edu.ucar.opensky::articles:18110 UCAR/NCAR - Library OpenSky Support PO Box 3000 Boulder CO 80307-3000 opensky@ucar.edu http://opensky.ucar.edu/ homepage pointOfContact 2025-12-26T14:48:43.833325 ISO 19115-2 Geographic Information - Metadata - Part 2: Extensions for Imagery and Gridded Data ISO 19115-2:2009(E) https://n2t.org/ark:/85065/d78p622h Atmospheric chemistry of isopropyl formate and tert-butyl formate 2010-08-01T00:00:00Z publication https://n2t.org/ark:/85065/d78p622h https://doi.org/10.1002/kin.20498 Pimentel, A. author Tyndall, Geoffrey S. author Orlando, John J. author Hurley, M. author Wallington, T. author Sulbaek Andersen, M. author Marshall, P. author Dibble, T. author UCAR/NCAR - Library publisher Formates are produced in the atmosphere as a result of the oxidation of a number of species, notably dialkyl ethers and vinyl ethers. This work describes experiments to define the oxidation mechanisms of isopropyl formate, HC(O)OCH(CH₃)₂, and tert-butyl formate, HC(O)OC(CH₃)₃. Product distributions are reported from both Cl- and OH-initiated oxidation, and reaction mechanisms are proposed to account for the observed products. The proposed mechanisms include examples of the α-ester rearrangement reaction, novel isomerization pathways, and chemically activated intermediates. The atmospheric oxidation of isopropyl formate by OH radicals gives the following products (molar yields): acetic formic anhydride (43%), acetone (43%), and HCOOH (15–20%). The OH radical initiated oxidation of tert-butyl formate gives acetone, formaldehyde, and CO&#8322 as major products. IR absorption cross sections were derived for two acylperoxy nitrates derived from the title compounds. Rate coefficients are derived for the kinetics of the reactions of isopropyl formate with OH (2.4 ± 0.6) × 10⁻ ¹ ², and with Cl (1.75 ± 0.35) × 10⁻ ¹ ¹, and for tert-butyl formate with Cl (1.45 ± 0.30) × 10⁻ ¹ ¹ cm³ molecule⁻ ¹ s⁻ ¹. Simple group additivity rules fail to explain the observed distribution of sites of H-atom abstraction for simple formates. UCAR/NCAR - Library OpenSky Support PO Box 3000 Boulder CO 80307-3000 opensky@ucar.edu http://opensky.ucar.edu/ homepage pointOfContact PDF Text theme Resource Type 2016-01-01T00:00:00Z publication Copyright 2010 Wiley Periodicals, Inc. None eng geoscientificInformation