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Title: Kinetics of elimination of several heterocyclic carbamates in the gas phase
Journal: J. Phys. Org. Chem.
Volume: 15
Page(s): 796 - 800
Year: 2002
Reference type: Journal article
Squib: 2002BRU/DOM796-800
Reaction:
tert-Butyl-1-pyrrole carboxylate → Pyrrole + iso-C4H8 + CO2
Reaction order:
1
Temperature:
467 - 528
K
Pressure: 3.53E-2 - 0.17 bar
Rate expression:
1.32x1012 [±1.5x1011 s-1] e-145200 [±1000 J/mole]/RT
Category: Experiment
Data type:
Absolute value measured directly
Pressure dependence:
None reported
Experimental procedure:
Static or low flow - Data taken vs time
Excitation technique:
Thermal
Time resolution:
In real time
Analytical technique:
Pressure measurement
Comments:
Overall kinetics were determined by following pressure vs. time, although the stoichiometry of the reaction was also confirmed by quantitative GLC analysis of the isobutene product and identification of products through GLC/MS analysis.
The authors suggest the reaction is a two-step process, first involving the molecular elimination to give the alkene + R2NCO2H , followed by the rapid decomposition of the latter species to R2NH and CO2.
Uncertainties are precision only and are at the 90% confidence level.
View full bibliographic record.
Rate constant values calculated from the Arrhenius expression:
| T (K) | k(T) [s-1] |
|---|---|
| 467 | 7.32E-5 |
| 475 | 1.42E-4 |
| 500 | 8.95E-4 |
| 525 | 4.72E-3 |
| 528 | 5.65E-3 |