Interactions of HBr, HCl, and HOBr with supercooled sulfuric acid solutions of stratospheric composition
Abbatt, Jonathan P. D.
Журнал:
Journal of Geophysical Research: Atmospheres
Дата:
1995
Аннотация:
The time‐dependent uptakes of HBr and HCl by supercooled solutions of sulfuric acid have been studied using a low‐temperature flow tube coupled to a mass spectrometer. From these experiments, typical values for the quantity H<sup>*</sup>D<sup>1/2</sup> (where H<sup>*</sup> is the effective Henry's law constant and D is the liquid phase diffusion coefficient) have been measured to be 1100 and 3.3 (M/atm)(cm<sup>2</sup>/s)<sup>1/2</sup> for HBr and HCl, respectively, on 59.6 wt% sulfuric acid at 210 K. By estimating values for the liquid phase diffusion coefficient, these measurements indicate that HBr is over 2 orders of magnitude more soluble in atmospheric sulfate aerosols than HCl. Similarly, HD<sup>1/2</sup> for HOBr on 69.8 wt% sulfuric acid at 228 K has been measured to be 20 (M/atm)(cm<sup>2</sup>/s)<sup>1/2</sup>, implying that HOBr, too, is highly soluble in sulfuric acid solutions. By exposing sulfuric acid films simultaneously to HOBr and either HCl or HBr, the liquid phase reactions HOBr + HCl → BrCl + H<sub>2</sub>O and HOBr + HBr → Br<sub>2</sub> + H<sub>2</sub>O have been studied. The results indicate that the HOBr/HCl heterogeneous reaction may play an important role in the activation of stratospheric chlorine under volcanic aerosol conditions.
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