EXPERIMENT 4: ACTIVATION ENERGY OF AN IONIC REACTION

Objectives

1. To investigate the rate of reaction of Peroxydisulphate ions (S2O82-) with large excess of
iodide at temperature between 30oC and 70oC.
2. To determine the activation energy of the reaction.
3. To show how faster the reaction is proceeding.

Abstract

Activation energy (Ea) is the minimum amount of energy required to initiate a chemical reaction.
The rate of a reaction is a function of temperature (through the rate constant) and concentration.
peroxydisulphate ions start to oxidize to the iodide and to liberate iodide as soon as the solution
is mixed. The thiosulphate immediately reacts with the generated iodide, so no color is seen for
as long as there is thiosulphate in solution. When all the thiosulphate has reached any further
iodide generated gives a color change. Because the same volume of the reagents is used at each
temperature, the same fraction of the origin peroxydisulphate has reached each time when the
color appears. Thus, the graph In1/ against 1/T will get linear graph and the activation energy
for reaction can be determined. Peroxydisulphate ions are powerful oxidizing agents and react
with iodide to form iodine via the overall reaction. The rate law expresses the relationship of the
rate of a reaction to the rate constant and the concentrations of the reactants rose to some powers.
The rate of reaction is dependant on the concentration of the peroxydisulphate and iodide ions.
The rate of reaction will appear to depend only on the concentration of peroxydisulphate ions.
Because the relationship of reaction rate to activation energy and temperature is exponential, a
small change in temperature or activation energy causes a large change in the rate of the reaction.
Many reactions have rate laws which depend only on the concentrations of the reactants :

rate = k[A]x[B]y
Introduction

In order to react, the colliding molecule must have total potential energy equal to or
greater than the activation energy (Ea), which is the minimum amount of energy required to
initiate a chemical reaction. The species temporary form by the reactant molecule as the result of
the collision before they form the product is called the activation energy. A rate law describes the
behavior of a reaction. The rate of a reaction is a function of temperature (through the rate
constant) and concentration.

Peroxydisulphate ions are powerful oxidizing agents and react with iodide to form iodine via the
overall reaction:

S2O8- + 2I- 2 SO4- + I2

The rate law expresses the relationship of the rate of a reaction to the rate constant and the
concentrations of the reactants raised to some powers The rate of reaction is dependant on the
concentration of the peroxydisulphate and iodide ions. The rate of reaction will appear to depend
only on the concentration of peroxydisulphate ions. Reaction order is always defined in terms of
reactant (not product) concentrations. The rate is:
 -d [S2O8-] = k[S2O8-]

Ea = action energy of reaction (J/mol)

R = molar gas constant (8.314 J/Kmol)
k = A exp T = the absolute temperature
A = frequency factor
.

In 1/

m=

1/T
T

In this experiment peroxydisulphate ions start to oxidize to the iodide and to liberate iodide as
soon as the solution is mixed. The thiosulphate immediately reacts with the generated iodide, so
no colour is seen for as long as there is thiosulphate in solution. When all the thiosulphate has
reached any further iodide generated gives a color change. Because the same volume of the
reagents is used at each temperature, the same fraction of the origin peroxydisulphate has
reached each time when the color appears. Thus, from graph above, activation energy for
reaction can be determined.
Materials

1. 0.2 M Potassium Iodide (KI)

2. 0.05 M Sodium Thiosulphate (Na2S2O3)
3. 0.1 M Potassium Peroxydisulphate (K2S2O8)
4. Iodine Indicator

Equipment

1. Beaker
2. Test Tube (10 test tubes)
3. Thermostat

Procedure
1. In this experiment, five thermostatically controlled water-baths are being used. The
temperatures used are 30, 40, 50, 60 and 70C. By using a mercury thermometer immersed in
the water, a more accurate measurement of water temperature was obtained.
2. Five test tubes were obtained and they were labeled with the differences temperature. 5 cm 3
of 0.05M sodium thiosulphate (Na2S2O3) and 10 cm3 of 0.2 M potassium iodide (KI) were
placed in five test tubes. All the test tubes were placed in the 5C ice bath.
3. Other five test tubes (new test tubes) were placed in with 10 cm 3 of 0.1 M Potassium
Peroxydisulphate (K2S2O8) and 5 drops of iodine indicator were added into them. All the test
tubes were placed in the plastic rack in the 30, 40, 50, 60 and 70C of water-bath.
4. By using a thermometer to monitor the temperature, the contents of the tubes were allowed to
reach the temperature of the thermostat.
5. The temperature of the water bath was recorded. The contents of one Erlenmeyer flask were
poured quickly into the test tube, and then the stopwatch was started. The reactant was stirred
and the time taken for the colorless solution to turn dark yellow was recorded.
6. The results were recorded and graph ln 1/ against 1/T was plotted.

