Experiment 18: Determination of the activation energy for the reaction of

bromide and bromate ions in acid solution

Objectives
1. To understand the chemistry of activation energy.
2. To determine the activation energy for the reaction of bromide and bromate ions in acid solution.

Introduction

Activation energy is defined as the minimum energy barrier that must be overcome for a chemical
reaction to take place. It is usually denoted as Ea, and given in unit of kiloJoule, kJ/mol. For a chemical
reaction, an appreciable number of molecules with the energy equal to or greater than activation energy
should be exist in the system. In order for a reaction to occur, the reactant particles must collide
according to the collision theory. However, not all collision are able cause the reaction to happen, only a
certain collisions in the system can cause chemical reaction, which is called effective collision. The
effective collisions of molecules must collide with the correct orientation and sufficient energy to
overcome the activation energy barrier. The energy is needed to break the existing bonds and form the
new bonds of the molecules which resulting in the formation of products.

The activation energy of a reaction can be measured by using Arrhenius equation as shown in the
equation below:
k = Ae-Ea/RT
Where k = rate constant
T = absolute temperature
Ea = energy of activation
R = gas constant

The pre-exponential term, A is the property of particular reaction related to the collision frequency of
the reactive species and thus is temperature dependent. However, according to the equation, the
dependence of k on temperature is dominated by the strong exponential term, so the dependence of A on
temperature is usually ignored as a first approximation. By taking logarithms of both sides,

Log10 k = -Ea / 2.303RT + log 10 A

= -Ea /2.303RT + constant

So, when a reaction has a rate constant that obeys Arrhenius equation, a plot of log10 k versus 1/T gives
a straight line. The gradient of the straight line is –Ea / 2.303R while the interception of the straight line
on the y-axis of the graph can be used to determine the values of log10 A.

Now, the rate of reaction is higher when the time taken for a fixed amount of reaction to complete is
shorter. This makes the time taken, t to complete a fixed amount of reaction is inversely proportional to
the rate constant, k.
T α 1/k

or t = constant/k

By taking logarithms of both sides,

Log10 t = - log10 k + constant

= Ea / 2.303RT + constant

A plot of log10 t versus 1/T gives a straight line as well and the slope of the graph is Ea / 2.303R. Thus,
if t is measured at several temperatures then the energy of activation can be found.

In this experiment, the above method is applied to the reaction of bromide and bromate ions in an acid
solution which occurs slowly at room temperature.

KBrO3 + 5 KBr + 3 H2SO4  3 K2SO4 + 3 Br2 + 3 H2O

or BrO3- + 5 Br- + 6H+  3 Br2 + 3 H2O

The time required for a fixed amount of the reaction to be completed, t is found by adding a fixed
amount of phenol and some methyl red indicator to the reaction mixture. The bromine produced in the
first reaction reacts very rapidly with the phenol to form tribromophenol.

C6H5OH + 3 Br2  C6H2Br3OH + 3 HBr

When all the phenol has reacted, the bromine continuously produced in the first reaction will then react
with the methyl red indicator and bleaches its colour.

Methyl red + Br2  colourless compound

Apparatus and material

1 dm-3 beaker, 3 100cm3 beakers, 2 boiling tubes, 1 5cm3 pipette, 1 10-cm3 pipette, thermometer (0-
110°C), stopwatch, 0.01 mole dm-3 aqueous phenol solution, bromide/bromate solution (0.0833 mole
dm-3 potassium bromide and 0.0167 mole dm-3 potassium bromate, equivalent to 0.05 mole dm-3
bromine), 0.3 mole dm-3 sulphuric acid, methyl red indicator.
Procedures

10 cm3 of phenol solution and 10 cm3 of bromide/bromate solution were pipette into one boiling tube.
Than four drops of methyl red indicator were added to the mixture. 5 cm3 of sulphuric acid was pipette
into another boiling tube. The two boiling tubes were immersed in the water bath of (75 ± 1) °C. The
contents of the two tubes were mixed by pouring rapidly from one tube to the other twice and the
stopwatch was started at the same time. The boiling tube containing the reaction mixture was kept
immersed in the water. The time required for the red colour of the methyl red indicator to disappear was
determined. The whole experiment was repeated at 65, 55, 45, 35, 25 and 15 °C. Ice was used to achieve
the lowest temperature.
Results and Calculations

