Pressure dependence of the reaction H+O-2 (+Ar) -> HO2 (+Ar) in the range 1-900 bar and 300-700 K

Abstract

The reaction H + O-2 (Ar+) --> HO2 (+Ar) was studied in a high pressure flow cell in the bath gas argon at pressures between 1 and 900 bar and temperatures between 300 and 700 K. H atoms were generated by laser Hash photolysis of NH3 at 193.3 nm, HO2 radicals were monitored by light absorption at 230 nm. The results are consistent with experimental low pressure rate constants k(0) = [Ar] 2.5 x 10(-32) (Tl300 K)(-1.3) cm(6) molecule(-2) s(-1) and theoretical high pressure rate constants k(infinity) = 9.5 x 10(-11) (Tl300 K)(+0.44) cm(3) molecule(-1) s(-1) from the literature. The intermediate falloff curve was found to be best represented by k/k(infinity) = [x/(1 + x)]F-cent (1/(1+(a + logx)2/(N +/- DeltaN)2)) with x = k(0)/k(infinity), a approximate to 0.3, N approximate to 1.05, DeltaN approximate to 0.1 (+DeltaN for (a + log x) < 0 and -&UDelta;N for (a + log x) > 0), and F-cent(Ar) approximate to 0.5 independent of the temperature. A comparison with literature data between 300 and 1200 K does not confirm major deviations from third order kinetics in earlier medium pressure experiments.