A search for a gas-phase free-radical inversion displacement reaction at a saturated carbon atom

1983 ◽  
Vol 61 (5) ◽  
pp. 916-920 ◽  
Author(s):  
R. A. Back

Five thermal and photochemical reaction systems have been examined in an attempt to detect or to place upper limits on the rates of the simple inversion reaction, CH3 + CH4 → C2H6 + H, and its reverse. No positive evidence was obtained for the occurrence of these reactions. An upper limit for the rate constant for the forward reaction of 0.063 M−1s−1 at 802 K was obtained from the thermal decomposition of methane, and upper limits of 0.044 and 0.14 at 823 and 983 K respectively were estimated from the thermal decomposition of ethane. Other systems examined were the thermal decomposition of azomethane in the presence of methane, and the mercury-photosensitized decompositions of methane and ethane, which were complicated by unexpected side reactions.


2018 ◽  
Vol 18 (19) ◽  
pp. 14005-14015 ◽  
Author(s):  
Terry J. Dillon ◽  
John N. Crowley

Abstract. Pulsed laser excitation of NO2 (532–647 nm) or NO3 (623–662 nm) in the presence of H2O was used to initiate the gas-phase reaction NO2∗+H2O → products (Reaction R5) and NO3∗+H2O → products (Reaction R12). No evidence for OH production in Reactions (R5) or (R12) was observed and upper limits for OH production of k5b/k5<1×10-5 and k12b/k12<0.03 were assigned. The upper limit for k5b∕k5 renders this reaction insignificant as a source of OH in the atmosphere and extends the studies (Crowley and Carl, 1997; Carr et al., 2009; Amedro et al., 2011) which demonstrate that the previously reported large OH yield by Li et al. (2008) was erroneous. The upper limit obtained for k12b∕k12 indicates that non-reactive energy transfer is the dominant mechanism for Reaction (R12), though generation of small but significant amounts of atmospheric HOx and HONO cannot be ruled out. In the course of this work, rate coefficients for overall removal of NO3∗ by N2 (Reaction R10) and by H2O (Reaction R12) were determined: k10=(2.1±0.1)×10-11 cm3 molecule−1 s−1 and k12=(1.6±0.3)×10-10 cm3 molecule−1 s−1. Our value of k12 is more than a factor of 4 smaller than the single previously reported value.



2013 ◽  
Vol 41 (01) ◽  
pp. 31-36
Author(s):  
E. Kienzle ◽  
N. Becker

ZusammenfassungIm Rahmen einer Eliminationsdiät wird regelmäßig Pferdefleisch eingesetzt. Aus Gründen der Praktikabilität verwenden Tierbesitzer häufig kommerziell erhältliches Pferdefleisch aus der Dose. Aufgrund eines Berichts von Zervikalspondylosen bei einer auf Futtermittel allergischen Katze erfolgte eine Analyse verschiedener auf Pferdefleisch basierender Produkte hinsichtlich des Vitamin-AGehalts.In 14 Pferdefleischerzeugnissen wurde der Vitamin-A-Gehalt (Retinol) analysiert. Der Gehalt an umsetzbarer Energie wurde mithilfe von Schätzformeln auf Basis der Deklaration berechnet.In Produkten mit deklarierten Anteilen von Leber, Innereien oder tierischen Nebenprodukten konnten zum Teil erhebliche Vitamin-A-Gehalte festgestellt werden. Bei alleiniger Verfütterung eines dieser Produkte (Deckung des durchschnittlichen Energiebedarfs) würde die Vitamin-A-Versorgung nur knapp unter dem Safe Upper Limit der Katze sowie oberhalb des Safe Upper Limits beim Hund liegen.Bei All-Meat-Produkten sollte nicht nur die Deklaration, sondern auch der Inhalt näher betrachtet werden, um einen Hinweis auf eventuell hohe Leberanteile zu erhalten.Aufgrund der Ergebnisse ist eine exzessive Vitamin-A-Aufnahme bei langfristiger Verfütterung von Pferdefleischprodukten mit hohen Leberanteilen nicht auszuschließen.



