Journal of Physical Chemistry A, Vol.101, No.5, 849-852, 1997
Unimolecular Decomposition of the FCO Radical
The kinetics of the unimolecular decomposition of the FCO radical has been studied experimentally in a heated tubular flow reactor coupled to a photoionization mass spectrometer. Rate constants for the decomposition were determined in time-resolved experiments as a function of temperature (951-1051 K) and bath gas density ((6-12) x 10(16) molecules cm(-3)) in two bath gases-He and N-2. The rate constants are in the low-pressure limit under the conditions of the experiments and can be described by the following expressions : k(l)(o)(He) 10(-8.74+/-0.28) exp(-(14169 +/- 653 K)/T) cm(3) molecule(-1) s(-1) (from the fitting of experimental data) and k(l)(o)(N-2) = 10(-8.71) exp(-14154 K)/T) cm(3) molecule(-1) s(-1) (evaluated from comparison of data obtained in nitrogen and helium bath gases). The thermochemistry of the reaction was analyzed on the basis of the data available in the literature and those obtained in the current study. An upper Limit estimate was obtained for the rate constant of the reaction of FCO radicals with Oz at the temperature of 800 K : k(FCO+O-2-->products) less than or equal to 4 x 10(-16) cm(3) molecule(-1) s(-1).