Enhancement of sonochemical degradation of phenol using hydrogen atom scavengers

Sonochemical degradation of phenol was found to be enhanced in the presence of the volatile hydrogen atom scavengers CCl4 and perfluorohexane. The non-volatile hydrogen atom scavenger iodate did not enhance phenol degradation. The first order rate constant for aqueous phenol degradation in separate experiments using different sonochemical probes increased in the presence of 150 microM CCl4 from 0.014 to 0.031 min(-1) (probe 1) and from 0.022 to 0.061 min(-1) (probe 2). In the presence of <1.5 microM C6H14, the first order rate constant increased from 0.014 to 0.032 min(-1) (probe 1). Hydroquinone was the major observed reaction intermediate both in the presence and absence of hydrogen atom scavengers. Hydroquinone yields were substantially higher in the presence of hydrogen atom scavengers, suggesting that hydroxyl radical pathways for phenol degradation were enhanced by the hydrogen atom scavengers. These additives may be useful in improving pollutant degradation efficiency or improving synthetic processes that rely on hydroxyl radical as a key intermediate.     

Investigation of termination reactions in free radical photopolymerization of UV powder formulations

The termination mechanisms occurring in a UV powder coating system during photopolymerization process are investigated and compared to a conventional acrylate monomer system. The influence of the photoinitiator concentration, viscosity and conversion percentage of the monomer are assessed leading to the study of curing kinetics of a UV powder urethane diacrylate based system. It is shown that termination occurs mainly by bimolecular termination (PRT). This mechanism is related to low reactive double bonds concentration and high photoinitiator concentration in the UV powder system. Moreover, the effect of surrounding atmosphere points out the role of the oxygen on polymerization mechanisms.     

Separation of CO2-CH4 mixtures in the mesoporous MIL-100(Cr) MOF: experimental and modelling approaches

Carbon dioxide is the main undesirable compound present in raw natural gas and biogas. Physisorption based adsorption processes such as pressure swing adsorption (PSA) are one of the solutions to selectively adsorb CO(2) from CH(4). Some hybrid crystalline porous materials that belong to the family of metal-organic frameworks (MOFs) show larger CO(2) adsorption capacity compared to the usual industrial adsorbents, such as zeolites and most activated carbons, which makes them potentially promising for such applications. However, their selectivity values have been most often determined using only single gas adsorption measurements combined with simple macroscopic thermodynamic models or by means of molecular simulations based on generic forcefields. The transfer of this systematic approach to all MOFs, whatever their complex physico-chemical features, needs to be considered with caution. In contrast, direct co-adsorption measurements collected on these new materials are still scarce. The aim of this study is to perform a complete analysis of the CO(2)-CH(4) co-adsorption in the mesoporous MIL-100(Cr) MOF (MIL stands for Materials from Institut Lavoisier) by means of a synergic combination of outstanding experimental and modelling tools. This solid has been chosen both for its fundamental interests, given its very large CO(2) adsorption capacities and its complexity with a combination of micropores and mesopores and the existence of unsaturated accessible metal sites. The predictions obtained by means of Grand Canonical Monte Carlo simulations based on generic forcefields as well as macroscopic thermodynamic (IAST, RAST) models will be compared to direct the co-adsorption experimental data (breakthrough curve and volumetric measurements).     

Allgemeine Eigenfunktionsentwicklungen,unitäre Darstellungen lokalkompakter Gruppen und automorphe Funktionen

Ohne ZusammenfassungHerrn Prof. Dr.Ernst Hölder zum 65. Geburtstag     

Direct and outer-sphere coordination of the magnesium ions in the crystal structures of complexes with 2-furancarboxylic acid (I) and 3-furancarboxylic acid (II)

(I) Mg₂C₂₀H₂₄O₁₈ monoclinic,PT,a=10.760(2) Å,b=11.052(2) Å,c=12.822(3) Å, α=105.31(3)^o, β=98.18(3)^o, γ=91.59(3)^o,Z=2. (II) MgC₁₀H₁₄O₁₀, monoclinic,C2/c,a=30.817(6)Å,b=10.499(2)Å,c=9.000(2)Å, β=91.31(3)^o,Z=8. Magnesium in complexes with furoic acids reveals two ways of coordination: direct, when furoic anions are bonded to Mg²⁺ in an ionic fashion and outer-sphere, when cations bind water in the first coordination sphere and furancarboxylic ligands are hydrogen bonded to the water molecules. This results in the formation of three bridging systems: ?Mg?O_carboxyl?C?O_carboxyl?Mg?, ?Mg?O_water ?O_carboxyl?C?O_carboxyl?C?O_carboxyl?Mg?, and ?Mg?O_water?O_carboxyl?C?O_carboxyl?O_water?Mg?. Magnesium 2-furancarboxylate (I) is dimeric, while magnesium 3-furancarboxylate (II) exhibits a polymeric structure.     

Mise au point dans le ternaire TlBiTe. Existence de deux phases nonstoechiometriques de type TlBiTe2

The cross section BiTeTlTe of the phase diagram TlBiTe was constructed by X-ray, microstructure, and DTA methods. Two phases were emphasized: Tl_1?xBi_1+xTe₂ with x = 0.06, and Tl_1?yBi_1+yTe₂ with y = 0.2. The first one is a nonstoichiometric representation of what so many authors studied as TlBiTe₂. The latter is a high-temperature phase which decomposes in eutectoïd reaction (415°C):

$\text{1.18{}\text{Tl}{}_{0.8}\text{Bi}{}_{1.2}\text{Te}{}_2\text{} ?}\text{Tl}{}_{0.94}\text{Bi}{}_{1.06}\text{Te}{}_2\text{+ 0.36 {}\text{BiTe}\text{}}$

.The high-temperature form undergoes a phase transformation by quenching, giving a metastable low-temperature form. The discussion includes electrical resistivity and thermoelectric measurements of each of them.