ABSTRACT

In this experiment, two clear solutions are added together in one container. At
first, no reaction can be visibly seen after mixing. But, after a short delay, the
clear solution turned into blue-black shade solution. This is due to the variations
that we did in our set-up. The first set-up was in a room-temperature having a
mixture of 10.0mL of 0.200M KI, 10.0mL of 0.200M KCl, 10.0mL of 0.0050M
Na2S2O3, 0.5 mL of Starch Solution, and 20.0 mL of 0.100M K2S2O8. The
second set-up was also in a room-temperature having a mixture of 20.0mL of
0.200M KI, 10.0mL of 0.0050M Na2S2O3, 0.5 mL of Starch Solution and 20mL of
0.100M K2S2O8. The third set-up was also in a room-temperature having a
mixture of 20.0mL 0.200M KI, 10.0mL 0.0050M Na2S2O3, 0.5 mL Starch Solution,
10mL of 0.100M K2S2O8 and 10mL of Na2SO4. Lastly, the fourth set-up was
under an ice-bath having a mixture of 20.0mL 0.200M KI, 10.0mL 0.0050M
Na2S2O3, 0.5 mL Starch Solution, and 20mL of 0.100M K2S2O8.
Through these, we were able to determine the order of reaction, computed for
the rate constant of the reaction at a given temperature and ionic strength.
And lastly, we proved that the temperature affects on the rate of the reaction.

INTRODUCTION
The purpose of this experiment is to determine the rate law and the activation
energy for the reaction between persulfate ion, S2O82-, and iodide ion, I-:
S2O82-(aq) + 2 I-(aq) 2 SO42-(aq) + I2(aq)
The rate law can be written as:
Reaction rate =
Where m and n are the orders with respect to S 2O82- and I-, respectively, and k is
the rate constant. Determining the rate law involves determining the values of
m and n.
The temperature dependence of the rate constant is given by:

The Arrhenius Equation, where A is the pre-exponential factor, E is the activation

energy with units of J/mol, T is the absolute temperature, and R is the gas
constant (R= 8.3145 J K-1mol-1) explains that the activation energy can be
obtained by measuring the rate constant at several temperatures, and then
plotting ln k versus 1/T.

Page 1 of 9

Self-

indicating
reactions
of
this
type, in
which
nothing
seems
to happen
for a while and then a change suddenly becomes visible, are known as clock
reactions. Clock reactions often appear in chemistry shows, and many involve
iodine, since the colour change resulting from the generation of iodine is
particularly marked.
The stoichiometric equation tells us that the rate of consumption of persulfate
equals the rate of iodine production. In each experiment, time measurement, t,
is taken to consume a known amount of thiosulfate (at which point the solution
turns blue).
In this experiment, the effect of reactant concentration on the rate of reaction
will be investigated, and thereby obtain the rate equation. The effect of
temperature is also later studied, and the results used to find the activation
energy for the reaction. Finally, the effect of the ionic strength of the solution on
the rate is measured, from which a possible structure of the reaction
intermediate may be deduced.

METHODOLOGY

Page 2 of 9

PROCEDURE

Four experiments had to be performed, the three had been done under room
temperature whilst the 4th experiment was under an ice bath.
All the solutions except KCl and Na2SO4 had to be prepared. These two
solutions were used to maintain the ionic strength of the solutions.

