Surfactant Control of Gas Transport and Reactions at the Surface of Sulfuric Acid

Aerosol particles in the atmosphere are tiny chemical reactors that catalyze numerous reactions, including the conversion of benign gases into ozone-destroying ones. In the lower stratosphere, these particles are often supercooled mixtures of water and sulfuric acid. The different species present at the surface of these droplets (H2O, H3O+, HSO4 −, H2SO4, and SO4 2−) stand at the “gas−liquid frontier”; as the first to be struck by impinging molecules, these species provide the initial environment for solvation and reaction. Furthermore, aerosol particles may contain a wide range of organic molecules, some of which migrate to the surface and coat the droplet. How do ambient gases dissolve in the droplet if it is coated with an organic layer? At one extreme, monolayer films of insoluble, long-chain alcohols can dramatically reduce gas transport, packing so tightly at the surface of water that they impede water evaporation by factors of 10 000 or more. Shorter chain surfactants are expected to pack less tightly, but we wondered whether these incomplete monolayers also block gas transport and whether this system could serve as a model for understanding the surfaces of atmospheric aerosol particles. To address these questions, our research focuses on small, soluble surfactants such as butanol and hexanol dissolved in supercooled sulfuric acid. These amphiphilic molecules spontaneously segregate to the surface and coat the acid but only to a degree. Gas−liquid scattering experiments reveal that these porous films behave in surprisingly diverse ways: they can impose a barrier (to N2O5 hydrolysis), be “invisible” (to water evaporation), or even enhance gas uptake (of HCl). The transition from obstacle to catalyst can be traced to specific interactions between the surfactant and each gas. For example, the hydrolysis of N2O5 may be impeded because of its large size and because alcohol molecules that straddle the interface limit contact between N2O5 and its H3O+ and H2O reaction partners. However, these same alcohol molecules assist HCl dissociation because the alcohol OH groups provide extra interfacial protonation sites. Interestingly, butanol does not impede water evaporation, in part because the butyl chains pack much more loosely than insoluble, long-chain surfactants. Through these investigations, we hope to gain insight into the mechanisms by which surfactants on sulfuric acid and other aqueous solutions affect transport and reactivity at the gas−liquid interf