Search results for "Reaction"

ESR study of photo-oxidation of phenol at low temperature on polycrystalline titanium dioxide

1994

The formation of oxygen radicals on hydrated TiO 2 (anatase) samples irradiated at 77 K in the near-UV region and their interaction with adsorbed phenol molecules have been studied by electron spin resonance. The results indicate that the irradiation determines the generation of O 2 H · and O − radicals which react with adsorbed phenol molecules. Phenol-derived radicals are generated after warming the sample at room temperature. A reaction mechanism is proposed on the basis of the observed species.

1987

ESR spectroscopic analyses of the deep-green solutions of living poly(2-isopropenylnaphthalene) [poly(2-IPN)] in THF at −80°C provided no evidence of the presence of radical anions as long as butyllithium (BuLi) was used as initiator. In contrast to this finding, radicals could indeed be detected if the polymerization was performed with metallic potassium in THF. These radicals were found to be only stable at low temperatures. UV/VIS spectra of solutions of 2-IPN in THF or toluene and of catalytic quantities of BuLi were recorded at temperatures between −45 and +20°C. On heating to >0°C, the colour of the deep-green solution changes irreversibly to reddish-brown, and this colour change is a…

Evidence for H2S gas as an intermediate species in the reaction mechanism of trapping hydrogen by cobalt disulfide

2011

Cobalt sulfide prepared by aqueous precipitation using Na2S and a Co(II) salt is known to trap hydrogen at room temperature and low pressure. The importance of oxidation of the primary CoS precipitate with atmospheric oxygen with respect to its efficiency as a hydrogen absorber is demonstrated. This stage of oxidation produces a mixture of two solid phases: a partially crystallized cobalt hydroxide Co(OH)2 and an amorphous cobalt sulfide CoS2 with a Co(OH)2/CoS2 molar ratio of 1 as predicted by thermodynamics. This biphasic product is probably the basic cobalt sulfide CoSOH considered in older and even more recent work. This product traps molecular hydrogen with a H2/Co molar ratio of 0.5 w…

Analytical control of photocatalytic treatments: degradation of a sulfonated azo dye

2003

The degradation of Methyl Orange (C(14)H(14)N(3)SO(3)Na), chosen as a model sulfonated azo dye, was investigated in aqueous solutions containing suspended polycrystalline TiO(2) particles under irradiation with simulated sunlight. The dye disappearance and the formation of the mineralization end products were monitored; the formation of the main transient intermediates was also examined in detail. Particular attention was devoted to the identification and to the evolution of fragments retaining the chromophoric group. The comparison of data coming from various analytical techniques led to a possible reaction mechanism for the degradation process, giving insight into an aspect of the treatme…

Theoretical Modeling on the Reaction Mechanism of p-Nitrophenylmethylphosphate Alkaline Hydrolysis and its Kinetic Isotope Effects

2015

We have studied the alkaline hydrolysis of p-nitrophenylmethylphosphate (p-NPmP) in aqueous solution by means of polarizable continuum models and by hybrid quantum-mechanical/molecular-mechanical (QM/MM) methods. The theoretical predictions of kinetic isotope effects (KIEs) are in very good agreement with the experimental data, confirming a concerted asynchronous molecular mechanism. In addition, comparison of high level DFT theory with semiempirical AM1/d Hamiltonian has allowed checking the reliability of the later to be used in modeling very large molecular models containing phosphorus atoms.

Visible-light-induced oxidation of trans-ferulic acid by TiO2 photocatalysis

2012

Abstract The oxidation of trans-ferulic acid (C10H10O4) in aqueous TiO2 dispersion occurs via the formation of a charge-transfer complex on the TiO2 surface that is able to absorb visible light (λ ⩾ 400 nm). The main product is CO2, whereas secondary oxidation products are organic species such as vanillin, caffeic acid, homovanillic acid, and vanillylmandelic acid. Oxidation through the formation of a charge-transfer complex occurs only in the presence of specific TiO2 samples. Experiments in the absence of oxygen, in the presence of bromate ions and by using a phosphate-modified TiO2, have been carried out for investigating the reaction mechanism. In order to study the interaction between …

Ab initio study on the mechanism of the atmospheric reaction OH + O3--HO2 + O2.

2003

The atmospheric reaction (1) OH + O 3 → + O 2 was investigated theoretically by using MP2, QCISD, QCISD(T), and CCSD(T) methods with various basis sets. At the highest level of theory, namely, QCISD, the reaction is direct, with only one transition state between reactants and products. However, at the MP2 level, the reaction proceeds through a two-step mechanism and shows two transition states, TS1 and TS2, separated by an intermediate, Int. The different methodologies employed in this paper consistently predict the barrier height of reaction (1) to be within the range 2.16 - 5.11 kcal mol -1 , somewhat higher than the experimental value of 2.0 kcal mol -1 .

Über eine neue Methode zum Nachweis des als Primärprodukt der Autoxydation der Metalle Eisen, Nickel und Kobalt in Säure- und Salzlösungen gebildeten…

1971

H2O2 als Zwischenprodukt der Autoxydation (bzw. · OOH oder · OH) kann mit Hilfe der Phosphin-, Phosphinoxid- Methode bei Fe, Ni und Co wirksamer als mit Hilfe der Jodometrie erfast werden. In saurem Medium sind Tris-(m-aminophenyl)-phosphin (1), im alkalischen Bereich Tris-(p-carboxyphenyl)- phosphin (2) wirksame auch fur quantitative Bestimmungen geeignete Reagentien auf H2O2 · 1 und 2 reagieren bei hoheren Konzentrationen bis zu 20 ma1 schneller mit H2O2 als dieses mit der Eisengrenzflache. Ni und Co erzeugen mehr H2O2 als Fe. Bei Eisen entsteht im neutralen Medium mehr H2O2 als im sauren Bereich. Die unterschiedlichen Anfangsgeschwindigkeiten des Sauerstoffverbrauchs in sauerstoffhaltige…

Systematic conformational search analysis of the SRR and RRR epimers of 7-hydroxymatairesinol

2009

An extensive and systematic conformational search was performed on the two epimers of the natural lignan 7-hydroxymatairesinol (HMR), by means of a home-made Systematic Conformational Search Analysis (SCSA) code, designed to select more and more stable conformers through sequential geometry optimization of trial structures at increasing levels of calculation theory. In the present case, the starting molecular structures were selected by the semi-empirical AM1 method and filtered – i.e. decreased in number by choosing the more stable species – on the basis of their energy calculated by the HF method and the 6-31G(d) basis set. The geometries obtained were further refined by performing densit…

Palladium‐Catalyzed Electrophilic C–H‐Bond Fluorination: Mechanistic Overview and Supporting Evidence

2018

International audience; Palladium-catalyzed electrophilic fluorination is a particularly attractive and challenging synthetic issue. Because of the rapid evolution of this topic, a critical point on the mechanistic and experimental advances is provided herein. In the present review, we focused on current mechanistic understanding in electrophilic fluorination (and related halogenations) catalyzed by palladium, mainly with N-directing group. Our discussion is based on the well-characterized or calculated pertinent metal species and intermediates used for analyzing the plausible catalytic cycles. A particular effort has been devoted to gathering supporting data for the putative species involv…