1. To prepare the needed solutions, computed amount of each solutions was

poured into the volumetric flask and distilled water had been added up to the
mark on the neck of the flask. These diluted solutions would be used along
the experiment.
2. For each experiment there were two reagents; A and B. All the experiments
had 0.5 mL of fresh starch solution in reagent A. And in the first experiment,
the other solutions in Reagent A, prepared in the e-flask were: 10mL of KI, KCl
and Na2S2O3 Meanwhile for reagent B which was prepared in a beaker
contained: 20 mL of K2S2O8 and there was no Na2SO4 present in the reagent.
3. Once the two reagents had been prepared, the contents of the beaker could
now then be added to the contents of the flask, the timer should be started
once the transferring started. The contents of the flask was poured back into
the beaker then returned it back to the flask to mix the reagents well.
4. The flask had been allowed to sit undisturbed and had been observed. The
timer was then stopped once the blue-black color appeared. The time then
was recorded and the experiment was duplicated.
5. This procedure was repeated for experiments 2, 3, and 4. For experiment 2,
Reagent A was composed of 20 mL KI, no KCl, 10 mL Na 2S2O3. For experiments
3 and 4, there were 20 mL KI, also no KCl, 15 mL of Na 2S2O3 in the reagent A
for the compositions in Reagent B, experiment 2 and 4 had 20 mL of K 2S2O8
and for experiment 3, there was 10 mL each of K 2S2O8 and Na2SO4.
6. In order to get the temperature of the solutions, the temperature of one of
the reaction solutions could be recorder for all. (since experiments had been
done under room temperature)
7. For experiment 4, the reagent A: 20 mL KI and 10 mL Na 2S2O3 and reagent B:
20 mL of K2S2O8 were put into two beakers with ice and they had been
allowed to remain in the ice for atleast 5 minutes.
8. The temperature of the ice bath was then recorded.
9. The reagents had been mixed and was put back to the ice back. The timer
then was started when the reaction flask started to show a color change.
10.Calculations had been done after performing the experiment: dilution
calculations, calculation of the average elapsed time for each experiment and
the rate for each reaction, the order of reaction with respect to the Iodide ion
and the Persulfate ion and the rate constant, k.

RESULTS AND DISCUSSIONS

Table 4-1 Initial Concentrations of the Ions

Page 3 of 9

Experiment

[I-]

[S2O8]2-

[S2O3]2-

0.0396 M

0.0396

9.901 x 10-4

0.0792 M

0.0396

9.901 x 10-5

0.0792 M

0.0198

9.901 x 10-6

Temperature of Solution (oC)

30

30

30

0.0792 M

0.0396

9.901 x 10-6

Temperature of Solution (oC)

10

10

10

Table 4-2 Determination of the rate of reaction with respect to iodide and
persulfate ions
Experiment
1

Elapsed Time (s)

Trial (A)

Trial (B)

Average
Time (s)

45.25

45.11

45.18

22.35

22.78

22.565

48.14

48.22

48.18

4 (ice bath)

97.52

99.34

Rate (M/s)
1.0957
10-5
2.1939
10-5
1.0275
10-5
5.0295
10-6

98.43

Table 4-3 Determination of rate constant,k, and activation energy

Reaction Order
Rounded
to
Calculated
numbers
With respect to Iodide Ion
1
1
With respect to Persulfate Ion
Overall
Value of k
Value of k
Value of k
Average
(including

1.07

from Expt 1
from Expt 2
from Expt 3
value
for
K
units) room temp

value of k from experiment 4

(ice bath) including units
activation energy, Ea (kJ/mol)

x
x
x
x

whole

1
2
0.006987 (1/M-s)
0.006995 (1/M-s)
0.006552 (1/M-s)
0.006845 (1/M-s)
0.001604 (1/M-s)
51.776 kJ/mol

Peroxydisulfate ion, S2O82- and Iodide ion, I- are clear in aqueous solution and
remains colorless when reacts which each other according to this equation:
S2O82-(aq) + 2 I-(aq) 2 SO42-(aq) + I2(aq)
Reaction (1) wascarried out in the presence of thiosulfate ion, S2O32- and starch.
The concentration of thiosulfate ion was maintained at a much lower value than
that of either the persulfate ion or the iodide ion. The reactions that occured are:
S2O82-(aq) + 2 I-(aq) 2 SO42-(aq) + Slow
I2(aq)

Page 4 of 9

(4-1)

I2(aq) + 2 S2O32-(aq) 2 I- + S4O62-(aq)

I2(aq) + starch blue complex

Fast
Slow

(4-2)
(4-3)

