Spectroscopic and Thermodynamic Studies of the Adsorption of Atmospherically Relevant Dicarboxylic Acids at the Vapor/Water Interface

摘要

Many important atmospheric processes are determined by the chemical composition of aerosols, including organic material. Dicarboxylic acids are a commonly detected class of organic material in urban, rural, and remote sites across the globe. Understanding the surface behavior of these molecules is imperative in characterizing the atmospheric fate of these molecules in aerosols, especially at an aerosol surface. In fact, little is known about their orientation, solvation, or pH dependence.This dissertation explores in molecular level detail the concentration and pH behavior of low molecular weight dicarboxylic acids at the air/water interface, which is used as a model for an aerosol surface. The solvation of the carboxylic head groups is shown to be dependent upon the length of the alkyl backbone. Indeed, the solvation of the head groups changes dramatically from very weakly solvated to typical surface solvation to near bulk solvation as the backbone increases. The orientation and conformation at the surface is fully explored to explain these differences in solvation. The pH dependence of surface adsorption is characterized, and it is shown that some acids are only surface active if they are fully protonated while others may still be surface active in singly or fully deprotonated forms. Using a combination of vibrational sum frequency spectroscopy (VSFS), surface tension, and computational modeling, the behavior at the air/water interface of four of the most relevant surface-active dicarboxylic acids (malonic, succinic, glutaric, and adipic acid) is completely described. VSFS, a surface specific optical technique, provides details about the solvation, orientation, and number density at the surface while surface tension measurements provide corollary information about the surface density. The use of computational modeling aids and confirms the spectral analysis while also providing molecular level details about the surface adsorption of the acids studied. By investigating the concentration and pH dependence of these molecules, molecular level detail is obtained which enables a complete description of these acids at an air/water interface and provides pertinent surface information on these atmospherically important organic molecules.This dissertation includes both previously published and unpublished co-authored material.