Criegee intermediates in the indoor environment: new insights.

Criegee intermediates are formed in the ozonolysis of alkenes and play an important role in indoor chemistry, notably as a source of OH radicals. Recent studies have shown that these Criegee intermediates react very quickly with NO2 , SO2 , and carbonyls, and in this study, steady-state calculations are used to inspect the potential impact of these data on indoor chemistry. It is shown that these reactions could accelerate NO3 formation and SO2 removal in the indoor environment significantly. In addition, reaction between Criegee intermediates and halogenated carbonyls could provide a significant loss process indoors, where currently one does not exist.

Criegee intermediates and their impacts on the troposphere.

Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have estimated surface-level stabilized Criegee intermediate (sCI) concentrations on the order of 1 × 104 cm-3 to 1 × 105 cm-3, which makes a non-negligible contribution to the oxidising capacity in the terrestrial boundary layer. The reactions of sCI with the water monomer and the water dimer have been found to be the most important bimolecular reactions to the tropospheric sCI loss rate, at least for the smallest carbonyl oxides; the products from these reactions (e.g. hydroxymethyl hydroperoxide, HMHP) are also of importance to the atmospheric oxidation cycle. The sCI can oxidise SO2 to form SO3, which can go on to form a significant amount of H2SO4 which is a key atmospheric nucleation species and therefore vital to the formation of clouds. The sCI can also react with carboxylic acids, carbonyl compounds, alcohols, peroxy radicals and hydroperoxides, and the products of these reactions are likely to be highly oxygenated species, with low vapour pressures, that can lead to nucleation and SOA formation over terrestrial regions.

Initial steps of aromatic ring formation in a laminar premixed fuel-rich cyclopentene flame.

A fuel-rich, nonsooting, premixed laminar cyclopentene flame (phi = 2.0) at 37.6 Torr (50 mbar) is investigated by flame-sampling photoionization molecular-beam mass spectrometry utilizing vacuum-ultraviolet synchrotron radiation. Mole fractions as a function of distance from the burner are measured for 49 intermediates with ion masses ranging from 2 (H2) to 106 (C8H10), providing a broad database for flame modeling studies. The isomeric composition is resolved for most species, and the identification of several C4Hx, C7H6, and C7H8 isomers is discussed in detail. The presence of C5H5CCH/C5H4CCH2 and cycloheptatriene is revealed by comparisons between flame-sampled photoionization efficiency data and theoretical simulations, based on calculated ionization energies and Franck-Condon factors. This insight suggests a new potential molecular- weight growth mechanism that is characterized by C5-C7 ring enlargement reactions.

Time-resolved wavelength modulation spectroscopy measurements of HO 2 kinetics.

High-frequency wavelength modulation spectroscopy (WMS) has been applied to the detection of the hydroperoxyl radical (HO2 ) in a laser photolysis and long-path absorption pump-probe kinetics reactor with a near-infrared distributed feedback diode laser. The HO2 is formed by the 355-nm photolysis of Cl2 in the presence of CH3 OH and O2 and monitored by a phase-sensitive detection of the second-harmonic (2f ) signal in the 2?1 band with a 1.5- ?m diode laser directly modulated at 5 MHz. The measured 2f WMS signal is calibrated by direct absorption and converted to an absolute number density with the known absorption line strength of the HO2 line at 6625.80cm-1 . The utility of time-resolved WMS as a second-order kinetics probe is demonstrated through the measurement of the HO2 self-reaction rate constant at 295 K.

Recent progress in infrared absorption techniques for elementary gas-phase reaction kinetics.

Sensitive and precise measurements of rate coefficients, branching fractions, and energy disposal from gas-phase radical reactions provide information about the mechanism of elementary reactions as well as furnish modelers of complicated chemical systems with rate data. This chapter describes the use of time-resolved infrared laser absorption as a tool for investigating gas-phase radical reactions, emphasizing the exploitation of the particular advantages of the technique. The reaction of Cl atoms with HD illustrates the complementarity of thermal kinetic measurements with molecular beam data. Measurements of second-order reactions, such as the self-reactions of SiH3 and C3H3 radicals, and determinations of product branching fractions in reactions such as CN + O2 rely on the wide applicability of infrared absorption and on the straightforward relationship of absorption to absolute concentration. Finally, investigations of product vibrational distributions, as in the CN + H2 reaction, provide additional insight into the details of reaction mechanisms.

Two-tone frequency modulation spectroscopy from laser light scattered off a hard target.

One can apply two-tone frequency modulation spectroscopy techniques to the detection of gas-phase species by using laser light scattered from hard targets. High sensitivities are demonstrated, with a minimum detectable absorption of 10(-4) possible with a simple apparatus. The effects of laser speckle on the FM signal are described, and we show that the detection signal-to-noise ratio can be improved by collecting an increased number of speckle cells.

Infrared frequency-modulation probing of product formation in alkyl + O2 reactions. Part IV. Reactions of propyl and butyl radicals with O2.

The time-resolved production of HO2 in the Cl-initiated oxidation of iso- and n-butane is measured using continuous-wave (CW) infrared frequency modulation spectroscopy between 298 and 693 K. The yield of HO2 is determined relative to the Cl2/CH3OH/O2 system. As in studies of smaller alkanes, the branching fraction to HO2 + alkene in butyl + O2 displays a dramatic rise with increasing temperature between about 550 and 700 K (the "transition region") which is accompanied by a qualitative change in the time behavior of the HO2 production. At low temperatures the HO2 is formed promptly; a second, slower production of HO2 is responsible for the bulk of the increased yield in the transition temperature region. In contrast to reactions of smaller alkyl radicals with O2, the total HO2 yield in the butyl radical reactions appears to remain significantly below 1 up to 700 K, implying a significant role for OH-producing channels. The slower HO2 production in butane oxidation displays an apparent activation energy similar to that measured for smaller alkyl + O2 reactions, suggesting that the energetics of the HO2 elimination transition state are similar for a broad range of R + O2 systems. A combination of QCISD(T) based characterizations of the propyl and butyl + O2 potential energy surfaces and master equation based characterization of the propyl + O2 kinetics provide the framework for explanation of the experimentally observed HO2 production in Cl-initiated propane and butane oxidation. These calculations suggest that the HO2 elimination channel is similar in all reaction systems, and that hydroperoxyalkyl (QOOH) species produced by internal H-atom abstraction in RO2 can provide a path to OH formation. However, the QOOH formed by the energetically favorable 1,5 isomerization (via a six-membered ring transition state) generally experiences significant barriers (relative to the radical + O2 reactants) to the production of an oxetane + OH. In contrast, the barriers to forming OH + an oxirane or an oxolane, via 1,4 or 1,6 isomerizations, respectively, are generally below reactants.