Studies of OH radicals and H[sub 2]O in catalytic reactions on Pt using REMPI and mass spectrometry

1997 ◽  
Author(s):  
A. P. Elg ◽  
M. Andersson ◽  
A. Rosén
1994 ◽  
Vol 49 (12) ◽  
pp. 1256-1258 ◽  
Author(s):  
G. Drechsler ◽  
C. Bäßmann ◽  
U. Boesl ◽  
E. W. Schlag

Abstract Zero-kinetic-energy (ZEKE) photoelectron spectra of metalcarbide anions are presented, allowing a high resolu­tion spectroscopic access to intermediates in catalytic reac­tions of hydrocarbons on metal surfaces. As a first compound, FeC2 (an intermediate of the iron/acetylene system) has been chosen. Important for successful ZEKE spectroscopy was a special anion source and the selection by time-of-flight mass spectrometry. In addition, conventional laser induced photo­ detachment photoelectron spectroscopy in combination with our anion source and mass analyzer delivered valuable new information.


2004 ◽  
Vol 50 (5) ◽  
pp. 329-334 ◽  
Author(s):  
S.G. Schrank ◽  
H.J. José ◽  
R.F.P.M. Moreira ◽  
H. Fr. Schröder

Many organic compounds contained in wastewater are resistant to conventional chemical and/or biological treatment. Because of this reason different degradation techniques are studied as an alternative to biological and classical physico-chemical processes. Advanced Oxidation Processes (AOPs) probably have developed to become the best options in the near future. AOP while making use of different reaction systems, are all characterised by the same chemical feature: production of OH radicals (*OH). The versatility of AOPs is also enhanced by the fact that they offer different possibilities for OH radical production, thus allowing them to conform to specific treatment requirements. The main problem with AOPs is their high cost. The application of solar technologies to these processes could help to diminish that problem by reducing the energy consumption required for generating UV radiation. In this work, different AOPs (O3, TiO2/UV, Fenton and H2O2/UV) were examined to treat tannery wastewater or as a pre-treatment step for improving the biodegradation of tannery wastewater, at different pH and dosage of the chemicals. Under certain circumstances retardation in biodegradation and/or an increase in toxicity may be observed within these treatment steps. Two different bioassays (Daphnia magna and Vibrio fischeri) have been used for testing the progress of toxicity during the treatment. In parallel other objectives were to analyse and identify organic compounds present in the untreated wastewater and arising degradation products in AOP treated wastewater samples. For this purpose substance specific techniques, e.g., gas chromatography - mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode and atmospheric pressure ionisation (API) in combination with flow injection analysis (FIA) or liquid chromatography - mass and tandem mass spectrometry (LC-MS or LC-MS-MS) were performed.


1961 ◽  
Vol 39 (1) ◽  
pp. 102-109 ◽  
Author(s):  
R. F. Pottie ◽  
A. G. Harrison, ◽  
F. P. Lossing

The Hg 3P1 photosensitized decomposition of methanol at low pressures proceeds mainly by a dissociation into CH3O radicals and H atoms. No formation of CH2OH radicals is observed. A subsidiary reaction to form CH3 and OH may also be a primary step. Formation of CH2OH radicals at higher pressures is attributed to an abstraction reaction of CH3O with CH3OH.Two primary modes of dissociation are found to occur for dimethyl ether:[Formula: see text]The relative probabilities of occurrence at low pressures are ∼45% and ∼50%, respectively. The possibility that the second reaction proceeds by formation of an excited molecule is discussed.


2010 ◽  
Vol 20 (3) ◽  
pp. 125-131 ◽  
Author(s):  
Pavel A. Belyakov ◽  
Valentine I. Kadentsev ◽  
Alexander O. Chizhov ◽  
Natal’ya G. Kolotyrkina ◽  
Alexander S. Shashkov ◽  
...  

2021 ◽  
Author(s):  
María Asensio ◽  
María Antiñolo ◽  
Sergio Blázquez ◽  
José Albaladejo ◽  
Elena Jiménez

Abstract. Saturated aldehydes, e.g. 2-methylbutanal (2MB, CH3CH2CH(CH3)C(O)H), are emitted into the atmosphere by several biogenic sources. The first step in the daytime atmospheric degradation of 2MB involves gas-phase reactions initiated by hydroxyl (OH) radicals, chlorine (Cl) atoms and/or sunlight. In this work, we report the rate coefficients for the gas-phase reaction of 2MB with OH (kOH) and Cl (kCl) together with the photolysis rate coefficient (J) in the ultraviolet solar actinic region in Valencia (Spain) at different times of the day. The temperature dependence of kOH was described in the 263–353 K range by the following Arrhenius expression: kOH(T)=(8.88±0.41)×10-12 exp[(331±14)/T] cm3 molecule-1 s-1. At 298 K, the reported kOH and kCl are (2.68±0.07)×10-11 cm3 molecule-1 s-1 and (2.16±0.16)×10-11 cm3 molecule-1 s-1. Identification and quantification of the gaseous products of the Cl-reaction and those from the photodissociation of 2MB were carried out in a smog chamber by different techniques (Fourier transform infrared spectroscopy, proton transfer time-of-flight mass spectrometry, and gas chromatography coupled to mass spectrometry). The formation and size distribution of secondary organic aerosols formed in the Cl-reaction was monitored by a fast mobility particle sizer spectrometer. A discussion on the relative importance of the first step in the daytime atmospheric degradation of 2MB is presented together with the impact of the degradation products in marine atmospheres.


