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Mbatyoti, Somelele, (Mr) (s215101278)

PHYSICAL CHEMISTRY

EXPERIMENT 6
KINETICSRATE
CONSTANTS
AND ACTIVATION
ENERGY FOR
THE
DECOMPOSITIO
N OF
HYDROGEN
PEROXIDE

Somlelele Mbatyoti PCC3001 Practical Report

Aim

Determine the volume of gas produce at different temperatures


Determine the half-life and rate constants
Calculate rate constants

Introduction
The reaction of hydrogen peroxide is in aqueous medium is very slow,
thats why in this experiments it is catalysed by Iodide ion. The
concentration of both iodide and the hydrogen peroxide determines the
reaction rate. Since iodide is catalyst in this reaction, it is not consumed
and the concentration remains constant so the reaction rate depends on
the hydrogen peroxide .the reaction rate for this reaction is first order only
depends on the decomposition of Hydrogen peroxide
2H2O2 (aq) = 2H2O+O2
Rate =k [H2O2]
By conducting the decomposition of hydrogen peroxide in a closed vessel,
have ability to determine the reaction rate as a function of the pressure
increase in the vessel that is caused by the production of oxygen gas. If
you vary the initial molar concentration of the H2O2 solution, the rate law
for the reaction can also be determined. Finally, by conducting the
reaction at different temperatures, the activation energy, Ea. can also be
calculated.
Equipment /Reagents
3*250 ml volumetric flask
50ml burette
Flexible tubing
Levelling bubble
Split ring clamp
Water bath
10% Hydrogen peroxide
1.1

M Potassium Iodide

5 ml pipette
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Procedure
Procedure found at the Physical chemistry Practical manual page31- 32

The above step up was set for measuring the gas produce.
The levelling was setup and the burette zeroed
5 ml of 10% hydrogen peroxide was add to 250 ml flask and the 5
ml of 0.1M KI was add to the other 250ml flask.
Temperature was taken which was 20 oC at normal pressures.
The 0.1M KI was add to the hydrogen peroxide.
The reaction was kept in a close system and after every 2 minutes
the change in volume was taken.
The method was repeated three times at different temperatures.
Each flask containing KI and H2O2 same concentration was taken
and heat on the water bath at 40 oC.
than the KI was add to hydrogen peroxide , while still immersed in
the water bath
.The reaction was in closed system
Swirled and after every 2 minutes the change volume was taken
until 20 minutes interval.
After every measurement the levelling was kept constant.

Results
Time
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-log(V-Vt/V)

-log(V-Vt/V)

-log(V-Vt/V)

Somlelele Mbatyoti PCC3001 Practical Report

0
2
4
6
8
10
12
14
16
18
20

20oC
0
0.032
0.062
0.102
0.14
0.177
0.211
0.244
0.277
0.317
0.377

40oC
0
0.144
0.268
0.346
0.45
0.548
0.689
0.768
0.824
0.946
0.992

60oC
0
0.55
1.11
1.63

-Log(Vinfinity-V)/Vinfinity vs Time
1.8

f(x) = 0.27x + 0.01


R = 1

1.6
1.4

-log(V-Vt/V) 20oC

1.2

Linear ( -log(V-Vt/V)
20oC)

-Log(V -Vt/V

f(x) = 0.05x + 0.05


R = 0.99

0.8

Linear ( -log(V-Vt/V)
40oC)

0.6

-log(V-Vt/V) 60oC

0.4

Linear ( -log(V-Vt/V)
60oC)
f(x) = 0.02x - 0.01
R = 1

0.2
0

8 10 12 14 16 18 20 22

Time(min)

Activation Energy Determination


-log( 1/T
k)
0.821 0.0034
1.3
0.0032

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-log(V-Vt/V) 40oC

Somlelele Mbatyoti PCC3001 Practical Report

Activation Energy
1.6
1.4

f(x) = 3162.5x - 9.28


R = 1

1.2
1

-log(k) 0.8
0.6
0.4
0.2
0

1/T (K-)

