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Full-Text Articles in Physical Sciences and Mathematics

Effects Of Water Vapor On The Kinetics Of The Methylperoxy Radical Self-Reaction And Reaction With Hydroperoxy, Alecia Mower Dec 2007

Effects Of Water Vapor On The Kinetics Of The Methylperoxy Radical Self-Reaction And Reaction With Hydroperoxy, Alecia Mower

Theses and Dissertations

The gas phase reactions of CH3O2 + CH3O2, HO2 + HO2, and CH3O2 + HO2 in the presence of water vapor have been studied at temperatures between 263 and 303 K using laser flash photolysis coupled with UV time-resolved absorption detection at 220 nm and 260 nm. Water vapor concentration was quantified using tunable diode laser spectroscopy operating in the mid-IR. The HO2 self-reaction rate constant is significantly enhanced by water vapor, consistent with what others have reported, whereas CH3O2 self-reaction and the cross-reaction (CH3O2 + HO2) rate constants are nearly unaffected. The enhancement in the HO2 self-reaction rate coefficient …


Laser Initiated Chain Reactions: The Kinetics Of The Chlorine/Cyclohexane/Oxygen Chain System, Robert Alan Forlines Jan 2007

Laser Initiated Chain Reactions: The Kinetics Of The Chlorine/Cyclohexane/Oxygen Chain System, Robert Alan Forlines

Browse all Theses and Dissertations

The combination of laser photolysis with infrared chemiluminescence detection has proven an effective technique for determining the propagation rate coefficients of halogen + RH chain reactions. This thesis will extend the technique to cyclic alkanes by determining the propagation rate coefficients of the Cl2/ cyclohexane chain system as well as the rate coefficient for the primary chain termination mechanism, R + O2 → RO2. The following reaction scheme is supported by the kinetic analysis: Cl2 → 2Cl Laser Photolysis Cl + RH → HCl(v) + R First Propagation Step (k1) R + …