Extent of H-atom abstraction from the reaction of the OH radical with 1-butene under atmospheric conditions

1985 ◽  
Vol 17 (7) ◽  
pp. 725-734 ◽  
Author(s):  
Roger Atkinson ◽  
Ernesto C. Tuazon ◽  
William P. L. Carter
Keyword(s):  
Oh Radical ◽  
Atmospheric Conditions

Importance of isomerization reactions for the OH radical regeneration from the photo-oxidation of isoprene investigated in the atmospheric simulation chamber SAPHIR

2020 ◽  
Author(s):  
Anna Novelli ◽  
Luc Vereecken ◽  
Birger Bohn ◽  
Hans-Peter Dorn ◽  
Georgios Gkatzelis ◽  
...  
Keyword(s):  
Oh Radicals ◽  
Oh Radical ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Unimolecular Reactions ◽  
Model Calculations ◽  
Hydrogen Shift ◽  
Wide Range ◽  
Regeneration Efficiency ◽  
Simulation Chamber

<p>Theoretical, laboratory and chamber studies have shown fast regeneration of hydroxyl radical (OH) in the photochemistry of isoprene largely due to previously disregarded unimolecular reactions which were previously thought not to be important under atmospheric conditions. Based on early field measurements, nearly complete regeneration was hypothesized for a wide range of tropospheric conditions, including areas such as the rainforest where slow regeneration of OH radicals is expected due to low concentrations of nitric oxide (NO). In this work the OH regeneration in the isoprene oxidation is directly quantified for the first time through experiments covering a wide range of atmospheric conditions (i.e. NO between 0.15 and 2 ppbv and temperature between 25 and 41°C) in the atmospheric simulation chamber SAPHIR. These conditions cover remote areas partially influenced by anthropogenic NO emissions, giving a regeneration efficiency of OH close to one, and areas like the Amazonian rainforest with very low NO, resulting in a surprisingly high regeneration efficiency of 0.5, i.e. a factor of 2 to 3 higher than explainable in the absence of unimolecular reactions. The measured radical concentrations were compared to model calculations and the best agreement was observed when at least 50% of the total loss of isoprene peroxy radicals conformers (weighted by their abundance) occurs via isomerization reactions for NO lower than 0.2 parts per billion (ppbv). For these levels of NO, up to 50% of the OH radicals are regenerated from the products of the 1,6 α-hydroxy-hydrogen shift (1,6-H shift) of Z-δ-RO<sub>2 </sub>radicals through photolysis of an unsaturated hydroperoxy aldehyde (HPALD) and/or through the fast aldehyde hydrogen shift (rate constant ~10 s<sup>-1</sup> at 300K) in di-hydroperoxy carbonyl peroxy radicals (di-HPCARP-RO<sub>2</sub>), depending on their relative yield. The agreement between all measured and modelled trace gases (hydroxyl, hydroperoxy and organic peroxy radicals, carbon monoxide and the sum of methyl vinyl ketone, methacrolein and hydroxyl hydroperoxides) is nearly independent on the adopted yield of HPALD and di-HPCARP-RO<sub>2</sub> as both degrade relatively fast (< 1 h), forming OH radical and CO among other products. Taking into consideration this and earlier isoprene studies, considerable uncertainties remain on the oxygenated products distribution, which affect radical levels and organic aerosol downwind of unpolluted isoprene dominated regions.</p>

Relative rate coefficient measurements of OH radical reactions with (Z)-2-hexen-1-ol and (E)-3-hexen-1-ol under simulated atmospheric conditions

2014 ◽  
Vol 85 ◽  
pp. 92-98 ◽  
Author(s):  
Silvina A. Peirone ◽  
Javier A. Barrera ◽  
Raúl A. Taccone ◽  
Pablo M. Cometto ◽  
Silvia I. Lane
Keyword(s):  
Rate Coefficient ◽  
Relative Rate ◽  
Radical Reactions ◽  
Oh Radical ◽  
Atmospheric Conditions

scholarly journals Investigation of the reaction of ozone with isoprene, methacrolein and methyl vinyl ketone using the HELIOS chamber

2017 ◽  
Vol 200 ◽  
pp. 289-311 ◽  
Author(s):  
Yangang Ren ◽  
Benoit Grosselin ◽  
Véronique Daële ◽  
Abdelwahid Mellouki
Keyword(s):  
Gas Phase ◽  
Organic Aerosol ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Radical Scavenger ◽  
Oh Radical ◽  
Atmospheric Conditions ◽  
Experimental Conditions ◽  
Methyl Vinyl ◽  
Analytical Equipment

