experiment with a greater range of temperature settings.
When introducing the homogenous catalyst ammonium molybdate into the reaction mix 1, the
reaction takes 15 seconds. The activation energy of the catalyzed reaction is smaller than the Ea of an
uncatalyzed reaction. Since the function of the catalyst is to lower the activation energy, the reactions
moves forward a lot quicker, in comparison to the 174 seconds for an uncatalyzed reaction to occur.

Although the catalyst doesnt get consumed in the reaction, it creates new transition states and
elementary steps to allow the reaction to precede a lot faster. Hence, the catalyst lowers the Ea for the
sodium thiosulfate and iodine reaction and this experiment demonstrated the function of a catalyst in
chemical kinetics.
Conclusion
From the three parts of this experiment, the use of different reactant concentrations,
temperatures and the use of a catalyst demonstrated the concepts of chemical kinetics and their
influence on the iodine clock reaction rates and the primary reaction. With more reactant
concentrations, increased temperatures, and a catalyst, the reaction occurs more quickly. The sodium
thiosulfate was quickly consumed in all three conditions and the excess iodine reacted with the starch
to turn the solution blue.
As a result, the order of the reaction was calculated to be 4, the rate constant was 2929 1/M 3s,
and the activation energy was 45.3 kJ/mol. For future improvements for this experiment, the starch
used needs to be fresh. The use of old starch turned the reaction into a red brown color and the reaction
times were slightly longer than the reactions that included freshly made starch. Overall, these
experimental results were fairly close to theoretical values.