Free Radical Reactions of Hydrocarbons at Aqueous Interfaces



Chemical reactions that occur at hydrocarbon/water and electrolyte interfaces govern a wide array of environmentally and technologically important processes, including electrochemistry, aerosol photo-oxidation, cloud chemistry, corrosion, and heterogeneous catalysis. Hydrocarbon free radicals, formed at these interfaces, play important roles in the chemistry as initiators or propagators of surface reactions or as reactive intermediates. Two experimental techniques will be used in new ways to examine the surface chemistry of hydrocarbon free radicals at gas/liquid interfaces. The atomic and molecular changes at the surface of micron-sized droplets will be measured by ambient pressure X-ray photoelectron spectroscopy. Direct Analysis in Real Time Mass Spectrometry will be used to make kinetic measurements of reaction rates and product distributions. The objective of this research is provide a molecular description of the reaction pathways that lead to either bulk solvation of an organic molecule or its removal from the interface through decomposition into gas phase products. These interfacial processes are important for understanding and eventually predicting the environmental fate of hydrocarbon byproducts of energy use and consumption.




For more information see:

T. Nah, M. Chan, S. R. Leone and K. R. Wilson, Anal. Chem., 2013, 85, 2087-2095