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Calculating activation energy of the bromidebromate reaction

Raw data
Temperatu
Time
Observati
re
(1s)
ons
(0.5C)
25.0
920
Solution
35.0
370
went from
45.0
140
clear red
55.0
59
color to a
65.0
41
cloudy pink
75.0
20
Table 1: Temperature and time taken for reaction to go to completion

Analysis
The experiment can be represented by the following reaction mechanism:
1. H2SO4 -> H+ + SO422. BrO3- + 5Br- + 6H+ -> 3Br2 + 3H2O
3. C6H5OH + Br2 -> C6H2Br3OH + HBr
Sulphuric acid dissociates into H+ and SO42- in solution (reaction 1); when added
to the bromide/bromate solution, the solution then dissociated into BrO 3- and Br-,
which reacted to form bromine and water (reaction 2).
Bromine usually acts as a strong oxidizing agent and reacts with methyl red, very
quickly bleaching its color. However, in this experiment, the reaction was slowed
by the presence of phenol, which reacts more readily with bromine to produce
tribromophenol (reaction 3).
Essentially, the phenol served to lengthen the time taken for the bromine to
react with the indicator. Otherwise, the bromine-bromate reaction, which I am
calculating the activation energy for, would complete too quickly to be
measured.
Bromine is in excess in this reaction, so when all the phenol has reacted, the
remaining bromine reacts very quickly with methyl red; the solution turns
colorless, indicating the endpoint of the reactions.
Finding the rate constant
Substance

Concentration
(mol dm-3)
0.01
1

Volume
(cm3 1)
10
10

C6H5OH
Bromide/bromate
mixture
H2SO4
0.5
5
Table 2: Concentrations and volumes of reagents

The activation energy of a reaction can be determined using the Arrhenius


equation:

kAe

Ea
RT

K is the rate constant, A is the pre-exponential factor (representing frequency of


particle collisions), Ea is the activation energy, R is the gas constant, and T is the
temperature in Kelvin. A is almost completely independent of temperature, so it
is assumed that A is the same for each reaction regardless of temperature.
The rate constant can be derived from the rate expression, which in turn is
derived from the chemical equation. The chemical equation and rate equation for
the reaction between bromide and bromate are as follows:
BrO3- + 5Br- + 6H+ -> 3Br2 + 3H2O
The order of the bromide-bromate reaction are first order with respect to
bromate, first order with respect to bromide, and second order with respect to H +
(Capriola, 2015).
Thus, the rate expression can be written:
Rate of reaction = k [BrO3-] [Br-] [H+]2

+
H

Br
Br O3
Rate of reaction=k

+
H

Br
Br O3

rate of reaction
k=

rate of reaction
(1)(1) ( 0.500 )2

rate of reaction 0.25


rate of reaction 4 mol

-3

dm s

-1

Rate = 1/time taken, so:


Temperatu

Time

Rate of

re
(s
reaction
(C 1)
1)
(s-1 )
25
919
0.001088
35
369
0.002710
45
144
0.006944
55
59
0.016949
65
41
0.024390
75
20
0.050000
Table 3: Time and rate of reaction at each temperature
The rate constant of a reaction is dependent on temperature, so k will be
different at every temperature. k is calculated in Table 4 using the
aforementioned rate expression.
Temperatu
re
(C 1)
25

Rate of
reaction
(s-1 )
0.001088

k
mol dm-9 s-1
0.001088

4=

35

0.002710

0.002710

45

0.006944

0.006944

4= 0.01084
4= 0.02778

55

0.016949

0.016949

65

0.024390

0.024390

4= 0.06780
4= 0.09756

75

0.050000

0.050000

4= 0.20000

-3

0.00435

Table 4: Rate of reaction, temperature, and k


Temperatu
re
(C 1)
25

1/T (temperature)
(1/K)

Rate constant (k)


(mol-3 dm-9 s-1)

1 (25 + 273) =
0.00336

0.001088

35

1 (35 + 273) =
0.00325

0.002710

45

1 (45 + 273) =
0.00314

55

1 (55 + 273) =
0.00305

65

1 (65 + 273) =
0.00296

75

1 (75 + 273) =
0.00287

4=

0.00435

-2.69119

4=

0.09756
0.050000

-3.58344

4=

0.06780
0.024390

-4.52451

4=

0.02778
0.016949

-5.43758

4=

0.01084
0.006944

ln k
(mol-3 dm-9 s1
)

-2.32729

4=

0.20000

-1.60944

Table 5: Calculating 1/T and ln k


The Arrhenius equation can be re-arranged to give the following:

ln k =

Ea
+ln A
R T

R is a constant, and A is assumed to be temperature independent. Thus,


graphing ln k against 1/T should give a linear plot.