Model Calculations
Half-Life
At 20oC
Y=0.0183x-0.0067
0.301=0.0183x-0.0067
X=20.11
At 40oC
X=5.12 min
At 60 oC
X=1.09 min
Rate Constant, k:
At 20 oC
k=

0.693
20.11 min

=0.0345 min-

At 40oC
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Somlelele Mbatyoti PCC3001 Practical Report

k=0.135minAt 60 oC
k=0.638 minActivation Energy
Slope = Ea/R
m = Ea/R
3162.5*8.314J/mol = Ea
Ea=26kJ/mol
Discussion
The decomposition of H2O2 was done by adding iodide solution which acts
as catalysts .The rate of the reaction is first order, that only the
decomposition is the substance that determines the rate law. The rate of
the reaction was determine by decomposing of the H2O2 which produce
the oxygen, which than can be used to measure the amount of oxygen
produce by measuring the change in the volume in the closed system. The
reaction was done under different temperature conditions. As the
temperature increase the rate of decomposing of the H2O2 also increase.
As it applies generally the heat increases the kinetic /motion of the
particles which enhance them to react rapidly, which than increases the
rate of the reaction. The graph of change in the volumes against time at
different temperatures gives very straight line with the R2 value at 0.99
which shows that the values are in a very straight line. This graph which
represent the change in the volumes against time at different
temperatures give a validation with the theory that as the temperature
increase the rate constants of the reaction also increase .
The activation energy was determine by plotting the log of k at different
1/T (K-) temperature values. The R2 of the graph is 0.99 which shows a
very linear graph. The activation energy was determine by the slop of the
graph multiple it by the R value which is 8.314 J/mol. The activation
energy was found to be 26kJ/mol.
The errors might be involve is that it easy not easy to work with the
movement of the liquid , cause as you try to record the results after 2
minutes the reaction is still produce oxygen which cause the water to
move while trying to record the results . The error can also because by not
swirling properly, because the was a lot of trapped gas which was

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Somlelele Mbatyoti PCC3001 Practical Report

released later in huge amounts which caused an irregular displacement in


the volume.
Conclusion
The volumes of the reaction which were produced by the oxygen gas
which was liberated from decomposition of H2O2 were record as
accurately as possible .the half-lifes were determine by substituting the
0.301 to each equation and then each half-life were substituted to the
equation of the half-life to determine the rate constant at 20 oC, 40oC and
60oC which was found to 0.0345 min -,0.135min- and 0.638 minrespectively. The activation is found to be 26kJ/mol which is not
corresponding to the theoretical value which is 56kJ/mol .The percentage
error of the activation energy is 46% .the method to determine the
activation energy needs to be changed because of this huge error. This
might be cause by the errors which were mention above or the method
itself is not validated enough to determine the corresponding theoretical
value of the activation energy.

Answers
1.

ln

[ A]t
=kt
[ A]o

ln

0.118 mol / L
=k (1200 s)
0.256 mol/ L

k=6.45x10^-4 s2.

x
3
ln =2.7710 (6000 s)
2
X=1.21*10-7 g

(t )
1
3. ln
=5.32 y r
100
t=0.87 years
k 2 Ea
1
1
ln
=
(

)
4.
k1
R
T2 T1

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Somlelele Mbatyoti PCC3001 Practical Report

2
Ea
1
1
ln =
(

)
1 8.314 J /mol 313 303
Ea. =55kJ/mol
k 2 Ea
1
1
5. ln k 1 = R ( T 2 T 1 )

ln

k2
30.0 103 J /mol
1
1
=(
)(

)
1
8.314 J / Kmol
600 K 300 K
0.0500 min

k 2=20.45 min

Reference
http://chem.libretexts.org/Core/Physical_Chemistry/Kinetics/Reaction_Rate
s/First-Order_Reactions
Physical Chemistry 3 Practical Manual Book
Hlangothi

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Compiled by Prof E Ferg & Dr P.