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Rate constant for the NH 3 + NO 2 → NH 2 + HONO reaction: Comparison of kinetically modeled and predicted results
Author(s) -
Thaxton A. Grant,
Hsu C.C.,
Lin M. C.
Publication year - 1997
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1997)29:4<245::aid-kin2>3.0.co;2-u
Subject(s) - chemistry , reaction rate constant , decomposition , kinetic energy , reaction rate , thermodynamics , kinetics , ab initio , constant (computer programming) , computational chemistry , catalysis , organic chemistry , physics , computer science , programming language , quantum mechanics
The rate constant for the NH 3 + NO 2 rlhar2; NH 2 + HONO reaction (1) has been kinetically modeled by using the photometrically measured NO 2 decay rates available in the literature. The rates of NO 2 decay were found to be strongly dependent on reaction (1) and, to a significant extent, on the secondary reactions of NH 2 with NO X and the decomposition of HONO formed in the initiation reaction. These secondary reactions lower the values of k 1 determined directly from the experiments. Kinetic modeling of the initial rates of NO 2 decay computed from the reported rate equation, ‐ d [NO 2 ]/ dt = k 1 [NH 3 ][NO 2 ] based on the conditions employed led to the following expression: $$k_1 = 10 ^{11.39\pm 0.16}\,e^{-(12620\pm 240)/T}\,cm^3 mole^{-1} s^{-1}$$ This result agrees closely with the values predicted by ab initio MO [G2M//B3LYP/6‐311 G( d,p )] and TST calculations. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 245–251, 1997.