A graph of the natural log of the rate constant against temperature


0
-1
R = 0.99

-2
ln k (mol-3 dm9 s-1) -3
-4
-5
-6

1/T (1/K)

The gradient of the line should be

Ea
R , and can be calculated using two

points on the graph, (x1, y1) and (x2, y2):

gradient=

y 2 y 1
x 2x 1

Ea y 2 y 1
=
R
x 2x 1

5.43759434(1.60437912 )
0.0033557030.002873563

7950.419421744721
Ea =7950.419421744721R
66067.98539469863 J mol-1

66.1 kJ mol

-1

Discussion
The literature value for the activation energy of this reaction was found to be
52.4 kJ mol-1. Thus, the percentage error in the calculated value is:

52.466.1 =26.1
52.4

literature valueexperimental value


=
literature value
error =
An error of 26.1% is quite large, which means it is unlikely to be caused merely
by random errors. It is more likely that systematic errors in the experimental
methodology resulted in the large percentage error. This will be discussed in the
evaluation section.
In the analysis, a graph of ln k against 1/T had a linear line of best fit with a
negative gradient. The correlation coefficient was calculated to be 0.9911, which
is very close to 1, showing a very strong correlation. Mathematically, this trend
shows that the rate constant increases with temperature.
This is in accordance with kinetic molecular theory, which states that Kelvin
temperature of a substance is proportional to the average kinetic energy of
particles in the substance. If particles have greater average kinetic energy, a
greater proportion of particles will have the energy necessary to initiate the
reaction (overcome the activation energy barrier), so a greater proportion of
particles will exceed the activation energy, increasing the rate of reaction. This is
in line with the negative gradient of the graph of ln k against 1/T.

Evaluation
Limitation

Effect

Improvement

Plot of ln k against 1/T


was not completely
linear due to random
errors in recorded
data.
Assumed that rate of
reaction of bromination
of phenol is
independent of
temperature even
though it is also part of
the rate expression

The calculation of the


gradient may not be
accurate, leading to an
inaccurate Ea value

Use technology to plot a


line of best fit, and use
its gradient to calculate
activation energy.

Bromide/bromate rate of
reaction values less
accurate, calculation of the
gradient and Ea value
affected

Conduct experiments at
same temperatures, but
repeat for varying
concentration of
reagents and average
the results to reduce the
significance of any
errors
Run a trial ahead of
time and allow sufficient
time for it to react
completely. Use color of
solution as baseline to
determine endpoint for

Difficult to determine
when endpoint of
reaction

Recorded time taken for


each reaction to complete
may be shorter or longer
than it should have been,
affecting the calculated
rate of reaction, gradient,

Lids of water baths had


to be kept open while
monitoring the
reaction in the flasks.

and thus Ea value


The temperature of the
water baths and thus the
solutions may have been
lower than recorded,
making 1/T values bigger
than expected. This would
make the calculated Ea
value bigger than it should
have been

other reactions.
Insulate the solution
flasks to reduce heat
loss.

Conclusion
The aim of this experiment was to calculate a value for the activation energy of
the bromide-bromate reaction. This was successfully done using empirical data
to determine the time taken for the reaction to complete at different
temperatures and then calculating rate of reaction to determine the rate
constant, which was in turn used to calculate the activation energy. Using the
Arrhenius equation, the activation energy was determined to be approximately
66.1 kJ mol-1, which was 26.1% away from the literature value of 52.4 kJ mol -1.
http://adamcap.com/schoolwork/the-kinetics-of-the-bromate-bromide-reaction/

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