1

QUIZ I

1. The mechanism of the pyrolysis of ethyl nitrate have been proposed as the following:
Initiation:
k1
C2 H 5ONO2 C2 H 5O* + NO2 (1)

Propagation:
k2
C2 H 5O* CH 3* + CH2O (2)

k3
*
CH3 + C2 H 5ONO2 CH 3NO2 + C2 H 5O* (3)

Termination:
k4
2 C2 H 5O* CH 3CHO + C2 H 5OH (4)

1.1) What rate expression is consistent with this mechanism? If the reaction (3) is rate-
limiting. (30 Scores)

1.2) From experimental studies, data of the reaction rate as a function of ethyl nitrate
concentration have been reported as in the below table. Is the proposed mechanism consistent
with this data?

Rate(moles/m3 .ksec) Ethyl nitrate concentration

(moles/m3 )
13.4 0.0975

12.2 0.0759

12.1 0.0713

23.0 0.2714

20.9 0.2346

(10 scores)
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Solution:

If the reaction (3) is rate-limiting,

-r C2 H 5ONO2 = k3 [CH3*] [C2 H 5ONO2]

In free radical reactions, radical concentrations are very small and change slowly.
We can assume the Pseudo Steady State Hypothesis (PSSH):

*
d (CH 3 ) d (C2 H 5O * )
0
dt dt
*
d (CH 3 )
0 = k2 [C2 H 5O*] k3 [CH3*] [C2 H 5ONO2]
dt

[CH3 ] = 2 [2 5 ]/ (k3 [C2 H 5ONO2])

d (C2 H 5O * )
0 = k1 [C2 H 5ONO2] k2 [C2 H 5O*] + k3 [CH3*] [C2 H 5ONO2]-2 k4 [C2 H 5O*]2
dt

0 = k1 [C2 H 5ONO2] k2 [C2 H 5O*] + k2 [C2 H 5O*] -2 k4 [C2 H 5O*]2

[C2 H 5O*] = (k1 [C2 H 5ONO2] / 2 k4 )1/2

Thus,
2 (k1 [C2 H5 ONO2 ]) 1/2
[CH3 ] =
(24 )1/2 3 [C2 H5 ONO2 ]

-r C2 H 5ONO2 = k3 [CH3*] [C2 H 5ONO2] =

2 (k1 [C2 H5 ONO2 ]) 1/2
3 [C2 H5 ONO2 ]
(24 )1/2 3 [C2 H5 ONO2 ]

2 k1 1/2 [C2 H5 ONO2 ]1/2

-r C2 H 5ONO2 = = [C2 H5 ONO2 ]1/2
(24 )1/2

2 k1 1/2
Where = (24 )1/2
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Rate(moles/m3 .ksec) Ethyl nitrate concentration k

(moles/m3)

13.4 0.0975 42.91

12.2 0.0759 44.28

12.1 0.0713 45.31

23.0 0.2714 44.15

20.9 0.2346 43.15

Therefore, the proposed mechanism is consistent with this data.