Glory Rose D.

Delas Llagas

Date Performed: March 11, 2014

3ChE-A Group No. 3

Date Submitted: February 4, 2014

EXPERIMENT 4: KINETICS OF THE PERSULFATE-IODIDE CLOCK REACTION

I.

Introduction:
Harcourt-Esson reaction or the Harcourt-Essesn reaction also known as the iodine
clock reaction is a classical chemical clock demonstration experiment to display
chemical kinetics in action. In this experiment two colorless solutions are put together,
at first there will be no visible reaction. After awhile, the solution suddenly turns to a
shade dark blue. In the experiment done in the laboratory Persulfate variation of iodine
clock reaction experiment was performed. In this clock reaction, sodium, potassium or
ammonium persulfate was used to oxidize iodide ions to iodine. On the otherhand,
sodium thiosulfate was used to reduce iodine back to iodide before iodine can complex
with the starch to form the characteristic blue-black color.
The reactions on the experiment are the following:
Generation of Iodine:
2 I + S2O82 I2 + 2 SO42
Iodine removal:
I2 + 2 S2O32 2 I + S4O62

When all the thiosulfate is consumed the iodine may form a complex with the starch.
Potassium persulfate is less soluble while ammonium persulfate has a higher solubility.

The purpose of this experiment is to investigate the kinetics of the reaction

between persulfate and iodide ions, the effect of reactant concentration on the rate of
reaction, the effect of temperature, and the effect of ionic strength of the solution.
Along the investigation, the experiment also aims to determine the rate equation and
activation energy.

II.

Methodology:
Preparation of solutions:
A 200 mL of 0.1M ammonium persulfate, 100 mL of 0.1M of ammonium thiosulfate,
100 mL of 0.1M sodium thiosulfate, and 200 mL of 0.1M potassium iodide were
prepared. The prepared solutions were labeled as A, B, C, and D respectively.
Starch indicator was prepared by adding 0.5 g of starch into 10 mL distilled water. The
produced solution was stirred until homogenous. The starch solution was added to a
vigorously boiling 50 mL of distilled water. The heating was continued until the
mixture was homogenous.
Determination of rate equation:
As showed in figure 1 a 10 mL of solution A was transferred in a 100 mL beaker. A
drop of the starch solution was added to the transferred solution A. 100 mL conical
flask was used to contain a 10 mL of solution D. 5 mL of solution C was added to the
solution D in the flask. The contents of the beaker were then poured to the flask. The
flask was gently swirled and the time was recorded when the resulting solution turned
to blue. The procedures were repeated to the different volumes of the S 2O82- and Isolutions specified in the laboratory manual.

Figure 1 Experimental set up for determining the rate constant

Effect of temperature
A mixture of a 10 mL of solution (a) was put in 2 large test tubes. A few drops of
starch, and a second solution containing 5 mL of solution (c) and 10 mL of solution (d)
were added to the test tubes. Both test tubes were put into a water bath afterwards for
10 minutes. The temperatures of the solutions in the test tubes were recoreded, as well
as the time when the solution changed its color to blue. The experimental set up is
illustrated in figure 2.

Figure 2 Experimental Set up for the determination of effect of temperature

Effect of ionic Strength

Solutions of (NH4)2S2O8 and 0.1 M (NH4)2SO4 with volumes of 10 mL were mixed
with 5mL Na2S2O3, and 10 mL of I-. The time of the appearance of the color blue was
recorded.
III.

Data and results:

Table 1 Compositions of the solutions
Solution
M
(NH4)2S2O8
0.1
(NH4)2SO4
0.1
Na2S2O3
0.01
KI
0.1
Starch
Determination of rate equation

Volume (mL)
250
500
250
200

MW
228
132.13
298
166

Mass (g)
5.7
6.6065
0.62
3.32
0.5128

Label
A
B
C
D

Table 2 The needed volumes of the solutions to be added and the time it took for the
solution to change its color
Solution

V of A (mL)

V of B (mL)

V of C (mL)

V of D (mL)

Time (mins)

1
2
3
4
5
6
7

8
8
8
8
8
6
4

0
2
4
6
2
4
6

7
7
7
7
5
5
5

10
8
6
4
10
10
10

3:18
4:12
7:52
8:06
1s
3:49
29:14

Effect of temperature
Table 3 List of temperatures and the corresponding time when the solution changed
its color to blue
Solution 7
Temperature (oC)
50

Time
4:14

45
40
35
30

6:00
7:24
10:23
14:03

Solution
10 mL B

Time (s)
1,500

Effect of ionic strength

Table 4

IV.

