Gas Phase Kinetics

Experiment 5
Decomposition of di-tert-butyl peroxide

Brian Malile

Oct.4.2010

Introduction

The purpose of this experiment is to determine the activation energy (Ea) and the preexponential frequency factor of the decomposition of Di-t-butyl peroxide. This will be
determined by the measurement of the pressure in the vessel throughout the reaction time at three
different temperatures. From this data the reaction constant will be obtained by plotting
Log(3pi-P) vs t. Its natural logarithm will be plotted with the inverse of temperature. The
activation energy and the pre-exponential frequency factor will be obtained from the Arrhenius
plot. The decomposition is shown below:

(CH3)3-C-O-O-C-(CH3)3 2 C3H6O + C2H6

d[DTBP]dt=k[DTBP]
1[DTBP]dDTBP=-kdt
DTBP=[DTBP]0e-kt
Experimental
The system described was already set up and evacuated. It remained to open the valve so
the gas would go to the reaction vessel in the hot oil. After that, the pressure was recorded in
mmHg every minute for 20 min. Once the first run finished, the temperature was adjusted and
the system was evacuated and allowed to equilibrate with the new temperature. The reactants
were allowed in the vessel as before and the pressure was measured. In the third trial however
the procedure was carried out the same way but the measurements of pressure were taken every
30 seconds for 15 minutes.

Calculations and Results

For the first trial of the decomposition of DTBP
Table 1: Data collected and converted for
the first run at T 155 C.

Pressu
time re
( 0 (0.05
.5 s) mmHg)
0
29.5
60
29.6
120
29.6
180
29.7
240
29.8
300
29.8
360
29.8
420
29.9
480
29.9
540
29.9
600
29.9
660
30
720
30.1
780
30.1
840
30.2
900
30.2
960
30.2
1020
30.3
1080
30.3
1040
30.3
1200
30.4

Pressu
re
(6.7
Pa)
3933
3946
3946
3960
3973
3973
3973
3986
3986
3986
3986
4000
4013
4013
4026
4026
4026
4040
4040
4040
4053

Log of
Differe
nce in
pressur
es( 0.
001)
3.895
3.895
3.8943
3.8935
3.8935
3.8935
3.8928
3.8928
3.8928
3.8928
3.8921
3.8913
3.8913
3.8906
3.8906
3.8906
3.8898
3.8898
3.8898
3.8891

Error in the pressure conversion

29.50.05mmHG706mmHgatm101325Paatm=39336.7
Error for Log(3pi-P)
Error for (3pi-P)
339336.7-39466.7)=78539.4
9.4=6.72+6.72
Log ( 78539.4)
=3.895 0.4349.47853
= 8.8950.001

Calculations for the slope of the graph ad its error.

3.89280.001 -3.8950.0014800.5-600.5

=5.2E-064.0E-06
Error for the slope
S=0.00170.00222+0.74202
S= 4.0E-06
Figure 1: Reaction progress in terms of pressures and a least Squares regression line for the most
precise slope.
Table 2:Decomposition of DTBP at 163 C

780
840
tim
900
e(
960
0.
102
5
s)
0
0
108
60
0
120
114
180
0
120
240
0
300
360
420
480
540
600
660
720

34.9
Press
35.1
ure
35.4
(0.05
35.7
mmHg
) 35.9
29.5
36.1
29.8
30.4
36.3
30.9
36.5
31.3
31.8
32.3
32.7
33
33.4
33.9
34.3
34.7

5008.8
5037.5
Press
5080.6
ure
5123.7
(6.7P
5152.4
a)

Log
3.8861
of
Differe
3.8845
nce
in
3.882
pressur
3.8795
es( 0.
3.8779
001)

4233.8
5181.1
4276.9
4363
5209.8
4434.8
5238.5
4492.2
4563.9
4635.7
4693.1
4736.2
4793.6
4865.3
4922.7
4980.1

3.8762
3.9255
3.9211
3.8746
3.9173
3.8729
3.9143
3.9105
3.9066
3.9035
3.9012
3.8981
3.8941
3.8909
3.8877

Figure 2 Decomposition of DTBP at 163C. the slope is equivalent to

the reaction constant and it is calculated with linear regression
analysis function. The Error bars are determined through the error
calculations shown above.

Decomposition of DTBP at 176.5C

Figure 3: Reaction occurring at 176.5 C and the slope of the

line of best fit determines the reaction constant.

