Formation of Gas-Phase Bromine from Interaction of Ozone with Frozen and Liquid NaCl/NaBr Solutions: Quantitative Separation of Surficial Chemistry from Bulk-Phase Reaction

The formation kinetics of gas-phase bromine (Br-2) from interaction of gas-phase ozone (O-3) with frozen and liquid solutions of NaCl (0.55 M) and NaBr (largely from 1.7 to 8.5 mM) have been studied from 40 to 0 degrees C in a coated-wall flow tube coupled to a chemical ionization mass spectrometer. The reactive uptake coefficient for O-3 is deduced from the product formation rate and then studied as a function of experimental conditions. In particular, for both the liquid and frozen solutions, we find that the uptake coefficient is inversely dependent on the gas-phase O-3 concentration in a manner that is quantitatively consistent with both surface- and bulk-phase kinetics. The reaction is fastest on acidic media (pH of the starting solution down to 2) but also proceeds at an appreciable rate on neutral substrates. Above 253 K, the uptake coefficient increases with increasing temperature on frozen solutions, consistent with an increasing brine content. The similarity of the absolute magnitude and form of the kinetics on the frozen and liquid substrates suggests that the reaction on the frozen solution is occurring with the associated brine, and not with the ice bulk or a quasi-liquid layer existing on the ice. The implications of these results to bromine activation in the tropospheric boundary layer are made.