FTIR gas-phase kinetic study of the reactions of Cl atoms with (CH3)2C CHC(O)H and CH3CH CHC(O)OCH3

Abstract

Rate coefficients for the gas-phase reactions of Cl atoms with (CH3)2C=CHC(O)H and CH3CH=CHC(O)OCH3 were determined to be (in units of 1010 cm3 molecule1 s1): 2.48 ± 0.71 and 2.04 ± 0.56, respectively. The experiments were performed by the relative technique in an environmental chamber with FTIR detection of the reactants at 298 K and 760 Torr. Structure activity relationships were developed for the reactions of Cl with a series of unsaturated esters and aldehydes. In addition, a comparison between the experimentally determined kCl with kCl predicted from k vs. HOMO correlations is presented. The atmospheric persistence of these compounds was calculated taking into account the measured rate coefficients.