The kinetics of the reaction between oxygen difluoride with carbon monoxide were studies in shock tubes between 800 and 1400deg;K. Some of the experiments were done with a single pulse tube; these provided data on the production of CO2, O2, and F2CO. In addition timehyphen;resolved optical measurements were made behind incident shock waves. The rate of formation of CO2was monitored through its emission at 4.3 mgr;m and, simultaneously, the decrement in F2O through its absorption at 220 nm, for the reactionOFplus;COrarr;k4CO2plus;F.Computer analysis of the experiments yieldedk4thinsp;equals;thinsp;7.5thinsp;times;thinsp;1010cm3moleminus;1middot;secminus;1, independent of temperature. This value is believed to be correct within a factor of 2 between 900 and 1400deg;K. Combining of our earlier data on the reactionF2Oplus;Mrarr;k1Fplus;OFplus;Mwith the highhyphen;temperature results from this work and the results from another independent work, we obtain:k1thinsp;equals;thinsp;1016.7explpar;minus;40 500thinsp;sol;thinsp;RTrpar;cm3moleminus;1middot;secminus;1from 770 to 1230deg;K. The error in activation energy is about plusmn;3 kcal/mole. The reaction between F2O and CO leads to the production of significant amounts of F2CO, which results in a temperature increase which becomes more important at the lower temperatures. The heating effect, on 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 CO2, with inverted (001)/(100) populations, by measuring the transmitted intensity of 10.6hyphen;mgr;m radiation from a CO2laser. No gain was observed, and we concluded that if the initially formed CO2is highly vibrationally excited, under the conditions of these experiments the extent of inversion was not sufficient to permit detection with our technique.
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