New Measurements and Calculations on the Kinetics of an Old Reaction: OH + HO → HO + O.

Literature rate coefficients for the prototypical radical-radical reaction at 298 K vary by close to an order of magnitude; such variations challenge our understanding of fundamental reaction kinetics. We have studied the title reaction at room temperature via the use of laser flash photolysis to generate OH and HO radicals, monitoring OH by laser-induced fluorescence using two different approaches, looking at the direct reaction and also the perturbation of the slow OH + HO reaction with radical concentration, and over a wide range of pressures. Both approaches give a consistent measurement of ∼1 × 10 cm molecule s, at the lowest limit of previous determinations.

Direct Measurements of Isoprene Autoxidation: Pinpointing Atmospheric Oxidation in Tropical Forests.

2-Methyl-1,3-butadiene (isoprene), released from biogenic sources, accounts for approximately a third of hydrocarbon emissions and is mainly removed by hydroxyl radicals, OH, the primary initiator of atmospheric oxidation. measurements in clean tropical forests (high isoprene and low NO ) have measured OH concentrations up to an order of magnitude higher than model predictions, which impacts our understanding of global oxidation. In this study, direct, laser flash photolysis, laser-induced fluorescence measurements at elevated temperatures have observed OH recycling in the presence of isoprene and oxygen under conditions where interference from secondary or heterogeneous chemistry is minimal.

OH Kinetics with a Range of Nitrogen-Containing Compounds: -Methylformamide, -Butylamine, and -Methyl-propane Diamine.

Emissions of amines and amides to the atmosphere are significant from both anthropogenic and natural sources, and amides can be formed as secondary pollutants. Relatively little kinetic data exist on overall rate coefficients with OH, the most important tropospheric oxidant, and even less on site-specific data which control the product distribution. Structure-activity relationships (SARs) can be used to estimate both quantities.

Unimolecular decomposition kinetics of the stabilised Criegee intermediates CHOO and CDOO.

Decomposition kinetics of stabilised CH2OO and CD2OO Criegee intermediates have been investigated as a function of temperature (450-650 K) and pressure (2-350 Torr) using flash photolysis coupled with time-resolved cavity-enhanced broadband UV absorption spectroscopy. Decomposition of CD2OO was observed to be faster than CH2OO under equivalent conditions. Production of OH radicals following CH2OO decomposition was also monitored using flash photolysis with laser-induced fluorescence (LIF), with results indicating direct production of OH in the v = 0 and v = 1 states in low yields.

Experimentally Determined Site-Specific Reactivity of the Gas-Phase OH and Cl + i-Butanol Reactions Between 251 and 340 K.

Product branching ratios for the gas-phase reactions of i-butanol, (CH)CHCHOH, with OH radicals (251, 294, and 340 K) and Cl atoms (294 K) were quantified in an environmental chamber study and used to interpret i-butanol site-specific reactivity. i-Butyraldehyde, acetone, acetaldehyde, and formaldehyde were observed as major stable end products in both reaction systems with carbon mass balance indistinguishable from unity. Product branching ratios for OH oxidation were found to be temperature-dependent with the α, β, and γ channels changing from 34 ± 6 to 47 ± 1%, from 58 ± 6 to 37 ± 9%, and from 8 ± 1 to 16 ± 4%, respectively, between 251 and 340 K.

An instrument to measure fast gas phase radical kinetics at high temperatures and pressures.

Fast radical reactions are central to the chemistry of planetary atmospheres and combustion systems. Laser-induced fluorescence is a highly sensitive and selective technique that can be used to monitor a number of radical species in kinetics experiments, but is typically limited to low pressure systems owing to quenching of fluorescent states at higher pressures. The design and characterisation of an instrument are reported using laser-induced fluorescence detection to monitor fast radical kinetics (up to 25 000 s(-1)) at high temperatures and pressures by sampling from a high pressure reaction region to a low pressure detection region.