Reactions of hydrazine with the amidogen radical and atomic hydrogen

Gao, Yide; Alecu, I. M.; Hashemi, Hamid; Glarborg, Peter; Marshall, Paul

doi:10.1016/j.proci.2022.07.045

Reactions of hydrazine with the amidogen radical and atomic hydrogen

Journal Article · Sat Aug 20 00:00:00 EDT 2022 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2022.07.045· OSTI ID:2421664

Gao, Yide ^[1]; Alecu, I. M. ^[2]; ^[3]; ^[3]; ^[2]

Univ. of North Texas, Denton, TX (United States); OSTI
Univ. of North Texas, Denton, TX (United States)
Technical Univ. of Denmark, Lyngby (Denmark)

The rate coefficient k₁ for NH₂ + N₂H₄ was measured to be (5.4 ± 0.4) × 10^–14 cm³ molecule^–1 s^–1 at 296 K. NH₂ was generated by pulsed laser photolysis of NH₃ at 193 nm, and monitored as a function of time by pulsed laser-induced fluorescence excited at 570.3 nm under pseudo-first order conditions in the presence of excess N₂H₄ in an Ar bath gas. This reaction was also investigated computationally, with geometries and scaled frequencies obtained with M06-2X/6-311+G(2df,2p) theory, and single-point energies from CCSD(T)-F12b/cc-pVTZ-F12 theory, plus a term to correct approximately for electron correlation through CCSDT(Q). Three connected transition states are involved and rate constants were obtained via Multistructural Improved Canonical Variational Transition State Theory with Small Curvature Tunneling. Combination of experiment and theory leads to a recommended rate coefficient for hydrogen abstraction of k₁ = 6.3 × 10^–23 T^3.44 exp(+289 K/T) cm³ molecule^–1 s^–1. The minor channel for H + N₂H₄ forming NH₂ + NH₃ was characterized computationally as well, to yield 5.0 × 10^–19 T^2.07 exp(-4032 K/T) cm³ molecule^–1 s^–1. Finally, these results are compared to several discordant prior estimates, and are employed in an overall mechanism to compare with measurements of half-lives of hydrazine in a shock tube.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0020952

OSTI ID:: 2421664

Alternate ID(s):: OSTI ID: 1984117

Journal Information:: Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 39; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Reactions of hydrazine with the amidogen radical and atomic hydrogen

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