2021 ◽  
Author(s):  
María Asensio ◽  
Sergio Blázquez ◽  
María Antiñolo ◽  
José Albadalejo ◽  
Elena Jiménez

<p>The biogenic oxygenated volatile compound 2-methylbutanal (2MB) is emitted into the low atmosphere from several natural sources such as microbiological processes, wildland fires, or emissions from vegetation<sup>1</sup>. Moreover, some industrial operations also generate 2MB<sup>2</sup>. During the day, the oxidation of 2MB can be initiated by sunlight, hydroxyl (OH) radicals or chlorine (Cl) atoms in marine atmospheres. Up to date, gas-phase kinetics of OH with 2MB has only been studied at room temperature<sup>3</sup>. The photolysis rate coefficients (<em>J</em>) of 2MB initiated by sunlight have also been reported<sup>4</sup>. However, there is no available data for the reaction of Cl atoms with 2MB and the photolysis products.</p><p>In this work, the photolysis rate coefficient (<em>J</em>) of 2MB has been measured using a solar simulator in a Pyrex cell coupled to a Fourier Transform Infrared (FTIR) spectrometer to monitor the loss of 2MB. Moreover, the gas-phase kinetics of the reaction of 2MB with Cl (<em>k</em><sub>Cl</sub>) and OH (<em>k</em><sub>OH</sub>) have been investigated to evaluate the contribution of these homogeneous degradation routes to the total loss of 2MB in the atmosphere. All the kinetic experiments were carried out under free-NO<sub>x</sub> conditions (simulating a clean atmosphere). Regarding the relative kinetic study on the Cl-reaction, an atmospheric simulation chamber coupled to a FTIR spectrometer was used at 298 K and 760 Torr <sup>5</sup> of air, whereas for the absolute kinetics of the OH-reaction, <em>k</em><sub>OH</sub> was determined as a function of temperature and pressure (T = 263-353 K and P = 50-600 Torr of helium) by using a pulsed laser photolysis-laser induced fluorescence system<sup>6</sup>. Finally, in addition to FTIR, gas chromatography coupled to mass spectrometry and proton transfer time-of-flight mass spectrometry were used to detect the gas-phase reaction products when 2MB was exposed to Cl and sunlight. The atmospheric implications will be discussed in terms of lifetimes and reactions products.</p><p><strong>REFERENCES:</strong> <strong>1</strong>. Szwajkowska-Michale, L., Busko, M., Lakomy, P., and Perkowski, J.: Determination of profiles of volatile metabolites produced by Trametes versicolor isolates antagonistic towards Armillaria spp. Sylwan. <strong>2018</strong>, 162, 499–508. <strong>2. </strong>Kolar, P.; Kastner, J. R. Low-Temperature Catalytic Oxidation of Aldehyde Mixtures Using Wood Fly Ash: Kinetics, Mechanism, and Effect of Ozone. Chemosphere. <strong>2010</strong>, 78 (9), 1110–1115. <strong>3. </strong>D’Anna, B.; Andresen, O.; Gefen, Z. and Nielsen, C.J.: Kinetic study of OH and NO<sub>3</sub> radical reactions with 14 aliphatic aldehydes. Phys.Chem.Chem.Phys. <strong>2001</strong>, 3, 3057-3063. <strong>4. </strong>Wenger, J.C.: Chamber Studies on the Photolysis of Aldehydes. Environmental Simulation Chambers: Application to Atmospheric Chemical Processes. <strong>2006. </strong>Nato Science Series: IV: Earth and Environmental Science, vol 62. Springer, Dordrecht. <strong>5. </strong>Antiñolo, M.; Asensio, M.; Albadalejo, J. and Jiménez E.: Gas-Phase Reaction of trans-2-methyl-2-butenal with Cl: Kinetics, Gaseous Products, and SOA Formation. Atmosphere <strong>2020</strong>, 11 (7), 715. <strong>6. </strong>Blázquez, S.; Antiñolo, M.; Nielsen, O. J.; Albadalejo, J. and Jiménez, E.: Reaction kinetics of (CF<sub>3</sub>)<sub>2</sub>CFCN with OH radicals as a function of temperature (278-358 K): A good replacement for greenhouse SF<sub>6</sub>? Chem.Phys.Lett. <strong>2017</strong>, 687, 297-302.</p>


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