UC Irvine UC Irvine Previously Published Works Title Rate constants for the reactions of chlorine atoms with a series of unsaturated aldehydes and ketones at 298 K: structure and reactivity Permalink https://escholarship.org/uc/item/4p41x6ph Journal Physical Chemistry Chemical Physics, 4(10) ISSN 14639076 14639084 Authors Wang, Weihong Ezell, Michael J Ezell, Alisa A et al. Publication Date 2002-05-01 DOI 10.1039/b111557j Peer reviewed eScholarship.org Powered by the California Digital Library University of California View Article Online / Journal Homepage / Table of Contents for this issue PCCP Rate constants for the reactions of chlorine atoms with a series of unsaturated aldehydes and ketones at 298 K: structure and reactivity Weihong Wang, Michael J. Ezell, Alisa A. Ezell, Gennady Soskin and Barbara J. Finlayson-Pitts* Department of Chemistry, University of California, Irvine, CA 92697-2025. E-mail: bjfi
[email protected]; Fax: 949 824-3168; Tel: 949 824-7670 Received 2nd January 2002, Accepted 31st January 2002 First published as an Advance Article on the web 18th April 2002 The kinetics and mechanisms of chlorine atom reactions with the products of organic oxidations in the atmosphere are of interest for understanding the chemistry of coastal areas. We report here the first kinetics measurements of the reactions of atomic chlorine with 4-chlorocrotonaldehyde and chloromethyl vinyl ketone, recently identified as products of the reaction of chlorine atoms with 1,3-butadiene. The reactions with acrolein, methacrolein, crotonaldehyde, methyl vinyl ketone and crotyl chloride were also studied to probe structure- reactivity relationships. Relative rate studies were carried out at 1 atm and 298 K using two different approaches: long path FTIR for the acrolein, methacrolein, crotonaldehyde and methyl vinyl ketone reactions with acetylene as the reference compound, and a collapsible Teflon reaction chamber with GC-FID detection of the organics using n-butane or n-nonane as the reference compounds for the entire series.