Activation Energy of An Ionic Reaction

Mohammad Bazil Bin Bolia
Activation Energy Of An Ionic Reaction

Abstract
In this experiment, the time taken for change in colour from the
reaction of peroxydisulphate (persulphate) ions with iodide ions
were taken from a different set of temperatures. It is founded that
the reaction is considered as a Pseudo first order because the
reaction only depends on the reaction of persulphate ions.
Calculated rate values were obtained with the established theory in
which it is used to plot the graph of ln against 1/T and the value
of Ea obtained from this reaction is equal to
45.211 KJ /mol .
Aim
The aim of this experiment is to evaluate the rate of reaction of
2
peroxydisulphate ions ( S 2 O8 ) with a large excess of iodide at a
number of temperatures between 5oC and 35oC, and determining
the activation energy of the reaction.
Introduction
Peroxydisulphate ions are a very strong oxidizer. It reacts with iodide
ions to form iodine via the overall reaction:
2
S 2 O8
+2 I
2 S O4
I2
This reaction can be referred as the Iodine Clock reaction- a reaction

to demonstrate chemical kinetics which was discovered by Hans
Heinrich Landolt in 1886.1
There are several factors that affects the rate of reaction of this
reaction such as concentration of reactants, the presence of
catalyst, total surface area of the reactants, pressure and the
temperature of the system. 2
Concentration of reactants and pressure were kept constant (the
experiment was carried out at atmospheric pressure) while the total
surface area of the reactants were neglected since the reactants
were in liquid form and there were no catalyst present to speed the
reaction. The only manipulated variable in this experiment was the
temperature in which collision theory, Arrhenius equation and the
rate law will be used to analyze the date obtained from the
experiment.
Theoretical Background
According to the chemical reaction
2
S 2 O8
+2
2 S O4
I2
The rate law can be written as;

2
S 2 O8
2
S 2 O8
I
d
d
[1]
Since Iodide present were in much higher than peroxydisulphate

ions, the rate law is reduced to;
2
S 2 O8
2
S 2 O8
d
[2]
From equation [2], the value of k for this reaction at different

temperature ranges can be determined and according to Arrhenius
equation;
k =A
Ea
RT
[3]
Equation [3] is then integrated and simplified to to get a relationship

between rate constant and time.
ln k =ln A
Ea
RT
[4]
By arranging the terms in equation [4],

ln k =
Ea
+ ln A
RT
[5]
This equation can be related with y = mx + c. In order to calculate

the activation energy of the reaction, a graph of ln k against 1/T
whereby T in this equation is the absolute temperature. A straight
line graph with a negative gradient is to be plotted and the gradient
obtained from the graph will be equal to;
m=
Ea
R
[6]
Thus, the activation energy of the reaction would be

Ea=mR
Consequently, a plot of the graph ln
[7]
is the time taken for
persulphate ions to be used up) against 1/T will yield the same
results as plotting the graph of ln k agasint 1/T.
Experimental Method
Figure 1: Material and Apparatus set up.
In this experiment, five thermostatically controlled water-baths were

set up in which the temperature ranges from 5, 17, 22, 25 and 30oC.
A mercury thermometer was immersed in the water to obtain a
more accurate measurement of the water temperature and the
temperature of each water bath was controlled by a control knob
located on the right-hand side of each bath.
After the water baths were set up, solutions of persulphate and
iodide were prepared. 20cm3 of 0.5 potassium iodide and 10cm3 of
0.01M sodium thiosulphate were measured by using a pipette with a
bulb and was placed in a boiling tube. The boiling tube is then
placed into a plastic rack in the 30oC water bath. Next, 20 cm3 of
0.02M potassium peroxydisulphate was measured by using a
separate pipette and a small amount of iodine indicator was added
by using a spatula. The boiling tube was then placed in the rack in
the water bath next to the first tube.
Thermometers were placed into each boiling tube to monitor the
temperature and the contents of the tubes were allowed to reach
the temperature of the water bath. The temperature of the water
bath was recorded and once the contents of each boiling tubes
reach the temperature of the water bath, the contents were quickly
poured from one tube to the other. The mixtures were stirred
accordingly and the time taken for the mixture to turn colourless to
blue was recorded. Procedures were repeated for 5, 17, 22, and 25oC
water baths.
Results
Water Bath KI Temperature
Persulphate
Time taken (min)
o
o
Temperatu ( C)
Temperature ( C)
st
nd
re
1 Set
2 Set 1st Set
2nd Set 1st Set 2nd Set
(oC)
5
5.5
5
6
6
7.54
8.06
17
17
17
17
17.5
3.43
3.47
22
21.5
22
22
22.5
2.41
2.44
25
25
24.5
25
25
2.05
2.08
30
30
30
30
30
1.41
1.33
The table below shows the various types of water baths
temperatures and the time taken for the colourless mixture of the
reactants to turn blue.
Analysis Of Data
Rate Constants for 5, 17, 22, 25 and 30oC
2
S 2 O8
S 2 O8
d
k 5 =
2
S2 O8
S2 O8
d
k 17=
Averag
e
8.00
3.45
2.425
2.065
1.37
2
S2 O 8
S2 O 8
d
k 22=
2
S2 O8
2
S2 O8
d
k 25=
2
S2 O8
2
S2 O8
d
k 30=
The table below shows the obtained values of the rate constants K,
and other experimental values.
Temperatu
re
(oC)
K (1st
set, s-1)
K (2nd
Set, s-1)
K
(Average,
s-1)
Ln k
(ln
)
1/T (k-1)
Rate (M s1
)
0.0021
10
0.0044
84
0.0062
11
0.0080
00
0.00205
8
0.00440
5
0.00609
8
0.00781
3
0.002084
6.173
5.416
5.090
4.840
0.0035
95
0.0034
46
0.0033
88
0.0033
54
4.168 x 10-
17
22
25
0.004445
0.006155
0.007907
8.890 x 105
1.231 x 104
1.581 x 104
30
0.0099
01
0.01075
0.01033
2.066 x 10-
0.0032
4.573 98
Below is the graph of ln k which is also equal to ln against 1/T.
Graph of ln k (ln ) against 1/T

