| Increasingly stringent regulations have and will likely continue to place considerable constraints on combustion-generated pollutants, including carbon monoxide, nitrogen oxides, and sulfur oxides. The speciation of these pollutants and, by extension, their impact, is likely affected by kinetic interactions that occur during post-combustion processes. To gain a fundamental understanding of these interactions, the oxidation of hydrogen and carbon monoxide in the presence of trace quantities of NO, NO2, and SO2 was experimentally and numerically studied at conditions relevant to modern internal combustion engines.; Experimental data were obtained using a well-characterized flow reactor over pressure and temperature ranges of 0.4–14.0 atm and 750–1040 K, respectively, using dilute (∼1% fuel) H2/O2 and CO/H2O/O2 mixtures perturbed with ppm quantities of NO, NO2, and/or SO2. The overall effects of these species were found to be highly sensitive to pressure, temperature, and equivalence ratio. In general, small quantities of NO promoted fuel consumption by converting HO2 radicals to highly reactive OH radicals, while high concentrations of NO and/or NO2 were inhibiting due to the catalysis of radical recombination reactions. In the absence of NO, SO2 strongly inhibited CO oxidation, but the simultaneous presence of NO and SO2 yielded synergistic effects that significantly reduced the inhibition from SO 2. Over the range of conditions explored, direct interactions between NOx and SOx species did rot appear to significantly influence the relative NO and NO2 concentrations; however, the reaction between NO2 and SO2 may be an important source of SO3 in certain circumstances.; A detailed reaction mechanism. has been developed in a hierarchical manner, beginning with the H2/O2 and CO/H2O/O 2 systems and sequentially adding reactions necessary to describe the perturbing effects of NOx and SOx species. The experimental data were used in conjunction with gradient sensitivity and reaction flux analyses to determine key reaction pathways and to derive rate data for the H+O2(+M)=HO2(+M), H2+NO2=HONO+H, and SO2+O(+M) SO3(+M) reactions. Modifications to the rate constants for these and other reactions are discussed in relation to the mechanism's predictive ability with respect to the H2/O 2, CO/H2O/O2, H2/NO2, H 2/O2/NOx, and CO/H2O/O2/NO x/SOx systems over a wide range of conditions. |
