Determination of uptake coefficient for ClO radicals on the surface of mineral salts

J Phys Chem A. 2012 Jun 21;116(24):6107-12. doi: 10.1021/jp211357y. Epub 2012 Feb 15.

Abstract

The uptake of ClO radicals on KBr, NaCl, and NaBr dry solid films was studied at 1 Torr pressure of helium over the temperature range 290-350 K using a flow tube technique with a modulated molecular beam mass spectrometer as the detection method. A Pyrex tube with the deposited salt sample was introduced into the flow reactor along its axis. The ClO uptake coefficient on the KBr surface did not depend on temperature within the experimental accuracy of ∼20%. Chlorine oxide radicals were prepared using the reaction of Cl with ozone. It was found out that the ClO uptake coefficient strongly depended on ozone concentration. The uptake coefficients at T = 293 K and [O(3)] = 4.6 × 10(13) molecules cm(-3) were found to be (9.6 ± 5.7) × 10(-4), (3.7 ± 1.5) × 10(-4), and (12.3 ± 3.6) × 10(-4) for KBr, NaCl, and NaBr, respectively. Bromine-containing species were not observed during the interaction of ClO radicals with KBr film. The results obtained indicate that the ClO loss through heterogeneous interaction with salt surface is not sufficiently rapid to compete with gas-phase self-reaction in the atmosphere.