Lal, Vinita (2012-02). Heterogeneous Reactions of Epoxides in Acidic Media. Master's Thesis.
Epoxides have been recently identified as one of the intermediate species in the gas phase oxidation of alkenes. This study investigates the reaction of isoprene oxide and alpha-pinene oxide with sulfuric acid to identify the potential of epoxides as important secondary organic aerosol (SOA) precursors. The reaction was explored using different methods to understand the factors governing the reaction rate and the types of products formed under different conditions. Uptake experiments of epoxides on sulfuric acid using Ion drift-Chemical Ionization Mass Spectrometry (ID-CIMS) showed an irreversible uptake of epoxides at room temperature resulting in the formation of less volatile products like diols, organosulfates and acetals. However, at lower temperatures, dehydration of diols and some rearrangement was the preferred reaction pathway resulting in the formation of higher volatility compounds like hydroxy-alkenes and aldehydes. The uptake coefficients of isoprene oxide and alpha-pinene oxide at room temperature using 96% wt acid were found to be 4x10^-2 and 0.8x10^-2, respectively. Spectroscopic study using Attenuated total reflection-Fourier transform infrared technique (ATR-FTIR) revealed that for both the epoxides, diols were the major identifiable products at low acid concentrations. At higher acid concentrations, acetal formation was observed in case of isoprene oxide, while organosulfate formation was seen for alpha-pinene oxide. No products were identified under neutral conditions due to slow reaction. Bulk studies using Nuclear Magnetic Resonance (NMR) spectroscopy conducted at low acid concentrations showed the presence of 1,2- and 1,4-diols as the major products for isoprene oxide, similar to the results from the ATR-FTIR experiments. Additionally, aldehyde formation was also observed. For alpha-pinene oxide, organosulfate formation was observed in all NMR experiments, unlike ATR-FTIR results, where organosulfate formation was observed only at high acid concentrations. These observations can be attributed to the kinetic isotope effect (KIE) due to use of D2SO4/D2O in NMR experiments rather than H2SO4/H2O. The percent yield of organosulfate products was proportional to the amount of available acidic sulfate. The results from this study suggest that acid hydrolysis of epoxides can result in the formation of a wide range of products under different conditions, that can contribute to SOA growth. It proves that epoxides can be efficient SOA precursors for ambient conditions prevailing in an urban atmosphere.