Abstract
A co‐oxidation model was constructed from available submechanisms for ammonia and ethanol oxidation. The ammonia submechanism validated for combustion at atmospheric pressure conditions was modified for the higher densities and lower temperatures (655–700°C) of supercritical water. The ethanol submechanism had previously been tested and validated at supercritical water conditions. The initial model poorly reproduced experimental ammonia conversion data and was not able to consistently match nitrous oxide production as a function of temperature over a range from 655–700°C at 246 bar. To improve model predictions, the low‐pressure NH~2~ + NO~x~ submechanism was replaced with a submechanism that included the H~2~NNO~x~ adduct species that are expected to be stabilized in the high‐pressure supercritical water environment. Thermochemical and kinetic parameters for the adduct species were estimated with quantum chemical calculations using Gaussian 98 with the CBS‐Q method. The explicit treatment of the H~2~NNO~x~ adducts resulted in nitrous oxide yield predictions that correctly reproduced experimental trends. This work represents a vital first step in improving the understanding of ammonia oxidation in supercritical water. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 653–662, 2008