Results and Discussion

Results:
 Temperature, 303.15 313.15 323.15 333.15 343.15
T(K)

Time, t (s) 302 195 131 84 59

1/T (K-1) 0.0033 0.0032 0.0031 0.0030 0.0029

1/ 0.0033 0.0051 0.0076 0.0119 0.0169

ln 1/ -5.7138 -5.2785 -4.8796 -4.4312 -4.0804

TABLE 1

GRAPH ln 1/ AGAINST 1/T

0

-1

-2

ln 1/ (s) -3

-4

-5

-6

1/T (K)

FIGURE 1
Calculations:

From Figure 1,
 Y
Slope , m = X

4.0804(3.7)
= 0.00290

= -131.17
Ea
From the value of the gradient, m we can calculate the activation energy, .

R = 8.314 J/mol.K

Ea

m = R

E a = mR

= (-131.17) (8.314)

= - 1090.547 J/mol

Ea
= 1090.547 J/mol
Discussion:

Based on the graph in FIGURE 1, we can conclude that ln 1/ is directly proportional to the 1/T.
When the value of 1/T increases, the ln 1/ also increases. This is because according to the
Arrhenius equation, the rate of reaction depends on the temperature.

Arrhenius Equation:

k = A exp [ ]
E
RT

E
ln k = ln A - RT

Where E is the activation energy of the reaction, R is the molar constant (8.314 J/mol.K) and A is
known as the A-factor, which is related to the frequency of the collision between the reacting
molecules. We have already shown that k is proportional to 1/.

From this theory, high temperature will made the time of solution taken to turn color from
colorless to dark yellow is short because higher and greater number of collision that
consequently the rate of reaction is faster. These means that the reaction of solution is depends on
temperature. The rate of the reaction can be determined by the reciprocal of time because a
constant amount of iodine is produced in each reaction and a graph of the ln 1/ against 1/T can
be plotted. This graph can be used to determine the order of the reaction. Based on our graph, the
gradient that we get from the graph in FIGURE 1 is m= -131.17. To calculate activation energy
(Ea) of the reaction, we can use the formula of gradient = Ea/R. Value of R is given as 8.314
J/mol.K. Finally, we obtained Ea = 1090.547 J/mol. Then, the objectives of the experiment were
achieved.
Conclusion & Recommendations

Conclusion:

The factor affecting rate of a chemical reaction is temperature and time. Time decreases as
temperature increases. Thats why the rate of reaction increases with the rise of temperature. The
other factor is temperature. It can be explain by the fact that at higher temperature, a greater
fraction of colliding molecules posse the necessary energy of activation. Thus, the graph In 1/
against 1/T will get linear graph and the activation energy for reaction can be determined thats is
1090.547 J/mol. By doing this experiment, the rate reaction of peroxydisulphate with large
excess of iodide at a number of temperatures between 30 oC and 70oC can be investigated. For the
precautions, never transfer the thermometer from one tube to the other because to avoid
contamination of the solution. Overall of this experiment can be concluding that all objective of
this experiment is success.

Recommendations:

Use a different amount of peroxydisulphate ion S2O8for same temperature. We can

investigate the rate of reaction from the graph amount of peroxydisulphate ion against the
temperature.
Use iodide in small concentration than peroxydisulphate, so the concentration of iodide will
easily change during the experiment.
Use catalyst to make the reactant become more faster to turns into dark yellow.
Use a different scale of thermometer, so we can avoid transferring the thermometer to wrong
tube.
For safety,

Always wear protective gloves and glasses during the experiment.

Waste solutions were placed in large beaker provided.
Solutions must not easily pour into the sink because they were strongly oxidizing solutions.
Tubes must always be in the water bath as long as the solutions do not turn into dark yelllow
in color.
Use thermometer only for the same solutions.

Questions

1. How good is the approximation that the iodide concentration remains constant? Use
evidence both from the experimental method and from your results to justify your
argument.
In this experiment, we want to investigate the rate of reaction of peroxydisulphate ions
(S2O82-) when it reacts with iodide ion to form iodine. Actually, the rate of reaction for this
reaction is depends on the concentrations of peroxydisulphate and iodide ions. If iodide is
present in much higher concentration than peroxydisulphate, then the concentration of iodide
will hardly change during the experiment. This will affect the rate of reaction. Therefore, the
rate of reaction in this experiment will depend on the concentration of iodide. This is totally
opposite with our objectives. Hence, to achieve our objectives we must constant the
concentration of iodide ion so that the rate of reaction for this experiment will depend only
on the temperature and time. Because of that, we must use different temperature of water-
bath to prove this experiment. As the same volumes of reagents are used at each temperature,
the same fraction of the original peroxydisulphate has reacted each time when the color
appears. Then, we had plotted the graph In 1/ against 1/T and we get linear graph. From the
graph, we can prove that when temperature is higher, the time taken for the iodine, , to
change color is shorter. Thus, the rate of reaction for this reaction will become faster. This
situation will help us a lot and much better for our experiment.
References

http://en.wikipedia.org/wiki/Activation_energy
Internet sources: Experiment 5: Fast, Faster, Fastest: Exploring Chemical CatalysisLarsen
4:20 Spring 2000.
Internet sources: Handbook of Chemistry and Physics, 71st edition, CRC Press, Ann
Arbor, Michigan, 1990.
Lecture note Chemistry Module Semester 2 Kolej Mara Kuala Nerang, 2010 topic of
Reaction Constant.