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• W2025743634 endingPage "10259" @default.
• W2025743634 startingPage "10241" @default.
• W2025743634 abstract "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." @default.
• W2025743634 created "2016-06-24" @default.
• W2025743634 creator A5009707274 @default.
• W2025743634 creator A5014055394 @default.
• W2025743634 creator A5017707133 @default.
• W2025743634 creator A5030482320 @default.
• W2025743634 creator A5035975028 @default.
• W2025743634 creator A5060098801 @default.
• W2025743634 creator A5064707932 @default.
• W2025743634 date "2009-09-01" @default.
• W2025743634 modified "2023-10-17" @default.
• W2025743634 title "Thermal Decomposition of NH₂OH and Subsequent Reactions: Ab Initio Transition State Theory and Reflected Shock Tube Experiments" @default.
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