Journal of Physical Chemistry A, Vol.104, No.31, 7284-7293, 2000
Gas-phase Br-2 production in heterogeneous reactions of Cl-2, HOCl, and BrCl with halide-ice surfaces
In order to evaluate the relative importance of different heterogeneous mechanisms that may release gasphase Br-2 into the Arctic boundary layer, interactions of Cl-2 HOCl, and BrCl with halide-containing ice surfaces were studied in the laboratory. Results are presented from experiments using a coated-wall, low-pressure flow tube coupled to a mass spectrometer. Gas-surface reaction probabilities were calculated from the first-order loss of Cl-2 HOCl, or BrCl on bromide-ice surfaces at 233 K and on chloride/bromide-ice surfaces at 248 K. In all cases, the reactions were relatively fast, and the primary product was gas-phase Br-2. To determine the main factors that influence the kinetics of these reactions, experiments were conducted over a range of temperatures, hydrogen ion concentrations in ice, and halide concentrations in ice. Cl-2 reaction probability increases with increasing bromide concentration in the ice film, up to approximately 3% bromide. At this point, the ice surface is completely saturated with bromide ions, and the maximum reaction probability is 0.1. In contrast, HOCl reaction probability is highest when the ice film is made from a solution with low pH. BrCl reaction probability on bromide-ice films is less than that of Cl-2 and less than or equal to that of HOCl, depending on hydrogen ion concentration. No reaction between Cl-2 or HOCl and chloride-ice films was observed. The impact of Cl-2, HOCl, and BrCl heterogeneous chemistry on catalytic ozone destruction in the Arctic boundary layer is discussed.