Atmospheric Chemistry of Tetrahydrofuran, 2‑Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 120; no. 37; pp. 7320 - 7326
• Main Authors: Andersen, Christina, Nielsen, Ole John, Østerstrøm, Freja F, Ausmeel, Stina, Nilsson, Elna J. K, Sulbaek Andersen, Mads P
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 22.09.2016
• Subjects: Fysik; Natural Sciences; Naturvetenskap; Physical Sciences
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.6b06618

FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were k THF+Cl = (1.96 ± 0.24) × 10–10, k THF+OD = (1.81 ± 0.27) × 10–11, k THF+O3 = (6.41 ± 2.90) × 10–21, k 2‑MTHF+Cl = (2.65 ± 0.43) × 10–10, k 2‑MTHF+OD = (2.41 ± 0.51) × 10–11, k 2‑MTHF+O3 = (1.87 ± 0.82) × 10–20, k 2,5‑DMTHF+OD = (4.56 ± 0.68) × 10–11, k 2,5‑DMTHF+Cl = (2.84 ± 0.34) × 10–10, k 2,5‑DMTHF+O3 = (4.58 ± 2.18), k furan+Cl = (2.39 ± 0.27) × 10–10, and k furan+O3 = (2.60 ± 0.31) × 10–18 molecules cm–3 s–1. Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.