Reaction (4-1) is much slower than reaction (4-2), and, as a result, the I 2 in
formed in reaction (4-1) is immediately consumed by reaction (4-2), and the
concentration of I2 remains at a very low value as long as thiosulfate ion is
present. When all of the thiosulfate ion was used up, the concentration of I 2 from
reaction (4-1) increased. The presence of I2 was detected by the formation of a
blue complex resulting from the reaction of I 2 with starch, reaction (4-3). The
rate of reaction (4-3) did not become significant until the concentration of
I2 became appreciable.
A characteristic of this reaction is that the reaction mixture remains colorless for
several minutes after the reactants are mixed. During this time both reactions (41) and (4-2) were occurring. The solution remained colorless because the I 2 from
reaction (4-1) was being consumed by reaction (4-2), and cant react with the
starch. As soon as the thiosulfate ion was used up, the I 2 reacted with the starch,
and an abrupt and dramatic color change, from colorless to blue, occured.
The rate of reaction (4-1) is the rate of consumption of S 2O82- ion. For every
S2O82- ion used up two S2O32- ions are consumed. Thus,:
(4-4)
Rate of reaction (4-1) =
If (S2O32-)o is the initial concentration of S2O32- ion, and t is the time interval from
the start of the reaction until the solution changed color, then in equation (4-4),
(S2O32-) = 0 - (S2O32-)o , and if the initial concentration of S2O32- is constant then
equation (4-4) becomes
(4-5)
Rate of reaction (4-1) =
As the name implies, rate constant, k must be constant at a specific. In this
experiment, the values of rate constant obtained at room temperature using 3
experiments were similar to each other. To be able to find the value of k, 3
experiments were carried out in which concentration of iodide ions were held
constant for experiments 2 and 3 while concentation of persulfate ions were held
constant for 1 and 2. This was done to be able to find the corresponding
exponents,m and n, to be used for the following rate equation: rate = k[I -]m
[(S2O82-]n. The values of m and n do not correspond to the coefficient of the ions
in the chemical equation. It can only be determined experimentally. It has been
observed that the rate, reported in molar/s, increased when the molarity of one
of the ion increased provided the other was held constant as in the case of
experiment 1 and 2 where [(S2O8) 2-] was held constant and exerment 2 has a
higher concentration of [I-]. When experiment 2 and 3 was compared in which [I -]
was constant while [(S2O8)2-] was higher in experiment 2, the rate of reaction had
a higher value in 2. This could be due to the fact that as ionic streghth increases,
the faster the reaction proceeds. Ionic strength is a factor of concentration and
charge of the ion.

Page 5 of 9

It is important to stress out that it is the rate of reaction which varies depending
on the concentration and values of m and n exponents while the rate constant, k,
is the same for a specific temperature no matter what the concentration is.
At lower temperature, K became lower as well which is expected already as
implied by the Arrhenius equation.

This is because at low temperatures, molecules have lower kinetic energy to

meet the required activation energy. In fact, had here been more values, the
graph of ln K vs 1/T would show a linear correlation which would support the said
observation.
Determination of activation energy was done using the following equation
derived from Arrhenius equation,

As the name implies, rate constant must be constant at a specific. In this

experiment, the values of rate constant obtained at room temperature are
similar to each other. At lower temperature though, K became lower as well
which is expected already as implied by the Arrhenius equation. This is because
at low temperatures, molecules have lower kinetic energy to meet the required
activation energy. In fact, had here been more values, the graph of ln K vs 1/T
would show a linear correlation which would support the said observation.
SAMPLE CALCULATIONS
Experiment 1: C1V1=C2V2
[Iodide]: (0.2M) (0.010L) = (C2) (0.0505L); C2=0.03960M
[Persulfate]: (01M) (0.02L) = (C2) (0.0505L); C2=0.03960M
[Thiosulfate]: (0.005M) (0.010L) = (C2) (0.0505L); C2=9.901x10-4M

Page 6 of 9

Rate:

[thiosulfate]
2t

9.901 x 104
2( 45.18)