2021 ◽  
Vol 2021 (2) ◽  
Author(s):  
E. Cortina Gil ◽  
◽  
A. Kleimenova ◽  
E. Minucci ◽  
S. Padolski ◽  
...  

Abstract The NA62 experiment at the CERN SPS reports a study of a sample of 4 × 109 tagged π0 mesons from K+ → π+π0(γ), searching for the decay of the π0 to invisible particles. No signal is observed in excess of the expected background fluctuations. An upper limit of 4.4 × 10−9 is set on the branching ratio at 90% confidence level, improving on previous results by a factor of 60. This result can also be interpreted as a model- independent upper limit on the branching ratio for the decay K+ → π+X, where X is a particle escaping detection with mass in the range 0.110–0.155 GeV/c2 and rest lifetime greater than 100 ps. Model-dependent upper limits are obtained assuming X to be an axion-like particle with dominant fermion couplings or a dark scalar mixing with the Standard Model Higgs boson.



2021 ◽  
Vol 7 (3) ◽  
pp. 50
Author(s):  
Emmi Välimäki ◽  
Lasse Yli-Varo ◽  
Henrik Romar ◽  
Ulla Lassi

The hydrogen economy will play a key role in future energy systems. Several thermal and catalytic methods for hydrogen production have been presented. In this review, methane thermocatalytic and thermal decomposition into hydrogen gas and solid carbon are considered. These processes, known as the thermal decomposition of methane (TDM) and thermocatalytic decomposition (TCD) of methane, respectively, appear to have the greatest potential for hydrogen production. In particular, the focus is on the different types and properties of carbons formed during the decomposition processes. The applications for carbons are also investigated.



2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Matthew O. Clarkson ◽  
Timothy M. Lenton ◽  
Morten B. Andersen ◽  
Marie-Laure Bagard ◽  
Alexander J. Dickson ◽  
...  

AbstractThe Paleocene Eocene Thermal Maximum (PETM) represents a major carbon cycle and climate perturbation that was associated with ocean de-oxygenation, in a qualitatively similar manner to the more extensive Mesozoic Oceanic Anoxic Events. Although indicators of ocean de-oxygenation are common for the PETM, and linked to biotic turnover, the global extent and temporal progression of de-oxygenation is poorly constrained. Here we present carbonate associated uranium isotope data for the PETM. A lack of resolvable perturbation to the U-cycle during the event suggests a limited expansion of seafloor anoxia on a global scale. We use this result, in conjunction with a biogeochemical model, to set an upper limit on the extent of global seafloor de-oxygenation. The model suggests that the new U isotope data, whilst also being consistent with plausible carbon emission scenarios and observations of carbon cycle recovery, permit a maximum ~10-fold expansion of anoxia, covering <2% of seafloor area.





1992 ◽  
Vol 286 ◽  
Author(s):  
Takeshi Okutani ◽  
Yoshinori Nakata ◽  
Masaakt Suzuki ◽  
Yves Maniette ◽  
Nobuyoshi Goto ◽  
...  

ABSTRACTSiC fine particles were synthesized by the gas-phase thermal decomposition of tetramethylsilane (Si(CH3)4) in hydrogen under microgravity of 10−4G for 10 sec. Rapid heating to the temperature over 800°C which is required for thermal decomposition of Si(CH3)4) under short-time microgravity was attained using a chemical oven where the heat of exothermic reaction of combustion synthesis of Ti-A1-4B composites was used as the heat source. Monodisperse and spherical SiC fine particles were synthesized under microgravity, whereas aggregates of SiC fine particles were synthesized under 1 G gravity. The SiC particles synthesized under microgravity (150-200 nm) were bigger in size and narrower in size distribution than those under 1 G gravity (100-150 nm).





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