T (°C) t1 (sec) t2 (sec) t3 (sec) t4 (sec) taverage (sec)

15.0 767.00 709.00 993.00 1115.0 896.00
25.0 364.35 316.62 342.20 353.11 344.02
35.0 142.80 135.40 141.88 135.20 138.82
45.0 83.00 65.00 79.00 87.00 78.50
55.0 40.40 36.55 45.26 37.80 40.00
65.0 23.00 29.00 22.00 27.00 25.25
75.0 17.24 15.31 12.24 11.00 13.95
Table 1

T (°C) T (°K) 1/T(K-1) log t (sec) t (sec)

15.0 288 0.0035 2.95 896.00
25.0 298 0.0034 2.54 344.02
35.0 308 0.0032 2.14 138.82
45.0 318 0.0031 1.89 78.50
55.0 328 0.0030 1.60 40.00
65.0 338 0.0030 1.40 25.25
75.0 348 0.0029 1.14 13.95
Table 2
 Graph 1

From Graph 1,
y= graph of log t per 1/T mx +
C
3.5 y = 2851.9x - 7.0525
y=
3

2.5
log t (sec) x 10-3

1.5 log t (sec)

Linear (log t (sec))
1

0.5

0
0.0028 0.003 0.0032 0.0034 0.0036
1/T (K-1)

2851.9x - 7.0525
Log10 t = Ea / 2.303RT + constant
Gradient = Ea / 2.303R
Ea / 2.303R = 2851.9
Ea = 2851.9 x 2.303R
Ea = 2851.9 x 2.303 x 8.314
Ea = 54606 J/ mol
Energy of activation, Ea = 54.61 kJ/ mol

Discussion
The reaction between bromide and bromate ions in acid solution is a slow chemical reaction at room
temperature. This may be due to the high activation energy of the reaction, which required 54.61 kJ of
energy in order for a reaction to take place. According to collision theory, high activation energy will
cause the product more difficult to form since it is not sufficient energy for that molecule collide without
enough energy. Any reaction cannot occur if the colliding molecules do not have the energy equal or
higher than its activation energy. There are also other factors that can reduce the effectiveness of
collisions of molecules such as present or absent of catalyst.
According to Table 1, we can observed that the higher the temperature of the reactant species, the
shorter the time taken for the disappearance of red colour of methyl red indicator. This is shows that
shorter time taken in the reaction once the reaction is faster and higher rate of reaction. Although the
activation energy for the reaction to occur remains unchanged at all the temperature, but the rate of
reaction increased as the temperature increased. This means that the rate of reaction is depends on the
temperature of the reactant. This has also been proven in Arrhenius equation where rate constant, log10
k is proportionally to 1/T with the slope of the graph, -Ea/R and a constant of log10 A.

Log10 k = -Ea/2.303RT + log10 A

The higher temperature caused the value of the -Ea/2.303RT closer to the value of 0. The constant log10
A will then minus off the value of -Ea/2.303RT and results in a larger value. The larger value will
caused the value of the rate constant, k to become larger as well. Larger value of k will then results in
faster reaction. Hence, this is proven that the higher the temperature of reactants, the reaction will
proceed faster with the higher rate of reaction.
Besides, the rate of reaction roughly doubles for every 10 °C increase in temperature. This is because
increase in temperature increase the kinetic energy of the molecules, the molecules with higher kinetic
energy can move faster. With the higher speed, the molecules will collide more frequently results the
larger amount of successful collision. With the higher kinetic energy of the molecules, the molecules can
overcome the activation energy barrier during the collision and hence the reaction can be take places. As
a result, the rate of the reaction could be increased if more heat energy is provided to the reactants.
Fixed amount of phenol and methyl red indicator were added to the mixture contents for the different
temperature. This is because phenol can provides an intermediate state before the bromine molecules
produced in the reaction between bromate and bromide ions in acid solution which is able to bleach the
methyl red immediately. In other words, phenol is used to observe the time taken for the bromine
molecules to react completely with phenol before bleach the methyl red indicator. The purpose of adding
methyl red into the solution is to provide a colour which can easily to be observed. When the sulphuric
acid was poured to the bromate/bromide ions solution, the methyl red indicator turns to pink colour. The
bleaching effect from the bromine molecules caused the methyl red indicator to turn colourless after all
the phenol is used up. This shows a colour changes which the time taken should be stopped. In order to
compare the time taken for the bleaching of methyl red colour, the amount of phenol used in the
repeated experiment must be equal.
The reason of choosing phenol as the reactant is due to it can form an intermediate state because phenol
can react with bromine molecules quickly to produce tribromophenol and hydrogen bromide. This is
happens before the bromine molecules react with the methyl red.

