New Measurements and Calculations on the Kinetics of an Old Reaction: OH + HO2 → H2O + O2.

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 HO2 radicals, monitoring OH by laser-induced fluorescence using two different approaches, looking at the direct reaction and also the perturbation of the slow OH + H2O2 reaction with radical concentration, and over a wide range of pressures. Both approaches give a consistent measurement of k1,298K ∼1 × 10-11 cm3 molecule-1 s-1, at the lowest limit of previous determinations. We observe, experimentally, for the first time, a significant enhancement in the rate coefficient in the presence of water, k1,H2O, 298K = (2.17 ± 0.09) × 10-28 cm6 molecule-2 s-1, where the error is statistical at the 1σ level. This result is consistent with previous theoretical calculations, and the effect goes some way to explaining some, but not all, of the variation in previous determinations of k1,298K. Supporting master equation calculations, using calculated potential energy surfaces at the RCCSD(T)-F12b/CBS//RCCSD/aug-cc-pVTZ and UCCSD(T)/CBS//UCCSD/aug-cc-pVTZ levels, are in agreement with our experimental observations. However, realistic variations in barrier heights and transition state frequencies give a wide range of calculated rate coefficients showing that the current precision and accuracy of calculations are insufficient to resolve the experimental discrepancies. The lower value of k1,298K is consistent with experimental observations of the rate coefficient of the related reaction, Cl + HO2 → HCl + O2. The implications of these results in atmospheric models are discussed.

OH Kinetics with a Range of Nitrogen-Containing Compounds: N-Methylformamide, t-Butylamine, and N-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. Rate coefficients for the reaction of OH with t-butylamine (k1), N-methyl-1,3-propanediamine (k2), and N-methylformamide (k3) have been measured using laser flash photolysis coupled with laser-induced fluorescence. Proton-transfer-reaction mass spectrometry (PTR-MS) has been used to ensure the reliable introduction of these low-vapor pressure N-containing compounds and to give qualitative information on products. Supporting ab initio calculations are presented for the t-butylamine system. The following rate coefficients have been determined: k1,298K= (1.66 ± 0.20) × 10-11 cm3 molecule-1 s-1, k(T)1 = 1.65 × 10-11 (T/300)-0.69 cm3 molecule-1 s-1, k2,293K = (7.09 ± 0.22) × 10-11 cm3 molecule-1 s-1, and k3,298K = (1.03 ± 0.23) × 10-11 cm3 molecule-1 s-1. For OH + t-butylamine, ab initio calculations predict that the fraction of N-H abstraction is 0.87. The dominance of this channel was qualitatively confirmed using end-product analysis. The reaction of OH with N-methyl-1,3-propanediamine also had a negative temperature dependence, but the reduction in the rate coefficient was complicated by reagent loss. The measured rate coefficient for reaction 3 is in good agreement with a recent relative rate study. The results of this work and the literature data are compared with the recent SAR estimates for the reaction of OH with reduced nitrogen compounds. Although the SARs reproduce the overall rate coefficients for reactions, site-specific agreement with this work and other literature studies is less strong.

Unimolecular decomposition kinetics of the stabilised Criegee intermediates CH2OO and CD2OO.

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. Master equation calculations performed using the Master Equation Solver for Multi-Energy well Reactions (MESMER) enabled fitting of the barriers for the decomposition of CH2OO and CD2OO to the experimental data. Parameterisations of the decomposition rate coefficients, calculated by MESMER, are provided for use in atmospheric models and implications of the results are discussed. For CH2OO, the MESMER fits require an increase in the calculated barrier height from 78.2 kJ mol-1 to 81.8 kJ mol-1 using a temperature-dependent exponential down model for collisional energy transfer with ΔEdown = 32.6(T/298 K)1.7 cm-1 in He. The low- and high-pressure limit rate coefficients are k1,0 = 3.2 × 10-4(T/298)-5.81exp(-12 770/T) cm3 s-1 and k1,∞ = 1.4 × 1013(T/298)0.06exp(-10 010/T) s-1, with median uncertainty of ∼12% over the range of experimental conditions used here. Extrapolation to atmospheric conditions yields k1(298 K, 760 Torr) = 1.1+1.5-1.1 × 10-3 s-1. For CD2OO, MESMER calculations result in ΔEdown = 39.6(T/298 K)1.3 cm-1 in He and a small decrease in the calculated barrier to decomposition from 81.0 kJ mol-1 to 80.1 kJ mol-1. The fitted rate coefficients for CD2OO are k2,0 = 5.2 × 10-5(T/298)-5.28exp(-11 610/T) cm3 s-1 and k2,∞ = 1.2 × 1013(T/298)0.06exp(-9800/T) s-1, with overall error of ∼6% over the present range of temperature and pressure. The extrapolated k2(298 K, 760 Torr) = 5.5+9.2-5.5 × 10-3 s-1. The master equation calculations for CH2OO indicate decomposition yields of 63.7% for H2 + CO2, 36.0% for H2O + CO and 0.3% for OH + HCO with no significant dependence on temperature between 400 and 1200 K or pressure between 1 and 3000 Torr.

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, (CH3)2CHCH2OH, 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, ß, 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. Recommended temperature-dependent site-specific modified Arrhenius expressions for the OH reaction rate coefficient are (cm3 molecule-1 s-1): kα(T) = 8.64 × 10-18 × T1.91exp(666/T); kß(T) = 5.15 × 10-19 × T2.04exp(1304/T); kγ(T) = 3.20 × 10-17 × T1.78exp(107/T); kOH(T) = 2.10 × 10-18 × T2exp(-23/T), where kTotal(T) = kα(T) + kß(T) + kγ(T) + kOH(T). The expressions were constrained using the product branching ratios measured in this study and previous total phenomenological rate coefficient measurements. The site-specific expressions compare reasonably well with recent theoretical work. It is shown that use of i-butanol would result in acetone as the dominant degradation product under most atmospheric conditions.

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. Kinetics have been characterised at temperatures reaching 740 K and pressures up to 2 atm, with expected maximum operational conditions of up to ∼900 K and ∼5 atm. The distance between the point of sampling from the high pressure region and the point of probing within the low pressure region is critical to the measurement of fast kinetics. The instrumentation described in this work can be applied to the measurement of kinetics relevant to atmospheric and combustion chemistry.