Kinetics and modeling of the H₂O₂NOx system

The addition of NO (0 to 400ppm) to mixtures of H 2 (ca. 1%) and O 2 (0.7 to 22%) has been studied over the temperature range 700 to 825 K, in a flow reactor at atmospheric pressure. The overall effect of NO is to promote the oxidation of H 2 but high concentrations of O 2 actually inhibit the NO‐promoted oxidation of H 2 . A detailed kinetic mechanism has been constructed and found to describe the experimental observations. The promotion of the oxidation of H 2 arises through the catalytic cycle equation image The ability of R.34 to reactivate chains normally terminated by the formation of HO 2 is a key feature of this system. The predictions are highly sensitive to the rate of the reaction R.5 and the rate constants for this reaction is the only adjustable parameter required in the model. The value of k 5,N2 found to describe all the results has an absolute uncertainty <35%. The uncertainty relative to other important rate constants in the H 2 O 2 system is less than 10%.