Rate Coefficients for the Gas-Phase Reactions of OH and NO3Radicals and O3with Ethyleneglycol Monovinyl Ether, Ethyleneglycol Divinyl Ether, and Diethyleneglycol Divinyl Ether

Abstract

Kinetic studies have been performed on the reactions of OH and NO(3) radicals and ozone with three ethyleneglycol vinyl ethers (EGVEs), that is, ethyleneglycol monovinyl ether (EGMVE, HOCH(2)CH(2)OCH=CH(2)), ethyleneglycol divinyl ether (EGDVE, H(2)C=CHOCH(2)CH(2)OCH=CH(2)), and diethyleneglycol divinyl ether (DEGDVE, H(2)C=CHOCH(2)CH(2)OCH(2)CH(2)OCH=CH(2)). Using a relative rate technique, rate coefficients have been determined for the reactions in a 405 L borosilicate glass chamber at (298 +/- 3) K in one atmosphere of synthetic air using in situ FTIR spectroscopy to monitor the reactants. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) were obtained: (1.04 +/- 0.22) x 10(-10), (1.23 +/- 0.33) x 10(-10), and (1.42 +/- 0.30) x 10(-10) for the reaction of OH with EGMVE, EGDVE, and DEGDVE, respectively; (2.23 +/- 0.46) x 10(-12), (1.95 +/- 0.50) x 10(-12), and (6.14 +/- 1.38) x 10(-12) for the reaction of NO(3) with EGMVE, EGDVE, and DEGDVE, respectively; and (2.02 +/- 0.41) x 10(-16), (1.69 +/- 0.41) x 10(-16), and (2.70 +/- 0.56) x 10(-16) for ozonolysis of EGMVE, EGDVE, and DEGDVE, respectively. Using the kinetic rate data, tropospheric lifetimes for EGMVE, EGDVE, and DEGDVE with respect to their reactions with OH, NO(3), and ozone have been estimated for typical ambient air concentrations of these oxidants.