Kinetics of hematite chlorination with Cl2 and Cl2 + O2: Part I. Chlorination with Cl2

Preliminary tests of the chlorination of two iron oxides (wüstite and hematite) in various chlorinating gas mixtures were performed by thermogravimetric analysis (TGA) under non-isothermal conditions. Wüstite started to react with chlorine from about 200 °C generating ferric chloride and hematite as the final reaction products. The presence of a reducing and oxidizing agent in the chlorinating gas mixtures influenced the chlorination reactions of both iron oxides, during non-isothermal treatment, only at temperatures higher than 500 °C.The chlorination kinetics of hematite with Cl₂ have been studied in details between 600 and 1025 °C under isothermal chlorination. The values of the apparent activation energy (E_a) were about 180 and 75 kJ/mol in the temperature ranges of 600–875 and 875–1025 °C, respectively. The apparent reaction order with respect to Cl₂ was found to be 0.67 at 750 °C. Mathematical model fitting of the kinetics data was carried out to determine the most probable reaction mechanisms.     

Phosphinites derived from the 7-phosphanorbornene skeleton: first results in asymmetric catalysis

[structure: see text] The bisphosphinite 4 incorporating two 7-phosphanorbornene subunits is an efficient ligand for the Rh-catalyzed enantioselective hydrogenation of functional alkenes in terms of rate and enantioselectivity. This type of structures is readily accessible by [4 + 2] cycloaddition of phospholes with dienophilic alkenes and can be easily fine-tuned.     

First-principles calculation of the 17O NMR parameters of a calcium aluminosilicate glass

We have computed the (17)O NMR parameters of an amorphous calcium aluminosilicate (CAS) from first-principles. The atomic coordinates of a CAS glass of composition (CaO)(0.21)(Al(2)O (3))(0.12)(SiO (2))(0.67) were obtained by quenching a liquid to room temperature by the means of ab initio molecular-dynamics simulations of the Car-Parrinello type. The structure of the glass is found to be overall in good agreement with diffraction experiments. Some excess nonbridging O (NBO) atoms are found and are compensated by tricluster O atoms, i.e., by 3-fold coordinated O atoms to 4-fold coordinated Al or Si atoms. The glass coordinates were used to compute the (17)O NMR parameters using GGA-DFT and a correction of the Ca 3d orbital energy. The chemical shifts and the electric field gradients were obtained with the gauge including projector augmented-wave (GIPAW) and the projector augmented-wave (PAW) methods, respectively. The simulated 2D-3QMAS NMR spectrum of the CAS glass is in very good agreement with the available experimental data, notably because it takes into account the disorder present in the glass. This agreement further validates our CAS glass model. We show that the oxygen triclusters are not visible in a 2D-3QMAS NMR (17)O spectrum since their NMR parameters overlap with those of the Al-O-Si, Si-O-Si, or Al-O-Al sites. Finally, correlations between the structural characteristics and the values of the NMR parameters are extracted from the calculation with the aim of helping the interpretation of NMR spectra of glasses of similar compositions.     

Semi-martingales indexées par une partie de ℝd et formule de lto. Cas continu

Sans résumé     

A neutron diffraction study of disorder in SrCl2 at high temperature

High temperature powder neutron diffraction study of SrCl₂ is reported. The intensity of some reflections decreases drastically in the region 900–1100K. The neutron data have been interpreted by assuming that the chlorine ions are displaced slightly towards the empty octahedral sites.     

Gravity driven instabilities in miscible non-Newtonian fluid displacements in porous media

Gravity driven instabilities in model porous packings of 1 mm diameter spheres are studied by comparing the broadening of the displacement front between fluids of slightly different densities in stable and unstable configurations. Water, water–glycerol and water–polymer solutions are used to vary independently viscosity and molecular diffusion and study the influence of shear-thinning properties. Both injected and displaced solutions are identical but for a different concentration of NaNO₃ salt used as an ionic tracer and to introduce the density contrast. Dispersivity in stable configuration increases with polymer concentration – as already reported for double porosity packings of porous grains. Gravity-induced instabilities are shown to develop below a same threshold Péclet number Pe for water and water–glycerol solutions of different viscosities and result in considerable increases of the dispersivity. Measured threshold Pe values decrease markedly on the contrary with polymer concentration. The quantitative analysis demonstrates that the development of the instabilities is controlled by viscosity through a characteristic gravity number G (ratio between hydrostatic and viscous pressure gradients). A single threshold value of G accounts for results obtained on Newtonian and non-Newtonian solutions.     

Discovery of Highly Selective Alkyne Semihydrogenation Catalysts Based on First‐Row Transition‐Metallated Porous Organic Polymers

Five different first‐row transition metal precursors (V^III, Cr^III, Mn^II, Co^II, Ni^II) were successfully incorporated into a catechol porous organic polymer (POP) and characterized using ATR‐IR and XAS analysis. The resulting metallated POPs were then evaluated for catalytic alkyne hydrogenation using high‐throughput screening techniques. All POPs were unexpectedly found to be active and selective catalysts for alkyne semihydrogenation. Three of the metallated POPs (V, Cr, Mn) are the first of their kind to be active single‐site hydrogenation catalysts. These results highlight the advantages of using a POP platform to develop new catalysts which are otherwise difficult to achieve through traditional heterogeneous and homogeneous routes.