The rate constants for the ozonolysis of isoprene (ISO), methacrolein (MACR) and methyl vinyl ketone (MVK) have been measured using the newly built large volume atmospheric simulation chamber at CNRS-Orleans (France), HELIOS (Chambre de simulation atmosphérique à irradiation naturelle d’Orléans). The OH radical yields from the ozonolysis of isoprene, MACR and MVK have also been determined, as well as the gas phase stable products and their yields. The secondary organic aerosol yield for the ozonolysis of isoprene has been tentatively measured in the presence and absence of an OH radical scavenger. The measurements were performed under different experimental conditions with and without adding cyclohexane (cHX) as an OH radical scavenger. All experiments have been conducted at 760 torr of purified dry air (RH < 1%) and ambient temperature (T = 281–295 K). The data obtained are discussed and compared with those from the literature. The use of the HELIOS facility and its associated analytical equipment enables the derivation of kinetic parameters as well as mechanistic information under near realistic atmospheric conditions.

scholarly journals Secondary Organic Aerosol Formation from Nitrophenols Photolysis under Atmospheric Conditions

Atmosphere ◽  
2020 ◽  
Vol 11 (12) ◽  
pp. 1346
Author(s):  
Iustinian Gabriel Bejan ◽  
Romeo-Iulian Olariu ◽  
Peter Wiesen
Keyword(s):  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Degradation Mechanism ◽  
Organic Aerosol ◽  
Radical Scavenger ◽  
Oh Radical ◽  
Atmospheric Conditions ◽  
Aerosol Formation ◽  
Chemical Models ◽  
Secondary Organic Aerosol Formation

Nitrophenols are important products of the aromatic compounds photooxidation and play a considerable role in urban chemistry. Nitrophenols are important components of agricultural biomass burning that could influence the climate. The formation of secondary organic aerosol from the direct photolysis of nitrophenols was investigated for the first time in a quartz glass simulation chamber under simulated solar radiation. The results from these experiments indicate rapid SOA formation. The proposed mechanism for the gas-phase degradation of nitrophenols through photolysis shows the formation of biradicals that could react further in the presence of oxygen to form low volatile highly oxygenated compounds responsible for secondary organic aerosol formation. The inhibiting effect of NOx and the presence of an OH radical scavenger on the aerosol formation were also studied. For 2-nitrophenol, significant aerosol formation yields were observed in the absence of an OH radical scavenger and NOx, varying in the range of 18%–24%. A gas-phase/aerosol partitioning model was applied assuming the presence of only one compound in both phases. A degradation mechanism is proposed to explain the aerosol formation observed in the photolysis of nitrophenols. The atmospheric impact of nitrophenol photolysis is discussed and the importance for atmospheric chemical models is assessed.

scholarly journals Investigations on the gas-phase photolysis and OH radical kinetics of nitrocatechols: Implications of intramolecular interactions on their atmospheric behavior

2021 ◽  
Author(s):  
Claudiu Roman ◽  
Cecilia Arsene ◽  
Iustinian Gabriel Bejan ◽  
Romeo-Iulian Olariu
Keyword(s):  
Gas Phase ◽  
Rate Coefficient ◽  
Relative Rate ◽  
Structural Features ◽  
Intramolecular Interactions ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Phase Reaction ◽  
Oh Radical ◽  
Atmospheric Conditions

Abstract. The Environmental Simulation Chamber made of Quartz from the University “Alexandru Ioan Cuza” from Iasi (ESC-Q-UAIC), Romania, was used to investigate for the first time the gas-phase reaction rate coefficients for four nitrocatechols towards OH radicals under simulated atmospheric conditions. Employing relative rate technique at a temperature of 298 ± 2 K and total air pressure of 1 atm, the obtained rate coefficients (in 10−12 cm3×s−1) were as followed: k3NCAT = (3.41 ± 0.37) for 3-nitrocatechol, k4NCAT = (1.27 ± 0.19) for 4-nitrocatechol, k5M3NCAT = (5.55 ± 0.45) for 5-methyl-3-nitrocatechol and k4M5NCAT = (0.92 ± 0.14) for 4-methyl-5-nitrocatechol. For the investigated compounds the photolysis rates in the actinic region, scaled to atmospheric relevant conditions, were evaluated as well. In this case the photolysis rate coefficient values were obtained only for 3-nitrocatechol and 5-methyl-3-nitrocatechol: J3NCAT = (3.06 ± 0.16) × 10−4 s−1 and J5M3NCAT = (2.14 ± 0.18) × 10−4 s−1, respectively. Considering the obtained results our study suggests that photolysis may be the main degradation process for 3-nitrocatechol and 5-methyl-3-nitrocatechol in the atmosphere. Results are discussed in terms of the reactivity of the investigated four nitrocatechols towards OH-radical initiated oxidation and their structural features. The rate coefficient values are also compared with those estimated from the structure-activity relationship for monocyclic aromatic hydrocarbons. Additional comparison with similar compounds is also presented underlining the implications towards possible degradation pathways and atmospheric behavior.

