Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O2 Reaction.

The concentration of formic acid in Earth's troposphere is underestimated by detailed chemical models compared to field observations. Phototautomerization of acetaldehyde to its less stable tautomer vinyl alcohol, followed by the OH-initiated oxidation of vinyl alcohol, has been proposed as a missing source of formic acid that improves the agreement between models and field measurements. Theoretical investigations of the OH + vinyl alcohol reaction in excess O2 conclude that OH addition to the α carbon of vinyl alcohol produces formaldehyde + formic acid + OH, whereas OH addition to the ß site leads to glycoaldehyde + HO2. Furthermore, these studies predict that the conformeric structure of vinyl alcohol controls the reaction pathway, with the anti-conformer of vinyl alcohol promoting α OH addition, whereas the syn-conformer promotes ß addition. However, the two theoretical studies reach different conclusions regarding which set of products dominate. We studied this reaction using time-resolved multiplexed photoionization mass spectrometry to quantify the product branching fractions. Our results, supported by a detailed kinetic model, conclude that the glycoaldehyde product channel (arising mostly from syn-vinyl alcohol) dominates over formic acid production with a 3.6:1.0 branching ratio. This result supports the conclusion of Lei et al. that conformer-dependent hydrogen bonding at the transition state for OH-addition controls the reaction outcome. As a result, tropospheric oxidation of vinyl alcohol creates less formic acid than recently thought, increasing again the discrepancy between models and field observations of Earth's formic acid budget.

Gas-Phase Reactions of Isoprene and Its Major Oxidation Products.

Isoprene carries approximately half of the flux of non-methane volatile organic carbon emitted to the atmosphere by the biosphere. Accurate representation of its oxidation rate and products is essential for quantifying its influence on the abundance of the hydroxyl radical (OH), nitrogen oxide free radicals (NO x), ozone (O3), and, via the formation of highly oxygenated compounds, aerosol. We present a review of recent laboratory and theoretical studies of the oxidation pathways of isoprene initiated by addition of OH, O3, the nitrate radical (NO3), and the chlorine atom. From this review, a recommendation for a nearly complete gas-phase oxidation mechanism of isoprene and its major products is developed. The mechanism is compiled with the aims of providing an accurate representation of the flow of carbon while allowing quantification of the impact of isoprene emissions on HO x and NO x free radical concentrations and of the yields of products known to be involved in condensed-phase processes. Finally, a simplified (reduced) mechanism is developed for use in chemical transport models that retains the essential chemistry required to accurately simulate isoprene oxidation under conditions where it occurs in the atmosphere-above forested regions remote from large NO x emissions.

Acetonyl Peroxy and Hydro Peroxy Self- and Cross-Reactions: Kinetics, Mechanism, and Chaperone Enhancement from the Perspective of the Hydroxyl Radical Product.

Pulsed laser photolysis coupled with infrared (IR) wavelength modulation spectroscopy and ultraviolet (UV) absorption spectroscopy was used to study the kinetics and branching fractions for the acetonyl peroxy (CH3C(O)CH2O2) self-reaction and its reaction with hydro peroxy (HO2) at a temperature of 298 K and pressure of 100 Torr. Near-IR and mid-IR lasers simultaneously monitored HO2 and hydroxyl, OH, respectively, while UV absorption measurements monitored the CH3C(O)CH2O2 concentrations. The overall rate constant for the reaction between CH3C(O)CH2O2 and HO2 was found to be (5.5 ± 0.5) × 10-12 cm3 molecule-1 s-1, and the branching fraction for OH yield from this reaction was directly measured as 0.30 ± 0.04. The CH3C(O)CH2O2 self-reaction rate constant was measured to be (4.8 ± 0.8) × 10-12 cm3 molecule-1 s-1, and the branching fraction for alkoxy formation was inferred from secondary chemistry as 0.33 ± 0.13. An increase in the rate of the HO2 self-reaction was also observed as a function of acetone (CH3C(O)CH3) concentration which is interpreted as a chaperone effect, resulting from hydrogen-bond complexation between HO2 and CH3C(O)CH3. The chaperone enhancement coefficient for CH3C(O)CH3 was determined to be kA″ = (4.0 ± 0.2) × 10-29 cm6 molecule-2 s-1, and the equilibrium constant for HO2·CH3C(O)CH3 complex formation was found to be Kc(R14) = (2.0 ± 0.89) × 10-18 cm3 molecule-1; from these values, the rate constant for the HO2 + HO2·CH3C(O)CH3 reaction was estimated to be (2 ± 1) × 10-11 cm3 molecule-1 s-1. Results from UV absorption cross-section measurements of CH3C(O)CH2O2 and prompt OH radical yields arising from possible oxidation of the CH3C(O)CH3-derived alkyl radical are also discussed. Using theoretical methods, no likely pathways for the observed prompt OH radical formation have been found and the prompt OH radical yields thus remain unexplained.

Performance of a high-resolution mid-IR optical-parametric-oscillator transient absorption spectrometer.

We report on a mid-IR optical parametric oscillator (OPO)-based high resolution transient absorption spectrometer for state-resolved collisional energy transfer. Transient Doppler-broadened line profiles at λ = 3.3 µm are reported for HCl R7 transitions following gas-phase collisions with vibrationally excited pyrazine. The instrument noise, analyzed as a function of IR wavelength across the absorption line, is as much as 10 times smaller than in diode laser-based measurements. The reduced noise is attributed to larger intensity IR light that has greater intensity stability, which in turn leads to reduced detector noise and better frequency locking for the OPO.