The Reaction Rates of Amidogen and Ammonia with Nitrous Oxide: Implications for Combustion Mechanisms

Marshall, Paul; Lowe, Vincent M.; Gao, Yide; Glarborg, Peter

doi:10.1021/acs.jpca.5c03777

The Reaction Rates of Amidogen and Ammonia with Nitrous Oxide: Implications for Combustion Mechanisms

Journal Article · Sun Sep 14 00:00:00 EDT 2025 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5c03777· OSTI ID:3001053

^[1]; ^[1]; Gao, Yide ^[1]; ^[2]

University of North Texas, Denton, TX (United States)
Technical University of Denmark, Lyngby (Denmark)

Pulsed laser photolysis experiments with laser-induced fluorescence detection of NH₂ set an upper limit to the rate constant for reaction with N₂O of k < 1 × 10⁻¹⁵ cm³ molecule⁻¹ s⁻¹ at 513 K. Computations were based on geometries and anharmonic frequency analysis (B2PLYP-D3/cc-pVTZ) followed by coupled cluster calculations extrapolated to the infinite basis set limit, with corrections for core−valence electron correlation, scalar relativistic effects, and correlation up to CCSDT(Q). Species that showed multireference character were quantified with MRCI(7,7)+Q/cc-pVTZ theory. Rate constants were obtained for the dominant product channel H₂NN + NO, along with HN₃ + OH, H₂NO + N₂, NNH + HNO, ON(NH)₂ and HNNH + NO. The last channel is slow even at 2500 K, contrary to an early empirical estimate and confirming recent suggestions. Modeling of literature experiments on oxidation of NH₃ by N₂O shows that all channels are too slow to make a significant impact on the loss of N₂O in ammonia flames. Similarly, the direct NH₃ + N₂O reaction is found to be negligibly slow.

View Accepted Manuscript (DOE)

Research Organization:: University of North Texas, Denton, TX (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0020952

OSTI ID:: 3001053

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 38 Vol. 129; ISSN 1089-5639; ISSN 1520-5215

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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