Competitive Adsorption of Acetic Acid and Water on Kaolinite.

Mineral dust is prevalent in the atmosphere as a result of emissions from natural and anthropogenic sources. As mineral dust particles undergo long-distance transport, they are exposed to trace gases and water vapor. We have characterized the interactions of acetic acid on kaolinite using diffuse reflectance infrared Fourier transform spectroscopy and molecular modeling to determine the chemisorbed species present. After the addition of acetic acid, gas-phase water was introduced to explore how water vapor competes with acetic acid for surface sites. We found that four chemisorbed acetate species are present on kaolinite after exposure to acetic acid in which acetate bonds through a monodentate, bidenatate, or bidentate bridging linkage with an aluminum atom. These species exhibit varying levels of stability after the introduction of water, indicating that water vapor affects the adsorption of organic acids. These results indicate that the type of chemisorbed species determines its stability toward competitive adsorption, which has potential implications for atmospheric composition and ice nucleation.