Solvation, Surface Propensity, and Chemical Reactions of Solutes at Atmospheric Liquid-Vapor Interfaces

Abstract

ConspectusLiquids are of overarching importance for the atmosphere, as 72% of the Earth's surface is covered by oceans, a large number of liquid aerosol particles fill the air, and clouds hold a tiny but critical fraction of Earth's water in the air to influence our climate and hydrology, enabling the lives of humans and ecosystems. The surfaces of these liquids provide the interface for the transfer of gases, for nucleation processes, and for catalyzing important chemical reactions. Coupling a range of spectroscopic tools to liquid microjets has become an important approach to better understanding dynamics, structure, and chemistry at liquid interfaces. Liquid microjets offer stability in vacuum and ambient pressure environments, thus also allowing X-ray photoelectron spectroscopy (XPS) with manageable efforts in terms of differential pumping. Liquid microjets are operated at speeds sufficient to allow for a locally equilibrated surface in terms of water dynamics and solute surface partitioning. XPS is based on the emission of core-level electrons, the binding energy of which is selective for the element and its chemical environment. Inelastic scattering of electrons establishes the probing depth of XPS in the nanometer range and thus its surface sensitivity.In this Account, we focus on aqueous solutions relevant to the surface of oceans, aqueous aerosols, or cloudwater. We are interested in understanding solvation and acid dissociation at the interface, interfacial aspects of reactions with gas-phase reactants, and the interplay of ions with organic molecules at the interface. The strategy is to obtain a link between the molecular-level picture and macroscopic properties and reactivity in the atmospheric context.We show consistency between surface tension and XPS for a range of surface-active organic species as an important proof for interrogating an equilibrated liquid surface. Measurements with organic acids and amines offer important insight into the question of apparent acidity or basicity at the interface. Liquid microjet XPS has settled the debate of the surface enhancement of halide ions, shown using the example of bromide and its oxidation products. Despite the absence of a strong enhancement for the bromide ion, its rate of oxidation by ozone is surface catalyzed through the stabilization of the bromide ozonide intermediate at the interface. In another reaction system, the one between Fe2+ and H2O2, a similar intermediate in the form of highly valent iron species could not be detected by XPS under the experimental conditions employed, shedding light on the abundance of this intermediate in the environment but also on the constraints within which surface species can be detected. Emphasizing the importance of electrostatic effects, we show how a cationic surfactant attracts charged bromide anions to the interface, accompanied by enhanced oxidation rates by ozone, overriding the role of surfactants as a barrier for the access of gas-phase reactants. The reactivity and structure at interfaces thus result from a subtle balance between hygroscopic and hydrophobic interactions, electrostatic effects, and the structural properties of both liquids and solutes.