The entry of HCl through soluble surfactants on sulfuric acid: effects of chain branching.

ABSTRACT

Gas-liquid scattering experiments are used to determine how a soluble, branched surfactant (2-ethylbutanol) controls the entry of gaseous HCl molecules into 60 and 68 wt % D2SO4 at 213 K. Short-chain alcohols spontaneously segregate to the surfaces of these sulfuric acid solutions, which are representative of aerosol droplets in the lower stratosphere. We find that 2-ethylbutanol enhances HCl entry at low surface coverages, most likely because it provides extra interfacial OH groups that aid HCl dissociation. This enhancement disappears at higher coverages as the alkyl chains crowd each other and block access to the acid. The branched alcohol impedes HCl entry more effectively than its unbranched isomer 1-hexanol, implying that the larger 2-ethybutanol footprint on the surface blocks more HCl molecules from reaching the alcohol-acid interface. This behavior contrasts sharply with gas transport through long-chain monolayers, where branching introduces gaps that allow more facile passage. The experiments suggest that short-chain surfactants with extended footprints may impede transport more effectively than their unbranched isomers.