Investigation into the pressure dependence between 1 and 10 Torr of the reactions of NO2 with CH3 and CH3O
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions
- Vol. 89 (23) , 4163-4169
- https://doi.org/10.1039/ft9938904163
Abstract
The kinetics and pressure dependence of the reactions of NO2 with CH3 and CH3O have been investigated in the gas phase at 298 K, at pressures from 1 to 10 Torr. A low-pressure discharge-flow laser-induced fluorescence (LIF) technique was used. In a consecutive process, CH3 reacted with NO2 to form CH3O, CH3+ NO2→ CH3O + NO (1), which further reacted with NO2 to form products, CH3O + NO2→ products (2). Reaction (1) displayed no discernible pressure dependence over the pressure range 1–7 Torr, and k1 was calculated to be (2.3 ± 0.3)× 10–11 cm3 molecule–1 s–1. Reaction (2) displayed a strong pressure dependence and an RRKM analysis yielded the following limiting low- and high-pressure rate constants in He, k0= 5.9 × 10–29 cm6 molecule–2 s–1 and k∞= 2.1 × 10–11 cm3 molecule–1 s–1. It is unrealistic to quote errors for this type of analysis. Parametrisation in the standard Troe form with Fc= 0.6 yielded k0=(5.3 ± 0.2)× 10–29 cm6 molecule–2 s–1 and k∞=(1.4 ± 0.1)× 10–11 cm3 molecule–1 s–1. Atmospheric implications and possible reaction mechanisms are discussed.Keywords
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