The –OH group in the phenol is an activating group in the benzene ring which can donates electron into
the benzene ring to stabilize it. So, the product can be easily to form in the reaction. –OH group is ortho-
para activating group in the benzene ring. This means that the incoming substituent will go into the ortho
position or the para position, but hardly go into the meta position. This is due to the high energy is
required for the product with a substituent at meta position to form in the reaction. The bromine
molecules undergo substitution reaction in this reaction by substituting three hydrogen atoms from the
benzene ring with three bromine atoms to maintain the aromaticity of the ring in phenol.
The reaction between bromate and bromide ions in acid solution is a redox reaction.
BrO3- + 5 Br- + 6H+  Br2 + 3H2O

Precaution
Materials such as phenol is very toxic, phenol should be handle carefully during the experiment. Wear a
lab coat and glove during the experiment to prevent an accident that cause by the slits of chemical .while
reading the thermometer make sure that read with an eye level to prevent a parallax error because
temperature is the manipulated variable the affect the results.
Questions
1. Indicator is use to determine the end point of the experiment. Once all the phenol is used up, further
bromine produced will bleach the methyl orange immediately. So the rate of the reaction can be
calculated from the time for the indicator to be decolorized.

2. Phenol is used to observe the time taken for bromide molecules to react completely with phenol it
bleach the methyl red indicator. Bromide molecule that produced in the reaction of bromide and
bromated which is able to bleach the methyl red immediately. Thus phenol serves as a media to provide
intermediate state and quickly produce tribromophenol and hydrogenbromide before bleaching the
reaction occurs.

3. Equation: e-EA/RT
For temperature, T=45°C e- 54.61 x 103/8.314 x 318 = 1.072 x 10-9
For temperature, T = 55°C e-54.61 x 103/8.314 x 328 = 2.009 x 10-9
Therefore, the rate of reaction doubled for every 10°C increase of temperature.

4. Molarity of phenol = c. V = (0.01 x 10) / 1000 = 0. 0001

Molarity of bromide/bromate = c. V = (0. 05 x 10)/1000 = 0. 0005
Ratio of the phenol and bromide/bromated = 0.0001 : 0.0005 = 1 : 5
Therefore, 1 mol of phenol can reacts with 5 mol of bromide/bromate ions.
But in experiment, C6H5OH + 3Br2  C6H5Br3OH + 3HBr, there are shows that 1 mol of phenol
should reacts with 3 moles bromide/bromated only. That means the bromide/bromated is excess by 2
moles phenol

5. Activation energy is minimum energy that used to start a reaction. To form a product from reactants.
When the activation energy is doubled, the amount of energy required to overcome the activation energy
that has to be possessed by the reactant have to be doubled too. Thus the rate of reaction decreases,the
higher the activation energy need, the slower of rate of reaction. In fact, the rate of reaction is actually
the rate in which the products formed.
Conclusion
When the temperature increase the rate of reaction increase due to the temperature increase the kinetic
energy of the particles, the increase the frequency of collision. The activation energy, Ea is 54.61kJ/mol.

References

1. Cann, P. a. H. P., 2015. Cambridge International AS and A Level Chemistry. s.l.:Hodder Education.

2. Determination of Reaction Rate and Reaction Rate Constant Practical Report, viewed on 15/03/2018,
https://dissa4ict.wordpress.com/2013/01/09/determination-of-reaction-rate-and-reaction-rate-constant/