Kinetics and products of the gas-phase reactions of divinyl sulfoxide with OH and NO3 radicals and O3

Using relative rate methods, rate constants for the gas-phase reactions of divinyl sulfoxide [CH2=CHS(O)CH=CH2; DVSO] with NO3 radicals and O-3 have been measured at 296 +/- 2 K, and rate constants for the reaction with OH radicals have been measured over the temperature range of 277-349 K. Rate constants obtained for the NO3 radical and O-3 reactions at 296 +/- 2 K were (6.1 +/- 1.4) x 10(-16) and (4.3 +/- 1.0) x 10(-19) cm(3) molecule(-1) s(-1), respectively. For the OH radical reaction, the temperature-dependent rate expression obtained was k = 4.17 x 10(-12)e((858) (+/-) (141)/T) cm(3) molecule(-1) s(-1) with a 298 K rate constant of (7.43 +/- 0.71) x 10(-11) cm(3) molecule(-1) s(-1), where, in all cases, the errors are two standard deviations and do not include the uncertainties in the rate constants for the reference compounds. Divinyl sulfone was observed as a minor product of both the OH radical and NO3 radical reactions at 296 +/- 2 K. Using in situ Fourier transform infrared spectroscopy, CO, CO2, SO2, HCHO, and divinyl sulfone were observed as products of the OH radical reaction, with molar formation yields of 35 +/- 11, 2.2 +/- 0.8, 33 +/- 4, 54 +/- 6, and 5.4 +/- 0.8%, respectively, in air. For the experimental conditions employed, aerosol formation from the OH radical-initiated reaction of DVSO in the presence of NO was minor, being similar to 1.5%. The data obtained here for DVSO are compared with literature data for the corresponding reactions of dimethyl sulfoxide.