The INNpinJeR: A new wall-free reactor for studying gas-phase reactions

Here we characterize the new Innsbruck wall free impinging jets reactor (INNpinJeR) and compare its performance with the TROPOS free jet flow system by quantifying oxidation products of the well-understood...

Kinetic Study of the Atmospheric Oxidation of a Series of Epoxy Compounds by OH Radicals

The kinetics of the gas-phase reactions of hydroxyl radicals with cyclohexene oxide (CHO), 1,2-epoxyhexane (EHX), 1,2-epoxybutane (12EB), trans-2,3-epoxybutane (tEB) and cis-2,3-epoxybutane (cEB) have been investigated using the relative rate technique. The experiments have been performed at (298 ± 3) K and (760 ± 10) Torr total pressure of synthetic air using different reference compounds in a 1080 l Quartz Reactor (QUAREC) and a 480 l Duran glass chamber. The following room temperature rate coefficients (cm3 molecule−1 s−1) were obtained: k1 (OH+CHO) = (5.93 ± 1.78) × 10−12, k2 (OH+EHX) = (5.77 ± 1.29) × 10−12, k3 (OH+12EB) = (1.98 ± 0.39) × 10−12, k4 (OH+cEB) = (1.50 ± 0.26) × 10−12, k5 (OH+tEB) = (1.81 ± 0.42) × 10−12. With the exception of previous studies for 1,2-epoxybutane and cyclohexene oxide, this is to the best of our knowledge the first kinetic study of the reaction of these compounds with OH radicals. Atmospheric lifetimes, reactivity trends and atmospheric implications are discussed considering the epoxy compound rate coefficients obtained in the present study. In addition to a direct comparison with the literature data where possible, the results from the present study are compared with values estimated from the Structure Activity Relationship method.

Green Leaf Volatiles in the Atmosphere—Properties, Transformation, and Significance

This review thoroughly covers the research on green leaf volatiles (GLV) in the context of atmospheric chemistry. It briefly takes on the GLV sources, in-plant synthesis, and emission inventory data. The discussion of properties includes GLV solubility in aqueous systems, Henry’s constants, partition coefficients, and UV spectra. The mechanisms of gas-phase reactions of GLV with OH, NO3, and Cl radicals, and O3 are explained and accompanied by a catalog of products identified experimentally. The rate constants of gas-phase reactions are collected in tables with brief descriptions of corresponding experiments. A similar presentation covers the aqueous-phase reactions of GLV. The review of multiphase and heterogeneous transformations of GLV covers the smog-chamber experiments, products identified therein, along with their yields and the yields of secondary organic aerosols (SOA) formed, if any. The components of ambient SOA linked to GLV are briefly presented. This review recognized GLV as atmospheric trace compounds that reside primarily in the gas phase but did not exclude their transformation in atmospheric waters. GLV have a proven potential to be a source of SOA with a global burden of 0.6 to 1 Tg yr−1 (estimated jointly for (Z)-hexen-1-ol, (Z)-3-hexenal, and 2-methyl-3-buten-2-ol), 0.03 Tg yr−1 from switch grass cultivation for biofuels, and 0.05 Tg yr−1 from grass mowing.

The First Detection of CH2CN in a Protoplanetary Disk

We report the first detection of the molecule cyanomethyl, CH2CN, in a protoplanetary disk. Until now, CH2CN had only been observed at earlier evolutionary stages, in the molecular clouds TMC-1, Sgr2, and L483, in the prestellar core L1544, and toward the protostar L1527. We detect six transitions of ortho-CH2CN toward the disk around nearby T Tauri star TW Hya. An excitation analysis reveals that the disk-averaged column density, N , for ortho-CH2CN is (6.3 ± 0.5) × 1012 cm−2, which is rescaled to reflect a 3:1 ortho-para ratio, resulting in a total column density, N tot, of (8.4 ± 0.7) × 1012 cm−2. We calculate a disk-average rotational temperature, T rot = 40 ± 5 K, while a radially resolved analysis shows that T rot remains relatively constant across the radius of the disk. This high rotation temperature suggests that in a static disk and if vertical mixing can be neglected, CH2CN is largely formed through gas-phase reactions in the upper layers of the disk, rather than solid-state reactions on the surface of grains in the disk midplane. The integrated intensity radial profiles show a ring structure consistent with molecules such as CN and DCN. We note that this is also consistent with previous lower-resolution observations of centrally peaked CH3CN emission toward the TW Hya disks, since the observed emission gap disappears when convolving our observations with a larger beam size. We obtain a CH2CN/CH3CN ratio ranging between 4 and 10. This high CH2CN/CH3CN is reproduced in a representative chemical model of the TW Hya disk that employs standard static disk chemistry model assumptions, i.e., without any additional tuning.

Distribution of the Deposition Rates in an Industrial-Size PECVD Reactor Using HMDSO Precursor

The deposition rates of protective coatings resembling polydimethylsiloxane (PDMS) were measured with numerous sensors placed at different positions on the walls of a plasma-enhanced chemical vapor deposition (PECVD) reactor with a volume of approximately 5 m3. The plasma was maintained by an asymmetric capacitively coupled radiofrequency (RF) discharge using a generator with a frequency 40 kHz and an adjustable power of up to 8 kW. Hexamethyldisiloxane (HMDSO) was leaked into the reactor at 130 sccm with continuous pumping using roots pumps with a nominal pumping speed of 8800 m3 h−1 backed by rotary pumps with a nominal pumping speed of 1260 m3 h−1. Deposition rates were measured versus the discharge power in an empty reactor and a reactor loaded with samples. The highest deposition rate of approximately 15 nm min–1 was observed in an empty reactor close to the powered electrodes and the lowest of approximately 1 nm min–1 was observed close to the precursor inlet. The deposition rate was about an order of magnitude lower if the reactor was fully loaded with the samples, and the ratio between deposition rates in an empty reactor and loaded reactor was the largest far from the powered electrodes. The results were explained by the loss of plasma radicals on the surfaces of the materials facing the plasma and by the peculiarities of the gas-phase reactions typical for asymmetric RF discharges.