Re-evaluation of rate constants for the reaction N2H4 (+ M) $^→_←$ NH2&nbsp;+&nbsp;NH2 (+ M)

Cobos, Carlos J.; Glarborg, Peter; Marshall, Paul; Troe, Jürgen

doi:10.1016/j.combustflame.2022.112374

Re-evaluation of rate constants for the reaction N₂H₄ (+ M) $$^→_←$$ NH₂ + NH₂ (+ M)

Journal Article · Fri Sep 30 00:00:00 EDT 2022 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2022.112374· OSTI ID:2345161

Cobos, Carlos J. ^[1]; ^[2]; ^[3]; Troe, Jürgen ^[4]

La Plata National University (Argentina); University of North Texas
Technical Univ. of Denmark (Denmark)
Univ. of North Texas, Denton, TX (United States)
Gottingen Univ. (Germany)

Rate constants for the dissociation/recombination reaction N₂H₄ (+ M) $$^→_←$$ NH₂ + NH₂ (+ M) are determined by a combination of quantum-chemical calculations and statistical unimolecular rate theory. Between 1100 and 2500 K, limiting low-pressure rate constants for hydrazine dissociation in the bath gas Ar of k₀ = [Ar] 6.1 × 10²⁰ (T/1000 K)^–7.3 exp (-34490 K/T) cm³ mol^–1 s^–1, limiting high-pressure rate constants of k_∞ = 7.6 × 10¹⁶ (T/1000 K)^–1.0 exp(-33600 K/T) s^–1, and center broadening factors of the falloff curves (between 1100 and 1600 K in Ar) of F_cent = 0.71 exp(- T/1460 K) + 0.29 exp(- T/21 K) + exp(-13400 K/T) were calculated. Using equilibrium constants K_C = 1.7 × 10³ (T/1000 K)^–1.5 exp(-33,460 K/T) mol cm^–3, between 300 and 600 K limiting low-pressure rate constants for the reverse recombination of NH₂ radicals in the bath gas N₂ of k_rec,0 = [N₂] 4.4 × 10²⁰(T/400 K)^–6.9 exp (-1630 K/T) cm⁶ mol^–2 s^–1, limiting high-pressure rate constants of k_rec,∞ = 4.4 × 10¹³ (T/1000 K)^0.44 exp(-140 K/T) cm³ mol^-1 s^–1, and center broadening factors (between 300 and 600 K in N₂) of F_cent = exp(- T/1130 K) + exp (-10340 K/T) were obtained. A comparison with experimental results for hydrazine dissociation from the literature suggests incomplete falloff extrapolations toward k_∞ and experimental problems in the determination of k₀ at temperatures above about 1600 K. Finally, implications of the present re-evaluated rate constants for the modeling of high temperature ammonia oxidation kinetics are discussed, showing an only small influence of their precise values on the overall properties of the process.

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). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0020952

OSTI ID:: 2345161

Journal Information:: Combustion and Flame, Journal Name: Combustion and Flame Vol. 257; ISSN 0010-2180

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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