The thermal decomposition of NH2OH and subsequent reactions: ab initio transition state theory and reflected shock tube experiments

Primary and secondary reactions involved in the thermal decomposition of NH2OH are studied with a combination of shock tube experiments and transition state theory based theoretical kinetics. This coupled theory and experiment study demonstrates the utility of NH2OH as a high temperature source of OH radicals. The reflected shock technique is employed in the determination of OH radical time profiles via multipass electronic absorption spectrometry. O-atoms are searched for with atomic resonance absorption spectrometry. The experiments provide a direct measurement of the rate coefficient, k1, for the thermal decomposition of NH2OH. Secondary rate measurements are obtained for the NH2 + OH (5a) and NH2OH + OH (6a) abstraction reactions. The experimental data are obtained for temperatures in the range from 1355 to 1889 K and are well represented by the respective rate expressions: log(k/(cm3 molecule-1 s-1)) = (?10.12 ± 0.20) + (?6793 ± 317 K/T) (k1); log(k/(cm3 molecule-1 s-1)) = (?10.00 ± 0.06) + (?879 ± 101 K/T) (k5a); log(k/(cm3 molecule-1 s-1)) = (?9.75 ± 0.08) + (?1248 ± 123 K/T) (k6a). Theoretical predictions are made for these rate coefficients as well for the reactions of NH2OH + NH2, NH2OH + NH, NH + OH, NH2 + NH2, NH2 + NH, and NH + NH, each of which could be of secondary importance in NH2OH thermal decomposition. The theoretical analyses employ a combination of ab initio transition state theory and master equation simulations. Comparisons between theory and experiment are made where possible. Modest adjustments of predicted barrier heights (i.e., by 2 kcal/mol or less) generally yield good agreement between theory and experiment. The rate coefficients obtained here should be of utility in modeling NOx in various combustion environments.