화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.103, No.36, 7199-7209, 1999
Kinetics and products of the reactions BrO+DMS and Br+DMS at 298 K
The kinetics of the reaction BrO + DMS --> products(1), were examined by use of pulsed-laser photolytic generation and time-resolved detection of the BrO radical by absorption spectroscopy at total pressures of 60, 100, and 200 Torr N-2 (1 Torr = 133.322 Pa). A value of k(1) = (4.40 +/- 0.66) x 10(-13) cm(3) s(-1) was obtained independent of pressure at 295 K. This value is significantly higher than that determined previously in low-pressure (<4 Ton He), discharge flow measurements (2.6 x 10(-13) cm(3) s(-1)). By observing the formation of DMSO directly, we obtain a value of 1.17 +/- 0.34 for its yield in reaction 1; the major uncertainty is the +/-30% in the DMSO cross section. The impact of these results on the chemistry of the remote marine boundary layer was assessed using a chemical box model. At daytime concentrations of 1-2 pmol/mol, the BrO radical was found to be an important sink for DMS and the dominant source of DMSO. In a second set of experiments, pulsed-laser photolysis coupled with resonance fluorescence detection of Br atoms was employed to study the equilibrium kinetics of Br + DMS + M <-> Br-DMS + M (4, -4) at 100 Torr N-2 and 295 K. Values of k(4) = (6.36 +/- 0.43) x 10(-11) cm(3) s(-1) and k(-4) = (1.02 +/- 0.07) x 10(4) s(-1) were obtained, and were used to calculate the equilibrium constant K-4 = (6.24 +/-0.56) x 10(-15) cm(3). The uncertainty is 2 sigma plus estimated systematic error. At high [Br] ((1-3) x 10(12) cm(-3)), Br atoms are lost from equilibrium via the fast reaction Br + Br-DMS --> Br-2 + DMS (5), and a value of k(5) = (4.2(-1.2)(+2.3)) x 10(-10) cm(3) s(-1) was obtained. The uncertainty is 2 sigma plus the major systematic error incurred by estimating [Br](o) from laser fluence measurements. Pulsed-laser photolysis combined with time-resolved UV absorption at selected wavelengths and diode array measurements in the wavelength range 300-450 nm showed a strong absorption centered at 365 nm due to Br-DMS. A value of sigma(max)(365nm) = (2.74(-1.1)(+1.6)) x 10(-17) cm(2) was obtained by fitting to the time-resolved absorption signal due to Br-DMS. The uncertainty is 2 sigma plus systematic error (as above).