= 1.0957x10-5 M/s

Experiment 2:
[Iodide]: (0.2M) (0.020L) = (C2) (0.0505L); C2=0.0792M
[Persulfate]: (0.1M) (0.02L) = (C2) (0.0505L); C2=0.03960M
[Thiosulfate]: (0.005M) (0.010L) = (C2) (0.0505L); C2=9.901x10-4M
Rate:

[thiosulfate]
2t

9.901 x 104
2( 22.565)

= 2.1939x10-5 M/s

Experiment 3:
[Iodide]: (0.2M) (0.020L) = (C2) (0.0505L); C2=0.0792M
[Persulfate]: (0.1M) (0.01L) = (C2) (0.0505L); C2=0.0198M
[Thiosulfate]: (0.005M) (0.010L) = (C2) (0.0505L); C2=9.901x10-4M
Rate:

[thiosulfate]
2t

9.901 x 104
2( 48.18)

= 1.0275x10-5 M/s

Experiment 4:
[Iodide]: (0.2M) (0.020L) = (C2) (0.0505L); C2=0.0792M
[Persulfate]: (01M) (0.02L) = (C2) (0.0505L); C2=0.03960M
[Thiosulfate]: (0.005M) (0.010L) = (C2) (0.0505L); C2=9.901x10-4M
Rate:

[thiosulfate]
2t

9.901 x 104
2( 98.43)

= 5.0295x10-6 M/s

Reaction order: rate = k[iodide]m[persulfate]n

i)

w/ respect to Iodide ion (m)

1: 1.0957x10-5 = k (0.03960)m (0.03960)n

2: 2.1939x10-5 = k (0.0792)m (0.0398)n
12: m=1
ii)

w/respect to Persulfate ion

2: 2.1939x10-5 = k (0.0792)m (0.0398)n

Page 7 of 9

3: 1.0275 x10-5 = k (0.0792)m (0.0198)n

12: n=1
Overall: m+n = 2
Experiment 1: 1.0957x10-5 = k (0.03960)1 (0.03960)1
K1= 0.006987 /M.s
Experiment 2: 2.1939x10-5 = k (0.0792)1 (0.0398)1
K2= 006995 /M.s
Experiment 3: 1.0275 x10-5 = k (0.0792)1 (0.0198)1
K3= 0.006552 /M.s
Experiment 4: 5.0295 x10-6 = k (0.0792)1 (0.0396)1
K4 = 0.001604 /M.s
lnK2 lnK1 =

Ea
R

( T2

ln(0.006845) ln(0.00604) =

1
T1 )
Ea
1
8.314 ( 10+ 273.15 -

1
30+ 273.15 )

Ea= 51775.82 J/mol

Ea = 51.776 kJ/mol

CONCLUSION
The process mainly involved proving the validity of rate law equations and
equilibrium constants so that the activation energy can be determined. The time
recorded, wherein the solution turned to blue-black symbolizing that the all of
the thiosulfate has converted to tetrathionate, was used for calculating the rate.
The overall order of reaction which was determined experimentally, is second
order. Literature value also shows that the peroxydisulfate-iodide reaction is a
second order reaction. A considerably high activation energy was obtained
which implied that the reaction was slow, this was also observed during the
fourth experiment in the procedure. The value of activation energy obtained is
dependent of the equilibrium constants and temperature at which the
equilibrium constants were obtained. Possible sources of errors are due to the
transferring of the substances, environmental factors, parallax error, etc.
although they are very minimal.
REFERENCES
(n.d.). Retrieved on March 2015, from
http://wwwchem.csustan.edu/chem1112/Persulfate.htm
Page 8 of 9

Arrhenius Equation. (n.d.). Retrieved on March 2015, mula sa UCDavis

CHEMWIKI:
http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinetics/Modeling_Reactio
n_Kinetics/Temperature_Dependence_of_Reaction_Rates/The_Arrhenius_La
w/Arrhenius_Equation
Liu, Y., Sheaffer, R. L., & Barker, J. R. (2003). Effects of Temperature and Ionic
Strength on the Rate and Equilibrium Constants for the Reaction Iaq + Iaq I2-aq. The Journal of Physical Chemistry.

Page 9 of 9