Predicted reaction rates of HxNyOz intermediates in the oxidation of hydroxylamine by aqueous nitric acid

This work reports computed rate coefficients of 90 reactions important in the autocatalytic oxidation of hydroxylamine in aqueous nitric acid. Rate coefficients were calculated using four approaches: Smoluchowski (Stokes -Einstein) diffusion, a solution-phase incarnation of transition state theory based on quantum chemistry calculations, simple Marcus theory for electron-transfer reactions, and a variational TST approach for dissociative isomerization reactions that occur in the solvent cage. Available experimental data were used to test the accuracy of the computations. There were significant discrepancies between the computed and experimental values for some key parameters, indicating a need for improvements in computational methodology. Nonetheless, the 90-reaction mechanism showed the ability to reproduce many of the trends seen in experimental studies of this very complicated kinetic system. This work highlights reactions that may govern the system evolution and branching behavior critical to the stability of the system. We hope that this analysis will guide experimental investigations to reduce the uncertainties in the critical rate coefficients and thermochemistry, allowing an unambiguous determination of the dominant reaction pathways in the system. Advances in efficient and accurate solvation models that effectively separate entropic and enthalpic contributions will most directly benefit solution-phase modeling efforts. Methods for more accurately estimating activity coefficients, including at infinite dilution in multicomponent mixtures, are needed for modeling high ionic strength aqueous systems. A detailed derivation of the solution-phase equilibrium and transition state theory rate expressions in solution is included in the Supporting Information.