Treatment of Results:
Determination of rate constant

Figure 3 The components of the solution, time of the reaction, computed rate constant and
other computed components

Solutions to complete the table:

S2O8 concentration =

0.1(Vol A )
(total Volume)

I concentration=

0.1(Vol D)
(total Volume)

To get the Rate constant K, use equation from the lab manual:

ln I
1
Where m and n can be
ln =lnK +m ln [ S 2 O8 ] +n
t
obtained from the graph
indicated on figure 5 and 6

Figure 4 Graph of -ln (dt) vs ln [SsO8 2-]

-4.50

-4.00
f(x) = 10.4x + 34.89
R = 0.88

- ln dt

-3.50
-6.50
-6.70
-6.90
-7.10
-7.30
-7.50
-7.70
-7.90
-8.10
-8.30
-8.50

ln [SsO8 2-]

Figure 5 Graph of -ln (dt) vs ln [I -]

-4.50

-4.00

-5.00
-3.50
-5.20
-5.40
-5.60

-ln dt
f(x) = 0.89x - 2.6
R = 0.7

-5.80
-6.00
-6.20
-6.40

ln [I -]

Determining the Activation Energy, Ea

In getting the activation energy, Ea plot (1/K) vs (1/T) and use the combined

equation of equations 4 and 6

lnK =lnA

Ea
R(x) , where x is equal to

the equation and the slope obtained from the graph will be equal to

Figure 6 Table for Activation Energy Computation

1
T . Arrange

Ea
R

Figure 7 Graph of ln K vs ln (1/T)

8.00
f(x) = - 5793.48x + 25.82
R = 1
7.50
ln K
7.00

Linear ()

6.50
0.0031 0.0031 0.0032 0.0032 0.0033 0.0033 0.0034
1/T

V.

Answers to Questions
a. What is the order of the reaction in terms of sodium persulfate and in terms
of potassium iodide? What is the overall order of the reaction?
- Based on the data gathered and computed results the slope from the graph
of sodium per sulfate is 10.39 which is also the order of the reaction with
respect to sodium per sulfate. And the slope from the graph of potassium
iodide is 0.890 which is also the order of the reaction with respect to
iodide. Adding the two the over-all order of the reaction based on the
experiment was 11.28. The computed over-all order of the reaction is far
from the theoretical value which is 2. Theoretical values with respect to
potassium iodide and sodium persulfate are both 1.
b. Comment on the effect of the reduction in ionic strength on the rate of
reaction and determine whether the reactants which form the activated
complex have charges of the same or different sign.

One factor that can affect the rate reaction is the charges of ions in the
reactants presents in the sample solution. The charges of ions are also
related to its ionic strength. The product of the charges of the ions can
indicate if the rate of the reaction would increase or decrease. When the
product is positive an increase in the rate would be expected and if the
product is negative a decrease would be expected. If it is neutral, then
there will be no changes observed on the rate of the reaction.

c. Identify sources of error in the experiment and estimate their magnitude.

- Errors may be caused due to contamination of the sample solutions. The
potential causes of the contamination are the chemical reagents may not
be properly sealed in the storage, students who get their sample return the
excess back to the container again, and also there are students who
directly put their instruments into the container of the chemical reagents.
VI.

Conclusion and recommendations:

Conclusion:
The experiment successfully demonstrated the reaction between iodide and
persulfate. When iodide reacts with persulfate ions, the reaction produces iodine
and sulfate. The iodine produced is immediately consumed by the added
thiosulfate ions, and the excess iodine, which the thiosulfate failed to consume,
causes the sample to change its color from clear to blue. The amount of the
thiosulfate that is added to the solution indicates how much iodine was produced
through the time taken by the reaction to turn blue.
On the other hand, the experiment for the rate constant k, also shows that it
is affected and have direct relationship with temperature. But there is an exception

when zero activation energy is observed. During this circumstance the temperature
does not affect the rate constant of the reaction.

Recommendations:
It is recommended to start from the last solution to check if a change in color will
occur within 30 minutes time span. If no changes are observed, adjustment on the
concentration of the persulfate is advised. If the mixture changed its color upon the
addition of solutions (a) and (b) to solutions (c) and (d), a decrease in the amount of
(NH4)2S2O8 solution and increase of the amount of Na2S2O3 solution by 1 mL is advised.
Also it is recommended to make sure that the apparatus that you will be using are clean.

VII.

References:
a. Andr P. Oliveira and Roberto B. Faria (2005). "The chlorate-iodine clock
reaction". J. Am. Chem. Soc
b. Oxford University (2006). Kinetics of the Persulfate-iodide clock reaction
c. Denes Varga et.al. (2010), Complex Kinetics of a Landolt-Type Reaction: The
Later Phase of the Thiosulfate-Iodate