Implications of the HCN → HNC process to high‐temperature nitrogen‐containing fuel chemistry

We have found in our recent kinetic study of the oxidation of HCN by NO₂ in the temperature range 623–773 K that HNCO and CO₂ are very important early products. The measured kinetic data cannot be accounted for by a “conventional” mechanism involving HCN reactions with NO₂, O, and OH. However, the introduction of the isomerization reaction HCN → HNC, followed by the rapid oxidation of HNC by NO₂, O, and OH, can quantitatively simulate all measured kinetic data. A similar study of the NO₂ + HCN reaction in shock waves at temperatures between 1500 and 2400 K also required the inclusion of HNC reactions in order to quantitatively account for measured product distributions. The effects of the HNC molecule on the high temperature HCN chemistry are discussed in terms of the predicted rate constants for HNC reactions with O and OH employing the BAC‐MP4 method. © John Wiley & Sons, Inc.