The gas-phase degradation of chlorpyrifos and chlorpyrifos-oxon towards OH radical under atmospheric conditions

Chemosphere ◽  
2014 ◽  
Vol 111 ◽  
pp. 522-528 ◽  
Author(s):  
Amalia Muñoz ◽  
Milagros Ródenas ◽  
Esther Borrás ◽  
Mónica Vázquez ◽  
Teresa Vera
Keyword(s):  
Gas Phase ◽  
Oh Radical ◽  
Atmospheric Conditions

Selective Corrosion of brazed joint between BNi-2 filler metal and stainless steel 316

1996 ◽  
Vol 54 ◽  
pp. 218-219
Author(s):  
H. S. Kim ◽  
R. U. Lee
Keyword(s):  
Stainless Steel ◽  
Filler Metal ◽  
Surface Preparation ◽  
Optical Microscope ◽  
Heating Element ◽  
Incomplete Fusion ◽  
Atmospheric Conditions ◽  
Leak Test ◽  
High Temperature Side ◽  
Inconel 600

A heating element/electrical conduit assembly used in the Orbiter Maneuvering System failed a leak test during a routine refurbishment inspection. The conduit, approximately 100 mm in length and 12 mm in diameter, was fabricated from two tubes and braze-joined with a sleeve. The tube on the high temperature side (heating element side) and the sleeve were made of Inconel 600 and the other tube was stainless steel (SS) 316. For the filler metal, a Ni-Cr-B brazing alloy per AWS BNi-2, was used. A Helium leak test spotted the leak located at the joint between the sleeve and SS 316 tubing. This joint was dissected, mounted in a plastic mold, polished, and examined with an optical microscope. Debonding of the brazed surfaces was noticed, more pronounced toward the sleeve end which was exposed to uncontrolled atmospheric conditions intermittently. Initially, lack of wetting was suspected, presumably caused by inadequate surface preparation or incomplete fusion of the filler metal. However, this postulation was later discarded based upon the following observations: (1) The angle of wetting between the fillet and tube was small, an indication of adequate wetting, (2) the fillet did not exhibit a globular microstructure which would be an indication of insufficient melting of the filler metal, and (3) debonding was intermittent toward the midsection of the sleeve.

Recent Progress In High-Resolution Shadowing For Biological Transmission Electron Microscopy

1990 ◽  
Vol 48 (1) ◽  
pp. 510-511 ◽  
Author(s):  
Heinz Gross ◽  
Katarina Krusche ◽  
Peter Tittmann
Keyword(s):  
Heavy Metal ◽  
High Resolution ◽  
Freeze Drying ◽  
Atmospheric Conditions ◽  
Vacuum Equipment ◽  
Transmission Electron ◽  
Gas Atmosphere ◽  
Gas Molecules ◽  
Residual Gas ◽  
Backing Layer

Freeze-drying followed by heavy metal shadowing is a long established and straight forward approach to routinely study the structure of dehydrated macromolecules. Very thin specimens such as isolated membranes or single macromolecules are directly adsorbed on C-coated grids. After rapid freezing the grids are transferred into a suitable vacuum equipment for freeze-drying and heavy metal shadowing.To improve the resolution power of shadowing films we introduced shadowing at very low specimen temperature (−250°C). To routinely do that without the danger of contamination we developed in collaboration with Balzers an UHV (p≤10-9 mbar) machine (BAF500K, Fig.2). It should be mentioned here that at −250°C the specimen surface acts as effective cryopump for practically all impinging residual gas molecules from the residual gas atmosphere.Common high resolution shadowing films (Pt/C, Ta/W) have to be protected from alterations due to air contact by a relatively thick C-backing layer, when transferred via atmospheric conditions into the TEM. Such an additional C-coat contributes disturbingly to the contrast at high resolution.

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