0
0
-1
-2
-3
ln k (ln )
-4
-5
f(x) = - 5437.94x + 13.36
-6
-7
1/T
From the graph, the value of the gradient is -5437.9. Thus, the
activation energy of the reaction is:
Ea=mR=(5437.9 ) x 8.314=45211
J
=45.211 KJ /mol
mol
Discussion
It is understood that the concentration of potassium iodide carried
out in this experiment was much more higher than the
concentration of the persulphate ions.
This type of reaction, where the concentration on one of the
reactants at such large amount is called as the pseudo first order
reaction3 in which the concentration of potassium iodide will not
change appreciably during the course of the reaction.
Since the concentration of potassium iodide were more than ten

times the concentration of persulphate ions, the consumption of
iodide ions during the whole course of the reaction will be very small
any may be neglected and that is why at equation [2],4 we
neglected the iodide concentration from equation [1] which is due to
this effect.
This can be illustrated by the iodide and persulphate reaction where;
[
2
= 0.5M; [ S 2 O8
= 0.02M
When the reaction has run to completion;
[ I =0.5 M ( 0.5 )( 0.02 M )=0.49 M 0.50 M
(From stoichiometry, 2 iodide
ions will readily react with one persulphate ions)

From the equation above, after the reaction is complete, the change
in concentration of iodide ions is not that significant.
To see the concentration dependence of iodide ions on the
persulphate ions in which it is considered as the limiting reactant5 of
this reaction, we have to react the persulphate ions with a few
percentage of iodide.
During the entire experiment, it is clearly apparent that the
temperature affects the rate of reaction. At the highest water bath
temperature, the time taken for mixture to turn colourless is the
fastest and vice versa. As the temperature of the reactants are
increased, the kinetic motion of the reactants molecules increases
as well. This causes the molecules of the reactants to move and
collide faster, thus increasing the frequency of collision.
To relate temperature with the activation energy, the MaxwellBoltzmann distribution is referred. 6
Image Source:
http://www.chemguide.co.uk/physical/basicrates/temperature.html
In the experiment, as described by the Maxwell-Boltzmann
distribution, the iodide and persulphate ions will react only when
they have sufficient energy that surpasses the required activation
energy and colliding at the same orientation. As the temperature
gets lower, the molecules of the reactants do not have the required
amount of energy to activate the overall reaction, thus, a slower
rate of reaction.
At the end of the reaction, it can be seen that the solution turns
from colourless to blue. This occurs when all the persulphate ions
has been used up during the reaction, indicating that Iodine is now
present at the mixture.
Conclusion
Ultimately, the experiment reached the aim successfully. It is
concluded that an increase in temperature would increase the rate
of reaction and the activation energy of the reaction can be
calculated by plotting a graph of ln against 1/T. Finally, the
higher the rate constant, the faster the reaction would occur, as
proved by the experimental results.
References
1. Ralph E. Oesper (1945), Hans Landolt [Online]. Available from:

http://pubs.acs.org/doi/pdf/10.1021/ed022p158 [Accessed 7
October 2011]
2. Rob Lewis, Wynne Evans, (2006), Speed of chemical reaction,
Chemistry Third Edition, pp241-251
3. Peter Atkins, Julio De Paula, (2006), The rates of chemical
reaction, Atkins Physical Chemistry, pp 797-798, 876-877
4. Rob Lewis, Wynne Evans, (2006), Speed of chemical reaction,
Chemistry Third Edition, pp253-255
5. Rob Lewis, Wynne Evans, (2006), The Mole, Chemistry Third
Edition, pp131-132
6. Maxwell Botlzman Distribution, [Online]. Available from:
http://ibchem.com/IB/ibnotes/full/sta_htm/Maxwell_Boltzmann.
htm [accessed 8 October 2011]
7. Experiment Module (Available from Mole).
Personal Statements
Based on the experiment, it has taught me several few things. One
of the things that Ive learnt throughout the experiment was to be
independent in handling all the apparatus and experiment
materials. The experiments were done individually so it took me
quite an effort to get everything done in such a limited amount of
time. This could benefit me in the working reality where being
independent and self taught is compulsory for any successful
projects. The experiment, Reaction Kinetics, has driven me to study
and research on this field which has increased some of my existing
knowledge in basic chemistry in which I could apply them for
everyday use or in my other subjects involving rate reactions.

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What is the aim of the experiment?

What is the aim of the experiment?

What factors affect the rate of reaction discussed in the experiment?

What factors affect the rate of reaction discussed in the experiment?

Mohammad Bazil Bin Bolia