CO Formation in the Thermal Decomposition of CH3ONO at High Temperatures: Kinetic Modeling of the CH3O Decomposition Rate

Article abstract of DOI:10.1021/j100369a038

CF3ONO was pyrolyzed in two different temperature regimes in order to determine the kinetics of the CH3O decomposition reaction.A static reactor operating between 550 and 770 K was used for the first set of experiments, with analysis of products (CO), CH2O, and CH3OH) by FTIR absorption.In the second set of experiments, a shock tupe operating in the range 1000 - 1600 K was employed and the CO product was measured by resonance absorption of the output of a stabilized CW CO laser.Kinetic modeling of CO product yields over the full range of temperature (550 - 1660 K)allowed us to obtain for the first time the rate constant for the decomposition of CH3O: CH3O + M -> H + CH2O + M (8), k₈ = (5.45 +/- 0.63) * 1E13 exp(-6794 +/- 102/T) cm³/(mol*s), where M = Ar or He, and the error limits represent only the internal consistency of the modeled values.Theoretical implications of this result are discussed.