Reactions of F2O in Shock Waves. II. Kinetics and mechanisms of the F2O-CO Reaction

Hans Henrici*, Ming-Chang Lin, S. H. Bauer

*Corresponding author for this work

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

The kinetics of the reaction between oxygen difluoride with carbon monoxide were studies in shock tubes between 800 and 1400°K. Some of the experiments were done with a single pulse tube; these provided data on the production of CO2O2 and F2CO. In addition time-resolved optical measurements were made behind incident shock waves. The rate of formation of CO2 was monitored through its emission at 4.3 pm and, simultaneously, the decrement in F2O through its absorption at 220 nm, for the reaction k4 OF+CO→CO2+F. Computer analysis of the experiments yielded k4 = .5X1010 cm 3mole-1sec-1, independent of temperature. This value is believed to be correct within a factor of 2 between 900 and 1400°K. Combining of our earlier data on the reaction k1F 2O+M→F+OF+M with the high-temperature results from this work and the results from another independent work, we obtain: k1= 10 16.7 exp(-40 500/RT) cm3mole-1sec-1 from 770 to 1230°K. The error in activation energy is about ±3 kcal/mole. The reaction between F2O and CO leads to the production of significant amounts of FCO, which results in a temperature increase which becomes more important at the lower temperatures. The heating effect, o3n the basis of the proposed mechanism, was found to be strongly dependent on the concentration of the FCO radical, which is believed to be the intermediate in the formation of F2CO. The thermochemistry of the FCO radical is discussed. We also very briefly investigated the possibility that Reaction (4) produces vibrationally excited CO2with inverted (001)/( 100) populations, by measuring the transmitted intensity of 10.6-μm radiation from a CO2 laser. No gain was observed, and we concluded that if the initially formed CO2 is highly vibrationally excited, under the conditions of these experiments the extent of inversion was not sufficient to permit detection with our technique.

Original languageEnglish
Pages (from-to)5834-5842
Number of pages9
JournalThe Journal of chemical physics
Volume52
Issue number11
DOIs
StatePublished - 1 Jan 1970

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