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DOI: 10.1039/A701471F (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1997, 93, 2807-2811

Rate constants for the reaction between OH and CH3ONO2 and C2H5ONO2 over a range of pressure and temperature

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Dudley E. Shallcross, Peter Biggs, Carlos E. Canosa-Mas, Kevin C. Clemitshaw, Mark G. Harrison, M. Reyes López Alañón, John A. Pyle, Alison Vipond and Richard P. Wayne

Abstract

A discharge-flow apparatus equipped with resonance-fluorescence detection for OH radicals has been used to measure rate coefficients for the two reactions over the pressure range 1–20 Torr at T=298 K and ca. 1–3 Torr over the temperature range 300–400 K. The rate constants, k1 and k2, were found to be invariant with pressure, but were found to increase with increasing temperature. In light of these findings, we conclude that at low pressure the reaction mechanism is consistent with an abstraction process. The rate constants derived are k1=(4.1±0.8)×10-13 exp(-604±121/T) cm3 molecule-1 s-1 and k2=(3.30±0.66)×10-12 exp(-699±140/T) cm3 molecule-1 s-1. The existence of pressure-dependent (association) channels for reactions (1) and (2) is briefly discussed. Model calculations are presented that imply that photolysis, and not reaction with the OH radical, is the dominant loss process in the atmosphere for CH3ONO2 and C2H5ONO2. Lifetimes of CH3ONO2 and C2H5ONO2 are derived for the lower atmosphere; they vary from a few years to several days depending upon season and location. Possible sources of these alkyl nitrates in the atmosphere are discussed.

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