Atmospheric chemistry of isopropyl formate and tert-butyl formate Metadata
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- Main Title Atmospheric chemistry of isopropyl formate and tert-butyl formate
Author: Pimentel, Andre SilvaCreator Type: PersonalCreator Info: Pontifícia Universidade Católica de Rio de Janeiro
Author: Tyndall, Geoffrey S. (Geoffrey Stuart) 1955-Creator Type: PersonalCreator Info: National Center for Atmospheric Research
Author: Orlando, John J.Creator Type: PersonalCreator Info: National Center for Atmospheric Research
Author: Hurley, Michale D.Creator Type: PersonalCreator Info: Ford Motor Company
Author: Wallington, Timothy J.Creator Type: PersonalCreator Info: Ford Motor Company
Author: Sulbaek Andersen, Mads PeterCreator Type: PersonalCreator Info: University of California, Irvine
Author: Marshall, PaulCreator Type: PersonalCreator Info: University of North Texas
Author: Dibble, Theodore S.Creator Type: PersonalCreator Info: State University of New York
Name: John Wiley & SonsPlace of Publication: [Hoboken, New Jersey]
- Submission Date: 2009-08-21
- Acceptance Date: 2010-03-03
- Creation: 2010-06-09
- Content Description: Article on the atmospheric chemistry of isopropyl formate and tert-butyl formate.
- Physical Description: 20 p.
- Keyword: formates
- Keyword: oxidation
- Keyword: esters
- Journal: International Journal of Chemical Kinetics, 2010, Hoboken: John Wiley & Sons, pp. 479-498
- Publication Title: International Journal of Chemical Kinetics
- Volume: 42
- Issue: 8
- Page Start: 479
- Page End: 498
- Pages: 20
- Peer Reviewed: True
Name: UNT Scholarly WorksCode: UNTSW
Name: UNT College of Arts and SciencesCode: UNTCAS
- Rights Access: public
- DOI: 10.1002/kin.20498
- Archival Resource Key: ark:/67531/metadc501407
- Academic Department: Chemistry
- Academic Department: Center for Advanced Scientific Computing and Modeling
- Display Note: Abstract: 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 CO2 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) × 10−12, and with Cl (1.75 ± 0.35) × 10−11, and for tert-butyl formate with Cl (1.45 ± 0.30) × 10−11 cm3 molecule−1 s−1. Simple group additivity rules fail to explain the observed distribution of sites of H-atom abstraction for simple formates.
- Display Note: Copyright © 2010 Wiley Periodicals, Inc.