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Thermal reaction of HNCO with NO2 at moderate temperatures

✍ Scribed by Y. He; Xiaoping Liu; M. C. Lin; C. F. Melius

Publisher
John Wiley and Sons
Year
1993
Tongue
English
Weight
826 KB
Volume
25
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The thermal reaction of HNCO with NO~2~ has been studied in the temperature range of 623 to 773 K by FTIR spectrometry. Major products measured are CO~2~ and NO with a small amount of N~2~O. Kinetic modeling of the time resolved concentration profiles of the reactants and products, aided by the thermochemical data of various likely reactive intermediates computed by means of the BAC‐MP4 method, allows us to conclude that the reaction is initiated exclusively by a new bimolecular process:
equation image
with a rate constant, k~1~ = 2.5 Γ— 10^12^e^βˆ’13,100^/T cm^3^/mols. The well‐known bimolecular reaction
equation image
is the only strong competitive process in this important reactive system throughout the temperature range studied. Kinetic modeling of NO formation and NO~2~ decay rates gave rise to values of k~10~ which were in close agreement with literature data. Β© 1993 John Wiley & Sons, Inc.

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