Table 3 : Decomposition reaction of

DTBP Throughout 15 min

tim
e(
0.5
s)
0
30
60
90
120
150
180
210
240
270
300
330
360
390
420
450
480
510
540
570
600
630
660
690
720
750
780
810
840
870
900

Press
ure
(0.05
mmHg
)
26.8
27.4
27.9
28.5
28.9
29.3
29.7
30
30.4
30.7
30.8
31.1
31.4
31.6
31.8
32
32.1
32.3
32.4
32.6
32.7
32.8
32.8
33
33
33.1
33.2
33.2
33.3
33.3
33.4

Press
ure
(6.7
Pa)
3573
3653
3719.7
3799.7
3853
3906.3
3959.7
3999.7
4053
4093
4106.3
4146.3
4186.3
4213
4239.7
4266.3
4279.6
4306.3
4319.6
4346.3
4359.6
4373
4373
4399.6
4399.6
4413
4426.3
4426.3
4439.6
4439.6
4453

Log of
Differe
nce in
pressur
es( 0.
001)

Calculation of the error in the activation energy.

Error in temperature in Fig 4.
T= (428).5)-1

Error= (n)R(Sx/x)
=1(0.0023364)(0.5/428)
3.84918
=3.0E-6
3.84506
T=
0.00233643.0E-6
3.84007
3.83671
3.83332
3.82991
3.82733
3.82387
3.82126
3.82038
3.81775
3.8151
3.81332
3.81154
3.80975
3.80885
3.80705
3.80614
3.80433
3.80342
3.80251
3.80251
3.80068
3.80068
3.79976
3.79884
3.79884
3.79792
3.79792
3.797

Error in ln k1
Ln (5.2E-064.0E-06)
= -12.166(4.0E-065.2E-06)
= -12.20.8
Ln k2= -9.903 0.044
Ln k3= -9.70.2
Activation energy/R is determined through linear
regression analysis. The error for the Ea is shown
below.
11.60.17 - 10.40.0440.0023363.0E-6
-0.0022763.0E-6=
1.20.186.0E-54.2E-6=
194923226 =Ea/R
Error
0.18=0.172+0.0442
4.2E-6=3.0E-6 2+3.0E-6 2
3226=194920.181.22+4.2E-66.0E-52

Ea= (194923226 K-1) x 8.314 J/mol K=

162056 26820

Table 4: calculated values of K and T needed to present the graph below.

Temp
k
0.5
1/Temp ( 3.0EK values
Ln K
06)
0.00000428
0.0023364
52436
-12.1669
o.8
0.0022936
0.00005450
-9.903490.044
0.0022222
0.00006
-9.721170.2
Figure 4: Plot of the Ln k versus the inverse of temperature with the error bars being the uncertainty of each
parameter. The slope of the line is Ea/R and from thet the activation energy is determined. The calculation is
shown above.

Calculating Arrhenius frequency factor.

k=Ae-EaRT Taking the Ln in both sides
lnk-EaRT=lnA
-9.9030.044 --44.77.1=lnA

34.87.1=lnA

Error
7.1=44.73226194922+0.54362
Disscussion
The values obtained from the experiment are not very far off from the literature values
presented in the lab manual. The Activation energy value obtained is 162056 26820 J/mol
while the literature Activation energy is 158 kJ/mol. The frequency factor A is has no large
difference from the experimentally determined one. The obtained value from the experiment for
ln(A) = 34.8 and the literature value in the lab manual for ln(A)=36.3. A, represents the collision
frequency and the orientation of the molecules ( Atkins and De Paula. 2008).
A large factor that creates uncertainty is the dead volume. This volume is the volume
gas in the pipeline that is exposed to the room temperature and the decomposition occur at a
different rate because of the difference in pressure between the room and the reaction vessel. The
reaction occurring in the dead volume follows different kinetics and therefore introduced
uncertainty in the measurements.
Another major source of error is the vacuum created by the pump. The vacuum is not
total vacuum and there is some gases left in the tubing. That will also have an effect on the rate
constant and activation energy. Having a consistent vacuum in the system will make it able to
subtract the little pressure that cannot be evacuated and therefore produce more accurate results.
The stability of the vacuum can be determined by measuring the pressure over time by a gauge.
If the pressure elevates the vacuum is not stable, but if the pressure is constant and close to 0
then one can subtract that pressure from the measurements and obtain a more accurate
measurement.

In conclusion the results of the experiment provided an explanation for the first order
kinetics and although a little different they were still within range and made sens.
References
Atkins,P,. De Paula,. 2008. Physical Chemistry. 8th ed. W.H.Freeman and Company. New
York.