CHP 305

PROCESS CONTROL AND REACTION ENGINEERING

LABORATORY

CRE 3: To determine the kinetics of the hydrogen

peroxide decomposition in a batch reactor.

Submitted By:
Yash Kumar Bhati 2012BB50048
Atul Verma 2012BB50012

Aim: To determine the kinetics of the hydrogen peroxide decomposition in a batch

reactor.
Apparatus: 3-necked round bottom flask, condenser, gas volume measuring unit at
atmospheric pressure, constant temperature bath, thermometer, stopwatch.
Chemicals: Hydrogen peroxide, Potassium iodide.
Theory and calculations:
Reaction : 2H2O2 2H2O + O2
(A)
(B) (O)
It is reported that the reaction is irreversible and first order.
The rate equation becomes,
-dCA/dt = K.CA
Integrating and solving for CA, we get
CA=CAo. e-Kt
From the expression, the graph between CA and t will be exponential in nature.
Now calculations from the experimental data:
Initial concentration of the hydrogen peroxide solution:
`
CH2O2 = VO2*2 / (22400*VH2O2) gm mole/ml
These are the gm moles of hydrogen peroxide in 1 ml of the sample.
So concentration of hydrogen peroxide in the initial reaction mixture is:
CAo = CH2O2 *VH2O2 / (VH2O + VH2O2 )
The concentration of hydrogen peroxide in the reaction mixture at any given time
is given by:
CA = (V Vt) / (V) * CAo
Where Vt is the volume of oxygen liberated at any time t.

Calculating values from above relations:

At temperature T=43.4 degree and using H2O2 volume 3ml
VO2

250 ml

VH2O2

3 ml

CH2O2

0.0074

CAo

0.00022

v*t

Plotting Vt v/s t

vt

vt

v*vt/v*

250

25

225

0.9

13

50

200

0.8

15

70

180

0.72

20

110

140

0.56

25

140

110

0.44

30

165

85

0.34

35

190

60

0.24

40

210

40

0.16

50
60

230
250

20
0

0.08
0

Ca
0.00022
0.00019
8
0.00017
6
0.00015
84
0.00012
32
0.00009
68
0.00007
48
0.00005
28
0.00003
52
0.00001
76
0

Plotting CA v/s t.

Similarly calculating values at Temperature T= 43.4 degree and 5ml H2O2 volume

VO2

420 ml

VH2O2

5 ml

CH2O2

0.0075

CAo

0.00036

To determine the rate constant of the reaction

We have seen that
CA=CAo. e-Kt
So

CA/CAo = e-Kt

Taking log on both sides, we get;

-ln(CA/CAo) = Kt
So on plotting this curve the slope of the line will give rate constant.
Calculating CA/CAo values.
At temperature T=43.4 degree and 3 ml H2O2 volume

Plotting -ln(CA/CAo) v/s t.

Slope = 2.52-0.1 / 50 -8
= 0.057

Similarly for T=43.4 degree and 5ml H2O2.

Plotting -ln(CA/CAo) v/s t.

Slope : 1.79-0.168 / 24-8

= 0.1

To determine the order of reaction

The rate equation,
-dCA/dt = K.CAn
Taking log on both sides;
We get;
ln(-dCA/dt) = ln(k)+nln(CA)
So a plot between ln(-dCA/dt) and ln(CA) will curve whose slope will be equal to
the order of the reaction.
Calculation for T=43.4 degree and volume 0f H2O2 3 ml
T
15
20
25
30
35
40
50

Ca
0.000158
4
0.000123
2
0.000096
8
0.000074
8
0.000052
8
0.000035
2
0.000017
6

-d(Ca)/dt ln(Ca)
8.8E-06
0.000007
04
0.000005
28
0.000004
4
0.000004
4
0.000003
52
0.000001
76

8.750387
08
9.001701
51
9.242863
56
9.500692
67
9.848999
37
10.25446
45
10.94761
17

ln(-dCa/dt)
11.64075
88
11.86390
24
12.15158
45
12.33390
6
12.33390
6
12.55704
96
13.25019
67

Slope of graph :
(13.25-11.64)/(10.94-8.75)
=1.61/2.19
= 0.73

Similarly calculating for T=43.4 degree 5ml H2O2.

T Ca
8
11
15
18
22
24
28

0.0003
04
0.0002
53
0.0001
8
0.0001
33
7.71E05
0.0000
6
1.71E05

-dCa/dt
1.39286
E-05
1.71429
E-05
1.82143
E-05
1.57143
E-05
1.39286
E-05
8.57143
E-06
1.07143
E-05

ln(Ca)
7.929406
527
8.097543
448
8.282685
881
8.622553
707
8.926236
121
9.469851
567
9.721165
996

ln(-dCa/dt)
11.181
57
10.973
93
10.913
3
11.060
94
11.181
57
11.667
08
11.443
93

30

8.57143
E-06

10.97392
896

Slope of graph :
(11.67 10.91) / (9.47-8.28)
= 0.76/1.19
= 0.64

11.667
08

Results
From the plots of CA v/s t we see that the nature of the curves is
exponential in nature which is in accordance with the rate
equation(theory).
From the plots of -ln(CA/CAo) v/s t the slope of the curves are:
Slope (T=34.6 deg) = 0.057
Slope (T=44 deg ) = 0.1
So rate constant values:
KT=34.6,experimental = 0.057
KT=44.0,experimental = 0.1

From the plots of ln(-dCA/dt) v/s ln(CA)

Slope (T=34.6 deg) = 0.73
Slope (T=44 deg ) = 0.64
So order of reaction:
n (T=34.6) = 0.73
n (T=44) = 0.64

Sources of error:
The tube draining the water out of the overflow glass bottle must be
shaken at regular intervals to ensure proper drainage of the water and
no air blockage.
Temperature of the reaction must be keep at an optimum level (say
around 35-40 deg.). Lower temperatures would retard the reaction rate
and higher temperature would enhance the reaction rate to such an
extent that the initial rates are too difficult to measure. (When the
reaction rate is maximum).
The three way stop cock must be properly closed to ensure proper
transport of oxygen.

Safety precautions:
As even traces of alkali (e.g. leaching from glass) can initiate decomposition, H2O2
is stored in wax-coated bottles, or plastic containers, with the addition of a
stabilizer (e.g. urea). Even a trace of dust can lead to explosive decomposition. The
handling of the water-free compound, or concentrated solutions thereof, should
therefore be carried out under dust-free conditions and with the exclusion of metal
ions.